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

Su, B.; Qin, W.-L.; Jiao, L.; Wang, J.-X.

doi:10.1107/S1600536812045849

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3326

doi:10.1107/S1600536812045849

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

Bi-yun Su,^a ^* Wen-Long Qin,^b Long Jiao ^a and Jia-Xiang Wang ^a

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

(Received 24 September 2012; accepted 6 November 2012; online 10 November 2012)

There are two independent molecules in the asymmetric unit of the title compound, C₁₃H₁₄N₂, in which the dihedral angles formed by the pyrrole and benzene rings are 83.63 (8) and 87.84 (8)°. In the crystal, molecules are linked via pairs of N—H⋯N hydrogen bonds, forming inversion dimers, which are further connected by C—H⋯π interactions.

Related literature

For general background to the iminopyrrole unit, see: Britovsek et al. (2003 ); Dawson et al. (2000 ); Kazushi & Hayato (2005 ). For pyrrole monoimine, see: He et al. (2009 ); Su et al. (2009a ,b ).

Experimental

Crystal data

C₁₃H₁₄N₂
M_r = 198.26
Triclinic, $[P \overline 1]$
a = 10.120 (2) Å
b = 10.400 (3) Å
c = 11.726 (3) Å
α = 79.138 (4)°
β = 67.021 (4)°
γ = 88.154 (4)°
V = 1114.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 296 K
0.38 × 0.29 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.973, T_max = 0.988
5729 measured reflections
3981 independent reflections
2530 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.149
S = 1.03
3981 reflections
276 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C7–C12 and C20–C25 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.86	2.27	3.070 (3)	154
N3—H3⋯N4ⁱⁱ	0.86	2.30	3.108 (2)	156
C1—H1A⋯Cg1ⁱⁱⁱ	0.93	2.70	3.488 (4)	143
C14—H14⋯Cg2^iv	0.93	2.75	3.531 (3)	142
Symmetry codes: (i) -x+1, -y+2, -z; (ii) -x, -y+1, -z+2; (iii) -x+1, -y, -z; (iv) -x, -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: 10.1107/S1600536812045849/lx2269sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812045849/lx2269Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812045849/lx2269Isup3.cml

checkCIF report

Comment top

Nitrogen-based ligands containing an iminopyrrole unit have recently drawn much attention because of their flexible complexation to transition metals (Kazushi & Hayato, 2005). Being the typical kind of iminopyrrole units, bis(imino)pyridine incorporated late transition metal catalysts have been investigated due to their antioxidant properties and outstanding activities for olefin polymerization. As a five-membered analogue of the pyridine ring (He et al., 2009), pyrrole has been frequently introduced into the skeleton of bis(imino)pyridine ligands to design new ligands and corresponding metal complexes (Britovsek et al., 2003; Dawson et al., 2000). As a part of our ongoing studies on mono(imino)pyrrole ligands (Su et al., 2009a,b), we report herein the crystal structure of the title compound, which crystallizes with two unique molecules, A & B, in the asymmetric unit (Fig. 1).

In the title compound, the dihedral angles formed by the pyrrole and benzene rings are 83.63 (8)° in A and 87.84 (8)° in B, respectively. The imino N–C bond lengths in the two molecules are slightly different [1.275 (3) Å for A, 1.278 (2) Å for B, respectively] and indicate C═N character. Although the two molecules in the asymmetric unit are similar, some minor differences in corresponding bond angles are evident, most notably C–N(imino)–C of 119.54 (18)° and 119.24 (17)°, for A and B, respectively. In the crystal structure, molecules are linked via pairs of N–H···N hydrogen bonds (Fig. 2 & Table 1), forming inversion dimers. These dimers are connected by C–H···π interactions (Fig. 2 & Table 1, Cg1 and Cg2 are the centroids of benzene rings in the molecule A and B, respectively).

Related literature top

For general background to the iminopyrrole unit, see: Britovsek et al. (2003); Dawson et al. (2000); Kazushi & Hayato (2005). For pyrrole monoimine, see: He et al. (2009); Su et al. (2009a,b).

Experimental top

The reagents 2-acetyl pyrrole (0.1528 g, 1.40 mmol), o-toluidine (0.3000 g, 2.80 mmol) were placed in a 50-ml flask, after a few drops of acetic acid was added in, the mixture was subjected to radiation in a 800 W microwave oven for 3 min and 2 min on a medium-heat setting. The reaction was monitored by TLC, and the crude product was purified by silica gel column chromatography (eluant: petroleum ether/ethyl acetate, 5:1 v/v), the colourless crystals of the title compound were at last obtained by recrystallization from ethanol (yield 0.1136 g, 40.91%). m.p. 396.5-398.9 K. Plate like colourless single crystals used in X-ray diffraction studies were grown in the mixture solvents of water and ethanol.

