Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056516/at2460sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056516/at2460Isup2.hkl |
CCDC reference: 672641
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).
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.
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).
[Sb(C5H8NOS2)3] | F(000) = 1224 |
Mr = 608.48 | Dx = 1.746 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2654 reflections |
a = 12.8891 (13) Å | θ = 2.5–25.3° |
b = 20.009 (2) Å | µ = 1.76 mm−1 |
c = 9.0073 (9) Å | T = 298 K |
β = 94.734 (2)° | Block, yellow |
V = 2315.0 (4) Å3 | 0.59 × 0.20 × 0.08 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 4056 independent reflections |
Radiation source: fine-focus sealed tube | 2716 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
phi and ω scans | θmax = 25.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→12 |
Tmin = 0.424, Tmax = 0.872 | k = −23→22 |
11465 measured reflections | l = −10→10 |
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)] = 0.044 | H-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 reflections | Δρmax = 0.88 e Å−3 |
253 parameters | Δρmin = −0.58 e Å−3 |
Primary atom site location: structure-invariant direct methods |
[Sb(C5H8NOS2)3] | V = 2315.0 (4) Å3 |
Mr = 608.48 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.8891 (13) Å | µ = 1.76 mm−1 |
b = 20.009 (2) Å | T = 298 K |
c = 9.0073 (9) Å | 0.59 × 0.20 × 0.08 mm |
β = 94.734 (2)° |
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 = 0.872 | Rint = 0.064 |
11465 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 253 parameters |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.88 e Å−3 |
4056 reflections | Δρmin = −0.58 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Sb1 | 0.15201 (3) | 0.046775 (19) | 0.10064 (5) | 0.03166 (16) | |
N1 | 0.3477 (3) | −0.1181 (2) | −0.0361 (6) | 0.0331 (12) | |
N2 | 0.0485 (4) | 0.1343 (2) | −0.3489 (6) | 0.0398 (14) | |
N3 | 0.3273 (4) | 0.1164 (2) | 0.5276 (6) | 0.0485 (15) | |
O1 | 0.4047 (4) | −0.1910 (2) | −0.2841 (5) | 0.0554 (13) | |
O2 | −0.1021 (4) | 0.2012 (2) | −0.5360 (6) | 0.0685 (16) | |
O3 | 0.4797 (4) | 0.1579 (3) | 0.7463 (6) | 0.0753 (17) | |
S1 | 0.32072 (12) | 0.01042 (7) | 0.01547 (19) | 0.0345 (4) | |
S2 | 0.16824 (12) | −0.09393 (8) | 0.07939 (19) | 0.0388 (4) | |
S3 | 0.07604 (12) | 0.02040 (7) | −0.19772 (19) | 0.0352 (4) | |
