(E)-3-tert-Butyl-4-(4-chloro­benz­yl)-N-(4-chloro­benzyl­idene)-1-phenyl-1H-pyrazol-5-amine: sheets built from [pi]-stacked hydrogen-bonded dimers

The title compound, C₂₇H₂₅Cl₂N₃, is an unexpected but high-yield product from the microwave-mediated reaction between 3-tert-butyl-N-4-chloro­benzyl-1-phenyl-1H-pyrazol-5-amine and 4-chloro­benzaldehyde. Inversion-related pairs of mol­ecules are linked by C-H...[pi](arene) hydrogen bonds to form cyclic centrosymmetric dimers, and dimers of this type are linked into sheets by two independent [pi]-[pi] stacking inter­actions.

S1. Introduction

As part of a programme for the development of synthetic strategies aimed at the production of new, functionalized heterocyclic compounds, we have concentrated recent efforts on the synthesis of bioactive nitro­gen-containing heterocycles (Quiroga et al., 1998, 2001, 2008a,b), latterly employing microwave irradiation. The use of microwave irradiation in solvent-free processes has a number of advantages over conventional reaction methods, including the simplicity of operation conferred by the ability to use open reaction vessels, milder reaction conditions and shorter reaction times, leading to better selectivities and hence cleaner reactions with higher product yields (Loupy et al., 1998; Deshayes et al., 1999; Varma, 1999a,b; Tanaka & Toda, 2000; Tu et al., 2006). Using this type of synthetic procedure we have obtained (E)-3-tert-butyl-4-(4-chloro­benzyl)-N-(4-chloro­benzyl­idene)-1-phenyl-1H-pyrazol-5-amine, (I) (Fig. 1), from the microwave-mediated reaction between 3-tert-butyl-N-4-chloro­benzyl-1-phenyl-1H-pyrazol-5-amine and 4-chloro­benzaldehyde. The reaction was originally carried out in the presence of an equimolar qu­antity of dimedone (cyclo­hexane-1,3-dione) with the aim of producing, in a tricomponent reaction, compound (II) which contains a fused tricyclic system (see Scheme 1). In the event, compound (I) was obtained both in the presence and in the absence of the dimedone, and its formation appears to involve a migratory rearrangement of the pyrazole component prior to a condensation reaction with the aldehyde component. An analogous rearrangement involving the migration of a benzotriazol-1-yl­methyl group, as opposed to a simple benzyl group as here, was postulated (Abonía et al., 2002) to proceed via an ionic mechanism (cf. Scheme 2). Any free benzyl cation must have a fairly short lifetime, otherwise scrambling of the location of the chloro substituent via a tropylium inter­mediate seems likely to occur: alternatively, the present rearrangement may proceed by a concerted pathway.

S2. Experimental

S2.1. Synthesis and crystallization

An mixture of equimolar qu­anti­ties of 3-tert-butyl-N-4-chloro­benzyl-1-phenyl-1H-pyrazol-5-amine and 4-chloro­benzaldehyde was subjected to microwave irradiation for 30 min at 423 K, with maximum power 200 W. The reaction mixture was cooled to ambient temperature and then dissolved in the minimum volume of boiling ethanol. Slow cooling to ambient temperature gave yellow crystals of (I) suitable for single-crystal X-ray diffraction which were collected by filtration and washed with hexane (3 ml) (yield 94%, m.p. 440–441 K). MS (EI, 70 eV) m/z (%): 463/461 (M⁺, 70/100), 201 (41), 125 (18); HRMS found 461.1414; C₂₇H₂₅³⁵Cl₂N₃ requires 461.1426.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic and alkenic), 0.98 (CH₃) or 0.99 Å (CH₂) and U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms.

S3. Results and discussion

Within the pyrazole ring of the title compound, (I), the lengths of the bonds N1—C5 and N2—C3 (Fig. 1 and Table 2) differ by only ca 0.04 Å, even though these bonds are formally single and double bonds, respectively; moreover, the N2—C3 bond is significantly longer than the isolated N51═ C57 double bond. Similarly, the C3—C4 and C4—C5 distances differ by only ca 0.04 Å, even though these bonds are again formally single and double bonds respectively. These observations are consistent with a significant degree of aromatic type electronic delocalization within the pyrazole ring.

