2-Methyl-3-p-tolyl-3H-benzo[e]indole-1-carbonitrile

Li, J.-S.; He, Q.-X.; Li, P.-Y.

doi:10.1107/S1600536809052441

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o111

doi:10.1107/S1600536809052441

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2-Methyl-3-p-tolyl-3H-benzo[e]indole-1-carbonitrile

Jiang-Sheng Li,^a ^* Qi-Xi He ^b and Peng-Yu Li ^a

^aSchool of Chemistry and Biological Engineering, Changsha University of Science & Technology, Changsha 410004, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China
^*Correspondence e-mail: js_li@yahoo.com.cn

(Received 5 December 2009; accepted 6 December 2009; online 12 December 2009)

In the title compound, C₂₁H₁₆N₂, the dihedral angle between the benzoindole and tosyl ring systems is 71.99 (7)°. In the crystal, molecules are linked into centrosymmetric dimers by pairs of C—H⋯N hydrogen bonds, generating R₂²(16) loops.

Related literature

For the synthesis, see: Du et al. (2006 ).

Experimental

Crystal data

C₂₁H₁₆N₂
M_r = 296.36
Monoclinic, P 2₁ /n
a = 10.321 (2) Å
b = 12.422 (3) Å
c = 13.258 (3) Å
β = 107.14 (3)°
V = 1624.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 K
0.28 × 0.20 × 0.18 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.980, T_max = 0.987
10714 measured reflections
2858 independent reflections
2092 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.168
S = 1.04
2858 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯N2ⁱ	0.93	2.60	3.480 (3)	158
Symmetry code: (i) -x, -y+2, -z.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052441/hb5275sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052441/hb5275Isup2.hkl

checkCIF report

Comment top

The title compound, (I), comprises of a benzoindole ring and tosyl ring (Fig. 1). The dihedral angle of both rings is 71.99 (7)°.

In the crystal packing, molecules are linked into centrosymmetric dimers by C—H···N hydrogen bonds (Table 1). Weak C—H···π interactions help dimers pack. No significant π-π stacking interaction was observed.

Related literature top

For the synthesis, see: Du et al. (2006).

Experimental top

The compound was obtained according to the method of Du and his coworkers (2006). Colourless block of (I) was grown by slow evaporation of its ethanolic solution.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecule of (I) showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Centrosymmetric dimers of (I) formed by C—H···N hydrogen bonds drawn as dashed lines.

2-Methyl-3-p-tolyl-3H-benzo[e]indole-1-carbonitrile top

Crystal data top

C₂₁H₁₆N₂	F(000) = 624
M_r = 296.36	D_x = 1.212 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3474 reflections
a = 10.321 (2) Å	θ = 2.2–27.5°
b = 12.422 (3) Å	µ = 0.07 mm⁻¹
c = 13.258 (3) Å	T = 293 K
β = 107.14 (3)°	Block, colourless
V = 1624.4 (6) Å³	0.28 × 0.20 × 0.18 mm
Z = 4

Data collection top

Rigaku Saturn CCD diffractometer	2858 independent reflections
Radiation source: rotating anode	2092 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.036
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ω and ϕ scans	h = −12→11
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −13→14
T_min = 0.980, T_max = 0.987	l = −15→14
10714 measured reflections

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)] = 0.056	H-atom parameters constrained
wR(F²) = 0.168	w = 1/[σ²(F_o²) + (0.1027P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2858 reflections	Δρ_max = 0.19 e Å⁻³
210 parameters	Δρ_min = −0.16 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: 0.070 (10)

Crystal data top

C₂₁H₁₆N₂	V = 1624.4 (6) Å³
M_r = 296.36	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.321 (2) Å	µ = 0.07 mm⁻¹
b = 12.422 (3) Å	T = 293 K
c = 13.258 (3) Å	0.28 × 0.20 × 0.18 mm
β = 107.14 (3)°

Data collection top

Rigaku Saturn CCD diffractometer	2858 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2092 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.987	R_int = 0.036
10714 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 1.04	Δρ_max = 0.19 e Å⁻³
2858 reflections	Δρ_min = −0.16 e Å⁻³
210 parameters

