3-tert-But­yl-4-(4-nitro­phen­yl)-1-phen­yl-1H-pyrazolo[3,4-b]pyridine

Abonia, R.; Rengifo, E.; Cobo, J.; Low, J.N.; Glidewell, C.

doi:10.1107/S160053680502177X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 8| August 2005| Pages o2625-o2627

https://doi.org/10.1107/S160053680502177X

3-tert-Butyl-4-(4-nitrophenyl)-1-phenyl-1H-pyrazolo[3,4-b]pyridine

Rodrigo Abonia,^a Emerson Rengifo,^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, St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 5 July 2005; accepted 7 July 2005; online 20 July 2005)

Molecules of the title compound, C₂₂H₂₀N₄O₂, are linked by paired C—H⋯O hydrogen bonds into centrosymmetric R₂²(18) dimers and these dimers are linked into chains by paired C—H⋯π(arene) hydrogen bonds.

Comment

We have recently described the preparation of pyrazolo[3,4-b]pyridines from 5-aminopyrazoles in solution with different reactants (Low et al., 2002 , and references therein), and we have reported the crystal structure of the fully aromatized 3-methyl-1,4-diphenyl-1H-pyrazolo[3,4-b]pyridine (Low et al., 2002). We report here an analogous structure, that of 3-tert-butyl-4-(4-nitrophenyl)-1-phenyl-1H-pyrazolo[3,4-b]pyridine, (I), obtained from the solvent-free reaction of the corresponding 5-aminopyrazole and the Mannich adduct β-dimethylamino-4-nitropropiophenone hydrochloride, under microwave irradiation. The title compound, (I), was obtained along with the reduced 6-(4-nitrophenyl) analogue, (II); however, in pyridine solution under reflux, a similar reaction yielded regioselectively the isomeric 6-arylpyrazolo[3,4-b]pyridine (Quiroga et al., 1998 ).

Neither of the aryl rings in compound (I) (Fig. 1) is coplanar with the pyrazolopyridine system; unsubstituted phenyl ring C11–C16 makes a dihedral angle of 25.3 (2)° with the adjacent pyrazole ring, while substituted ring C41–C46 is nearly orthogonal to the pyridine ring, with a dihedral angle between these ring planes of 85.1 (2)°; in addition, the nitro group makes a dihedral angle of 11.6 (2)° with the adjacent aryl ring. The bond distances within the fused heterocyclic ring system (Table 1) are consistent with electronic delocalization in the pyridine ring and strong bond fixation in the pyrazole ring.

The molecules of compound (I) are linked into chains of fused rings by a combination of one C—H⋯O hydrogen bond and one C—H⋯π(arene) hydrogen bond (Table 2). Pyridine atom C5 in the molecule at (x, y, z) acts as hydrogen-bond donor to nitro atom O41 in the molecule at (1 − x, 1 − y, 1 − z), generating a centrosymmetric R₂²(18) dimer centred at ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ) (Fig. 2). In addition, aryl atoms C43 in the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z), which are both components of the R₂²(18) dimer centred at ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ), act as donors respectively to aryl rings C11–C16 in the molecules at (−x, 1 − y, −z) and (1 + x, y, 1 + z), which themselves are components of the R₂²(18) dimers centred at (− $[{1\over 2}]$ , $[{1\over 2}]$ , − $[{1\over 2}]$ ) and ( $[{3\over 2}]$ , $[{1\over 2}]$ , $[{3\over 2}]$ ). Propagation by inversion of these two interactions thus generates a chain of edge-fused rings running parallel to the [101] direction, rings built from paired C—H⋯O hydrogen bonds centred at (n + $[{1\over 2}]$ , $[{1\over 2}]$ , n + $[{1\over 2}]$ ) (n = zero or integer) and rings built from paired C—H⋯π(arene) hydrogen bonds centred at (n, $[{1\over 2}]$ , n) (n = zero or integer) (Fig. 3).

Figure 1
The molecule of compound (I)

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

Figure 2
Part of the crystal structure of (I)

, showing the formation of a centrosymmetric R₂²(18) dimer. For the sake of clarity, the H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z). Dashed lines indicate hydrogen bonds.

