Dimeric supra­molecular motifs of two carboxylate-guanidinium compounds

The structures of N-benzyl-N'-{6-[(4-carboxylatobenzyl)aminocarbonyl]-2-pyridylmethyl}guanidinium, C₂₃H₂₃N₅O₃, (I), and N-[2-(benzylaminocarbonyl)ethyl]-N'-{6-[(4-carboxylatobenzyl)aminocarbonyl]-2-pyridylmethyl}guanidinium monohydrate, C₂₆H₂₈N₆O₄·H₂O, (II), both form three-dimensional supra­molecular hydrogen-bonded networks based on a dimeric primary synthon involving carboxyl­ate-guanidinium linkages. The differences in the geometries and hydrogen-bonding connectivities are driven by the additional methyl­propionamide group and water of crystallization of (II).

S1. Comment

Guanidnium salts have been widely employed as motifs for carboxylate binding (Blondeau et al., 2007; Fitzmaurice et al., 2002) owing to a structural complementarity that results in well aligned hydrogen-bond donor and acceptor groups and favourable electrostatic interaction in the ion pair. We have recently reported a pyridylguanidinium receptor in which two additional, cooperative (amide) hydrogen-bond donors for binding carboxylate are incorporated, and in which the pyridine lone pair participates in intramolecular hydrogen bonding for preorganization of the binding motif (Fitzmaurice et al., 2007). Entropy-driven binding of acetate has been achieved in this system in competitive solution-phase media, and we have now prepared analogous systems, (I) and (II), extended in structure to incorporate a tethered carboxylate terminus. We aim to develop a simple supramolecular model based on dimerization of zwitterions (I) and (II), in which the energetic contribution of individual intermolecular binding interactions to the overall self-assembly, driven primarily by the guanidinium–carboxylate binding, can be determined. The present study of dimeric self-association of (I) and (II) was undertaken in order to investigate the ion-pair interaction and other contributing intramolecular interactions in the context of the overall assembly, and to inform monomer design.

The structure of (I) (Fig. 1) comprises an anionic benzoate group linked through a methylene group to a pyridinecarboxylic acid amide; this is in turn linked via another methylene group to a guanidinium cationic group terminated by a methylene-linked benzene ring. These four groups are individually essentially planar, with the three methylene groups acting as hinges, allowing the molecule to adopt a twisted conformation driven by steric and hydrogen-bonding influences. This can be described using the least-squares planes through the groups; the defined planes, the r.m.s. deviation from planarity and the atom with the maximum deviation from the plane are as follows: O1/O2/C1–C7, 0.097, O1 = 0.184 (2) Å; N1/N2/O3/C9–C14, 0.053, O3 = 0.095 (2) Å; N3/N4/N5/C16, 0.001, C16 = 0.001 (2) Å; and C18–C23, 0.032, C18 = 0.05 (2) Å. The angles between adjacent planes are 77.33 (6), 87.22 (8) and 81.97 (9)°, respectively, and infer that the groups are mutually perpendicular.

With the exception of a water of crystallization the molecular structure of (II) (Fig. 2) differs from (I) solely in the insertion of a methylpropionamide group before the terminal benzene ring. This additional group has a dramatic effect on the overall structure and geometry of the molecule. The least-squares planes, including the additional methylpropionamide group, are defined as previously as follows: O1/O2/C1–C7, 0.057, O1 =-0.111 (2) Å; N1/N2/O3/C9–C14, 0.036, C10 = -0.059 (2) Å; N3/N4/N5/C16, 0.004, C16 = 0.006 (2) Å; C18/C19/N6/O4, 0.007, C19 = -0.012 (2) Å; and C21–C26, 0.002, C26 = -0.004 (2) Å; these planes make angles of 67.43 (5), 4.11 (12), 73.16 (13) and 75.76 (10)°. It can be seen from these angles that the twist at the methylene connecting the pyridinecarboxylic acid amide and the guanidinium group is now much smaller [dihedral angle = 4.11 (12)°], making the combined group essentially flat. The remaining two hinges revert to rotations approaching 90° [73.16 (13) and 75.76 (10)°], continuing the corkscrew-like twist of the molecule.

Both (I) and (II) exist as zwitterions with a formal negative charge associated with the carboxylate group and a formal positive charge with the guanidinium group. Analysis of the bond lengths shows the guanidinium to be in a resonance hybrid form and in both (I) and (II) the differences between the bonds are within 3 s.u. of their values. In (I) the carboxylate group is clearly in its resonance hybrid form [O1—C1 = 1.263 (3) Å and O2—C1 1.264 (3) Å]. A similar case exists for (II) although a possible asymmetrical lengthening in favour of the stronger hydrogen-bond environment can be seen [O1—C1 = 1.254 (3) Å and O2—C1 = 1.261 (3) Å].

With their plethora of potential hydrogen-bond donors and acceptors it is unsurprising that both (I) and (II) form three-dimensional networks, and it is the interaction between the carboxylate and guanidinium groups that is responsible for the formation of a basic supramolecular building block (Figs. 3 and 4).

In (I), the guanidinium group is in the trans configuration [atom H93 is on the opposite side to the NH_{2 group} (N4)], so that it is an NH (N5) and an NH₂ (N4) group that participate in the carboxylate hydrogen bonding [N4···O2ⁱⁱⁱ and N5···O1ⁱⁱⁱ; symmetry code: (iii) -x + 2,-y + 1, -z + 1], whereas in (II) the group is in the cis form [both H atoms (H3 and H5) are on the opposite side from the NH_{2 group} (N4)] and both NH groups (N3 and N5) are oriented towards the carboxylate group [N3···O1ⁱ and N5..O1ⁱ; symmetry code: (i) -x - 1, -y, -z; see Tables 1 and 2 for details]. In (I) both carboxylate O atoms hydrogen bond to separate H atoms of the guanidinium group, but the interaction is not planar, with the amine twisting away below the plane of the carboxylate group (the angle between the least-squares planes through each group is 42.76°). The (inversion) symmetry-related interactions complete a dimer or 34-membered ring [N4 ···O2ⁱⁱⁱ and N5···O1ⁱⁱⁱ; symmetry code: (iii) -x + 2, -y + 1, -z + 1], as depicted in Fig. 3.

In (II), the approach of the carboxylate and quanidinium units is characterized by a single bifurcated hydrogen bond from O1ⁱ to N3 and N5. The hydrogen-bonding environment of the carboxylate unit is now very different from that in (I), with atom O1 acting as a receptor in three hydrogen bonds, two from the guanidinium unit (N3···O1ⁱ and N5···O1ⁱ) and one from the amide group of the pyridinecarboxylic acid amide group (N1···O1ⁱ), see Fig. 4.

