



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989014027297/sj5432sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S2056989014027297/sj5432Isup2.hkl |
![]() | Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989014027297/sj5432Isup3.cml |
CCDC reference: 1039130
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean
(C-C) = 0.002 Å
- R factor = 0.038
- wR factor = 0.100
- Data-to-parameter ratio = 16.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 12 Report
Alert level G PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size .... 0.98 mm PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 31 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 1 ALERT level C = Check. Ensure it is not caused by an omission or oversight 2 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound, C6H11NH3+.SCN-, has previously been synthesized by reacting an aqueous solution of cyclohexylamine (CHA) with ammonium thiocyanate (H4N+SCN-) at 85–90 °C, followed by extraction of C6H11NH3+.SCN- with benzene, and then recrystallization from ethanol (Mathes et al., 1948). This compound is used as an animal repellent and also as an insecticide or fungicide (Stewart, 1951). It is also a starting material for the preparation of other compounds (Baluja et al., 1960; Morrison et al., 1953; Stewart, 1951), an accelerator and activator for rubber vulcanization (Mathes et al., 1955) and an accelerator for the curing of polyepoxide-polyimine materials (Goel, 1988). It has also been used as a stationary phase for gas chromatography (Coddens et al., 1986). Nevertheless, the crystal structure of this important compound has not been determined. We report here the crystal structure of C6H11NH3+.SCN- together with a new room-temperature synthesis using a salt metathesis reaction. This is a simpler process and results in a higher yield than the one published in the literature. Furthermore, we aim to use this compound to prepare new metal complexes based on both the cyclohexylammonium cation and the thiocyanate anion.
The assymmetric unit of the title compound (Fig. 1), contains one cyclohexylammonium cation (C1–C6/N1) and one thiocynate anion (S1/C7/N2). The cyclohexylammonium ring adopts a slightly distorted chair conformation, with puckering parameters: Q = 0.5669 (18) Å, θ = 177.95 (18)°, and φ = 161 (5)°. For an ideal chair configuration, θ has a value of 0 or 180°. The ammonium functional group is at an equatorial position to minimize 1,3 and 1,5 di-axial interactions. The bond lengths and bond angles are in normal ranges and are comparable with those reported earlier for similar compounds (Bagabas et al., 2014; Shimada et al., 1955; Smith et al., 1994; Odendal et al., 2010).
In the asymmetric unit, a strong N1–H2N···N2 hydrogen bond links the cation and the anion. In the crystal structure, these contacts are supported by intermolecular N1–H1N···S1 and N1–H3N···S1 hydrogen bonds (Symmetry codes: x-y+2/3, x+1/3, -z+4/3; -x+1/3, -y+2/3, -z+2/3) with S1 as a bifurcated acceptor (Fig. 2) to produce a three-dimensional network.
The title compound, C6H11NH3+.SCN-, was prepared by exchanging counter ions in a salt metathesis reaction between sodium thiocyanate (NaSCN) and cyclohexylammonium chloride (C6H11NH3+. Cl-) in ethanolic medium, where the precipitation of sodium chloride (NaCl) is the driving force for the reaction. In typical reaction, 100 mmol of NaSCN was dissolved in 350 ml absolute ethanol, while 100 mmol C6H11NH3+Cl- was dissolved separately in 250 ml absolute ethanol. Combining these two solutions at room temperature resulted in white precipitate of NaCl, as confirmed by X-ray powder diffraction (PXRD), which was filtered off through F-size fritted filter. The filtrate was left for the solvent to evaporate to dryness at room temperature. About 200 ml absolute ethanol was added to the residual solid to dissolve the desired product, C6H11NH3+.SCN-. It was noticed at this step that a small amount of the residual solid did not dissolve and it was separated by filtration. This undissolved material was NaCl, again identified by PXRD. Slow evaporation at room temperature over a period of 10 days of the ethanolic solution resluted in colorless crystals of C6H11NH3+.SCN- (yield = around 100%) suitable for single crystal X-ray diffraction studies. It is advisable to recrystallize this light-sensitive material in the dark. The chemical composition of the desired product was also confirmed by C, H, N, S elemental microanalysis: (%C: 52.67 exp.; 53.11 cal.), (%H: 9.30 exp.; 8.93 cal.), (%N: 17.85 exp.; 17.70 cal.), and (%S: 20.18 exp.; 20.25 cal.). Potassium thiocyanate (KSCN) can be used instead of NaSCN for executing the reaction, where KCl precipitates and C6H11NH3+.SCN- produces with around 98% yield.
