2,3-Dihydro-1H-pyrrolo­[1,2-a]indole-9-carbonitrile

Madeley, L.G.; Lemmerer, A.; Michael, J.P.

doi:10.1107/S1600536812045345

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3306

doi:10.1107/S1600536812045345

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2,3-Dihydro-1H-pyrrolo[1,2-a]indole-9-carbonitrile

Lee G. Madeley,^a Andreas Lemmerer ^a and Joseph P. Michael ^a ^*

^aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Private Bag 3, PO WITS, 2050, Johannesburg, South Africa
^*Correspondence e-mail: joseph.michael@wits.ac.za

(Received 26 October 2012; accepted 2 November 2012; online 10 November 2012)

The asymmetric unit of the title compound, C₁₂H₁₀N₂, which may serve as a model for mitosenes, contains two independent molecules. The conformation of the five-membered rings in both molecules is envelope, with the central CH₂—CH₂—CH₂ C atom at the flap in each case. In the crystal, they interact by a combination of weak C—H⋯N and π–π interactions [centroid–centroid distances = 3.616 (1) and 3.499 (1) Å] and C—H⋯π contacts.

Related literature

For the synthesis of the title compound by intramolecular Heck reaction of [1-(2-bromophenyl)pyrrolidin-2-ylidene]-acetonitrile, see: Michael et al. (1993 ). For an alternative synthesis by cyclization of [2-(2-oxopyrrolidin-1-yl)phenyl]acetonitrile with sodium hydride, see: Verboom et al. (1986 ). For background to mitosenes, see: Franck (1978 ); Kasai & Kono (1992 ).

Experimental

Crystal data

C₁₂H₁₀N₂
M_r = 182.22
Triclinic, $[P \overline 1]$
a = 9.1383 (3) Å
b = 9.5340 (3) Å
c = 12.3138 (4) Å
α = 90.794 (2)°
β = 90.528 (2)°
γ = 116.272 (2)°
V = 961.78 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 173 K
0.50 × 0.45 × 0.30 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.963, T_max = 0.978
7592 measured reflections
3498 independent reflections
2809 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.097
S = 1.04
3498 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C6A–C11A and C6B–C11B rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1A—H1A1⋯N2B	0.99	2.68	3.338 (2)	124
C2A—H2A1⋯N2B	0.99	2.66	3.373 (2)	129
C3A—H3A2⋯N2Aⁱ	0.99	2.66	3.634 (2)	168
C3B—H3B1⋯N2Bⁱⁱ	0.99	2.57	3.495 (2)	156
C3A—H3A1⋯Cg1ⁱⁱⁱ	0.99	2.79	3.545 (2)	135
C3B—H3B2⋯Cg2^iv	0.99	2.67	3.523 (2)	146
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x, -y+1, -z+1; (iii) -x, -y, -z; (iv) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2004 ); data reduction: SAINT-Plus and XPREP (Bruker 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812045345/bh2462sup1.cif

Supporting information file. DOI: 10.1107/S1600536812045345/bh2462Isup2.mol

Structure factors: contains datablock I. DOI: 10.1107/S1600536812045345/bh2462Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536812045345/bh2462Isup4.cml

checkCIF report

Comment top

The mitosenes, naturally occurring biologically active degradation products of the important mitomycin antibiotics (Franck, 1978; Kasai & Kono, 1992) are characterized by the presence of a pyrrolo[1,2-a]indole core. The title compound, 2,3-dihydro-1H-pyrrolo[1,2-a]indole-9-carbonitrile, was prepared as part of a model study on the use of intramolecular Heck reactions for creating this core from various [1-(2-bromoaryl)pyrrolidin-2-ylidene]acetates and analogues (Michael et al., 1993).

