Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021256/ya6141sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021256/ya6141Isup2.hkl |
CCDC reference: 202303
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C) = 0.014 Å
- R factor = 0.059
- wR factor = 0.162
- Data-to-parameter ratio = 25.7
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.254 0.433 Tmin and Tmax expected: 0.167 0.366 RR = 1.288 Please check that your absorption correction is appropriate. PLAT_213 Alert C Atom C6 has ADP max/min Ratio ........... 3.50 prolate PLAT_702 Alert C Angle Calc 136.16(5), Rep 136.10(10), Dev. 1.20 Sigma S2 -BI1 -S6 1.555 1.555 1.555 PLAT_702 Alert C Angle Calc 124.56(5), Rep 124.50(10), Dev. 1.20 Sigma S1 -BI1 -S5 1.555 1.555 2.666 PLAT_731 Alert C Bond Calc 1.51(3), Rep 1.509(9) .... 3.33 su-Ratio C6 -C7 1.555 1.555 General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.846 Tmax scaled 0.366 Tmin scaled 0.215
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
5 Alert Level C = Please check
Bismuth trichloride (3.15 g, 10 mmol) was dissolved in a small volume of ethanol. The solution was cooled in an ice bath, then ethylbutylamine (3.03 g, 30 mmol) and an excess of carbon disulfide (2 ml) were added; the mixture was stirred for several hours. The solid which separated had a melting point of 396–397 K. Elemental analysis, found: C 33.94, H,4.93, N 5.69, S 26.94%; calculated for C21H42BiN3S6: C 31.48, H 5.74, N 5.70 S 26.07%.
Although the cell dimensions define almost exactly a C-centered monoclinic lattice (β = 89.87°), the structure does not have true monoclinic symmetry (Rint = 0.468) and was solved and refined as triclinic. The C—C distances in the ethyl and butyl groups were restrained to 1.54±0.01 Å; in the butyl chain, an additional restriction of C···C = 2.51±0.01 Å was used. The N—Calkyl distances in each dithiocarbamate unit were restrained to be equal to each other by a SADI 0.01 instruction in SHELXL97. The H atoms were positioned geometrically and allowed to ride on their parent C atoms, with Uiso(H) = 1.2Ueq(C) for the methylene H atoms and 1.5Ueq(C) for the methyl H atoms. The final difference Fourier map had a large peak/hole near the Bi atom.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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.
[Bi(C7H14NS2)3] | Z = 2 |
Mr = 737.92 | F(000) = 736 |
Triclinic, P1 | Dx = 1.627 Mg m−3 |
