The title compound, C
12H
24N
+·C
6H
5S
−, has been obtained by the reaction of C
6H
5SH with dicyclohexylamine. The two ionic fragments are linked together in long chains by
N—H
S
hydrogen bonds. There are two formula units in the asymmetric unit.
Supporting information
CCDC reference: 214812
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.008 Å
- R factor = 0.039
- wR factor = 0.144
- Data-to-parameter ratio = 9.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
PLAT_353 Alert B Long N-H Bond (0.87A) N(2) - H(2A) = 1.12 Ang.
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 26.42
From the CIF: _reflns_number_total 3593
Count of symmetry unique reflns 3711
Completeness (_total/calc) 96.82%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 0
Fraction of Friedel pairs measured 0.000
Are heavy atom types Z>Si present yes
WARNING: Large fraction of Friedel related reflns may
be needed to determine absolute structure
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
0 Alert Level C = Please check
All manipulations were carried out under argon by means of standard Schlenk techniques. The solvent and the amine were dried by standard methods and distilled under argon prior to use. To a solution of benzenethiol (0.22 g, 2 mmol) in acetonitrile, freshly prepared dicyclohexylamine (0.36 g, 2 mmol) was added. Immediately a white precipitate formed. Eecrystallization from hot acetonitrile afforded colourless crystals of (I) suitable for X-ray diffraction analysis.
H atoms bonded to C atoms were treated as riding, with fixed isotropic displacement parameters. The coordinates of the H atoms bonded to N atoms were refined.
Data collection: KM4 System (Gałdecki, Kowalski & Uszyński, 1996); cell refinement: KM4 System; data reduction: DATAPROC (Gałdecki, Kowalski, Kucharczyk & Uszyński, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: RESVIEW (Schwenk, 1998); software used to prepare material for publication: SHELXL97.
Dicyclohexylammonium benzenethiolate
top
Crystal data top
C12H24N+·C6H5S− | Dx = 1.119 Mg m−3 |
Mr = 291.50 | Melting point = 99–100 K |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 40 reflections |
a = 21.208 (4) Å | θ = 2.8–18.7° |
b = 11.678 (2) Å | µ = 0.18 mm−1 |
c = 13.974 (3) Å | T = 200 K |
V = 3460.9 (12) Å3 | Plate, colourless |
Z = 8 | 0.5 × 0.4 × 0.1 mm |
F(000) = 1280 | |
Data collection top
Oxford Diffraction KM-4 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 26.4°, θmin = 1.7° |
Graphite monochromator | h = −26→0 |
w–2θ scans | k = −14→0 |
3593 measured reflections | l = 0→17 |
3593 independent reflections | 3 standard reflections every 200 reflections |