The asymmetric unit of (I) consists of two molecules, labelled A and B, on general positions. Fig. 1 shows the atomic numbering scheme. The hydrogen bonding of (I) consists of weak C—H···N hydrogen bonds and various π–π interactions. Each molecule in the asymmetric unit makes centrosymmetric dimers using the C3A—H3A2···N2A and C3B—H3B1···N2B hydrogen bonds, shown explicitly for the B molecule in Fig. 2. Between the A and B molecules, two ethylene groups from the A molecule hydrogen bond to the cyanide N atom of the B molecule, through C1A—H1A1···N2B and C2A—H2A1···N2B hydrogen bonds. In addition, both A/A and B/B molecules sit parallel to each other and undergo π–π interactions, with distances of 3.616 (1) Å for A···A and 3.499 (1) Å for B···B (Fig. 2). Also C—H···π contacts are formed between those same A/A and B/B molecules, C3A—H3A1···Cg1ⁱⁱⁱ [Cg1: C6A to C11A; symmetry operator: (iii) -x, -y, -z] and C3B—H3B2···Cg2^iv [Cg2: C6B to C11B; symmetry operator: (iv) 1-x, 1-y, 1-z].

Related literature top

For the synthesis of the title compound by intramolecular Heck reaction of [1-(2-bromophenyl)pyrrolidin-2-ylidene]-acetonitrile, see: Michael et al. (1993). For an alternative synthesis by cyclization of [2-(2-oxopyrrolidin-1-yl)phenyl]acetonitrile with sodium hydride, see: Verboom et al. (1986). For background to mitosenes, see: Franck (1978); Kasai & Kono (1992).

Experimental top

The title compound was prepared by reaction of [1-(2-bromophenyl)pyrrolidin-2-ylidene]acetonitrile (350 mg, 1.33 mmol) with palladium(II) acetate (299 mg, 1.33 mmol, 1 eq.), tri-o-tolylphosphine (407 mg, 1.33 mmol) and triethylamine (0.19 ml, 1.33 mmol), heated under reflux in acetonitrile (7 ml) for 96 h. The crude oil obtained after evaporation of the solvent (1.20 g) was purified by column chromatography on silica gel with hexane/ethyl acetate (5:1 v/v) as eluent to yield a colourless solid (133 mg, 55%). Recrystallization from ethyl acetate produced colourless blocks, m.p. 400–401 K. An alternative synthesis is available from the literature, based on cyclization of [2-(2-oxopyrrolidin-1-yl)phenyl]acetonitrile with sodium hydride (Verboom et al., 1986).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of (I) showing the atomic numbering scheme. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. View of the hydrogen bonds of (I). C—H···N are shown as dashed red lines and C—H···π as dashed blue lines. H atoms not involved in hydrogen bonding are omitted for clarity.

2,3-Dihydro-1H-pyrrolo[1,2-a]indole-9-carbonitrile top

Crystal data top

C₁₂H₁₀N₂	Z = 4
M_r = 182.22	F(000) = 384
Triclinic, P1	D_x = 1.258 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1383 (3) Å	Cell parameters from 3160 reflections
b = 9.5340 (3) Å	θ = 2.4–28.2°
c = 12.3138 (4) Å	µ = 0.08 mm⁻¹
α = 90.794 (2)°	T = 173 K
β = 90.528 (2)°	Block, colourless
γ = 116.272 (2)°	0.50 × 0.45 × 0.30 mm
V = 961.78 (5) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	2809 reflections with I > 2σ(I)
ω scans	R_int = 0.023
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θ_max = 25.5°, θ_min = 1.7°
T_min = 0.963, T_max = 0.978	h = −10→11
7592 measured reflections	k = −11→11
3498 independent reflections	l = −14→14

Refinement top

Refinement on F²	0 constraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0414P)² + 0.2024P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.097	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.19 e Å⁻³
3498 reflections	Δρ_min = −0.15 e Å⁻³
254 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.027 (2)

Crystal data top

C₁₂H₁₀N₂	γ = 116.272 (2)°
M_r = 182.22	V = 961.78 (5) Å³
Triclinic, P1	Z = 4
a = 9.1383 (3) Å	Mo Kα radiation
b = 9.5340 (3) Å	µ = 0.08 mm⁻¹
c = 12.3138 (4) Å	T = 173 K
α = 90.794 (2)°	0.50 × 0.45 × 0.30 mm
β = 90.528 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3498 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2809 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.978	R_int = 0.023
7592 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.04	Δρ_max = 0.19 e Å⁻³
3498 reflections	Δρ_min = −0.15 e Å⁻³
254 parameters

