Dicyclo­hexyl­ammonium thio­cyanate

Khawar Rauf, M.; Ebihara, M.; Imtiaz-ud-Din; Badshah, A.

doi:10.1107/S1600536807067773

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o366

doi:10.1107/S1600536807067773

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Dicyclohexylammonium thiocyanate

M. Khawar Rauf,^a Masahiro Ebihara,^a Imtiaz-ud-Din ^b and Amin Badshah ^b ^*

^aDepartment of Chemistry, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan, and ^bDepartment of Chemistry, Quaid-i-Azam University Islamabad, 45320-Pakistan
^*Correspondence e-mail: aminbadshah@yahoo.com

(Received 30 November 2007; accepted 19 December 2007; online 4 January 2008)

In the crystal structure of the title compound, C₁₂H₂₄N⁺·NCS⁻, the anions and cations are linked through N—H⋯N and N—H⋯S hydrogen bonds, resulting in a chain along the a axis.

Related literature

For related literature, see: Ng (1992 , 1993 , 1995a ,b ).

Experimental

Crystal data

C₁₂H₂₄N⁺·CNS⁻
M_r = 240.40
Orthorhombic, P b c a
a = 8.781 (2) Å
b = 16.479 (4) Å
c = 19.026 (4) Å
V = 2753.2 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 123 (2) K
0.38 × 0.32 × 0.26 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer
Absorption correction: none
20885 measured reflections
3151 independent reflections
3014 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.092
S = 1.20
3151 reflections
153 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯N2	0.901 (18)	1.986 (19)	2.8811 (17)	172.8 (16)
N1—H1A⋯S1ⁱ	0.926 (17)	2.440 (17)	3.3610 (13)	172.8 (13)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001 ); cell refinement: CrystalClear; data reduction: TEXSAN (Rigaku/MSC, 2004 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97 and TEXSAN.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067773/hg2363sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807067773/hg2363Isup2.hkl

checkCIF report

Comment top

Ethanolic solution of dicyclohexylamine, when treated with equimolar amount of a dicarboxylic acid, affords the dicyclohexylammonium hydrogen dicarboxylate, which can be used in a condensation reaction with an organotin(IV) hydroxides or oxides to produce the corresponding organostannate (Ng, 1995b). The dicyclohexylammonium cation has been used in earlier studies to form crystalline derivatives of the dicarboxylic acids (Ng, 1992, 1993). The title compound (I) is an unexpected product of a reaction to synthesis a bifunctionalthiourea. As a result of the steric hindrance of the two cyclohexyl rings in the cation, the C—N—C angle is opened up to 117.23 (9)°, relative to the typical tetrahedral angle of 109.5°. Both of the cyclohexyl rings, exhibit chair conformations. The anionic thiocyanate group is strongly hydrogen bonded to the cation through N—H···N and N—H···S. All the other geometric parameters are in agreement with the previous studies of similar compounds (Ng, 1995a).

Related literature top

For related literature, see: Ng (1992, 1993, 1995a,b).

Experimental top

The title compound was obtained as an unexpected product from a reaction mixture containing dicyclhexylamine, benzoylchloride and potassiumthiocyanate in acetone, refluxed at 60 °C. Crystals were grown from a solution of the compound in toluene.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); data reduction: TEXSAN (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and TEXSAN (Rigaku/MSC, 2004).

Figures top

	Fig. 1. Molecular structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 30% probability level.
	Fig. 2. Showing hydrogen bonded anion to the cation through N—H···N and N—H···S.

Dicyclohexylammonium thiocyanate top

Crystal data top

C₁₂H₂₄N⁺·CNS⁻	F(000) = 1056
M_r = 240.40	D_x = 1.160 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7454 reflections
a = 8.781 (2) Å	θ = 3.2–27.5°
b = 16.479 (4) Å	µ = 0.21 mm⁻¹
c = 19.026 (4) Å	T = 123 K
V = 2753.2 (11) Å³	Block, colorless
Z = 8	0.38 × 0.32 × 0.26 mm

Data collection top

Rigaku/MSC Mercury CCD diffractometer	3014 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 14.62 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −11→7
20885 measured reflections	k = −17→21
3151 independent reflections	l = −23→24

