Quaternary cocrystals: combinatorial synthetic strategies based on long-range synthon Aufbau modules (LSAM)

A synthetic strategy is outlined whereby a binary cocrystal may be developed in turn into a ternary and finally into a quaternary cocrystal. The strategy hinges on the concept of the long-range synthon Aufbau module (LSAM) which is a large supramolecular synthon containing more than one type of intermolecular interaction. Modulation of these interactions may be possible with the use of additional molecular components so that higher level cocrystals are produced. We report six quaternary cocrystals here. All are obtained as nearly exclusive crystallization products when four appropriate solid compounds are taken together in solution for crystallization.

1. Introduction

The design of multicomponent molecular crystals is recognized as one of the challenging areas in modern crystal engineering (Aakeröy et al., 2005; Tothadi & Desiraju, 2013; Tothadi et al., 2011; Bolla & Nangia, 2015; Tothadi et al., 2014). Any good synthetic scheme directed towards a higher cocrystal (ternary, quaternary) should ensure its appearance from a solution containing the various solid constituents in high yield, in other words, without two- or single-component byproducts (Dubey & Desiraju, 2014, 2015). The product should also be obtained in high supramolecular yield (Aakeröy et al., 2001), in other words, it should be obtained without various polymorphs or compounds containing different synthons. In all cocrystals, there are favorable hetero-molecular interactions (Almarsson et al., 2004; Desiraju et al., 2011; Resnati et al., 2015). The main difficulty in the design of higher component cocrystals is that it is very difficult to establish synthon hierarchies in systems where there are a large number of functionalities that can form numerous and diverse intermolecular interactions (Aakeröy et al., 2005; Tothadi & Desiraju, 2013; Tothadi et al., 2011, 2014; Bolla & Nangia, 2015). Out of this pool of competing interactions, it is necessary to avoid interaction crossover, or in other words certain supramolecular features need to be amplified at the expense of others (Aakeröy et al., 2011; Saha et al., 2005). Although supramolecular synthons have been invoked as retrosynthetic constructs to analyze and fashion crystal structures (Desiraju, 1995), simple synthon information is often insufficient to design real solids with tangible properties. As one moves to more complex and larger hydrogen-bonded architectures, the concept of the long range synthon Aufbau module (LSAM) may be more fruitful as these larger synthons contain more representative and characteristic information about symmetry, long range order and topology in the crystal structure (Ganguly & Desiraju, 2008, 2010). The concepts of the supramolecular synthon and the LSAM are not merely restricted to the understanding of crystal structures. Recent studies show that some of these smaller and larger synthons exist in solution prior to crystallization (Mukherjee et al., 2014). The build-up of a crystal from individual molecules may well be considered as occurring through a smooth and systematic build-up in structural complexity. It is in this context that the extended synthon or LSAM becomes useful in crystal structure design.

Recently some of us (Dubey & Desiraju, 2014, 2015) have shown that the principles of constitutional dynamic chemistry (Lehn, 2013, 2015) may be applied to combinatorial crystal synthesis and that the process of building up of LSAMs in solution involves a selection of certain preferred molecular conformations and small synthons. In this view, there are libraries (Lehn, 1999) of real and virtual synthons in solution and an associated library of crystal structures which in themselves constitute a landscape (Thakur et al., 2015a). These ideas were demonstrated by us in the synthesis of ternary cocrystals of phloroglucinol (PGL) (Dubey & Desiraju, 2014) and the related polyhydroxy natural product, quercetin (Dubey & Desiraju, 2015). We showed that these polyhydric phenols form a large number of polymorphic and pseudopolymorphic binary cocrystals with ditopic bases like 1,2-bis(4-pyridyl)ethane (DPE), phenazine (PHE) and so on. These binaries lead to a much smaller number of ternaries when a selected third component was taken for co-crystallization. A small number of ternary cocrystals in a system where there are many binary possibilities showed that the binary to ternary progression is convergent; our results hinted that such convergence may be further exploited for the design of quaternary cocrystals. These ideas are illustrated in the present article. Implicit in this analysis is that stable large synthons persist in solution and that suitably selected compounds may be further attached to these LSAMs leading to higher component crystals. It is unnecessary and impractical to consider the design of every new crystal as an ab initio exercise (Dunitz, 2015; Thakur et al., 2015b; Lecomte et al., 2015). Supramolecular synthons are kinetically favored crystallization intermediates and may be homologated to more elaborate structures, in solution, provided that the additional components are properly modulated in terms of intermolecular interactions (Desiraju, 2007).

2. Results and discussion

This article argues for the synthetic design of complex quaternary solids by systematic selection and fabrication from LSAMs in binary and ternary cocrystals. Fig. 1(a) shows a list of the compounds in this study with their acronyms, whilst Fig. 1(b) shows the relevant synthons (MacGillivray et al., 2008). The starting points in this crystal engineering exercise are the binary O—H⋯N based cocrystals formed by the polyhydric phenols, orcinol (ORC) and phloroglucinol (PGL) with tetramethylpyrazine (TMP). Fig. 2 shows two crystal forms of ORC·TMP, and also the single form of 2:3 PGL·TMP. It is noted that each of the ORC·TMP forms (actually pseudopolymorphs) has a different LSAM. In one of them (2:3 Form I obtained from MeNO₂), the TMP molecules form a more or less continuous one-dimensional array. This array is made up of closed TMP·ORC tetramers (synthon B, Fig. 2) and `free' TMP molecules that are intercalated via C—H⋯π interactions. The second (1:1 Form II obtained from MeOH in an attempted ternary crystallization) consists of discrete synthon B modules that are laterally offset with respect to one another so that there are no C—H⋯π interactions. Fig. 2 also shows the structure of the 2:3 PGL·TMP binary and it may be seen that it takes a packing similar to Form I of ORC·TMP. We also note that the intercalated LSAM is capable of further structural modification: the `free' TMP molecule could in principle be substituted with another flat aromatic molecule to yield a ternary (Tothadi et al., 2011). However, the laterally offset LSAM is not capable of such extension. It has been suggested that LSAMs are generally one-dimensional in nature (Ganguly & Desiraju, 2010). In these prototype binary systems, the O—H⋯N and C—H⋯π interactions facilitate collinear molecular arrangements. Once this critical LSAM is identified, the next step is to fabricate it with optimized synthon hierarchies established during the landscape exploration to realise higher multi-component systems. Effectively, the one-dimensional LSAM is modular with respect to the three-dimensional structure, unlike the smaller synthons.

Figure 1 (a) Compounds in this study; (b) operating supramolecular synthons (A and B) in the crystal synthesis of multi-component systems. Polyhydric phenols ORC, PGL are shown in green. Blue, red are connector bases. Synthon B with different connector bases is not observed.

Figure 2 Binary cocrystals. (a) 2:3 ORC·TMP Form I; (b) 1:1 ORC·TMP Form II (hydrated); (c) 2:3 PGL·TMP. Distinct chemical species are color coded. Note the continuous one-dimensional LSAMs in ORC·TMP Form I and PGL·TMP and the different orientations of the pink-shaded TMP molecules in the two cases.

Cocrystallization of a mixture of ORC and TMP with each of PHE, acridine (ACR), 1,10-phenanthroline (PHEN), 2,2-bisthiophene (22TP), hexamethylbenzene (HMB) and pyrene (PYR) results in stoichiometric ternary cocrystals. The structures of three of them (2:2:1 ORC·TMP·22TP, 2:2:1 ORC·TMP·HMB and 2:2:1 ORC·TMP·PYR) are along predicted lines and they may be considered as being obtained by substitution of the `free' TMP molecule in Form I of the ORC·TMP binary with the new aromatic compound (Fig. 3). The other three structures (2:1:2 ORC·TMP·PHE, 2:1:2 ORC·TMP·ACR, 2:1:2 ORC·TMP·PHEN), however, are based on the open synthon A (Fig. 4) and the third compound is actually a part of this synthon. This third component is an electron-deficient species and stacks with itself leading to a one-dimensional array. The TMP molecule forms C—H⋯π interactions with the third component within synthon A. The fact that an ORC·TMP binary with open synthon A is not isolated indicates that this synthon is virtual (Dubey & Desiraju, 2014) with respect to the binary system but becomes accessible in the ternary system. A virtual synthon is defined as one which is the product of a potential molecular recognition event that does not take place in a certain system. In summary, the ORC·TMP system is quite adaptive: it can sustain continuous and discrete one-dimensional LSAMs; it can sustain open and closed O—H⋯N based synthons.

Figure 3 2:2:1 stoichiometric ternary cocrystals with supramolecular synthon B. (a) Orcinol-tetramethylpyrazine-pyrene; (b) orcinol-tetramethylpyrazine-hexamethylbenzene.

Figure 4 2:1:2 stoichiometricternary cocrystals with supramolecular synthon A. (a) Orcinol-tetramethylpyrazine-phenazine; (b) orcinol-tetramethylpyrazine-acridine.

Let us consider next the ternary cocrystals formed by PGL. Co-crystallization of equimolar amounts of PGL and TMP with each of PHE, PYR and DPE resulted in four structurally distinct ternaries. When PGL, TMP and PHE were cocrystallized, two forms were obtained depending on the solvent used. From MeCN we obtained the 2:1:3 Form I (Fig. 5) in which closed synthon B is constructed exclusively with PHE and the TMP molecules provide cross links via the third `hook' hydroxy group of the PGL molecule. From MeCN also but under different conditions, we obtained the 2:1:2 Form II which is reminiscent of the ORC·TMP·PHE ternary except that PHE is in the `inner' part of synthon A rather than in the `outer' part. There was no contamination of either of these ternaries by the `other' ternary in the crystallization experiments. A priori, it would not be possible to predict which structure one would obtain from MeCN under what conditions. What is important, however, is that there are a number of topologically similar crystal structures available to the system. Which one is actually obtained would seem to depend on the exact experimental conditions used. The system lends itself to high throughput methods. We maintain that we carried out a very large number of crystallization experiments on an entire array of compounds and solvent systems in a combinatorial manner. It is of interest to note that such examples of (pseudo)polymorphism are very rare in three component systems (Tothadi et al., 2011).

Figure 5 Pseudopolymorphs of the stoichiometric ternary cocrystal phloroglucinol-tetramethylpyrazine-phenazine. (a) 2:1:3 solid from MeCN; (b) 2:1:2 solid also obtained from MeCN.

We now discuss the 2:2:1 PGL·TMP·PYR and 2:2:1 PGL·TMP·DPE ternary cocrystals (Fig. 6). The former is exactly like the synthon B based ternaries formed by ORC and TMP (with PYR, HMB and 22TP, Fig. 3). There is a clean replacement of the `free' TMP in the ORC·TMP binary by the third compound. We note that the PGL·TMP binary does not contain any `free' TMP once again showing synthon virtuality. The 2:2:1 PGL·TMP·DPE ternary cocrystal is similar to the 2:2:1 PGL·PHE·DPE ternary which we have already reported. Closed synthon B modules are cross linked with DPE through the third `hook' hydroxy group of the PGL molecule. A study of the 10 ternary structures in this work shows that there are three regions which are capable of higher elaboration into quaternaries: open synthons of the type A can contain more than one heterocyclic base; open and closed synthons, A and B, can be intercalated/stacked with appropriate new planar molecules; the third `hook' hydroxy group in PGL can be cross linked with a new component. We never observed a closed synthon B with two different heterocyclic bases and feel this to be an unlikely outcome (Fig. 1). These results open the way for isolation of quaternaries based on ORC and PGL. Fig. 7 is a flow chart of possible events. Because of synthon virtuality, it is not required that quaternaries in either of systems (ORC or PGL) must necessarily follow from ternaries in the same system. In the same way, a ternary may be based on a binary of the other phenol. All these structure types would appear to be isolable and which particular crystal form is isolated would seem to depend on experimental conditions of crystallization.

Figure 6 2:2:1 stoichiometric ternary cocrystals with supramolecular synthon B. (a) Phloroglucinol-tetramethylpyrazine-pyrene; (b) phloroglucinol-tetramethylpyrazine-1,2-bis(4-pyridyl)ethane.

Figure 7 Schematic representation of the long range synthon Aufbau modules (LSAMs) in the crystal synthesis of multi-component crystals. Color coding signifies distinct chemical species in the LSAMs.

In practice, a total of six quaternaries were obtained, three each from ORC and PGL (Fig. 8 and section S3 of the supporting information). Let us consider these structures in turn. The 2:1:2:1 ORC·TMP·PHE·HMB structure follows smoothly from the ternary 2:1:2 ORC·TMP·PHE in a chemically reasonable manner. In the ternary, one observes π⋯π stacking between electron-deficient PHE molecules (3.29 Å, 3.54 Å). In the quaternary, HMB inserts in a classical donor–acceptor fashion (∼ 3.56 Å). Replacement of the electron-rich HMB by PYR and the ditopic PHE by ACR achieves the same result and one obtains the stoichiometric quaternaries 2:1:2:1 ORC·TMP·PHE·PYR and 2:1:2:1 ORC·TMP·ACR·PYR (see section S3 ). Coming next to PGL, it is not difficult to understand the crystal structure of the quaternary 2:1:1:1 PGL·TMP.PHE.DPE wherein an infinite synthon A based structure with two ditopic heterocycles is cross linked with DPE. The quaternaries 2:2:1:1 PGL.TMP.PHE.ANT and 2:2:1:1 PGL.TMP.PHE.PYR have very similar structures. Synthon A is constructed with TMP in the `outer' locations and PHE in the `inner' location. ANT and PYR intercalate with C—H⋯π interactions to give a columnar LSAM.

Figure 8 Stoichiometric quaternary cocrystals. (a) Orcinol-tetramethylpyrazine-phenazine-pyrene; (b) phloroglucinol-tetramethylpyrazine-phenazine-pyrene (obtained as a hydrate).

3. Conclusions

The results obtained in this work validate the idea of using a supramolecular combinatorial library in the isolation of stoichiometric three- and four-component molecular crystals. We have earlier used this concept to make a single ternary cocrystal (Dubey & Desiraju, 2014). In the present study, 10 new ternaries have been reported. The crystal structures of these compounds contain extended synthon assemblies which are referred to as long-range synthon Aufbau modules or LSAMs. These LSAMs are modular units and new molecules can be appended or exchanged with molecules in the LSAM to obtain larger synthons that contain four distinct chemical entities, each of which forms a solid under ambient conditions in its native crystal structure. These larger units are the precursors to stoichiometric quaternary cocrystals, of which six are reported in this paper. While there is no spectroscopic evidence as yet for the existence of these LSAMs in solution (unlike in other cases already reported; Mukherjee et al., 2014), the fact that there is so much fidelity between the ternary and quaternary crystal structures suggests the stability of the LSAMs in solution. We also note the degree of reversibility among synthons in solution. This leads to the concept of a virtual synthon, a supramolecular unit that may not lead to an isolable solid but manifests itself in a crystal structure of a higher-component solid. In other words, two compounds A and B may result in two putative synthons S₁ and S₂. While S₁ may be found in a binary cocrystal, S₂ may not be similarly found. However S₂ (or a close equivalent) may be found in a ternary cocrystal between say, A, B and C. Similarly, a synthon that is virtual in a three-component system may be seen in a four-component cocrystal. This also implies that proof correction mechanisms exist in the crystallizations, perhaps leading to the specificity of outcome.¹ It is impressive to note the specificity of these crystallizations in systems containing a large number of energetically similar intermolecular interactions. We found very little contamination of the crystalline products by other solids, whether they are of the same complexity level or whether they are simpler in nature. None of the quaternaries we isolated, save one, were contaminated for instance by polymorphic or pseudopolymorphic quaternaries or by ternaries and binaries. The key to using the LSAM concept in designing higher-component cocrystals seems to be a judicious choice of starting compounds, well balanced intermolecular interactions and high throughput methodologies of crystallization and crystallography, in other words a combinatorial approach.

Supporting information

Computing details

For all compounds, program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013).

(BS_ORC_TMP)

Crystal data

C38H52N6O4	V = 897.56 (15) Å^3
Mr = 656.85	Z = 1
Triclinic, P1	F(000) = 354
a = 8.8712 (8) Å	Dx = 1.215 Mg m^−3
b = 10.1819 (9) Å	Mo Kα radiation, λ = 0.71073 Å
c = 11.2862 (10) Å	µ = 0.08 mm^−1
α = 114.633 (8)°	T = 150 K
β = 93.749 (7)°	Plate, colorless
γ = 101.000 (7)°	0.48 × 0.25 × 0.15 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	3555 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.020
profile data from ω–scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −11→11
Tmin = 0.850, Tmax = 1.000	k = −13→13
9617 measured reflections	l = −14→14
4113 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.124	w = 1/[σ^2(Fo^2) + (0.058P)^2 + 0.3975P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
4113 reflections	Δρmax = 0.31 e Å^−3
226 parameters	Δρmin = −0.27 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.44502 (14)	0.50013 (14)	0.23039 (13)	0.0176 (3)
C2	0.41232 (15)	0.54440 (14)	0.35846 (13)	0.0189 (3)
H2	0.4500	0.5027	0.4122	0.023*
C3	0.32454 (15)	0.64961 (14)	0.40809 (13)	0.0178 (3)
C4	0.27023 (14)	0.71307 (14)	0.33137 (13)	0.0176 (3)
H4	0.2112	0.7854	0.3657	0.021*
C5	0.30368 (15)	0.66908 (14)	0.20318 (13)	0.0176 (3)
C6	0.39006 (15)	0.56246 (14)	0.15261 (13)	0.0182 (3)
H6	0.4114	0.5324	0.0649	0.022*
C7	0.53436 (17)	0.38112 (15)	0.17558 (15)	0.0235 (3)
H7A	0.5898	0.3717	0.2485	0.035*
H7B	0.6095	0.4086	0.1250	0.035*
H7C	0.4617	0.2859	0.1177	0.035*
C8	0.28890 (16)	−0.06667 (16)	−0.06807 (15)	0.0252 (3)
H8A	0.3686	0.0263	−0.0397	0.038*
H8B	0.2781	−0.1249	−0.1639	0.038*
H8C	0.3197	−0.1242	−0.0234	0.038*
C9	0.13595 (15)	−0.03159 (14)	−0.03299 (13)	0.0185 (3)
C10	0.00062 (15)	0.14434 (14)	0.07142 (13)	0.0183 (3)
C11	0.00087 (17)	0.30556 (15)	0.14974 (15)	0.0245 (3)
H11A	0.1080	0.3663	0.1741	0.037*
H11B	−0.0437	0.3183	0.2299	0.037*
H11C	−0.0615	0.3371	0.0962	0.037*
C12	−0.05460 (15)	0.83295 (14)	0.59691 (13)	0.0189 (3)
C13	−0.14339 (15)	0.92883 (15)	0.67063 (13)	0.0181 (3)
C14	0.07366 (15)	1.12628 (14)	0.74744 (13)	0.0186 (3)
C15	0.16284 (15)	1.03029 (15)	0.67567 (13)	0.0197 (3)
C16	−0.12390 (17)	0.67050 (16)	0.51069 (16)	0.0282 (3)
H16A	−0.0448	0.6249	0.4633	0.042*
H16B	−0.2117	0.6591	0.4469	0.042*
H16C	−0.1604	0.6215	0.5656	0.042*
C17	−0.31221 (16)	0.87402 (17)	0.67158 (16)	0.0266 (3)
H17A	−0.3554	0.9587	0.7222	0.040*
H17B	−0.3234	0.8054	0.7125	0.040*
H17C	−0.3683	0.8221	0.5807	0.040*
C18	0.14247 (18)	1.28915 (16)	0.83228 (16)	0.0282 (3)
H18A	0.0587	1.3414	0.8534	0.042*
H18B	0.2110	1.3297	0.7846	0.042*
H18C	0.2026	1.3027	0.9142	0.042*
C19	0.33355 (17)	1.08352 (17)	0.67812 (17)	0.0300 (3)
H19A	0.3737	0.9999	0.6203	0.045*
H19B	0.3891	1.1243	0.7686	0.045*
H19C	0.3492	1.1610	0.6471	0.045*
N1	0.09765 (13)	0.88507 (12)	0.60240 (11)	0.0198 (2)
N2	−0.07764 (13)	1.07368 (12)	0.74435 (11)	0.0187 (2)
N3	0.13574 (13)	0.11187 (12)	0.03815 (11)	0.0198 (2)
O1	0.29392 (12)	0.68723 (11)	0.53369 (9)	0.0238 (2)
H1	0.2348	0.7458	0.5508	0.036*
O2	0.25516 (12)	0.72802 (12)	0.12338 (10)	0.0254 (2)
H2A	0.2019	0.7882	0.1625	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0133 (6)	0.0131 (6)	0.0231 (6)	0.0022 (4)	0.0025 (5)	0.0054 (5)
C2	0.0177 (6)	0.0183 (6)	0.0219 (6)	0.0055 (5)	0.0012 (5)	0.0096 (5)
C3	0.0175 (6)	0.0164 (6)	0.0169 (6)	0.0029 (5)	0.0021 (5)	0.0056 (5)
C4	0.0165 (6)	0.0164 (6)	0.0197 (6)	0.0057 (5)	0.0041 (5)	0.0067 (5)
C5	0.0165 (6)	0.0181 (6)	0.0191 (6)	0.0044 (5)	0.0029 (5)	0.0089 (5)
C6	0.0179 (6)	0.0178 (6)	0.0181 (6)	0.0050 (5)	0.0063 (5)	0.0063 (5)
C7	0.0240 (7)	0.0198 (6)	0.0290 (7)	0.0109 (5)	0.0085 (6)	0.0097 (6)
C8	0.0175 (6)	0.0252 (7)	0.0346 (8)	0.0071 (5)	0.0051 (6)	0.0138 (6)
C9	0.0171 (6)	0.0200 (6)	0.0201 (6)	0.0060 (5)	0.0012 (5)	0.0101 (5)
C10	0.0190 (6)	0.0185 (6)	0.0188 (6)	0.0054 (5)	0.0011 (5)	0.0093 (5)
C11	0.0239 (7)	0.0180 (6)	0.0275 (7)	0.0053 (5)	0.0021 (6)	0.0063 (6)
C12	0.0189 (6)	0.0183 (6)	0.0188 (6)	0.0037 (5)	0.0026 (5)	0.0079 (5)
C13	0.0168 (6)	0.0202 (6)	0.0186 (6)	0.0046 (5)	0.0018 (5)	0.0098 (5)
C14	0.0211 (6)	0.0174 (6)	0.0181 (6)	0.0047 (5)	0.0030 (5)	0.0085 (5)
C15	0.0185 (6)	0.0199 (6)	0.0208 (6)	0.0044 (5)	0.0035 (5)	0.0090 (5)
C16	0.0248 (7)	0.0196 (7)	0.0319 (8)	0.0025 (5)	0.0037 (6)	0.0045 (6)
C17	0.0164 (6)	0.0285 (7)	0.0322 (8)	0.0038 (5)	0.0036 (6)	0.0116 (6)
C18	0.0294 (7)	0.0175 (7)	0.0313 (8)	0.0023 (6)	0.0065 (6)	0.0057 (6)
C19	0.0200 (7)	0.0250 (7)	0.0412 (9)	0.0031 (6)	0.0092 (6)	0.0114 (7)
N1	0.0201 (5)	0.0194 (6)	0.0196 (5)	0.0053 (4)	0.0053 (4)	0.0079 (5)
N2	0.0201 (5)	0.0189 (5)	0.0201 (5)	0.0077 (4)	0.0036 (4)	0.0099 (5)
N3	0.0177 (5)	0.0194 (5)	0.0224 (6)	0.0043 (4)	0.0007 (4)	0.0098 (5)
O1	0.0302 (5)	0.0274 (5)	0.0183 (5)	0.0147 (4)	0.0078 (4)	0.0105 (4)
O2	0.0335 (6)	0.0313 (6)	0.0230 (5)	0.0206 (4)	0.0123 (4)	0.0165 (4)

Geometric parameters (Å, º)

C1—C6	1.3920 (19)	C11—H11C	0.9800
C1—C2	1.3922 (19)	C12—N1	1.3408 (17)
C1—C7	1.5116 (17)	C12—C13	1.4028 (18)
C2—C3	1.3939 (18)	C12—C16	1.5009 (19)
C2—H2	0.9500	C13—N2	1.3391 (17)
C3—O1	1.3665 (16)	C13—C17	1.4975 (18)
C3—C4	1.3893 (18)	C14—N2	1.3393 (17)
C4—C5	1.3959 (18)	C14—C15	1.3986 (18)
C4—H4	0.9500	C14—C18	1.5010 (19)
C5—O2	1.3620 (16)	C15—N1	1.3403 (17)
C5—C6	1.3963 (17)	C15—C19	1.5022 (19)
C6—H6	0.9500	C16—H16A	0.9800
C7—H7A	0.9800	C16—H16B	0.9800
C7—H7B	0.9800	C16—H16C	0.9800
C7—H7C	0.9800	C17—H17A	0.9800
C8—C9	1.5042 (18)	C17—H17B	0.9800
C8—H8A	0.9800	C17—H17C	0.9800
C8—H8B	0.9800	C18—H18A	0.9800
C8—H8C	0.9800	C18—H18B	0.9800
C9—N3	1.3423 (17)	C18—H18C	0.9800
C9—C10^i	1.3997 (18)	C19—H19A	0.9800
C10—N3	1.3393 (17)	C19—H19B	0.9800
C10—C9^i	1.3997 (18)	C19—H19C	0.9800
C10—C11	1.5049 (18)	O1—H1	0.8400
C11—H11A	0.9800	O2—H2A	0.8400
C11—H11B	0.9800
C6—C1—C2	119.43 (11)	N1—C12—C13	120.18 (12)
C6—C1—C7	120.73 (12)	N1—C12—C16	117.64 (12)
C2—C1—C7	119.80 (12)	C13—C12—C16	122.18 (12)
C1—C2—C3	120.27 (12)	N2—C13—C12	120.27 (12)
C1—C2—H2	119.9	N2—C13—C17	117.83 (12)
C3—C2—H2	119.9	C12—C13—C17	121.90 (12)
O1—C3—C4	121.59 (11)	N2—C14—C15	120.26 (12)
O1—C3—C2	117.79 (12)	N2—C14—C18	117.57 (12)
C4—C3—C2	120.61 (12)	C15—C14—C18	122.15 (12)
C3—C4—C5	119.06 (12)	N1—C15—C14	120.40 (12)
C3—C4—H4	120.5	N1—C15—C19	117.39 (12)
C5—C4—H4	120.5	C14—C15—C19	122.20 (12)
O2—C5—C4	121.96 (11)	C12—C16—H16A	109.5
O2—C5—C6	117.56 (11)	C12—C16—H16B	109.5
C4—C5—C6	120.48 (12)	H16A—C16—H16B	109.5
C1—C6—C5	120.13 (12)	C12—C16—H16C	109.5
C1—C6—H6	119.9	H16A—C16—H16C	109.5
C5—C6—H6	119.9	H16B—C16—H16C	109.5
C1—C7—H7A	109.5	C13—C17—H17A	109.5
C1—C7—H7B	109.5	C13—C17—H17B	109.5
H7A—C7—H7B	109.5	H17A—C17—H17B	109.5
C1—C7—H7C	109.5	C13—C17—H17C	109.5
H7A—C7—H7C	109.5	H17A—C17—H17C	109.5
H7B—C7—H7C	109.5	H17B—C17—H17C	109.5
C9—C8—H8A	109.5	C14—C18—H18A	109.5
C9—C8—H8B	109.5	C14—C18—H18B	109.5
H8A—C8—H8B	109.5	H18A—C18—H18B	109.5
C9—C8—H8C	109.5	C14—C18—H18C	109.5
H8A—C8—H8C	109.5	H18A—C18—H18C	109.5
H8B—C8—H8C	109.5	H18B—C18—H18C	109.5
N3—C9—C10^i	121.22 (12)	C15—C19—H19A	109.5
N3—C9—C8	117.46 (12)	C15—C19—H19B	109.5
C10^i—C9—C8	121.32 (12)	H19A—C19—H19B	109.5
N3—C10—C9^i	120.76 (12)	C15—C19—H19C	109.5
N3—C10—C11	117.73 (12)	H19A—C19—H19C	109.5
C9^i—C10—C11	121.51 (12)	H19B—C19—H19C	109.5
C10—C11—H11A	109.5	C15—N1—C12	119.36 (11)
C10—C11—H11B	109.5	C13—N2—C14	119.49 (11)
H11A—C11—H11B	109.5	C10—N3—C9	118.02 (11)
C10—C11—H11C	109.5	C3—O1—H1	109.5
H11A—C11—H11C	109.5	C5—O2—H2A	109.5
H11B—C11—H11C	109.5

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N2^ii	0.95	2.64	3.3369 (17)	131
O1—H1···N1	0.84	1.97	2.8114 (15)	176
O2—H2A···N2^ii	0.84	1.95	2.7917 (15)	179

Symmetry code: (ii) −x, −y+2, −z+1.

(BS_ORC_TMP_Hydrate)

Crystal data

C120H160N16O17	Z = 1
Mr = 2098.63	F(000) = 1128
Monoclinic, C2/c	Dx = 1.204 Mg m^−3
a = 15.533 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.564 (4) Å	µ = 0.08 mm^−1
c = 21.80 (1) Å	T = 150 K
β = 93.873 (7)°	Plate, light brown
V = 2893 (2) Å^3	0.50 × 0.35 × 0.25 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	2733 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.035
profile data from ω–scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −20→20
Tmin = 0.797, Tmax = 1.000	k = −11→11
14570 measured reflections	l = −28→28
3316 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.145	w = 1/[σ^2(Fo^2) + (0.0739P)^2 + 1.925P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3316 reflections	Δρmax = 0.24 e Å^−3
184 parameters	Δρmin = −0.23 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O6	0.0000	−0.0054 (18)	0.7500	0.144 (6)	0.25
C1	0.20192 (10)	−0.2097 (2)	0.70590 (6)	0.0357 (4)
C2	0.18902 (10)	−0.08328 (19)	0.66720 (7)	0.0335 (4)
H2	0.1380	−0.0225	0.6682	0.040*
C3	0.25132 (9)	−0.04525 (18)	0.62671 (6)	0.0303 (3)
C4	0.32485 (9)	−0.13499 (18)	0.62405 (7)	0.0300 (3)
H4	0.3670	−0.1088	0.5961	0.036*
C5	0.33682 (10)	−0.26305 (18)	0.66219 (7)	0.0326 (3)
C6	0.27568 (11)	−0.3004 (2)	0.70343 (7)	0.0364 (4)
H6	0.2843	−0.3879	0.7299	0.044*
C7	0.13602 (14)	−0.2473 (3)	0.75162 (8)	0.0527 (5)
H7A	0.1333	−0.1614	0.7811	0.079*
H7B	0.1527	−0.3437	0.7736	0.079*
H7C	0.0793	−0.2614	0.7298	0.079*
C8	0.08807 (9)	0.33628 (17)	0.58985 (7)	0.0286 (3)
C9	0.14432 (9)	0.38774 (18)	0.54694 (7)	0.0305 (3)
C10	0.05315 (9)	0.28951 (17)	0.46845 (7)	0.0289 (3)
C11	−0.00261 (9)	0.23759 (17)	0.51126 (7)	0.0289 (3)
C12	0.10687 (12)	0.3602 (2)	0.65741 (7)	0.0434 (4)
H12A	0.0571	0.3267	0.6794	0.065*
H12B	0.1183	0.4710	0.6656	0.065*
H12C	0.1575	0.2984	0.6715	0.065*
C13	0.22686 (12)	0.4697 (3)	0.56597 (9)	0.0498 (5)
H13A	0.2582	0.4928	0.5295	0.075*
H13B	0.2624	0.4027	0.5940	0.075*
H13C	0.2141	0.5674	0.5869	0.075*
C14	0.03565 (12)	0.2639 (2)	0.40092 (8)	0.0426 (4)
H14A	0.0747	0.3290	0.3784	0.064*
H14B	−0.0243	0.2921	0.3889	0.064*
H14C	0.0451	0.1537	0.3912	0.064*
C15	−0.08499 (11)	0.1534 (2)	0.49286 (8)	0.0439 (4)
H15A	−0.1079	0.1060	0.5293	0.066*
H15B	−0.0737	0.0717	0.4630	0.066*
H15C	−0.1272	0.2276	0.4743	0.066*
N1	0.01605 (8)	0.26083 (14)	0.57142 (6)	0.0296 (3)
N2	0.12649 (8)	0.36261 (15)	0.48714 (6)	0.0307 (3)
O1	0.23737 (7)	0.08193 (14)	0.59026 (6)	0.0424 (3)
H1	0.2800	0.0958	0.5692	0.064*
O2	0.40716 (8)	−0.35715 (15)	0.65971 (6)	0.0473 (3)
H2A	0.4406	−0.3198	0.6348	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O6	0.158 (14)	0.089 (10)	0.184 (17)	0.000	0.002 (12)	0.000
C1	0.0413 (8)	0.0452 (9)	0.0218 (7)	−0.0152 (7)	0.0102 (6)	−0.0070 (6)
C2	0.0309 (8)	0.0415 (9)	0.0290 (7)	−0.0057 (6)	0.0091 (6)	−0.0061 (6)
C3	0.0299 (7)	0.0335 (8)	0.0279 (7)	−0.0049 (6)	0.0053 (5)	−0.0012 (6)
C4	0.0282 (7)	0.0328 (8)	0.0299 (7)	−0.0069 (6)	0.0091 (5)	0.0003 (6)
C5	0.0329 (8)	0.0348 (8)	0.0300 (7)	−0.0060 (6)	0.0014 (6)	−0.0002 (6)
C6	0.0460 (9)	0.0389 (9)	0.0243 (7)	−0.0103 (7)	0.0021 (6)	0.0037 (6)
C7	0.0630 (12)	0.0623 (12)	0.0363 (9)	−0.0172 (9)	0.0287 (8)	−0.0023 (8)
C8	0.0274 (7)	0.0278 (7)	0.0306 (7)	0.0015 (5)	0.0017 (5)	0.0018 (6)
C9	0.0289 (7)	0.0293 (7)	0.0332 (7)	−0.0038 (6)	0.0015 (6)	0.0031 (6)
C10	0.0293 (7)	0.0271 (7)	0.0306 (7)	−0.0001 (6)	0.0040 (5)	0.0013 (6)
C11	0.0248 (7)	0.0292 (7)	0.0328 (8)	−0.0008 (5)	0.0033 (5)	−0.0014 (6)
C12	0.0483 (10)	0.0511 (10)	0.0305 (8)	−0.0057 (8)	0.0000 (7)	−0.0009 (7)
C13	0.0418 (10)	0.0603 (12)	0.0469 (10)	−0.0242 (9)	−0.0003 (7)	0.0005 (9)
C14	0.0482 (10)	0.0494 (10)	0.0303 (8)	−0.0081 (8)	0.0034 (7)	−0.0014 (7)
C15	0.0314 (8)	0.0542 (11)	0.0461 (9)	−0.0128 (7)	0.0029 (7)	−0.0044 (8)
N1	0.0255 (6)	0.0323 (7)	0.0315 (6)	0.0005 (5)	0.0063 (5)	0.0009 (5)
N2	0.0304 (6)	0.0306 (6)	0.0315 (6)	−0.0048 (5)	0.0057 (5)	0.0040 (5)
O1	0.0376 (6)	0.0438 (7)	0.0479 (7)	0.0063 (5)	0.0174 (5)	0.0145 (5)
O2	0.0421 (7)	0.0462 (7)	0.0550 (8)	0.0049 (5)	0.0127 (5)	0.0170 (6)

Geometric parameters (Å, º)

C1—C2	1.379 (2)	C10—N2	1.3390 (19)
C1—C6	1.388 (2)	C10—C11	1.389 (2)
C1—C7	1.511 (2)	C10—C14	1.495 (2)
C2—C3	1.392 (2)	C11—N1	1.339 (2)
C2—H2	0.9500	C11—C15	1.499 (2)
C3—O1	1.357 (2)	C12—H12A	0.9800
C3—C4	1.381 (2)	C12—H12B	0.9800
C4—C5	1.381 (2)	C12—H12C	0.9800
C4—H4	0.9500	C13—H13A	0.9800
C5—O2	1.362 (2)	C13—H13B	0.9800
C5—C6	1.388 (2)	C13—H13C	0.9800
C6—H6	0.9500	C14—H14A	0.9800
C7—H7A	0.9800	C14—H14B	0.9800
C7—H7B	0.9800	C14—H14C	0.9800
C7—H7C	0.9800	C15—H15A	0.9800
C8—N1	1.3303 (19)	C15—H15B	0.9800
C8—C9	1.394 (2)	C15—H15C	0.9800
C8—C12	1.496 (2)	O1—H1	0.8400
C9—N2	1.332 (2)	O2—H2A	0.8400
C9—C13	1.496 (2)
C2—C1—C6	120.11 (14)	C11—C10—C14	122.32 (14)
C2—C1—C7	119.62 (16)	N1—C11—C10	120.48 (13)
C6—C1—C7	120.27 (16)	N1—C11—C15	117.25 (13)
C1—C2—C3	119.56 (15)	C10—C11—C15	122.27 (14)
C1—C2—H2	120.2	C8—C12—H12A	109.5
C3—C2—H2	120.2	C8—C12—H12B	109.5
O1—C3—C4	121.46 (13)	H12A—C12—H12B	109.5
O1—C3—C2	117.96 (14)	C8—C12—H12C	109.5
C4—C3—C2	120.59 (14)	H12A—C12—H12C	109.5
C3—C4—C5	119.64 (13)	H12B—C12—H12C	109.5
C3—C4—H4	120.2	C9—C13—H13A	109.5
C5—C4—H4	120.2	C9—C13—H13B	109.5
O2—C5—C4	121.46 (14)	H13A—C13—H13B	109.5
O2—C5—C6	118.37 (14)	C9—C13—H13C	109.5
C4—C5—C6	120.16 (15)	H13A—C13—H13C	109.5
C1—C6—C5	119.92 (15)	H13B—C13—H13C	109.5
C1—C6—H6	120.0	C10—C14—H14A	109.5
C5—C6—H6	120.0	C10—C14—H14B	109.5
C1—C7—H7A	109.5	H14A—C14—H14B	109.5
C1—C7—H7B	109.5	C10—C14—H14C	109.5
H7A—C7—H7B	109.5	H14A—C14—H14C	109.5
C1—C7—H7C	109.5	H14B—C14—H14C	109.5
H7A—C7—H7C	109.5	C11—C15—H15A	109.5
H7B—C7—H7C	109.5	C11—C15—H15B	109.5
N1—C8—C9	120.22 (13)	H15A—C15—H15B	109.5
N1—C8—C12	117.90 (13)	C11—C15—H15C	109.5
C9—C8—C12	121.86 (14)	H15A—C15—H15C	109.5
N2—C9—C8	120.49 (13)	H15B—C15—H15C	109.5
N2—C9—C13	117.71 (13)	C8—N1—C11	119.34 (12)
C8—C9—C13	121.78 (14)	C9—N2—C10	119.33 (12)
N2—C10—C11	120.10 (14)	C3—O1—H1	109.5
N2—C10—C14	117.56 (13)	C5—O2—H2A	109.5

(BS_PGL_TMP.cif)

Crystal data

C36H48N6O6	Z = 4
Mr = 660.82	F(000) = 1416
Monoclinic, P21/c	Dx = 1.212 Mg m^−3
a = 15.6084 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.4786 (7) Å	µ = 0.08 mm^−1
c = 17.2209 (9) Å	T = 150 K
β = 90.200 (2)°	Block, colorless
V = 3622.9 (3) Å^3	0.42 × 0.27 × 0.18 mm