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

	x	y	z	U_iso*/U_eq
C1A	−0.10944 (18)	0.17265 (18)	0.14642 (13)	0.0397 (4)
H1A1	−0.1299	0.1843	0.2241	0.048*
H1A2	−0.211	0.0937	0.1114	0.048*
C2A	−0.0463 (2)	0.32983 (19)	0.08862 (13)	0.0447 (4)
H2A1	−0.018	0.4164	0.1424	0.054*
H2A2	−0.1311	0.3303	0.0382	0.054*
C3A	0.10660 (19)	0.35042 (18)	0.02512 (13)	0.0419 (4)
H3A1	0.0836	0.3383	−0.0541	0.05*
H3A2	0.1987	0.4544	0.0405	0.05*
C4A	0.14316 (17)	0.22297 (16)	0.06621 (11)	0.0323 (3)
C5A	0.25796 (16)	0.16684 (15)	0.05611 (11)	0.0307 (3)
C6A	0.20402 (16)	0.02878 (15)	0.12165 (11)	0.0296 (3)
C7A	0.26457 (17)	−0.07929 (17)	0.14459 (12)	0.0358 (3)
H7A	0.3632	−0.0697	0.1133	0.043*
C8A	0.17821 (18)	−0.20006 (17)	0.21350 (13)	0.0407 (4)
H8A	0.2178	−0.2746	0.2291	0.049*
C9A	0.03390 (18)	−0.21502 (18)	0.26077 (12)	0.0422 (4)
H9A	−0.0218	−0.2986	0.3087	0.051*
C10A	−0.02975 (18)	−0.11093 (17)	0.23936 (12)	0.0375 (4)
H10A	−0.1283	−0.1214	0.2712	0.045*
C11A	0.05677 (16)	0.00985 (16)	0.16923 (11)	0.0304 (3)
C12A	0.40232 (18)	0.23407 (17)	−0.00564 (12)	0.0361 (3)
N1A	0.02493 (14)	0.13034 (13)	0.13356 (9)	0.0325 (3)
N2A	0.52063 (17)	0.28700 (16)	−0.05460 (11)	0.0503 (4)
C1B	0.49796 (18)	0.56982 (17)	0.73859 (12)	0.0365 (3)
H1B1	0.6163	0.6215	0.7237	0.044*
H1B2	0.4801	0.5177	0.8096	0.044*
C2B	0.4245 (2)	0.68616 (19)	0.73518 (13)	0.0463 (4)
H2B1	0.5104	0.7941	0.7484	0.056*
H2B2	0.3405	0.6617	0.7915	0.056*
C3B	0.34765 (17)	0.67027 (16)	0.62107 (12)	0.0346 (3)
H3B1	0.2426	0.6768	0.6243	0.041*
H3B2	0.4221	0.7519	0.5724	0.041*
C4B	0.32309 (15)	0.51204 (15)	0.58477 (11)	0.0281 (3)
C5B	0.24306 (16)	0.40067 (15)	0.50510 (11)	0.0297 (3)
C6B	0.27990 (16)	0.27070 (15)	0.52490 (11)	0.0292 (3)
C7B	0.23096 (18)	0.12242 (16)	0.47682 (12)	0.0375 (4)
H7B	0.1594	0.0902	0.4153	0.045*
C8B	0.28912 (19)	0.02423 (17)	0.52084 (13)	0.0422 (4)
H8B	0.2565	−0.0768	0.4891	0.051*
C9B	0.39485 (19)	0.06978 (17)	0.61108 (13)	0.0406 (4)
H9B	0.4336	−0.0004	0.6387	0.049*
C10B	0.44413 (17)	0.21428 (16)	0.66078 (12)	0.0344 (3)
H10B	0.5156	0.2452	0.7224	0.041*
C11B	0.38481 (16)	0.31282 (15)	0.61696 (11)	0.0285 (3)
C12B	0.14474 (18)	0.41506 (17)	0.42058 (12)	0.0359 (3)
