3-tert-Butyl-1-(4-chloro­phenyl)-7,7-dimethyl-5,6,7,8-tetrahydro­pyrazolo[3,4-b]quinolin-5-one: centrosymmetric dimers generated by C—H⋯π(arene) hydrogen bonds

Low, J.N.; Cobo, J.; Mera, J.; Quiroga, J.; Glidewell, C.

doi:10.1107/S1600536804031927

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 1| January 2005| Pages o49-o51

https://doi.org/10.1107/S1600536804031927

3-tert-Butyl-1-(4-chlorophenyl)-7,7-dimethyl-5,6,7,8-tetrahydropyrazolo[3,4-b]quinolin-5-one: centrosymmetric dimers generated by C—H⋯π(arene) hydrogen bonds

John N. Low,^a ^*‡ Justo Cobo,^b Jaime Mera,^c Jairo Quiroga ^c and Christopher Glidewell ^d

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, ^bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, ^cGrupo de Investigación de Compuestos Heterociclícos, Departamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: che562@abdn.ac.uk

(Received 30 November 2004; accepted 2 December 2004; online 11 December 2004)

Molecules of the title compound, C₂₂H₂₄ClN₃O, are linked by two pairs of C—H⋯π(arene) hydrogen bonds into centrosymmetric dimers.

Keywords: .

Comment

We report here the structure of the title compound, (I) (Fig. 1), whose supramolecular aggregation shows some interesting differences from that in the unsubstituted analogue (II) (Low et al., 2004 ).

The bond lengths in (I) are very similar to those in (II) and require no further discussion here. The ring-puckering parameters (Cremer & Pople, 1975 ) for the carbocyclic rings in (I) and (II) are quite similar [for the atom sequence C4A—C5—C6—C7—C8—C8A, θ = 132.1 (4)° and φ = 351.0 (5) in (I), and θ = 127.4 (3)° and φ = 353.8 (3) in (II)] and indicate an envelope conformation in each compound (Evans & Boeyens, 1989 ).

The principal difference between (I) and (II) arises from the intermolecular aggregation. In (I), the molecules are linked into centrosymmetric dimers by two pairs of C—H⋯π(arene) interactions (Table 1). Atoms C6 and C8 in the molecule at (x, y, z) act as donors, via the axial H atoms H6A and H8A, to the aryl and pyrazole rings, respectively, in the molecule at (−x, 1 − y, 1 − z) (Fig. 2). There are no other types of intermolecular hydrogen bond in the structure of (I) and there are no direction-specific interactions between the dimers. By contrast, in (II), the molecules are linked into chains by means of a C—H⋯N hydrogen bond, and C—H⋯π(arene) hydrogen bonds are absent from the structure of (II). It is striking that the presence of a single remote Cl substituent in (I) is associated with such a change in the hydrogen bonding.

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 centrosymmetric hydrogen-bonded dimer. For clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted. C—H⋯π hydrogen bonds are shown as dashed lines.

Experimental

A mixture of 5-amino-3-tert-butyl-1-(4-chlorophenyl)pyrazole (1 mmol), 5,5-dimethyl-1,3-cyclohexanedione (dimedone) (1 mmol) and formaldehyde (3 mmol) was placed in an open Pyrex-glass vessel and irradiated in a domestic microwave oven for 3 min (at 600 watts). After reaction, the mixture was extracted with ethanol; the extract was filtered and the product, (I), was purified by column chromatography on silica gel, with dichloromethane/hexane (7:3, v/v) as eluant. Yield 39%, m.p. 428 K. MS (EI 70 eV) m/z (%): 383/381 (15/49), 382 (12), 368/366 (37/100), 149 (16), 57 (11). Crystals suitable for single-crystal X-ray diffraction were grown from ethanol.

