2-(4-Bromo-1H-indol-3-yl)acetonitrile

Mao, Q.-X.; Zhang, C.-G.; Li, J.-F.

doi:10.1107/S1600536811054936

organic compounds

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Volume 68| Part 2| February 2012| Page o451

doi:10.1107/S1600536811054936

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2-(4-Bromo-1H-indol-3-yl)acetonitrile

Qiu-Xia Mao,^a ^* Chen-Guang Zhang ^a and Jin-Feng Li ^a

^aCollege of Chemistry and Chemical, Engineering, Southeast UniVersity, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: chmsunbw@seu.edu.cn

(Received 2 December 2011; accepted 21 December 2011; online 18 January 2012)

In the title compound, C₁₀H₇BrN₂, the non-H atoms, except the N atom of the acetonitrile group and the C atom bonded to it, lie in the least-squares plane defined by the atoms of the indole ring system (r.m.s deviation = 0.019 Å), with the N and C atom of the cyano group displaced by 2.278 (1) and 1.289 (1) Å, respectively, out of that plane. In the crystal, N—H⋯N hydrogen bonds link the molecules into a C(7) chain along [100].

Related literature

For natural products with a bromo indole moiety, see: Walker et al. (2009 ). For the use of 4-bromo indole derivatives in the synthesis of biologically active compounds, see: Hendrickson & Wang (2004 ); Giraud et al. (2011 ). For the structures of related halo indoles, see: Kunzer & Wendt (2011 ).

Experimental

Crystal data

C₁₀H₇BrN₂
M_r = 235.09
Monoclinic, P 2₁ /c
a = 8.3971 (17) Å
b = 11.237 (2) Å
c = 9.979 (2) Å
β = 104.82 (3)°
V = 910.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.46 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.983, T_max = 0.983
9047 measured reflections
2082 independent reflections
1489 reflections with I > 2σ(I)
R_int = 0.115

Refinement

R[F² > 2σ(F²)] = 0.073
wR(F²) = 0.188
S = 1.09
2082 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −1.84 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	2.45	3.218 (7)	148
Symmetry code: (i) x+1, y, z.

Data collection: CrystalClear (Rigaku, 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: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811054936/lr2041sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811054936/lr2041Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811054936/lr2041Isup3.cml

checkCIF report

Comment top

The derivatives of halo indole present in several natural products (Walker et al., 2009) are also excellent intermediates for the synthesis of many biological active compounds (Giraud et al., 2011; Hendrickson & Wang, 2004) . As part of our interest in these materials, we report the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The non-H atoms, except the nitrogen of the acetonitrile moiety and the carbon atom bonded to it, are lying in the least-squares plane defined by the atoms of the indole ring system (r.m.s deviation= 0.019 Å ), with the nitrogen and carbon of the cyano moiety shifted by 2.278 (1) and 1.289 (1) Å, respectively, out of that plane.

In the crystal, N1—H1A···N2 hydrogen bonds link the molecules into chain along the [100] direction (Fig. 2).

Related literature top

For natural products with a bromo indole moiety, see: Walker et al. (2009). For the use of 4-bromo indole derivatives in the synthesis of biologically active compounds, see: Hendrickson & Wang (2004); Giraud et al. (2011). For the structures of related halo indoles, see: Kunzer & Wendt (2011).

Experimental top

The title compound was obtained commercially from ChemFuture PharmaTech, Ltd (Nanjing, Jiangsu). Crystals suitable for X-ray diffraction were obtained by slow evaporation from a methanol solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing view. Intermolecular hydrogen bonds are shown as dashed lines.

