Hydro­gen-bonded molecular ladders in trans-1,2-bis(2-nitro­anilino)­cyclo­hexane

Crystals of the title compound, C₁₈H₂₀N₄O₄, contain equal numbers of (R,R) and (S,S) mol­ecules, but these are not precise enantiomorphs, neither are they related by crystallographic symmetry; in addition, each mol­ecule exhibits approximate, but not exact, twofold rotational symmetry. There are intramolecular N-H...O hydrogen bonds [N...O 2.609 (4)-2.638 (5) Å; N-H...O 125-132°] and the mol­ecules are linked into molecular ladders by C-H...O hydrogen bonds [C...O 3.306 (6)-3.386 (6) Å; C-H...O 146-160°].

S1. Comment

As part of a continuing study of the interplay between molecular conformation and supramolecular aggregation in compounds containing 2-nitrophenyl groups (Low, Storey et al., 2000; Low, Glidewell & Wardell, 2000), we now report the structure of trans-1,2-bis(2-nitroanilino)cyclohexane, (O₂NC₆H₄NH)₂C₆H₁₀, (I), which exhibits pseudosymmetry as well as a supramolecular arrangement in the form of hydrogen-bonded molecular ladders. \sch

Compound (I) (Scheme 1) crystallizes in P2₁/n with two independent molecules in the asymmetric unit (Fig. 1). In both molecules the cyclohexane rings adopt the chair conformation with the two amino substituents in mutually trans equatorial sites. There are two enantiomeric forms present and the asymmetric unit was selected to contain one (R,R) molecule and one (S,S) molecule. In molecule 1 (defined by N1—N4) the stereogenic atoms C1 and C2 both have the R configuration, while in molecule 2 (defined by N5—N8) the corresponding atoms C19 and C20 both have the S configuration. Each molecule in addition has approximate C₂ rotational symmetry. However, despite these observations, a search for possible additional crystallographic symmetry showed that none was present.

When the H atoms in the amino groups were all refined isotropically, the configurations about all the amino N atoms were found to be planar, within experimental uncertainty: subsequently the configurations of these N atoms were constrained to be planar. Associated with this planarity are the very wide C—N—C angles (Table 1), all around 125°, and the short N—C(aryl) distances [range 1.334 (5)–1.379 (5) Å; mean 1.356 Å], which are typical of such distances involving planar N [mean value, 1.355 Å (Allen et al., 1987)]. The corresponding mean distance for bonds involving pyramidal N is 1.394 Å (Allen et al., 1987). The N—H bonds are all essentially coplanar with the adjacent aryl rings, as are the nitro groups, and there is thus an intramolecular N—H···O hydrogen bond formed by each amino group (Table 2), forming an S(6) motif (Bernstein et al., 1995). The C(aryl)-NO₂ bonds are all significantly shorter than the mean value, 1.468 Å, for bonds of this type (Allen et al., 1987).

Within the aryl rings, there is evidence of some bond fixation: together with the short C(aryl)-N bonds, this is consistent with a significant admixture of the canonical form (Ic) into the more conventional forms (Ia) and (Ib) (Scheme 2). Form (Ic), where both the hydrogen-bond donor and the acceptor are charged strongly favours the formation of a strong intermolecular hydrogen bond (Aakeröy & Seddon, 1993; Gilli et al., 1994). Also worthy of note are the consistently small C—C—C angles in the aryl rings ipso to the amino substituents (i.e. at C7, C13, C25 and C31), associated with the electron-donating properties of the amino group (Domenicano & Murray-Rust, 1979). There is a consistent difference between the two exocyclic C—C—NO₂ angles (Table 2) and, in every case, the angle nearer the amino group is the larger. This arises from the need to accommodate the long H···O distances within the planar S(6) ring.

In the structure of 2-nitroaniline itself (Dhaneshwar et al., 1978) the geometries reported for the two independent molecules are so different that no firm conclusions can be drawn. However, in 4-methyl-2-nitroaniline (Ellena et al., 1996) there is evidence for bond fixation of exactly the type observed here in compound (I): of particular note in 4-methyl-2-nitroaniline are the C—NO₂ bond length, 1.434 (3) Å, and the range of C—C bond lengths in the aryl ring, 1.343 (5)–1.406 (4) Å.

In each of the two independent molecules in (I), the two aryl rings are nearly parallel: in molecule 1, the dihedral angles between the two ring planes is 16.1 (2)°, while in molecule 2 the corresponding angle in 11.5 (2)°. The distance between the rings is ca 3.39 Å in molecule 1 and ca 3.31 Å in molecule 2, and the centroid offsets are 1.46 Å and 1.29 Å respectively: these values are appropriate for intramolecular aromatic π···π stacking interactions. On the other hand, there are no intermolecular interactions of this type.

