metal-organic compounds
Iodidobis(morpholine-4-carbodithioato-κ2S,S′)(1,10-phenanthroline-κ2N,N′)bismuth(III)
aDepartment of Chemistry and Chemical Engineering, Lvliang University, Lishi Shanxi 033000, People's Republic of China, and bCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
*Correspondence e-mail: lifeng1982@163.com
The title compound, [Bi(C4H8NOS2)2I(C12H8N2)], is monomeric, with the BiIII atom chelated by the two S atoms of two morpholine-4-carbodithioate ligands and the two N atoms of a 1,10-phenanthroline ligand. An iodide ligand completes the coordination sphere, with the seven-coordinate BiIII atom adopting a highly distorted monocapped octahedral geometry.
CCDC reference: 283571
Related literature
For dithiocarbamates as ligands to transition metals, see: Xu et al. (2001); Bardaji et al. (1994). For bismuth(III)–dithiocarbamate complexes, see: Yin et al. (2003). For related Bi/N structures, see: Baraanyi et al. (1977).
Experimental
Crystal data
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Data collection: SMART (Siemens, 1996); cell SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
CCDC reference: 283571
https://doi.org/10.1107/S1600536813033515/sj5375sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813033515/sj5375Isup2.hkl
To a stirred solution of BiI3 (0.15 mmol) in acetonitrile (ca 20 ml), phenanthroline (0.15 mmol) and sodium morpholine-4-carbodithioate (0.30 mmol) were added. A yellow coloured solution was obtained and, after concentration and cooling, small yellow crystals of the title compound were obtained. These were collected and dried in a vacuum [yield 82%, m.p. 452 K]. Analysis calculated for C24H28BiIN4S4: C 34.45, H 3.37, N 6.70%; found: C 32.78, H 3.24, N 6.77%.
All H atoms were positioned geometrically and treated as riding on their parent atoms [C—H = 0.93 Å and Uiso=1.2Ueq (C) for aromatic, C—H =0.97 Å and Uiso = 1.2Ueq (C) for CH2 H atoms].
Dithiocarbamates have been known as effective ligands for transition metal ions for many years. They can form chelates (Xu et al., 2001) or act as bridging ligands (Bardaji et al., 1994). However, the chemistry of main-group metal complexes with dithiocarbamates has been less extensively studied, and only a few reports describing bismuth(III) dithiocarbamate complexes have appeared (Yin et al., 2003). As a continuation of our interest in sulfur-containing ligands, we report here the synthesis and structure of the title compound, (I).
The title compound, (I), is monomeric, with the Bi atom chelated by the S atoms of two morpholine-4-carbodithioate ligands and the two N atoms of 1,10-phenanthroline. An iodido ligand completes the coordination environment of the seven coordinate Bi atom (Fig. 1). The Bi atom is in a capped octahedral environment, with atoms S3 and N3 in axial positions, and atoms S1, S2, S4 and I1 in the equatorial plane. The remaining N atom (N4) of the 1,10-phenanthroline ligand caps the S2/S4/N3 face of this octahedron, giving a highly distorted capped octahedral coordination geometry. One of the bidentate pyrrolidinyldithiocarbamate ligands forms a significantly longer Bi—S bond [Bi1—S4 = 2.962 (2) Å] than the others in the complex. This variation in coordination strength is also signalled by the fact that the C7—S4 bond is significantly shorter than the other C—S bonds, suggesting some delocalization in the system. In addition, the chelating phenanthroline ligand is bound to the Bi atom through both of its N atoms. The Bi1—N3 and Bi1—N4 distances fall in the same range as in other Bi/N complexes (Baraanyi et al., 1977).
For dithiocarbamamates as ligands to transition metals, see: Xu et al. (2001); Bardaji et al. (1994). For bismuth(III)–dithiocarbamate complexes, see: Yin et al. (2003). For related Bi/N structures, see: Baraanyi et al. (1977).