The phenyl ring (C11–C16) makes a dihedral angle of only 7.4 (2)° with the adjacent pyrazole ring; the near coplanarity of these two rings may be associated with a short, and attractive, intra­molecular contact involving atoms H12 and N51 (Table 3). The rings in the benzyl and benzyl­idene substituents (rings C41–C46 and C51—C56, respectively) are very far from being coplanar with the pyrazole ring, as indicated by the leading torsion angles (Table 2). The dihedral angles made between the pyrazole ring, and each of these two aryl rings are 84.7 (2) and 54.5 (2)°, respectively. One of the methyl C atoms of the tert-butyl group, atom C32, lies close to, but not coincident with the plane of the pyrazole ring: the displacement of this atom form the ring plane is 0.436 (3) Å.

There are no inter­molecular C—H···N hydrogen bonds in the crystal structure, and the supra­molecular assembly is determined by a combination of one C—H···π(arene) hydrogen bond (Table 3) and two independent π–π stacking inter­actions. The C—H···π(arene) hydrogen bond links molecules related by inversion to form a cyclic dimer unit, where the reference dimer is centred at (1/2, 1/2, 1/2) which can conveniently be regarded as the key building block in the supra­molecular assembly (Figs. 2 and 3).

An aromatic π–π stacking inter­action links the C51–C56 benzyl­idene rings of the molecules at (x, y, z) and (-x+2, -y+1, -z+1). These two rings are strictly planar, with an inter­planar spacing of 3.359 (2) Å and a ring-centroid separation of 3.979 (2) Å, and this stacking inter­action links the hydrogen-bonded dimers centred at (n+0,5, 1/2, 1/2), where n represents an integer, into a chain running parallel to the [100] direction (Fig. 2).

The pyrazole ring of the molecule at (x, y, z) and the C11–C16 phenyl ring of the molecule at (-x+1, -y, -z+1) make a dihedral angle of only 7.4 (2)°. The ring-centroid separation is 3.842 (2) Å and the shortest perpendicular distance from the centroid of one ring to the plane of the other ring is ca 3.60 Å. This inter­action links the hydrogen-bonded dimers centred at (1/2, n+1/2, 1/2) into a chain running parallel to the [010] direction (Fig. 3). The combination of the chains along [100] and [010] generates a sheet of π-stacked hydrogen-bonded dimers lying parallel to (001).

Related literature

For related literature, see: Abonía et al. (2002); Deshayes et al. (1999); Loupy et al. (1998); Quiroga et al. (1998, 2001, 2008a, 2008b); Tanaka & Toda (2000); Tu et al. (2006); Varma (1999a, 1999b).

Computing details

Data collection: COLLECT (Hooft, 1998); 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 compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2. A stereoview of part of the crystal structure of compound (I), showing the formation of a chain of π-stacked hydrogen-bonded dimers along [100]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Fig. 3. A stereoview of part of the crystal structure of compound (I), showing the formation of a chain of π-stacked hydrogen-bonded dimers along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

(E)-3-tert-Butyl-4-(4-chlorobenzyl)-N-(4-chlorobenzylidene)-1-phenyl-1H-pyrazol-5-amine