The title compound, C6H11NH3+.SCN-, has previously been synthesized by reacting an aqueous solution of cyclohexylamine (CHA) with ammonium thiocyanate (H4N+SCN-) at 85–90 °C, followed by extraction of C6H11NH3+.SCN- with benzene, and then recrystallization from ethanol (Mathes et al., 1948). This compound is used as an animal repellent and also as an insecticide or fungicide (Stewart, 1951). It is also a starting material for the preparation of other compounds (Baluja et al., 1960; Morrison et al., 1953; Stewart, 1951), an accelerator and activator for rubber vulcanization (Mathes et al., 1955) and an accelerator for the curing of polyepoxide-polyimine materials (Goel, 1988). It has also been used as a stationary phase for gas chromatography (Coddens et al., 1986). Nevertheless, the crystal structure of this important compound has not been determined. We report here the crystal structure of C6H11NH3+.SCN- together with a new room-temperature synthesis using a salt metathesis reaction. This is a simpler process and results in a higher yield than the one published in the literature. Furthermore, we aim to use this compound to prepare new metal complexes based on both the cyclohexylammonium cation and the thiocyanate anion.
The assymmetric unit of the title compound (Fig. 1), contains one cyclohexylammonium cation (C1–C6/N1) and one thiocynate anion (S1/C7/N2). The cyclohexylammonium ring adopts a slightly distorted chair conformation, with puckering parameters: Q = 0.5669 (18) Å, θ = 177.95 (18)°, and φ = 161 (5)°. For an ideal chair configuration, θ has a value of 0 or 180°. The ammonium functional group is at an equatorial position to minimize 1,3 and 1,5 di-axial interactions. The bond lengths and bond angles are in normal ranges and are comparable with those reported earlier for similar compounds (Bagabas et al., 2014; Shimada et al., 1955; Smith et al., 1994; Odendal et al., 2010).
In the asymmetric unit, a strong N1–H2N···N2 hydrogen bond links the cation and the anion. In the crystal structure, these contacts are supported by intermolecular N1–H1N···S1 and N1–H3N···S1 hydrogen bonds (Symmetry codes: x-y+2/3, x+1/3, -z+4/3; -x+1/3, -y+2/3, -z+2/3) with S1 as a bifurcated acceptor (Fig. 2) to produce a three-dimensional network.
For the synthesis and uses of the title compound, see: Baluja et al. (1960); Coddens et al. (1986); Goel (1988); Mathes et al. (1948) 1955); Mathes & Stewart (1955); Morrison & Ratcliffe (1953); Stewart (1951); For the structures of other cyclohexylammonium salts, see: Bagabas et al. (2014); Shimada et al. (1955); Smith et al. (1994); Odendal et al. (2010).
The title compound, C6H11NH3+.SCN-, was prepared by exchanging counter ions in a salt metathesis reaction between sodium thiocyanate (NaSCN) and cyclohexylammonium chloride (C6H11NH3+. Cl-) in ethanolic medium, where the precipitation of sodium chloride (NaCl) is the driving force for the reaction. In typical reaction, 100 mmol of NaSCN was dissolved in 350 ml absolute ethanol, while 100 mmol C6H11NH3+Cl- was dissolved separately in 250 ml absolute ethanol. Combining these two solutions at room temperature resulted in white precipitate of NaCl, as confirmed by X-ray powder diffraction (PXRD), which was filtered off through F-size fritted filter. The filtrate was left for the solvent to evaporate to dryness at room temperature. About 200 ml absolute ethanol was added to the residual solid to dissolve the desired product, C6H11NH3+.SCN-. It was noticed at this step that a small amount of the residual solid did not dissolve and it was separated by filtration. This undissolved material was NaCl, again identified by PXRD. Slow evaporation at room temperature over a period of 10 days of the ethanolic solution resluted in colorless crystals of C6H11NH3+.SCN- (yield = around 100%) suitable for single crystal X-ray diffraction studies. It is advisable to recrystallize this light-sensitive material in the dark. The chemical composition of the desired product was also confirmed by C, H, N, S elemental microanalysis: (%C: 52.67 exp.; 53.11 cal.), (%H: 9.30 exp.; 8.93 cal.), (%N: 17.85 exp.; 17.70 cal.), and (%S: 20.18 exp.; 20.25 cal.). Potassium thiocyanate (KSCN) can be used instead of NaSCN for executing the reaction, where KCl precipitates and C6H11NH3+.SCN- produces with around 98% yield.