Data collection: SMART (Siemens, 1996); cell
SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity. |
[Bi(C4H8NOS2)2I(C12H8N2)] | F(000) = 1600 |
Mr = 836.62 | Dx = 1.946 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4986 reflections |
a = 14.782 (4) Å | θ = 2.2–25.8° |
b = 10.883 (3) Å | µ = 7.57 mm−1 |
c = 18.030 (4) Å | T = 298 K |
β = 100.035 (4)° | Block, orange-red |
V = 2856.2 (12) Å3 | 0.52 × 0.42 × 0.13 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 5013 independent reflections |
Radiation source: fine-focus sealed tube | 3883 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
φ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→17 |
Tmin = 0.111, Tmax = 0.440 | k = −12→12 |
14581 measured reflections | l = −19→21 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0573P)2 + 0.7329P] where P = (Fo2 + 2Fc2)/3 |
5013 reflections | (Δ/σ)max = 0.001 |
307 parameters | Δρmax = 2.14 e Å−3 |
162 restraints | Δρmin = −1.18 e Å−3 |
[Bi(C4H8NOS2)2I(C12H8N2)] | V = 2856.2 (12) Å3 |
Mr = 836.62 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.782 (4) Å | µ = 7.57 mm−1 |
b = 10.883 (3) Å | T = 298 K |
c = 18.030 (4) Å | 0.52 × 0.42 × 0.13 mm |
β = 100.035 (4)° |
Siemens SMART CCD area-detector diffractometer | 5013 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3883 reflections with I > 2σ(I) |
Tmin = 0.111, Tmax = 0.440 | Rint = 0.051 |
14581 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 162 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.00 | Δρmax = 2.14 e Å−3 |
5013 reflections | Δρmin = −1.18 e Å−3 |
307 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Bi1 | 0.239399 (17) | 0.06921 (2) | 0.229937 (14) | 0.04234 (11) | |
I1 | 0.14675 (4) | 0.32613 (5) | 0.21768 (3) | 0.06751 (18) | |
N1 | 0.5244 (5) | 0.0651 (5) | 0.1730 (4) | 0.0645 (17) | |
N2 | 0.2870 (4) | 0.0260 (6) | 0.4879 (3) | 0.0530 (15) | |
N3 | 0.1809 (4) | 0.0545 (5) | 0.0775 (3) | 0.0480 (14) | |
N4 | 0.1352 (4) | −0.1340 (5) | 0.1647 (3) | 0.0527 (15) | |
S1 | 0.38192 (12) | 0.19983 (16) | 0.19532 (10) | 0.0474 (4) | |
S2 | 0.38367 (15) | −0.07187 (17) | 0.19689 (14) | 0.0632 (6) | |
S3 | 0.33747 (13) | 0.1194 (2) | 0.36628 (11) | 0.0568 (5) | |
S4 | 0.17373 (15) | −0.0365 (2) | 0.36236 (12) | 0.0680 (6) | |
C1 | 0.4392 (5) | 0.0635 (6) | 0.1872 (4) | 0.0510 (17) | |
C2 | 0.5748 (6) | 0.1789 (8) | 0.1643 (6) | 0.075 (2) | |
