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Acta Cryst. (2007). E63, m2989    [ doi:10.1107/S1600536807056516 ]

Tris(morpholine-4-dithiocarboxylato-[kappa]2S,S')antimony(III)

J. Zhai, H. Yin and D. Wang

Abstract top

In the title compound, [Sb(C5H8NOS2)3], the SbIII ion adopts a distorted pentagonal-pyramidal geometry because of its stereochemically active lone pair of electrons. In the crystal structure, the molecules are associated into dimers by short intermolecular Sb...S contacts [3.4111 (17) Å].

Comment top

Dithiocarbamates have been known as effective ligands for transition metal ions, which can form chelates (Xu et al., 2001) or act as bridging ligands (Bardaji et al., 1994). As a contribution to the chemistry of main-group metal complexes with dithiocarbamates, we present here the synthesis and crystal structure of the title compound (I).

In (I) (Fig. 1), the SbIII ion is coordinated by the six S atoms [Sb—S 2.474 (2)–2.833 (2) Å] belonging to three morpholine-4-dithiocarboxylate ligands. The resulting SbS6 coordination polyhedron approximates to a pentagonal pyramid with atoms Sb1 and S2—S6 at the base of the pyramid and S1 in the apical position. Three of the five equatorial Sb—S bonds are long (to S2, S3 and S5), two are short (to S4 and S6), while the apical donor atom forms the strongest bond [Sb1—S1=2.474 (2)]. The SbIII lone pair of electrons may project in a direction roughly trans to the Sb1—S1 bond. The short intermolecular distance Sb1···S3i of 3.411 (2) Å suggests a presence of Sb···S interactions (sSymmetry code as in Fig. 2), which lead to the dimeric associations in the crystal (Fig. 2).

Related literature top

For descriptions of the versatile coordination fashions of dithiocarbamates, see: Xu et al. (2001); Bardaji et al. (1994).

Experimental top

The title compound were prepared by reaction of antimony tribromide (36.1 mg, 0.1 mmol) with the corresponding sodium dithiocarbamate (36.3 mg, 0.3 mmol), in absolute acetone. After stirring for 5 h at room temperature, the yellow paste was obtained and then filtered. Yellow crystals suitable for X-ray analysis were obtained by slow evaporation of methanol/dichloromethane (1:2 v/v) solution over a period of two weeks (yield 90%. m.p. 435 Kk).

