A three-dimensional hydrogen-bonded framework in 4,4′-tri­methyl­ene­di­piperidinium–2,5-di­carboxy­benzene-1,4-di­carboxyl­ate–water (1/1/1)

The title compound is a salt, C₁₃H₂₈N₂²⁺·C₁₀H₄O₈²⁻·H₂O. In the anion, there are two short intramolecular hydrogen bonds [O...O 2.395 (2) and 2.383 (2) Å; O...H...O 175 and 172°]. Pairs of anions and pairs of water mol­ecules are linked by further O—H...O hydrogen bonds [O...O 2.756 (2) and 2.980 (2) Å; O—H...O 171 and 175°] into cyclic centrosymmetric R₆⁶(16) aggregates; these aggregates are linked via the cations into a three-dimensional framework by means of four distinct N—H...O hydrogen bonds [N...O 2.787 (2)–3.204 (2) Å; N—H...O 148–173°].

S1. Comment

Benzene-1,2,4,5-tetracarboxylic acid, C₆H₂(COOH)₄ pyromellitic acid, readily forms an anion [C₁₀H₄O₈]^2- and the behaviour of this anion in the solid state is dominated by two distinct patterns of hydrogen bonding (Lough et al., 2000). In form (I), there are two intramolecular hydrogen bonds which are very short with O···O distances around 2.40 Å and with the H nearly, or exactly, centred along the O···O vector: this isomer can thus act only as an acceptor of hard intermolecular hydrogen bonds. In the alternative form (II), there are no intramolecular hydrogen bonds so that it can act both as a twofold donor of hydrogen bonds and as a multiple acceptor.

Continuing our earlier structural study (Lough et al., 2000) of salts formed between this acid and organic diamines, we have now characterized a hydrated salt formed with the chain-extended diamine 4,4'-trimethylenedipiperidine HNC₅H₉-(CH₂)₃-C₅H₉NH: double protonation of this amine will provide a chain-extended dication [H₂NC₅H₉-(CH₂)₃-C₅H₉NH₂]²⁺ capable of acting as a fourfold donor of hydrogen bonds, while the distance between the two NH₂ units can provide an effective spacer between the anionic components.

The title compound is a hydrated salt [C₁₃H₂₈N₂]²⁺·[C₁₀H₄O₈]^2-·H₂O, (1), in which each of the components lies in a general position (Fig. 1). The anion adopts form (I) with two intramolecular hydrogen bonds and acts as a fivefold acceptor of intermolecular hydrogen bonds; the cation acts as a fourfold donor, and the neutral water molecule acts as a double donor and as a single acceptor of hydrogen bonds. There are thus six distinct intermolecular hydrogen bonds, four of N—H···O type and two of O—H···O type (Table 2). These link the components into a single three-dimensional framework. While frameworks containing so many different hydrogen bonds can generally be described in a large number of ways, the supramolecular structure of (1) is most simply described in terms of the formation of finite clusters of anions and water molecules, and the subsequent linking of these clusters by the cations. \sch

Pairs of anions and pairs of water molecules form cyclic centrosymmetric aggregates. The water molecule at (x, y, z) acts as donor, via H91, to O6 also at (x, y, z) and, via H92, to O8 at (1 - x, 1 - y, 1 - z), thus generating a centrosymmetric R⁶₆(16) motif (Fig. 2). There is one of these four-component aggregates at the centre of each unit cell, so that the cell contains two anions and two water molecules. The linking of the clusters by the cations can itself be conveniently described in two steps.

