meso-5,5,7,12,12,14-Hexa­methyl-4,11-di­aza-1,8-diazo­nia­cyclo­tetra­decane (S)-malate(2-) methanol disolvate: a chain of rings generated by two pairs of N-H...O hydrogen bonds

The title compound is a methanol-solvated salt, C₁₆H₃₈N₄²⁺·C₄H₄O₅^2-·2CH₃OH, in which the ionic components are linked into chains by two pairs of N-H...O hydrogen bonds [H...O = 1.78-2.21 Å, N...O = 2.702 (14)-3.094 (8) Å and N-H...O = 160-179°]. The methanol mol­ecules are pendent from the chain and are linked to it by O-H...O hydrogen bonds [H...O = 1.86 and 1.89 Å, O...O = 2.691 (9) and 2.708 (16) Å, and O-H...O = 168 and 165°].

S1. Comment

In the salt-type adducts formed between meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (tet-a, C₁₆H₃₆N₄) and phenols or carboxylic acids, the [{(C₁₆H₃₆N₄)H₂}²⁺] cations generally lie across centres of inversion (Gregson et al., 2000; Lough et al., 2000; Burchell et al., 2000; Bowes et al., 2003a,b). An exception occurs in the salt formed with 5-hydroxyisophthalic acid, where the cation lies in a general position in space group P2₁2₁2₁ (Burchell et al., 2000). In all of these examples the cation adopts the trans-III configuration (Barefield et al., 1986) and, even in the 5-hydroxyisophthalate salt, the cation is very nearly centrosymmetric.

We have now investigated an example in which a non-centrosymmetric cation environment is specifically imposed by the presence of an enantiopure chiral acid component, chosen in this case to be (S)-malic acid [(S)-2-hydroxy-butane-1,4-dioic acid, C₄H₆O₅]. The 1:1 salt formed by tet-a and (S)-malic acid crystallizes from methanol solution as a solvate [{(C₁₆H₃₆N₄)H₂}²⁺].[(C₄H₄O₅)²⁻]·2(CH₃OH), (I), in space group P1, so that none of the components has any internal crystallographic symmetry. The presence of the chiral anion precludes any further symmetry.

The fully ordered cation adopts the usual trans-III configuration (Fig. 1), with four methyl groups in equatorial sites and two in axial sites, and with paired intracation N—H···N hydrogen bonds generating an R²₂(10) motif (Bernstein et al., 1995). There is almost perfect staggering about all of the C—C and C—N bonds in the cation, and the values of the torsion angles are clearly indicative of the near-centrosymmetric conformation of the cation (Table 1). There are four axial N—H bonds available for intermolecular hydrogen-bond formation, viz. two on each face of the disk-like cation.

The anion, by contrast, exhibits orientational disorder, which was modelled using two sets of atomic sites with refined occupancies of 0.702 (8) and 0.298 (8) (Fig. 2). This disorder is such that the O22 and O32 atom sites are very close to one another, as are the O23 and O33 sites. Accordingly, the interion hydrogen bonding is very similar for the two orientations, and hence only the major orientation will be considered further. The anion disorder observed in (I) is similar to that observed for the racemic tartrate anions (C₄H₅O₆)⁻ in the salt with the monocation derived from 1,2-bis(4-pyridyl)ethene (Farrell et al., 2002a). Within the anion there is an O—H···O hydrogen bond, forming an S(6) motif, and this bond undoubtedly plays a role in controlling the anion conformation (Fig. 1 and Table 2).

The ionic components within the asymmetric unit are linked by paired N—H···O hydrogen bonds. Atoms N4 and N8 act as hydrogen-bond donors, via the axial H4 and H8A atoms, respectively, to carboxylate atoms O22 and O21, so generating an R²₂(10) motif (Fig. 1) of precisely the same type as that observed in the tetrahydrate salt formed between the tet-a cation and the terephthalate anion (Lough et al., 2000). The two independent methanol molecules are linked to the anion via O—H···O hydrogen bonds, both having a carboxylate O atom as the acceptor.