a = 10.5120 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.5128 (1) Å | Cell parameters from 8192 reflections |
c = 14.5755 (1) Å | θ = 1.5–28.3° |
α = 99.713 (1)° | µ = 6.28 mm−1 |
β = 99.927 (1)° | T = 183 K |
γ = 103.383 (1)° | Block, yellow |
V = 1506.52 (2) Å3 | 0.30 × 0.26 × 0.16 mm |
Siemens SMART CCD area-detector diffractometer | 7197 independent reflections |
Radiation source: fine-focus sealed tube | 6368 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 1.5° |
ω scans | h = −13→13 |
Absorption correction: empirical (SADABS; Sheldrick, 1996) | k = −13→12 |
Tmin = 0.254, Tmax = 0.433 | l = −17→19 |
11016 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.162 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0686P)2] where P = (Fo2 + 2Fc2)/3 |
7197 reflections | (Δ/σ)max < 0.001 |
280 parameters | Δρmax = 4.01 e Å−3 |
21 restraints | Δρmin = −5.77 e Å−3 |
[Bi(C7H14NS2)3] | γ = 103.383 (1)° |
Mr = 737.92 | V = 1506.52 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.5120 (1) Å | Mo Kα radiation |
b = 10.5128 (1) Å | µ = 6.28 mm−1 |
c = 14.5755 (1) Å | T = 183 K |
α = 99.713 (1)° | 0.30 × 0.26 × 0.16 mm |
β = 99.927 (1)° |
Siemens SMART CCD area-detector diffractometer | 7197 independent reflections |
Absorption correction: empirical (SADABS; Sheldrick, 1996) | 6368 reflections with I > 2σ(I) |
Tmin = 0.254, Tmax = 0.433 | Rint = 0.076 |
11016 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 21 restraints |
wR(F2) = 0.162 | H-atom parameters constrained |
S = 1.07 | Δρmax = 4.01 e Å−3 |
7197 reflections | Δρmin = −5.77 e Å−3 |
280 parameters |
x | y | z | Uiso*/Ueq | ||
Bi1 | 0.42854 (2) | 0.51202 (2) | 0.64238 (2) | 0.0187 (1) | |
S1 | 0.3720 (2) | 0.6719 (2) | 0.7991 (1) | 0.0330 (5) | |
S2 | 0.5886 (2) | 0.5357 (2) | 0.8272 (1) | 0.0301 (4) | |
S3 | 0.5129 (2) | 0.2752 (2) | 0.6059 (1) | 0.0253 (4) | |
S4 | 0.2706 (2) | 0.3040 (2) | 0.6779 (1) | 0.0246 (4) | |
S5 | 0.2989 (2) | 0.4029 (2) | 0.4456 (1) | 0.0215 (3) | |
S6 | 0.2158 (2) | 0.6122 (2) | 0.5672 (1) | 0.024 (1) | |
N1 | 0.5341 (7) | 0.6973 (9) | 0.9674 (5) | 0.041 (2) | |
N2 | 0.3461 (5) | 0.0791 (6) | 0.6542 (4) | 0.022 (1) | |
N3 | 0.1371 (6) | 0.5432 (6) | 0.3792 (4) | 0.023 (1) | |
C1 | 0.5041 (8) | 0.6395 (9) | 0.8746 (6) | 0.030 (2) | |
C2 | 0.474 (1) | 0.801 (1) | 1.0091 (7) | 0.057 (3) | |
C3 | 0.344 (1) | 0.746 (1) | 1.0418 (9) | 0.064 (3) | |
C4 | 0.6362 (7) | 0.668 (1) | 1.0355 (7) | 0.052 (3) | |
C5 | 0.7721 (8) | 0.763 (1) | 1.0386 (7) | 0.067 (4) | |