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ²(F_o²) + (0.037P)² + 1.0451P] where P = (F_o² + 2F_c²)/3
3151 reflections	(Δ/σ)_max = 0.001
153 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₂H₂₄N⁺·CNS⁻	V = 2753.2 (11) Å³
M_r = 240.40	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.781 (2) Å	µ = 0.21 mm⁻¹
b = 16.479 (4) Å	T = 123 K
c = 19.026 (4) Å	0.38 × 0.32 × 0.26 mm

Data collection top

Rigaku/MSC Mercury CCD diffractometer	3014 reflections with I > 2σ(I)
20885 measured reflections	R_int = 0.029
3151 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	Δρ_max = 0.32 e Å⁻³
3151 reflections	Δρ_min = −0.17 e Å⁻³
153 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
N1	0.37002 (12)	0.15566 (6)	0.52333 (5)	0.0141 (2)
H1A	0.4620 (19)	0.1381 (9)	0.5417 (8)	0.024 (4)*
H1B	0.371 (2)	0.2103 (11)	0.5215 (9)	0.028 (4)*
C1	0.36414 (14)	0.12612 (7)	0.44808 (6)	0.0145 (2)
H1	0.3743	0.0657	0.4479	0.017*
C2	0.49937 (14)	0.16257 (8)	0.40919 (6)	0.0176 (3)
H2A	0.5952	0.1431	0.4308	0.021*
H2B	0.4966	0.2224	0.4135	0.021*
C3	0.49638 (15)	0.13897 (8)	0.33142 (7)	0.0209 (3)
H3A	0.5820	0.1657	0.3067	0.025*
H3B	0.5097	0.0795	0.3269	0.025*
C4	0.34657 (15)	0.16400 (9)	0.29723 (7)	0.0220 (3)
H4A	0.3372	0.2239	0.2980	0.026*
H4B	0.3455	0.1461	0.2476	0.026*
C5	0.21236 (15)	0.12627 (8)	0.33614 (7)	0.0208 (3)
H5A	0.2169	0.0665	0.3314	0.025*
H5B	0.1161	0.1451	0.3145	0.025*
C6	0.21305 (14)	0.14887 (8)	0.41423 (6)	0.0173 (3)
H6A	0.1958	0.2079	0.4193	0.021*
H6B	0.1291	0.1202	0.4385	0.021*
C7	0.24518 (14)	0.12773 (7)	0.57191 (6)	0.0151 (2)
H7	0.1450	0.1455	0.5522	0.018*
C8	0.26768 (15)	0.16798 (8)	0.64351 (6)	0.0184 (3)
H8A	0.2641	0.2277	0.6382	0.022*
H8B	0.3687	0.1531	0.6627	0.022*
C9	0.14262 (17)	0.14035 (8)	0.69417 (7)	0.0239 (3)
H9A	0.1596	0.1653	0.7408	0.029*
H9B	0.0424	0.1588	0.6765	0.029*
C10	0.14189 (17)	0.04800 (8)	0.70150 (7)	0.0263 (3)
H10A	0.2385	0.0300	0.7233	0.032*
H10B	0.0572	0.0314	0.7327	0.032*
C11	0.12341 (16)	0.00738 (8)	0.62991 (7)	0.0241 (3)
H11A	0.0214	0.0203	0.6108	0.029*
H11B	0.1302	−0.0522	0.6357	0.029*
C12	0.24540 (15)	0.03553 (7)	0.57788 (7)	0.0197 (3)
H12A	0.3467	0.0168	0.5940	0.024*
H12B	0.2255	0.0113	0.5312	0.024*
N2	0.36405 (13)	0.32916 (7)	0.50487 (6)	0.0223 (2)
C13	0.29457 (14)	0.35958 (7)	0.45967 (7)	0.0175 (3)
S1	0.19380 (4)	0.40074 (2)	0.396108 (18)	0.02252 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0148 (5)	0.0155 (5)	0.0121 (5)	0.0004 (4)	−0.0009 (4)	0.0003 (4)
C1	0.0159 (6)	0.0167 (5)	0.0108 (5)	−0.0004 (4)	−0.0004 (4)	−0.0018 (4)
C2	0.0130 (6)	0.0258 (6)	0.0141 (6)	−0.0001 (5)	0.0000 (5)	−0.0015 (5)
C3	0.0170 (6)	0.0309 (7)	0.0146 (6)	0.0008 (5)	0.0024 (5)	−0.0026 (5)
C4	0.0212 (7)	0.0322 (7)	0.0126 (6)	−0.0012 (5)	−0.0007 (5)	0.0018 (5)
C5	0.0176 (6)	0.0302 (7)	0.0145 (6)	−0.0033 (5)	−0.0034 (5)	−0.0002 (5)
C6	0.0134 (6)	0.0237 (6)	0.0147 (6)	−0.0020 (5)	−0.0001 (5)	−0.0008 (5)
C7	0.0144 (6)	0.0177 (5)	0.0132 (6)	−0.0002 (5)	0.0015 (5)	0.0016 (4)
C8	0.0208 (6)	0.0204 (6)	0.0142 (6)	−0.0004 (5)	0.0004 (5)	−0.0010 (5)
C9	0.0269 (7)	0.0285 (7)	0.0161 (6)	0.0002 (6)	0.0050 (5)	−0.0006 (5)
C10	0.0307 (7)	0.0287 (7)	0.0196 (7)	−0.0019 (6)	0.0054 (6)	0.0078 (5)
C11	0.0258 (7)	0.0218 (6)	0.0248 (7)	−0.0045 (5)	0.0045 (6)	0.0046 (5)
C12	0.0224 (6)	0.0172 (6)	0.0196 (6)	−0.0016 (5)	0.0031 (5)	0.0008 (5)
N2	0.0192 (6)	0.0197 (5)	0.0279 (6)	−0.0004 (4)	0.0000 (5)	−0.0013 (5)
C13	0.0151 (6)	0.0149 (6)	0.0226 (6)	−0.0022 (5)	0.0061 (5)	−0.0035 (5)
S1	0.02052 (18)	0.02481 (18)	0.02222 (18)	0.00004 (12)	0.00086 (13)	0.00398 (12)