Despite the large number of hydrogen bonds within the asymmetric unit, the supramolecular structure depends on just one further pair of N—H···O hydrogen bonds. Atoms N1 and N11 in the cation at (x, y, z) act as hydrogen-bond donors, via H1B and H11, respectively, to carboxylate atoms O23 and O24 in the anion at (−1 + x, −1 + y, z), so generating by translation a chain of rings (Fig. 3) running parallel to the [110] direction. The methanol molecules are simply pendent from this chain and play no further role in the supramolecular aggregation. The only significant direction-specific interaction between adjacent chains is provided by a C—H···O hydrogen bond. Atom C2 in the cation at (x, y, z), which is adjacent to the cationic N1 atom, acts as hydrogen-bond donor, via H2B, to carboxylate atom O21 in the anion at (−1 + x, y, z), and propagation of this interaction thus links the [110] chains generated by the hard (Desiraju & Steiner, 1999) hydrogen bonds into (001) sheets.

As with other amine salts of (S)-malic acid (Farrell et al., 2002b), the supramolecular structure of (I) closely mimics a centrosymmetric arrangement, even though exact centrosymmetry is ruled out by the chiral anion.

S2. Experimental

Equimolar quantities of tet-a (Hay et al., 1975) and (S)-malic acid (purchased from Aldrich) were separately dissolved in methanol. The solutions were mixed, and the mixture was set aside to crystallize, providing analytically pure (I). Analysis found: C 54.7, H 11.0, N 11.7%; C₂₂H₅₀N₄O₇ requires: C 54.7, H 10.4, N 11.6%. Crystals of (I) suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared.

S3. Refinement

Crystals of (I) are triclinic, and space group P1 was chosen as the acid component used was enantiopure (S)-malic acid. The anion is disordered over a major and a minor orientation, with refined occupancies of 0.702 (8) and 0.298 (8). Standard DFIX (SHELXL97; Sheldrick, 1997) restraints were used for the dimensions of the disordered anion. The atoms of the minor anion were refined with a common U_iso value, and all other non-H atoms were refined anisotropically. H atoms were visible in difference maps and were subsequently treated as riding atoms with C—H distances 0.98 (CH₃), 0.99 (CH₂) or 1.00 Å (CH) and N—H distances of 0.92 and O—H 0.84 Å. The cation was positioned so that it lies with its centre at (1/2, 1/2, 1/2) and the anion is then centred approximately at (1.0, 1.0, 1/2). In the absence of any significant anomalous scattering, the Flack parameter (Flack, 1983) was indeterminate (Flack & Bernardinelli, 2000). Hence the Friedel equivalents were merged prior to the final refinements, and the absolute structure was set by reference to the known chirality of the enantiopure acid employed.

Computing details

Data collection: KappaCCD 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: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The independent components of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and, for the sake of clarity, only the major component of the anion is shown.
	Fig. 2. The major (full lines) and minor (broken lines) components of the anion. For the sake of clarity, all H atoms have been omitted.
	Fig. 3. Part of the crystal structure of (I), showing the formation of a chain along [110]. For the sake of clarity, H atoms bonded to C atoms have been omitted, and only the major orientation of the anion is shown. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−1 + x, −1 + y, z) and (1 + x, 1 + y, z), respectively.

meso-5,5,7,12,12,14-Hexamethyl-4,11-diaza-1,8-diazoniacyclotetradecane (S)-malate(2-) methanol disolvate

Crystal data

C16H38N4^2+·C4H4O5^2^−·2CH4O	Z = 1
Mr = 482.66	F(000) = 266
Triclinic, P1	Dx = 1.210 Mg m^−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6559 (9) Å	Cell parameters from 8456 reflections
b = 9.3275 (9) Å	θ = 3.5–27.6°
c = 10.1044 (12) Å	µ = 0.09 mm^−1
α = 113.379 (5)°	T = 150 K
β = 108.908 (4)°	Plate, colourless
γ = 100.345 (4)°	0.30 × 0.28 × 0.10 mm
V = 662.31 (12) Å^3