The molecules are linked into ladders by C—H···O hydrogen bonds (Table 2 and Fig. 2). The ladders are generated by translation along the [100] direction and alternate molecules within any ladder are of opposite chirality. Each molecule acts as a double donor and a double acceptor of hydrogen bonds (Table 2) and in the ladder, the uprights are formed by antiparallel C²₂(12) chains, one containing O1 and O5 as acceptors, the other containing O3 and O7. Only half of the O atoms participate in the hydrogen bonding (Table 2). The rungs of the ladder are formed by the diaminocyclohexane units, and each neighbouring pair of rungs encloses an R²₂(22) ring. These rings are approximately, but not exactly centrosymmetric, and they are centred close to (n/2 + 0.47, 0.17, 1/4) (n = zero or integer). Hence each individual molecule exhibits pseudosymmetry, having near C₂ rotational symmetry, and the two independent molecules also exhibit a pseudosymmetric relationship in that neighbouring pairs lie across pseudo centres of inversion. The precise values of corresponding geometric parameters, both intra- and intermolecular are however significantly different in many cases (Tables 1 and 2).

The pseudosymmetry can perhaps best be understood by reference to Fig. 2, which shows both the approximate twofold axes running through each molecule and lying approximately normal to the [100] direction, and the pseudo inversions between adjacent molecules. While only a minor adjustment in the angle β, from 105.594 (7) to 108.23°, is required to generate a metrically orthorhombic cell, the cell contents do not exhibit orthorhombic symmetry.

S2. Experimental

A mixture of 2-fluoronitrobenzene (5.64 g, 40 mmol), trans-cyclohexane-1,2-diamine (2.28 g, 20 mmol) and sodium hydrogencarbonate (3.70 g, 44 mmol) was heated in refluxing ethanol (50 cm³) for 2 h. The hot reaction mixture was poured into ice-water (100 cm³) and extracted with CH₂Cl₂ (3 x 150 cm³). The combined organic extracts were dried over MgSO₄ and the solvent was removed in vacuo to yield an oily orange solid, which was crystallized from ethanol to yield bright orange needle-like crystals (5.17 g, 73%), m.p. 493–494 K.

S3. Refinement

Compound (I) crystallized in the monoclinic system; space group P2₁/n from the systematic absences. H atoms were treated as riding atoms with C—H 0.95 to 1.00 Å, N—H 0.88 Å. Examination of the structure with PLATON (Spek, 1999) 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 (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A view of the two independent molecules of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I), showing formation of a molecular ladder [symmetry codes: (i) 1 + x, y, z; (ii) −1 + x, y, z].

Trans-1,2-bis(2-nitroanilino)cyclohexane

Crystal data

C18H20N4O4	F(000) = 1504
Mr = 356.38	Dx = 1.407 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.114 (1) Å	Cell parameters from 6356 reflections
b = 12.7121 (19) Å	θ = 1.7–25.9°
c = 20.959 (3) Å	µ = 0.10 mm^−1
β = 105.594 (7)°	T = 150 K
V = 3365.3 (8) Å^3	Needle, orange
Z = 8	0.30 × 0.03 × 0.02 mm

Data collection

Kappa-CCD diffractometer	6356 independent reflections
Radiation source: fine-focus sealed X-ray tube	1853 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.107
ϕ scans and ω scans with κ offsets	θmax = 25.9°, θmin = 1.7°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −16→15
Tmin = 0.970, Tmax = 0.998	k = −14→15
19380 measured reflections	l = −23→25

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H-atom parameters constrained
S = 0.86	w = 1/[σ^2(Fo^2) + (0.0276P)^2] where P = (Fo^2 + 2Fc^2)/3
6356 reflections	(Δ/σ)max = 0.003
472 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

