11-(4-Chloro­phenyl)-10-methyl-8-phenyl-6,8-di­hydro-5H-benzo­[f]­pyrazolo­[3,4-b]­quinoline

Serrano, H.; Quiroga, J.; Cobo, J.; Low, J.N.; Glidewell, C.

doi:10.1107/S160053680500797X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 4| April 2005| Pages o1058-o1060

https://doi.org/10.1107/S160053680500797X

11-(4-Chlorophenyl)-10-methyl-8-phenyl-6,8-dihydro-5H-benzo[f]pyrazolo[3,4-b]quinoline

Hugo Serrano,^a Jairo Quiroga,^a Justo Cobo,^b John N. Low ^c and Christopher Glidewell ^d ^*

^aGrupo de Investigación de Compuestos Heterocíclicos, Departamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, ^bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 9 March 2005; accepted 14 March 2005; online 25 March 2005)

Molecules of the title compound, C₂₇H₂₀ClN₃, are linked by two independent C—H⋯π(arene) hydrogen bonds into chains of edge-fused rings.

Comment

Pyrazolo[3,4-b]quinolines are of interest as possible antiviral and antimalarial agents, and because of their other biological properties, such as parasiticidic, bactericidal, vasodilator and enzyme-inhibitory activity (Quiroga et al., 2001 ). We have recently focused on the synthesis of fused heterocyclic systems containing the pyrazolo[3,4-b]quinoline moiety using multicomponent cyclocondensation reactions under solvent-free conditions. We describe here the molecular and supramolecular structure of the title compound, (I), prepared using a three-component cyclocondensation involving 5-amino-3-methyl-1-phenylpyrazole, 2-tetralone and 4-chlorobenzaldehyde under solvent-free microwave irradiation.

Within the pyridine-type ring, the C—N bond lengths (Table 1) are very close to the mean value of 1.337 Å for bonds of this type (Allen et al., 1987 ), and there is very strong bond fixation in the five-membered ring. The pyridine ring and the benzene ring containing atom C1 are not coplanar, and their planes make a dihedral angle of 25.5 (2)°. The carbocylic ring containing atoms C5 and C6 accordingly adopts a screw-boat conformation (Evans & Boeyens, 1989 ), with total puckering amplitude Q = 0.537 (2) Å, and ring-puckering parameters θ = 70.5 (2)° and φ = 92.5 (2)° (Cremer & Pople, 1975 ); the idealized values of the angular parameters for a screw-boat conformer are θ = 67.5° and φ = (60k + 30)°. The dihedral angle between the pyrazole-type ring and aryl ring C81–C86 is 28.1 (2)°, whereas that between the pyridine-type ring and aryl ring C111–C116 is 70.1 (2)°, possibly as a consequence of repulsive interactions between the H atoms bonded to C112 and C116 and those bonded to C101 and C1, respectively.

The molecules of (I) are linked by two independent C—H⋯π(arene) hydrogen bonds into a chain of edge-fused rings. Aryl atom C113 in the molecule at (x, y, z) acts as donor to the phenyl ring C81–C86 in the molecule at (−x, 1 − y, −z), so forming a centrosymmetric ring, centred at (0, ½, 0). In a similar way, atom C115 at (x, y, z) acts as donor to the fused aryl ring, containing C1, in the molecule at (1 − x, 1 − y, 1 − z), so generating a second centrosymmetric ring, centred at (½, ½, ½). Propagation by inversion of these two interactions then generates a chain of edge-fused centrosymmetric rings running parallel to the [101] direction (Fig. 2). There are no direction-specific interactions between adjacent chains: C—H⋯N and C—H⋯Cl hydrogen bonds, and aromatic π–π stacking interactions are all absent from the structure of (I).

Figure 1
The molecule of compound (I

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
Stereoview of part of the crystal structure of compound (I

), showing the formation of a chain of edge-fused rings along [101]. For the sake of clarity, the H atoms not involved in these motifs have been omitted.