Figure 3
Stereoview of part of the crystal structure of (I)

, showing the formation of a [101] chain of edge-fused rings. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted. Dashed lines indicate hydrogen bonds.

Experimental

Equimolar quantities (0.465 mmol) of 5-amino-3-tert-butyl-1-phenyl-1H-pyrazole and β-dimethylamino-4-nitropropiophenone hydrochloride were placed in open Pyrex-glass vessels and irradiated in a domestic microwave oven for 15 s (at 600 W). The reaction mixture was extracted with ethyl acetate and the product was purified by column chromatography on silica gel, using hexane/ethyl acetate (15:1 (v/v) as eluent. Evaporation of the eluate yielded colourless crystals of compound (I) (yield 45%; m.p. 448–450 K) suitable for single-crystal X-ray diffraction, accompanied by a small quantity of the reduced 6-(4-nitrophenyl) derivative, (II). MS (EI 30 eV), m/z (%): 372 (M⁺, 10), 357, (17), 149 (58), 57 (100).

Crystal data

C₂₂H₂₀N₄O₂
M_r = 372.42
Triclinic, $[P \overline 1]$
a = 9.5877 (5) Å
b = 9.8541 (5) Å
c = 11.7050 (4) Å
α = 105.982 (2)°
β = 103.570 (2)°
γ = 108.433 (2)°
V = 943.75 (8) Å³
Z = 2
D_x = 1.311 Mg m⁻³
Mo Kα radiation
Cell parameters from 4338 reflections
θ = 3.2–27.7°
μ = 0.09 mm⁻¹
T = 120 (2) K
Plate, colourless
0.19 × 0.08 × 0.05 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.980, T_max = 0.996
23240 measured reflections
4338 independent reflections
2724 reflections with I > 2σ(I)
R_int = 0.070
θ_max = 27.7°
h = −12 → 12
k = −12 → 12
l = −15 → 15

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.137
S = 1.02
4338 reflections
256 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0643P)² + 0.1475P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected bond lengths (Å)

N1—N2	1.371 (2)
N2—C3	1.327 (2)
C3—C3A	1.447 (3)
C3A—C4	1.415 (3)
C4—C5	1.386 (3)
C5—C6	1.394 (3)
C6—N7	1.332 (2)
N7—C7A	1.340 (2)
C7A—N1	1.363 (2)
C3A—C7A	1.419 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O41ⁱ	0.95	2.46	3.399 (2)	169
C43—H43⋯Cgⁱⁱ	0.95	2.65	3.501 (2)	149
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z.

All H atoms were located in difference maps and then treated as riding atoms, with C—H distances of 0.95 (aromatic) or 0.98 Å (methyl), and with U_iso(H) = 1.2U_eq(C), or 1.5U_eq(C) for the methyl groups.

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/S160053680502177X/lh6471sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680502177X/lh6471Isup2.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).

3-tert-butyl-4-(4-nitrophenyl)-1-phenyl-1H-pyrazolo[3,4-b]pyridine top

Crystal data top

C₂₂H₂₀N₄O₂	Z = 2
M_r = 372.42	F(000) = 392
Triclinic, P1	D_x = 1.311 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5877 (5) Å	Cell parameters from 4338 reflections
b = 9.8541 (5) Å	θ = 3.2–27.7°
c = 11.7050 (4) Å	µ = 0.09 mm⁻¹
α = 105.982 (2)°	T = 120 K
β = 103.570 (2)°	Plate, colourless
γ = 108.433 (2)°	0.19 × 0.08 × 0.05 mm
V = 943.75 (8) Å³

Data collection top

Bruker–Nonius 95mm CCD camera on κ goniostat diffractometer	4338 independent reflections
Radiation source: Bruker–Nonius FR91 rotating anode	2724 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.7°, θ_min = 3.2°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
T_min = 0.980, T_max = 0.996	l = −15→15
23240 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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0643P)² + 0.1475P] where P = (F_o² + 2F_c²)/3
4338 reflections	(Δ/σ)_max < 0.001
256 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