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

	x	y	z	Uiso*/Ueq
O1	−0.0423 (2)	0.0934 (3)	0.18727 (18)	0.0341 (10)
O2	−0.0812 (2)	0.0784 (3)	0.07987 (18)	0.0428 (11)
O3	0.4292 (2)	0.2568 (3)	0.18483 (17)	0.0367 (11)
O4	0.3822 (2)	0.2938 (3)	0.0798 (2)	0.0637 (14)
N1	0.1558 (2)	0.0794 (3)	0.2596 (2)	0.0224 (11)
N2	0.2899 (2)	0.2593 (3)	0.2538 (2)	0.0213 (11)
N3	−0.0155 (3)	0.0787 (3)	0.1349 (2)	0.0293 (12)
N4	0.3605 (3)	0.2822 (3)	0.1335 (2)	0.0349 (13)
C1	0.2376 (3)	0.1133 (4)	0.3184 (2)	0.0227 (14)
C2	0.2623 (3)	0.2320 (4)	0.3147 (2)	0.0234 (14)
C3	0.3509 (3)	0.2620 (4)	0.3748 (2)	0.0212 (13)
C4	0.3212 (3)	0.2395 (4)	0.4389 (2)	0.0263 (14)
C5	0.2907 (3)	0.1241 (4)	0.4418 (2)	0.0283 (14)
C6	0.2043 (3)	0.0915 (4)	0.3808 (2)	0.0219 (14)
C7	0.1741 (3)	0.0554 (4)	0.2005 (3)	0.0195 (14)
C8	0.0941 (3)	0.0568 (4)	0.1390 (3)	0.0244 (14)
C9	0.1182 (3)	0.0397 (3)	0.0787 (3)	0.0248 (14)
C10	0.2195 (4)	0.0147 (4)	0.0777 (3)	0.0325 (15)
C11	0.2972 (4)	0.0066 (4)	0.1367 (3)	0.0305 (15)
C12	0.2767 (3)	0.0263 (4)	0.1961 (3)	0.0253 (15)
C13	0.2224 (3)	0.2896 (4)	0.1960 (3)	0.0203 (13)
C14	0.2540 (3)	0.3003 (4)	0.1367 (3)	0.0219 (14)
C15	0.1811 (3)	0.3276 (4)	0.0765 (3)	0.0294 (14)
C16	0.0777 (3)	0.3478 (4)	0.0739 (3)	0.0307 (15)
C17	0.0464 (3)	0.3407 (4)	0.1318 (3)	0.0266 (14)
C18	0.1153 (3)	0.3127 (4)	0.1906 (3)	0.0254 (14)
O5	0.5095 (2)	0.0850 (3)	0.30688 (17)	0.0296 (10)
O6	0.5671 (2)	0.0848 (3)	0.41390 (18)	0.0415 (11)
O7	0.9749 (2)	0.2546 (3)	0.29533 (18)	0.0350 (11)
O8	1.0252 (2)	0.2997 (3)	0.39799 (17)	0.0442 (12)
N5	0.6430 (3)	0.0703 (3)	0.2333 (2)	0.0230 (11)
N6	0.7745 (2)	0.2553 (3)	0.2315 (2)	0.0237 (12)
N7	0.5837 (3)	0.0761 (3)	0.3592 (2)	0.0269 (12)
N8	0.9540 (3)	0.2818 (3)	0.3474 (2)	0.0299 (13)
C19	0.6707 (3)	0.1031 (4)	0.1734 (2)	0.0191 (13)
C20	0.6915 (3)	0.2228 (4)	0.1734 (2)	0.0230 (14)
C21	0.7222 (3)	0.2526 (4)	0.1105 (2)	0.0230 (14)
C22	0.6342 (3)	0.2244 (4)	0.0494 (2)	0.0278 (14)
C23	0.6088 (3)	0.1071 (4)	0.0496 (2)	0.0281 (14)
C24	0.5809 (3)	0.0754 (4)	0.1126 (2)	0.0239 (14)
C25	0.7146 (3)	0.0511 (4)	0.2936 (3)	0.0205 (14)
C26	0.6895 (3)	0.0560 (4)	0.3547 (3)	0.0207 (14)
C27	0.7663 (3)	0.0433 (3)	0.4147 (3)	0.0296 (15)
C28	0.8681 (4)	0.0229 (4)	0.4156 (3)	0.0323 (15)
C29	0.8946 (3)	0.0138 (4)	0.3561 (3)	0.0311 (16)
C30	0.8210 (3)	0.0270 (3)	0.2973 (3)	0.0230 (14)
C31	0.7611 (3)	0.2838 (4)	0.2900 (3)	0.0226 (14)
C32	0.8450 (3)	0.2950 (4)	0.3485 (3)	0.0211 (14)
C33	0.8279 (4)	0.3155 (4)	0.4103 (3)	0.0270 (14)
C34	0.7284 (3)	0.3330 (4)	0.4165 (3)	0.0302 (14)
