(E)-N-{[6-Chloro-4-(4-chloro­phen­yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridin-5-yl]methyl­ene}benzene-1,2-diamine: a three-dimensional framework structure built from only two hydrogen bonds

The mol­ecules of the title compound, C₂₆H₁₉Cl₂N₅, are conformationally chiral, with none of the aryl groups coplanar with the pyrazolo[3,4-b]pyridine core of the mol­ecule. A single unique N-H...N hydrogen bond links the mol­ecules into two symmetry-related sets of C(11) chains running parallel to the [011] and [01] directions, respectively, and these two sets of chains are linked into a continuous three-dimensional framework structure by a single unique C-H...N hydrogen bond which forms a chain parallel to the [100] direction.

S1. Comment

Simple nitrogen heterocycles, such pyridines, pyrazoles, pyrimidines or pyrroles, are of interest in chemical biology or medicinal chemistry, and also for the preparation of new fused pyrazolo-heterocyclic derivatives. We are currently exploring the use of 6-chloro-4-(4-chlorophenyl)-3-methyl-1-phenyl-1H- pyrazolo[3,4-b]pyridine-5-carbaldehyde, itself readily prepared under Vilsmeier–Haack formylation conditions from 4-(4-chlorophenyl)-3-methyl-1-phenyl-4,5-dihydro-1H- pyrazolo[3,4-b]pyridin-6(7H)-one, as a building-block for the synthesis of polyannellated heterocyclic systems (Verdecía et al., 1996; Girreser et al., 2004; Quiroga et al., 1998, 2005). It was hoped that the reaction of this carbaldehyde with 1,2-benzenediamine would lead to a cyclization, forming a dihydropyrazolo[4',3':5,6]pyrido[2,3-b][1,5]benzodiazepine system, but instead this reaction led to the formation and isolation of the intermediate title compound, (I) (Fig. 1). In the formation of (I), condensation has occurred between the aldehyde function and one of the amino groups in the benzenediamine reactant (see first scheme), but the cyclization step, involving nucleophilic displacement of the 6-chloro atom on the pyridine ring by the second amino group, has not occurred. We report here the structure of (I), which proves to be of interest as the molecules are linked into a single three-dimensional framework structure by the action of just two hydrogen bonds.

The molecular conformation of (I) can readily be defined in terms of five torsion angles (Fig. 1, Table 1), which show that while the Schiff base-type space unit comprising atoms C57, N57 and C51 is almost coplanar with the pyrazolopyridine unit, the three pendent aryl rings are all markedly rotated out of this plane. The dihedral angles made between the plane of the pyrazolopyridine unit and the planes of the aryl rings C11–C16, C41–C46 and C51–C56 are 21.4 (2), 75.3 (2) and 29.9 (2)°, respectively. It is reasonable to associate the much large dihedral angle involving ring C41–C46 with the greater steric congestion in the vicinity of this ring. In particular, a small dihedral angle between this ring and the heterocyclic unit is almost certainly prevented by the presence of both the methyl group containing atom C31 and the C—H bond at atom C57 (Fig. 1). Consistent with this idea, the smallest dihedral angle is found for ring C11–C16, where the intramolecular steric constraints are the least for any of the rings. This conformation means that the molecule of (I) exhibits no internal symmetry and so is conformationally chiral. However, the space group accommodates equal numbers of the two conformational enantiomers, and the choice of the selected asymmetric unit has no chemical significance. The bond distances (Table 1) in the heterocyclic fragment of the molecule, which show the same pattern as found in similar pyrazolo[3,4-b]pyridines (Low et al., 2002, 2007; Abonia et al., 2005; Quiroga et al., 2009), having due regard to the differences between the peripheral substituents, are consistent with the occurrence of aromatic-type electronic delocalization within the pyridine and strong bond fixation in the pyrazole ring. Likewise, there is strong bond fixation, as expected, in the spacer unit between the pyridine and the aminophenyl rings.

