Tris(N-cyclo­hexyl-N-methyl­di­thio­carbamato-S)antimony(III)

Baba, I.; Ibrahim, S.; Farina, Y.; Othman, A.H.; Razak, I.A.; Fun, H.-K.; Ng, S.W.

doi:10.1107/S1600536800020122

Tris(N-cyclohexyl-N-methyldithiocarbamato-S)antimony(III)

I. Baba, S. Ibrahim, Y. Farina, A. H. Othman, I. A. Razak, H.-K. Fun and S. W. Ng

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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020122/na6026sup1.cif Contains datablocks I, aho32m
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020122/na6026Isup2.hkl Contains datablock I

CCDC reference: 155846

checkCIF report

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

Comment top

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).

Experimental top

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%).

Computing details top

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.

Figures top

Fig. 1. ORTEPII (Johnson, 1976) plot of (I) at the 50% probability level. H atoms are shown as circles of arbitrary radii.

Tris(N-cyclohexyl-N-methyldithiocarbamato)antimony(III) top

Crystal data top

[Sb(C₈H₁₄NS₂)₃]	D_x = 1.438 Mg m⁻³
M_r = 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	R_int = 0.029
ω scans	θ_max = 33.2°, θ_min = 2.7°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −19→21
T_min = 0.504, T_max = 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(F_o²) + (0.0249P)² + 0.0788P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
3970 reflections	Δρ_max = 0.21 e Å⁻³
104 parameters	Δρ_min = −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
M_r = 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)
T_min = 0.504, T_max = 0.748	R_int = 0.029
14627 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.054	Δρ_max = 0.21 e Å⁻³
S = 1.01	Δρ_min = −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	U_iso*/U_eq
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]
M_r	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)
T_min, T_max	0.504, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	14627, 3970, 3486
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.34
Absolute structure	Flack & Schwarzenbach (1988)
Absolute structure parameter	−0.02 (1)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top

Sb1—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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Tris(N-cyclo­hexyl-N-methyl­di­thio­carbamato-S)antimony(III)

Supporting information

Key indicators

checkCIF results

Tris(N-cyclohexyl-N-methyldithiocarbamato-S)antimony(III)