S4 | 0.15521 (13) | 0.15062 (7) | −0.08730 (19) | 0.0391 (4) | |
S5 | 0.24492 (15) | 0.01171 (8) | 0.3820 (2) | 0.0473 (5) | |
S6 | 0.24826 (15) | 0.14712 (8) | 0.2552 (2) | 0.0478 (5) | |
C1 | 0.2839 (4) | −0.0739 (3) | 0.0153 (6) | 0.0281 (14) | |
C2 | 0.4407 (5) | −0.1006 (3) | −0.1099 (8) | 0.0446 (18) | |
H2A | 0.5011 | −0.1227 | −0.0608 | 0.054* | |
H2B | 0.4522 | −0.0527 | −0.1046 | 0.054* | |
C3 | 0.4259 (6) | −0.1222 (4) | −0.2688 (8) | 0.056 (2) | |
H3A | 0.3687 | −0.0971 | −0.3186 | 0.067* | |
H3B | 0.4882 | −0.1118 | −0.3176 | 0.067* | |
C4 | 0.3158 (5) | −0.2091 (3) | −0.2104 (7) | 0.0483 (18) | |
H4A | 0.3059 | −0.2571 | −0.2180 | 0.058* | |
H4B | 0.2549 | −0.1878 | −0.2600 | 0.058* | |
C5 | 0.3251 (5) | −0.1894 (3) | −0.0484 (7) | 0.0404 (17) | |
H5A | 0.2605 | −0.1992 | −0.0046 | 0.048* | |
H5B | 0.3804 | −0.2147 | 0.0050 | 0.048* | |
C6 | 0.0875 (4) | 0.1039 (3) | −0.2247 (7) | 0.0310 (14) | |
C7 | −0.0106 (5) | 0.0991 (3) | −0.4706 (8) | 0.0520 (19) | |
H7A | −0.0212 | 0.0530 | −0.4424 | 0.062* | |
H7B | 0.0281 | 0.0995 | −0.5585 | 0.062* | |
C8 | −0.1123 (6) | 0.1322 (3) | −0.5040 (9) | 0.061 (2) | |
H8A | −0.1492 | 0.1103 | −0.5888 | 0.073* | |
H8B | −0.1536 | 0.1271 | −0.4194 | 0.073* | |
C9 | −0.0489 (5) | 0.2341 (3) | −0.4159 (9) | 0.060 (2) | |
H9A | −0.0891 | 0.2308 | −0.3298 | 0.072* | |
H9B | −0.0425 | 0.2811 | −0.4402 | 0.072* | |
C10 | 0.0562 (5) | 0.2058 (3) | −0.3781 (8) | 0.0462 (18) | |
H10A | 0.0992 | 0.2131 | −0.4600 | 0.055* | |
H10B | 0.0888 | 0.2281 | −0.2907 | 0.055* | |
C11 | 0.2771 (5) | 0.0935 (3) | 0.4024 (7) | 0.0341 (15) | |
C12 | 0.3629 (6) | 0.0738 (3) | 0.6512 (8) | 0.059 (2) | |
H12A | 0.3596 | 0.0275 | 0.6199 | 0.070* | |
H12B | 0.3180 | 0.0794 | 0.7316 | 0.070* | |
C13 | 0.4711 (6) | 0.0911 (4) | 0.7045 (9) | 0.069 (2) | |
H13A | 0.4935 | 0.0631 | 0.7890 | 0.083* | |
H13B | 0.5165 | 0.0824 | 0.6261 | 0.083* | |
C14 | 0.4465 (7) | 0.1995 (4) | 0.6268 (11) | 0.088 (3) | |
H14A | 0.4951 | 0.1950 | 0.5507 | 0.105* | |
H14B | 0.4501 | 0.2454 | 0.6614 | 0.105* | |
C15 | 0.3438 (6) | 0.1874 (3) | 0.5596 (8) | 0.058 (2) | |
H15A | 0.3332 | 0.2127 | 0.4677 | 0.070* | |
H15B | 0.2931 | 0.2026 | 0.6260 | 0.070* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sb1 | 0.0340 (3) | 0.0308 (2) | 0.0303 (3) | −0.00067 (18) | 0.00391 (18) | −0.00238 (19) |
N1 | 0.026 (3) | 0.033 (3) | 0.042 (3) | −0.001 (2) | 0.007 (2) | −0.003 (2) |
