N-[1-(1H-Pyrrol-2-yl)ethyl­idene]aniline

Su, B.-Y.; Li, L.; Wang, J.-X.; Li, X.-Y.

doi:10.1107/S1600536812037695

organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2888

https://doi.org/10.1107/S1600536812037695

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N-[1-(1H-Pyrrol-2-yl)ethylidene]aniline

Bi-Yun Su,^a ^* Lei Li,^a Jia-Xiang Wang ^a and Xuan-Yan Li ^a

^aCollege of Chemistry and Chemical Engineering, Xi'an ShiYou University, Xi'an, Shaanxi 710065, People's Republic of China
^*Correspondence e-mail: subiyun@xsyu.edu.cn

(Received 6 August 2012; accepted 2 September 2012; online 8 September 2012)

There are two independent molecules in the asymmetric unit of the title compound, C₁₂H₁₂N₂, in which the pyrrole and benzene rings form dihedral angles of 72.37 (7) and 82.34 (8)°. The imino N—C bond lengths in the two molecules are equal [1.286 (2) Å] and indicate C=N character. In the crystal, each molecule forms a dimer with an inversion-related molecule through a pair of classical N—H⋯N hydrogen bonds.

Related literature

For general background to the iminopyrrole unit, see: Small et al. (1998 ); Su et al. (2009a ,b ); Britovsek et al. (2003 ); Dawson et al. (2000 ). For the pyrrole diimine unit, see: Matsuo et al. (2001 ) and for the pyrrole monoimine unit, see: He et al. (2009 ).

Experimental

Crystal data

C₁₂H₁₂N₂
M_r = 184.24
Triclinic, $[P \overline 1]$
a = 8.2236 (14) Å
b = 11.3306 (19) Å
c = 11.913 (2) Å
α = 95.984 (3)°
β = 93.202 (3)°
γ = 109.274 (3)°
V = 1037.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 296 K
0.37 × 0.25 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.974, T_max = 0.987
5277 measured reflections
3655 independent reflections
2567 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.142
S = 1.10
3655 reflections
256 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.86	2.38	3.150 (2)	150
N3—H3A⋯N4ⁱⁱ	0.86	2.27	3.065 (2)	153
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker,2008); cell refinement: SAINT (Bruker,2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812037695/rk2378sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037695/rk2378Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812037695/rk2378Isup3.cml

checkCIF report

Comment top

In recent years, the bis(imino)pyridine incorporated late transition metal catalysts have received considerable attention because of their antioxidant property and outstanding activity for olefin polymerization (Small et al., 1998; Su et al., 2009a,b). As the five-memberd ring substitute of pyridine six-memberd ring (Matsuo et al., 2001; He et al., 2009), pyrrole was frequently introduced into the skeleton of bis(imino)pyridine ligand to design new ligand and corresponding metal complexes (Britovsek et al., 2003; Dawson et al., 2000). Bis(imino)pyrrole was usually prepared from Schiff base condensation of 2,5-diacetylpyrrole and the aromatic amine (Matsuo et al., 2001). As a contribution to this research field, we report herein the synthesis of mono(imino)pyrrole from 2-acetyl pyrrole and aromatic anime, as well as the crystal structure of the title compound 2-(1-phenyliminoethyl)pyrrole.

The asymmetric unit of the title compound (Fig. 1) comprises of two crystallographically independent molecules A and B. In each molecule the pyrrole ring and benzene ring are essentially perpendicular, with dihedral angles of 72.37 (7)° and 82.34 (8)° respectively. The benzene ring of molecules A are nearly parallel with the benzene ring of molecules B with dihedral angle of 14.33 (14)°, but pyrrole ring of molecules A forms a comparative large 39.42 (9)° dihedral angle with the pyrrole ring of molecules B. On the whole, bond lengths and angles in both molecules are equal in the s.u. range. The crystal packing is stabilized by N–H···N classical intermolecular hydrogen bonds (Table 1, Fig. 2).

Related literature top

For general background to the iminopyrrole unit, see: Small et al. (1998); Su et al. (2009a,b); Britovsek et al. (2003); Dawson et al. (2000). For the pyrrole diimine unit, see: Matsuo et al. (2001) and for the pyrrole monoimine unit, see: He et al. (2009).