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 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. A view of N–H···N and C–H···π interactions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity. [Symmetry codes: (i) - x + 1, - y + 2, - z; (ii) - x, - y + 1, - z + 2; (iii) - x + 1, - y, - z; (iv) - x, - y + 1, - z.]

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

Crystal data top

C₁₃H₁₄N₂	Z = 4
M_r = 198.26	F(000) = 424
Triclinic, P1	D_x = 1.181 Mg m⁻³
Hall symbol: -P 1	Melting point = 396.5–398.9 K
a = 10.120 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.400 (3) Å	Cell parameters from 1216 reflections
c = 11.726 (3) Å	θ = 2.3–25.2°
α = 79.138 (4)°	µ = 0.07 mm⁻¹
β = 67.021 (4)°	T = 296 K
γ = 88.154 (4)°	Block, colourless
V = 1114.7 (5) Å³	0.38 × 0.29 × 0.17 mm

Data collection top

Bruker APEXII CCD diffractometer	3981 independent reflections
Radiation source: fine-focus sealed tube	2530 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 25.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→12
T_min = 0.973, T_max = 0.988	k = −12→12
5729 measured reflections	l = −10→14

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)] = 0.051	H-atom parameters constrained
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0703P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3981 reflections	Δρ_max = 0.19 e Å⁻³
276 parameters	Δρ_min = −0.16 e Å⁻³
2 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: 0.012 (3)

Crystal data top

C₁₃H₁₄N₂	γ = 88.154 (4)°
M_r = 198.26	V = 1114.7 (5) Å³
Triclinic, P1	Z = 4
a = 10.120 (2) Å	Mo Kα radiation
b = 10.400 (3) Å	µ = 0.07 mm⁻¹
c = 11.726 (3) Å	T = 296 K
α = 79.138 (4)°	0.38 × 0.29 × 0.17 mm
β = 67.021 (4)°

Data collection top

Bruker APEXII CCD diffractometer	3981 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2530 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.988	R_int = 0.022
5729 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	2 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.03	Δρ_max = 0.19 e Å⁻³
3981 reflections	Δρ_min = −0.16 e Å⁻³
276 parameters