N1B	0.40605 (13)	0.45930 (12)	0.65134 (9)	0.0282 (3)
N2B	0.06647 (18)	0.42763 (17)	0.35107 (12)	0.0546 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.0365 (8)	0.0434 (9)	0.0459 (9)	0.0241 (7)	−0.0033 (7)	−0.0072 (7)
C2A	0.0552 (10)	0.0451 (9)	0.0449 (9)	0.0325 (8)	−0.0066 (8)	−0.0048 (7)
C3A	0.0459 (9)	0.0358 (8)	0.0463 (9)	0.0202 (7)	−0.0062 (7)	0.0025 (7)
C4A	0.0342 (8)	0.0300 (7)	0.0291 (7)	0.0111 (6)	−0.0051 (6)	−0.0002 (6)
C5A	0.0299 (7)	0.0304 (7)	0.0295 (7)	0.0113 (6)	−0.0013 (6)	0.0010 (6)
C6A	0.0268 (7)	0.0304 (7)	0.0285 (7)	0.0100 (6)	−0.0044 (6)	−0.0013 (6)
C7A	0.0294 (7)	0.0363 (8)	0.0416 (8)	0.0147 (6)	−0.0052 (6)	0.0001 (6)
C8A	0.0386 (8)	0.0353 (8)	0.0490 (9)	0.0172 (7)	−0.0094 (7)	0.0060 (7)
C9A	0.0397 (9)	0.0385 (8)	0.0403 (9)	0.0098 (7)	−0.0012 (7)	0.0101 (7)
C10A	0.0316 (8)	0.0392 (8)	0.0369 (8)	0.0111 (7)	0.0024 (6)	0.0042 (6)
C11A	0.0302 (7)	0.0316 (7)	0.0285 (7)	0.0131 (6)	−0.0028 (6)	−0.0015 (6)
C12A	0.0379 (8)	0.0341 (8)	0.0345 (8)	0.0142 (7)	0.0007 (7)	0.0028 (6)
N1A	0.0317 (6)	0.0331 (6)	0.0344 (6)	0.0160 (5)	0.0001 (5)	−0.0001 (5)
N2A	0.0452 (8)	0.0503 (8)	0.0512 (8)	0.0169 (7)	0.0130 (7)	0.0078 (7)
C1B	0.0389 (8)	0.0356 (8)	0.0350 (8)	0.0169 (7)	−0.0070 (6)	−0.0070 (6)
C2B	0.0563 (10)	0.0428 (9)	0.0467 (9)	0.0287 (8)	−0.0098 (8)	−0.0113 (7)
C3B	0.0345 (8)	0.0295 (7)	0.0429 (8)	0.0171 (6)	0.0002 (6)	−0.0007 (6)
C4B	0.0263 (7)	0.0274 (7)	0.0319 (7)	0.0131 (6)	0.0043 (6)	0.0047 (6)
C5B	0.0272 (7)	0.0297 (7)	0.0304 (7)	0.0111 (6)	−0.0003 (6)	0.0034 (6)
C6B	0.0271 (7)	0.0274 (7)	0.0313 (7)	0.0105 (6)	0.0036 (6)	0.0029 (6)
C7B	0.0376 (8)	0.0310 (8)	0.0381 (8)	0.0102 (6)	−0.0006 (7)	−0.0028 (6)
C8B	0.0489 (9)	0.0264 (7)	0.0503 (9)	0.0158 (7)	0.0057 (8)	−0.0028 (7)
C9B	0.0460 (9)	0.0325 (8)	0.0507 (9)	0.0237 (7)	0.0073 (7)	0.0077 (7)
C10B	0.0342 (8)	0.0351 (8)	0.0379 (8)	0.0188 (6)	0.0019 (6)	0.0047 (6)
C11B	0.0272 (7)	0.0263 (7)	0.0318 (7)	0.0115 (6)	0.0043 (6)	0.0035 (5)
C12B	0.0352 (8)	0.0347 (8)	0.0375 (8)	0.0153 (7)	−0.0025 (7)	0.0012 (6)
N1B	0.0285 (6)	0.0279 (6)	0.0297 (6)	0.0139 (5)	−0.0022 (5)	−0.0002 (5)
N2B	0.0565 (9)	0.0606 (9)	0.0494 (9)	0.0287 (8)	−0.0155 (7)	0.0012 (7)

