Two di­benzodiazepinone mol­ecules with dissimilar dimeric associations and apparent different tautomeric forms

In two dibenzodiazepinones, viz. the tricyclic core structure, 5H-dibenzo[b,e]diazepin-11(10H)-one, C₁₃H₁₀N₂O, and an acyl­ated derivative, 1-(11-hydroxy-5H-dibenzo[b,e]diazepin-5-yl)-2-{4-[3-(1H-imidazol-1-yl)propyl]piperidin-1-yl}ethanone ethanol monosolvate, C₂₆H₂₉N₅O₂·C₂H₅OH, dimeric association via hydrogen-bond bridging between the cyclic amide entities is evident, but there are considerable differences between the parent compound and the amidated derivative. Highly consistent with reported structures of related tricyclic lactams, two mol­ecules of the nonsubstituted compound are bridged through two N-H...O hydrogen bonds across a crystallographic centre of symmetry and the bond lengths of the cyclic amide entity correspond to the amino-oxo (lactam) tautomeric form. In contrast, the structure of the derivative shows two similar, but crystallographically unique, mol­ecules hydrogen bonded into a dimeric unit exhibiting an approximate (noncrystallographic) C2 axis. The bond lengths of the two derivative cyclic amide groups support their potential presence in the hy­droxy­imine (lactim) tautomeric forms, with the resulting possibility of inter­molecular tautomerism. Likely driving forces for the two extreme configurations are discussed.

S1. Comment

Crystal structures of molecules that contain the dibenzodiazepinone nucleus have not been reported to date, even though the synthesis and crystallization of the parent dibenzodiazepinone, 5H-dibenzo[b,e]diazepin-11(10H)-one, (I) (Fig. 1), has been known for decades (Clemo et al., 1924; Giani et al., 1985). Substitution at the 5-position (positional numbering based on systematic IUPAC nomenclature and used throughout the text, but different from crystallographic positional numbering) of (I) with acyl residues containing one or two aminergic basic entities was reported to be a promising strategy for the development of highly potent ligands for muscarinic receptors (Cohen et al., 1993; Kassiou et al., 1997). Aiming at the preparation of muscarinic receptor ligands with improved selectivity, as well as potential radioligands for muscarinic receptors, we synthesized dibenzodiazepinone derivatives with basic heterocycles at the terminal 5-position of the side chain of (I). This approach prompted us to synthesize the dibenzodiazepinone derivative 5-(2-{4-[3-(1H-imidazol-1-yl)propyl]piperidin-1-yl}ethanoyl)-5H-benzo[b,e]diazepin-11(10H)-one ethanol monosolvate, (II) (Fig. 2), which crystallizes from ethanol–diethyl ether as translucent needles. The previously described parent compound (I), a crucial intermediate for the preparation of (II), was crystallized from ethanol–ethyl acetate as a mixture of hexagonal and rhombic plates with a yellow–green appearance.

X-ray crystallographic analyses of the parent compound, (I) (hexagonal plates), and of its amide derivative, (II), reveal consistencies and differences in the molecular and intermolecular structures of the two dibenzodiazepinones. A major and obvious common feature is the hydrogen-bond bridging of two monomers through the dibenzodiazepinone lactam group (Figs. 3a and 3b). In a second point of similarity, the seven-membered diazepinone rings adopt a puckered conformation (Figs. 1, 2, 3c and 3d), such that the two aromatic rings are parallel, adopting a butterfly conformation; the puckering is more pronounced in lactam (II) [angles between the benzene rings: (I) 139.3°, and (II) 120.0 (molecule A) and 126.6 ° (molecule B).

Closer examination reveals the first point of difference. In the case of (I), the hydrogen-bonded pair exhibits a centre of symmetry, which implies a relative association between the curved dibenzodiazepinone ring systems as two cupped hands held side-by-side, with one cup upright and the other inverted (Fig. 3c). A completely different situation is found in the crystal structure of (II). Here, the association between the two butterfly-shaped tricyclic systems is such that the aromatic rings of both molecules are oriented in the same direction. It is noted that in this structure the N5-bound side chains are folded back over the convex surface of the two molecules (Fig. 3d). This latter type of dimeric structure normally assumes a C2 symmetry, with the axis extended perpendicular to the mean planes of the two tricyclic entities of the pair. In practice there is only an approximate twofold symmetry, as there are minor conformational differences between the two molecules in the dimeric unit of (II).

It should be noted at the outset that the crystallographic data for (II) were relatively weak and there is a level of disorder brought about in part by the presence of disordered solvent in the crystal. However, with this in mind, and within the limits of the data, an overlay of the two individual molecules A and B (Fig. 4) reveals that most differences occur in the orientation of the remote sections of the N5 amide side chain (see Supplementary materials). Compounding these differences is the observation of a degree of apparent disorder in the position of the N—C—O atoms within each of the H-bound partner lactam/lactim moieties. Modelling of this disorder leads to the conclusion that there is the equivalent of an approximately 0.75:0.25 ratio of contributors in which the H—N and C—O atom pairs are interchanged. This amounts to there being present an identical ratio of diastereoisomeric pairs of H-bound molecules in the unit cell. These diastereoisomeric molecules would equate to the E and Z rotameric molecules that are evident by ¹H and ¹³C NMR spectroscopy in solution (see below), but within the crystallographic constraints in which the side chains remain fixed.

In order to determine the propensity of the symmetry involved in the overall dimeric association of similar tricyclic structures, a search of the Cambridge Structural Database (CSD, Version ????; Allen, 2002) for seven-membered lactams fused with two six-membered aromatic rings was carried out. The search gave seven hits, namely dimeric units of dibenzazepinone, (III), dibenzoxazepinone, (IV), dibenzothiazepinone, (V), and dipyridodiazepinones, (VIa)–(VId), all of which show the former crystallographic behaviour of (I), i.e. a centrosymmetric association of hydrogen-bonded molecules. The type of association found for structure (II) has not been reported so far. Geometric parameters for dimeric units of the related lactams (I)–(IV) and (VIa)–(VId) are given in Table 1.

In the wider crystal structure of the parent compound, (I), the N5 H atom serves as a hydrogen-bond donor and forms an additional hydrogen-bond contact to the lactam carbonyl O atom, over and above the contact of the O atom with the N10 H atom of its partner lactam (Fig. 5a). This can not take place in the derivative, (II), but leads, in (I), to both lone pairs of the carbonyl O atom being involved in hydrogen bonding. As a consequence, there is a hydrogen bond cross-coupling between hydrogen-bonded dimeric pairs of molecules in (I) that creates a second dimension parallel to (100). This second dimension is reinforced through an additional interaction (2.61 Å) between H10A and N2ⁱⁱⁱ [symmetry code: (iii) x, -y+1/2, z+1/2] (Fig. 5a). Furthermore, π–π interactions [3.372 (3) Å] between aromatic atom C6 of one molecule and at atom C8 of its symmetry-related partner molecule at (-x+1, -y+1, -z+1) and atom C8 of the original molecule and atom C6 of the same partner, and H···π interactions (2.86 and 2.80 Å) between aromatic atom H7 from one molecule and C1/C13 of its symmetry-related partner at (-x+1, -y, -z+1) are identified in the crystal structure of (I) (cf. Fig. 5a).

In contrast with the situation in (I), the unit cell of (II) comprises two chemically equivalent but crystallographically non-identical hydrogen-bonded partner molecules. These partner pairs are in turn held together in part by H···π interactions through atom H10A from one molecule and C14A/C1A/C2A/C3A from a benzenoid aromatic ring of its equivalent molecule in an adjacent partner pair (Fig. 5b). Cocrystallized solvent ethanol is evident both in the ¹H NMR spectrum and the X-ray crystal structure. Present in a 1:1 ratio, the ethanol molecule is in a hydrogen-bond donor contact with the unsubstituted N atoms [N5A and N5B, respectively) in each of the imidazole heterocycles in the pendant side chains (contacts H1Eⁱⁱⁱ···N5A and H1Fⁱⁱ···N5B in Figs. 3d and 5b; symmetry codes: (ii) x-1, y, z; (iii) x+1, y+1, z]. The ethanol molecule bonded to atom N5B is also in a hydrogen-bond acceptor contact with one of the aromatic H atoms (H2A) from the partner molecule of an adjacent molecular pair [O1F···H2A^iv; symmetry code: (iv) -x, -y+1, -z+1]. These contacts reinforce the H···π contact in holding the partner pairs together (Fig. 5b). In contrast, the second ethanol solvent molecule is slightly disordered, possibly due to a partial escape of the solvent. It is also associated as a hydrogen-bond donor with an imidazole N atom (H1E—N5A), but not as an acceptor.

In addition to the main hydrogen bond between the cyclic amide groups, there is a hydrogen-bond contact between the exocyclic amide carbonyl atom O2A of one molecule and atom H24D of the methylene group adjacent to the imidazole ring of its partner molecule, as well as H···π interactions between the π bond between atoms C7A and C12A of the original molecule and the same partner methylene H atom (H24C), and between atom C10A of the original molecule and imidazole atom H27B of its partner molecule, all evident within the asymmetric dimeric unit of (II) (Figs. 3d and 5b). As a further example of the non-equivalence of the two sub-units, atom H24A of the methylene group next to the imidazole ring of the original molecule interacts with exocyclic amide atom O2B of the second molecule, while imidazole atom H27A from the original molecule participates in an H···π interaction with atoms C9B and C10B of the adjacent molecule. Both sets of interactions occur across the non-identical molecules of the asymmetric pair and most likely stabilize the complementary back-folding of the N5-bound side chains (Fig. 3d).

In the two crystal structures, within the limits imposed by the quality of the data for (II), the cyclic amide (lactam) entities, which form the interface of the dibenzodiazepinone dimeric structure, show significant features in their C—N and C═O bond lengths. The parent compound, (I), contains a relatively short C—N bond [1.330 (3) Å; shorter than for the comparable compounds (III)–(V) and (VIa)–(VId), but equal to (VIb)] and a relatively long carbonyl bond [1.265 (3) Å; longer than for (III)–(V) and (VIa)–(VId)]. These observations indicate the presence of some hydroxyimine character in the molecule but a preference for the amide (keto) tautomer (cf. Fig. 6). However, the two monomeric species in the structure of (II) has considerably shorter C—N bonds [1.298 (6) and 1.309 (7) Å] and longer lactam carbonyl bonds [1.311 (6) and 1.309 (6) Å], even than for (I). This provides strong support for primarily hydroxyimine character. Interestingly, the two C—N and C═O bond lengths for the two partner molecules in (II) are the same, within experimental error. This is despite the fact that the two component molecules were refined freely, and similarity restraints (SADI in SHELXL97; Sheldrick, 2008) were applied only for the amide moieties of the major (3/4) and minor (1/4) diastereomers, where they occupy the same crystallographic coordinates.