Experimental

Equimolar amounts of 5-amino-3-methyl-1-phenylpyrazole (173 mg, 1.0 mmol), 2-tetralone (146 mg, 1.0 mmol) and 4-chlorobenzaldehyde (140.6 mg, 1.0 mmol) were placed in open Pyrex glass vessels and irradiated in a domestic microwave oven for 4 min at 600 W. The reaction mixture was then extracted with ethanol and, after removal of the solvent, the product was recrystallized from ethanol/dimethylformamide to give crystals suitable for single-crystal X-ray diffraction. Pale-green crystals (m.p. 467 K, yield 58%). MS: (30 eV) m/z (%) 279 (100, M⁺), 264 (27).

Crystal data

C₂₇H₂₀ClN₃
M_r = 421.91
Triclinic, $[P\overline 1]$
a = 7.1270 (1) Å
b = 12.6300 (4) Å
c = 13.2847 (4) Å
α = 107.3380 (13)°
β = 103.6230 (17)°
γ = 101.4230 (18)°
V = 1061.98 (5) Å³
Z = 2
D_x = 1.319 Mg m⁻³
Mo Kα radiation
Cell parameters from 4871 reflections
θ = 3.0–27.6°
μ = 0.20 mm⁻¹
T = 120 (2) K
Plate, pale green
0.53 × 0.20 × 0.08 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.906, T_max = 0.984
21 625 measured reflections
4871 independent reflections
3853 reflections with I > 2σ(I)
R_int = 0.037
θ_max = 27.6°
h = −9 → 9
k = −16 → 16
l = −17 → 17

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.110
S = 1.08
4871 reflections
281 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.054P)² + 0.2795P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Selected bond lengths (Å)

C6A—N7	1.3336 (18)
N7—C7A	1.3415 (19)
C7A—N8	1.3730 (17)
N8—N9	1.3791 (17)
N9—C10	1.3190 (19)
C10—C10A	1.436 (2)
C10A—C11	1.4055 (19)
C11—C11A	1.403 (2)
C11A—C6A	1.4324 (19)
C7A—C10A	1.398 (2)

Table 2
Hydrogen-bonding geometry (Å, °)

Cg1 is the centroid of ring C81–C86, and Cg2 is the centroid of ring C1–C4/C4A/C11B.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C113—H113⋯Cg1ⁱ	0.95	2.65	3.5214 (16)	152
C115—H115⋯Cg2ⁱⁱ	0.95	2.90	3.6403 (17)	136
Symmetry codes: (i) -x,1-y,-z; (ii) 1-x,1-y,1-z.

All H atoms were located in difference maps in fully ordered sites; they were then treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (methyl) or 0.99 Å (CH₂), and with U_iso(H) = 1.2U_eq(C), or 1.5U_eq(C) for the methyl group.

Data collection: COLLECT (Hooft, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053680500797X/lh6385sup1.cif

Structure factors: contains datablock s0235. DOI: https://doi.org/10.1107/S160053680500797X/lh6385Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

11-(4-chlorophenyl)-10-methyl-8-phenyl-6,8-dihydro-5H- benzo[f]pyrazolo[3,4-b]quinoline top

Crystal data top

C₂₇H₂₀ClN₃	Z = 2
M_r = 421.91	F(000) = 440
Triclinic, P1	D_x = 1.319 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1270 (1) Å	Cell parameters from 4871 reflections
b = 12.6300 (4) Å	θ = 3.0–27.6°
c = 13.2847 (4) Å	µ = 0.20 mm⁻¹
α = 107.3380 (13)°	T = 120 K
β = 103.6230 (17)°	Plate, pale green
γ = 101.4230 (18)°	0.53 × 0.20 × 0.08 mm
V = 1061.98 (5) Å³