2159 reflections with I > 2σ(I) | intensity decay: 0.3% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.144 | w = 1/[σ2(Fo2) + (0.079P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.032 |
3593 reflections | Δρmax = 0.30 e Å−3 |
373 parameters | Δρmin = −0.26 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.06 (13) |
Crystal data top
C12H24N+·C6H5S− | V = 3460.9 (12) Å3 |
Mr = 291.50 | Z = 8 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 21.208 (4) Å | µ = 0.18 mm−1 |
b = 11.678 (2) Å | T = 200 K |
c = 13.974 (3) Å | 0.5 × 0.4 × 0.1 mm |
Data collection top
Oxford Diffraction KM-4 diffractometer | Rint = 0.000 |
3593 measured reflections | 3 standard reflections every 200 reflections |
3593 independent reflections | intensity decay: 0.3% |
2159 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.144 | Δρmax = 0.30 e Å−3 |
S = 1.04 | Δρmin = −0.26 e Å−3 |
3593 reflections | Absolute structure: Flack (1983) |
373 parameters | Absolute structure parameter: −0.06 (13) |
1 restraint | |
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 | x | y | z | Uiso*/Ueq | |
S1 | 0.02122 (6) | 0.74871 (11) | 0.10577 (10) | 0.0338 (3) | |
S2 | 0.02996 (7) | 0.82635 (14) | 0.73194 (11) | 0.0500 (4) | |
N1 | −0.0231 (2) | 0.9837 (4) | 0.5563 (3) | 0.0270 (9) | |
H1A | −0.028 (2) | 1.060 (5) | 0.573 (4) | 0.032* | |
H1B | 0.000 (2) | 0.947 (4) | 0.604 (4) | 0.032* | |
N2 | −0.01441 (19) | 0.3655 (4) | 0.3983 (3) | 0.0296 (9) | |
H2A | −0.023 (2) | 0.291 (5) | 0.350 (4) | 0.035* | |
H2B | −0.016 (2) | 0.323 (5) | 0.450 (4) | 0.035* | |
C1 | −0.0546 (2) | 0.7407 (4) | 0.1570 (3) | 0.0317 (11) | |
C2 | −0.0904 (3) | 0.6414 (5) | 0.1502 (4) | 0.0427 (14) | |
H2 | −0.0727 | 0.5752 | 0.1212 | 0.051* | |
C3 | −0.1519 (3) | 0.6375 (5) | 0.1853 (5) | 0.0520 (16) | |
H3 | −0.1759 | 0.5692 | 0.1791 | 0.062* | |
C4 | −0.1777 (3) | 0.7308 (5) | 0.2286 (5) | 0.0495 (15) | |
H4 | −0.2196 | 0.7281 | 0.2523 | 0.059* | |
C5 | −0.1423 (2) | 0.8292 (5) | 0.2376 (4) | 0.0411 (13) | |
H5 | −0.1601 | 0.8945 | 0.2678 | 0.049* | |
C6 | −0.0812 (2) | 0.8339 (4) | 0.2033 (4) | 0.0341 (12) | |
H6 | −0.0572 | 0.9018 | 0.2115 | 0.041* | |
C7 | −0.0902 (2) | 0.9442 (4) | 0.5506 (4) | 0.0298 (11) | |
H7 | −0.0900 | 0.8602 | 0.5368 | 0.036* | |
C8 | −0.1208 (2) | 0.9619 (6) | 0.6454 (4) | 0.0409 (13) | |
H8A | −0.1200 | 1.0443 | 0.6618 | 0.049* | |
H8B | −0.0969 | 0.9200 | 0.6952 | 0.049* | |
C9 | −0.1888 (3) | 0.9197 (6) | 0.6441 (5) | 0.0528 (16) | |
H9A | −0.1891 | 0.8354 | 0.6363 | 0.063* | |
H9B | −0.2090 | 0.9380 | 0.7061 | 0.063* | |
C10 | −0.2259 (3) | 0.9732 (7) | 0.5648 (4) | 0.0607 (19) | |
H10A | −0.2317 | 1.0557 | 0.5785 | 0.073* | |