C6 | 0.8907 (9) | 0.740 (2) | 1.1018 (9) | 0.13 (1) | |
C7 | 0.891 (2) | 0.594 (2) | 1.081 (1) | 0.115 (7) | |
C8 | 0.3746 (7) | 0.2055 (7) | 0.6458 (5) | 0.020 (1) | |
C9 | 0.2333 (8) | 0.0179 (8) | 0.6918 (6) | 0.036 (2) | |
C10 | 0.1024 (8) | −0.040 (1) | 0.6145 (7) | 0.045 (2) | |
C11 | 0.4285 (7) | −0.0092 (8) | 0.6279 (5) | 0.028 (2) | |
C12 | 0.5438 (7) | −0.0030 (8) | 0.7111 (5) | 0.030 (2) | |
C13 | 0.6284 (7) | −0.0939 (9) | 0.6798 (6) | 0.038 (2) | |
C14 | 0.739 (1) | −0.092 (1) | 0.7636 (9) | 0.063 (3) | |
C15 | 0.2080 (6) | 0.5220 (7) | 0.4543 (5) | 0.018 (1) | |
C16 | 0.0573 (7) | 0.6412 (7) | 0.3824 (6) | 0.028 (2) | |
C17 | 0.142 (1) | 0.7762 (8) | 0.3715 (8) | 0.049 (3) | |
C18 | 0.1290 (6) | 0.4684 (7) | 0.2826 (5) | 0.026 (2) | |
C19 | 0.0127 (7) | 0.3400 (8) | 0.2510 (5) | 0.033 (2) | |
C20 | 0.0021 (8) | 0.2760 (8) | 0.1466 (5) | 0.038 (2) | |
C21 | −0.098 (1) | 0.1375 (9) | 0.1174 (7) | 0.055 (3) | |
H2a | 0.4547 | 0.8541 | 0.9613 | 0.068* | |
H2b | 0.5406 | 0.8616 | 1.0646 | 0.068* | |
H3a | 0.3100 | 0.8215 | 1.0672 | 0.097* | |
H3b | 0.3621 | 0.6969 | 1.0915 | 0.097* | |
H3c | 0.2762 | 0.6866 | 0.9873 | 0.097* | |
H4a | 0.6384 | 0.5736 | 1.0158 | 0.062* | |
H4b | 0.6153 | 0.6804 | 1.0996 | 0.062* | |
H5a | 0.7870 | 0.7542 | 0.9728 | 0.081* | |
H5b | 0.7685 | 0.8559 | 1.0609 | 0.081* | |
H6a | 0.9748 | 0.7948 | 1.0913 | 0.156* | |
H6b | 0.8877 | 0.7677 | 1.1695 | 0.156* | |
H7a | 0.9683 | 0.5816 | 1.1226 | 0.172* | |
H7b | 0.8948 | 0.5662 | 1.0141 | 0.172* | |
H7c | 0.8081 | 0.5392 | 1.0923 | 0.172* | |
H9a | 0.2195 | 0.0858 | 0.7423 | 0.043* | |
H9b | 0.2548 | −0.0549 | 0.7214 | 0.043* | |
H10a | 0.0296 | −0.0794 | 0.6436 | 0.067* | |
H10b | 0.1146 | −0.1089 | 0.5652 | 0.067* | |
H10c | 0.0797 | 0.0320 | 0.5857 | 0.067* | |
H11a | 0.4666 | 0.0161 | 0.5739 | 0.034* | |
H11b | 0.3712 | −0.1024 | 0.6062 | 0.034* | |
H12a | 0.6007 | 0.0903 | 0.7339 | 0.035* | |
H12b | 0.5063 | −0.0308 | 0.7646 | 0.035* | |
H13a | 0.6688 | −0.0639 | 0.6279 | 0.046* | |
H13b | 0.5709 | −0.1866 | 0.6547 | 0.046* | |
H14a | 0.7942 | −0.1492 | 0.7418 | 0.094* | |
H14b | 0.6992 | −0.1242 | 0.8139 | 0.094* | |
H14c | 0.7959 | 0.0004 | 0.7886 | 0.094* | |
H16a | 0.0288 | 0.6531 | 0.4438 | 0.034* | |
H16b | −0.0240 | 0.6081 | 0.3301 | 0.034* | |
H17a | 0.0887 | 0.8413 | 0.3735 | 0.074* | |
H17b | 0.1693 | 0.7641 | 0.3103 | 0.074* | |
H17c | 0.2218 | 0.8090 | 0.4237 | 0.074* | |
H18a | 0.2143 | 0.4445 | 0.2807 | 0.031* | |