H2A | 0.5378 | 0.2489 | 0.1736 | 0.090* | |
H2B | 0.6310 | 0.1805 | 0.2011 | 0.090* | |
C3 | 0.5971 (7) | 0.1885 (8) | 0.0886 (6) | 0.088 (2) | |
H3A | 0.6322 | 0.2628 | 0.0846 | 0.106* | |
H3B | 0.5409 | 0.1929 | 0.0517 | 0.106* | |
C4 | 0.6531 (9) | 0.0761 (9) | 0.0728 (8) | 0.105 (3) | |
H4A | 0.7120 | 0.0763 | 0.1065 | 0.126* | |
H4B | 0.6644 | 0.0792 | 0.0215 | 0.126* | |
C5 | 0.5999 (8) | −0.0423 (9) | 0.0847 (6) | 0.091 (3) | |
H5A | 0.5443 | −0.0463 | 0.0471 | 0.110* | |
H5B | 0.6373 | −0.1132 | 0.0780 | 0.110* | |
C6 | 0.5759 (7) | −0.0457 (8) | 0.1590 (6) | 0.078 (2) | |
H6A | 0.6314 | −0.0515 | 0.1965 | 0.093* | |
H6B | 0.5389 | −0.1180 | 0.1636 | 0.093* | |
C7 | 0.2667 (5) | 0.0334 (6) | 0.4124 (4) | 0.0460 (16) | |
C8 | 0.3662 (6) | 0.0842 (7) | 0.5339 (4) | 0.060 (2) | |
H8A | 0.3453 | 0.1427 | 0.5678 | 0.072* | |
H8B | 0.4007 | 0.1289 | 0.5015 | 0.072* | |
C9 | 0.4270 (6) | −0.0084 (8) | 0.5785 (5) | 0.066 (2) | |
H9A | 0.4773 | 0.0334 | 0.6103 | 0.079* | |
H9B | 0.4529 | −0.0617 | 0.5445 | 0.079* | |
C10 | 0.3754 (7) | −0.0844 (8) | 0.6265 (5) | 0.078 (3) | |
H10A | 0.3571 | −0.0330 | 0.6653 | 0.093* | |
H10B | 0.4152 | −0.1487 | 0.6511 | 0.093* | |
C11 | 0.2915 (7) | −0.1413 (8) | 0.5798 (5) | 0.076 (3) | |
H11A | 0.2559 | −0.1826 | 0.6128 | 0.091* | |
H11B | 0.3104 | −0.2024 | 0.5465 | 0.091* | |
C12 | 0.2312 (6) | −0.0449 (9) | 0.5330 (4) | 0.071 (3) | |
H12A | 0.1811 | −0.0852 | 0.4999 | 0.085* | |
H12B | 0.2050 | 0.0099 | 0.5660 | 0.085* | |
C13 | 0.1992 (5) | 0.1464 (8) | 0.0334 (5) | 0.060 (2) | |
H13 | 0.2324 | 0.2130 | 0.0561 | 0.072* | |
C14 | 0.1719 (6) | 0.1489 (9) | −0.0440 (5) | 0.066 (2) | |
H14 | 0.1868 | 0.2154 | −0.0719 | 0.079* | |
C15 | 0.1235 (5) | 0.0534 (8) | −0.0783 (4) | 0.059 (2) | |
H15 | 0.1050 | 0.0537 | −0.1303 | 0.070* | |
C16 | 0.1010 (5) | −0.0468 (7) | −0.0353 (4) | 0.0534 (19) | |
C17 | 0.1315 (4) | −0.0417 (6) | 0.0438 (4) | 0.0435 (16) | |
C18 | 0.1079 (4) | −0.1412 (6) | 0.0895 (4) | 0.0448 (16) | |
C19 | 0.0559 (5) | −0.2401 (7) | 0.0535 (5) | 0.056 (2) | |
C20 | 0.0328 (6) | −0.3350 (7) | 0.1006 (6) | 0.069 (2) | |
H20 | −0.0014 | −0.4021 | 0.0796 | 0.083* | |
C21 | 0.0604 (6) | −0.3282 (7) | 0.1759 (6) | 0.074 (3) | |
H21 | 0.0450 | −0.3900 | 0.2071 | 0.088* | |
C22 | 0.1124 (6) | −0.2273 (8) | 0.2064 (5) | 0.072 (2) | |
H22 | 0.1323 | −0.2248 | 0.2582 | 0.087* | |
C23 | 0.0497 (5) | −0.1488 (9) | −0.0675 (5) | 0.066 (2) | |
H23 | 0.0304 | −0.1511 | −0.1194 | 0.080* | |
C24 | 0.0282 (6) | −0.2412 (8) | −0.0262 (5) | 0.069 (2) | |
H24 | −0.0052 | −0.3074 | −0.0494 | 0.083* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi1 | 0.04840 (17) | 0.03802 (17) | 0.03946 (17) | −0.00219 (11) | 0.00451 (12) | 0.00165 (11) |
I1 | 0.0847 (4) | 0.0605 (4) | 0.0538 (3) | 0.0195 (3) | 0.0024 (3) | −0.0045 (2) |
N1 | 0.068 (4) | 0.046 (3) | 0.086 (4) | 0.001 (3) | 0.031 (3) | 0.001 (3) |
N2 | 0.065 (4) | 0.056 (4) | 0.036 (3) | −0.010 (3) | 0.002 (3) | −0.003 (3) |
N3 | 0.051 (3) | 0.048 (4) | 0.045 (3) | −0.006 (3) | 0.006 (3) | 0.001 (3) |
N4 | 0.066 (4) | 0.045 (4) | 0.050 (4) | −0.011 (3) | 0.016 (3) | 0.001 (3) |
S1 | 0.0550 (10) | 0.0340 (9) | 0.0541 (11) | −0.0003 (8) | 0.0121 (8) | 0.0044 (8) |
S2 | 0.0688 (13) | 0.0349 (10) | 0.0890 (16) | 0.0004 (9) | 0.0228 (12) | 0.0065 (9) |
S3 | 0.0581 (11) | 0.0625 (12) | 0.0457 (11) | −0.0173 (10) | −0.0026 (9) | 0.0103 (9) |
S4 | 0.0658 (13) | 0.0913 (16) | 0.0444 (11) | −0.0299 (12) | 0.0026 (10) | 0.0025 (11) |
C1 | 0.061 (4) | 0.039 (4) | 0.055 (4) | 0.003 (3) | 0.013 (3) | 0.007 (3) |
C2 | 0.080 (5) | 0.057 (4) | 0.094 (5) | −0.004 (4) | 0.034 (4) | 0.000 (4) |
C3 | 0.108 (6) | 0.065 (5) | 0.100 (6) | 0.010 (5) | 0.040 (5) | 0.014 (4) |
C4 | 0.122 (7) | 0.084 (6) | 0.124 (7) | 0.021 (5) | 0.063 (6) | 0.012 (5) |
C5 | 0.112 (6) | 0.065 (5) | 0.103 (6) | 0.023 (5) | 0.033 (5) | 0.004 (5) |
C6 | 0.084 (5) | 0.059 (4) | 0.098 (5) | 0.014 (4) | 0.038 (4) | 0.008 (4) |
C7 | 0.043 (4) | 0.044 (4) | 0.051 (4) | 0.003 (3) | 0.008 (3) | 0.007 (3) |
C8 | 0.074 (5) | 0.059 (5) | 0.040 (4) | −0.004 (4) | −0.010 (4) | −0.001 (4) |
C9 | 0.061 (5) | 0.070 (6) | 0.060 (5) | 0.001 (4) | −0.007 (4) | 0.010 (4) |
C10 | 0.087 (7) | 0.083 (7) | 0.061 (6) | 0.003 (5) | 0.005 (5) | 0.025 (5) |
C11 | 0.099 (7) | 0.072 (6) | 0.060 (6) | −0.020 (5) | 0.021 (5) | 0.012 (5) |
C12 | 0.069 (5) | 0.106 (7) | 0.039 (4) | −0.018 (5) | 0.012 (4) | 0.009 (4) |
C13 | 0.057 (5) | 0.060 (5) | 0.061 (5) | −0.008 (4) | 0.003 (4) | 0.017 (4) |
C14 | 0.063 (5) | 0.081 (6) | 0.055 (5) | 0.007 (4) | 0.014 (4) | 0.021 (5) |
C15 | 0.056 (5) | 0.082 (6) | 0.036 (4) | 0.014 (4) | 0.005 (4) | 0.006 (4) |
C16 | 0.041 (4) | 0.074 (5) | 0.046 (4) | 0.012 (4) | 0.008 (3) | −0.003 (4) |
C17 | 0.037 (3) | 0.050 (4) | 0.045 (4) | 0.007 (3) | 0.012 (3) | −0.001 (3) |
C18 | 0.038 (4) | 0.042 (4) | 0.055 (5) | 0.003 (3) | 0.010 (3) | −0.004 (3) |
C19 | 0.045 (4) | 0.049 (5) | 0.076 (6) | 0.001 (3) | 0.012 (4) | −0.018 (4) |
C20 | 0.070 (5) | 0.043 (5) | 0.094 (7) | −0.016 (4) | 0.015 (5) | −0.024 (5) |
C21 | 0.090 (6) | 0.039 (5) | 0.097 (8) | −0.014 (4) | 0.029 (6) | −0.007 (5) |
C22 | 0.098 (7) | 0.059 (5) | 0.063 (6) | −0.010 (5) | 0.024 (5) | −0.007 (4) |
C23 | 0.057 (5) | 0.075 (6) | 0.063 (5) | 0.003 (4) | −0.001 (4) | −0.023 (5) |
C24 | 0.057 (5) | 0.062 (6) | 0.083 (7) | −0.003 (4) | −0.004 (4) | −0.028 (5) |
Bi1—S3 | 2.683 (2) | C8—C9 | 1.489 (11) |
Bi1—S1 | 2.7032 (18) | C8—H8A | 0.9700 |
Bi1—N3 | 2.738 (6) | C8—H8B | 0.9700 |
Bi1—S2 | 2.775 (2) | C9—C10 | 1.499 (11) |
Bi1—N4 | 2.831 (6) | C9—H9A | 0.9700 |
Bi1—S4 | 2.962 (2) | C9—H9B | 0.9700 |
Bi1—I1 | 3.1043 (9) | C10—C11 | 1.506 (13) |
N1—C1 | 1.328 (9) | C10—H10A | 0.9700 |
N1—C2 | 1.468 (10) | C10—H10B | 0.9700 |
N1—C6 | 1.472 (10) | C11—C12 | 1.532 (12) |
N2—C7 | 1.344 (9) | C11—H11A | 0.9700 |
N2—C8 | 1.456 (10) | C11—H11B | 0.9700 |
N2—C12 | 1.472 (9) | C12—H12A | 0.9700 |
N3—C13 | 1.335 (9) | C12—H12B | 0.9700 |
N3—C17 | 1.358 (9) | C13—C14 | 1.383 (11) |
N4—C22 | 1.341 (10) | C13—H13 | 0.9300 |
N4—C18 | 1.347 (9) | C14—C15 | 1.349 (11) |
S1—C1 | 1.727 (7) | C14—H14 | 0.9300 |
S2—C1 | 1.710 (7) | C15—C16 | 1.411 (11) |
S3—C7 | 1.722 (7) | C15—H15 | 0.9300 |
S4—C7 | 1.689 (7) | C16—C23 | 1.411 (11) |
C2—C3 | 1.463 (13) | C16—C17 | 1.420 (10) |
C2—H2A | 0.9700 | C17—C18 | 1.440 (9) |
C2—H2B | 0.9700 | C18—C19 | 1.413 (10) |
C3—C4 | 1.531 (12) | C19—C20 | 1.416 (11) |
C3—H3A | 0.9700 | C19—C24 | 1.424 (11) |
C3—H3B | 0.9700 | C20—C21 | 1.350 (13) |
C4—C5 | 1.544 (13) | C20—H20 | 0.9300 |
C4—H4A | 0.9700 | C21—C22 | 1.397 (11) |
C4—H4B | 0.9700 | C21—H21 | 0.9300 |
C5—C6 | 1.445 (13) | C22—H22 | 0.9300 |
C5—H5A | 0.9700 | C23—C24 | 1.323 (12) |
C5—H5B | 0.9700 | C23—H23 | 0.9300 |
C6—H6A | 0.9700 | C24—H24 | 0.9300 |
C6—H6B | 0.9700 | ||
S3—Bi1—S1 | 77.65 (6) | N2—C7—S4 | 122.1 (5) |
S3—Bi1—N3 | 163.15 (13) | N2—C7—S3 | 118.4 (5) |
S1—Bi1—N3 | 85.50 (13) | S4—C7—S3 | 119.5 (4) |
S3—Bi1—S2 | 89.80 (7) | N2—C8—C9 | 111.3 (7) |
S1—Bi1—S2 | 65.31 (6) | N2—C8—H8A | 109.4 |
N3—Bi1—S2 | 82.66 (13) | C9—C8—H8A | 109.4 |
S3—Bi1—N4 | 135.03 (13) | N2—C8—H8B | 109.4 |
S1—Bi1—N4 | 134.78 (12) | C9—C8—H8B | 109.4 |
N3—Bi1—N4 | 58.91 (17) | H8A—C8—H8B | 108.0 |