A search of the CSD for bond lengths of doubly hydrogen-bonded amides revealed that of those amides (2091 hits), 89% had C═O bonds in the range 1.22–1.26 Å (Fig. 7a), and 95% had C—N bonds in the range 1.32–1.40 Å. Amongst the outliers, only two cases (highlighted with shading in Fig. 7b) had C—N and C═O bond lengths (<1.31 Å and >1.30 Å, respectively) that come close to those observed for lactam (II) (Antoniadis et al., 2005; Romero & Woerpel, 2006).

A referee has rightly questioned the wisdom of placing too much emphasis on these differences, given the poor data quality for (II). However, the untypical values indicated for the bond lengths of the cyclic amide entity in (II) suggest its occurrence as the hydroxyimine (enol) tautomer (cf. Fig. 6), and consequently infer an example of intermolecular tautomerism in the crystal structure. This possibility should be investigated further. Such an intermolecular exchange of H atoms in the crystal structure was recently described in the study of 1H,2H-indazolin-3-one dimers, where O was hydrogen-bonded to O and N to N (enol form to keto form) (Perez-Torralba et al., 2010). The source of such a preference for the hydroxyimine structure of this heterocyclic portion of the N5-acyl derivative, (II), remains unknown but it might be brought about by the unique additional intermolecular interactions observed between the acyl side-chain elements in the crystal structure. Resolution of this matter requires further structural studies on similar molecules but this fell outside the bounds of the current investigation.

Related literature

For related literature, see: Allen (2002); Antoniadis et al. (2005); Clemo et al. (1924); Cohen et al. (1993); Giani et al. (1985); Kassiou et al. (1997); Perez-Torralba, Lopez, Perez-Medina, Claramunt, Pinilla, Torres, Alkorta & Elguero (2010); Romero & Woerpel (2006); Sheldrick (2008); Wei & Weigele (1984).

S2. Experimental

Compound (I) was prepared as described previously (Clemo et al., 1924; Giani et al., 1985). It was recrystallized from EtOH–EtOAc [Solvent ratio?] to yield yellow–green rhombic and hexagonal plates [m.p. 532–534 K; literature m.p. 529–530 K (Giani et al., 1985)].

For the preparation of (II), 5-(2-chloroacetyl)-5H-dibenzo[b,e][1,4]diazepin- 11(10H)-one (254 mg, 0.886 mmol) and 4-[3-(1H-imidazol-1-yl)propyl]piperidine (180 mg, 0.93 mmol) were dissolved together in anhydrous MeCN (2 ml). [5-(2-Chloroacetyl)-5H-dibenzo[b,e][1,4]diazepin-11(10H)-one was synthesized from (I) and 2-chloroacetyl chloride as described by Cohen et al. (1993). The preparation of 4-[3-(1H-imidazol-1-yl)propyl]piperidine was reported by Wei & Weigele (1984), but a different synthetic route was used. A description of the synthetic route for (II), general experimental conditions, experimental protocols and analytical data for all intermediates for the preparation of (II), as well as ¹H and ¹³C NMR spectra of (II) and all intermediates, are provided as Supplementary materials. [Please supply]

Finely ground potassium carbonate (122 mg, 0.886 mmol) was added to the above mixture and the whole kept under stirring in a microwave reactor (Biotage Initiator 8) at 373 K (microwave power?, pressure ca 2 bar; 1 bar = 100 000 Pa) for 100 min. Solid material was removed by filtration, the filtrate evaporated to dryness and the residue subjected to column chromatography using mixtures of CH₂Cl₂, Et₂O and MeOH as solvent. The major fraction (CH₂Cl₂–Et₂O–MeOH 20:4:1 to 10:2:1) was evaporated to dryness under reduced pressure, then taken up in CH₂Cl₂ (0.5 ml) and pentane (0.8 ml). Removal of the solvent in vacuo afforded the product, 5-(2-{4-[3-(1H-imidazol-1-yl)propyl]piperidin-1-yl}ethanoyl)-5H-benzo[b,e]diazepin-11(10H)-one, as a pale-tan glass (yield 187 mg, 48%; m.p. 368–370 K). R_F = 0.4 (CH₂Cl₂–MeOH 5:1). IR (Nujol): 1660, 1600 cm^-1.

A portion (150 mg) of this material was dissolved in EtOH (0.8 ml), Et₂O (1 ml) was added, and the solution was kept at 253 K to afford white rosettes (ca 100 mg), which were kept in vacuo at 353 K for 7 h. Separation of the mother liquor and storage at 253 K afforded the ethanol solvate of the same substance, (II), as translucent needles (10 mg; m.p. 371–373 K) that were suitable for X-ray crystallographic analysis (contained one equivalent of cocrystallized EtOH, as evident from NMR spectroscopic and X-ray crystallographic analyses). Analysis, calculated for C₂₆H₂₉N₅O₂.C₂H₆O: C 68.83, H 7.01, N 14.33%; found: C 68.78, H 7.13, N 14.18%.

Due to a slow rotation about the exocyclic amide group on the NMR time scale, two isomers (ratio 1:1) were evident in the NMR spectra of (II). ¹H NMR (700 MHz, [D₄]MeOH, δ, p.p.m.): 1.00–1.11 (m, 1H), 1.12–1.30 (m, 6.5H), 1.49 (d, 0.5H, J = 11.8 Hz), 1.56 (m, 1H), 1.64 (d, 0.5H, J = 12.2 Hz), 1.79 (m, 2H), 1.90–2.04 (m, 2H), 2.50 (d, 0.5H, J = 9.5 Hz), 2.65 (d, 0.5H, J = 10.1 Hz), 2.82 (d, 1H, J = 10.2 Hz), 2.85 (d, 1H, J = 10.2 Hz), 3.06 (m, 0.5H), 3.16 (m, 0.5H), 3.20–3.25 (m, 1H), 3.64 (q, 1.3H, J = 7.1 Hz), 4.01 (t, 2H, J = 7.0 Hz), 6.97 (t, 1H, J = ca 0.9 Hz), 7.13 (t, 1H, J = ca 1.1 Hz), 7.23–7.31 (m, 2H), 7.36 (t, 0.5H, J = 7.2 Hz), 7.42 (t, 0.5H, J = 7.4 Hz), 7.46–7.52 (m, 1.5H), 7.54 (t, 0.5H, J = 7.4 Hz), 7.58 (t, 1H, J = 7.7 Hz), 7.65 (s, 1H), 7.68 (m, 1H), 7.89 (d, 0.5H, J = 7.5 Hz), 7.92 (d, 0.5H, J = 7.4 Hz). ¹H NMR [600 MHz, [D₆]DMSO–D₂O 15:1 (v/v), rosettes, δ, p.p.m.]: 0.64–0.79 (m, 1H), 0.92–1.10 (m, 4H), 1.24–1.48 (m, 2H), 1.62 (m, 2H), 1.73–1.86 (m, 2H), 2.11 (d, 0.5H, J = 10.0 Hz), 2.66 (d, 0.5H, J = 10.1 Hz), 2.57 (m, 1H), 2.86 (d, 0.5H, J = 14.3 Hz), 2.93 (d, 0.5H, J = 14.5 Hz), 3.11 (d, 0.5H, J = 14.5 Hz), 3.29 (d, 0.5H, J = 14.3 Hz), 3.88 (br s, 2H), 6.86 (s, 1H), 7.13 (s, 1H), 7.14–7.23 (m, 2H), 7.25–7.32 (m, 1H), 7.37–7.46 (m, 2H), 7.54–7.63 (m, 3H), 7.73–7.79 (m, 1H). ¹³C NMR [150 MHz, [D₆]DMSO–D₂O 15:1 (v/v), rosettes, δ, p.p.m.; provided that adjacent signals in the ¹³C NMR spectra could be unambiguously clarified (using ¹H COSY and HSQC spectra) to arise from one carbon nucleus, these signals are depicted as a set of signals (e.g. 123.7/123.9 p.p.m.)]: 28.1, 31.3/31.67/31.74/31.9, 32.9, 34.4/34.5, 46.5, 52.8/53.0/53.36/53.41, 60.3/60.8, 119.6, 121.7/121.8, 124.9/125.2, 126.4, 127.5, 128.17, 128.24, 128.30, 128.37, 128.5/128.9, 129.2, 130.2, 130.7, 130.8, 132.9/133.2, 134.6, 134.9, 135.0, 135.8, 137.4, 142.6/142.9, 166.8, 169.0/169.4. MS (ESI, MeOH) m/z (%) 887 (8) [2M + H]⁺, 444 (100) [M + H]⁺. HRMS (ESI, MeOH) m/z, calculated for [C₂₆H₃₀N₅O₂]⁺: 444.2394; found: 444.2390. C₂₆H₂₉N₅O₂ (443.5).

S3. Refinement

For (I), the H atom on N1 [and that on N2?] was [were?] allowed to refine freely without using the stereochemical constraints available in the riding-model option in SHELX97 (Sheldrick, 2008). For (II), the O-bound H atom was located in a difference map and treated as riding, with O—H = 0.82 Å and with U_iso(H) = 1.5U_eq(O). For both compounds, C-bound H atoms were positioned geometrically and treated as riding, with C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C). [Please check added text]

Crystals of (II), in the form of thin plates, diffracted weakly (37% of the reflections were observed), as reflected in the higher values of R_int (0.148), final weighted R factor (0.294) and R factor (0.098). The final difference Fourier contained two strong peaks (1.4 e Å^-3) between hydrogen-bonded N/O pairs N1A···O1B and N1B···O1A, which as H atoms were not stable in the least-squares refinement. Therefore, H atoms with half-occupancy each were fixed on atoms O1A and O1B (as the C13—O lengths were > 1.30 A). The final difference Fourier still contained two strong peaks (1.4 Å^-3) near the centres of the N···O pairs. These were interpreted as traces of O atoms arising from the diastereomeric disorder. This disorder implied that a pair of hydrogen-bonded diasteromers occupied the same location, keeping the positions of all atoms unchanged, and only affecting the positions of atoms N1A/C13A/O1A and N1B/C13B/O1B. The structure was refined with this disorder model, in which alternative positions of N1A/C13A and N1B/C13B overlap with C13A'/N1A' and C13B'/N1B', respectively. At the same time, new positions were generated for atoms O1A' and O1B', accounting for the electron density observed in the difference Fourier map. The full-matrix least-squares refinement thus modelled did not contain any significant residual electron density and the ratio of the two diastereomers converged to 0.75:0.25.