Data collection top

Bruker–Nonius 95mm CCD camera on κ goniostat diffractometer	4871 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	3853 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.0°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −16→16
T_min = 0.906, T_max = 0.984	l = −17→17
21625 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.054P)² + 0.2795P] where P = (F_o² + 2F_c²)/3
4871 reflections	(Δ/σ)_max < 0.001
281 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl14	0.41830 (6)	0.13253 (3)	0.25576 (3)	0.03150 (13)
N7	0.28893 (18)	0.82176 (10)	0.27569 (10)	0.0221 (3)
N8	−0.04974 (18)	0.71127 (11)	0.15444 (10)	0.0230 (3)
N9	−0.16306 (18)	0.59652 (11)	0.10792 (10)	0.0239 (3)
C1	0.7802 (2)	0.60892 (13)	0.36213 (13)	0.0230 (3)
C2	0.9656 (2)	0.61188 (14)	0.42735 (14)	0.0294 (4)
C3	1.0767 (2)	0.70935 (15)	0.52083 (15)	0.0332 (4)
C4	1.0043 (2)	0.80434 (14)	0.54597 (14)	0.0294 (4)
C4A	0.8184 (2)	0.80333 (13)	0.48129 (12)	0.0226 (3)
C5	0.7424 (2)	0.90812 (13)	0.50638 (13)	0.0263 (3)
C6	0.6306 (2)	0.91716 (12)	0.39763 (13)	0.0242 (3)
C6A	0.4606 (2)	0.80831 (12)	0.32939 (12)	0.0204 (3)
C7A	0.1426 (2)	0.72218 (13)	0.21502 (12)	0.0212 (3)
C10	−0.0445 (2)	0.53571 (13)	0.13762 (12)	0.0216 (3)
C10A	0.1534 (2)	0.61046 (12)	0.20561 (12)	0.0198 (3)
C11	0.3345 (2)	0.59779 (12)	0.26387 (11)	0.0186 (3)
C11A	0.4943 (2)	0.69932 (12)	0.32585 (11)	0.0187 (3)
C11B	0.6994 (2)	0.70225 (13)	0.38950 (12)	0.0199 (3)
C81	−0.1403 (2)	0.79824 (13)	0.13851 (12)	0.0249 (3)
C82	−0.3462 (2)	0.77830 (15)	0.11958 (13)	0.0289 (4)
C83	−0.4338 (3)	0.86323 (17)	0.10284 (14)	0.0350 (4)
C84	−0.3185 (3)	0.96645 (16)	0.10570 (14)	0.0375 (4)
C85	−0.1139 (3)	0.98489 (16)	0.12430 (16)	0.0425 (5)
C86	−0.0237 (2)	0.90067 (15)	0.14042 (16)	0.0369 (4)
C101	−0.1276 (2)	0.40710 (13)	0.09992 (14)	0.0281 (3)
C111	0.34498 (19)	0.48015 (12)	0.25989 (12)	0.0184 (3)
C112	0.3473 (2)	0.39855 (13)	0.16309 (12)	0.0225 (3)
C113	0.3674 (2)	0.29104 (13)	0.16129 (12)	0.0238 (3)
C114	0.3829 (2)	0.26520 (12)	0.25674 (12)	0.0218 (3)
C115	0.3725 (2)	0.34275 (13)	0.35236 (12)	0.0221 (3)
C116	0.3542 (2)	0.45043 (12)	0.35347 (12)	0.0198 (3)
H1	0.7064	0.5423	0.2976	0.028*
H2	1.0166	0.5472	0.4080	0.035*
H3	1.2017	0.7107	0.5672	0.040*
H4	1.0827	0.8719	0.6087	0.035*
H5A	0.8572	0.9788	0.5499	0.032*
H5B	0.6505	0.9014	0.5511	0.032*
H6A	0.5764	0.9846	0.4137	0.029*
H6B	0.7252	0.9291	0.3554	0.029*
H82	−0.4262	0.7077	0.1181	0.035*
H83	−0.5750	0.8501	0.0892	0.042*
H84	−0.3796	1.0243	0.0949	0.045*
H85	−0.0341	1.0557	0.1261	0.051*