2-(4-Bromo-1H-indol-3-yl)acetonitrile top

Crystal data top

C₁₀H₇BrN₂	F(000) = 464
M_r = 235.09	D_x = 1.715 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2082 reflections
a = 8.3971 (17) Å	θ = 3.1–27.5°
b = 11.237 (2) Å	µ = 4.46 mm⁻¹
c = 9.979 (2) Å	T = 293 K
β = 104.82 (3)°	Prism, colourless
V = 910.2 (3) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2082 independent reflections
Radiation source: fine-focus sealed tube	1489 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.115
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD_Profile_fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
T_min = 0.983, T_max = 0.983	l = −12→12
9047 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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.188	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0915P)²] where P = (F_o² + 2F_c²)/3
2082 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −1.84 e Å⁻³

Crystal data top

C₁₀H₇BrN₂	V = 910.2 (3) Å³
M_r = 235.09	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3971 (17) Å	µ = 4.46 mm⁻¹
b = 11.237 (2) Å	T = 293 K
c = 9.979 (2) Å	0.20 × 0.20 × 0.20 mm
β = 104.82 (3)°

Data collection top

Rigaku SCXmini diffractometer	2082 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1489 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.983	R_int = 0.115
9047 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	0 restraints
wR(F²) = 0.188	H-atom parameters constrained
S = 1.09	Δρ_max = 0.64 e Å⁻³
2082 reflections	Δρ_min = −1.84 e Å⁻³
118 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	0.72608 (9)	1.02919 (6)	0.23625 (7)	0.0565 (3)
C10	0.9402 (7)	0.9743 (4)	0.2351 (5)	0.0344 (12)
N1	1.1261 (6)	0.7932 (4)	0.0298 (5)	0.0433 (11)
H1A	1.2109	0.7600	0.0124	0.052*
C5	0.9637 (6)	0.8989 (4)	0.1306 (5)	0.0285 (10)
C2	0.8646 (6)	0.8483 (4)	0.0068 (5)	0.0341 (11)
C9	1.0709 (8)	1.0096 (4)	0.3397 (6)	0.0447 (14)
H9A	1.0531	1.0623	0.4063	0.054*
C6	1.1290 (6)	0.8616 (4)	0.1422 (5)	0.0333 (11)
C8	1.2297 (8)	0.9690 (5)	0.3493 (7)	0.0520 (15)
H8A	1.3158	0.9924	0.4234	0.062*
C1	0.9703 (8)	0.7850 (5)	−0.0511 (6)	0.0410 (13)
H1B	0.9393	0.7426	−0.1338	0.049*
C3	0.6815 (6)	0.8582 (5)	−0.0559 (5)	0.0439 (13)
H3A	0.6489	0.9410	−0.0547	0.053*
H3B	0.6565	0.8326	−0.1519	0.053*
C4	0.5863 (7)	0.7872 (5)	0.0176 (6)	0.0444 (13)
N2	0.5110 (7)	0.7337 (5)	0.0738 (6)	0.0608 (14)
C7	1.2599 (7)	0.8940 (6)	0.2491 (5)	0.0490 (15)
H7A	1.3656	0.8664	0.2540	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0551 (5)	0.0581 (5)	0.0607 (5)	0.0174 (3)	0.0226 (4)	−0.0069 (3)
C10	0.038 (3)	0.033 (3)	0.035 (3)	0.004 (2)	0.014 (2)	0.007 (2)
N1	0.047 (3)	0.040 (2)	0.052 (3)	0.008 (2)	0.029 (3)	0.0010 (19)
C5	0.033 (3)	0.024 (2)	0.031 (2)	0.0024 (17)	0.010 (2)	0.0062 (17)
C2	0.039 (3)	0.034 (3)	0.029 (2)	−0.006 (2)	0.008 (2)	0.0037 (19)
C9	0.062 (4)	0.035 (3)	0.038 (3)	−0.005 (2)	0.014 (3)	−0.004 (2)
C6	0.033 (3)	0.034 (3)	0.036 (3)	0.003 (2)	0.015 (2)	0.011 (2)
C8	0.044 (4)	0.061 (4)	0.043 (3)	−0.012 (3)	−0.004 (3)	0.007 (3)
C1	0.060 (4)	0.036 (3)	0.032 (3)	−0.005 (2)	0.020 (3)	−0.002 (2)
C3	0.045 (3)	0.052 (3)	0.031 (3)	−0.009 (3)	0.002 (2)	0.004 (2)
C4	0.035 (3)	0.050 (3)	0.046 (3)	−0.001 (2)	0.007 (3)	0.001 (2)
N2	0.045 (3)	0.070 (4)	0.069 (4)	−0.009 (3)	0.017 (3)	0.004 (3)
C7	0.039 (3)	0.051 (4)	0.055 (4)	0.000 (2)	0.008 (3)	0.013 (3)