C35	0.6436 (3)	0.3301 (4)	0.3583 (3)	0.0302 (15)
C36	0.6593 (3)	0.3073 (4)	0.2987 (2)	0.0240 (14)
H1N1	0.0904	0.0742	0.2627	0.027*
H1N2	0.3574	0.2555	0.2549	0.026*
H1	0.3037	0.0727	0.3205	0.014 (5)*
H2	0.1977	0.2728	0.3160	0.014 (5)*
H3A	0.3669	0.3378	0.3726	0.022 (3)*
H3B	0.4155	0.2219	0.3745	0.022 (3)*
H4A	0.2610	0.2848	0.4415	0.022 (3)*
H4B	0.3819	0.2561	0.4773	0.022 (3)*
H5A	0.3540	0.0796	0.4454	0.022 (3)*
H5B	0.2658	0.1122	0.4818	0.022 (3)*
H6A	0.1893	0.0155	0.3834	0.022 (3)*
H6B	0.1385	0.1308	0.3794	0.022 (3)*
H9	0.0641	0.0455	0.0383	0.028 (3)*
H10	0.2359	0.0032	0.0368	0.028 (3)*
H11	0.3667	−0.0133	0.1360	0.028 (3)*
H12	0.3327	0.0205	0.2356	0.028 (3)*
H15	0.2039	0.3319	0.0372	0.028 (3)*
H16	0.0284	0.3664	0.0333	0.028 (3)*
H17	−0.0250	0.3557	0.1306	0.028 (3)*
H18	0.0904	0.3087	0.2291	0.028 (3)*
H1N5	0.5754	0.0622	0.2307	0.028*
H1N6	0.8396	0.2561	0.2277	0.028*
H19	0.7361	0.0649	0.1708	0.014 (5)*
H20	0.6247	0.2606	0.1736	0.014 (5)*
H21A	0.7363	0.3291	0.1107	0.022 (3)*
H21B	0.7878	0.2151	0.1094	0.022 (3)*
H22A	0.6564	0.2419	0.0090	0.022 (3)*
H22B	0.5700	0.2660	0.0487	0.022 (3)*
H23A	0.5487	0.0905	0.0109	0.022 (3)*
H23B	0.6709	0.0659	0.0455	0.022 (3)*
H24A	0.5674	−0.0012	0.1120	0.022 (3)*
H24B	0.5155	0.1122	0.1150	0.022 (3)*
H27	0.7472	0.0488	0.4552	0.028 (3)*
H28	0.9206	0.0149	0.4565	0.028 (3)*
H29	0.9656	−0.0019	0.3565	0.028 (3)*
H30	0.8418	0.0199	0.2575	0.028 (3)*
H33	0.8864	0.3174	0.4486	0.028 (3)*
H34	0.7165	0.3467	0.4584	0.028 (3)*
H35	0.5739	0.3445	0.3611	0.028 (3)*
H36	0.5999	0.3069	0.2608	0.028 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0243 (19)	0.052 (3)	0.026 (3)	−0.0009 (16)	0.0065 (17)	−0.007 (2)
O2	0.0281 (19)	0.067 (3)	0.026 (3)	0.0057 (18)	−0.0057 (18)	−0.006 (2)
O3	0.0206 (18)	0.060 (3)	0.028 (3)	0.0010 (18)	0.0050 (17)	0.005 (2)
O4	0.045 (2)	0.124 (4)	0.031 (3)	0.020 (2)	0.026 (2)	0.022 (3)
N1	0.014 (2)	0.033 (3)	0.021 (3)	−0.0040 (18)	0.007 (2)	−0.003 (2)
N2	0.013 (2)	0.034 (3)	0.020 (3)	−0.0014 (19)	0.009 (2)	−0.005 (3)
N3	0.028 (3)	0.027 (3)	0.031 (4)	0.000 (2)	0.005 (2)	−0.005 (3)
N4	0.029 (3)	0.048 (4)	0.029 (4)	0.001 (2)	0.010 (3)	0.004 (3)
C1	0.019 (3)	0.029 (4)	0.020 (4)	0.007 (2)	0.003 (3)	0.000 (3)
C2	0.019 (3)	0.030 (4)	0.022 (4)	0.008 (2)	0.006 (2)	0.000 (3)
C3	0.021 (3)	0.023 (4)	0.018 (4)	0.000 (2)	0.003 (2)	−0.005 (3)
C4	0.022 (3)	0.037 (4)	0.014 (4)	0.003 (2)	−0.004 (2)	−0.002 (3)
C5	0.037 (3)	0.024 (4)	0.025 (4)	−0.001 (3)	0.010 (3)	0.003 (3)
C6	0.021 (3)	0.021 (3)	0.023 (4)	−0.001 (2)	0.004 (2)	0.003 (3)