Experimental top

The 2-acetyl pyrrole (0.1313 g, 1.20 mmol), aniline (0.1118 g, 1.20 mmol) were placed in a 50 ml flask, after a few drops of acetic acid were added in, the mixture was subjected to radiation in a 800 W microwave oven for 2 min and 3 min on a medium-heat setting. The reaction was monitored by TLC, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether/ethyl acetate, 5:1 v/v), the colourless or light yellow crystals of the title compound were at last obtained by recrystallization from ethanol (yield 0.063 g, 28.4%). M.p. 405.25-406.85 K. The purity and the composition of the compound were checked and characterized by IR spectrum, ¹H NMR spectrum, mass spectrum, as well as elemental analysis. IR (KBr): ν_C_═_N 1653 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ 7.33 (t, H, benzene ring aromatic H), 7.15 (t, 2H, benzene ring aromatic H), 7.02 (d, 2H, benzene ring aromatic H), 6.97 (t, 1H, pyrrole ring aromatic H), 6.33 (d, 1H, pyrrole ring aromatic H), 6.10 (d, 1H, pyrrole ring aromatic H), 2.03 (s, 3H, -N═C(CH₃)-). MS (EI): m/z 184 (M). Anal. Calcd for C₁₂H₁₂N₂: C, 78.23; H, 6.57; N, 15.21. Found: C, 78.50; H, 7.01; N, 14.96.

Plate like colourless single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation of the solvent at room temperature.

Structure description top

For general background to the iminopyrrole unit, see: Small et al. (1998); Su et al. (2009a,b); Britovsek et al. (2003); Dawson et al. (2000). For the pyrrole diimine unit, see: Matsuo et al. (2001) and for the pyrrole monoimine unit, see: He et al. (2009).

Computing details top

Data collection: APEX2 (Bruker,2008); cell refinement: SAINT (Bruker,2008); data reduction: SAINT (Bruker,2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Two independent molecules in the asymmetric unit of the title compound showing the atomic numbering scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

N-[1-(1H-Pyrrol-2-yl)ethylidene]aniline top

Crystal data top

C₁₂H₁₂N₂	Z = 4
M_r = 184.24	F(000) = 392
Triclinic, P1	D_x = 1.180 Mg m⁻³
Hall symbol: -P 1	Melting point = 405.25–406.85 K
a = 8.2236 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.3306 (19) Å	Cell parameters from 1351 reflections
c = 11.913 (2) Å	θ = 2.4–25.1°
α = 95.984 (3)°	µ = 0.07 mm⁻¹
β = 93.202 (3)°	T = 296 K
γ = 109.274 (3)°	Block, colourless
V = 1037.3 (3) Å³	0.37 × 0.25 × 0.19 mm

Data collection top

Bruker APEXII CCD diffractometer	3655 independent reflections
Radiation source: fine-focus sealed tube	2567 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 25.1°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
T_min = 0.974, T_max = 0.987	k = −9→13
5277 measured reflections	l = −14→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0689P)²] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
3655 reflections	Δρ_max = 0.20 e Å⁻³
256 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.043 (5)

Crystal data top

C₁₂H₁₂N₂	γ = 109.274 (3)°
M_r = 184.24	V = 1037.3 (3) Å³
Triclinic, P1	Z = 4
a = 8.2236 (14) Å	Mo Kα radiation
b = 11.3306 (19) Å	µ = 0.07 mm⁻¹
c = 11.913 (2) Å	T = 296 K
α = 95.984 (3)°	0.37 × 0.25 × 0.19 mm
β = 93.202 (3)°