H86	0.1170	0.9134	0.1527	0.044*
H10A	−0.2733	0.3843	0.0626	0.042*
H10B	−0.1019	0.3831	0.1643	0.042*
H10C	−0.0622	0.3696	0.0481	0.042*
H112	0.3351	0.4167	0.0978	0.027*
H113	0.3706	0.2358	0.0955	0.029*
H115	0.3777	0.3227	0.4162	0.027*
H116	0.3478	0.5046	0.4189	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl14	0.0414 (2)	0.0201 (2)	0.0309 (2)	0.01009 (16)	0.00622 (17)	0.00961 (16)
N7	0.0202 (6)	0.0235 (6)	0.0227 (6)	0.0084 (5)	0.0051 (5)	0.0085 (5)
N8	0.0184 (6)	0.0253 (7)	0.0238 (7)	0.0079 (5)	0.0025 (5)	0.0090 (5)
N9	0.0201 (6)	0.0271 (7)	0.0226 (7)	0.0059 (5)	0.0046 (5)	0.0083 (6)
C1	0.0193 (7)	0.0253 (8)	0.0259 (8)	0.0066 (6)	0.0080 (6)	0.0106 (6)
C2	0.0217 (8)	0.0319 (9)	0.0398 (10)	0.0126 (6)	0.0098 (7)	0.0169 (8)
C3	0.0189 (7)	0.0374 (10)	0.0402 (10)	0.0069 (7)	−0.0004 (7)	0.0181 (8)
C4	0.0246 (8)	0.0291 (8)	0.0273 (8)	0.0012 (6)	−0.0002 (6)	0.0109 (7)
C4A	0.0212 (7)	0.0250 (8)	0.0222 (7)	0.0051 (6)	0.0058 (6)	0.0112 (6)
C5	0.0264 (8)	0.0243 (8)	0.0223 (8)	0.0059 (6)	0.0023 (6)	0.0052 (6)
C6	0.0239 (7)	0.0201 (7)	0.0253 (8)	0.0065 (6)	0.0036 (6)	0.0071 (6)
C6A	0.0203 (7)	0.0231 (7)	0.0189 (7)	0.0071 (6)	0.0063 (6)	0.0084 (6)
C7A	0.0203 (7)	0.0257 (8)	0.0198 (7)	0.0096 (6)	0.0057 (6)	0.0099 (6)
C10	0.0195 (7)	0.0269 (8)	0.0185 (7)	0.0068 (6)	0.0055 (6)	0.0089 (6)
C10A	0.0203 (7)	0.0221 (7)	0.0180 (7)	0.0070 (6)	0.0066 (6)	0.0078 (6)
C11	0.0207 (7)	0.0226 (7)	0.0152 (7)	0.0079 (6)	0.0074 (5)	0.0082 (6)
C11A	0.0189 (7)	0.0214 (7)	0.0172 (7)	0.0071 (5)	0.0065 (5)	0.0077 (6)
C11B	0.0183 (7)	0.0241 (7)	0.0206 (7)	0.0070 (6)	0.0071 (6)	0.0113 (6)
C81	0.0255 (8)	0.0304 (8)	0.0184 (7)	0.0147 (6)	0.0029 (6)	0.0072 (6)
C82	0.0256 (8)	0.0468 (10)	0.0212 (8)	0.0182 (7)	0.0094 (6)	0.0156 (7)
C83	0.0301 (9)	0.0599 (12)	0.0258 (8)	0.0292 (8)	0.0116 (7)	0.0181 (8)
C84	0.0446 (10)	0.0421 (10)	0.0257 (9)	0.0301 (9)	0.0027 (7)	0.0074 (8)
C85	0.0382 (10)	0.0297 (9)	0.0513 (12)	0.0155 (8)	−0.0027 (8)	0.0126 (9)
C86	0.0247 (8)	0.0295 (9)	0.0507 (11)	0.0116 (7)	−0.0004 (7)	0.0135 (8)
C101	0.0221 (8)	0.0267 (8)	0.0304 (9)	0.0029 (6)	0.0034 (6)	0.0096 (7)
C111	0.0155 (6)	0.0193 (7)	0.0191 (7)	0.0045 (5)	0.0038 (5)	0.0069 (6)
C112	0.0259 (7)	0.0248 (8)	0.0174 (7)	0.0080 (6)	0.0055 (6)	0.0088 (6)
C113	0.0282 (8)	0.0215 (8)	0.0182 (7)	0.0075 (6)	0.0062 (6)	0.0033 (6)
C114	0.0217 (7)	0.0175 (7)	0.0235 (8)	0.0047 (6)	0.0035 (6)	0.0071 (6)
C115	0.0232 (7)	0.0231 (8)	0.0196 (7)	0.0044 (6)	0.0050 (6)	0.0101 (6)
C116	0.0183 (7)	0.0228 (7)	0.0159 (7)	0.0047 (6)	0.0045 (5)	0.0053 (6)

