3-Cyano­anilinium chloride

Wen, X.-C.

doi:10.1107/S1600536808020485

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1462

doi:10.1107/S1600536808020485

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3-Cyanoanilinium chloride

Xiao-Chun Wen ^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 30 June 2008; accepted 3 July 2008; online 12 July 2008)

In the title salt, C₇H₇N₂⁺·Cl⁻, all non-H atoms of the cation are essentially coplanar (r.m.s. deviation = 0.005 Å). In the crystal structure, the organic cations and chloride ions are linked to form a two-dimensional network parallel to the (001) plane by N—H⋯Cl hydrogen bonds.

Related literature

For the use of amine derivatives in coordination chemistry, see: Manzur et al. (2007 ); Ismayilov et al. (2007 ); Austria et al. (2007 ).

Experimental

Crystal data

C₇H₇N₂⁺·Cl⁻
M_r = 154.60
Triclinic, $[P \overline 1]$
a = 4.663 (3) Å
b = 6.074 (5) Å
c = 13.212 (9) Å
α = 93.37 (5)°
β = 96.201 (19)°
γ = 96.22 (4)°
V = 368.9 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 298 (2) K
0.25 × 0.18 × 0.18 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.901, T_max = 0.917
2486 measured reflections
1618 independent reflections
1342 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.157
S = 1.07
1618 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H9A⋯Cl1ⁱ	0.89	2.61	3.111 (3)	116
N2—H9A⋯Cl1ⁱⁱ	0.89	2.65	3.178 (3)	119
N2—H9C⋯Cl1ⁱⁱⁱ	0.89	2.73	3.278 (3)	121
N2—H9B⋯Cl1	0.89	2.76	3.338 (3)	124
Symmetry codes: (i) -x, -y+1, -z; (ii) x, y+1, z; (iii) -x+1, -y+1, -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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808020485/ci2624sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020485/ci2624Isup2.hkl

checkCIF report

Comment top

In the past five years, we have focused on the chemistry of amine derivatives because of their multiple coordination modes as ligands to metal ions and for the construction of novel metal-organic frameworks (Manzur et al. 2007; Ismayilov et al. 2007; Austria et al. 2007). We report here the crystal structure of the title compound, 3-cyanobenzenaminium monochloride.

In the title compound (Fig.1), the N2 atom of the amine group is protonated. The nitrile group is coplanar with the benzene ring. Bond lengths and angles lie within normal ranges.

In the crystal structure the organic cation and Cl^- ions are linked to form a two-dimensional network parallel to the (0 0 1) plane (Fig.2) by N—H···Cl hydrogen bonds (Table 1).

Related literature top

For the use of amine derivatives in coordination chemistry, see: Manzur et al. (2007); Ismayilov et al. (2007); Austria et al. (2007).

Experimental top

3-Cyanobenzenaminium monochloride (3 mmol) was dissolved in ethanol (20 ml). The solution was allowed to evaporate to obtain colourless block-shaped crystals of the title compound.

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. Part of the crystal packing of the title compound viewed along the a axis. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.

3-Cyanoanilinium chloride top

Crystal data top

C₇H₇N₂⁺·Cl⁻	Z = 2
M_r = 154.60	F(000) = 160
Triclinic, P1	D_x = 1.392 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.663 (3) Å	Cell parameters from 1678 reflections
b = 6.074 (5) Å	θ = 2.3–24.4°
c = 13.212 (9) Å	µ = 0.44 mm⁻¹
α = 93.37 (5)°	T = 298 K
β = 96.201 (19)°	Block, colourless
γ = 96.22 (4)°	0.25 × 0.18 × 0.18 mm
V = 368.9 (5) Å³

Data collection top

Rigaku Mercury2 diffractometer	1618 independent reflections
Radiation source: fine-focus sealed tube	1342 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −7→5
T_min = 0.901, T_max = 0.917	l = −16→17
2486 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) = 0.157	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0787P)² + 0.2472P] where P = (F_o² + 2F_c²)/3
1618 reflections	(Δ/σ)_max = 0.001
91 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₇H₇N₂⁺·Cl⁻	γ = 96.22 (4)°
M_r = 154.60	V = 368.9 (5) Å³
Triclinic, P1	Z = 2
a = 4.663 (3) Å	Mo Kα radiation
b = 6.074 (5) Å	µ = 0.44 mm⁻¹
c = 13.212 (9) Å	T = 298 K
α = 93.37 (5)°	0.25 × 0.18 × 0.18 mm
β = 96.201 (19)°