Special details top

Experimental. The purity and the composition of the compound were checked and characterized by Infrared spectrum, ¹H NMR spectrum, mass spectrum, as well as elemental analysis. IR (KBr): ν_C_═_N 1645 cm^-1. ¹H NMR (400MHz, CDCl₃): δ 7.36 (d, 1H, benzene ring aromatic H), 7.15 (t, 2H, benzene ring aromatic H), 7.88 (t, 1H, benzene ring aromatic H), 6.90 (d, 1H,pyrrole ring aromatic H), 6.71 (t, 1H, pyrrole ring aromatic H), 6.34 (d, 1H,pyrrole ring aromatic H), 2.48 (s, 3H, phenyl-CH₃), 2.25 (s, 3H,-N═C(CH₃)-). MS (EI): m/z 197 (M⁺). Anal. Calcd. for C₁₃H₁₄N₂: C, 78.75; H, 7.12; N, 14.13. Found: C, 78.22; H, 6.95; N,14.68.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > 2sigma(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	0.37284 (18)	0.91215 (17)	0.19040 (14)	0.0510 (5)
H1	0.4426	0.9579	0.1289	0.061*
N2	0.34013 (18)	0.93166 (17)	−0.03844 (14)	0.0507 (5)
N3	0.14266 (18)	0.49423 (17)	0.80750 (14)	0.0541 (5)
H3	0.0662	0.5111	0.8678	0.065*
N4	0.16015 (18)	0.41253 (17)	1.04284 (14)	0.0498 (5)
C1	0.3590 (3)	0.8857 (2)	0.31132 (18)	0.0626 (6)
H1A	0.4226	0.9137	0.3422	0.075*
C2	0.2371 (3)	0.8118 (3)	0.3801 (2)	0.0689 (7)
H2	0.2016	0.7798	0.4666	0.083*
C3	0.1742 (3)	0.7922 (2)	0.2987 (2)	0.0633 (6)
H3A	0.0888	0.7445	0.3208	0.076*
C4	0.2595 (2)	0.8553 (2)	0.18026 (17)	0.0473 (5)
C5	0.2429 (2)	0.8691 (2)	0.06202 (19)	0.0491 (5)
C6	0.1083 (2)	0.8091 (3)	0.0660 (2)	0.0724 (7)
H6A	0.0392	0.8752	0.0691	0.109*
H6B	0.0696	0.7412	0.1396	0.109*
H6C	0.1299	0.7724	−0.0082	0.109*
C7	0.3199 (2)	0.95209 (18)	−0.15330 (18)	0.0502 (5)
C8	0.3676 (2)	0.8647 (2)	−0.2347 (2)	0.0562 (6)
C9	0.3553 (3)	0.8960 (3)	−0.3496 (2)	0.0681 (7)
H9	0.3870	0.8379	−0.4052	0.082*
C10	0.2981 (3)	1.0095 (3)	−0.3841 (2)	0.0753 (8)
H10	0.2898	1.0276	−0.4617	0.090*
C11	0.2530 (3)	1.0965 (3)	−0.3044 (2)	0.0712 (7)
H11	0.2154	1.1749	−0.3284	0.085*
C12	0.2627 (2)	1.06875 (19)	−0.18953 (19)	0.0589 (6)
H12	0.2311	1.1280	−0.1352	0.071*
C13	0.4357 (3)	0.7415 (3)	−0.2007 (2)	0.0795 (8)
H13A	0.4550	0.6895	−0.2645	0.119*
H13B	0.3716	0.6927	−0.1209	0.119*
H13C	0.5240	0.7633	−0.1949	0.119*
C14	0.1659 (3)	0.5221 (3)	0.68454 (19)	0.0672 (7)
H14	0.1023	0.5622	0.6508	0.081*
C15	0.2975 (3)	0.4818 (3)	0.6179 (2)	0.0707 (7)
H15	0.3410	0.4898	0.5307	0.085*
C16	0.3551 (2)	0.4261 (2)	0.70452 (19)	0.0630 (6)
H16	0.4442	0.3890	0.6856	0.076*
C17	0.2584 (2)	0.4353 (2)	0.82227 (17)	0.0462 (5)
C18	0.2667 (2)	0.3960 (2)	0.94336 (19)	0.0475 (5)
C19	0.4037 (2)	0.3381 (3)	0.9440 (2)	0.0737 (8)
H19A	0.4699	0.4068	0.9358	0.111*
H19B	0.4450	0.2930	0.8747	0.111*
H19C	0.3843	0.2775	1.0219	0.111*
C20	0.1708 (2)	0.37695 (19)	1.16170 (18)	0.0489 (5)
C21	0.1223 (2)	0.2549 (2)	1.23561 (19)	0.0544 (6)
C22	0.1255 (3)	0.2295 (3)	1.3541 (2)	0.0698 (7)