The molecules of (I) are linked into a continuous three-dimensional framework structure by just two hydrogen bonds, one each of N—H···N and C—H···N types (Table 2), and the formation of the framework structure is readily analysed in terms of two simple one-dimensional sub-structures, each of which depends on only one hydrogen bond. The N—H···N hydrogen bond links molecules related by an n-glide plane. Amino atom N52 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyrazole ring atom N2 in the molecule at (1/2 − x, 1/2 + y, −1/2 + z), so linking molecules related by the n-glide plane at x = 1/4 into a C(11) [see Bernstein et al. (1995) for graph-set notation] chain running parallel to the [011] direction (Fig. 2). A similar chain is formed by molecules related by the n-glide plane at x = 3/4, and this second chain is related to the first by the action of the 2₁ screw axes parallel to [001]. Hence, the chain based on the n-glide plane at x = 3/4 runs parallel to [011] (Fig. 2), so that the structure consists of alternating layers of C(11) chains along [011] and [011], stacked in the [100] direction. Within each layer, the chains are related to one another by unit translations along [010] or [001].

The second sub-structure is simpler and consists of just a simple chain. The aryl atom C46 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyridine ring atom N7 in the molecule at (1/2 + x, 3/2 − y, z), so forming a C(7) chain running parallel to the [100] direction and containing molecules related by the a-glide plane at y = 3/4 (Fig. 3). Within this chain, adjacent molecules, for example those at (x, y, z) and (1/2 + x, 3/2 − y, z), are components of C(11) chains along [011] and [011], respectively. Hence, the overall action of all the chains parallel to [100] is to link each chain along [011] to each chain along [011], so linking all of the molecules into a single three-dimensional framework. There are neither C—H···π(arene) nor C—H···π(pyridine) hydrogen bonds, nor any π–π stacking interactions, in the structure of (I).

It is of interest briefly to compare the crystal structure of (I) reported here with those of some close analogues, compounds (II)–(VI) (see second scheme). The crystallization characteristics of (II)-(VI) differ markedly from those of (I). Firstly, (IV) and (V) both crystallize as stoichiometric monosolvates with dimethylformamide (Low et al., 2007). Secondly, unlike (I), which crystallizes in the Sohnke space group Pna2₁, compounds (II)–(VI) all crystallize in the centrosymmetric space groups P1 [for (II) (Low et al., 2002), (III) (Abonia et al., 2005) and (IV) (Low et al., 2007)] or C2/c [for (V) (Low et al., 2007) and (VI) (Quiroga et al., 2009)]. In addition, the crystal structures of (II)–(VI) all contain C—H···π(arene) hydrogen bonds, whereas such interactions are absent from the structure of (I).

In the structure of (II), there are two independent C—H···π(arene) hydrogen bonds, each using a different arene ring as acceptor, and their action is to link the molecules into chains of centrosymmetric rings. These chains are linked into sheets by a π–π stacking interaction between pairs of pyridine rings, giving a two-dimensional supramolecular structure. In (III), the supramolecular structure is one-dimensional and contains two types of centrosymmetric ring built alternately from pairs of C—H···π(arene) hydrogen bonds and pairs of C—H···O hydrogen bonds. Symmetry-related pairs of C—H···π(arene) hydrogen bonds in the structure of (IV) link pairs of molecules into centrosymmetric dimers, i.e. a finite zero-dimensional hydrogen-bonded structure, while in (V) C—H···π(arene) and C—H···N hydrogen bonds once again generate a chain in which two types of centrosymmetric ring alternate. Finally, in the structure of (VI), the molecules are linked into rather complex double chains by a combination of N—H···N, C—H···N and C—H···π(arene) hydrogen bonds. Thus, overall, the supramolecular structures generated by direction-specific interactions are zero-dimensional in (IV), one-dimensional for (III), (V) and (VI), two-dimensional for (II), and three-dimensional for (I). However, in terms just of hydrogen bonds, as opposed to π–π stacking interactions, the hydrogen-bonded structures in (II), (III), (V) and (VI) are one-dimensional. The sharp contrast between this behaviour and that of (I) can be traced directly to the space group for (I), Pna2₁, where the combination of two hydrogen bonds connecting molecules related by a glide plane and a screw axis, respectively, generates a three-dimensional array. But this simply raises the question of why (I) crystallizes in the relatively uncommon space group Pna2₁, representing only ca 1.4% of the entries in the Cambridge Strcutural Database (release 5.31, November 2009; Allen, 2002), rather than P1 (23.0% of entries) or C2/c (8.0% of entries).