In (II), the crystal lattice contained two ethanol solvent molecules, of which one was found to be orientationally disordered over two positions, viz. C1E/C2E/O1E and C1E'/C2E'/O1E'. In this model, atoms C2E and C2E' and the H atoms of O1E and O1E'(H1E) shared common positions, respectively. SADI restraints were applied to keep the bond lengths in the two positions similar (s.u. = 0.01 Å). Restraints DELU (0.008) and SIMU (0.008) were applied to keep the atomic displacement parameters of atoms in both the positions similar and within reasonable limits.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: APEX2 (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of dibenzodiazepinone (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. The molecular structure of dibenzodiazepinone (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 3. (a) Perpendicular and (c) parallel views of the dimeric unit in (I) [symmetry code: (i) -x+1, -y, -z+1], and (b) perpendicular and (b) parallel views of the dimeric unit in (II) [symmetry codes: (ii) x-1, y, z; (iii) x+1, y+1, z]. Only the major contributing diastereomeric pair is shown for (II). Displacement ellipsoids are drawn at the 40% probability level and dotted lines indicate hydrogen bonds.
	Fig. 4. Overlay of the near identical components of the diastereomeric pair A (light; pale green in the electronic version of the paper) and B (dark; dark green) for (II), in accordance with Figs. 4(b), 4(d) and 7(b).
	Fig. 5. The crystal packing of molecules in the unit cells of (a) (I) [symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, y+1/2, -z+1/2; (iii) x, -y+1/2, z+1/2; (iv) -x+1, -y+1, -z+1] and (b) (II) [symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z; (iii) x+1, y+1, z]. Significant intermolecular interactions are indicated (dotted lines).
	Fig. 6. Possible mesomeric and tautomeric structures of the dibenzodiazepinone amide group.
	Fig. 7. Cambridge Structural Database search for doubly bridged N—H···O-bonded amide dimers (1924 hits). Medial carbonyl bond length (a, a') = 1.235 Å.

(I) 5H-dibenzo[b,e]diazepin-11(10H)-one

Crystal data

C13H10N2O	F(000) = 440
Mr = 210.23	Dx = 1.393 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 872 reflections
a = 7.4767 (16) Å	θ = 2.8–24.2°
b = 10.861 (2) Å	µ = 0.09 mm^−1
c = 12.475 (2) Å	T = 147 K
β = 98.277 (6)°	Hexagonal plate, green
V = 1002.5 (3) Å^3	0.28 × 0.25 × 0.07 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	1698 independent reflections
Radiation source: fine-focus sealed tube	1161 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ϕ scans, and ω scans with κ offsets	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −8→8
Tmin = 0.975, Tmax = 0.994	k = −12→12
6162 measured reflections	l = −8→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0518P)^2 + 0.3703P] where P = (Fo^2 + 2Fc^2)/3
1698 reflections	(Δ/σ)max < 0.001
153 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1	0.6631 (2)	0.01813 (15)	0.41768 (14)	0.0357 (5)
N1	0.4645 (3)	0.16498 (17)	0.44435 (17)	0.0286 (5)
H1N	0.392 (3)	0.106 (2)	0.502 (2)	0.040 (7)*
N2	0.4677 (3)	0.35066 (19)	0.27848 (17)	0.0279 (5)
C1	0.9002 (3)	0.1774 (2)	0.3407 (2)	0.0314 (6)
H1	0.9521	0.1128	0.3863	0.038*
C2	1.0033 (4)	0.2348 (3)	0.2735 (2)	0.0365 (7)
H2	1.1258	0.2116	0.2735	0.044*
C3	0.9266 (4)	0.3272 (2)	0.2056 (2)	0.0391 (7)
H3	0.9952	0.3652	0.1563	0.047*
C4	0.7517 (4)	0.3644 (2)	0.2090 (2)	0.0339 (7)
H4	0.7018	0.4287	0.1625	0.041*
C5	0.6455 (3)	0.3097 (2)	0.27932 (19)	0.0268 (6)
C6	0.3950 (3)	0.3754 (2)	0.37451 (19)	0.0240 (6)
C7	0.3124 (3)	0.4885 (2)	0.3868 (2)	0.0276 (6)
H7	0.3138	0.5501	0.3329	0.033*
C8	0.2288 (3)	0.5122 (2)	0.4760 (2)	0.0309 (6)
H8	0.1715	0.5892	0.4830	0.037*
C9	0.2285 (3)	0.4226 (2)	0.5558 (2)	0.0316 (6)
H9	0.1715	0.4385	0.6177	0.038*
C10	0.3109 (3)	0.3113 (2)	0.5446 (2)	0.0299 (6)
H10	0.3108	0.2503	0.5992	0.036*
C11	0.3939 (3)	0.2869 (2)	0.45485 (19)	0.0245 (6)
C12	0.6121 (3)	0.1287 (2)	0.4049 (2)	0.0274 (6)
C13	0.7191 (3)	0.2114 (2)	0.34418 (19)	0.0262 (6)
H2N	0.439 (3)	0.406 (3)	0.226 (2)	0.041 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0494 (12)	0.0189 (10)	0.0408 (11)	0.0023 (8)	0.0130 (9)	0.0015 (8)
N1	0.0380 (13)	0.0173 (11)	0.0308 (13)	−0.0033 (9)	0.0056 (10)	0.0025 (9)
N2	0.0374 (13)	0.0250 (12)	0.0209 (12)	0.0011 (10)	0.0032 (10)	0.0051 (9)
C1	0.0401 (16)	0.0215 (14)	0.0312 (15)	−0.0002 (11)	0.0001 (12)	−0.0082 (11)
C2	0.0318 (15)	0.0372 (17)	0.0407 (17)	−0.0062 (12)	0.0061 (13)	−0.0107 (13)
C3	0.0474 (18)	0.0337 (17)	0.0388 (17)	−0.0109 (14)	0.0146 (14)	−0.0040 (13)
C4	0.0444 (17)	0.0248 (15)	0.0339 (16)	−0.0036 (12)	0.0108 (13)	0.0001 (11)
C5	0.0338 (14)	0.0222 (14)	0.0236 (14)	−0.0037 (11)	0.0014 (11)	−0.0063 (11)
C6	0.0278 (13)	0.0214 (13)	0.0218 (14)	−0.0055 (10)	−0.0003 (10)	0.0003 (10)
C7	0.0304 (14)	0.0207 (13)	0.0300 (14)	−0.0039 (11)	−0.0006 (11)	0.0038 (11)
C8	0.0284 (14)	0.0249 (14)	0.0385 (17)	−0.0003 (11)	0.0020 (12)	−0.0031 (12)
C9	0.0310 (15)	0.0369 (16)	0.0277 (15)	−0.0041 (12)	0.0064 (12)	−0.0030 (12)
C10	0.0340 (15)	0.0262 (14)	0.0296 (15)	−0.0055 (11)	0.0051 (12)	0.0046 (11)
C11	0.0277 (13)	0.0193 (13)	0.0262 (14)	−0.0059 (10)	0.0023 (11)	0.0010 (10)
C12	0.0356 (15)	0.0208 (14)	0.0244 (14)	−0.0038 (11)	0.0002 (11)	−0.0034 (10)
C13	0.0357 (15)	0.0175 (13)	0.0248 (14)	−0.0040 (10)	0.0024 (11)	−0.0052 (10)

Geometric parameters (Å, º)

O1—C12	1.263 (3)	C4—C5	1.397 (3)
N1—C12	1.331 (3)	C4—H4	0.9500
N1—C11	1.439 (3)	C5—C13	1.404 (3)
N1—H1N	1.15 (3)	C6—C11	1.389 (3)
N2—C5	1.400 (3)	C6—C7	1.393 (3)
N2—C6	1.411 (3)	C7—C8	1.377 (3)
N2—H2N	0.89 (3)	C7—H7	0.9500
C1—C2	1.368 (4)	C8—C9	1.392 (4)
C1—C13	1.410 (3)	C8—H8	0.9500
C1—H1	0.9500	C9—C10	1.374 (3)
C2—C3	1.383 (4)	C9—H9	0.9500
C2—H2	0.9500	C10—C11	1.382 (3)
C3—C4	1.375 (4)	C10—H10	0.9500
C3—H3	0.9500	C12—C13	1.482 (3)
C12—N1—C11	129.9 (2)	C7—C6—N2	119.5 (2)
C12—N1—H1N	123.6 (13)	C8—C7—C6	120.9 (2)
C11—N1—H1N	104.1 (13)	C8—C7—H7	119.6
C5—N2—C6	122.4 (2)	C6—C7—H7	119.6
C5—N2—H2N	110.4 (17)	C7—C8—C9	119.7 (2)
C6—N2—H2N	114.5 (18)	C7—C8—H8	120.1
C2—C1—C13	121.9 (2)	C9—C8—H8	120.1
C2—C1—H1	119.1	C10—C9—C8	119.7 (2)
C13—C1—H1	119.1	C10—C9—H9	120.2
C1—C2—C3	119.1 (3)	C8—C9—H9	120.2
C1—C2—H2	120.5	C9—C10—C11	120.7 (2)
C3—C2—H2	120.5	C9—C10—H10	119.6
C4—C3—C2	120.4 (3)	C11—C10—H10	119.6
C4—C3—H3	119.8	C10—C11—C6	120.2 (2)
C2—C3—H3	119.8	C10—C11—N1	117.6 (2)
C3—C4—C5	121.6 (3)	C6—C11—N1	122.0 (2)
C3—C4—H4	119.2	O1—C12—N1	119.1 (2)
C5—C4—H4	119.2	O1—C12—C13	117.7 (2)
C4—C5—N2	119.0 (2)	N1—C12—C13	123.1 (2)
C4—C5—C13	118.3 (2)	C5—C13—C1	118.6 (2)
N2—C5—C13	122.6 (2)	C5—C13—C12	124.1 (2)
C11—C6—C7	118.8 (2)	C1—C13—C12	116.7 (2)
C11—C6—N2	121.6 (2)
C13—C1—C2—C3	−1.3 (4)	N2—C6—C11—C10	−175.7 (2)
C1—C2—C3—C4	2.8 (4)	C7—C6—C11—N1	175.4 (2)
C2—C3—C4—C5	−0.9 (4)	N2—C6—C11—N1	−0.7 (3)
C3—C4—C5—N2	−179.4 (2)	C12—N1—C11—C10	−144.3 (3)
C3—C4—C5—C13	−2.6 (4)	C12—N1—C11—C6	40.7 (4)
C6—N2—C5—C4	−134.3 (2)	C11—N1—C12—O1	169.8 (2)
C6—N2—C5—C13	49.0 (3)	C11—N1—C12—C13	−11.5 (4)
C5—N2—C6—C11	−56.1 (3)	C4—C5—C13—C1	4.1 (3)
C5—N2—C6—C7	127.8 (2)	N2—C5—C13—C1	−179.3 (2)
C11—C6—C7—C8	−0.9 (3)	C4—C5—C13—C12	−166.9 (2)
N2—C6—C7—C8	175.3 (2)	N2—C5—C13—C12	9.8 (4)
C6—C7—C8—C9	0.8 (3)	C2—C1—C13—C5	−2.2 (4)
C7—C8—C9—C10	−0.3 (4)	C2—C1—C13—C12	169.4 (2)
C8—C9—C10—C11	−0.1 (4)	O1—C12—C13—C5	148.0 (2)
C9—C10—C11—C6	0.1 (4)	N1—C12—C13—C5	−30.7 (4)
C9—C10—C11—N1	−175.1 (2)	O1—C12—C13—C1	−23.1 (3)
C7—C6—C11—C10	0.4 (3)	N1—C12—C13—C1	158.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	1.15 (3)	1.77 (3)	2.881 (3)	161 (2)
C10—H10···N2^ii	0.95	2.61	3.463 (3)	149
N2—H2N···O1^iii	0.89 (3)	2.21 (3)	3.093 (3)	170 (2)
C7—H7···C1^iii	0.95	2.86	3.673 (3)	145

