supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m1577    [ doi:10.1107/S1600536807021137 ]

(2,2'-Bipyridine-[kappa]2N,N')(nitrato-[kappa]2O,O')bis(pyrrolidine-1-dithiocarboxylato-[kappa]2S,S')bismuth(III)

F. Li, H.-D. Yin and D.-Q. Wang

Abstract top

The title compound, [Bi(C4H8NS2)2(NO3)(C10H8N2)], is monomeric, with the Bi atom chelated by the S atoms of two pyrrolidine-1-dithiocarboxylate ligands and the N atoms of a 2,2'-bipyridine ligand. A nitrate ligand completes the coordination, with the eight-coordinated Bi atom adopting a highly distorted capped pentagonal-bipyramidal geometry.

Comment top

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 pyrrolidine-1-dithiocarboxylate ligands and the N atoms of 2,2'-bipyridine. A nitrate ligand completes the coordination environment of the eight coordinated Bi atom (Fig. 1). The Bi atom is in a distorted pentagonal bipyramid environment, with atoms S1 and O2 in axial positions, and atoms S2, S3, S4, N3 and N4 in the equatorial plane. The remaining O atom (O1) of the nitrate ligand caps the O2/S2/N3 face of this pentagonal bipyramid, giving a highly distorted capped pentagonal bipyramid coordination geometry. One of the bidentate pyrrolidine-1-dithiocarboxylate ligands forms a significantly longer Bi—S bond [Bi1—S4 = 2.900 (4) Å] than the others in the complex. This variation in coordination strength is also signalled by the fact that the C6—S4 bond is significantly shorter than the other C—S bonds, suggesting some delocalization in the system. In addition, the chelating phenanthroline ligands are bonded to the Bi atom through two N atoms. The Bi1—N3 and Bi1—N4 distances fall in the same range as in other Bi/N complexes (Baraanyi et al., 1977).

Related literature top

For related literature, see: Baraanyi et al. (1977); Bardaji et al. (1994); Xu et al. (2001); Yin et al. (2003).

Experimental top

To an aqueous solution of Bi(NO3)35H2O (2.0 mmol) and mannite (2.0 mmol) was added another aqueous solution of sodium pyrrolidine-1-dithiocarboxylate (4.0 mmol) and 2,2'-bipyridine (2.0 mmol). The resulted solution was stirred for 2 h at 298 K, and then yellow solid was obtained by filtration. The solid was recrystallized from ethanol and yellow crystals of (I) were formed.

Refinement top

All H atoms were positioned geometrically and treated as riding on their parent atoms [C—H = 0.97 Å with Uiso(H) = 1.2Ueq for CH2, and C—H =0.93 Å with Uiso(H) = 1.2Ueq for aromatic H atoms].

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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.

