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Acta Cryst. (2008). E64, o366    [ doi:10.1107/S1600536807067773 ]

Dicyclohexylammonium thiocyanate

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

Abstract top

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.

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.

Refinement top

The nitrogen H atoms were refined isotropically. Other H atoms were placed in idealized positions and treated as riding atoms with C—H distance in the range 0.95–0.99 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C).

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
[Figure 1] Fig. 1. Molecular structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 30% probability level.
[Figure 2] 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–F000 = 1056
Mr = 240.40Dx = 1.160 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71070 Å
Hall symbol: -P 2ac 2abCell parameters from 7454 reflections
a = 8.781 (2) Åθ = 3.2–27.5º
b = 16.479 (4) ŵ = 0.21 mm−1
c = 19.026 (4) ÅT = 123 (2) K
V = 2753.2 (11) Å3Block, colorless
Z = 80.38 × 0.32 × 0.26 mm
Data collection top
Rigaku/MSC Mercury CCD
diffractometer		3014 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.029
Detector resolution: 14.62 pixels mm-1θmax = 27.5º
T = 123(2) Kθmin = 3.2º
ω scansh = −11→7
Absorption correction: nonek = −17→21
20885 measured reflectionsl = −23→24
3151 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.092  w = 1/[σ2(Fo2) + (0.037P)2 + 1.0451P]
where P = (Fo2 + 2Fc2)/3
S = 1.20(Δ/σ)max = 0.001
3151 reflectionsΔρmax = 0.32 e Å−3
153 parametersΔρmin = −0.17 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C12H24N+·CNS–V = 2753.2 (11) Å3
Mr = 240.40Z = 8
Orthorhombic, PbcaMo Kα
a = 8.781 (2) ŵ = 0.21 mm−1
b = 16.479 (4) ÅT = 123 (2) K
c = 19.026 (4) Å0.38 × 0.32 × 0.26 mm
Data collection top
Rigaku/MSC Mercury CCD
diffractometer		3151 independent reflections
Absorption correction: none3014 reflections with I > 2σ(I)
20885 measured reflectionsRint = 0.029
Refinement top
R[F2 > 2σ(F2)] = 0.041153 parameters
wR(F2) = 0.092H atoms treated by a mixture of
independent and constrained refinement
S = 1.20Δρmax = 0.32 e Å−3
3151 reflectionsΔρmin = −0.17 e Å−3
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
xyzUiso*/Ueq
N10.37002 (12)0.15566 (6)0.52333 (5)0.0141 (2)
H1A0.4620 (19)0.1381 (9)0.5417 (8)0.024 (4)*
H1B0.371 (2)0.2103 (11)0.5215 (9)0.028 (4)*
C10.36414 (14)0.12612 (7)0.44808 (6)0.0145 (2)
H10.37430.06570.44790.017*
C20.49937 (14)0.16257 (8)0.40919 (6)0.0176 (3)
H2A0.59520.14310.43080.021*