H18b | 0.1177 | 0.5269 | 0.2370 | 0.031* | |
H19a | 0.0284 | 0.2762 | 0.2917 | 0.039* | |
H19b | −0.0722 | 0.3617 | 0.2584 | 0.039* | |
H20a | −0.0271 | 0.3342 | 0.1052 | 0.045* | |
H20b | 0.0913 | 0.2680 | 0.1375 | 0.045* | |
H21a | −0.1026 | 0.0986 | 0.0504 | 0.082* | |
H21b | −0.1864 | 0.1456 | 0.1253 | 0.082* | |
H21c | −0.0681 | 0.0795 | 0.1577 | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi1 | 0.0199 (2) | 0.0187 (2) | 0.0212 (2) | 0.0110 (1) | 0.0050 (1) | 0.0059 (1) |
S1 | 0.035 (1) | 0.044 (1) | 0.024 (1) | 0.0248 (9) | 0.0030 (8) | −0.0005 (8) |
S2 | 0.0271 (9) | 0.043 (1) | 0.0260 (9) | 0.0204 (9) | 0.0056 (8) | 0.0079 (8) |
S3 | 0.0230 (8) | 0.0263 (9) | 0.037 (1) | 0.0156 (7) | 0.0151 (8) | 0.0133 (8) |
S4 | 0.0245 (8) | 0.0249 (9) | 0.034 (1) | 0.0154 (7) | 0.0147 (8) | 0.0117 (7) |
S5 | 0.0235 (8) | 0.0199 (8) | 0.0251 (9) | 0.0137 (7) | 0.0047 (7) | 0.0054 (7) |
S6 | 0.0278 (9) | 0.0244 (9) | 0.0239 (9) | 0.0177 (7) | 0.0051 (7) | 0.0026 (7) |
N1 | 0.036 (4) | 0.067 (6) | 0.020 (3) | 0.025 (4) | 0.001 (3) | −0.001 (3) |
N2 | 0.021 (3) | 0.023 (3) | 0.027 (3) | 0.013 (2) | 0.008 (2) | 0.008 (2) |
N3 | 0.020 (3) | 0.028 (3) | 0.027 (3) | 0.015 (3) | 0.004 (2) | 0.010 (3) |
C1 | 0.033 (4) | 0.039 (5) | 0.025 (4) | 0.019 (4) | 0.008 (3) | 0.010 (3) |
C2 | 0.063 (6) | 0.084 (9) | 0.027 (5) | 0.044 (6) | 0.002 (5) | −0.005 (5) |
C3 | 0.068 (7) | 0.084 (9) | 0.056 (7) | 0.046 (7) | 0.022 (6) | 0.012 (6) |
C4 | 0.023 (4) | 0.11 (1) | 0.029 (5) | 0.019 (5) | 0.003 (4) | 0.020 (5) |
C5 | 0.032 (5) | 0.12 (1) | 0.038 (6) | 0.022 (6) | 0.005 (4) | −0.005 (6) |
C6 | 0.063 (9) | 0.31 (3) | 0.049 (8) | 0.11 (1) | 0.023 (7) | 0.05 (1) |
C7 | 0.10 (1) | 0.19 (2) | 0.10 (1) | 0.10 (2) | 0.02 (1) | 0.06 (1) |
C8 | 0.026 (3) | 0.024 (3) | 0.019 (3) | 0.017 (3) | 0.010 (3) | 0.004 (3) |
C9 | 0.057 (5) | 0.019 (4) | 0.042 (5) | 0.014 (4) | 0.027 (4) | 0.013 (3) |
C10 | 0.032 (5) | 0.034 (5) | 0.067 (7) | 0.006 (4) | 0.016 (5) | 0.008 (4) |
C11 | 0.036 (4) | 0.022 (4) | 0.035 (4) | 0.018 (3) | 0.013 (4) | 0.008 (3) |
C12 | 0.038 (4) | 0.022 (4) | 0.033 (4) | 0.017 (3) | 0.007 (3) | 0.007 (3) |
C13 | 0.029 (4) | 0.034 (5) | 0.060 (6) | 0.022 (4) | 0.008 (4) | 0.016 (4) |
C14 | 0.040 (5) | 0.057 (7) | 0.090 (9) | 0.027 (5) | −0.009 (6) | 0.018 (6) |
C15 | 0.012 (3) | 0.017 (3) | 0.030 (4) | 0.009 (2) | 0.007 (3) | 0.006 (3) |
C16 | 0.023 (3) | 0.035 (4) | 0.035 (4) | 0.020 (3) | 0.007 (3) | 0.013 (3) |
