1-(4-Bromo­phen­yl)-2-methyl-1H-indole-3-carbonitrile

Yan, Q.; Qi, X.

doi:10.1107/S1600536811034246

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2509

doi:10.1107/S1600536811034246

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1-(4-Bromophenyl)-2-methyl-1H-indole-3-carbonitrile

Qiao Yan ^a and Xiuxiang Qi ^a ^*

^aSchool of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, People's Republic of China
^*Correspondence e-mail: qxx@zzu.edu.cn

(Received 17 August 2011; accepted 20 August 2011; online 27 August 2011)

In the title compound, C₁₆H₁₁BrN₂, the dihedral angle between the indole ring system and the phenyl ring is 58.85 (11)°.

Related literature

For the synthesis of the title compound, see: Du et al. (2006 ). For its precursor, see: Jin et al. (2009 ). For related structures, see: Yang et al. (2011 ); Yan & Qi (2011 ).

Experimental

Crystal data

C₁₆H₁₁BrN₂
M_r = 311.18
Monoclinic, P 2₁ /n
a = 9.170 (7) Å
b = 8.849 (6) Å
c = 16.337 (12) Å
β = 94.415 (15)°
V = 1321.7 (16) Å³
Z = 4
Mo Kα radiation
μ = 3.10 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.14 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009 ) T_min = 0.576, T_max = 0.671
12992 measured reflections
3147 independent reflections
2309 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.106
S = 1.00
3147 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.90 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2009); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811034246/hb6373sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034246/hb6373Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811034246/hb6373Isup3.cml

checkCIF report

Comment top

In our continuing investigation of indole derivatives, herein, we reported the title compound (I). In the molecular structure,(Fig. 1), the indole ring is essentially planar with a dihedral angle of 0.95 (16)% between its pyrrole ring and fused benzene ring, similar to that [0.85 (6)°] of the 1-(2-chlorophenyl)- 6-fluoro-2-methyl-1H-indole-3-carbonitrile (Yang et al., 2011), but less than that [2.66 (6)°] of our previously reported 1-(4-methoxyphenyl)-2-methyl-1H-indole-3-carbonitrile (Yan & Qi, 2011).

The indole ring constructs an angle of 58.85 (11) ° with the bromobenzene ring, similar to that [58.41 (4)°] reported by our group (Yan & Qi, 2011), but less than that [80.91 (5)°] reported by Yang et al. (2011). All the difference might be attributed to the steric substituent on the N-phenyl motif.

In the crystal packing, no significant π-π stacking interaction and C—H···π interaction were detected, unlike those reported in its anolog 1-(4-methoxyphenyl) -2-methyl-1H-indole-3-carbonitrile.

Related literature top

For the synthesis of the title compound, see: Du et al. (2006). For its precursor, see: Jin et al. (2009). For related structures, see: Yang et al. (2011); Yan & Qi (2011).

Experimental top

The title compound was prepared according to the method of the literature (Du, et al., 2006). Colourless prisms of (I) were grown from a mixture of ethyl actate and petroleum ether.

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell refinement: CrystalClear-SM Expert (Rigaku, 2009); data reduction: CrystalClear-SM Expert (Rigaku, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2009); software used to prepare material for publication: CrystalStructure (Rigaku, 2009).

Figures top

Fig. 1. The molecular structure of (I) with 50% probability displacement ellipsoids.

1-(4-Bromophenyl)-2-methyl-1H-indole-3-carbonitrile top

Crystal data top

C₁₆H₁₁BrN₂	F(000) = 624
M_r = 311.18	D_x = 1.564 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4781 reflections
a = 9.170 (7) Å	θ = 2.2–27.9°
b = 8.849 (6) Å	µ = 3.10 mm⁻¹
c = 16.337 (12) Å	T = 113 K
β = 94.415 (15)°	Prism, colorless
V = 1321.7 (16) Å³	0.20 × 0.18 × 0.14 mm
Z = 4