H22	0.0941	0.1472	1.4047	0.084*
C23	0.1739 (3)	0.3221 (3)	1.3993 (2)	0.0791 (8)
H23	0.1750	0.3026	1.4796	0.095*
C24	0.2206 (3)	0.4433 (3)	1.3258 (2)	0.0766 (8)
H24	0.2528	0.5068	1.3564	0.092*
C25	0.2199 (2)	0.4712 (2)	1.2078 (2)	0.0611 (6)
H25	0.2524	0.5535	1.1577	0.073*
C26	0.0651 (3)	0.1542 (3)	1.1890 (2)	0.0790 (8)
H26A	−0.0239	0.1815	1.1831	0.119*
H26B	0.0491	0.0719	1.2467	0.119*
H26C	0.1333	0.1444	1.1073	0.119*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0470 (10)	0.0660 (12)	0.0362 (9)	−0.0026 (9)	−0.0132 (8)	−0.0066 (8)
N2	0.0493 (11)	0.0624 (12)	0.0430 (9)	−0.0007 (9)	−0.0207 (8)	−0.0098 (8)
N3	0.0512 (11)	0.0680 (12)	0.0406 (9)	0.0081 (9)	−0.0185 (8)	−0.0047 (8)
N4	0.0497 (11)	0.0586 (11)	0.0420 (9)	0.0077 (8)	−0.0210 (8)	−0.0060 (8)
C1	0.0668 (16)	0.0836 (18)	0.0405 (12)	−0.0020 (13)	−0.0240 (11)	−0.0119 (11)
C2	0.0707 (17)	0.0882 (19)	0.0382 (12)	−0.0102 (14)	−0.0159 (12)	0.0010 (12)
C3	0.0568 (14)	0.0754 (17)	0.0507 (13)	−0.0094 (12)	−0.0173 (11)	−0.0019 (11)
C4	0.0446 (12)	0.0539 (13)	0.0447 (11)	0.0020 (10)	−0.0188 (10)	−0.0092 (10)
C5	0.0465 (12)	0.0529 (13)	0.0485 (12)	0.0058 (10)	−0.0204 (10)	−0.0081 (10)
C6	0.0546 (15)	0.099 (2)	0.0655 (15)	−0.0131 (13)	−0.0301 (12)	−0.0033 (14)
C7	0.0441 (12)	0.0617 (14)	0.0469 (11)	−0.0025 (10)	−0.0198 (10)	−0.0101 (10)
C8	0.0521 (13)	0.0617 (15)	0.0578 (13)	−0.0028 (11)	−0.0231 (11)	−0.0140 (11)
C9	0.0709 (16)	0.089 (2)	0.0518 (13)	0.0025 (14)	−0.0272 (12)	−0.0235 (13)
C10	0.0771 (18)	0.106 (2)	0.0484 (13)	0.0019 (16)	−0.0318 (13)	−0.0121 (14)
C11	0.0731 (17)	0.0820 (18)	0.0615 (14)	0.0102 (14)	−0.0348 (13)	−0.0030 (13)
C12	0.0620 (15)	0.0655 (16)	0.0542 (13)	0.0093 (12)	−0.0272 (11)	−0.0147 (11)
C13	0.093 (2)	0.0716 (18)	0.0840 (17)	0.0206 (15)	−0.0420 (15)	−0.0266 (14)
C14	0.0681 (16)	0.0907 (19)	0.0418 (12)	0.0079 (14)	−0.0256 (11)	−0.0023 (12)
C15	0.0711 (17)	0.096 (2)	0.0401 (12)	0.0057 (14)	−0.0187 (12)	−0.0096 (12)
C16	0.0558 (14)	0.0799 (17)	0.0514 (13)	0.0084 (12)	−0.0185 (11)	−0.0143 (12)
C17	0.0457 (12)	0.0503 (13)	0.0423 (11)	0.0044 (10)	−0.0181 (9)	−0.0068 (9)
C18	0.0471 (12)	0.0495 (13)	0.0497 (12)	0.0050 (10)	−0.0232 (10)	−0.0097 (10)
C19	0.0567 (15)	0.106 (2)	0.0635 (14)	0.0267 (14)	−0.0295 (12)	−0.0191 (14)
C20	0.0426 (12)	0.0603 (14)	0.0442 (11)	0.0097 (10)	−0.0195 (9)	−0.0069 (10)
C21	0.0506 (13)	0.0588 (15)	0.0515 (13)	0.0090 (11)	−0.0210 (10)	−0.0041 (11)
C22	0.0703 (17)	0.0769 (18)	0.0546 (14)	0.0055 (14)	−0.0248 (12)	0.0057 (13)
C23	0.0847 (19)	0.106 (2)	0.0515 (14)	0.0099 (17)	−0.0372 (14)	−0.0048 (15)
C24	0.090 (2)	0.089 (2)	0.0695 (16)	0.0069 (16)	−0.0487 (15)	−0.0221 (15)
C25	0.0683 (16)	0.0643 (16)	0.0566 (13)	0.0023 (12)	−0.0324 (12)	−0.0078 (11)
C26	0.092 (2)	0.0623 (17)	0.0823 (17)	−0.0068 (14)	−0.0358 (15)	−0.0085 (13)

