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In the title compound, [Sb(C8H14NS2)3], the dithiocarbamate groups chelate to the Sb atom in an anisobidentate manner [Sb-S = 2.530 (1) and 2.975 (1) Å]. The Sb atom lies on a threefold axis and the lone pair is also stereochemically active.
Supporting information
CCDC reference: 155846
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- R factor = 0.026
- wR factor = 0.054
- Data-to-parameter ratio = 38.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
PLAT_732 Alert B Angle Calc 64.70(2), Rep 64.70(10) .... 5.00 s.u-Ratio
S1 -SB1 -S2 1.555 1.555 1.555
| Author response: I have rounded up the last decimal place.
|
PLAT_732 Alert B Angle Calc 150.27(2), Rep 150.30(10) .... 5.00 s.u-Ratio
S1 -SB1 -S2 2.665 1.555 1.555
| Author response: I have rounded up the last decimal place.
|
PLAT_732 Alert B Angle Calc 82.34(2), Rep 82.30(10) .... 5.00 s.u-Ratio
S1 -SB1 -S2 3.565 1.555 1.555
| Author response: I have rounded up the last decimal place.
|
Alert Level C:
PLAT_702 Alert C Angle Calc 87.14(2), Rep 87.10(10), Dev. 2.00 Sigma
S1 -SB1 -S1 1.555 1.555 2.665
PLAT_702 Alert C Angle Calc 87.14(2), Rep 87.10(10), Dev. 2.00 Sigma
S1 -SB1 -S1 1.555 1.555 3.565
PLAT_702 Alert C Angle Calc 87.14(2), Rep 87.10(10), Dev. 2.00 Sigma
S1 -SB1 -S1 2.665 1.555 3.565
PLAT_702 Alert C Angle Calc 150.27(2), Rep 150.30(10), Dev. 1.50 Sigma
S1 -SB1 -S2 2.665 1.555 1.555
PLAT_702 Alert C Angle Calc 82.34(2), Rep 82.30(10), Dev. 2.00 Sigma
S1 -SB1 -S2 3.565 1.555 1.555
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and _chemical_formula_moiety. This is
usually due to the moiety formula being in the wrong format.
Atom count from _chemical_formula_sum: C24 H42 N3 S6 Sb1
Atom count from _chemical_formula_moiety:C24 H42 N3 S6
REFLT_03
From the CIF: _diffrn_reflns_theta_max 33.18
From the CIF: _reflns_number_total 3970
Count of symmetry unique reflns 2133
Completeness (_total/calc) 186.12%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1837
Fraction of Friedel pairs measured 0.861
Are heavy atom types Z>Si present yes
Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
3 Alert Level B = Potential problem
5 Alert Level C = Please check
An ethanol solution of carbon disulfide was added to a solution of
cyclohexylmethylamine in ethanol at 277 K followed by an aqueous solution of
concentrated ammonia. The solid ammonium dithiocarbamate was isolated and this
was reacted with antimony(III) trichloride in ethanol (3/1 molar
stoichiometry) at 277 K. The solid product was collected and recrystallized
from ethanol (m.p. 483–484 K). Elemental analysis (calculated in parenthesis)
for C24H42N3S6Sb: C 42.07 (42.02), H 5.90 (6.12), N 6.15 (6.12), S
28.58% (28.01%).