Additionally, the benzoate rings are arranged parallel in (II) such that π–π interactions become relevant; the C2–C7 centroid to C2ⁱ–C7ⁱ centroid separation is 3.662 Å, with the perpendicular distance between the least-squares planes through each benzene ring being 3.372 Å, as depecited with a dashed line in Fig. 4. It is possible that the π–π interaction arises from the changed geometry of the guanidinium–carboxylate interaction compared to (I), but more likely provides a cooperative driving-force for this offset ion-pair interaction in combination with the hydrogen bonding from the propionamide group to the water molecule (N6···O1W) described below.

For the packing of (I), the dimer rings are stacked via other hydrogen bonds (N4···O2ⁱ and N1···O1) to form a one-dimensional molecular chain structure along the a axis. In the structure, guanidinium–carboxylate hydrogen-bonded pairs are connected via N4···O2ⁱ hydrogen bonds. A herringbone-like arrangement is also observed when the structure is viewed down the c axis. The supramolecular structure of (II) is punctuated by hydrogen-bonded rings formed around a centre of symmetry via two water molecules and two O atoms of two separate carboxylate groups [O1W···O2ⁱ and O1W···O2^iv; symmetry code: (iv) x + 1, y + 1, z]. The water molecules also act as acceptors in hydrogen bonds to the methyl propionamide groups (N6···O1W) such that the rings connect four individual molecules.

As a general point hydrogen-bond interactions between a guanidinium and carboxylate group often form a subunit characterized by linear bidendate interactions. However, it is often observed that other competitive interactions can force a nonplanar geometry for this unit (e.g. Zafar et al., 2002). Preliminary searches of the Cambridge Structural Database (Allen, 2002) for such interactions show a wide range of geometries and will be the subject of a subsequent study.

Related literature

For related literature, see: Allen (2002); Blondeau et al. (2007); Fitzmaurice et al. (2002, 2007); Zafar et al. (2002).

S2. Experimental

Full synthetic procedures for the stepwise preparation of (I) and (II) from ethyl 6-{[bis(tert-butoxycarbonyl)amino]methyl}pyridine-2-carboxylate will be reported elsewhere. Single crystals were obtained by slow diffusion of a 40 mM solution of each in MeOH with CH₂Cl₂ for (I) and with Et₂O for (II).

S3. Refinement

C-bound H atoms were identified in a difference map and subsequently placed in idealized positions and refined using a riding model (aromatic C—H = 0.95 Å and methylene C—H = 0.99 Å). N-bound H atoms were located in the difference map and their coordinates set as riding on their parent atoms. For all C- and N-bound atoms the displacement parameters were set at 1.2 times U_eq of the parent atom. In (II), the H atoms of the water molecule were clearly visible in the difference map as the two highest residual density peaks. These were included in the model and refined using distance restraints [O—H = 0.84 (2) Å and H···H = 1.37 (2) Å]; displacement parameters were constrained to 1.5 times those of the parent O atom. Also in (II), a void of 76 ų exists around a centre of symmetry (1/2, 1, 1/2), but no significant residual electron density was observed in this region.

Computing details

For both compounds, data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (CrystalMaker, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of (I); displacement ellipsoids are drawn at the 35% probability level and H atoms are drawn with an arbitrary radius.
	Fig. 2. The molecular structure of (II); displacement ellipsoids are drawn at the 35% probability level and H atoms are drawn with an arbitrary radius.
	Fig. 3. The dimeric primary synthon in (I), showing the extended hydrogen-bonding environment. H atoms not involved in significant close contacts have been omitted for clarity. [Symmetry codes: (i) x - 1, y, z; (ii) x - 1/2, -y + 1/2, z + 1/2; (iii) -x + 2, -y + 1, -z + 1.]
	Fig. 4. The dimeric primary synthon in (II), showing the extended hydrogen-bonding environment. H atoms not involved in significant close contacts have been omitted for clarity. π–π interactions are depicted using a dashed line between ring centroids. [Symmetry codes: (i) -x - 1, -y, -z; (ii) x + 1, y, z; (iii) -x + 1, -y + 1, -z + 1; (iv) x + 1, y + 1, z.]

(I) N-benzyl-N'-{6-[(4-carboxylatobenzyl)aminocarbonyl]- 2-pyridylmethyl}guanidinium

Crystal data

C23H23N5O3	F(000) = 880
Mr = 417.46	Dx = 1.387 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 23640 reflections
a = 8.1826 (3) Å	θ = 2.9–27.5°
b = 18.1530 (7) Å	µ = 0.10 mm^−1
c = 13.4723 (4) Å	T = 120 K
β = 92.601 (2)°	Prism, colourless
V = 1999.10 (12) Å^3	0.15 × 0.1 × 0.1 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	3519 independent reflections
Radiation source: Bruker Nonius FR591 Rotating Anode	2719 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
Detector resolution: 9.091 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ϕ & ω scans to fill the asymmetric unit	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −21→21
Tmin = 0.986, Tmax = 0.991	l = −16→15
16252 measured reflections

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0158P)^2 + 3.0515P] where P = (Fo^2 + 2Fc^2)/3
3519 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Experimental. SADABS was used to perform the Absorption correction Parameter refinement on 15081 reflections reduced R(int) from 0.1139 to 0.0766 Ratio of minimum to maximum apparent transmission: 0.625353 The given Tmin and Tmax were generated using the SHELX SIZE command

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

[O1,O2, C1 > C7; 0.097, O1 = 0.184?(2) Å] [N1, N2,O3, C9 > C14; 0.053, O3 = 0.095?(2) Å] [N3, N4, N5, C16; 0.001; C16 = 0.001?(2) Å] [C18 > C23; 0.032; C18 = 0.05?(2) Å]

