Cyclo­hexane-1,4-di­ammonium di­thio­cyanate

Mague, J.T.; Akkurt, M.; Mohamed, S.K.; Abdelhamid, A.A.; Albayati, M.R.

doi:10.1107/S2414314616008646

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160864

doi:10.1107/S2414314616008646

Open

access

Cyclohexane-1,4-diammonium dithiocyanate

Joel T. Mague,^a Mehmet Akkurt,^b Shaaban K. Mohamed,^c,^d Antar A. Abdelhamid ^e and Mustafa R. Albayati ^f ^*

^aDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, ^dChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, ^eChemistry Department, Faculty of Science, Sohag University, Sohag, Egypt, and ^fKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq
^*Correspondence e-mail: shaabankamel@yahoo.com

Edited by J. Simpson, University of Otago, New Zealand (Received 27 May 2016; accepted 29 May 2016; online 10 June 2016)

In the title salt, C₆H₁₆N₂²⁺·2CNS⁻, the cyclohexane ring adopts a chair conformation. In the crystal, N—H⋯N hydrogen bonds enclose R₄²(8) rings involving two N atoms from the cyclohexane-1,4-diammonium cations as donors with the N atoms of two thiocyanate anions as acceptors. The crystal structure is further stabilized by intermolecular N—H⋯S hydrogen bonds that combine with these contacts to form a three-dimensional network.

Keywords: crystal structure; thiocyanate salts; cyclohexane-1,4-diammonium thiocyanate; hydrogen bonds.

CCDC reference: 1482434

Structure description

Thiocyanate salt systems have numerous applications in applied chemistry. For example, a hydrazine/thiocyanate salt was found to act as an excellent solvent for cellulose at room temperature (Hattori et al., 2002 ). Moreover, incorporation of thiocyante anions into imidazolium or pyrolidinium cations produces ionic liquids (Pringle et al., 2002 ). In addition, a thiocyanate salt of guanidine was recently found to act as a plasticizer for rheological solutions (Selling et al., 2013 ). In this context we report here the synthesis and crystal structure of the title compound.

As shown in Fig. 1, the cyclohexane ring of the title compound adopts a chair conformation with puckering parameters Q_T = 0.594 (2) Å, θ = 0.00 (19)° and φ = 206 (13)°. The lengths of the equatorial C—N(H₃) bonds in the cyclohexane ring are normal [N1—C1 = 1.502 (2) and N2—C4 = 1.502 (2) Å]. In the two thiocyanate anions, the lengths of the C—S and C≡N bonds are also within normal ranges [S1—C7 = 1.6344 (19), S2—C8 = 1.636 (2), C7—N3 = 1.174 (3), and C8—N4 = 1.167 (3) Å].

Figure 1
The title molecule with labeling scheme and 50% probability ellipsoids.

In the crystal, N1—H1A⋯N4, N1—H1B⋯N3, and N2—H2B⋯N4, N2—H2C⋯N3, hydrogen bonds enclose R₄²(8) rings involving two H atoms from each of the different N atoms of separate cyclohexane-1,4-diammonium cations as donors with the N atoms of the two thiocyanate anions as acceptors. Additional intermolecular N1—H1C⋯S2 and N2—H2A⋯S1 hydrogen bonds mean that both of the N atoms of the cations are trifurcated donors and these combine with the N—H⋯N contacts to form a three-dimensional network (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N4ⁱ	0.91	2.04	2.890 (2)	156
N1—H1B⋯N3	0.91	2.00	2.880 (2)	163
N1—H1C⋯S2ⁱⁱ	0.91	2.45	3.3511 (16)	173
N2—H2A⋯S1ⁱⁱⁱ	0.91	2.47	3.3621 (16)	169
N2—H2B⋯N4^iv	0.91	2.06	2.933 (2)	160
N2—H2C⋯N3^v	0.91	2.08	2.931 (2)	156
Symmetry codes: (i) x, y, z-1; (ii) -x+1, -y+1, -z+1; (iii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x-1, y, z-1; (v) x-1, y, z.