The cations link the anion/water clusters into chains of fused rings running parallel to the [001] direction, by the action of N21 as a double donor of hydrogen bonds, while hydrogen bonds having N31 as donor link the [001] chain into a continuous framework. Atom N21 at (x, y, z) is donor, via H21A, to O9 at (x, y, z) and via H21B to O4 at (x, y, -1 + z); N21 at (1 - x, 1 - y, -z) likewise acts as donor to O9 at (1 - x, 1 - y, -z) and to O4 at (1 - x, 1 - y, -1 - z). In this manner, a centrosymmetric R⁶₆(26) ring is formed: in the [001] chain the R⁶₆(16) rings are centred at (1/2, 1/2, 0.5 + n) and the R⁶₆(26) rings at (1/2, 1/2, n) (n = zero or integer) (Fig. 2), and a single chain of this type runs through each unit cell.

The N31 donors pendent from chains of this type link all the chains together. N31 at (x, y, z) is a component of the chain along (1/2, 1/2, z): it acts as donor, via H31A, to O1 at (-1 + x, 1 + y, z) which is a component of the chain along (-0.5, 1.5, z) and, via H31B, to O2 at (1 - x, 2 - y, 2 - z) which is a component of the chain along (1/2, 1.5, z). Propagation of these links by inversion and translation serves to join all the [001] chains into a continuous framework.

In each of the two independent intramolecular hydrogen bonds in the anion, the H atom is equidistant from the O atoms and O···H···O is almost linear (Table 2). The formation of these short strong hydrogen bonds evidently occurs at some energy cost to the rest of the anion, as manifested in geometric distortion elsewhere in the anion. Not only are all the –COO^- units significantly twisted out of the plane of the aryl ring (Table 1), but the exocyclic C—C—C bond angles within the S(7) ring are all just above 128°, indicative of considerable steric strain. The rotations of the carboxylate substituents are concerted (Table 1). The rotations of the pairs containing C17 and C18, and C19 and C110 are disrotatory, while those of the pairs containing C18 and C19, and C17 and C110 are conrotatory. The molecular symmetry of the anion is thus approximately C_{2 h} (2/m) rather than the optimum D_{2 h} (mmm), with the approximate twofold axis running through the two C—H bonds. The same, approximately C_{2 h}, conformation is observed for each of the two independent [C₁₀H₄O₈]^2- anions in the salt with mono-protonated hexamethylenetetramine and, indeed, one of these anions lies across a centre of inversion (Lough et al., 2000), while in the salt [Ni(H₂O)₆]²⁺·[C₁₀H₄O₈]^2-, the anions lie is special positions of 2/m symmetry (Jessen et al., 1992). In the 1:1 salt formed from 2,2'-bipyridyl, [{(C₁₀H₈N₂)H}⁺]₂·[C₁₀H₄O₈]^2-·[C₁₀H₆O₈], where the carboxylate rotations in the centrosymmetric anion again generate approximate C_{2 h} symmetry, it is now the approximate mirror plane which contains the two C—H bonds (Mrvos-Sermek et al., 1996). In each of the substituents the C—O bond involved in the intramolecular hydrogen bond is very much longer than its companion, by between 0.048 (2) and 0.077 (2) Å, indicative of some bond fixation within the carboxylate groups; of the C—O bonds not so involved, C19—O5, where the O is not involved in either inter- or intramolecular hydrogen bonding, is significantly shorter than the remainder.

In the cation, the two independent rings both adopt chair conformations with the central -(CH₂)₃– spacer unit occupying equatorial sites in both: this spacer has an extended all-trans conformation, and the cation as a whole has approximate C₂ symmetry. There is a long sequence of antiperiplanar torsional angles between C26 and C32, all within 10° of 180° (Table 1, Fig. 1). The similar magnitudes of the torsional angles C23—C24—C4—C5 and C35—C34—C6—C5 and their identical signs confirm the approximate C₂ symmetry. The bond lengths and angles in the cation all have normal values.

S2. Experimental

Equimolar quantities of 4,4'-trimethylenedipiperidine and benzene-1,2,4,5-tetracarboxylic acid dihydrate were separately dissolved in methanol. The solutions were mixed and the mixture was set aside to crystallize, producing analytically pure (1). Analysis: found C 57.4, H 7.0, N 5.8%: C₂₃H₃₄N₂O₉ requires C 57.2, H 7.1, N 5.8%. Crystals suitable for single-crystal X-ray diffraction were selected directly from the analytical sample.