Data collection top

Bruker APEXII CCD diffractometer	3655 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2567 reflections with I > 2σ(I)
T_min = 0.974, T_max = 0.987	R_int = 0.023
5277 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.10	Δρ_max = 0.20 e Å⁻³
3655 reflections	Δρ_min = −0.13 e Å⁻³
256 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
N1	0.1204 (2)	1.17200 (13)	0.61426 (13)	0.0613 (4)
H1A	0.0627	1.1263	0.5534	0.074*
N2	0.19520 (19)	0.94813 (13)	0.57233 (12)	0.0557 (4)
N3	0.38995 (19)	0.64751 (14)	−0.01282 (12)	0.0557 (4)
H3A	0.4486	0.6007	−0.0354	0.067*
N4	0.31361 (19)	0.43111 (14)	0.10218 (13)	0.0569 (4)
C1	0.1184 (3)	1.28776 (18)	0.6531 (2)	0.0780 (6)
H1	0.0539	1.3305	0.6192	0.094*
C2	0.2261 (3)	1.3311 (2)	0.7498 (2)	0.0812 (7)
H2	0.2502	1.4089	0.7935	0.097*
C3	0.2940 (3)	1.23792 (19)	0.77152 (17)	0.0699 (6)
H3	0.3710	1.2419	0.8332	0.084*
C4	0.2279 (2)	1.13853 (16)	0.68614 (15)	0.0524 (5)
C5	0.2640 (2)	1.02211 (16)	0.66444 (14)	0.0519 (5)
C6	0.3844 (3)	0.9990 (2)	0.75197 (17)	0.0783 (6)
H6A	0.3216	0.9665	0.8140	0.117*
H6B	0.4757	1.0767	0.7793	0.117*
H6C	0.4331	0.9389	0.7187	0.117*
C7	0.2301 (2)	0.83354 (16)	0.54888 (15)	0.0525 (5)
C8	0.1630 (3)	0.73360 (18)	0.60871 (18)	0.0726 (6)
H8	0.0976	0.7418	0.6684	0.087*
C9	0.1917 (3)	0.62193 (19)	0.5811 (2)	0.0814 (7)
H9	0.1457	0.5553	0.6224	0.098*
C10	0.2873 (3)	0.6075 (2)	0.4936 (2)	0.0781 (6)
H10	0.3072	0.5319	0.4756	0.094*
C11	0.3536 (3)	0.7066 (2)	0.43257 (19)	0.0772 (6)
H11	0.4184	0.6980	0.3727	0.093*
C12	0.3241 (3)	0.81884 (18)	0.46002 (17)	0.0664 (5)
H12	0.3683	0.8850	0.4179	0.080*
C13	0.4041 (3)	0.76033 (19)	−0.04693 (17)	0.0651 (5)
H13	0.4783	0.8000	−0.0982	0.078*
C14	0.2908 (3)	0.8061 (2)	0.00674 (18)	0.0698 (6)
H14	0.2736	0.8820	−0.0013	0.084*
C15	0.2060 (3)	0.71803 (18)	0.07579 (17)	0.0627 (5)
H15	0.1218	0.7249	0.1225	0.075*
C16	0.2679 (2)	0.61897 (16)	0.06320 (14)	0.0507 (4)
C17	0.2239 (2)	0.50444 (16)	0.11674 (14)	0.0503 (4)
C18	0.0726 (3)	0.47986 (18)	0.18618 (16)	0.0656 (5)
H18A	−0.0259	0.4157	0.1446	0.098*
H18B	0.0462	0.5560	0.2025	0.098*
H18C	0.1006	0.4522	0.2559	0.098*
C19	0.2680 (2)	0.31984 (17)	0.15675 (16)	0.0561 (5)
C20	0.3454 (3)	0.3213 (2)	0.26340 (17)	0.0708 (6)
H20	0.4238	0.3961	0.3014	0.085*
C21	0.3063 (3)	0.2120 (3)	0.3132 (2)	0.0850 (7)
H21	0.3581	0.2136	0.3851	0.102*
C22	0.1926 (3)	0.1014 (2)	0.2583 (2)	0.0873 (7)
H22	0.1663	0.0283	0.2927	0.105*
C23	0.1175 (3)	0.0987 (2)	0.1524 (2)	0.0869 (7)
H23	0.0404	0.0233	0.1147	0.104*
C24	0.1551 (3)	0.2071 (2)	0.10094 (19)	0.0730 (6)
H24	0.1042	0.2042	0.0285	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0669 (10)	0.0474 (9)	0.0668 (10)	0.0195 (8)	−0.0074 (8)	0.0011 (7)
N2	0.0601 (9)	0.0484 (8)	0.0593 (9)	0.0191 (7)	0.0030 (8)	0.0102 (7)
N3	0.0549 (9)	0.0621 (10)	0.0579 (9)	0.0271 (7)	0.0110 (7)	0.0155 (7)
N4	0.0530 (9)	0.0618 (9)	0.0627 (9)	0.0236 (8)	0.0156 (7)	0.0197 (7)
C1	0.0800 (15)	0.0517 (12)	0.1002 (17)	0.0274 (11)	−0.0127 (13)	−0.0059 (11)
C2	0.0714 (14)	0.0616 (13)	0.1009 (17)	0.0213 (11)	−0.0030 (13)	−0.0218 (12)
C3	0.0603 (12)	0.0749 (14)	0.0679 (13)	0.0209 (11)	−0.0028 (10)	−0.0087 (11)
C4	0.0485 (10)	0.0518 (10)	0.0555 (11)	0.0150 (8)	0.0054 (8)	0.0070 (8)
C5	0.0497 (10)	0.0543 (11)	0.0520 (10)	0.0155 (8)	0.0071 (8)	0.0141 (9)
C6	0.0889 (16)	0.0862 (15)	0.0665 (13)	0.0400 (13)	−0.0089 (12)	0.0134 (11)
C7	0.0519 (10)	0.0509 (10)	0.0556 (10)	0.0183 (8)	0.0031 (8)	0.0092 (8)
C8	0.0878 (15)	0.0604 (12)	0.0798 (14)	0.0309 (11)	0.0335 (12)	0.0210 (10)
C9	0.1039 (18)	0.0574 (13)	0.0943 (16)	0.0343 (12)	0.0340 (14)	0.0233 (11)
C10	0.0847 (16)	0.0590 (13)	0.0935 (16)	0.0301 (12)	0.0134 (13)	0.0005 (12)
C11	0.0715 (14)	0.0779 (15)	0.0800 (15)	0.0235 (12)	0.0208 (12)	−0.0006 (12)
C12	0.0682 (13)	0.0598 (12)	0.0673 (13)	0.0145 (10)	0.0140 (10)	0.0109 (10)
C13	0.0620 (12)	0.0718 (13)	0.0703 (13)	0.0282 (10)	0.0107 (10)	0.0277 (10)
C14	0.0744 (14)	0.0705 (13)	0.0780 (14)	0.0382 (11)	0.0132 (11)	0.0213 (11)
C15	0.0641 (12)	0.0711 (13)	0.0634 (12)	0.0339 (10)	0.0145 (10)	0.0142 (10)
C16	0.0457 (10)	0.0615 (11)	0.0473 (10)	0.0208 (8)	0.0051 (8)	0.0084 (8)
C17	0.0472 (10)	0.0583 (11)	0.0457 (10)	0.0188 (8)	0.0033 (8)	0.0055 (8)
C18	0.0647 (12)	0.0725 (13)	0.0672 (12)	0.0293 (10)	0.0216 (10)	0.0146 (10)
C19	0.0474 (10)	0.0639 (12)	0.0649 (12)	0.0248 (9)	0.0165 (9)	0.0176 (9)
C20	0.0742 (14)	0.0770 (14)	0.0659 (13)	0.0280 (11)	0.0095 (11)	0.0200 (11)
C21	0.0857 (17)	0.1045 (19)	0.0803 (15)	0.0435 (15)	0.0171 (13)	0.0376 (14)
C22	0.0747 (16)	0.0889 (18)	0.118 (2)	0.0381 (14)	0.0315 (15)	0.0529 (16)
C23	0.0701 (15)	0.0685 (14)	0.121 (2)	0.0177 (11)	0.0122 (14)	0.0271 (14)
C24	0.0618 (13)	0.0717 (14)	0.0846 (15)	0.0196 (11)	0.0001 (11)	0.0195 (11)