N2 | 0.046 (3) | 0.030 (3) | 0.041 (4) | 0.000 (2) | −0.011 (3) | 0.004 (3) |
N3 | 0.075 (4) | 0.031 (3) | 0.035 (4) | −0.014 (3) | −0.017 (3) | 0.003 (3) |
O1 | 0.072 (3) | 0.052 (3) | 0.044 (3) | 0.004 (3) | 0.017 (3) | −0.010 (2) |
O2 | 0.071 (4) | 0.049 (3) | 0.080 (4) | −0.004 (3) | −0.030 (3) | 0.017 (3) |
O3 | 0.084 (4) | 0.076 (4) | 0.062 (4) | −0.025 (3) | −0.022 (3) | 0.005 (3) |
S1 | 0.0309 (9) | 0.0300 (8) | 0.0432 (11) | −0.0040 (7) | 0.0070 (8) | 0.0009 (7) |
S2 | 0.0384 (10) | 0.0340 (9) | 0.0459 (12) | −0.0059 (7) | 0.0146 (8) | −0.0017 (8) |
S3 | 0.0397 (9) | 0.0282 (8) | 0.0366 (10) | −0.0016 (7) | −0.0041 (8) | −0.0003 (7) |
S4 | 0.0501 (10) | 0.0301 (8) | 0.0351 (11) | −0.0022 (7) | −0.0086 (8) | −0.0017 (7) |
S5 | 0.0728 (13) | 0.0321 (9) | 0.0356 (11) | −0.0122 (8) | −0.0032 (10) | 0.0030 (8) |
S6 | 0.0751 (13) | 0.0305 (9) | 0.0350 (11) | −0.0057 (8) | −0.0128 (10) | 0.0035 (8) |
C1 | 0.024 (3) | 0.030 (3) | 0.030 (4) | 0.000 (3) | −0.001 (3) | 0.003 (3) |
C2 | 0.035 (4) | 0.044 (4) | 0.056 (5) | 0.004 (3) | 0.012 (4) | −0.009 (4) |
C3 | 0.058 (5) | 0.060 (5) | 0.053 (5) | 0.003 (4) | 0.021 (4) | 0.003 (4) |
C4 | 0.061 (5) | 0.045 (4) | 0.037 (5) | −0.002 (3) | −0.010 (4) | −0.003 (3) |
C5 | 0.051 (4) | 0.026 (3) | 0.045 (5) | 0.007 (3) | 0.008 (3) | −0.003 (3) |
C6 | 0.026 (3) | 0.036 (3) | 0.031 (4) | 0.008 (3) | −0.004 (3) | −0.001 (3) |
C7 | 0.073 (5) | 0.042 (4) | 0.038 (5) | 0.004 (4) | −0.014 (4) | −0.008 (3) |
C8 | 0.069 (5) | 0.047 (4) | 0.062 (6) | −0.013 (4) | −0.028 (4) | 0.012 (4) |
C9 | 0.059 (5) | 0.035 (4) | 0.082 (6) | 0.007 (3) | −0.009 (5) | 0.012 (4) |
C10 | 0.052 (4) | 0.037 (4) | 0.047 (5) | −0.009 (3) | −0.013 (4) | 0.011 (3) |
C11 | 0.045 (4) | 0.032 (3) | 0.026 (4) | 0.000 (3) | 0.005 (3) | −0.002 (3) |
C12 | 0.086 (6) | 0.045 (4) | 0.042 (5) | −0.019 (4) | −0.019 (4) | 0.010 (4) |
C13 | 0.072 (6) | 0.085 (7) | 0.047 (6) | −0.008 (5) | −0.015 (4) | 0.009 (5) |
C14 | 0.103 (8) | 0.057 (5) | 0.098 (8) | −0.035 (5) | −0.020 (6) | 0.002 (5) |
C15 | 0.082 (6) | 0.043 (4) | 0.045 (5) | −0.010 (4) | −0.019 (4) | −0.006 (3) |
Sb1—S1 | 2.4742 (16) | C2—H2A | 0.9700 |
Sb1—S4 | 2.6826 (16) | C2—H2B | 0.9700 |
Sb1—S6 | 2.6876 (17) | C3—H3A | 0.9700 |
Sb1—S5 | 2.8015 (18) | C3—H3B | 0.9700 |
Sb1—S2 | 2.8307 (16) | C4—C5 | 1.507 (9) |
Sb1—S3 | 2.8329 (17) | C4—H4A | 0.9700 |
Sb1—S3i | 3.4111 (17) | C4—H4B | 0.9700 |
N1—C1 | 1.316 (7) | C5—H5A | 0.9700 |