Geometric parameters (Å, º) top

N1—C7	1.5060 (16)	C6—H6B	0.9900
N1—C1	1.5132 (15)	C7—C12	1.5237 (17)
N1—H1A	0.926 (17)	C7—C8	1.5280 (17)
N1—H1B	0.901 (18)	C7—H7	1.0000
C1—C6	1.5216 (17)	C8—C9	1.5304 (18)
C1—C2	1.5226 (17)	C8—H8A	0.9900
C1—H1	1.0000	C8—H8B	0.9900
C2—C3	1.5301 (17)	C9—C10	1.528 (2)
C2—H2A	0.9900	C9—H9A	0.9900
C2—H2B	0.9900	C9—H9B	0.9900
C3—C4	1.5244 (18)	C10—C11	1.526 (2)
C3—H3A	0.9900	C10—H10A	0.9900
C3—H3B	0.9900	C10—H10B	0.9900
C4—C5	1.5243 (18)	C11—C12	1.5304 (18)
C4—H4A	0.9900	C11—H11A	0.9900
C4—H4B	0.9900	C11—H11B	0.9900
C5—C6	1.5317 (17)	C12—H12A	0.9900
C5—H5A	0.9900	C12—H12B	0.9900
C5—H5B	0.9900	N2—C13	1.1676 (18)
C6—H6A	0.9900	C13—S1	1.6448 (14)

