4-Chloro­anilinium thio­cyanate

Abstract

In the title compound, C₆H₇ClN⁺·NCS⁻, the benzene ring and the protonated amine and chloro substituents are nearly planar, with a maximum deviation of 0.002 (2) Å for the N atom. In the crystal, the mol­ecules are linked by N—H⋯N and N—H⋯S hydrogen bonds into a chain along the b axis.

Related literature  

For bond-length data see: Allen et al. (1987 ▶) and for a description of the Cambridge Structural Database, see: Allen (2002 ▶). For related thio­cyanate structures, see: Salem et al. (2012 ▶); Selvakumaran et al. (2011 ▶); Khawar Rauf et al. (2008 ▶).

Experimental  

Crystal data  

• C₆H₇ClN⁺·NCS⁻

• M _r = 186.66

• Orthorhombic,

• a = 7.743 (2) Å

• b = 7.199 (2) Å

• c = 31.913 (10) Å

• V = 1778.8 (10) ų

• Z = 8

• Mo Kα radiation

• μ = 0.60 mm⁻¹

• T = 298 K

• 0.50 × 0.43 × 0.30 mm

Data collection  

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.754, T _max = 0.841

• 10422 measured reflections

• 1846 independent reflections

• 1628 reflections with I > 2σ(I)

• R _int = 0.024

Refinement  

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.108

• S = 1.18

• 1846 reflections

• 112 parameters

• 3 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; 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, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681202377X/bq2362Isup3.cml

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
N1—H1A⋯N2i	0.87 (2)	2.03 (1)	2.888 (2)	172 (2)
N1—H1B⋯N2ii	0.86 (1)	2.08 (1)	2.911 (3)	162 (2)
N1—H1C⋯S1iii	0.87 (2)	2.48 (3)	3.285 (2)	155 (2)

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

The title compound (Fig. 1) is an organic thiocyanate similar to dicylohexylammonium thiocyanate (Khawar Rauf et al., 2008; Selvakumaran et al., 2011) and recently 2-cyclohexan-1-iminium thiocyanate (Salem et al., 2012). The para-anilinium cation is planar except the hydrogen atoms of the ammonium moiety. The maximum deviation is 0.002 (2) Å for N1 atom from the least square plane. The thiocyanate ion is linear with N2–C7–S1 bond angle of 179.5 (2)°. The bond lengths and angles are in normal range (Allen et al., 1987; 2002). In the crystal structure, the molecules are linked by the intermolecular hydrogen bonds between the hydrogen atoms of the ammonium moiety with the nitrogen and sulfur atoms of the thiocynato anion (Table 1) to form one-dimensional chain along the b axis (Fig. 2).

Experimental

All solvents and chemicals were of analytical grade and were used without purification. The title compound was prepared by mixing ammonium thiocyanate (0.76 g, 0.01 mol) and para-chloroaniline (1.27 g, 0.01 mol) in the presence of HCl. The mixture was refluxed for 1 h. Single crystals were obtained from the solution after one day of evaporation. Yield 85%; m.p: 390.5–393.2 K.

Refinement

After their location in the difference map, the H-atoms attached to the C were fixed geometrically at ideal positions and allowed to ride on the parent atoms with C—H = 0.93 Å, with U_iso(H)=1.2U_eq(C,) However, the protonated amino hydrogen atoms were located from the Fourier map and refined isotropically.

Figures

Fig. 1.

: Molecular structure of the title compound, (I), with 50% probability displacement ellipsoids.

Fig. 2.

: Packing diagram of (I), viewed down b axis. The dashed lines denote hydrogen bonds.

Crystal data

C6H7ClN+·NCS−	F(000) = 768
Mr = 186.66	Dx = 1.394 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4443 reflections
a = 7.743 (2) Å	θ = 1.2–26.5°
b = 7.199 (2) Å	µ = 0.60 mm−1
c = 31.913 (10) Å	T = 298 K
V = 1778.8 (10) Å3	Slab, colourless
Z = 8	0.50 × 0.43 × 0.30 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	1846 independent reflections
Radiation source: fine-focus sealed tube	1628 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 83.66 pixels mm-1	θmax = 26.5°, θmin = 1.2°
ω scan	h = −5→9
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −9→8
Tmin = 0.754, Tmax = 0.841	l = −38→40
10422 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ2(Fo2) + (0.0501P)2 + 0.6879P] where P = (Fo2 + 2Fc2)/3
1846 reflections	(Δ/σ)max < 0.002
112 parameters	Δρmax = 0.31 e Å−3
3 restraints	Δρmin = −0.19 e Å−3