Figure 2
View of the molecular packing and the hydrogen bonding of the title compound.

Synthesis and crystallization

The title compound was obtained as an unexpected product in a very good yield (81%) from an attempted multi-component reaction in which phenylacetyl chloride (155 mg, 1 mmol), cyclohexane-1,4-diamine (114 mg, 1 mmol) and potassium thiocyanate (97 mg, 1 mmol) in 30 ml ethanol were refluxed for 5 h. The solid product was collected by filtration, dried under vacuum and recrystallized from ethanol to afford good quality crystals suitable for X-ray diffraction.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Analysis of 2284 reflections with I/σ(I) > 13 and chosen from the full data set with CELL_NOW (Sheldrick, 2008b ) showed the crystal to belong to the monoclinic system and to be twinned by a 180° rotation about the a axis. The raw data were processed using the multi-component version of SAINT (Bruker, 2015 ) under control of the two-component orientation file generated by CELL_NOW.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₁₆N₂²⁺·2CNS⁻
M_r	232.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	8.2286 (3), 14.9146 (6), 10.4058 (4)
β (°)	111.423 (1)
V (Å³)	1188.83 (8)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	3.82
Crystal size (mm)	0.23 × 0.19 × 0.11

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2015)
T_min, T_max	0.47, 0.67
No. of measured, independent and observed [I > 2σ(I)] reflections	15185, 4260, 3809
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.101, 1.04
No. of reflections	4260
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.32
Computer programs: APEX2 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008a ).

Structural data

CCDC reference: 1482434

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616008646/sj4044sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616008646/sj4044Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Cyclohexane-1,4-diammonium dithiocyanate top

Crystal data top

C₆H₁₆N₂²⁺·2CNS⁻	F(000) = 496
M_r = 232.37	D_x = 1.298 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 8.2286 (3) Å	Cell parameters from 9989 reflections
b = 14.9146 (6) Å	θ = 5.8–72.3°
c = 10.4058 (4) Å	µ = 3.82 mm⁻¹
β = 111.423 (1)°	T = 150 K
V = 1188.83 (8) Å³	Prism, colourless
Z = 4	0.23 × 0.19 × 0.11 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	4260 independent reflections
Radiation source: INCOATEC IµS micro–focus source	3809 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.032
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.4°, θ_min = 5.5°
ω scans	h = −10→9
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = 0→18
T_min = 0.47, T_max = 0.67	l = 0→12
15185 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0542P)² + 0.366P] where P = (F_o² + 2F_c²)/3
4260 reflections	(Δ/σ)_max = 0.001
130 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Special details top

Experimental. Analysis of 2284 reflections having I/σ(I) > 13 and chosen from the full data set with CELL_NOW (Sheldrick, 2008) showed the crystal to belong to the monoclinic system and to be twinned by a 180° rotation about the a axis. The raw data were processed using the multi-component version of SAINT under control of the two-component orientation file generated by CELL_NOW.