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 > 2σ(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	1.3365 (2)	0.52932 (10)	0.26253 (14)	0.0268 (4)
O2	1.2351 (2)	0.52170 (10)	0.41360 (14)	0.0283 (5)
O3	0.5851 (2)	0.28738 (10)	0.13782 (14)	0.0291 (5)
N1	0.4844 (3)	0.39583 (12)	0.18880 (16)	0.0236 (5)
H91	0.4220	0.4188	0.2310	0.028*
N2	0.3162 (3)	0.32837 (12)	0.33001 (16)	0.0235 (5)
N3	0.2331 (3)	0.34011 (12)	0.57518 (16)	0.0242 (5)
H93	0.1950	0.3034	0.6110	0.029*
N4	0.4363 (3)	0.42461 (12)	0.54329 (16)	0.0248 (5)
H94A	0.5481	0.4406	0.5580	0.030*
H94B	0.3671	0.4474	0.5000	0.030*
N5	0.4694 (3)	0.34621 (13)	0.67591 (16)	0.0270 (5)
H95	0.5460	0.3768	0.6930	0.032*
C1	1.2223 (3)	0.51636 (14)	0.3200 (2)	0.0237 (6)
C2	1.0593 (3)	0.49319 (14)	0.2726 (2)	0.0242 (6)
C3	1.0473 (3)	0.47355 (15)	0.1726 (2)	0.0263 (6)
H3	1.1427	0.4734	0.1349	0.032*
C4	0.8978 (3)	0.45428 (16)	0.1274 (2)	0.0274 (6)
H4	0.8925	0.4403	0.0594	0.033*
C5	0.7564 (3)	0.45501 (14)	0.1797 (2)	0.0241 (6)
C6	0.7694 (3)	0.47318 (15)	0.2807 (2)	0.0267 (6)
H6	0.6741	0.4730	0.3185	0.032*
C7	0.9188 (3)	0.49143 (15)	0.3264 (2)	0.0259 (6)
H7	0.9252	0.5028	0.3953	0.031*
C8	0.5908 (3)	0.43965 (15)	0.1286 (2)	0.0252 (6)
H8A	0.5362	0.4871	0.1123	0.030*
H8B	0.6072	0.4134	0.0654	0.030*
C9	0.4953 (3)	0.32265 (15)	0.19234 (19)	0.0232 (6)
C10	0.3965 (3)	0.28445 (15)	0.26769 (19)	0.0230 (6)
C11	0.3983 (3)	0.20860 (15)	0.2743 (2)	0.0270 (6)
H11	0.4539	0.1797	0.2277	0.032*
C12	0.3170 (4)	0.17546 (16)	0.3506 (2)	0.0291 (7)
H12	0.3157	0.1234	0.3573	0.035*
C13	0.2381 (3)	0.21964 (15)	0.4166 (2)	0.0262 (6)
H13	0.1839	0.1983	0.4705	0.031*
C14	0.2386 (3)	0.29581 (15)	0.40364 (19)	0.0235 (6)
C15	0.1531 (3)	0.34495 (15)	0.47563 (19)	0.0240 (6)
H15A	0.1559	0.3966	0.4520	0.029*
H15B	0.0372	0.3299	0.4786	0.029*
C16	0.3784 (3)	0.37029 (15)	0.59783 (19)	0.0233 (6)
C17	0.4386 (3)	0.27784 (15)	0.7282 (2)	0.0265 (6)
H17A	0.5451	0.2544	0.7463	0.032*
H17B	0.3778	0.2442	0.6821	0.032*
C18	0.3437 (3)	0.28563 (15)	0.8213 (2)	0.0253 (6)
C19	0.2908 (3)	0.22244 (17)	0.8686 (2)	0.0308 (7)
H19	0.3087	0.1756	0.8394	0.037*
C20	0.2126 (4)	0.22667 (19)	0.9575 (2)	0.0373 (8)
H20	0.1780	0.1830	0.9891	0.045*
C21	0.1848 (4)	0.29461 (19)	1.0001 (2)	0.0402 (8)
H21	0.1315	0.2977	1.0611	0.048*
C22	0.2353 (4)	0.35811 (19)	0.9533 (2)	0.0400 (8)
H22	0.2159	0.4049	0.9820	0.048*
C23	0.3140 (4)	0.35338 (16)	0.8645 (2)	0.0340 (7)
H23	0.3481	0.3972	0.8328	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0273 (10)	0.0251 (11)	0.0281 (10)	−0.0015 (8)	0.0033 (8)	−0.0014 (8)
O2	0.0333 (11)	0.0258 (11)	0.0256 (11)	−0.0011 (8)	−0.0025 (8)	0.0008 (8)
O3	0.0336 (11)	0.0262 (11)	0.0277 (10)	0.0049 (9)	0.0046 (9)	−0.0007 (8)
N1	0.0267 (12)	0.0212 (12)	0.0232 (12)	0.0000 (9)	0.0042 (9)	−0.0023 (9)
N2	0.0242 (12)	0.0251 (12)	0.0210 (11)	−0.0026 (9)	−0.0015 (9)	−0.0011 (10)
N3	0.0294 (13)	0.0228 (12)	0.0205 (11)	−0.0036 (10)	0.0019 (9)	0.0031 (9)
N4	0.0302 (13)	0.0214 (12)	0.0226 (12)	−0.0039 (10)	−0.0005 (9)	0.0044 (10)
N5	0.0308 (13)	0.0244 (13)	0.0254 (12)	−0.0079 (10)	−0.0035 (10)	0.0030 (10)
C1	0.0302 (15)	0.0114 (13)	0.0295 (15)	0.0032 (11)	0.0019 (12)	0.0004 (11)
C2	0.0295 (15)	0.0159 (14)	0.0271 (14)	0.0012 (11)	0.0002 (11)	0.0027 (11)
C3	0.0259 (15)	0.0281 (15)	0.0254 (14)	0.0020 (12)	0.0060 (11)	−0.0010 (12)
C4	0.0318 (16)	0.0287 (16)	0.0218 (14)	0.0009 (12)	0.0018 (12)	−0.0030 (12)
C5	0.0286 (15)	0.0157 (13)	0.0278 (14)	−0.0003 (11)	0.0009 (11)	0.0013 (11)
C6	0.0264 (15)	0.0248 (15)	0.0291 (15)	0.0018 (12)	0.0048 (12)	−0.0009 (12)
C7	0.0327 (16)	0.0228 (15)	0.0223 (14)	−0.0001 (12)	0.0015 (12)	−0.0001 (11)
C8	0.0284 (15)	0.0211 (14)	0.0262 (14)	−0.0014 (11)	0.0015 (11)	0.0003 (11)
C9	0.0236 (14)	0.0262 (16)	0.0197 (13)	0.0015 (11)	−0.0006 (11)	−0.0028 (11)
C10	0.0228 (14)	0.0242 (15)	0.0217 (13)	−0.0003 (11)	−0.0012 (11)	−0.0014 (11)
C11	0.0290 (15)	0.0241 (16)	0.0277 (15)	0.0004 (12)	−0.0003 (12)	−0.0032 (12)
C12	0.0388 (17)	0.0198 (15)	0.0285 (15)	−0.0028 (12)	−0.0026 (12)	−0.0014 (12)
C13	0.0309 (15)	0.0227 (15)	0.0250 (14)	−0.0035 (12)	−0.0008 (12)	0.0014 (11)
C14	0.0243 (14)	0.0251 (15)	0.0208 (13)	−0.0002 (11)	−0.0047 (11)	−0.0015 (11)
C15	0.0265 (14)	0.0224 (15)	0.0228 (14)	−0.0013 (11)	−0.0009 (11)	−0.0009 (11)
C16	0.0268 (15)	0.0209 (14)	0.0221 (14)	0.0000 (11)	0.0018 (11)	−0.0026 (11)
C17	0.0344 (16)	0.0212 (14)	0.0235 (14)	−0.0002 (12)	−0.0041 (12)	0.0021 (11)
C18	0.0247 (14)	0.0275 (15)	0.0233 (14)	0.0006 (12)	−0.0023 (11)	0.0055 (12)
C19	0.0317 (16)	0.0300 (16)	0.0302 (15)	−0.0030 (13)	−0.0040 (12)	0.0061 (13)
C20	0.0334 (17)	0.045 (2)	0.0334 (17)	−0.0054 (14)	−0.0012 (13)	0.0142 (15)
C21	0.0354 (18)	0.057 (2)	0.0281 (16)	0.0056 (15)	0.0036 (13)	0.0063 (15)
C22	0.049 (2)	0.041 (2)	0.0305 (17)	0.0082 (15)	0.0054 (14)	−0.0012 (14)
C23	0.0466 (19)	0.0257 (16)	0.0300 (16)	0.0013 (14)	0.0030 (13)	0.0018 (13)