C17 | 0.072 (7) | 0.035 (5) | 0.063 (7) | 0.038 (5) | 0.026 (6) | 0.026 (5) |
C18 | 0.023 (3) | 0.039 (4) | 0.024 (4) | 0.016 (3) | 0.008 (3) | 0.014 (3) |
C19 | 0.025 (4) | 0.042 (5) | 0.032 (4) | 0.011 (4) | 0.009 (3) | 0.008 (4) |
C20 | 0.039 (5) | 0.046 (5) | 0.027 (4) | 0.015 (4) | 0.006 (4) | 0.005 (4) |
C21 | 0.078 (8) | 0.048 (6) | 0.039 (6) | 0.021 (6) | 0.016 (5) | 0.004 (5) |
Bi1—S1 | 2.834 (2) | C3—H3c | 0.9800 |
Bi1—S2 | 2.858 (2) | C4—H4a | 0.9900 |
Bi1—S3 | 2.830 (2) | C4—H4b | 0.9900 |
Bi1—S4 | 2.608 (2) | C5—H5a | 0.9900 |
Bi1—S5 | 2.867 (2) | C5—H5b | 0.9900 |
Bi1—S6 | 2.819 (2) | C6—H6a | 0.9900 |
Bi1—S5i | 3.334 (2) | C6—H6b | 0.9900 |
S1—C1 | 1.753 (8) | C7—H7a | 0.9800 |
S2—C1 | 1.692 (8) | C7—H7b | 0.9800 |
S3—C8 | 1.712 (7) | C7—H7c | 0.9800 |
S4—C8 | 1.739 (7) | C9—H9a | 0.9900 |
S5—C15 | 1.744 (7) | C9—H9b | 0.9900 |
S6—C15 | 1.734 (7) | C10—H10a | 0.9800 |
N1—C1 | 1.34 (1) | C10—H10b | 0.9800 |
N1—C4 | 1.458 (9) | C10—H10c | 0.9800 |
N1—C2 | 1.476 (9) | C11—H11a | 0.9900 |
N2—C8 | 1.32 (1) | C11—H11b | 0.9900 |
N2—C9 | 1.453 (7) | C12—H12a | 0.9900 |
N2—C11 | 1.458 (7) | C12—H12b | 0.9900 |
N3—C15 | 1.296 (9) | C13—H13a | 0.9900 |
N3—C16 | 1.471 (7) | C13—H13b | 0.9900 |
N3—C18 | 1.470 (7) | C14—H14a | 0.9800 |
C2—C3 | 1.543 (9) | C14—H14b | 0.9800 |
C4—C5 | 1.531 (8) | C14—H14c | 0.9800 |
C5—C6 | 1.512 (8) | C16—H16a | 0.9900 |
C6—C7 | 1.509 (9) | C16—H16b | 0.9900 |
C9—C10 | 1.543 (8) | C17—H17a | 0.9800 |
C11—C12 | 1.540 (7) | C17—H17b | 0.9800 |
C12—C13 | 1.516 (7) | C17—H17c | 0.9800 |
C13—C14 | 1.529 (8) | C18—H18a | 0.9900 |
C16—C17 | 1.540 (8) | C18—H18b | 0.9900 |
C18—C19 | 1.536 (7) | C19—H19a | 0.9900 |
C19—C20 | 1.531 (7) | C19—H19b | 0.9900 |
C20—C21 | 1.527 (8) | C20—H20a | 0.9900 |
C2—H2a | 0.9900 | C20—H20b | 0.9900 |
C2—H2b | 0.9900 | C21—H21a | 0.9800 |
C3—H3a | 0.9800 | C21—H21b | 0.9800 |
C3—H3b | 0.9800 | C21—H21c | 0.9800 |
S1—Bi1—S2 | 62.8 (1) | H5a—C5—H5b | 107.5 |
S1—Bi1—S3 | 137.5 (1) | C7—C6—H6a | 109.4 |
S1—Bi1—S4 | 88.1 (1) | C5—C6—H6a | 109.4 |
S1—Bi1—S5 | 135.6 (1) | C7—C6—H6b | 109.4 |
S1—Bi1—S6 | 73.4 (1) | C5—C6—H6b | 109.4 |
S2—Bi1—S3 | 81.1 (1) | H6a—C6—H6b | 108.0 |
S2—Bi1—S4 | 85.4 (1) | C6—C7—H7a | 109.5 |
S2—Bi1—S5 | 159.5 (1) | C6—C7—H7b | 109.5 |
S2—Bi1—S6 | 136.1 (1) | H7a—C7—H7b | 109.5 |
S3—Bi1—S4 | 66.2 (1) | C6—C7—H7c | 109.5 |
S3—Bi1—S5 | 78.4 (1) | H7a—C7—H7c | 109.5 |
S3—Bi1—S6 | 138.0 (1) | H7b—C7—H7c | 109.5 |
S4—Bi1—S5 | 86.2 (1) | N2—C9—H9a | 109.0 |