H10B | −0.2681 | 0.9372 | 0.5618 | 0.073* | |
C11 | −0.1932 (3) | 0.9596 (7) | 0.4686 (5) | 0.062 (2) | |
H11A | −0.1932 | 0.8778 | 0.4502 | 0.075* | |
H11B | −0.2169 | 1.0027 | 0.4193 | 0.075* | |
C12 | −0.1261 (3) | 1.0030 (6) | 0.4723 (4) | 0.0468 (16) | |
H12A | −0.1052 | 0.9884 | 0.4101 | 0.056* | |
H12B | −0.1261 | 1.0866 | 0.4837 | 0.056* | |
C13 | 0.0174 (2) | 0.9679 (4) | 0.4696 (3) | 0.0265 (11) | |
H13 | 0.0005 | 1.0172 | 0.4169 | 0.032* | |
C14 | 0.0832 (2) | 1.0082 (5) | 0.4942 (4) | 0.0374 (13) | |
H14A | 0.0991 | 0.9648 | 0.5501 | 0.045* | |
H14B | 0.0821 | 1.0903 | 0.5117 | 0.045* | |
C15 | 0.1273 (3) | 0.9910 (6) | 0.4098 (5) | 0.0453 (15) | |
H15A | 0.1138 | 1.0408 | 0.3562 | 0.054* | |
H15B | 0.1706 | 1.0134 | 0.4283 | 0.054* | |
C16 | 0.1269 (3) | 0.8681 (6) | 0.3778 (5) | 0.0532 (17) | |
H16A | 0.1549 | 0.8595 | 0.3216 | 0.064* | |
H16B | 0.1437 | 0.8193 | 0.4298 | 0.064* | |
C17 | 0.0622 (3) | 0.8286 (6) | 0.3522 (5) | 0.0532 (16) | |
H17A | 0.0638 | 0.7470 | 0.3334 | 0.064* | |
H17B | 0.0468 | 0.8731 | 0.2967 | 0.064* | |
C18 | 0.0161 (3) | 0.8432 (5) | 0.4363 (4) | 0.0394 (13) | |
H18A | −0.0271 | 0.8222 | 0.4158 | 0.047* | |
H18B | 0.0284 | 0.7921 | 0.4897 | 0.047* | |
C19 | 0.1037 (3) | 0.7770 (4) | 0.6926 (4) | 0.0377 (13) | |
C20 | 0.1590 (3) | 0.8229 (5) | 0.7266 (5) | 0.0515 (15) | |
H20 | 0.1571 | 0.8848 | 0.7707 | 0.062* | |
C21 | 0.2168 (3) | 0.7822 (7) | 0.6990 (6) | 0.067 (2) | |
H21 | 0.2542 | 0.8156 | 0.7241 | 0.081* | |
C22 | 0.2209 (4) | 0.6929 (7) | 0.6348 (6) | 0.075 (2) | |
H22 | 0.2606 | 0.6631 | 0.6157 | 0.090* | |
C23 | 0.1659 (4) | 0.6486 (6) | 0.5994 (6) | 0.073 (2) | |
H23 | 0.1680 | 0.5894 | 0.5529 | 0.088* | |
C24 | 0.1087 (3) | 0.6861 (4) | 0.6281 (4) | 0.0480 (15) | |
H24 | 0.0716 | 0.6503 | 0.6043 | 0.058* | |
C25 | −0.0691 (2) | 0.4456 (5) | 0.3995 (4) | 0.0340 (12) | |
H25 | −0.0732 | 0.4821 | 0.3351 | 0.041* | |
C26 | −0.1279 (2) | 0.3764 (5) | 0.4200 (4) | 0.0349 (12) | |
H26A | −0.1237 | 0.3377 | 0.4827 | 0.042* | |
H26B | −0.1333 | 0.3169 | 0.3702 | 0.042* | |
C27 | −0.1857 (2) | 0.4554 (5) | 0.4211 (5) | 0.0440 (14) | |
H27A | −0.1908 | 0.4917 | 0.3575 | 0.053* | |
H27B | −0.2240 | 0.4097 | 0.4344 | 0.053* | |
C28 | −0.1786 (3) | 0.5468 (6) | 0.4963 (5) | 0.0519 (16) | |
H28A | −0.1772 | 0.5109 | 0.5604 | 0.062* | |
H28B | −0.2155 | 0.5987 | 0.4941 | 0.062* | |
C29 | −0.1188 (3) | 0.6155 (5) | 0.4801 (6) | 0.0531 (17) | |
H29A | −0.1135 | 0.6709 | 0.5331 | 0.064* | |
H29B | −0.1228 | 0.6594 | 0.4198 | 0.064* | |
C30 | −0.0607 (3) | 0.5386 (4) | 0.4745 (4) | 0.0385 (13) | |
H30A | −0.0233 | 0.5856 | 0.4584 | 0.046* | |
H30B | −0.0532 | 0.5028 | 0.5377 | 0.046* | |