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 > 2sigma(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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.98 - 1.0 Å) while those attached to nitrogen were placed in locations derived from a difference map and their parameters adjusted to give N—H = 0.91 Å. All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.56447 (18)	0.45162 (11)	0.25836 (16)	0.0221 (3)
H1A	0.5902	0.4406	0.1819	0.033*
H1B	0.6616	0.4431	0.3353	0.033*
H1C	0.5272	0.5092	0.2562	0.033*
N2	−0.06213 (18)	0.29200 (11)	0.27141 (16)	0.0226 (3)
H2A	−0.0251	0.2342	0.2761	0.034*
H2B	−0.1584	0.2997	0.1936	0.034*
H2C	−0.0891	0.3047	0.3468	0.034*
C1	0.4231 (2)	0.38878 (13)	0.26112 (18)	0.0201 (4)
H1	0.4652	0.3259	0.2615	0.024*
C2	0.2610 (2)	0.40194 (14)	0.13238 (19)	0.0247 (4)
H2D	0.2890	0.3899	0.0492	0.030*
H2E	0.2204	0.4648	0.1278	0.030*
C3	0.1169 (2)	0.33831 (13)	0.13575 (19)	0.0248 (4)
H3A	0.0093	0.3491	0.0542	0.030*
H3B	0.1536	0.2754	0.1324	0.030*
C4	0.0802 (2)	0.35377 (12)	0.26759 (19)	0.0207 (4)
H4	0.0400	0.4170	0.2676	0.025*
C5	0.2427 (2)	0.33951 (13)	0.39591 (19)	0.0241 (4)
H5A	0.2830	0.2767	0.3992	0.029*
H5B	0.2154	0.3509	0.4796	0.029*
C6	0.3865 (2)	0.40364 (13)	0.39237 (19)	0.0242 (4)
H6A	0.3493	0.4664	0.3959	0.029*
H6B	0.4942	0.3930	0.4738	0.029*
S1	1.10256 (6)	0.41245 (3)	0.75714 (5)	0.02824 (16)
N3	0.8593 (2)	0.38720 (13)	0.48827 (18)	0.0313 (4)
C7	0.9609 (2)	0.39952 (12)	0.6002 (2)	0.0224 (4)
S2	0.60809 (6)	0.34284 (3)	0.76345 (5)	0.02790 (16)
N4	0.6417 (2)	0.36365 (14)	1.03977 (18)	0.0352 (4)
C8	0.6273 (2)	0.35421 (13)	0.9248 (2)	0.0240 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0216 (7)	0.0231 (8)	0.0213 (7)	−0.0007 (6)	0.0073 (6)	0.0014 (6)
N2	0.0228 (7)	0.0224 (8)	0.0234 (8)	−0.0016 (6)	0.0094 (6)	−0.0013 (6)
C1	0.0225 (8)	0.0187 (8)	0.0187 (9)	−0.0012 (7)	0.0070 (7)	0.0002 (7)
C2	0.0254 (9)	0.0302 (10)	0.0167 (9)	−0.0037 (7)	0.0055 (7)	0.0022 (7)
C3	0.0254 (9)	0.0301 (11)	0.0183 (9)	−0.0054 (7)	0.0073 (7)	−0.0031 (7)
C4	0.0230 (8)	0.0182 (8)	0.0214 (9)	−0.0027 (7)	0.0086 (7)	−0.0014 (7)
C5	0.0266 (9)	0.0280 (10)	0.0177 (9)	−0.0046 (7)	0.0080 (7)	0.0009 (7)
C6	0.0257 (9)	0.0281 (10)	0.0178 (9)	−0.0055 (7)	0.0069 (7)	−0.0023 (7)
S1	0.0312 (3)	0.0230 (3)	0.0239 (3)	−0.00248 (17)	0.00225 (19)	0.00112 (18)
N3	0.0304 (8)	0.0382 (10)	0.0241 (9)	0.0031 (7)	0.0085 (7)	0.0010 (7)
C7	0.0237 (8)	0.0199 (9)	0.0262 (10)	0.0029 (7)	0.0120 (7)	0.0016 (7)
S2	0.0386 (3)	0.0239 (3)	0.0236 (3)	0.00396 (18)	0.0142 (2)	0.00093 (18)
N4	0.0347 (9)	0.0459 (11)	0.0252 (9)	0.0026 (8)	0.0111 (7)	−0.0011 (8)
C8	0.0213 (8)	0.0226 (9)	0.0282 (10)	0.0011 (7)	0.0091 (7)	0.0029 (8)

Geometric parameters (Å, º) top

N1—C1	1.502 (2)	C3—C4	1.526 (2)
N1—H1A	0.9100	C3—H3A	0.9900
N1—H1B	0.9100	C3—H3B	0.9900
N1—H1C	0.9100	C4—C5	1.520 (2)
N2—C4	1.502 (2)	C4—H4	1.0000
N2—H2A	0.9100	C5—C6	1.533 (2)
N2—H2B	0.9100	C5—H5A	0.9900
N2—H2C	0.9100	C5—H5B	0.9900
C1—C6	1.518 (2)	C6—H6A	0.9900
C1—C2	1.519 (2)	C6—H6B	0.9900
C1—H1	1.0000	S1—C7	1.6344 (19)
C2—C3	1.529 (2)	N3—C7	1.174 (3)
C2—H2D	0.9900	S2—C8	1.636 (2)
C2—H2E	0.9900	N4—C8	1.167 (3)