Geometric parameters (Å, º) top

N1—C1	1.344 (2)	C11—H11	0.9300
N1—C4	1.362 (3)	C12—H12	0.9300
N1—H1	0.8600	C13—H13A	0.9600
N2—C5	1.275 (3)	C13—H13B	0.9600
N2—C7	1.416 (2)	C13—H13C	0.9600
N3—C14	1.342 (2)	C14—C15	1.355 (3)
N3—C17	1.360 (2)	C14—H14	0.9300
N3—H3	0.8600	C15—C16	1.388 (3)
N4—C18	1.278 (2)	C15—H15	0.9300
N4—C20	1.418 (2)	C16—C17	1.364 (3)
C1—C2	1.347 (3)	C16—H16	0.9300
C1—H1A	0.9300	C17—C18	1.436 (3)
C2—C3	1.383 (3)	C18—C19	1.496 (3)
C2—H2	0.9300	C19—H19A	0.9600
C3—C4	1.364 (3)	C19—H19B	0.9600
C3—H3A	0.9300	C19—H19C	0.9600
C4—C5	1.441 (3)	C20—C21	1.377 (3)
C5—C6	1.497 (3)	C20—C25	1.3927 (10)
C6—H6A	0.9600	C21—C22	1.378 (3)
C6—H6B	0.9600	C21—C26	1.494 (3)
C6—H6C	0.9600	C22—C23	1.369 (4)
C7—C8	1.382 (3)	C22—H22	0.9300
C7—C12	1.3925 (10)	C23—C24	1.366 (4)
C8—C9	1.378 (3)	C23—H23	0.9300
C8—C13	1.497 (3)	C24—C25	1.362 (3)
C9—C10	1.360 (3)	C24—H24	0.9300
C9—H9	0.9300	C25—H25	0.9300
C10—C11	1.364 (3)	C26—H26A	0.9600
C10—H10	0.9300	C26—H26B	0.9600
C11—C12	1.366 (3)	C26—H26C	0.9600

C1—N1—C4	109.55 (18)	H13A—C13—H13B	109.5
C1—N1—H1	125.2	C8—C13—H13C	109.5
C4—N1—H1	125.2	H13A—C13—H13C	109.5
C5—N2—C7	119.54 (18)	H13B—C13—H13C	109.5
C14—N3—C17	109.63 (17)	N3—C14—C15	108.52 (19)
C14—N3—H3	125.2	N3—C14—H14	125.7
C17—N3—H3	125.2	C15—C14—H14	125.7
C18—N4—C20	119.24 (17)	C14—C15—C16	106.91 (19)
N1—C1—C2	108.3 (2)	C14—C15—H15	126.5
N1—C1—H1A	125.9	C16—C15—H15	126.5
C2—C1—H1A	125.9	C17—C16—C15	108.2 (2)
C1—C2—C3	107.55 (19)	C17—C16—H16	125.9
C1—C2—H2	126.2	C15—C16—H16	125.9
C3—C2—H2	126.2	N3—C17—C16	106.70 (17)
C4—C3—C2	108.0 (2)	N3—C17—C18	122.69 (17)
C4—C3—H3A	126.0	C16—C17—C18	130.61 (19)
C2—C3—H3A	126.0	N4—C18—C17	119.61 (18)
N1—C4—C3	106.62 (18)	N4—C18—C19	123.84 (18)
N1—C4—C5	122.36 (18)	C17—C18—C19	116.54 (18)
C3—C4—C5	131.0 (2)	C18—C19—H19A	109.5
N2—C5—C4	119.52 (19)	C18—C19—H19B	109.5
N2—C5—C6	123.74 (18)	H19A—C19—H19B	109.5
C4—C5—C6	116.74 (19)	C18—C19—H19C	109.5
C5—C6—H6A	109.5	H19A—C19—H19C	109.5
C5—C6—H6B	109.5	H19B—C19—H19C	109.5
H6A—C6—H6B	109.5	C21—C20—C25	120.03 (19)
C5—C6—H6C	109.5	C21—C20—N4	120.84 (17)
H6A—C6—H6C	109.5	C25—C20—N4	118.90 (19)
H6B—C6—H6C	109.5	C20—C21—C22	118.1 (2)
C8—C7—C12	119.60 (18)	C20—C21—C26	120.66 (19)
C8—C7—N2	121.35 (16)	C22—C21—C26	121.2 (2)
C12—C7—N2	118.78 (17)	C23—C22—C21	121.8 (2)
C9—C8—C7	118.4 (2)	C23—C22—H22	119.1
C9—C8—C13	120.9 (2)	C21—C22—H22	119.1
C7—C8—C13	120.72 (19)	C24—C23—C22	119.7 (2)
C10—C9—C8	121.8 (2)	C24—C23—H23	120.1
C10—C9—H9	119.1	C22—C23—H23	120.1
C8—C9—H9	119.1	C25—C24—C23	120.0 (2)
C9—C10—C11	119.8 (2)	C25—C24—H24	120.0
C9—C10—H10	120.1	C23—C24—H24	120.0
C11—C10—H10	120.1	C24—C25—C20	120.4 (2)
C10—C11—C12	120.1 (2)	C24—C25—H25	119.8
C10—C11—H11	119.9	C20—C25—H25	119.8
C12—C11—H11	119.9	C21—C26—H26A	109.5
C11—C12—C7	120.3 (2)	C21—C26—H26B	109.5
C11—C12—H12	119.8	H26A—C26—H26B	109.5
C7—C12—H12	119.8	C21—C26—H26C	109.5
C8—C13—H13A	109.5	H26A—C26—H26C	109.5
C8—C13—H13B	109.5	H26B—C26—H26C	109.5

