1-(2-Chloro­phenyl)-6-fluoro-2-methyl-1H-indole-3-carbonitrile

Yang, K.; Li, P.-F.; Liu, Y.; Fang, Z.-Z.

doi:10.1107/S1600536811011214

organic compounds

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Volume 67| Part 5| May 2011| Page o1041

doi:10.1107/S1600536811011214

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1-(2-Chlorophenyl)-6-fluoro-2-methyl-1H-indole-3-carbonitrile

Kun Yang,^a ^* Pei-Fan Li,^b ^* Yan Liu ^b and Zhi-Zhong Fang ^a

^aTeaching & Research Center, Tianjin Medical University, Tianjin 300070, People's Republic of China, and ^bPharmacy Department, Tianjin Medical College, Tianjin 300222, People's Republic of China
^*Correspondence e-mail: tijmu@tijmu.edu.cn, austinmm@126.com

(Received 24 March 2011; accepted 25 March 2011; online 7 April 2011)

In the title compound, C₁₆H₁₀ClFN₂, the dihedral angle between the indole ring system and the benzyl ring is 80.91 (5)°. The crystal packing features C—H⋯Cl, C—H⋯F and C—H⋯π interactions.

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: Li & Huang (2009 ); Li et al. (2009 , 2010a ,b ).

Experimental

Crystal data

C₁₆H₁₀ClFN₂
M_r = 284.71
Orthorhombic, P b c a
a = 7.4581 (9) Å
b = 16.8480 (15) Å
c = 21.356 (2) Å
V = 2683.5 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 113 K
0.26 × 0.22 × 0.20 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009 ) T_min = 0.929, T_max = 0.945
28426 measured reflections
3893 independent reflections
3219 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.113
S = 1.11
3893 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C3–C8 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯F1ⁱ	0.95	2.54	3.1638 (16)	123
C7—H7⋯Cl1ⁱⁱ	0.95	2.73	3.5296 (14)	142
C15—H15⋯Cg1ⁱⁱⁱ	0.95	2.92	3.7246 (14)	143
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) x-1, y, z.

Data collection: CrystalClear (Rigaku, 2009); 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: CrystalStructure (Rigaku, 2009); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011214/hb5823sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011214/hb5823Isup2.hkl

checkCIF report

Comment top

Indoles are an important compound possessing pharmaceutical properties. Extensive investigation on the crystal structures of indoles helps disclose their structure-activity relationship. For continuing our reseach, herein, we reported the crystal structure of the title indole derivative.

In the molecular structure, (I) (Fig. 1), the indole ring system is almost planar with a dihedral angle of 0.85 (6)° between its pyrrole ring and fused benzene ring. The indole ring forms an angle of 80.91 (5)° with the chlorobenzene ring.

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: Li & Huang (2009); Li et al. (2009, 2010a,b).

Experimental top

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

Computing details top

Data collection: CrystalClear (Rigaku, 2009); cell refinement: CrystalClear (Rigaku, 2009); data reduction: CrystalClear (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-(2-Chlorophenyl)-6-fluoro-2-methyl-1H-indole-3-carbonitrile top

Crystal data top

C₁₆H₁₀ClFN₂	F(000) = 1168
M_r = 284.71	D_x = 1.409 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 10281 reflections
a = 7.4581 (9) Å	θ = 1.5–31.4°
b = 16.8480 (15) Å	µ = 0.29 mm⁻¹
c = 21.356 (2) Å	T = 113 K
V = 2683.5 (5) Å³	Prism, colorless
Z = 8	0.26 × 0.22 × 0.20 mm

Data collection top

Rigaku Saturn724 CCD diffractometer	3893 independent reflections
Radiation source: rotating anode	3219 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.034
Detector resolution: 14.222 pixels mm^-1	θ_max = 30.0°, θ_min = 1.9°
ω scans	h = −10→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	k = −23→23
T_min = 0.929, T_max = 0.945	l = −30→30
28426 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0644P)² + 0.1004P] where P = (F_o² + 2F_c²)/3
3893 reflections	(Δ/σ)_max = 0.001
182 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₆H₁₀ClFN₂	V = 2683.5 (5) Å³
M_r = 284.71	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.4581 (9) Å	µ = 0.29 mm⁻¹
b = 16.8480 (15) Å	T = 113 K
c = 21.356 (2) Å	0.26 × 0.22 × 0.20 mm