Figures top
[Figure 1] Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering schemes. H atoms have been omitted for clarity.
(2,2'-Bipyridine-κ2N,N')(nitrato-κ2O,O')bis(pyrrolidine-1- dithiocarboxylato-κ2S,S')bismuth(III) top
Crystal data top
[Bi(C4H8NS2)2(NO3)(C10H8N2)]Z = 2
Mr = 719.66F(000) = 700
Triclinic, P1Dx = 1.887 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.565 (4) ÅCell parameters from 3168 reflections
b = 10.171 (4) Åθ = 2.2–27.3°
c = 14.555 (5) ŵ = 7.32 mm−1
α = 73.634 (4)°T = 298 K
β = 76.032 (4)°Block, yellow
γ = 70.916 (4)°0.28 × 0.24 × 0.22 mm
V = 1266.5 (8) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		4305 independent reflections
Radiation source: fine-focus sealed tube3408 reflections with I > 2σ(I)
graphiteRint = 0.048
φ and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→11
Tmin = 0.149, Tmax = 0.212k = −12→11
6375 measured reflectionsl = −17→17
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.163H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0971P)2]
where P = (Fo2 + 2Fc2)/3
4305 reflections(Δ/σ)max = 0.001
280 parametersΔρmax = 2.34 e Å−3
0 restraintsΔρmin = −5.28 e Å−3
Crystal data top
[Bi(C4H8NS2)2(NO3)(C10H8N2)]γ = 70.916 (4)°
Mr = 719.66V = 1266.5 (8) Å3
Triclinic, P1Z = 2
a = 9.565 (4) ÅMo Kα radiation
b = 10.171 (4) ŵ = 7.32 mm−1
c = 14.555 (5) ÅT = 298 K
α = 73.634 (4)°0.28 × 0.24 × 0.22 mm
β = 76.032 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		4305 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3408 reflections with I > 2σ(I)
Tmin = 0.149, Tmax = 0.212Rint = 0.048
6375 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.063H-atom parameters constrained
wR(F2) = 0.163Δρmax = 2.34 e Å−3
S = 0.99Δρmin = −5.28 e Å−3
4305 reflectionsAbsolute structure: ?
280 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Bi10.23149 (5)0.12616 (4)0.76237 (3)0.03393 (19)
N10.1198 (11)0.1522 (10)0.4758 (7)0.039 (2)
N20.4937 (11)0.4557 (10)0.6654 (7)0.039 (2)
N30.0613 (13)−0.0558 (13)0.8613 (7)0.051 (3)
N4−0.0642 (12)0.2242 (10)0.8629 (7)0.038 (2)
N50.4987 (12)−0.1193 (12)0.8582 (8)0.045 (3)
O10.4437 (13)−0.1199 (11)0.7882 (8)0.065 (3)
O20.4517 (13)−0.0073 (12)0.8887 (7)0.065 (3)
O30.5935 (13)−0.2224 (11)0.8937 (9)0.076 (3)
S10.0555 (4)0.2701 (4)0.6269 (2)0.0454 (8)
S20.2802 (4)−0.0071 (3)0.6127 (2)0.0426 (8)
S30.4664 (4)0.2134 (4)0.6517 (3)0.0509 (9)
S40.2474 (4)0.3986 (4)0.7783 (3)0.0541 (9)
C10.1489 (12)0.1406 (12)0.5627 (8)0.033 (3)
C20.2027 (15)0.0460 (15)0.4155 (9)0.047 (3)
H2A0.1917−0.04820.44860.057*
H2B0.30850.04120.39890.057*
C30.126 (2)0.105 (2)0.3250 (12)0.074 (5)
H3A0.19950.09150.26700.088*
H3B0.05120.05750.32980.088*
C40.057 (2)0.2562 (18)0.3221 (11)0.078 (5)
H4A−0.02970.29040.28960.093*
H4B0.12770.31040.28690.093*
C50.0100 (15)0.2742 (16)0.4259 (9)0.052 (4)
H5A0.01800.36420.43130.062*
H5B−0.09180.26830.45140.062*
C60.4078 (15)0.3696 (13)0.6979 (9)0.042 (3)
C70.6380 (16)0.4308 (14)0.6002 (12)0.0552 (19)
H7A0.62470.43490.53540.066*
H7B0.70500.33880.62430.066*
C80.6979 (16)0.5501 (14)0.6004 (11)0.0552 (19)
H8A0.76320.52000.64860.066*
H8B0.75380.58110.53720.066*
C90.5667 (16)0.6638 (14)0.6241 (11)0.0552 (19)
H9A0.52920.72380.56540.066*
H9B0.59150.72240.65660.066*
C100.4503 (16)0.5946 (14)0.6899 (11)0.0552 (19)