C7	0.021 (3)	0.016 (3)	0.024 (4)	−0.003 (2)	0.009 (3)	−0.004 (3)
C8	0.024 (3)	0.027 (4)	0.023 (4)	−0.001 (2)	0.008 (3)	−0.003 (3)
C9	0.030 (3)	0.020 (4)	0.022 (4)	−0.003 (2)	0.001 (3)	0.003 (3)
C10	0.047 (3)	0.024 (4)	0.033 (5)	0.000 (3)	0.024 (3)	−0.004 (3)
C11	0.025 (3)	0.028 (4)	0.039 (5)	−0.003 (2)	0.009 (3)	−0.013 (3)
C12	0.022 (3)	0.026 (4)	0.025 (4)	−0.001 (2)	0.002 (3)	−0.009 (3)
C13	0.019 (3)	0.021 (4)	0.019 (4)	0.000 (2)	0.000 (2)	0.002 (3)
C14	0.022 (3)	0.021 (4)	0.025 (4)	−0.004 (2)	0.009 (3)	−0.003 (3)
C15	0.033 (3)	0.038 (4)	0.018 (4)	−0.002 (3)	0.008 (3)	−0.001 (3)
C16	0.033 (3)	0.031 (4)	0.025 (4)	0.001 (2)	0.002 (3)	−0.002 (3)
C17	0.025 (3)	0.025 (4)	0.032 (4)	0.005 (2)	0.011 (3)	0.003 (3)
C18	0.020 (3)	0.026 (4)	0.030 (4)	−0.006 (2)	0.006 (3)	0.003 (3)
O5	0.0246 (17)	0.044 (3)	0.019 (3)	0.0006 (17)	0.0038 (16)	−0.001 (2)
O6	0.042 (2)	0.061 (3)	0.027 (3)	0.0044 (18)	0.020 (2)	0.003 (2)
O7	0.0224 (19)	0.058 (3)	0.027 (3)	−0.0009 (16)	0.0102 (17)	−0.010 (2)
O8	0.0260 (19)	0.071 (3)	0.029 (3)	0.0035 (18)	−0.0040 (18)	−0.019 (2)
N5	0.017 (2)	0.035 (3)	0.018 (3)	−0.0073 (19)	0.007 (2)	0.001 (3)
N6	0.015 (2)	0.037 (3)	0.019 (3)	−0.0035 (18)	0.005 (2)	−0.002 (2)
N7	0.033 (3)	0.026 (3)	0.027 (4)	−0.003 (2)	0.017 (2)	0.003 (3)
N8	0.025 (3)	0.031 (3)	0.032 (4)	−0.003 (2)	0.005 (2)	−0.004 (3)
C19	0.016 (2)	0.019 (4)	0.022 (4)	0.000 (2)	0.004 (2)	0.003 (3)
C20	0.015 (3)	0.037 (4)	0.017 (4)	0.002 (2)	0.005 (2)	−0.004 (3)
C21	0.022 (3)	0.026 (4)	0.021 (4)	0.001 (2)	0.006 (2)	0.003 (3)
C22	0.026 (3)	0.039 (4)	0.019 (4)	0.004 (3)	0.007 (2)	0.008 (3)
C23	0.027 (3)	0.037 (4)	0.017 (4)	0.001 (3)	−0.001 (2)	0.001 (3)
C24	0.026 (3)	0.023 (4)	0.023 (4)	−0.002 (2)	0.007 (3)	−0.003 (3)
C25	0.022 (3)	0.015 (4)	0.024 (4)	−0.003 (2)	0.003 (3)	−0.001 (3)
C26	0.018 (3)	0.025 (4)	0.021 (4)	−0.002 (2)	0.009 (3)	−0.003 (3)
C27	0.030 (3)	0.033 (4)	0.024 (4)	0.003 (3)	0.004 (3)	0.004 (3)
C28	0.032 (3)	0.042 (4)	0.017 (4)	0.002 (3)	−0.003 (3)	0.002 (3)
C29	0.020 (3)	0.034 (4)	0.036 (5)	0.005 (2)	0.002 (3)	0.004 (3)
C30	0.017 (3)	0.023 (4)	0.030 (4)	−0.001 (2)	0.008 (3)	0.001 (3)
C31	0.021 (3)	0.025 (4)	0.024 (4)	−0.005 (2)	0.009 (3)	0.004 (3)
C32	0.020 (3)	0.025 (4)	0.021 (4)	−0.002 (2)	0.010 (3)	−0.001 (3)
C33	0.035 (3)	0.024 (4)	0.020 (4)	−0.006 (2)	0.003 (3)	−0.004 (3)
C34	0.040 (3)	0.033 (4)	0.023 (4)	−0.003 (3)	0.020 (3)	−0.012 (3)
C35	0.026 (3)	0.034 (4)	0.034 (4)	−0.006 (2)	0.016 (3)	−0.004 (3)
C36	0.022 (3)	0.029 (4)	0.021 (4)	0.001 (2)	0.006 (2)	−0.002 (3)