Geometric parameters (Å, º) top

Br1—C10	1.904 (5)	C9—H9A	0.9300
C10—C9	1.365 (8)	C6—C7	1.371 (7)
C10—C5	1.397 (6)	C8—C7	1.379 (9)
N1—C6	1.355 (6)	C8—H8A	0.9300
N1—C1	1.353 (8)	C1—H1B	0.9300
N1—H1A	0.8600	C3—C4	1.454 (7)
C5—C2	1.420 (7)	C3—H3A	0.9700
C5—C6	1.425 (6)	C3—H3B	0.9700
C2—C1	1.374 (7)	C4—N2	1.121 (7)
C2—C3	1.509 (7)	C7—H7A	0.9300
C9—C8	1.389 (9)

C9—C10—C5	120.5 (5)	C7—C6—C5	123.7 (5)
C9—C10—Br1	118.5 (4)	C7—C8—C9	120.1 (6)
C5—C10—Br1	121.0 (4)	C7—C8—H8A	119.9
C6—N1—C1	110.0 (4)	C9—C8—H8A	119.9
C6—N1—H1A	125.0	C2—C1—N1	110.1 (5)
C1—N1—H1A	125.0	C2—C1—H1B	125.0
C10—C5—C2	136.8 (5)	N1—C1—H1B	125.0
C10—C5—C6	116.0 (5)	C4—C3—C2	112.6 (4)
C2—C5—C6	107.1 (4)	C4—C3—H3A	109.1
C1—C2—C5	106.0 (4)	C2—C3—H3A	109.1
C1—C2—C3	124.3 (5)	C4—C3—H3B	109.1
C5—C2—C3	129.7 (4)	C2—C3—H3B	109.1
C10—C9—C8	121.8 (5)	H3A—C3—H3B	107.8
C10—C9—H9A	119.1	N2—C4—C3	178.9 (6)
C8—C9—H9A	119.1	C6—C7—C8	117.8 (5)
N1—C6—C7	129.5 (5)	C6—C7—H7A	121.1
N1—C6—C5	106.8 (5)	C8—C7—H7A	121.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.45	3.218 (7)	148

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₇BrN₂
M_r	235.09
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.3971 (17), 11.237 (2), 9.979 (2)
β (°)	104.82 (3)
V (Å³)	910.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.46
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.983, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	9047, 2082, 1489
R_int	0.115
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.188, 1.09
No. of reflections	2082
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −1.84

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.45	3.218 (7)	148.4

Symmetry code: (i) x+1, y, z.

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Giraud, F., Alves, G., Debiton, E., Nauton, L., Théry, V., Durieu, E., Ferandin, Y., Lozach, O., Meijer, L., Anizon, F., Pereira, E. & Moreau, P. (2011). J. Med. Chem., 54, 4474–4489. Web of Science CrossRef CAS PubMed Google Scholar
Hendrickson, J. B. & Wang, J. (2004). Org. Lett., 6, 3–5. Web of Science CrossRef PubMed CAS Google Scholar
Kunzer, A. R. & Wendt, M. D. (2011). Tetrahedron Lett., 52, 1815–1818. Web of Science CrossRef CAS Google Scholar
Rigaku. (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Walker, S. R., Carter, E. J., Huff, B. C. & Morris, J. C. (2009). Chem. Rev. 109, 3080–3098. Web of Science CrossRef PubMed CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o451

doi:10.1107/S1600536811054936

Open

access