catena-Poly[[(N,N-diethyl­dithio­carbamato-κ2S:S′)phenyl­bismuth(III)]-μ-chlorido]

Cui, L.; Yin, H.; Yang, M.; Quan, L.; Wang, D.

doi:10.1107/S1600536808032820

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1452

doi:10.1107/S1600536808032820

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catena-Poly[[(N,N-diethyldithiocarbamato-κ²S:S′)phenylbismuth(III)]-μ-chlorido]

Liansheng Cui,^a Handong Yin,^a ^* Minglei Yang,^a Li Quan ^a and Daqi Wang ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: handongyin@sohu.com

(Received 16 September 2008; accepted 10 October 2008; online 22 October 2008)

In the title compound, [Bi(C₆H₅)(C₅H₁₀NS₂)Cl]_n, the Bi atom is coordinated by two S atoms of the dithiocarbamate ligand, one C atom of the phenyl group and one Cl atom in a four-coordinated tetrahedral configuration. Molecules are linked by Cl atoms to form a zigzag chain extending in the c direction.

Related literature

For related literature see: Yin et al. (2003 ); Bardaji et al. (1994 ); Xu et al. (2001 ).

Experimental

Crystal data

[Bi(C₆H₅)(C₅H₁₀NS₂)Cl]
M_r = 469.79
Monoclinic, P 2₁ /c
a = 9.2029 (9) Å
b = 18.1432 (17) Å
c = 9.0779 (8) Å
β = 106.811 (2)°
V = 1451.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 12.60 mm⁻¹
T = 298 (2) K
0.23 × 0.22 × 0.21 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.160, T_max = 0.177 (expected range = 0.064–0.071)
6443 measured reflections
2444 independent reflections
1877 reflections with I > 2σ(I)
R_int = 0.095

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.149
S = 0.92
2444 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 2.04 e Å⁻³
Δρ_min = −2.84 e Å⁻³

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808032820/su2063sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032820/su2063Isup2.hkl

checkCIF report

Comment top

Dithiocarbamates have been known as effective ligands 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 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.

The molecular structure of the title compound is illustrated in Fig. 1. The geometry of the Bi atom is four-coordinated tetrahedral. Two Bi—S bonds distance are not similar, the Bi1—S1 bond length is 2.647 (3) Å and the Bi1—S2 bond length is 2.690 (4) Å. The molecules are linked by the chlorine atom Cl1 [Bi1-Cl1 = 2.908 (3) Å and Bi1···Cl1ⁱ = 2.920 (3); (i) = x, -y+0.5, z+0.5] to form a one-dimensional zig-zag polymer chain extending in the c direction (Fig. 2).

Related literature top

For related literature see: Yin et al. (2003); Bardaji et al. (1994); Xu et al. (2001).

Experimental top

A mixture of (N,N-diethylcarbamato-1k² S:S)sodium (0.2 mmol) and phenylbismuth dichloride (0.1 mmol) in absolute THF was heated under reflux with stirring for 24 h. Diethyl ether and hexane were added to this solution to precipitate the product, which was then recrystallized from a dichloromethane-hexane mixture (1:1 v/v). After 14 days large colorless block-shaped crystals of the title complex, suitable for X-ray diffraction analysis, were obtained.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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).

Figures top

	Fig. 1. The moleculare structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound, viewed approximately along the a axis.

catena-Poly[[(N,N-diethyldithiocarbamato- κ²S:S')phenylbismuth(III)]-µ-chlorido] top

Crystal data top

[Bi(C₆H₅)(C₅H₁₀NS₂)Cl]	F(000) = 880
M_r = 469.79	D_x = 2.151 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.2029 (9) Å	Cell parameters from 3883 reflections
b = 18.1432 (17) Å	θ = 2.3–28.2°
c = 9.0779 (8) Å	µ = 12.60 mm⁻¹
β = 106.811 (2)°	T = 298 K
V = 1451.0 (2) Å³	Block, colorless
Z = 4	0.23 × 0.22 × 0.21 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2444 independent reflections
Radiation source: fine-focus sealed tube	1877 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.095
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→10
T_min = 0.160, T_max = 0.177	k = −21→19
6443 measured reflections	l = −10→10