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

(II) 1-(11-hydroxy-5H-dibenzo[b,e]diazepin-5-yl)-2- {4-[3-(1H-imidazol-1-yl)propyl]piperidin-1-yl}ethanone ethanol monosolvate

Crystal data

C26H29N5O2·C2H6O	Z = 4
Mr = 489.61	F(000) = 1048
Triclinic, P1	Dx = 1.215 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7319 (8) Å	Cell parameters from 1679 reflections
b = 16.0343 (16) Å	θ = 2.5–17.8°
c = 19.2802 (18) Å	µ = 0.08 mm^−1
α = 93.029 (5)°	T = 293 K
β = 95.427 (5)°	Plate, colourless
γ = 93.662 (5)°	0.22 × 0.13 × 0.08 mm
V = 2677.1 (4) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	9341 independent reflections
Radiation source: fine-focus sealed tube	3471 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.143
ϕ scans, and ω scans with κ offsets	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→10
Tmin = 0.983, Tmax = 0.994	k = −19→19
35426 measured reflections	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.086	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.270	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.1212P)^2] where P = (Fo^2 + 2Fc^2)/3
9341 reflections	(Δ/σ)max < 0.001
690 parameters	Δρmax = 0.50 e Å^−3
88 restraints	Δρmin = −0.67 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Crystals of 2, in the form of thin plates, diffracted weakly (37% of the reflections were observed) as reflected in higher values of Rint (0.143), final weighted R factor (0.270) and R factor (0.086). The final difference Fourier contained two strong peaks ( 1.4 eA-3) between hydrogen bonded nitrogen and oxygen pairs N1A ···O1B and N1B···O1A, which as H-atoms were not stable in the least-squares refinement. Therefore, H-atoms with half occupancy each were fixed on the oxygens O1A, O1B (as C13-O lengths were > 1.30?A). The final difference Fourier still contained two strong peaks ( 1.4 eA-3) near the centres of the N···O pairs.These have been interpreted as the traces of oxygen atoms that arise from the diastereomeric disorder. This disorder implied that a pair of hydrogen bonded diasteromers occupied the same location, keeping positions of all atoms unchanged, and only affecting positions of N1A, C13A, O1A and N1B, C13B, O1B. The structure was refined with this disorder model, in which alternative positions of N1A, C13A and N1B, C13B overlap with C13A', N1A' and C13B' and N1B', respectively. At the same time, new positions were generated for oxygen atoms O1A' and O1B', accounting for the electron density observed in the difference Fourier. The full-matrix least-squares refinement thus modelled did not contain any significant residual electron density and the ratio of two diastereomers converged to 75: 25.