S3. Refinement

All H atoms were clearly defined in difference maps and were then treated as riding atoms with C—H 0.95 to 1.00 Å, N—H 0.94 Å, water O—H 0.89 Å (initially allowed to refine then restrained to the refined value with a DFIX command), carboxyl O—H 1.20 Å (placed at the centre of each of the short O.·H.·O hydrogen bonds). Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent-accessible voids in the crystal lattice.

Computing details

Data collection: Kappa-CCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: NRCVAX96 (Gabe et al., 1989) and SHELXL97 (Sheldrick, 1997); molecular graphics: NRCVAX96, ORTEP (Johnson, 1976) and PLATON (Spek, 2000); software used to prepare material for publication: NRCVAX96, SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The asymmetric unit of (1) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (1), showing linking of the anion/water aggregates by the cations into a chain of alternating R^66(16) and R^66(26) rings along [001]. Atoms marked with a star (*) or hash (#) are at the symmetry positions (1 - x, 1 - y, 1 - z) and (x, y, -1 + z), respectively.

4,4'-Trimethylenedipiperidine–benzene-1,2,4,5-tetracarboxylic acid–water (1/1/1)

Crystal data

C13H28N2^2+·C10H4O8^2^−·H2O	Z = 2
Mr = 482.52	F(000) = 516
Triclinic, P1	Dx = 1.401 Mg m^−3
a = 10.5885 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.5840 (6) Å	Cell parameters from 8817 reflections
c = 11.8301 (6) Å	θ = 2.8–30.1°
α = 61.453 (2)°	µ = 0.11 mm^−1
β = 80.999 (3)°	T = 150 K
γ = 64.055 (3)°	Block, colourless
V = 1143.63 (9) Å^3	0.31 × 0.26 × 0.16 mm

Data collection

Kappa-CCD diffractometer	6632 independent reflections
Radiation source: fine-focus sealed X-ray tube	4752 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ϕ scans and ω scans with κ offsets	θmax = 30.1°, θmin = 2.8°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→14
Tmin = 0.967, Tmax = 0.983	k = −14→16
8817 measured reflections	l = −16→16

