3-Cyano­anilinium bromide

Abstract

In the cation of the title compound, C₇H₇N₂ ⁺·Br⁻, all non-H atoms are essentially coplanar [r.m.s. deviation = 0.010 (5) Å]. The compound is isomorphous with the chloride analogue. In the crystal, the cations and anions are connected by N—H⋯Br hydrogen bonds.

Related literature

For applications of metal-organic coordination compounds, see: Fu et al. (2007 ▶); Chen et al. (2001 ▶); Fu & Xiong (2008 ▶); Xiong et al. (1999 ▶); Xie et al. (2003 ▶); Zhao et al. (2004 ▶). For nitrile derivatives, see: Fu et al. (2008 ▶); Wang et al. 2002 ▶. For the chloride analogue, see: Wen (2008 ▶).

Experimental

Crystal data

• C₇H₇N₂ ⁺·Br⁻

• M _r = 199.06

• Triclinic,

• a = 4.6396 (9) Å

• b = 6.1757 (12) Å

• c = 13.542 (3) Å

• α = 93.07 (3)°

• β = 96.22 (3)°

• γ = 97.33 (3)°

• V = 381.68 (13) ų

• Z = 2

• Mo Kα radiation

• μ = 5.31 mm⁻¹

• T = 298 K

• 0.40 × 0.05 × 0.05 mm

Data collection

• Rigaku Mercury2 diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.90, T _max = 1.00

• 3777 measured reflections

• 1716 independent reflections

• 1378 reflections with I > 2σ(I)

• R _int = 0.063

Refinement

• R[F ² > 2σ(F ²)] = 0.052

• wR(F ²) = 0.134

• S = 1.10

• 1716 reflections

• 92 parameters

• H-atom parameters constrained

• Δρ_max = 0.71 e Å⁻³

• Δρ_min = −0.75 e Å⁻³

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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Br1i	0.89	2.59	3.434 (4)	159
N2—H2B⋯Br1ii	0.89	2.46	3.337 (4)	169
N2—H2C⋯Br1	0.89	2.45	3.299 (4)	160

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The construction of metal-organic coordination compounds has attracted much attention owing to potential functions, such as permittivity, fluorescence, magnetism and optical properties (Fu et al., 2007; Chen et al., 2001; Fu & Xiong (2008); Xie et al., 2003; Zhao et al.,2004; Xiong et al., 1999). Nitrile derivatives are a class of excellent ligands for the construction of novel metal-organic frameworks. (Wang et al. 2002; Fu et al., 2008). We report here the crystal structure of the title compound, which is isomorphous with the chloride analogue (Wen, 2008). In the cation all non-H atoms are essentially coplanar [r.m.s. deviation 0.010 (5) Å]. In the crystal structure, the organic cations and bromide ions are connected by N—H···Br hydrogen bonds along b axis, (Table 1), (Fig. 2).

Experimental

The commercial 3-aminobenzonitrile (3 mmol, 0.55 g) and HBr (0.5 ml) were dissolved in ethanol (20 ml). Colourless block-shaped crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation at room temperature.

Refinement

All H atoms attached to C and N atoms were positioned geometrically and treated as riding, with C-H = 0.93 Å, N-H = 0.89 Å and U_iso(H) = 1.2U_eq(C) and U_iso(H) = 1.5U_eq(N). A rotating-group model was used for the -NH₃ group.

Figures

Fig. 1.

A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2.

The crystal packing of the title compound, viewed along the a axis showing the N—H···Br interactions (dotted line) in the title compound. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.

Crystal data

C7H7N2+·Br−	Z = 2
Mr = 199.06	F(000) = 196
Triclinic, P1	Dx = 1.732 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.6396 (9) Å	Cell parameters from 1378 reflections
b = 6.1757 (12) Å	θ = 3.0–27.5°
c = 13.542 (3) Å	µ = 5.31 mm−1
α = 93.07 (3)°	T = 298 K
β = 96.22 (3)°	Block, colourless
γ = 97.33 (3)°	0.40 × 0.05 × 0.05 mm
V = 381.68 (13) Å3

Data collection

Rigaku Mercury2 diffractometer	1716 independent reflections
Radiation source: fine-focus sealed tube	1378 reflections with I > 2σ(I)
graphite	Rint = 0.063
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.0°
CCD profile fitting scans	h = −6→5
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
Tmin = 0.90, Tmax = 1.00	l = −17→17
3777 measured reflections