Special details top

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 > 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	0.10089 (15)	0.87702 (12)	0.23973 (11)	0.0575 (5)
N2	−0.2675 (2)	1.06928 (18)	0.01735 (16)	0.1025 (8)
C1	0.00439 (18)	0.79674 (14)	0.23281 (13)	0.0547 (5)
C2	0.0217 (2)	0.69469 (15)	0.27979 (14)	0.0629 (5)
H2	0.1053	0.6728	0.3241	0.075*
C3	−0.0883 (2)	0.62878 (16)	0.25826 (15)	0.0679 (6)
H3	−0.0790	0.5606	0.2885	0.081*
C4	−0.2171 (2)	0.66084 (17)	0.19091 (15)	0.0631 (6)
C5	−0.3298 (2)	0.5901 (2)	0.16630 (16)	0.0806 (7)
H5	−0.3197	0.5211	0.1947	0.097*
C6	−0.4540 (2)	0.6220 (2)	0.10095 (19)	0.0900 (8)
H6	−0.5266	0.5742	0.0854	0.108*
C7	−0.4715 (2)	0.7253 (2)	0.05799 (18)	0.0860 (7)
H7	−0.5561	0.7467	0.0150	0.103*
C8	−0.3656 (2)	0.79452 (19)	0.07884 (15)	0.0692 (6)
H8	−0.3783	0.8630	0.0491	0.083*
C9	−0.23647 (19)	0.76498 (16)	0.14464 (13)	0.0580 (5)
C10	−0.12000 (19)	0.83318 (14)	0.16682 (12)	0.0542 (5)
C11	−0.0941 (2)	0.93897 (14)	0.13370 (13)	0.0589 (5)
C12	0.0402 (2)	0.96343 (15)	0.17945 (14)	0.0608 (5)
C13	0.1146 (3)	1.06418 (17)	0.17368 (17)	0.0812 (7)
H13A	0.1546	1.0918	0.2436	0.122*
H13B	0.0529	1.1164	0.1323	0.122*
H13C	0.1847	1.0496	0.1414	0.122*
C14	−0.1898 (2)	1.01126 (18)	0.06895 (15)	0.0722 (6)
C15	0.24140 (19)	0.86902 (14)	0.29878 (14)	0.0556 (5)
C16	0.3392 (2)	0.85881 (17)	0.24716 (15)	0.0670 (6)
H16	0.3146	0.8569	0.1738	0.080*
C17	0.4734 (2)	0.85143 (16)	0.30554 (17)	0.0722 (6)
H17	0.5388	0.8442	0.2704	0.087*
C18	0.5142 (2)	0.85442 (15)	0.41425 (17)	0.0670 (6)
C19	0.4147 (2)	0.86356 (17)	0.46373 (16)	0.0717 (6)
H19	0.4395	0.8647	0.5371	0.086*
C20	0.2793 (2)	0.87108 (16)	0.40767 (14)	0.0661 (6)
H20	0.2140	0.8775	0.4430	0.079*
C21	0.6620 (2)	0.8465 (2)	0.4766 (2)	0.1000 (9)
H21A	0.6952	0.7759	0.4682	0.150*
H21B	0.6720	0.8594	0.5499	0.150*
H21C	0.7128	0.8993	0.4513	0.150*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0540 (10)	0.0542 (9)	0.0598 (9)	0.0010 (7)	0.0098 (7)	0.0032 (7)
N2	0.1048 (18)	0.1026 (16)	0.0931 (13)	0.0401 (13)	0.0185 (12)	0.0307 (12)
C1	0.0532 (11)	0.0564 (11)	0.0521 (9)	0.0020 (9)	0.0115 (8)	0.0003 (8)
C2	0.0582 (12)	0.0630 (12)	0.0618 (11)	0.0065 (10)	0.0091 (9)	0.0085 (9)
C3	0.0706 (15)	0.0630 (12)	0.0686 (12)	−0.0020 (10)	0.0181 (10)	0.0123 (9)
C4	0.0561 (13)	0.0752 (14)	0.0595 (11)	−0.0083 (10)	0.0193 (9)	−0.0022 (9)
C5	0.0756 (17)	0.0909 (16)	0.0801 (13)	−0.0151 (13)	0.0306 (12)	−0.0002 (11)
C6	0.0581 (16)	0.124 (2)	0.0903 (16)	−0.0246 (14)	0.0249 (13)	−0.0114 (15)
C7	0.0544 (14)	0.123 (2)	0.0797 (14)	−0.0008 (13)	0.0185 (11)	−0.0047 (14)
C8	0.0516 (12)	0.0883 (15)	0.0654 (12)	0.0054 (11)	0.0137 (9)	−0.0024 (10)
C9	0.0517 (12)	0.0728 (13)	0.0502 (10)	0.0031 (9)	0.0162 (8)	−0.0029 (8)
C10	0.0531 (11)	0.0601 (11)	0.0475 (9)	0.0074 (9)	0.0120 (8)	−0.0010 (7)
C11	0.0616 (13)	0.0571 (11)	0.0550 (10)	0.0116 (9)	0.0128 (9)	0.0036 (8)
C12	0.0653 (13)	0.0532 (11)	0.0628 (10)	0.0061 (9)	0.0171 (9)	0.0013 (8)
C13	0.0884 (17)	0.0583 (13)	0.0960 (14)	−0.0013 (11)	0.0257 (13)	0.0075 (11)
C14	0.0755 (15)	0.0725 (14)	0.0667 (12)	0.0194 (11)	0.0181 (10)	0.0103 (10)
C15	0.0481 (11)	0.0550 (11)	0.0584 (10)	−0.0029 (8)	0.0078 (8)	−0.0001 (8)
C16	0.0665 (14)	0.0746 (13)	0.0614 (11)	0.0013 (10)	0.0213 (10)	−0.0024 (9)
C17	0.0578 (14)	0.0732 (14)	0.0902 (15)	0.0001 (10)	0.0288 (11)	−0.0033 (10)
C18	0.0535 (13)	0.0555 (12)	0.0852 (14)	−0.0010 (9)	0.0102 (11)	0.0016 (10)
C19	0.0628 (14)	0.0818 (14)	0.0627 (11)	−0.0043 (11)	0.0062 (10)	0.0005 (10)
C20	0.0564 (13)	0.0825 (14)	0.0593 (11)	−0.0021 (10)	0.0169 (9)	0.0014 (9)
C21	0.0563 (15)	0.0937 (18)	0.133 (2)	0.0003 (12)	0.0011 (14)	0.0023 (15)