Data collection

Kappa-CCD diffractometer	3022 independent reflections
Radiation source: fine-focus sealed X-ray tube	1802 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ϕ scans, and ω scans with κ offsets	θmax = 27.6°, θmin = 3.5°
Absorption correction: multi-scan DENZO–SMN (Otwinowski & Minor, 1997)	h = −11→11
Tmin = 0.950, Tmax = 0.988	k = −12→12
8456 measured reflections	l = −12→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.064	H-atom parameters constrained
wR(F^2) = 0.202	w = 1/[σ^2(Fo^2) + (0.1019P)^2 + 0.0709P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3022 reflections	Δρmax = 0.36 e Å^−3
333 parameters	Δρmin = −0.32 e Å^−3
23 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.08 (2)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.3490 (7)	0.5886 (7)	0.6152 (6)	0.0348 (12)
C2	0.2646 (9)	0.6456 (9)	0.5044 (8)	0.0417 (17)
C3	0.2031 (9)	0.5122 (10)	0.3277 (9)	0.0454 (18)
N4	0.3509 (7)	0.4851 (7)	0.2942 (6)	0.0351 (13)
C5	0.3038 (9)	0.3576 (8)	0.1258 (8)	0.0427 (17)
C51	0.2029 (11)	0.4108 (11)	0.0063 (8)	0.052 (2)
C52	0.1843 (9)	0.1879 (9)	0.0882 (9)	0.051 (2)
C6	0.4699 (9)	0.3468 (8)	0.1112 (7)	0.0409 (17)
C7	0.5846 (9)	0.2865 (9)	0.2113 (8)	0.0392 (16)
C71	0.7346 (11)	0.2657 (11)	0.1687 (10)	0.054 (2)
N8	0.6494 (8)	0.4112 (7)	0.3859 (6)	0.0406 (14)
C9	0.7363 (9)	0.3547 (9)	0.5016 (8)	0.0429 (18)
C10	0.8003 (8)	0.4854 (9)	0.6700 (8)	0.0396 (16)
N11	0.6540 (7)	0.5162 (8)	0.7066 (6)	0.0395 (14)
C12	0.7037 (8)	0.6402 (9)	0.8750 (8)	0.0406 (17)
C121	0.7940 (10)	0.5848 (12)	0.9938 (9)	0.057 (2)
C122	0.8195 (10)	0.8099 (10)	0.9186 (10)	0.057 (2)
C13	0.5337 (9)	0.6519 (9)	0.8909 (8)	0.0427 (18)
C14	0.4196 (9)	0.7124 (9)	0.7900 (8)	0.0404 (16)
C141	0.2675 (10)	0.7357 (11)	0.8319 (10)	0.055 (2)
O21	0.8761 (18)	0.6984 (15)	0.4528 (14)	0.055 (3)	0.702 (8)
O22	0.6487 (12)	0.767 (2)	0.352 (2)	0.060 (3)	0.702 (8)
O23	1.1226 (15)	1.2848 (13)	0.5314 (17)	0.053 (2)	0.702 (8)
O24	1.3506 (8)	1.2325 (8)	0.6507 (9)	0.0422 (17)	0.702 (8)
O25	0.8473 (7)	0.9921 (7)	0.3250 (7)	0.0543 (16)	0.702 (8)
C21	0.8080 (11)	0.7899 (11)	0.4108 (12)	0.042 (3)	0.702 (8)
C22	0.9351 (13)	0.9296 (15)	0.4161 (15)	0.0670 (17)	0.702 (8)
C23	1.0659 (14)	1.0562 (15)	0.5800 (15)	0.0670 (17)	0.702 (8)
C24	1.1900 (8)	1.2041 (11)	0.5920 (12)	0.045 (3)	0.702 (8)
O41	0.4707 (9)	0.9442 (8)	0.2526 (8)	0.0758 (19)