C31 | 0.0501 (2) | 0.4152 (4) | 0.3808 (4) | 0.0288 (11) | |
H31 | 0.0599 | 0.4701 | 0.4337 | 0.035* | |
C32 | 0.0527 (2) | 0.4797 (5) | 0.2867 (4) | 0.0374 (13) | |
H32A | 0.0232 | 0.5453 | 0.2885 | 0.045* | |
H32B | 0.0401 | 0.4285 | 0.2337 | 0.045* | |
C33 | 0.1202 (2) | 0.5229 (5) | 0.2703 (5) | 0.0481 (16) | |
H33A | 0.1225 | 0.5619 | 0.2075 | 0.058* | |
H33B | 0.1311 | 0.5795 | 0.3204 | 0.058* | |
C34 | 0.1676 (3) | 0.4259 (5) | 0.2727 (5) | 0.0485 (15) | |
H34A | 0.1590 | 0.3721 | 0.2196 | 0.058* | |
H34B | 0.2107 | 0.4570 | 0.2639 | 0.058* | |
C35 | 0.1638 (3) | 0.3629 (5) | 0.3673 (5) | 0.0454 (14) | |
H35A | 0.1937 | 0.2978 | 0.3669 | 0.054* | |
H35B | 0.1760 | 0.4152 | 0.4199 | 0.054* | |
C36 | 0.0975 (2) | 0.3186 (5) | 0.3847 (4) | 0.0361 (12) | |
H36A | 0.0868 | 0.2607 | 0.3355 | 0.043* | |
H36B | 0.0955 | 0.2812 | 0.4481 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0368 (6) | 0.0339 (6) | 0.0307 (6) | 0.0028 (6) | 0.0023 (7) | −0.0034 (6) |
S2 | 0.0481 (8) | 0.0581 (10) | 0.0440 (9) | 0.0101 (7) | 0.0064 (7) | 0.0254 (8) |
N1 | 0.032 (2) | 0.029 (2) | 0.020 (2) | 0.0034 (19) | 0.0018 (19) | 0.0016 (19) |
N2 | 0.029 (2) | 0.031 (2) | 0.028 (2) | −0.0014 (19) | −0.0026 (18) | −0.001 (2) |
C1 | 0.042 (3) | 0.035 (3) | 0.018 (2) | −0.002 (2) | −0.002 (2) | 0.004 (2) |
C2 | 0.057 (4) | 0.035 (3) | 0.036 (3) | −0.002 (3) | 0.006 (3) | −0.001 (3) |
C3 | 0.064 (4) | 0.051 (4) | 0.041 (4) | −0.026 (3) | 0.010 (3) | −0.005 (3) |
C4 | 0.044 (3) | 0.065 (4) | 0.040 (3) | −0.003 (3) | 0.012 (3) | 0.011 (4) |
C5 | 0.045 (3) | 0.039 (3) | 0.039 (3) | 0.001 (3) | 0.008 (3) | 0.000 (3) |
C6 | 0.043 (3) | 0.033 (3) | 0.026 (3) | −0.002 (2) | 0.002 (2) | −0.003 (2) |
C7 | 0.023 (2) | 0.034 (3) | 0.032 (3) | −0.005 (2) | 0.002 (2) | −0.006 (2) |
C8 | 0.038 (3) | 0.061 (4) | 0.024 (3) | −0.001 (3) | 0.005 (2) | 0.004 (3) |
C9 | 0.033 (3) | 0.086 (5) | 0.040 (3) | −0.004 (3) | 0.012 (3) | 0.003 (4) |
C10 | 0.031 (3) | 0.108 (6) | 0.044 (4) | 0.014 (3) | 0.005 (3) | −0.002 (4) |
C11 | 0.028 (3) | 0.122 (6) | 0.037 (4) | 0.004 (4) | 0.000 (2) | −0.007 (4) |
C12 | 0.037 (3) | 0.073 (4) | 0.030 (3) | −0.004 (3) | 0.001 (3) | 0.001 (3) |
C13 | 0.028 (3) | 0.029 (2) | 0.022 (2) | 0.000 (2) | 0.003 (2) | 0.003 (2) |
C14 | 0.035 (3) | 0.054 (3) | 0.023 (3) | 0.004 (3) | 0.001 (2) | 0.000 (3) |
C15 | 0.030 (3) | 0.074 (4) | 0.032 (3) | −0.007 (3) | 0.003 (2) | 0.002 (3) |
C16 | 0.043 (3) | 0.075 (4) | 0.041 (4) | 0.020 (3) | 0.011 (3) | −0.002 (3) |
C17 | 0.059 (4) | 0.055 (4) | 0.045 (4) | 0.019 (3) | 0.013 (3) | −0.010 (3) |
C18 | 0.043 (3) | 0.037 (3) | 0.038 (3) | 0.002 (3) | 0.005 (3) | −0.002 (3) |