Crystal lattice contained two solvent (ethanol) molecules, ofwhich one was found to be orientationally disordered over two positions C1E, C2E and O1E and C1E', C2E' and O1E'. In this model, atoms C2E and C2E' and the H-atoms of the O1E and O1E'(H1E) shared common positions respectively. SADI restraints were applied to keep the bond lengths in the two positions similar (with s.u. 0.01).Restraints DELU (0.008) and SIMU (0.008) were applied to keep the atomic displacement parameters of atoms in both the positions similar and within reasonable limits.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1A	0.2827 (7)	0.2274 (3)	0.4720 (4)	0.0470 (16)
H1A	0.1926	0.2233	0.4419	0.056*
C2A	0.2816 (8)	0.1983 (4)	0.5376 (4)	0.0569 (19)
H2A	0.1902	0.1748	0.5516	0.068*
C3A	0.4143 (8)	0.2035 (3)	0.5834 (3)	0.0480 (17)
H3A	0.4126	0.1837	0.6278	0.058*
C4A	0.5506 (7)	0.2390 (3)	0.5618 (3)	0.0404 (15)
H4A	0.6409	0.2431	0.5918	0.048*
C5A	0.5508 (6)	0.2678 (3)	0.4958 (3)	0.0323 (14)
N2A	0.6895 (5)	0.3058 (3)	0.4734 (2)	0.0298 (11)
C7A	0.6866 (6)	0.3931 (3)	0.4629 (3)	0.0292 (13)
C8A	0.7850 (6)	0.4510 (3)	0.5034 (3)	0.0327 (14)
H8A	0.8541	0.4329	0.5382	0.039*
C9A	0.7821 (7)	0.5360 (4)	0.4930 (3)	0.0404 (15)
H9A	0.8502	0.5745	0.5199	0.048*
C10A	0.6774 (6)	0.5623 (4)	0.4425 (3)	0.0385 (15)
H10A	0.6729	0.6192	0.4360	0.046*
C11A	0.5792 (7)	0.5055 (4)	0.4014 (3)	0.0430 (16)
H11A	0.5091	0.5244	0.3674	0.052*
C12A	0.5836 (6)	0.4201 (3)	0.4103 (3)	0.0308 (13)
C13A	0.4814 (6)	0.3605 (4)	0.3624 (3)	0.0407 (15)	0.751 (4)
N1A	0.4141 (5)	0.2918 (3)	0.3809 (2)	0.0353 (12)	0.751 (4)
O1A	0.4552 (5)	0.3875 (3)	0.2997 (2)	0.0345 (14)	0.751 (4)
H1A1	0.3986	0.3528	0.2751	0.052*	0.751 (4)
C13'	0.4141 (5)	0.2918 (3)	0.3809 (2)	0.0353 (12)	0.249 (4)
N1A'	0.4814 (6)	0.3605 (4)	0.3624 (3)	0.0407 (15)	0.249 (4)
O1A'	0.3156 (13)	0.2353 (7)	0.3470 (6)	0.036 (2)	0.249 (4)
H1A'	0.3043	0.2455	0.3057	0.054*	0.249 (4)
O2A	0.9346 (4)	0.2999 (2)	0.4447 (2)	0.0434 (11)
N3A	0.6746 (5)	0.1347 (3)	0.4094 (2)	0.0319 (11)
N4A	0.2242 (7)	−0.1338 (3)	0.1328 (2)	0.0457 (13)
N5A	0.0200 (7)	−0.2170 (4)	0.1512 (3)	0.0642 (16)
C14A	0.4168 (6)	0.2627 (3)	0.4507 (3)	0.0360 (14)
C15A	0.8181 (7)	0.2631 (3)	0.4600 (3)	0.0349 (14)
C16A	0.7981 (6)	0.1685 (3)	0.4613 (3)	0.0374 (15)
H16A	0.8936	0.1444	0.4518	0.045*
H16B	0.7742	0.1533	0.5073	0.045*
C17A	0.7257 (6)	0.1367 (3)	0.3394 (3)	0.0394 (15)
H17A	0.8109	0.1012	0.3362	0.047*
H17B	0.7622	0.1934	0.3312	0.047*
C18A	0.5965 (6)	0.1071 (3)	0.2841 (3)	0.0395 (15)
H18A	0.6346	0.1078	0.2385	0.047*
H18B	0.5145	0.1451	0.2851	0.047*
C19A	0.5322 (7)	0.0185 (3)	0.2958 (3)	0.0422 (16)
H19A	0.6156	−0.0192	0.2930	0.051*
C20A	0.4845 (7)	0.0199 (3)	0.3700 (3)	0.0432 (16)
H20A	0.4481	−0.0362	0.3801	0.052*
H20B	0.3999	0.0558	0.3733	0.052*
C21A	0.6175 (7)	0.0513 (3)	0.4241 (3)	0.0412 (15)
H21A	0.5824	0.0523	0.4704	0.049*
H21B	0.7000	0.0137	0.4231	0.049*
C22A	0.3998 (7)	−0.0134 (4)	0.2420 (3)	0.0469 (16)
H22A	0.3237	0.0280	0.2393	0.056*
H22B	0.3510	−0.0641	0.2578	0.056*
C23A	0.4478 (7)	−0.0322 (4)	0.1691 (3)	0.0526 (17)
H23A	0.5013	0.0175	0.1540	0.063*
H23B	0.5192	−0.0761	0.1710	0.063*
C24A	0.3126 (8)	−0.0592 (4)	0.1163 (3)	0.0537 (18)
H24A	0.2446	−0.0138	0.1125	0.064*
H24B	0.3505	−0.0691	0.0711	0.064*
C25A	0.2757 (10)	−0.2108 (4)	0.1446 (3)	0.060 (2)
H25A	0.3766	−0.2261	0.1447	0.072*
C26A	0.1514 (10)	−0.2602 (4)	0.1561 (3)	0.062 (2)
H26A	0.1539	−0.3163	0.1661	0.074*
C27A	0.0702 (9)	−0.1425 (4)	0.1378 (3)	0.0523 (18)
H27A	0.0062	−0.0986	0.1321	0.063*
C1B	0.2282 (7)	0.4230 (4)	0.1298 (4)	0.0559 (18)
H1B	0.2572	0.4526	0.1723	0.067*
C2B	0.1871 (8)	0.4660 (4)	0.0727 (4)	0.066 (2)
H2B	0.1903	0.5242	0.0762	0.079*
C3B	0.1396 (8)	0.4222 (4)	0.0082 (4)	0.062 (2)
H3B	0.1073	0.4510	−0.0306	0.074*
C4B	0.1416 (7)	0.3362 (4)	0.0030 (3)	0.0493 (17)
H4B	0.1107	0.3064	−0.0392	0.059*
C5B	0.1902 (6)	0.2948 (3)	0.0616 (3)	0.0376 (14)
C7B	0.0948 (7)	0.1576 (3)	0.0918 (3)	0.0376 (15)
C8B	−0.0136 (7)	0.1020 (4)	0.0548 (3)	0.0465 (16)
H8B	−0.0180	0.0972	0.0064	0.056*
C9B	−0.1156 (8)	0.0535 (4)	0.0884 (4)	0.063 (2)
H9B	−0.1881	0.0167	0.0622	0.076*
C10B	−0.1123 (9)	0.0585 (4)	0.1580 (5)	0.068 (2)
H10B	−0.1813	0.0247	0.1798	0.082*
C11B	−0.0072 (9)	0.1133 (5)	0.1970 (4)	0.061 (2)
H11B	−0.0049	0.1164	0.2454	0.073*
C12B	0.0990 (7)	0.1659 (4)	0.1640 (3)	0.0411 (15)
C13B	0.2127 (8)	0.2237 (4)	0.2071 (3)	0.0574 (18)	0.751 (4)
N1B	0.2738 (6)	0.2948 (4)	0.1884 (3)	0.0442 (13)	0.751 (4)
O1B	0.2383 (5)	0.1971 (3)	0.2699 (2)	0.0383 (14)	0.751 (4)
H1B1	0.3016	0.2298	0.2933	0.057*	0.751 (4)
C13"	0.2738 (6)	0.2948 (4)	0.1884 (3)	0.0442 (13)	0.249 (4)
N1B'	0.2127 (8)	0.2237 (4)	0.2071 (3)	0.0574 (18)	0.249 (4)
O1B'	0.3615 (15)	0.3594 (8)	0.2192 (7)	0.046 (2)	0.249 (4)
H1B'	0.3997	0.3467	0.2573	0.070*	0.249 (4)
O2B	0.3131 (5)	0.0925 (2)	0.0165 (2)	0.0523 (12)
N3B	0.5202 (5)	0.2769 (3)	0.0553 (2)	0.0375 (12)
N4B	1.0497 (6)	0.5129 (3)	0.3226 (2)	0.0412 (12)
N5B	1.0864 (7)	0.6516 (3)	0.3218 (3)	0.0528 (14)
C14B	0.2278 (7)	0.3372 (4)	0.1263 (3)	0.0433 (16)
C15B	0.3129 (7)	0.1683 (4)	0.0220 (3)	0.0383 (15)
C16B	0.4387 (7)	0.2250 (4)	−0.0027 (3)	0.0442 (16)
H16C	0.5112	0.1914	−0.0247	0.053*
H16D	0.3940	0.2606	−0.0372	0.053*
C17B	0.6262 (7)	0.2280 (4)	0.0972 (3)	0.0507 (17)
H17C	0.7088	0.2121	0.0700	0.061*
H17D	0.5716	0.1772	0.1097	0.061*
N2B	0.2007 (5)	0.2057 (3)	0.0559 (2)	0.0364 (12)
C18B	0.6931 (7)	0.2783 (3)	0.1624 (3)	0.0444 (16)
H18C	0.7679	0.2462	0.1878	0.053*
H18D	0.6113	0.2880	0.1920	0.053*
C19B	0.7707 (6)	0.3621 (3)	0.1476 (3)	0.0413 (15)
H19B	0.8623	0.3510	0.1238	0.050*
C20B	0.6622 (7)	0.4058 (4)	0.0982 (3)	0.0528 (18)
H20C	0.5769	0.4233	0.1229	0.063*
H20D	0.7164	0.4557	0.0839	0.063*
C21B	0.5992 (8)	0.3527 (4)	0.0343 (3)	0.0580 (19)
H21C	0.5278	0.3835	0.0056	0.070*
H21D	0.6826	0.3383	0.0070	0.070*
C22B	0.8233 (7)	0.4160 (4)	0.2141 (3)	0.0445 (16)
H22C	0.8690	0.4689	0.2011	0.053*
H22D	0.7330	0.4280	0.2376	0.053*
C23B	0.9374 (7)	0.3789 (4)	0.2654 (3)	0.0484 (17)
H23C	1.0308	0.3706	0.2432	0.058*
H23D	0.8948	0.3244	0.2764	0.058*
C24B	0.9792 (8)	0.4314 (4)	0.3327 (3)	0.0601 (19)
H24C	0.8867	0.4381	0.3560	0.072*
H24D	1.0496	0.4019	0.3630	0.072*
C25B	1.1952 (7)	0.5309 (4)	0.3047 (3)	0.0469 (16)
H25B	1.2666	0.4925	0.2947	0.056*
C26B	1.2157 (8)	0.6147 (4)	0.3043 (3)	0.0517 (17)
H26B	1.3053	0.6437	0.2936	0.062*
C27B	0.9903 (7)	0.5877 (4)	0.3321 (3)	0.0499 (17)
H27B	0.8911	0.5937	0.3446	0.060*
C1E	0.5884 (19)	0.6271 (9)	0.2102 (9)	0.096 (4)	0.50