Geometric parameters (Å, º) top

N1—C1	1.350 (2)	C10—C11	1.378 (3)
N1—C4	1.365 (2)	C10—H10	0.9300
N1—H1A	0.8600	C11—C12	1.381 (3)
N2—C5	1.286 (2)	C11—H11	0.9300
N2—C7	1.423 (2)	C12—H12	0.9300
N3—C13	1.352 (2)	C13—C14	1.364 (3)
N3—C16	1.371 (2)	C13—H13	0.9300
N3—H3A	0.8600	C14—C15	1.391 (3)
N4—C17	1.286 (2)	C14—H14	0.9300
N4—C19	1.428 (2)	C15—C16	1.376 (2)
C1—C2	1.355 (3)	C15—H15	0.9300
C1—H1	0.9300	C16—C17	1.453 (2)
C2—C3	1.387 (3)	C17—C18	1.498 (2)
C2—H2	0.9300	C18—H18A	0.9600
C3—C4	1.376 (2)	C18—H18B	0.9600
C3—H3	0.9300	C18—H18C	0.9600
C4—C5	1.446 (2)	C19—C24	1.381 (3)
C5—C6	1.500 (3)	C19—C20	1.385 (3)
C6—H6A	0.9600	C20—C21	1.379 (3)
C6—H6B	0.9600	C20—H20	0.9300
C6—H6C	0.9600	C21—C22	1.363 (3)
C7—C12	1.373 (3)	C21—H21	0.9300
C7—C8	1.376 (3)	C22—C23	1.366 (3)
C8—C9	1.373 (3)	C22—H22	0.9300
C8—H8	0.9300	C23—C24	1.381 (3)
C9—C10	1.368 (3)	C23—H23	0.9300
C9—H9	0.9300	C24—H24	0.9300