C19 | 0.052 (3) | 0.033 (3) | 0.028 (3) | −0.001 (2) | 0.003 (3) | 0.012 (2) |
C20 | 0.058 (4) | 0.058 (4) | 0.039 (3) | −0.015 (3) | −0.001 (3) | 0.006 (3) |
C21 | 0.043 (4) | 0.088 (5) | 0.071 (5) | −0.003 (4) | 0.001 (3) | 0.024 (5) |
C22 | 0.068 (5) | 0.077 (5) | 0.079 (6) | 0.014 (4) | 0.022 (4) | 0.028 (5) |
C23 | 0.109 (6) | 0.053 (4) | 0.056 (4) | 0.022 (4) | 0.026 (5) | 0.012 (4) |
C24 | 0.070 (4) | 0.031 (3) | 0.043 (4) | 0.005 (3) | −0.004 (3) | 0.000 (3) |
C25 | 0.028 (3) | 0.041 (3) | 0.033 (3) | 0.009 (2) | −0.002 (2) | 0.003 (3) |
C26 | 0.030 (3) | 0.039 (3) | 0.036 (3) | −0.008 (2) | 0.001 (2) | −0.010 (2) |
C27 | 0.031 (3) | 0.055 (4) | 0.046 (4) | 0.002 (3) | 0.001 (3) | 0.000 (3) |
C28 | 0.038 (3) | 0.058 (4) | 0.060 (4) | 0.015 (3) | 0.003 (3) | −0.004 (3) |
C29 | 0.043 (3) | 0.044 (3) | 0.072 (5) | 0.010 (3) | 0.008 (3) | 0.000 (3) |
C30 | 0.039 (3) | 0.030 (3) | 0.047 (3) | 0.002 (2) | −0.001 (3) | −0.002 (3) |
C31 | 0.023 (2) | 0.034 (3) | 0.029 (3) | 0.001 (2) | −0.004 (2) | −0.002 (2) |
C32 | 0.032 (3) | 0.038 (3) | 0.043 (3) | 0.002 (2) | 0.001 (3) | 0.006 (3) |
C33 | 0.039 (3) | 0.053 (4) | 0.053 (4) | −0.002 (3) | 0.008 (3) | 0.009 (3) |
C34 | 0.036 (3) | 0.058 (4) | 0.051 (4) | −0.001 (3) | 0.009 (3) | 0.000 (3) |
C35 | 0.033 (3) | 0.054 (4) | 0.049 (4) | 0.009 (3) | −0.004 (3) | −0.003 (3) |
C36 | 0.036 (3) | 0.038 (3) | 0.035 (3) | 0.005 (2) | −0.002 (2) | 0.002 (3) |
Geometric parameters (Å, º) top
S1—C1 | 1.762 (5) | C17—C18 | 1.539 (8) |
S2—C19 | 1.755 (6) | C17—H17A | 0.9900 |
N1—C13 | 1.498 (6) | C17—H17B | 0.9900 |
N1—C7 | 1.497 (6) | C18—H18A | 0.9900 |
N1—H1A | 0.92 (5) | C18—H18B | 0.9900 |
N1—H1B | 0.93 (6) | C19—C20 | 1.374 (8) |
N2—C25 | 1.490 (6) | C19—C24 | 1.397 (8) |
N2—C31 | 1.507 (6) | C20—C21 | 1.372 (9) |
N2—H2A | 1.11 (5) | C20—H20 | 0.9500 |
N2—H2B | 0.87 (6) | C21—C22 | 1.378 (11) |
C1—C6 | 1.387 (7) | C21—H21 | 0.9500 |
C1—C2 | 1.389 (7) | C22—C23 | 1.369 (11) |
C2—C3 | 1.394 (8) | C22—H22 | 0.9500 |
C2—H2 | 0.9500 | C23—C24 | 1.350 (9) |
C3—C4 | 1.361 (9) | C23—H23 | 0.9500 |
C3—H3 | 0.9500 | C24—H24 | 0.9500 |
C4—C5 | 1.377 (8) | C25—C26 | 1.513 (7) |
C4—H4 | 0.9500 | C25—C30 | 1.520 (8) |
C5—C6 | 1.383 (7) | C25—H25 | 1.0000 |
C5—H5 | 0.9500 | C26—C27 | 1.535 (7) |
C6—H6 | 0.9500 | C26—H26A | 0.9900 |
C7—C8 | 1.490 (7) | C26—H26B | 0.9900 |
C7—C12 | 1.500 (8) | C27—C28 | 1.505 (9) |
C7—H7 | 1.0000 | C27—H27A | 0.9900 |
C8—C9 | 1.523 (7) | C27—H27B | 0.9900 |
C8—H8A | 0.9900 | C28—C29 | 1.517 (8) |
C8—H8B | 0.9900 | C28—H28A | 0.9900 |
C9—C10 | 1.495 (9) | C28—H28B | 0.9900 |
C9—H9A | 0.9900 | C29—C30 | 1.527 (7) |
C9—H9B | 0.9900 | C29—H29A | 0.9900 |
C10—C11 | 1.520 (9) | C29—H29B | 0.9900 |