S2. Experimental

Glacial acetic acid (3 drops) was added to a solution of 6-chloro-4-(4-chlorophenyl)-3-methyl-1-phenyl-1H- pyrazolo[3,4-b]pyridine-5-carbaldehyde (0.64 mmol) and 1,2-benzenediamine (0.64 mmol) in ethanol (5 ml) and the mixture was heated under reflux for 1 h. The mixture was then cooled to ambient temperature, and the resulting precipitate was collected by filtration, washed with cold ethanol and recrystallized from ethanol to afford yellow crystals of (I) suitable for single-crystal X-ray diffraction (yield 80%, m.p. 474–476 K). MS (EI, 70 eV) m/z (%): 475/473/471 (M+, 2/5/10), 359 (5), 119 (100), 77 (11). Analysis: found: C 66.3, H 4.0, N 14.6%; C₂₆H₁₉Cl₂N₅ requires: C 66.1, H 4.1, N 14.8%.

S3. Refinement

All H atoms were located in difference maps. H atoms bonded to C atoms were then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic and alkenyl) or 0.98 Å (methyl), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl group, which was permitted to rotate but not to tilt, and 1.2 for all other H atoms bonded to C atoms. The coordinates of the H atoms bonded to N52 were refined with U_iso(H) = 1.2U_eq(N), giving N—H distances of 1.00 (6) and 1.02 (6) Å. The correct orientation of the structure with respect to the polar axis direction was established by means of the Flack x parameter (Flack, 1983), x = 0.12 (10), and the Hooft y parameter (Hooft et al., 2008), y = 0.15 (8), both calculated with 1792 Bijvoet pairs (96.4% coverage).

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of (I), showing symmetry-related hydrogen-bonded C(11) chains running parallel to the [011] and [011] directions, and linked by the C—H···N hydrogen bond. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted.
	Fig. 3. Part of the crystal structure of (I), showing a hydrogen-bonded C(7) chain running parallel to the [100] direction, in which alternate molecules lie in C(11) chains along [011] and [011]. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (1/2 + x, 3/2 − y, z), (1 + x, y, z) and (−1/2 + x, 3/2 − y, z), respectively.

(E)-N-{[6-Chloro-4-(4-chlorophenyl)-3-methyl-1-phenyl-1H- pyrazolo[3,4-b]pyridin-5-yl]methylene}benzene-1,2-diamine

Crystal data

C26H19Cl2N5	F(000) = 976
Mr = 472.36	Dx = 1.436 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 3777 reflections
a = 10.013 (2) Å	θ = 2.9–25.1°
b = 12.3487 (12) Å	µ = 0.32 mm^−1
c = 17.666 (4) Å	T = 120 K
V = 2184.4 (7) Å^3	Needle, yellow
Z = 4	0.37 × 0.06 × 0.04 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3777 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2630 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.104
Detector resolution: 9.091 pixels mm^-1	θmax = 25.1°, θmin = 2.9°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
Tmin = 0.899, Tmax = 0.987	l = −20→21
15595 measured reflections

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)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.127	w = 1/[σ^2(Fo^2) + (0.0407P)^2 + 1.7541P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
3777 reflections	Δρmax = 0.39 e Å^−3
306 parameters	Δρmin = −0.34 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 1792 pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.12 (10)