H2B0.49660.22240.41350.021*
C30.49638 (15)0.13897 (8)0.33142 (7)0.0209 (3)
H3A0.58200.16570.30670.025*
H3B0.50970.07950.32690.025*
C40.34657 (15)0.16400 (9)0.29723 (7)0.0220 (3)
H4A0.33720.22390.29800.026*
H4B0.34550.14610.24760.026*
C50.21236 (15)0.12627 (8)0.33614 (7)0.0208 (3)
H5A0.21690.06650.33140.025*
H5B0.11610.14510.31450.025*
C60.21305 (14)0.14887 (8)0.41423 (6)0.0173 (3)
H6A0.19580.20790.41930.021*
H6B0.12910.12020.43850.021*
C70.24518 (14)0.12773 (7)0.57191 (6)0.0151 (2)
H70.14500.14550.55220.018*
C80.26768 (15)0.16798 (8)0.64351 (6)0.0184 (3)
H8A0.26410.22770.63820.022*
H8B0.36870.15310.66270.022*
C90.14262 (17)0.14035 (8)0.69417 (7)0.0239 (3)
H9A0.15960.16530.74080.029*
H9B0.04240.15880.67650.029*
C100.14189 (17)0.04800 (8)0.70150 (7)0.0263 (3)
H10A0.23850.03000.72330.032*
H10B0.05720.03140.73270.032*
C110.12341 (16)0.00738 (8)0.62991 (7)0.0241 (3)
H11A0.02140.02030.61080.029*
H11B0.1302−0.05220.63570.029*
C120.24540 (15)0.03553 (7)0.57788 (7)0.0197 (3)
H12A0.34670.01680.59400.024*
H12B0.22550.01130.53120.024*
N20.36405 (13)0.32916 (7)0.50487 (6)0.0223 (2)
C130.29457 (14)0.35958 (7)0.45967 (7)0.0175 (3)
S10.19380 (4)0.40074 (2)0.396108 (18)0.02252 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0148 (5)0.0155 (5)0.0121 (5)0.0004 (4)−0.0009 (4)0.0003 (4)
C10.0159 (6)0.0167 (5)0.0108 (5)−0.0004 (4)−0.0004 (4)−0.0018 (4)
C20.0130 (6)0.0258 (6)0.0141 (6)−0.0001 (5)0.0000 (5)−0.0015 (5)
C30.0170 (6)0.0309 (7)0.0146 (6)0.0008 (5)0.0024 (5)−0.0026 (5)
C40.0212 (7)0.0322 (7)0.0126 (6)−0.0012 (5)−0.0007 (5)0.0018 (5)
C50.0176 (6)0.0302 (7)0.0145 (6)−0.0033 (5)−0.0034 (5)−0.0002 (5)
C60.0134 (6)0.0237 (6)0.0147 (6)−0.0020 (5)−0.0001 (5)−0.0008 (5)
C70.0144 (6)0.0177 (5)0.0132 (6)−0.0002 (5)0.0015 (5)0.0016 (4)
C80.0208 (6)0.0204 (6)0.0142 (6)−0.0004 (5)0.0004 (5)−0.0010 (5)
C90.0269 (7)0.0285 (7)0.0161 (6)0.0002 (6)0.0050 (5)−0.0006 (5)
C100.0307 (7)0.0287 (7)0.0196 (7)−0.0019 (6)0.0054 (6)0.0078 (5)
C110.0258 (7)0.0218 (6)0.0248 (7)−0.0045 (5)0.0045 (6)0.0046 (5)
C120.0224 (6)0.0172 (6)0.0196 (6)−0.0016 (5)0.0031 (5)0.0008 (5)
N20.0192 (6)0.0197 (5)0.0279 (6)−0.0004 (4)0.0000 (5)−0.0013 (5)
C130.0151 (6)0.0149 (6)0.0226 (6)−0.0022 (5)0.0061 (5)−0.0035 (5)
S10.02052 (18)0.02481 (18)0.02222 (18)0.00004 (12)0.00086 (13)0.00398 (12)
Geometric parameters (Å, °) top
N1—C71.5060 (16)C6—H6B0.9900
N1—C11.5132 (15)C7—C121.5237 (17)
N1—H1A0.926 (17)C7—C81.5280 (17)
N1—H1B0.901 (18)C7—H71.0000
C1—C61.5216 (17)C8—C91.5304 (18)
C1—C21.5226 (17)C8—H8A0.9900
C1—H11.0000C8—H8B0.9900
C2—C31.5301 (17)C9—C101.528 (2)
C2—H2A0.9900C9—H9A0.9900
C2—H2B0.9900C9—H9B0.9900
