3-Cyano­anilinium bromide

Wang, B.

doi:10.1107/S1600536809034941

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2396

doi:10.1107/S1600536809034941

Open

access

3-Cyanoanilinium bromide

Bo Wang ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 19 August 2009; accepted 31 August 2009; online 9 September 2009)

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.052
wR(F²) = 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

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) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z+1.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034941/bx2236sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034941/bx2236Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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 top

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.

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

Figures top

	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.

3-Cyanoanilinium bromide top

Crystal data top

C₇H₇N₂⁺·Br⁻	Z = 2
M_r = 199.06	F(000) = 196
Triclinic, P1	D_x = 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 top

Rigaku Mercury2 diffractometer	1716 independent reflections
Radiation source: fine-focus sealed tube	1378 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD profile fitting scans	h = −6→5
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
T_min = 0.90, T_max = 1.00	l = −17→17
3777 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.053P)² + 0.0394P] where P = (F_o² + 2F_c²)/3
1716 reflections	(Δ/σ)_max < 0.001
92 parameters	Δρ_max = 0.71 e Å⁻³
0 restraints	Δρ_min = −0.75 e Å⁻³

Crystal data top

C₇H₇N₂⁺·Br⁻	γ = 97.33 (3)°
M_r = 199.06	V = 381.68 (13) Å³
Triclinic, P1	Z = 2
a = 4.6396 (9) Å	Mo Kα radiation
b = 6.1757 (12) Å	µ = 5.31 mm⁻¹
c = 13.542 (3) Å	T = 298 K
α = 93.07 (3)°	0.40 × 0.05 × 0.05 mm
β = 96.22 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1716 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1378 reflections with I > 2σ(I)
T_min = 0.90, T_max = 1.00	R_int = 0.063
3777 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.10	Δρ_max = 0.71 e Å⁻³
1716 reflections	Δρ_min = −0.75 e Å⁻³
92 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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.

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·Br⁻
M_r	199.06
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	4.6396 (9), 6.1757 (12), 13.542 (3)
α, β, γ (°)	93.07 (3), 96.22 (3), 97.33 (3)
V (Å³)	381.68 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.31
Crystal size (mm)	0.40 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.90, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	3777, 1716, 1378
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.134, 1.10
No. of reflections	1716
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.75

Computer programs: CrystalClear (Rigaku, 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
N2—H2A···Br1ⁱ	0.89	2.59	3.434 (4)	159.3
N2—H2B···Br1ⁱⁱ	0.89	2.46	3.337 (4)	169.2
N2—H2C···Br1	0.89	2.45	3.299 (4)	160.0

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

Acknowledgements

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

References

Chen, Z.-F., Li, B.-Q., Xie, Y.-R., Xiong, R.-G., You, X.-Z. & Feng, X.-L. (2001). Inorg. Chem. Commun. 4, 346–349. Web of Science CSD CrossRef CAS Google Scholar
Fu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H., Huang, S.-P. & -, D. (2007). J. Am. Chem. Soc. 129, 5346–5347. Web of Science CSD CrossRef PubMed CAS Google Scholar
Fu, D.-W. & Xiong, R.-G. (2008). Dalton Trans. pp. 3946–3948. Web of Science CSD CrossRef Google Scholar
Fu, D.-W., Zhang, W. & Xiong, R.-G. (2008). Cryst. Growth Des. 8, 3461–3464. Web of Science CSD 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
Wang, L.-Z., Wang, X.-S., Li, Y.-H., Bai, Z.-P., Xiong, R.-G., Xiong, M. & Li, G.-W. (2002). Chin. J. Inorg. Chem. 18, 1191–1194. CAS Google Scholar
Wen, X.-C. (2008). Acta Cryst. E64, o1462. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xie, Y.-R., Zhao, H., Wang, X.-S., Qu, Z.-R., Xiong, R.-G., Xue, X.-A., Xue, Z.-L. & You, X.-Z. (2003). Eur. J. Inorg. Chem. 20, 3712–3715. Web of Science CSD CrossRef Google Scholar
Xiong, R.-G., Zuo, J.-L., You, X.-Z., Fun, H.-K. & Raj, S. S. S. (1999). New J. Chem. 23, 1051–1052. Web of Science CSD CrossRef CAS Google Scholar
Zhao, H., Ye, Q., Wu, Q., Song, Y.-M., Liu, Y.-J. & Xiong, R.-G. (2004). Z. Anorg. Allg. Chem. 630, 1367–1370. Web of Science CSD CrossRef CAS Google Scholar