N1—C5 | 1.459 (7) | C5—H5B | 0.9700 |
N1—C2 | 1.460 (7) | C7—C8 | 1.477 (9) |
N2—C6 | 1.335 (7) | C7—H7A | 0.9700 |
N2—C10 | 1.460 (7) | C7—H7B | 0.9700 |
N2—C7 | 1.462 (7) | C8—H8A | 0.9700 |
N3—C11 | 1.334 (7) | C8—H8B | 0.9700 |
N3—C12 | 1.446 (8) | C9—C10 | 1.482 (8) |
N3—C15 | 1.461 (8) | C9—H9A | 0.9700 |
O1—C3 | 1.409 (8) | C9—H9B | 0.9700 |
O1—C4 | 1.418 (8) | C10—H10A | 0.9700 |
O2—C9 | 1.397 (8) | C10—H10B | 0.9700 |
O2—C8 | 1.419 (7) | C12—C13 | 1.478 (9) |
O3—C13 | 1.390 (9) | C12—H12A | 0.9700 |
O3—C14 | 1.399 (9) | C12—H12B | 0.9700 |
S1—C1 | 1.753 (6) | C13—H13A | 0.9700 |
S2—C1 | 1.691 (6) | C13—H13B | 0.9700 |
S3—C6 | 1.696 (6) | C14—C15 | 1.431 (9) |
S4—C6 | 1.729 (6) | C14—H14A | 0.9700 |
S5—C11 | 1.695 (6) | C14—H14B | 0.9700 |
S6—C11 | 1.722 (6) | C15—H15A | 0.9700 |
C2—C3 | 1.492 (9) | C15—H15B | 0.9700 |
S1—Sb1—S4 | 88.42 (5) | N1—C5—C4 | 109.3 (5) |
S1—Sb1—S6 | 90.02 (6) | N1—C5—H5A | 109.8 |
S4—Sb1—S6 | 73.60 (5) | C4—C5—H5A | 109.8 |
S1—Sb1—S5 | 83.44 (6) | N1—C5—H5B | 109.8 |
S4—Sb1—S5 | 137.49 (5) | C4—C5—H5B | 109.8 |
S6—Sb1—S5 | 64.78 (5) | H5A—C5—H5B | 108.3 |
S1—Sb1—S2 | 67.35 (5) | N2—C6—S3 | 122.5 (4) |
S4—Sb1—S2 | 136.27 (5) | N2—C6—S4 | 119.1 (4) |
S6—Sb1—S2 | 138.11 (5) | S3—C6—S4 | 118.4 (3) |
S5—Sb1—S2 | 77.50 (5) | N2—C7—C8 | 109.7 (6) |
S1—Sb1—S3 | 83.97 (5) | N2—C7—H7A | 109.7 |
S4—Sb1—S3 | 64.39 (5) | C8—C7—H7A | 109.7 |
S6—Sb1—S3 | 137.66 (5) | N2—C7—H7B | 109.7 |
S5—Sb1—S3 | 154.16 (5) | C8—C7—H7B | 109.7 |
S2—Sb1—S3 | 76.84 (5) | H7A—C7—H7B | 108.2 |
S1—Sb1—S3i | 139.61 (4) | O2—C8—C7 | 112.4 (6) |
S4—Sb1—S3i | 121.70 (5) | O2—C8—H8A | 109.1 |
S6—Sb1—S3i | 122.16 (5) | C7—C8—H8A | 109.1 |
S5—Sb1—S3i | 88.99 (5) | O2—C8—H8B | 109.1 |
S2—Sb1—S3i | 72.27 (4) | C7—C8—H8B | 109.1 |
S3—Sb1—S3i | 86.11 (5) | H8A—C8—H8B | 107.9 |
C1—N1—C5 | 123.8 (5) | O2—C9—C10 | 112.3 (6) |
C1—N1—C2 | 124.0 (5) | O2—C9—H9A | 109.2 |
C5—N1—C2 | 111.4 (5) | C10—C9—H9A | 109.2 |
C6—N2—C10 | 124.8 (5) | O2—C9—H9B | 109.2 |
C6—N2—C7 | 123.1 (5) | C10—C9—H9B | 109.2 |
C10—N2—C7 | 112.0 (5) | H9A—C9—H9B | 107.9 |
C11—N3—C12 | 123.4 (5) | N2—C10—C9 | 110.0 (5) |
C11—N3—C15 | 123.5 (5) | N2—C10—H10A | 109.7 |
C12—N3—C15 | 112.9 (5) | C9—C10—H10A | 109.7 |
C3—O1—C4 | 111.2 (5) | N2—C10—H10B | 109.7 |
C9—O2—C8 | 110.4 (5) | C9—C10—H10B | 109.7 |
C13—O3—C14 | 110.6 (6) | H10A—C10—H10B | 108.2 |
C1—S1—Sb1 | 92.21 (19) | N3—C11—S5 | 121.3 (5) |
C1—S2—Sb1 | 81.9 (2) | N3—C11—S6 | 119.7 (4) |