C1—N1—H1A	109.5	C4—C3—H3A	109.7
C1—N1—H1B	109.5	C2—C3—H3A	109.7
H1A—N1—H1B	109.5	C4—C3—H3B	109.7
C1—N1—H1C	109.5	C2—C3—H3B	109.7
H1A—N1—H1C	109.5	H3A—C3—H3B	108.2
H1B—N1—H1C	109.5	N2—C4—C5	109.56 (14)
C4—N2—H2A	109.5	N2—C4—C3	110.06 (14)
C4—N2—H2B	109.5	C5—C4—C3	111.69 (15)
H2A—N2—H2B	109.5	N2—C4—H4	108.5
C4—N2—H2C	109.5	C5—C4—H4	108.5
H2A—N2—H2C	109.5	C3—C4—H4	108.5
H2B—N2—H2C	109.5	C4—C5—C6	109.30 (15)
N1—C1—C6	109.60 (14)	C4—C5—H5A	109.8
N1—C1—C2	109.84 (14)	C6—C5—H5A	109.8
C6—C1—C2	112.07 (15)	C4—C5—H5B	109.8
N1—C1—H1	108.4	C6—C5—H5B	109.8
C6—C1—H1	108.4	H5A—C5—H5B	108.3
C2—C1—H1	108.4	C1—C6—C5	109.82 (15)
C1—C2—C3	109.77 (15)	C1—C6—H6A	109.7
C1—C2—H2D	109.7	C5—C6—H6A	109.7
C3—C2—H2D	109.7	C1—C6—H6B	109.7
C1—C2—H2E	109.7	C5—C6—H6B	109.7
C3—C2—H2E	109.7	H6A—C6—H6B	108.2
H2D—C2—H2E	108.2	N3—C7—S1	177.77 (18)
C4—C3—C2	109.65 (15)	N4—C8—S2	179.0 (2)

N1—C1—C2—C3	−179.67 (14)	N2—C4—C5—C6	−179.20 (14)
C6—C1—C2—C3	−57.6 (2)	C3—C4—C5—C6	58.6 (2)
C1—C2—C3—C4	56.5 (2)	N1—C1—C6—C5	−179.85 (14)
C2—C3—C4—N2	179.60 (15)	C2—C1—C6—C5	57.9 (2)
C2—C3—C4—C5	−58.5 (2)	C4—C5—C6—C1	−57.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N4ⁱ	0.91	2.04	2.890 (2)	156
N1—H1B···N3	0.91	2.00	2.880 (2)	163
N1—H1C···S2ⁱⁱ	0.91	2.45	3.3511 (16)	173
N2—H2A···S1ⁱⁱⁱ	0.91	2.47	3.3621 (16)	169
N2—H2B···N4^iv	0.91	2.06	2.933 (2)	160
N2—H2C···N3^v	0.91	2.08	2.931 (2)	156

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

Acknowledgements

The support of NSF–MRI Grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

References

Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2015). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hattori, K., Cuculo, J. A. & Hudson, S. M. (2002). J. Polym. Sci. A Polym. Chem. 40, 601–611. Web of Science CrossRef CAS Google Scholar
Pringle, J. M., Golding, J., Forsyth, C. M., Deacon, G. B., Forsyth, M. & MacFarlane, D. R. (2002). J. Mater. Chem. 12, 3475–3480. Web of Science CSD CrossRef CAS Google Scholar
Selling, G. W., Maness, A., Bean, S. & Smith, B. (2013). Cereal Chem. J. 90, 204–210. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008a). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008b). CELL_NOW. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.