Data collection top

Rigaku Saturn724 CCD diffractometer	3893 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	3219 reflections with I > 2σ(I)
T_min = 0.929, T_max = 0.945	R_int = 0.034
28426 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.11	Δρ_max = 0.39 e Å⁻³
3893 reflections	Δρ_min = −0.20 e Å⁻³
182 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
Cl1	0.50520 (4)	0.220294 (19)	0.641958 (16)	0.03226 (11)
F1	0.61121 (11)	0.54670 (5)	0.76153 (4)	0.0480 (2)
N1	0.39260 (12)	0.37712 (5)	0.59488 (4)	0.0236 (2)
N2	0.79477 (16)	0.43384 (7)	0.42798 (6)	0.0420 (3)
C1	0.45553 (17)	0.36559 (7)	0.53489 (5)	0.0258 (2)
C2	0.60108 (16)	0.41469 (7)	0.52619 (6)	0.0271 (3)
C3	0.63160 (15)	0.45816 (7)	0.58328 (6)	0.0265 (3)
C4	0.49938 (14)	0.43272 (7)	0.62558 (6)	0.0237 (2)
C5	0.48747 (16)	0.46061 (7)	0.68659 (6)	0.0280 (3)
H5	0.3986	0.4427	0.7151	0.034*
C6	0.61408 (17)	0.51607 (7)	0.70243 (6)	0.0337 (3)
C7	0.74735 (17)	0.54359 (8)	0.66235 (7)	0.0361 (3)
H7	0.8315	0.5819	0.6765	0.043*
C8	0.75667 (16)	0.51503 (7)	0.60210 (7)	0.0318 (3)
H8	0.8460	0.5336	0.5740	0.038*
C9	0.36953 (19)	0.30813 (8)	0.49124 (6)	0.0333 (3)
H9A	0.3812	0.2543	0.5081	0.040*
H9B	0.4286	0.3109	0.4503	0.040*
H9C	0.2423	0.3213	0.4866	0.040*
C10	0.70533 (17)	0.42350 (7)	0.47083 (6)	0.0317 (3)
C11	0.25337 (16)	0.33290 (7)	0.62467 (5)	0.0223 (2)
C12	0.28935 (15)	0.25756 (7)	0.64802 (5)	0.0230 (2)
C13	0.15588 (16)	0.21330 (7)	0.67690 (5)	0.0271 (3)
H13	0.1800	0.1612	0.6918	0.032*
C14	−0.01309 (16)	0.24642 (8)	0.68363 (6)	0.0277 (3)
H14	−0.1052	0.2169	0.7037	0.033*
C15	−0.04958 (18)	0.32238 (7)	0.66141 (6)	0.0295 (3)
H15	−0.1658	0.3446	0.6664	0.035*
C16	0.08411 (16)	0.36557 (7)	0.63194 (6)	0.0276 (3)
H16	0.0598	0.4175	0.6167	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02051 (19)	0.02941 (18)	0.0468 (2)	0.00492 (11)	0.00001 (12)	0.00824 (12)
F1	0.0450 (5)	0.0454 (5)	0.0535 (5)	−0.0100 (4)	−0.0018 (4)	−0.0201 (4)
N1	0.0198 (5)	0.0213 (4)	0.0298 (5)	−0.0031 (4)	0.0030 (4)	0.0022 (4)
N2	0.0363 (7)	0.0436 (7)	0.0461 (6)	0.0006 (5)	0.0128 (5)	0.0089 (5)
C1	0.0240 (6)	0.0243 (5)	0.0290 (5)	0.0016 (5)	0.0019 (5)	0.0054 (4)
C2	0.0218 (6)	0.0250 (5)	0.0344 (6)	0.0014 (4)	0.0040 (5)	0.0079 (5)
C3	0.0199 (6)	0.0210 (5)	0.0385 (6)	0.0020 (4)	0.0007 (5)	0.0081 (4)
C4	0.0178 (6)	0.0181 (5)	0.0353 (6)	0.0001 (4)	−0.0013 (4)	0.0036 (4)
C5	0.0234 (6)	0.0230 (6)	0.0376 (6)	−0.0001 (4)	0.0013 (5)	0.0006 (5)
C6	0.0311 (7)	0.0253 (6)	0.0446 (7)	0.0007 (5)	−0.0046 (6)	−0.0057 (5)
C7	0.0267 (7)	0.0220 (6)	0.0597 (8)	−0.0050 (5)	−0.0061 (6)	0.0016 (6)
C8	0.0199 (6)	0.0225 (6)	0.0528 (7)	−0.0007 (4)	0.0011 (6)	0.0100 (5)
C9	0.0349 (7)	0.0345 (7)	0.0304 (6)	−0.0037 (6)	0.0011 (5)	0.0007 (5)
C10	0.0259 (7)	0.0291 (6)	0.0402 (6)	0.0026 (5)	0.0047 (5)	0.0088 (5)
C11	0.0194 (6)	0.0216 (5)	0.0259 (5)	−0.0029 (4)	0.0004 (4)	0.0022 (4)
C12	0.0188 (6)	0.0235 (5)	0.0267 (5)	0.0008 (4)	−0.0021 (4)	0.0014 (4)
C13	0.0263 (6)	0.0255 (5)	0.0295 (5)	−0.0022 (5)	−0.0015 (5)	0.0070 (4)
C14	0.0230 (6)	0.0324 (6)	0.0275 (5)	−0.0069 (5)	0.0020 (5)	0.0031 (5)
C15	0.0199 (6)	0.0318 (6)	0.0369 (6)	0.0006 (5)	0.0032 (5)	−0.0002 (5)
C16	0.0229 (6)	0.0241 (6)	0.0358 (6)	0.0015 (5)	0.0009 (5)	0.0041 (5)