The nitrogen-bound H-atoms were located in a difference Fourier map and were refined freely (NH = 0.87 (2), 0.90 (2) and 0.89 (2) Å). Other H atoms were positioned geometrically (C—H 0.97–0.98 Å) and refined using a riding model with Uiso(H) = 1.2 Ueq(C)
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
C6H14N+·NCS− | Dx = 1.196 Mg m−3 |
Mr = 158.26 | Cu Kα radiation, λ = 1.54178 Å |
Trigonal, R3:H | Cell parameters from 3689 reflections |
a = 23.4036 (6) Å | θ = 3.8–71.3° |
c = 8.3373 (2) Å | µ = 2.71 mm−1 |
V = 3954.8 (2) Å3 | T = 296 K |
Z = 18 | Needle, colourless |
F(000) = 1548 | 0.98 × 0.25 × 0.11 mm |
Bruker APEXII CCD diffractometer | 1530 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.051 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | θmax = 72.1°, θmin = 3.8° |
Tmin = 0.176, Tmax = 0.748 | h = −28→28 |
10355 measured reflections | k = −28→28 |
1670 independent reflections | l = −7→9 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0622P)2 + 1.6831P]
where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
1670 reflections | Δρmax = 0.22 e Å−3 |
103 parameters | Δρmin = −0.28 e Å−3 |
C6H14N+·NCS− | Z = 18 |
Mr = 158.26 | Cu Kα radiation |
Trigonal, R3:H | µ = 2.71 mm−1 |
a = 23.4036 (6) Å | T = 296 K |
c = 8.3373 (2) Å | 0.98 × 0.25 × 0.11 mm |
V = 3954.8 (2) Å3 |
Bruker APEXII CCD diffractometer | 1670 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1530 reflections with I > 2σ(I) |
Tmin = 0.176, Tmax = 0.748 | Rint = 0.051 |
10355 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.22 e Å−3 |
1670 reflections | Δρmin = −0.28 e Å−3 |
103 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.06708 (2) | 0.40416 (2) | 0.39763 (4) | 0.04932 (18) | |
N1 | 0.22496 (6) | 0.30544 (6) | 0.62467 (16) | 0.0396 (3) | |
N2 | 0.15453 (8) | 0.36894 (8) | 0.5327 (2) | 0.0628 (4) | |
C1 | 0.17544 (6) | 0.24495 (6) | 0.71255 (15) | 0.0339 (3) | |
H1A | 0.1541 | 0.2582 | 0.7939 | 0.041* | |
C2 | 0.12316 (7) | 0.19773 (7) | 0.59728 (17) | 0.0433 (3) | |
H2A | 0.1437 | 0.1862 | 0.5119 | 0.052* | |
H2B | 0.1005 | 0.2187 | 0.5496 | 0.052* | |
C3 | 0.07361 (7) | 0.13543 (8) | 0.6863 (2) | 0.0525 (4) | |
H3A | 0.0494 | 0.1465 | 0.7626 | 0.063* | |
H3B | 0.0422 | 0.1041 | 0.6102 | 0.063* | |
C4 | 0.10721 (9) | 0.10360 (7) | 0.7747 (2) | 0.0570 (4) | |
H4A | 0.1264 | 0.0871 | 0.6973 | 0.068* | |
H4B | 0.0746 | 0.0664 | 0.8364 | 0.068* | |
C5 | 0.16092 (8) | 0.15210 (8) | 0.88648 (19) | 0.0502 (4) | |
H5A | 0.1836 | 0.1312 | 0.9345 | 0.060* | |
H5B | 0.1410 | 0.1643 | 0.9721 | 0.060* | |
C6 | 0.21055 (7) | 0.21389 (7) | 0.79664 (18) | 0.0422 (3) | |
H6A | 0.2427 | 0.2452 | 0.8715 | 0.051* | |
H6B | 0.2339 | 0.2025 | 0.7184 | 0.051* | |
C7 | 0.11856 (7) | 0.38340 (7) | 0.47760 (17) | 0.0426 (3) | |
H3N | 0.2412 (9) | 0.2942 (10) | 0.545 (2) | 0.055 (5)* | |
H2N | 0.2062 (9) | 0.3280 (9) | 0.587 (2) | 0.046 (4)* | |
H1N | 0.2572 (10) | 0.3321 (10) | 0.691 (3) | 0.061 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0485 (2) | 0.0679 (3) | 0.0414 (3) | 0.03650 (19) | 0.00383 (14) | 0.00618 (15) |