C7—N1—C1	117.23 (9)	C5—C6—H6B	109.5
C7—N1—H1A	107.9 (10)	H6A—C6—H6B	108.1
C1—N1—H1A	106.6 (10)	N1—C7—C12	110.47 (10)
C7—N1—H1B	109.4 (11)	N1—C7—C8	108.69 (10)
C1—N1—H1B	106.6 (11)	C12—C7—C8	111.48 (10)
H1A—N1—H1B	108.8 (15)	N1—C7—H7	108.7
N1—C1—C6	110.54 (10)	C12—C7—H7	108.7
N1—C1—C2	107.84 (10)	C8—C7—H7	108.7
C6—C1—C2	112.16 (10)	C7—C8—C9	109.85 (11)
N1—C1—H1	108.7	C7—C8—H8A	109.7
C6—C1—H1	108.7	C9—C8—H8A	109.7
C2—C1—H1	108.7	C7—C8—H8B	109.7
C1—C2—C3	110.87 (10)	C9—C8—H8B	109.7
C1—C2—H2A	109.5	H8A—C8—H8B	108.2
C3—C2—H2A	109.5	C10—C9—C8	110.90 (11)
C1—C2—H2B	109.5	C10—C9—H9A	109.5
C3—C2—H2B	109.5	C8—C9—H9A	109.5
H2A—C2—H2B	108.1	C10—C9—H9B	109.5
C4—C3—C2	111.02 (10)	C8—C9—H9B	109.5
C4—C3—H3A	109.4	H9A—C9—H9B	108.0
C2—C3—H3A	109.4	C11—C10—C9	110.85 (11)
C4—C3—H3B	109.4	C11—C10—H10A	109.5
C2—C3—H3B	109.4	C9—C10—H10A	109.5
H3A—C3—H3B	108.0	C11—C10—H10B	109.5
C5—C4—C3	110.46 (11)	C9—C10—H10B	109.5
C5—C4—H4A	109.6	H10A—C10—H10B	108.1
C3—C4—H4A	109.6	C10—C11—C12	111.70 (11)
C5—C4—H4B	109.6	C10—C11—H11A	109.3
C3—C4—H4B	109.6	C12—C11—H11A	109.3
H4A—C4—H4B	108.1	C10—C11—H11B	109.3
C4—C5—C6	111.65 (11)	C12—C11—H11B	109.3
C4—C5—H5A	109.3	H11A—C11—H11B	107.9
C6—C5—H5A	109.3	C7—C12—C11	110.47 (11)
C4—C5—H5B	109.3	C7—C12—H12A	109.6
C6—C5—H5B	109.3	C11—C12—H12A	109.6
H5A—C5—H5B	108.0	C7—C12—H12B	109.6
C1—C6—C5	110.73 (10)	C11—C12—H12B	109.6
C1—C6—H6A	109.5	H12A—C12—H12B	108.1
C5—C6—H6A	109.5	N2—C13—S1	178.68 (12)
C1—C6—H6B	109.5

C7—N1—C1—C6	56.44 (13)	C1—N1—C7—C12	60.50 (14)
C7—N1—C1—C2	179.38 (10)	C1—N1—C7—C8	−176.89 (10)
N1—C1—C2—C3	−176.97 (10)	N1—C7—C8—C9	−179.73 (10)
C6—C1—C2—C3	−55.03 (13)	C12—C7—C8—C9	−57.74 (14)
C1—C2—C3—C4	56.09 (14)	C7—C8—C9—C10	57.46 (14)
C2—C3—C4—C5	−56.87 (15)	C8—C9—C10—C11	−56.47 (15)
C3—C4—C5—C6	56.52 (15)	C9—C10—C11—C12	55.21 (16)
N1—C1—C6—C5	174.64 (10)	N1—C7—C12—C11	177.35 (10)
C2—C1—C6—C5	54.26 (13)	C8—C7—C12—C11	56.39 (14)
C4—C5—C6—C1	−54.99 (14)	C10—C11—C12—C7	−54.95 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···N2	0.901 (18)	1.986 (19)	2.8811 (17)	172.8 (16)
N1—H1A···S1ⁱ	0.926 (17)	2.440 (17)	3.3610 (13)	172.8 (13)

Symmetry code: (i) x+1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₂₄N⁺·CNS⁻
M_r	240.40
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	123
a, b, c (Å)	8.781 (2), 16.479 (4), 19.026 (4)
V (Å³)	2753.2 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.38 × 0.32 × 0.26

Data collection
Diffractometer	Rigaku/MSC Mercury CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	20885, 3151, 3014
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.092, 1.20
No. of reflections	3151
No. of parameters	153
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.17

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2001), SIR97 (Altomare et al., 1999), ORTEPII (Johnson, 1976), SHELXL97 (Sheldrick, 1997) and TEXSAN (Rigaku/MSC, 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···N2	0.901 (18)	1.986 (19)	2.8811 (17)	172.8 (16)
N1—H1A···S1ⁱ	0.926 (17)	2.440 (17)	3.3610 (13)	172.8 (13)

Symmetry code: (i) x+1/2, −y+1/2, −z+1.

Acknowledgements

MKR is grateful to the Higher Education Commission of Pakistan for financial support under the International Support Initiative Program for a Doctoral Fellowship at Gifu University, Japan.

References

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