Refinement top

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 0.92	w = 1/[σ²(F_o²) + (0.0942P)²] where P = (F_o² + 2F_c²)/3
2444 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 2.04 e Å⁻³
0 restraints	Δρ_min = −2.84 e Å⁻³

Crystal data top

[Bi(C₆H₅)(C₅H₁₀NS₂)Cl]	V = 1451.0 (2) Å³
M_r = 469.79	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.2029 (9) Å	µ = 12.60 mm⁻¹
b = 18.1432 (17) Å	T = 298 K
c = 9.0779 (8) Å	0.23 × 0.22 × 0.21 mm
β = 106.811 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2444 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1877 reflections with I > 2σ(I)
T_min = 0.160, T_max = 0.177	R_int = 0.095
6443 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 0.92	Δρ_max = 2.04 e Å⁻³
2444 reflections	Δρ_min = −2.84 e Å⁻³
147 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Bi1	0.83539 (5)	0.19587 (2)	0.77837 (4)	0.0353 (2)
Cl1	0.8497 (4)	0.32758 (19)	0.6005 (3)	0.0448 (8)
N1	0.7954 (11)	−0.0056 (5)	0.4907 (10)	0.036 (2)
S1	0.8233 (4)	0.14036 (18)	0.5054 (3)	0.0435 (8)
S2	0.8036 (4)	0.0484 (2)	0.7681 (3)	0.0462 (8)
C1	0.8051 (13)	0.0546 (7)	0.5771 (12)	0.040 (3)
C2	0.7991 (16)	0.0000 (7)	0.3290 (12)	0.051 (3)
H2A	0.8309	−0.0470	0.2976	0.061*
H2B	0.8737	0.0366	0.3225	0.061*
C3	0.6464 (14)	0.0208 (8)	0.2196 (11)	0.053 (4)
H3A	0.5721	−0.0154	0.2255	0.079*
H3B	0.6540	0.0227	0.1164	0.079*
H3C	0.6163	0.0682	0.2477	0.079*
C4	0.7770 (14)	−0.0790 (7)	0.5486 (14)	0.045 (3)
H4A	0.8283	−0.0807	0.6581	0.054*
H4B	0.8252	−0.1148	0.4985	0.054*
C5	0.6136 (17)	−0.0998 (9)	0.5216 (18)	0.069 (4)
H5A	0.5645	−0.0637	0.5679	0.103*
H5B	0.6078	−0.1472	0.5667	0.103*
H5C	0.5641	−0.1020	0.4130	0.103*
C6	1.0885 (14)	0.1853 (6)	0.8490 (12)	0.035 (3)
C7	1.1620 (16)	0.1381 (8)	0.9745 (13)	0.052 (4)
H7	1.1050	0.1124	1.0271	0.063*
C8	1.3156 (18)	0.1310 (9)	1.0167 (15)	0.063 (4)
H8	1.3624	0.1002	1.0985	0.076*
C9	1.4023 (18)	0.1673 (9)	0.9431 (17)	0.064 (4)
H9	1.5074	0.1626	0.9761	0.077*
C10	1.3332 (13)	0.2117 (8)	0.8179 (18)	0.055 (4)
H10	1.3919	0.2351	0.7639	0.066*
C11	1.1787 (15)	0.2213 (7)	0.7736 (15)	0.048 (3)
H11	1.1339	0.2524	0.6915	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Bi1	0.0391 (4)	0.0378 (4)	0.0300 (3)	0.00102 (19)	0.0113 (2)	−0.00018 (16)
Cl1	0.059 (2)	0.0432 (18)	0.0374 (14)	0.0086 (16)	0.0221 (14)	0.0032 (13)
N1	0.035 (6)	0.034 (6)	0.039 (5)	0.008 (5)	0.009 (4)	0.003 (4)
S1	0.064 (2)	0.0374 (18)	0.0303 (13)	−0.0063 (16)	0.0152 (13)	0.0013 (12)
S2	0.061 (2)	0.043 (2)	0.0348 (14)	−0.0054 (17)	0.0142 (14)	0.0066 (13)
C1	0.040 (7)	0.043 (8)	0.037 (6)	0.002 (6)	0.010 (5)	0.005 (5)
C2	0.073 (10)	0.043 (8)	0.039 (6)	0.014 (7)	0.022 (6)	−0.003 (5)
C3	0.060 (10)	0.048 (9)	0.046 (7)	0.008 (7)	0.008 (6)	0.003 (5)
C4	0.039 (8)	0.030 (7)	0.063 (7)	−0.001 (6)	0.012 (6)	0.002 (6)
C5	0.073 (11)	0.052 (10)	0.093 (10)	−0.010 (9)	0.042 (9)	0.009 (8)
C6	0.041 (8)	0.032 (7)	0.037 (6)	0.009 (5)	0.019 (5)	−0.002 (5)
C7	0.058 (9)	0.057 (10)	0.043 (6)	0.021 (7)	0.016 (6)	0.005 (6)
C8	0.069 (11)	0.068 (11)	0.051 (7)	0.031 (9)	0.016 (7)	0.004 (7)
C9	0.046 (9)	0.067 (11)	0.071 (9)	0.006 (8)	0.000 (8)	−0.028 (9)
C10	0.012 (7)	0.059 (10)	0.094 (10)	−0.009 (6)	0.016 (7)	−0.006 (8)
C11	0.055 (9)	0.039 (8)	0.055 (7)	−0.012 (7)	0.023 (6)	0.000 (6)

