3-Cyano­anilinium chloride

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.052

• wR(F ²) = 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

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—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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms were fixed geometrically [C-H = 0.93 Å and N-H = 0.89 Å] and treated as riding, with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(N).

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.

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.

Crystal data

C7H7N2+·Cl–	Z = 2
Mr = 154.60	F000 = 160
Triclinic, P1	Dx = 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 = 2.3–24.4º
c = 13.212 (9) Å	µ = 0.44 mm−1
α = 93.37 (5)º	T = 298 (2) K
β = 96.201 (19)º	Block, colourless
γ = 96.22 (4)º	0.25 × 0.18 × 0.18 mm
V = 368.9 (5) Å3

Data collection

Rigaku Mercury2 diffractometer	1618 independent reflections
Radiation source: fine-focus sealed tube	1342 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.021
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5º
T = 298(2) K	θmin = 3.1º
ω scans	h = −6→6
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)	k = −7→5
Tmin = 0.901, Tmax = 0.917	l = −16→17
2486 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052	H-atom parameters constrained
wR(F2) = 0.157	w = 1/[σ2(Fo2) + (0.0787P)2 + 0.2472P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
1618 reflections	Δρmax = 0.52 e Å−3
91 parameters	Δρmin = −0.52 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.