H10A0.45370.58470.75760.066*
H10B0.35030.64900.67670.066*
C110.1268 (17)−0.1947 (15)0.8675 (10)0.054 (4)
H110.2276−0.22370.84100.065*
C120.0511 (19)−0.2988 (15)0.9121 (9)0.055 (4)
H120.1009−0.39500.91590.066*
C13−0.0973 (18)−0.2565 (16)0.9498 (10)0.056 (4)
H13−0.1509−0.32340.97890.068*
C14−0.1677 (16)−0.1112 (14)0.9441 (9)0.049 (3)
H14−0.2676−0.07970.97180.059*
C15−0.0852 (14)−0.0156 (13)0.8964 (8)0.037 (3)
C16−0.1560 (14)0.1400 (14)0.8881 (8)0.038 (3)
C17−0.3107 (15)0.2003 (16)0.9061 (10)0.057 (4)
H17−0.37400.14180.92150.069*
C18−0.3706 (17)0.3411 (16)0.9016 (11)0.064 (5)
H18−0.47410.37970.91400.077*
C19−0.2774 (15)0.4260 (14)0.8787 (10)0.051 (4)
H19−0.31480.52310.87710.062*
C20−0.1275 (16)0.3639 (15)0.8580 (10)0.050 (3)
H20−0.06440.42290.83910.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Bi10.0336 (3)0.0278 (3)0.0343 (3)0.00256 (18)0.00025 (18)−0.01551 (18)
N10.036 (6)0.039 (6)0.032 (6)0.004 (5)−0.002 (4)−0.012 (4)
N20.030 (5)0.029 (6)0.050 (6)0.003 (5)0.009 (5)−0.023 (5)
N30.056 (8)0.061 (8)0.029 (6)−0.014 (6)0.007 (5)−0.015 (5)
N40.041 (6)0.028 (6)0.036 (6)0.004 (5)0.000 (5)−0.017 (4)
N50.034 (6)0.043 (7)0.049 (7)−0.003 (5)0.005 (5)−0.017 (5)
O10.076 (7)0.060 (7)0.065 (7)0.003 (5)−0.032 (6)−0.034 (5)
O20.084 (8)0.062 (7)0.049 (6)−0.010 (6)−0.010 (5)−0.025 (5)
O30.070 (8)0.047 (7)0.099 (9)0.020 (6)−0.044 (7)−0.016 (6)
S10.0452 (19)0.0365 (18)0.0375 (17)0.0169 (14)−0.0010 (14)−0.0202 (14)
S20.051 (2)0.0252 (16)0.0432 (18)0.0126 (14)−0.0111 (15)−0.0183 (13)
S30.0430 (19)0.043 (2)0.062 (2)−0.0057 (16)0.0204 (16)−0.0368 (17)
S40.0420 (19)0.050 (2)0.067 (2)−0.0104 (17)0.0253 (17)−0.0395 (18)
C10.024 (6)0.034 (7)0.032 (6)0.001 (5)0.003 (5)−0.009 (5)
C20.048 (8)0.050 (9)0.043 (8)−0.005 (7)0.003 (6)−0.029 (6)
C30.081 (12)0.091 (14)0.052 (10)−0.011 (10)−0.009 (9)−0.037 (9)
C40.115 (16)0.064 (12)0.054 (10)−0.001 (11)−0.039 (10)−0.021 (8)
C50.040 (8)0.062 (10)0.045 (8)−0.003 (7)−0.014 (6)−0.005 (7)
C60.042 (7)0.028 (7)0.044 (7)0.011 (6)0.002 (6)−0.019 (5)
C70.045 (4)0.036 (4)0.070 (5)0.002 (3)0.010 (4)−0.019 (3)
C80.045 (4)0.036 (4)0.070 (5)0.002 (3)0.010 (4)−0.019 (3)
C90.045 (4)0.036 (4)0.070 (5)0.002 (3)0.010 (4)−0.019 (3)
C100.045 (4)0.036 (4)0.070 (5)0.002 (3)0.010 (4)−0.019 (3)
C110.054 (9)0.046 (9)0.056 (9)0.000 (7)−0.002 (7)−0.021 (7)
C120.093 (12)0.039 (8)0.039 (8)−0.025 (8)−0.012 (8)−0.008 (6)
C130.065 (10)0.058 (10)0.048 (9)−0.029 (8)0.002 (7)−0.010 (7)
C140.050 (8)0.046 (9)0.048 (8)−0.007 (7)0.011 (6)−0.028 (6)
C150.038 (7)0.045 (8)0.026 (6)−0.003 (6)0.002 (5)−0.022 (5)
C160.039 (7)0.046 (8)0.023 (6)−0.009 (6)−0.002 (5)−0.004 (5)
C170.031 (7)0.061 (10)0.063 (10)−0.002 (7)−0.001 (7)−0.005 (7)
C180.038 (8)0.048 (9)0.070 (11)0.005 (7)0.005 (7)0.011 (8)
C190.045 (8)0.030 (7)0.056 (9)0.020 (6)−0.006 (7)−0.013 (6)
C200.046 (8)0.049 (9)0.045 (8)−0.004 (7)0.005 (6)−0.016 (6)
Geometric parameters (Å, °) top
Bi1—O12.653 (10)C4—H4B0.9700
Bi1—S32.680 (3)C5—H5A0.9700
Bi1—S12.688 (3)C5—H5B0.9700
Bi1—N32.736 (11)C7—C81.503 (19)
Bi1—S22.749 (3)C7—H7A0.9700
Bi1—S42.900 (4)C7—H7B0.9700
N1—C11.326 (14)C8—C91.448 (18)
N1—C51.475 (15)C8—H8A0.9700
N1—C21.484 (16)C8—H8B0.9700
N2—C61.309 (16)C9—C101.507 (18)
N2—C101.458 (16)C9—H9A0.9700
N2—C71.464 (16)C9—H9B0.9700