Geometric parameters (Å, º) top

Cl1—C12	1.7328 (12)	C7—C8	1.375 (2)
F1—C6	1.3636 (15)	C7—H7	0.9500
N1—C1	1.3780 (15)	C8—H8	0.9500
N1—C4	1.3934 (14)	C9—H9A	0.9800
N1—C11	1.4276 (14)	C9—H9B	0.9800
N2—C10	1.1457 (16)	C9—H9C	0.9800
C1—C2	1.3775 (16)	C11—C16	1.3857 (16)
C1—C9	1.4892 (17)	C11—C12	1.3900 (15)
C2—C10	1.4227 (17)	C12—C13	1.3883 (16)
C2—C3	1.4404 (18)	C13—C14	1.3857 (17)
C3—C8	1.3963 (17)	C13—H13	0.9500
C3—C4	1.4045 (16)	C14—C15	1.3918 (18)
C4—C5	1.3879 (18)	C14—H14	0.9500
C5—C6	1.3708 (17)	C15—C16	1.3855 (17)
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.3914 (19)	C16—H16	0.9500

C1—N1—C4	109.73 (9)	C3—C8—H8	120.8
C1—N1—C11	126.05 (10)	C1—C9—H9A	109.5
C4—N1—C11	123.83 (9)	C1—C9—H9B	109.5
C2—C1—N1	108.01 (10)	H9A—C9—H9B	109.5
C2—C1—C9	130.19 (11)	C1—C9—H9C	109.5
N1—C1—C9	121.80 (11)	H9A—C9—H9C	109.5
C1—C2—C10	127.27 (12)	H9B—C9—H9C	109.5
C1—C2—C3	108.40 (10)	N2—C10—C2	176.12 (15)
C10—C2—C3	124.33 (11)	C16—C11—C12	119.89 (10)
C8—C3—C4	119.56 (12)	C16—C11—N1	120.35 (10)
C8—C3—C2	134.28 (11)	C12—C11—N1	119.73 (10)
C4—C3—C2	106.16 (10)	C13—C12—C11	120.76 (11)
C5—C4—N1	129.26 (11)	C13—C12—Cl1	120.31 (9)
C5—C4—C3	123.06 (11)	C11—C12—Cl1	118.91 (9)
N1—C4—C3	107.68 (11)	C14—C13—C12	118.81 (11)
C6—C5—C4	114.73 (11)	C14—C13—H13	120.6
C6—C5—H5	122.6	C12—C13—H13	120.6
C4—C5—H5	122.6	C13—C14—C15	120.85 (11)
F1—C6—C5	118.39 (12)	C13—C14—H14	119.6
F1—C6—C7	117.04 (11)	C15—C14—H14	119.6
C5—C6—C7	124.57 (13)	C16—C15—C14	119.80 (12)
C8—C7—C6	119.68 (12)	C16—C15—H15	120.1
C8—C7—H7	120.2	C14—C15—H15	120.1
C6—C7—H7	120.2	C15—C16—C11	119.86 (11)
C7—C8—C3	118.39 (12)	C15—C16—H16	120.1
C7—C8—H8	120.8	C11—C16—H16	120.1