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

	x	y	z	Uiso*/Ueq
N1	0.0770 (4)	0.7263 (3)	0.8465 (2)	0.0271 (10)
N2	0.0567 (5)	0.6149 (3)	0.8539 (3)	0.0321 (11)
C3	0.1374 (6)	0.5667 (4)	0.8067 (3)	0.0260 (13)
C3A	0.2136 (5)	0.6443 (4)	0.7656 (3)	0.0244 (12)
C4	0.3103 (5)	0.6428 (4)	0.7105 (3)	0.0254 (13)
C5	0.3612 (5)	0.7420 (4)	0.6849 (3)	0.0243 (11)
C6	0.3053 (6)	0.8363 (4)	0.7174 (3)	0.0269 (13)
N7	0.2149 (4)	0.8408 (3)	0.7708 (2)	0.0250 (10)
C7A	0.1703 (5)	0.7441 (4)	0.7935 (3)	0.0246 (12)
C11	0.0024 (5)	0.7974 (4)	0.8919 (3)	0.0281 (13)
C12	0.0496 (6)	0.9013 (5)	0.9051 (3)	0.0357 (14)
H12	0.1319	0.9247	0.8839	0.043*
C13	−0.0261 (6)	0.9706 (5)	0.9501 (3)	0.0400 (15)
H13	0.0042	1.0423	0.9591	0.048*
C14	−0.1446 (7)	0.9362 (5)	0.9815 (3)	0.0392 (15)
H14	−0.1960	0.9842	1.0117	0.047*
C15	−0.1877 (6)	0.8329 (4)	0.9691 (3)	0.0341 (14)
H15	−0.2687	0.8089	0.9915	0.041*
C16	−0.1147 (5)	0.7631 (4)	0.9243 (3)	0.0273 (13)
H16	−0.1454	0.6913	0.9160	0.033*
C31	0.1393 (7)	0.4479 (4)	0.8027 (3)	0.0358 (15)
H31A	0.2296	0.4216	0.8138	0.054*
H31B	0.1130	0.4246	0.7519	0.054*
H31C	0.0766	0.4182	0.8400	0.054*
C41	0.3566 (5)	0.5375 (4)	0.6806 (3)	0.0229 (11)
C42	0.2732 (6)	0.4787 (4)	0.6345 (3)	0.0317 (13)
H42	0.1904	0.5088	0.6188	0.038*
C43	0.3085 (5)	0.3779 (4)	0.6111 (3)	0.0339 (13)
H43	0.2519	0.3387	0.5777	0.041*
C44	0.4259 (6)	0.3327 (4)	0.6359 (3)	0.0294 (13)
Cl44	0.46779 (14)	0.20246 (10)	0.61010 (9)	0.0367 (3)
C45	0.5117 (6)	0.3897 (4)	0.6819 (4)	0.0426 (15)
H45	0.5933	0.3587	0.6986	0.051*
C46	0.4753 (6)	0.4941 (4)	0.7033 (3)	0.0373 (14)
H46	0.5339	0.5356	0.7341	0.045*
C57	0.4555 (5)	0.7422 (4)	0.6223 (3)	0.0300 (13)
H57	0.4733	0.6748	0.5985	0.036*
N57	0.5150 (5)	0.8236 (4)	0.5970 (2)	0.0337 (11)
C51	0.5980 (6)	0.8139 (5)	0.5336 (3)	0.0306 (13)
C52	0.5967 (5)	0.9016 (4)	0.4832 (3)	0.0271 (12)
C53	0.6762 (6)	0.8957 (5)	0.4201 (3)	0.0411 (16)
H53	0.6741	0.9533	0.3845	0.049*
C54	0.7583 (6)	0.8094 (5)	0.4072 (3)	0.0412 (15)
H54	0.8132	0.8076	0.3633	0.049*
C55	0.7611 (7)	0.7254 (5)	0.4577 (3)	0.0431 (16)
H55	0.8191	0.6658	0.4493	0.052*
C56	0.6805 (6)	0.7270 (5)	0.5205 (3)	0.0381 (15)
H56	0.6819	0.6680	0.5550	0.046*
N52	0.5177 (5)	0.9882 (4)	0.4982 (3)	0.0369 (12)
H52A	0.495 (6)	1.038 (5)	0.454 (3)	0.044*
H52B	0.442 (6)	0.987 (4)	0.535 (3)	0.044*