Geometric parameters (Å, º) top

N1—C12	1.374 (2)	C10—C11	1.435 (3)
N1—C1	1.393 (2)	C11—C12	1.373 (3)
N1—C15	1.434 (2)	C11—C14	1.421 (3)
N2—C14	1.143 (2)	C12—C13	1.483 (3)
C1—C10	1.399 (2)	C13—H13A	0.9600
C1—C2	1.400 (2)	C13—H13B	0.9600
C2—C3	1.360 (3)	C13—H13C	0.9600
C2—H2	0.9300	C15—C20	1.380 (3)
C3—C4	1.422 (3)	C15—C16	1.382 (3)
C3—H3	0.9300	C16—C17	1.376 (3)
C4—C5	1.417 (3)	C16—H16	0.9300
C4—C9	1.420 (3)	C17—C18	1.378 (3)
C5—C6	1.377 (3)	C17—H17	0.9300
C5—H5	0.9300	C18—C19	1.376 (3)
C6—C7	1.394 (4)	C18—C21	1.509 (3)
C6—H6	0.9300	C19—C20	1.379 (3)
C7—C8	1.354 (3)	C19—H19	0.9300
C7—H7	0.9300	C20—H20	0.9300
C8—C9	1.409 (3)	C21—H21A	0.9600
C8—H8	0.9300	C21—H21B	0.9600
C9—C10	1.429 (3)	C21—H21C	0.9600

C12—N1—C1	109.04 (15)	C14—C11—C10	127.20 (19)
C12—N1—C15	125.88 (15)	C11—C12—N1	108.18 (17)
C1—N1—C15	125.07 (14)	C11—C12—C13	129.44 (18)
N1—C1—C10	108.42 (15)	N1—C12—C13	122.34 (18)
N1—C1—C2	128.59 (17)	C12—C13—H13A	109.5
C10—C1—C2	122.97 (17)	C12—C13—H13B	109.5
C3—C2—C1	117.55 (18)	H13A—C13—H13B	109.5
C3—C2—H2	121.2	C12—C13—H13C	109.5
C1—C2—H2	121.2	H13A—C13—H13C	109.5
C2—C3—C4	122.07 (18)	H13B—C13—H13C	109.5
C2—C3—H3	119.0	N2—C14—C11	179.4 (3)
C4—C3—H3	119.0	C20—C15—C16	119.78 (18)
C5—C4—C9	117.6 (2)	C20—C15—N1	119.91 (18)
C5—C4—C3	121.5 (2)	C16—C15—N1	120.31 (16)
C9—C4—C3	120.85 (18)	C17—C16—C15	119.24 (17)
C6—C5—C4	121.0 (2)	C17—C16—H16	120.4
C6—C5—H5	119.5	C15—C16—H16	120.4
C4—C5—H5	119.5	C16—C17—C18	122.2 (2)
C5—C6—C7	120.4 (2)	C16—C17—H17	118.9
C5—C6—H6	119.8	C18—C17—H17	118.9
C7—C6—H6	119.8	C19—C18—C17	117.41 (19)
C8—C7—C6	120.1 (2)	C19—C18—C21	121.3 (2)
C8—C7—H7	120.0	C17—C18—C21	121.2 (2)
C6—C7—H7	120.0	C18—C19—C20	121.91 (19)
C7—C8—C9	121.4 (2)	C18—C19—H19	119.0
C7—C8—H8	119.3	C20—C19—H19	119.0
C9—C8—H8	119.3	C19—C20—C15	119.5 (2)
C8—C9—C4	119.45 (19)	C19—C20—H20	120.3
C8—C9—C10	123.90 (19)	C15—C20—H20	120.3
C4—C9—C10	116.63 (17)	C18—C21—H21A	109.5
C1—C10—C9	119.89 (17)	C18—C21—H21B	109.4
C1—C10—C11	105.56 (17)	H21A—C21—H21B	109.5
C9—C10—C11	134.53 (16)	C18—C21—H21C	109.4
C12—C11—C14	123.93 (19)	H21A—C21—H21C	109.5
C12—C11—C10	108.80 (15)	H21B—C21—H21C	109.5