C4—N1—C1—C2	−1.08 (13)	C4—C5—C6—C7	−0.48 (18)
C11—N1—C1—C2	−174.11 (10)	F1—C6—C7—C8	−179.81 (11)
C4—N1—C1—C9	178.91 (11)	C5—C6—C7—C8	0.4 (2)
C11—N1—C1—C9	5.89 (17)	C6—C7—C8—C3	−0.63 (18)
N1—C1—C2—C10	−178.61 (11)	C4—C3—C8—C7	0.91 (17)
C9—C1—C2—C10	1.4 (2)	C2—C3—C8—C7	−178.87 (13)
N1—C1—C2—C3	0.59 (13)	C1—C2—C10—N2	177 (100)
C9—C1—C2—C3	−179.40 (12)	C3—C2—C10—N2	−2 (2)
C1—C2—C3—C8	179.90 (13)	C1—N1—C11—C16	−104.36 (13)
C10—C2—C3—C8	−0.9 (2)	C4—N1—C11—C16	83.56 (14)
C1—C2—C3—C4	0.10 (13)	C1—N1—C11—C12	77.42 (15)
C10—C2—C3—C4	179.33 (11)	C4—N1—C11—C12	−94.66 (13)
C1—N1—C4—C5	−178.37 (12)	C16—C11—C12—C13	2.09 (17)
C11—N1—C4—C5	−5.16 (18)	N1—C11—C12—C13	−179.69 (10)
C1—N1—C4—C3	1.15 (13)	C16—C11—C12—Cl1	−176.62 (9)
C11—N1—C4—C3	174.36 (10)	N1—C11—C12—Cl1	1.61 (15)
C8—C3—C4—C5	−1.03 (17)	C11—C12—C13—C14	−1.76 (17)
C2—C3—C4—C5	178.81 (11)	Cl1—C12—C13—C14	176.93 (9)
C8—C3—C4—N1	179.41 (10)	C12—C13—C14—C15	0.59 (18)
C2—C3—C4—N1	−0.75 (12)	C13—C14—C15—C16	0.24 (19)
N1—C4—C5—C6	−179.77 (11)	C14—C15—C16—C11	0.07 (19)
C3—C4—C5—C6	0.78 (17)	C12—C11—C16—C15	−1.22 (17)
C4—C5—C6—F1	179.77 (11)	N1—C11—C16—C15	−179.44 (11)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C3–C8 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···F1ⁱ	0.95	2.54	3.1638 (16)	123
C7—H7···Cl1ⁱⁱ	0.95	2.73	3.5296 (14)	142
C15—H15···Cg1ⁱⁱⁱ	0.95	2.92	3.7246 (14)	143

Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) −x+3/2, y+1/2, z; (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₀ClFN₂
M_r	284.71
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	113
a, b, c (Å)	7.4581 (9), 16.8480 (15), 21.356 (2)
V (Å³)	2683.5 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.26 × 0.22 × 0.20

Data collection
Diffractometer	Rigaku Saturn724 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2009)
T_min, T_max	0.929, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	28426, 3893, 3219
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.113, 1.11
No. of reflections	3893
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.20

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C3–C8 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···F1ⁱ	0.95	2.54	3.1638 (16)	123
C7—H7···Cl1ⁱⁱ	0.95	2.73	3.5296 (14)	142
C15—H15···Cg1ⁱⁱⁱ	0.95	2.92	3.7246 (14)	143

Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) −x+3/2, y+1/2, z; (iii) x−1, y, z.

References

Du, Y., Liu, R., Linn, G. & Zhao, K. (2006). Org. Lett. 8, 5919–5922. Web of Science CSD CrossRef PubMed CAS Google Scholar
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doi:10.1107/S1600536811011214

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