N1 | 0.0367 (6) | 0.0371 (6) | 0.0419 (7) | 0.0162 (5) | −0.0010 (5) | 0.0025 (5) |
N2 | 0.0598 (8) | 0.0673 (9) | 0.0734 (10) | 0.0408 (8) | −0.0064 (7) | 0.0012 (7) |
C1 | 0.0320 (6) | 0.0350 (6) | 0.0344 (7) | 0.0165 (5) | 0.0010 (5) | 0.0007 (5) |
C2 | 0.0362 (7) | 0.0460 (7) | 0.0398 (8) | 0.0145 (6) | −0.0040 (5) | −0.0015 (6) |
C3 | 0.0374 (7) | 0.0488 (8) | 0.0518 (9) | 0.0070 (6) | 0.0015 (6) | −0.0043 (7) |
C4 | 0.0615 (9) | 0.0362 (7) | 0.0624 (10) | 0.0162 (7) | 0.0150 (8) | 0.0050 (7) |
C5 | 0.0567 (9) | 0.0488 (8) | 0.0500 (9) | 0.0299 (7) | 0.0048 (7) | 0.0119 (6) |
C6 | 0.0379 (7) | 0.0437 (7) | 0.0469 (8) | 0.0218 (6) | −0.0034 (6) | 0.0032 (6) |
C7 | 0.0416 (7) | 0.0437 (7) | 0.0417 (8) | 0.0207 (6) | 0.0031 (6) | −0.0006 (6) |
S1—C7 | 1.6486 (15) | C3—C4 | 1.517 (3) |
N1—C1 | 1.4978 (16) | C3—H3A | 0.9700 |
N1—H3N | 0.87 (2) | C3—H3B | 0.9700 |
N1—H2N | 0.90 (2) | C4—C5 | 1.520 (2) |
N1—H1N | 0.89 (2) | C4—H4A | 0.9700 |
N2—C7 | 1.148 (2) | C4—H4B | 0.9700 |
C1—C2 | 1.5132 (18) | C5—C6 | 1.524 (2) |
C1—C6 | 1.5142 (18) | C5—H5A | 0.9700 |
C1—H1A | 0.9800 | C5—H5B | 0.9700 |
C2—C3 | 1.527 (2) | C6—H6A | 0.9700 |
C2—H2A | 0.9700 | C6—H6B | 0.9700 |
C2—H2B | 0.9700 | ||
C1—N1—H3N | 109.8 (13) | C2—C3—H3B | 109.2 |
C1—N1—H2N | 110.7 (11) | H3A—C3—H3B | 107.9 |
H3N—N1—H2N | 108.9 (17) | C3—C4—C5 | 111.65 (13) |
C1—N1—H1N | 109.9 (13) | C3—C4—H4A | 109.3 |
H3N—N1—H1N | 110.1 (18) | C5—C4—H4A | 109.3 |
H2N—N1—H1N | 107.5 (16) | C3—C4—H4B | 109.3 |
N1—C1—C2 | 109.91 (11) | C5—C4—H4B | 109.3 |
N1—C1—C6 | 109.33 (11) | H4A—C4—H4B | 108.0 |
C2—C1—C6 | 112.22 (11) | C4—C5—C6 | 111.14 (13) |
N1—C1—H1A | 108.4 | C4—C5—H5A | 109.4 |
C2—C1—H1A | 108.4 | C6—C5—H5A | 109.4 |
C6—C1—H1A | 108.4 | C4—C5—H5B | 109.4 |
C1—C2—C3 | 109.83 (11) | C6—C5—H5B | 109.4 |
C1—C2—H2A | 109.7 | H5A—C5—H5B | 108.0 |
C3—C2—H2A | 109.7 | C1—C6—C5 | 110.12 (11) |
C1—C2—H2B | 109.7 | C1—C6—H6A | 109.6 |
C3—C2—H2B | 109.7 | C5—C6—H6A | 109.6 |
H2A—C2—H2B | 108.2 | C1—C6—H6B | 109.6 |
C4—C3—C2 | 111.86 (13) | C5—C6—H6B | 109.6 |
C4—C3—H3A | 109.2 | H6A—C6—H6B | 108.2 |
C2—C3—H3A | 109.2 | N2—C7—S1 | 179.71 (16) |
C4—C3—H3B | 109.2 | ||
N1—C1—C2—C3 | 178.72 (12) | C3—C4—C5—C6 | −54.67 (18) |
C6—C1—C2—C3 | 56.83 (16) | N1—C1—C6—C5 | −179.85 (12) |
C1—C2—C3—C4 | −54.73 (17) | C2—C1—C6—C5 | −57.63 (16) |
C2—C3—C4—C5 | 54.43 (18) | C4—C5—C6—C1 | 55.66 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···S1i | 0.89 (2) | 2.62 (2) | 3.4955 (14) | 167 (2) |
N1—H2N···N2 | 0.90 (2) | 1.94 (2) | 2.822 (2) | 170.4 (18) |
N1—H3N···S1ii | 0.87 (2) | 2.573 (18) | 3.4214 (14) | 165.5 (19) |
Symmetry codes: (i) x−y+2/3, x+1/3, −z+4/3; (ii) −x+1/3, −y+2/3, −z+2/3. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···S1i | 0.89 (2) | 2.62 (2) | 3.4955 (14) | 167 (2) |
N1—H2N···N2 | 0.90 (2) | 1.94 (2) | 2.822 (2) | 170.4 (18) |
N1—H3N···S1ii | 0.87 (2) | 2.573 (18) | 3.4214 (14) | 165.5 (19) |
Symmetry codes: (i) x−y+2/3, x+1/3, −z+4/3; (ii) −x+1/3, −y+2/3, −z+2/3. |