Data collection top

Rigaku Saturn724 CCD diffractometer	3147 independent reflections
Radiation source: rotating anode	2309 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.052
Detector resolution: 14.22 pixels mm^-1	θ_max = 27.9°, θ_min = 2.5°
ω and ϕ scans	h = −12→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	k = −11→11
T_min = 0.576, T_max = 0.671	l = −21→21
12992 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0495P)²] where P = (F_o² + 2F_c²)/3
3147 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.90 e Å⁻³
0 restraints	Δρ_min = −0.73 e Å⁻³

Crystal data top

C₁₆H₁₁BrN₂	V = 1321.7 (16) Å³
M_r = 311.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.170 (7) Å	µ = 3.10 mm⁻¹
b = 8.849 (6) Å	T = 113 K
c = 16.337 (12) Å	0.20 × 0.18 × 0.14 mm
β = 94.415 (15)°

Data collection top

Rigaku Saturn724 CCD diffractometer	3147 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	2309 reflections with I > 2σ(I)
T_min = 0.576, T_max = 0.671	R_int = 0.052
12992 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.00	Δρ_max = 0.90 e Å⁻³
3147 reflections	Δρ_min = −0.73 e Å⁻³
173 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
Br1	1.31610 (4)	0.01069 (4)	0.08227 (2)	0.03260 (14)
N1	0.8376 (3)	0.4726 (3)	0.12974 (16)	0.0204 (6)
N2	0.3390 (3)	0.6165 (3)	0.11113 (18)	0.0341 (7)
C1	1.1681 (3)	0.1574 (3)	0.0968 (2)	0.0229 (7)
C2	1.1611 (4)	0.2252 (3)	0.1735 (2)	0.0248 (7)
H2	1.2302	0.2002	0.2178	0.030*
C3	1.0509 (4)	0.3301 (3)	0.18380 (19)	0.0243 (7)
H3	1.0444	0.3783	0.2354	0.029*
C4	0.9508 (3)	0.3642 (3)	0.11868 (19)	0.0205 (6)
C5	0.9610 (3)	0.2969 (3)	0.04233 (19)	0.0215 (7)
H5	0.8934	0.3230	−0.0024	0.026*
C6	1.0702 (3)	0.1913 (3)	0.0317 (2)	0.0236 (7)
H6	1.0770	0.1434	−0.0199	0.028*
C7	0.8620 (3)	0.6253 (3)	0.15065 (18)	0.0198 (6)
C8	0.9938 (3)	0.6992 (3)	0.17217 (18)	0.0225 (7)
H8	1.0846	0.6470	0.1749	0.027*
C9	0.9861 (4)	0.8520 (3)	0.18934 (19)	0.0250 (7)
H9	1.0732	0.9057	0.2058	0.030*
C10	0.8526 (4)	0.9285 (4)	0.18296 (19)	0.0264 (7)