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

	x	y	z	U_iso*/U_eq
O41	0.69225 (17)	0.83405 (17)	0.65880 (13)	0.0458 (4)
O42	0.46382 (19)	0.7917 (2)	0.67528 (13)	0.0557 (5)
N1	0.11065 (16)	0.35207 (17)	−0.22947 (13)	0.0253 (4)
N2	0.17138 (16)	0.51029 (17)	−0.17602 (13)	0.0267 (4)
N7	0.09648 (17)	0.14201 (17)	−0.16190 (14)	0.0294 (4)
N44	0.5484 (2)	0.77491 (19)	0.61333 (15)	0.0361 (4)
C3	0.23820 (19)	0.5540 (2)	−0.05157 (16)	0.0250 (4)
C3A	0.22141 (19)	0.4193 (2)	−0.01952 (16)	0.0245 (4)
C4	0.2566 (2)	0.3797 (2)	0.08789 (17)	0.0266 (4)
C5	0.2111 (2)	0.2236 (2)	0.06525 (18)	0.0328 (5)
C6	0.1342 (2)	0.1116 (2)	−0.05761 (17)	0.0324 (5)
C7A	0.14011 (19)	0.2932 (2)	−0.13833 (16)	0.0249 (4)
C11	0.0266 (2)	0.2763 (2)	−0.36273 (16)	0.0258 (4)
C12	0.0587 (2)	0.3567 (2)	−0.44065 (17)	0.0289 (4)
C13	−0.0246 (2)	0.2847 (2)	−0.57028 (18)	0.0337 (5)
C14	−0.1388 (2)	0.1357 (2)	−0.62257 (18)	0.0350 (5)
C15	−0.1704 (2)	0.0575 (2)	−0.54349 (18)	0.0368 (5)
C16	−0.0891 (2)	0.1262 (2)	−0.41376 (18)	0.0331 (5)
C31	0.3120 (2)	0.7265 (2)	0.02705 (16)	0.0264 (4)
C32	0.3095 (2)	0.8158 (2)	−0.06107 (18)	0.0358 (5)
C33	0.2145 (3)	0.7647 (2)	0.10799 (19)	0.0406 (5)
C34	0.4821 (2)	0.7785 (2)	0.1107 (2)	0.0400 (5)
C41	0.3343 (2)	0.4888 (2)	0.22334 (16)	0.0261 (4)
C42	0.2448 (2)	0.5348 (2)	0.29180 (17)	0.0311 (4)
C43	0.3139 (2)	0.6283 (2)	0.41949 (17)	0.0329 (5)
C44	0.4730 (2)	0.6759 (2)	0.47773 (16)	0.0282 (4)
C45	0.5651 (2)	0.6324 (2)	0.41341 (17)	0.0305 (4)
C46	0.4945 (2)	0.5371 (2)	0.28592 (17)	0.0296 (4)
H5	0.2327	0.1924	0.1349	0.039*
H6	0.1070	0.0065	−0.0676	0.039*
H12	0.1367	0.4596	−0.4056	0.035*
H13	−0.0026	0.3390	−0.6240	0.040*
H14	−0.1950	0.0874	−0.7115	0.042*
H15	−0.2492	−0.0450	−0.5789	0.044*
H16	−0.1118	0.0718	−0.3603	0.040*
H32A	0.3549	0.9269	−0.0101	0.054*
H32B	0.2008	0.7838	−0.1154	0.054*
H32C	0.3711	0.7940	−0.1141	0.054*
H33A	0.1066	0.7333	0.0524	0.061*
H33B	0.2610	0.8761	0.1577	0.061*
H33C	0.2137	0.7089	0.1656	0.061*
H34A	0.5295	0.8911	0.1553	0.060*
H34B	0.5411	0.7487	0.0577	0.060*
H34C	0.4850	0.7292	0.1729	0.060*
H42	0.1353	0.5015	0.2501	0.037*
H43	0.2528	0.6590	0.4660	0.040*
H45	0.6748	0.6670	0.4557	0.037*
H46	0.5559	0.5043	0.2408	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O41	0.0379 (9)	0.0472 (9)	0.0333 (8)	0.0042 (7)	0.0039 (6)	0.0107 (7)
O42	0.0562 (10)	0.0796 (12)	0.0316 (8)	0.0369 (9)	0.0180 (7)	0.0084 (8)
N1	0.0255 (8)	0.0228 (8)	0.0254 (8)	0.0090 (6)	0.0085 (6)	0.0073 (7)
N2	0.0232 (8)	0.0255 (9)	0.0280 (8)	0.0081 (7)	0.0084 (6)	0.0078 (7)
N7	0.0299 (8)	0.0266 (9)	0.0322 (9)	0.0134 (7)	0.0108 (7)	0.0100 (7)
N44	0.0426 (11)	0.0359 (10)	0.0282 (9)	0.0167 (8)	0.0098 (8)	0.0117 (8)
C3	0.0188 (9)	0.0294 (10)	0.0283 (10)	0.0102 (8)	0.0109 (7)	0.0105 (8)
C3A	0.0192 (8)	0.0267 (10)	0.0272 (9)	0.0094 (7)	0.0092 (7)	0.0088 (8)
C4	0.0218 (9)	0.0308 (11)	0.0291 (10)	0.0117 (8)	0.0107 (7)	0.0115 (8)
C5	0.0369 (11)	0.0340 (12)	0.0299 (10)	0.0166 (9)	0.0103 (8)	0.0144 (9)
C6	0.0360 (11)	0.0276 (11)	0.0368 (11)	0.0154 (9)	0.0139 (9)	0.0131 (9)
C7A	0.0207 (9)	0.0276 (10)	0.0278 (10)	0.0112 (8)	0.0103 (7)	0.0096 (8)
C11	0.0256 (9)	0.0284 (10)	0.0229 (9)	0.0136 (8)	0.0082 (7)	0.0065 (8)
C12	0.0246 (9)	0.0322 (11)	0.0273 (10)	0.0103 (8)	0.0107 (8)	0.0079 (8)
C13	0.0343 (11)	0.0406 (12)	0.0299 (10)	0.0167 (9)	0.0158 (8)	0.0133 (9)
C14	0.0383 (11)	0.0370 (12)	0.0235 (10)	0.0175 (10)	0.0071 (8)	0.0035 (9)
C15	0.0330 (11)	0.0299 (11)	0.0339 (11)	0.0088 (9)	0.0029 (9)	0.0048 (9)
C16	0.0334 (11)	0.0300 (11)	0.0315 (10)	0.0103 (9)	0.0079 (8)	0.0113 (9)
C31	0.0249 (9)	0.0253 (10)	0.0270 (10)	0.0087 (8)	0.0094 (7)	0.0086 (8)
C32	0.0402 (12)	0.0286 (11)	0.0351 (11)	0.0113 (9)	0.0110 (9)	0.0123 (9)
C33	0.0475 (13)	0.0306 (11)	0.0436 (12)	0.0143 (10)	0.0250 (10)	0.0082 (10)
C34	0.0311 (11)	0.0308 (11)	0.0437 (12)	0.0048 (9)	0.0017 (9)	0.0120 (9)
C41	0.0282 (10)	0.0263 (10)	0.0265 (9)	0.0120 (8)	0.0103 (8)	0.0122 (8)
C42	0.0254 (10)	0.0382 (11)	0.0300 (10)	0.0135 (9)	0.0093 (8)	0.0130 (9)
C43	0.0341 (11)	0.0403 (12)	0.0309 (10)	0.0189 (9)	0.0168 (9)	0.0141 (9)
C44	0.0322 (10)	0.0282 (10)	0.0253 (10)	0.0130 (8)	0.0094 (8)	0.0115 (8)
C45	0.0248 (10)	0.0334 (11)	0.0321 (10)	0.0109 (8)	0.0082 (8)	0.0133 (9)
C46	0.0279 (10)	0.0339 (11)	0.0312 (10)	0.0151 (9)	0.0127 (8)	0.0132 (9)

Geometric parameters (Å, º) top

N1—N2	1.371 (2)	C32—H32A	0.98
N2—C3	1.327 (2)	C32—H32B	0.98
C3—C3A	1.447 (3)	C32—H32C	0.98
C3A—C4	1.415 (3)	C33—H33A	0.98
C4—C5	1.386 (3)	C33—H33B	0.98
C5—C6	1.394 (3)	C33—H33C	0.98
C6—N7	1.332 (2)	C34—H34A	0.98
N7—C7A	1.340 (2)	C34—H34B	0.98
C7A—N1	1.363 (2)	C34—H34C	0.98
C3A—C7A	1.419 (2)	C4—C41	1.492 (2)
N1—C11	1.424 (2)	C41—C46	1.393 (3)
C11—C12	1.389 (3)	C41—C42	1.397 (2)
C11—C16	1.393 (3)	C42—C43	1.383 (3)
C12—C13	1.387 (3)	C42—H42	0.95
C12—H12	0.95	C43—C44	1.377 (3)
C13—C14	1.380 (3)	C43—H43	0.95
C13—H13	0.95	C44—C45	1.380 (2)
C14—C15	1.385 (3)	C44—N44	1.468 (2)
C14—H14	0.95	N44—O41	1.225 (2)
C15—C16	1.384 (3)	N44—O42	1.227 (2)
C15—H15	0.95	C45—C46	1.385 (2)
C16—H16	0.95	C45—H45	0.95
C3—C31	1.520 (3)	C46—H46	0.95
C31—C34	1.525 (3)	C5—H5	0.95
C31—C32	1.530 (3)	C6—H6	0.95
C31—C33	1.535 (2)

C7A—N1—N2	110.38 (14)	C31—C34—H34A	109.5
C7A—N1—C11	130.66 (15)	C31—C34—H34B	109.5
N2—N1—C11	118.93 (14)	H34A—C34—H34B	109.5
C12—C11—C16	120.50 (17)	C31—C34—H34C	109.5
C12—C11—N1	118.72 (16)	H34A—C34—H34C	109.5
C16—C11—N1	120.75 (16)	H34B—C34—H34C	109.5
C13—C12—C11	119.10 (18)	C4—C3A—C7A	115.63 (17)
C13—C12—H12	120.4	C4—C3A—C3	140.28 (17)
C11—C12—H12	120.4	C7A—C3A—C3	104.07 (15)
C14—C13—C12	121.16 (18)	C5—C4—C3A	116.79 (17)
C14—C13—H13	119.4	C5—C4—C41	116.73 (16)
C12—C13—H13	119.4	C3A—C4—C41	126.46 (17)
C13—C14—C15	119.05 (17)	C46—C41—C42	119.02 (16)
C13—C14—H14	120.5	C46—C41—C4	120.66 (16)
C15—C14—H14	120.5	C42—C41—C4	120.15 (15)
C16—C15—C14	121.09 (19)	C43—C42—C41	120.77 (17)
C16—C15—H15	119.5	C43—C42—H42	119.6
C14—C15—H15	119.5	C41—C42—H42	119.6
C15—C16—C11	119.09 (18)	C44—C43—C42	118.61 (17)
C15—C16—H16	120.5	C44—C43—H43	120.7
C11—C16—H16	120.5	C42—C43—H43	120.7
C3—N2—N1	108.20 (15)	C43—C44—C45	122.28 (17)
N2—C3—C3A	109.76 (15)	C43—C44—N44	119.38 (16)
N2—C3—C31	116.96 (16)	C45—C44—N44	118.33 (16)
C3A—C3—C31	133.27 (16)	O41—N44—O42	123.63 (16)
C3—C31—C34	111.06 (16)	O41—N44—C44	118.17 (15)
C3—C31—C32	109.66 (14)	O42—N44—C44	118.18 (16)
C34—C31—C32	108.49 (15)	C44—C45—C46	118.68 (16)
C3—C31—C33	109.37 (14)	C44—C45—H45	120.7
C34—C31—C33	110.76 (16)	C46—C45—H45	120.7
C32—C31—C33	107.42 (16)	C45—C46—C41	120.62 (16)
C31—C32—H32A	109.5	C45—C46—H46	119.7
C31—C32—H32B	109.5	C41—C46—H46	119.7
H32A—C32—H32B	109.5	C4—C5—C6	121.42 (18)
C31—C32—H32C	109.5	C4—C5—H5	119.3
H32A—C32—H32C	109.5	C6—C5—H5	119.3
H32B—C32—H32C	109.5	N7—C6—C5	124.38 (18)
C31—C33—H33A	109.5	N7—C6—H6	117.8
C31—C33—H33B	109.5	C5—C6—H6	117.8
H33A—C33—H33B	109.5	C6—N7—C7A	113.47 (16)
C31—C33—H33C	109.5	N7—C7A—N1	124.13 (16)
H33A—C33—H33C	109.5	N7—C7A—C3A	128.29 (17)
H33B—C33—H33C	109.5	N1—C7A—C3A	107.58 (16)

C7A—N1—C11—C12	−157.30 (17)	C3A—C4—C41—C46	−98.4 (2)
N2—N1—C11—C12	25.1 (2)	C5—C4—C41—C42	−92.0 (2)
C7A—N1—C11—C16	24.6 (3)	C3A—C4—C41—C42	86.5 (2)
N2—N1—C11—C16	−152.94 (16)	C46—C41—C42—C43	0.7 (3)
C16—C11—C12—C13	−0.8 (3)	C4—C41—C42—C43	175.98 (17)
N1—C11—C12—C13	−178.89 (15)	C41—C42—C43—C44	0.4 (3)
C11—C12—C13—C14	0.4 (3)	C42—C43—C44—C45	−0.6 (3)
C12—C13—C14—C15	0.1 (3)	C42—C43—C44—N44	−179.87 (17)
C13—C14—C15—C16	−0.2 (3)	C43—C44—N44—O41	−169.59 (18)
C14—C15—C16—C11	−0.2 (3)	C45—C44—N44—O41	11.1 (3)
C12—C11—C16—C15	0.7 (3)	C43—C44—N44—O42	11.6 (3)
N1—C11—C16—C15	178.75 (16)	C45—C44—N44—O42	−167.64 (18)
C7A—N1—N2—C3	−0.60 (18)	C43—C44—C45—C46	−0.2 (3)
C11—N1—N2—C3	177.44 (14)	N44—C44—C45—C46	179.05 (17)
N1—N2—C3—C3A	−0.19 (18)	C44—C45—C46—C41	1.3 (3)
N1—N2—C3—C31	−179.34 (13)	C42—C41—C46—C45	−1.6 (3)
N2—C3—C31—C34	−126.87 (17)	C4—C41—C46—C45	−176.80 (17)
C3A—C3—C31—C34	54.2 (2)	C3A—C4—C5—C6	−0.1 (3)
N2—C3—C31—C32	−7.0 (2)	C41—C4—C5—C6	178.52 (16)
C3A—C3—C31—C32	174.12 (18)	C4—C5—C6—N7	−0.8 (3)
N2—C3—C31—C33	110.58 (17)	C5—C6—N7—C7A	0.2 (3)
C3A—C3—C31—C33	−68.3 (2)	C6—N7—C7A—N1	−178.24 (16)
N2—C3—C3A—C4	−177.3 (2)	C6—N7—C7A—C3A	1.3 (3)
C31—C3—C3A—C4	1.7 (4)	N2—N1—C7A—N7	−179.27 (15)
N2—C3—C3A—C7A	0.86 (18)	C11—N1—C7A—N7	3.0 (3)
C31—C3—C3A—C7A	179.81 (17)	N2—N1—C7A—C3A	1.15 (18)
C7A—C3A—C4—C5	1.3 (2)	C11—N1—C7A—C3A	−176.59 (16)
C3—C3A—C4—C5	179.3 (2)	C4—C3A—C7A—N7	−2.1 (3)
C7A—C3A—C4—C41	−177.14 (16)	C3—C3A—C7A—N7	179.25 (16)
C3—C3A—C4—C41	0.9 (3)	C4—C3A—C7A—N1	177.51 (14)
C5—C4—C41—C46	83.2 (2)	C3—C3A—C7A—N1	−1.19 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O41ⁱ	0.95	2.46	3.399 (2)	169
C43—H43···Cgⁱⁱ	0.95	2.65	3.501 (2)	149

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

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. RA and ER thank COLCIENCIAS and UNIVALLE (Universidad del Valle, Colombia) for financial support.

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