H1E1	0.5591	0.6178	0.1610	0.145*	0.50
H1E2	0.4977	0.6252	0.2348	0.145*	0.50
H1E3	0.6535	0.5844	0.2258	0.145*	0.50
C2E	0.6696 (13)	0.7068 (8)	0.2237 (6)	0.138 (3)	0.50
H2E1	0.7602	0.7006	0.2558	0.166*	0.50
H2E2	0.6044	0.7437	0.2471	0.166*	0.50
O1E	0.718 (4)	0.7464 (16)	0.1638 (13)	0.118 (5)	0.50
H1E	0.7618	0.7923	0.1760	0.177*
C1E'	0.693 (3)	0.6339 (11)	0.1834 (10)	0.127 (5)	0.50
H1E4	0.7545	0.6481	0.1466	0.190*	0.50
H1E5	0.5948	0.6083	0.1637	0.190*	0.50
H1E6	0.7445	0.5955	0.2125	0.190*	0.50
C2E'	0.6696 (13)	0.7068 (8)	0.2237 (6)	0.138 (3)	0.50
H2E3	0.7445	0.7157	0.2644	0.166*	0.50
H2E4	0.5662	0.7062	0.2382	0.166*	0.50
O1E'	0.694 (4)	0.7673 (18)	0.1731 (14)	0.114 (5)	0.50
O1F	0.0465 (6)	0.8115 (3)	0.3772 (2)	0.0778 (15)
H1F	0.0494	0.7663	0.3555	0.117*
C1F	0.0436 (12)	0.9543 (6)	0.3619 (6)	0.145 (5)
H1F1	0.0642	0.9943	0.3281	0.218*
H1F2	0.1122	0.9671	0.4036	0.218*
H1F3	−0.0611	0.9565	0.3728	0.218*
C2F	0.0664 (13)	0.8736 (5)	0.3344 (4)	0.117 (4)
H2F1	−0.0040	0.8616	0.2926	0.140*
H2F2	0.1704	0.8736	0.3207	0.140*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.025 (4)	0.042 (4)	0.073 (5)	0.000 (3)	0.009 (3)	−0.007 (3)
C2A	0.034 (4)	0.042 (4)	0.099 (6)	0.001 (3)	0.030 (4)	0.000 (4)
C3A	0.047 (5)	0.045 (4)	0.055 (4)	0.007 (3)	0.023 (4)	0.000 (3)
C4A	0.036 (4)	0.044 (4)	0.042 (4)	0.002 (3)	0.012 (3)	−0.005 (3)
C5A	0.022 (3)	0.042 (3)	0.033 (4)	0.002 (3)	0.007 (3)	−0.003 (3)
N2A	0.017 (3)	0.036 (3)	0.037 (3)	0.003 (2)	0.004 (2)	0.001 (2)
C7A	0.018 (3)	0.043 (4)	0.027 (3)	0.005 (3)	0.005 (3)	−0.001 (3)
C8A	0.023 (3)	0.043 (4)	0.032 (3)	0.004 (3)	0.002 (3)	0.001 (3)
C9A	0.037 (4)	0.047 (4)	0.037 (4)	0.002 (3)	0.009 (3)	−0.003 (3)
C10A	0.027 (4)	0.043 (4)	0.047 (4)	0.007 (3)	0.010 (3)	−0.002 (3)
C11A	0.033 (4)	0.057 (4)	0.043 (4)	0.022 (3)	0.006 (3)	0.013 (3)
C12A	0.022 (3)	0.044 (4)	0.026 (3)	0.008 (3)	0.002 (3)	−0.004 (3)
C13A	0.022 (3)	0.059 (4)	0.040 (4)	0.009 (3)	0.002 (3)	−0.013 (3)
N1A	0.032 (3)	0.045 (3)	0.028 (3)	0.005 (2)	−0.001 (2)	−0.008 (2)
O1A	0.033 (3)	0.034 (3)	0.032 (3)	−0.002 (2)	−0.009 (2)	−0.002 (2)
C13'	0.032 (3)	0.045 (3)	0.028 (3)	0.005 (2)	−0.001 (2)	−0.008 (2)
N1A'	0.022 (3)	0.059 (4)	0.040 (4)	0.009 (3)	0.002 (3)	−0.013 (3)
O1A'	0.034 (5)	0.051 (5)	0.022 (4)	0.007 (4)	−0.004 (4)	−0.009 (4)
O2A	0.019 (2)	0.049 (3)	0.066 (3)	0.0053 (19)	0.014 (2)	0.012 (2)
N3A	0.026 (3)	0.035 (3)	0.037 (3)	0.002 (2)	0.011 (2)	0.005 (2)
N4A	0.061 (4)	0.044 (3)	0.032 (3)	0.007 (3)	0.000 (3)	0.004 (2)
N5A	0.087 (5)	0.053 (4)	0.048 (4)	−0.011 (4)	−0.004 (3)	0.000 (3)
C14A	0.020 (3)	0.039 (3)	0.048 (4)	0.008 (3)	0.005 (3)	−0.012 (3)
C15A	0.027 (4)	0.044 (4)	0.034 (4)	0.012 (3)	−0.002 (3)	0.006 (3)
C16A	0.035 (4)	0.037 (4)	0.042 (4)	0.009 (3)	0.010 (3)	0.005 (3)
C17A	0.038 (4)	0.038 (3)	0.045 (4)	0.004 (3)	0.011 (3)	0.009 (3)
C18A	0.036 (4)	0.044 (4)	0.039 (4)	0.004 (3)	0.007 (3)	0.002 (3)
C19A	0.053 (4)	0.033 (3)	0.045 (4)	0.008 (3)	0.020 (3)	0.005 (3)
C20A	0.045 (4)	0.042 (4)	0.044 (4)	−0.006 (3)	0.018 (3)	0.006 (3)
C21A	0.039 (4)	0.041 (4)	0.047 (4)	0.007 (3)	0.013 (3)	0.007 (3)
C22A	0.045 (4)	0.047 (4)	0.049 (4)	0.000 (3)	0.012 (3)	−0.002 (3)
C23A	0.058 (5)	0.049 (4)	0.050 (4)	−0.002 (3)	0.009 (4)	−0.003 (3)
C24A	0.078 (5)	0.035 (4)	0.049 (4)	−0.003 (3)	0.012 (4)	0.005 (3)
C25A	0.098 (6)	0.041 (4)	0.044 (4)	0.020 (4)	0.009 (4)	0.003 (3)
C26A	0.099 (7)	0.040 (4)	0.047 (5)	0.002 (5)	0.006 (4)	0.008 (3)
C27A	0.062 (5)	0.051 (5)	0.041 (4)	0.011 (4)	−0.006 (4)	−0.006 (3)
C1B	0.048 (5)	0.055 (5)	0.062 (5)	−0.004 (4)	0.005 (4)	−0.013 (4)
C2B	0.063 (5)	0.042 (4)	0.093 (6)	−0.002 (4)	0.025 (5)	−0.015 (4)
C3B	0.063 (5)	0.038 (4)	0.087 (6)	0.007 (3)	0.011 (4)	0.013 (4)
C4B	0.045 (4)	0.054 (4)	0.049 (4)	0.010 (3)	0.002 (3)	0.008 (3)
C5B	0.035 (4)	0.036 (3)	0.042 (4)	0.006 (3)	0.001 (3)	−0.005 (3)
C7B	0.039 (4)	0.038 (3)	0.036 (4)	0.012 (3)	0.004 (3)	0.002 (3)
C8B	0.039 (4)	0.050 (4)	0.051 (4)	0.007 (3)	0.003 (3)	0.008 (3)
C9B	0.043 (5)	0.061 (5)	0.089 (6)	0.018 (4)	0.012 (4)	0.007 (4)
C10B	0.054 (5)	0.055 (5)	0.100 (7)	0.014 (4)	0.026 (5)	0.010 (5)
C11B	0.070 (5)	0.077 (5)	0.050 (4)	0.050 (4)	0.037 (4)	0.025 (4)
C12B	0.041 (4)	0.050 (4)	0.034 (4)	0.021 (3)	0.002 (3)	−0.001 (3)
C13B	0.057 (5)	0.073 (5)	0.044 (4)	0.041 (4)	−0.003 (4)	−0.008 (4)
N1B	0.027 (3)	0.073 (4)	0.032 (3)	0.013 (3)	−0.002 (2)	−0.012 (3)
O1B	0.040 (3)	0.038 (3)	0.032 (3)	−0.010 (2)	−0.009 (3)	−0.003 (2)
C13"	0.027 (3)	0.073 (4)	0.032 (3)	0.013 (3)	−0.002 (2)	−0.012 (3)
N1B'	0.057 (5)	0.073 (5)	0.044 (4)	0.041 (4)	−0.003 (4)	−0.008 (4)
O1B'	0.031 (5)	0.078 (5)	0.030 (5)	0.017 (4)	−0.006 (4)	−0.005 (4)
O2B	0.055 (3)	0.039 (3)	0.067 (3)	0.010 (2)	0.022 (2)	−0.001 (2)
N3B	0.035 (3)	0.039 (3)	0.039 (3)	0.005 (2)	0.002 (2)	0.003 (2)
N4B	0.032 (3)	0.053 (3)	0.039 (3)	0.003 (3)	0.004 (2)	0.005 (2)
N5B	0.055 (4)	0.058 (4)	0.047 (3)	0.017 (3)	0.007 (3)	0.004 (3)
C14B	0.036 (4)	0.047 (4)	0.046 (4)	0.005 (3)	0.003 (3)	−0.016 (3)
C15B	0.037 (4)	0.042 (4)	0.036 (4)	0.012 (3)	0.001 (3)	−0.002 (3)
C16B	0.043 (4)	0.050 (4)	0.042 (4)	0.006 (3)	0.017 (3)	0.006 (3)
C17B	0.036 (4)	0.044 (4)	0.073 (5)	0.013 (3)	0.005 (3)	0.003 (3)
N2B	0.038 (3)	0.041 (3)	0.030 (3)	0.000 (2)	0.006 (2)	−0.002 (2)
C18B	0.035 (4)	0.037 (4)	0.060 (4)	0.003 (3)	−0.007 (3)	0.009 (3)
C19B	0.029 (4)	0.043 (4)	0.054 (4)	0.000 (3)	0.010 (3)	0.015 (3)
C20B	0.058 (5)	0.040 (4)	0.059 (4)	−0.009 (3)	0.002 (4)	0.013 (3)
C21B	0.063 (5)	0.050 (4)	0.060 (5)	−0.017 (4)	0.002 (4)	0.014 (3)
C22B	0.036 (4)	0.049 (4)	0.050 (4)	0.003 (3)	0.007 (3)	0.008 (3)
C23B	0.034 (4)	0.053 (4)	0.058 (4)	−0.004 (3)	−0.002 (3)	0.012 (3)
C24B	0.050 (5)	0.071 (5)	0.058 (5)	−0.008 (4)	−0.004 (4)	0.020 (4)
C25B	0.027 (4)	0.064 (5)	0.049 (4)	0.009 (3)	0.003 (3)	−0.007 (3)
C26B	0.044 (4)	0.061 (5)	0.049 (4)	−0.006 (4)	0.016 (3)	−0.009 (3)
C27B	0.035 (4)	0.074 (5)	0.041 (4)	0.010 (4)	0.003 (3)	0.008 (4)
C1E	0.090 (9)	0.107 (8)	0.104 (9)	0.040 (7)	0.031 (7)	0.035 (7)
C2E	0.124 (5)	0.175 (6)	0.114 (5)	0.004 (5)	−0.008 (4)	0.042 (5)
O1E	0.101 (10)	0.164 (10)	0.085 (7)	−0.013 (9)	−0.017 (6)	0.049 (8)
C1E'	0.127 (10)	0.142 (8)	0.113 (10)	0.026 (9)	−0.017 (8)	0.043 (7)
C2E'	0.124 (5)	0.175 (6)	0.114 (5)	0.004 (5)	−0.008 (4)	0.042 (5)
O1E'	0.088 (9)	0.155 (8)	0.098 (8)	0.002 (8)	−0.014 (7)	0.049 (7)
O1F	0.090 (4)	0.066 (3)	0.078 (4)	0.001 (3)	0.028 (3)	−0.014 (3)
C1F	0.137 (9)	0.098 (8)	0.232 (13)	0.060 (7)	0.105 (9)	0.081 (8)
C2F	0.227 (12)	0.068 (6)	0.061 (6)	−0.015 (7)	0.061 (7)	0.015 (5)