Cl61	0.35055 (15)	0.96467 (10)	0.68734 (8)	0.0361 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.023 (2)	0.031 (3)	0.028 (2)	−0.0010 (19)	0.001 (2)	−0.0001 (19)
N2	0.037 (3)	0.022 (2)	0.037 (2)	−0.005 (2)	−0.005 (2)	0.008 (2)
C3	0.026 (3)	0.024 (3)	0.027 (3)	0.007 (3)	−0.001 (3)	0.003 (2)
C3A	0.031 (3)	0.021 (3)	0.021 (3)	0.003 (2)	−0.005 (2)	0.001 (2)
C4	0.023 (3)	0.023 (3)	0.031 (3)	0.001 (2)	−0.009 (2)	0.002 (2)
C5	0.019 (3)	0.031 (3)	0.023 (2)	−0.002 (2)	−0.003 (3)	−0.003 (2)
C6	0.034 (3)	0.016 (3)	0.031 (3)	−0.006 (2)	−0.012 (3)	0.002 (2)
N7	0.025 (3)	0.027 (2)	0.024 (2)	−0.001 (2)	−0.003 (2)	0.0035 (18)
C7A	0.024 (3)	0.025 (3)	0.025 (3)	−0.006 (2)	−0.006 (2)	0.002 (2)
C11	0.026 (3)	0.026 (3)	0.032 (3)	0.005 (3)	−0.004 (2)	0.005 (2)
C12	0.027 (3)	0.036 (4)	0.044 (3)	−0.001 (3)	0.001 (3)	0.001 (3)
C13	0.035 (4)	0.032 (3)	0.053 (4)	0.000 (3)	0.008 (3)	−0.009 (3)
C14	0.036 (4)	0.038 (3)	0.043 (3)	0.007 (3)	−0.001 (3)	−0.002 (3)
C15	0.023 (3)	0.038 (4)	0.041 (3)	0.003 (3)	0.005 (3)	0.008 (3)
C16	0.026 (3)	0.032 (3)	0.024 (2)	−0.002 (2)	−0.001 (2)	0.007 (2)
C31	0.054 (4)	0.018 (3)	0.035 (3)	0.001 (3)	0.005 (3)	0.004 (2)
C41	0.022 (3)	0.020 (2)	0.027 (3)	0.002 (2)	0.003 (3)	0.004 (2)
C42	0.029 (3)	0.034 (3)	0.033 (3)	0.000 (3)	−0.008 (3)	−0.001 (2)
C43	0.028 (3)	0.029 (3)	0.045 (3)	0.002 (2)	−0.012 (3)	−0.006 (3)
C44	0.031 (3)	0.014 (3)	0.043 (3)	−0.002 (2)	0.002 (3)	0.000 (2)
Cl44	0.0341 (8)	0.0258 (7)	0.0501 (8)	0.0040 (6)	−0.0012 (8)	−0.0056 (6)
C45	0.032 (4)	0.037 (3)	0.059 (4)	0.009 (3)	−0.013 (3)	−0.011 (3)
C46	0.034 (4)	0.030 (3)	0.048 (4)	−0.003 (3)	−0.005 (3)	−0.011 (3)
C57	0.028 (3)	0.023 (3)	0.039 (3)	0.002 (2)	−0.001 (3)	−0.002 (2)
N57	0.034 (3)	0.033 (3)	0.033 (3)	−0.004 (2)	0.002 (2)	0.002 (2)
C51	0.024 (3)	0.039 (3)	0.029 (3)	−0.007 (3)	−0.001 (3)	−0.001 (3)
C52	0.013 (3)	0.030 (3)	0.039 (3)	0.000 (2)	−0.006 (3)	0.002 (2)
C53	0.036 (4)	0.046 (4)	0.042 (3)	−0.018 (3)	−0.005 (3)	0.010 (3)
C54	0.036 (4)	0.048 (4)	0.039 (3)	0.001 (3)	0.007 (3)	−0.005 (3)
C55	0.048 (4)	0.032 (4)	0.049 (4)	0.004 (3)	0.004 (3)	−0.001 (3)
C56	0.035 (4)	0.043 (4)	0.036 (3)	0.006 (3)	−0.002 (3)	0.001 (3)
N52	0.038 (3)	0.028 (3)	0.044 (3)	0.003 (2)	0.005 (3)	0.005 (2)
Cl61	0.0420 (9)	0.0241 (7)	0.0423 (7)	−0.0014 (7)	0.0091 (8)	0.0039 (6)