S4—Bi1—S6 | 93.9 (1) | C10—C9—H9a | 109.0 |
S5—Bi1—S6 | 63.1 (1) | N2—C9—H9b | 109.0 |
S4—Bi1—S5i | 141.0 (1) | C10—C9—H9b | 109.0 |
S6—Bi1—S5i | 114.2 (1) | H9a—C9—H9b | 107.8 |
S3—Bi1—S5i | 74.9 (1) | C9—C10—H10a | 109.5 |
S1—Bi1—S5i | 124.5 (1) | C9—C10—H10b | 109.5 |
S2—Bi1—S5i | 91.4 (1) | H10a—C10—H10b | 109.5 |
S5—Bi1—S5i | 83.5 (1) | C9—C10—H10c | 109.5 |
C1—S1—Bi1 | 89.0 (3) | H10a—C10—H10c | 109.5 |
C1—S2—Bi1 | 89.4 (3) | H10b—C10—H10c | 109.5 |
C8—S3—Bi1 | 84.0 (2) | N2—C11—H11a | 109.1 |
C8—S4—Bi1 | 90.6 (3) | C12—C11—H11a | 109.1 |
C15—S5—Bi1 | 88.0 (2) | N2—C11—H11b | 109.1 |
C15—S6—Bi1 | 89.8 (2) | C12—C11—H11b | 109.1 |
C1—N1—C4 | 121.9 (7) | H11a—C11—H11b | 107.8 |
C1—N1—C2 | 123.8 (7) | C13—C12—H12a | 109.5 |
C4—N1—C2 | 114.2 (8) | C11—C12—H12a | 109.5 |
C8—N2—C9 | 123.3 (6) | C13—C12—H12b | 109.5 |
C8—N2—C11 | 122.1 (6) | C11—C12—H12b | 109.5 |
C9—N2—C11 | 114.6 (6) | H12a—C12—H12b | 108.1 |
C15—N3—C16 | 123.8 (6) | C12—C13—H13a | 109.5 |
C15—N3—C18 | 121.9 (6) | C14—C13—H13a | 109.5 |
C16—N3—C18 | 114.2 (6) | C12—C13—H13b | 109.5 |
N1—C1—S2 | 122.4 (6) | C14—C13—H13b | 109.5 |
N1—C1—S1 | 118.9 (6) | H13a—C13—H13b | 108.1 |
S2—C1—S1 | 118.7 (5) | C13—C14—H14a | 109.5 |
N1—C2—C3 | 115.1 (9) | C13—C14—H14b | 109.5 |
N1—C4—C5 | 108.4 (8) | H14a—C14—H14b | 109.5 |
C6—C5—C4 | 115.1 (7) | C13—C14—H14c | 109.5 |
C7—C6—C5 | 111.2 (8) | H14a—C14—H14c | 109.5 |
N2—C8—S3 | 121.6 (5) | H14b—C14—H14c | 109.5 |
N2—C8—S4 | 119.3 (5) | N3—C16—H16a | 109.8 |
S3—C8—S4 | 119.1 (4) | C17—C16—H16a | 109.8 |
N2—C9—C10 | 112.7 (7) | N3—C16—H16b | 109.8 |
N2—C11—C12 | 112.7 (6) | C17—C16—H16b | 109.8 |
C13—C12—C11 | 110.7 (5) | H16a—C16—H16b | 108.2 |
C12—C13—C14 | 110.5 (7) | C16—C17—H17a | 109.5 |
N3—C15—S6 | 120.8 (5) | C16—C17—H17b | 109.5 |
N3—C15—S5 | 121.5 (5) | H17a—C17—H17b | 109.5 |
S6—C15—S5 | 117.7 (4) | C16—C17—H17c | 109.5 |
N3—C16—C17 | 109.6 (6) | H17a—C17—H17c | 109.5 |
N3—C18—C19 | 112.9 (5) | H17b—C17—H17c | 109.5 |
C20—C19—C18 | 109.7 (5) | N3—C18—H18a | 109.0 |
C21—C20—C19 | 111.0 (6) | C19—C18—H18a | 109.0 |
N1—C2—H2a | 108.5 | N3—C18—H18b | 109.0 |
C3—C2—H2a | 108.5 | C19—C18—H18b | 109.0 |
N1—C2—H2b | 108.5 | H18a—C18—H18b | 107.8 |
C3—C2—H2b | 108.5 | C20—C19—H19a | 109.7 |
H2a—C2—H2b | 107.5 | C18—C19—H19a | 109.7 |
C2—C3—H3a | 109.5 | C20—C19—H19b | 109.7 |
C2—C3—H3b | 109.5 | C18—C19—H19b | 109.7 |
H3a—C3—H3b | 109.5 | H19a—C19—H19b | 108.2 |
C2—C3—H3c | 109.5 | C21—C20—H20a | 109.4 |