Data collection top

Rigaku Mercury2 diffractometer	1618 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1342 reflections with I > 2σ(I)
T_min = 0.901, T_max = 0.917	R_int = 0.021
2486 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.07	Δρ_max = 0.52 e Å⁻³
1618 reflections	Δρ_min = −0.52 e Å⁻³
91 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	0.38158 (16)	0.25924 (11)	0.07001 (5)	0.0414 (3)
C1	0.0572 (5)	0.7649 (4)	0.19904 (18)	0.0302 (5)
N2	0.1472 (5)	0.7573 (4)	0.09653 (16)	0.0377 (6)
H9A	0.0747	0.8643	0.0622	0.057*
H9B	0.0816	0.6259	0.0641	0.057*
H9C	0.3402	0.7770	0.1008	0.057*
C3	−0.1968 (5)	0.9320 (4)	0.3237 (2)	0.0329 (6)
C7	−0.3747 (6)	1.0962 (5)	0.3564 (2)	0.0391 (6)
C6	0.1466 (6)	0.6149 (5)	0.2669 (2)	0.0374 (6)
H6A	0.2625	0.5081	0.2475	0.045*
N1	−0.5144 (6)	1.2233 (5)	0.3856 (2)	0.0545 (7)
C4	−0.1099 (6)	0.7815 (5)	0.3928 (2)	0.0395 (6)
H4A	−0.1675	0.7865	0.4580	0.047*
C2	−0.1148 (5)	0.9263 (4)	0.2256 (2)	0.0322 (6)
H2A	−0.1732	1.0271	0.1794	0.039*
C5	0.0624 (7)	0.6251 (5)	0.3633 (2)	0.0443 (7)
H5A	0.1229	0.5248	0.4094	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0519 (5)	0.0373 (4)	0.0395 (4)	0.0155 (3)	0.0126 (3)	0.0062 (3)
C1	0.0334 (12)	0.0304 (13)	0.0285 (12)	0.0073 (10)	0.0074 (10)	0.0027 (9)
N2	0.0446 (13)	0.0398 (13)	0.0324 (12)	0.0139 (10)	0.0107 (10)	0.0040 (9)
C3	0.0308 (12)	0.0338 (14)	0.0360 (13)	0.0102 (10)	0.0063 (10)	0.0020 (10)
C7	0.0404 (14)	0.0421 (16)	0.0380 (14)	0.0140 (12)	0.0093 (12)	0.0045 (11)
C6	0.0442 (15)	0.0333 (14)	0.0388 (14)	0.0165 (11)	0.0094 (11)	0.0065 (11)
N1	0.0597 (17)	0.0551 (17)	0.0558 (17)	0.0274 (14)	0.0191 (14)	0.0036 (13)
C4	0.0491 (16)	0.0429 (16)	0.0307 (13)	0.0136 (12)	0.0130 (12)	0.0063 (11)
C2	0.0325 (13)	0.0316 (13)	0.0346 (13)	0.0099 (10)	0.0048 (10)	0.0062 (10)
C5	0.0577 (18)	0.0420 (17)	0.0398 (15)	0.0216 (13)	0.0132 (13)	0.0154 (12)

Geometric parameters (Å, º) top

C1—C6	1.380 (4)	C3—C7	1.440 (4)
C1—C2	1.385 (3)	C7—N1	1.139 (4)
C1—N2	1.460 (3)	C6—C5	1.374 (4)
N2—H9A	0.89	C6—H6A	0.93
N2—H9B	0.89	C4—C5	1.374 (4)
N2—H9C	0.89	C4—H4A	0.93
C3—C4	1.390 (4)	C2—H2A	0.93
C3—C2	1.391 (4)	C5—H5A	0.93

C6—C1—C2	121.9 (2)	C5—C6—C1	119.2 (2)
C6—C1—N2	119.8 (2)	C5—C6—H6A	120.4
C2—C1—N2	118.3 (2)	C1—C6—H6A	120.4
C1—N2—H9A	109.5	C5—C4—C3	119.1 (2)
C1—N2—H9B	109.5	C5—C4—H4A	120.4
H9A—N2—H9B	109.5	C3—C4—H4A	120.4
C1—N2—H9C	109.5	C1—C2—C3	117.5 (2)
H9A—N2—H9C	109.5	C1—C2—H2A	121.2
H9B—N2—H9C	109.5	C3—C2—H2A	121.2
C4—C3—C2	121.3 (2)	C6—C5—C4	121.0 (2)
C4—C3—C7	118.2 (2)	C6—C5—H5A	119.5
C2—C3—C7	120.4 (2)	C4—C5—H5A	119.5
N1—C7—C3	177.6 (3)

C2—C1—C6—C5	0.2 (4)	N2—C1—C2—C3	−179.6 (2)
N2—C1—C6—C5	179.4 (3)	C4—C3—C2—C1	0.0 (4)
C2—C3—C4—C5	0.5 (4)	C7—C3—C2—C1	179.8 (2)
C7—C3—C4—C5	−179.3 (3)	C1—C6—C5—C4	0.3 (5)
C6—C1—C2—C3	−0.3 (4)	C3—C4—C5—C6	−0.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H9A···Cl1ⁱ	0.89	2.61	3.111 (3)	116
N2—H9A···Cl1ⁱⁱ	0.89	2.65	3.178 (3)	119
N2—H9C···Cl1ⁱⁱⁱ	0.89	2.73	3.278 (3)	121
N2—H9B···Cl1	0.89	2.76	3.338 (3)	124

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·Cl⁻
M_r	154.60
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	4.663 (3), 6.074 (5), 13.212 (9)
α, β, γ (°)	93.37 (5), 96.201 (19), 96.22 (4)
V (Å³)	368.9 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.25 × 0.18 × 0.18

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.901, 0.917
No. of measured, independent and observed [I > 2σ(I)] reflections	2486, 1618, 1342
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.157, 1.07
No. of reflections	1618
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.52

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—H9A···Cl1ⁱ	0.89	2.61	3.111 (3)	116
N2—H9A···Cl1ⁱⁱ	0.89	2.65	3.178 (3)	119
N2—H9C···Cl1ⁱⁱⁱ	0.89	2.73	3.278 (3)	121
N2—H9B···Cl1	0.89	2.76	3.338 (3)	124

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

Acknowledgements

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

References

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