C1—N1—C4	109.71 (17)	C12—C11—H11	119.9
C1—N1—H1A	125.1	C7—C12—C11	120.60 (19)
C4—N1—H1A	125.1	C7—C12—H12	119.7
C5—N2—C7	119.64 (15)	C11—C12—H12	119.7
C13—N3—C16	109.70 (15)	N3—C13—C14	108.30 (18)
C13—N3—H3A	125.2	N3—C13—H13	125.9
C16—N3—H3A	125.2	C14—C13—H13	125.9
C17—N4—C19	118.11 (15)	C13—C14—C15	107.20 (18)
N1—C1—C2	108.44 (19)	C13—C14—H14	126.4
N1—C1—H1	125.8	C15—C14—H14	126.4
C2—C1—H1	125.8	C16—C15—C14	108.33 (17)
C1—C2—C3	107.24 (18)	C16—C15—H15	125.8
C1—C2—H2	126.4	C14—C15—H15	125.8
C3—C2—H2	126.4	N3—C16—C15	106.47 (15)
C4—C3—C2	108.29 (18)	N3—C16—C17	123.18 (15)
C4—C3—H3	125.9	C15—C16—C17	130.35 (16)
C2—C3—H3	125.9	N4—C17—C16	119.49 (16)
N1—C4—C3	106.31 (16)	N4—C17—C18	124.21 (16)
N1—C4—C5	122.82 (16)	C16—C17—C18	116.31 (15)
C3—C4—C5	130.76 (18)	C17—C18—H18A	109.5
N2—C5—C4	118.71 (16)	C17—C18—H18B	109.5
N2—C5—C6	124.98 (17)	H18A—C18—H18B	109.5
C4—C5—C6	116.29 (16)	C17—C18—H18C	109.5
C5—C6—H6A	109.5	H18A—C18—H18C	109.5
C5—C6—H6B	109.5	H18B—C18—H18C	109.5
H6A—C6—H6B	109.5	C24—C19—C20	118.90 (19)
C5—C6—H6C	109.5	C24—C19—N4	120.50 (18)
H6A—C6—H6C	109.5	C20—C19—N4	120.46 (17)
H6B—C6—H6C	109.5	C21—C20—C19	120.0 (2)
C12—C7—C8	118.78 (17)	C21—C20—H20	120.0
C12—C7—N2	119.48 (16)	C19—C20—H20	120.0
C8—C7—N2	121.62 (17)	C22—C21—C20	120.7 (2)
C9—C8—C7	120.61 (19)	C22—C21—H21	119.6
C9—C8—H8	119.7	C20—C21—H21	119.6
C7—C8—H8	119.7	C23—C22—C21	119.7 (2)
C10—C9—C8	120.8 (2)	C23—C22—H22	120.2
C10—C9—H9	119.6	C21—C22—H22	120.2
C8—C9—H9	119.6	C22—C23—C24	120.5 (2)
C9—C10—C11	119.0 (2)	C22—C23—H23	119.7
C9—C10—H10	120.5	C24—C23—H23	119.7
C11—C10—H10	120.5	C19—C24—C23	120.2 (2)
C10—C11—C12	120.2 (2)	C19—C24—H24	119.9
C10—C11—H11	119.9	C23—C24—H24	119.9