Crystal data

C₂₂H₂₄ClN₃O
M_r = 381.89
Triclinic, P $[\overline1]$
a = 8.6851 (11) Å
b = 10.6167 (9) Å
c = 12.4330 (12) Å
α = 106.724 (8)°
β = 101.049 (10)°
γ = 107.406 (8)°
V = 998.1 (2) Å³
Z = 2
D_x = 1.271 Mg m⁻³
Mo Kα radiation
Cell parameters from 4289 reflections
θ = 5.0–27.5°
μ = 0.21 mm⁻¹
T = 293 (2) K
Block, colourless
0.40 × 0.20 × 0.10 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (EVALCCD; Duisenberg et al., 2003 )
T_min = 0.925, T_max = 0.980
13 573 measured reflections
4289 independent reflections
1940 reflections with I > 2σ(I)
R_int = 0.091
θ_max = 27.5°
h = −11 → 11
k = −13 → 13
l = −13 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.122
S = 0.93
4289 reflections
250 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0419P)² + 0.3921P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯Cg1ⁱ	0.97	2.77	3.649 (3)	151
C8—H8A⋯Cg2ⁱ	0.97	2.82	3.768 (3)	165
Symmetry code: (i) -x, -y+1, -z+1. Notes: Cg1 and Cg2 are the centroids of rings C11–C16 and N1/N2/C3/C3A/C9A, respectively.

All H atoms were located in difference maps and then treated as riding atoms, with C—H distances 0.93 Å (aromatic), 0.96 Å (CH₃) or 0.97 Å (CH₂), and with U_iso(H) = 1.2U_eq(C), or 1.5U_eq(C) for the methyl groups. This structure was determined at room temperature and both the data completeness and the ratio of observed-to-unique reflections are rather low. Since this structure is, in all respects, similar to its non-chlorinated analogue (II), a second data-collection, at low temperature, was not justified.

Data collection: COLLECT (Hooft, 1999 ); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000 ); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: OSCAIL (McArdle, 2003 ) 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/S1600536804031927/lh6332sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804031927/lh6332Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

3-tert-Butyl-1-(4-chlorophenyl)-7,7-dimethyl-5,6,7,8- tetrahydroimidazo[3,4-b]quinolin-5-one top

Crystal data top

C₂₂H₂₄ClN₃O	Z = 2
M_r = 381.89	F(000) = 404
Triclinic, P1	D_x = 1.271 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6851 (11) Å	Cell parameters from 4289 reflections
b = 10.6167 (9) Å	θ = 5.0–27.5°
c = 12.4330 (12) Å	µ = 0.21 mm⁻¹
α = 106.724 (8)°	T = 293 K
β = 101.049 (10)°	Block, colourless
γ = 107.406 (8)°	0.40 × 0.20 × 0.10 mm
V = 998.1 (2) Å³

Data collection top

Nonius KappaCCD area-detector diffractometer	4289 independent reflections
Radiation source: fine-focus sealed X-ray tube	1940 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.091
φ and ω scans	θ_max = 27.5°, θ_min = 5.0°
Absorption correction: multi-scan EvalCCD, (Duisenberg et al., 2003)	h = −11→11
T_min = 0.925, T_max = 0.980	k = −13→13
13573 measured reflections	l = −13→16

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0419P)² + 0.3921P] where P = (F_o² + 2F_c²)/3
4289 reflections	(Δ/σ)_max < 0.001
250 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

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

	x	y	z	U_iso*/U_eq
Cl14	0.25042 (9)	0.12483 (9)	0.88047 (7)	0.0675 (3)
O5	0.1443 (2)	0.6703 (2)	0.18979 (16)	0.0659 (6)
N1	0.3639 (2)	0.5147 (2)	0.62204 (16)	0.0367 (5)
N2	0.4930 (2)	0.6473 (2)	0.68344 (16)	0.0388 (5)
N9	0.1388 (2)	0.4006 (2)	0.43698 (16)	0.0363 (5)
C3	0.4865 (3)	0.7244 (2)	0.61863 (19)	0.0350 (6)
C3A	0.3525 (3)	0.6432 (2)	0.50982 (19)	0.0348 (6)
C4	0.2845 (3)	0.6615 (3)	0.40730 (19)	0.0377 (6)
C4A	0.1440 (3)	0.5504 (3)	0.32209 (19)	0.0351 (6)
C5	0.0714 (3)	0.5675 (3)	0.2111 (2)	0.0411 (6)
C6	−0.0937 (3)	0.4546 (3)	0.13021 (19)	0.0403 (6)
C7	−0.1159 (3)	0.3051 (3)	0.12727 (19)	0.0373 (6)
C8	−0.0857 (3)	0.3079 (3)	0.25340 (19)	0.0410 (6)
C8A	0.0735 (3)	0.4244 (2)	0.34112 (19)	0.0353 (6)
C9A	0.2751 (3)	0.5102 (3)	0.51641 (19)	0.0341 (5)
C11	0.3375 (3)	0.4160 (2)	0.67918 (19)	0.0351 (6)
C12	0.1866 (3)	0.3007 (3)	0.6409 (2)	0.0436 (6)
C13	0.1620 (3)	0.2101 (3)	0.7022 (2)	0.0468 (7)
C14	0.2860 (3)	0.2358 (3)	0.8012 (2)	0.0441 (6)
C15	0.4363 (3)	0.3484 (3)	0.8392 (2)	0.0528 (7)
C16	0.4628 (3)	0.4393 (3)	0.7780 (2)	0.0484 (7)
C31	0.6009 (3)	0.8794 (2)	0.66531 (19)	0.0388 (6)
C32	0.7361 (4)	0.9172 (3)	0.7800 (2)	0.0710 (9)
C33	0.6879 (3)	0.9129 (3)	0.5760 (2)	0.0653 (8)
C34	0.4916 (3)	0.9676 (3)	0.6879 (3)	0.0637 (8)
C71	0.0095 (3)	0.2563 (3)	0.0723 (2)	0.0521 (7)
C72	−0.2966 (3)	0.2042 (3)	0.0534 (2)	0.0531 (7)
H4	0.3319	0.7459	0.3961	0.045*
H6A	−0.1847	0.4782	0.1540	0.048*
H6E	−0.1044	0.4544	0.0511	0.048*
H8A	−0.1814	0.3177	0.2793	0.049*
H8E	−0.0818	0.2174	0.2531	0.049*
H12	0.1020	0.2840	0.5741	0.052*
H13	0.0611	0.1317	0.6761	0.056*
H15	0.5206	0.3641	0.9058	0.063*
H16	0.5651	0.5161	0.8036	0.058*
H32A	0.6828	0.8979	0.8375	0.107*
H32B	0.8066	1.0162	0.8087	0.107*
H32C	0.8043	0.8614	0.7660	0.107*
H33A	0.7608	0.8610	0.5649	0.098*
H33B	0.7538	1.0128	0.6046	0.098*
H33C	0.6040	0.8859	0.5023	0.098*
H34A	0.4068	0.9443	0.6156	0.096*
H34B	0.5617	1.0668	0.7175	0.096*
H34C	0.4378	0.9472	0.7449	0.096*
H71A	−0.0036	0.2643	−0.0036	0.078*
H71B	−0.0121	0.1592	0.0635	0.078*
H71C	0.1230	0.3148	0.1225	0.078*
H72A	−0.3151	0.2014	−0.0260	0.080*
H72B	−0.3752	0.2370	0.0863	0.080*
H72C	−0.3130	0.1107	0.0536	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl14	0.0747 (5)	0.0743 (6)	0.0797 (5)	0.0312 (4)	0.0329 (4)	0.0558 (5)
O5	0.0719 (13)	0.0574 (14)	0.0505 (12)	−0.0006 (11)	0.0009 (10)	0.0324 (11)
N1	0.0409 (11)	0.0282 (12)	0.0303 (11)	0.0050 (9)	0.0027 (9)	0.0096 (9)
N2	0.0402 (11)	0.0304 (12)	0.0341 (11)	0.0060 (10)	0.0034 (9)	0.0080 (10)
N9	0.0400 (11)	0.0315 (12)	0.0290 (10)	0.0064 (10)	0.0053 (9)	0.0099 (9)
C3	0.0365 (13)	0.0309 (14)	0.0307 (13)	0.0087 (11)	0.0067 (10)	0.0079 (11)
C3A	0.0404 (13)	0.0293 (15)	0.0306 (13)	0.0092 (11)	0.0102 (11)	0.0095 (11)
C4	0.0455 (14)	0.0316 (15)	0.0350 (14)	0.0103 (12)	0.0119 (12)	0.0154 (12)
C4A	0.0389 (13)	0.0335 (15)	0.0272 (13)	0.0093 (12)	0.0059 (11)	0.0104 (11)
C5	0.0472 (15)	0.0380 (17)	0.0352 (14)	0.0138 (13)	0.0114 (12)	0.0125 (13)
C6	0.0426 (14)	0.0478 (17)	0.0286 (13)	0.0175 (13)	0.0074 (11)	0.0134 (12)
C7	0.0376 (13)	0.0388 (15)	0.0277 (13)	0.0114 (11)	0.0027 (10)	0.0092 (11)
C8	0.0416 (13)	0.0383 (16)	0.0339 (13)	0.0063 (12)	0.0062 (11)	0.0128 (12)
C8A	0.0392 (13)	0.0347 (15)	0.0288 (13)	0.0115 (12)	0.0103 (11)	0.0096 (11)
C9A	0.0400 (13)	0.0328 (15)	0.0260 (12)	0.0105 (12)	0.0079 (11)	0.0104 (11)
C11	0.0395 (13)	0.0331 (15)	0.0319 (13)	0.0124 (12)	0.0117 (11)	0.0120 (11)
C12	0.0478 (15)	0.0410 (17)	0.0356 (14)	0.0108 (14)	0.0072 (12)	0.0146 (12)
C13	0.0483 (15)	0.0391 (17)	0.0484 (16)	0.0087 (13)	0.0142 (13)	0.0180 (13)
C14	0.0527 (16)	0.0453 (18)	0.0472 (15)	0.0222 (14)	0.0213 (13)	0.0273 (13)
C15	0.0472 (16)	0.061 (2)	0.0522 (17)	0.0167 (16)	0.0046 (13)	0.0338 (15)
C16	0.0385 (13)	0.0490 (18)	0.0522 (16)	0.0095 (13)	0.0043 (12)	0.0246 (14)
C31	0.0421 (13)	0.0302 (15)	0.0324 (13)	0.0061 (12)	0.0043 (11)	0.0075 (11)
C32	0.0683 (19)	0.0462 (19)	0.0589 (19)	0.0005 (15)	−0.0160 (15)	0.0086 (15)
C33	0.0610 (18)	0.055 (2)	0.0609 (19)	−0.0015 (15)	0.0218 (15)	0.0169 (16)
C34	0.0635 (18)	0.0392 (18)	0.081 (2)	0.0181 (15)	0.0216 (16)	0.0134 (16)
C71	0.0578 (16)	0.0582 (19)	0.0378 (14)	0.0273 (15)	0.0102 (12)	0.0112 (13)
C72	0.0506 (15)	0.0494 (18)	0.0417 (15)	0.0086 (14)	−0.0018 (12)	0.0129 (13)

Geometric parameters (Å, º) top

N1—C9A	1.370 (3)	C34—H34B	0.96
N1—N2	1.390 (2)	C34—H34C	0.96
N1—C11	1.415 (3)	C3A—C4	1.390 (3)
C11—C16	1.381 (3)	C3A—C9A	1.404 (3)
C11—C12	1.381 (3)	C4—C4A	1.388 (3)
C12—C13	1.383 (3)	C4—H4	0.93
C12—H12	0.93	C4A—C8A	1.403 (3)
C13—C14	1.368 (3)	C4A—C5	1.488 (3)
C13—H13	0.93	C5—O5	1.217 (3)
C14—C15	1.365 (3)	C5—C6	1.493 (3)
C14—Cl14	1.738 (2)	C6—C7	1.529 (3)
C15—C16	1.384 (3)	C6—H6E	0.97
C15—H15	0.93	C6—H6A	0.97
C16—H16	0.93	C7—C8	1.530 (3)
N2—C3	1.309 (3)	C7—C71	1.531 (3)
C3—C3A	1.433 (3)	C7—C72	1.526 (3)
C3—C31	1.511 (3)	C71—H71A	0.96
C31—C33	1.522 (3)	C71—H71B	0.96
C31—C32	1.523 (3)	C71—H71C	0.96
C31—C34	1.529 (3)	C72—H72A	0.96
C32—H32A	0.96	C72—H72B	0.96
C32—H32B	0.96	C72—H72C	0.96
C32—H32C	0.96	C8—C8A	1.501 (3)
C33—H33A	0.96	C8—H8A	0.97
C33—H33B	0.96	C8—H8E	0.97
C33—H33C	0.96	C8A—N9	1.344 (3)
C34—H34A	0.96	N9—C9A	1.341 (3)