Geometric parameters (Å, º)

O1—N3	1.253 (5)	O5—N7	1.261 (4)
O2—N3	1.240 (5)	O6—N7	1.227 (5)
O3—N4	1.247 (5)	O7—N8	1.244 (5)
O4—N4	1.242 (5)	O8—N8	1.231 (4)
N1—C1	1.465 (5)	N5—C19	1.459 (5)
N1—C7	1.357 (5)	N5—C25	1.379 (5)
N1—H1N1	0.8800	N5—H1N5	0.8800
N2—C2	1.459 (5)	N6—C20	1.458 (5)
N2—C13	1.351 (5)	N6—C31	1.334 (5)
N2—H1N2	0.8800	N6—H1N6	0.8800
N3—C8	1.444 (5)	N7—C26	1.437 (5)
N4—C14	1.435 (5)	N8—C32	1.445 (5)
C1—C6	1.513 (6)	C19—C24	1.525 (5)
C1—C2	1.549 (6)	C19—C20	1.545 (6)
C1—H1	1.0000	C19—H19	1.0000
C2—C3	1.515 (5)	C20—C21	1.525 (6)
C2—H2	1.0000	C20—H20	1.0000
C3—C4	1.523 (6)	C21—C22	1.519 (5)
C3—H3A	0.9900	C21—H21A	0.9900
C3—H3B	0.9900	C21—H21B	0.9900
C4—C5	1.526 (5)	C22—C23	1.529 (6)
C4—H4A	0.9900	C22—H22A	0.9900
C4—H4B	0.9900	C22—H22B	0.9900
C5—C6	1.520 (5)	C23—C24	1.517 (6)
C5—H5A	0.9900	C23—H23A	0.9900
C5—H5B	0.9900	C23—H23B	0.9900
C6—H6A	0.9900	C24—H24A	0.9900
C6—H6B	0.9900	C24—H24B	0.9900
C7—C8	1.427 (6)	C25—C26	1.407 (6)
C8—C9	1.400 (6)	C26—C27	1.394 (6)
C9—C10	1.371 (5)	C27—C28	1.355 (5)
C9—H9	0.9500	C27—H27	0.9500
C10—C11	1.378 (6)	C28—C29	1.388 (6)
C10—H10	0.9500	C28—H28	0.9500
C11—C12	1.365 (6)	C29—C30	1.355 (6)
C11—H11	0.9500	C29—H29	0.9500
C12—C7	1.423 (5)	C30—C25	1.410 (5)
C12—H12	0.9500	C30—H30	0.9500
C13—C14	1.419 (6)	C31—C32	1.417 (6)
C14—C15	1.407 (6)	C32—C33	1.398 (6)
C15—C16	1.368 (5)	C33—C34	1.364 (5)
C15—H15	0.9500	C33—H33	0.9500
C16—C17	1.385 (6)	C34—C35	1.413 (6)
C16—H16	0.9500	C34—H34	0.9500
C17—C18	1.365 (6)	C35—C36	1.351 (6)
C17—H17	0.9500	C35—H35	0.9500
C18—C13	1.409 (5)	C36—C31	1.427 (5)
C18—H18	0.9500	C36—H36	0.9500
C1—N1—C7	124.3 (4)	C19—N5—C25	125.0 (4)
C7—N1—H1N1	117.8	C25—N5—H1N5	117.5
C1—N1—H1N1	117.8	C19—N5—H1N5	117.5
C2—N2—C13	126.5 (4)	C20—N6—C31	126.3 (4)
C13—N2—H1N2	116.7	C31—N6—H1N6	116.8
C2—N2—H1N2	116.7	C20—N6—H1N6	116.8
O1—N3—O2	121.8 (4)	O5—N7—O6	121.0 (4)
O2—N3—C8	119.1 (5)	O6—N7—C26	119.6 (4)
O1—N3—C8	119.0 (4)	O5—N7—C26	119.4 (4)
O3—N4—O4	121.7 (4)	O7—N8—O8	120.8 (4)
O4—N4—C14	119.1 (5)	O8—N8—C32	119.3 (5)
O3—N4—C14	119.2 (5)	O7—N8—C32	119.9 (4)
N1—C1—C6	110.9 (4)	N5—C19—C24	109.7 (4)
N1—C1—C2	111.2 (4)	N5—C19—C20	111.5 (4)
C6—C1—C2	109.5 (4)	C24—C19—C20	108.9 (4)
N1—C1—H1	108.4	N5—C19—H19	108.9
C6—C1—H1	108.4	C24—C19—H19	108.9
C2—C1—H1	108.4	C20—C19—H19	108.9
N2—C2—C3	110.6 (4)	N6—C20—C21	110.0 (4)
N2—C2—C1	112.3 (4)	N6—C20—C19	111.8 (4)
C3—C2—C1	109.1 (4)	C21—C20—C19	109.4 (4)
N2—C2—H2	108.2	N6—C20—H20	108.5
C3—C2—H2	108.2	C21—C20—H20	108.5
C1—C2—H2	108.2	C19—C20—H20	108.5
C2—C3—C4	111.4 (4)	C22—C21—C20	110.7 (4)