H10	0.8513	1.0340	0.1938	0.032*
C11	0.7227 (4)	0.8555 (3)	0.16141 (18)	0.0236 (7)
H11	0.6327	0.9093	0.1574	0.028*
C12	0.7265 (3)	0.6991 (3)	0.14552 (18)	0.0206 (7)
C13	0.6191 (3)	0.5860 (3)	0.12233 (18)	0.0219 (7)
C14	0.6892 (3)	0.4497 (3)	0.11365 (19)	0.0218 (7)
C15	0.6229 (4)	0.2960 (3)	0.0985 (2)	0.0283 (8)
H15A	0.6327	0.2370	0.1494	0.042*
H15B	0.6736	0.2440	0.0560	0.042*
H15C	0.5190	0.3068	0.0803	0.042*
C16	0.4642 (4)	0.6019 (3)	0.11543 (19)	0.0245 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02374 (19)	0.0305 (2)	0.0430 (2)	0.01071 (15)	−0.00149 (15)	−0.00554 (15)
N1	0.0142 (12)	0.0235 (14)	0.0236 (14)	0.0045 (10)	0.0013 (11)	−0.0011 (10)
N2	0.0214 (16)	0.0380 (17)	0.0430 (18)	0.0044 (13)	0.0025 (14)	−0.0032 (13)
C1	0.0152 (15)	0.0197 (15)	0.0338 (18)	0.0052 (13)	0.0009 (13)	−0.0005 (13)
C2	0.0201 (16)	0.0257 (17)	0.0273 (17)	0.0019 (14)	−0.0059 (14)	0.0001 (13)
C3	0.0238 (17)	0.0261 (16)	0.0229 (17)	0.0023 (14)	0.0007 (14)	−0.0023 (12)
C4	0.0144 (15)	0.0214 (16)	0.0260 (16)	0.0040 (12)	0.0029 (13)	0.0004 (12)
C5	0.0185 (16)	0.0249 (16)	0.0211 (16)	0.0032 (13)	0.0018 (13)	−0.0012 (12)
C6	0.0219 (17)	0.0252 (16)	0.0238 (17)	0.0020 (13)	0.0017 (14)	−0.0027 (12)
C7	0.0184 (16)	0.0219 (16)	0.0194 (15)	0.0016 (13)	0.0031 (13)	−0.0001 (12)
C8	0.0164 (16)	0.0262 (17)	0.0249 (17)	0.0029 (13)	0.0021 (13)	0.0000 (12)
C9	0.0222 (18)	0.0271 (17)	0.0254 (17)	−0.0042 (14)	0.0004 (14)	0.0013 (13)
C10	0.0339 (19)	0.0220 (16)	0.0236 (17)	0.0031 (15)	0.0045 (15)	−0.0014 (12)
C11	0.0215 (17)	0.0245 (17)	0.0254 (17)	0.0059 (13)	0.0059 (14)	0.0000 (12)
C12	0.0190 (16)	0.0221 (16)	0.0211 (16)	0.0035 (13)	0.0039 (13)	0.0011 (12)
C13	0.0165 (15)	0.0259 (16)	0.0237 (16)	0.0034 (13)	0.0044 (13)	0.0022 (12)
C14	0.0180 (16)	0.0261 (16)	0.0216 (16)	−0.0003 (13)	0.0024 (13)	−0.0003 (12)
C15	0.0212 (17)	0.0278 (18)	0.036 (2)	0.0005 (14)	0.0003 (15)	−0.0058 (14)
C16	0.0201 (17)	0.0251 (17)	0.0283 (17)	0.0010 (14)	0.0019 (14)	−0.0014 (13)