Geometric parameters (Å, º)

C1A—C2A	1.372 (8)	C5B—N2B	1.436 (6)
C1A—C14A	1.375 (7)	C7B—C8B	1.377 (8)
C1A—H1A	0.9300	C7B—C12B	1.388 (7)
C2A—C3A	1.383 (8)	C7B—N2B	1.420 (7)
C2A—H2A	0.9300	C8B—C9B	1.374 (8)
C3A—C4A	1.395 (8)	C8B—H8B	0.9300
C3A—H3A	0.9300	C9B—C10B	1.337 (9)
C4A—C5A	1.375 (7)	C9B—H9B	0.9300
C4A—H4A	0.9300	C10B—C11B	1.371 (9)
C5A—C14A	1.385 (7)	C10B—H10B	0.9300
C5A—N2A	1.435 (6)	C11B—C12B	1.430 (8)
N2A—C15A	1.389 (6)	C11B—H11B	0.9300
N2A—C7A	1.427 (6)	C12B—C13B	1.476 (8)
C7A—C8A	1.380 (7)	C13B—N1B	1.310 (8)
C7A—C12A	1.396 (7)	C13B—O1B	1.310 (6)
C8A—C9A	1.388 (7)	N1B—C14B	1.445 (8)
C8A—H8A	0.9300	O1B—H1B1	0.8200
C9A—C10A	1.374 (7)	O1B'—H1B'	0.8200
C9A—H9A	0.9300	O2B—C15B	1.215 (6)
C10A—C11A	1.374 (8)	N3B—C21B	1.453 (6)
C10A—H10A	0.9300	N3B—C16B	1.458 (7)
C11A—C12A	1.393 (7)	N3B—C17B	1.464 (7)
C11A—H11A	0.9300	N4B—C27B	1.348 (7)
C12A—C13A	1.484 (7)	N4B—C25B	1.365 (7)
C13A—N1A	1.299 (7)	N4B—C24B	1.439 (7)
C13A—O1A	1.309 (6)	N5B—C27B	1.318 (7)
N1A—C14A	1.446 (7)	N5B—C26B	1.369 (7)
O1A—H1A1	0.8200	C15B—N2B	1.380 (7)
O1A'—H1A'	0.8200	C15B—C16B	1.510 (8)
O2A—C15A	1.212 (6)	C16B—H16C	0.9700
N3A—C21A	1.449 (6)	C16B—H16D	0.9700
N3A—C16A	1.455 (6)	C17B—C18B	1.506 (8)
N3A—C17A	1.462 (6)	C17B—H17C	0.9700
N4A—C27A	1.356 (8)	C17B—H17D	0.9700
N4A—C25A	1.363 (7)	C18B—C19B	1.518 (7)
N4A—C24A	1.449 (7)	C18B—H18C	0.9700
N5A—C27A	1.294 (7)	C18B—H18D	0.9700
N5A—C26A	1.375 (8)	C19B—C20B	1.509 (8)
C15A—C16A	1.518 (7)	C19B—C22B	1.525 (7)
C16A—H16A	0.9700	C19B—H19B	0.9800
C16A—H16B	0.9700	C20B—C21B	1.499 (8)
C17A—C18A	1.511 (7)	C20B—H20C	0.9700
C17A—H17A	0.9700	C20B—H20D	0.9700
C17A—H17B	0.9700	C21B—H21C	0.9700
C18A—C19A	1.529 (7)	C21B—H21D	0.9700
C18A—H18A	0.9700	C22B—C23B	1.508 (7)
C18A—H18B	0.9700	C22B—H22C	0.9700
C19A—C22A	1.522 (8)	C22B—H22D	0.9700
C19A—C20A	1.526 (7)	C23B—C24B	1.510 (8)
C19A—H19A	0.9800	C23B—H23C	0.9700
C20A—C21A	1.528 (7)	C23B—H23D	0.9700
C20A—H20A	0.9700	C24B—H24C	0.9700
C20A—H20B	0.9700	C24B—H24D	0.9700
C21A—H21A	0.9700	C25B—C26B	1.345 (8)
C21A—H21B	0.9700	C25B—H25B	0.9300
C22A—C23A	1.523 (7)	C26B—H26B	0.9300
C22A—H22A	0.9700	C27B—H27B	0.9300
C22A—H22B	0.9700	C1E—C2E	1.421 (14)
C23A—C24A	1.510 (8)	C1E—H1E1	0.9600
C23A—H23A	0.9700	C1E—H1E2	0.9600
C23A—H23B	0.9700	C1E—H1E3	0.9600
C24A—H24A	0.9700	C2E—O1E	1.432 (12)
C24A—H24B	0.9700	C2E—H2E1	0.9700
C25A—C26A	1.345 (9)	C2E—H2E2	0.9700
C25A—H25A	0.9300	O1E—H1E	0.8200
C26A—H26A	0.9300	C1E'—H1E4	0.9600
C27A—H27A	0.9300	C1E'—H1E5	0.9600
C1B—C2B	1.362 (9)	C1E'—H1E6	0.9600
C1B—C14B	1.374 (8)	O1F—C2F	1.339 (7)
C1B—H1B	0.9300	O1F—H1F	0.8200
C2B—C3B	1.409 (9)	C1F—C2F	1.405 (10)
C2B—H2B	0.9300	C1F—H1F1	0.9600
C3B—C4B	1.378 (8)	C1F—H1F2	0.9600
C3B—H3B	0.9300	C1F—H1F3	0.9600
C4B—C5B	1.387 (7)	C2F—H2F1	0.9700
C4B—H4B	0.9300	C2F—H2F2	0.9700
C5B—C14B	1.389 (7)
C2A—C1A—C14A	120.2 (6)	C5B—C4B—H4B	120.4
C2A—C1A—H1A	119.9	C4B—C5B—C14B	121.6 (6)
C14A—C1A—H1A	119.9	C4B—C5B—N2B	119.5 (5)
C1A—C2A—C3A	121.0 (6)	C14B—C5B—N2B	118.8 (5)
C1A—C2A—H2A	119.5	C8B—C7B—C12B	119.5 (6)
C3A—C2A—H2A	119.5	C8B—C7B—N2B	119.8 (5)
C2A—C3A—C4A	118.9 (6)	C12B—C7B—N2B	120.7 (5)
C2A—C3A—H3A	120.6	C9B—C8B—C7B	121.0 (6)
C4A—C3A—H3A	120.6	C9B—C8B—H8B	119.5
C5A—C4A—C3A	119.7 (6)	C7B—C8B—H8B	119.5
C5A—C4A—H4A	120.2	C10B—C9B—C8B	121.1 (7)
C3A—C4A—H4A	120.2	C10B—C9B—H9B	119.4
C4A—C5A—C14A	120.8 (5)	C8B—C9B—H9B	119.4
C4A—C5A—N2A	120.2 (5)	C9B—C10B—C11B	120.0 (7)
C14A—C5A—N2A	118.9 (5)	C9B—C10B—H10B	120.0
C15A—N2A—C7A	120.4 (4)	C11B—C10B—H10B	120.0
C15A—N2A—C5A	124.6 (4)	C10B—C11B—C12B	120.6 (7)
C7A—N2A—C5A	114.9 (4)	C10B—C11B—H11B	119.7
C8A—C7A—C12A	119.6 (5)	C12B—C11B—H11B	119.7
C8A—C7A—N2A	121.1 (5)	C7B—C12B—C11B	117.8 (6)
C12A—C7A—N2A	119.3 (5)	C7B—C12B—C13B	122.4 (6)
C7A—C8A—C9A	121.0 (5)	C11B—C12B—C13B	119.8 (6)
C7A—C8A—H8A	119.5	N1B—C13B—O1B	123.2 (6)
C9A—C8A—H8A	119.5	N1B—C13B—C12B	126.3 (6)
C10A—C9A—C8A	119.1 (6)	O1B—C13B—C12B	110.4 (6)
C10A—C9A—H9A	120.4	C13B—N1B—C14B	126.6 (5)
C8A—C9A—H9A	120.4	C13B—O1B—H1B1	109.5
C11A—C10A—C9A	120.7 (6)	C21B—N3B—C16B	113.9 (4)
C11A—C10A—H10A	119.6	C21B—N3B—C17B	111.1 (5)
C9A—C10A—H10A	119.6	C16B—N3B—C17B	110.6 (5)
C10A—C11A—C12A	120.6 (5)	C27B—N4B—C25B	105.2 (5)
C10A—C11A—H11A	119.7	C27B—N4B—C24B	127.8 (6)
C12A—C11A—H11A	119.7	C25B—N4B—C24B	126.9 (5)
C11A—C12A—C7A	118.9 (5)	C27B—N5B—C26B	103.7 (5)
C11A—C12A—C13A	118.9 (5)	C1B—C14B—C5B	118.0 (6)
C7A—C12A—C13A	122.2 (5)	C1B—C14B—N1B	119.4 (6)
N1A—C13A—O1A	122.5 (5)	C5B—C14B—N1B	122.5 (5)
N1A—C13A—C12A	124.4 (5)	O2B—C15B—N2B	120.2 (5)
O1A—C13A—C12A	112.9 (5)	O2B—C15B—C16B	122.4 (5)
C13A—N1A—C14A	126.9 (5)	N2B—C15B—C16B	117.3 (5)
C13A—O1A—H1A1	109.5	N3B—C16B—C15B	111.1 (4)
C21A—N3A—C16A	111.9 (4)	N3B—C16B—H16C	109.4
C21A—N3A—C17A	111.6 (4)	C15B—C16B—H16C	109.4
C16A—N3A—C17A	110.3 (4)	N3B—C16B—H16D	109.4
C27A—N4A—C25A	105.1 (6)	C15B—C16B—H16D	109.4
C27A—N4A—C24A	126.9 (5)	H16C—C16B—H16D	108.0
C25A—N4A—C24A	128.0 (6)	N3B—C17B—C18B	110.3 (5)
C27A—N5A—C26A	103.3 (6)	N3B—C17B—H17C	109.6
C1A—C14A—C5A	119.4 (6)	C18B—C17B—H17C	109.6
C1A—C14A—N1A	118.7 (5)	N3B—C17B—H17D	109.6
C5A—C14A—N1A	121.9 (5)	C18B—C17B—H17D	109.6
O2A—C15A—N2A	121.1 (5)	H17C—C17B—H17D	108.1
O2A—C15A—C16A	123.2 (5)	C15B—N2B—C7B	120.9 (5)
N2A—C15A—C16A	115.6 (5)	C15B—N2B—C5B	122.9 (5)
N3A—C16A—C15A	110.7 (4)	C7B—N2B—C5B	116.0 (4)
N3A—C16A—H16A	109.5	C17B—C18B—C19B	112.9 (5)
C15A—C16A—H16A	109.5	C17B—C18B—H18C	109.0
N3A—C16A—H16B	109.5	C19B—C18B—H18C	109.0
C15A—C16A—H16B	109.5	C17B—C18B—H18D	109.0
H16A—C16A—H16B	108.1	C19B—C18B—H18D	109.0
N3A—C17A—C18A	111.4 (5)	H18C—C18B—H18D	107.8
N3A—C17A—H17A	109.3	C20B—C19B—C18B	108.7 (5)
C18A—C17A—H17A	109.3	C20B—C19B—C22B	112.1 (5)
N3A—C17A—H17B	109.3	C18B—C19B—C22B	112.3 (5)
C18A—C17A—H17B	109.3	C20B—C19B—H19B	107.8
H17A—C17A—H17B	108.0	C18B—C19B—H19B	107.8
C17A—C18A—C19A	111.3 (5)	C22B—C19B—H19B	107.8
C17A—C18A—H18A	109.4	C21B—C20B—C19B	113.8 (5)
C19A—C18A—H18A	109.4	C21B—C20B—H20C	108.8
C17A—C18A—H18B	109.4	C19B—C20B—H20C	108.8
C19A—C18A—H18B	109.4	C21B—C20B—H20D	108.8
H18A—C18A—H18B	108.0	C19B—C20B—H20D	108.8
C22A—C19A—C20A	112.0 (5)	H20C—C20B—H20D	107.7
C22A—C19A—C18A	113.2 (5)	N3B—C21B—C20B	109.2 (5)
C20A—C19A—C18A	106.9 (4)	N3B—C21B—H21C	109.8
C22A—C19A—H19A	108.2	C20B—C21B—H21C	109.9
C20A—C19A—H19A	108.2	N3B—C21B—H21D	109.8
C18A—C19A—H19A	108.2	C20B—C21B—H21D	109.8
C19A—C20A—C21A	112.1 (5)	H21C—C21B—H21D	108.3
C19A—C20A—H20A	109.2	C23B—C22B—C19B	116.0 (5)