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.97 Å for methylene H atoms, and with Uiso(H) = 1.2Ueq(C) for C-bound H atoms.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering schems. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. Crystal packing of (I), showing the Sb···S interactions as dashed lines. [Symmetry code: (i) −x,-y,-z.]
Tris(morpholine-4-dithiocarboxylato-κ2S,S')antimony(III) top
Crystal data top
[Sb(C5H8NOS2)3]F000 = 1224
Mr = 608.48Dx = 1.746 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2654 reflections
a = 12.8891 (13) Åθ = 2.5–25.3º
b = 20.009 (2) ŵ = 1.76 mm−1
c = 9.0073 (9) ÅT = 298 (2) K
β = 94.734 (2)ºBlock, yellow
V = 2315.0 (4) Å30.59 × 0.20 × 0.08 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		4056 independent reflections
Radiation source: fine-focus sealed tube2716 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.064
T = 298(2) Kθmax = 25.0º
phi and ω scansθmin = 1.6º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→12
Tmin = 0.424, Tmax = 0.872k = −23→22
11465 measured reflectionsl = −10→10
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.111  w = 1/[σ2(Fo2) + (0.0475P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
4056 reflectionsΔρmax = 0.88 e Å−3
253 parametersΔρmin = −0.58 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Sb(C5H8NOS2)3]V = 2315.0 (4) Å3
Mr = 608.48Z = 4
Monoclinic, P21/cMo Kα
a = 12.8891 (13) ŵ = 1.76 mm−1
b = 20.009 (2) ÅT = 298 (2) K
c = 9.0073 (9) Å0.59 × 0.20 × 0.08 mm
β = 94.734 (2)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		4056 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2716 reflections with I > 2σ(I)
Tmin = 0.424, Tmax = 0.872Rint = 0.064
11465 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044? restraints
wR(F2) = 0.111H-atom parameters constrained
S = 1.01Δρmax = 0.88 e Å−3
4056 reflectionsΔρmin = −0.58 e Å−3
253 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sb10.15201 (3)0.046775 (19)0.10064 (5)0.03166 (16)
N10.3477 (3)−0.1181 (2)−0.0361 (6)0.0331 (12)
N20.0485 (4)0.1343 (2)−0.3489 (6)0.0398 (14)
N30.3273 (4)0.1164 (2)0.5276 (6)0.0485 (15)
O10.4047 (4)−0.1910 (2)−0.2841 (5)0.0554 (13)
O2−0.1021 (4)0.2012 (2)−0.5360 (6)0.0685 (16)
O30.4797 (4)0.1579 (3)0.7463 (6)0.0753 (17)
S10.32072 (12)0.01042 (7)0.01547 (19)0.0345 (4)
S20.16824 (12)−0.09393 (8)0.07939 (19)0.0388 (4)
S30.07604 (12)0.02040 (7)−0.19772 (19)0.0352 (4)
S40.15521 (13)0.15062 (7)−0.08730 (19)0.0391 (4)
S50.24492 (15)0.01171 (8)0.3820 (2)0.0473 (5)
S60.24826 (15)0.14712 (8)0.2552 (2)0.0478 (5)
C10.2839 (4)−0.0739 (3)0.0153 (6)0.0281 (14)
C20.4407 (5)−0.1006 (3)−0.1099 (8)0.0446 (18)
H2A0.5011−0.1227−0.06080.054*
H2B0.4522−0.0527−0.10460.054*
C30.4259 (6)−0.1222 (4)−0.2688 (8)0.056 (2)
H3A0.3687−0.0971−0.31860.067*
H3B0.4882−0.1118−0.31760.067*
C40.3158 (5)−0.2091 (3)−0.2104 (7)0.0483 (18)
H4A0.3059−0.2571−0.21800.058*
H4B0.2549−0.1878−0.26000.058*
C50.3251 (5)−0.1894 (3)−0.0484 (7)0.0404 (17)
H5A0.2605−0.1992−0.00460.048*
H5B0.3804−0.21470.00500.048*
C60.0875 (4)0.1039 (3)−0.2247 (7)0.0310 (14)
C7−0.0106 (5)0.0991 (3)−0.4706 (8)0.0520 (19)
H7A−0.02120.0530−0.44240.062*
H7B0.02810.0995−0.55850.062*
C8−0.1123 (6)0.1322 (3)−0.5040 (9)0.061 (2)