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0403P)^2 + 0.3818P] where P = (Fo^2 + 2Fc^2)/3
6632 reflections	(Δ/σ)max < 0.001
317 parameters	Δρmax = 0.37 e Å^−3
2 restraints	Δρmin = −0.23 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G. C. & Holmes, K. C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
O1	0.82375 (10)	0.64403 (13)	0.90569 (12)	0.0376 (3)
O2	0.68001 (11)	0.79086 (13)	0.98085 (11)	0.0343 (3)
O3	0.44084 (11)	0.87211 (13)	1.03762 (11)	0.0331 (3)
H3	0.5587	0.8354	1.0043	0.050*
O4	0.26730 (10)	0.80737 (13)	1.06721 (10)	0.0303 (2)
O5	0.14771 (11)	0.67892 (15)	0.80144 (13)	0.0449 (3)
O6	0.30076 (11)	0.50765 (13)	0.75328 (12)	0.0382 (3)
O7	0.53272 (11)	0.44656 (12)	0.68017 (11)	0.0330 (3)
H7	0.4199	0.4727	0.7242	0.049*
O8	0.69639 (11)	0.52896 (12)	0.63499 (10)	0.0309 (3)
C11	0.58191 (13)	0.69456 (14)	0.89256 (12)	0.0182 (3)
C12	0.44423 (14)	0.73143 (15)	0.93550 (12)	0.0190 (3)
C13	0.35288 (14)	0.69758 (15)	0.89673 (12)	0.0206 (3)
H13	0.2602	0.7225	0.9254	0.025*
C14	0.38860 (14)	0.62966 (15)	0.81884 (12)	0.0194 (3)
C15	0.52497 (13)	0.59507 (14)	0.77408 (12)	0.0189 (3)
C16	0.61582 (14)	0.63032 (14)	0.81167 (13)	0.0194 (3)
H16	0.7071	0.6091	0.7799	0.023*
C17	0.70384 (14)	0.70970 (15)	0.92861 (13)	0.0220 (3)
C18	0.37939 (14)	0.80657 (16)	1.01991 (13)	0.0228 (3)
C19	0.26865 (15)	0.60609 (17)	0.78939 (14)	0.0259 (3)
C110	0.58958 (14)	0.51981 (15)	0.68957 (13)	0.0222 (3)
N21	0.27499 (12)	0.87121 (14)	0.27730 (11)	0.0246 (3)
H21A	0.2590	0.7929	0.3442	0.030*
H21B	0.2780	0.8650	0.2005	0.030*
N31	0.02798 (12)	1.42914 (14)	0.84862 (12)	0.0256 (3)
H31A	−0.0324	1.5047	0.8680	0.031*
H31B	0.1198	1.3980	0.8790	0.031*
C22	0.15624 (15)	1.00982 (17)	0.26397 (14)	0.0257 (3)
H22A	0.0664	1.0129	0.2459	0.031*
H22B	0.1700	1.0926	0.1908	0.031*
C23	0.14959 (15)	1.02207 (17)	0.38747 (14)	0.0254 (3)
H23A	0.1235	0.9463	0.4577	0.030*
H23B	0.0748	1.1172	0.3747	0.030*
C24	0.28887 (14)	1.00635 (16)	0.42863 (13)	0.0225 (3)
