2-Cyano­anilinium bromide

Zhang, L.

doi:10.1107/S1600536809035223

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2407

doi:10.1107/S1600536809035223

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2-Cyanoanilinium bromide

Li Zhang ^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 18 August 2009; accepted 1 September 2009; online 9 September 2009)

In the cation of the title compound, C₇H₇N₂⁺·Br⁻, the nitrile group and the benzene ring are almost coplanar (r.m.s. deviation = 0.0043 Å). In the crystal, the cations and anions are connected by intermolecular N—H⋯Br hydrogen bonds, forming a two-dimensional network parallel to (010).

Related literature

For nitrile derivatives, see: Fu et al. (2008 ); Wang et al. (2002 ). Nitrile derivatives used in the construction of novel metal-organic frameworks. For applications of metal-organic coordination compounds, see: Fu et al. (2007 ); Chen et al. (2000 ); Fu & Xiong (2008 ); Xiong et al. (1999 ); Xie et al. (2003 ); Zhang et al. (2001 ).

Experimental

Crystal data

C₇H₇N₂⁺·Br⁻
M_r = 199.06
Monoclinic, C c
a = 5.7844 (12) Å
b = 15.896 (3) Å
c = 8.4882 (17) Å
β = 92.72 (3)°
V = 779.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 5.19 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 = 0.65, T_max = 0.77
3848 measured reflections
1773 independent reflections
1581 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.050
S = 0.87
1773 reflections
93 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.41 e Å⁻³
Absolute structure: Flack (1983 ), 872 Friedels pairs
Flack parameter: 0.004 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1	0.89	2.36	3.234 (3)	168
N1—H1B⋯Br1ⁱ	0.89	2.47	3.355 (3)	173
N1—H1C⋯Br1ⁱⁱ	0.89	2.42	3.286 (3)	164
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035223/xu2593sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035223/xu2593Isup2.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., 2000; Fu & Xiong (2008); Xie et al., 2003; Zhang et al., 2001; 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.

In the 2-cyanoanilinium cation (Fig.1), the nitrile group and the benzene ring are almost coplanar. The nitrile group C7≡N2 bond length of 1.142 (4) Å is within the normal range.

In the crystal structure, all the amine group H atoms are involved in N—H···Br hydrogen bonds (Table 1) with Br^- anions. These hydrogen bonds along with N—H···Br hydrogen bonds link the ionic units into a two-dimensional network (Fig. 2) parallel to the (0 1 0) plane.

Related literature top

For applications of metal-organic coordination compounds, see: Fu et al. (2007); Chen et al. (2000); Fu & Xiong (2008); Xiong et al. (1999); Xie et al. (2003); Zhang et al. (2001). For nitrile derivatives, see: Fu et al. (2008); Wang et al. (2002).

Experimental top

The commercial 2-aminobenzonitrile (3 mmol, 0.55 g) and HBr (0.5 ml) were dissolved in ethanol (20 ml). Colourless needle-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: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure 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 b axis showing the N—H···Br hydrogen bonding (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

2-Cyanoanilinium bromide top

Crystal data top

C₇H₇N₂⁺·Br⁻	F(000) = 392
M_r = 199.06	D_x = 1.696 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1581 reflections
a = 5.7844 (12) Å	θ = 2.6–27.5°
b = 15.896 (3) Å	µ = 5.19 mm⁻¹
c = 8.4882 (17) Å	T = 298 K
β = 92.72 (3)°	Needle, colourless
V = 779.6 (3) Å³	0.40 × 0.05 × 0.05 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	1773 independent reflections
Radiation source: fine-focus sealed tube	1581 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.6°
CCD profile fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −20→20
T_min = 0.65, T_max = 0.77	l = −10→11
3848 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.0143P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.050	(Δ/σ)_max < 0.001
S = 0.87	Δρ_max = 0.47 e Å⁻³
1773 reflections	Δρ_min = −0.41 e Å⁻³
93 parameters	Extinction correction: SHELXTL (Version 5.1; Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0206 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 872 Friedels pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.004 (13)

Crystal data top

C₇H₇N₂⁺·Br⁻	V = 779.6 (3) Å³
M_r = 199.06	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 5.7844 (12) Å	µ = 5.19 mm⁻¹
b = 15.896 (3) Å	T = 298 K
c = 8.4882 (17) Å	0.40 × 0.05 × 0.05 mm
β = 92.72 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1773 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1581 reflections with I > 2σ(I)
T_min = 0.65, T_max = 0.77	R_int = 0.034
3848 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.050	Δρ_max = 0.47 e Å⁻³
S = 0.87	Δρ_min = −0.41 e Å⁻³
1773 reflections	Absolute structure: Flack (1983), 872 Friedels pairs
93 parameters	Absolute structure parameter: 0.004 (13)
2 restraints