C42	0.3300 (13)	0.8999 (12)	0.2782 (10)	0.069 (2)
O51	1.5287 (9)	1.0569 (8)	0.7487 (8)	0.0758 (18)
C53	1.6701 (12)	1.0910 (10)	0.7186 (10)	0.063 (2)
C31	0.829 (3)	0.820 (3)	0.461 (3)	0.074 (3)*	0.298 (8)
C32	0.956 (2)	0.995 (3)	0.538 (2)	0.074 (3)*	0.298 (8)
C33	1.062 (3)	1.010 (2)	0.450 (2)	0.074 (3)*	0.298 (8)
C34	1.179 (2)	1.186 (2)	0.519 (2)	0.074 (3)*	0.298 (8)
O31	0.891 (6)	0.719 (5)	0.490 (5)	0.074 (3)*	0.298 (8)
O32	0.671 (4)	0.782 (6)	0.372 (6)	0.074 (3)*	0.298 (8)
O33	1.127 (5)	1.305 (4)	0.531 (4)	0.074 (3)*	0.298 (8)
O34	1.337 (2)	1.203 (2)	0.561 (2)	0.074 (3)*	0.298 (8)
O35	1.100 (2)	1.028 (2)	0.679 (2)	0.074 (3)*	0.298 (8)
H1A	0.4394	0.5615	0.5957	0.042*
H1B	0.2694	0.4927	0.5932	0.042*
H2A	0.3479	0.7505	0.5285	0.050*
H2B	0.1629	0.6693	0.5198	0.050*
H3A	0.1248	0.4056	0.3055	0.054*
H3B	0.1357	0.5488	0.2557	0.054*
H4	0.4233	0.5853	0.3166	0.042*
H51A	0.0864	0.3997	0.0020	0.078*
H51B	0.1917	0.3389	−0.1006	0.078*
H51C	0.2669	0.5273	0.0421	0.078*
H52A	0.2320	0.1680	0.1788	0.076*
H52B	0.1787	0.0981	−0.0083	0.076*
H52C	0.0667	0.1901	0.0702	0.076*
H6A	0.5417	0.4591	0.1393	0.049*
H6B	0.4379	0.2715	−0.0029	0.049*
H7	0.5120	0.1761	0.1891	0.047*
H71A	0.8043	0.3725	0.1864	0.082*
H71B	0.6883	0.1812	0.0558	0.082*
H71C	0.8083	0.2301	0.2365	0.082*
H8A	0.7276	0.5086	0.4090	0.049*
H8B	0.5564	0.4351	0.4021	0.049*
H9A	0.6518	0.2523	0.4807	0.052*
H9B	0.8356	0.3269	0.4841	0.052*
H10A	0.8688	0.4500	0.7427	0.048*
H10B	0.8784	0.5903	0.6890	0.048*
H11	0.5790	0.4165	0.6825	0.047*
H12A	0.9022	0.5736	0.9875	0.086*
H12B	0.7162	0.4771	0.9670	0.086*
H12C	0.8214	0.6684	1.1028	0.086*
H12D	0.9325	0.8051	0.9210	0.086*
H12E	0.8375	0.8932	1.0245	0.086*
H12F	0.7634	0.8413	0.8386	0.086*
H13A	0.4617	0.5399	0.8632	0.051*
H13B	0.5661	0.7278	1.0049	0.051*
H14	0.4930	0.8220	0.8112	0.048*
H14A	0.2035	0.7844	0.7728	0.082*
H14B	0.3131	0.8105	0.9474	0.082*
H14C	0.1886	0.6271	0.8022	0.082*
H25	0.9017	1.0949	0.3674	0.081*	0.702 (8)
H22	1.0025	0.8756	0.3607	0.080*	0.702 (8)
H23A	1.1360	1.0012	0.6275	0.080*	0.702 (8)
H23B	1.0038	1.0989	0.6452	0.080*	0.702 (8)
H41	0.5415	0.9003	0.2832	0.114*
H42D	0.3664	0.9442	0.3935	0.103*
H42E	0.2773	0.7778	0.2229	0.103*
H42F	0.2443	0.9455	0.2367	0.103*
H51	1.4668	1.1114	0.7266	0.114*
H53A	1.6645	1.1695	0.6769	0.095*
H53B	1.6697	0.9873	0.6393	0.095*
H53C	1.7776	1.1407	0.8182	0.095*