S2—Bi1—N4 | 82.04 (13) | C8—C9—C10 | 111.4 (7) |
S3—Bi1—S4 | 62.69 (6) | C8—C9—H9A | 109.3 |
S1—Bi1—S4 | 140.22 (6) | C10—C9—H9A | 109.3 |
N3—Bi1—S4 | 134.08 (12) | C8—C9—H9B | 109.3 |
S2—Bi1—S4 | 109.28 (7) | C10—C9—H9B | 109.3 |
N4—Bi1—S4 | 78.49 (12) | H9A—C9—H9B | 108.0 |
S3—Bi1—I1 | 92.47 (5) | C9—C10—C11 | 110.9 (7) |
S1—Bi1—I1 | 82.06 (4) | C9—C10—H10A | 109.5 |
N3—Bi1—I1 | 85.58 (12) | C11—C10—H10A | 109.5 |
S2—Bi1—I1 | 145.99 (4) | C9—C10—H10B | 109.5 |
N4—Bi1—I1 | 118.20 (13) | C11—C10—H10B | 109.5 |
S4—Bi1—I1 | 101.82 (5) | H10A—C10—H10B | 108.1 |
C1—N1—C2 | 123.2 (6) | C10—C11—C12 | 111.7 (7) |
C1—N1—C6 | 124.0 (6) | C10—C11—H11A | 109.3 |
C2—N1—C6 | 112.7 (7) | C12—C11—H11A | 109.3 |
C7—N2—C8 | 124.4 (6) | C10—C11—H11B | 109.3 |
C7—N2—C12 | 122.9 (6) | C12—C11—H11B | 109.3 |
C8—N2—C12 | 112.7 (6) | H11A—C11—H11B | 107.9 |
C13—N3—C17 | 117.4 (6) | N2—C12—C11 | 109.6 (7) |
C13—N3—Bi1 | 119.6 (5) | N2—C12—H12A | 109.8 |
C17—N3—Bi1 | 123.1 (4) | C11—C12—H12A | 109.8 |
C22—N4—C18 | 117.3 (7) | N2—C12—H12B | 109.8 |
C22—N4—Bi1 | 122.0 (5) | C11—C12—H12B | 109.8 |
C18—N4—Bi1 | 120.6 (4) | H12A—C12—H12B | 108.2 |
C1—S1—Bi1 | 88.9 (2) | N3—C13—C14 | 124.3 (8) |
C1—S2—Bi1 | 86.9 (3) | N3—C13—H13 | 117.9 |
C7—S3—Bi1 | 93.2 (3) | C14—C13—H13 | 117.9 |
C7—S4—Bi1 | 84.6 (2) | C15—C14—C13 | 119.0 (8) |
N1—C1—S2 | 121.3 (5) | C15—C14—H14 | 120.5 |
N1—C1—S1 | 120.0 (5) | C13—C14—H14 | 120.5 |
S2—C1—S1 | 118.7 (4) | C14—C15—C16 | 120.1 (7) |
C3—C2—N1 | 111.2 (8) | C14—C15—H15 | 120.0 |
C3—C2—H2A | 109.4 | C16—C15—H15 | 120.0 |
N1—C2—H2A | 109.4 | C23—C16—C15 | 122.9 (8) |
C3—C2—H2B | 109.4 | C23—C16—C17 | 119.9 (8) |
N1—C2—H2B | 109.4 | C15—C16—C17 | 117.2 (7) |
H2A—C2—H2B | 108.0 | N3—C17—C16 | 122.1 (7) |
C2—C3—C4 | 109.5 (8) | N3—C17—C18 | 119.2 (6) |
C2—C3—H3A | 109.8 | C16—C17—C18 | 118.7 (7) |
C4—C3—H3A | 109.8 | N4—C18—C19 | 123.4 (7) |
C2—C3—H3B | 109.8 | N4—C18—C17 | 118.2 (6) |
C4—C3—H3B | 109.8 | C19—C18—C17 | 118.4 (7) |
H3A—C3—H3B | 108.2 | C18—C19—C20 | 116.6 (8) |
C3—C4—C5 | 109.6 (8) | C18—C19—C24 | 120.6 (8) |
C3—C4—H4A | 109.7 | C20—C19—C24 | 122.8 (8) |
C5—C4—H4A | 109.7 | C21—C20—C19 | 120.1 (7) |
C3—C4—H4B | 109.7 | C21—C20—H20 | 120.0 |
C5—C4—H4B | 109.7 | C19—C20—H20 | 120.0 |
H4A—C4—H4B | 108.2 | C20—C21—C22 | 119.2 (8) |
C6—C5—C4 | 111.3 (9) | C20—C21—H21 | 120.4 |
C6—C5—H5A | 109.4 | C22—C21—H21 | 120.4 |