Geometric parameters (Å, º)

O1—C1	1.263 (3)	C7—H7	0.9500
O2—C1	1.264 (3)	C8—H8A	0.9900
O3—C9	1.241 (3)	C8—H8B	0.9900
N1—C9	1.332 (3)	C9—C10	1.496 (4)
N1—C8	1.453 (3)	C10—C11	1.380 (4)
N1—H91	0.8856	C11—C12	1.387 (4)
N2—C14	1.339 (3)	C11—H11	0.9500
N2—C10	1.350 (3)	C12—C13	1.379 (4)
N3—C16	1.332 (3)	C12—H12	0.9500
N3—C15	1.468 (3)	C13—C14	1.394 (4)
N3—H93	0.8875	C13—H13	0.9500
N4—C16	1.330 (3)	C14—C15	1.512 (4)
N4—H94A	0.9716	C15—H15A	0.9900
N4—H94B	0.8953	C15—H15B	0.9900
N5—C16	1.335 (3)	C17—C18	1.512 (4)
N5—C17	1.455 (3)	C17—H17A	0.9900
N5—H95	0.8611	C17—H17B	0.9900
C1—C2	1.512 (4)	C18—C23	1.386 (4)
C2—C7	1.387 (4)	C18—C19	1.390 (4)
C2—C3	1.394 (4)	C19—C20	1.386 (4)
C3—C4	1.386 (4)	C19—H19	0.9500
C3—H3	0.9500	C20—C21	1.383 (5)
C4—C5	1.381 (4)	C20—H20	0.9500
C4—H4	0.9500	C21—C22	1.386 (5)
C5—C6	1.399 (4)	C21—H21	0.9500
C5—C8	1.518 (4)	C22—C23	1.387 (4)
C6—C7	1.385 (4)	C22—H22	0.9500
C6—H6	0.9500	C23—H23	0.9500
C9—N1—C8	121.7 (2)	C10—C11—C12	118.5 (3)
C9—N1—H91	119.1	C10—C11—H11	120.8
C8—N1—H91	118.5	C12—C11—H11	120.8
C14—N2—C10	117.4 (2)	C13—C12—C11	118.7 (3)
C16—N3—C15	122.7 (2)	C13—C12—H12	120.7
C16—N3—H93	121.1	C11—C12—H12	120.7
C15—N3—H93	112.9	C12—C13—C14	119.5 (3)
C16—N4—H94A	117.7	C12—C13—H13	120.3
C16—N4—H94B	118.2	C14—C13—H13	120.3
H94A—N4—H94B	123.8	N2—C14—C13	122.3 (2)
C16—N5—C17	123.9 (2)	N2—C14—C15	117.6 (2)
C16—N5—H95	111.9	C13—C14—C15	120.1 (2)
C17—N5—H95	124.1	N3—C15—C14	110.5 (2)
O1—C1—O2	124.6 (2)	N3—C15—H15A	109.5
O1—C1—C2	117.1 (2)	C14—C15—H15A	109.5
O2—C1—C2	118.3 (2)	N3—C15—H15B	109.5
C7—C2—C3	118.4 (3)	C14—C15—H15B	109.5
C7—C2—C1	121.5 (2)	H15A—C15—H15B	108.1
C3—C2—C1	120.1 (2)	N4—C16—N3	121.0 (2)
C4—C3—C2	120.7 (2)	N4—C16—N5	118.6 (2)
C4—C3—H3	119.6	N3—C16—N5	120.4 (2)
C2—C3—H3	119.6	N5—C17—C18	115.4 (2)
C5—C4—C3	121.1 (3)	N5—C17—H17A	108.4
C5—C4—H4	119.4	C18—C17—H17A	108.4
C3—C4—H4	119.4	N5—C17—H17B	108.4
C4—C5—C6	118.0 (2)	C18—C17—H17B	108.4
C4—C5—C8	121.2 (2)	H17A—C17—H17B	107.5
C6—C5—C8	120.7 (2)	C23—C18—C19	118.4 (3)
C7—C6—C5	121.0 (3)	C23—C18—C17	122.5 (3)
C7—C6—H6	119.5	C19—C18—C17	119.0 (3)
C5—C6—H6	119.5	C20—C19—C18	121.0 (3)
C6—C7—C2	120.6 (3)	C20—C19—H19	119.5
C6—C7—H7	119.7	C18—C19—H19	119.5
C2—C7—H7	119.7	C21—C20—C19	119.9 (3)
N1—C8—C5	113.1 (2)	C21—C20—H20	120.0
N1—C8—H8A	109.0	C19—C20—H20	120.0
C5—C8—H8A	109.0	C20—C21—C22	119.7 (3)
N1—C8—H8B	109.0	C20—C21—H21	120.2
C5—C8—H8B	109.0	C22—C21—H21	120.2
H8A—C8—H8B	107.8	C21—C22—C23	120.0 (3)
O3—C9—N1	122.3 (2)	C21—C22—H22	120.0
O3—C9—C10	121.0 (2)	C23—C22—H22	120.0
N1—C9—C10	116.7 (2)	C18—C23—C22	120.9 (3)
N2—C10—C11	123.6 (2)	C18—C23—H23	119.6
N2—C10—C9	116.2 (2)	C22—C23—H23	119.6
C11—C10—C9	120.1 (2)
O1—C1—C2—C7	−167.4 (2)	C9—C10—C11—C12	174.4 (2)
O2—C1—C2—C7	12.3 (4)	C10—C11—C12—C13	−0.1 (4)
O1—C1—C2—C3	12.0 (4)	C11—C12—C13—C14	1.6 (4)
O2—C1—C2—C3	−168.2 (2)	C10—N2—C14—C13	−0.4 (4)
C7—C2—C3—C4	1.4 (4)	C10—N2—C14—C15	178.0 (2)
C1—C2—C3—C4	−178.1 (2)	C12—C13—C14—N2	−1.4 (4)
C2—C3—C4—C5	1.0 (4)	C12—C13—C14—C15	−179.8 (2)
C3—C4—C5—C6	−2.3 (4)	C16—N3—C15—C14	72.7 (3)
C3—C4—C5—C8	175.3 (3)	N2—C14—C15—N3	−113.7 (3)
C4—C5—C6—C7	1.3 (4)	C13—C14—C15—N3	64.7 (3)
C8—C5—C6—C7	−176.2 (2)	C15—N3—C16—N4	21.1 (4)
C5—C6—C7—C2	1.0 (4)	C15—N3—C16—N5	−158.6 (2)
C3—C2—C7—C6	−2.4 (4)	C17—N5—C16—N4	−166.1 (2)
C1—C2—C7—C6	177.1 (2)	C17—N5—C16—N3	13.6 (4)
C9—N1—C8—C5	−83.0 (3)	C16—N5—C17—C18	−97.2 (3)
C4—C5—C8—N1	141.1 (3)	N5—C17—C18—C23	−11.5 (4)
C6—C5—C8—N1	−41.4 (3)	N5—C17—C18—C19	171.8 (2)
C8—N1—C9—O3	−7.0 (4)	C23—C18—C19—C20	−1.0 (4)
C8—N1—C9—C10	171.5 (2)	C17—C18—C19—C20	175.9 (3)
C14—N2—C10—C11	2.0 (4)	C18—C19—C20—C21	0.5 (4)
C14—N2—C10—C9	−174.3 (2)	C19—C20—C21—C22	0.2 (5)
O3—C9—C10—N2	173.4 (2)	C20—C21—C22—C23	−0.4 (5)
N1—C9—C10—N2	−5.1 (3)	C19—C18—C23—C22	0.8 (4)
O3—C9—C10—C11	−3.1 (4)	C17—C18—C23—C22	−176.0 (3)
N1—C9—C10—C11	178.5 (2)	C21—C22—C23—C18	−0.1 (5)
N2—C10—C11—C12	−1.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H91···O1^i	0.89	2.17	2.904 (3)	140
N3—H93···O3^ii	0.89	1.92	2.762 (3)	158
N4—H94A···O2^iii	0.97	1.92	2.894 (3)	177
N4—H94B···O2^i	0.90	2.06	2.934 (3)	167
N5—H95···O1^iii	0.86	2.03	2.863 (3)	162