H32	0.8992	1.0809	0.5596	0.089*	0.298 (8)
H33A	1.1340	0.9393	0.4530	0.089*	0.298 (8)
H33B	0.9819	0.9676	0.3363	0.089*	0.298 (8)
H35	1.0814	0.9467	0.6964	0.111*	0.298 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.026 (3)	0.034 (3)	0.038 (3)	0.012 (2)	0.012 (2)	0.014 (2)
C2	0.033 (4)	0.044 (4)	0.052 (4)	0.016 (3)	0.018 (3)	0.026 (4)
C3	0.035 (4)	0.049 (4)	0.045 (4)	0.014 (3)	0.012 (3)	0.022 (4)
N4	0.027 (3)	0.031 (3)	0.043 (3)	0.006 (2)	0.014 (3)	0.017 (3)
C5	0.046 (4)	0.036 (4)	0.047 (4)	0.016 (3)	0.023 (4)	0.019 (3)
C51	0.067 (5)	0.057 (5)	0.036 (4)	0.027 (4)	0.024 (4)	0.023 (4)
C52	0.042 (4)	0.029 (3)	0.063 (5)	−0.001 (3)	0.019 (4)	0.014 (3)
C6	0.037 (4)	0.034 (4)	0.037 (4)	0.006 (3)	0.012 (3)	0.011 (3)
C7	0.038 (4)	0.035 (3)	0.042 (4)	0.008 (3)	0.017 (3)	0.018 (3)
C71	0.060 (5)	0.065 (5)	0.058 (5)	0.038 (5)	0.032 (5)	0.037 (5)
N8	0.041 (3)	0.041 (3)	0.045 (3)	0.013 (3)	0.017 (3)	0.028 (3)
C9	0.044 (4)	0.050 (4)	0.046 (4)	0.024 (3)	0.018 (3)	0.031 (4)
C10	0.026 (4)	0.049 (4)	0.047 (4)	0.013 (3)	0.013 (3)	0.029 (4)
N11	0.033 (3)	0.041 (3)	0.041 (3)	0.010 (2)	0.012 (3)	0.022 (3)
C12	0.027 (3)	0.043 (4)	0.038 (4)	0.006 (3)	0.002 (3)	0.019 (3)
C121	0.042 (4)	0.074 (5)	0.056 (5)	0.027 (4)	0.009 (4)	0.039 (4)
C122	0.044 (5)	0.055 (5)	0.062 (5)	0.014 (4)	0.016 (4)	0.025 (4)
C13	0.048 (5)	0.050 (4)	0.042 (4)	0.021 (3)	0.020 (4)	0.032 (4)
C14	0.039 (4)	0.042 (4)	0.044 (4)	0.020 (3)	0.018 (3)	0.022 (3)
C141	0.048 (5)	0.073 (6)	0.047 (5)	0.026 (4)	0.022 (4)	0.029 (4)
O21	0.039 (4)	0.047 (5)	0.075 (7)	0.003 (4)	0.017 (5)	0.039 (5)
O22	0.040 (5)	0.039 (5)	0.087 (8)	0.007 (4)	0.018 (5)	0.029 (6)
O23	0.030 (4)	0.035 (4)	0.082 (5)	0.000 (3)	0.010 (3)	0.034 (4)
O24	0.039 (4)	0.029 (3)	0.050 (4)	0.006 (3)	0.019 (3)	0.015 (3)
O25	0.044 (3)	0.045 (3)	0.058 (3)	0.006 (2)	0.005 (2)	0.029 (3)
C21	0.050 (7)	0.025 (5)	0.046 (6)	−0.002 (4)	0.025 (5)	0.018 (5)
C22	0.047 (3)	0.065 (3)	0.064 (3)	−0.013 (2)	−0.003 (2)	0.045 (3)
C23	0.047 (3)	0.065 (3)	0.064 (3)	−0.013 (2)	−0.003 (2)	0.045 (3)
C24	0.027 (5)	0.041 (5)	0.045 (6)	0.002 (4)	0.002 (4)	0.016 (5)
O41	0.071 (5)	0.068 (4)	0.075 (4)	0.017 (3)	0.015 (3)	0.041 (4)
C42	0.068 (6)	0.061 (5)	0.059 (5)	0.017 (5)	0.017 (5)	0.024 (5)
O51	0.086 (5)	0.071 (4)	0.083 (4)	0.025 (4)	0.039 (4)	0.048 (4)
C53	0.083 (7)	0.053 (5)	0.069 (6)	0.027 (5)	0.034 (5)	0.043 (5)

