4-Chloro­anilinium thio­cyanate

Yusoff, S.F.M.; Halima, F.S.; Yamin, B.M.

doi:10.1107/S160053681202377X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o1988

https://doi.org/10.1107/S160053681202377X

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4-Chloroanilinium thiocyanate

Siti Fairus M. Yusoff,^a F. Salem Halima ^a and Bohari M. Yamin ^a ^*

^aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
^*Correspondence e-mail: bohari@pkrisc.cc.ukm.my

(Received 23 May 2012; accepted 24 May 2012; online 2 June 2012)

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, P b c a
a = 7.743 (2) Å
b = 7.199 (2) Å
c = 31.913 (10) Å
V = 1778.8 (10) Å³
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[F² > 2σ(F²)] = 0.039
wR(F²) = 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

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) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y, -z+1.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681202377X/bq2362sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681202377X/bq2362Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681202377X/bq2362Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Structure description top

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).

Computing details top

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

Figures top

	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.

4-Chloroanilinium thiocyanate top

Crystal data top

C₆H₇ClN⁺·NCS⁻	F(000) = 768
M_r = 186.66	D_x = 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 top

Bruker SMART APEX CCD area-detector diffractometer	1846 independent reflections
Radiation source: fine-focus sealed tube	1628 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 83.66 pixels mm^-1	θ_max = 26.5°, θ_min = 1.2°
ω scan	h = −5→9
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −9→8
T_min = 0.754, T_max = 0.841	l = −38→40
10422 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)] = 0.039	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(F_o²) + (0.0501P)² + 0.6879P] where P = (F_o² + 2F_c²)/3
1846 reflections	(Δ/σ)_max < 0.002
112 parameters	Δρ_max = 0.31 e Å⁻³
3 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₆H₇ClN⁺·NCS⁻	V = 1778.8 (10) Å³
M_r = 186.66	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.743 (2) Å	µ = 0.60 mm⁻¹
b = 7.199 (2) Å	T = 298 K
c = 31.913 (10) Å	0.50 × 0.43 × 0.30 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1846 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1628 reflections with I > 2σ(I)
T_min = 0.754, T_max = 0.841	R_int = 0.024
10422 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	3 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	Δρ_max = 0.31 e Å⁻³
1846 reflections	Δρ_min = −0.19 e Å⁻³
112 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	0.41886 (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 (Å²) top

	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) top

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) top

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.

Experimental details

Crystal data
Chemical formula	C₆H₇ClN⁺·NCS⁻
M_r	186.66
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	7.743 (2), 7.199 (2), 31.913 (10)
V (Å³)	1778.8 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.50 × 0.43 × 0.30

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.754, 0.841
No. of measured, independent and observed [I > 2σ(I)] reflections	10422, 1846, 1628
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.108, 1.18
No. of reflections	1846
No. of parameters	112
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.19

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.866 (15)	2.029 (14)	2.888 (2)	172 (2)
N1—H1B···N2ⁱⁱ	0.860 (14)	2.081 (13)	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.

Acknowledgements

The authors would like to thank the Malaysian Government and Universiti Kebangsaan Malaysia for the research grants UKM-GUP-NBT-68–27–110.

References

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