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
Br1	0.05750 (10)	0.208462 (17)	0.44566 (9)	0.04064 (12)
N1	0.0515 (5)	0.32177 (17)	0.7619 (3)	0.0347 (6)
H1A	0.0332	0.2950	0.6701	0.052*
H1B	−0.0713	0.3127	0.8188	0.052*
H1C	0.1780	0.3027	0.8140	0.052*
C6	−0.0799 (6)	0.4675 (3)	0.7945 (5)	0.0372 (10)
H6	−0.2028	0.4473	0.8503	0.045*
C3	0.2867 (8)	0.5276 (3)	0.6309 (5)	0.0451 (11)
H3	0.4102	0.5483	0.5762	0.054*
C1	0.0755 (6)	0.4115 (2)	0.7337 (5)	0.0309 (9)
C4	0.1322 (8)	0.5822 (3)	0.6917 (5)	0.0500 (12)
H4	0.1516	0.6399	0.6788	0.060*
C7	0.4233 (6)	0.3856 (2)	0.5783 (4)	0.0410 (8)
N2	0.5521 (6)	0.3440 (2)	0.5163 (4)	0.0618 (10)
C2	0.2611 (6)	0.4411 (3)	0.6501 (4)	0.0346 (9)
C5	−0.0547 (7)	0.5521 (3)	0.7733 (5)	0.0474 (12)
H5	−0.1613	0.5894	0.8130	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03349 (17)	0.04202 (18)	0.04729 (19)	−0.0034 (2)	0.01111 (12)	−0.0112 (3)
N1	0.0284 (14)	0.0369 (15)	0.0396 (16)	−0.0027 (12)	0.0104 (12)	−0.0036 (13)
C6	0.031 (2)	0.043 (2)	0.038 (2)	−0.0023 (18)	0.0075 (17)	−0.0038 (18)
C3	0.044 (3)	0.046 (3)	0.046 (3)	−0.012 (2)	0.007 (2)	0.003 (2)
C1	0.027 (2)	0.035 (2)	0.0309 (18)	0.0005 (15)	0.0021 (15)	−0.0028 (15)
C4	0.065 (3)	0.031 (2)	0.055 (3)	−0.004 (2)	0.008 (2)	0.003 (2)
C7	0.0303 (18)	0.049 (2)	0.044 (2)	−0.0078 (17)	0.0101 (16)	0.0045 (18)
N2	0.049 (2)	0.070 (2)	0.069 (2)	0.0068 (19)	0.031 (2)	0.0025 (18)
C2	0.032 (2)	0.039 (2)	0.032 (2)	−0.0017 (17)	0.0039 (17)	0.0032 (16)
C5	0.056 (3)	0.041 (2)	0.045 (3)	0.012 (2)	0.006 (2)	−0.007 (2)

Geometric parameters (Å, º) top

N1—C1	1.455 (5)	C3—C2	1.393 (6)
N1—H1A	0.8900	C3—H3	0.9300
N1—H1B	0.8900	C1—C2	1.396 (5)
N1—H1C	0.8900	C4—C5	1.396 (6)
C6—C5	1.366 (6)	C4—H4	0.9300
C6—C1	1.382 (5)	C7—N2	1.142 (4)
C6—H6	0.9300	C7—C2	1.444 (6)
C3—C4	1.365 (6)	C5—H5	0.9300

C1—N1—H1A	109.5	C6—C1—N1	120.1 (3)
C1—N1—H1B	109.5	C2—C1—N1	119.7 (3)
H1A—N1—H1B	109.5	C3—C4—C5	120.4 (4)
C1—N1—H1C	109.5	C3—C4—H4	119.8
H1A—N1—H1C	109.5	C5—C4—H4	119.8
H1B—N1—H1C	109.5	N2—C7—C2	177.0 (4)
C5—C6—C1	120.6 (4)	C3—C2—C1	118.7 (4)
C5—C6—H6	119.7	C3—C2—C7	118.6 (4)
C1—C6—H6	119.7	C1—C2—C7	122.6 (4)
C4—C3—C2	120.5 (4)	C6—C5—C4	119.5 (4)
C4—C3—H3	119.7	C6—C5—H5	120.2
C2—C3—H3	119.7	C4—C5—H5	120.2
C6—C1—C2	120.2 (4)

C5—C6—C1—C2	0.2 (6)	N1—C1—C2—C3	−177.0 (4)
C5—C6—C1—N1	177.8 (4)	C6—C1—C2—C7	−177.4 (4)
C2—C3—C4—C5	−0.4 (7)	N1—C1—C2—C7	5.0 (6)
C4—C3—C2—C1	−0.5 (6)	C1—C6—C5—C4	−1.1 (7)
C4—C3—C2—C7	177.6 (4)	C3—C4—C5—C6	1.2 (7)
C6—C1—C2—C3	0.6 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1	0.89	2.36	3.234 (3)	168
N1—H1B···Br1ⁱ	0.89	2.47	3.355 (3)	173
N1—H1C···Br1ⁱⁱ	0.89	2.42	3.286 (3)	164

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·Br⁻
M_r	199.06
Crystal system, space group	Monoclinic, Cc
Temperature (K)	298
a, b, c (Å)	5.7844 (12), 15.896 (3), 8.4882 (17)
β (°)	92.72 (3)
V (Å³)	779.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.19
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	0.65, 0.77
No. of measured, independent and observed [I > 2σ(I)] reflections	3848, 1773, 1581
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.050, 0.87
No. of reflections	1773
No. of parameters	93
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.41
Absolute structure	Flack (1983), 872 Friedels pairs
Absolute structure parameter	0.004 (13)

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1	0.89	2.36	3.234 (3)	167.6
N1—H1B···Br1ⁱ	0.89	2.47	3.355 (3)	172.6
N1—H1C···Br1ⁱⁱ	0.89	2.42	3.286 (3)	163.7

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

Acknowledgements

This work was supported by the Outstanding Doctoral Dissertation Fund from Southeast University.

References

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