organic compounds
Cyclohexane-1,4-diammonium dithiocyanate
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
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 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 of the title compound.
As shown in Fig. 1, the cyclohexane ring of the title compound adopts a chair conformation with puckering parameters QT = 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].
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).
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 . 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.
details are summarized in Table 2
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Structural data
CCDC reference: 1482434
10.1107/S2414314616008646/sj4044sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616008646/sj4044Isup2.hkl
Data collection: APEX2 (Bruker, 2015); cell
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).C6H16N22+·2CNS− | F(000) = 496 |
Mr = 232.37 | Dx = 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 |
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 | Rint = 0.032 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 72.4°, θmin = 5.5° |
ω scans | h = −10→9 |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | k = 0→18 |
Tmin = 0.47, Tmax = 0.67 | l = 0→12 |
15185 measured reflections |
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(Fo2) + (0.0542P)2 + 0.366P] where P = (Fo2 + 2Fc2)/3 |
4260 reflections | (Δ/σ)max = 0.001 |
130 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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···N4iv | 0.91 | 2.06 | 2.933 (2) | 160 |
N2—H2C···N3v | 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.
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