C21A—C20A—H20A	109.2	C23B—C22B—H22C	108.3
C19A—C20A—H20B	109.2	C19B—C22B—H22C	108.3
C21A—C20A—H20B	109.2	C23B—C22B—H22D	108.3
H20A—C20A—H20B	107.9	C19B—C22B—H22D	108.3
N3A—C21A—C20A	110.1 (4)	H22C—C22B—H22D	107.4
N3A—C21A—H21A	109.6	C22B—C23B—C24B	114.6 (5)
C20A—C21A—H21A	109.6	C22B—C23B—H23C	108.6
N3A—C21A—H21B	109.6	C24B—C23B—H23C	108.6
C20A—C21A—H21B	109.6	C22B—C23B—H23D	108.6
H21A—C21A—H21B	108.2	C24B—C23B—H23D	108.6
C19A—C22A—C23A	114.3 (5)	H23C—C23B—H23D	107.6
C19A—C22A—H22A	108.7	N4B—C24B—C23B	113.3 (5)
C23A—C22A—H22A	108.7	N4B—C24B—H24C	108.9
C19A—C22A—H22B	108.7	C23B—C24B—H24C	108.9
C23A—C22A—H22B	108.7	N4B—C24B—H24D	108.9
H22A—C22A—H22B	107.6	C23B—C24B—H24D	108.9
C24A—C23A—C22A	112.8 (5)	H24C—C24B—H24D	107.7
C24A—C23A—H23A	109.0	C26B—C25B—N4B	107.0 (5)
C22A—C23A—H23A	109.0	C26B—C25B—H25B	126.5
C24A—C23A—H23B	109.0	N4B—C25B—H25B	126.5
C22A—C23A—H23B	109.0	C25B—C26B—N5B	110.7 (6)
H23A—C23A—H23B	107.8	C25B—C26B—H26B	124.7
N4A—C24A—C23A	114.2 (5)	N5B—C26B—H26B	124.7
N4A—C24A—H24A	108.7	N5B—C27B—N4B	113.4 (6)
C23A—C24A—H24A	108.7	N5B—C27B—H27B	123.3
N4A—C24A—H24B	108.7	N4B—C27B—H27B	123.3
C23A—C24A—H24B	108.7	C1E—C2E—O1E	115.7 (18)
H24A—C24A—H24B	107.6	C1E—C2E—H2E1	108.4
C26A—C25A—N4A	106.4 (7)	O1E—C2E—H2E1	108.4
C26A—C25A—H25A	126.8	C1E—C2E—H2E2	108.4
N4A—C25A—H25A	126.8	O1E—C2E—H2E2	108.4
C25A—C26A—N5A	111.1 (6)	H2E1—C2E—H2E2	107.4
C25A—C26A—H26A	124.4	H1E4—C1E'—H1E5	109.5
N5A—C26A—H26A	124.4	H1E4—C1E'—H1E6	109.5
N5A—C27A—N4A	114.1 (6)	H1E5—C1E'—H1E6	109.5
N5A—C27A—H27A	122.9	C2F—O1F—H1F	109.5
N4A—C27A—H27A	122.9	C2F—C1F—H1F1	109.5
C2B—C1B—C14B	121.7 (6)	C2F—C1F—H1F2	109.5
C2B—C1B—H1B	119.1	H1F1—C1F—H1F2	109.5
C14B—C1B—H1B	119.1	C2F—C1F—H1F3	109.5
C1B—C2B—C3B	119.9 (6)	H1F1—C1F—H1F3	109.5
C1B—C2B—H2B	120.1	H1F2—C1F—H1F3	109.5
C3B—C2B—H2B	120.1	O1F—C2F—C1F	115.8 (7)
C4B—C3B—C2B	119.4 (7)	O1F—C2F—H2F1	108.3
C4B—C3B—H3B	120.3	C1F—C2F—H2F1	108.3
C2B—C3B—H3B	120.3	O1F—C2F—H2F2	108.3
C3B—C4B—C5B	119.1 (6)	C1F—C2F—H2F2	108.3
C3B—C4B—H4B	120.4	H2F1—C2F—H2F2	107.4
C14A—C1A—C2A—C3A	−0.2 (9)	C14B—C1B—C2B—C3B	1.3 (10)
C1A—C2A—C3A—C4A	0.0 (9)	C1B—C2B—C3B—C4B	−2.7 (10)
C2A—C3A—C4A—C5A	−0.1 (8)	C2B—C3B—C4B—C5B	0.0 (9)
C3A—C4A—C5A—C14A	0.6 (8)	C3B—C4B—C5B—C14B	4.1 (9)
C3A—C4A—C5A—N2A	178.8 (5)	C3B—C4B—C5B—N2B	−176.6 (5)
C4A—C5A—N2A—C15A	69.8 (7)	C12B—C7B—C8B—C9B	−1.4 (9)
C14A—C5A—N2A—C15A	−111.9 (6)	N2B—C7B—C8B—C9B	178.8 (5)
C4A—C5A—N2A—C7A	−112.3 (5)	C7B—C8B—C9B—C10B	−0.3 (9)
C14A—C5A—N2A—C7A	66.0 (6)	C8B—C9B—C10B—C11B	0.8 (10)
C15A—N2A—C7A—C8A	−66.0 (6)	C9B—C10B—C11B—C12B	0.3 (10)
C5A—N2A—C7A—C8A	116.0 (5)	C8B—C7B—C12B—C11B	2.4 (8)
C15A—N2A—C7A—C12A	113.4 (5)	N2B—C7B—C12B—C11B	−177.8 (5)
C5A—N2A—C7A—C12A	−64.7 (6)	C8B—C7B—C12B—C13B	179.5 (5)
C12A—C7A—C8A—C9A	0.6 (8)	N2B—C7B—C12B—C13B	−0.6 (8)
N2A—C7A—C8A—C9A	179.9 (4)	C10B—C11B—C12B—C7B	−1.9 (9)
C7A—C8A—C9A—C10A	1.3 (8)	C10B—C11B—C12B—C13B	−179.1 (6)
C8A—C9A—C10A—C11A	−1.7 (8)	C7B—C12B—C13B—N1B	31.0 (9)
C9A—C10A—C11A—C12A	0.1 (8)	C11B—C12B—C13B—N1B	−151.9 (6)
C10A—C11A—C12A—C7A	1.8 (8)	C7B—C12B—C13B—O1B	−153.4 (5)
C10A—C11A—C12A—C13A	−176.8 (5)	C11B—C12B—C13B—O1B	23.7 (7)
C8A—C7A—C12A—C11A	−2.1 (7)	O1B—C13B—N1B—C14B	−165.9 (5)
N2A—C7A—C12A—C11A	178.6 (4)	C12B—C13B—N1B—C14B	9.3 (9)
C8A—C7A—C12A—C13A	176.4 (5)	C2B—C1B—C14B—C5B	2.6 (9)
N2A—C7A—C12A—C13A	−2.9 (7)	C2B—C1B—C14B—N1B	179.4 (6)
C11A—C12A—C13A—N1A	−143.5 (5)	C4B—C5B—C14B—C1B	−5.4 (8)
C7A—C12A—C13A—N1A	38.1 (8)	N2B—C5B—C14B—C1B	175.3 (5)
C11A—C12A—C13A—O1A	31.4 (7)	C4B—C5B—C14B—N1B	177.9 (5)
C7A—C12A—C13A—O1A	−147.1 (5)	N2B—C5B—C14B—N1B	−1.4 (8)
O1A—C13A—N1A—C14A	−170.3 (5)	C13B—N1B—C14B—C1B	141.9 (6)
C12A—C13A—N1A—C14A	4.1 (8)	C13B—N1B—C14B—C5B	−41.4 (9)
C2A—C1A—C14A—C5A	0.7 (8)	C21B—N3B—C16B—C15B	−157.8 (5)
C2A—C1A—C14A—N1A	179.3 (5)	C17B—N3B—C16B—C15B	76.2 (6)
C4A—C5A—C14A—C1A	−0.8 (8)	O2B—C15B—C16B—N3B	−117.8 (6)
N2A—C5A—C14A—C1A	−179.1 (5)	N2B—C15B—C16B—N3B	57.9 (7)
C4A—C5A—C14A—N1A	−179.5 (5)	C21B—N3B—C17B—C18B	60.5 (6)
N2A—C5A—C14A—N1A	2.3 (7)	C16B—N3B—C17B—C18B	−172.0 (5)
C13A—N1A—C14A—C1A	138.5 (6)	O2B—C15B—N2B—C7B	7.3 (8)
C13A—N1A—C14A—C5A	−42.9 (8)	C16B—C15B—N2B—C7B	−168.4 (5)
C7A—N2A—C15A—O2A	6.0 (8)	O2B—C15B—N2B—C5B	−177.3 (5)
C5A—N2A—C15A—O2A	−176.2 (5)	C16B—C15B—N2B—C5B	6.9 (7)
C7A—N2A—C15A—C16A	−170.1 (4)	C8B—C7B—N2B—C15B	−67.8 (7)
C5A—N2A—C15A—C16A	7.7 (7)	C12B—C7B—N2B—C15B	112.4 (6)
C21A—N3A—C16A—C15A	−160.6 (4)	C8B—C7B—N2B—C5B	116.5 (6)
C17A—N3A—C16A—C15A	74.5 (5)	C12B—C7B—N2B—C5B	−63.3 (7)
O2A—C15A—C16A—N3A	−116.4 (6)	C4B—C5B—N2B—C15B	71.5 (7)
N2A—C15A—C16A—N3A	59.7 (6)	C14B—C5B—N2B—C15B	−109.2 (6)
C21A—N3A—C17A—C18A	58.5 (6)	C4B—C5B—N2B—C7B	−112.9 (6)
C16A—N3A—C17A—C18A	−176.4 (4)	C14B—C5B—N2B—C7B	66.4 (7)
N3A—C17A—C18A—C19A	−57.7 (6)	N3B—C17B—C18B—C19B	−55.0 (6)
C17A—C18A—C19A—C22A	179.0 (5)	C17B—C18B—C19B—C20B	49.5 (7)
C17A—C18A—C19A—C20A	55.2 (6)	C17B—C18B—C19B—C22B	174.2 (5)
C22A—C19A—C20A—C21A	179.6 (5)	C18B—C19B—C20B—C21B	−51.2 (7)
C18A—C19A—C20A—C21A	−55.8 (6)	C22B—C19B—C20B—C21B	−176.0 (5)
C16A—N3A—C21A—C20A	177.9 (4)	C16B—N3B—C21B—C20B	173.2 (5)
C17A—N3A—C21A—C20A	−58.0 (6)	C17B—N3B—C21B—C20B	−61.0 (7)
C19A—C20A—C21A—N3A	58.3 (6)	C19B—C20B—C21B—N3B	57.5 (7)
C20A—C19A—C22A—C23A	−168.7 (5)	C20B—C19B—C22B—C23B	−177.5 (5)
C18A—C19A—C22A—C23A	70.2 (6)	C18B—C19B—C22B—C23B	59.6 (7)
C19A—C22A—C23A—C24A	−176.8 (5)	C19B—C22B—C23B—C24B	−176.2 (5)
C27A—N4A—C24A—C23A	125.8 (6)	C27B—N4B—C24B—C23B	111.0 (7)
C25A—N4A—C24A—C23A	−56.4 (8)	C25B—N4B—C24B—C23B	−72.6 (8)
C22A—C23A—C24A—N4A	−59.5 (7)	C22B—C23B—C24B—N4B	−60.8 (7)
C27A—N4A—C25A—C26A	−0.3 (6)	C27B—N4B—C25B—C26B	0.0 (6)
C24A—N4A—C25A—C26A	−178.5 (5)	C24B—N4B—C25B—C26B	−177.0 (5)
N4A—C25A—C26A—N5A	0.7 (7)	N4B—C25B—C26B—N5B	0.2 (7)
C27A—N5A—C26A—C25A	−0.9 (7)	C27B—N5B—C26B—C25B	−0.3 (7)
C26A—N5A—C27A—N4A	0.7 (7)	C26B—N5B—C27B—N4B	0.3 (7)
C25A—N4A—C27A—N5A	−0.3 (7)	C25B—N4B—C27B—N5B	−0.2 (7)
C24A—N4A—C27A—N5A	177.9 (5)	C24B—N4B—C27B—N5B	176.8 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A1···N1B	0.82	2.05	2.835 (7)	160
O1B—H1B1···N1A	0.82	2.05	2.824 (6)	158
O1A′—H1A′···N1B′	0.82	2.00	2.755 (13)	154
O1B′—H1B′···N1A′	0.82	2.08	2.857 (14)	159
C10A—H10A···C1A^i	0.93	2.94	3.655 (8)	135
O1F—H1F···N5B^ii	0.82	1.97	2.779 (7)	167
O1E—H1E···N5A^iii	0.82	2.36	2.70 (3)	106
C2A—H2A···O1F^iv	0.93	2.60	3.433 (8)	149

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