Geometric parameters (Å, º)

N1—C2	1.466 (7)	C121—H12C	0.98
N1—C14	1.502 (8)	C122—H12D	0.98
N1—H1A	0.92	C122—H12E	0.98
N1—H1B	0.92	C122—H12F	0.98
C2—C3	1.550 (9)	C13—C14	1.529 (9)
C2—H2A	0.99	C13—H13A	0.99
C2—H2B	0.99	C13—H13B	0.99
C3—N4	1.465 (8)	C14—C141	1.533 (10)
C3—H3A	0.99	C14—H14	1.00
C3—H3B	0.99	C141—H14A	0.98
N4—C5	1.499 (8)	C141—H14B	0.98
N4—H4	0.92	C141—H14C	0.98
C5—C6	1.509 (9)	O21—C21	1.250 (5)
C5—C52	1.549 (9)	O22—C21	1.250 (5)
C5—C51	1.554 (9)	O23—C24	1.254 (5)
C51—H51A	0.98	O24—C24	1.250 (5)
C51—H51B	0.98	O25—C22	1.377 (11)
C51—H51C	0.98	O25—H25	0.84
C52—H52A	0.98	C21—C22	1.518 (7)
C52—H52B	0.98	C22—C23	1.474 (7)
C52—H52C	0.98	C22—H22	1.00
C6—C7	1.525 (9)	C23—C24	1.524 (8)
C6—H6A	0.99	C23—H23A	0.99
C6—H6B	0.99	C23—H23B	0.99
C7—N8	1.509 (9)	O41—C42	1.352 (10)
C7—C71	1.515 (10)	O41—H41	0.84
C7—H7	1.00	C42—H42D	0.98
C71—H71A	0.98	C42—H42E	0.98
C71—H71B	0.98	C42—H42F	0.98
C71—H71C	0.98	O51—C53	1.367 (9)
N8—C9	1.507 (7)	O51—H51	0.84
N8—H8A	0.92	C53—H53A	0.98
N8—H8B	0.92	C53—H53B	0.98
C9—C10	1.480 (9)	C53—H53C	0.98
C9—H9A	0.99	C31—O31	1.250 (5)
C9—H9B	0.99	C31—O32	1.251 (5)
C10—N11	1.474 (8)	C31—C32	1.504 (5)
C10—H10A	0.99	C32—O35	1.432 (10)
C10—H10B	0.99	C32—C33	1.498 (5)
N11—C12	1.484 (8)	C32—H32	1.00
N11—H11	0.92	C33—C34	1.498 (5)
C12—C122	1.515 (10)	C33—H33A	0.99
C12—C121	1.531 (8)	C33—H33B	0.99
C12—C13	1.549 (9)	C34—O33	1.249 (5)
C121—H12A	0.98	C34—O34	1.249 (5)
C121—H12B	0.98	O35—H35	0.84
C2—N1—C14	115.2 (5)	N11—C12—C121	112.2 (6)
C2—N1—H1A	108.5	C122—C12—C121	110.2 (6)
C14—N1—H1A	108.5	N11—C12—C13	107.8 (5)
C2—N1—H1B	108.5	C122—C12—C13	109.8 (6)
C14—N1—H1B	108.5	C121—C12—C13	106.0 (5)
H1A—N1—H1B	107.5	C12—C121—H12A	109.5
N1—C2—C3	111.2 (5)	C12—C121—H12B	109.5
N1—C2—H2A	109.4	H12A—C121—H12B	109.5
C3—C2—H2A	109.4	C12—C121—H12C	109.5
N1—C2—H2B	109.4	H12A—C121—H12C	109.5
C3—C2—H2B	109.4	H12B—C121—H12C	109.5