Data collection

CCD area detector diffractometer	5040 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.042
phi and ω scans	θmax = 26.0°, θmin = 3.0°
Absorption correction: analytical Bruker, AXS, 2008	h = −19→19
Tmin = 0.973, Tmax = 0.985	k = −16→16
109213 measured reflections	l = −21→21
7113 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.211	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.85	(Δ/σ)max = 0.020
7113 reflections	Δρmax = 0.24 e Å^−3
451 parameters	Δρmin = −0.26 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O6	0.90188 (7)	0.89146 (8)	0.15658 (6)	0.0535 (3)
H6	0.8670	0.9103	0.1224	0.080*
O3	0.40053 (8)	1.30840 (9)	−0.33977 (7)	0.0637 (4)
H3	0.3813	1.2556	−0.3590	0.096*
N4	0.18146 (7)	1.13651 (9)	−0.55086 (7)	0.0434 (3)
N1	0.72228 (8)	1.37025 (10)	−0.04770 (7)	0.0476 (3)
C9	1.04170 (9)	1.03465 (11)	0.28154 (8)	0.0401 (3)
O2	0.59700 (8)	1.43145 (8)	−0.15866 (7)	0.0628 (4)
H2	0.6342	1.4133	−0.1263	0.094*
O4	0.95897 (9)	1.24052 (8)	0.16985 (8)	0.0710 (4)
H4	0.9165	1.2428	0.1398	0.107*
C2	0.57685 (8)	1.25477 (10)	−0.16537 (8)	0.0414 (3)
H2A	0.6180	1.2436	−0.1255	0.050*
C6	0.47577 (9)	1.18990 (11)	−0.25925 (8)	0.0435 (4)
H6A	0.4483	1.1350	−0.2834	0.052*
C11	0.94268 (8)	0.97191 (10)	0.18742 (7)	0.0383 (3)
O1	0.54723 (8)	1.08114 (8)	−0.17511 (8)	0.0743 (4)
H1	0.5888	1.0798	−0.1440	0.111*
O5	1.09631 (7)	1.01215 (8)	0.34095 (6)	0.0590 (3)
H5	1.1114	1.0646	0.3635	0.088*
C5	0.45832 (9)	1.28641 (11)	−0.28288 (8)	0.0427 (4)
N3	0.30153 (8)	1.18600 (9)	−0.44037 (7)	0.0484 (3)
C10	1.00066 (9)	0.95481 (11)	0.24707 (8)	0.0433 (4)
H10	1.0121	0.8891	0.2641	0.052*
C12	0.92707 (8)	1.06717 (10)	0.16089 (8)	0.0400 (3)
H12	0.8873	1.0786	0.1199	0.048*
C3	0.55839 (8)	1.34996 (11)	−0.19020 (8)	0.0423 (4)
C30	0.25540 (9)	1.17867 (11)	−0.57146 (8)	0.0446 (4)
C4	0.49851 (10)	1.36649 (11)	−0.24831 (8)	0.0473 (4)
H4A	0.4852	1.4322	−0.2642	0.057*
C1	0.53415 (9)	1.17586 (11)	−0.19973 (8)	0.0439 (4)
C13	0.70482 (10)	1.37164 (11)	0.02791 (9)	0.0484 (4)
N2	0.82840 (9)	1.27715 (10)	0.05611 (8)	0.0576 (4)
C8	1.02740 (8)	1.13089 (10)	0.25612 (8)	0.0416 (3)
H8	1.0559	1.1854	0.2799	0.050*
C16	0.79230 (10)	1.32258 (12)	−0.07266 (8)	0.0499 (4)
C7	0.97043 (9)	1.14567 (10)	0.19511 (8)	0.0428 (3)
C31	0.16618 (9)	1.11939 (11)	−0.47571 (8)	0.0443 (4)
C29	0.31616 (9)	1.20267 (12)	−0.51544 (8)	0.0471 (4)
C14	0.75864 (11)	1.32517 (12)	0.08065 (8)	0.0523 (4)
C15	0.84597 (10)	1.27449 (13)	−0.01942 (9)	0.0534 (4)
C32	0.22691 (9)	1.14513 (11)	−0.41935 (8)	0.0464 (4)
C34	0.26833 (13)	1.19826 (17)	−0.65628 (9)	0.0732 (6)
H34A	0.3130	1.1540	−0.6763	0.110*
H34B	0.2859	1.2674	−0.6637	0.110*
H34C	0.2146	1.1862	−0.6843	0.110*
C18	0.74221 (16)	1.3259 (2)	0.16638 (10)	0.0965 (8)
H18A	0.7936	1.3033	0.1940	0.145*
H18B	0.6943	1.2815	0.1782	0.145*
H18C	0.7280	1.3934	0.1830	0.145*
C35	0.08248 (11)	1.07301 (17)	−0.45536 (11)	0.0752 (6)
H35A	0.0493	1.0611	−0.5029	0.113*
H35B	0.0505	1.1176	−0.4211	0.113*
H35C	0.0927	1.0098	−0.4287	0.113*
C36	0.21262 (14)	1.12957 (19)	−0.33477 (10)	0.0862 (7)
H36A	0.2646	1.1477	−0.3060	0.129*
H36B	0.1991	1.0596	−0.3252	0.129*
H36C	0.1648	1.1711	−0.3175	0.129*
C20	0.80882 (13)	1.32221 (19)	−0.15797 (10)	0.0827 (6)
H20A	0.7592	1.3501	−0.1853	0.124*
H20B	0.8184	1.2539	−0.1755	0.124*
H20C	0.8597	1.3623	−0.1691	0.124*
C17	0.62476 (13)	1.42612 (16)	0.05263 (12)	0.0772 (6)
H17A	0.5952	1.4521	0.0066	0.116*
H17B	0.6404	1.4812	0.0870	0.116*
H17C	0.5868	1.3804	0.0803	0.116*
C19	0.92416 (14)	1.21952 (18)	−0.04480 (13)	0.0904 (7)
H19A	0.9570	1.1985	0.0009	0.136*
H19B	0.9597	1.2630	−0.0770	0.136*
H19C	0.9071	1.1611	−0.0750	0.136*
C33	0.40061 (12)	1.2483 (2)	−0.53587 (12)	0.0867 (7)
H33A	0.4330	1.2620	−0.4882	0.130*
H33B	0.3909	1.3104	−0.5641	0.130*
H33C	0.4331	1.2024	−0.5686	0.130*
N6	0.32962 (8)	0.95515 (10)	0.05765 (7)	0.0484 (3)
N5	0.22419 (7)	1.04417 (9)	−0.04902 (7)	0.0422 (3)
C21	0.20634 (9)	1.04912 (11)	0.02631 (8)	0.0422 (3)
C23	0.34730 (9)	0.94920 (11)	−0.01828 (8)	0.0440 (4)
C22	0.26022 (9)	1.00502 (11)	0.08082 (8)	0.0457 (4)
C24	0.29428 (9)	0.99501 (11)	−0.07244 (8)	0.0427 (4)
C26	0.24364 (14)	1.01047 (19)	0.16632 (10)	0.0815 (6)
H26A	0.2947	0.9885	0.1948	0.122*
H26B	0.1952	0.9674	0.1794	0.122*
H26C	0.2302	1.0790	0.1807	0.122*
C27	0.42540 (12)	0.89281 (16)	−0.04136 (12)	0.0751 (6)
H27A	0.4568	0.8722	0.0053	0.113*
H27B	0.4621	0.9352	−0.0733	0.113*
H27C	0.4085	0.8340	−0.0712	0.113*
C28	0.31195 (12)	0.99093 (15)	−0.15779 (10)	0.0699 (5)
H28A	0.2629	1.0181	−0.1864	0.105*
H28B	0.3213	0.9219	−0.1735	0.105*
H28C	0.3632	1.0302	−0.1694	0.105*
C25	0.12686 (11)	1.10466 (15)	0.04913 (11)	0.0681 (5)
H25A	0.0996	1.1325	0.0026	0.102*
H25B	0.1422	1.1585	0.0848	0.102*
H25C	0.0870	1.0592	0.0748	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O6	0.0597 (7)	0.0465 (6)	0.0541 (7)	−0.0061 (5)	−0.0276 (5)	0.0001 (5)
O3	0.0710 (8)	0.0619 (7)	0.0580 (7)	−0.0110 (6)	−0.0383 (6)	0.0115 (6)
N4	0.0394 (6)	0.0561 (7)	0.0347 (7)	−0.0087 (5)	−0.0078 (5)	−0.0002 (5)
N1	0.0477 (7)	0.0575 (8)	0.0376 (7)	−0.0040 (6)	−0.0120 (5)	0.0010 (5)
C9	0.0346 (7)	0.0545 (8)	0.0312 (7)	−0.0011 (6)	−0.0063 (5)	0.0009 (6)
O2	0.0766 (8)	0.0484 (6)	0.0633 (8)	−0.0141 (5)	−0.0360 (6)	0.0053 (5)
O4	0.0882 (10)	0.0425 (6)	0.0821 (9)	−0.0010 (6)	−0.0465 (7)	0.0030 (6)
C2	0.0381 (7)	0.0495 (8)	0.0365 (7)	−0.0001 (6)	−0.0096 (6)	0.0015 (6)
C6	0.0413 (8)	0.0484 (8)	0.0408 (8)	−0.0038 (6)	−0.0073 (6)	−0.0036 (6)
C11	0.0362 (7)	0.0446 (8)	0.0342 (7)	−0.0025 (6)	−0.0036 (6)	−0.0016 (6)
O1	0.0882 (10)	0.0429 (7)	0.0914 (10)	0.0027 (6)	−0.0520 (7)	0.0002 (6)
O5	0.0639 (7)	0.0602 (7)	0.0525 (7)	−0.0050 (5)	−0.0320 (6)	0.0046 (5)
C5	0.0389 (7)	0.0548 (9)	0.0344 (7)	−0.0051 (6)	−0.0084 (6)	0.0066 (6)
N3	0.0419 (7)	0.0625 (8)	0.0408 (7)	−0.0135 (6)	−0.0111 (5)	0.0009 (6)
C10	0.0429 (8)	0.0470 (8)	0.0400 (8)	−0.0010 (6)	−0.0081 (6)	0.0052 (6)
C12	0.0372 (7)	0.0473 (8)	0.0353 (7)	0.0015 (6)	−0.0097 (5)	−0.0007 (6)
C3	0.0417 (8)	0.0478 (8)	0.0372 (7)	−0.0088 (6)	−0.0065 (6)	0.0022 (6)
C30	0.0403 (8)	0.0575 (9)	0.0359 (8)	−0.0086 (7)	−0.0027 (6)	−0.0015 (6)
C4	0.0509 (8)	0.0476 (8)	0.0433 (8)	−0.0061 (7)	−0.0115 (6)	0.0110 (6)
C1	0.0426 (8)	0.0444 (8)	0.0447 (8)	0.0015 (6)	−0.0084 (6)	−0.0017 (6)
C13	0.0488 (9)	0.0547 (9)	0.0418 (8)	−0.0024 (7)	−0.0038 (7)	−0.0039 (7)
N2	0.0628 (9)	0.0652 (9)	0.0448 (8)	0.0051 (7)	−0.0129 (6)	0.0041 (6)
C8	0.0379 (7)	0.0477 (8)	0.0392 (7)	−0.0042 (6)	−0.0038 (6)	−0.0067 (6)
C16	0.0434 (8)	0.0678 (10)	0.0386 (8)	−0.0059 (7)	−0.0060 (6)	−0.0043 (7)
C7	0.0426 (8)	0.0431 (8)	0.0426 (8)	0.0013 (6)	−0.0046 (6)	−0.0016 (6)
C31	0.0415 (8)	0.0535 (8)	0.0378 (8)	−0.0115 (6)	−0.0061 (6)	0.0005 (6)
C29	0.0389 (8)	0.0632 (9)	0.0391 (8)	−0.0102 (7)	−0.0026 (6)	0.0001 (6)
C14	0.0610 (10)	0.0600 (9)	0.0357 (8)	−0.0027 (8)	−0.0080 (7)	0.0002 (7)
C15	0.0480 (9)	0.0649 (10)	0.0473 (9)	0.0010 (7)	−0.0094 (7)	−0.0073 (7)
C32	0.0466 (8)	0.0592 (9)	0.0335 (7)	−0.0151 (7)	−0.0059 (6)	0.0036 (6)
C34	0.0732 (12)	0.1120 (16)	0.0344 (9)	−0.0224 (11)	0.0000 (8)	0.0034 (9)
C18	0.1089 (18)	0.145 (2)	0.0361 (10)	0.0077 (15)	0.0000 (10)	0.0037 (11)
C35	0.0533 (10)	0.1138 (16)	0.0585 (11)	−0.0385 (10)	−0.0047 (8)	0.0105 (10)
C36	0.0940 (15)	0.1274 (18)	0.0371 (9)	−0.0519 (13)	−0.0109 (9)	0.0130 (10)
C20	0.0703 (12)	0.1387 (19)	0.0392 (9)	0.0028 (12)	−0.0008 (9)	−0.0062 (11)
C17	0.0695 (12)	0.0900 (14)	0.0722 (13)	0.0211 (11)	0.0034 (10)	−0.0112 (10)
C19	0.0699 (13)	0.1172 (18)	0.0841 (15)	0.0310 (12)	−0.0072 (11)	−0.0193 (13)
C33	0.0487 (10)	0.145 (2)	0.0663 (12)	−0.0426 (12)	−0.0008 (9)	0.0054 (12)
N6	0.0463 (7)	0.0582 (8)	0.0407 (7)	0.0089 (6)	−0.0073 (6)	0.0066 (6)
N5	0.0367 (6)	0.0524 (7)	0.0375 (7)	0.0060 (5)	−0.0065 (5)	−0.0017 (5)
C21	0.0349 (7)	0.0521 (8)	0.0396 (8)	0.0016 (6)	−0.0020 (6)	−0.0030 (6)
C23	0.0378 (8)	0.0510 (8)	0.0431 (8)	0.0081 (6)	−0.0045 (6)	−0.0013 (6)
C22	0.0415 (8)	0.0582 (9)	0.0376 (8)	0.0004 (7)	−0.0018 (6)	0.0021 (6)
C24	0.0379 (7)	0.0533 (8)	0.0369 (8)	0.0051 (6)	−0.0021 (6)	−0.0013 (6)
C26	0.0754 (13)	0.1314 (19)	0.0378 (9)	0.0116 (12)	0.0031 (9)	0.0054 (10)
C27	0.0588 (11)	0.0948 (15)	0.0716 (13)	0.0359 (10)	−0.0046 (9)	−0.0060 (10)
C28	0.0650 (11)	0.1057 (15)	0.0389 (9)	0.0197 (10)	0.0005 (8)	−0.0033 (9)
C25	0.0520 (10)	0.0915 (13)	0.0609 (11)	0.0257 (9)	0.0046 (8)	−0.0073 (9)

Geometric parameters (Å, º)

O6—C11	1.3642 (16)	C15—C19	1.494 (3)
O6—H6	0.8400	C32—C36	1.489 (2)
O3—C5	1.3620 (17)	C34—H34A	0.9800
O3—H3	0.8400	C34—H34B	0.9800
N4—C30	1.3355 (18)	C34—H34C	0.9800
N4—C31	1.3368 (18)	C18—H18A	0.9800
N1—C13	1.3313 (19)	C18—H18B	0.9800
N1—C16	1.340 (2)	C18—H18C	0.9800
C9—O5	1.3636 (16)	C35—H35A	0.9800
C9—C10	1.385 (2)	C35—H35B	0.9800
C9—C8	1.387 (2)	C35—H35C	0.9800
O2—C3	1.3646 (17)	C36—H36A	0.9800
O2—H2	0.8400	C36—H36B	0.9800
O4—C7	1.3620 (17)	C36—H36C	0.9800
O4—H4	0.8400	C20—H20A	0.9800
C2—C3	1.382 (2)	C20—H20B	0.9800
C2—C1	1.387 (2)	C20—H20C	0.9800
C2—H2A	0.9500	C17—H17A	0.9800
C6—C1	1.382 (2)	C17—H17B	0.9800
C6—C5	1.390 (2)	C17—H17C	0.9800
C6—H6A	0.9500	C19—H19A	0.9800
C11—C12	1.3841 (19)	C19—H19B	0.9800
C11—C10	1.3859 (19)	C19—H19C	0.9800
O1—C1	1.3605 (17)	C33—H33A	0.9800
O1—H1	0.8400	C33—H33B	0.9800
O5—H5	0.8400	C33—H33C	0.9800
C5—C4	1.382 (2)	N6—C22	1.3371 (19)
N3—C29	1.3327 (18)	N6—C23	1.3397 (19)
N3—C32	1.3394 (18)	N5—C21	1.3295 (18)
C10—H10	0.9500	N5—C24	1.3423 (18)
C12—C7	1.3863 (19)	C21—C22	1.392 (2)
C12—H12	0.9500	C21—C25	1.502 (2)
C3—C4	1.3850 (19)	C23—C24	1.390 (2)
C30—C29	1.389 (2)	C23—C27	1.492 (2)
C30—C34	1.499 (2)	C22—C26	1.498 (2)
C4—H4A	0.9500	C24—C28	1.497 (2)
C13—C14	1.385 (2)	C26—H26A	0.9800
C13—C17	1.512 (2)	C26—H26B	0.9800
N2—C15	1.331 (2)	C26—H26C	0.9800
N2—C14	1.336 (2)	C27—H27A	0.9800
C8—C7	1.3885 (19)	C27—H27B	0.9800
C8—H8	0.9500	C27—H27C	0.9800
C16—C15	1.399 (2)	C28—H28A	0.9800
C16—C20	1.493 (2)	C28—H28B	0.9800
C31—C32	1.3981 (19)	C28—H28C	0.9800
C31—C35	1.491 (2)	C25—H25A	0.9800
C29—C33	1.498 (2)	C25—H25B	0.9800
C14—C18	1.499 (2)	C25—H25C	0.9800
C11—O6—H6	109.5	H18A—C18—H18B	109.5
C5—O3—H3	109.5	C14—C18—H18C	109.5
C30—N4—C31	119.20 (12)	H18A—C18—H18C	109.5
C13—N1—C16	119.36 (13)	H18B—C18—H18C	109.5
O5—C9—C10	115.84 (13)	C31—C35—H35A	109.5
O5—C9—C8	122.98 (13)	C31—C35—H35B	109.5
C10—C9—C8	121.19 (13)	H35A—C35—H35B	109.5
C3—O2—H2	109.5	C31—C35—H35C	109.5
C7—O4—H4	109.5	H35A—C35—H35C	109.5
C3—C2—C1	118.71 (13)	H35B—C35—H35C	109.5
C3—C2—H2A	120.6	C32—C36—H36A	109.5
C1—C2—H2A	120.6	C32—C36—H36B	109.5
C1—C6—C5	118.25 (13)	H36A—C36—H36B	109.5
C1—C6—H6A	120.9	C32—C36—H36C	109.5
C5—C6—H6A	120.9	H36A—C36—H36C	109.5
O6—C11—C12	121.83 (12)	H36B—C36—H36C	109.5
O6—C11—C10	117.32 (12)	C16—C20—H20A	109.5
C12—C11—C10	120.84 (13)	C16—C20—H20B	109.5
C1—O1—H1	109.5	H20A—C20—H20B	109.5
C9—O5—H5	109.5	C16—C20—H20C	109.5
O3—C5—C4	116.00 (13)	H20A—C20—H20C	109.5
O3—C5—C6	122.88 (13)	H20B—C20—H20C	109.5
C4—C5—C6	121.11 (13)	C13—C17—H17A	109.5
C29—N3—C32	118.92 (12)	C13—C17—H17B	109.5
C11—C10—C9	119.23 (13)	H17A—C17—H17B	109.5
C11—C10—H10	120.4	C13—C17—H17C	109.5
C9—C10—H10	120.4	H17A—C17—H17C	109.5
C11—C12—C7	118.85 (13)	H17B—C17—H17C	109.5
C11—C12—H12	120.6	C15—C19—H19A	109.5
C7—C12—H12	120.6	C15—C19—H19B	109.5
O2—C3—C2	122.19 (12)	H19A—C19—H19B	109.5
O2—C3—C4	117.00 (13)	C15—C19—H19C	109.5
C2—C3—C4	120.81 (13)	H19A—C19—H19C	109.5
N4—C30—C29	120.21 (13)	H19B—C19—H19C	109.5
N4—C30—C34	116.96 (13)	C29—C33—H33A	109.5
C29—C30—C34	122.82 (13)	C29—C33—H33B	109.5
C5—C4—C3	119.32 (13)	H33A—C33—H33B	109.5
C5—C4—H4A	120.3	C29—C33—H33C	109.5
C3—C4—H4A	120.3	H33A—C33—H33C	109.5
O1—C1—C6	117.22 (13)	H33B—C33—H33C	109.5
O1—C1—C2	121.02 (13)	C22—N6—C23	119.42 (12)
C6—C1—C2	121.75 (13)	C21—N5—C24	119.46 (12)
N1—C13—C14	120.62 (14)	N5—C21—C22	120.57 (13)
N1—C13—C17	117.02 (14)	N5—C21—C25	117.15 (13)
C14—C13—C17	122.35 (15)	C22—C21—C25	122.28 (14)
C15—N2—C14	119.54 (13)	N6—C23—C24	120.29 (13)
C9—C8—C7	118.36 (12)	N6—C23—C27	117.50 (14)
C9—C8—H8	120.8	C24—C23—C27	122.21 (14)
C7—C8—H8	120.8	N6—C22—C21	120.12 (13)
N1—C16—C15	119.95 (13)	N6—C22—C26	117.45 (14)
N1—C16—C20	117.46 (15)	C21—C22—C26	122.43 (14)
C15—C16—C20	122.58 (15)	N5—C24—C23	120.12 (12)
O4—C7—C12	121.15 (13)	N5—C24—C28	117.79 (13)
O4—C7—C8	117.35 (12)	C23—C24—C28	122.09 (13)
C12—C7—C8	121.50 (13)	C22—C26—H26A	109.5
N4—C31—C32	120.43 (13)	C22—C26—H26B	109.5
N4—C31—C35	117.34 (13)	H26A—C26—H26B	109.5
C32—C31—C35	122.23 (13)	C22—C26—H26C	109.5
N3—C29—C30	121.05 (13)	H26A—C26—H26C	109.5
N3—C29—C33	116.80 (14)	H26B—C26—H26C	109.5
C30—C29—C33	122.14 (14)	C23—C27—H27A	109.5
N2—C14—C13	120.31 (14)	C23—C27—H27B	109.5
N2—C14—C18	117.19 (15)	H27A—C27—H27B	109.5
C13—C14—C18	122.50 (16)	C23—C27—H27C	109.5
N2—C15—C16	120.21 (14)	H27A—C27—H27C	109.5
N2—C15—C19	118.07 (15)	H27B—C27—H27C	109.5
C16—C15—C19	121.72 (15)	C24—C28—H28A	109.5
N3—C32—C31	120.16 (13)	C24—C28—H28B	109.5
N3—C32—C36	117.11 (13)	H28A—C28—H28B	109.5
C31—C32—C36	122.72 (14)	C24—C28—H28C	109.5
C30—C34—H34A	109.5	H28A—C28—H28C	109.5
C30—C34—H34B	109.5	H28B—C28—H28C	109.5
H34A—C34—H34B	109.5	C21—C25—H25A	109.5
C30—C34—H34C	109.5	C21—C25—H25B	109.5
H34A—C34—H34C	109.5	H25A—C25—H25B	109.5
H34B—C34—H34C	109.5	C21—C25—H25C	109.5
C14—C18—H18A	109.5	H25A—C25—H25C	109.5
C14—C18—H18B	109.5	H25B—C25—H25C	109.5

(QS_ORC_TMP_ACR_PYR)

Crystal data

C64H56N4O4	V = 1212.0 (2) Å^3
Mr = 945.12	Z = 1
Triclinic, P1	F(000) = 500
a = 9.0005 (8) Å	Dx = 1.295 Mg m^−3
b = 10.0381 (9) Å	Mo Kα radiation, λ = 0.71073 Å
c = 14.4894 (13) Å	µ = 0.08 mm^−1
α = 108.432 (8)°	T = 150 K
β = 101.780 (7)°	Plate, light yellow
γ = 90.484 (6)°	0.30 × 0.20 × 0.12 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	4285 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.028
profile data from ω–scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −11→11
Tmin = 0.838, Tmax = 1.000	k = −13→13
12950 measured reflections	l = −18→18
5546 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.138	w = 1/[σ^2(Fo^2) + (0.0679P)^2 + 0.3403P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
5546 reflections	Δρmax = 0.23 e Å^−3
336 parameters	Δρmin = −0.31 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
H2O	−0.765 (2)	0.721 (2)	0.4708 (15)	0.051 (6)*
H1O	−0.745 (3)	0.405 (2)	0.1710 (16)	0.056 (6)*
N2	0.10086 (13)	0.32086 (12)	0.20218 (9)	0.0222 (3)
O1	−0.66608 (12)	0.45109 (11)	0.15674 (8)	0.0284 (3)
O2	−0.69317 (13)	0.79014 (12)	0.47213 (8)	0.0302 (3)
C4	−0.68342 (16)	0.61594 (15)	0.31507 (11)	0.0219 (3)
H4	−0.7566	0.5542	0.3232	0.026*
N1	−0.89705 (14)	0.58432 (13)	0.48083 (9)	0.0236 (3)
C12	0.01187 (17)	0.18555 (15)	0.29637 (11)	0.0246 (3)
C19	−0.07653 (18)	0.40789 (16)	0.09209 (11)	0.0264 (3)
H19	0.0054	0.4496	0.0758	0.032*
C16	0.28436 (18)	0.24150 (16)	0.31283 (12)	0.0292 (3)
H16	0.3641	0.2849	0.2957	0.035*
C23	−0.17101 (17)	0.27083 (15)	0.18486 (11)	0.0244 (3)
C6	−0.52894 (16)	0.83626 (15)	0.37590 (11)	0.0237 (3)
H6	−0.4969	0.9248	0.4260	0.028*
C32	−0.13798 (17)	0.19780 (16)	0.25314 (12)	0.0275 (3)
H32	−0.2188	0.1559	0.2703	0.033*
C17	0.12989 (16)	0.25064 (14)	0.26835 (11)	0.0230 (3)
C2	−0.51442 (16)	0.66705 (15)	0.21861 (11)	0.0237 (3)
H2	−0.4723	0.6395	0.1610	0.028*
C18	−0.04555 (16)	0.33202 (14)	0.16110 (10)	0.0216 (3)
C5	−0.63632 (16)	0.74628 (15)	0.38777 (10)	0.0217 (3)
C3	−0.62232 (15)	0.57693 (14)	0.23039 (11)	0.0215 (3)
C1	−0.46837 (16)	0.79757 (15)	0.29147 (11)	0.0232 (3)
C10	−1.04555 (17)	0.57701 (15)	0.43924 (11)	0.0235 (3)
C21	−0.34644 (18)	0.36157 (17)	0.07334 (12)	0.0315 (4)
H21	−0.4477	0.3725	0.0432	0.038*
C14	0.2016 (2)	0.10454 (18)	0.40599 (12)	0.0351 (4)
H14	0.2278	0.0542	0.4518	0.042*
C22	−0.32201 (17)	0.28871 (17)	0.13926 (12)	0.0294 (3)
H22	−0.4062	0.2496	0.1549	0.035*
C9	−0.84975 (16)	0.50816 (16)	0.54084 (11)	0.0238 (3)
C13	0.05299 (19)	0.11208 (17)	0.36640 (12)	0.0311 (4)
H13	−0.0242	0.0682	0.3854	0.037*
C20	−0.22269 (19)	0.42107 (17)	0.04921 (12)	0.0307 (3)
H20	−0.2417	0.4708	0.0026	0.037*
C11	−1.09354 (19)	0.66147 (18)	0.37098 (12)	0.0332 (4)
H11A	−1.0070	0.7240	0.3743	0.050*
H11B	−1.1766	0.7179	0.3915	0.050*
H11C	−1.1284	0.5977	0.3025	0.050*
C8	−0.68199 (17)	0.51731 (19)	0.58438 (13)	0.0337 (4)
H8A	−0.6289	0.5852	0.5640	0.050*
H8B	−0.6433	0.4245	0.5603	0.050*
H8C	−0.6644	0.5481	0.6573	0.050*
C7	−0.35687 (19)	0.89960 (17)	0.27861 (13)	0.0330 (4)
H7A	−0.3426	0.9872	0.3351	0.049*
H7B	−0.3964	0.9198	0.2166	0.049*
H7C	−0.2590	0.8582	0.2757	0.049*
C15	0.31818 (19)	0.17116 (17)	0.37945 (12)	0.0338 (4)
H15	0.4216	0.1664	0.4088	0.041*
C31	0.00735 (17)	0.95801 (15)	0.03187 (11)	0.0246 (3)
C29	0.15275 (19)	0.94492 (16)	0.08704 (12)	0.0321 (4)
C25	−0.1234 (2)	0.88654 (16)	0.03960 (12)	0.0324 (4)
C24	−0.2687 (2)	0.90310 (19)	−0.01594 (14)	0.0421 (5)
H24	−0.3573	0.8562	−0.0108	0.051*
C30	0.28245 (19)	1.0170 (2)	0.07483 (14)	0.0419 (5)
H30	0.3810	1.0073	0.1098	0.050*
C26	−0.1053 (3)	0.80253 (19)	0.10154 (14)	0.0466 (5)
H26	−0.1918	0.7519	0.1060	0.056*
C28	0.1635 (3)	0.8626 (2)	0.14947 (13)	0.0470 (5)
H28	0.2600	0.8550	0.1880	0.056*
C27	0.0357 (3)	0.7923 (2)	0.15595 (14)	0.0522 (6)
H27	0.0453	0.7361	0.1985	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N2	0.0212 (6)	0.0191 (6)	0.0237 (6)	−0.0026 (5)	0.0043 (5)	0.0037 (5)
O1	0.0293 (6)	0.0245 (5)	0.0279 (6)	−0.0060 (4)	0.0114 (5)	0.0008 (4)
O2	0.0365 (6)	0.0274 (6)	0.0256 (6)	−0.0072 (5)	0.0133 (5)	0.0029 (5)
C4	0.0196 (7)	0.0222 (7)	0.0256 (7)	−0.0020 (5)	0.0052 (6)	0.0098 (6)
N1	0.0233 (6)	0.0265 (6)	0.0235 (6)	0.0017 (5)	0.0083 (5)	0.0096 (5)
C12	0.0279 (7)	0.0208 (7)	0.0240 (7)	−0.0015 (6)	0.0065 (6)	0.0052 (6)
C19	0.0292 (8)	0.0248 (7)	0.0258 (8)	−0.0011 (6)	0.0080 (6)	0.0079 (6)
C16	0.0252 (8)	0.0280 (8)	0.0306 (8)	−0.0011 (6)	0.0030 (6)	0.0060 (7)
C23	0.0237 (7)	0.0219 (7)	0.0249 (7)	−0.0020 (6)	0.0059 (6)	0.0035 (6)
C6	0.0241 (7)	0.0205 (7)	0.0249 (7)	−0.0018 (6)	0.0022 (6)	0.0072 (6)
C32	0.0260 (8)	0.0256 (7)	0.0311 (8)	−0.0056 (6)	0.0083 (6)	0.0085 (6)
C17	0.0243 (7)	0.0182 (7)	0.0224 (7)	−0.0012 (5)	0.0039 (6)	0.0019 (6)
C2	0.0218 (7)	0.0271 (7)	0.0248 (7)	0.0010 (6)	0.0084 (6)	0.0098 (6)
C18	0.0228 (7)	0.0178 (7)	0.0207 (7)	−0.0015 (5)	0.0052 (5)	0.0013 (5)
C5	0.0211 (7)	0.0242 (7)	0.0204 (7)	0.0005 (5)	0.0041 (5)	0.0084 (6)
C3	0.0181 (6)	0.0207 (7)	0.0250 (7)	0.0010 (5)	0.0034 (5)	0.0074 (6)
C1	0.0185 (7)	0.0236 (7)	0.0300 (8)	0.0005 (5)	0.0034 (6)	0.0133 (6)
C10	0.0253 (7)	0.0257 (7)	0.0215 (7)	0.0054 (6)	0.0076 (6)	0.0087 (6)
C21	0.0255 (8)	0.0331 (8)	0.0308 (8)	0.0042 (6)	0.0004 (6)	0.0067 (7)
C14	0.0437 (10)	0.0316 (9)	0.0300 (9)	0.0052 (7)	0.0022 (7)	0.0135 (7)
C22	0.0217 (7)	0.0325 (8)	0.0321 (8)	−0.0009 (6)	0.0052 (6)	0.0081 (7)
C9	0.0220 (7)	0.0283 (7)	0.0212 (7)	0.0036 (6)	0.0061 (6)	0.0073 (6)
C13	0.0357 (9)	0.0284 (8)	0.0312 (8)	−0.0003 (7)	0.0075 (7)	0.0121 (7)
C20	0.0363 (9)	0.0287 (8)	0.0266 (8)	0.0045 (7)	0.0038 (7)	0.0101 (6)
C11	0.0365 (9)	0.0379 (9)	0.0318 (9)	0.0077 (7)	0.0073 (7)	0.0203 (7)
C8	0.0215 (7)	0.0437 (9)	0.0358 (9)	0.0027 (7)	0.0032 (6)	0.0148 (8)
C7	0.0319 (8)	0.0297 (8)	0.0401 (9)	−0.0060 (7)	0.0118 (7)	0.0128 (7)
C15	0.0297 (8)	0.0327 (9)	0.0331 (9)	0.0052 (7)	−0.0018 (7)	0.0080 (7)
C31	0.0286 (8)	0.0201 (7)	0.0208 (7)	0.0039 (6)	0.0049 (6)	0.0007 (6)
C29	0.0376 (9)	0.0259 (8)	0.0234 (8)	0.0099 (7)	0.0002 (7)	−0.0014 (6)
C25	0.0409 (9)	0.0229 (7)	0.0297 (8)	0.0002 (7)	0.0144 (7)	−0.0008 (6)
C24	0.0288 (9)	0.0379 (10)	0.0464 (11)	−0.0072 (7)	0.0125 (8)	−0.0071 (8)
C30	0.0247 (8)	0.0428 (10)	0.0393 (10)	0.0072 (7)	−0.0036 (7)	−0.0061 (8)
C26	0.0753 (14)	0.0280 (9)	0.0413 (10)	−0.0005 (9)	0.0329 (10)	0.0053 (8)
C28	0.0662 (13)	0.0413 (10)	0.0251 (9)	0.0267 (10)	0.0001 (8)	0.0046 (8)
C27	0.0966 (18)	0.0346 (10)	0.0321 (10)	0.0185 (11)	0.0219 (11)	0.0149 (8)

Geometric parameters (Å, º)

N2—C17	1.3463 (19)	C21—H21	0.9500
N2—C18	1.3519 (18)	C14—C13	1.357 (2)
O1—C3	1.3628 (17)	C14—C15	1.418 (2)
O1—H1O	0.93 (2)	C14—H14	0.9500
O2—C5	1.3669 (17)	C22—H22	0.9500
O2—H2O	0.93 (2)	C9—C10^i	1.398 (2)
C4—C3	1.392 (2)	C9—C8	1.503 (2)
C4—C5	1.3921 (19)	C13—H13	0.9500
C4—H4	0.9500	C20—H20	0.9500
N1—C9	1.3404 (19)	C11—H11A	0.9800
N1—C10	1.3404 (19)	C11—H11B	0.9800
C12—C32	1.390 (2)	C11—H11C	0.9800
C12—C13	1.427 (2)	C8—H8A	0.9800
C12—C17	1.433 (2)	C8—H8B	0.9800
C19—C20	1.362 (2)	C8—H8C	0.9800
C19—C18	1.424 (2)	C7—H7A	0.9800
C19—H19	0.9500	C7—H7B	0.9800
C16—C15	1.356 (2)	C7—H7C	0.9800
C16—C17	1.425 (2)	C15—H15	0.9500
C16—H16	0.9500	C31—C25	1.415 (2)
C23—C32	1.395 (2)	C31—C29	1.418 (2)
C23—C22	1.424 (2)	C31—C31^ii	1.423 (3)
C23—C18	1.432 (2)	C29—C28	1.396 (3)
C6—C1	1.386 (2)	C29—C30	1.438 (3)
C6—C5	1.3896 (19)	C25—C26	1.402 (3)
C6—H6	0.9500	C25—C24	1.430 (3)
C32—H32	0.9500	C24—C30^ii	1.334 (3)
C2—C1	1.393 (2)	C24—H24	0.9500
C2—C3	1.3932 (19)	C30—C24^ii	1.334 (3)
C2—H2	0.9500	C30—H30	0.9500
C1—C7	1.507 (2)	C26—C27	1.374 (3)
C10—C9^i	1.399 (2)	C26—H26	0.9500
C10—C11	1.499 (2)	C28—C27	1.379 (3)
C21—C22	1.362 (2)	C28—H28	0.9500
C21—C20	1.414 (2)	C27—H27	0.9500
C17—N2—C18	118.88 (12)	N1—C9—C10^i	120.36 (13)
C3—O1—H1O	109.4 (13)	N1—C9—C8	117.65 (13)
C5—O2—H2O	109.7 (13)	C10^i—C9—C8	121.98 (14)
C3—C4—C5	119.38 (13)	C14—C13—C12	120.39 (15)
C3—C4—H4	120.3	C14—C13—H13	119.8
C5—C4—H4	120.3	C12—C13—H13	119.8
C9—N1—C10	119.37 (13)	C19—C20—C21	120.74 (15)
C32—C12—C13	123.44 (14)	C19—C20—H20	119.6
C32—C12—C17	117.59 (13)	C21—C20—H20	119.6
C13—C12—C17	118.97 (14)	C10—C11—H11A	109.5
C20—C19—C18	120.51 (14)	C10—C11—H11B	109.5
C20—C19—H19	119.7	H11A—C11—H11B	109.5
C18—C19—H19	119.7	C10—C11—H11C	109.5
C15—C16—C17	120.36 (15)	H11A—C11—H11C	109.5
C15—C16—H16	119.8	H11B—C11—H11C	109.5
C17—C16—H16	119.8	C9—C8—H8A	109.5
C32—C23—C22	123.37 (14)	C9—C8—H8B	109.5
C32—C23—C18	117.69 (13)	H8A—C8—H8B	109.5
C22—C23—C18	118.93 (14)	C9—C8—H8C	109.5
C1—C6—C5	120.39 (13)	H8A—C8—H8C	109.5
C1—C6—H6	119.8	H8B—C8—H8C	109.5
C5—C6—H6	119.8	C1—C7—H7A	109.5
C12—C32—C23	120.78 (14)	C1—C7—H7B	109.5
C12—C32—H32	119.6	H7A—C7—H7B	109.5
C23—C32—H32	119.6	C1—C7—H7C	109.5
N2—C17—C16	118.64 (13)	H7A—C7—H7C	109.5
N2—C17—C12	122.71 (13)	H7B—C7—H7C	109.5
C16—C17—C12	118.66 (14)	C16—C15—C14	121.08 (15)
C1—C2—C3	119.90 (13)	C16—C15—H15	119.5
C1—C2—H2	120.0	C14—C15—H15	119.5
C3—C2—H2	120.0	C25—C31—C29	119.94 (15)
N2—C18—C19	118.96 (13)	C25—C31—C31^ii	119.87 (17)
N2—C18—C23	122.35 (13)	C29—C31—C31^ii	120.19 (18)
C19—C18—C23	118.69 (13)	C28—C29—C31	118.88 (17)
O2—C5—C6	117.98 (13)	C28—C29—C30	123.32 (17)
O2—C5—C4	121.80 (12)	C31—C29—C30	117.80 (16)
C6—C5—C4	120.23 (13)	C26—C25—C31	118.68 (17)
O1—C3—C4	121.50 (12)	C26—C25—C24	122.62 (17)
O1—C3—C2	118.12 (13)	C31—C25—C24	118.71 (16)
C4—C3—C2	120.38 (13)	C30^ii—C24—C25	121.32 (16)
C6—C1—C2	119.71 (13)	C30^ii—C24—H24	119.3
C6—C1—C7	119.26 (13)	C25—C24—H24	119.3
C2—C1—C7	121.01 (14)	C24^ii—C30—C29	122.09 (16)
N1—C10—C9^i	120.27 (13)	C24^ii—C30—H30	119.0
N1—C10—C11	117.77 (13)	C29—C30—H30	119.0
C9^i—C10—C11	121.96 (14)	C27—C26—C25	120.98 (19)
C22—C21—C20	120.69 (14)	C27—C26—H26	119.5
C22—C21—H21	119.7	C25—C26—H26	119.5
C20—C21—H21	119.7	C27—C28—C29	120.85 (18)
C13—C14—C15	120.52 (15)	C27—C28—H28	119.6
C13—C14—H14	119.7	C29—C28—H28	119.6
C15—C14—H14	119.7	C26—C27—C28	120.64 (18)
C21—C22—C23	120.43 (14)	C26—C27—H27	119.7
C21—C22—H22	119.8	C28—C27—H27	119.7
C23—C22—H22	119.8

Symmetry codes: (i) −x−2, −y+1, −z+1; (ii) −x, −y+2, −z.