C4—N1—C1—C2	0.0 (3)	C17—N3—C14—C15	−0.2 (3)
N1—C1—C2—C3	0.0 (3)	N3—C14—C15—C16	0.7 (3)
C1—C2—C3—C4	−0.1 (3)	C14—C15—C16—C17	−0.9 (3)
C1—N1—C4—C3	−0.1 (2)	C14—N3—C17—C16	−0.4 (3)
C1—N1—C4—C5	178.53 (18)	C14—N3—C17—C18	178.8 (2)
C2—C3—C4—N1	0.1 (3)	C15—C16—C17—N3	0.8 (3)
C2—C3—C4—C5	−178.4 (2)	C15—C16—C17—C18	−178.3 (2)
C7—N2—C5—C4	−176.19 (16)	C20—N4—C18—C17	−178.17 (18)
C7—N2—C5—C6	2.9 (3)	C20—N4—C18—C19	1.2 (3)
N1—C4—C5—N2	3.2 (3)	N3—C17—C18—N4	2.2 (3)
C3—C4—C5—N2	−178.6 (2)	C16—C17—C18—N4	−178.8 (2)
N1—C4—C5—C6	−176.01 (19)	N3—C17—C18—C19	−177.2 (2)
C3—C4—C5—C6	2.3 (3)	C16—C17—C18—C19	1.8 (4)
C5—N2—C7—C8	−91.5 (2)	C18—N4—C20—C21	−93.6 (2)
C5—N2—C7—C12	94.5 (3)	C18—N4—C20—C25	91.8 (2)
C12—C7—C8—C9	−0.7 (3)	C25—C20—C21—C22	−0.7 (3)
N2—C7—C8—C9	−174.6 (2)	N4—C20—C21—C22	−175.18 (18)
C12—C7—C8—C13	177.2 (2)	C25—C20—C21—C26	178.1 (2)
N2—C7—C8—C13	3.2 (3)	N4—C20—C21—C26	3.6 (3)
C7—C8—C9—C10	0.0 (4)	C20—C21—C22—C23	0.7 (3)
C13—C8—C9—C10	−177.8 (3)	C26—C21—C22—C23	−178.1 (2)
C8—C9—C10—C11	0.9 (4)	C21—C22—C23—C24	−0.1 (4)
C9—C10—C11—C12	−1.2 (4)	C22—C23—C24—C25	−0.5 (4)
C10—C11—C12—C7	0.5 (4)	C23—C24—C25—C20	0.5 (4)
C8—C7—C12—C11	0.4 (3)	C21—C20—C25—C24	0.1 (3)
N2—C7—C12—C11	174.5 (2)	N4—C20—C25—C24	174.74 (19)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C7–C12 and C20–C25 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.86	2.27	3.070 (3)	154
N3—H3···N4ⁱⁱ	0.86	2.30	3.108 (2)	156
C1—H1A···Cg1ⁱⁱⁱ	0.93	2.70	3.488 (4)	143
C14—H14···Cg2^iv	0.93	2.75	3.531 (3)	142

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂
M_r	198.26
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	10.120 (2), 10.400 (3), 11.726 (3)
α, β, γ (°)	79.138 (4), 67.021 (4), 88.154 (4)
V (Å³)	1114.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.38 × 0.29 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.973, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	5729, 3981, 2530
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.149, 1.03
No. of reflections	3981
No. of parameters	276
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.16

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

Cg1 and Cg2 are the centroids of the C7–C12 and C20–C25 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.86	2.27	3.070 (3)	154.3
N3—H3···N4ⁱⁱ	0.86	2.30	3.108 (2)	156.2
C1—H1A···Cg1ⁱⁱⁱ	0.93	2.70	3.488 (4)	143.0
C14—H14···Cg2^iv	0.93	2.75	3.531 (3)	142.0

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

Acknowledgements

This work was supported by the Natural Science Basic Research Plan in Shaanxi Province (Nos. 2009JQ2006 and 2010JQ2003) and the Scientific Research Plan Project of Shaanxi Education Department (Nos. 12 J K0620 and 2010 J K784).

References

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