H2A—C2—H2B	108.0	C12—C122—H12D	109.5
N4—C3—C2	111.6 (5)	C12—C122—H12E	109.5
N4—C3—H3A	109.3	H12D—C122—H12E	109.5
C2—C3—H3A	109.3	C12—C122—H12F	109.5
N4—C3—H3B	109.3	H12D—C122—H12F	109.5
C2—C3—H3B	109.3	H12E—C122—H12F	109.5
H3A—C3—H3B	108.0	C14—C13—C12	117.5 (5)
C3—N4—C5	115.4 (5)	C14—C13—H13A	107.9
C3—N4—H4	108.4	C12—C13—H13A	107.9
C5—N4—H4	108.4	C14—C13—H13B	107.9
N4—C5—C6	108.6 (5)	C12—C13—H13B	107.9
N4—C5—C52	108.7 (5)	H13A—C13—H13B	107.2
C6—C5—C52	111.6 (5)	N1—C14—C13	109.6 (5)
N4—C5—C51	109.9 (5)	N1—C14—C141	109.5 (6)
C6—C5—C51	109.2 (5)	C13—C14—C141	111.5 (5)
C52—C5—C51	108.8 (6)	N1—C14—H14	108.7
C5—C51—H51A	109.5	C13—C14—H14	108.7
C5—C51—H51B	109.5	C141—C14—H14	108.7
H51A—C51—H51B	109.5	C14—C141—H14A	109.5
C5—C51—H51C	109.5	C14—C141—H14B	109.5
H51A—C51—H51C	109.5	H14A—C141—H14B	109.5
H51B—C51—H51C	109.5	C14—C141—H14C	109.5
C5—C52—H52A	109.5	H14A—C141—H14C	109.5
C5—C52—H52B	109.5	H14B—C141—H14C	109.5
H52A—C52—H52B	109.5	O21—C21—O22	126.8 (11)
C5—C52—H52C	109.5	O21—C21—C22	114.1 (10)
H52A—C52—H52C	109.5	O22—C21—C22	118.7 (10)
H52B—C52—H52C	109.5	O25—C22—C23	115.1 (7)
C5—C6—C7	118.0 (6)	O25—C22—C21	110.8 (8)
C5—C6—H6A	107.8	C23—C22—C21	113.2 (7)
C7—C6—H6A	107.8	O25—C22—H22	105.6
C5—C6—H6B	107.8	C23—C22—H22	105.6
C7—C6—H6B	107.8	C21—C22—H22	105.6
H6A—C6—H6B	107.1	C22—C23—C24	115.1 (7)
N8—C7—C71	111.5 (6)	C22—C23—H23A	108.5
N8—C7—C6	108.0 (5)	C24—C23—H23A	108.5
C71—C7—C6	110.9 (5)	C22—C23—H23B	108.5
N8—C7—H7	108.8	C24—C23—H23B	108.5
C71—C7—H7	108.8	H23A—C23—H23B	107.5
C6—C7—H7	108.8	O24—C24—O23	123.2 (9)
C7—C71—H71A	109.5	O24—C24—C23	119.4 (8)
C7—C71—H71B	109.5	O23—C24—C23	117.2 (8)
H71A—C71—H71B	109.5	C53—O51—H51	109.5
C7—C71—H71C	109.5	O51—C53—H53A	109.5
H71A—C71—H71C	109.5	O51—C53—H53B	109.5
H71B—C71—H71C	109.5	H53A—C53—H53B	109.5
C9—N8—C7	114.8 (5)	O51—C53—H53C	109.5
C9—N8—H8A	108.6	H53A—C53—H53C	109.5
C7—N8—H8A	108.6	H53B—C53—H53C	109.5