(QS_ORC_TMP_PHE_HMB)

Crystal data

C29H31N3O2	V = 1199.2 (4) Å^3
Mr = 453.57	Z = 2
Triclinic, P1	F(000) = 484
a = 8.9943 (15) Å	Dx = 1.256 Mg m^−3
b = 9.5169 (16) Å	Mo Kα radiation, λ = 0.71073 Å
c = 14.927 (3) Å	µ = 0.08 mm^−1
α = 74.162 (5)°	T = 150 K
β = 77.589 (5)°	Plate, yellow
γ = 89.115 (6)°	0.20 × 0.20 × 0.15 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	3925 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.037
profile data from ω–scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −11→11
Tmin = 0.796, Tmax = 1.000	k = −12→12
12751 measured reflections	l = −19→19
5486 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.154	w = 1/[σ^2(Fo^2) + (0.0723P)^2 + 0.2791P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.008
5486 reflections	Δρmax = 0.26 e Å^−3
321 parameters	Δρmin = −0.22 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C30	0.2473 (3)	0.1475 (3)	0.04114 (17)	0.0523 (6)
H30A	0.2058	0.2181	0.0759	0.078*
H30B	0.3156	0.1990	−0.0193	0.078*
H30C	0.3042	0.0759	0.0798	0.078*
H2O	0.751 (3)	0.283 (3)	0.4660 (16)	0.051 (6)*
H1O	0.749 (3)	0.584 (3)	0.1716 (16)	0.054 (6)*
N2	0.89990 (15)	0.67758 (15)	0.20159 (10)	0.0260 (3)
N3	1.13781 (16)	0.79807 (16)	0.25887 (11)	0.0316 (3)
C13	0.87034 (19)	0.74366 (17)	0.27193 (12)	0.0260 (4)
C5	0.68503 (17)	0.37273 (17)	0.31334 (11)	0.0229 (3)
H5	0.7593	0.4369	0.3199	0.028*
O2	0.68945 (15)	0.20761 (14)	0.46667 (8)	0.0320 (3)
O1	0.66969 (14)	0.53096 (14)	0.15973 (8)	0.0316 (3)
C23	1.0838 (2)	0.59719 (19)	0.08716 (13)	0.0311 (4)
H23	1.0047	0.5577	0.0669	0.037*
C24	1.04651 (18)	0.66972 (17)	0.15972 (12)	0.0258 (4)
N1	0.89673 (15)	0.41726 (15)	0.47763 (10)	0.0261 (3)
C18	0.99089 (19)	0.80540 (18)	0.30018 (12)	0.0280 (4)
C14	0.7168 (2)	0.74971 (19)	0.32091 (13)	0.0319 (4)
H14	0.6361	0.7066	0.3040	0.038*
C19	1.16663 (19)	0.73017 (18)	0.18940 (12)	0.0280 (4)
C7	0.52713 (18)	0.15131 (18)	0.37499 (12)	0.0253 (4)
H7	0.4930	0.0644	0.4246	0.030*
C20	1.3201 (2)	0.7145 (2)	0.14482 (14)	0.0360 (4)
H20	1.4013	0.7544	0.1631	0.043*
C17	0.9525 (2)	0.8764 (2)	0.37444 (13)	0.0355 (4)
H17	1.0307	0.9198	0.3933	0.043*
C6	0.63539 (18)	0.24531 (18)	0.38466 (11)	0.0233 (3)
C2	0.51718 (18)	0.31131 (18)	0.22194 (11)	0.0252 (4)
H2	0.4769	0.3344	0.1660	0.030*
C11	1.04460 (18)	0.42497 (18)	0.43466 (12)	0.0254 (4)
C4	0.62503 (18)	0.40597 (18)	0.23193 (11)	0.0240 (4)
C21	1.3511 (2)	0.6424 (2)	0.07591 (14)	0.0387 (5)
H21	1.4542	0.6315	0.0474	0.046*
C15	0.6860 (2)	0.8167 (2)	0.39133 (14)	0.0371 (4)
H15	0.5834	0.8205	0.4236	0.045*
C10	0.85016 (18)	0.49176 (18)	0.54252 (12)	0.0258 (4)
C12	1.0912 (2)	0.3401 (2)	0.36269 (14)	0.0365 (4)
H12A	1.0023	0.2845	0.3598	0.055*
H12B	1.1695	0.2725	0.3815	0.055*
H12C	1.1322	0.4078	0.2998	0.055*
C9	0.68336 (19)	0.4796 (2)	0.58861 (14)	0.0363 (4)
H9A	0.6276	0.4298	0.5556	0.054*
H9B	0.6452	0.5777	0.5845	0.054*
H9C	0.6684	0.4235	0.6558	0.054*
C1	0.46840 (18)	0.18330 (18)	0.29350 (12)	0.0250 (4)
C16	0.8054 (2)	0.8817 (2)	0.41776 (14)	0.0394 (5)
H16	0.7810	0.9297	0.4668	0.047*
C22	1.2326 (2)	0.5836 (2)	0.04613 (13)	0.0357 (4)
H22	1.2565	0.5346	−0.0024	0.043*
C8	0.3555 (2)	0.0767 (2)	0.28332 (14)	0.0339 (4)
H8A	0.4059	0.0243	0.2378	0.051*
H8B	0.2710	0.1298	0.2600	0.051*
H8C	0.3162	0.0065	0.3455	0.051*
C27	0.1184 (2)	0.06971 (19)	0.02108 (13)	0.0326 (4)
C26	−0.0317 (2)	0.07488 (19)	0.07073 (12)	0.0317 (4)
C28	0.1496 (2)	−0.0069 (2)	−0.04833 (12)	0.0322 (4)
C29	0.3139 (2)	−0.0126 (3)	−0.10032 (16)	0.0524 (6)
H29A	0.3241	−0.0980	−0.1256	0.079*
H29B	0.3813	−0.0202	−0.0558	0.079*
H29C	0.3420	0.0765	−0.1531	0.079*
C25	−0.0669 (3)	0.1548 (2)	0.14746 (15)	0.0519 (6)
H25A	0.0201	0.1510	0.1777	0.078*
H25B	−0.1573	0.1081	0.1956	0.078*
H25C	−0.0863	0.2570	0.1186	0.078*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C30	0.0491 (13)	0.0526 (14)	0.0535 (14)	−0.0106 (11)	−0.0198 (11)	−0.0047 (11)
N2	0.0233 (7)	0.0245 (7)	0.0286 (8)	−0.0012 (6)	−0.0054 (6)	−0.0047 (6)
N3	0.0299 (8)	0.0315 (8)	0.0333 (8)	−0.0059 (6)	−0.0074 (6)	−0.0079 (7)
C13	0.0271 (8)	0.0206 (8)	0.0268 (9)	−0.0004 (6)	−0.0041 (7)	−0.0020 (7)
C5	0.0182 (8)	0.0254 (8)	0.0273 (9)	−0.0021 (6)	−0.0043 (6)	−0.0112 (7)
O2	0.0393 (7)	0.0309 (7)	0.0268 (7)	−0.0076 (6)	−0.0138 (5)	−0.0040 (5)
O1	0.0305 (7)	0.0332 (7)	0.0282 (7)	−0.0084 (5)	−0.0101 (5)	0.0000 (5)
C23	0.0312 (9)	0.0304 (9)	0.0328 (10)	−0.0009 (7)	−0.0074 (7)	−0.0102 (8)
C24	0.0250 (8)	0.0225 (8)	0.0270 (9)	−0.0024 (6)	−0.0055 (7)	−0.0022 (7)
N1	0.0217 (7)	0.0297 (8)	0.0295 (8)	0.0032 (6)	−0.0083 (6)	−0.0107 (6)
C18	0.0297 (9)	0.0242 (8)	0.0281 (9)	−0.0024 (7)	−0.0063 (7)	−0.0039 (7)
C14	0.0276 (9)	0.0293 (9)	0.0362 (10)	0.0001 (7)	−0.0053 (7)	−0.0060 (8)
C19	0.0253 (8)	0.0250 (8)	0.0310 (9)	−0.0037 (7)	−0.0060 (7)	−0.0034 (7)
C7	0.0248 (8)	0.0244 (8)	0.0255 (8)	−0.0020 (7)	−0.0016 (7)	−0.0075 (7)
C20	0.0234 (9)	0.0425 (11)	0.0395 (11)	−0.0040 (8)	−0.0052 (8)	−0.0082 (9)
C17	0.0414 (11)	0.0315 (10)	0.0346 (10)	−0.0031 (8)	−0.0084 (8)	−0.0105 (8)
C6	0.0224 (8)	0.0275 (9)	0.0228 (8)	0.0015 (6)	−0.0050 (6)	−0.0112 (7)
C2	0.0236 (8)	0.0325 (9)	0.0220 (8)	−0.0002 (7)	−0.0069 (6)	−0.0101 (7)
C11	0.0246 (8)	0.0278 (9)	0.0254 (9)	0.0054 (7)	−0.0075 (7)	−0.0087 (7)
C4	0.0212 (8)	0.0272 (9)	0.0237 (8)	0.0010 (6)	−0.0031 (6)	−0.0083 (7)
C21	0.0255 (9)	0.0440 (11)	0.0408 (11)	0.0022 (8)	0.0008 (8)	−0.0083 (9)
C15	0.0346 (10)	0.0343 (10)	0.0366 (10)	0.0058 (8)	0.0012 (8)	−0.0074 (8)
C10	0.0226 (8)	0.0291 (9)	0.0262 (9)	0.0042 (7)	−0.0063 (7)	−0.0077 (7)
C12	0.0335 (10)	0.0441 (11)	0.0387 (11)	0.0070 (8)	−0.0082 (8)	−0.0228 (9)
C9	0.0219 (9)	0.0482 (12)	0.0398 (11)	0.0019 (8)	−0.0038 (8)	−0.0162 (9)
C1	0.0192 (8)	0.0288 (9)	0.0304 (9)	−0.0004 (6)	−0.0028 (7)	−0.0157 (7)
C16	0.0483 (12)	0.0356 (11)	0.0338 (10)	0.0036 (9)	−0.0024 (9)	−0.0138 (8)
C22	0.0367 (10)	0.0352 (10)	0.0335 (10)	0.0039 (8)	−0.0015 (8)	−0.0114 (8)
C8	0.0287 (9)	0.0375 (10)	0.0390 (10)	−0.0080 (8)	−0.0064 (8)	−0.0163 (8)
C27	0.0338 (10)	0.0295 (9)	0.0308 (10)	−0.0001 (8)	−0.0109 (8)	0.0008 (7)
C26	0.0415 (10)	0.0266 (9)	0.0238 (9)	0.0078 (8)	−0.0065 (8)	−0.0024 (7)
C28	0.0296 (9)	0.0319 (10)	0.0262 (9)	0.0063 (7)	−0.0010 (7)	0.0028 (7)
C29	0.0353 (11)	0.0602 (15)	0.0475 (13)	0.0103 (10)	0.0029 (9)	−0.0013 (11)
C25	0.0724 (16)	0.0495 (13)	0.0390 (12)	0.0176 (11)	−0.0152 (11)	−0.0191 (10)

Geometric parameters (Å, º)

C30—C27	1.509 (3)	C2—C4	1.392 (2)
C30—H30A	0.9800	C2—H2	0.9500
C30—H30B	0.9800	C11—C10^i	1.396 (2)
C30—H30C	0.9800	C11—C12	1.501 (2)
N2—C24	1.343 (2)	C21—C22	1.416 (3)
N2—C13	1.343 (2)	C21—H21	0.9500
N3—C18	1.342 (2)	C15—C16	1.424 (3)
N3—C19	1.343 (2)	C15—H15	0.9500
C13—C14	1.425 (2)	C10—C11^i	1.396 (2)
C13—C18	1.432 (2)	C10—C9	1.502 (2)
C5—C6	1.382 (2)	C12—H12A	0.9800
C5—C4	1.391 (2)	C12—H12B	0.9800
C5—H5	0.9500	C12—H12C	0.9800
O2—C6	1.3690 (19)	C9—H9A	0.9800
O2—H2O	0.91 (2)	C9—H9B	0.9800
O1—C4	1.366 (2)	C9—H9C	0.9800
O1—H1O	0.95 (2)	C1—C8	1.505 (2)
C23—C22	1.367 (3)	C16—H16	0.9500
C23—C24	1.417 (2)	C22—H22	0.9500
C23—H23	0.9500	C8—H8A	0.9800
C24—C19	1.435 (2)	C8—H8B	0.9800
N1—C11	1.340 (2)	C8—H8C	0.9800
N1—C10	1.344 (2)	C27—C26	1.401 (3)
C18—C17	1.429 (2)	C27—C28	1.401 (3)
C14—C15	1.350 (3)	C26—C28^ii	1.395 (3)
C14—H14	0.9500	C26—C25	1.518 (3)
C19—C20	1.422 (2)	C28—C26^ii	1.395 (3)
C7—C1	1.386 (2)	C28—C29	1.522 (3)
C7—C6	1.388 (2)	C29—H29A	0.9800
C7—H7	0.9500	C29—H29B	0.9800
C20—C21	1.365 (3)	C29—H29C	0.9800
C20—H20	0.9500	C25—H25A	0.9800
C17—C16	1.349 (3)	C25—H25B	0.9800
C17—H17	0.9500	C25—H25C	0.9800
C2—C1	1.386 (2)
C27—C30—H30A	109.5	C22—C21—H21	119.4
C27—C30—H30B	109.5	C14—C15—C16	120.81 (17)
H30A—C30—H30B	109.5	C14—C15—H15	119.6
C27—C30—H30C	109.5	C16—C15—H15	119.6
H30A—C30—H30C	109.5	N1—C10—C11^i	120.14 (15)
H30B—C30—H30C	109.5	N1—C10—C9	117.28 (15)
C24—N2—C13	117.62 (14)	C11^i—C10—C9	122.57 (15)
C18—N3—C19	116.80 (14)	C11—C12—H12A	109.5
N2—C13—C14	119.61 (15)	C11—C12—H12B	109.5
N2—C13—C18	121.10 (15)	H12A—C12—H12B	109.5
C14—C13—C18	119.27 (16)	C11—C12—H12C	109.5
C6—C5—C4	119.31 (14)	H12A—C12—H12C	109.5
C6—C5—H5	120.3	H12B—C12—H12C	109.5
C4—C5—H5	120.3	C10—C9—H9A	109.5
C6—O2—H2O	108.2 (14)	C10—C9—H9B	109.5
C4—O1—H1O	111.2 (14)	H9A—C9—H9B	109.5
C22—C23—C24	120.58 (16)	C10—C9—H9C	109.5
C22—C23—H23	119.7	H9A—C9—H9C	109.5
C24—C23—H23	119.7	H9B—C9—H9C	109.5
N2—C24—C23	119.76 (15)	C7—C1—C2	119.42 (15)
N2—C24—C19	120.87 (15)	C7—C1—C8	119.35 (16)
C23—C24—C19	119.34 (15)	C2—C1—C8	121.21 (15)
C11—N1—C10	119.32 (14)	C17—C16—C15	121.19 (17)
N3—C18—C17	119.57 (16)	C17—C16—H16	119.4
N3—C18—C13	121.77 (15)	C15—C16—H16	119.4
C17—C18—C13	118.66 (16)	C23—C22—C21	120.05 (17)
C15—C14—C13	119.99 (17)	C23—C22—H22	120.0
C15—C14—H14	120.0	C21—C22—H22	120.0
C13—C14—H14	120.0	C1—C8—H8A	109.5
N3—C19—C20	119.61 (16)	C1—C8—H8B	109.5
N3—C19—C24	121.83 (15)	H8A—C8—H8B	109.5
C20—C19—C24	118.54 (16)	C1—C8—H8C	109.5
C1—C7—C6	120.50 (15)	H8A—C8—H8C	109.5
C1—C7—H7	119.8	H8B—C8—H8C	109.5
C6—C7—H7	119.8	C26—C27—C28	120.05 (17)
C21—C20—C19	120.24 (17)	C26—C27—C30	120.40 (18)
C21—C20—H20	119.9	C28—C27—C30	119.55 (18)
C19—C20—H20	119.9	C28^ii—C26—C27	119.32 (17)
C16—C17—C18	120.03 (17)	C28^ii—C26—C25	120.01 (18)
C16—C17—H17	120.0	C27—C26—C25	120.66 (18)
C18—C17—H17	120.0	C26^ii—C28—C27	120.60 (16)
O2—C6—C5	121.86 (14)	C26^ii—C28—C29	120.35 (18)
O2—C6—C7	117.80 (15)	C27—C28—C29	119.04 (18)
C5—C6—C7	120.33 (15)	C28—C29—H29A	109.5
C1—C2—C4	120.05 (15)	C28—C29—H29B	109.5
C1—C2—H2	120.0	H29A—C29—H29B	109.5
C4—C2—H2	120.0	C28—C29—H29C	109.5
N1—C11—C10^i	120.54 (15)	H29A—C29—H29C	109.5
N1—C11—C12	117.41 (15)	H29B—C29—H29C	109.5
C10^i—C11—C12	122.04 (15)	C26—C25—H25A	109.5
O1—C4—C5	121.53 (14)	C26—C25—H25B	109.5
O1—C4—C2	118.10 (14)	H25A—C25—H25B	109.5
C5—C4—C2	120.38 (15)	C26—C25—H25C	109.5
C20—C21—C22	121.23 (17)	H25A—C25—H25C	109.5
C20—C21—H21	119.4	H25B—C25—H25C	109.5

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x, −y, −z.

(QS_ORC_TMP_PHE_PYR)

Crystal data

C62H54N6O4	V = 1206.5 (5) Å^3
Mr = 947.11	Z = 1
Triclinic, P1	F(000) = 500
a = 9.034 (2) Å	Dx = 1.304 Mg m^−3
b = 9.889 (2) Å	Mo Kα radiation, λ = 0.71073 Å
c = 14.505 (4) Å	µ = 0.08 mm^−1
α = 107.761 (8)°	T = 150 K
β = 101.019 (7)°	Plate, yellow-red
γ = 91.432 (6)°	0.30 × 0.20 × 0.15 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	3640 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.041
profile data from ω–scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −11→11
Tmin = 0.793, Tmax = 1.000	k = −12→12
12197 measured reflections	l = −18→18
5504 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.163	w = 1/[σ^2(Fo^2) + (0.0731P)^2 + 0.3701P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.003
5504 reflections	Δρmax = 0.25 e Å^−3
336 parameters	Δρmin = −0.23 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
H2O	0.250 (3)	0.278 (3)	0.0299 (19)	0.053 (8)*
H1O	0.238 (3)	0.595 (3)	0.330 (2)	0.074 (9)*
N1	0.39533 (17)	0.68009 (16)	0.29807 (12)	0.0267 (4)
O1	0.16264 (17)	0.54186 (15)	0.34748 (11)	0.0350 (4)
O2	0.18504 (17)	0.20716 (16)	0.03057 (11)	0.0352 (4)
N2	0.63383 (19)	0.80472 (18)	0.24066 (13)	0.0318 (4)
C19	0.6616 (2)	0.7355 (2)	0.30794 (15)	0.0281 (4)
C15	0.5776 (2)	0.5977 (2)	0.40755 (15)	0.0308 (5)
H15	0.4987	0.5557	0.4275	0.037*
C5	0.1768 (2)	0.3794 (2)	0.18790 (14)	0.0261 (4)
H5	0.2499	0.4432	0.1797	0.031*
C8	0.4881 (2)	0.8135 (2)	0.20280 (15)	0.0296 (5)
C12	0.2144 (2)	0.7584 (2)	0.18599 (16)	0.0346 (5)
H12	0.1332	0.7153	0.2033	0.041*
C14	0.5412 (2)	0.67156 (19)	0.33714 (14)	0.0254 (4)
C7	0.0213 (2)	0.1561 (2)	0.12671 (15)	0.0281 (4)
H7	−0.0117	0.0675	0.0765	0.034*
C13	0.3668 (2)	0.7492 (2)	0.23130 (15)	0.0276 (4)
C6	0.1290 (2)	0.2492 (2)	0.11506 (14)	0.0259 (4)
C3	0.0092 (2)	0.3228 (2)	0.28473 (15)	0.0299 (5)
H3	−0.0319	0.3483	0.3427	0.036*
C2	−0.0381 (2)	0.1928 (2)	0.21173 (15)	0.0287 (4)
C18	0.8141 (2)	0.7212 (2)	0.35086 (16)	0.0350 (5)
H18	0.8955	0.7629	0.3329	0.042*
C17	0.8433 (2)	0.6487 (2)	0.41695 (17)	0.0370 (5)
H17	0.9454	0.6392	0.4441	0.044*
C4	0.1170 (2)	0.4158 (2)	0.27290 (15)	0.0267 (4)
C10	0.3039 (3)	0.8945 (2)	0.09166 (17)	0.0406 (5)
H10	0.2805	0.9453	0.0455	0.049*
C9	0.4502 (3)	0.8859 (2)	0.13104 (16)	0.0370 (5)
H9	0.5285	0.9284	0.1109	0.044*
C16	0.7245 (2)	0.5867 (2)	0.44651 (16)	0.0359 (5)
H16	0.7477	0.5374	0.4936	0.043*
C11	0.1847 (3)	0.8284 (2)	0.11836 (17)	0.0393 (5)
H11	0.0827	0.8332	0.0884	0.047*
C1	−0.1504 (3)	0.0869 (2)	0.22415 (18)	0.0406 (6)
H1A	−0.1159	0.0708	0.2879	0.061*
H1B	−0.1582	−0.0034	0.1705	0.061*
H1C	−0.2498	0.1248	0.2221	0.061*
N3	0.39626 (18)	0.41555 (17)	0.02092 (12)	0.0281 (4)
C21	0.5441 (2)	0.4237 (2)	0.06185 (14)	0.0269 (4)
C22	0.3504 (2)	0.4907 (2)	−0.04037 (14)	0.0268 (4)
C20	0.5902 (3)	0.3391 (2)	0.13139 (17)	0.0386 (5)
H20A	0.6216	0.4042	0.1992	0.058*
H20B	0.6747	0.2843	0.1127	0.058*
H20C	0.5043	0.2738	0.1276	0.058*
C23	0.1845 (2)	0.4795 (3)	−0.08341 (17)	0.0410 (5)
H23A	0.1306	0.4140	−0.0595	0.061*
H23B	0.1675	0.4432	−0.1558	0.061*
H23C	0.1467	0.5738	−0.0631	0.061*
C31	0.4916 (2)	0.0421 (2)	0.46769 (14)	0.0283 (4)
C29	0.6215 (3)	0.1176 (2)	0.45866 (17)	0.0387 (5)
C25	0.3479 (3)	0.0530 (2)	0.41313 (16)	0.0390 (5)
C30	0.7659 (3)	0.1020 (3)	0.5139 (2)	0.0505 (7)
H30	0.8539	0.1503	0.5078	0.061*
C24	0.2192 (3)	−0.0224 (3)	0.42662 (19)	0.0499 (7)
H24	0.1209	−0.0148	0.3919	0.060*
C28	0.6018 (4)	0.2028 (3)	0.3966 (2)	0.0554 (8)
H28	0.6870	0.2562	0.3915	0.066*
C26	0.3358 (4)	0.1372 (3)	0.35024 (18)	0.0574 (8)
H26	0.2399	0.1438	0.3121	0.069*
C27	0.4638 (4)	0.2104 (3)	0.3438 (2)	0.0629 (9)
H27	0.4544	0.2675	0.3012	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0259 (9)	0.0209 (8)	0.0309 (9)	−0.0024 (6)	0.0073 (7)	0.0039 (7)
O1	0.0371 (8)	0.0283 (8)	0.0365 (9)	−0.0070 (6)	0.0173 (7)	0.0007 (6)
O2	0.0447 (9)	0.0289 (8)	0.0317 (8)	−0.0077 (7)	0.0172 (7)	0.0046 (6)
N2	0.0305 (10)	0.0292 (9)	0.0356 (10)	−0.0040 (7)	0.0089 (7)	0.0095 (8)
C19	0.0280 (11)	0.0234 (10)	0.0300 (11)	−0.0028 (8)	0.0089 (8)	0.0030 (8)
C15	0.0357 (12)	0.0240 (10)	0.0338 (11)	0.0007 (8)	0.0119 (9)	0.0083 (9)
C5	0.0232 (10)	0.0251 (10)	0.0323 (11)	−0.0022 (7)	0.0084 (8)	0.0113 (8)
C8	0.0333 (11)	0.0231 (10)	0.0315 (11)	−0.0015 (8)	0.0085 (9)	0.0063 (9)
C12	0.0308 (11)	0.0291 (11)	0.0405 (13)	−0.0008 (8)	0.0063 (9)	0.0071 (10)
C14	0.0269 (10)	0.0185 (9)	0.0279 (10)	−0.0008 (7)	0.0081 (8)	0.0018 (8)
C7	0.0276 (10)	0.0237 (10)	0.0313 (11)	−0.0026 (8)	0.0054 (8)	0.0067 (8)
C13	0.0290 (11)	0.0214 (9)	0.0295 (11)	−0.0013 (8)	0.0062 (8)	0.0041 (8)
C6	0.0269 (10)	0.0263 (10)	0.0258 (10)	0.0014 (8)	0.0073 (8)	0.0089 (8)
C3	0.0280 (11)	0.0303 (11)	0.0340 (11)	0.0010 (8)	0.0130 (8)	0.0099 (9)
C2	0.0237 (10)	0.0275 (10)	0.0385 (12)	0.0008 (8)	0.0083 (8)	0.0145 (9)
C18	0.0256 (11)	0.0366 (12)	0.0406 (13)	−0.0025 (8)	0.0085 (9)	0.0086 (10)
C17	0.0295 (11)	0.0352 (12)	0.0409 (13)	0.0040 (9)	0.0023 (9)	0.0070 (10)
C4	0.0248 (10)	0.0242 (10)	0.0308 (11)	0.0002 (7)	0.0076 (8)	0.0073 (8)
C10	0.0505 (15)	0.0339 (12)	0.0363 (13)	0.0027 (10)	0.0024 (10)	0.0134 (10)
C9	0.0439 (13)	0.0321 (11)	0.0363 (12)	−0.0018 (9)	0.0100 (10)	0.0119 (10)
C16	0.0407 (13)	0.0303 (11)	0.0355 (12)	0.0046 (9)	0.0057 (9)	0.0100 (10)
C11	0.0364 (12)	0.0343 (12)	0.0407 (13)	0.0044 (9)	−0.0003 (10)	0.0073 (10)
C1	0.0392 (13)	0.0336 (12)	0.0519 (14)	−0.0063 (9)	0.0175 (10)	0.0137 (11)
N3	0.0281 (9)	0.0292 (9)	0.0305 (9)	0.0014 (7)	0.0107 (7)	0.0119 (7)
C21	0.0303 (11)	0.0287 (10)	0.0252 (10)	0.0061 (8)	0.0099 (8)	0.0107 (8)
C22	0.0265 (10)	0.0281 (10)	0.0266 (10)	0.0036 (8)	0.0089 (8)	0.0077 (8)
C20	0.0456 (14)	0.0411 (13)	0.0358 (12)	0.0078 (10)	0.0112 (10)	0.0198 (10)
C23	0.0291 (12)	0.0514 (14)	0.0423 (13)	0.0029 (10)	0.0061 (9)	0.0153 (11)
C31	0.0363 (12)	0.0202 (9)	0.0263 (10)	0.0037 (8)	0.0100 (8)	0.0022 (8)
C29	0.0527 (15)	0.0231 (10)	0.0386 (13)	0.0003 (9)	0.0214 (11)	0.0003 (9)
C25	0.0474 (14)	0.0301 (11)	0.0297 (12)	0.0106 (10)	0.0016 (10)	−0.0014 (9)
C30	0.0383 (14)	0.0397 (14)	0.0612 (17)	−0.0094 (10)	0.0222 (12)	−0.0081 (13)
C24	0.0318 (13)	0.0472 (15)	0.0511 (16)	0.0075 (10)	−0.0020 (11)	−0.0068 (12)
C28	0.091 (2)	0.0298 (13)	0.0544 (17)	0.0030 (13)	0.0431 (16)	0.0094 (12)
C26	0.083 (2)	0.0474 (15)	0.0312 (13)	0.0327 (15)	−0.0008 (13)	0.0027 (12)
C27	0.119 (3)	0.0391 (15)	0.0415 (16)	0.0220 (16)	0.0333 (17)	0.0179 (13)

Geometric parameters (Å, º)

N1—C13	1.337 (3)	C9—H9	0.9500
N1—C14	1.347 (2)	C16—H16	0.9500
O1—C4	1.369 (2)	C11—H11	0.9500
O1—H1O	0.97 (3)	C1—H1A	0.9800
O2—C6	1.367 (2)	C1—H1B	0.9800
O2—H2O	0.91 (3)	C1—H1C	0.9800
N2—C8	1.342 (3)	N3—C22	1.339 (3)
N2—C19	1.344 (3)	N3—C21	1.343 (3)
C19—C18	1.428 (3)	C21—C22^i	1.399 (3)
C19—C14	1.437 (3)	C21—C20	1.504 (3)
C15—C16	1.360 (3)	C22—C21^i	1.399 (3)
C15—C14	1.422 (3)	C22—C23	1.497 (3)
C15—H15	0.9500	C20—H20A	0.9800
C5—C6	1.389 (3)	C20—H20B	0.9800
C5—C4	1.391 (3)	C20—H20C	0.9800
C5—H5	0.9500	C23—H23A	0.9800
C8—C9	1.430 (3)	C23—H23B	0.9800
C8—C13	1.440 (3)	C23—H23C	0.9800
C12—C11	1.355 (3)	C31—C25	1.411 (3)
C12—C13	1.426 (3)	C31—C31^ii	1.423 (4)
C12—H12	0.9500	C31—C29	1.423 (3)
C7—C2	1.389 (3)	C29—C28	1.401 (4)
C7—C6	1.391 (3)	C29—C30	1.433 (4)
C7—H7	0.9500	C25—C26	1.402 (4)
C3—C2	1.388 (3)	C25—C24	1.442 (4)
C3—C4	1.393 (3)	C30—C24^ii	1.325 (4)
C3—H3	0.9500	C30—H30	0.9500
C2—C1	1.513 (3)	C24—C30^ii	1.325 (4)
C18—C17	1.355 (3)	C24—H24	0.9500
C18—H18	0.9500	C28—C27	1.349 (4)
C17—C16	1.420 (3)	C28—H28	0.9500
C17—H17	0.9500	C26—C27	1.383 (4)
C10—C9	1.351 (3)	C26—H26	0.9500
C10—C11	1.420 (3)	C27—H27	0.9500
C10—H10	0.9500
C13—N1—C14	117.81 (16)	C17—C16—H16	119.9
C4—O1—H1O	109.6 (17)	C12—C11—C10	120.9 (2)
C6—O2—H2O	109.6 (16)	C12—C11—H11	119.5
C8—N2—C19	116.94 (16)	C10—C11—H11	119.5
N2—C19—C18	119.96 (17)	C2—C1—H1A	109.5
N2—C19—C14	121.80 (18)	C2—C1—H1B	109.5
C18—C19—C14	118.22 (19)	H1A—C1—H1B	109.5
C16—C15—C14	120.54 (19)	C2—C1—H1C	109.5
C16—C15—H15	119.7	H1A—C1—H1C	109.5
C14—C15—H15	119.7	H1B—C1—H1C	109.5
C6—C5—C4	119.52 (17)	C22—N3—C21	119.46 (16)
C6—C5—H5	120.2	N3—C21—C22^i	120.43 (18)
C4—C5—H5	120.2	N3—C21—C20	117.64 (17)
N2—C8—C9	119.97 (18)	C22^i—C21—C20	121.93 (19)
N2—C8—C13	121.61 (18)	N3—C22—C21^i	120.11 (18)
C9—C8—C13	118.41 (19)	N3—C22—C23	117.58 (17)
C11—C12—C13	120.32 (19)	C21^i—C22—C23	122.32 (19)
C11—C12—H12	119.8	C21—C20—H20A	109.5
C13—C12—H12	119.8	C21—C20—H20B	109.5
N1—C14—C15	120.01 (17)	H20A—C20—H20B	109.5
N1—C14—C19	120.74 (18)	C21—C20—H20C	109.5
C15—C14—C19	119.25 (18)	H20A—C20—H20C	109.5
C2—C7—C6	120.04 (18)	H20B—C20—H20C	109.5
C2—C7—H7	120.0	C22—C23—H23A	109.5
C6—C7—H7	120.0	C22—C23—H23B	109.5
N1—C13—C12	120.03 (17)	H23A—C23—H23B	109.5
N1—C13—C8	121.09 (18)	C22—C23—H23C	109.5
C12—C13—C8	118.88 (18)	H23A—C23—H23C	109.5
O2—C6—C5	122.06 (16)	H23B—C23—H23C	109.5
O2—C6—C7	117.68 (17)	C25—C31—C31^ii	120.9 (2)
C5—C6—C7	120.26 (17)	C25—C31—C29	119.5 (2)
C2—C3—C4	119.88 (18)	C31^ii—C31—C29	119.5 (2)
C2—C3—H3	120.1	C28—C29—C31	118.5 (2)
C4—C3—H3	120.1	C28—C29—C30	123.6 (2)
C3—C2—C7	119.98 (17)	C31—C29—C30	117.9 (2)
C3—C2—C1	121.16 (19)	C26—C25—C31	119.3 (2)
C7—C2—C1	118.83 (18)	C26—C25—C24	123.2 (2)
C17—C18—C19	120.46 (19)	C31—C25—C24	117.5 (2)
C17—C18—H18	119.8	C24^ii—C30—C29	122.2 (2)
C19—C18—H18	119.8	C24^ii—C30—H30	118.9
C18—C17—C16	121.3 (2)	C29—C30—H30	118.9
C18—C17—H17	119.3	C30^ii—C24—C25	121.9 (2)
C16—C17—H17	119.3	C30^ii—C24—H24	119.1
O1—C4—C5	121.64 (16)	C25—C24—H24	119.1
O1—C4—C3	118.05 (17)	C27—C28—C29	121.2 (3)
C5—C4—C3	120.30 (18)	C27—C28—H28	119.4
C9—C10—C11	120.9 (2)	C29—C28—H28	119.4
C9—C10—H10	119.6	C27—C26—C25	119.9 (3)
C11—C10—H10	119.6	C27—C26—H26	120.1
C10—C9—C8	120.6 (2)	C25—C26—H26	120.1
C10—C9—H9	119.7	C28—C27—C26	121.5 (3)
C8—C9—H9	119.7	C28—C27—H27	119.2
C15—C16—C17	120.2 (2)	C26—C27—H27	119.2
C15—C16—H16	119.9

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y, −z+1.

(QS_PGL_TMP_PHE_ANT)

Crystal data

C54H54N6O6	V = 1116.4 (3) Å^3
Mr = 883.03	Z = 1
Triclinic, P1	F(000) = 468
a = 8.6332 (13) Å	Dx = 1.313 Mg m^−3
b = 9.0194 (14) Å	Mo Kα radiation, λ = 0.71073 Å
c = 14.869 (2) Å	µ = 0.09 mm^−1
α = 105.200 (4)°	T = 150 K
β = 91.263 (4)°	Block, red
γ = 91.519 (4)°	0.62 × 0.38 × 0.20 mm

Data collection

CCD area detector diffractometer	2524 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.095
phi and ω scans	θmax = 27.0°, θmin = 3.0°
Absorption correction: analytical Bruker, AXS, 2008	h = −11→11
Tmin = 0.961, Tmax = 0.983	k = −11→11
29237 measured reflections	l = −18→18
4848 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.088	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.275	w = 1/[σ^2(Fo^2) + (0.1412P)^2 + 1.1598P] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
4848 reflections	Δρmax = 0.47 e Å^−3
314 parameters	Δρmin = −0.39 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N2	0.9164 (3)	0.9289 (3)	0.22405 (19)	0.0264 (7)
H2O	0.768 (5)	0.773 (5)	0.166 (3)	0.039 (11)*
H1O	0.304 (6)	0.299 (6)	0.242 (4)	0.075 (18)*
H3O	0.724 (6)	0.727 (6)	0.461 (4)	0.080 (17)*
C13	0.8829 (4)	1.0753 (4)	0.2311 (2)	0.0283 (9)
C14	0.9966 (5)	1.1922 (4)	0.2612 (2)	0.0305 (9)
C15	1.1745 (4)	1.0130 (5)	0.2761 (2)	0.0309 (9)
C16	1.0601 (4)	0.8962 (4)	0.2470 (2)	0.0265 (8)
C17	0.7218 (5)	1.1085 (5)	0.2052 (3)	0.0413 (10)
H17A	0.6600	1.0122	0.1858	0.062*
H17B	0.7248	1.1576	0.1538	0.062*
H17C	0.6749	1.1775	0.2592	0.062*
C18	0.9636 (6)	1.3561 (5)	0.2675 (3)	0.0498 (12)
H18A	1.0473	1.4226	0.3035	0.075*
H18B	0.8652	1.3821	0.2984	0.075*
H18C	0.9567	1.3712	0.2046	0.075*
C19	1.3370 (5)	0.9807 (6)	0.3000 (3)	0.0498 (12)
H19A	1.3961	1.0779	0.3240	0.075*
H19B	1.3856	0.9195	0.2441	0.075*
H19C	1.3359	0.9234	0.3477	0.075*
C20	1.0931 (5)	0.7320 (5)	0.2404 (3)	0.0402 (10)
H20A	1.1117	0.7190	0.3031	0.060*
H20B	1.1852	0.7028	0.2032	0.060*
H20C	1.0042	0.6664	0.2105	0.060*
N3	1.1408 (4)	1.1594 (4)	0.2820 (2)	0.0341 (8)
C7	0.6642 (6)	1.2127 (6)	0.4669 (3)	0.0621 (14)
H7	0.5602	1.2378	0.4569	0.075*
C8	0.6973 (5)	1.0684 (5)	0.4624 (3)	0.0374 (10)
H8	0.6182	0.9900	0.4459	0.045*
C9	0.8516 (4)	1.0306 (4)	0.4823 (2)	0.0270 (8)
C10	1.0287 (4)	0.8534 (4)	0.4997 (2)	0.0267 (8)
C11	1.0647 (5)	0.6998 (5)	0.4976 (3)	0.0395 (10)
H11	0.9857	0.6211	0.4857	0.047*
C12	1.2152 (7)	0.6675 (6)	0.5130 (3)	0.0638 (14)
H12	1.2411	0.5649	0.5105	0.077*
N1	0.8824 (4)	0.8859 (3)	0.4829 (2)	0.0290 (7)
C1	0.4500 (4)	0.4469 (4)	0.2369 (2)	0.0332 (9)
C2	0.5159 (4)	0.5149 (4)	0.1741 (3)	0.0335 (9)
H2	0.4847	0.4826	0.1101	0.040*
C3	0.6276 (4)	0.6303 (4)	0.2043 (2)	0.0287 (9)
C4	0.6741 (4)	0.6784 (4)	0.2974 (2)	0.0272 (8)
H4	0.7514	0.7577	0.3182	0.033*
C5	0.6056 (4)	0.6085 (4)	0.3592 (2)	0.0320 (9)
C6	0.4946 (4)	0.4919 (4)	0.3309 (3)	0.0351 (10)
H6	0.4498	0.4437	0.3743	0.042*
O1	0.3435 (4)	0.3314 (4)	0.2013 (2)	0.0548 (10)
O2	0.6928 (3)	0.6951 (3)	0.14014 (18)	0.0376 (7)
O3	0.6498 (4)	0.6511 (3)	0.45275 (18)	0.0468 (8)
C21	0.3457 (5)	−0.2131 (5)	0.0382 (3)	0.0413 (10)
H21	0.4489	−0.2351	0.0527	0.050*
C22	0.3065 (5)	−0.0651 (5)	0.0474 (3)	0.0373 (10)
H22	0.3821	0.0156	0.0694	0.045*
C23	0.1529 (4)	−0.0296 (4)	0.0246 (2)	0.0305 (9)
C24	0.1096 (4)	0.1199 (4)	0.0309 (2)	0.0316 (9)
H24	0.1842	0.2017	0.0521	0.038*
C25	−0.0397 (4)	0.1536 (4)	0.0071 (2)	0.0308 (9)
C26	−0.0875 (5)	0.3061 (5)	0.0138 (3)	0.0374 (10)
H26	−0.0139	0.3892	0.0335	0.045*
C27	−0.2336 (5)	0.3357 (5)	−0.0070 (3)	0.0406 (10)
H27	−0.2623	0.4388	−0.0009	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N2	0.0300 (18)	0.0284 (17)	0.0221 (15)	−0.0064 (13)	0.0057 (12)	0.0093 (13)
C13	0.031 (2)	0.033 (2)	0.0223 (18)	0.0010 (17)	0.0079 (15)	0.0101 (16)
C14	0.043 (2)	0.029 (2)	0.0213 (18)	−0.0063 (17)	0.0057 (16)	0.0107 (16)
C15	0.031 (2)	0.042 (2)	0.0200 (18)	−0.0056 (17)	−0.0004 (15)	0.0103 (16)
C16	0.027 (2)	0.033 (2)	0.0225 (17)	−0.0031 (16)	0.0058 (15)	0.0136 (16)
C17	0.042 (2)	0.049 (3)	0.036 (2)	0.003 (2)	0.0041 (19)	0.014 (2)
C18	0.077 (3)	0.034 (2)	0.041 (2)	0.002 (2)	0.009 (2)	0.013 (2)
C19	0.034 (2)	0.084 (4)	0.032 (2)	−0.006 (2)	−0.0023 (18)	0.018 (2)
C20	0.045 (3)	0.036 (2)	0.045 (2)	0.0039 (19)	0.0072 (19)	0.0189 (19)
N3	0.039 (2)	0.037 (2)	0.0250 (16)	−0.0156 (15)	0.0000 (14)	0.0083 (14)
C7	0.057 (3)	0.075 (4)	0.058 (3)	−0.001 (3)	0.001 (3)	0.025 (3)
C8	0.034 (2)	0.044 (3)	0.036 (2)	−0.0052 (19)	−0.0039 (17)	0.0155 (19)
C9	0.030 (2)	0.033 (2)	0.0176 (17)	−0.0050 (16)	0.0007 (14)	0.0060 (15)
C10	0.036 (2)	0.027 (2)	0.0160 (16)	−0.0067 (16)	−0.0023 (15)	0.0056 (14)
C11	0.046 (3)	0.036 (2)	0.039 (2)	−0.004 (2)	−0.0052 (19)	0.0140 (19)
C12	0.086 (4)	0.051 (3)	0.055 (3)	0.005 (3)	0.003 (3)	0.015 (2)
N1	0.0362 (19)	0.0291 (18)	0.0210 (15)	−0.0081 (14)	−0.0009 (13)	0.0061 (13)
C1	0.033 (2)	0.034 (2)	0.031 (2)	−0.0160 (17)	−0.0015 (16)	0.0066 (17)
C2	0.035 (2)	0.036 (2)	0.0274 (19)	−0.0135 (17)	−0.0014 (16)	0.0052 (16)
C3	0.030 (2)	0.034 (2)	0.0228 (18)	−0.0089 (16)	0.0004 (15)	0.0095 (16)
C4	0.0243 (19)	0.0266 (19)	0.0294 (19)	−0.0151 (15)	−0.0050 (15)	0.0073 (15)
C5	0.034 (2)	0.038 (2)	0.0229 (18)	−0.0133 (18)	−0.0049 (16)	0.0082 (16)
C6	0.038 (2)	0.041 (2)	0.028 (2)	−0.0141 (18)	−0.0007 (17)	0.0133 (17)
O1	0.062 (2)	0.064 (2)	0.0354 (16)	−0.0464 (17)	−0.0054 (15)	0.0124 (15)
O2	0.0425 (16)	0.0395 (16)	0.0306 (14)	−0.0235 (13)	−0.0012 (12)	0.0112 (12)
O3	0.058 (2)	0.0539 (19)	0.0276 (14)	−0.0337 (16)	−0.0127 (13)	0.0137 (13)
C21	0.035 (2)	0.056 (3)	0.034 (2)	0.004 (2)	−0.0028 (18)	0.015 (2)
C22	0.034 (2)	0.051 (3)	0.027 (2)	−0.0072 (19)	−0.0002 (17)	0.0095 (18)
C23	0.033 (2)	0.038 (2)	0.0193 (17)	−0.0037 (17)	0.0035 (15)	0.0057 (16)
C24	0.032 (2)	0.035 (2)	0.0240 (19)	−0.0101 (17)	−0.0029 (16)	0.0017 (16)
C25	0.036 (2)	0.036 (2)	0.0195 (17)	−0.0050 (17)	0.0015 (16)	0.0060 (16)
C26	0.051 (3)	0.037 (2)	0.0249 (19)	−0.006 (2)	0.0017 (18)	0.0102 (17)
C27	0.049 (3)	0.040 (2)	0.035 (2)	0.007 (2)	0.0051 (19)	0.0129 (19)

Geometric parameters (Å, º)

N2—C13	1.337 (5)	C11—H11	0.9500
N2—C16	1.340 (5)	C12—C7^i	1.449 (7)
C13—C14	1.397 (5)	C12—H12	0.9500
C13—C17	1.493 (5)	C1—O1	1.360 (4)
C14—N3	1.336 (5)	C1—C2	1.370 (5)
C14—C18	1.492 (5)	C1—C6	1.392 (5)
C15—N3	1.341 (5)	C2—C3	1.377 (5)
C15—C16	1.400 (5)	C2—H2	0.9500
C15—C19	1.495 (6)	C3—O2	1.367 (4)
C16—C20	1.494 (5)	C3—C4	1.385 (5)
C17—H17A	0.9800	C4—C5	1.377 (5)
C17—H17B	0.9800	C4—H4	0.9500
C17—H17C	0.9800	C5—C6	1.378 (5)
C18—H18A	0.9800	C5—O3	1.385 (4)
C18—H18B	0.9800	C6—H6	0.9500
C18—H18C	0.9800	O1—H1O	0.82 (6)
C19—H19A	0.9800	O2—H2O	0.94 (4)
C19—H19B	0.9800	O3—H3O	0.91 (6)
C19—H19C	0.9800	C21—C22	1.359 (6)
C20—H20A	0.9800	C21—C27^ii	1.425 (6)
C20—H20B	0.9800	C21—H21	0.9500
C20—H20C	0.9800	C22—C23	1.427 (5)
C7—C8	1.324 (6)	C22—H22	0.9500
C7—C12^i	1.449 (7)	C23—C24	1.389 (5)
C7—H7	0.9500	C23—C25^ii	1.441 (5)
C8—C9	1.427 (5)	C24—C25	1.391 (5)
C8—H8	0.9500	C24—H24	0.9500
C9—N1	1.341 (5)	C25—C26	1.426 (6)
C9—C10^i	1.421 (5)	C25—C23^ii	1.441 (5)
C10—N1	1.337 (5)	C26—C27	1.341 (6)
C10—C11	1.420 (5)	C26—H26	0.9500
C10—C9^i	1.421 (5)	C27—C21^ii	1.425 (6)
C11—C12	1.366 (7)	C27—H27	0.9500
C13—N2—C16	119.0 (3)	C12—C11—C10	118.6 (4)
N2—C13—C14	120.4 (3)	C12—C11—H11	120.7
N2—C13—C17	117.9 (3)	C10—C11—H11	120.7
C14—C13—C17	121.7 (4)	C11—C12—C7^i	121.1 (5)
N3—C14—C13	120.7 (3)	C11—C12—H12	119.5
N3—C14—C18	117.7 (3)	C7^i—C12—H12	119.5
C13—C14—C18	121.6 (4)	C10—N1—C9	118.3 (3)
N3—C15—C16	120.2 (3)	O1—C1—C2	116.1 (3)
N3—C15—C19	117.6 (3)	O1—C1—C6	122.8 (3)
C16—C15—C19	122.2 (4)	C2—C1—C6	121.1 (3)
N2—C16—C15	120.6 (3)	C1—C2—C3	119.6 (3)
N2—C16—C20	117.8 (3)	C1—C2—H2	120.2
C15—C16—C20	121.6 (4)	C3—C2—H2	120.2
C13—C17—H17A	109.5	O2—C3—C2	118.5 (3)
C13—C17—H17B	109.5	O2—C3—C4	120.7 (3)
H17A—C17—H17B	109.5	C2—C3—C4	120.8 (3)
C13—C17—H17C	109.5	C5—C4—C3	118.4 (3)
H17A—C17—H17C	109.5	C5—C4—H4	120.8
H17B—C17—H17C	109.5	C3—C4—H4	120.8
C14—C18—H18A	109.5	C4—C5—C6	122.1 (3)
C14—C18—H18B	109.5	C4—C5—O3	120.6 (3)
H18A—C18—H18B	109.5	C6—C5—O3	117.3 (3)
C14—C18—H18C	109.5	C5—C6—C1	117.9 (3)
H18A—C18—H18C	109.5	C5—C6—H6	121.0
H18B—C18—H18C	109.5	C1—C6—H6	121.0
C15—C19—H19A	109.5	C1—O1—H1O	112 (4)
C15—C19—H19B	109.5	C3—O2—H2O	113 (2)
H19A—C19—H19B	109.5	C5—O3—H3O	108 (3)
C15—C19—H19C	109.5	C22—C21—C27^ii	120.7 (4)
H19A—C19—H19C	109.5	C22—C21—H21	119.7
H19B—C19—H19C	109.5	C27^ii—C21—H21	119.7
C16—C20—H20A	109.5	C21—C22—C23	120.6 (4)
C16—C20—H20B	109.5	C21—C22—H22	119.7
H20A—C20—H20B	109.5	C23—C22—H22	119.7
C16—C20—H20C	109.5	C24—C23—C22	122.3 (4)
H20A—C20—H20C	109.5	C24—C23—C25^ii	119.0 (3)
H20B—C20—H20C	109.5	C22—C23—C25^ii	118.7 (4)
C14—N3—C15	119.1 (3)	C23—C24—C25	122.1 (3)
C8—C7—C12^i	120.7 (5)	C23—C24—H24	119.0
C8—C7—H7	119.6	C25—C24—H24	119.0
C12^i—C7—H7	119.6	C24—C25—C26	123.2 (3)
C7—C8—C9	120.1 (4)	C24—C25—C23^ii	118.9 (4)
C7—C8—H8	119.9	C26—C25—C23^ii	117.9 (4)
C9—C8—H8	119.9	C27—C26—C25	121.9 (4)
N1—C9—C10^i	120.7 (3)	C27—C26—H26	119.1
N1—C9—C8	119.8 (3)	C25—C26—H26	119.1
C10^i—C9—C8	119.5 (4)	C26—C27—C21^ii	120.2 (4)
N1—C10—C11	119.2 (3)	C26—C27—H27	119.9
N1—C10—C9^i	121.0 (3)	C21^ii—C27—H27	119.9
C11—C10—C9^i	119.8 (4)

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···N2	0.94 (4)	1.89 (4)	2.833 (4)	177 (4)
O1—H1O···N3^iii	0.82 (6)	2.06 (6)	2.798 (4)	149 (5)
O3—H3O···N1	0.91 (6)	1.91 (6)	2.820 (4)	178 (5)
C4—H4···N1	0.95	2.63	3.352 (4)	133

Symmetry code: (iii) x−1, y−1, z.

(QS_PGL_TMP_PHE_DPE)

Crystal data

C44H44N6O6	V = 950.9 (19) Å^3
Mr = 752.85	Z = 1
Triclinic, P1	F(000) = 398
a = 7.812 (9) Å	Dx = 1.315 Mg m^−3
b = 8.763 (10) Å	Mo Kα radiation, λ = 0.71073 Å
c = 14.300 (16) Å	µ = 0.09 mm^−1
α = 95.009 (14)°	T = 150 K
β = 95.415 (11)°	Block, orange
γ = 101.04 (2)°	0.64 × 0.37 × 0.24 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	3654 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.066
profile data from ω–scans	θmax = 27.6°, θmin = 1.4°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −10→10
Tmin = 0.801, Tmax = 1.000	k = −11→11
10088 measured reflections	l = −18→18
4348 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.171	w = 1/[σ^2(Fo^2) + (0.0917P)^2 + 0.1007P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
4348 reflections	Δρmax = 0.34 e Å^−3
266 parameters	Δρmin = −0.37 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
H22B	−0.576 (4)	0.421 (4)	1.077 (2)	0.087 (9)*
H22A	−0.457 (3)	0.603 (3)	1.088 (2)	0.072 (8)*
O1	0.06489 (15)	0.14728 (14)	0.67499 (9)	0.0384 (3)
H1O	0.0590	0.2187	0.6400	0.058*
O2	−0.25825 (16)	−0.12950 (14)	0.89622 (8)	0.0369 (3)
H2O	−0.1731	−0.1753	0.8973	0.055*
O3	−0.50913 (15)	0.23058 (15)	0.73087 (9)	0.0374 (3)
H3O	−0.4979	0.2785	0.6827	0.056*
C6	−0.22141 (19)	0.19463 (16)	0.70024 (10)	0.0265 (3)
H6	−0.2152	0.2682	0.6550	0.032*
C2	−0.0905 (2)	0.01131 (17)	0.78597 (11)	0.0282 (3)
H2	0.0052	−0.0389	0.7994	0.034*
C4	−0.3798 (2)	0.05217 (17)	0.81357 (10)	0.0286 (3)
H4	−0.4815	0.0291	0.8455	0.034*
C1	−0.08287 (19)	0.11928 (16)	0.71986 (11)	0.0266 (3)
C5	−0.36904 (19)	0.16068 (17)	0.74777 (11)	0.0271 (3)
C3	−0.2401 (2)	−0.02197 (17)	0.83202 (10)	0.0273 (3)
N3	−0.0059 (2)	0.29841 (17)	1.09074 (10)	0.0383 (4)
C18	−0.1447 (2)	0.5198 (2)	1.10294 (12)	0.0380 (4)
H18	−0.1335	0.6287	1.1205	0.046*
C20	−0.3129 (3)	0.2705 (2)	1.03948 (12)	0.0403 (4)
H20	−0.4201	0.2038	1.0128	0.048*
C19	−0.3066 (2)	0.4291 (2)	1.06520 (11)	0.0374 (4)
C17	0.0006 (2)	0.4510 (2)	1.11491 (12)	0.0384 (4)
H17	0.1097	0.5148	1.1415	0.046*
C21	−0.1626 (3)	0.2121 (2)	1.05310 (12)	0.0405 (4)
H21	−0.1696	0.1040	1.0348	0.049*
C22	−0.4707 (3)	0.4951 (3)	1.05194 (13)	0.0454 (5)
N1	0.47831 (16)	0.59520 (14)	0.42967 (9)	0.0265 (3)
C7	0.3074 (2)	0.3799 (2)	0.32048 (12)	0.0370 (4)
H7A	0.3253	0.4612	0.2774	0.055*
H7B	0.1822	0.3507	0.3276	0.055*
H7C	0.3487	0.2880	0.2946	0.055*
C8	0.40889 (19)	0.44127 (17)	0.41530 (10)	0.0256 (3)
C9	0.56859 (18)	0.65521 (16)	0.51370 (11)	0.0251 (3)
C10	0.6414 (2)	0.82867 (18)	0.52753 (13)	0.0371 (4)
H10A	0.6201	0.8733	0.4680	0.056*
H10B	0.7680	0.8477	0.5472	0.056*
H10C	0.5835	0.8779	0.5764	0.056*
N2	0.03971 (17)	0.37846 (14)	0.55175 (9)	0.0271 (3)
C13	0.10393 (19)	0.53013 (16)	0.58380 (10)	0.0253 (3)
C12	0.2134 (2)	0.56851 (18)	0.67155 (11)	0.0310 (3)
H12	0.2417	0.4881	0.7069	0.037*
C14	−0.06428 (19)	0.34700 (17)	0.46911 (11)	0.0265 (3)
C16	−0.2371 (2)	0.15554 (18)	0.34724 (12)	0.0334 (4)
H16	−0.2826	0.0497	0.3227	0.040*
C15	−0.1340 (2)	0.18854 (17)	0.43183 (12)	0.0315 (4)
H15	−0.1085	0.1058	0.4660	0.038*
C11	0.2771 (2)	0.7220 (2)	0.70436 (12)	0.0340 (4)
H11	0.3497	0.7474	0.7629	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0361 (6)	0.0355 (6)	0.0523 (8)	0.0154 (5)	0.0146 (5)	0.0249 (5)
O2	0.0469 (7)	0.0343 (6)	0.0350 (6)	0.0134 (5)	0.0091 (5)	0.0183 (5)
O3	0.0338 (6)	0.0451 (7)	0.0401 (7)	0.0184 (5)	0.0061 (5)	0.0173 (5)
C6	0.0325 (7)	0.0209 (7)	0.0270 (7)	0.0067 (6)	0.0008 (6)	0.0068 (5)
C2	0.0318 (7)	0.0239 (7)	0.0300 (8)	0.0085 (6)	−0.0008 (6)	0.0069 (6)
C4	0.0305 (7)	0.0283 (7)	0.0262 (7)	0.0036 (6)	0.0031 (6)	0.0044 (6)
C1	0.0291 (7)	0.0207 (7)	0.0295 (8)	0.0039 (6)	0.0012 (6)	0.0044 (6)
C5	0.0288 (7)	0.0258 (7)	0.0261 (7)	0.0078 (6)	−0.0027 (6)	0.0014 (6)
C3	0.0367 (8)	0.0214 (7)	0.0233 (7)	0.0048 (6)	0.0000 (6)	0.0058 (5)
N3	0.0498 (8)	0.0396 (8)	0.0306 (7)	0.0184 (7)	0.0032 (6)	0.0136 (6)
C18	0.0579 (11)	0.0319 (8)	0.0267 (8)	0.0148 (8)	0.0015 (7)	0.0077 (6)
C20	0.0498 (10)	0.0385 (9)	0.0321 (9)	0.0118 (8)	−0.0028 (7)	0.0033 (7)
C19	0.0529 (10)	0.0393 (9)	0.0243 (8)	0.0201 (8)	0.0005 (7)	0.0069 (6)
C17	0.0487 (10)	0.0376 (9)	0.0304 (8)	0.0100 (8)	0.0004 (7)	0.0125 (7)
C21	0.0587 (11)	0.0342 (9)	0.0318 (8)	0.0184 (8)	0.0010 (8)	0.0055 (7)
C22	0.0554 (11)	0.0550 (11)	0.0311 (9)	0.0263 (10)	−0.0005 (8)	0.0064 (8)
N1	0.0309 (6)	0.0230 (6)	0.0267 (6)	0.0089 (5)	0.0007 (5)	0.0045 (5)
C7	0.0425 (9)	0.0355 (8)	0.0300 (8)	0.0071 (7)	−0.0062 (7)	0.0000 (7)
C8	0.0277 (7)	0.0236 (7)	0.0257 (7)	0.0081 (6)	0.0002 (5)	0.0012 (5)
C9	0.0256 (7)	0.0203 (6)	0.0297 (7)	0.0069 (5)	0.0011 (6)	0.0010 (5)
C10	0.0413 (9)	0.0206 (7)	0.0471 (10)	0.0035 (6)	0.0004 (7)	0.0023 (7)
N2	0.0324 (6)	0.0210 (6)	0.0302 (7)	0.0064 (5)	0.0081 (5)	0.0088 (5)
C13	0.0304 (7)	0.0216 (7)	0.0269 (7)	0.0076 (6)	0.0094 (6)	0.0069 (5)
C12	0.0384 (8)	0.0304 (8)	0.0269 (8)	0.0103 (7)	0.0071 (6)	0.0078 (6)
C14	0.0299 (7)	0.0212 (7)	0.0310 (8)	0.0063 (6)	0.0095 (6)	0.0078 (6)
C16	0.0365 (8)	0.0236 (7)	0.0394 (9)	0.0047 (6)	0.0060 (7)	−0.0002 (6)
C15	0.0362 (8)	0.0196 (7)	0.0401 (9)	0.0062 (6)	0.0055 (7)	0.0075 (6)
C11	0.0381 (8)	0.0339 (8)	0.0300 (8)	0.0080 (7)	0.0040 (6)	0.0011 (6)

Geometric parameters (Å, º)

O1—C1	1.365 (2)	C22—H22A	1.02 (3)
O1—H1O	0.8400	N1—C9	1.344 (2)
O2—C3	1.369 (2)	N1—C8	1.344 (2)
O2—H2O	0.8400	C7—C8	1.504 (2)
O3—C5	1.365 (2)	C7—H7A	0.9800
O3—H3O	0.8400	C7—H7B	0.9800
C6—C5	1.390 (3)	C7—H7C	0.9800
C6—C1	1.391 (2)	C8—C9^ii	1.396 (2)
C6—H6	0.9500	C9—C8^ii	1.396 (2)
C2—C3	1.391 (3)	C9—C10	1.506 (3)
C2—C1	1.392 (2)	C10—H10A	0.9800
C2—H2	0.9500	C10—H10B	0.9800
C4—C3	1.389 (2)	C10—H10C	0.9800
C4—C5	1.392 (2)	N2—C14	1.345 (2)
C4—H4	0.9500	N2—C13	1.350 (2)
N3—C17	1.341 (3)	C13—C12	1.426 (2)
N3—C21	1.345 (3)	C13—C14^iii	1.433 (2)
C18—C17	1.387 (3)	C12—C11	1.366 (3)
C18—C19	1.391 (3)	C12—H12	0.9500
C18—H18	0.9500	C14—C15	1.426 (2)
C20—C21	1.373 (3)	C14—C13^iii	1.433 (2)
C20—C19	1.397 (3)	C16—C15	1.365 (3)
C20—H20	0.9500	C16—C11^iii	1.420 (3)
C19—C22	1.507 (3)	C16—H16	0.9500
C17—H17	0.9500	C15—H15	0.9500
C21—H21	0.9500	C11—C16^iii	1.420 (3)
C22—C22^i	1.527 (4)	C11—H11	0.9500
C22—H22B	1.06 (3)
C1—O1—H1O	109.5	C22^i—C22—H22A	108.5 (16)
C3—O2—H2O	109.5	H22B—C22—H22A	107 (2)
C5—O3—H3O	109.5	C9—N1—C8	119.01 (13)
C5—C6—C1	119.01 (15)	C8—C7—H7A	109.5
C5—C6—H6	120.5	C8—C7—H7B	109.5
C1—C6—H6	120.5	H7A—C7—H7B	109.5
C3—C2—C1	119.02 (14)	C8—C7—H7C	109.5
C3—C2—H2	120.5	H7A—C7—H7C	109.5
C1—C2—H2	120.5	H7B—C7—H7C	109.5
C3—C4—C5	119.18 (15)	N1—C8—C9^ii	120.54 (14)
C3—C4—H4	120.4	N1—C8—C7	117.04 (13)
C5—C4—H4	120.4	C9^ii—C8—C7	122.42 (15)
O1—C1—C6	121.58 (15)	N1—C9—C8^ii	120.44 (15)
O1—C1—C2	117.42 (14)	N1—C9—C10	117.33 (14)
C6—C1—C2	121.00 (15)	C8^ii—C9—C10	122.23 (15)
O3—C5—C6	121.44 (15)	C9—C10—H10A	109.5
O3—C5—C4	117.67 (14)	C9—C10—H10B	109.5
C6—C5—C4	120.89 (14)	H10A—C10—H10B	109.5
O2—C3—C4	116.93 (14)	C9—C10—H10C	109.5
O2—C3—C2	122.17 (14)	H10A—C10—H10C	109.5
C4—C3—C2	120.90 (15)	H10B—C10—H10C	109.5
C17—N3—C21	116.70 (16)	C14—N2—C13	117.66 (13)
C17—C18—C19	119.85 (18)	N2—C13—C12	119.42 (13)
C17—C18—H18	120.1	N2—C13—C14^iii	121.06 (15)
C19—C18—H18	120.1	C12—C13—C14^iii	119.52 (15)
C21—C20—C19	119.34 (18)	C11—C12—C13	119.41 (14)
C21—C20—H20	120.3	C11—C12—H12	120.3
C19—C20—H20	120.3	C13—C12—H12	120.3
C18—C19—C20	117.05 (17)	N2—C14—C15	119.77 (14)
C18—C19—C22	122.81 (18)	N2—C14—C13^iii	121.28 (14)
C20—C19—C22	120.14 (18)	C15—C14—C13^iii	118.94 (16)
N3—C17—C18	123.03 (17)	C15—C16—C11^iii	120.56 (15)
N3—C17—H17	118.5	C15—C16—H16	119.7
C18—C17—H17	118.5	C11^iii—C16—H16	119.7
N3—C21—C20	124.02 (18)	C16—C15—C14	120.16 (14)
N3—C21—H21	118.0	C16—C15—H15	119.9
C20—C21—H21	118.0	C14—C15—H15	119.9
C19—C22—C22^i	112.4 (2)	C12—C11—C16^iii	121.40 (17)
C19—C22—H22B	109.7 (16)	C12—C11—H11	119.3
C22^i—C22—H22B	106.1 (16)	C16^iii—C11—H11	119.3
C19—C22—H22A	112.4 (15)
C5—C6—C1—O1	179.61 (14)	C17—N3—C21—C20	−0.7 (3)
C5—C6—C1—C2	0.0 (2)	C19—C20—C21—N3	0.3 (3)
C3—C2—C1—O1	−179.02 (13)	C18—C19—C22—C22^i	108.6 (3)
C3—C2—C1—C6	0.6 (2)	C20—C19—C22—C22^i	−71.6 (3)
C1—C6—C5—O3	−179.64 (13)	C9—N1—C8—C9^ii	−0.5 (2)
C1—C6—C5—C4	−0.5 (2)	C9—N1—C8—C7	179.39 (13)
C3—C4—C5—O3	179.56 (13)	C8—N1—C9—C8^ii	0.5 (2)
C3—C4—C5—C6	0.4 (2)	C8—N1—C9—C10	−178.91 (13)
C5—C4—C3—O2	−179.01 (13)	C14—N2—C13—C12	179.42 (13)
C5—C4—C3—C2	0.2 (2)	C14—N2—C13—C14^iii	−0.8 (2)
C1—C2—C3—O2	178.47 (13)	N2—C13—C12—C11	−179.45 (14)
C1—C2—C3—C4	−0.7 (2)	C14^iii—C13—C12—C11	0.7 (2)
C17—C18—C19—C20	−1.1 (2)	C13—N2—C14—C15	179.39 (13)
C17—C18—C19—C22	178.76 (16)	C13—N2—C14—C13^iii	0.8 (2)
C21—C20—C19—C18	0.6 (2)	C11^iii—C16—C15—C14	−0.3 (2)
C21—C20—C19—C22	−179.23 (17)	N2—C14—C15—C16	−178.89 (14)
C21—N3—C17—C18	0.2 (2)	C13^iii—C14—C15—C16	−0.2 (2)
C19—C18—C17—N3	0.7 (3)	C13—C12—C11—C16^iii	−0.2 (2)

Symmetry codes: (i) −x−1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2	0.84	1.98	2.821 (3)	177
O2—H2O···N3^iv	0.84	1.93	2.762 (3)	173
O3—H3O···N1^iii	0.84	2.03	2.870 (3)	176
C6—H6···N2	0.95	2.67	3.379 (3)	132
O1—H1O···N2	0.84	1.98	2.821 (3)	177
O2—H2O···N3^iv	0.84	1.93	2.762 (3)	173
O3—H3O···N1^iii	0.84	2.03	2.870 (3)	176
C6—H6···N2	0.95	2.67	3.379 (3)	132

Symmetry codes: (iii) −x, −y+1, −z+1; (iv) −x, −y, −z+2.

(QS_PGL_TMP_PHE_PYR_hydrate)

Crystal data

C56H56N6O8	V = 1176.1 (2) Å^3
Mr = 941.06	Z = 1
Triclinic, P1	F(000) = 498
a = 10.1510 (11) Å	Dx = 1.329 Mg m^−3
b = 11.2084 (12) Å	Mo Kα radiation, λ = 0.71073 Å
c = 12.3363 (13) Å	µ = 0.09 mm^−1
α = 102.012 (3)°	T = 150 K
β = 105.153 (3)°	Block, orange
γ = 112.368 (3)°	0.75 × 0.43 × 0.22 mm

Data collection

CCD area detector diffractometer	3988 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.036
phi and ω scans	θmax = 26.0°, θmin = 3.2°
Absorption correction: analytical Bruker, AXS, 2008	h = −12→12
Tmin = 0.955, Tmax = 0.980	k = −13→13
42928 measured reflections	l = −15→15
4600 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.105	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.412	w = 1/[σ^2(Fo^2) + (0.1504P)^2 + 12.4077P] where P = (Fo^2 + 2Fc^2)/3
S = 1.19	(Δ/σ)max = 0.001
4600 reflections	Δρmax = 1.12 e Å^−3
327 parameters	Δρmin = −0.60 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O4	1.1503 (6)	0.3103 (5)	0.5643 (4)	0.0288 (11)
H4A	1.181 (9)	0.413 (9)	0.626 (7)	0.03 (2)*
N2	0.3966 (6)	0.8030 (5)	0.1875 (4)	0.0172 (10)
N1	0.6183 (6)	0.7451 (5)	0.3122 (4)	0.0190 (11)
C7	0.4685 (7)	0.6546 (6)	0.2730 (5)	0.0183 (12)
C10	0.6577 (7)	0.8631 (6)	0.2909 (5)	0.0176 (12)
C14	0.8257 (7)	0.9640 (6)	0.3384 (6)	0.0224 (13)
H14A	0.8865	0.9270	0.3824	0.034*
H14B	0.8435	1.0512	0.3921	0.034*
H14C	0.8564	0.9794	0.2715	0.034*
C13	0.5858 (7)	1.0212 (7)	0.1969 (6)	0.0239 (13)
H13A	0.4915	1.0227	0.1522	0.036*
H13B	0.6487	1.0249	0.1482	0.036*
H13C	0.6439	1.1008	0.2712	0.036*
C9	0.5451 (7)	0.8919 (6)	0.2259 (5)	0.0167 (12)
C8	0.3557 (7)	0.6846 (6)	0.2102 (5)	0.0166 (12)
C12	0.1877 (7)	0.5857 (7)	0.1638 (6)	0.0256 (14)
H12A	0.1271	0.6277	0.1279	0.038*
H12B	0.1599	0.5632	0.2299	0.038*
H12C	0.1662	0.5015	0.1032	0.038*
C11	0.4284 (8)	0.5230 (7)	0.2988 (6)	0.0270 (14)
H11A	0.5230	0.5197	0.3398	0.041*
H11B	0.3674	0.4449	0.2235	0.041*
H11C	0.3686	0.5184	0.3500	0.041*
O1	0.8147 (5)	0.4578 (5)	0.2637 (4)	0.0223 (10)
H1	0.7506	0.4601	0.2062	0.033*
O2	1.1337 (5)	0.2404 (5)	0.3394 (4)	0.0233 (10)
H2	1.1445	0.2766	0.4101	0.035*
O3	0.8272 (5)	0.1413 (5)	−0.0574 (4)	0.0224 (10)
H3	0.7546	0.1520	−0.0976	0.034*
C6	0.8161 (6)	0.3005 (6)	0.1005 (5)	0.0156 (12)
H6	0.7433	0.3142	0.0450	0.019*
C4	0.9816 (7)	0.1942 (6)	0.1423 (5)	0.0194 (12)
H4	1.0229	0.1361	0.1152	0.023*
C2	0.9723 (6)	0.3501 (6)	0.3065 (5)	0.0153 (11)
H2A	1.0047	0.3961	0.3897	0.018*
C3	1.0281 (6)	0.2615 (6)	0.2630 (5)	0.0150 (11)
C21	1.5274 (7)	0.0635 (6)	0.4896 (5)	0.0165 (12)
C5	0.8731 (6)	0.2124 (6)	0.0602 (5)	0.0162 (12)
C20	1.6882 (7)	0.1537 (6)	0.5375 (5)	0.0202 (13)
C16	1.4228 (7)	0.0998 (6)	0.4213 (5)	0.0203 (13)
C1	0.8660 (6)	0.3673 (6)	0.2208 (5)	0.0148 (11)
C19	1.7403 (8)	0.2778 (6)	0.5163 (6)	0.0238 (13)
H19	1.8474	0.3386	0.5478	0.029*
C17	1.4814 (8)	0.2267 (7)	0.4035 (6)	0.0252 (14)
H17	1.4126	0.2531	0.3589	0.030*
C15	1.2622 (7)	0.0064 (7)	0.3744 (6)	0.0229 (13)
H15	1.1912	0.0301	0.3289	0.028*
C22	1.7909 (7)	0.1138 (7)	0.6070 (6)	0.0235 (13)
H22	1.8983	0.1737	0.6403	0.028*
C18	1.6376 (8)	0.3134 (7)	0.4499 (6)	0.0275 (15)
H18	1.6751	0.3982	0.4362	0.033*
N3	0.6120 (6)	0.4810 (5)	0.0789 (4)	0.0189 (11)
C23	0.4639 (7)	0.3857 (6)	0.0304 (5)	0.0181 (12)
C26	0.6497 (7)	0.5937 (6)	0.0486 (5)	0.0171 (12)
C24	0.4195 (8)	0.2629 (7)	0.0597 (6)	0.0230 (13)
H24	0.4950	0.2484	0.1113	0.028*
C27	0.8063 (7)	0.6977 (7)	0.0961 (6)	0.0240 (13)
H27	0.8840	0.6872	0.1495	0.029*
C28	0.8431 (8)	0.8120 (7)	0.0644 (6)	0.0269 (14)
H28	0.9475	0.8801	0.0953	0.032*
C25	0.2710 (8)	0.1679 (7)	0.0141 (6)	0.0261 (14)
H25	0.2419	0.0870	0.0344	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.037 (3)	0.032 (3)	0.020 (2)	0.024 (2)	0.003 (2)	0.006 (2)
N2	0.018 (2)	0.020 (3)	0.012 (2)	0.010 (2)	0.0032 (19)	0.0047 (19)
N1	0.021 (3)	0.025 (3)	0.015 (2)	0.015 (2)	0.007 (2)	0.007 (2)
C7	0.026 (3)	0.018 (3)	0.014 (3)	0.012 (3)	0.011 (2)	0.006 (2)
C10	0.020 (3)	0.022 (3)	0.014 (3)	0.012 (2)	0.007 (2)	0.006 (2)
C14	0.019 (3)	0.024 (3)	0.021 (3)	0.010 (3)	0.004 (2)	0.006 (2)
C13	0.024 (3)	0.023 (3)	0.025 (3)	0.012 (3)	0.007 (3)	0.011 (3)
C9	0.019 (3)	0.018 (3)	0.014 (3)	0.010 (2)	0.005 (2)	0.005 (2)
C8	0.019 (3)	0.018 (3)	0.012 (3)	0.008 (2)	0.006 (2)	0.005 (2)
C12	0.020 (3)	0.026 (3)	0.025 (3)	0.005 (3)	0.006 (3)	0.010 (3)
C11	0.034 (4)	0.024 (3)	0.030 (3)	0.015 (3)	0.015 (3)	0.014 (3)
O1	0.029 (2)	0.026 (2)	0.018 (2)	0.022 (2)	0.0042 (18)	0.0070 (18)
O2	0.025 (2)	0.031 (2)	0.019 (2)	0.021 (2)	0.0041 (18)	0.0102 (19)
O3	0.025 (2)	0.030 (2)	0.016 (2)	0.020 (2)	0.0029 (17)	0.0061 (18)
C6	0.014 (3)	0.020 (3)	0.018 (3)	0.012 (2)	0.005 (2)	0.010 (2)
C4	0.020 (3)	0.025 (3)	0.024 (3)	0.018 (3)	0.010 (2)	0.012 (3)
C2	0.015 (3)	0.015 (3)	0.014 (3)	0.007 (2)	0.003 (2)	0.005 (2)
C3	0.012 (3)	0.016 (3)	0.019 (3)	0.008 (2)	0.004 (2)	0.010 (2)
C21	0.020 (3)	0.018 (3)	0.012 (3)	0.010 (2)	0.006 (2)	0.003 (2)
C5	0.014 (3)	0.021 (3)	0.018 (3)	0.011 (2)	0.006 (2)	0.009 (2)
C20	0.021 (3)	0.023 (3)	0.018 (3)	0.011 (3)	0.010 (2)	0.005 (2)
C16	0.025 (3)	0.023 (3)	0.020 (3)	0.016 (3)	0.011 (3)	0.008 (2)
C1	0.015 (3)	0.014 (3)	0.021 (3)	0.010 (2)	0.009 (2)	0.010 (2)
C19	0.024 (3)	0.019 (3)	0.028 (3)	0.008 (3)	0.013 (3)	0.006 (3)
C17	0.032 (4)	0.028 (3)	0.029 (3)	0.021 (3)	0.016 (3)	0.017 (3)
C15	0.023 (3)	0.026 (3)	0.023 (3)	0.017 (3)	0.006 (3)	0.007 (3)
C22	0.016 (3)	0.027 (3)	0.025 (3)	0.010 (3)	0.005 (2)	0.006 (3)
C18	0.037 (4)	0.020 (3)	0.035 (4)	0.014 (3)	0.021 (3)	0.015 (3)
N3	0.022 (3)	0.023 (3)	0.016 (2)	0.016 (2)	0.006 (2)	0.006 (2)
C23	0.021 (3)	0.023 (3)	0.015 (3)	0.014 (3)	0.007 (2)	0.006 (2)
C26	0.020 (3)	0.021 (3)	0.015 (3)	0.013 (2)	0.008 (2)	0.007 (2)
C24	0.030 (3)	0.024 (3)	0.022 (3)	0.017 (3)	0.010 (3)	0.011 (3)
C27	0.021 (3)	0.027 (3)	0.020 (3)	0.010 (3)	0.005 (2)	0.004 (3)
C28	0.024 (3)	0.023 (3)	0.032 (4)	0.010 (3)	0.013 (3)	0.007 (3)
C25	0.031 (3)	0.023 (3)	0.026 (3)	0.014 (3)	0.012 (3)	0.009 (3)

Geometric parameters (Å, º)

O4—H4A	1.11 (8)	C4—H4	0.9500
N2—C9	1.333 (8)	C2—C3	1.400 (8)
N2—C8	1.344 (8)	C2—C1	1.402 (8)
N1—C10	1.333 (8)	C2—H2A	0.9500
N1—C7	1.347 (8)	C21—C16	1.416 (8)
C7—C8	1.401 (8)	C21—C20	1.424 (9)
C7—C11	1.499 (8)	C21—C21^i	1.422 (12)
C10—C9	1.401 (8)	C20—C19	1.395 (9)
C10—C14	1.504 (8)	C20—C22	1.438 (9)
C14—H14A	0.9800	C16—C17	1.407 (9)
C14—H14B	0.9800	C16—C15	1.429 (9)
C14—H14C	0.9800	C19—C18	1.387 (10)
C13—C9	1.496 (8)	C19—H19	0.9500
C13—H13A	0.9800	C17—C18	1.381 (10)
C13—H13B	0.9800	C17—H17	0.9500
C13—H13C	0.9800	C15—C22^i	1.341 (9)
C8—C12	1.501 (8)	C15—H15	0.9500
C12—H12A	0.9800	C22—C15^i	1.341 (9)
C12—H12B	0.9800	C22—H22	0.9500
C12—H12C	0.9800	C18—H18	0.9500
C11—H11A	0.9800	N3—C26	1.336 (8)
C11—H11B	0.9800	N3—C23	1.342 (8)
C11—H11C	0.9800	C23—C26^ii	1.429 (8)
O1—C1	1.379 (7)	C23—C24	1.431 (9)
O1—H1	0.8400	C26—C23^ii	1.429 (8)
O2—C3	1.361 (7)	C26—C27	1.431 (9)
O2—H2	0.8400	C24—C25	1.345 (10)
O3—C5	1.356 (7)	C24—H24	0.9500
O3—H3	0.8400	C27—C28	1.362 (9)
C6—C1	1.369 (8)	C27—H27	0.9500
C6—C5	1.392 (8)	C28—C25^ii	1.425 (10)
C6—H6	0.9500	C28—H28	0.9500
C4—C3	1.380 (8)	C25—C28^ii	1.425 (10)
C4—C5	1.398 (8)	C25—H25	0.9500
C9—N2—C8	119.6 (5)	O2—C3—C2	120.6 (5)
C10—N1—C7	119.3 (5)	C4—C3—C2	122.1 (5)
N1—C7—C8	120.1 (5)	C16—C21—C20	120.1 (6)
N1—C7—C11	117.9 (5)	C16—C21—C21^i	120.3 (7)
C8—C7—C11	122.1 (6)	C20—C21—C21^i	119.6 (7)
N1—C10—C9	120.6 (5)	O3—C5—C6	122.6 (5)
N1—C10—C14	118.3 (5)	O3—C5—C4	117.5 (5)
C9—C10—C14	121.1 (5)	C6—C5—C4	119.9 (5)
C10—C14—H14A	109.5	C19—C20—C21	119.0 (6)
C10—C14—H14B	109.5	C19—C20—C22	122.4 (6)
H14A—C14—H14B	109.5	C21—C20—C22	118.6 (6)
C10—C14—H14C	109.5	C17—C16—C21	118.6 (6)
H14A—C14—H14C	109.5	C17—C16—C15	122.9 (6)
H14B—C14—H14C	109.5	C21—C16—C15	118.5 (6)
C9—C13—H13A	109.5	C6—C1—O1	120.9 (5)
C9—C13—H13B	109.5	C6—C1—C2	122.7 (5)
H13A—C13—H13B	109.5	O1—C1—C2	116.4 (5)
C9—C13—H13C	109.5	C18—C19—C20	120.8 (6)
H13A—C13—H13C	109.5	C18—C19—H19	119.6
H13B—C13—H13C	109.5	C20—C19—H19	119.6
N2—C9—C10	120.2 (5)	C18—C17—C16	120.9 (6)
N2—C9—C13	117.9 (5)	C18—C17—H17	119.5
C10—C9—C13	121.9 (5)	C16—C17—H17	119.5
N2—C8—C7	120.2 (5)	C22^i—C15—C16	121.8 (6)
N2—C8—C12	118.1 (5)	C22^i—C15—H15	119.1
C7—C8—C12	121.6 (5)	C16—C15—H15	119.1
C8—C12—H12A	109.5	C15^i—C22—C20	121.2 (6)
C8—C12—H12B	109.5	C15^i—C22—H22	119.4
H12A—C12—H12B	109.5	C20—C22—H22	119.4
C8—C12—H12C	109.5	C17—C18—C19	120.6 (6)
H12A—C12—H12C	109.5	C17—C18—H18	119.7
H12B—C12—H12C	109.5	C19—C18—H18	119.7
C7—C11—H11A	109.5	C26—N3—C23	117.7 (5)
C7—C11—H11B	109.5	N3—C23—C26^ii	120.8 (6)
H11A—C11—H11B	109.5	N3—C23—C24	119.3 (5)
C7—C11—H11C	109.5	C26^ii—C23—C24	119.8 (6)
H11A—C11—H11C	109.5	N3—C26—C23^ii	121.4 (6)
H11B—C11—H11C	109.5	N3—C26—C27	120.2 (5)
C1—O1—H1	109.5	C23^ii—C26—C27	118.4 (6)
C3—O2—H2	109.5	C25—C24—C23	120.1 (6)
C5—O3—H3	109.5	C25—C24—H24	120.0
C1—C6—C5	119.4 (5)	C23—C24—H24	120.0
C1—C6—H6	120.3	C28—C27—C26	119.6 (6)
C5—C6—H6	120.3	C28—C27—H27	120.2
C3—C4—C5	119.3 (5)	C26—C27—H27	120.2
C3—C4—H4	120.3	C27—C28—C25^ii	121.6 (6)
C5—C4—H4	120.3	C27—C28—H28	119.2
C3—C2—C1	116.5 (5)	C25^ii—C28—H28	119.2
C3—C2—H2A	121.7	C24—C25—C28^ii	120.4 (6)
C1—C2—H2A	121.7	C24—C25—H25	119.8
O2—C3—C4	117.2 (5)	C28^ii—C25—H25	119.8
C10—N1—C7—C8	0.2 (8)	C20—C21—C16—C17	−0.7 (9)
C10—N1—C7—C11	−179.9 (5)	C21^i—C21—C16—C17	179.6 (6)
C7—N1—C10—C9	−1.6 (8)	C20—C21—C16—C15	179.8 (5)
C7—N1—C10—C14	178.5 (5)	C21^i—C21—C16—C15	0.2 (10)
C8—N2—C9—C10	−0.9 (8)	C5—C6—C1—O1	178.5 (5)
C8—N2—C9—C13	178.9 (5)	C5—C6—C1—C2	−0.5 (9)
N1—C10—C9—N2	2.0 (9)	C3—C2—C1—C6	0.9 (8)
C14—C10—C9—N2	−178.1 (5)	C3—C2—C1—O1	−178.1 (5)
N1—C10—C9—C13	−177.8 (5)	C21—C20—C19—C18	0.1 (9)
C14—C10—C9—C13	2.1 (9)	C22—C20—C19—C18	−179.4 (6)
C9—N2—C8—C7	−0.4 (8)	C21—C16—C17—C18	1.0 (9)
C9—N2—C8—C12	−178.9 (5)	C15—C16—C17—C18	−179.6 (6)
N1—C7—C8—N2	0.8 (8)	C17—C16—C15—C22^i	−179.7 (6)
C11—C7—C8—N2	−179.1 (5)	C21—C16—C15—C22^i	−0.4 (9)
N1—C7—C8—C12	179.2 (5)	C19—C20—C22—C15^i	−179.7 (6)
C11—C7—C8—C12	−0.7 (9)	C21—C20—C22—C15^i	0.8 (9)
C5—C4—C3—O2	179.9 (5)	C16—C17—C18—C19	−0.7 (10)
C5—C4—C3—C2	−1.2 (9)	C20—C19—C18—C17	0.1 (10)
C1—C2—C3—O2	178.8 (5)	C26—N3—C23—C26^ii	−1.5 (9)
C1—C2—C3—C4	0.0 (8)	C26—N3—C23—C24	179.3 (5)
C1—C6—C5—O3	179.0 (5)	C23—N3—C26—C23^ii	1.5 (9)
C1—C6—C5—C4	−0.8 (8)	C23—N3—C26—C27	−179.1 (5)
C3—C4—C5—O3	−178.1 (5)	N3—C23—C24—C25	178.4 (6)
C3—C4—C5—C6	1.6 (9)	C26^ii—C23—C24—C25	−0.8 (9)
C16—C21—C20—C19	0.2 (9)	N3—C26—C27—C28	179.9 (6)
C21^i—C21—C20—C19	179.9 (6)	C23^ii—C26—C27—C28	−0.6 (9)
C16—C21—C20—C22	179.7 (5)	C26—C27—C28—C25^ii	0.9 (10)
C21^i—C21—C20—C22	−0.6 (10)	C23—C24—C25—C28^ii	0.6 (10)

Symmetry codes: (i) −x+3, −y, −z+1; (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1^iii	1.11 (8)	1.75 (8)	2.828 (6)	162 (7)
O1—H1···N3	0.84	1.94	2.775 (6)	176
O2—H2···O4	0.84	1.84	2.662 (6)	165
O3—H3···N2^ii	0.84	1.94	2.779 (6)	174
C6—H6···N2^ii	0.95	2.62	3.317 (7)	131

Symmetry codes: (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z+1.

(TS_ORC_TMP_22TP)

Crystal data

C38H46N4O4S2	V = 903.5 (4) Å^3
Mr = 686.91	Z = 1
Triclinic, P1	F(000) = 366
a = 8.662 (2) Å	Dx = 1.262 Mg m^−3
b = 10.289 (3) Å	Mo Kα radiation, λ = 0.71073 Å
c = 11.523 (3) Å	µ = 0.19 mm^−1
α = 65.003 (5)°	T = 150 K
β = 76.930 (5)°	Plate, colorless
γ = 80.277 (6)°	0.30 × 0.20 × 0.12 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	2854 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.064
profile data from ω–scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −11→11
Tmin = 0.677, Tmax = 1.000	k = −13→13
9411 measured reflections	l = −14→14
4129 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.073	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.201	w = 1/[σ^2(Fo^2) + (0.0957P)^2 + 0.3868P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.013
4129 reflections	Δρmax = 0.53 e Å^−3
230 parameters	Δρmin = −0.42 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.26071 (10)	0.10673 (10)	0.51228 (9)	0.0435 (3)
H2O	−0.288 (4)	0.262 (4)	1.036 (3)	0.030 (9)*
H1O	−0.138 (5)	0.206 (5)	0.644 (4)	0.069 (17)*
O1	−0.0808 (3)	0.2540 (2)	0.6187 (2)	0.0314 (5)
O2	−0.2263 (3)	0.3193 (2)	1.0203 (2)	0.0335 (5)
C4	−0.1603 (3)	0.2835 (3)	0.8208 (3)	0.0240 (6)
H4	−0.2400	0.2182	0.8498	0.029*
C1	0.0716 (3)	0.4767 (3)	0.7333 (3)	0.0240 (6)
C6	−0.0223 (3)	0.4444 (3)	0.8561 (3)	0.0267 (6)
H6	−0.0072	0.4885	0.9100	0.032*
C5	−0.1382 (3)	0.3475 (3)	0.8996 (3)	0.0250 (6)
C2	0.0507 (3)	0.4129 (3)	0.6556 (3)	0.0244 (6)
H2	0.1148	0.4350	0.5721	0.029*
C3	−0.0653 (3)	0.3152 (3)	0.6994 (3)	0.0228 (6)
C16	0.4594 (3)	0.0699 (3)	0.4663 (3)	0.0270 (6)
C7	0.1925 (3)	0.5862 (3)	0.6861 (3)	0.0329 (7)
H7A	0.2911	0.5525	0.6419	0.049*
H7B	0.2144	0.5986	0.7604	0.049*
H7C	0.1504	0.6784	0.6253	0.049*
C17	0.5232 (3)	0.1912 (3)	0.3633 (3)	0.0291 (6)
H17	0.6321	0.1946	0.3237	0.035*
C18	0.4089 (5)	0.3062 (4)	0.3256 (4)	0.0478 (9)
H18	0.4315	0.3966	0.2565	0.057*
C19	0.2634 (5)	0.2769 (4)	0.3966 (4)	0.0490 (10)
H19	0.1723	0.3439	0.3835	0.059*
N1	0.3186 (3)	0.9417 (2)	0.2528 (2)	0.0261 (5)
N2	0.5486 (3)	1.1208 (2)	0.0878 (2)	0.0260 (5)
C9	0.5892 (3)	0.9827 (3)	0.1575 (3)	0.0246 (6)
C11	0.2784 (3)	1.0795 (3)	0.1822 (3)	0.0256 (6)
C8	0.4729 (3)	0.8915 (3)	0.2413 (3)	0.0244 (6)
C10	0.3957 (3)	1.1710 (3)	0.0980 (3)	0.0256 (6)
C13	0.7630 (3)	0.9331 (3)	0.1404 (3)	0.0333 (7)
H13A	0.8207	1.0072	0.0649	0.050*
H13B	0.7770	0.8437	0.1268	0.050*
H13C	0.8046	0.9158	0.2185	0.050*
C12	0.5109 (4)	0.7357 (3)	0.3233 (3)	0.0354 (7)
H12A	0.4161	0.6963	0.3863	0.053*
H12B	0.5966	0.7267	0.3697	0.053*
H12C	0.5448	0.6823	0.2675	0.053*
C15	0.1059 (3)	1.1317 (4)	0.1972 (3)	0.0377 (7)
H15A	0.0448	1.0550	0.2668	0.057*
H15B	0.0680	1.1587	0.1154	0.057*
H15C	0.0920	1.2156	0.2192	0.057*
C14	0.3555 (4)	1.3260 (3)	0.0171 (3)	0.0380 (7)
H14A	0.4525	1.3699	−0.0385	0.057*
H14B	0.3081	1.3762	0.0741	0.057*
H14C	0.2795	1.3334	−0.0373	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0283 (4)	0.0566 (6)	0.0463 (5)	0.0099 (4)	−0.0088 (3)	−0.0250 (4)
O1	0.0339 (12)	0.0355 (12)	0.0305 (12)	−0.0104 (10)	−0.0019 (9)	−0.0175 (10)
O2	0.0355 (12)	0.0389 (12)	0.0298 (12)	−0.0125 (10)	0.0002 (9)	−0.0168 (10)
C4	0.0216 (13)	0.0240 (13)	0.0265 (14)	−0.0022 (11)	−0.0069 (10)	−0.0087 (12)
C1	0.0200 (13)	0.0207 (13)	0.0287 (15)	0.0004 (10)	−0.0092 (10)	−0.0058 (11)
C6	0.0265 (14)	0.0261 (14)	0.0326 (16)	0.0001 (11)	−0.0126 (11)	−0.0138 (12)
C5	0.0261 (14)	0.0231 (13)	0.0246 (14)	0.0018 (11)	−0.0075 (11)	−0.0082 (12)
C2	0.0201 (13)	0.0225 (13)	0.0262 (14)	0.0006 (10)	−0.0050 (10)	−0.0059 (11)
C3	0.0213 (13)	0.0225 (13)	0.0246 (14)	0.0009 (10)	−0.0073 (10)	−0.0088 (11)
C16	0.0222 (13)	0.0326 (15)	0.0344 (16)	0.0019 (11)	−0.0089 (11)	−0.0207 (14)
C7	0.0302 (15)	0.0308 (15)	0.0374 (17)	−0.0080 (12)	−0.0074 (12)	−0.0105 (14)
C17	0.0297 (15)	0.0276 (14)	0.0312 (16)	−0.0058 (12)	−0.0066 (12)	−0.0109 (13)
C18	0.069 (3)	0.0332 (17)	0.045 (2)	−0.0023 (17)	−0.0250 (18)	−0.0119 (16)
C19	0.055 (2)	0.053 (2)	0.053 (2)	0.0283 (18)	−0.0334 (18)	−0.0361 (19)
N1	0.0255 (12)	0.0269 (12)	0.0308 (13)	−0.0030 (9)	−0.0065 (9)	−0.0152 (11)
N2	0.0238 (12)	0.0283 (12)	0.0264 (12)	−0.0003 (10)	−0.0049 (9)	−0.0119 (10)
C9	0.0251 (14)	0.0268 (14)	0.0223 (14)	0.0014 (11)	−0.0060 (10)	−0.0106 (12)
C11	0.0231 (13)	0.0277 (14)	0.0301 (15)	0.0018 (11)	−0.0087 (11)	−0.0149 (12)
C8	0.0236 (13)	0.0261 (14)	0.0279 (15)	0.0042 (11)	−0.0099 (11)	−0.0146 (12)
C10	0.0241 (14)	0.0267 (14)	0.0254 (14)	−0.0007 (11)	−0.0063 (11)	−0.0094 (12)
C13	0.0226 (14)	0.0357 (16)	0.0363 (17)	0.0021 (12)	−0.0043 (12)	−0.0113 (14)
C12	0.0319 (16)	0.0272 (15)	0.0423 (18)	0.0010 (12)	−0.0090 (13)	−0.0094 (14)
C15	0.0214 (15)	0.0406 (18)	0.050 (2)	0.0018 (13)	−0.0078 (13)	−0.0185 (16)
C14	0.0344 (16)	0.0269 (15)	0.0431 (19)	0.0037 (13)	−0.0102 (14)	−0.0054 (14)

Geometric parameters (Å, º)

S1—C19	1.694 (4)	C18—H18	0.9500
S1—C16	1.710 (3)	C19—H19	0.9500
O1—C3	1.363 (3)	N1—C11	1.334 (4)
O1—H1O	0.68 (4)	N1—C8	1.348 (3)
O2—C5	1.362 (3)	N2—C9	1.335 (3)
O2—H2O	0.80 (3)	N2—C10	1.336 (3)
C4—C5	1.386 (4)	C9—C8	1.393 (4)
C4—C3	1.388 (4)	C9—C13	1.503 (4)
C4—H4	0.9500	C11—C10	1.402 (4)
C1—C2	1.369 (4)	C11—C15	1.497 (4)
C1—C6	1.396 (4)	C8—C12	1.501 (4)
C1—C7	1.511 (4)	C10—C14	1.495 (4)
C6—C5	1.394 (4)	C13—H13A	0.9800
C6—H6	0.9500	C13—H13B	0.9800
C2—C3	1.399 (4)	C13—H13C	0.9800
C2—H2	0.9500	C12—H12A	0.9800
C16—C17	1.399 (4)	C12—H12B	0.9800
C16—C16^i	1.458 (6)	C12—H12C	0.9800
C7—H7A	0.9800	C15—H15A	0.9800
C7—H7B	0.9800	C15—H15B	0.9800
C7—H7C	0.9800	C15—H15C	0.9800
C17—C18	1.391 (5)	C14—H14A	0.9800
C17—H17	0.9500	C14—H14B	0.9800
C18—C19	1.342 (5)	C14—H14C	0.9800
C19—S1—C16	92.18 (17)	C11—N1—C8	119.2 (2)
C3—O1—H1O	114 (4)	C9—N2—C10	119.7 (2)
C5—O2—H2O	109 (2)	N2—C9—C8	120.3 (2)
C5—C4—C3	119.6 (2)	N2—C9—C13	116.9 (2)
C5—C4—H4	120.2	C8—C9—C13	122.8 (2)
C3—C4—H4	120.2	N1—C11—C10	120.3 (2)
C2—C1—C6	120.2 (2)	N1—C11—C15	117.8 (3)
C2—C1—C7	120.8 (3)	C10—C11—C15	121.9 (3)
C6—C1—C7	119.0 (3)	N1—C8—C9	120.4 (2)
C5—C6—C1	119.9 (3)	N1—C8—C12	116.8 (2)
C5—C6—H6	120.1	C9—C8—C12	122.8 (2)
C1—C6—H6	120.1	N2—C10—C11	120.2 (2)
O2—C5—C4	122.4 (2)	N2—C10—C14	117.9 (2)
O2—C5—C6	117.6 (3)	C11—C10—C14	121.9 (3)
C4—C5—C6	120.0 (3)	C9—C13—H13A	109.5
C1—C2—C3	120.0 (3)	C9—C13—H13B	109.5
C1—C2—H2	120.0	H13A—C13—H13B	109.5
C3—C2—H2	120.0	C9—C13—H13C	109.5
O1—C3—C4	122.0 (2)	H13A—C13—H13C	109.5
O1—C3—C2	117.7 (2)	H13B—C13—H13C	109.5
C4—C3—C2	120.3 (2)	C8—C12—H12A	109.5
C17—C16—C16^i	128.7 (3)	C8—C12—H12B	109.5
C17—C16—S1	110.0 (2)	H12A—C12—H12B	109.5
C16^i—C16—S1	121.3 (3)	C8—C12—H12C	109.5
C1—C7—H7A	109.5	H12A—C12—H12C	109.5
C1—C7—H7B	109.5	H12B—C12—H12C	109.5
H7A—C7—H7B	109.5	C11—C15—H15A	109.5
C1—C7—H7C	109.5	C11—C15—H15B	109.5
H7A—C7—H7C	109.5	H15A—C15—H15B	109.5
H7B—C7—H7C	109.5	C11—C15—H15C	109.5
C18—C17—C16	112.2 (3)	H15A—C15—H15C	109.5
C18—C17—H17	123.9	H15B—C15—H15C	109.5
C16—C17—H17	123.9	C10—C14—H14A	109.5
C19—C18—C17	113.3 (3)	C10—C14—H14B	109.5
C19—C18—H18	123.3	H14A—C14—H14B	109.5
C17—C18—H18	123.3	C10—C14—H14C	109.5
C18—C19—S1	112.3 (3)	H14A—C14—H14C	109.5
C18—C19—H19	123.9	H14B—C14—H14C	109.5
S1—C19—H19	123.9

Symmetry code: (i) −x+1, −y, −z+1.

(TS_ORC_TMP_ACR)

Crystal data

C24H23N2O2	V = 989.5 (7) Å^3
Mr = 371.44	Z = 2
Triclinic, P1	F(000) = 394
a = 8.971 (4) Å	Dx = 1.247 Mg m^−3
b = 10.078 (4) Å	Mo Kα radiation, λ = 0.71073 Å
c = 11.666 (5) Å	µ = 0.08 mm^−1
α = 109.665 (8)°	T = 293 K
β = 94.353 (7)°	Plate, colorless
γ = 90.742 (7)°	0.25 × 0.25 × 0.10 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	1683 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.128
profile data from ω–scans	θmax = 27.0°, θmin = 3.1°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −11→11
Tmin = 0.591, Tmax = 1.000	k = −12→12
9373 measured reflections	l = −14→14
4291 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.095	w = 1/[σ^2(Fo^2) + (0.1142P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.276	(Δ/σ)max = 0.001
S = 0.97	Δρmax = 0.35 e Å^−3
4291 reflections	Δρmin = −0.35 e Å^−3
259 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.029 (6)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.1924 (3)	0.3176 (3)	0.5288 (3)	0.0427 (9)
H1O	0.2524	0.2566	0.5279	0.064*
N2	−0.6554 (4)	0.1035 (4)	0.8671 (3)	0.0349 (9)
O2	0.0956 (3)	0.2644 (3)	0.9121 (3)	0.0431 (9)
H2O	0.1699	0.2169	0.8982	0.065*
C4	0.1493 (4)	0.2869 (4)	0.7207 (4)	0.0307 (10)
H4	0.2233	0.2210	0.7106	0.037*
C23	−0.5482 (5)	−0.1214 (4)	0.7609 (4)	0.0335 (10)
C18	−0.6702 (4)	−0.0291 (5)	0.7914 (4)	0.0346 (11)
C12	−0.3896 (4)	0.0711 (5)	0.8993 (4)	0.0345 (11)
C24	−0.4063 (5)	−0.0647 (5)	0.8206 (4)	0.0423 (12)
H24	−0.3235	−0.1207	0.8059	0.051*
C2	0.0083 (4)	0.4502 (4)	0.6483 (4)	0.0346 (10)
H2	−0.0121	0.4921	0.5892	0.041*
C1	−0.0695 (4)	0.4871 (4)	0.7518 (4)	0.0314 (10)
C3	0.1177 (4)	0.3498 (4)	0.6332 (4)	0.0306 (10)
C16	−0.5016 (5)	0.2976 (5)	1.0011 (4)	0.0443 (12)
H16	−0.5845	0.3536	1.0138	0.053*
C5	0.0688 (4)	0.3232 (4)	0.8248 (4)	0.0310 (10)
C6	−0.0402 (4)	0.4236 (4)	0.8391 (4)	0.0351 (11)
H6	−0.0938	0.4481	0.9080	0.042*
C17	−0.5176 (4)	0.1556 (5)	0.9223 (4)	0.0332 (10)
C19	−0.8152 (5)	−0.0832 (5)	0.7307 (4)	0.0415 (12)
H19	−0.8964	−0.0253	0.7469	0.050*
C22	−0.5738 (5)	−0.2610 (5)	0.6781 (5)	0.0481 (13)
H22	−0.4947	−0.3213	0.6595	0.058*
C20	−0.8360 (5)	−0.2154 (5)	0.6515 (4)	0.0456 (12)
H20	−0.9308	−0.2471	0.6131	0.055*
C21	−0.7154 (5)	−0.3071 (5)	0.6257 (5)	0.0517 (14)
H21	−0.7323	−0.3994	0.5727	0.062*
C13	−0.2477 (5)	0.1333 (6)	0.9612 (5)	0.0515 (14)
H13	−0.1630	0.0798	0.9487	0.062*
C14	−0.2360 (5)	0.2701 (6)	1.0380 (5)	0.0544 (14)
H14	−0.1435	0.3092	1.0770	0.065*
C7	−0.1832 (5)	0.6018 (5)	0.7701 (4)	0.0437 (12)
H7A	−0.1927	0.6304	0.6994	0.066*
H7B	−0.1501	0.6813	0.8408	0.066*
H7C	−0.2784	0.5658	0.7818	0.066*
C15	−0.3648 (6)	0.3532 (5)	1.0585 (4)	0.0520 (14)
H15	−0.3559	0.4460	1.1115	0.062*
N1	0.3945 (3)	0.1024 (4)	0.5190 (3)	0.0332 (9)
C9	0.3584 (4)	−0.0295 (5)	0.4474 (4)	0.0339 (11)
C10	0.5350 (4)	0.1342 (4)	0.5741 (4)	0.0335 (11)
C8	0.2004 (4)	−0.0630 (5)	0.3899 (5)	0.0506 (14)
H8A	0.1445	0.0212	0.4133	0.076*
H8B	0.1546	−0.1325	0.4170	0.076*
H8C	0.2013	−0.0989	0.3026	0.076*
C11	0.5713 (5)	0.2820 (5)	0.6543 (4)	0.0471 (13)
H11A	0.4863	0.3383	0.6525	0.071*
H11B	0.6548	0.3188	0.6258	0.071*
H11C	0.5965	0.2845	0.7365	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0400 (19)	0.051 (2)	0.0397 (19)	0.0148 (15)	0.0202 (15)	0.0147 (17)
N2	0.0295 (19)	0.036 (2)	0.038 (2)	0.0037 (17)	0.0067 (16)	0.0095 (19)
O2	0.0325 (17)	0.058 (2)	0.046 (2)	0.0189 (15)	0.0152 (14)	0.0240 (18)
C4	0.022 (2)	0.031 (2)	0.036 (2)	0.0043 (18)	0.0065 (18)	0.007 (2)
C23	0.032 (2)	0.031 (3)	0.037 (3)	0.003 (2)	0.006 (2)	0.011 (2)
C18	0.027 (2)	0.040 (3)	0.037 (3)	0.000 (2)	0.0029 (19)	0.013 (2)
C12	0.029 (2)	0.037 (3)	0.036 (3)	−0.001 (2)	0.0034 (19)	0.011 (2)
C24	0.027 (2)	0.048 (3)	0.055 (3)	0.007 (2)	0.009 (2)	0.021 (3)
C2	0.030 (2)	0.038 (3)	0.034 (3)	0.004 (2)	0.0054 (19)	0.010 (2)
C1	0.023 (2)	0.032 (2)	0.038 (3)	0.0040 (18)	0.0035 (18)	0.011 (2)
C3	0.022 (2)	0.036 (2)	0.034 (3)	−0.0001 (19)	0.0072 (18)	0.011 (2)
C16	0.048 (3)	0.043 (3)	0.040 (3)	0.000 (2)	0.004 (2)	0.012 (3)
C5	0.026 (2)	0.035 (3)	0.033 (2)	0.0027 (19)	0.0060 (18)	0.011 (2)
C6	0.028 (2)	0.039 (3)	0.035 (3)	0.001 (2)	0.0078 (19)	0.007 (2)
C17	0.029 (2)	0.040 (3)	0.034 (3)	0.002 (2)	0.0037 (19)	0.016 (2)
C19	0.028 (2)	0.045 (3)	0.053 (3)	0.004 (2)	0.002 (2)	0.020 (3)
C22	0.043 (3)	0.046 (3)	0.055 (3)	0.007 (2)	0.010 (2)	0.015 (3)
C20	0.036 (3)	0.046 (3)	0.050 (3)	−0.002 (2)	−0.005 (2)	0.012 (3)
C21	0.053 (3)	0.047 (3)	0.050 (3)	−0.010 (3)	−0.002 (3)	0.011 (3)
C13	0.027 (2)	0.069 (4)	0.055 (3)	−0.014 (2)	−0.006 (2)	0.020 (3)
C14	0.035 (3)	0.066 (4)	0.061 (4)	−0.017 (3)	−0.005 (2)	0.023 (3)
C7	0.038 (3)	0.042 (3)	0.047 (3)	0.014 (2)	0.006 (2)	0.008 (2)
C15	0.061 (3)	0.043 (3)	0.041 (3)	−0.018 (3)	−0.002 (3)	0.004 (3)
N1	0.0250 (19)	0.035 (2)	0.036 (2)	−0.0012 (16)	0.0098 (16)	0.0047 (19)
C9	0.023 (2)	0.044 (3)	0.032 (3)	0.001 (2)	0.0086 (18)	0.009 (2)
C10	0.029 (2)	0.028 (2)	0.042 (3)	0.0019 (19)	0.013 (2)	0.008 (2)
C8	0.024 (2)	0.055 (3)	0.066 (4)	0.003 (2)	0.005 (2)	0.011 (3)
C11	0.042 (3)	0.046 (3)	0.045 (3)	0.001 (2)	0.009 (2)	0.003 (3)

Geometric parameters (Å, º)

O1—C3	1.379 (5)	C19—C20	1.343 (6)
O1—H1O	0.8200	C19—H19	0.9300
N2—C18	1.329 (5)	C22—C21	1.371 (6)
N2—C17	1.362 (5)	C22—H22	0.9300
O2—C5	1.349 (5)	C20—C21	1.415 (6)
O2—H2O	0.8200	C20—H20	0.9300
C4—C3	1.386 (6)	C21—H21	0.9300
C4—C5	1.404 (5)	C13—C14	1.366 (7)
C4—H4	0.9300	C13—H13	0.9300
C23—C24	1.418 (6)	C14—C15	1.422 (7)
C23—C22	1.418 (6)	C14—H14	0.9300
C23—C18	1.432 (6)	C7—H7A	0.9600
C18—C19	1.440 (6)	C7—H7B	0.9600
C12—C24	1.366 (6)	C7—H7C	0.9600
C12—C17	1.426 (6)	C15—H15	0.9300
C12—C13	1.438 (6)	N1—C9	1.331 (5)
C24—H24	0.9300	N1—C10	1.353 (5)
C2—C1	1.384 (6)	C9—C10^i	1.405 (6)
C2—C3	1.397 (6)	C9—C8	1.505 (6)
C2—H2	0.9300	C10—C9^i	1.405 (6)
C1—C6	1.386 (6)	C10—C11	1.485 (6)
C1—C7	1.523 (5)	C8—H8A	0.9600
C16—C15	1.369 (6)	C8—H8B	0.9600
C16—C17	1.415 (6)	C8—H8C	0.9600
C16—H16	0.9300	C11—H11A	0.9600
C5—C6	1.394 (5)	C11—H11B	0.9600
C6—H6	0.9300	C11—H11C	0.9600
C3—O1—H1O	109.5	C21—C22—H22	120.1
C18—N2—C17	119.0 (4)	C23—C22—H22	120.1
C5—O2—H2O	109.5	C19—C20—C21	120.8 (4)
C3—C4—C5	119.5 (4)	C19—C20—H20	119.6
C3—C4—H4	120.2	C21—C20—H20	119.6
C5—C4—H4	120.2	C22—C21—C20	120.5 (5)
C24—C23—C22	124.0 (4)	C22—C21—H21	119.7
C24—C23—C18	115.8 (4)	C20—C21—H21	119.7
C22—C23—C18	120.2 (4)	C14—C13—C12	120.8 (5)
N2—C18—C23	123.9 (4)	C14—C13—H13	119.6
N2—C18—C19	119.0 (4)	C12—C13—H13	119.6
C23—C18—C19	117.0 (4)	C13—C14—C15	120.3 (5)
C24—C12—C17	119.1 (4)	C13—C14—H14	119.9
C24—C12—C13	122.8 (4)	C15—C14—H14	119.9
C17—C12—C13	118.0 (4)	C1—C7—H7A	109.5
C12—C24—C23	120.9 (4)	C1—C7—H7B	109.5
C12—C24—H24	119.6	H7A—C7—H7B	109.5
C23—C24—H24	119.6	C1—C7—H7C	109.5
C1—C2—C3	119.5 (4)	H7A—C7—H7C	109.5
C1—C2—H2	120.2	H7B—C7—H7C	109.5
C3—C2—H2	120.2	C16—C15—C14	120.6 (5)
C2—C1—C6	120.2 (4)	C16—C15—H15	119.7
C2—C1—C7	119.0 (4)	C14—C15—H15	119.7
C6—C1—C7	120.7 (4)	C9—N1—C10	119.1 (4)
O1—C3—C4	122.1 (4)	N1—C9—C10^i	120.9 (4)
O1—C3—C2	117.2 (4)	N1—C9—C8	118.0 (4)
C4—C3—C2	120.7 (4)	C10^i—C9—C8	121.1 (4)
C15—C16—C17	120.4 (5)	N1—C10—C9^i	120.0 (4)
C15—C16—H16	119.8	N1—C10—C11	117.7 (4)
C17—C16—H16	119.8	C9^i—C10—C11	122.2 (4)
O2—C5—C6	119.1 (4)	C9—C8—H8A	109.5
O2—C5—C4	121.5 (4)	C9—C8—H8B	109.5
C6—C5—C4	119.4 (4)	H8A—C8—H8B	109.5
C1—C6—C5	120.6 (4)	C9—C8—H8C	109.5
C1—C6—H6	119.7	H8A—C8—H8C	109.5
C5—C6—H6	119.7	H8B—C8—H8C	109.5
N2—C17—C16	118.9 (4)	C10—C11—H11A	109.5
N2—C17—C12	121.2 (4)	C10—C11—H11B	109.5
C16—C17—C12	119.9 (4)	H11A—C11—H11B	109.5
C20—C19—C18	121.5 (4)	C10—C11—H11C	109.5
C20—C19—H19	119.2	H11A—C11—H11C	109.5
C18—C19—H19	119.2	H11B—C11—H11C	109.5
C21—C22—C23	119.9 (5)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N2^ii	0.93	2.67	3.340 (5)	130

Symmetry code: (ii) x+1, y, z.

(TS_ORC_TMP_HMB)

Crystal data

C42H58N4O4	Z = 2
Mr = 682.92	F(000) = 740
Monoclinic, P21/c	Dx = 1.169 Mg m^−3
a = 11.4579 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.8325 (13) Å	µ = 0.08 mm^−1
c = 14.9792 (16) Å	T = 150 K
β = 107.229 (7)°	Plate, colorless
V = 1939.7 (4) Å^3	0.50 × 0.25 × 0.12 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	3282 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.048
profile data from ω–scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −14→14
Tmin = 0.790, Tmax = 1.000	k = −15→15
19976 measured reflections	l = −19→19
4441 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.153	w = 1/[σ^2(Fo^2) + (0.0733P)^2 + 0.7126P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
4441 reflections	Δρmax = 0.23 e Å^−3
242 parameters	Δρmin = −0.24 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
H2O	0.582 (2)	0.0494 (19)	0.2458 (17)	0.053 (7)*
H1O	0.219 (3)	−0.016 (2)	0.299 (2)	0.074 (8)*
O2	0.55829 (12)	0.05567 (12)	0.18426 (9)	0.0394 (3)
N2	0.36445 (13)	−0.04221 (12)	0.61958 (10)	0.0293 (3)
N1	0.30067 (13)	−0.02681 (12)	0.42802 (10)	0.0308 (3)
O1	0.17058 (13)	−0.01344 (14)	0.23674 (10)	0.0460 (4)
C2	0.37765 (16)	0.04485 (14)	0.05759 (11)	0.0286 (4)
H2	0.4245	0.0582	0.0159	0.034*
C3	0.43485 (15)	0.04135 (13)	0.15356 (11)	0.0271 (4)
C12	0.30003 (15)	0.06531 (14)	0.47994 (12)	0.0283 (4)
C4	0.36692 (15)	0.02270 (14)	0.21501 (11)	0.0270 (4)
H4	0.4059	0.0206	0.2805	0.032*
C11	0.33223 (15)	0.05755 (14)	0.57692 (12)	0.0275 (4)
C1	0.25228 (16)	0.02887 (13)	0.02287 (11)	0.0286 (4)
C6	0.18418 (16)	0.01081 (14)	0.08401 (12)	0.0313 (4)
H6	0.0982	0.0009	0.0604	0.038*
C8	0.33433 (16)	−0.12638 (15)	0.47093 (12)	0.0322 (4)
C9	0.36627 (15)	−0.13415 (14)	0.56784 (12)	0.0303 (4)
C5	0.24127 (16)	0.00711 (15)	0.17991 (12)	0.0294 (4)
C7	0.19019 (19)	0.02890 (16)	−0.08159 (12)	0.0381 (4)
H7A	0.1433	−0.0411	−0.0994	0.057*
H7B	0.2521	0.0339	−0.1147	0.057*
H7C	0.1350	0.0939	−0.0982	0.057*
C15	0.3347 (2)	0.15868 (17)	0.63807 (14)	0.0427 (5)
H15A	0.3400	0.1335	0.7015	0.064*
H15B	0.2599	0.2030	0.6127	0.064*
H15C	0.4059	0.2055	0.6399	0.064*
C16	0.26336 (19)	0.17490 (16)	0.42908 (13)	0.0414 (5)
H16A	0.2511	0.1634	0.3621	0.062*
H16B	0.3278	0.2311	0.4531	0.062*
H16C	0.1871	0.2018	0.4388	0.062*
C14	0.4050 (2)	−0.24309 (17)	0.61987 (15)	0.0466 (5)
H14A	0.4195	−0.2303	0.6869	0.070*
H14B	0.4802	−0.2703	0.6088	0.070*
H14C	0.3403	−0.2997	0.5978	0.070*
C13	0.3364 (2)	−0.22638 (18)	0.40983 (15)	0.0526 (6)
H13A	0.3078	−0.2034	0.3441	0.079*
H13B	0.2827	−0.2856	0.4212	0.079*
H13C	0.4200	−0.2555	0.4243	0.079*
C19	0.03937 (16)	0.55097 (16)	0.08841 (12)	0.0326 (4)
C20	0.02446 (16)	0.61585 (15)	0.00767 (13)	0.0320 (4)
C18	0.01547 (16)	0.43454 (15)	0.08053 (12)	0.0325 (4)
C22	0.0808 (2)	0.6045 (2)	0.18489 (14)	0.0545 (6)
H22A	0.1674	0.5876	0.2144	0.082*
H22B	0.0324	0.5739	0.2234	0.082*
H22C	0.0693	0.6865	0.1791	0.082*
C17	0.0324 (2)	0.3633 (2)	0.16773 (15)	0.0572 (6)
H17A	−0.0433	0.3636	0.1855	0.086*
H17B	0.0990	0.3947	0.2188	0.086*
H17C	0.0525	0.2856	0.1552	0.086*
C21	0.0522 (2)	0.74131 (18)	0.01529 (17)	0.0537 (6)
H21A	−0.0245	0.7840	−0.0024	0.081*
H21B	0.1005	0.7613	−0.0266	0.081*
H21C	0.0987	0.7598	0.0798	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0310 (7)	0.0577 (9)	0.0284 (7)	−0.0082 (6)	0.0068 (6)	0.0082 (6)
N2	0.0274 (7)	0.0287 (8)	0.0283 (7)	−0.0043 (6)	0.0029 (6)	0.0011 (6)
N1	0.0324 (8)	0.0337 (8)	0.0267 (7)	−0.0020 (6)	0.0093 (6)	−0.0003 (6)
O1	0.0318 (7)	0.0795 (11)	0.0268 (7)	−0.0087 (7)	0.0088 (6)	0.0024 (7)
C2	0.0380 (10)	0.0249 (8)	0.0239 (8)	0.0011 (7)	0.0106 (7)	0.0025 (6)
C3	0.0307 (9)	0.0235 (8)	0.0256 (8)	−0.0020 (6)	0.0059 (7)	0.0024 (6)
C12	0.0263 (8)	0.0270 (9)	0.0313 (9)	−0.0029 (6)	0.0082 (7)	0.0017 (7)
C4	0.0302 (9)	0.0289 (9)	0.0194 (7)	−0.0025 (7)	0.0032 (7)	0.0003 (6)
C11	0.0253 (8)	0.0265 (9)	0.0295 (9)	−0.0030 (6)	0.0063 (7)	−0.0014 (7)
C1	0.0404 (10)	0.0204 (8)	0.0215 (8)	0.0021 (7)	0.0039 (7)	−0.0016 (6)
C6	0.0297 (9)	0.0329 (9)	0.0265 (9)	−0.0013 (7)	0.0010 (7)	−0.0017 (7)
C8	0.0310 (9)	0.0298 (9)	0.0359 (10)	−0.0006 (7)	0.0104 (8)	−0.0024 (7)
C9	0.0257 (8)	0.0277 (9)	0.0343 (9)	−0.0012 (7)	0.0042 (7)	0.0020 (7)
C5	0.0293 (9)	0.0324 (9)	0.0263 (8)	−0.0020 (7)	0.0076 (7)	0.0007 (7)
C7	0.0508 (12)	0.0364 (10)	0.0218 (8)	0.0011 (8)	0.0027 (8)	−0.0022 (7)
C15	0.0547 (12)	0.0345 (10)	0.0379 (10)	−0.0042 (9)	0.0123 (9)	−0.0082 (8)
C16	0.0508 (12)	0.0316 (10)	0.0387 (10)	−0.0001 (8)	0.0083 (9)	0.0079 (8)
C14	0.0535 (13)	0.0314 (10)	0.0476 (12)	0.0030 (9)	0.0036 (10)	0.0085 (9)
C13	0.0680 (15)	0.0416 (12)	0.0498 (12)	0.0056 (10)	0.0201 (11)	−0.0126 (10)
C19	0.0270 (9)	0.0423 (10)	0.0266 (9)	0.0029 (7)	0.0052 (7)	−0.0057 (7)
C20	0.0271 (9)	0.0314 (9)	0.0398 (10)	0.0008 (7)	0.0133 (8)	−0.0026 (8)
C18	0.0314 (9)	0.0384 (10)	0.0289 (9)	0.0078 (7)	0.0107 (7)	0.0061 (7)
C22	0.0549 (14)	0.0677 (15)	0.0356 (11)	0.0024 (11)	0.0052 (10)	−0.0152 (10)
C17	0.0691 (16)	0.0645 (15)	0.0459 (12)	0.0218 (12)	0.0291 (12)	0.0213 (11)
C21	0.0584 (14)	0.0363 (11)	0.0724 (15)	−0.0045 (10)	0.0285 (12)	−0.0048 (11)

Geometric parameters (Å, º)

O2—C3	1.362 (2)	C15—H15B	0.9800
O2—H2O	0.88 (2)	C15—H15C	0.9800
N2—C9	1.340 (2)	C16—H16A	0.9800
N2—C11	1.341 (2)	C16—H16B	0.9800
N1—C12	1.340 (2)	C16—H16C	0.9800
N1—C8	1.343 (2)	C14—H14A	0.9800
O1—C5	1.359 (2)	C14—H14B	0.9800
O1—H1O	0.93 (3)	C14—H14C	0.9800
C2—C1	1.388 (2)	C13—H13A	0.9800
C2—C3	1.393 (2)	C13—H13B	0.9800
C2—H2	0.9500	C13—H13C	0.9800
C3—C4	1.388 (2)	C19—C20	1.400 (3)
C12—C11	1.392 (2)	C19—C18	1.403 (3)
C12—C16	1.500 (2)	C19—C22	1.519 (2)
C4—C5	1.391 (2)	C20—C18^i	1.397 (2)
C4—H4	0.9500	C20—C21	1.515 (3)
C11—C15	1.502 (2)	C18—C20^i	1.397 (2)
C1—C6	1.384 (2)	C18—C17	1.518 (3)
C1—C7	1.515 (2)	C22—H22A	0.9800
C6—C5	1.392 (2)	C22—H22B	0.9800
C6—H6	0.9500	C22—H22C	0.9800
C8—C9	1.391 (2)	C17—H17A	0.9800
C8—C13	1.500 (3)	C17—H17B	0.9800
C9—C14	1.504 (2)	C17—H17C	0.9800
C7—H7A	0.9800	C21—H21A	0.9800
C7—H7B	0.9800	C21—H21B	0.9800
C7—H7C	0.9800	C21—H21C	0.9800
C15—H15A	0.9800
C3—O2—H2O	107.9 (15)	C12—C16—H16A	109.5
C9—N2—C11	119.24 (14)	C12—C16—H16B	109.5
C12—N1—C8	119.08 (15)	H16A—C16—H16B	109.5
C5—O1—H1O	110.3 (17)	C12—C16—H16C	109.5
C1—C2—C3	120.07 (15)	H16A—C16—H16C	109.5
C1—C2—H2	120.0	H16B—C16—H16C	109.5
C3—C2—H2	120.0	C9—C14—H14A	109.5
O2—C3—C4	121.74 (15)	C9—C14—H14B	109.5
O2—C3—C2	117.97 (15)	H14A—C14—H14B	109.5
C4—C3—C2	120.29 (15)	C9—C14—H14C	109.5
N1—C12—C11	120.44 (15)	H14A—C14—H14C	109.5
N1—C12—C16	117.22 (15)	H14B—C14—H14C	109.5
C11—C12—C16	122.34 (16)	C8—C13—H13A	109.5
C3—C4—C5	119.43 (15)	C8—C13—H13B	109.5
C3—C4—H4	120.3	H13A—C13—H13B	109.5
C5—C4—H4	120.3	C8—C13—H13C	109.5
N2—C11—C12	120.39 (15)	H13A—C13—H13C	109.5
N2—C11—C15	117.24 (15)	H13B—C13—H13C	109.5
C12—C11—C15	122.36 (16)	C20—C19—C18	119.68 (16)
C6—C1—C2	119.78 (15)	C20—C19—C22	121.13 (18)
C6—C1—C7	119.93 (16)	C18—C19—C22	119.19 (17)
C2—C1—C7	120.28 (16)	C18^i—C20—C19	120.33 (16)
C1—C6—C5	120.19 (16)	C18^i—C20—C21	119.46 (18)
C1—C6—H6	119.9	C19—C20—C21	120.21 (17)
C5—C6—H6	119.9	C20^i—C18—C19	119.98 (16)
N1—C8—C9	120.46 (16)	C20^i—C18—C17	119.95 (18)
N1—C8—C13	117.01 (16)	C19—C18—C17	120.07 (18)
C9—C8—C13	122.52 (17)	C19—C22—H22A	109.5
N2—C9—C8	120.38 (16)	C19—C22—H22B	109.5
N2—C9—C14	116.69 (16)	H22A—C22—H22B	109.5
C8—C9—C14	122.93 (17)	C19—C22—H22C	109.5
O1—C5—C4	121.94 (15)	H22A—C22—H22C	109.5
O1—C5—C6	117.83 (16)	H22B—C22—H22C	109.5
C4—C5—C6	120.23 (16)	C18—C17—H17A	109.5
C1—C7—H7A	109.5	C18—C17—H17B	109.5
C1—C7—H7B	109.5	H17A—C17—H17B	109.5
H7A—C7—H7B	109.5	C18—C17—H17C	109.5
C1—C7—H7C	109.5	H17A—C17—H17C	109.5
H7A—C7—H7C	109.5	H17B—C17—H17C	109.5
H7B—C7—H7C	109.5	C20—C21—H21A	109.5
C11—C15—H15A	109.5	C20—C21—H21B	109.5
C11—C15—H15B	109.5	H21A—C21—H21B	109.5
H15A—C15—H15B	109.5	C20—C21—H21C	109.5
C11—C15—H15C	109.5	H21A—C21—H21C	109.5
H15A—C15—H15C	109.5	H21B—C21—H21C	109.5
H15B—C15—H15C	109.5

Symmetry code: (i) −x, −y+1, −z.

(TS_ORC_TMP_PHE)

Crystal data

C46H44N6O4	V = 1933 (2) Å^3
Mr = 744.87	Z = 2
Triclinic, P1	F(000) = 788
a = 8.983 (6) Å	Dx = 1.280 Mg m^−3
b = 12.712 (9) Å	Mo Kα radiation, λ = 0.71073 Å
c = 17.561 (12) Å	µ = 0.08 mm^−1
α = 89.485 (9)°	T = 150 K
β = 76.291 (9)°	Plate, yellow
γ = 82.933 (10)°	0.45 × 0.30 × 0.15 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	5292 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.051
profile data from ω–scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −11→11
Tmin = 0.797, Tmax = 1.000	k = −16→16
19746 measured reflections	l = −22→22
8807 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.066	H-atom parameters constrained
wR(F^2) = 0.192	w = 1/[σ^2(Fo^2) + (0.0955P)^2 + 0.1092P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.003
8807 reflections	Δρmax = 0.28 e Å^−3
515 parameters	Δρmin = −0.30 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N3	0.0088 (2)	0.57096 (13)	0.38081 (10)	0.0294 (4)
C38	−0.1333 (2)	0.62043 (16)	0.38543 (12)	0.0290 (5)
N4	−0.2551 (2)	0.46791 (14)	0.43833 (11)	0.0350 (4)
C32	−0.1130 (2)	0.41891 (17)	0.43308 (12)	0.0308 (5)
C27	0.0221 (2)	0.47037 (17)	0.40443 (12)	0.0294 (5)
C37	−0.1529 (3)	0.72697 (17)	0.36140 (14)	0.0378 (5)
H37	−0.0654	0.7624	0.3407	0.045*
C33	−0.2667 (2)	0.56838 (17)	0.41507 (12)	0.0307 (5)
C34	−0.4151 (3)	0.6254 (2)	0.42175 (15)	0.0421 (6)
H34	−0.5049	0.5922	0.4424	0.051*
C28	0.1696 (3)	0.41490 (19)	0.40169 (13)	0.0373 (5)
H28	0.2596	0.4485	0.3826	0.045*
C31	−0.0932 (3)	0.31297 (18)	0.45823 (14)	0.0405 (6)
H31	−0.1807	0.2769	0.4774	0.049*
C36	−0.2965 (3)	0.77785 (19)	0.36803 (15)	0.0453 (6)
H36	−0.3090	0.8492	0.3517	0.054*
C35	−0.4287 (3)	0.7270 (2)	0.39879 (16)	0.0476 (6)
H35	−0.5285	0.7648	0.4034	0.057*
C30	0.0500 (3)	0.26312 (18)	0.45496 (14)	0.0436 (6)
H30	0.0618	0.1923	0.4724	0.052*
C29	0.1825 (3)	0.31422 (19)	0.42622 (14)	0.0432 (6)
H29	0.2819	0.2772	0.4241	0.052*
N2	0.8213 (2)	0.04367 (14)	0.11302 (10)	0.0327 (4)
O1	1.29205 (18)	−0.54043 (11)	0.10137 (9)	0.0358 (4)
H1	1.2189	−0.5647	0.1327	0.054*
N1	1.0851 (2)	0.14784 (15)	0.05633 (11)	0.0372 (5)
N6	0.8226 (2)	−0.74151 (14)	0.28274 (11)	0.0310 (4)
C4	1.2769 (2)	−0.43394 (15)	0.21564 (12)	0.0259 (4)
H4	1.1905	−0.4657	0.2438	0.031*
O2	1.26989 (18)	−0.32333 (13)	0.32664 (9)	0.0400 (4)
H2	1.1930	−0.3552	0.3449	0.060*
N5	1.0517 (2)	−0.63175 (13)	0.20117 (11)	0.0311 (4)
C22	0.6602 (3)	0.19708 (19)	0.08868 (14)	0.0382 (5)
H22	0.5708	0.1629	0.1079	0.046*
O4	1.54702 (19)	−0.03763 (13)	0.18600 (10)	0.0449 (4)
H4A	1.6300	−0.0146	0.1640	0.067*
C2	1.4701 (2)	−0.41723 (16)	0.09806 (12)	0.0292 (5)
H2A	1.5170	−0.4382	0.0452	0.035*
C11	1.5800 (2)	0.06958 (16)	0.29113 (13)	0.0309 (5)
H11	1.6633	0.0987	0.2574	0.037*
C1	1.5274 (2)	−0.33943 (16)	0.13330 (12)	0.0281 (5)
C3	1.3457 (2)	−0.46476 (15)	0.13891 (12)	0.0267 (4)
C6	1.4603 (2)	−0.30966 (16)	0.21057 (13)	0.0312 (5)
H6	1.5002	−0.2573	0.2356	0.037*
C26	0.9420 (2)	0.19477 (17)	0.05838 (12)	0.0316 (5)
C25	0.9219 (3)	0.29999 (19)	0.03169 (14)	0.0408 (6)
H25	1.0091	0.3365	0.0127	0.049*
C15	1.0974 (3)	0.04887 (18)	0.08229 (13)	0.0348 (5)
C21	0.8090 (2)	0.14278 (17)	0.08686 (12)	0.0298 (5)
C12	1.5044 (2)	−0.00433 (16)	0.26214 (13)	0.0318 (5)
C40	0.9710 (2)	−0.78383 (16)	0.26903 (12)	0.0287 (5)
C20	0.9641 (3)	−0.00365 (17)	0.11111 (13)	0.0339 (5)
C39	1.0879 (2)	−0.72775 (16)	0.22817 (13)	0.0294 (5)
C10	1.5333 (3)	0.10045 (17)	0.36927 (14)	0.0356 (5)
C5	1.3343 (2)	−0.35664 (16)	0.25134 (12)	0.0279 (5)
C19	0.9839 (3)	−0.10765 (18)	0.14007 (16)	0.0468 (6)
H19	0.8967	−0.1438	0.1599	0.056*
C41	0.7872 (2)	−0.64625 (17)	0.25543 (13)	0.0317 (5)
C42	0.9036 (2)	−0.59040 (16)	0.21447 (13)	0.0310 (5)
C9	1.4130 (3)	0.05631 (18)	0.41823 (15)	0.0408 (6)
H9	1.3826	0.0761	0.4723	0.049*
C8	1.3369 (2)	−0.01632 (17)	0.38892 (15)	0.0390 (6)
O3	1.6025 (2)	0.17335 (14)	0.40019 (10)	0.0517 (5)
H3	1.6740	0.1933	0.3651	0.077*
C16	1.2451 (3)	−0.0043 (2)	0.08277 (16)	0.0475 (6)
H16	1.3346	0.0297	0.0633	0.057*
C13	1.3825 (2)	−0.04651 (17)	0.31052 (15)	0.0393 (6)
H13	1.3301	−0.0960	0.2901	0.047*
C23	0.6463 (3)	0.2969 (2)	0.06314 (14)	0.0439 (6)
H23	0.5466	0.3335	0.0652	0.053*
C45	0.6197 (3)	−0.6035 (2)	0.27128 (16)	0.0470 (6)
H45A	0.5898	−0.5910	0.2215	0.071*
H45B	0.6017	−0.5366	0.3013	0.071*
H45C	0.5577	−0.6548	0.3015	0.071*
C44	1.0042 (3)	−0.89188 (17)	0.29943 (15)	0.0403 (6)
H44A	0.9087	−0.9138	0.3317	0.060*
H44B	1.0800	−0.8908	0.3313	0.060*
H44C	1.0458	−0.9421	0.2553	0.060*
C46	0.8699 (3)	−0.48197 (18)	0.18361 (16)	0.0458 (6)
H46A	0.9662	−0.4584	0.1537	0.069*
H46B	0.8229	−0.4323	0.2275	0.069*
H46C	0.7985	−0.4843	0.1494	0.069*
C24	0.7786 (3)	0.34825 (19)	0.03323 (14)	0.0435 (6)
H24	0.7664	0.4180	0.0139	0.052*
C18	1.1273 (4)	−0.1551 (2)	0.13938 (17)	0.0564 (8)
H18	1.1399	−0.2250	0.1585	0.068*
C7	1.6601 (2)	−0.28554 (18)	0.08761 (14)	0.0392 (6)
H7A	1.7442	−0.2933	0.1149	0.059*
H7B	1.6254	−0.2101	0.0832	0.059*
H7C	1.6972	−0.3182	0.0351	0.059*
C17	1.2587 (3)	−0.1029 (2)	0.11083 (17)	0.0548 (8)
H17	1.3582	−0.1379	0.1114	0.066*
C43	1.2543 (2)	−0.77012 (19)	0.21286 (16)	0.0443 (6)
H43A	1.3168	−0.7166	0.1863	0.066*
H43B	1.2741	−0.8341	0.1795	0.066*
H43C	1.2817	−0.7876	0.2627	0.066*
C14	1.2047 (3)	−0.0636 (2)	0.44161 (18)	0.0584 (8)
H14A	1.1103	−0.0134	0.4488	0.088*
H14B	1.2282	−0.0786	0.4926	0.088*
H14C	1.1897	−0.1296	0.4176	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N3	0.0278 (9)	0.0321 (9)	0.0250 (10)	−0.0040 (8)	0.0000 (7)	0.0026 (7)
C38	0.0306 (11)	0.0325 (11)	0.0223 (11)	−0.0047 (9)	−0.0024 (8)	−0.0009 (9)
N4	0.0333 (10)	0.0372 (10)	0.0352 (11)	−0.0108 (8)	−0.0065 (8)	0.0025 (8)
C32	0.0349 (12)	0.0332 (11)	0.0245 (11)	−0.0060 (9)	−0.0065 (9)	0.0000 (9)
C27	0.0315 (11)	0.0345 (11)	0.0207 (11)	−0.0032 (9)	−0.0034 (8)	−0.0016 (9)
C37	0.0407 (13)	0.0347 (12)	0.0380 (14)	−0.0084 (10)	−0.0074 (10)	0.0066 (10)
C33	0.0297 (11)	0.0328 (11)	0.0290 (12)	−0.0037 (9)	−0.0056 (9)	−0.0004 (9)
C34	0.0264 (12)	0.0501 (14)	0.0487 (15)	−0.0052 (11)	−0.0066 (10)	0.0020 (12)
C28	0.0314 (12)	0.0465 (13)	0.0305 (13)	0.0014 (10)	−0.0037 (9)	−0.0019 (10)
C31	0.0513 (15)	0.0332 (12)	0.0404 (14)	−0.0112 (11)	−0.0145 (11)	0.0039 (10)
C36	0.0479 (15)	0.0343 (12)	0.0528 (16)	0.0027 (11)	−0.0145 (12)	0.0070 (11)
C35	0.0349 (13)	0.0496 (15)	0.0541 (17)	0.0102 (12)	−0.0100 (11)	−0.0004 (12)
C30	0.0635 (17)	0.0300 (12)	0.0403 (14)	−0.0003 (12)	−0.0210 (12)	0.0024 (10)
C29	0.0477 (15)	0.0440 (14)	0.0345 (14)	0.0133 (12)	−0.0128 (11)	−0.0034 (11)
N2	0.0333 (10)	0.0354 (10)	0.0298 (10)	−0.0026 (8)	−0.0096 (8)	0.0018 (8)
O1	0.0394 (9)	0.0351 (8)	0.0314 (9)	−0.0151 (7)	0.0004 (7)	−0.0035 (7)
N1	0.0275 (10)	0.0425 (11)	0.0376 (11)	0.0018 (8)	−0.0035 (8)	0.0013 (9)
N6	0.0269 (9)	0.0321 (9)	0.0356 (11)	−0.0072 (8)	−0.0084 (8)	−0.0007 (8)
C4	0.0219 (10)	0.0277 (10)	0.0264 (11)	−0.0056 (8)	−0.0017 (8)	0.0035 (8)
O2	0.0363 (9)	0.0512 (10)	0.0302 (9)	−0.0190 (7)	0.0042 (7)	−0.0103 (7)
N5	0.0295 (10)	0.0289 (9)	0.0372 (11)	−0.0073 (8)	−0.0106 (8)	0.0026 (8)
C22	0.0279 (12)	0.0480 (14)	0.0364 (13)	0.0010 (10)	−0.0061 (9)	0.0040 (11)
O4	0.0420 (10)	0.0488 (10)	0.0459 (11)	−0.0209 (8)	−0.0062 (8)	−0.0043 (8)
C2	0.0262 (11)	0.0312 (11)	0.0269 (12)	−0.0028 (9)	−0.0001 (8)	0.0039 (9)
C11	0.0269 (11)	0.0302 (11)	0.0337 (12)	−0.0056 (9)	−0.0028 (9)	0.0070 (9)
C1	0.0212 (10)	0.0265 (10)	0.0333 (12)	−0.0007 (8)	−0.0011 (8)	0.0071 (9)
C3	0.0270 (10)	0.0230 (10)	0.0291 (11)	−0.0013 (8)	−0.0057 (8)	0.0020 (8)
C6	0.0267 (11)	0.0297 (11)	0.0382 (13)	−0.0079 (9)	−0.0076 (9)	0.0009 (9)
C26	0.0291 (11)	0.0374 (12)	0.0252 (11)	0.0002 (9)	−0.0023 (9)	0.0013 (9)
C25	0.0397 (13)	0.0404 (13)	0.0380 (14)	−0.0036 (11)	−0.0017 (10)	0.0094 (10)
C15	0.0312 (12)	0.0409 (13)	0.0307 (12)	0.0043 (10)	−0.0088 (9)	−0.0058 (10)
C21	0.0289 (11)	0.0353 (11)	0.0234 (11)	0.0007 (9)	−0.0052 (8)	−0.0006 (9)
C12	0.0258 (11)	0.0261 (10)	0.0422 (14)	−0.0015 (9)	−0.0063 (9)	0.0048 (9)
C40	0.0284 (11)	0.0268 (10)	0.0326 (12)	−0.0034 (9)	−0.0103 (9)	−0.0013 (9)
C20	0.0373 (12)	0.0331 (11)	0.0328 (13)	0.0021 (10)	−0.0143 (10)	−0.0052 (9)
C39	0.0258 (11)	0.0273 (10)	0.0358 (12)	0.0012 (9)	−0.0108 (9)	−0.0034 (9)
C10	0.0325 (12)	0.0324 (11)	0.0398 (14)	−0.0047 (10)	−0.0039 (10)	0.0067 (10)
C5	0.0240 (10)	0.0298 (10)	0.0275 (11)	−0.0020 (9)	−0.0019 (8)	0.0014 (9)
C19	0.0608 (17)	0.0328 (12)	0.0539 (17)	−0.0020 (12)	−0.0294 (13)	0.0030 (11)
C41	0.0279 (11)	0.0329 (11)	0.0354 (13)	−0.0002 (9)	−0.0114 (9)	−0.0035 (9)
C42	0.0294 (11)	0.0292 (11)	0.0371 (13)	−0.0019 (9)	−0.0141 (9)	−0.0017 (9)
C9	0.0358 (13)	0.0391 (13)	0.0390 (14)	0.0019 (11)	0.0044 (10)	0.0101 (10)
C8	0.0250 (11)	0.0269 (11)	0.0581 (16)	0.0026 (9)	0.0008 (10)	0.0160 (11)
O3	0.0576 (12)	0.0576 (11)	0.0376 (10)	−0.0243 (9)	0.0019 (8)	−0.0065 (9)
C16	0.0359 (13)	0.0537 (15)	0.0521 (16)	0.0106 (12)	−0.0167 (11)	−0.0068 (12)
C13	0.0257 (11)	0.0274 (11)	0.0620 (17)	−0.0025 (9)	−0.0057 (11)	0.0107 (11)
C23	0.0343 (13)	0.0496 (14)	0.0418 (15)	0.0133 (11)	−0.0068 (10)	0.0020 (11)
C45	0.0275 (12)	0.0509 (15)	0.0616 (18)	0.0035 (11)	−0.0125 (11)	−0.0049 (13)
C44	0.0442 (14)	0.0304 (12)	0.0474 (15)	−0.0031 (10)	−0.0139 (11)	0.0063 (10)
C46	0.0483 (15)	0.0332 (12)	0.0588 (17)	−0.0021 (11)	−0.0205 (13)	0.0087 (11)
C24	0.0501 (15)	0.0374 (13)	0.0387 (14)	0.0064 (11)	−0.0081 (11)	0.0042 (10)
C18	0.078 (2)	0.0358 (13)	0.0644 (19)	0.0112 (14)	−0.0434 (16)	−0.0036 (13)
C7	0.0286 (12)	0.0368 (12)	0.0475 (15)	−0.0084 (10)	0.0021 (10)	0.0085 (10)
C17	0.0545 (17)	0.0512 (16)	0.0617 (19)	0.0208 (14)	−0.0328 (14)	−0.0156 (14)
C43	0.0258 (12)	0.0437 (13)	0.0621 (17)	−0.0011 (10)	−0.0093 (11)	−0.0007 (12)
C14	0.0350 (14)	0.0425 (14)	0.083 (2)	−0.0040 (11)	0.0134 (13)	0.0211 (14)

Geometric parameters (Å, º)

N3—C38	1.336 (3)	C6—C5	1.387 (3)
N3—C27	1.341 (3)	C6—H6	0.9500
C38—C37	1.418 (3)	C26—C25	1.418 (3)
C38—C33	1.428 (3)	C26—C21	1.421 (3)
N4—C32	1.333 (3)	C25—C24	1.350 (3)
N4—C33	1.337 (3)	C25—H25	0.9500
C32—C31	1.417 (3)	C15—C16	1.415 (3)
C32—C27	1.433 (3)	C15—C20	1.428 (3)
C27—C28	1.413 (3)	C12—C13	1.380 (3)
C37—C36	1.349 (3)	C40—C39	1.394 (3)
C37—H37	0.9500	C40—C44	1.491 (3)
C33—C34	1.416 (3)	C20—C19	1.418 (3)
C34—C35	1.349 (4)	C39—C43	1.487 (3)
C34—H34	0.9500	C10—O3	1.360 (3)
C28—C29	1.347 (3)	C10—C9	1.386 (3)
C28—H28	0.9500	C19—C18	1.351 (4)
C31—C30	1.351 (3)	C19—H19	0.9500
C31—H31	0.9500	C41—C42	1.390 (3)
C36—C35	1.414 (4)	C41—C45	1.497 (3)
C36—H36	0.9500	C42—C46	1.499 (3)
C35—H35	0.9500	C9—C8	1.384 (4)
C30—C29	1.411 (4)	C9—H9	0.9500
C30—H30	0.9500	C8—C13	1.384 (4)
C29—H29	0.9500	C8—C14	1.508 (3)
N2—C21	1.338 (3)	O3—H3	0.8400
N2—C20	1.340 (3)	C16—C17	1.346 (4)
O1—C3	1.367 (2)	C16—H16	0.9500
O1—H1	0.8400	C13—H13	0.9500
N1—C15	1.335 (3)	C23—C24	1.415 (3)
N1—C26	1.342 (3)	C23—H23	0.9500
N6—C41	1.328 (3)	C45—H45A	0.9800
N6—C40	1.341 (3)	C45—H45B	0.9800
C4—C3	1.381 (3)	C45—H45C	0.9800
C4—C5	1.383 (3)	C44—H44A	0.9800
C4—H4	0.9500	C44—H44B	0.9800
O2—C5	1.360 (3)	C44—H44C	0.9800
O2—H2	0.8400	C46—H46A	0.9800
N5—C42	1.335 (3)	C46—H46B	0.9800
N5—C39	1.336 (3)	C46—H46C	0.9800
C22—C23	1.343 (3)	C24—H24	0.9500
C22—C21	1.420 (3)	C18—C17	1.411 (4)
C22—H22	0.9500	C18—H18	0.9500
O4—C12	1.357 (3)	C7—H7A	0.9800
O4—H4A	0.8400	C7—H7B	0.9800
C2—C3	1.381 (3)	C7—H7C	0.9800
C2—C1	1.383 (3)	C17—H17	0.9500
C2—H2A	0.9500	C43—H43A	0.9800
C11—C10	1.382 (3)	C43—H43B	0.9800
C11—C12	1.390 (3)	C43—H43C	0.9800
C11—H11	0.9500	C14—H14A	0.9800
C1—C6	1.383 (3)	C14—H14B	0.9800
C1—C7	1.508 (3)	C14—H14C	0.9800
C38—N3—C27	117.79 (18)	C39—C40—C44	122.15 (19)
N3—C38—C37	119.73 (19)	N2—C20—C19	119.5 (2)
N3—C38—C33	121.22 (19)	N2—C20—C15	121.7 (2)
C37—C38—C33	119.0 (2)	C19—C20—C15	118.8 (2)
C32—N4—C33	116.76 (18)	N5—C39—C40	119.76 (19)
N4—C32—C31	119.5 (2)	N5—C39—C43	117.51 (19)
N4—C32—C27	122.3 (2)	C40—C39—C43	122.72 (19)
C31—C32—C27	118.2 (2)	O3—C10—C11	121.9 (2)
N3—C27—C28	120.1 (2)	O3—C10—C9	118.5 (2)
N3—C27—C32	120.23 (19)	C11—C10—C9	119.7 (2)
C28—C27—C32	119.7 (2)	O2—C5—C4	121.89 (18)
C36—C37—C38	119.7 (2)	O2—C5—C6	117.62 (19)
C36—C37—H37	120.1	C4—C5—C6	120.49 (19)
C38—C37—H37	120.1	C18—C19—C20	119.7 (3)
N4—C33—C34	119.2 (2)	C18—C19—H19	120.1
N4—C33—C38	121.65 (19)	C20—C19—H19	120.1
C34—C33—C38	119.1 (2)	N6—C41—C42	120.07 (19)
C35—C34—C33	119.9 (2)	N6—C41—C45	117.2 (2)
C35—C34—H34	120.0	C42—C41—C45	122.7 (2)
C33—C34—H34	120.0	N5—C42—C41	120.83 (19)
C29—C28—C27	119.9 (2)	N5—C42—C46	117.1 (2)
C29—C28—H28	120.1	C41—C42—C46	122.1 (2)
C27—C28—H28	120.1	C8—C9—C10	120.5 (2)
C30—C31—C32	120.1 (2)	C8—C9—H9	119.8
C30—C31—H31	119.9	C10—C9—H9	119.8
C32—C31—H31	119.9	C9—C8—C13	119.9 (2)
C37—C36—C35	121.2 (2)	C9—C8—C14	120.7 (2)
C37—C36—H36	119.4	C13—C8—C14	119.3 (2)
C35—C36—H36	119.4	C10—O3—H3	109.5
C34—C35—C36	120.9 (2)	C17—C16—C15	120.0 (3)
C34—C35—H35	119.5	C17—C16—H16	120.0
C36—C35—H35	119.5	C15—C16—H16	120.0
C31—C30—C29	121.3 (2)	C12—C13—C8	119.6 (2)
C31—C30—H30	119.4	C12—C13—H13	120.2
C29—C30—H30	119.4	C8—C13—H13	120.2
C28—C29—C30	120.8 (2)	C22—C23—C24	120.7 (2)
C28—C29—H29	119.6	C22—C23—H23	119.6
C30—C29—H29	119.6	C24—C23—H23	119.6
C21—N2—C20	117.01 (19)	C41—C45—H45A	109.5
C3—O1—H1	109.5	C41—C45—H45B	109.5
C15—N1—C26	116.69 (19)	H45A—C45—H45B	109.5
C41—N6—C40	119.37 (18)	C41—C45—H45C	109.5
C3—C4—C5	119.80 (18)	H45A—C45—H45C	109.5
C3—C4—H4	120.1	H45B—C45—H45C	109.5
C5—C4—H4	120.1	C40—C44—H44A	109.5
C5—O2—H2	109.5	C40—C44—H44B	109.5
C42—N5—C39	119.34 (18)	H44A—C44—H44B	109.5
C23—C22—C21	119.8 (2)	C40—C44—H44C	109.5
C23—C22—H22	120.1	H44A—C44—H44C	109.5
C21—C22—H22	120.1	H44B—C44—H44C	109.5
C12—O4—H4A	109.5	C42—C46—H46A	109.5
C3—C2—C1	120.74 (19)	C42—C46—H46B	109.5
C3—C2—H2A	119.6	H46A—C46—H46B	109.5
C1—C2—H2A	119.6	C42—C46—H46C	109.5
C10—C11—C12	119.7 (2)	H46A—C46—H46C	109.5
C10—C11—H11	120.2	H46B—C46—H46C	109.5
C12—C11—H11	120.2	C25—C24—C23	121.3 (2)
C2—C1—C6	119.63 (19)	C25—C24—H24	119.4
C2—C1—C7	120.5 (2)	C23—C24—H24	119.4
C6—C1—C7	119.9 (2)	C19—C18—C17	121.3 (2)
O1—C3—C4	121.63 (18)	C19—C18—H18	119.3
O1—C3—C2	118.65 (18)	C17—C18—H18	119.3
C4—C3—C2	119.72 (19)	C1—C7—H7A	109.5
C1—C6—C5	119.6 (2)	C1—C7—H7B	109.5
C1—C6—H6	120.2	H7A—C7—H7B	109.5
C5—C6—H6	120.2	C1—C7—H7C	109.5
N1—C26—C25	119.2 (2)	H7A—C7—H7C	109.5
N1—C26—C21	122.2 (2)	H7B—C7—H7C	109.5
C25—C26—C21	118.6 (2)	C16—C17—C18	120.9 (2)
C24—C25—C26	119.9 (2)	C16—C17—H17	119.6
C24—C25—H25	120.0	C18—C17—H17	119.6
C26—C25—H25	120.0	C39—C43—H43A	109.5
N1—C15—C16	119.3 (2)	C39—C43—H43B	109.5
N1—C15—C20	121.3 (2)	H43A—C43—H43B	109.5
C16—C15—C20	119.3 (2)	C39—C43—H43C	109.5
N2—C21—C22	119.3 (2)	H43A—C43—H43C	109.5
N2—C21—C26	121.04 (19)	H43B—C43—H43C	109.5
C22—C21—C26	119.7 (2)	C8—C14—H14A	109.5
O4—C12—C13	117.7 (2)	C8—C14—H14B	109.5
O4—C12—C11	121.72 (19)	H14A—C14—H14B	109.5
C13—C12—C11	120.6 (2)	C8—C14—H14C	109.5
N6—C40—C39	120.60 (19)	H14A—C14—H14C	109.5
N6—C40—C44	117.25 (19)	H14B—C14—H14C	109.5

(TS_ORC_TMP_PHEN)

Crystal data

C23H22N3O2	V = 956.7 (4) Å^3
Mr = 372.43	Z = 2
Triclinic, P1	F(000) = 394
a = 8.778 (2) Å	Dx = 1.293 Mg m^−3
b = 10.491 (2) Å	Mo Kα radiation, λ = 0.71073 Å
c = 12.095 (3) Å	µ = 0.08 mm^−1
α = 66.387 (5)°	T = 293 K
β = 81.548 (6)°	Plate, light brown
γ = 69.631 (5)°	0.12 × 0.12 × 0.10 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	2911 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.046
profile data from ω–scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −11→11
Tmin = 0.769, Tmax = 1.000	k = −13→13
10145 measured reflections	l = −15→15
4377 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.060	H-atom parameters constrained
wR(F^2) = 0.156	w = 1/[σ^2(Fo^2) + (0.0668P)^2 + 0.2488P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
4377 reflections	Δρmax = 0.27 e Å^−3
258 parameters	Δρmin = −0.28 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.37176 (19)	0.99018 (17)	0.07961 (14)	0.0273 (4)
C22	0.3461 (2)	1.0490 (2)	−0.03939 (17)	0.0263 (4)
C21	0.5239 (2)	0.9394 (2)	0.12057 (17)	0.0272 (4)
C23	0.1748 (2)	1.0995 (2)	−0.0805 (2)	0.0363 (5)
H23A	0.1047	1.0774	−0.0116	0.054*
H23B	0.1690	1.0499	−0.1307	0.054*
H23C	0.1410	1.2035	−0.1257	0.054*
C20	0.5473 (3)	0.8710 (2)	0.25490 (18)	0.0378 (5)
H20A	0.4435	0.8895	0.2946	0.057*
H20B	0.6138	0.9127	0.2770	0.057*
H20C	0.5995	0.7670	0.2789	0.057*
O2	0.12150 (19)	0.05129 (16)	0.23849 (14)	0.0393 (4)
H2	0.1956	0.0309	0.1924	0.059*
C4	0.1265 (2)	−0.1924 (2)	0.27225 (16)	0.0256 (4)
H4	0.2080	−0.2000	0.2145	0.031*
O1	0.11383 (18)	−0.43073 (17)	0.30803 (14)	0.0395 (4)
H1	0.2022	−0.4377	0.2734	0.059*
C3	0.0628 (2)	−0.3069 (2)	0.33287 (17)	0.0284 (4)
C2	−0.0594 (2)	−0.2949 (2)	0.41932 (18)	0.0324 (5)
H2A	−0.1032	−0.3708	0.4587	0.039*
C1	−0.1156 (2)	−0.1703 (3)	0.44675 (18)	0.0338 (5)
C5	0.0672 (2)	−0.0667 (2)	0.29879 (17)	0.0281 (4)
C6	−0.0525 (2)	−0.0555 (2)	0.38667 (18)	0.0328 (5)
H6	−0.0902	0.0283	0.4051	0.039*
C7	−0.2452 (3)	−0.1593 (3)	0.5436 (2)	0.0493 (6)
H7A	−0.3475	−0.0945	0.5062	0.074*
H7B	−0.2157	−0.1216	0.5948	0.074*
H7C	−0.2542	−0.2548	0.5909	0.074*
N2	0.4601 (2)	0.5004 (2)	0.28208 (15)	0.0342 (4)
N3	0.3243 (2)	0.65428 (19)	0.05862 (16)	0.0348 (4)
C19	0.4857 (2)	0.6267 (2)	0.06822 (18)	0.0293 (4)
C8	0.5577 (2)	0.5456 (2)	0.18707 (18)	0.0290 (4)
C12	0.7260 (2)	0.5141 (2)	0.1995 (2)	0.0337 (5)
C15	0.5869 (3)	0.6712 (2)	−0.03243 (19)	0.0336 (5)
C18	0.2625 (3)	0.7244 (2)	−0.0512 (2)	0.0421 (6)
H18	0.1520	0.7439	−0.0589	0.051*
C16	0.5137 (3)	0.7447 (2)	−0.1462 (2)	0.0451 (6)
H16	0.5755	0.7757	−0.2149	0.054*
C13	0.8221 (3)	0.5642 (2)	0.0951 (2)	0.0396 (5)
H13	0.9324	0.5450	0.1037	0.047*
C14	0.7558 (3)	0.6385 (2)	−0.0148 (2)	0.0406 (6)
H14	0.8212	0.6695	−0.0812	0.049*
C9	0.5290 (3)	0.4223 (3)	0.3892 (2)	0.0441 (6)
H9	0.4634	0.3896	0.4549	0.053*
C17	0.3518 (3)	0.7708 (3)	−0.1559 (2)	0.0491 (7)
H17	0.3022	0.8186	−0.2310	0.059*
C11	0.7915 (3)	0.4321 (3)	0.3159 (2)	0.0453 (6)
H11	0.9015	0.4099	0.3281	0.054*
C10	0.6937 (3)	0.3858 (3)	0.4099 (2)	0.0501 (6)
H10	0.7356	0.3305	0.4872	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0252 (9)	0.0272 (9)	0.0302 (9)	−0.0108 (7)	0.0007 (7)	−0.0099 (7)
C22	0.0236 (10)	0.0248 (10)	0.0322 (11)	−0.0083 (8)	−0.0045 (8)	−0.0105 (8)
C21	0.0276 (10)	0.0262 (10)	0.0296 (10)	−0.0104 (8)	−0.0036 (8)	−0.0096 (8)
C23	0.0259 (11)	0.0393 (13)	0.0451 (13)	−0.0081 (9)	−0.0071 (9)	−0.0171 (10)
C20	0.0435 (13)	0.0385 (13)	0.0280 (11)	−0.0127 (10)	−0.0043 (9)	−0.0081 (9)
O2	0.0414 (9)	0.0355 (9)	0.0451 (10)	−0.0158 (7)	0.0126 (7)	−0.0206 (7)
C4	0.0195 (9)	0.0340 (11)	0.0211 (9)	−0.0079 (8)	0.0015 (7)	−0.0094 (8)
O1	0.0328 (9)	0.0395 (9)	0.0515 (10)	−0.0183 (7)	0.0145 (7)	−0.0217 (7)
C3	0.0213 (10)	0.0361 (12)	0.0265 (10)	−0.0093 (8)	−0.0013 (8)	−0.0102 (8)
C2	0.0222 (10)	0.0414 (13)	0.0293 (11)	−0.0125 (9)	0.0012 (8)	−0.0077 (9)
C1	0.0236 (10)	0.0501 (14)	0.0241 (10)	−0.0090 (9)	−0.0005 (8)	−0.0126 (9)
C5	0.0238 (10)	0.0340 (11)	0.0248 (10)	−0.0086 (8)	−0.0029 (8)	−0.0089 (8)
C6	0.0269 (10)	0.0408 (12)	0.0305 (11)	−0.0030 (9)	−0.0026 (8)	−0.0190 (9)
C7	0.0334 (13)	0.0730 (18)	0.0393 (13)	−0.0144 (12)	0.0123 (10)	−0.0252 (12)
N2	0.0343 (10)	0.0391 (10)	0.0329 (10)	−0.0119 (8)	0.0032 (8)	−0.0182 (8)
N3	0.0282 (9)	0.0351 (10)	0.0461 (11)	−0.0036 (8)	−0.0046 (8)	−0.0244 (9)
C19	0.0282 (11)	0.0253 (10)	0.0372 (11)	−0.0047 (8)	0.0003 (8)	−0.0182 (9)
C8	0.0266 (10)	0.0283 (11)	0.0366 (11)	−0.0075 (8)	0.0013 (8)	−0.0182 (9)
C12	0.0277 (11)	0.0302 (11)	0.0479 (13)	−0.0060 (9)	−0.0023 (9)	−0.0216 (10)
C15	0.0402 (12)	0.0234 (10)	0.0365 (12)	−0.0068 (9)	0.0035 (9)	−0.0147 (9)
C18	0.0414 (13)	0.0325 (12)	0.0533 (15)	0.0029 (10)	−0.0164 (11)	−0.0240 (11)
C16	0.0650 (17)	0.0275 (12)	0.0375 (13)	−0.0090 (11)	0.0048 (11)	−0.0135 (10)
C13	0.0229 (11)	0.0345 (12)	0.0645 (16)	−0.0085 (9)	0.0064 (10)	−0.0247 (11)
C14	0.0369 (13)	0.0316 (12)	0.0527 (15)	−0.0126 (10)	0.0172 (11)	−0.0198 (11)
C9	0.0540 (15)	0.0497 (15)	0.0309 (12)	−0.0185 (12)	0.0017 (10)	−0.0166 (11)
C17	0.0697 (18)	0.0303 (12)	0.0413 (14)	0.0012 (12)	−0.0178 (12)	−0.0162 (10)
C11	0.0359 (13)	0.0449 (14)	0.0565 (16)	−0.0048 (11)	−0.0152 (11)	−0.0224 (12)
C10	0.0555 (16)	0.0542 (16)	0.0385 (14)	−0.0131 (13)	−0.0161 (12)	−0.0138 (11)

Geometric parameters (Å, º)

N1—C22	1.338 (2)	C7—H7B	0.9600
N1—C21	1.342 (2)	C7—H7C	0.9600
C22—C21^i	1.397 (3)	N2—C9	1.323 (3)
C22—C23	1.497 (3)	N2—C8	1.355 (3)
C21—C22^i	1.397 (3)	N3—C18	1.323 (3)
C21—C20	1.503 (3)	N3—C19	1.357 (3)
C23—H23A	0.9600	C19—C15	1.416 (3)
C23—H23B	0.9600	C19—C8	1.450 (3)
C23—H23C	0.9600	C8—C12	1.414 (3)
C20—H20A	0.9600	C12—C11	1.406 (3)
C20—H20B	0.9600	C12—C13	1.430 (3)
C20—H20C	0.9600	C15—C16	1.402 (3)
O2—C5	1.370 (2)	C15—C14	1.429 (3)
O2—H2	0.8200	C18—C17	1.391 (4)
C4—C5	1.388 (3)	C18—H18	0.9300
C4—C3	1.390 (3)	C16—C17	1.364 (4)
C4—H4	0.9300	C16—H16	0.9300
O1—C3	1.359 (2)	C13—C14	1.340 (3)
O1—H1	0.8200	C13—H13	0.9300
C3—C2	1.393 (3)	C14—H14	0.9300
C2—C1	1.383 (3)	C9—C10	1.394 (4)
C2—H2A	0.9300	C9—H9	0.9300
C1—C6	1.389 (3)	C17—H17	0.9300
C1—C7	1.518 (3)	C11—C10	1.352 (4)
C5—C6	1.390 (3)	C11—H11	0.9300
C6—H6	0.9300	C10—H10	0.9300
C7—H7A	0.9600
C22—N1—C21	119.48 (17)	C1—C7—H7C	109.5
N1—C22—C21^i	120.35 (16)	H7A—C7—H7C	109.5
N1—C22—C23	117.45 (18)	H7B—C7—H7C	109.5
C21^i—C22—C23	122.19 (18)	C9—N2—C8	117.24 (19)
N1—C21—C22^i	120.15 (17)	C18—N3—C19	117.0 (2)
N1—C21—C20	117.59 (18)	N3—C19—C15	123.04 (19)
C22^i—C21—C20	122.25 (18)	N3—C19—C8	118.18 (18)
C22—C23—H23A	109.5	C15—C19—C8	118.77 (18)
C22—C23—H23B	109.5	N2—C8—C12	122.54 (19)
H23A—C23—H23B	109.5	N2—C8—C19	118.09 (17)
C22—C23—H23C	109.5	C12—C8—C19	119.36 (18)
H23A—C23—H23C	109.5	C11—C12—C8	117.5 (2)
H23B—C23—H23C	109.5	C11—C12—C13	122.9 (2)
C21—C20—H20A	109.5	C8—C12—C13	119.63 (19)
C21—C20—H20B	109.5	C16—C15—C19	117.0 (2)
H20A—C20—H20B	109.5	C16—C15—C14	123.3 (2)
C21—C20—H20C	109.5	C19—C15—C14	119.69 (19)
H20A—C20—H20C	109.5	N3—C18—C17	124.4 (2)
H20B—C20—H20C	109.5	N3—C18—H18	117.8
C5—O2—H2	109.5	C17—C18—H18	117.8
C5—C4—C3	119.38 (18)	C17—C16—C15	119.9 (2)
C5—C4—H4	120.3	C17—C16—H16	120.0
C3—C4—H4	120.3	C15—C16—H16	120.0
C3—O1—H1	109.5	C14—C13—C12	121.0 (2)
O1—C3—C4	121.64 (17)	C14—C13—H13	119.5
O1—C3—C2	118.28 (18)	C12—C13—H13	119.5
C4—C3—C2	120.06 (19)	C13—C14—C15	121.5 (2)
C1—C2—C3	120.15 (19)	C13—C14—H14	119.2
C1—C2—H2A	119.9	C15—C14—H14	119.2
C3—C2—H2A	119.9	N2—C9—C10	124.1 (2)
C2—C1—C6	120.12 (19)	N2—C9—H9	117.9
C2—C1—C7	120.1 (2)	C10—C9—H9	117.9
C6—C1—C7	119.8 (2)	C16—C17—C18	118.6 (2)
O2—C5—C4	121.63 (17)	C16—C17—H17	120.7
O2—C5—C6	117.70 (19)	C18—C17—H17	120.7
C4—C5—C6	120.66 (19)	C10—C11—C12	119.5 (2)
C1—C6—C5	119.6 (2)	C10—C11—H11	120.2
C1—C6—H6	120.2	C12—C11—H11	120.2
C5—C6—H6	120.2	C11—C10—C9	119.0 (2)
C1—C7—H7A	109.5	C11—C10—H10	120.5
C1—C7—H7B	109.5	C9—C10—H10	120.5
H7A—C7—H7B	109.5

Symmetry code: (i) −x+1, −y+2, −z.

(TS_ORC_TMP_PYR)

Crystal data

C46H50N4O4	V = 944.3 (9) Å^3
Mr = 722.90	Z = 1
Triclinic, P1	F(000) = 386
a = 8.921 (5) Å	Dx = 1.271 Mg m^−3
b = 10.723 (6) Å	Mo Kα radiation, λ = 0.71073 Å
c = 10.954 (6) Å	µ = 0.08 mm^−1
α = 67.417 (10)°	T = 150 K
β = 81.183 (9)°	Plate, yellow
γ = 78.367 (8)°	0.35 × 0.20 × 0.12 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	2534 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.050
profile data from ω–scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −11→11
Tmin = 0.753, Tmax = 1.000	k = −13→13
8881 measured reflections	l = −14→14
4266 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.074	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.209	w = 1/[σ^2(Fo^2) + (0.0783P)^2 + 0.6671P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
4266 reflections	Δρmax = 0.35 e Å^−3
257 parameters	Δρmin = −0.22 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
H1O	−0.801 (6)	0.242 (5)	0.562 (5)	0.090 (16)*
H2O	−0.697 (5)	0.153 (4)	0.178 (4)	0.073 (13)*
N2	0.1584 (3)	0.0399 (2)	0.2682 (2)	0.0279 (5)
C15	−0.0289 (3)	0.0704 (3)	−0.0312 (3)	0.0260 (6)
N1	−0.0525 (3)	−0.1295 (3)	0.4001 (2)	0.0293 (6)
O2	−0.6261 (3)	0.2174 (2)	0.1362 (2)	0.0375 (6)
O1	−0.7358 (3)	0.3108 (2)	0.5390 (2)	0.0399 (6)
C4	−0.6863 (3)	0.2609 (3)	0.3394 (3)	0.0277 (6)
H4	−0.7590	0.1995	0.3706	0.033*
C9	−0.1883 (3)	0.1157 (3)	−0.0261 (3)	0.0308 (7)
C16	−0.0982 (3)	0.0031 (3)	0.3400 (3)	0.0287 (6)
C13	0.0738 (3)	0.1629 (3)	−0.0968 (3)	0.0305 (7)
C19	0.0978 (3)	−0.1792 (3)	0.3970 (3)	0.0285 (6)
C14	0.2354 (4)	0.1132 (3)	−0.1002 (3)	0.0375 (7)
H14	0.3053	0.1757	−0.1453	0.045*
C6	−0.5009 (3)	0.3719 (3)	0.1691 (3)	0.0293 (6)
H6	−0.4472	0.3873	0.0840	0.035*
C2	−0.5544 (3)	0.4177 (3)	0.3713 (3)	0.0297 (7)
H2	−0.5366	0.4641	0.4248	0.036*
C10	−0.2419 (4)	0.2531 (3)	−0.0869 (3)	0.0354 (7)
H10	−0.3493	0.2847	−0.0836	0.043*
C12	0.0144 (4)	0.3000 (3)	−0.1577 (3)	0.0401 (8)
H12	0.0823	0.3641	−0.2039	0.048*
C21	−0.0380 (4)	0.2385 (3)	0.2053 (3)	0.0391 (8)
H21A	−0.0762	0.2805	0.2716	0.059*
H21B	−0.1195	0.2543	0.1479	0.059*
H21C	0.0505	0.2792	0.1515	0.059*
C18	0.2044 (3)	−0.0929 (3)	0.3295 (3)	0.0274 (6)
C17	0.0090 (3)	0.0892 (3)	0.2734 (3)	0.0283 (6)
C3	−0.6603 (3)	0.3285 (3)	0.4165 (3)	0.0285 (6)
C1	−0.4739 (3)	0.4395 (3)	0.2475 (3)	0.0305 (7)
C23	0.1443 (4)	−0.3277 (3)	0.4687 (3)	0.0395 (8)
H23A	0.0532	−0.3693	0.5148	0.059*
H23B	0.2163	−0.3414	0.5336	0.059*
H23C	0.1940	−0.3706	0.4053	0.059*
C22	0.3732 (3)	−0.1429 (3)	0.3215 (3)	0.0388 (8)
H22A	0.4278	−0.0656	0.2703	0.058*
H22B	0.3949	−0.2098	0.2779	0.058*
H22C	0.4077	−0.1860	0.4112	0.058*
C8	−0.2892 (4)	0.0177 (3)	0.0420 (3)	0.0367 (7)
H8	−0.3970	0.0473	0.0455	0.044*
C5	−0.6057 (3)	0.2827 (3)	0.2154 (3)	0.0283 (6)
C20	−0.2669 (4)	0.0542 (4)	0.3488 (3)	0.0407 (8)
H20A	−0.3220	−0.0228	0.3999	0.061*
H20B	−0.3019	0.0981	0.2593	0.061*
H20C	−0.2873	0.1207	0.3929	0.061*
C11	−0.1425 (4)	0.3446 (3)	−0.1521 (3)	0.0391 (8)
H11	−0.1814	0.4389	−0.1935	0.047*
C7	−0.3597 (4)	0.5362 (3)	0.1974 (3)	0.0393 (8)
H7A	−0.2578	0.4864	0.1833	0.059*
H7B	−0.3570	0.5775	0.2626	0.059*
H7C	−0.3895	0.6081	0.1133	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N2	0.0320 (13)	0.0298 (13)	0.0256 (12)	−0.0072 (11)	−0.0030 (10)	−0.0128 (10)
C15	0.0311 (15)	0.0296 (15)	0.0220 (13)	−0.0072 (12)	−0.0024 (11)	−0.0132 (12)
N1	0.0282 (13)	0.0335 (14)	0.0257 (12)	−0.0060 (11)	0.0012 (10)	−0.0109 (11)
O2	0.0476 (14)	0.0401 (13)	0.0321 (11)	−0.0207 (11)	0.0085 (10)	−0.0187 (10)
O1	0.0461 (14)	0.0492 (14)	0.0316 (11)	−0.0194 (11)	0.0055 (10)	−0.0200 (11)
C4	0.0264 (15)	0.0263 (14)	0.0303 (15)	−0.0110 (12)	0.0013 (12)	−0.0082 (12)
C9	0.0333 (16)	0.0361 (17)	0.0280 (15)	−0.0029 (13)	−0.0040 (12)	−0.0180 (13)
C16	0.0299 (15)	0.0334 (16)	0.0245 (14)	−0.0012 (13)	−0.0049 (12)	−0.0131 (13)
C13	0.0330 (16)	0.0331 (16)	0.0290 (15)	−0.0071 (13)	−0.0019 (12)	−0.0145 (13)
C19	0.0311 (16)	0.0313 (16)	0.0250 (14)	−0.0021 (13)	−0.0033 (12)	−0.0133 (12)
C14	0.0335 (17)	0.0401 (18)	0.0420 (18)	−0.0147 (14)	0.0036 (14)	−0.0163 (15)
C6	0.0297 (15)	0.0257 (15)	0.0288 (15)	−0.0058 (12)	0.0015 (12)	−0.0066 (12)
C2	0.0315 (16)	0.0267 (15)	0.0344 (16)	−0.0058 (12)	−0.0073 (13)	−0.0127 (13)
C10	0.0325 (16)	0.0399 (18)	0.0382 (17)	0.0048 (14)	−0.0092 (13)	−0.0219 (15)
C12	0.053 (2)	0.0343 (17)	0.0359 (17)	−0.0190 (16)	−0.0012 (15)	−0.0111 (14)
C21	0.049 (2)	0.0277 (16)	0.0412 (18)	−0.0015 (14)	−0.0109 (15)	−0.0126 (14)
C18	0.0267 (15)	0.0326 (15)	0.0263 (14)	−0.0035 (12)	−0.0043 (12)	−0.0141 (12)
C17	0.0346 (16)	0.0303 (15)	0.0241 (14)	−0.0027 (13)	−0.0061 (12)	−0.0143 (12)
C3	0.0261 (15)	0.0315 (15)	0.0279 (15)	−0.0034 (12)	−0.0020 (12)	−0.0116 (13)
C1	0.0268 (15)	0.0201 (14)	0.0403 (17)	−0.0029 (12)	−0.0071 (13)	−0.0052 (13)
C23	0.0429 (19)	0.0324 (17)	0.0367 (17)	−0.0016 (14)	−0.0035 (14)	−0.0074 (14)
C22	0.0264 (16)	0.0450 (19)	0.0458 (19)	−0.0025 (14)	−0.0032 (14)	−0.0188 (16)
C8	0.0248 (15)	0.046 (2)	0.0425 (18)	−0.0071 (14)	0.0010 (13)	−0.0200 (16)
C5	0.0291 (15)	0.0262 (14)	0.0308 (15)	−0.0031 (12)	−0.0021 (12)	−0.0126 (12)
C20	0.0306 (17)	0.046 (2)	0.0410 (18)	0.0048 (15)	−0.0060 (14)	−0.0153 (16)
C11	0.051 (2)	0.0291 (16)	0.0354 (17)	−0.0007 (15)	−0.0118 (15)	−0.0100 (14)
C7	0.0348 (17)	0.0281 (16)	0.054 (2)	−0.0100 (13)	−0.0064 (15)	−0.0098 (15)

Geometric parameters (Å, º)

N2—C18	1.327 (4)	C2—C1	1.391 (4)
N2—C17	1.332 (4)	C2—H2	0.9500
C15—C13	1.399 (4)	C10—C11	1.370 (5)
C15—C9	1.406 (4)	C10—H10	0.9500
C15—C15^i	1.420 (6)	C12—C11	1.385 (5)
N1—C16	1.323 (4)	C12—H12	0.9500
N1—C19	1.339 (4)	C21—C17	1.484 (4)
O2—C5	1.357 (3)	C21—H21A	0.9800
O2—H2O	0.96 (5)	C21—H21B	0.9800
O1—C3	1.367 (3)	C21—H21C	0.9800
O1—H1O	0.96 (5)	C18—C22	1.495 (4)
C4—C3	1.375 (4)	C1—C7	1.494 (4)
C4—C5	1.393 (4)	C23—H23A	0.9800
C4—H4	0.9500	C23—H23B	0.9800
C9—C10	1.379 (4)	C23—H23C	0.9800
C9—C8	1.430 (4)	C22—H22A	0.9800
C16—C17	1.387 (4)	C22—H22B	0.9800
C16—C20	1.496 (4)	C22—H22C	0.9800
C13—C12	1.389 (4)	C8—C14^i	1.319 (4)
C13—C14	1.433 (4)	C8—H8	0.9500
C19—C18	1.387 (4)	C20—H20A	0.9800
C19—C23	1.482 (4)	C20—H20B	0.9800
C14—C8^i	1.319 (4)	C20—H20C	0.9800
C14—H14	0.9500	C11—H11	0.9500
C6—C5	1.375 (4)	C7—H7A	0.9800
C6—C1	1.390 (4)	C7—H7B	0.9800
C6—H6	0.9500	C7—H7C	0.9800
C2—C3	1.382 (4)
C18—N2—C17	119.2 (2)	N2—C18—C22	117.1 (3)
C13—C15—C9	120.7 (3)	C19—C18—C22	122.6 (3)
C13—C15—C15^i	119.4 (3)	N2—C17—C16	120.8 (3)
C9—C15—C15^i	119.9 (3)	N2—C17—C21	117.7 (3)
C16—N1—C19	119.5 (3)	C16—C17—C21	121.5 (3)
C5—O2—H2O	112 (2)	O1—C3—C4	122.3 (3)
C3—O1—H1O	110 (3)	O1—C3—C2	117.6 (3)
C3—C4—C5	119.8 (3)	C4—C3—C2	120.1 (3)
C3—C4—H4	120.1	C6—C1—C2	119.8 (3)
C5—C4—H4	120.1	C6—C1—C7	119.6 (3)
C10—C9—C15	118.9 (3)	C2—C1—C7	120.6 (3)
C10—C9—C8	122.3 (3)	C19—C23—H23A	109.5
C15—C9—C8	118.8 (3)	C19—C23—H23B	109.5
N1—C16—C17	120.0 (3)	H23A—C23—H23B	109.5
N1—C16—C20	117.5 (3)	C19—C23—H23C	109.5
C17—C16—C20	122.5 (3)	H23A—C23—H23C	109.5
C12—C13—C15	118.3 (3)	H23B—C23—H23C	109.5
C12—C13—C14	122.4 (3)	C18—C22—H22A	109.5
C15—C13—C14	119.2 (3)	C18—C22—H22B	109.5
N1—C19—C18	120.3 (3)	H22A—C22—H22B	109.5
N1—C19—C23	117.7 (3)	C18—C22—H22C	109.5
C18—C19—C23	122.0 (3)	H22A—C22—H22C	109.5
C8^i—C14—C13	121.4 (3)	H22B—C22—H22C	109.5
C8^i—C14—H14	119.3	C14^i—C8—C9	121.3 (3)
C13—C14—H14	119.3	C14^i—C8—H8	119.4
C5—C6—C1	119.6 (3)	C9—C8—H8	119.4
C5—C6—H6	120.2	O2—C5—C6	117.4 (3)
C1—C6—H6	120.2	O2—C5—C4	122.1 (3)
C3—C2—C1	120.1 (3)	C6—C5—C4	120.5 (3)
C3—C2—H2	119.9	C16—C20—H20A	109.5
C1—C2—H2	119.9	C16—C20—H20B	109.5
C11—C10—C9	121.0 (3)	H20A—C20—H20B	109.5
C11—C10—H10	119.5	C16—C20—H20C	109.5
C9—C10—H10	119.5	H20A—C20—H20C	109.5
C11—C12—C13	120.9 (3)	H20B—C20—H20C	109.5
C11—C12—H12	119.6	C10—C11—C12	120.2 (3)
C13—C12—H12	119.6	C10—C11—H11	119.9
C17—C21—H21A	109.5	C12—C11—H11	119.9
C17—C21—H21B	109.5	C1—C7—H7A	109.5
H21A—C21—H21B	109.5	C1—C7—H7B	109.5
C17—C21—H21C	109.5	H7A—C7—H7B	109.5
H21A—C21—H21C	109.5	C1—C7—H7C	109.5
H21B—C21—H21C	109.5	H7A—C7—H7C	109.5
N2—C18—C19	120.2 (3)	H7B—C7—H7C	109.5

Symmetry code: (i) −x, −y, −z.

(TS_PGL_TMP_DPE)

Crystal data

C40H48N6O6	V = 915 (2) Å^3
Mr = 708.84	Z = 1
Triclinic, P1	F(000) = 378
a = 8.284 (11) Å	Dx = 1.286 Mg m^−3
b = 8.564 (12) Å	Mo Kα radiation, λ = 0.71073 Å
c = 14.60 (2) Å	µ = 0.09 mm^−1
α = 78.65 (5)°	T = 150 K
β = 87.26 (6)°	Block, orange
γ = 64.40 (4)°	0.45 × 0.32 × 0.17 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	2728 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.087
profile data from ω–scans	θmax = 27.0°, θmin = 1.4°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −10→10
Tmin = 0.678, Tmax = 1.000	k = −10→10
8969 measured reflections	l = −18→18
3974 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.074	H-atom parameters constrained
wR(F^2) = 0.245	w = 1/[σ^2(Fo^2) + (0.0962P)^2 + 0.7189P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max < 0.001
3974 reflections	Δρmax = 0.30 e Å^−3
235 parameters	Δρmin = −0.31 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.0752 (3)	0.3931 (3)	0.12050 (15)	0.0312 (5)
H1	0.0140	0.3502	0.0996	0.047*
O2	−0.4559 (3)	0.6418 (3)	0.28256 (17)	0.0370 (6)
H2	−0.4984	0.7071	0.3220	0.056*
N3	−0.4001 (4)	1.1596 (3)	0.57434 (18)	0.0284 (6)
O3	0.0412 (3)	0.7667 (3)	0.32344 (16)	0.0358 (6)
H3	−0.0297	0.8284	0.3591	0.054*
N2	−0.2009 (4)	0.9739 (3)	0.44379 (19)	0.0290 (6)
C6	0.0590 (4)	0.5764 (4)	0.2239 (2)	0.0279 (7)
H6	0.1791	0.5573	0.2117	0.034*
C2	−0.1958 (4)	0.5200 (4)	0.1998 (2)	0.0280 (7)
H2A	−0.2506	0.4650	0.1699	0.034*
C1	−0.0217 (4)	0.4963 (4)	0.1809 (2)	0.0272 (7)
C15	−0.4479 (4)	1.2185 (4)	0.4836 (2)	0.0272 (7)
C4	−0.2114 (4)	0.7095 (4)	0.3052 (2)	0.0282 (7)
H4	−0.2770	0.7834	0.3476	0.034*
C13	−0.1561 (4)	0.9118 (4)	0.5344 (2)	0.0266 (7)
C5	−0.0384 (4)	0.6850 (4)	0.2851 (2)	0.0273 (7)
C3	−0.2878 (4)	0.6251 (4)	0.2630 (2)	0.0280 (7)
C14	−0.2552 (4)	1.0060 (4)	0.6009 (2)	0.0286 (7)
N1	−0.1167 (4)	0.2316 (4)	0.0638 (2)	0.0349 (7)
C16	−0.3460 (4)	1.1253 (4)	0.4167 (2)	0.0274 (7)
C9	−0.3226 (4)	0.0876 (4)	−0.0010 (2)	0.0299 (7)
C18	−0.2079 (5)	0.9445 (5)	0.7027 (2)	0.0406 (9)
H18A	−0.2947	1.0301	0.7370	0.061*
H18B	−0.0876	0.9332	0.7147	0.061*
H18C	−0.2104	0.8295	0.7236	0.061*
C20	−0.3906 (5)	1.1907 (5)	0.3145 (2)	0.0387 (8)
H20A	−0.3030	1.1063	0.2798	0.058*
H20B	−0.3872	1.3055	0.2955	0.058*
H20C	−0.5108	1.2033	0.3009	0.058*
C17	0.0034 (5)	0.7385 (4)	0.5608 (3)	0.0374 (8)
H17A	0.0543	0.6934	0.5043	0.056*
H17B	−0.0327	0.6542	0.6012	0.056*
H17C	0.0935	0.7539	0.5944	0.056*
C19	−0.6126 (5)	1.3865 (4)	0.4567 (3)	0.0375 (8)
H19A	−0.6650	1.4318	0.5130	0.056*
H19B	−0.6995	1.3648	0.4243	0.056*
H19C	−0.5817	1.4736	0.4152	0.056*
C8	−0.1982 (5)	−0.0034 (4)	0.0720 (2)	0.0328 (7)
H8	−0.1811	−0.1189	0.1018	0.039*
C7	−0.0995 (5)	0.0703 (5)	0.1020 (2)	0.0339 (7)
H7	−0.0144	0.0038	0.1525	0.041*
C10	−0.3412 (5)	0.2559 (5)	−0.0411 (2)	0.0372 (8)
H10	−0.4246	0.3249	−0.0920	0.045*
C12	−0.4317 (5)	0.0079 (5)	−0.0356 (2)	0.0358 (8)
H12A	−0.3511	−0.1106	−0.0476	0.043*
H12B	−0.4953	0.0824	−0.0953	0.043*
C11	−0.2374 (5)	0.3209 (5)	−0.0063 (3)	0.0381 (8)
H11	−0.2527	0.4368	−0.0339	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0343 (13)	0.0325 (12)	0.0320 (12)	−0.0156 (10)	0.0084 (9)	−0.0165 (9)
O2	0.0311 (13)	0.0393 (14)	0.0460 (14)	−0.0157 (11)	0.0100 (10)	−0.0207 (11)
N3	0.0277 (14)	0.0248 (13)	0.0320 (14)	−0.0102 (11)	0.0041 (11)	−0.0079 (11)
O3	0.0376 (13)	0.0380 (13)	0.0412 (14)	−0.0201 (11)	0.0061 (10)	−0.0203 (10)
N2	0.0320 (15)	0.0235 (13)	0.0347 (15)	−0.0132 (11)	0.0024 (11)	−0.0101 (11)
C6	0.0307 (17)	0.0261 (16)	0.0280 (15)	−0.0133 (13)	0.0018 (12)	−0.0051 (12)
C2	0.0332 (17)	0.0252 (15)	0.0269 (15)	−0.0131 (13)	0.0011 (12)	−0.0070 (12)
C1	0.0330 (17)	0.0222 (15)	0.0229 (14)	−0.0088 (13)	0.0024 (12)	−0.0046 (11)
C15	0.0238 (15)	0.0227 (15)	0.0352 (17)	−0.0102 (12)	−0.0012 (12)	−0.0045 (12)
C4	0.0333 (17)	0.0229 (15)	0.0270 (15)	−0.0103 (13)	0.0050 (12)	−0.0069 (12)
C13	0.0238 (15)	0.0227 (15)	0.0338 (16)	−0.0098 (12)	−0.0003 (12)	−0.0067 (12)
C5	0.0341 (17)	0.0231 (15)	0.0253 (15)	−0.0130 (13)	−0.0026 (12)	−0.0033 (12)
C3	0.0289 (17)	0.0236 (15)	0.0292 (16)	−0.0101 (13)	0.0033 (12)	−0.0037 (12)
C14	0.0289 (16)	0.0225 (15)	0.0359 (17)	−0.0121 (13)	0.0002 (13)	−0.0064 (12)
N1	0.0381 (16)	0.0413 (17)	0.0346 (15)	−0.0224 (14)	0.0080 (12)	−0.0167 (12)
C16	0.0304 (16)	0.0223 (15)	0.0311 (16)	−0.0125 (13)	−0.0013 (12)	−0.0057 (12)
C9	0.0308 (17)	0.0329 (17)	0.0284 (16)	−0.0147 (14)	0.0032 (13)	−0.0093 (13)
C18	0.047 (2)	0.0363 (19)	0.0328 (18)	−0.0130 (17)	−0.0037 (15)	−0.0051 (14)
C20	0.046 (2)	0.0371 (19)	0.0327 (18)	−0.0172 (16)	−0.0029 (15)	−0.0053 (14)
C17	0.0316 (18)	0.0275 (17)	0.046 (2)	−0.0065 (14)	0.0010 (15)	−0.0066 (14)
C19	0.0309 (18)	0.0281 (17)	0.046 (2)	−0.0067 (14)	−0.0025 (15)	−0.0035 (14)
C8	0.0376 (19)	0.0308 (17)	0.0308 (17)	−0.0156 (15)	0.0032 (14)	−0.0063 (13)
C7	0.0359 (18)	0.0400 (19)	0.0274 (16)	−0.0162 (15)	0.0014 (13)	−0.0110 (14)
C10	0.039 (2)	0.0345 (18)	0.0342 (18)	−0.0144 (15)	−0.0029 (15)	−0.0011 (14)
C12	0.039 (2)	0.043 (2)	0.0315 (18)	−0.0223 (16)	0.0003 (14)	−0.0093 (14)
C11	0.042 (2)	0.0322 (18)	0.044 (2)	−0.0188 (16)	0.0060 (16)	−0.0086 (15)

Geometric parameters (Å, º)

O1—C1	1.352 (4)	C16—C20	1.491 (5)
O1—H1	0.8400	C9—C8	1.375 (5)
O2—C3	1.359 (4)	C9—C10	1.389 (5)
O2—H2	0.8400	C9—C12	1.500 (5)
N3—C15	1.335 (5)	C18—H18A	0.9800
N3—C14	1.342 (4)	C18—H18B	0.9800
O3—C5	1.351 (4)	C18—H18C	0.9800
O3—H3	0.8400	C20—H20A	0.9800
N2—C13	1.330 (5)	C20—H20B	0.9800
N2—C16	1.334 (4)	C20—H20C	0.9800
C6—C1	1.385 (5)	C17—H17A	0.9800
C6—C5	1.387 (5)	C17—H17B	0.9800
C6—H6	0.9500	C17—H17C	0.9800
C2—C3	1.382 (5)	C19—H19A	0.9800
C2—C1	1.389 (5)	C19—H19B	0.9800
C2—H2A	0.9500	C19—H19C	0.9800
C15—C16	1.396 (5)	C8—C7	1.360 (5)
C15—C19	1.489 (5)	C8—H8	0.9500
C4—C5	1.382 (5)	C7—H7	0.9500
C4—C3	1.383 (5)	C10—C11	1.369 (5)
C4—H4	0.9500	C10—H10	0.9500
C13—C14	1.389 (5)	C12—C12^i	1.531 (7)
C13—C17	1.492 (5)	C12—H12A	0.9900
C14—C18	1.487 (5)	C12—H12B	0.9900
N1—C11	1.327 (5)	C11—H11	0.9500
N1—C7	1.332 (5)
C1—O1—H1	109.5	H18A—C18—H18B	109.5
C3—O2—H2	109.5	C14—C18—H18C	109.5
C15—N3—C14	119.0 (3)	H18A—C18—H18C	109.5
C5—O3—H3	109.5	H18B—C18—H18C	109.5
C13—N2—C16	119.7 (3)	C16—C20—H20A	109.5
C1—C6—C5	118.9 (3)	C16—C20—H20B	109.5
C1—C6—H6	120.5	H20A—C20—H20B	109.5
C5—C6—H6	120.5	C16—C20—H20C	109.5
C3—C2—C1	118.7 (3)	H20A—C20—H20C	109.5
C3—C2—H2A	120.6	H20B—C20—H20C	109.5
C1—C2—H2A	120.6	C13—C17—H17A	109.5
O1—C1—C6	117.8 (3)	C13—C17—H17B	109.5
O1—C1—C2	121.2 (3)	H17A—C17—H17B	109.5
C6—C1—C2	121.0 (3)	C13—C17—H17C	109.5
N3—C15—C16	120.8 (3)	H17A—C17—H17C	109.5
N3—C15—C19	117.6 (3)	H17B—C17—H17C	109.5
C16—C15—C19	121.6 (3)	C15—C19—H19A	109.5
C5—C4—C3	119.1 (3)	C15—C19—H19B	109.5
C5—C4—H4	120.4	H19A—C19—H19B	109.5
C3—C4—H4	120.4	C15—C19—H19C	109.5
N2—C13—C14	120.7 (3)	H19A—C19—H19C	109.5
N2—C13—C17	117.4 (3)	H19B—C19—H19C	109.5
C14—C13—C17	121.9 (3)	C7—C8—C9	120.6 (3)
O3—C5—C4	121.3 (3)	C7—C8—H8	119.7
O3—C5—C6	117.7 (3)	C9—C8—H8	119.7
C4—C5—C6	120.9 (3)	N1—C7—C8	122.9 (3)
O2—C3—C2	117.6 (3)	N1—C7—H7	118.5
O2—C3—C4	121.2 (3)	C8—C7—H7	118.5
C2—C3—C4	121.3 (3)	C11—C10—C9	119.0 (3)
N3—C14—C13	120.1 (3)	C11—C10—H10	120.5
N3—C14—C18	117.2 (3)	C9—C10—H10	120.5
C13—C14—C18	122.7 (3)	C9—C12—C12^i	111.3 (3)
C11—N1—C7	116.9 (3)	C9—C12—H12A	109.4
N2—C16—C15	119.7 (3)	C12^i—C12—H12A	109.4
N2—C16—C20	117.9 (3)	C9—C12—H12B	109.4
C15—C16—C20	122.4 (3)	C12^i—C12—H12B	109.4
C8—C9—C10	116.7 (3)	H12A—C12—H12B	108.0
C8—C9—C12	121.4 (3)	N1—C11—C10	123.9 (3)
C10—C9—C12	121.9 (3)	N1—C11—H11	118.1
C14—C18—H18A	109.5	C10—C11—H11	118.1
C14—C18—H18B	109.5
C5—C6—C1—O1	179.1 (3)	C17—C13—C14—N3	−178.5 (3)
C5—C6—C1—C2	−1.5 (5)	N2—C13—C14—C18	−178.4 (3)
C3—C2—C1—O1	179.2 (3)	C17—C13—C14—C18	1.5 (5)
C3—C2—C1—C6	−0.2 (5)	C13—N2—C16—C15	1.0 (5)
C14—N3—C15—C16	−2.0 (5)	C13—N2—C16—C20	179.6 (3)
C14—N3—C15—C19	178.2 (3)	N3—C15—C16—N2	1.2 (5)
C16—N2—C13—C14	−2.4 (5)	C19—C15—C16—N2	−179.0 (3)
C16—N2—C13—C17	177.7 (3)	N3—C15—C16—C20	−177.3 (3)
C3—C4—C5—O3	179.0 (3)	C19—C15—C16—C20	2.5 (5)
C3—C4—C5—C6	−0.5 (5)	C10—C9—C8—C7	−0.2 (5)
C1—C6—C5—O3	−177.6 (3)	C12—C9—C8—C7	179.5 (3)
C1—C6—C5—C4	1.9 (5)	C11—N1—C7—C8	0.3 (5)
C1—C2—C3—O2	−178.0 (3)	C9—C8—C7—N1	0.2 (5)
C1—C2—C3—C4	1.7 (5)	C8—C9—C10—C11	−0.3 (5)
C5—C4—C3—O2	178.3 (3)	C12—C9—C10—C11	−179.9 (3)
C5—C4—C3—C2	−1.3 (5)	C8—C9—C12—C12^i	70.0 (5)
C15—N3—C14—C13	0.7 (5)	C10—C9—C12—C12^i	−110.3 (4)
C15—N3—C14—C18	−179.4 (3)	C7—N1—C11—C10	−0.8 (5)
N2—C13—C14—N3	1.5 (5)	C9—C10—C11—N1	0.8 (6)

Symmetry code: (i) −x−1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	1.92	2.758 (4)	174
O2—H2···N3^ii	0.84	2.01	2.844 (5)	174
O3—H3···N2	0.84	2.00	2.841 (5)	179
C2—H2A···N1	0.95	2.60	3.299 (6)	131
C4—H4···N2	0.95	2.63	3.350 (5)	133
C18—H18A···O2^ii	0.98	2.64	3.474 (6)	143
C18—H18C···O1^iii	0.98	2.60	3.289 (6)	127
C20—H20B···O2^iv	0.98	2.65	3.598 (7)	162
C17—H17A···O3	0.98	2.59	3.436 (7)	145
C19—H19C···O2^iv	0.98	2.63	3.589 (6)	166
C11—H11···O1^v	0.95	2.61	3.407 (5)	141

Symmetry codes: (ii) −x−1, −y+2, −z+1; (iii) −x, −y+1, −z+1; (iv) x, y+1, z; (v) −x, −y+1, −z.

(TS_PGL_TMP_PHE_Form_I)

Crystal data

C44H40N6O6	V = 1850 (2) Å^3
Mr = 748.82	Z = 2
Triclinic, P1	F(000) = 788
a = 9.012 (7) Å	Dx = 1.345 Mg m^−3
b = 11.241 (8) Å	Mo Kα radiation, λ = 0.71073 Å
c = 18.355 (13) Å	µ = 0.09 mm^−1
α = 94.296 (13)°	T = 150 K
β = 93.207 (11)°	Block, orange
γ = 92.248 (6)°	0.51 × 0.34 × 0.19 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	6912 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.116
profile data from ω–scans	θmax = 27.6°, θmin = 1.1°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −11→11
Tmin = 0.744, Tmax = 1.000	k = −14→14
19286 measured reflections	l = −23→23
8468 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.066	H-atom parameters constrained
wR(F^2) = 0.204	w = 1/[σ^2(Fo^2) + (0.1052P)^2 + 0.1496P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
8468 reflections	Δρmax = 0.52 e Å^−3
515 parameters	Δρmin = −0.43 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O4	0.56332 (16)	0.63441 (12)	0.26935 (8)	0.0373 (3)
H4O	0.6238	0.6876	0.2891	0.056*
O5	0.19120 (17)	0.56414 (11)	0.08090 (8)	0.0401 (4)
H5O	0.1456	0.5988	0.0480	0.060*
C8	0.37838 (19)	0.60294 (15)	0.17519 (9)	0.0261 (4)
H8	0.3855	0.5195	0.1788	0.031*
O6	0.34650 (12)	0.96915 (10)	0.16355 (6)	0.0233 (3)
H6O	0.2780	0.9835	0.1329	0.035*
C7	0.46824 (18)	0.68362 (15)	0.22074 (9)	0.0240 (3)
C12	0.46007 (17)	0.80691 (14)	0.21666 (9)	0.0221 (3)
H12	0.5226	0.8614	0.2478	0.027*
C10	0.26601 (18)	0.76839 (14)	0.11919 (9)	0.0229 (3)
H10	0.1965	0.7973	0.0846	0.027*
C9	0.27821 (18)	0.64565 (14)	0.12435 (9)	0.0244 (3)
C11	0.35706 (17)	0.84772 (14)	0.16538 (8)	0.0194 (3)
N1	0.16722 (15)	0.29675 (13)	0.15494 (8)	0.0237 (3)
N2	−0.02454 (16)	0.34001 (12)	0.03363 (8)	0.0240 (3)
C13	0.21416 (18)	0.28967 (14)	0.08670 (9)	0.0229 (3)
C19	−0.07114 (18)	0.35143 (15)	0.10210 (9)	0.0237 (3)
C24	0.02667 (18)	0.32868 (14)	0.16384 (9)	0.0232 (3)
C20	−0.2184 (2)	0.38754 (17)	0.11395 (12)	0.0350 (4)
H20	−0.2839	0.4021	0.0735	0.042*
C17	0.1732 (2)	0.30321 (17)	−0.04644 (11)	0.0359 (4)
H17	0.1095	0.3150	−0.0881	0.043*
C18	0.11661 (19)	0.31058 (14)	0.02484 (9)	0.0231 (3)
C23	−0.0275 (2)	0.34218 (18)	0.23543 (11)	0.0351 (4)
H23	0.0347	0.3265	0.2768	0.042*
C14	0.3656 (2)	0.26351 (17)	0.07540 (11)	0.0331 (4)
H14	0.4309	0.2484	0.1158	0.040*
C15	0.4163 (2)	0.2603 (2)	0.00692 (14)	0.0460 (5)
H15	0.5178	0.2453	0.0001	0.055*
C22	−0.1682 (2)	0.3775 (2)	0.24418 (13)	0.0452 (5)
H22	−0.2033	0.3868	0.2920	0.054*
C16	0.3191 (3)	0.2791 (2)	−0.05470 (13)	0.0483 (6)
H16	0.3562	0.2749	−0.1022	0.058*
C21	−0.2649 (2)	0.4010 (2)	0.18268 (13)	0.0439 (5)
H21	−0.3625	0.4262	0.1903	0.053*
O3	0.33898 (15)	0.36692 (12)	0.28388 (8)	0.0356 (3)
H3O	0.3091	0.3183	0.2486	0.053*
O1	0.72011 (15)	0.43532 (11)	0.46924 (8)	0.0343 (3)
H1O	0.7906	0.4014	0.4898	0.051*
N5	0.88356 (14)	0.01002 (12)	0.44618 (7)	0.0202 (3)
C6	0.52971 (19)	0.39855 (14)	0.37568 (9)	0.0252 (4)
H6A	0.4992	0.4781	0.3843	0.030*
N4	1.19708 (16)	0.27822 (13)	0.63911 (8)	0.0262 (3)
C5	0.45607 (18)	0.32142 (15)	0.32152 (9)	0.0240 (3)
N3	0.96130 (15)	0.33774 (12)	0.54810 (8)	0.0234 (3)
C2	0.69376 (17)	0.24092 (14)	0.40429 (9)	0.0214 (3)
H2	0.7750	0.2133	0.4326	0.026*
O2	0.65813 (13)	0.04886 (10)	0.33625 (7)	0.0248 (3)
H2O	0.7261	0.0337	0.3669	0.037*
C4	0.49970 (18)	0.20406 (14)	0.30715 (9)	0.0227 (3)
H4A	0.4496	0.1525	0.2695	0.027*
C27	1.02500 (17)	−0.00466 (14)	0.42748 (9)	0.0191 (3)
C1	0.64866 (18)	0.35775 (15)	0.41705 (9)	0.0240 (3)
C31	1.09465 (18)	0.31624 (14)	0.52116 (9)	0.0218 (3)
C26	1.0585 (2)	−0.00787 (16)	0.35276 (9)	0.0268 (4)
H26	0.9814	−0.0006	0.3161	0.032*
C34	0.94431 (19)	0.33023 (15)	0.61972 (9)	0.0245 (3)
C3	0.61848 (17)	0.16526 (14)	0.34965 (9)	0.0204 (3)
C33	1.06379 (19)	0.30013 (15)	0.66595 (9)	0.0256 (4)
C28	0.85748 (17)	0.01554 (14)	0.51765 (9)	0.0192 (3)
C32	1.21397 (18)	0.28646 (14)	0.56767 (9)	0.0234 (3)
C36	1.3657 (2)	0.26665 (17)	0.54038 (12)	0.0341 (4)
H36A	1.4104	0.3428	0.5277	0.051*
H36B	1.3571	0.2101	0.4969	0.051*
H36C	1.4287	0.2342	0.5787	0.051*
C29	0.70954 (18)	0.03292 (15)	0.53989 (10)	0.0252 (4)
H29	0.6310	0.0426	0.5044	0.030*
C30	0.68185 (19)	0.03551 (16)	0.61224 (10)	0.0296 (4)
H30	0.5835	0.0468	0.6267	0.035*
C38	0.7951 (2)	0.35615 (19)	0.64808 (12)	0.0376 (4)
H38A	0.7235	0.3650	0.6069	0.056*
H38B	0.8031	0.4303	0.6800	0.056*
H38C	0.7611	0.2902	0.6759	0.056*
C35	1.1103 (2)	0.32844 (17)	0.44114 (10)	0.0322 (4)
H35A	1.0197	0.3609	0.4199	0.048*
H35B	1.1257	0.2499	0.4165	0.048*
H35C	1.1957	0.3825	0.4347	0.048*
C25	1.2019 (2)	−0.02147 (17)	0.33348 (10)	0.0305 (4)
H25	1.2241	−0.0215	0.2835	0.037*
C37	1.0520 (3)	0.2928 (2)	0.74671 (11)	0.0420 (5)
H37A	1.1431	0.2606	0.7676	0.063*
H37B	0.9665	0.2402	0.7553	0.063*
H37C	1.0388	0.3727	0.7700	0.063*
N6	0.11792 (14)	0.00142 (12)	0.05447 (7)	0.0206 (3)
C42	−0.02396 (17)	0.01577 (14)	0.07267 (9)	0.0201 (3)
C41	0.14310 (17)	−0.01493 (14)	−0.01686 (9)	0.0201 (3)
C43	−0.0566 (2)	0.03136 (17)	0.14744 (10)	0.0294 (4)
H43	0.0212	0.0319	0.1846	0.035*
C40	0.29131 (18)	−0.03214 (16)	−0.03859 (10)	0.0276 (4)
H40	0.3710	−0.0334	−0.0026	0.033*
C39	0.3179 (2)	−0.04664 (18)	−0.11098 (11)	0.0338 (4)
H39	0.4166	−0.0576	−0.1249	0.041*
C44	−0.2002 (2)	0.04567 (18)	0.16622 (11)	0.0349 (4)
H44	−0.2216	0.0550	0.2164	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0364 (8)	0.0349 (7)	0.0390 (8)	−0.0010 (6)	−0.0190 (6)	0.0092 (6)
O5	0.0522 (9)	0.0231 (6)	0.0412 (9)	−0.0074 (6)	−0.0273 (7)	0.0047 (5)
C8	0.0280 (8)	0.0240 (8)	0.0263 (9)	0.0000 (6)	−0.0030 (7)	0.0060 (6)
O6	0.0237 (6)	0.0219 (6)	0.0235 (6)	−0.0016 (4)	−0.0023 (4)	0.0017 (4)
C7	0.0202 (7)	0.0321 (9)	0.0201 (8)	0.0009 (6)	−0.0012 (6)	0.0062 (6)
C12	0.0195 (7)	0.0277 (8)	0.0187 (8)	−0.0038 (6)	0.0007 (6)	0.0011 (6)
C10	0.0223 (8)	0.0251 (8)	0.0209 (8)	−0.0011 (6)	−0.0041 (6)	0.0048 (6)
C9	0.0258 (8)	0.0246 (8)	0.0218 (8)	−0.0044 (6)	−0.0040 (6)	0.0026 (6)
C11	0.0200 (7)	0.0223 (7)	0.0163 (7)	−0.0018 (6)	0.0047 (5)	0.0020 (5)
N1	0.0226 (7)	0.0273 (7)	0.0210 (7)	0.0003 (5)	−0.0010 (5)	0.0033 (5)
N2	0.0250 (7)	0.0237 (7)	0.0226 (7)	−0.0031 (5)	−0.0038 (5)	0.0030 (5)
C13	0.0226 (8)	0.0222 (8)	0.0238 (9)	−0.0014 (6)	0.0016 (6)	0.0018 (6)
C19	0.0206 (8)	0.0250 (8)	0.0249 (9)	−0.0026 (6)	−0.0006 (6)	0.0018 (6)
C24	0.0226 (8)	0.0256 (8)	0.0214 (8)	−0.0017 (6)	0.0008 (6)	0.0040 (6)
C20	0.0219 (8)	0.0364 (10)	0.0463 (12)	0.0014 (7)	−0.0018 (7)	0.0035 (8)
C17	0.0525 (12)	0.0339 (10)	0.0214 (9)	−0.0032 (8)	0.0082 (8)	0.0017 (7)
C18	0.0286 (8)	0.0208 (7)	0.0194 (8)	−0.0041 (6)	0.0010 (6)	0.0016 (6)
C23	0.0368 (10)	0.0437 (11)	0.0254 (10)	0.0000 (8)	0.0077 (7)	0.0038 (8)
C14	0.0227 (8)	0.0339 (9)	0.0424 (11)	0.0011 (7)	0.0039 (7)	0.0002 (8)
C15	0.0360 (11)	0.0443 (12)	0.0589 (15)	0.0015 (9)	0.0217 (10)	−0.0030 (10)
C22	0.0444 (12)	0.0532 (13)	0.0396 (12)	−0.0019 (10)	0.0208 (9)	0.0022 (10)
C16	0.0607 (14)	0.0481 (12)	0.0377 (12)	−0.0029 (10)	0.0255 (10)	0.0001 (9)
C21	0.0276 (10)	0.0453 (12)	0.0598 (15)	0.0021 (8)	0.0158 (9)	0.0005 (10)
O3	0.0361 (7)	0.0345 (7)	0.0340 (8)	0.0083 (6)	−0.0168 (6)	−0.0002 (5)
O1	0.0369 (7)	0.0259 (6)	0.0370 (8)	0.0025 (5)	−0.0178 (6)	−0.0038 (5)
N5	0.0184 (7)	0.0232 (7)	0.0196 (7)	0.0013 (5)	0.0022 (5)	0.0040 (5)
C6	0.0267 (8)	0.0223 (8)	0.0263 (9)	0.0024 (6)	−0.0031 (6)	0.0027 (6)
N4	0.0270 (7)	0.0271 (7)	0.0241 (8)	−0.0029 (6)	−0.0028 (6)	0.0047 (6)
C5	0.0206 (7)	0.0305 (8)	0.0214 (8)	0.0005 (6)	−0.0021 (6)	0.0071 (6)
N3	0.0214 (7)	0.0248 (7)	0.0235 (7)	−0.0028 (5)	−0.0012 (5)	0.0021 (5)
C2	0.0178 (7)	0.0254 (8)	0.0206 (8)	−0.0005 (6)	−0.0031 (6)	0.0038 (6)
O2	0.0244 (6)	0.0244 (6)	0.0250 (6)	0.0035 (5)	−0.0024 (4)	−0.0014 (4)
C4	0.0225 (8)	0.0248 (8)	0.0198 (8)	−0.0039 (6)	−0.0024 (6)	0.0016 (6)
C27	0.0189 (7)	0.0197 (7)	0.0192 (8)	0.0004 (6)	0.0036 (6)	0.0026 (5)
C1	0.0231 (8)	0.0251 (8)	0.0230 (9)	−0.0042 (6)	−0.0028 (6)	0.0024 (6)
C31	0.0218 (8)	0.0222 (7)	0.0209 (8)	−0.0050 (6)	0.0018 (6)	0.0015 (6)
C26	0.0285 (9)	0.0341 (9)	0.0186 (8)	0.0033 (7)	0.0042 (6)	0.0051 (6)
C34	0.0241 (8)	0.0260 (8)	0.0230 (9)	−0.0036 (6)	0.0029 (6)	0.0008 (6)
C3	0.0186 (7)	0.0231 (7)	0.0197 (8)	−0.0023 (6)	0.0032 (5)	0.0038 (6)
C33	0.0294 (9)	0.0267 (8)	0.0204 (8)	−0.0046 (7)	0.0017 (6)	0.0029 (6)
C28	0.0183 (7)	0.0192 (7)	0.0204 (8)	−0.0006 (6)	0.0031 (6)	0.0028 (6)
C32	0.0223 (8)	0.0215 (7)	0.0261 (9)	−0.0026 (6)	0.0001 (6)	0.0027 (6)
C36	0.0265 (9)	0.0348 (10)	0.0412 (11)	−0.0001 (7)	0.0075 (7)	0.0011 (8)
C29	0.0185 (8)	0.0291 (8)	0.0286 (9)	0.0003 (6)	0.0056 (6)	0.0036 (7)
C30	0.0240 (8)	0.0342 (9)	0.0317 (10)	0.0010 (7)	0.0125 (7)	0.0026 (7)
C38	0.0318 (10)	0.0435 (11)	0.0387 (11)	0.0018 (8)	0.0134 (8)	0.0020 (8)
C35	0.0374 (10)	0.0377 (10)	0.0208 (9)	−0.0068 (8)	0.0024 (7)	0.0019 (7)
C25	0.0334 (9)	0.0385 (10)	0.0209 (9)	0.0020 (7)	0.0123 (7)	0.0028 (7)
C37	0.0521 (13)	0.0519 (12)	0.0217 (10)	−0.0082 (10)	0.0032 (8)	0.0048 (8)
N6	0.0183 (6)	0.0228 (6)	0.0212 (7)	0.0002 (5)	0.0018 (5)	0.0050 (5)
C42	0.0190 (7)	0.0203 (7)	0.0219 (8)	0.0000 (6)	0.0030 (6)	0.0060 (6)
C41	0.0177 (7)	0.0202 (7)	0.0232 (8)	0.0001 (6)	0.0042 (6)	0.0052 (6)
C43	0.0306 (9)	0.0378 (10)	0.0207 (9)	0.0015 (7)	0.0044 (6)	0.0059 (7)
C40	0.0177 (8)	0.0330 (9)	0.0330 (10)	0.0012 (7)	0.0055 (6)	0.0047 (7)
C39	0.0257 (9)	0.0391 (10)	0.0384 (11)	0.0021 (7)	0.0159 (7)	0.0034 (8)
C44	0.0369 (10)	0.0434 (11)	0.0263 (10)	0.0026 (8)	0.0148 (7)	0.0047 (8)

Geometric parameters (Å, º)

O4—C7	1.365 (2)	N3—C31	1.349 (2)
O4—H4O	0.8400	C2—C3	1.393 (2)
O5—C9	1.362 (2)	C2—C1	1.397 (2)
O5—H5O	0.8400	C2—H2	0.9500
C8—C9	1.387 (2)	O2—C3	1.378 (2)
C8—C7	1.389 (2)	O2—H2O	0.8400
C8—H8	0.9500	C4—C3	1.392 (2)
O6—C11	1.375 (2)	C4—H4A	0.9500
O6—H6O	0.8400	C27—C26	1.419 (2)
C7—C12	1.398 (2)	C27—C28^i	1.435 (2)
C12—C11	1.399 (2)	C31—C32	1.402 (2)
C12—H12	0.9500	C31—C35	1.499 (3)
C10—C11	1.392 (2)	C26—C25	1.370 (3)
C10—C9	1.398 (2)	C26—H26	0.9500
C10—H10	0.9500	C34—C33	1.401 (2)
N1—C13	1.342 (2)	C34—C38	1.500 (3)
N1—C24	1.345 (2)	C33—C37	1.500 (3)
N2—C18	1.342 (2)	C28—C29	1.432 (2)
N2—C19	1.346 (2)	C28—C27^i	1.436 (2)
C13—C14	1.431 (2)	C32—C36	1.502 (3)
C13—C18	1.436 (2)	C36—H36A	0.9800
C19—C20	1.427 (3)	C36—H36B	0.9800
C19—C24	1.441 (2)	C36—H36C	0.9800
C24—C23	1.427 (3)	C29—C30	1.363 (3)
C20—C21	1.351 (3)	C29—H29	0.9500
C20—H20	0.9500	C30—C25^i	1.426 (3)
C17—C16	1.367 (3)	C30—H30	0.9500
C17—C18	1.428 (3)	C38—H38A	0.9800
C17—H17	0.9500	C38—H38B	0.9800
C23—C22	1.358 (3)	C38—H38C	0.9800
C23—H23	0.9500	C35—H35A	0.9800
C14—C15	1.360 (3)	C35—H35B	0.9800
C14—H14	0.9500	C35—H35C	0.9800
C15—C16	1.425 (4)	C25—C30^i	1.426 (3)
C15—H15	0.9500	C25—H25	0.9500
C22—C21	1.434 (3)	C37—H37A	0.9800
C22—H22	0.9500	C37—H37B	0.9800
C16—H16	0.9500	C37—H37C	0.9800
C21—H21	0.9500	N6—C41	1.342 (2)
O3—C5	1.366 (2)	N6—C42	1.352 (2)
O3—H3O	0.8400	C42—C43	1.419 (3)
O1—C1	1.362 (2)	C42—C41^ii	1.441 (2)
O1—H1O	0.8400	C41—C40	1.431 (2)
N5—C28	1.343 (2)	C41—C42^ii	1.441 (2)
N5—C27	1.352 (2)	C43—C44	1.370 (3)
C6—C5	1.390 (2)	C43—H43	0.9500
C6—C1	1.391 (2)	C40—C39	1.362 (3)
C6—H6A	0.9500	C40—H40	0.9500
N4—C32	1.338 (2)	C39—C44^ii	1.427 (3)
N4—C33	1.348 (2)	C39—H39	0.9500
C5—C4	1.402 (2)	C44—C39^ii	1.427 (3)
N3—C34	1.341 (2)	C44—H44	0.9500
C7—O4—H4O	109.5	N5—C27—C28^i	120.86 (15)
C9—O5—H5O	109.5	C26—C27—C28^i	119.41 (15)
C9—C8—C7	119.24 (15)	O1—C1—C6	118.06 (15)
C9—C8—H8	120.4	O1—C1—C2	121.44 (14)
C7—C8—H8	120.4	C6—C1—C2	120.50 (15)
C11—O6—H6O	109.5	N3—C31—C32	120.24 (16)
O4—C7—C8	115.59 (15)	N3—C31—C35	117.66 (14)
O4—C7—C12	122.79 (15)	C32—C31—C35	122.08 (15)
C8—C7—C12	121.62 (15)	C25—C26—C27	120.03 (16)
C7—C12—C11	118.01 (14)	C25—C26—H26	120.0
C7—C12—H12	121.0	C27—C26—H26	120.0
C11—C12—H12	121.0	N3—C34—C33	120.29 (15)
C11—C10—C9	119.12 (14)	N3—C34—C38	117.89 (15)
C11—C10—H10	120.4	C33—C34—C38	121.81 (17)
C9—C10—H10	120.4	O2—C3—C4	117.64 (14)
O5—C9—C8	117.70 (15)	O2—C3—C2	121.09 (14)
O5—C9—C10	121.58 (14)	C4—C3—C2	121.27 (15)
C8—C9—C10	120.71 (15)	N4—C33—C34	120.58 (16)
O6—C11—C10	121.19 (14)	N4—C33—C37	116.82 (16)
O6—C11—C12	117.49 (14)	C34—C33—C37	122.59 (17)
C10—C11—C12	121.30 (15)	N5—C28—C29	119.54 (14)
C13—N1—C24	117.61 (13)	N5—C28—C27^i	121.39 (15)
C18—N2—C19	118.13 (13)	C29—C28—C27^i	119.07 (16)
N1—C13—C14	119.37 (15)	N4—C32—C31	120.64 (15)
N1—C13—C18	121.45 (16)	N4—C32—C36	117.48 (15)
C14—C13—C18	119.17 (16)	C31—C32—C36	121.86 (16)
N2—C19—C20	119.80 (15)	C32—C36—H36A	109.5
N2—C19—C24	120.71 (16)	C32—C36—H36B	109.5
C20—C19—C24	119.48 (17)	H36A—C36—H36B	109.5
N1—C24—C23	120.07 (15)	C32—C36—H36C	109.5
N1—C24—C19	121.17 (16)	H36A—C36—H36C	109.5
C23—C24—C19	118.75 (16)	H36B—C36—H36C	109.5
C21—C20—C19	120.00 (17)	C30—C29—C28	119.73 (15)
C21—C20—H20	120.0	C30—C29—H29	120.1
C19—C20—H20	120.0	C28—C29—H29	120.1
C16—C17—C18	119.90 (18)	C29—C30—C25^i	121.08 (16)
C16—C17—H17	120.1	C29—C30—H30	119.5
C18—C17—H17	120.1	C25^i—C30—H30	119.5
N2—C18—C17	120.10 (15)	C34—C38—H38A	109.5
N2—C18—C13	120.86 (16)	C34—C38—H38B	109.5
C17—C18—C13	119.01 (17)	H38A—C38—H38B	109.5
C22—C23—C24	119.76 (18)	C34—C38—H38C	109.5
C22—C23—H23	120.1	H38A—C38—H38C	109.5
C24—C23—H23	120.1	H38B—C38—H38C	109.5
C15—C14—C13	120.10 (18)	C31—C35—H35A	109.5
C15—C14—H14	120.0	C31—C35—H35B	109.5
C13—C14—H14	120.0	H35A—C35—H35B	109.5
C14—C15—C16	120.8 (2)	C31—C35—H35C	109.5
C14—C15—H15	119.6	H35A—C35—H35C	109.5
C16—C15—H15	119.6	H35B—C35—H35C	109.5
C23—C22—C21	121.4 (2)	C26—C25—C30^i	120.63 (17)
C23—C22—H22	119.3	C26—C25—H25	119.7
C21—C22—H22	119.3	C30^i—C25—H25	119.7
C17—C16—C15	121.0 (2)	C33—C37—H37A	109.5
C17—C16—H16	119.5	C33—C37—H37B	109.5
C15—C16—H16	119.5	H37A—C37—H37B	109.5
C20—C21—C22	120.63 (19)	C33—C37—H37C	109.5
C20—C21—H21	119.7	H37A—C37—H37C	109.5
C22—C21—H21	119.7	H37B—C37—H37C	109.5
C5—O3—H3O	109.5	C41—N6—C42	117.77 (13)
C1—O1—H1O	109.5	N6—C42—C43	119.91 (14)
C28—N5—C27	117.75 (13)	N6—C42—C41^ii	120.69 (16)
C5—C6—C1	119.12 (15)	C43—C42—C41^ii	119.40 (16)
C5—C6—H6A	120.4	N6—C41—C40	119.67 (14)
C1—C6—H6A	120.4	N6—C41—C42^ii	121.53 (15)
C32—N4—C33	119.00 (14)	C40—C41—C42^ii	118.80 (16)
O3—C5—C6	115.92 (15)	C44—C43—C42	120.18 (16)
O3—C5—C4	122.49 (15)	C44—C43—H43	119.9
C6—C5—C4	121.59 (14)	C42—C43—H43	119.9
C34—N3—C31	119.24 (14)	C39—C40—C41	119.90 (16)
C3—C2—C1	119.39 (14)	C39—C40—H40	120.0
C3—C2—H2	120.3	C41—C40—H40	120.0
C1—C2—H2	120.3	C40—C39—C44^ii	121.26 (16)
C3—O2—H2O	109.5	C40—C39—H39	119.4
C3—C4—C5	118.12 (14)	C44^ii—C39—H39	119.4
C3—C4—H4A	120.9	C43—C44—C39^ii	120.44 (18)
C5—C4—H4A	120.9	C43—C44—H44	119.8
N5—C27—C26	119.73 (14)	C39^ii—C44—H44	119.8
C9—C8—C7—O4	179.80 (15)	C6—C5—C4—C3	1.0 (2)
C9—C8—C7—C12	0.1 (3)	C28—N5—C27—C26	−178.37 (14)
O4—C7—C12—C11	−179.16 (15)	C28—N5—C27—C28^i	0.8 (3)
C8—C7—C12—C11	0.5 (2)	C5—C6—C1—O1	179.29 (16)
C7—C8—C9—O5	−179.59 (16)	C5—C6—C1—C2	0.1 (3)
C7—C8—C9—C10	−0.7 (3)	C3—C2—C1—O1	−179.16 (15)
C11—C10—C9—O5	179.52 (16)	C3—C2—C1—C6	0.0 (3)
C11—C10—C9—C8	0.7 (3)	C34—N3—C31—C32	0.0 (2)
C9—C10—C11—O6	−178.38 (15)	C34—N3—C31—C35	−178.54 (15)
C9—C10—C11—C12	0.0 (2)	N5—C27—C26—C25	179.31 (15)
C7—C12—C11—O6	177.86 (14)	C28^i—C27—C26—C25	0.1 (3)
C7—C12—C11—C10	−0.6 (2)	C31—N3—C34—C33	−0.1 (2)
C24—N1—C13—C14	176.02 (14)	C31—N3—C34—C38	179.27 (14)
C24—N1—C13—C18	−2.5 (2)	C5—C4—C3—O2	178.46 (15)
C18—N2—C19—C20	177.35 (15)	C5—C4—C3—C2	−0.9 (2)
C18—N2—C19—C24	−2.0 (2)	C1—C2—C3—O2	−178.93 (15)
C13—N1—C24—C23	−177.57 (15)	C1—C2—C3—C4	0.4 (2)
C13—N1—C24—C19	1.6 (2)	C32—N4—C33—C34	0.5 (2)
N2—C19—C24—N1	0.7 (2)	C32—N4—C33—C37	−178.46 (16)
C20—C19—C24—N1	−178.69 (15)	N3—C34—C33—N4	−0.1 (2)
N2—C19—C24—C23	179.86 (16)	C38—C34—C33—N4	−179.46 (16)
C20—C19—C24—C23	0.5 (2)	N3—C34—C33—C37	178.78 (17)
N2—C19—C20—C21	−178.93 (17)	C38—C34—C33—C37	−0.6 (3)
C24—C19—C20—C21	0.5 (3)	C27—N5—C28—C29	179.03 (13)
C19—N2—C18—C17	−176.92 (15)	C27—N5—C28—C27^i	−0.8 (3)
C19—N2—C18—C13	1.2 (2)	C33—N4—C32—C31	−0.6 (2)
C16—C17—C18—N2	176.71 (17)	C33—N4—C32—C36	177.41 (14)
C16—C17—C18—C13	−1.4 (3)	N3—C31—C32—N4	0.4 (2)
N1—C13—C18—N2	1.2 (2)	C35—C31—C32—N4	178.87 (15)
C14—C13—C18—N2	−177.34 (15)	N3—C31—C32—C36	−177.53 (15)
N1—C13—C18—C17	179.26 (15)	C35—C31—C32—C36	0.9 (3)
C14—C13—C18—C17	0.8 (2)	N5—C28—C29—C30	178.32 (15)
N1—C24—C23—C22	178.26 (17)	C27^i—C28—C29—C30	−1.8 (2)
C19—C24—C23—C22	−0.9 (3)	C28—C29—C30—C25^i	0.2 (3)
N1—C13—C14—C15	−177.63 (17)	C27—C26—C25—C30^i	1.6 (3)
C18—C13—C14—C15	0.9 (3)	C41—N6—C42—C43	178.96 (14)
C13—C14—C15—C16	−1.9 (3)	C41—N6—C42—C41^ii	−0.8 (2)
C24—C23—C22—C21	0.4 (3)	C42—N6—C41—C40	−179.15 (13)
C18—C17—C16—C15	0.4 (3)	C42—N6—C41—C42^ii	0.8 (3)
C14—C15—C16—C17	1.3 (3)	N6—C42—C43—C44	−179.85 (15)
C19—C20—C21—C22	−1.0 (3)	C41^ii—C42—C43—C44	−0.1 (3)
C23—C22—C21—C20	0.5 (3)	N6—C41—C40—C39	−178.83 (15)
C1—C6—C5—O3	179.01 (15)	C42^ii—C41—C40—C39	1.2 (3)
C1—C6—C5—C4	−0.6 (3)	C41—C40—C39—C44^ii	−0.3 (3)
O3—C5—C4—C3	−178.60 (15)	C42—C43—C44—C39^ii	−0.8 (3)

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···N4^iii	0.84	2.03	2.762 (2)	145
O5—H5O···N2^iv	0.84	1.98	2.819 (2)	173
O6—H6O···N6^v	0.84	2.01	2.844 (2)	174
C10—H10···N6^v	0.95	2.52	3.258 (3)	135
O3—H3O···N1	0.84	2.08	2.799 (2)	144
O1—H1O···N3	0.84	2.01	2.845 (2)	173
C2—H2···N5	0.95	2.54	3.279 (3)	134
O2—H2O···N5	0.84	2.01	2.852 (2)	175
C35—H35C···O1^iii	0.98	2.66	3.292 (3)	123
O4—H4O···N4^iii	0.84	2.03	2.762 (2)	145
O5—H5O···N2^iv	0.84	1.98	2.819 (2)	173
O6—H6O···N6^v	0.84	2.01	2.844 (2)	174
C10—H10···N6^v	0.95	2.52	3.258 (3)	135
O3—H3O···N1	0.84	2.08	2.799 (2)	144
O1—H1O···N3	0.84	2.01	2.845 (2)	173
C2—H2···N5	0.95	2.54	3.279 (3)	134
O2—H2O···N5	0.84	2.01	2.852 (2)	175
C35—H35C···O1^iii	0.98	2.66	3.292 (3)	123

Symmetry codes: (iii) −x+2, −y+1, −z+1; (iv) −x, −y+1, −z; (v) x, y+1, z.

(TS_PGL_TMP_PHE_Form_II)

Crystal data

C56H48N8O6	V = 1127.3 (13) Å^3
Mr = 929.02	Z = 1
Triclinic, P1	F(000) = 488
a = 7.576 (5) Å	Dx = 1.369 Mg m^−3
b = 9.081 (6) Å	Mo Kα radiation, λ = 0.71073 Å
c = 16.503 (11) Å	µ = 0.09 mm^−1
α = 96.651 (13)°	T = 150 K
β = 90.601 (11)°	Block, orange
γ = 91.433 (8)°	0.54 × 0.38 × 0.24 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	4445 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.106
profile data from ω–scans	θmax = 27.5°, θmin = 1.2°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −9→9
Tmin = 0.813, Tmax = 1.000	k = −11→11
12024 measured reflections	l = −21→21
5147 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.056	H-atom parameters constrained
wR(F^2) = 0.171	w = 1/[σ^2(Fo^2) + (0.0761P)^2 + 0.3328P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
5147 reflections	Δρmax = 0.33 e Å^−3
316 parameters	Δρmin = −0.41 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C29	0.46852 (19)	0.61536 (16)	0.45781 (9)	0.0191 (3)
N1	0.25869 (17)	0.57971 (14)	0.03002 (8)	0.0205 (3)
N2	0.27145 (17)	0.35054 (15)	−0.10137 (8)	0.0218 (3)
C11	0.31885 (19)	0.49128 (18)	−0.11078 (9)	0.0210 (3)
C10	0.3801 (2)	0.5268 (2)	−0.18792 (10)	0.0296 (4)
H10	0.3840	0.4518	−0.2330	0.036*
C18	0.31298 (19)	0.60735 (17)	−0.04393 (9)	0.0195 (3)
C12	0.2203 (2)	0.32264 (17)	−0.02672 (10)	0.0210 (3)
C16	0.1507 (2)	0.4049 (2)	0.11680 (10)	0.0289 (4)
H16	0.1415	0.4813	0.1609	0.035*
C17	0.21075 (19)	0.43893 (17)	0.03946 (9)	0.0207 (3)
C13	0.1763 (2)	0.17413 (19)	−0.01246 (12)	0.0305 (4)
H13	0.1845	0.0953	−0.0553	0.037*
C7	0.3666 (2)	0.75502 (19)	−0.05647 (11)	0.0289 (4)
H7	0.3617	0.8328	−0.0128	0.035*
C14	0.1228 (3)	0.1461 (2)	0.06230 (13)	0.0388 (5)
H14	0.0956	0.0468	0.0717	0.047*
C15	0.1066 (3)	0.2622 (2)	0.12715 (12)	0.0384 (5)
H15	0.0643	0.2398	0.1784	0.046*
C8	0.4243 (3)	0.7842 (2)	−0.13063 (12)	0.0367 (4)
H8	0.4593	0.8826	−0.1386	0.044*
C9	0.4332 (2)	0.6689 (2)	−0.19663 (11)	0.0373 (4)
H9	0.4768	0.6913	−0.2477	0.045*
O1	0.78126 (15)	0.89833 (13)	0.23260 (7)	0.0288 (3)
H1	0.7598	0.8234	0.1988	0.043*
O2	1.38254 (16)	0.78376 (15)	0.16194 (8)	0.0339 (3)
H2	1.3316	0.7162	0.1305	0.051*
O3	1.27084 (15)	1.18897 (13)	0.35391 (8)	0.0301 (3)
H3	1.1888	1.2354	0.3784	0.045*
C4	1.32244 (19)	0.98455 (16)	0.25877 (8)	0.0186 (3)
H4	1.4457	1.0043	0.2658	0.022*
C6	1.01977 (19)	1.04440 (16)	0.29338 (9)	0.0199 (3)
H6	0.9382	1.1060	0.3236	0.024*
C3	1.2597 (2)	0.86646 (16)	0.20453 (9)	0.0201 (3)
C5	1.2016 (2)	1.07353 (16)	0.30272 (9)	0.0190 (3)
C2	1.0789 (2)	0.83414 (17)	0.19424 (9)	0.0210 (3)
H2A	1.0379	0.7522	0.1572	0.025*
C1	0.95979 (19)	0.92400 (16)	0.23919 (9)	0.0198 (3)
N4	0.54494 (17)	0.49791 (14)	0.41590 (8)	0.0199 (3)
C25	0.6541 (2)	0.25434 (17)	0.41715 (10)	0.0218 (3)
H25	0.6862	0.2523	0.3615	0.026*
C27	0.6394 (2)	0.13665 (17)	0.54114 (10)	0.0244 (3)
H27	0.6610	0.0521	0.5683	0.029*
C28	0.5672 (2)	0.25800 (17)	0.58280 (10)	0.0221 (3)
H28	0.5405	0.2585	0.6389	0.027*
C26	0.6830 (2)	0.13475 (17)	0.45736 (10)	0.0242 (3)
H26	0.7329	0.0488	0.4292	0.029*
C24	0.57604 (19)	0.38277 (16)	0.45793 (9)	0.0187 (3)
N3	0.07011 (17)	0.38669 (13)	0.44930 (8)	0.0194 (3)
C19	0.04643 (19)	0.37248 (16)	0.52832 (9)	0.0186 (3)
C22	0.0529 (3)	0.5209 (2)	0.33120 (10)	0.0318 (4)
H22A	0.1027	0.4282	0.3061	0.048*
H22B	0.1345	0.6039	0.3243	0.048*
H22C	−0.0606	0.5364	0.3049	0.048*
C20	0.02579 (19)	0.51188 (17)	0.42015 (9)	0.0192 (3)
C21	0.0990 (2)	0.23075 (18)	0.55824 (12)	0.0299 (4)
H21A	0.1447	0.1641	0.5127	0.045*
H21B	−0.0040	0.1837	0.5810	0.045*
H21C	0.1909	0.2514	0.6006	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C29	0.0205 (7)	0.0147 (7)	0.0226 (7)	0.0009 (5)	−0.0015 (5)	0.0045 (5)
N1	0.0246 (6)	0.0176 (6)	0.0189 (6)	0.0023 (5)	−0.0009 (5)	0.0006 (5)
N2	0.0204 (6)	0.0208 (7)	0.0229 (6)	0.0030 (5)	−0.0020 (5)	−0.0031 (5)
C11	0.0196 (7)	0.0238 (8)	0.0195 (7)	0.0025 (6)	−0.0012 (5)	0.0020 (6)
C10	0.0273 (8)	0.0437 (10)	0.0176 (7)	0.0008 (7)	0.0006 (6)	0.0030 (7)
C18	0.0218 (7)	0.0181 (7)	0.0190 (7)	0.0018 (6)	−0.0011 (5)	0.0029 (6)
C12	0.0213 (7)	0.0163 (7)	0.0251 (7)	0.0023 (6)	−0.0042 (6)	0.0016 (6)
C16	0.0321 (8)	0.0345 (9)	0.0208 (8)	−0.0021 (7)	−0.0017 (6)	0.0073 (7)
C17	0.0217 (7)	0.0209 (7)	0.0196 (7)	0.0016 (6)	−0.0026 (6)	0.0030 (6)
C13	0.0319 (9)	0.0177 (8)	0.0419 (10)	−0.0012 (6)	−0.0112 (7)	0.0045 (7)
C7	0.0334 (9)	0.0211 (8)	0.0330 (9)	−0.0014 (7)	−0.0037 (7)	0.0069 (6)
C14	0.0415 (10)	0.0268 (9)	0.0508 (12)	−0.0113 (8)	−0.0168 (9)	0.0204 (8)
C15	0.0403 (10)	0.0468 (12)	0.0310 (9)	−0.0103 (9)	−0.0076 (8)	0.0200 (8)
C8	0.0389 (10)	0.0342 (10)	0.0402 (10)	−0.0073 (8)	−0.0052 (8)	0.0199 (8)
C9	0.0332 (9)	0.0555 (12)	0.0262 (9)	−0.0042 (8)	−0.0004 (7)	0.0188 (8)
O1	0.0229 (6)	0.0274 (6)	0.0330 (6)	0.0007 (5)	0.0006 (5)	−0.0102 (5)
O2	0.0261 (6)	0.0350 (7)	0.0352 (7)	0.0076 (5)	0.0002 (5)	−0.0203 (5)
O3	0.0250 (6)	0.0226 (6)	0.0383 (7)	0.0031 (5)	0.0008 (5)	−0.0156 (5)
C4	0.0224 (7)	0.0168 (7)	0.0167 (7)	0.0030 (6)	0.0007 (5)	0.0013 (5)
C6	0.0232 (7)	0.0162 (7)	0.0201 (7)	0.0053 (6)	0.0031 (6)	−0.0003 (5)
C3	0.0248 (7)	0.0177 (7)	0.0176 (7)	0.0073 (6)	0.0019 (5)	−0.0003 (5)
C5	0.0271 (7)	0.0117 (6)	0.0179 (7)	0.0025 (5)	0.0001 (5)	0.0001 (5)
C2	0.0265 (8)	0.0168 (7)	0.0184 (7)	0.0021 (6)	−0.0009 (6)	−0.0032 (5)
C1	0.0224 (7)	0.0178 (7)	0.0194 (7)	0.0024 (6)	0.0001 (5)	0.0028 (5)
N4	0.0236 (6)	0.0152 (6)	0.0217 (6)	0.0022 (5)	−0.0013 (5)	0.0048 (5)
C25	0.0243 (7)	0.0170 (7)	0.0240 (7)	0.0033 (6)	−0.0007 (6)	0.0017 (6)
C27	0.0258 (8)	0.0152 (7)	0.0339 (8)	0.0036 (6)	−0.0019 (6)	0.0103 (6)
C28	0.0253 (7)	0.0184 (7)	0.0241 (7)	0.0027 (6)	−0.0009 (6)	0.0081 (6)
C26	0.0256 (7)	0.0147 (7)	0.0324 (8)	0.0047 (6)	0.0000 (6)	0.0029 (6)
C24	0.0211 (7)	0.0139 (7)	0.0216 (7)	0.0007 (5)	−0.0022 (5)	0.0045 (5)
N3	0.0234 (6)	0.0136 (6)	0.0206 (6)	0.0022 (5)	−0.0003 (5)	−0.0008 (5)
C19	0.0220 (7)	0.0118 (7)	0.0223 (7)	0.0018 (5)	−0.0012 (5)	0.0036 (5)
C22	0.0414 (10)	0.0370 (10)	0.0177 (7)	0.0019 (8)	0.0011 (7)	0.0057 (7)
C20	0.0236 (7)	0.0171 (7)	0.0171 (7)	0.0005 (6)	−0.0012 (5)	0.0026 (5)
C21	0.0335 (8)	0.0178 (8)	0.0406 (9)	0.0060 (6)	−0.0020 (7)	0.0120 (7)

Geometric parameters (Å, º)

C29—N4	1.349 (2)	C4—C3	1.386 (2)
C29—C28^i	1.427 (2)	C4—C5	1.390 (2)
C29—C24^i	1.433 (2)	C4—H4	0.9500
N1—C18	1.341 (2)	C6—C1	1.393 (2)
N1—C17	1.347 (2)	C6—C5	1.400 (2)
N2—C12	1.345 (2)	C6—H6	0.9500
N2—C11	1.346 (2)	C3—C2	1.399 (2)
C11—C10	1.428 (2)	C2—C1	1.393 (2)
C11—C18	1.437 (2)	C2—H2A	0.9500
C10—C9	1.366 (3)	N4—C24	1.344 (2)
C10—H10	0.9500	C25—C26	1.358 (2)
C18—C7	1.430 (2)	C25—C24	1.423 (2)
C12—C13	1.428 (2)	C25—H25	0.9500
C12—C17	1.432 (2)	C27—C28	1.360 (2)
C16—C15	1.361 (3)	C27—C26	1.423 (2)
C16—C17	1.424 (2)	C27—H27	0.9500
C16—H16	0.9500	C28—C29^i	1.427 (2)
C13—C14	1.352 (3)	C28—H28	0.9500
C13—H13	0.9500	C26—H26	0.9500
C7—C8	1.357 (3)	C24—C29^i	1.433 (2)
C7—H7	0.9500	N3—C20	1.334 (2)
C14—C15	1.421 (3)	N3—C19	1.339 (2)
C14—H14	0.9500	C19—C20^ii	1.399 (2)
C15—H15	0.9500	C19—C21	1.493 (2)
C8—C9	1.424 (3)	C22—C20	1.496 (2)
C8—H8	0.9500	C22—H22A	0.9800
C9—H9	0.9500	C22—H22B	0.9800
O1—C1	1.368 (2)	C22—H22C	0.9800
O1—H1	0.8400	C20—C19^ii	1.399 (2)
O2—C3	1.3602 (18)	C21—H21A	0.9800
O2—H2	0.8400	C21—H21B	0.9800
O3—C5	1.3588 (19)	C21—H21C	0.9800
O3—H3	0.8400
N4—C29—C28^i	118.97 (14)	C5—C6—H6	120.4
N4—C29—C24^i	121.94 (13)	O2—C3—C4	116.76 (14)
C28^i—C29—C24^i	119.09 (14)	O2—C3—C2	121.75 (14)
C18—N1—C17	117.55 (13)	C4—C3—C2	121.49 (13)
C12—N2—C11	117.36 (13)	O3—C5—C4	116.06 (14)
N2—C11—C10	119.91 (14)	O3—C5—C6	122.91 (13)
N2—C11—C18	121.26 (14)	C4—C5—C6	121.04 (14)
C10—C11—C18	118.81 (15)	C1—C2—C3	118.93 (14)
C9—C10—C11	119.78 (16)	C1—C2—H2A	120.5
C9—C10—H10	120.1	C3—C2—H2A	120.5
C11—C10—H10	120.1	O1—C1—C2	122.07 (14)
N1—C18—C7	119.40 (14)	O1—C1—C6	117.36 (13)
N1—C18—C11	121.24 (14)	C2—C1—C6	120.58 (14)
C7—C18—C11	119.36 (15)	C24—N4—C29	115.93 (14)
N2—C12—C13	119.66 (14)	C26—C25—C24	120.29 (15)
N2—C12—C17	121.35 (14)	C26—C25—H25	119.9
C13—C12—C17	118.98 (15)	C24—C25—H25	119.9
C15—C16—C17	119.58 (17)	C28—C27—C26	120.84 (14)
C15—C16—H16	120.2	C28—C27—H27	119.6
C17—C16—H16	120.2	C26—C27—H27	119.6
N1—C17—C16	119.42 (14)	C27—C28—C29^i	120.00 (15)
N1—C17—C12	121.19 (14)	C27—C28—H28	120.0
C16—C17—C12	119.39 (15)	C29^i—C28—H28	120.0
C14—C13—C12	119.74 (17)	C25—C26—C27	120.79 (14)
C14—C13—H13	120.1	C25—C26—H26	119.6
C12—C13—H13	120.1	C27—C26—H26	119.6
C8—C7—C18	120.05 (17)	N4—C24—C25	118.90 (14)
C8—C7—H7	120.0	N4—C24—C29^i	122.13 (13)
C18—C7—H7	120.0	C25—C24—C29^i	118.97 (13)
C13—C14—C15	121.32 (17)	C20—N3—C19	119.71 (12)
C13—C14—H14	119.3	N3—C19—C20^ii	120.04 (14)
C15—C14—H14	119.3	N3—C19—C21	117.77 (13)
C16—C15—C14	120.91 (17)	C20^ii—C19—C21	122.18 (15)
C16—C15—H15	119.5	C20—C22—H22A	109.5
C14—C15—H15	119.5	C20—C22—H22B	109.5
C7—C8—C9	120.73 (17)	H22A—C22—H22B	109.5
C7—C8—H8	119.6	C20—C22—H22C	109.5
C9—C8—H8	119.6	H22A—C22—H22C	109.5
C10—C9—C8	121.26 (16)	H22B—C22—H22C	109.5
C10—C9—H9	119.4	N3—C20—C19^ii	120.25 (14)
C8—C9—H9	119.4	N3—C20—C22	117.42 (14)
C1—O1—H1	109.5	C19^ii—C20—C22	122.32 (14)
C3—O2—H2	109.5	C19—C21—H21A	109.5
C5—O3—H3	109.5	C19—C21—H21B	109.5
C3—C4—C5	118.76 (14)	H21A—C21—H21B	109.5
C3—C4—H4	120.6	C19—C21—H21C	109.5
C5—C4—H4	120.6	H21A—C21—H21C	109.5
C1—C6—C5	119.21 (13)	H21B—C21—H21C	109.5
C1—C6—H6	120.4
C12—N2—C11—C10	177.86 (13)	C11—C10—C9—C8	−1.7 (3)
C12—N2—C11—C18	−0.7 (2)	C7—C8—C9—C10	1.5 (3)
N2—C11—C10—C9	−178.04 (15)	C5—C4—C3—O2	179.03 (13)
C18—C11—C10—C9	0.6 (2)	C5—C4—C3—C2	−1.0 (2)
C17—N1—C18—C7	−179.46 (14)	C3—C4—C5—O3	−178.96 (13)
C17—N1—C18—C11	0.3 (2)	C3—C4—C5—C6	0.6 (2)
N2—C11—C18—N1	−0.5 (2)	C1—C6—C5—O3	179.67 (14)
C10—C11—C18—N1	−179.15 (13)	C1—C6—C5—C4	0.1 (2)
N2—C11—C18—C7	179.26 (13)	O2—C3—C2—C1	−179.42 (14)
C10—C11—C18—C7	0.7 (2)	C4—C3—C2—C1	0.6 (2)
C11—N2—C12—C13	−177.19 (13)	C3—C2—C1—O1	−179.56 (13)
C11—N2—C12—C17	2.1 (2)	C3—C2—C1—C6	0.2 (2)
C18—N1—C17—C16	−179.43 (13)	C5—C6—C1—O1	179.22 (13)
C18—N1—C17—C12	1.0 (2)	C5—C6—C1—C2	−0.5 (2)
C15—C16—C17—N1	−178.28 (15)	C28^i—C29—N4—C24	179.55 (13)
C15—C16—C17—C12	1.3 (2)	C24^i—C29—N4—C24	0.2 (2)
N2—C12—C17—N1	−2.4 (2)	C26—C27—C28—C29^i	1.0 (2)
C13—C12—C17—N1	176.94 (14)	C24—C25—C26—C27	−1.3 (2)
N2—C12—C17—C16	178.08 (14)	C28—C27—C26—C25	0.3 (2)
C13—C12—C17—C16	−2.6 (2)	C29—N4—C24—C25	179.13 (13)
N2—C12—C13—C14	−179.22 (15)	C29—N4—C24—C29^i	−0.2 (2)
C17—C12—C13—C14	1.4 (2)	C26—C25—C24—N4	−178.30 (14)
N1—C18—C7—C8	178.99 (15)	C26—C25—C24—C29^i	1.1 (2)
C11—C18—C7—C8	−0.8 (2)	C20—N3—C19—C20^ii	0.5 (2)
C12—C13—C14—C15	1.0 (3)	C20—N3—C19—C21	−179.63 (14)
C17—C16—C15—C14	1.2 (3)	C19—N3—C20—C19^ii	−0.5 (2)
C13—C14—C15—C16	−2.5 (3)	C19—N3—C20—C22	−179.23 (14)
C18—C7—C8—C9	−0.3 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2^iii	0.84	2.13	2.960 (2)	172
O2—H2···N1^iv	0.84	2.01	2.826 (2)	162
O3—H3···N3^v	0.84	1.94	2.7470 (19)	160
C2—H2A···N2^iii	0.95	2.62	3.362 (3)	135
O1—H1···N2^iii	0.84	2.13	2.960 (2)	172
O2—H2···N1^iv	0.84	2.01	2.826 (2)	162
O3—H3···N3^v	0.84	1.94	2.7470 (19)	160
C2—H2A···N2^iii	0.95	2.62	3.362 (3)	135

Symmetry codes: (iii) −x+1, −y+1, −z; (iv) x+1, y, z; (v) x+1, y+1, z.

(TS_PGL_TMP_PYR)

Crystal data

C44H46N4O6	Z = 2
Mr = 726.85	F(000) = 772
Monoclinic, P21/c	Dx = 1.276 Mg m^−3
a = 8.876 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.941 (6) Å	µ = 0.09 mm^−1
c = 17.980 (9) Å	T = 150 K
β = 97.072 (4)°	Block, orange
V = 1891.2 (16) Å^3	0.44 × 0.31 × 0.17 mm

Data collection

Rigaku Mercury375R (2x2 bin mode) diffractometer	3403 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.098
profile data from ω–scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan Jacobson, R. (1998) Private communication	h = −10→10
Tmin = 0.847, Tmax = 1.000	k = −14→14
17330 measured reflections	l = −22→22
3710 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.153	w = 1/[σ^2(Fo^2) + (0.0818P)^2 + 0.4644P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
3710 reflections	Δρmax = 0.25 e Å^−3
251 parameters	Δρmin = −0.28 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.37877 (13)	0.82145 (10)	0.28241 (6)	0.0324 (3)
H1	0.3795	0.7521	0.2902	0.049*
O3	0.65089 (14)	1.10222 (9)	0.17003 (7)	0.0363 (3)
H3	0.7195	1.1097	0.1422	0.054*
N1	0.92555 (14)	0.79791 (11)	0.01904 (7)	0.0274 (3)
O2	0.73956 (13)	0.71211 (9)	0.12094 (7)	0.0356 (3)
H2	0.7911	0.7392	0.0891	0.053*
N2	1.12725 (14)	0.85993 (10)	−0.07855 (7)	0.0278 (3)
C4	0.70181 (16)	0.90899 (12)	0.14365 (8)	0.0241 (3)
H4	0.7766	0.9302	0.1128	0.029*
C3	0.66989 (16)	0.79636 (12)	0.15462 (8)	0.0242 (3)
C10	1.17018 (16)	0.86153 (12)	−0.00407 (8)	0.0265 (3)
C6	0.51119 (16)	0.96051 (12)	0.22398 (8)	0.0262 (3)
H6	0.4546	1.0163	0.2460	0.031*
C21	1.07636 (17)	0.51942 (12)	0.00738 (8)	0.0286 (3)
C8	0.88188 (17)	0.79785 (12)	−0.05545 (8)	0.0275 (3)
C5	0.62172 (16)	0.99031 (12)	0.17884 (8)	0.0250 (3)
C1	0.48549 (16)	0.84742 (12)	0.23612 (7)	0.0243 (3)
C2	0.56307 (16)	0.76506 (12)	0.20168 (8)	0.0257 (3)
H2A	0.5437	0.6881	0.2100	0.031*
C9	1.06750 (17)	0.82962 (13)	0.04561 (8)	0.0270 (3)
C20	1.14842 (19)	0.52464 (14)	0.08275 (9)	0.0337 (4)
C16	1.15749 (19)	0.55231 (13)	−0.05267 (9)	0.0323 (4)
C14	1.32970 (18)	0.89821 (16)	0.02332 (10)	0.0382 (4)
H14A	1.3863	0.9092	−0.0196	0.057*
H14B	1.3799	0.8406	0.0564	0.057*
H14C	1.3268	0.9687	0.0510	0.057*
C7	0.98515 (17)	0.82919 (13)	−0.10517 (8)	0.0284 (3)
C12	0.72104 (18)	0.76355 (17)	−0.08216 (10)	0.0407 (4)
H12A	0.6723	0.7362	−0.0396	0.061*
H12B	0.7214	0.7039	−0.1196	0.061*
H12C	0.6647	0.8282	−0.1047	0.061*
C11	0.9427 (2)	0.82999 (17)	−0.18892 (9)	0.0437 (4)
H11A	1.0320	0.8491	−0.2134	0.066*
H11B	0.8628	0.8856	−0.2023	0.066*
H11C	0.9056	0.7557	−0.2056	0.066*
C17	1.3077 (2)	0.58971 (15)	−0.03674 (11)	0.0395 (4)
H17	1.3623	0.6120	−0.0765	0.047*
C15	1.0808 (2)	0.54613 (15)	−0.12852 (10)	0.0402 (4)
H15	1.1333	0.5679	−0.1692	0.048*
C19	1.2989 (2)	0.56247 (16)	0.09561 (10)	0.0427 (4)
H19	1.3481	0.5664	0.1455	0.051*
C13	1.1101 (2)	0.82922 (17)	0.12938 (9)	0.0403 (4)
H13A	1.0236	0.8032	0.1537	0.060*
H13B	1.1378	0.9052	0.1465	0.060*
H13C	1.1967	0.7790	0.1424	0.060*
C18	1.3774 (2)	0.59437 (16)	0.03684 (12)	0.0435 (4)
H18	1.4794	0.6195	0.0470	0.052*
C22	1.0633 (2)	0.48985 (16)	0.14227 (9)	0.0419 (4)
H22	1.1107	0.4925	0.1926	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0382 (6)	0.0311 (6)	0.0318 (6)	−0.0040 (5)	0.0196 (5)	0.0021 (5)
O3	0.0449 (7)	0.0234 (6)	0.0462 (7)	−0.0061 (5)	0.0283 (5)	−0.0040 (5)
N1	0.0262 (6)	0.0295 (7)	0.0277 (6)	0.0011 (5)	0.0082 (5)	−0.0002 (5)
O2	0.0423 (7)	0.0245 (5)	0.0450 (7)	0.0017 (5)	0.0250 (5)	−0.0013 (5)
N2	0.0297 (6)	0.0270 (6)	0.0278 (6)	−0.0034 (5)	0.0083 (5)	0.0009 (5)
C4	0.0243 (7)	0.0265 (7)	0.0229 (7)	−0.0028 (5)	0.0087 (5)	−0.0011 (5)
C3	0.0249 (7)	0.0251 (7)	0.0230 (7)	0.0014 (5)	0.0044 (5)	−0.0012 (5)
C10	0.0272 (7)	0.0240 (7)	0.0284 (7)	−0.0009 (5)	0.0042 (6)	−0.0008 (6)
C6	0.0290 (7)	0.0260 (7)	0.0255 (7)	−0.0020 (6)	0.0103 (6)	−0.0048 (6)
C21	0.0334 (8)	0.0219 (7)	0.0301 (8)	0.0049 (6)	0.0026 (6)	−0.0035 (6)
C8	0.0271 (7)	0.0271 (7)	0.0287 (7)	0.0003 (6)	0.0049 (6)	−0.0013 (6)
C5	0.0277 (7)	0.0232 (7)	0.0247 (7)	−0.0033 (5)	0.0058 (5)	−0.0023 (5)
C1	0.0244 (7)	0.0309 (7)	0.0182 (6)	−0.0042 (5)	0.0050 (5)	0.0009 (5)
C2	0.0296 (7)	0.0233 (7)	0.0246 (7)	−0.0024 (6)	0.0054 (6)	0.0021 (5)
C9	0.0270 (7)	0.0282 (7)	0.0262 (7)	0.0018 (6)	0.0052 (6)	−0.0011 (6)
C20	0.0377 (9)	0.0304 (8)	0.0315 (8)	0.0018 (6)	−0.0020 (6)	−0.0039 (6)
C16	0.0357 (8)	0.0270 (8)	0.0348 (8)	0.0038 (6)	0.0061 (6)	−0.0027 (6)
C14	0.0298 (8)	0.0449 (10)	0.0395 (9)	−0.0085 (7)	0.0023 (7)	0.0009 (7)
C7	0.0311 (8)	0.0278 (7)	0.0265 (7)	−0.0022 (6)	0.0045 (6)	−0.0006 (6)
C12	0.0280 (8)	0.0527 (11)	0.0409 (9)	−0.0062 (7)	0.0022 (7)	−0.0034 (8)
C11	0.0482 (10)	0.0563 (11)	0.0265 (8)	−0.0124 (9)	0.0041 (7)	0.0023 (7)
C17	0.0368 (9)	0.0358 (9)	0.0478 (10)	0.0006 (7)	0.0121 (7)	−0.0003 (7)
C15	0.0478 (10)	0.0450 (10)	0.0289 (8)	0.0004 (8)	0.0095 (7)	−0.0006 (7)
C19	0.0415 (10)	0.0429 (10)	0.0402 (9)	−0.0019 (8)	−0.0087 (7)	−0.0021 (8)
C13	0.0389 (9)	0.0569 (11)	0.0252 (8)	−0.0015 (8)	0.0045 (7)	−0.0010 (7)
C18	0.0298 (8)	0.0407 (10)	0.0584 (11)	−0.0029 (7)	−0.0016 (8)	−0.0022 (8)
C22	0.0522 (10)	0.0470 (10)	0.0252 (8)	−0.0003 (8)	−0.0008 (7)	−0.0028 (7)

Geometric parameters (Å, º)

O1—C1	1.3712 (17)	C20—C19	1.402 (3)
O1—H1	0.8400	C20—C22	1.445 (3)
O3—C5	1.3740 (19)	C16—C17	1.402 (2)
O3—H3	0.8400	C16—C15	1.449 (2)
N1—C9	1.346 (2)	C14—H14A	0.9800
N1—C8	1.348 (2)	C14—H14B	0.9800
O2—C3	1.3614 (18)	C14—H14C	0.9800
O2—H2	0.8400	C7—C11	1.507 (2)
N2—C7	1.344 (2)	C12—H12A	0.9800
N2—C10	1.347 (2)	C12—H12B	0.9800
C4—C3	1.393 (2)	C12—H12C	0.9800
C4—C5	1.400 (2)	C11—H11A	0.9800
C4—H4	0.9500	C11—H11B	0.9800
C3—C2	1.397 (2)	C11—H11C	0.9800
C10—C9	1.405 (2)	C17—C18	1.391 (3)
C10—C14	1.506 (2)	C17—H17	0.9500
C6—C1	1.391 (2)	C15—C22^i	1.343 (3)
C6—C5	1.394 (2)	C15—H15	0.9500
C6—H6	0.9500	C19—C18	1.389 (3)
C21—C16	1.425 (2)	C19—H19	0.9500
C21—C21^i	1.426 (3)	C13—H13A	0.9800
C21—C20	1.427 (2)	C13—H13B	0.9800
C8—C7	1.408 (2)	C13—H13C	0.9800
C8—C12	1.506 (2)	C18—H18	0.9500
C1—C2	1.389 (2)	C22—C15^i	1.343 (3)
C2—H2A	0.9500	C22—H22	0.9500
C9—C13	1.507 (2)
C1—O1—H1	109.5	C10—C14—H14B	109.5
C5—O3—H3	109.5	H14A—C14—H14B	109.5
C9—N1—C8	119.68 (13)	C10—C14—H14C	109.5
C3—O2—H2	109.5	H14A—C14—H14C	109.5
C7—N2—C10	119.76 (13)	H14B—C14—H14C	109.5
C3—C4—C5	118.82 (13)	N2—C7—C8	120.16 (14)
C3—C4—H4	120.6	N2—C7—C11	117.55 (14)
C5—C4—H4	120.6	C8—C7—C11	122.29 (14)
O2—C3—C4	122.60 (13)	C8—C12—H12A	109.5
O2—C3—C2	116.81 (13)	C8—C12—H12B	109.5
C4—C3—C2	120.59 (13)	H12A—C12—H12B	109.5
N2—C10—C9	120.14 (13)	C8—C12—H12C	109.5
N2—C10—C14	117.97 (13)	H12A—C12—H12C	109.5
C9—C10—C14	121.89 (14)	H12B—C12—H12C	109.5
C1—C6—C5	118.67 (13)	C7—C11—H11A	109.5
C1—C6—H6	120.7	C7—C11—H11B	109.5
C5—C6—H6	120.7	H11A—C11—H11B	109.5
C16—C21—C21^i	120.41 (17)	C7—C11—H11C	109.5
C16—C21—C20	119.89 (15)	H11A—C11—H11C	109.5
C21^i—C21—C20	119.70 (18)	H11B—C11—H11C	109.5
N1—C8—C7	120.06 (14)	C18—C17—C16	120.50 (17)
N1—C8—C12	117.55 (13)	C18—C17—H17	119.7
C7—C8—C12	122.39 (14)	C16—C17—H17	119.7
O3—C5—C6	118.13 (13)	C22^i—C15—C16	121.05 (16)
O3—C5—C4	120.60 (13)	C22^i—C15—H15	119.5
C6—C5—C4	121.27 (14)	C16—C15—H15	119.5
O1—C1—C2	121.86 (13)	C18—C19—C20	121.33 (16)
O1—C1—C6	116.97 (13)	C18—C19—H19	119.3
C2—C1—C6	121.15 (13)	C20—C19—H19	119.3
C1—C2—C3	119.42 (13)	C9—C13—H13A	109.5
C1—C2—H2A	120.3	C9—C13—H13B	109.5
C3—C2—H2A	120.3	H13A—C13—H13B	109.5
N1—C9—C10	120.19 (13)	C9—C13—H13C	109.5
N1—C9—C13	117.57 (14)	H13A—C13—H13C	109.5
C10—C9—C13	122.25 (14)	H13B—C13—H13C	109.5
C19—C20—C21	118.50 (16)	C19—C18—C17	120.45 (16)
C19—C20—C22	123.01 (15)	C19—C18—H18	119.8
C21—C20—C22	118.48 (15)	C17—C18—H18	119.8
C17—C16—C21	119.32 (15)	C15^i—C22—C20	121.90 (15)
C17—C16—C15	122.22 (16)	C15^i—C22—H22	119.0
C21—C16—C15	118.46 (15)	C20—C22—H22	119.0
C10—C14—H14A	109.5
C5—C4—C3—O2	178.21 (13)	C21^i—C21—C20—C19	179.61 (17)
C5—C4—C3—C2	−1.9 (2)	C16—C21—C20—C22	−179.53 (15)
C7—N2—C10—C9	0.9 (2)	C21^i—C21—C20—C22	0.1 (3)
C7—N2—C10—C14	−179.07 (14)	C21^i—C21—C16—C17	−179.72 (17)
C9—N1—C8—C7	1.0 (2)	C20—C21—C16—C17	−0.1 (2)
C9—N1—C8—C12	−178.97 (14)	C21^i—C21—C16—C15	0.5 (3)
C1—C6—C5—O3	−177.09 (13)	C20—C21—C16—C15	−179.91 (14)
C1—C6—C5—C4	2.5 (2)	C10—N2—C7—C8	−0.5 (2)
C3—C4—C5—O3	179.36 (13)	C10—N2—C7—C11	179.41 (15)
C3—C4—C5—C6	−0.3 (2)	N1—C8—C7—N2	−0.4 (2)
C5—C6—C1—O1	178.32 (12)	C12—C8—C7—N2	179.52 (15)
C5—C6—C1—C2	−2.7 (2)	N1—C8—C7—C11	179.63 (15)
O1—C1—C2—C3	179.54 (12)	C12—C8—C7—C11	−0.4 (2)
C6—C1—C2—C3	0.7 (2)	C21—C16—C17—C18	0.2 (2)
O2—C3—C2—C1	−178.39 (13)	C15—C16—C17—C18	−179.96 (16)
C4—C3—C2—C1	1.7 (2)	C17—C16—C15—C22^i	−179.89 (17)
C8—N1—C9—C10	−0.6 (2)	C21—C16—C15—C22^i	−0.1 (3)
C8—N1—C9—C13	179.43 (14)	C21—C20—C19—C18	0.0 (3)
N2—C10—C9—N1	−0.4 (2)	C22—C20—C19—C18	179.48 (17)
C14—C10—C9—N1	179.63 (14)	C20—C19—C18—C17	0.2 (3)
N2—C10—C9—C13	179.61 (15)	C16—C17—C18—C19	−0.3 (3)
C14—C10—C9—C13	−0.4 (2)	C19—C20—C22—C15^i	−179.99 (18)
C16—C21—C20—C19	0.0 (2)	C21—C20—C22—C15^i	−0.5 (3)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^ii	0.84	1.96	2.7765 (19)	165
O3—H3···N2^iii	0.84	1.92	2.7541 (19)	175
O2—H2···N1	0.84	1.97	2.8066 (18)	176

Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) −x+2, −y+2, −z.

 

Footnotes

¹Proof correction is an essential feature in all crystallizations. It is especially important in complicated systems like MOFs and globular proteins, and it is achieved by virtue of the fact that the assembling interactions are relatively weak and the crystallization events are reversible. It is an important feature in the present sequence, which appears to be convergent in nature. See Feng et al. (2012).