H3a—C3—H3c | 109.5 | C19—C20—H20a | 109.4 |
H3b—C3—H3c | 109.5 | C21—C20—H20b | 109.4 |
N1—C4—H4a | 110.0 | C19—C20—H20b | 109.4 |
C5—C4—H4a | 110.0 | H20a—C20—H20b | 108.0 |
N1—C4—H4b | 110.0 | C20—C21—H21a | 109.5 |
C5—C4—H4b | 110.0 | C20—C21—H21b | 109.5 |
H4a—C4—H4b | 108.4 | H21a—C21—H21b | 109.5 |
C6—C5—H5a | 108.5 | C20—C21—H21c | 109.5 |
C4—C5—H5a | 108.5 | H21a—C21—H21c | 109.5 |
C6—C5—H5b | 108.5 | H21b—C21—H21c | 109.5 |
C4—C5—H5b | 108.5 | ||
S4—Bi1—S1—C1 | 87.3 (3) | Bi1—S1—C1—N1 | 177.5 (8) |
S6—Bi1—S1—C1 | −178.1 (3) | Bi1—S1—C1—S2 | −2.7 (5) |
S3—Bi1—S1—C1 | 36.6 (3) | C1—N1—C2—C3 | 90 (1) |
S2—Bi1—S1—C1 | 1.6 (3) | C4—N1—C2—C3 | −94 (1) |
S5—Bi1—S1—C1 | 169.9 (3) | C1—N1—C4—C5 | 88 (1) |
S4—Bi1—S2—C1 | −91.9 (3) | C2—N1—C4—C5 | −89 (1) |
S6—Bi1—S2—C1 | −1.1 (3) | N1—C4—C5—C6 | −176.4 (9) |
S3—Bi1—S2—C1 | −158.5 (3) | C4—C5—C6—C7 | 50 (2) |
S1—Bi1—S2—C1 | −1.6 (3) | C9—N2—C8—S3 | 177.1 (6) |
S5—Bi1—S2—C1 | −157.9 (3) | C11—N2—C8—S3 | −2 (1) |
S4—Bi1—S3—C8 | −1.3 (3) | C9—N2—C8—S4 | −2 (1) |
S6—Bi1—S3—C8 | −68.9 (3) | C11—N2—C8—S4 | 179.6 (5) |
S1—Bi1—S3—C8 | 56.5 (3) | Bi1—S3—C8—N2 | −176.9 (6) |
S2—Bi1—S3—C8 | 87.6 (3) | Bi1—S3—C8—S4 | 2.0 (4) |
S5—Bi1—S3—C8 | −92.2 (3) | Bi1—S4—C8—N2 | 176.7 (6) |
S6—Bi1—S4—C8 | 143.0 (3) | Bi1—S4—C8—S3 | −2.2 (4) |
S3—Bi1—S4—C8 | 1.3 (2) | C8—N2—C9—C10 | 86.8 (9) |
S1—Bi1—S4—C8 | −143.8 (3) | C11—N2—C9—C10 | −94.5 (8) |
S2—Bi1—S4—C8 | −81.0 (3) | C8—N2—C11—C12 | 88.8 (9) |
S5—Bi1—S4—C8 | 80.2 (3) | C9—N2—C11—C12 | −89.9 (8) |
S4—Bi1—S5—C15 | 103.0 (2) | N2—C11—C12—C13 | −178.7 (7) |
S6—Bi1—S5—C15 | 6.7 (2) | C11—C12—C13—C14 | −177.8 (8) |
S3—Bi1—S5—C15 | 169.5 (2) | C18—N3—C15—S6 | 179.9 (5) |
S1—Bi1—S5—C15 | 19.6 (2) | C16—N3—C15—S6 | −1 (1) |
S2—Bi1—S5—C15 | 168.9 (2) | C18—N3—C15—S5 | 0.0 (9) |
S4—Bi1—S6—C15 | −90.5 (2) | C16—N3—C15—S5 | 179.3 (5) |
S3—Bi1—S6—C15 | −32.5 (2) | Bi1—S6—C15—N3 | −168.6 (6) |
S1—Bi1—S6—C15 | −177.4 (2) | Bi1—S6—C15—S5 | 11.2 (4) |
S2—Bi1—S6—C15 | −177.9 (2) | Bi1—S5—C15—N3 | 168.8 (6) |
S5—Bi1—S6—C15 | −6.8 (2) | Bi1—S5—C15—S6 | −11.0 (4) |
C4—N1—C1—S2 | −4 (1) | C15—N3—C16—C17 | 92.5 (9) |
C2—N1—C1—S2 | 172.3 (8) | C18—N3—C16—C17 | −88.2 (8) |
C4—N1—C1—S1 | 175.6 (7) | C15—N3—C18—C19 | 90.5 (8) |
C2—N1—C1—S1 | −8 (1) | C16—N3—C18—C19 | −88.9 (8) |
Bi1—S2—C1—N1 | −177.5 (8) | N3—C18—C19—C20 | 174.1 (7) |
Bi1—S2—C1—S1 | 2.6 (5) | C18—C19—C20—C21 | 171.2 (8) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Bi(C7H14NS2)3] |
Mr | 737.92 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 183 |
a, b, c (Å) | 10.5120 (1), 10.5128 (1), 14.5755 (1) |
α, β, γ (°) | 99.713 (1), 99.927 (1), 103.383 (1) |
V (Å3) | 1506.52 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 6.28 |
Crystal size (mm) | 0.30 × 0.26 × 0.16 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.254, 0.433 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11016, 7197, 6368 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.162, 1.07 |
No. of reflections | 7197 |
No. of parameters | 280 |
No. of restraints | 21 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 4.01, −5.77 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Bi1—S1 | 2.834 (2) | Bi1—S5 | 2.867 (2) |
Bi1—S2 | 2.858 (2) | Bi1—S6 | 2.819 (2) |
Bi1—S3 | 2.830 (2) | Bi1—S5i | 3.334 (2) |
Bi1—S4 | 2.608 (2) | ||
S1—Bi1—S2 | 62.8 (1) | S3—Bi1—S6 | 138.0 (1) |
S1—Bi1—S3 | 137.5 (1) | S4—Bi1—S5 | 86.2 (1) |
S1—Bi1—S4 | 88.1 (1) | S4—Bi1—S6 | 93.9 (1) |
S1—Bi1—S5 | 135.6 (1) | S5—Bi1—S6 | 63.1 (1) |
S1—Bi1—S6 | 73.4 (1) | S4—Bi1—S5i | 141.0 (1) |
S2—Bi1—S3 | 81.1 (1) | S6—Bi1—S5i | 114.2 (1) |
S2—Bi1—S4 | 85.4 (1) | S3—Bi1—S5i | 74.9 (1) |
S2—Bi1—S5 | 159.5 (1) | S1—Bi1—S5i | 124.5 (1) |
S2—Bi1—S6 | 136.1 (1) | S2—Bi1—S5i | 91.4 (1) |
S3—Bi1—S4 | 66.2 (1) | S5—Bi1—S5i | 83.5 (1) |
S3—Bi1—S5 | 78.4 (1) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
The tris(dithiocarbamato)bismuth(III) and tris(dithiocarbamato)antimony(III) complexes generally have the chelated metal atom with a capped octahedral geometry as the lone pair of electrons is stereochemically active (Raston & White, 1976; Venkatachalam et al., 1997). Our recent study of the tris(2-hydroxyethylisopropyl)bismuth complex has documented this geometry for the metal atom (Low et al., 2001).
The nature of the substituents in the dithiocarbamate group appears to affect the stereochemical activity; the Bi atom in the title compound, (I) (Fig. 1), is seven-coordinated and has a distorted pentagonal–bipyramidal environment with one short axial distance [Bi1—S4 2.608 (2) Å], one long axial interaction [Bi1···S5i 3.334 (2) Å; symmetry code: (i) 1 − x, 1 − y, 1 − z], and five `regular' equatorial bonds [2.819 (2)–2.867 (2) Å]; the angle formed by two axial bonds, S4—Bi1···S5i, is 141.0 (1) Å. The long axial Bi1···S5i interaction links two adjacent tris(N-butyl-N-ethyldithiocarbamato)bismuth fragments into a centrosymmetric dinuclear entity (Fig. 2).