C10—H10A | 0.9900 | C30—H30A | 0.9900 |
C10—H10B | 0.9900 | C30—H30B | 0.9900 |
C11—C12 | 1.512 (8) | C31—C36 | 1.511 (7) |
C11—H11A | 0.9900 | C31—C32 | 1.516 (7) |
C11—H11B | 0.9900 | C31—H31 | 1.0000 |
C12—H12A | 0.9900 | C32—C33 | 1.535 (7) |
C12—H12B | 0.9900 | C32—H32A | 0.9900 |
C13—C14 | 1.513 (7) | C32—H32B | 0.9900 |
C13—C18 | 1.529 (7) | C33—C34 | 1.514 (8) |
C13—H13 | 1.0000 | C33—H33A | 0.9900 |
C14—C15 | 1.518 (8) | C33—H33B | 0.9900 |
C14—H14A | 0.9900 | C34—C35 | 1.515 (9) |
C14—H14B | 0.9900 | C34—H34A | 0.9900 |
C15—C16 | 1.504 (9) | C34—H34B | 0.9900 |
C15—H15A | 0.9900 | C35—C36 | 1.518 (7) |
C15—H15B | 0.9900 | C35—H35A | 0.9900 |
C16—C17 | 1.491 (9) | C35—H35B | 0.9900 |
C16—H16A | 0.9900 | C36—H36A | 0.9900 |
C16—H16B | 0.9900 | C36—H36B | 0.9900 |
| | | |
C13—N1—C7 | 117.6 (4) | C13—C18—C17 | 109.0 (5) |
C13—N1—H1A | 113 (3) | C13—C18—H18A | 109.9 |
C7—N1—H1A | 102 (3) | C17—C18—H18A | 109.9 |
C13—N1—H1B | 103 (3) | C13—C18—H18B | 109.9 |
C7—N1—H1B | 113 (3) | C17—C18—H18B | 109.9 |
H1A—N1—H1B | 109 (4) | H18A—C18—H18B | 108.3 |
C25—N2—C31 | 117.9 (4) | C20—C19—C24 | 117.1 (6) |
C25—N2—H2A | 111 (3) | C20—C19—S2 | 121.6 (5) |
C31—N2—H2A | 111 (3) | C24—C19—S2 | 121.3 (5) |
C25—N2—H2B | 109 (4) | C19—C20—C21 | 122.0 (7) |
C31—N2—H2B | 112 (4) | C19—C20—H20 | 119.0 |
H2A—N2—H2B | 93 (4) | C21—C20—H20 | 119.0 |
C6—C1—C2 | 117.6 (5) | C22—C21—C20 | 120.1 (7) |
C6—C1—S1 | 121.3 (4) | C22—C21—H21 | 120.0 |
C2—C1—S1 | 121.1 (4) | C20—C21—H21 | 120.0 |
C1—C2—C3 | 121.0 (5) | C23—C22—C21 | 117.9 (7) |
C1—C2—H2 | 119.5 | C23—C22—H22 | 121.0 |
C3—C2—H2 | 119.5 | C21—C22—H22 | 121.0 |
C4—C3—C2 | 120.4 (5) | C24—C23—C22 | 122.4 (8) |
C4—C3—H3 | 119.8 | C24—C23—H23 | 118.8 |
C2—C3—H3 | 119.8 | C22—C23—H23 | 118.8 |
C3—C4—C5 | 119.4 (5) | C23—C24—C19 | 120.4 (6) |
C3—C4—H4 | 120.3 | C23—C24—H24 | 119.8 |
C5—C4—H4 | 120.3 | C19—C24—H24 | 119.8 |
C4—C5—C6 | 120.7 (5) | N2—C25—C26 | 108.0 (4) |
C4—C5—H5 | 119.6 | N2—C25—C30 | 111.4 (4) |
C6—C5—H5 | 119.6 | C26—C25—C30 | 110.3 (4) |
C5—C6—C1 | 120.8 (5) | N2—C25—H25 | 109.0 |
C5—C6—H6 | 119.6 | C26—C25—H25 | 109.0 |
C1—C6—H6 | 119.6 | C30—C25—H25 | 109.0 |
C8—C7—C12 | 111.4 (4) | C25—C26—C27 | 109.9 (4) |
C8—C7—N1 | 108.9 (4) | C25—C26—H26A | 109.7 |
C12—C7—N1 | 112.3 (4) | C27—C26—H26A | 109.7 |
C8—C7—H7 | 108.0 | C25—C26—H26B | 109.7 |
C12—C7—H7 | 108.0 | C27—C26—H26B | 109.7 |
N1—C7—H7 | 108.0 | H26A—C26—H26B | 108.2 |
C7—C8—C9 | 110.9 (5) | C28—C27—C26 | 110.7 (5) |
C7—C8—H8A | 109.5 | C28—C27—H27A | 109.5 |
C9—C8—H8A | 109.5 | C26—C27—H27A | 109.5 |
C7—C8—H8B | 109.5 | C28—C27—H27B | 109.5 |
C9—C8—H8B | 109.5 | C26—C27—H27B | 109.5 |