C4—N1—C1—C2	0.7 (2)	C16—N3—C13—C14	−0.1 (2)
N1—C1—C2—C3	−0.9 (3)	N3—C13—C14—C15	0.2 (2)
C1—C2—C3—C4	0.8 (2)	C13—C14—C15—C16	−0.2 (2)
C1—N1—C4—C3	−0.2 (2)	C13—N3—C16—C15	−0.1 (2)
C1—N1—C4—C5	−176.80 (17)	C13—N3—C16—C17	−179.24 (16)
C2—C3—C4—N1	−0.3 (2)	C14—C15—C16—N3	0.2 (2)
C2—C3—C4—C5	175.84 (19)	C14—C15—C16—C17	179.27 (18)
C7—N2—C5—C4	179.53 (15)	C19—N4—C17—C16	179.47 (15)
C7—N2—C5—C6	1.0 (3)	C19—N4—C17—C18	−0.9 (3)
N1—C4—C5—N2	1.6 (3)	N3—C16—C17—N4	7.2 (3)
C3—C4—C5—N2	−174.05 (19)	C15—C16—C17—N4	−171.75 (18)
N1—C4—C5—C6	−179.77 (17)	N3—C16—C17—C18	−172.52 (16)
C3—C4—C5—C6	4.6 (3)	C15—C16—C17—C18	8.6 (3)
C5—N2—C7—C12	−112.9 (2)	C17—N4—C19—C24	92.6 (2)
C5—N2—C7—C8	71.2 (2)	C17—N4—C19—C20	−91.9 (2)
C12—C7—C8—C9	1.0 (3)	C24—C19—C20—C21	−1.4 (3)
N2—C7—C8—C9	176.9 (2)	N4—C19—C20—C21	−177.05 (18)
C7—C8—C9—C10	−0.1 (4)	C19—C20—C21—C22	0.4 (3)
C8—C9—C10—C11	−0.5 (4)	C20—C21—C22—C23	0.5 (4)
C9—C10—C11—C12	0.2 (3)	C21—C22—C23—C24	−0.4 (4)
C8—C7—C12—C11	−1.2 (3)	C20—C19—C24—C23	1.5 (3)
N2—C7—C12—C11	−177.28 (17)	N4—C19—C24—C23	177.15 (18)
C10—C11—C12—C7	0.6 (3)	C22—C23—C24—C19	−0.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.38	3.150 (2)	150
N3—H3A···N4ⁱⁱ	0.86	2.27	3.065 (2)	153

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂
M_r	184.24
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.2236 (14), 11.3306 (19), 11.913 (2)
α, β, γ (°)	95.984 (3), 93.202 (3), 109.274 (3)
V (Å³)	1037.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.37 × 0.25 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.974, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	5277, 3655, 2567
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.142, 1.10
No. of reflections	3655
No. of parameters	256
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.13

Computer programs: APEX2 (Bruker,2008), SAINT (Bruker,2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.38	3.150 (2)	149.6
N3—H3A···N4ⁱⁱ	0.86	2.27	3.065 (2)	153.2

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z.

Acknowledgements

This work was supported by the Natural Science Basic Research Plan in Shaanxi Province (No. 2009JQ2006), the Scientific Research Plan Project of Shaanxi Education Department (12 J K0620) and the Important Science & Technology Specific Projects of the Innovative Program of Shaanxi Province (No. 2010ZDKG-46).

References

Britovsek, G. J. P., Gibson, V. C., Hoarau, O. D., Spitzmesser, S. K., White, A. J. P. & Williams, D. J. (2003). Inorg. Chem. 42, 3454–3465. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dawson, D. M., Walker, D. A., Thornton-Pett, M. & Bochmann, M. (2000). J. Chem. Soc. Dalton Trans. pp. 459–466. Web of Science CSD CrossRef Google Scholar
He, L.-P., Liu, J.-Y., Pan, L., Wu, J.-Q., Xu, B.-C. & Li, Y.-S. (2009). J. Polym. Sci. Part A Polym. Chem. 47, 713–721. Web of Science CrossRef CAS Google Scholar
Matsuo, Y., Mashima, K. & Tani, K. (2001). Organometallics, 20, 3510–3518. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Small, B. L., Bennett, A. M. A. & Brookhart, M. (1998). J. Am. Chem. Soc. 120, 4049–4050. Web of Science CSD CrossRef CAS Google Scholar
Su, B.-Y., Zhao, J.-S., Zhang, Q.-Z. & Qin, W.-L. (2009a). Synth. Commun. 39, 4429–4440. Web of Science CrossRef CAS Google Scholar
Su, B.-Y., Zhao, J.-S., Zhang, Q.-Z. & Qin, W.-L. (2009b). Polym. Int. 58, 1051–1057. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar