2-Amino­cyclo­hexan-1-aminium thio­cyanate

Salem, H.F.; Hasbullah, S.A.; Yamin, B.M.

doi:10.1107/S1600536812020879

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1732

doi:10.1107/S1600536812020879

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2-Aminocyclohexan-1-aminium thiocyanate

Halima F. Salem,^a Siti Aishah Hasbullah ^a and Bohari M. Yamin ^a ^*

^aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, UKM 43500 Bangi Selangor, Malaysia
^*Correspondence e-mail: bohari@ukm.my

(Received 25 April 2012; accepted 8 May 2012; online 16 May 2012)

The title compound, C₆H₁₅N₂⁺·NCS⁻, was obtained unexpectedly from the reaction mixture of benzoyl chloride, ammonium thiocyanate and cyclohexane-1,2-diamine. The cyclohexane ring adopts a chair conformation. In the crystal, N—H⋯S and N—H⋯N interactions involving the thiocyanate anion and both the amine and the aminium N atoms link the molecules, forming two-dimensional networks parallel to (001).

Related literature

For a description of the Cambridge Structural Database, see: Allen (2002 ). For related thiocyanate structures, see: Selvakumaran et al. (2011 ); Khawar Rauf et al. (2008 ).

Experimental

Crystal data

C₆H₁₅N₂⁺·NCS⁻
M_r = 173.28
Orthorhombic, P b c a
a = 8.590 (3) Å
b = 12.885 (5) Å
c = 17.237 (7) Å
V = 1907.8 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 298 K
0.50 × 0.50 × 0.25 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.870, T_max = 0.932
10172 measured reflections
1685 independent reflections
1449 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.112
S = 1.14
1685 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1ⁱ	0.87	2.53	3.3914 (19)	172
N1—H1B⋯N3ⁱⁱ	0.82	2.10	2.895 (3)	166
N1—H1C⋯N2ⁱⁱⁱ	1.01	1.83	2.841 (2)	175
N2—H2A⋯N3ⁱⁱ	0.99	2.31	3.231 (3)	155
N2—H2B⋯S1	0.97	2.81	3.681 (2)	149
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker,2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812020879/lr2062sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020879/lr2062Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020879/lr2062Isup3.cml

checkCIF report

Comment top

The thiocyanate salts such as ammonium, potassium and sodium thiocyanate are useful reagents for organic synthesis specially for the formation of thiourea moiety. There are also some organic salts of thiocyanate such as dicyclohexylammonium thiocyanate which formed polymorph with orthorhombic (Khawar Rauf et al., 2008) and monoclinic (Selvakumaran et al., 2011) system respectively. Both salts were obtained rather unexpectedly from the mixture of benzoyl chloride, KSCN and dicyclohexylamine in the first and similarly, in the latter when isopthaloyl dichloride was used instead of benzoyl chloride. The title compound is analogous to the said compounds except the cation is a cyclohexane ring having a protonated and unprotonated amines at 1 and 2 positions respectively (Fig.1). The thiocyanate is linear with N3—C7—S1 bond angle of 178.22 (19)°. The cyclohexane ring adopts a chair conformation. The bond lengths and angles are in normal ranges (Allen, 2002). In the crystal structure, the molecules are linked by N1–H1A···S1, N1–H1B···N3, N1–H1C···N2 ,N2–H2A···N3 and N2–H2B···S1 intermolecular hydrogen bonds (symmetry codes as shown in Table 1) to form two-dimensional network (Fig. 2) parallel to (001).

Related literature top

For a description of the Cambridge Structural Database, see: Allen (2002). For related thiocyanate structures, see: 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 mixture of benzoyl chloride (1.41 g, 0.01 mol), ammonium thiocyanate (0.76 g, 0.01 mol) and 1,2-diaminocyclohexane (1.14 g, 0.01 mol) in acetone was refluxed for 1 h. After cooling the solution was filtered and left to evaporate at room temperature. Some good crystals were obtained after 5 days of evaporation. (Yield 82%, m.p 395.9- 397.1 K). IR, NH: 3435.2, 3184.3 cm^-1, C—N—S: 2058 cm^-1, C—N: 1459 cm^-1; CHNS, expt C: 48.22%, N: 24.50%, H: 8.73%, S: 17.50%), Calc C: 48.57, N: 24.20, H: 8.67, S: 18.49).

Computing details top

Data collection: SMART (Bruker,2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsods drawn at the 50% probability level.
	Fig. 2. Molecular packing of (I) viewed down c axis. The dashed lines indicate intermolecular hydrogen bonds.