Geometric parameters (Å, º)

N1—N2	1.397 (6)	C31—H31C	0.9800
N2—C3	1.304 (7)	C41—C46	1.365 (7)
C3—C3A	1.424 (7)	C41—C42	1.374 (7)
C3A—C4	1.373 (7)	C42—C43	1.358 (7)
C4—C5	1.402 (7)	C42—H42	0.9500
C5—C6	1.414 (7)	C43—C44	1.373 (7)
C6—N7	1.308 (7)	C43—H43	0.9500
N7—C7A	1.336 (6)	C44—C45	1.376 (8)
C7A—N1	1.341 (6)	C44—Cl44	1.724 (5)
C3A—C7A	1.397 (7)	C45—C46	1.392 (7)
N1—C11	1.404 (7)	C45—H45	0.9500
C3—C31	1.470 (7)	C46—H46	0.9500
C4—C41	1.478 (7)	C57—N57	1.250 (6)
C5—C57	1.454 (7)	C57—H57	0.9500
C6—Cl61	1.732 (5)	N57—C51	1.400 (7)
C11—C16	1.372 (7)	C51—C56	1.373 (8)
C11—C12	1.388 (8)	C51—C52	1.402 (8)
C12—C13	1.392 (8)	C52—N52	1.356 (7)
C12—H12	0.9500	C52—C53	1.371 (8)
C13—C14	1.377 (8)	C53—C54	1.366 (8)
C13—H13	0.9500	C53—H53	0.9500
C14—C15	1.364 (8)	C54—C55	1.368 (8)
C14—H14	0.9500	C54—H54	0.9500
C15—C16	1.380 (7)	C55—C56	1.372 (8)
C15—H15	0.9500	C55—H55	0.9500
C16—H16	0.9500	C56—H56	0.9500
C31—H31A	0.9800	N52—H52A	1.02 (6)
C31—H31B	0.9800	N52—H52B	1.00 (6)
C7A—N1—N2	109.2 (4)	H31A—C31—H31C	109.5
C7A—N1—C11	131.8 (4)	H31B—C31—H31C	109.5
N2—N1—C11	119.0 (4)	C46—C41—C42	119.8 (5)
C3—N2—N1	107.4 (4)	C46—C41—C4	120.9 (5)
N2—C3—C3A	110.6 (5)	C42—C41—C4	119.1 (5)
N2—C3—C31	119.6 (5)	C43—C42—C41	120.4 (5)
C3A—C3—C31	129.8 (5)	C43—C42—H42	119.8
C4—C3A—C7A	118.7 (5)	C41—C42—H42	119.8
C4—C3A—C3	137.0 (5)	C42—C43—C44	119.9 (5)
C7A—C3A—C3	104.3 (5)	C42—C43—H43	120.1
C3A—C4—C5	118.3 (5)	C44—C43—H43	120.1
C3A—C4—C41	119.1 (4)	C43—C44—C45	121.0 (5)
C5—C4—C41	122.6 (5)	C43—C44—Cl44	120.2 (4)
C4—C5—C6	116.4 (5)	C45—C44—Cl44	118.8 (4)
C4—C5—C57	118.9 (4)	C44—C45—C46	118.1 (5)
C6—C5—C57	124.4 (5)	C44—C45—H45	120.9
N7—C6—C5	127.0 (5)	C46—C45—H45	120.9
N7—C6—Cl61	111.3 (4)	C41—C46—C45	120.8 (5)
C5—C6—Cl61	121.7 (4)	C41—C46—H46	119.6
C6—N7—C7A	114.2 (5)	C45—C46—H46	119.6
N7—C7A—N1	126.1 (5)	N57—C57—C5	125.6 (5)
N7—C7A—C3A	125.4 (5)	N57—C57—H57	117.2
N1—C7A—C3A	108.5 (4)	C5—C57—H57	117.2
C16—C11—C12	120.4 (5)	C57—N57—C51	120.0 (5)
C16—C11—N1	120.0 (5)	C56—C51—N57	123.9 (5)
C12—C11—N1	119.6 (5)	C56—C51—C52	120.1 (5)
C11—C12—C13	118.6 (6)	N57—C51—C52	115.9 (5)
C11—C12—H12	120.7	N52—C52—C53	122.6 (5)
C13—C12—H12	120.7	N52—C52—C51	119.4 (5)
C14—C13—C12	120.7 (6)	C53—C52—C51	118.0 (5)
C14—C13—H13	119.7	C54—C53—C52	121.8 (5)
C12—C13—H13	119.7	C54—C53—H53	119.1
C15—C14—C13	119.8 (6)	C52—C53—H53	119.1
C15—C14—H14	120.1	C53—C54—C55	119.6 (6)
C13—C14—H14	120.1	C53—C54—H54	120.2