C9—N8—H8B	108.6	O31—C31—O32	123 (4)
C7—N8—H8B	108.6	O31—C31—C32	116 (3)
H8A—N8—H8B	107.5	O32—C31—C32	121 (3)
C10—C9—N8	111.5 (5)	O35—C32—C33	95.1 (15)
C10—C9—H9A	109.3	O35—C32—C31	110 (2)
N8—C9—H9A	109.3	C33—C32—C31	112.7 (5)
C10—C9—H9B	109.3	O35—C32—H32	112.8
N8—C9—H9B	109.3	C33—C32—H32	112.8
H9A—C9—H9B	108.0	C31—C32—H32	112.8
N11—C10—C9	111.1 (5)	C34—C33—C32	113.1 (5)
N11—C10—H10A	109.4	C34—C33—H33A	109.0
C9—C10—H10A	109.4	C32—C33—H33A	109.0
N11—C10—H10B	109.4	C34—C33—H33B	109.0
C9—C10—H10B	109.4	C32—C33—H33B	109.0
H10A—C10—H10B	108.0	H33A—C33—H33B	107.8
C10—N11—C12	115.5 (5)	O33—C34—O34	122 (3)
C10—N11—H11	108.4	O33—C34—C33	124 (3)
C12—N11—H11	108.4	O34—C34—C33	113.2 (19)
N11—C12—C122	110.7 (6)	C32—O35—H35	109.5
N1—C2—C3—N4	−65.0 (9)	N8—C9—C10—N11	65.8 (9)
C2—C3—N4—C5	179.9 (7)	C9—C10—N11—C12	177.4 (7)
C3—N4—C5—C6	179.2 (7)	C10—N11—C12—C13	−178.5 (7)
N4—C5—C6—C7	63.6 (9)	N11—C12—C13—C14	−62.2 (9)
C5—C6—C7—N8	−63.6 (9)	C12—C13—C14—N1	64.9 (9)
C6—C7—N8—C9	168.9 (7)	C13—C14—N1—C2	−169.1 (7)
C7—N8—C9—C10	178.4 (7)	C14—N1—C2—C3	177.7 (7)
O22—C21—C22—C23	119.7 (14)	O25—C22—C23—C24	−47.8 (15)
C21—C22—C23—C24	−176.7 (10)	C22—C23—C24—O23	55.5 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N11	0.92	2.05	2.799 (8)	138
N8—H8B···N4	0.92	2.00	2.758 (8)	138
O25—H25···O23	0.84	1.98	2.721 (12)	146
O35—H35···O31	0.84	2.14	2.60 (5)	114
N4—H4···O22	0.92	2.17	3.046 (15)	160
N4—H4···O32	0.92	2.29	3.17 (4)	159
N8—H8A···O21	0.92	1.78	2.702 (14)	179
N8—H8A···O31	0.92	1.87	2.78 (5)	171
O41—H41···O22	0.84	1.89	2.708 (16)	165
O51—H51···O24	0.84	1.86	2.691 (9)	168
O51—H51···O34	0.84	2.25	3.005 (18)	150
N1—H1B···O23^i	0.92	1.85	2.760 (11)	172
N1—H1B···O33^i	0.92	1.68	2.60 (4)	173
N11—H11···O24^i	0.92	2.21	3.094 (8)	161
N11—H11···O34^i	0.92	2.18	3.06 (2)	158
C2—H2B···O21^ii	0.99	2.45	3.39 (2)	159

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