Geometric parameters (Å, º) top

Bi1—C6	2.238 (13)	C4—C5	1.500 (17)
Bi1—S1	2.647 (3)	C4—H4A	0.9700
Bi1—S2	2.690 (4)	C4—H4B	0.9700
Bi1—Cl1	2.908 (3)	C5—H5A	0.9600
Bi1—Cl1ⁱ	2.920 (3)	C5—H5B	0.9600
Cl1—Bi1ⁱⁱ	2.920 (3)	C5—H5C	0.9600
N1—C1	1.332 (15)	C6—C11	1.383 (16)
N1—C4	1.459 (14)	C6—C7	1.429 (16)
N1—C2	1.481 (13)	C7—C8	1.360 (19)
S1—C1	1.714 (13)	C7—H7	0.9300
S2—C1	1.742 (10)	C8—C9	1.35 (2)
C2—C3	1.516 (15)	C8—H8	0.9300
C2—H2A	0.9700	C9—C10	1.39 (2)
C2—H2B	0.9700	C9—H9	0.9300
C3—H3A	0.9600	C10—C11	1.373 (16)
C3—H3B	0.9600	C10—H10	0.9300
C3—H3C	0.9600	C11—H11	0.9300

C6—Bi1—S1	89.7 (3)	N1—C4—C5	112.7 (11)
C6—Bi1—S2	91.1 (3)	N1—C4—H4A	109.0
S1—Bi1—S2	67.33 (9)	C5—C4—H4A	109.0
C6—Bi1—Cl1	91.1 (3)	N1—C4—H4B	109.0
S1—Bi1—Cl1	77.84 (9)	C5—C4—H4B	109.0
S2—Bi1—Cl1	145.09 (8)	H4A—C4—H4B	107.8
C6—Bi1—Cl1ⁱ	87.6 (3)	C4—C5—H5A	109.5
S1—Bi1—Cl1ⁱ	149.27 (10)	C4—C5—H5B	109.5
S2—Bi1—Cl1ⁱ	82.11 (8)	H5A—C5—H5B	109.5
Cl1—Bi1—Cl1ⁱ	132.80 (6)	C4—C5—H5C	109.5
Bi1—Cl1—Bi1ⁱⁱ	116.11 (11)	H5A—C5—H5C	109.5
C1—N1—C4	122.1 (9)	H5B—C5—H5C	109.5
C1—N1—C2	120.7 (10)	C11—C6—C7	117.6 (12)
C4—N1—C2	117.2 (9)	C11—C6—Bi1	122.8 (9)
C1—S1—Bi1	88.4 (4)	C7—C6—Bi1	119.5 (9)
C1—S2—Bi1	86.5 (4)	C8—C7—C6	119.7 (13)
N1—C1—S1	121.2 (8)	C8—C7—H7	120.2
N1—C1—S2	121.0 (9)	C6—C7—H7	120.2
S1—C1—S2	117.8 (7)	C7—C8—C9	122.0 (14)
N1—C2—C3	112.5 (10)	C7—C8—H8	119.0
N1—C2—H2A	109.1	C9—C8—H8	119.0
C3—C2—H2A	109.1	C8—C9—C10	119.4 (15)
N1—C2—H2B	109.1	C8—C9—H9	120.3
C3—C2—H2B	109.1	C10—C9—H9	120.3
H2A—C2—H2B	107.8	C11—C10—C9	120.2 (14)
C2—C3—H3A	109.5	C11—C10—H10	119.9
C2—C3—H3B	109.5	C9—C10—H10	119.9
H3A—C3—H3B	109.5	C6—C11—C10	121.0 (13)
C2—C3—H3C	109.5	C6—C11—H11	119.5
H3A—C3—H3C	109.5	C10—C11—H11	119.5
H3B—C3—H3C	109.5