C14—C15—C16	120.6 (6)	C55—C54—H54	120.2
C14—C15—H15	119.7	C54—C55—C56	120.3 (6)
C16—C15—H15	119.7	C54—C55—H55	119.8
C11—C16—C15	119.9 (5)	C56—C55—H55	119.8
C11—C16—H16	120.0	C55—C56—C51	120.1 (6)
C15—C16—H16	120.0	C55—C56—H56	120.0
C3—C31—H31A	109.5	C51—C56—H56	120.0
C3—C31—H31B	109.5	C52—N52—H52A	117 (3)
H31A—C31—H31B	109.5	C52—N52—H52B	124 (3)
C3—C31—H31C	109.5	H52A—N52—H52B	110 (5)
C7A—N1—N2—C3	0.7 (5)	N1—C11—C12—C13	179.8 (5)
C11—N1—N2—C3	−179.5 (4)	C11—C12—C13—C14	0.8 (9)
N1—N2—C3—C3A	−0.6 (6)	C12—C13—C14—C15	0.6 (9)
N1—N2—C3—C31	179.2 (5)	C13—C14—C15—C16	−1.0 (9)
N2—C3—C3A—C4	−180.0 (6)	C12—C11—C16—C15	1.5 (7)
C31—C3—C3A—C4	0.2 (10)	N1—C11—C16—C15	179.8 (5)
N2—C3—C3A—C7A	0.4 (6)	C14—C15—C16—C11	0.0 (8)
C31—C3—C3A—C7A	−179.5 (5)	C3A—C4—C41—C46	−102.5 (6)
C7A—C3A—C4—C5	0.0 (7)	C5—C4—C41—C46	77.6 (7)
C3—C3A—C4—C5	−179.7 (6)	C3A—C4—C41—C42	71.8 (7)
C7A—C3A—C4—C41	−179.9 (5)	C5—C4—C41—C42	−108.1 (6)
C3—C3A—C4—C41	0.4 (9)	C46—C41—C42—C43	−0.3 (8)
C3A—C4—C5—C6	−1.3 (7)	C4—C41—C42—C43	−174.6 (5)
C41—C4—C5—C6	178.6 (5)	C41—C42—C43—C44	2.3 (9)
C3A—C4—C5—C57	−174.9 (5)	C42—C43—C44—C45	−2.5 (9)
C41—C4—C5—C57	5.0 (7)	C42—C43—C44—Cl44	177.0 (4)
C4—C5—C6—N7	2.7 (8)	C43—C44—C45—C46	0.6 (9)
C57—C5—C6—N7	175.9 (5)	Cl44—C44—C45—C46	−178.9 (5)
C4—C5—C6—Cl61	−175.9 (4)	C42—C41—C46—C45	−1.6 (9)
C57—C5—C6—Cl61	−2.8 (7)	C4—C41—C46—C45	172.6 (5)
C5—C6—N7—C7A	−2.3 (8)	C44—C45—C46—C41	1.5 (9)
Cl61—C6—N7—C7A	176.5 (3)	C4—C5—C57—N57	−175.1 (5)
C6—N7—C7A—N1	−179.2 (5)	C6—C5—C57—N57	11.9 (9)
C6—N7—C7A—C3A	0.7 (7)	C5—C57—N57—C51	−176.5 (5)
N2—N1—C7A—N7	179.5 (5)	C57—N57—C51—C56	−38.9 (8)
C11—N1—C7A—N7	−0.3 (9)	C57—N57—C51—C52	143.2 (5)
N2—N1—C7A—C3A	−0.5 (5)	C56—C51—C52—N52	−177.9 (5)
C11—N1—C7A—C3A	179.8 (5)	N57—C51—C52—N52	0.0 (7)
C4—C3A—C7A—N7	0.4 (8)	C56—C51—C52—C53	2.2 (8)
C3—C3A—C7A—N7	−179.8 (5)	N57—C51—C52—C53	−179.9 (5)
C4—C3A—C7A—N1	−179.7 (4)	N52—C52—C53—C54	177.8 (6)
C3—C3A—C7A—N1	0.1 (5)	C51—C52—C53—C54	−2.2 (8)
C7A—N1—C11—C16	159.5 (5)	C52—C53—C54—C55	0.7 (9)
N2—N1—C11—C16	−20.3 (7)	C53—C54—C55—C56	1.0 (9)
C7A—N1—C11—C12	−22.2 (8)	C54—C55—C56—C51	−1.0 (9)
N2—N1—C11—C12	158.1 (5)	N57—C51—C56—C55	−178.4 (5)
C16—C11—C12—C13	−1.8 (8)	C52—C51—C56—C55	−0.6 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N52—H52A···N2^i	1.02 (6)	2.07 (6)	3.082 (7)	170 (5)
C46—H46···N7^ii	0.95	2.46	3.367 (7)	160

Symmetry codes: (i) −x+1/2, y+1/2, z−1/2; (ii) x+1/2, −y+3/2, z.