C6—S3—Sb1 | 85.7 (2) | S5—C11—S6 | 118.9 (4) |
C6—S4—Sb1 | 90.0 (2) | N3—C12—C13 | 110.1 (6) |
C11—S5—Sb1 | 86.5 (2) | N3—C12—H12A | 109.6 |
C11—S6—Sb1 | 89.7 (2) | C13—C12—H12A | 109.6 |
N1—C1—S2 | 123.7 (4) | N3—C12—H12B | 109.6 |
N1—C1—S1 | 118.0 (4) | C13—C12—H12B | 109.6 |
S2—C1—S1 | 118.3 (3) | H12A—C12—H12B | 108.2 |
N1—C2—C3 | 108.8 (5) | O3—C13—C12 | 111.4 (7) |
N1—C2—H2A | 109.9 | O3—C13—H13A | 109.3 |
C3—C2—H2A | 109.9 | C12—C13—H13A | 109.3 |
N1—C2—H2B | 109.9 | O3—C13—H13B | 109.3 |
C3—C2—H2B | 109.9 | C12—C13—H13B | 109.3 |
H2A—C2—H2B | 108.3 | H13A—C13—H13B | 108.0 |
O1—C3—C2 | 112.7 (6) | O3—C14—C15 | 116.0 (7) |
O1—C3—H3A | 109.1 | O3—C14—H14A | 108.3 |
C2—C3—H3A | 109.1 | C15—C14—H14A | 108.3 |
O1—C3—H3B | 109.1 | O3—C14—H14B | 108.3 |
C2—C3—H3B | 109.1 | C15—C14—H14B | 108.3 |
H3A—C3—H3B | 107.8 | H14A—C14—H14B | 107.4 |
O1—C4—C5 | 112.6 (5) | C14—C15—N3 | 111.2 (6) |
O1—C4—H4A | 109.1 | C14—C15—H15A | 109.4 |
C5—C4—H4A | 109.1 | N3—C15—H15A | 109.4 |
O1—C4—H4B | 109.1 | C14—C15—H15B | 109.4 |
C5—C4—H4B | 109.1 | N3—C15—H15B | 109.4 |
H4A—C4—H4B | 107.8 | H15A—C15—H15B | 108.0 |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Sb(C5H8NOS2)3] |
Mr | 608.48 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 12.8891 (13), 20.009 (2), 9.0073 (9) |
β (°) | 94.734 (2) |
V (Å3) | 2315.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.76 |
Crystal size (mm) | 0.59 × 0.20 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.424, 0.872 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11465, 4056, 2716 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.111, 1.01 |
No. of reflections | 4056 |
No. of parameters | 253 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.88, −0.58 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
Sb1—S1 | 2.4742 (16) | Sb1—S2 | 2.8307 (16) |
Sb1—S4 | 2.6826 (16) | Sb1—S3 | 2.8329 (17) |
Sb1—S6 | 2.6876 (17) | Sb1—S3i | 3.4111 (17) |
Sb1—S5 | 2.8015 (18) | ||
S1—Sb1—S4 | 88.42 (5) | S6—Sb1—S2 | 138.11 (5) |
S1—Sb1—S6 | 90.02 (6) | S5—Sb1—S2 | 77.50 (5) |
S4—Sb1—S6 | 73.60 (5) | S1—Sb1—S3 | 83.97 (5) |
S1—Sb1—S5 | 83.44 (6) | S4—Sb1—S3 | 64.39 (5) |
S4—Sb1—S5 | 137.49 (5) | S6—Sb1—S3 | 137.66 (5) |
S6—Sb1—S5 | 64.78 (5) | S5—Sb1—S3 | 154.16 (5) |
S1—Sb1—S2 | 67.35 (5) | S2—Sb1—S3 | 76.84 (5) |
S4—Sb1—S2 | 136.27 (5) |
Symmetry code: (i) −x, −y, −z. |
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).