Refinement

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.053P)2 + 0.0394P] where P = (Fo2 + 2Fc2)/3
1716 reflections	(Δ/σ)max < 0.001
92 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −0.75 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 (Ų)

	x	y	z	Uiso*/Ueq
N2	0.6256 (9)	0.2461 (6)	0.6051 (3)	0.0419 (10)
H2A	0.7437	0.1446	0.5990	0.063*
H2B	0.7175	0.3755	0.5927	0.063*
H2C	0.4653	0.2118	0.5619	0.063*
N1	−0.0113 (11)	0.7158 (8)	0.8871 (4)	0.0575 (13)
C4	0.5438 (10)	0.2565 (7)	0.7064 (4)	0.0339 (10)
C3	0.3783 (10)	0.4177 (7)	0.7330 (3)	0.0349 (10)
H3	0.3215	0.5166	0.6877	0.042*
C2	0.3001 (10)	0.4273 (7)	0.8286 (4)	0.0350 (10)
C5	0.6331 (11)	0.1113 (7)	0.7719 (4)	0.0389 (11)
H5	0.7446	0.0048	0.7527	0.047*
C7	0.3878 (12)	0.2814 (8)	0.8962 (4)	0.0429 (12)
H7	0.3345	0.2889	0.9604	0.051*
C6	0.5540 (12)	0.1259 (8)	0.8677 (4)	0.0473 (13)
H6	0.6146	0.0287	0.9132	0.057*
C1	0.1216 (11)	0.5910 (8)	0.8593 (4)	0.0422 (12)
Br1	0.09268 (11)	0.23870 (7)	0.42210 (4)	0.0448 (2)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N2	0.053 (3)	0.044 (2)	0.032 (2)	0.0176 (19)	0.0038 (19)	0.0003 (18)
N1	0.058 (3)	0.052 (3)	0.067 (3)	0.020 (2)	0.016 (3)	−0.004 (2)
C4	0.040 (3)	0.028 (2)	0.033 (3)	0.0073 (18)	0.004 (2)	−0.0017 (18)
C3	0.039 (3)	0.033 (2)	0.032 (3)	0.010 (2)	0.000 (2)	0.0010 (19)
C2	0.030 (2)	0.034 (2)	0.041 (3)	0.0057 (18)	0.005 (2)	−0.002 (2)
C5	0.049 (3)	0.034 (2)	0.037 (3)	0.018 (2)	0.007 (2)	−0.001 (2)
C7	0.056 (3)	0.039 (3)	0.035 (3)	0.011 (2)	0.010 (2)	0.000 (2)
C6	0.062 (4)	0.040 (3)	0.045 (3)	0.015 (2)	0.010 (3)	0.014 (2)
C1	0.045 (3)	0.040 (3)	0.044 (3)	0.012 (2)	0.011 (2)	0.000 (2)
Br1	0.0573 (4)	0.0399 (3)	0.0423 (4)	0.0214 (2)	0.0112 (3)	0.0037 (2)

Geometric parameters (Å, °)

N2—C4	1.463 (6)	C3—H3	0.9300
N2—H2A	0.8900	C2—C7	1.384 (7)
N2—H2B	0.8900	C2—C1	1.457 (6)
N2—H2C	0.8900	C5—C6	1.388 (7)
N1—C1	1.121 (6)	C5—H5	0.9300
C4—C5	1.365 (6)	C7—C6	1.371 (7)
C4—C3	1.388 (6)	C7—H7	0.9300
C3—C2	1.383 (7)	C6—H6	0.9300
C4—N2—H2A	109.5	C3—C2—C1	120.2 (4)
C4—N2—H2B	109.5	C7—C2—C1	119.1 (5)
H2A—N2—H2B	109.5	C4—C5—C6	118.6 (4)
C4—N2—H2C	109.5	C4—C5—H5	120.7
H2A—N2—H2C	109.5	C6—C5—H5	120.7
H2B—N2—H2C	109.5	C6—C7—C2	119.4 (5)
C5—C4—C3	122.0 (4)	C6—C7—H7	120.3
C5—C4—N2	119.8 (4)	C2—C7—H7	120.3
C3—C4—N2	118.2 (4)	C7—C6—C5	121.0 (5)
C2—C3—C4	118.2 (4)	C7—C6—H6	119.5
C2—C3—H3	120.9	C5—C6—H6	119.5
C4—C3—H3	120.9	N1—C1—C2	177.0 (6)
C3—C2—C7	120.7 (4)
C5—C4—C3—C2	−0.9 (7)	N2—C4—C5—C6	179.6 (5)
N2—C4—C3—C2	179.8 (4)	C3—C2—C7—C6	0.0 (7)
C4—C3—C2—C7	0.7 (7)	C1—C2—C7—C6	179.5 (5)
C4—C3—C2—C1	−178.8 (4)	C2—C7—C6—C5	−0.6 (8)
C3—C4—C5—C6	0.3 (7)	C4—C5—C6—C7	0.5 (8)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Br1i	0.89	2.59	3.434 (4)	159
N2—H2B···Br1ii	0.89	2.46	3.337 (4)	169
N2—H2C···Br1	0.89	2.45	3.299 (4)	160

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