2-Aminocyclohexan-1-aminium thiocyanate top

Crystal data top

C₆H₁₅N₂⁺·NCS⁻	F(000) = 752
M_r = 173.28	D_x = 1.207 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2210 reflections
a = 8.590 (3) Å	θ = 3.0–25.0°
b = 12.885 (5) Å	µ = 0.29 mm⁻¹
c = 17.237 (7) Å	T = 298 K
V = 1907.8 (13) Å³	Block, colourless
Z = 8	0.50 × 0.50 × 0.25 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1685 independent reflections
Radiation source: fine-focus sealed tube	1449 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 83.66 pixels mm^-1	θ_max = 25.0°, θ_min = 3.0°
ω scan	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −15→12
T_min = 0.870, T_max = 0.932	l = −20→18
10172 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.051P)² + 0.6001P] where P = (F_o² + 2F_c²)/3
1685 reflections	(Δ/σ)_max = 0.001
100 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₆H₁₅N₂⁺·NCS⁻	V = 1907.8 (13) Å³
M_r = 173.28	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.590 (3) Å	µ = 0.29 mm⁻¹
b = 12.885 (5) Å	T = 298 K
c = 17.237 (7) Å	0.50 × 0.50 × 0.25 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1685 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1449 reflections with I > 2σ(I)
T_min = 0.870, T_max = 0.932	R_int = 0.028
10172 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.14	Δρ_max = 0.25 e Å⁻³
1685 reflections	Δρ_min = −0.16 e Å⁻³
100 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.87938 (18)	0.27887 (13)	0.03084 (9)	0.0437 (4)
H1A	0.9431	0.3073	0.0637	0.052*
H1B	0.8343	0.3242	0.0065	0.052*
H1C	0.9375	0.2357	−0.0090	0.052*
N2	0.55776 (18)	0.33551 (13)	0.07851 (9)	0.0436 (4)
H2A	0.6130	0.3926	0.0516	0.052*
H2B	0.4757	0.3638	0.1112	0.052*
C1	0.7706 (2)	0.20856 (14)	0.07357 (10)	0.0354 (4)
H1D	0.7077	0.1708	0.0355	0.043*
C2	0.8674 (2)	0.13050 (15)	0.11858 (12)	0.0433 (5)
H2C	0.9300	0.0902	0.0827	0.052*
H2D	0.9374	0.1671	0.1532	0.052*
C3	0.7648 (3)	0.05792 (16)	0.16548 (12)	0.0493 (5)
H3A	0.7022	0.0162	0.1305	0.059*
H3B	0.8297	0.0114	0.1957	0.059*
C4	0.6591 (3)	0.11804 (17)	0.21932 (12)	0.0513 (5)
H4A	0.7213	0.1539	0.2579	0.062*
H4B	0.5904	0.0703	0.2462	0.062*
C5	0.5629 (2)	0.19625 (16)	0.17426 (11)	0.0463 (5)
H5A	0.5010	0.2366	0.2104	0.056*
H5B	0.4919	0.1593	0.1403	0.056*
C6	0.6618 (2)	0.26985 (14)	0.12574 (10)	0.0371 (4)
H6A	0.7235	0.3141	0.1603	0.045*
S1	0.15812 (8)	0.37823 (5)	0.14873 (3)	0.0610 (2)
N3	0.2362 (3)	0.53658 (16)	0.04577 (11)	0.0678 (6)
C7	0.2023 (2)	0.47221 (16)	0.08883 (11)	0.0443 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0428 (9)	0.0436 (9)	0.0446 (9)	0.0029 (7)	0.0051 (7)	0.0088 (7)
N2	0.0366 (8)	0.0421 (9)	0.0520 (10)	0.0063 (7)	0.0000 (7)	0.0027 (7)
C1	0.0349 (9)	0.0353 (10)	0.0361 (9)	−0.0039 (8)	0.0002 (7)	0.0009 (8)
C2	0.0421 (11)	0.0409 (11)	0.0469 (11)	0.0055 (9)	0.0019 (9)	0.0032 (9)
C3	0.0586 (13)	0.0400 (11)	0.0493 (11)	0.0026 (10)	0.0020 (10)	0.0085 (9)
C4	0.0582 (13)	0.0522 (13)	0.0435 (11)	−0.0042 (10)	0.0079 (10)	0.0075 (9)
C5	0.0408 (10)	0.0531 (12)	0.0451 (10)	−0.0008 (9)	0.0078 (8)	−0.0006 (9)
C6	0.0366 (10)	0.0366 (10)	0.0383 (9)	−0.0002 (8)	−0.0025 (8)	−0.0029 (8)
S1	0.0708 (4)	0.0589 (4)	0.0535 (4)	−0.0088 (3)	0.0002 (3)	0.0116 (3)
N3	0.0815 (15)	0.0521 (12)	0.0697 (12)	0.0012 (11)	0.0043 (11)	0.0167 (11)
C7	0.0420 (11)	0.0442 (12)	0.0467 (11)	0.0070 (9)	−0.0023 (9)	−0.0063 (10)