C2—C3—H3A	109.3	C22—C21—H21A	109.5
C4—C3—H3A	109.3	C20—C21—H21A	109.5
C2—C3—H3B	109.3	C22—C21—H21B	109.5
C4—C3—H3B	109.3	C20—C21—H21B	109.5
H3A—C3—H3B	108.0	H21A—C21—H21B	108.1
C3—C4—C5	110.3 (4)	C21—C22—C23	110.1 (4)
C3—C4—H4A	109.6	C21—C22—H22A	109.6
C5—C4—H4A	109.6	C23—C22—H22A	109.6
C3—C4—H4B	109.6	C21—C22—H22B	109.6
C5—C4—H4B	109.6	C23—C22—H22B	109.6
H4A—C4—H4B	108.1	H22A—C22—H22B	108.1
C6—C5—C4	111.9 (4)	C24—C23—C22	111.4 (4)
C6—C5—H5A	109.2	C24—C23—H23A	109.3
C4—C5—H5A	109.2	C22—C23—H23A	109.3
C6—C5—H5B	109.2	C24—C23—H23B	109.3
C4—C5—H5B	109.2	C22—C23—H23B	109.3
H5A—C5—H5B	107.9	H23A—C23—H23B	108.0
C1—C6—C5	110.7 (4)	C23—C24—C19	110.7 (4)
C1—C6—H6A	109.5	C23—C24—H24A	109.5
C5—C6—H6A	109.5	C19—C24—H24A	109.5
C1—C6—H6B	109.5	C23—C24—H24B	109.5
C5—C6—H6B	109.5	C19—C24—H24B	109.5
H6A—C6—H6B	108.1	H24A—C24—H24B	108.1
N1—C7—C12	121.4 (5)	N5—C25—C26	123.9 (4)
N1—C7—C8	123.6 (4)	N5—C25—C30	120.6 (5)
C8—C7—C12	115.0 (5)	C26—C25—C30	115.4 (5)
C7—C8—C9	121.7 (4)	C25—C26—C27	121.8 (5)
C7—C8—N3	122.3 (5)	C25—C26—N7	122.3 (5)
C9—C8—N3	116.0 (5)	C27—C26—N7	115.9 (5)
C10—C9—C8	120.2 (5)	C28—C27—C26	120.4 (5)
C10—C9—H9	119.9	C28—C27—H27	119.8
C8—C9—H9	119.9	C26—C27—H27	119.8
C9—C10—C11	119.3 (5)	C27—C28—C29	119.2 (5)
C9—C10—H10	120.3	C27—C28—H28	120.4
C11—C10—H10	120.3	C29—C28—H28	120.4
C12—C11—C10	121.7 (5)	C30—C29—C28	121.1 (5)
C12—C11—H11	119.2	C30—C29—H29	119.4
C10—C11—H11	119.2	C28—C29—H29	119.4
C11—C12—C7	121.9 (5)	C29—C30—C25	122.0 (5)
C11—C12—H12	119.0	C29—C30—H30	119.0
C7—C12—H12	119.0	C25—C30—H30	119.0
N2—C13—C18	122.1 (5)	N6—C31—C32	124.0 (4)
N2—C13—C14	122.5 (4)	N6—C31—C36	122.1 (4)
C14—C13—C18	115.4 (5)	C32—C31—C36	113.9 (5)
C13—C14—C15	121.4 (4)	C31—C32—C33	122.7 (4)
C13—C14—N4	122.9 (5)	C31—C32—N8	121.0 (5)
C15—C14—N4	115.6 (5)	C33—C32—N8	116.3 (4)
C16—C15—C14	120.6 (5)	C34—C33—C32	120.9 (5)
C16—C15—H15	119.7	C34—C33—H33	119.5
C14—C15—H15	119.7	C32—C33—H33	119.5
C15—C16—C17	118.5 (5)	C33—C34—C35	117.8 (5)
C15—C16—H16	120.7	C33—C34—H34	121.1
C17—C16—H16	120.7	C35—C34—H34	121.1
C18—C17—C16	121.9 (5)	C36—C35—C34	121.6 (4)
C18—C17—H17	119.1	C36—C35—H35	119.2
C16—C17—H17	119.1	C34—C35—H35	119.2
C17—C18—C13	122.1 (5)	C35—C36—C31	122.8 (5)
C17—C18—H18	119.0	C35—C36—H36	118.6
C13—C18—H18	119.0	C31—C36—H36	118.6
C7—N1—C1—C6	−156.9 (4)	C25—N5—C19—C24	157.7 (4)
C7—N1—C1—C2	81.0 (5)	C25—N5—C19—C20	−81.5 (5)
C13—N2—C2—C3	−147.7 (4)	C31—N6—C20—C21	149.7 (5)
C13—N2—C2—C1	90.1 (5)	C31—N6—C20—C19	−88.6 (6)
N1—C1—C2—N2	−54.2 (5)	N5—C19—C20—N6	56.9 (5)