H8A—C8—H8B | 108.0 | H27A—C27—H27B | 108.1 |
C10—C9—C8 | 111.8 (5) | C27—C28—C29 | 110.8 (5) |
C10—C9—H9A | 109.3 | C27—C28—H28A | 109.5 |
C8—C9—H9A | 109.3 | C29—C28—H28A | 109.5 |
C10—C9—H9B | 109.3 | C27—C28—H28B | 109.5 |
C8—C9—H9B | 109.3 | C29—C28—H28B | 109.5 |
H9A—C9—H9B | 107.9 | H28A—C28—H28B | 108.1 |
C9—C10—C11 | 111.9 (5) | C28—C29—C30 | 111.8 (5) |
C9—C10—H10A | 109.2 | C28—C29—H29A | 109.3 |
C11—C10—H10A | 109.2 | C30—C29—H29A | 109.3 |
C9—C10—H10B | 109.2 | C28—C29—H29B | 109.3 |
C11—C10—H10B | 109.2 | C30—C29—H29B | 109.3 |
H10A—C10—H10B | 107.9 | H29A—C29—H29B | 107.9 |
C12—C11—C10 | 111.4 (5) | C25—C30—C29 | 111.2 (5) |
C12—C11—H11A | 109.4 | C25—C30—H30A | 109.4 |
C10—C11—H11A | 109.4 | C29—C30—H30A | 109.4 |
C12—C11—H11B | 109.4 | C25—C30—H30B | 109.4 |
C10—C11—H11B | 109.4 | C29—C30—H30B | 109.4 |
H11A—C11—H11B | 108.0 | H30A—C30—H30B | 108.0 |
C7—C12—C11 | 110.5 (5) | C36—C31—N2 | 108.1 (4) |
C7—C12—H12A | 109.6 | C36—C31—C32 | 112.2 (4) |
C11—C12—H12A | 109.6 | N2—C31—C32 | 111.4 (4) |
C7—C12—H12B | 109.6 | C36—C31—H31 | 108.3 |
C11—C12—H12B | 109.6 | N2—C31—H31 | 108.3 |
H12A—C12—H12B | 108.1 | C32—C31—H31 | 108.3 |
N1—C13—C14 | 107.9 (4) | C31—C32—C33 | 109.1 (5) |
N1—C13—C18 | 110.7 (4) | C31—C32—H32A | 109.9 |
C14—C13—C18 | 112.5 (4) | C33—C32—H32A | 109.9 |
N1—C13—H13 | 108.6 | C31—C32—H32B | 109.9 |
C14—C13—H13 | 108.6 | C33—C32—H32B | 109.9 |
C18—C13—H13 | 108.6 | H32A—C32—H32B | 108.3 |
C13—C14—C15 | 110.5 (4) | C34—C33—C32 | 111.7 (5) |
C13—C14—H14A | 109.6 | C34—C33—H33A | 109.3 |
C15—C14—H14A | 109.6 | C32—C33—H33A | 109.3 |
C13—C14—H14B | 109.6 | C34—C33—H33B | 109.3 |
C15—C14—H14B | 109.6 | C32—C33—H33B | 109.3 |
H14A—C14—H14B | 108.1 | H33A—C33—H33B | 107.9 |
C16—C15—C14 | 110.7 (5) | C35—C34—C33 | 110.3 (5) |
C16—C15—H15A | 109.5 | C35—C34—H34A | 109.6 |
C14—C15—H15A | 109.5 | C33—C34—H34A | 109.6 |
C16—C15—H15B | 109.5 | C35—C34—H34B | 109.6 |
C14—C15—H15B | 109.5 | C33—C34—H34B | 109.6 |
H15A—C15—H15B | 108.1 | H34A—C34—H34B | 108.1 |
C17—C16—C15 | 111.8 (5) | C36—C35—C34 | 110.8 (5) |
C17—C16—H16A | 109.3 | C36—C35—H35A | 109.5 |
C15—C16—H16A | 109.3 | C34—C35—H35A | 109.5 |
C17—C16—H16B | 109.3 | C36—C35—H35B | 109.5 |
C15—C16—H16B | 109.3 | C34—C35—H35B | 109.5 |
H16A—C16—H16B | 107.9 | H35A—C35—H35B | 108.1 |
C16—C17—C18 | 111.6 (5) | C31—C36—C35 | 110.9 (4) |
C16—C17—H17A | 109.3 | C31—C36—H36A | 109.5 |
C18—C17—H17A | 109.3 | C35—C36—H36A | 109.5 |
C16—C17—H17B | 109.3 | C31—C36—H36B | 109.5 |
C18—C17—H17B | 109.3 | C35—C36—H36B | 109.5 |
H17A—C17—H17B | 108.0 | H36A—C36—H36B | 108.1 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S1i | 0.92 (5) | 2.29 (6) | 3.200 (4) | 170 (4) |