C9A—N1—N2	110.15 (18)	C4—C3A—C9A	116.4 (2)
C9A—N1—C11	131.75 (19)	C4—C3A—C3	138.0 (2)
N2—N1—C11	117.86 (17)	C9A—C3A—C3	105.5 (2)
C16—C11—C12	119.6 (2)	C4A—C4—C3A	118.3 (2)
C16—C11—N1	119.0 (2)	C4A—C4—H4	120.9
C12—C11—N1	121.3 (2)	C3A—C4—H4	120.9
C11—C12—C13	119.8 (2)	C4—C4A—C8A	120.0 (2)
C11—C12—H12	120.1	C4—C4A—C5	118.9 (2)
C13—C12—H12	120.1	C8A—C4A—C5	121.1 (2)
C14—C13—C12	120.0 (2)	O5—C5—C4A	120.5 (2)
C14—C13—H13	120.0	O5—C5—C6	122.7 (2)
C12—C13—H13	120.0	C4A—C5—C6	116.8 (2)
C15—C14—C13	120.8 (2)	C5—C6—C7	114.50 (19)
C15—C14—Cl14	119.66 (19)	C5—C6—H6E	108.6
C13—C14—Cl14	119.6 (2)	C7—C6—H6E	108.6
C14—C15—C16	119.7 (2)	C5—C6—H6A	108.6
C14—C15—H15	120.2	C7—C6—H6A	108.6
C16—C15—H15	120.2	H6E—C6—H6A	107.6
C11—C16—C15	120.1 (2)	C72—C7—C6	108.89 (18)
C11—C16—H16	119.9	C72—C7—C8	109.43 (19)
C15—C16—H16	119.9	C6—C7—C8	108.65 (19)
C3—N2—N1	107.66 (17)	C72—C7—C71	109.6 (2)
N2—C3—C3A	110.1 (2)	C6—C7—C71	109.7 (2)
N2—C3—C31	120.81 (19)	C8—C7—C71	110.59 (18)
C3A—C3—C31	128.9 (2)	C7—C71—H71A	109.5
C3—C31—C33	110.5 (2)	C7—C71—H71B	109.5
C3—C31—C32	110.7 (2)	H71A—C71—H71B	109.5
C33—C31—C32	108.7 (2)	C7—C71—H71C	109.5
C3—C31—C34	107.98 (19)	H71A—C71—H71C	109.5
C33—C31—C34	109.6 (2)	H71B—C71—H71C	109.5
C32—C31—C34	109.4 (2)	C7—C72—H72A	109.5
C31—C32—H32A	109.5	C7—C72—H72B	109.5
C31—C32—H32B	109.5	H72A—C72—H72B	109.5
H32A—C32—H32B	109.5	C7—C72—H72C	109.5
C31—C32—H32C	109.5	H72A—C72—H72C	109.5
H32A—C32—H32C	109.5	H72B—C72—H72C	109.5
H32B—C32—H32C	109.5	C8A—C8—C7	114.8 (2)
C31—C33—H33A	109.5	C8A—C8—H8A	108.6
C31—C33—H33B	109.5	C7—C8—H8A	108.6
H33A—C33—H33B	109.5	C8A—C8—H8E	108.6
C31—C33—H33C	109.5	C7—C8—H8E	108.6
H33A—C33—H33C	109.5	H8A—C8—H8E	107.5
H33B—C33—H33C	109.5	N9—C8A—C4A	123.6 (2)
C31—C34—H34A	109.5	N9—C8A—C8	116.1 (2)
C31—C34—H34B	109.5	C4A—C8A—C8	120.3 (2)
H34A—C34—H34B	109.5	C9A—N9—C8A	114.3 (2)
C31—C34—H34C	109.5	N9—C9A—N1	126.1 (2)
H34A—C34—H34C	109.5	N9—C9A—C3A	127.4 (2)
H34B—C34—H34C	109.5	N1—C9A—C3A	106.52 (19)

