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

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.019 Å
• R factor = 0.056
• wR factor = 0.149
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found





Alert level C
            Value of measurement temperature given =   298.000
            Value of melting point given =     0.000
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT213_ALERT_2_C Atom C10     has ADP max/min Ratio .............       3.40 oblat
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         19
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.40
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?

Alert level G
ABSTM02_ALERT_3_G  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      0.400
            Tmax scaled      0.071 Tmin scaled      0.064

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

All H atoms were placed geometrically and treated as riding on their parent atoms, with methylene C—H distances of 0.97Å and aromatic C—H distances of 0.93Å. The U_iso(H) values were set at 1.2U_eq(C).

Computing details

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

	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]

Crystal data

[Bi(C6H5)(C5H10NS2)Cl]	F(000) = 880
Mr = 469.79	Dx = 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) Å^3	Block, colorless
Z = 4	0.23 × 0.22 × 0.21 mm

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 0.92	w = 1/[σ^2(Fo^2) + (0.0942P)^2] where P = (Fo^2 + 2Fc^2)/3
2444 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 2.04 e Å^−3
0 restraints	Δρmin = −2.84 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—Cl1^i	2.920 (3)	C5—H5B	0.9600
Cl1—Bi1^ii	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—Cl1^i	87.6 (3)	C4—C5—H5A	109.5
S1—Bi1—Cl1^i	149.27 (10)	C4—C5—H5B	109.5
S2—Bi1—Cl1^i	82.11 (8)	H5A—C5—H5B	109.5
Cl1—Bi1—Cl1^i	132.80 (6)	C4—C5—H5C	109.5
Bi1—Cl1—Bi1^ii	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—Bi1^ii	90.5 (3)	C1—N1—C2—C3	−81.2 (14)
S1—Bi1—Cl1—Bi1^ii	1.09 (12)	C4—N1—C2—C3	97.5 (13)
S2—Bi1—Cl1—Bi1^ii	−2.9 (2)	C1—N1—C4—C5	89.4 (14)
Cl1^i—Bi1—Cl1—Bi1^ii	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)
Cl1^i—Bi1—S1—C1	6.4 (5)	Cl1^i—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)
Cl1^i—Bi1—S2—C1	−176.6 (4)	Cl1^i—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.