Crystal data

C27H25Cl2N3	Z = 2
Mr = 462.40	F(000) = 484
Triclinic, P1	Dx = 1.340 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8820 (5) Å	Cell parameters from 5272 reflections
b = 10.1168 (17) Å	θ = 2.9–27.5°
c = 14.279 (3) Å	µ = 0.30 mm^−1
α = 69.627 (13)°	T = 120 K
β = 72.298 (10)°	Block, yellow
γ = 84.381 (11)°	0.41 × 0.32 × 0.27 mm
V = 1145.8 (3) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	5272 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	3063 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.069
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ & ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→13
Tmin = 0.886, Tmax = 0.923	l = −18→18
29852 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.175	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0773P)^2 + 0.9567P] where P = (Fo^2 + 2Fc^2)/3
5272 reflections	(Δ/σ)max = 0.001
292 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.3312 (3)	0.0990 (2)	0.55902 (18)	0.0242 (5)
N2	0.2201 (3)	0.0123 (3)	0.64175 (18)	0.0253 (5)
C3	0.2567 (3)	0.0056 (3)	0.7275 (2)	0.0237 (6)
C4	0.3905 (3)	0.0913 (3)	0.7018 (2)	0.0240 (6)
C5	0.4329 (3)	0.1503 (3)	0.5945 (2)	0.0243 (6)
C11	0.3183 (3)	0.1277 (3)	0.4564 (2)	0.0233 (6)
C12	0.4111 (3)	0.2290 (3)	0.3688 (2)	0.0282 (7)
H12	0.4886	0.2810	0.3753	0.034*
C13	0.3895 (4)	0.2534 (3)	0.2722 (2)	0.0301 (7)
H13	0.4527	0.3227	0.2125	0.036*
C14	0.2778 (3)	0.1788 (3)	0.2607 (2)	0.0294 (7)
H14	0.2634	0.1970	0.1941	0.035*
C15	0.1870 (4)	0.0768 (3)	0.3481 (2)	0.0297 (7)
H51	0.1104	0.0245	0.3411	0.036*
C16	0.2072 (3)	0.0510 (3)	0.4447 (2)	0.0261 (7)
H16	0.1451	−0.0197	0.5039	0.031*
C31	0.1481 (3)	−0.0852 (3)	0.8316 (2)	0.0254 (6)
C32	0.2263 (4)	−0.1243 (3)	0.9198 (2)	0.0301 (7)
H32A	0.3267	−0.1717	0.9003	0.045*
H32B	0.1561	−0.1877	0.9839	0.045*
H32C	0.2461	−0.0386	0.9315	0.045*
C33	0.1067 (4)	−0.2215 (3)	0.8211 (2)	0.0282 (7)
H33A	0.0556	−0.1987	0.7655	0.042*
H33B	0.0346	−0.2786	0.8872	0.042*
H33C	0.2035	−0.2745	0.8038	0.042*
C34	−0.0046 (4)	−0.0033 (4)	0.8606 (2)	0.0341 (8)
H34A	0.0213	0.0827	0.8697	0.051*
H34B	−0.0767	−0.0624	0.9259	0.051*
H34C	−0.0555	0.0221	0.8048	0.051*
C47	0.4830 (3)	0.1089 (3)	0.7692 (2)	0.0243 (6)
H47A	0.5893	0.1456	0.7235	0.029*
H47B	0.4974	0.0142	0.8176	0.029*
C41	0.4148 (3)	0.2042 (3)	0.8337 (2)	0.0254 (6)
C42	0.2926 (3)	0.2991 (3)	0.8161 (2)	0.0264 (7)
H42	0.2476	0.3043	0.7625	0.032*
C43	0.2363 (4)	0.3862 (3)	0.8762 (2)	0.0301 (7)
H43	0.1507	0.4480	0.8656	0.036*
C44	0.3060 (3)	0.3817 (3)	0.9515 (2)	0.0269 (7)
Cl44	0.24118 (9)	0.49264 (8)	1.02640 (6)	0.0346 (2)
C45	0.4269 (3)	0.2891 (3)	0.9710 (2)	0.0263 (7)
H45	0.4735	0.2864	1.0234	0.032*
C46	0.4791 (3)	0.2003 (3)	0.9125 (2)	0.0259 (6)
H46	0.5606	0.1350	0.9265	0.031*
N51	0.5643 (3)	0.2308 (3)	0.52313 (19)	0.0264 (6)
C57	0.6082 (3)	0.3365 (3)	0.5393 (2)	0.0248 (6)
H57	0.5476	0.3624	0.5976	0.030*
C51	0.7509 (3)	0.4172 (3)	0.4683 (2)	0.0245 (6)
C52	0.7865 (3)	0.5434 (3)	0.4763 (2)	0.0268 (7)