C3—C41.5244 (18)C10—C111.526 (2)
C3—H3A0.9900C10—H10A0.9900
C3—H3B0.9900C10—H10B0.9900
C4—C51.5243 (18)C11—C121.5304 (18)
C4—H4A0.9900C11—H11A0.9900
C4—H4B0.9900C11—H11B0.9900
C5—C61.5317 (17)C12—H12A0.9900
C5—H5A0.9900C12—H12B0.9900
C5—H5B0.9900N2—C131.1676 (18)
C6—H6A0.9900C13—S11.6448 (14)
C7—N1—C1117.23 (9)C5—C6—H6B109.5
C7—N1—H1A107.9 (10)H6A—C6—H6B108.1
C1—N1—H1A106.6 (10)N1—C7—C12110.47 (10)
C7—N1—H1B109.4 (11)N1—C7—C8108.69 (10)
C1—N1—H1B106.6 (11)C12—C7—C8111.48 (10)
H1A—N1—H1B108.8 (15)N1—C7—H7108.7
N1—C1—C6110.54 (10)C12—C7—H7108.7
N1—C1—C2107.84 (10)C8—C7—H7108.7
C6—C1—C2112.16 (10)C7—C8—C9109.85 (11)
N1—C1—H1108.7C7—C8—H8A109.7
C6—C1—H1108.7C9—C8—H8A109.7
C2—C1—H1108.7C7—C8—H8B109.7
C1—C2—C3110.87 (10)C9—C8—H8B109.7
C1—C2—H2A109.5H8A—C8—H8B108.2
C3—C2—H2A109.5C10—C9—C8110.90 (11)
C1—C2—H2B109.5C10—C9—H9A109.5
C3—C2—H2B109.5C8—C9—H9A109.5
H2A—C2—H2B108.1C10—C9—H9B109.5
C4—C3—C2111.02 (10)C8—C9—H9B109.5
C4—C3—H3A109.4H9A—C9—H9B108.0
C2—C3—H3A109.4C11—C10—C9110.85 (11)
C4—C3—H3B109.4C11—C10—H10A109.5
C2—C3—H3B109.4C9—C10—H10A109.5
H3A—C3—H3B108.0C11—C10—H10B109.5
C5—C4—C3110.46 (11)C9—C10—H10B109.5
C5—C4—H4A109.6H10A—C10—H10B108.1
C3—C4—H4A109.6C10—C11—C12111.70 (11)
C5—C4—H4B109.6C10—C11—H11A109.3
C3—C4—H4B109.6C12—C11—H11A109.3
H4A—C4—H4B108.1C10—C11—H11B109.3
C4—C5—C6111.65 (11)C12—C11—H11B109.3
C4—C5—H5A109.3H11A—C11—H11B107.9
C6—C5—H5A109.3C7—C12—C11110.47 (11)
C4—C5—H5B109.3C7—C12—H12A109.6
C6—C5—H5B109.3C11—C12—H12A109.6
H5A—C5—H5B108.0C7—C12—H12B109.6
C1—C6—C5110.73 (10)C11—C12—H12B109.6
C1—C6—H6A109.5H12A—C12—H12B108.1
C5—C6—H6A109.5N2—C13—S1178.68 (12)
C1—C6—H6B109.5
C7—N1—C1—C656.44 (13)C1—N1—C7—C1260.50 (14)
C7—N1—C1—C2179.38 (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—C456.09 (14)C7—C8—C9—C1057.46 (14)
C2—C3—C4—C5−56.87 (15)C8—C9—C10—C11−56.47 (15)
C3—C4—C5—C656.52 (15)C9—C10—C11—C1255.21 (16)
N1—C1—C6—C5174.64 (10)N1—C7—C12—C11177.35 (10)
C2—C1—C6—C554.26 (13)C8—C7—C12—C1156.39 (14)
C4—C5—C6—C1−54.99 (14)C10—C11—C12—C7−54.95 (15)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···N20.901 (18)1.986 (19)2.8811 (17)172.8 (16)
N1—H1A···S1i0.926 (17)2.440 (17)3.3610 (13)172.8 (13)
Symmetry codes: (i) x+1/2, −y+1/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···N20.901 (18)1.986 (19)2.8811 (17)172.8 (16)
N1—H1A···S1i0.926 (17)2.440 (17)3.3610 (13)172.8 (13)
Symmetry codes: (i) x+1/2, −y+1/2, −z+1.
Acknowledgements top

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
References top

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Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.