Geometric parameters (Å, º) top

C1—C2	1.386 (2)	C81—C86	1.382 (2)
C1—C11B	1.402 (2)	C81—C82	1.386 (2)
C1—H1	0.95	C82—C83	1.390 (2)
C2—C3	1.387 (2)	C82—H82	0.95
C2—H2	0.95	C83—C84	1.381 (3)
C3—C4	1.380 (2)	C83—H83	0.95
C3—H3	0.95	C84—C85	1.379 (3)
C4—C4A	1.394 (2)	C84—H84	0.95
C4—H4	0.95	C85—C86	1.390 (2)
C4A—C11B	1.411 (2)	C85—H85	0.95
C4A—C5	1.504 (2)	C86—H86	0.95
C5—C6	1.525 (2)	C10—C101	1.495 (2)
C5—H5A	0.99	C101—H10A	0.98
C5—H5B	0.99	C101—H10B	0.98
C6—C6A	1.503 (2)	C101—H10C	0.98
C6—H6A	0.99	C11—C111	1.4883 (19)
C6—H6B	0.99	C11A—C11B	1.4937 (19)
C6A—N7	1.3336 (18)	C111—C116	1.393 (2)
N7—C7A	1.3415 (19)	C111—C112	1.394 (2)
C7A—N8	1.3730 (17)	C112—C113	1.387 (2)
N8—N9	1.3791 (17)	C112—H112	0.95
N9—C10	1.3190 (19)	C113—C114	1.386 (2)
C10—C10A	1.436 (2)	C113—H113	0.95
C10A—C11	1.4055 (19)	C114—C115	1.382 (2)
C11—C11A	1.403 (2)	C114—Cl14	1.7399 (14)
C11A—C6A	1.4324 (19)	C115—C116	1.388 (2)
C7A—C10A	1.398 (2)	C115—H115	0.95
N8—C81	1.4225 (18)	C116—H116	0.95