H8A−0.14920.1103−0.58880.073*
H8B−0.15360.1271−0.41940.073*
C9−0.0489 (5)0.2341 (3)−0.4159 (9)0.060 (2)
H9A−0.08910.2308−0.32980.072*
H9B−0.04250.2811−0.44020.072*
C100.0562 (5)0.2058 (3)−0.3781 (8)0.0462 (18)
H10A0.09920.2131−0.46000.055*
H10B0.08880.2281−0.29070.055*
C110.2771 (5)0.0935 (3)0.4024 (7)0.0341 (15)
C120.3629 (6)0.0738 (3)0.6512 (8)0.059 (2)
H12A0.35960.02750.61990.070*
H12B0.31800.07940.73160.070*
C130.4711 (6)0.0911 (4)0.7045 (9)0.069 (2)
H13A0.49350.06310.78900.083*
H13B0.51650.08240.62610.083*
C140.4465 (7)0.1995 (4)0.6268 (11)0.088 (3)
H14A0.49510.19500.55070.105*
H14B0.45010.24540.66140.105*
C150.3438 (6)0.1874 (3)0.5596 (8)0.058 (2)
H15A0.33320.21270.46770.070*
H15B0.29310.20260.62600.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sb10.0340 (3)0.0308 (2)0.0303 (3)−0.00067 (18)0.00391 (18)−0.00238 (19)
N10.026 (3)0.033 (3)0.042 (3)−0.001 (2)0.007 (2)−0.003 (2)
N20.046 (3)0.030 (3)0.041 (4)0.000 (2)−0.011 (3)0.004 (3)
N30.075 (4)0.031 (3)0.035 (4)−0.014 (3)−0.017 (3)0.003 (3)
O10.072 (3)0.052 (3)0.044 (3)0.004 (3)0.017 (3)−0.010 (2)
O20.071 (4)0.049 (3)0.080 (4)−0.004 (3)−0.030 (3)0.017 (3)
O30.084 (4)0.076 (4)0.062 (4)−0.025 (3)−0.022 (3)0.005 (3)
S10.0309 (9)0.0300 (8)0.0432 (11)−0.0040 (7)0.0070 (8)0.0009 (7)
S20.0384 (10)0.0340 (9)0.0459 (12)−0.0059 (7)0.0146 (8)−0.0017 (8)
S30.0397 (9)0.0282 (8)0.0366 (10)−0.0016 (7)−0.0041 (8)−0.0003 (7)
S40.0501 (10)0.0301 (8)0.0351 (11)−0.0022 (7)−0.0086 (8)−0.0017 (7)
S50.0728 (13)0.0321 (9)0.0356 (11)−0.0122 (8)−0.0032 (10)0.0030 (8)
S60.0751 (13)0.0305 (9)0.0350 (11)−0.0057 (8)−0.0128 (10)0.0035 (8)
C10.024 (3)0.030 (3)0.030 (4)0.000 (3)−0.001 (3)0.003 (3)
C20.035 (4)0.044 (4)0.056 (5)0.004 (3)0.012 (4)−0.009 (4)
C30.058 (5)0.060 (5)0.053 (5)0.003 (4)0.021 (4)0.003 (4)
C40.061 (5)0.045 (4)0.037 (5)−0.002 (3)−0.010 (4)−0.003 (3)
C50.051 (4)0.026 (3)0.045 (5)0.007 (3)0.008 (3)−0.003 (3)
C60.026 (3)0.036 (3)0.031 (4)0.008 (3)−0.004 (3)−0.001 (3)
C70.073 (5)0.042 (4)0.038 (5)0.004 (4)−0.014 (4)−0.008 (3)
C80.069 (5)0.047 (4)0.062 (6)−0.013 (4)−0.028 (4)0.012 (4)
C90.059 (5)0.035 (4)0.082 (6)0.007 (3)−0.009 (5)0.012 (4)
C100.052 (4)0.037 (4)0.047 (5)−0.009 (3)−0.013 (4)0.011 (3)
C110.045 (4)0.032 (3)0.026 (4)0.000 (3)0.005 (3)−0.002 (3)
C120.086 (6)0.045 (4)0.042 (5)−0.019 (4)−0.019 (4)0.010 (4)
C130.072 (6)0.085 (7)0.047 (6)−0.008 (5)−0.015 (4)0.009 (5)
C140.103 (8)0.057 (5)0.098 (8)−0.035 (5)−0.020 (6)0.002 (5)
C150.082 (6)0.043 (4)0.045 (5)−0.010 (4)−0.019 (4)−0.006 (3)
Geometric parameters (Å, °) top
Sb1—S12.4742 (16)C2—H2A0.9700
Sb1—S42.6826 (16)C2—H2B0.9700
Sb1—S62.6876 (17)C3—H3A0.9700
Sb1—S52.8015 (18)C3—H3B0.9700
Sb1—S22.8307 (16)C4—C51.507 (9)
Sb1—S32.8329 (17)C4—H4A0.9700
Sb1—S3i3.4111 (17)C4—H4B0.9700
N1—C11.316 (7)C5—H5A0.9700
N1—C51.459 (7)C5—H5B0.9700
N1—C21.460 (7)C7—C81.477 (9)
N2—C61.335 (7)C7—H7A0.9700
N2—C101.460 (7)C7—H7B0.9700
N2—C71.462 (7)C8—H8A0.9700
N3—C111.334 (7)C8—H8B0.9700
N3—C121.446 (8)C9—C101.482 (8)
N3—C151.461 (8)C9—H9A0.9700
O1—C31.409 (8)C9—H9B0.9700
O1—C41.418 (8)C10—H10A0.9700
O2—C91.397 (8)C10—H10B0.9700
O2—C81.419 (7)C12—C131.478 (9)
O3—C131.390 (9)C12—H12A0.9700
O3—C141.399 (9)C12—H12B0.9700
S1—C11.753 (6)C13—H13A0.9700