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

(II) N-[2-(benzylaminocarbonyl)ethyl]-N'-{6-[(4- carboxylatobenzyl)aminocarbonyl]-2-pyridylmethyl}guanidinium monohydrate

Crystal data

C26H28N6O4·H2O	Z = 2
Mr = 506.56	F(000) = 536
Triclinic, P1	Dx = 1.308 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.0848 (9) Å	Cell parameters from 98818 reflections
b = 11.5591 (7) Å	θ = 2.9–27.5°
c = 11.9676 (11) Å	µ = 0.09 mm^−1
α = 99.956 (5)°	T = 120 K
β = 98.908 (3)°	Prism, colourless
γ = 117.818 (4)°	0.2 × 0.17 × 0.06 mm
V = 1286.03 (18) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	5835 independent reflections
Radiation source: Bruker Nonius FR591 Rotating Anode	4304 reflections with I > 2σ(I)
10cm confocal mirrors monochromator	Rint = 0.049
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ϕ & ω scans to fill the asymmetric unit	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→15
Tmin = 0.982, Tmax = 0.994	l = −15→15
20604 measured reflections

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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.145	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.021P)^2 + 1.6724P] where P = (Fo^2 + 2Fc^2)/3
5835 reflections	(Δ/σ)max < 0.001
334 parameters	Δρmax = 0.31 e Å^−3
3 restraints	Δρmin = −0.24 e Å^−3

Special details

Experimental. SADABS was used to perform the Absorption correction Parameter refinement on 17133 reflections reduced R(int) from 0.1329 to 0.0460 Ratio of minimum to maximum apparent transmission: 0.653021 The given Tmin and Tmax were generated using the SHELX SIZE command

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

[O1, O2, C1 > C7; 0.057; O1 =-0.111 (2) Å] [N1, N2, O3, C9 > C14; 0.036; C10 = -0.059 (2) Å] [N3, N4, N5,C16; 0.004; C16 = 0.006 (2) Å] [C18, C19, N6, O4; 0.007; C19 = -0.012 (2) Å] [C21> C26; 0.002; C26 = -0.004 (2) Å]