C6—Bi1—Cl1—Bi1ⁱⁱ	90.5 (3)	C1—N1—C2—C3	−81.2 (14)
S1—Bi1—Cl1—Bi1ⁱⁱ	1.09 (12)	C4—N1—C2—C3	97.5 (13)
S2—Bi1—Cl1—Bi1ⁱⁱ	−2.9 (2)	C1—N1—C4—C5	89.4 (14)
Cl1ⁱ—Bi1—Cl1—Bi1ⁱⁱ	178.29 (5)	C2—N1—C4—C5	−89.2 (13)
C6—Bi1—S1—C1	91.2 (5)	S1—Bi1—C6—C11	60.6 (10)
S2—Bi1—S1—C1	−0.1 (4)	S2—Bi1—C6—C11	127.9 (10)
Cl1—Bi1—S1—C1	−177.6 (4)	Cl1—Bi1—C6—C11	−17.2 (10)
Cl1ⁱ—Bi1—S1—C1	6.4 (5)	Cl1ⁱ—Bi1—C6—C11	−150.0 (10)
C6—Bi1—S2—C1	−89.1 (5)	S1—Bi1—C6—C7	−117.6 (9)
S1—Bi1—S2—C1	0.1 (4)	S2—Bi1—C6—C7	−50.3 (9)
Cl1—Bi1—S2—C1	4.3 (4)	Cl1—Bi1—C6—C7	164.6 (9)
Cl1ⁱ—Bi1—S2—C1	−176.6 (4)	Cl1ⁱ—Bi1—C6—C7	31.8 (9)
C4—N1—C1—S1	−178.9 (8)	C11—C6—C7—C8	1.0 (19)
C2—N1—C1—S1	−0.3 (15)	Bi1—C6—C7—C8	179.3 (10)
C4—N1—C1—S2	2.4 (15)	C6—C7—C8—C9	0 (2)
C2—N1—C1—S2	−179.0 (8)	C7—C8—C9—C10	−2 (2)
Bi1—S1—C1—N1	−178.6 (10)	C8—C9—C10—C11	3 (2)
Bi1—S1—C1—S2	0.1 (7)	C7—C6—C11—C10	0.1 (19)
Bi1—S2—C1—N1	178.6 (10)	Bi1—C6—C11—C10	−178.2 (10)
Bi1—S2—C1—S1	−0.1 (6)	C9—C10—C11—C6	−2 (2)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Bi(C₆H₅)(C₅H₁₀NS₂)Cl]
M_r	469.79
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	9.2029 (9), 18.1432 (17), 9.0779 (8)
β (°)	106.811 (2)
V (Å³)	1451.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	12.60
Crystal size (mm)	0.23 × 0.22 × 0.21

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.160, 0.177
No. of measured, independent and observed [I > 2σ(I)] reflections	6443, 2444, 1877
R_int	0.095
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.149, 0.92
No. of reflections	2444
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.04, −2.84

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors acknowledge the National Natural Science Foundation of China (grant No. 20771053), and the Natural Science Foundation of Shandong Province (grant No. 2005ZX09) for financial support.

References

Bardaji, M., Connelly, N. G., Gimeno, M. C., Jimenez, J., Jones, P. G., Laguna, A. & Laguna, M. (1994). J. Chem. Soc. Dalton Trans. pp. 1163–1168. CSD CrossRef Web of Science Google Scholar
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