H52	0.7180	0.5765	0.5288	0.032*
C53	0.9204 (3)	0.6217 (3)	0.4085 (2)	0.0296 (7)
H53	0.9426	0.7090	0.4129	0.035*
C54	1.0212 (3)	0.5692 (3)	0.3343 (2)	0.0295 (7)
Cl54	1.19456 (9)	0.65966 (9)	0.25172 (7)	0.0403 (2)
C55	0.9899 (4)	0.4437 (3)	0.3247 (2)	0.0300 (7)
H55	1.0601	0.4100	0.2730	0.036*
C56	0.8542 (3)	0.3683 (3)	0.3918 (2)	0.0283 (7)
H56	0.8311	0.2823	0.3859	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0257 (13)	0.0263 (13)	0.0199 (12)	−0.0025 (10)	−0.0047 (10)	−0.0080 (11)
N2	0.0258 (13)	0.0280 (13)	0.0194 (13)	−0.0041 (10)	−0.0035 (10)	−0.0063 (11)
C3	0.0268 (15)	0.0227 (15)	0.0229 (15)	0.0027 (12)	−0.0062 (12)	−0.0106 (13)
C4	0.0260 (15)	0.0230 (15)	0.0253 (16)	0.0032 (12)	−0.0083 (12)	−0.0111 (13)
C5	0.0264 (15)	0.0259 (15)	0.0234 (15)	0.0026 (12)	−0.0088 (12)	−0.0109 (13)
C11	0.0249 (15)	0.0269 (15)	0.0174 (14)	0.0037 (12)	−0.0048 (12)	−0.0085 (12)
C12	0.0278 (16)	0.0311 (17)	0.0259 (16)	−0.0034 (13)	−0.0067 (13)	−0.0096 (14)
C13	0.0298 (16)	0.0339 (17)	0.0239 (16)	0.0017 (13)	−0.0046 (13)	−0.0096 (14)
C14	0.0307 (16)	0.0355 (17)	0.0216 (16)	0.0050 (14)	−0.0077 (13)	−0.0103 (14)
C15	0.0290 (16)	0.0369 (18)	0.0273 (16)	−0.0001 (13)	−0.0102 (13)	−0.0138 (14)
C16	0.0262 (15)	0.0264 (16)	0.0241 (16)	−0.0010 (12)	−0.0068 (13)	−0.0065 (13)
C31	0.0293 (16)	0.0244 (15)	0.0215 (15)	−0.0015 (12)	−0.0061 (12)	−0.0073 (13)
C32	0.0363 (17)	0.0316 (17)	0.0217 (16)	−0.0022 (14)	−0.0068 (13)	−0.0089 (14)
C33	0.0323 (16)	0.0265 (16)	0.0232 (16)	−0.0067 (13)	−0.0060 (13)	−0.0050 (13)
C34	0.0361 (18)	0.0375 (18)	0.0266 (17)	0.0032 (15)	−0.0069 (14)	−0.0109 (15)
C47	0.0259 (15)	0.0234 (15)	0.0246 (15)	−0.0011 (12)	−0.0092 (12)	−0.0072 (13)
C41	0.0276 (16)	0.0252 (15)	0.0231 (15)	−0.0029 (12)	−0.0075 (12)	−0.0066 (13)
C42	0.0299 (16)	0.0285 (16)	0.0243 (16)	0.0012 (13)	−0.0115 (13)	−0.0102 (13)
C43	0.0339 (17)	0.0298 (17)	0.0307 (17)	0.0040 (13)	−0.0145 (14)	−0.0118 (14)
C44	0.0314 (16)	0.0245 (15)	0.0237 (16)	−0.0039 (13)	−0.0038 (13)	−0.0093 (13)
Cl44	0.0465 (5)	0.0299 (4)	0.0316 (4)	0.0012 (3)	−0.0122 (4)	−0.0148 (3)
C45	0.0279 (16)	0.0308 (16)	0.0205 (15)	−0.0033 (13)	−0.0074 (12)	−0.0079 (13)
C46	0.0261 (15)	0.0281 (16)	0.0225 (15)	0.0007 (12)	−0.0077 (12)	−0.0067 (13)
N51	0.0250 (13)	0.0274 (13)	0.0253 (13)	−0.0018 (10)	−0.0065 (10)	−0.0074 (11)
C57	0.0240 (15)	0.0267 (16)	0.0240 (15)	0.0028 (12)	−0.0078 (12)	−0.0089 (13)
C51	0.0248 (15)	0.0271 (15)	0.0233 (15)	−0.0006 (12)	−0.0102 (12)	−0.0073 (13)
C52	0.0271 (15)	0.0278 (16)	0.0269 (16)	0.0022 (12)	−0.0098 (13)	−0.0096 (13)
C53	0.0297 (17)	0.0258 (16)	0.0358 (18)	−0.0017 (13)	−0.0137 (14)	−0.0094 (14)
C54	0.0270 (16)	0.0285 (16)	0.0303 (17)	−0.0022 (13)	−0.0108 (13)	−0.0037 (14)
Cl54	0.0322 (4)	0.0386 (5)	0.0416 (5)	−0.0092 (3)	−0.0036 (4)	−0.0068 (4)
C55	0.0309 (17)	0.0313 (17)	0.0276 (17)	0.0019 (13)	−0.0053 (13)	−0.0128 (14)
C56	0.0294 (16)	0.0270 (16)	0.0305 (17)	−0.0017 (13)	−0.0080 (13)	−0.0120 (14)