H24	0.3074	1.0917	0.3641	0.027*
C25	0.40838 (15)	0.86854 (16)	0.43099 (14)	0.0256 (3)
H25A	0.4993	0.8639	0.4486	0.031*
H25B	0.3968	0.7833	0.5024	0.031*
C26	0.41294 (15)	0.86098 (17)	0.30566 (14)	0.0265 (3)
H26A	0.4319	0.9415	0.2344	0.032*
H26B	0.4894	0.7687	0.3134	0.032*
C32	−0.01515 (15)	1.30647 (17)	0.91628 (14)	0.0272 (3)
H32A	−0.1140	1.3402	0.8888	0.033*
H32B	−0.0092	1.2715	1.0106	0.033*
C33	0.07980 (15)	1.18368 (16)	0.88507 (13)	0.0253 (3)
H33A	0.0456	1.1065	0.9256	0.030*
H33B	0.1763	1.1423	0.9226	0.030*
C34	0.08470 (14)	1.23283 (15)	0.73985 (13)	0.0207 (3)
H34	−0.0113	1.2641	0.7051	0.025*
C35	0.12204 (15)	1.36314 (16)	0.67410 (14)	0.0243 (3)
H35A	0.2199	1.3321	0.7020	0.029*
H35B	0.1170	1.3997	0.5795	0.029*
C36	0.02358 (14)	1.48433 (16)	0.70614 (13)	0.0237 (3)
H36A	0.0526	1.5653	0.6645	0.028*
H36B	−0.0736	1.5209	0.6729	0.028*
C4	0.28495 (16)	0.99856 (16)	0.56186 (14)	0.0268 (3)
H4A	0.2575	0.9196	0.6232	0.032*
H4B	0.3816	0.9713	0.5898	0.032*
C5	0.18704 (16)	1.13499 (16)	0.57331 (14)	0.0264 (3)
H5A	0.0902	1.1667	0.5423	0.032*
H5B	0.2177	1.2133	0.5184	0.032*
C6	0.18756 (15)	1.10743 (16)	0.71347 (14)	0.0250 (3)
H6A	0.1660	1.0225	0.7680	0.030*
H6B	0.2839	1.0818	0.7409	0.030*
O9	0.20536 (12)	0.65392 (13)	0.47598 (11)	0.0308 (3)
H91	0.238 (2)	0.612 (2)	0.5572 (8)	0.076 (8)*
H92	0.243 (2)	0.5873 (16)	0.4483 (19)	0.057 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0200 (5)	0.0430 (7)	0.0652 (8)	−0.0083 (5)	−0.0002 (5)	−0.0397 (7)
O2	0.0338 (6)	0.0505 (8)	0.0449 (7)	−0.0249 (6)	0.0119 (5)	−0.0375 (6)
O3	0.0357 (6)	0.0433 (7)	0.0410 (6)	−0.0210 (5)	0.0128 (5)	−0.0335 (6)
O4	0.0271 (5)	0.0418 (7)	0.0295 (6)	−0.0145 (5)	0.0085 (4)	−0.0239 (5)
O5	0.0241 (6)	0.0724 (10)	0.0641 (8)	−0.0214 (6)	0.0099 (5)	−0.0515 (8)
O6	0.0285 (6)	0.0431 (7)	0.0629 (8)	−0.0166 (5)	0.0012 (5)	−0.0370 (7)
O7	0.0323 (6)	0.0353 (7)	0.0466 (7)	−0.0144 (5)	0.0019 (5)	−0.0297 (6)