Of the 3970 reflections, 2118 were unique reflections and 1582 were Friedel
pairs.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Tris(
N-cyclohexyl-
N-methyldithiocarbamato)antimony(III)
top
Crystal data top
[Sb(C8H14NS2)3] | Dx = 1.438 Mg m−3 |
Mr = 686.72 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P63 | Cell parameters from 8192 reflections |
a = 13.8948 (4) Å | θ = 2.7–33.2° |
c = 9.4868 (3) Å | µ = 1.28 mm−1 |
V = 1586.19 (8) Å3 | T = 298 K |
Z = 2 | Block, yellow |
F(000) = 708 | 0.62 × 0.28 × 0.24 mm |
Data collection top
Siemens CCD area-detector diffractometer | 3970 independent reflections |
Radiation source: fine-focus sealed tube | 3486 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω scans | θmax = 33.2°, θmin = 2.7° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −19→21 |
Tmin = 0.504, Tmax = 0.748 | k = −21→9 |
14627 measured reflections | l = −14→14 |
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)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.054 | w = 1/[σ2(Fo2) + (0.0249P)2 + 0.0788P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
3970 reflections | Δρmax = 0.21 e Å−3 |
104 parameters | Δρmin = −0.34 e Å−3 |
1 restraint | Absolute structure: Flack & Schwarzenbach (1988) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (1) |
Crystal data top
[Sb(C8H14NS2)3] | Z = 2 |
Mr = 686.72 | Mo Kα radiation |
Hexagonal, P63 | µ = 1.28 mm−1 |
a = 13.8948 (4) Å | T = 298 K |
c = 9.4868 (3) Å | 0.62 × 0.28 × 0.24 mm |
V = 1586.19 (8) Å3 | |
Data collection top
Siemens CCD area-detector diffractometer | 3970 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3486 reflections with I > 2σ(I) |
Tmin = 0.504, Tmax = 0.748 | Rint = 0.029 |
14627 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.054 | Δρmax = 0.21 e Å−3 |
S = 1.01 | Δρmin = −0.34 e Å−3 |
3970 reflections | Absolute structure: Flack & Schwarzenbach (1988) |
104 parameters | Absolute structure parameter: −0.02 (1) |
1 restraint | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Sb1 | 0.3333 | 0.6667 | 0.50001 (2) | 0.03526 (5) | |
S1 | 0.40736 (4) | 0.83364 (4) | 0.33855 (6) | 0.04611 (11) | |
S2 | 0.56729 (4) | 0.84268 (4) | 0.55316 (6) | 0.04187 (10) | |
N1 | 0.6063 (1) | 1.0107 (1) | 0.3813 (2) | 0.039 (1) | |
C1 | 0.5365 (1) | 0.9065 (1) | 0.4227 (2) | 0.033 (1) | |
C2 | 0.5784 (2) | 1.0621 (2) | 0.2656 (2) | 0.050 (1) | |
C3 | 0.7189 (2) | 1.0752 (2) | 0.4434 (2) | 0.045 (1) | |
C4 | 0.8014 (2) | 1.0577 (2) | 0.3581 (3) | 0.058 (1) | |
C5 | 0.9167 (2) | 1.1198 (3) | 0.4275 (4) | 0.088 (1) | |
C6 | 0.9543 (2) | 1.2418 (3) | 0.4457 (4) | 0.091 (1) | |
C7 | 0.8714 (3) | 1.2580 (2) | 0.5280 (4) | 0.087 (1) | |
C8 | 0.7570 (2) | 1.1985 (2) | 0.4593 (3) | 0.062 (1) | |
H2a | 0.5160 | 1.0058 | 0.2143 | 0.075* | |
H2b | 0.6410 | 1.0993 | 0.2034 | 0.075* | |
H2C | 0.5599 | 1.1150 | 0.3031 | 0.075* | |
H3 | 0.7158 | 1.0456 | 0.5381 | 0.055* | |
H4a | 0.8056 | 1.0849 | 0.2629 | 0.070* | |