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	0.41886 (10)	0.01916 (11)	0.749321 (18)	0.0681 (2)
S1	0.66687 (7)	0.20120 (7)	0.468838 (17)	0.04316 (18)
N1	0.5614 (2)	0.1442 (3)	0.56935 (6)	0.0404 (4)
H1A	0.6668 (16)	0.111 (4)	0.5642 (7)	0.048 (7)*
H1B	0.550 (3)	0.2589 (17)	0.5623 (8)	0.062 (8)*
H1C	0.490 (3)	0.082 (4)	0.5539 (7)	0.068 (8)*
N2	0.4214 (2)	0.4537 (3)	0.43930 (7)	0.0510 (5)
C1	0.4128 (3)	0.2283 (4)	0.63414 (7)	0.0581 (6)
H1	0.3576	0.3241	0.6199	0.070*
C2	0.3805 (4)	0.1992 (4)	0.67630 (8)	0.0638 (7)
H2	0.3038	0.2757	0.6906	0.077*
C3	0.4620 (3)	0.0576 (3)	0.69664 (6)	0.0446 (5)
C4	0.5754 (3)	−0.0562 (3)	0.67624 (7)	0.0561 (6)
H4	0.6301	−0.1524	0.6904	0.067*
C5	0.6076 (3)	−0.0262 (3)	0.63414 (7)	0.0526 (6)
H5	0.6847	−0.1023	0.6198	0.063*
C6	0.5263 (2)	0.1152 (3)	0.61366 (6)	0.0363 (4)
C7	0.5235 (3)	0.3494 (3)	0.45172 (6)	0.0367 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0875 (5)	0.0781 (5)	0.0387 (3)	−0.0028 (4)	0.0118 (3)	0.0012 (3)
S1	0.0390 (3)	0.0415 (3)	0.0490 (3)	0.0027 (2)	0.0001 (2)	0.0058 (2)
N1	0.0408 (10)	0.0419 (10)	0.0387 (9)	−0.0012 (8)	−0.0013 (8)	0.0028 (7)
N2	0.0441 (10)	0.0450 (10)	0.0639 (12)	0.0019 (9)	−0.0057 (9)	0.0067 (9)
C1	0.0664 (16)	0.0605 (14)	0.0473 (13)	0.0269 (13)	−0.0001 (11)	0.0027 (11)
C2	0.0710 (16)	0.0712 (16)	0.0491 (13)	0.0305 (14)	0.0105 (12)	−0.0039 (12)
C3	0.0497 (12)	0.0505 (12)	0.0338 (9)	−0.0063 (10)	0.0016 (9)	−0.0028 (9)
C4	0.0690 (16)	0.0528 (13)	0.0465 (12)	0.0168 (12)	0.0043 (11)	0.0104 (10)
C5	0.0606 (14)	0.0531 (13)	0.0440 (12)	0.0189 (11)	0.0098 (10)	0.0047 (10)
C6	0.0354 (9)	0.0366 (10)	0.0368 (10)	−0.0023 (8)	−0.0018 (8)	−0.0012 (7)
C7	0.0372 (10)	0.0338 (9)	0.0392 (10)	−0.0066 (8)	0.0024 (8)	−0.0005 (8)

Geometric parameters (Å, º)

Cl1—C3	1.736 (2)	C1—H1	0.9300
S1—C7	1.634 (2)	C2—C3	1.363 (3)
N1—C6	1.455 (3)	C2—H2	0.9300
N1—H1A	0.866 (10)	C3—C4	1.365 (3)
N1—H1B	0.860 (10)	C4—C5	1.384 (3)
N1—H1C	0.868 (10)	C4—H4	0.9300
N2—C7	1.160 (3)	C5—C6	1.364 (3)
C1—C6	1.365 (3)	C5—H5	0.9300
C1—C2	1.385 (4)
C6—N1—H1A	108.8 (16)	C2—C3—Cl1	119.39 (18)
C6—N1—H1B	111.9 (19)	C4—C3—Cl1	119.33 (18)
H1A—N1—H1B	108 (3)	C3—C4—C5	119.0 (2)
C6—N1—H1C	110.9 (19)	C3—C4—H4	120.5
H1A—N1—H1C	111 (3)	C5—C4—H4	120.5
H1B—N1—H1C	107 (3)	C6—C5—C4	119.9 (2)
C6—C1—C2	119.4 (2)	C6—C5—H5	120.1
C6—C1—H1	120.3	C4—C5—H5	120.1
C2—C1—H1	120.3	C5—C6—C1	120.9 (2)
C3—C2—C1	119.5 (2)	C5—C6—N1	119.10 (18)
C3—C2—H2	120.3	C1—C6—N1	120.02 (19)
C1—C2—H2	120.3	N2—C7—S1	179.5 (2)
C2—C3—C4	121.3 (2)
C6—C1—C2—C3	−0.3 (4)	C3—C4—C5—C6	−0.1 (4)
C1—C2—C3—C4	0.2 (4)	C4—C5—C6—C1	0.0 (4)
C1—C2—C3—Cl1	−179.0 (2)	C4—C5—C6—N1	−179.8 (2)
C2—C3—C4—C5	0.1 (4)	C2—C1—C6—C5	0.2 (4)
Cl1—C3—C4—C5	179.2 (2)	C2—C1—C6—N1	180.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2i	0.87 (2)	2.03 (1)	2.888 (2)	172 (2)
N1—H1B···N2ii	0.86 (1)	2.08 (1)	2.911 (3)	162 (2)
N1—H1C···S1iii	0.87 (2)	2.48 (3)	3.285 (2)	155 (2)

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