C9A—N1—C11—C16	170.1 (2)	C3A—C4—C4A—C5	−179.1 (2)
N2—N1—C11—C16	−16.2 (3)	C4—C4A—C5—O5	7.9 (3)
C9A—N1—C11—C12	−12.6 (4)	C8A—C4A—C5—O5	−171.7 (2)
N2—N1—C11—C12	161.1 (2)	C4—C4A—C5—C6	−171.2 (2)
C16—C11—C12—C13	0.4 (3)	C8A—C4A—C5—C6	9.1 (3)
N1—C11—C12—C13	−176.9 (2)	O5—C5—C6—C7	145.9 (2)
C11—C12—C13—C14	0.8 (4)	C4A—C5—C6—C7	−35.0 (3)
C12—C13—C14—C15	−1.6 (4)	C5—C6—C7—C72	173.2 (2)
C12—C13—C14—Cl14	177.65 (19)	C5—C6—C7—C8	54.1 (2)
C13—C14—C15—C16	1.1 (4)	C5—C6—C7—C71	−66.9 (2)
Cl14—C14—C15—C16	−178.1 (2)	C72—C7—C8—C8A	−168.0 (2)
C12—C11—C16—C15	−0.8 (4)	C6—C7—C8—C8A	−49.2 (2)
N1—C11—C16—C15	176.5 (2)	C71—C7—C8—C8A	71.2 (3)
C14—C15—C16—C11	0.1 (4)	C4—C4A—C8A—N9	−3.0 (3)
C9A—N1—N2—C3	−0.2 (2)	C5—C4A—C8A—N9	176.6 (2)
C11—N1—N2—C3	−175.16 (18)	C4—C4A—C8A—C8	175.6 (2)
N1—N2—C3—C3A	−0.9 (2)	C5—C4A—C8A—C8	−4.8 (3)
N1—N2—C3—C31	174.51 (18)	C7—C8—C8A—N9	−155.06 (19)
N2—C3—C31—C33	131.2 (2)	C7—C8—C8A—C4A	26.2 (3)
C3A—C3—C31—C33	−54.4 (3)	C4A—C8A—N9—C9A	2.4 (3)
N2—C3—C31—C32	10.7 (3)	C8—C8A—N9—C9A	−176.26 (19)
C3A—C3—C31—C32	−174.8 (2)	C8A—N9—C9A—N1	179.0 (2)
N2—C3—C31—C34	−109.0 (2)	C8A—N9—C9A—C3A	0.6 (3)
C3A—C3—C31—C34	65.4 (3)	N2—N1—C9A—N9	−177.52 (19)
N2—C3—C3A—C4	−178.6 (2)	C11—N1—C9A—N9	−3.5 (4)
C31—C3—C3A—C4	6.5 (4)	N2—N1—C9A—C3A	1.2 (2)
N2—C3—C3A—C9A	1.6 (2)	C11—N1—C9A—C3A	175.2 (2)
C31—C3—C3A—C9A	−173.3 (2)	C4—C3A—C9A—N9	−2.8 (3)
C9A—C3A—C4—C4A	2.0 (3)	C3—C3A—C9A—N9	177.0 (2)
C3—C3A—C4—C4A	−177.7 (2)	C4—C3A—C9A—N1	178.53 (18)
C3A—C4—C4A—C8A	0.6 (3)	C3—C3A—C9A—N1	−1.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Cg1ⁱ	0.97	2.77	3.649 (3)	151
C8—H8A···Cg2ⁱ	0.97	2.82	3.768 (3)	165

Symmetry code: (i) −x, −y+1, −z+1.

Footnotes

‡Correspondance address: Department of Electrical Engineering and Physics, School of Engineering and Physical Science, University of Dundee, Dundee DD1 4HN, Scotland.

Acknowledgements

X-ray data were collected at the `Servicios Técnicos de Investigación', University of Jaén. JC thanks the Consejería de Educación y Ciencia (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. JQ and JM thank COLCIENCIAS and UNIVALLE (Universidad del Valle) for financial support. JNL thanks NCR Self-Service, Dundee, for grants which have provided computing facilities for this work.

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