H4b | 0.7767 | 0.9790 | 0.3530 | 0.070* | |
H5a | 0.9139 | 1.0872 | 0.5189 | 0.105* | |
H5b | 0.9700 | 1.1121 | 0.3695 | 0.105* | |
H6a | 1.0253 | 1.2784 | 0.4941 | 0.109* | |
H6b | 0.9646 | 1.2761 | 0.3537 | 0.109* | |
H7a | 0.8967 | 1.3367 | 0.5347 | 0.104* | |
H7b | 0.8662 | 1.2296 | 0.6229 | 0.104* | |
H8a | 0.7604 | 1.2307 | 0.3674 | 0.075* | |
H8b | 0.7044 | 1.2075 | 0.5170 | 0.075* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sb1 | 0.03185 (5) | 0.03185 (5) | 0.04209 (9) | 0.01592 (3) | 0.000 | 0.000 |
S1 | 0.0350 (2) | 0.0411 (2) | 0.0554 (3) | 0.0139 (2) | −0.0090 (2) | 0.0096 (2) |
S2 | 0.0386 (2) | 0.0388 (2) | 0.0480 (2) | 0.0192 (2) | −0.0057 (2) | 0.0074 (2) |
N1 | 0.037 (1) | 0.035 (1) | 0.041 (1) | 0.015 (1) | −0.003 (1) | 0.005 (1) |
C1 | 0.033 (1) | 0.034 (1) | 0.036 (1) | 0.018 (1) | 0.000 (1) | 0.001 (1) |
C2 | 0.053 (1) | 0.042 (1) | 0.052 (1) | 0.020 (1) | −0.005 (1) | 0.011 (1) |
C3 | 0.040 (1) | 0.039 (1) | 0.045 (1) | 0.010 (1) | −0.006 (1) | 0.005 (1) |
C4 | 0.041 (1) | 0.053 (1) | 0.077 (2) | 0.019 (1) | −0.006 (1) | −0.005 (1) |
C5 | 0.042 (1) | 0.095 (2) | 0.113 (3) | 0.024 (1) | −0.015 (1) | 0.002 (2) |
C6 | 0.051 (1) | 0.078 (2) | 0.097 (2) | −0.003 (1) | −0.022 (2) | 0.005 (2) |
C7 | 0.085 (2) | 0.056 (1) | 0.081 (3) | 0.006 (1) | −0.025 (2) | −0.015 (1) |
C8 | 0.065 (1) | 0.043 (1) | 0.063 (2) | 0.014 (1) | −0.002 (1) | −0.009 (1) |
Geometric parameters (Å, º) top
Sb1—S1 | 2.530 (1) | C2—H2a | 0.9600 |
Sb1—S1i | 2.530 (1) | C2—H2b | 0.9600 |
Sb1—S1ii | 2.530 (1) | C2—H2C | 0.9600 |
Sb1—S2 | 2.975 (1) | C3—H3 | 0.9800 |
S1—C1 | 1.751 (2) | C4—H4a | 0.9700 |
S2—C1 | 1.698 (2) | C4—H4b | 0.9700 |
N1—C1 | 1.336 (2) | C5—H5a | 0.9700 |
N1—C2 | 1.464 (3) | C5—H5b | 0.9700 |
N1—C3 | 1.482 (2) | C6—H6a | 0.9700 |
C3—C4 | 1.520 (3) | C6—H6b | 0.9700 |
C3—C8 | 1.527 (3) | C7—H7a | 0.9700 |
C4—C5 | 1.538 (4) | C7—H7b | 0.9700 |
C5—C6 | 1.513 (5) | C8—H8a | 0.9700 |
C6—C7 | 1.499 (5) | C8—H8b | 0.9700 |
C7—C8 | 1.523 (4) | | |
| | | |
S1—Sb1—S1i | 87.1 (1) | N1—C3—H3 | 107.4 |
S1—Sb1—S1ii | 87.1 (1) | C4—C3—H3 | 107.4 |
S1—Sb1—S2 | 64.7 (1) | C8—C3—H3 | 107.4 |
S1i—Sb1—S1ii | 87.1 (1) | C3—C4—H4a | 109.7 |
S1i—Sb1—S2 | 150.3 (1) | C5—C4—H4a | 109.7 |
S1ii—Sb1—S2 | 82.3 (1) | C3—C4—H4b | 109.7 |
C1—S1—Sb1 | 94.8 (1) | C5—C4—H4b | 109.7 |
C1—S2—Sb1 | 81.3 (1) | H4a—C4—H4b | 108.2 |
C1—N1—C2 | 121.6 (2) | C6—C5—H5a | 109.5 |
C1—N1—C3 | 120.9 (2) | C4—C5—H5a | 109.5 |
C2—N1—C3 | 117.4 (2) | C6—C5—H5b | 109.5 |
N1—C1—S2 | 123.0 (1) | C4—C5—H5b | 109.5 |
N1—C1—S1 | 118.1 (1) | H5a—C5—H5b | 108.0 |
S2—C1—S1 | 118.9 (1) | C7—C6—H6a | 109.3 |
N1—C3—C4 | 110.1 (2) | C5—C6—H6a | 109.3 |
N1—C3—C8 | 112.8 (2) | C7—C6—H6b | 109.3 |
C4—C3—C8 | 111.5 (2) | C5—C6—H6b | 109.3 |
C3—C4—C5 | 109.9 (2) | H6a—C6—H6b | 108.0 |
C6—C5—C4 | 110.9 (2) | C6—C7—H7a | 109.3 |
C7—C6—C5 | 111.5 (3) | C8—C7—H7a | 109.3 |
C6—C7—C8 | 111.6 (3) | C6—C7—H7b | 109.3 |