Geometric parameters (Å, º) top

N1—C1	1.495 (2)	C3—C4	1.512 (3)
N1—H1A	0.8682	C3—H3A	0.9700
N1—H1B	0.8173	C3—H3B	0.9700
N1—H1C	1.0147	C4—C5	1.517 (3)
N2—C6	1.475 (2)	C4—H4A	0.9700
N2—H2A	0.9911	C4—H4B	0.9700
N2—H2B	0.9740	C5—C6	1.523 (3)
C1—C2	1.518 (3)	C5—H5A	0.9700
C1—C6	1.519 (2)	C5—H5B	0.9700
C1—H1D	0.9800	C6—H6A	0.9800
C2—C3	1.518 (3)	S1—C7	1.636 (2)
C2—H2C	0.9700	N3—C7	1.150 (3)
C2—H2D	0.9700

C1—N1—H1A	109.2	C2—C3—H3A	109.4
C1—N1—H1B	112.9	C4—C3—H3B	109.4
H1A—N1—H1B	109.4	C2—C3—H3B	109.4
C1—N1—H1C	108.0	H3A—C3—H3B	108.0
H1A—N1—H1C	111.2	C3—C4—C5	110.68 (17)
H1B—N1—H1C	106.1	C3—C4—H4A	109.5
C6—N2—H2A	113.2	C5—C4—H4A	109.5
C6—N2—H2B	109.5	C3—C4—H4B	109.5
H2A—N2—H2B	109.9	C5—C4—H4B	109.5
N1—C1—C2	108.11 (15)	H4A—C4—H4B	108.1
N1—C1—C6	111.17 (15)	C4—C5—C6	113.01 (16)
C2—C1—C6	112.27 (15)	C4—C5—H5A	109.0
N1—C1—H1D	108.4	C6—C5—H5A	109.0
C2—C1—H1D	108.4	C4—C5—H5B	109.0
C6—C1—H1D	108.4	C6—C5—H5B	109.0
C3—C2—C1	111.24 (17)	H5A—C5—H5B	107.8
C3—C2—H2C	109.4	N2—C6—C1	110.14 (15)
C1—C2—H2C	109.4	N2—C6—C5	108.79 (15)
C3—C2—H2D	109.4	C1—C6—C5	110.16 (15)
C1—C2—H2D	109.4	N2—C6—H6A	109.2
H2C—C2—H2D	108.0	C1—C6—H6A	109.2
C4—C3—C2	111.09 (17)	C5—C6—H6A	109.2
C4—C3—H3A	109.4	N3—C7—S1	178.2 (2)

N1—C1—C2—C3	178.41 (15)	C2—C1—C6—N2	−173.39 (15)
C6—C1—C2—C3	55.4 (2)	N1—C1—C6—C5	−174.63 (15)
C1—C2—C3—C4	−56.1 (2)	C2—C1—C6—C5	−53.4 (2)
C2—C3—C4—C5	55.6 (2)	C4—C5—C6—N2	174.46 (16)
C3—C4—C5—C6	−55.2 (2)	C4—C5—C6—C1	53.6 (2)
N1—C1—C6—N2	65.36 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.87	2.53	3.3914 (19)	172
N1—H1B···N3ⁱⁱ	0.82	2.10	2.895 (3)	166
N1—H1C···N2ⁱⁱⁱ	1.01	1.83	2.841 (2)	175
N2—H2A···N3ⁱⁱ	0.99	2.31	3.231 (3)	155
N2—H2B···S1	0.97	2.81	3.681 (2)	149

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

Experimental details

Crystal data
Chemical formula	C₆H₁₅N₂⁺·NCS⁻
M_r	173.28
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	8.590 (3), 12.885 (5), 17.237 (7)
V (Å³)	1907.8 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.50 × 0.50 × 0.25

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.870, 0.932
No. of measured, independent and observed [I > 2σ(I)] reflections	10172, 1685, 1449
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.112, 1.14
No. of reflections	1685
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.16

Computer programs: SMART (Bruker,2000), SAINT (Bruker, 2000), 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···S1ⁱ	0.87	2.53	3.3914 (19)	172.1
N1—H1B···N3ⁱⁱ	0.82	2.10	2.895 (3)	165.8
N1—H1C···N2ⁱⁱⁱ	1.01	1.83	2.841 (2)	174.9
N2—H2A···N3ⁱⁱ	0.99	2.31	3.231 (3)	154.6
N2—H2B···S1	0.97	2.81	3.681 (2)	149.4

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

Acknowledgements

The authors thank Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia, for research grant No. UKM-GUP-NBT-08–27-110.

References

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