C6—C1—C2—N2	−177.1 (4)	C24—C19—C20—N6	178.1 (4)
N1—C1—C2—C3	−177.3 (4)	N5—C19—C20—C21	178.9 (3)
C6—C1—C2—C3	59.8 (5)	C24—C19—C20—C21	−59.8 (5)
N2—C2—C3—C4	177.0 (4)	N6—C20—C21—C22	−177.1 (4)
C1—C2—C3—C4	−59.0 (5)	C19—C20—C21—C22	59.8 (5)
C2—C3—C4—C5	56.1 (5)	C20—C21—C22—C23	−57.3 (5)
C3—C4—C5—C6	−54.1 (5)	C21—C22—C23—C24	55.8 (5)
N1—C1—C6—C5	178.4 (4)	C22—C23—C24—C19	−57.2 (5)
C2—C1—C6—C5	−58.5 (5)	N5—C19—C24—C23	−179.0 (4)
C4—C5—C6—C1	56.3 (5)	C20—C19—C24—C23	58.7 (5)
C1—N1—C7—C12	21.9 (7)	C19—N5—C25—C26	156.7 (5)
C1—N1—C7—C8	−158.2 (4)	C19—N5—C25—C30	−21.8 (7)
N1—C7—C8—C9	174.8 (5)	N5—C25—C26—C27	−175.4 (4)
C12—C7—C8—C9	−5.4 (7)	C30—C25—C26—C27	3.2 (7)
N1—C7—C8—N3	−3.4 (8)	N5—C25—C26—N7	3.7 (7)
C12—C7—C8—N3	176.4 (4)	C30—C25—C26—N7	−177.8 (4)
O2—N3—C8—C9	1.9 (7)	O6—N7—C26—C27	2.8 (7)
O1—N3—C8—C9	179.2 (4)	O5—N7—C26—C27	−177.7 (4)
O1—N3—C8—C7	−2.5 (7)	O5—N7—C26—C25	3.2 (7)
O2—N3—C8—C7	−179.8 (5)	O6—N7—C26—C25	−176.3 (5)
C7—C8—C9—C10	4.0 (7)	C25—C26—C27—C28	−1.6 (7)
N3—C8—C9—C10	−177.7 (4)	N7—C26—C27—C28	179.2 (4)
C8—C9—C10—C11	0.0 (7)	C26—C27—C28—C29	−0.7 (7)
C9—C10—C11—C12	−2.3 (8)	C27—C28—C29—C30	1.3 (8)
C10—C11—C12—C7	0.6 (8)	C28—C29—C30—C25	0.4 (8)
N1—C7—C12—C11	−177.0 (5)	N5—C25—C30—C29	176.1 (4)
C8—C7—C12—C11	3.1 (7)	C26—C25—C30—C29	−2.5 (7)
C2—N2—C13—C18	9.0 (7)	C20—N6—C31—C32	167.2 (4)
C2—N2—C13—C14	−170.9 (4)	C20—N6—C31—C36	−13.6 (8)
N2—C13—C14—C15	177.1 (4)	N6—C31—C32—C33	−173.9 (5)
C18—C13—C14—C15	−2.8 (7)	C36—C31—C32—C33	6.8 (7)
N2—C13—C14—N4	−1.5 (7)	N6—C31—C32—N8	3.8 (7)
C18—C13—C14—N4	178.6 (4)	C36—C31—C32—N8	−175.4 (4)
O4—N4—C14—C15	1.8 (7)	O8—N8—C32—C33	−7.4 (6)
O3—N4—C14—C15	−179.4 (4)	O7—N8—C32—C33	174.0 (5)
O3—N4—C14—C13	−0.7 (7)	O7—N8—C32—C31	−4.0 (7)
O4—N4—C14—C13	−179.5 (5)	O8—N8—C32—C31	174.7 (5)
C13—C14—C15—C16	2.1 (8)	C31—C32—C33—C34	−4.5 (8)
N4—C14—C15—C16	−179.2 (4)	N8—C32—C33—C34	177.6 (4)
C14—C15—C16—C17	−0.1 (7)	C32—C33—C34—C35	−0.3 (7)
C15—C16—C17—C18	−1.0 (8)	C33—C34—C35—C36	2.2 (8)
C16—C17—C18—C13	0.1 (8)	C34—C35—C36—C31	0.6 (8)
N2—C13—C18—C17	−178.2 (5)	N6—C31—C36—C35	175.9 (5)
C14—C13—C18—C17	1.7 (7)	C32—C31—C36—C35	−4.9 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···O1	0.88	2.03	2.638 (5)	126
N2—H12N···O3	0.88	1.95	2.617 (4)	132
N5—H15N···O5	0.88	2.03	2.632 (5)	125
N6—H16N···O7	0.88	1.95	2.609 (4)	131
C12—H12···O5	0.95	2.53	3.385 (6)	149
C18—H18···O7^i	0.95	2.41	3.306 (6)	156
C30—H30···O1^ii	0.95	2.56	3.386 (6)	146
C36—H36···O3	0.95	2.46	3.368 (5)	160

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