C12—N1—C1—C10	−0.03 (19)	C1—C10—C11—C12	−0.5 (2)
C15—N1—C1—C10	−178.86 (14)	C9—C10—C11—C12	−178.67 (19)
C12—N1—C1—C2	178.88 (18)	C1—C10—C11—C14	−177.42 (17)
C15—N1—C1—C2	0.0 (3)	C9—C10—C11—C14	4.4 (3)
N1—C1—C2—C3	−177.95 (18)	C14—C11—C12—N1	177.53 (16)
C10—C1—C2—C3	0.8 (3)	C10—C11—C12—N1	0.5 (2)
C1—C2—C3—C4	−0.1 (3)	C14—C11—C12—C13	0.0 (3)
C2—C3—C4—C5	177.9 (2)	C10—C11—C12—C13	−177.0 (2)
C2—C3—C4—C9	−1.2 (3)	C1—N1—C12—C11	−0.3 (2)
C9—C4—C5—C6	−0.8 (3)	C15—N1—C12—C11	178.55 (16)
C3—C4—C5—C6	−179.95 (19)	C1—N1—C12—C13	177.43 (18)
C4—C5—C6—C7	−0.4 (4)	C15—N1—C12—C13	−3.8 (3)
C5—C6—C7—C8	1.2 (4)	C12—C11—C14—N2	−129 (29)
C6—C7—C8—C9	−0.7 (3)	C10—C11—C14—N2	47 (29)
C7—C8—C9—C4	−0.6 (3)	C12—N1—C15—C20	110.1 (2)
C7—C8—C9—C10	177.95 (18)	C1—N1—C15—C20	−71.3 (2)
C5—C4—C9—C8	1.3 (3)	C12—N1—C15—C16	−70.1 (2)
C3—C4—C9—C8	−179.57 (17)	C1—N1—C15—C16	108.5 (2)
C5—C4—C9—C10	−177.31 (17)	C20—C15—C16—C17	−0.4 (3)
C3—C4—C9—C10	1.8 (3)	N1—C15—C16—C17	179.90 (17)
N1—C1—C10—C9	178.82 (15)	C15—C16—C17—C18	−0.3 (3)
C2—C1—C10—C9	−0.2 (3)	C16—C17—C18—C19	1.0 (3)
N1—C1—C10—C11	0.30 (19)	C16—C17—C18—C21	−179.8 (2)
C2—C1—C10—C11	−178.68 (16)	C17—C18—C19—C20	−0.9 (3)
C8—C9—C10—C1	−179.70 (15)	C21—C18—C19—C20	179.9 (2)
C4—C9—C10—C1	−1.1 (2)	C18—C19—C20—C15	0.3 (3)
C8—C9—C10—C11	−1.7 (3)	C16—C15—C20—C19	0.4 (3)
C4—C9—C10—C11	176.86 (18)	N1—C15—C20—C19	−179.86 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···N2ⁱ	0.93	2.60	3.480 (3)	158

Symmetry code: (i) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₆N₂
M_r	296.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	10.321 (2), 12.422 (3), 13.258 (3)
β (°)	107.14 (3)
V (Å³)	1624.4 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.28 × 0.20 × 0.18

Data collection
Diffractometer	Rigaku Saturn CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.980, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	10714, 2858, 2092
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.168, 1.04
No. of reflections	2858
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.16

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···N2ⁱ	0.93	2.60	3.480 (3)	158

Symmetry code: (i) −x, −y+2, −z.

References

Du, Y. F., Liu, R. H., Linn, G. & Zhao, K. (2006). Org. Lett. 8, 5919–5922. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 66| Part 1| January 2010| Page o111

doi:10.1107/S1600536809052441

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