Geometric parameters (Å, º) top

C1A—N1A	1.4616 (17)	C1B—N1B	1.4624 (17)
C1A—C2A	1.535 (2)	C1B—C2B	1.530 (2)
C1A—H1A1	0.99	C1B—H1B1	0.99
C1A—H1A2	0.99	C1B—H1B2	0.99
C2A—C3A	1.544 (2)	C2B—C3B	1.540 (2)
C2A—H2A1	0.99	C2B—H2B1	0.99
C2A—H2A2	0.99	C2B—H2B2	0.99
C3A—C4A	1.4891 (19)	C3B—C4B	1.4852 (18)
C3A—H3A1	0.99	C3B—H3B1	0.99
C3A—H3A2	0.99	C3B—H3B2	0.99
C4A—N1A	1.3517 (18)	C4B—N1B	1.3552 (16)
C4A—C5A	1.3784 (19)	C4B—C5B	1.3767 (19)
C5A—C12A	1.419 (2)	C5B—C12B	1.4161 (19)
C5A—C6A	1.4455 (19)	C5B—C6B	1.4437 (19)
C6A—C7A	1.3990 (19)	C6B—C7B	1.4005 (19)
C6A—C11A	1.4104 (19)	C6B—C11B	1.4114 (19)
C7A—C8A	1.380 (2)	C7B—C8B	1.379 (2)
C7A—H7A	0.95	C7B—H7B	0.95
C8A—C9A	1.396 (2)	C8B—C9B	1.397 (2)
C8A—H8A	0.95	C8B—H8B	0.95
C9A—C10A	1.381 (2)	C9B—C10B	1.378 (2)
C9A—H9A	0.95	C9B—H9B	0.95
C10A—C11A	1.3896 (19)	C10B—C11B	1.3882 (18)
C10A—H10A	0.95	C10B—H10B	0.95
C11A—N1A	1.3800 (17)	C11B—N1B	1.3818 (17)
C12A—N2A	1.1508 (19)	C12B—N2B	1.1515 (18)