C2—C1—C11B	121.33 (15)	C83—C84—H84	120.3
C2—C1—H1	119.3	C84—C85—C86	120.47 (18)
C11B—C1—H1	119.3	C84—C85—H85	119.8
C1—C2—C3	119.97 (15)	C86—C85—H85	119.8
C1—C2—H2	120.0	C81—C86—C85	119.52 (16)
C3—C2—H2	120.0	C81—C86—H86	120.2
C4—C3—C2	119.51 (14)	C85—C86—H86	120.2
C4—C3—H3	120.2	C10—N9—N8	107.06 (12)
C2—C3—H3	120.2	N9—C10—C10A	110.55 (13)
C3—C4—C4A	121.42 (15)	N9—C10—C101	119.21 (13)
C3—C4—H4	119.3	C10A—C10—C101	130.24 (13)
C4A—C4—H4	119.3	C10—C101—H10A	109.5
C4—C4A—C11B	119.43 (14)	C10—C101—H10B	109.5
C4—C4A—C5	121.47 (14)	H10A—C101—H10B	109.5
C11B—C4A—C5	119.10 (13)	C10—C101—H10C	109.5
C4A—C5—C6	109.32 (13)	H10A—C101—H10C	109.5
C4A—C5—H5A	109.8	H10B—C101—H10C	109.5
C6—C5—H5A	109.8	C7A—C10A—C11	118.41 (13)
C4A—C5—H5B	109.8	C7A—C10A—C10	104.91 (12)
C6—C5—H5B	109.8	C11—C10A—C10	136.58 (13)
H5A—C5—H5B	108.3	C11A—C11—C10A	117.00 (13)
C6A—C6—C5	110.02 (12)	C11A—C11—C111	123.84 (12)
C6A—C6—H6A	109.7	C10A—C11—C111	119.12 (12)
C5—C6—H6A	109.7	C11—C11A—C6A	118.51 (12)
C6A—C6—H6B	109.7	C11—C11A—C11B	124.46 (13)
C5—C6—H6B	109.7	C6A—C11A—C11B	117.03 (12)
H6A—C6—H6B	108.2	C1—C11B—C4A	118.14 (13)
N7—C6A—C11A	125.12 (13)	C1—C11B—C11A	122.97 (13)
N7—C6A—C6	116.43 (12)	C4A—C11B—C11A	118.89 (13)
C11A—C6A—C6	118.45 (12)	C116—C111—C112	119.07 (13)
C6A—N7—C7A	114.21 (12)	C116—C111—C11	120.28 (12)
N7—C7A—N8	126.25 (13)	C112—C111—C11	120.65 (12)
N7—C7A—C10A	126.71 (13)	C113—C112—C111	120.52 (13)
N8—C7A—C10A	106.98 (12)	C113—C112—H112	119.7
C7A—N8—N9	110.50 (11)	C111—C112—H112	119.7
C7A—N8—C81	129.74 (13)	C114—C113—C112	119.14 (14)
N9—N8—C81	119.72 (12)	C114—C113—H113	120.4
C86—C81—C82	120.67 (14)	C112—C113—H113	120.4
C86—C81—N8	119.98 (14)	C115—C114—C113	121.44 (13)
C82—C81—N8	119.34 (14)	C115—C114—Cl14	119.59 (11)
C81—C82—C83	118.94 (16)	C113—C114—Cl14	118.97 (12)
C81—C82—H82	120.5	C114—C115—C116	118.87 (14)
C83—C82—H82	120.5	C114—C115—H115	120.6
C84—C83—C82	120.90 (16)	C116—C115—H115	120.6
C84—C83—H83	119.5	C115—C116—C111	120.88 (13)
C82—C83—H83	119.5	C115—C116—H116	119.6
C85—C84—C83	119.49 (16)	C111—C116—H116	119.6
C85—C84—H84	120.3