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 > 2σ(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	−0.93390 (18)	−0.24852 (18)	−0.18249 (15)	0.0291 (4)
O2	−0.95992 (19)	−0.31392 (18)	−0.01815 (17)	0.0330 (4)
O3	−0.41538 (19)	0.30624 (19)	0.41625 (16)	0.0323 (4)
O4	0.52503 (19)	0.52348 (18)	0.30600 (15)	0.0297 (4)
N1	−0.2870 (2)	0.2710 (2)	0.29848 (18)	0.0241 (5)
H1	−0.2194	0.2523	0.2932	0.029*
N2	−0.0828 (2)	0.3245 (2)	0.48999 (18)	0.0224 (4)
N3	0.1416 (2)	0.3363 (2)	0.43571 (18)	0.0256 (5)
H3	0.0718	0.3374	0.3906	0.031*
N4	0.3476 (2)	0.3298 (2)	0.45022 (18)	0.0272 (5)
H4A	0.4068	0.3163	0.4165	0.033*
H4B	0.3648	0.3511	0.5275	0.033*
N5	0.2005 (2)	0.2865 (2)	0.26816 (18)	0.0274 (5)
H5	0.1207	0.2791	0.2322	0.033*
N6	0.4363 (2)	0.6172 (2)	0.19247 (19)	0.0291 (5)
H6	0.3743	0.6037	0.1288	0.035*
C1	−0.8961 (3)	−0.2312 (2)	−0.0737 (2)	0.0244 (5)
C2	−0.7599 (3)	−0.1018 (2)	−0.0019 (2)	0.0225 (5)
C3	−0.7016 (3)	−0.0832 (3)	0.1158 (2)	0.0266 (6)
H3A	−0.7483	−0.1517	0.1529	0.032*
C4	−0.5752 (3)	0.0352 (3)	0.1796 (2)	0.0265 (6)
H4	−0.5359	0.0468	0.2599	0.032*
C5	−0.5062 (2)	0.1366 (2)	0.1269 (2)	0.0227 (5)
C6	−0.5654 (3)	0.1186 (2)	0.0098 (2)	0.0243 (5)
H6A	−0.5196	0.1879	−0.0269	0.029*
C7	−0.6909 (3)	0.0000 (2)	−0.0544 (2)	0.0250 (5)
H7	−0.7298	−0.0115	−0.1347	0.030*
C8	−0.3723 (3)	0.2706 (2)	0.1928 (2)	0.0248 (5)
H8A	−0.3125	0.2989	0.1382	0.030*
H8B	−0.3990	0.3403	0.2152	0.030*
C9	−0.3101 (3)	0.2994 (2)	0.4039 (2)	0.0257 (5)
C10	−0.1971 (2)	0.3290 (2)	0.5095 (2)	0.0231 (5)
C11	−0.2091 (3)	0.3678 (3)	0.6208 (2)	0.0286 (6)
H11	−0.2917	0.3692	0.6313	0.034*
C12	−0.0985 (3)	0.4047 (3)	0.7172 (2)	0.0328 (6)
H12	−0.1036	0.4325	0.7949	0.039*
C13	0.0191 (3)	0.4005 (2)	0.6984 (2)	0.0261 (5)
H13	0.0963	0.4250	0.7629	0.031*
C14	0.0228 (2)	0.3596 (2)	0.5833 (2)	0.0220 (5)
C15	0.1495 (3)	0.3540 (3)	0.5598 (2)	0.0250 (5)
H15A	0.2373	0.4395	0.6067	0.030*
H15B	0.1522	0.2772	0.5836	0.030*
C16	0.2328 (3)	0.3182 (2)	0.3849 (2)	0.0230 (5)
C17	0.2822 (3)	0.2627 (3)	0.1935 (2)	0.0264 (6)
H17A	0.2217	0.1727	0.1343	0.032*
H17B	0.3621	0.2611	0.2419	0.032*
C18	0.3393 (3)	0.3726 (3)	0.1312 (2)	0.0272 (6)
H18A	0.2594	0.3750	0.0838	0.033*
H18B	0.3892	0.3506	0.0768	0.033*
C19	0.4406 (3)	0.5116 (3)	0.2181 (2)	0.0251 (5)
C20	0.5333 (3)	0.7555 (3)	0.2686 (2)	0.0323 (6)
H20A	0.5274	0.7568	0.3505	0.039*
H20B	0.5017	0.8167	0.2443	0.039*
C21	0.6865 (3)	0.8112 (3)	0.2671 (2)	0.0299 (6)
C22	0.7891 (3)	0.9325 (3)	0.3518 (3)	0.0397 (7)
H22	0.7622	0.9764	0.4092	0.048*
C23	0.9306 (4)	0.9888 (3)	0.3518 (3)	0.0501 (9)
H23	1.0000	1.0711	0.4099	0.060*
C24	0.9720 (3)	0.9273 (3)	0.2689 (3)	0.0466 (8)
H24	1.0689	0.9668	0.2695	0.056*
C25	0.8705 (3)	0.8073 (3)	0.1850 (3)	0.0382 (7)
H25	0.8976	0.7641	0.1272	0.046*
C26	0.7302 (3)	0.7503 (3)	0.1849 (2)	0.0321 (6)
H26	0.6617	0.6672	0.1272	0.038*
O1W	0.19025 (19)	0.54508 (18)	0.00970 (16)	0.0317 (4)