Geometric parameters (Å, º) top

Br1—C1	1.906 (3)	C7—C12	1.401 (4)
N1—C14	1.381 (4)	C8—C9	1.384 (4)
N1—C7	1.408 (4)	C8—H8	0.9500
N1—C4	1.435 (4)	C9—C10	1.396 (4)
N2—C16	1.152 (4)	C9—H9	0.9500
C1—C6	1.371 (4)	C10—C11	1.377 (4)
C1—C2	1.396 (4)	C10—H10	0.9500
C2—C3	1.393 (4)	C11—C12	1.410 (4)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.384 (4)	C12—C13	1.434 (4)
C3—H3	0.9500	C13—C14	1.379 (4)
C4—C5	1.392 (4)	C13—C16	1.423 (4)
C5—C6	1.391 (4)	C14—C15	1.503 (4)
C5—H5	0.9500	C15—H15A	0.9800
C6—H6	0.9500	C15—H15B	0.9800
C7—C8	1.395 (4)	C15—H15C	0.9800

C14—N1—C7	108.8 (2)	C7—C8—H8	121.6
C14—N1—C4	126.1 (3)	C8—C9—C10	121.1 (3)
C7—N1—C4	124.7 (3)	C8—C9—H9	119.4
C6—C1—C2	122.1 (3)	C10—C9—H9	119.4
C6—C1—Br1	118.8 (2)	C11—C10—C9	121.9 (3)
C2—C1—Br1	119.1 (2)	C11—C10—H10	119.1
C3—C2—C1	118.6 (3)	C9—C10—H10	119.1
C3—C2—H2	120.7	C10—C11—C12	118.3 (3)
C1—C2—H2	120.7	C10—C11—H11	120.8
C4—C3—C2	119.8 (3)	C12—C11—H11	120.8
C4—C3—H3	120.1	C7—C12—C11	118.7 (3)
C2—C3—H3	120.1	C7—C12—C13	106.2 (3)
C3—C4—C5	120.6 (3)	C11—C12—C13	135.1 (3)
C3—C4—N1	119.5 (3)	C14—C13—C16	123.2 (3)
C5—C4—N1	119.9 (3)	C14—C13—C12	108.8 (3)
C6—C5—C4	119.9 (3)	C16—C13—C12	127.8 (3)
C6—C5—H5	120.0	C13—C14—N1	108.2 (3)
C4—C5—H5	120.0	C13—C14—C15	128.5 (3)
C1—C6—C5	119.0 (3)	N1—C14—C15	123.0 (3)
C1—C6—H6	120.5	C14—C15—H15A	109.5
C5—C6—H6	120.5	C14—C15—H15B	109.5
C8—C7—C12	123.0 (3)	H15A—C15—H15B	109.5
C8—C7—N1	129.0 (3)	C14—C15—H15C	109.5
C12—C7—N1	108.0 (3)	H15A—C15—H15C	109.5
C9—C8—C7	116.9 (3)	H15B—C15—H15C	109.5
C9—C8—H8	121.6	N2—C16—C13	178.7 (4)

C6—C1—C2—C3	0.1 (5)	C9—C10—C11—C12	0.0 (5)
Br1—C1—C2—C3	−178.9 (2)	C8—C7—C12—C11	1.1 (5)
C1—C2—C3—C4	0.4 (5)	N1—C7—C12—C11	−178.1 (3)
C2—C3—C4—C5	−1.4 (5)	C8—C7—C12—C13	−179.8 (3)
C2—C3—C4—N1	−179.9 (3)	N1—C7—C12—C13	1.0 (3)
C14—N1—C4—C3	−125.7 (3)	C10—C11—C12—C7	−1.3 (4)
C7—N1—C4—C3	61.5 (4)	C10—C11—C12—C13	179.9 (3)
C14—N1—C4—C5	55.8 (4)	C7—C12—C13—C14	−0.3 (3)
C7—N1—C4—C5	−117.1 (3)	C11—C12—C13—C14	178.6 (3)
C3—C4—C5—C6	1.7 (5)	C7—C12—C13—C16	174.7 (3)
N1—C4—C5—C6	−179.7 (3)	C11—C12—C13—C16	−6.4 (6)
C2—C1—C6—C5	0.2 (5)	C16—C13—C14—N1	−175.8 (3)
Br1—C1—C6—C5	179.2 (2)	C12—C13—C14—N1	−0.6 (3)
C4—C5—C6—C1	−1.1 (5)	C16—C13—C14—C15	−2.0 (5)
C14—N1—C7—C8	179.4 (3)	C12—C13—C14—C15	173.2 (3)
C4—N1—C7—C8	−6.7 (5)	C7—N1—C14—C13	1.2 (3)
C14—N1—C7—C12	−1.4 (3)	C4—N1—C14—C13	−172.6 (3)
C4—N1—C7—C12	172.5 (3)	C7—N1—C14—C15	−173.0 (3)
C12—C7—C8—C9	0.4 (5)	C4—N1—C14—C15	13.2 (5)
N1—C7—C8—C9	179.5 (3)	C14—C13—C16—N2	136 (18)
C7—C8—C9—C10	−1.8 (5)	C12—C13—C16—N2	−38 (18)
C8—C9—C10—C11	1.6 (5)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₁BrN₂
M_r	311.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	9.170 (7), 8.849 (6), 16.337 (12)
β (°)	94.415 (15)
V (Å³)	1321.7 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.10
Crystal size (mm)	0.20 × 0.18 × 0.14

Data collection
Diffractometer	Rigaku Saturn724 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2009)
T_min, T_max	0.576, 0.671
No. of measured, independent and observed [I > 2σ(I)] reflections	12992, 3147, 2309
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.106, 1.00
No. of reflections	3147
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.90, −0.73

Computer programs: CrystalClear-SM Expert (Rigaku, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku, 2009), CrystalStructure (Rigaku, 2009).

Acknowledgements

XQ is grateful for financial support from the China Postdoctoral Science Foundation (grant No. 200904507610).

References

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