C11B—C1—C2—C3	−1.1 (2)	C101—C10—C10A—C7A	−178.83 (15)
C1—C2—C3—C4	−2.2 (3)	N9—C10—C10A—C11	176.65 (16)
C2—C3—C4—C4A	2.0 (3)	C101—C10—C10A—C11	−2.7 (3)
C3—C4—C4A—C11B	1.4 (2)	C7A—C10A—C11—C11A	−1.42 (19)
C3—C4—C4A—C5	−177.96 (15)	C10—C10A—C11—C11A	−177.13 (16)
C4—C4A—C5—C6	143.03 (15)	C7A—C10A—C11—C111	176.61 (13)
C11B—C4A—C5—C6	−36.33 (19)	C10—C10A—C11—C111	0.9 (2)
C4A—C5—C6—C6A	57.48 (16)	C10A—C11—C11A—C6A	2.45 (19)
C5—C6—C6A—N7	140.28 (13)	C111—C11—C11A—C6A	−175.48 (13)
C5—C6—C6A—C11A	−40.26 (18)	C10A—C11—C11A—C11B	−177.73 (13)
C11A—C6A—N7—C7A	−0.1 (2)	C111—C11—C11A—C11B	4.4 (2)
C6—C6A—N7—C7A	179.29 (13)	N7—C6A—C11A—C11	−1.8 (2)
C6A—N7—C7A—N8	178.03 (14)	C6—C6A—C11A—C11	178.82 (13)
C6A—N7—C7A—C10A	1.3 (2)	N7—C6A—C11A—C11B	178.38 (13)
N7—C7A—N8—N9	−176.39 (14)	C6—C6A—C11A—C11B	−1.02 (19)
C10A—C7A—N8—N9	0.84 (16)	C2—C1—C11B—C4A	4.4 (2)
N7—C7A—N8—C81	1.4 (2)	C2—C1—C11B—C11A	−175.73 (14)
C10A—C7A—N8—C81	178.62 (14)	C4—C4A—C11B—C1	−4.5 (2)
C7A—N8—C81—C86	30.1 (2)	C5—C4A—C11B—C1	174.84 (13)
N9—N8—C81—C86	−152.28 (15)	C4—C4A—C11B—C11A	175.61 (13)
C7A—N8—C81—C82	−150.81 (15)	C5—C4A—C11B—C11A	−5.0 (2)
N9—N8—C81—C82	26.8 (2)	C11—C11A—C11B—C1	25.6 (2)
C86—C81—C82—C83	−0.2 (2)	C6A—C11A—C11B—C1	−154.57 (14)
N8—C81—C82—C83	−179.27 (14)	C11—C11A—C11B—C4A	−154.55 (14)
C81—C82—C83—C84	−0.5 (2)	C6A—C11A—C11B—C4A	25.28 (19)
C82—C83—C84—C85	0.7 (3)	C11A—C11—C111—C116	68.91 (18)
C83—C84—C85—C86	−0.2 (3)	C10A—C11—C111—C116	−108.97 (15)
C82—C81—C86—C85	0.7 (3)	C11A—C11—C111—C112	−110.59 (16)
N8—C81—C86—C85	179.73 (16)	C10A—C11—C111—C112	71.52 (18)
C84—C85—C86—C81	−0.5 (3)	C116—C111—C112—C113	−2.8 (2)
C7A—N8—N9—C10	−0.49 (16)	C11—C111—C112—C113	176.71 (13)
C81—N8—N9—C10	−178.53 (13)	C111—C112—C113—C114	0.7 (2)
N8—N9—C10—C10A	−0.05 (16)	C112—C113—C114—C115	2.0 (2)
N8—N9—C10—C101	179.41 (13)	C112—C113—C114—Cl14	−177.44 (11)
N7—C7A—C10A—C11	−0.6 (2)	C113—C114—C115—C116	−2.6 (2)
N8—C7A—C10A—C11	−177.78 (12)	Cl14—C114—C115—C116	176.87 (10)
N7—C7A—C10A—C10	176.39 (14)	C114—C115—C116—C111	0.4 (2)
N8—C7A—C10A—C10	−0.82 (15)	C112—C111—C116—C115	2.2 (2)
N9—C10—C10A—C7A	0.55 (16)	C11—C111—C116—C115	−177.29 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C113—H113···Cg1ⁱ	0.95	2.65	3.5214 (16)	152
C115—H115···Cg2ⁱⁱ	0.95	2.90	3.6403 (17)	136

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

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England. JC thanks the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. JQ and HS thank COLCIENCIAS and UNIVALLE (Universidad del Valle, Colombia) for financial support.

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