N1A—C1A—C2A	102.51 (12)	N1B—C1B—C2B	101.64 (11)
N1A—C1A—H1A1	111.3	N1B—C1B—H1B1	111.4
C2A—C1A—H1A1	111.3	C2B—C1B—H1B1	111.4
N1A—C1A—H1A2	111.3	N1B—C1B—H1B2	111.4
C2A—C1A—H1A2	111.3	C2B—C1B—H1B2	111.4
H1A1—C1A—H1A2	109.2	H1B1—C1B—H1B2	109.3
C1A—C2A—C3A	107.49 (12)	C1B—C2B—C3B	106.64 (12)
C1A—C2A—H2A1	110.2	C1B—C2B—H2B1	110.4
C3A—C2A—H2A1	110.2	C3B—C2B—H2B1	110.4
C1A—C2A—H2A2	110.2	C1B—C2B—H2B2	110.4
C3A—C2A—H2A2	110.2	C3B—C2B—H2B2	110.4
H2A1—C2A—H2A2	108.5	H2B1—C2B—H2B2	108.6
C4A—C3A—C2A	103.49 (12)	C4B—C3B—C2B	102.46 (11)
C4A—C3A—H3A1	111.1	C4B—C3B—H3B1	111.3
C2A—C3A—H3A1	111.1	C2B—C3B—H3B1	111.3
C4A—C3A—H3A2	111.1	C4B—C3B—H3B2	111.3
C2A—C3A—H3A2	111.1	C2B—C3B—H3B2	111.3
H3A1—C3A—H3A2	109	H3B1—C3B—H3B2	109.2
N1A—C4A—C5A	109.25 (12)	N1B—C4B—C5B	109.20 (11)
N1A—C4A—C3A	110.47 (12)	N1B—C4B—C3B	110.27 (11)
C5A—C4A—C3A	140.26 (13)	C5B—C4B—C3B	140.53 (12)
C4A—C5A—C12A	126.19 (12)	C4B—C5B—C12B	125.28 (13)
C4A—C5A—C6A	106.83 (12)	C4B—C5B—C6B	106.93 (11)
C12A—C5A—C6A	126.98 (13)	C12B—C5B—C6B	127.78 (13)
C7A—C6A—C11A	118.89 (12)	C7B—C6B—C11B	118.82 (12)
C7A—C6A—C5A	134.72 (13)	C7B—C6B—C5B	134.60 (13)
C11A—C6A—C5A	106.40 (12)	C11B—C6B—C5B	106.53 (11)
C8A—C7A—C6A	118.66 (14)	C8B—C7B—C6B	118.46 (14)
C8A—C7A—H7A	120.7	C8B—C7B—H7B	120.8
C6A—C7A—H7A	120.7	C6B—C7B—H7B	120.8
C7A—C8A—C9A	121.37 (14)	C7B—C8B—C9B	121.55 (13)
C7A—C8A—H8A	119.3	C7B—C8B—H8B	119.2
C9A—C8A—H8A	119.3	C9B—C8B—H8B	119.2
C10A—C9A—C8A	121.45 (14)	C10B—C9B—C8B	121.40 (13)
C10A—C9A—H9A	119.3	C10B—C9B—H9B	119.3
C8A—C9A—H9A	119.3	C8B—C9B—H9B	119.3
C9A—C10A—C11A	117.06 (14)	C9B—C10B—C11B	117.09 (14)
C9A—C10A—H10A	121.5	C9B—C10B—H10B	121.5
C11A—C10A—H10A	121.5	C11B—C10B—H10B	121.5
N1A—C11A—C10A	130.29 (13)	N1B—C11B—C10B	130.31 (13)
N1A—C11A—C6A	107.14 (11)	N1B—C11B—C6B	106.98 (11)
C10A—C11A—C6A	122.57 (13)	C10B—C11B—C6B	122.67 (13)
N2A—C12A—C5A	178.68 (16)	N2B—C12B—C5B	179.15 (17)
C4A—N1A—C11A	110.38 (11)	C4B—N1B—C11B	110.34 (11)
C4A—N1A—C1A	114.62 (11)	C4B—N1B—C1B	113.89 (11)
C11A—N1A—C1A	134.86 (12)	C11B—N1B—C1B	135.75 (11)