C7—C8—C3 | 109.5 (2) | C8—C7—H7b | 109.3 |
N1—C2—H2a | 109.5 | H7a—C7—H7b | 108.0 |
N1—C2—H2b | 109.5 | C7—C8—H8a | 109.8 |
H2a—C2—H2b | 109.5 | C3—C8—H8a | 109.8 |
N1—C2—H2c | 109.5 | C7—C8—H8b | 109.8 |
H2a—C2—H2c | 109.5 | C3—C8—H8b | 109.8 |
H2b—C2—H2c | 109.5 | H8a—C8—H8b | 108.2 |
| | | |
S1i—Sb1—S1—C1 | −173.3 (1) | Sb1—S1—C1—S2 | 5.7 (1) |
S1ii—Sb1—S1—C1 | −86.0 (1) | C1—N1—C3—C4 | 90.2 (2) |
S2—Sb1—S1—C1 | −3.2 (1) | C2—N1—C3—C4 | −84.9 (2) |
S1i—Sb1—S2—C1 | 23.4 (1) | C1—N1—C3—C8 | −144.6 (2) |
S1—Sb1—S2—C1 | 3.3 (1) | C2—N1—C3—C8 | 40.3 (3) |
S1ii—Sb1—S2—C1 | 93.7 (1) | N1—C3—C4—C5 | −177.0 (2) |
C2—N1—C1—S2 | 178.2 (2) | C8—C3—C4—C5 | 57.0 (3) |
C3—N1—C1—S2 | 3.3 (3) | C3—C4—C5—C6 | −55.6 (4) |
C2—N1—C1—S1 | −2.3 (3) | C4—C5—C6—C7 | 56.0 (4) |
C3—N1—C1—S1 | −177.2 (2) | C5—C6—C7—C8 | −56.9 (4) |
Sb1—S2—C1—N1 | 174.6 (2) | C6—C7—C8—C3 | 56.8 (3) |
Sb1—S2—C1—S1 | −4.9 (1) | N1—C3—C8—C7 | 178.2 (2) |
Sb1—S1—C1—N1 | −173.8 (1) | C4—C3—C8—C7 | −57.3 (3) |
Symmetry codes: (i) −y+1, x−y+1, z; (ii) −x+y, −x+1, z. |
Experimental details
Crystal data |
Chemical formula | [Sb(C8H14NS2)3] |
Mr | 686.72 |
Crystal system, space group | Hexagonal, P63 |
Temperature (K) | 298 |
a, c (Å) | 13.8948 (4), 9.4868 (3) |
V (Å3) | 1586.19 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.28 |
Crystal size (mm) | 0.62 × 0.28 × 0.24 |
|
Data collection |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.504, 0.748 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14627, 3970, 3486 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.770 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.054, 1.01 |
No. of reflections | 3970 |
No. of parameters | 104 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.34 |
Absolute structure | Flack & Schwarzenbach (1988) |
Absolute structure parameter | −0.02 (1) |
Selected geometric parameters (Å, º) topSb1—S1 | 2.530 (1) | Sb1—S2 | 2.975 (1) |
| | | |
S1—Sb1—S1i | 87.1 (1) | S1i—Sb1—S2 | 150.3 (1) |
S1—Sb1—S2 | 64.7 (1) | S1ii—Sb1—S2 | 82.3 (1) |
S1i—Sb1—S1ii | 87.1 (1) | | |
Symmetry codes: (i) −y+1, x−y+1, z; (ii) −x+y, −x+1, z. |
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The electron lone-pair is stereochemically active in antimony(III) and bismuth(III) tri(diethyldithiocarbamates); the dithiocarbamate group coordinates to metal atom in an anisobidentate manner and the covalent is shorter than the dative distance (Raston & White, 1976). In the title compound, (I), the dithiocarbamate anions chelate to the Sb atom in an anisobidentate manner and the lone pair is also stereochemically active; the Sb atom exists in a distorted octahedral environment.
The conformation of the dithiocabamate ligand appears to be governed by two interactions [C2···S1 = 2.943 (2) Å and C3···S2 = 3.026 (2) Å] that are characterized by H···S [H···S1 = 2.40 Å and H···S2 = 2.53 Å] distances that significantly shorter than the sum of Pauling's van der Waals radii (3.05 Å).