O8	0.0315 (6)	0.0396 (7)	0.0352 (6)	−0.0172 (5)	0.0105 (5)	−0.0275 (5)
C11	0.0213 (6)	0.0165 (6)	0.0166 (6)	−0.0077 (5)	−0.0007 (5)	−0.0071 (5)
C12	0.0228 (6)	0.0180 (7)	0.0149 (6)	−0.0079 (5)	0.0012 (5)	−0.0071 (5)
C13	0.0206 (6)	0.0226 (7)	0.0171 (6)	−0.0092 (5)	0.0021 (5)	−0.0082 (6)
C14	0.0220 (6)	0.0188 (7)	0.0165 (6)	−0.0091 (5)	−0.0006 (5)	−0.0065 (5)
C15	0.0220 (6)	0.0161 (7)	0.0172 (6)	−0.0065 (5)	−0.0015 (5)	−0.0072 (5)
C16	0.0187 (6)	0.0189 (7)	0.0205 (6)	−0.0064 (5)	0.0006 (5)	−0.0100 (6)
C17	0.0242 (7)	0.0217 (7)	0.0226 (7)	−0.0099 (6)	−0.0011 (5)	−0.0110 (6)
C18	0.0265 (7)	0.0244 (8)	0.0175 (6)	−0.0085 (6)	0.0014 (5)	−0.0117 (6)
C19	0.0256 (7)	0.0330 (8)	0.0252 (7)	−0.0154 (6)	0.0015 (6)	−0.0151 (7)
C110	0.0245 (7)	0.0203 (7)	0.0228 (7)	−0.0058 (5)	−0.0031 (5)	−0.0124 (6)
N21	0.0302 (6)	0.0286 (7)	0.0227 (6)	−0.0145 (5)	0.0056 (5)	−0.0165 (5)
N31	0.0237 (6)	0.0273 (7)	0.0297 (6)	−0.0055 (5)	−0.0017 (5)	−0.0196 (6)
C22	0.0269 (7)	0.0282 (8)	0.0240 (7)	−0.0106 (6)	0.0002 (6)	−0.0138 (6)
C23	0.0259 (7)	0.0268 (8)	0.0255 (7)	−0.0085 (6)	0.0029 (6)	−0.0162 (6)
C24	0.0262 (7)	0.0217 (7)	0.0216 (7)	−0.0083 (6)	0.0013 (5)	−0.0128 (6)
C25	0.0247 (7)	0.0258 (8)	0.0279 (7)	−0.0065 (6)	−0.0005 (6)	−0.0166 (6)
C26	0.0255 (7)	0.0292 (8)	0.0307 (8)	−0.0108 (6)	0.0056 (6)	−0.0197 (7)
C32	0.0286 (7)	0.0278 (8)	0.0222 (7)	−0.0080 (6)	0.0030 (6)	−0.0132 (6)
C33	0.0294 (7)	0.0252 (8)	0.0217 (7)	−0.0106 (6)	0.0020 (6)	−0.0119 (6)
C34	0.0209 (6)	0.0219 (7)	0.0214 (6)	−0.0073 (5)	0.0001 (5)	−0.0125 (6)
C35	0.0253 (7)	0.0255 (8)	0.0251 (7)	−0.0107 (6)	0.0057 (6)	−0.0148 (6)
C36	0.0236 (7)	0.0230 (7)	0.0264 (7)	−0.0098 (6)	0.0024 (5)	−0.0129 (6)
C4	0.0329 (8)	0.0220 (8)	0.0236 (7)	−0.0051 (6)	−0.0030 (6)	−0.0135 (6)
C5	0.0321 (7)	0.0227 (8)	0.0233 (7)	−0.0065 (6)	−0.0009 (6)	−0.0135 (6)
C6	0.0294 (7)	0.0225 (7)	0.0232 (7)	−0.0068 (6)	−0.0019 (6)	−0.0131 (6)
O9	0.0391 (6)	0.0316 (7)	0.0284 (6)	−0.0166 (5)	0.0081 (5)	−0.0188 (5)