C4—C5—H5A | 109.4 | N4—C22—C21 | 123.3 (9) |
C6—C5—H5B | 109.4 | N4—C22—H22 | 118.3 |
C4—C5—H5B | 109.4 | C21—C22—H22 | 118.3 |
H5A—C5—H5B | 108.0 | C24—C23—C16 | 122.1 (8) |
C5—C6—N1 | 110.8 (8) | C24—C23—H23 | 119.0 |
C5—C6—H6A | 109.5 | C16—C23—H23 | 119.0 |
N1—C6—H6A | 109.5 | C23—C24—C19 | 120.4 (8) |
C5—C6—H6B | 109.5 | C23—C24—H24 | 119.8 |
N1—C6—H6B | 109.5 | C19—C24—H24 | 119.8 |
H6A—C6—H6B | 108.1 |
Bi1—S3 | 2.683 (2) | Bi1—N4 | 2.831 (6) |
Bi1—S1 | 2.7032 (18) | Bi1—S4 | 2.962 (2) |
Bi1—N3 | 2.738 (6) | Bi1—I1 | 3.1043 (9) |
Bi1—S2 | 2.775 (2) |
Acknowledgements
We acknowledge financial support from the Luliang University Campus Youth Foundation.
References
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Dithiocarbamates have been known as effective ligands for transition metal ions for many years. They can form chelates (Xu et al., 2001) or act as bridging ligands (Bardaji et al., 1994). However, the chemistry of main-group metal complexes with dithiocarbamates has been less extensively studied, and only a few reports describing bismuth(III) dithiocarbamate complexes have appeared (Yin et al., 2003). As a continuation of our interest in sulfur-containing ligands, we report here the synthesis and structure of the title compound, (I).
The title compound, (I), is monomeric, with the Bi atom chelated by the S atoms of two morpholine-4-carbodithioate ligands and the two N atoms of 1,10-phenanthroline. An iodido ligand completes the coordination environment of the seven coordinate Bi atom (Fig. 1). The Bi atom is in a capped octahedral environment, with atoms S3 and N3 in axial positions, and atoms S1, S2, S4 and I1 in the equatorial plane. The remaining N atom (N4) of the 1,10-phenanthroline ligand caps the S2/S4/N3 face of this octahedron, giving a highly distorted capped octahedral coordination geometry. One of the bidentate pyrrolidinyldithiocarbamate ligands forms a significantly longer Bi—S bond [Bi1—S4 = 2.962 (2) Å] than the others in the complex. This variation in coordination strength is also signalled by the fact that the C7—S4 bond is significantly shorter than the other C—S bonds, suggesting some delocalization in the system. In addition, the chelating phenanthroline ligand is bound to the Bi atom through both of its N atoms. The Bi1—N3 and Bi1—N4 distances fall in the same range as in other Bi/N complexes (Baraanyi et al., 1977).