Geometric parameters (Å, º)

N1—N2	1.370 (3)	C34—H34B	0.9800
N2—C3	1.337 (4)	C34—H34C	0.9800
C3—C4	1.419 (4)	C47—C41	1.520 (4)
C4—C5	1.379 (4)	C47—H47A	0.9900
C5—N1	1.377 (4)	C47—H47B	0.9900
N1—C11	1.429 (4)	C41—C46	1.396 (4)
C3—C31	1.528 (4)	C41—C42	1.399 (4)
C4—C47	1.505 (4)	C42—C43	1.394 (4)
C5—N51	1.396 (4)	C42—H42	0.9500
C11—C12	1.393 (4)	C43—C44	1.381 (4)
C11—C16	1.395 (4)	C43—H43	0.9500
C12—C13	1.384 (4)	C44—C45	1.382 (4)
C12—H12	0.9500	C44—Cl44	1.752 (3)
C13—C14	1.383 (4)	C45—C46	1.387 (4)
C13—H13	0.9500	C45—H45	0.9500
C14—C15	1.387 (4)	C46—H46	0.9500
C14—H14	0.9500	N51—C57	1.287 (4)
C15—C16	1.377 (4)	C57—C51	1.465 (4)
C15—H51	0.9500	C57—H57	0.9500
C16—H16	0.9500	C51—C52	1.395 (4)
C31—C33	1.528 (4)	C51—C56	1.399 (4)
C31—C32	1.535 (4)	C52—C53	1.389 (4)
C31—C34	1.541 (4)	C52—H52	0.9500
C32—H32A	0.9800	C53—C54	1.388 (4)
C32—H32B	0.9800	C53—H53	0.9500
C32—H32C	0.9800	C54—C55	1.387 (4)
C33—H33A	0.9800	C54—Cl54	1.737 (3)
C33—H33B	0.9800	C55—C56	1.387 (4)
C33—H33C	0.9800	C55—H55	0.9500
C34—H34A	0.9800	C56—H56	0.9500
N2—N1—C5	110.0 (2)	H34A—C34—H34B	109.5
N2—N1—C11	118.2 (2)	C31—C34—H34C	109.5
C5—N1—C11	131.7 (2)	H34A—C34—H34C	109.5
C3—N2—N1	106.2 (2)	H34B—C34—H34C	109.5
N2—C3—C4	111.1 (2)	C4—C47—C41	117.6 (2)
N2—C3—C31	116.4 (2)	C4—C47—H47A	107.9
C4—C3—C31	132.5 (3)	C41—C47—H47A	107.9
C5—C4—C3	104.7 (2)	C4—C47—H47B	107.9
C5—C4—C47	124.4 (3)	C41—C47—H47B	107.9
C3—C4—C47	130.7 (3)	H47A—C47—H47B	107.2
N1—C5—C4	108.0 (2)	C46—C41—C42	118.1 (3)
N1—C5—N51	119.7 (2)	C46—C41—C47	118.9 (3)
C4—C5—N51	131.7 (3)	C42—C41—C47	123.0 (3)
C12—C11—C16	119.3 (3)	C43—C42—C41	120.7 (3)
C12—C11—N1	122.7 (3)	C43—C42—H42	119.6
C16—C11—N1	118.0 (2)	C41—C42—H42	119.6
C13—C12—C11	119.5 (3)	C44—C43—C42	119.3 (3)
C13—C12—H12	120.2	C44—C43—H43	120.3
C11—C12—H12	120.2	C42—C43—H43	120.3
C14—C13—C12	121.3 (3)	C43—C44—C45	121.4 (3)
C14—C13—H13	119.4	C43—C44—Cl44	120.5 (2)
C12—C13—H13	119.4	C45—C44—Cl44	118.1 (2)
C13—C14—C15	119.0 (3)	C44—C45—C46	118.7 (3)
C13—C14—H14	120.5	C44—C45—H45	120.6
C15—C14—H14	120.5	C46—C45—H45	120.6
C16—C15—C14	120.5 (3)	C45—C46—C41	121.7 (3)
C16—C15—H51	119.7	C45—C46—H46	119.1
C14—C15—H51	119.7	C41—C46—H46	119.1
C15—C16—C11	120.5 (3)	C57—N51—C5	119.7 (3)
C15—C16—H16	119.8	N51—C57—C51	120.4 (3)
C11—C16—H16	119.8	N51—C57—H57	119.8
C3—C31—C33	109.3 (2)	C51—C57—H57	119.8
C3—C31—C32	112.0 (2)	C52—C51—C56	119.0 (3)