Geometric parameters (Å, º)

O1—C17	1.2283 (17)	C23—H23A	0.99
O2—C17	1.2761 (17)	C23—H23B	0.99
O3—C18	1.2926 (17)	C24—C4	1.5300 (19)
O3—H3	1.20	C24—C25	1.5334 (19)
O4—C18	1.2286 (17)	C24—H24	1.00
O5—C19	1.2184 (18)	C25—C26	1.519 (2)
O6—C19	1.2958 (18)	C25—H25A	0.99
O7—C110	1.2857 (17)	C25—H25B	0.99
O7—H7	1.20	C26—H26A	0.99
O8—C110	1.2321 (17)	C26—H26B	0.99
C11—C16	1.3920 (18)	C32—C33	1.518 (2)
C11—C12	1.4129 (18)	C32—H32A	0.99
C11—C17	1.5237 (18)	C32—H32B	0.99
C12—C13	1.3936 (19)	C33—C34	1.5302 (19)
C12—C18	1.5230 (19)	C33—H33A	0.99
C13—C14	1.3908 (19)	C33—H33B	0.99
C13—H13	0.95	C34—C6	1.5285 (19)
C14—C15	1.4083 (18)	C34—C35	1.5309 (19)
C14—C19	1.5304 (18)	C34—H34	1.00
C15—C16	1.3933 (18)	C35—C36	1.5185 (19)
C15—C110	1.5247 (19)	C35—H35A	0.99
C16—H16	0.95	C35—H35B	0.99
N21—C22	1.4958 (19)	C36—H36A	0.99
N21—C26	1.4913 (18)	C36—H36B	0.99
N21—H21A	0.94	C4—C5	1.522 (2)
N21—H21B	0.94	C4—H4A	0.99
N31—C32	1.4950 (19)	C4—H4B	0.99
N31—C36	1.4902 (18)	C5—C6	1.5319 (19)
N31—H31A	0.94	C5—H5A	0.99
N31—H31B	0.94	C5—H5B	0.99
C22—C23	1.5221 (19)	C6—H6A	0.99
C22—H22A	0.99	C6—H6B	0.99
C22—H22B	0.99	O9—H91	0.89
C23—C24	1.5330 (19)	O9—H92	0.89
C18—O3—H3	109.5	C26—C25—C24	113.10 (12)
C110—O7—H7	109.5	C26—C25—H25A	109.0
C16—C11—C12	117.72 (12)	C24—C25—H25A	109.0
C12—C11—C17	128.03 (12)	C26—C25—H25B	109.0
C16—C11—C17	114.19 (11)	C24—C25—H25B	109.0
C13—C12—C11	117.79 (12)	H25A—C25—H25B	107.8
C11—C12—C18	128.15 (12)	N21—C26—C25	109.11 (11)
C13—C12—C18	114.06 (11)	N21—C26—H26A	109.9
C14—C13—C12	124.24 (12)	C25—C26—H26A	109.9
C14—C13—H13	117.9	N21—C26—H26B	109.9
C12—C13—H13	117.9	C25—C26—H26B	109.9
C13—C14—C15	118.08 (12)	H26A—C26—H26B	108.3
C13—C14—C19	113.87 (11)	N31—C32—C33	110.23 (11)
C15—C14—C19	128.02 (12)	N31—C32—H32A	109.6
C16—C15—C14	117.68 (12)	C33—C32—H32A	109.6
C14—C15—C110	128.12 (12)	N31—C32—H32B	109.6
C16—C15—C110	114.19 (11)	C33—C32—H32B	109.6
C11—C16—C15	124.44 (12)	H32A—C32—H32B	108.1
C11—C16—H16	117.8	C32—C33—C34	112.50 (12)
C15—C16—H16	117.8	C32—C33—H33A	109.1
O1—C17—O2	121.11 (13)	C34—C33—H33A	109.1
O1—C17—C11	119.10 (12)	C32—C33—H33B	109.1
O2—C17—C11	119.79 (12)	C34—C33—H33B	109.1
O3—C18—O4	120.99 (13)	H33A—C33—H33B	107.8
O4—C18—C12	119.40 (13)	C6—C34—C33	110.43 (11)
O3—C18—C12	119.58 (12)	C6—C34—C35	112.31 (11)
O5—C19—O6	122.61 (13)	C33—C34—C35	109.59 (11)
O5—C19—C14	119.31 (13)	C6—C34—H34	108.1
O6—C19—C14	118.08 (12)	C33—C34—H34	108.1
O7—C110—O8	122.43 (13)	C35—C34—H34	108.1
O8—C110—C15	118.61 (12)	C36—C35—C34	111.93 (11)
O7—C110—C15	118.94 (12)	C36—C35—H35A	109.2
C26—N21—C22	111.68 (11)	C34—C35—H35A	109.2
C26—N21—H21A	109.3	C36—C35—H35B	109.2
C22—N21—H21A	109.3	C34—C35—H35B	109.2
C26—N21—H21B	109.3	H35A—C35—H35B	107.9
C22—N21—H21B	109.3	N31—C36—C35	109.52 (11)
H21A—N21—H21B	107.9	N31—C36—H36A	109.8