H1W	0.1257	0.4710	0.0186	0.048*
H2W	0.1544	0.5962	0.0079	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0222 (9)	0.0326 (10)	0.0229 (10)	0.0121 (8)	−0.0035 (7)	−0.0006 (7)
O2	0.0259 (10)	0.0290 (10)	0.0354 (11)	0.0085 (8)	0.0040 (8)	0.0087 (8)
O3	0.0249 (10)	0.0433 (11)	0.0310 (11)	0.0213 (9)	0.0058 (8)	0.0054 (8)
O4	0.0242 (10)	0.0342 (10)	0.0241 (10)	0.0131 (8)	−0.0022 (8)	0.0056 (8)
N1	0.0169 (10)	0.0288 (11)	0.0224 (11)	0.0120 (9)	−0.0004 (8)	0.0013 (9)
N2	0.0190 (10)	0.0221 (10)	0.0208 (11)	0.0089 (8)	0.0014 (8)	0.0018 (8)
N3	0.0208 (11)	0.0363 (12)	0.0194 (11)	0.0164 (9)	0.0007 (9)	0.0056 (9)
N4	0.0219 (11)	0.0414 (13)	0.0184 (11)	0.0191 (10)	0.0025 (9)	0.0020 (9)
N5	0.0198 (11)	0.0392 (12)	0.0204 (11)	0.0163 (10)	0.0009 (9)	0.0022 (9)
N6	0.0278 (12)	0.0327 (12)	0.0224 (11)	0.0151 (10)	−0.0014 (9)	0.0053 (9)
C1	0.0182 (12)	0.0265 (13)	0.0280 (14)	0.0137 (10)	0.0022 (10)	0.0031 (10)
C2	0.0197 (12)	0.0243 (12)	0.0232 (13)	0.0129 (10)	0.0022 (10)	0.0036 (10)
C3	0.0258 (13)	0.0285 (13)	0.0228 (13)	0.0133 (11)	0.0029 (11)	0.0056 (10)
C4	0.0247 (13)	0.0307 (13)	0.0203 (13)	0.0140 (11)	0.0000 (10)	0.0042 (10)
C5	0.0175 (12)	0.0253 (12)	0.0227 (13)	0.0112 (10)	0.0024 (10)	0.0021 (10)
C6	0.0243 (13)	0.0251 (12)	0.0234 (13)	0.0132 (10)	0.0039 (10)	0.0065 (10)
C7	0.0244 (13)	0.0286 (13)	0.0204 (13)	0.0146 (11)	0.0017 (10)	0.0032 (10)
C8	0.0212 (13)	0.0282 (13)	0.0219 (13)	0.0120 (10)	0.0023 (10)	0.0048 (10)
C9	0.0200 (13)	0.0236 (12)	0.0297 (14)	0.0104 (10)	0.0038 (11)	0.0034 (10)
C10	0.0172 (12)	0.0231 (12)	0.0250 (13)	0.0094 (10)	0.0020 (10)	0.0032 (10)
C11	0.0226 (13)	0.0348 (14)	0.0266 (14)	0.0145 (11)	0.0074 (11)	0.0041 (11)
C12	0.0359 (16)	0.0391 (15)	0.0200 (13)	0.0187 (13)	0.0060 (12)	0.0027 (11)
C13	0.0241 (13)	0.0295 (13)	0.0202 (13)	0.0126 (11)	0.0011 (10)	0.0036 (10)
C14	0.0198 (12)	0.0200 (12)	0.0221 (13)	0.0086 (10)	0.0026 (10)	0.0037 (9)
C15	0.0221 (13)	0.0297 (13)	0.0196 (13)	0.0133 (11)	0.0006 (10)	0.0024 (10)
C16	0.0181 (12)	0.0210 (12)	0.0224 (13)	0.0067 (10)	0.0013 (10)	0.0020 (10)
C17	0.0232 (13)	0.0309 (13)	0.0209 (13)	0.0140 (11)	0.0018 (10)	0.0005 (10)
C18	0.0233 (13)	0.0321 (14)	0.0200 (13)	0.0137 (11)	−0.0013 (10)	0.0007 (10)
C19	0.0213 (13)	0.0329 (14)	0.0214 (13)	0.0146 (11)	0.0050 (10)	0.0065 (10)
C20	0.0349 (16)	0.0334 (15)	0.0300 (15)	0.0197 (12)	0.0062 (12)	0.0073 (12)
C21	0.0347 (15)	0.0276 (13)	0.0227 (13)	0.0130 (12)	0.0025 (11)	0.0089 (11)
C22	0.0429 (18)	0.0311 (15)	0.0334 (16)	0.0140 (13)	0.0024 (14)	0.0039 (12)
C23	0.0422 (19)	0.0317 (16)	0.046 (2)	0.0021 (14)	−0.0032 (15)	0.0043 (14)
C24	0.0311 (17)	0.0451 (18)	0.050 (2)	0.0088 (14)	0.0059 (15)	0.0180 (15)
C25	0.0381 (17)	0.0410 (16)	0.0326 (16)	0.0174 (14)	0.0065 (13)	0.0144 (13)
C26	0.0347 (15)	0.0306 (14)	0.0229 (14)	0.0130 (12)	0.0006 (12)	0.0060 (11)
O1W	0.0261 (10)	0.0336 (10)	0.0330 (11)	0.0134 (8)	0.0046 (8)	0.0118 (8)