N1A—C1A—C2A—C3A	11.78 (15)	N1B—C1B—C2B—C3B	−21.63 (16)
C1A—C2A—C3A—C4A	−10.85 (16)	C1B—C2B—C3B—C4B	21.44 (16)
C2A—C3A—C4A—N1A	5.68 (16)	C2B—C3B—C4B—N1B	−13.05 (15)
C2A—C3A—C4A—C5A	−175.95 (17)	C2B—C3B—C4B—C5B	166.94 (17)
N1A—C4A—C5A—C12A	−178.53 (13)	N1B—C4B—C5B—C12B	−179.62 (13)
C3A—C4A—C5A—C12A	3.1 (3)	C3B—C4B—C5B—C12B	0.4 (3)
N1A—C4A—C5A—C6A	0.56 (15)	N1B—C4B—C5B—C6B	0.12 (15)
C3A—C4A—C5A—C6A	−177.82 (17)	C3B—C4B—C5B—C6B	−179.87 (16)
C4A—C5A—C6A—C7A	179.59 (15)	C4B—C5B—C6B—C7B	176.58 (15)
C12A—C5A—C6A—C7A	−1.3 (3)	C12B—C5B—C6B—C7B	−3.7 (3)
C4A—C5A—C6A—C11A	−0.40 (14)	C4B—C5B—C6B—C11B	−0.84 (15)
C12A—C5A—C6A—C11A	178.68 (13)	C12B—C5B—C6B—C11B	178.89 (13)
C11A—C6A—C7A—C8A	−0.4 (2)	C11B—C6B—C7B—C8B	−0.8 (2)
C5A—C6A—C7A—C8A	179.65 (14)	C5B—C6B—C7B—C8B	−177.95 (15)
C6A—C7A—C8A—C9A	−0.5 (2)	C6B—C7B—C8B—C9B	−0.2 (2)
C7A—C8A—C9A—C10A	0.9 (2)	C7B—C8B—C9B—C10B	0.7 (2)
C8A—C9A—C10A—C11A	−0.4 (2)	C8B—C9B—C10B—C11B	−0.3 (2)
C9A—C10A—C11A—N1A	−179.53 (14)	C9B—C10B—C11B—N1B	176.69 (13)
C9A—C10A—C11A—C6A	−0.5 (2)	C9B—C10B—C11B—C6B	−0.7 (2)
C7A—C6A—C11A—N1A	−179.89 (12)	C7B—C6B—C11B—N1B	−176.67 (12)
C5A—C6A—C11A—N1A	0.10 (14)	C5B—C6B—C11B—N1B	1.24 (14)
C7A—C6A—C11A—C10A	0.9 (2)	C7B—C6B—C11B—C10B	1.2 (2)
C5A—C6A—C11A—C10A	−179.10 (13)	C5B—C6B—C11B—C10B	179.14 (12)
C5A—C4A—N1A—C11A	−0.52 (15)	C5B—C4B—N1B—C11B	0.68 (15)
C3A—C4A—N1A—C11A	178.38 (11)	C3B—C4B—N1B—C11B	−179.33 (11)
C5A—C4A—N1A—C1A	−176.82 (11)	C5B—C4B—N1B—C1B	179.18 (11)
C3A—C4A—N1A—C1A	2.08 (16)	C3B—C4B—N1B—C1B	−0.83 (16)
C10A—C11A—N1A—C4A	179.36 (14)	C10B—C11B—N1B—C4B	−178.89 (14)
C6A—C11A—N1A—C4A	0.25 (15)	C6B—C11B—N1B—C4B	−1.21 (15)
C10A—C11A—N1A—C1A	−5.4 (3)	C10B—C11B—N1B—C1B	3.1 (3)
C6A—C11A—N1A—C1A	175.50 (14)	C6B—C11B—N1B—C1B	−179.25 (14)
C2A—C1A—N1A—C4A	−8.84 (16)	C2B—C1B—N1B—C4B	14.35 (16)
C2A—C1A—N1A—C11A	176.06 (14)	C2B—C1B—N1B—C11B	−167.66 (15)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C6A–C11A and C6B–C11B rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C1A—H1A1···N2B	0.99	2.68	3.338 (2)	124
C2A—H2A1···N2B	0.99	2.66	3.373 (2)	129
C3A—H3A2···N2Aⁱ	0.99	2.66	3.634 (2)	168
C3B—H3B1···N2Bⁱⁱ	0.99	2.57	3.495 (2)	156
C3A—H3A1···Cg1ⁱⁱⁱ	0.99	2.79	3.545 (2)	135
C3B—H3B2···Cg2^iv	0.99	2.67	3.523 (2)	146

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₂
M_r	182.22
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	9.1383 (3), 9.5340 (3), 12.3138 (4)
α, β, γ (°)	90.794 (2), 90.528 (2), 116.272 (2)
V (Å³)	961.78 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.50 × 0.45 × 0.30

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.963, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	7592, 3498, 2809
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.097, 1.04
No. of reflections	3498
No. of parameters	254
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.15

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C6A–C11A and C6B–C11B rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C1A—H1A1···N2B	0.99	2.68	3.338 (2)	124
C2A—H2A1···N2B	0.99	2.66	3.373 (2)	129
C3A—H3A2···N2Aⁱ	0.99	2.66	3.634 (2)	168
C3B—H3B1···N2Bⁱⁱ	0.99	2.57	3.495 (2)	156
C3A—H3A1···Cg1ⁱⁱⁱ	0.99	2.79	3.545 (2)	135
C3B—H3B2···Cg2^iv	0.99	2.67	3.523 (2)	146

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

Acknowledgements

This work was supported by the University of the Witwatersrand and the Molecular Sciences Institute, which are thanked for providing the infrastructure required to do this work. Ms C. Wilson is thanked for carrying out the preliminary synthesis.

References

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