C36—N31—C32	111.91 (11)	C35—C36—H36A	109.8
C36—N31—H31A	109.2	N31—C36—H36B	109.8
C32—N31—H31A	109.2	C35—C36—H36B	109.8
C36—N31—H31B	109.2	H36A—C36—H36B	108.2
C32—N31—H31B	109.2	C5—C4—C24	116.90 (12)
H31A—N31—H31B	107.9	C5—C4—H4A	108.1
N21—C22—C23	110.12 (12)	C24—C4—H4A	108.1
N21—C22—H22A	109.6	C5—C4—H4B	108.1
C23—C22—H22A	109.6	C24—C4—H4B	108.1
N21—C22—H22B	109.6	H4A—C4—H4B	107.3
C23—C22—H22B	109.6	C4—C5—C6	110.74 (12)
H22A—C22—H22B	108.2	C4—C5—H5A	109.5
C22—C23—C24	113.13 (11)	C6—C5—H5A	109.5
C22—C23—H23A	109.0	C4—C5—H5B	109.5
C24—C23—H23A	109.0	C6—C5—H5B	109.5
C22—C23—H23B	109.0	H5A—C5—H5B	108.1
C24—C23—H23B	109.0	C34—C6—C5	115.94 (12)
H23A—C23—H23B	107.8	C34—C6—H6A	108.3
C4—C24—C23	111.78 (11)	C5—C6—H6A	108.3
C4—C24—C25	109.34 (11)	C34—C6—H6B	108.3
C23—C24—C25	109.09 (12)	C5—C6—H6B	108.3
C4—C24—H24	108.9	H6A—C6—H6B	107.4
C23—C24—H24	108.9	H91—O9—H92	108
C25—C24—H24	108.9
C16—C11—C12—C13	1.64 (19)	C15—C14—C19—O6	22.9 (2)
C17—C11—C12—C13	−175.23 (13)	C16—C15—C110—O7	160.19 (13)
C16—C11—C12—C18	−177.74 (13)	C16—C15—C110—O8	−18.25 (19)
C17—C11—C12—C18	5.4 (2)	C14—C15—C110—O8	162.91 (14)
C11—C12—C13—C14	0.2 (2)	C14—C15—C110—O7	−18.7 (2)
C18—C12—C13—C14	179.61 (13)	C26—N21—C22—C23	−58.88 (15)
C12—C13—C14—C15	−1.2 (2)	N21—C22—C23—C24	54.78 (16)
C12—C13—C14—C19	−179.47 (13)	C22—C23—C24—C4	−172.26 (12)
C13—C14—C15—C16	0.46 (19)	C22—C23—C24—C25	−51.22 (16)
C19—C14—C15—C16	178.41 (13)	C26—C25—C24—C4	175.31 (12)
C13—C14—C15—C110	179.27 (13)	C25—C24—C4—C5	171.36 (12)
C19—C14—C15—C110	−2.8 (2)	C24—C4—C5—C6	176.32 (12)
C12—C11—C16—C15	−2.5 (2)	C4—C5—C6—C34	−175.44 (12)
C17—C11—C16—C15	174.80 (12)	C5—C6—C34—C33	171.36 (12)
C14—C15—C16—C11	1.4 (2)	C6—C34—C35—C36	−177.21 (11)
C110—C15—C16—C11	−177.56 (12)	C23—C24—C25—C26	52.79 (16)
C16—C11—C17—O1	−12.92 (19)	C22—N21—C26—C25	59.88 (15)
C12—C11—C17—O1	164.04 (14)	C24—C25—C26—N21	−57.42 (16)
C16—C11—C17—O2	166.49 (13)	C36—N31—C32—C33	58.17 (15)
C12—C11—C17—O2	−16.5 (2)	N31—C32—C33—C34	−54.82 (15)
C13—C12—C18—O3	−164.37 (13)	C32—C33—C34—C6	176.95 (12)
C13—C12—C18—O4	13.61 (19)	C32—C33—C34—C35	52.72 (15)
C11—C12—C18—O4	−167.00 (14)	C33—C34—C35—C36	−54.09 (15)
C11—C12—C18—O3	15.0 (2)	C32—N31—C36—C35	−59.46 (14)
C13—C14—C19—O5	20.4 (2)	C34—C35—C36—N31	57.56 (15)
C15—C14—C19—O5	−157.67 (15)	C23—C24—C4—C5	−67.74 (17)
C13—C14—C19—O6	−159.13 (13)	C35—C34—C6—C5	−65.98 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	1.20	1.20	2.395 (2)	175
O6—H7···O7	1.20	1.20	2.383 (2)	172
O9—H91···O6	0.89	2.09	2.980 (2)	175
O9—H92···O8^i	0.89	1.87	2.756 (2)	171
N21—H21A···O9	0.94	1.86	2.798 (2)	173
N21—H21B···O4^ii	0.94	2.02	2.933 (2)	164
N31—H31A···O1^iii	0.94	1.86	2.787 (2)	170
N31—H31B···O2^iv	0.94	2.37	3.204 (2)	148

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