S2—C11.691 (6)C13—H13B0.9700
S3—C61.696 (6)C14—C151.431 (9)
S4—C61.729 (6)C14—H14A0.9700
S5—C111.695 (6)C14—H14B0.9700
S6—C111.722 (6)C15—H15A0.9700
C2—C31.492 (9)C15—H15B0.9700
S1—Sb1—S488.42 (5)N1—C5—C4109.3 (5)
S1—Sb1—S690.02 (6)N1—C5—H5A109.8
S4—Sb1—S673.60 (5)C4—C5—H5A109.8
S1—Sb1—S583.44 (6)N1—C5—H5B109.8
S4—Sb1—S5137.49 (5)C4—C5—H5B109.8
S6—Sb1—S564.78 (5)H5A—C5—H5B108.3
S1—Sb1—S267.35 (5)N2—C6—S3122.5 (4)
S4—Sb1—S2136.27 (5)N2—C6—S4119.1 (4)
S6—Sb1—S2138.11 (5)S3—C6—S4118.4 (3)
S5—Sb1—S277.50 (5)N2—C7—C8109.7 (6)
S1—Sb1—S383.97 (5)N2—C7—H7A109.7
S4—Sb1—S364.39 (5)C8—C7—H7A109.7
S6—Sb1—S3137.66 (5)N2—C7—H7B109.7
S5—Sb1—S3154.16 (5)C8—C7—H7B109.7
S2—Sb1—S376.84 (5)H7A—C7—H7B108.2
S1—Sb1—S3i139.61 (4)O2—C8—C7112.4 (6)
S4—Sb1—S3i121.70 (5)O2—C8—H8A109.1
S6—Sb1—S3i122.16 (5)C7—C8—H8A109.1
S5—Sb1—S3i88.99 (5)O2—C8—H8B109.1
S2—Sb1—S3i72.27 (4)C7—C8—H8B109.1
S3—Sb1—S3i86.11 (5)H8A—C8—H8B107.9
C1—N1—C5123.8 (5)O2—C9—C10112.3 (6)
C1—N1—C2124.0 (5)O2—C9—H9A109.2
C5—N1—C2111.4 (5)C10—C9—H9A109.2
C6—N2—C10124.8 (5)O2—C9—H9B109.2
C6—N2—C7123.1 (5)C10—C9—H9B109.2
C10—N2—C7112.0 (5)H9A—C9—H9B107.9
C11—N3—C12123.4 (5)N2—C10—C9110.0 (5)
C11—N3—C15123.5 (5)N2—C10—H10A109.7
C12—N3—C15112.9 (5)C9—C10—H10A109.7
C3—O1—C4111.2 (5)N2—C10—H10B109.7
C9—O2—C8110.4 (5)C9—C10—H10B109.7
C13—O3—C14110.6 (6)H10A—C10—H10B108.2
C1—S1—Sb192.21 (19)N3—C11—S5121.3 (5)
C1—S2—Sb181.9 (2)N3—C11—S6119.7 (4)
C6—S3—Sb185.7 (2)S5—C11—S6118.9 (4)
C6—S4—Sb190.0 (2)N3—C12—C13110.1 (6)
C11—S5—Sb186.5 (2)N3—C12—H12A109.6
C11—S6—Sb189.7 (2)C13—C12—H12A109.6
N1—C1—S2123.7 (4)N3—C12—H12B109.6
N1—C1—S1118.0 (4)C13—C12—H12B109.6
S2—C1—S1118.3 (3)H12A—C12—H12B108.2
N1—C2—C3108.8 (5)O3—C13—C12111.4 (7)
N1—C2—H2A109.9O3—C13—H13A109.3
C3—C2—H2A109.9C12—C13—H13A109.3
N1—C2—H2B109.9O3—C13—H13B109.3
C3—C2—H2B109.9C12—C13—H13B109.3
H2A—C2—H2B108.3H13A—C13—H13B108.0
O1—C3—C2112.7 (6)O3—C14—C15116.0 (7)
O1—C3—H3A109.1O3—C14—H14A108.3
C2—C3—H3A109.1C15—C14—H14A108.3
O1—C3—H3B109.1O3—C14—H14B108.3
C2—C3—H3B109.1C15—C14—H14B108.3
H3A—C3—H3B107.8H14A—C14—H14B107.4
O1—C4—C5112.6 (5)C14—C15—N3111.2 (6)
O1—C4—H4A109.1C14—C15—H15A109.4
C5—C4—H4A109.1N3—C15—H15A109.4
O1—C4—H4B109.1C14—C15—H15B109.4
C5—C4—H4B109.1N3—C15—H15B109.4
H4A—C4—H4B107.8H15A—C15—H15B108.0
Symmetry codes: (i) −x, −y, −z.
Table 1
Selected geometric parameters (Å, °) top
Sb1—S12.4742 (16)Sb1—S22.8307 (16)
Sb1—S42.6826 (16)Sb1—S32.8329 (17)
Sb1—S62.6876 (17)Sb1—S3i3.4111 (17)
Sb1—S52.8015 (18)
S1—Sb1—S488.42 (5)S6—Sb1—S2138.11 (5)
S1—Sb1—S690.02 (6)S5—Sb1—S277.50 (5)
S4—Sb1—S673.60 (5)S1—Sb1—S383.97 (5)
S1—Sb1—S583.44 (6)S4—Sb1—S364.39 (5)
S4—Sb1—S5137.49 (5)S6—Sb1—S3137.66 (5)
S6—Sb1—S564.78 (5)S5—Sb1—S3154.16 (5)
S1—Sb1—S267.35 (5)S2—Sb1—S376.84 (5)
S4—Sb1—S2136.27 (5)
Symmetry codes: (i) −x, −y, −z.
Acknowledgements top

We acknowledge the National Natural Foundation of China (grant No. 20771053), Shandong Province Science Foundation and the State Key Laboratory of Crystalline Material, Shandong University, China.

references
References top

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Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-Ray Instruments Inc., Madison, Wisconsin, USA.

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