N1—H1B···S2 | 0.93 (6) | 2.37 (6) | 3.266 (5) | 163 (4) |
N2—H2B···S1ii | 0.87 (6) | 2.34 (6) | 3.194 (5) | 167 (5) |
N2—H2A···S2iii | 1.11 (5) | 2.15 (6) | 3.246 (5) | 166 (4) |
Symmetry codes: (i) −x, −y+2, z+1/2; (ii) −x, −y+1, z+1/2; (iii) −x, −y+1, z−1/2. |
Experimental details
Crystal data |
Chemical formula | C12H24N+·C6H5S− |
Mr | 291.50 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 200 |
a, b, c (Å) | 21.208 (4), 11.678 (2), 13.974 (3) |
V (Å3) | 3460.9 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.5 × 0.4 × 0.1 |
|
Data collection |
Diffractometer | Oxford Diffraction KM-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3593, 3593, 2159 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.626 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.144, 1.04 |
No. of reflections | 3593 |
No. of parameters | 373 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.26 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.06 (13) |
Selected geometric parameters (Å, º) topS1—C1 | 1.762 (5) | N1—C7 | 1.497 (6) |
S2—C19 | 1.755 (6) | N2—C25 | 1.490 (6) |
N1—C13 | 1.498 (6) | N2—C31 | 1.507 (6) |
| | | |
C13—N1—C7 | 117.6 (4) | C13—N1—H1B | 103 (3) |
C13—N1—H1A | 113 (3) | C7—N1—H1B | 113 (3) |
C7—N1—H1A | 102 (3) | H1A—N1—H1B | 109 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S1i | 0.92 (5) | 2.29 (6) | 3.200 (4) | 170 (4) |
N1—H1B···S2 | 0.93 (6) | 2.37 (6) | 3.266 (5) | 163 (4) |
N2—H2B···S1ii | 0.87 (6) | 2.34 (6) | 3.194 (5) | 167 (5) |
N2—H2A···S2iii | 1.11 (5) | 2.15 (6) | 3.246 (5) | 166 (4) |
Symmetry codes: (i) −x, −y+2, z+1/2; (ii) −x, −y+1, z+1/2; (iii) −x, −y+1, z−1/2. |
The title compound, (I), was obtained previously in polycrystalline form (Dance, 1979). It was found to be a good isolatable source of the benzenethiolate anion for preparation of metal thiolates. On the other hand, there is a need for information in the study of N—H···S bonding. Such bonding plays a crucial role in biological systems, e.g. on the modification of redox potential in iron–sulfur proteins (Nakamura et al., 1988). Detailed research on N—H···S hydrogen bonding in simple molecules is therefore important.
The asymmetric unit of (I) consists of two benzenethiolate anions and two dicyclohexylammonium cations. The ions are linked in zigzag chains by S···H—N—H··· hydrogen bonding, motif C(4) (Etter, 1990). The donor–acceptor S···N distances [range 3.194 (5)–3.266 (5) Å] are comparable with the data observed in complex zinc and cobalt benzenethiolates [(C6H11)2NH2]2[Zn2(SC6H5)6] (Chung et al., 1991a), [(C6H11)2NH2]2[Co(SC6H5)4] (Chung et al., 1991b) and in [(CH3)3NCH2CONH2][SC6H5] (Walters et al., 1991).