Geometric parameters (Å, º)

O1—C1	1.254 (3)	C8—H8B	0.9900
O2—C1	1.261 (3)	C9—C10	1.497 (3)
O3—C9	1.235 (3)	C10—C11	1.378 (3)
O4—C19	1.236 (3)	C11—C12	1.385 (4)
N1—C9	1.342 (3)	C11—H11	0.9500
N1—C8	1.455 (3)	C12—C13	1.378 (4)
N1—H1	0.8794	C12—H12	0.9500
N2—C14	1.333 (3)	C13—C14	1.390 (3)
N2—C10	1.346 (3)	C13—H13	0.9500
N3—C16	1.333 (3)	C14—C15	1.502 (3)
N3—C15	1.446 (3)	C15—H15A	0.9900
N3—H3	0.8789	C15—H15B	0.9900
N4—C16	1.320 (3)	C17—C18	1.515 (4)
N4—H4A	0.8796	C17—H17A	0.9900
N4—H4B	0.8804	C17—H17B	0.9900
N5—C16	1.327 (3)	C18—C19	1.517 (3)
N5—C17	1.447 (3)	C18—H18A	0.9900
N5—H5	0.8796	C18—H18B	0.9900
N6—C19	1.329 (3)	C20—C21	1.513 (4)
N6—C20	1.459 (3)	C20—H20A	0.9900
N6—H6	0.8797	C20—H20B	0.9900
C1—C2	1.517 (3)	C21—C26	1.387 (4)
C2—C7	1.389 (3)	C21—C22	1.396 (4)
C2—C3	1.390 (3)	C22—C23	1.389 (5)
C3—C4	1.391 (3)	C22—H22	0.9500
C3—H3A	0.9500	C23—C24	1.380 (5)
C4—C5	1.387 (3)	C23—H23	0.9500
C4—H4	0.9500	C24—C25	1.382 (4)
C5—C6	1.388 (3)	C24—H24	0.9500
C5—C8	1.514 (3)	C25—C26	1.377 (4)
C6—C7	1.389 (3)	C25—H25	0.9500
C6—H6A	0.9500	C26—H26	0.9500
C7—H7	0.9500	O1W—H1W	0.8601
C8—H8A	0.9900	O1W—H2W	0.8536
C9—N1—C8	120.9 (2)	C12—C13—C14	118.8 (2)
C9—N1—H1	119.5	C12—C13—H13	120.6
C8—N1—H1	119.6	C14—C13—H13	120.6
C14—N2—C10	117.9 (2)	N2—C14—C13	122.7 (2)
C16—N3—C15	124.6 (2)	N2—C14—C15	117.1 (2)
C16—N3—H3	117.7	C13—C14—C15	120.1 (2)
C15—N3—H3	117.7	N3—C15—C14	109.7 (2)
C16—N4—H4A	120.0	N3—C15—H15A	109.7
C16—N4—H4B	119.9	C14—C15—H15A	109.7
H4A—N4—H4B	120.1	N3—C15—H15B	109.7
C16—N5—C17	127.1 (2)	C14—C15—H15B	109.7
C16—N5—H5	116.5	H15A—C15—H15B	108.2
C17—N5—H5	116.4	N4—C16—N5	123.1 (2)
C19—N6—C20	120.8 (2)	N4—C16—N3	120.1 (2)
C19—N6—H6	119.6	N5—C16—N3	116.8 (2)
C20—N6—H6	119.5	N5—C17—C18	111.0 (2)
O1—C1—O2	125.7 (2)	N5—C17—H17A	109.4
O1—C1—C2	117.9 (2)	C18—C17—H17A	109.4
O2—C1—C2	116.4 (2)	N5—C17—H17B	109.4
C7—C2—C3	119.0 (2)	C18—C17—H17B	109.4
C7—C2—C1	119.7 (2)	H17A—C17—H17B	108.0
C3—C2—C1	121.2 (2)	C17—C18—C19	111.5 (2)
C2—C3—C4	120.4 (2)	C17—C18—H18A	109.3
C2—C3—H3A	119.8	C19—C18—H18A	109.3
C4—C3—H3A	119.8	C17—C18—H18B	109.3
C5—C4—C3	120.5 (2)	C19—C18—H18B	109.3
C5—C4—H4	119.7	H18A—C18—H18B	108.0
C3—C4—H4	119.7	O4—C19—N6	122.9 (2)
C4—C5—C6	119.0 (2)	O4—C19—C18	120.1 (2)
C4—C5—C8	123.2 (2)	N6—C19—C18	116.9 (2)
C6—C5—C8	117.7 (2)	N6—C20—C21	114.5 (2)
C5—C6—C7	120.6 (2)	N6—C20—H20A	108.6
C5—C6—H6A	119.7	C21—C20—H20A	108.6
C7—C6—H6A	119.7	N6—C20—H20B	108.6
C2—C7—C6	120.5 (2)	C21—C20—H20B	108.6
C2—C7—H7	119.8	H20A—C20—H20B	107.6
C6—C7—H7	119.8	C26—C21—C22	118.3 (3)
N1—C8—C5	116.3 (2)	C26—C21—C20	123.8 (2)
N1—C8—H8A	108.2	C22—C21—C20	118.0 (3)
C5—C8—H8A	108.2	C23—C22—C21	119.9 (3)
N1—C8—H8B	108.2	C23—C22—H22	120.1
C5—C8—H8B	108.2	C21—C22—H22	120.1
H8A—C8—H8B	107.4	C24—C23—C22	121.1 (3)
O3—C9—N1	123.2 (2)	C24—C23—H23	119.5
O3—C9—C10	120.3 (2)	C22—C23—H23	119.5
N1—C9—C10	116.4 (2)	C23—C24—C25	119.1 (3)
N2—C10—C11	122.9 (2)	C23—C24—H24	120.4
N2—C10—C9	117.3 (2)	C25—C24—H24	120.4
C11—C10—C9	119.6 (2)	C26—C25—C24	120.2 (3)
C10—C11—C12	118.7 (2)	C26—C25—H25	119.9
C10—C11—H11	120.6	C24—C25—H25	119.9
C12—C11—H11	120.6	C25—C26—C21	121.5 (3)
C13—C12—C11	118.9 (2)	C25—C26—H26	119.2
C13—C12—H12	120.5	C21—C26—H26	119.2
C11—C12—H12	120.5	H1W—O1W—H2W	105.4
O1—C1—C2—C7	7.8 (3)	C10—N2—C14—C13	−0.2 (3)
O2—C1—C2—C7	−173.8 (2)	C10—N2—C14—C15	−180.0 (2)
O1—C1—C2—C3	−171.7 (2)	C12—C13—C14—N2	0.2 (4)
O2—C1—C2—C3	6.7 (3)	C12—C13—C14—C15	179.9 (2)
C7—C2—C3—C4	−0.6 (4)	C16—N3—C15—C14	−175.2 (2)
C1—C2—C3—C4	178.9 (2)	N2—C14—C15—N3	11.4 (3)
C2—C3—C4—C5	0.4 (4)	C13—C14—C15—N3	−168.4 (2)
C3—C4—C5—C6	0.4 (4)	C17—N5—C16—N4	−1.5 (4)
C3—C4—C5—C8	177.0 (2)	C17—N5—C16—N3	179.7 (2)
C4—C5—C6—C7	−0.9 (4)	C15—N3—C16—N4	−7.1 (4)
C8—C5—C6—C7	−177.7 (2)	C15—N3—C16—N5	171.8 (2)
C3—C2—C7—C6	0.1 (4)	C16—N5—C17—C18	−113.2 (3)
C1—C2—C7—C6	−179.4 (2)	N5—C17—C18—C19	62.8 (3)
C5—C6—C7—C2	0.6 (4)	C20—N6—C19—O4	0.0 (4)
C9—N1—C8—C5	−89.2 (3)	C20—N6—C19—C18	−177.8 (2)
C4—C5—C8—N1	23.5 (4)	C17—C18—C19—O4	39.2 (3)
C6—C5—C8—N1	−159.8 (2)	C17—C18—C19—N6	−143.0 (2)
C8—N1—C9—O3	11.3 (4)	C19—N6—C20—C21	69.6 (3)
C8—N1—C9—C10	−166.2 (2)	N6—C20—C21—C26	12.2 (4)
C14—N2—C10—C11	0.0 (3)	N6—C20—C21—C22	−169.2 (2)
C14—N2—C10—C9	175.6 (2)	C26—C21—C22—C23	0.2 (4)
O3—C9—C10—N2	−177.6 (2)	C20—C21—C22—C23	−178.5 (3)
N1—C9—C10—N2	−0.1 (3)	C21—C22—C23—C24	0.3 (5)
O3—C9—C10—C11	−1.8 (4)	C22—C23—C24—C25	−0.2 (5)
N1—C9—C10—C11	175.7 (2)	C23—C24—C25—C26	−0.3 (5)
N2—C10—C11—C12	0.4 (4)	C24—C25—C26—C21	0.7 (4)
C9—C10—C11—C12	−175.1 (2)	C22—C21—C26—C25	−0.7 (4)
C10—C11—C12—C13	−0.4 (4)	C20—C21—C26—C25	178.0 (3)
C11—C12—C13—C14	0.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.88	2.32	3.084 (3)	145
N3—H3···O1^i	0.88	2.46	3.180 (3)	139
N4—H4A···O3^ii	0.88	2.03	2.847 (3)	154
N4—H4B···O4^iii	0.88	2.04	2.856 (3)	154
N5—H5···O1^i	0.88	1.91	2.770 (3)	167
N6—H6···O1W	0.88	2.03	2.884 (3)	163
O1W—H1W···O2^i	0.86	1.88	2.734 (3)	169
O1W—H2W···O2^iv	0.85	2.00	2.844 (3)	170

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