C33—C31—C32	108.2 (2)	C52—C51—C57	120.6 (3)
C3—C31—C34	109.0 (2)	C56—C51—C57	120.4 (3)
C33—C31—C34	109.3 (2)	C53—C52—C51	121.1 (3)
C32—C31—C34	108.9 (2)	C53—C52—H52	119.5
C31—C32—H32A	109.5	C51—C52—H52	119.5
C31—C32—H32B	109.5	C54—C53—C52	118.4 (3)
H32A—C32—H32B	109.5	C54—C53—H53	120.8
C31—C32—H32C	109.5	C52—C53—H53	120.8
H32A—C32—H32C	109.5	C55—C54—C53	122.0 (3)
H32B—C32—H32C	109.5	C55—C54—Cl54	118.0 (2)
C31—C33—H33A	109.5	C53—C54—Cl54	120.0 (2)
C31—C33—H33B	109.5	C54—C55—C56	118.7 (3)
H33A—C33—H33B	109.5	C54—C55—H55	120.6
C31—C33—H33C	109.5	C56—C55—H55	120.6
H33A—C33—H33C	109.5	C55—C56—C51	120.8 (3)
H33B—C33—H33C	109.5	C55—C56—H56	119.6
C31—C34—H34A	109.5	C51—C56—H56	119.6
C31—C34—H34B	109.5
C5—N1—N2—C3	−2.4 (3)	N2—C3—C31—C34	−77.7 (3)
C11—N1—N2—C3	−178.6 (2)	C4—C3—C31—C34	99.9 (4)
N1—N2—C3—C4	1.5 (3)	C5—C4—C47—C41	107.1 (3)
N1—N2—C3—C31	179.6 (2)	C3—C4—C47—C41	−79.8 (4)
N2—C3—C4—C5	−0.1 (3)	C4—C47—C41—C46	166.8 (3)
C31—C3—C4—C5	−177.8 (3)	C4—C47—C41—C42	−14.9 (4)
N2—C3—C4—C47	−174.3 (3)	C46—C41—C42—C43	−0.5 (4)
C31—C3—C4—C47	8.0 (5)	C47—C41—C42—C43	−178.8 (3)
N2—N1—C5—C4	2.3 (3)	C41—C42—C43—C44	2.3 (5)
C11—N1—C5—C4	177.9 (3)	C42—C43—C44—C45	−2.3 (5)
N2—N1—C5—N51	174.2 (2)	C42—C43—C44—Cl44	178.5 (2)
C11—N1—C5—N51	−10.3 (5)	C43—C44—C45—C46	0.5 (4)
C3—C4—C5—N1	−1.3 (3)	Cl44—C44—C45—C46	179.8 (2)
C47—C4—C5—N1	173.3 (3)	C44—C45—C46—C41	1.3 (4)
C3—C4—C5—N51	−171.8 (3)	C42—C41—C46—C45	−1.3 (4)
C47—C4—C5—N51	2.8 (5)	C47—C41—C46—C45	177.1 (3)
N2—N1—C11—C12	170.9 (3)	N1—C5—N51—C57	142.2 (3)
C5—N1—C11—C12	−4.4 (5)	C4—C5—N51—C57	−48.2 (5)
N2—N1—C11—C16	−8.8 (4)	C5—N51—C57—C51	176.5 (2)
C5—N1—C11—C16	176.0 (3)	N51—C57—C51—C52	170.6 (3)
C16—C11—C12—C13	1.1 (4)	N51—C57—C51—C56	−9.8 (4)
N1—C11—C12—C13	−178.5 (3)	C56—C51—C52—C53	1.2 (4)
C11—C12—C13—C14	−0.2 (5)	C57—C51—C52—C53	−179.2 (3)
C12—C13—C14—C15	−0.6 (5)	C51—C52—C53—C54	−1.9 (4)
C13—C14—C15—C16	0.4 (5)	C52—C53—C54—C55	1.5 (4)
C14—C15—C16—C11	0.5 (5)	C52—C53—C54—Cl54	−177.2 (2)
C12—C11—C16—C15	−1.3 (4)	C53—C54—C55—C56	−0.4 (5)
N1—C11—C16—C15	178.3 (3)	Cl54—C54—C55—C56	178.3 (2)
N2—C3—C31—C32	161.8 (3)	C54—C55—C56—C51	−0.3 (4)
C4—C3—C31—C32	−20.7 (4)	C52—C51—C56—C55	−0.1 (4)
N2—C3—C31—C33	41.8 (3)	C57—C51—C56—C55	−179.7 (3)
C4—C3—C31—C33	−140.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N51	0.95	2.28	2.927 (4)	124
C42—H42···Cg1^i	0.95	2.99	3.788 (3)	143

Symmetry code: (i) −x+1, −y+1, −z+1.