N3—C111.331 (17)C10—H10A0.9700
N3—C151.338 (16)C10—H10B0.9700
N4—C201.338 (16)C11—C121.398 (18)
N4—C161.341 (15)C11—H110.9300
N5—O31.220 (13)C12—C131.36 (2)
N5—O21.245 (14)C12—H120.9300
N5—O11.257 (14)C13—C141.397 (19)
S1—C11.711 (12)C13—H130.9300
S2—C11.719 (12)C14—C151.381 (17)
S3—C61.768 (13)C14—H140.9300
S4—C61.686 (13)C15—C161.486 (17)
C2—C31.54 (2)C16—C171.395 (19)
C2—H2A0.9700C17—C181.35 (2)
C2—H2B0.9700C17—H170.9300
C3—C41.45 (2)C18—C191.36 (2)
C3—H3A0.9700C18—H180.9300
C3—H3B0.9700C19—C201.361 (19)
C4—C51.51 (2)C19—H190.9300
C4—H4A0.9700C20—H200.9300
O1—Bi1—S380.9 (3)H5A—C5—H5B109.3
O1—Bi1—S1135.0 (2)N2—C6—S4124.8 (10)
S3—Bi1—S192.34 (12)N2—C6—S3116.4 (9)
O1—Bi1—N379.5 (4)S4—C6—S3118.8 (8)
S3—Bi1—N3158.8 (3)N2—C7—C8103.9 (11)
S1—Bi1—N395.9 (3)N2—C7—H7A111.0
O1—Bi1—S269.1 (2)C8—C7—H7A111.0
S3—Bi1—S280.63 (11)N2—C7—H7B111.0
S1—Bi1—S265.96 (10)C8—C7—H7B111.0
N3—Bi1—S285.0 (2)H7A—C7—H7B109.0
O1—Bi1—S4126.4 (2)C9—C8—C7105.1 (12)
S3—Bi1—S464.27 (9)C9—C8—H8A110.7
S1—Bi1—S487.93 (12)C7—C8—H8A110.7
N3—Bi1—S4135.3 (3)C9—C8—H8B110.7
S2—Bi1—S4135.41 (10)C7—C8—H8B110.7
C1—N1—C5124.5 (11)H8A—C8—H8B108.8
C1—N1—C2122.7 (10)C8—C9—C10107.1 (11)
C5—N1—C2112.7 (10)C8—C9—H9A110.3
C6—N2—C10121.8 (10)C10—C9—H9A110.3
C6—N2—C7126.6 (11)C8—C9—H9B110.3
C10—N2—C7111.6 (10)C10—C9—H9B110.3
C11—N3—C15117.6 (12)H9A—C9—H9B108.5
C11—N3—Bi1117.1 (9)N2—C10—C9102.9 (10)
C15—N3—Bi1125.0 (9)N2—C10—H10A111.2
C20—N4—C16117.3 (11)C9—C10—H10A111.2
O3—N5—O2122.0 (12)N2—C10—H10B111.2
O3—N5—O1121.8 (12)C9—C10—H10B111.2
O2—N5—O1116.3 (11)H10A—C10—H10B109.1
N5—O1—Bi1104.5 (8)N3—C11—C12123.1 (14)
C1—S1—Bi188.3 (4)N3—C11—H11118.5
C1—S2—Bi186.2 (4)C12—C11—H11118.5
C6—S3—Bi191.2 (4)C13—C12—C11118.7 (15)
C6—S4—Bi185.7 (5)C13—C12—H12120.7
N1—C1—S1120.8 (9)C11—C12—H12120.7
N1—C1—S2119.9 (9)C12—C13—C14119.0 (13)
S1—C1—S2119.3 (7)C12—C13—H13120.5
N1—C2—C3102.5 (11)C14—C13—H13120.5
N1—C2—H2A111.3C15—C14—C13118.4 (13)
C3—C2—H2A111.3C15—C14—H14120.8
N1—C2—H2B111.3C13—C14—H14120.8
C3—C2—H2B111.3N3—C15—C14123.1 (12)
H2A—C2—H2B109.2N3—C15—C16116.6 (11)
C4—C3—C2105.9 (13)C14—C15—C16120.1 (11)
C4—C3—H3A110.6N4—C16—C17119.6 (13)
C2—C3—H3A110.6N4—C16—C15117.3 (11)
C4—C3—H3B110.6C17—C16—C15123.2 (12)
C2—C3—H3B110.6C18—C17—C16121.6 (14)
H3A—C3—H3B108.7C18—C17—H17119.2
C3—C4—C5107.5 (12)C16—C17—H17119.2
C3—C4—H4A110.2C17—C18—C19118.9 (14)
C5—C4—H4A110.2C17—C18—H18120.6
C3—C4—H4B110.2C19—C18—H18120.6
C5—C4—H4B110.2C18—C19—C20117.7 (14)
H4A—C4—H4B108.5C18—C19—H19121.1
N1—C5—C4101.8 (12)C20—C19—H19121.1
N1—C5—H5A111.4N4—C20—C19124.9 (13)
C4—C5—H5A111.4N4—C20—H20117.6
N1—C5—H5B111.4C19—C20—H20117.6
C4—C5—H5B111.4
Acknowledgements top

The authors acknowledge financial support from the Shandong Province Science Foundation and from the State Key Laboratory of Crystal Material, Shandong University, China.

references
References top

Baraanyi, A. D., Cook, J. & Onyszchuk, M. (1977). Inorg. Nucl. Chem. Lett. 13, 385–394.

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.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen,Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Xu, L. Z., Zhao, P. S. & Zhang, S. S. (2001). Chin. J. Chem. . 19, 436–440.

Yin, H. D., Wang, C. H. & Xing, Q. J. (2003). Chin. J. Inorg. Chem. 19, 955–958.