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Acta Cryst. (2008). E64, m639    [ doi:10.1107/S1600536808008945 ]

(2,2'-Bipyridine-[kappa]2N,N')iodido(pyrrolidine-1-dithiocarboxylato-[kappa]2S,S')copper(II)

L.-Q. Fan and J.-H. Wu

Abstract top

In the title compound, [Cu(C5H8NS2)I(C10H8N2)], the CuII ion is coordinated by one iodide ion, two N atoms of the bipyridine ligand and two S atoms from the pyrrolidine-1-dithiocarboxylate ligand in a distorted square-pyramidal environment.

Comment top

Research into transition metal complexes has been rapidly expanding because of their fascinating structural diversity, as well as their potential applications as functional materials and enzymes (Noro et al., 2000; Yaghi et al., 1998). Dialkyldithiocarbamates anions, which are typical sulfur ligands, acting as monodentate, bidentate or bridging ligands, are often chosen for the preparation of a considerable structural variety of complexes (Englhardt et al., 1998; Fernández et al., 2000; Koh, et al., 2003). We report here the crystal structure of the title copper(II) complex, (I), contanining a pyrrolidine-1-dithiocarboxylate ligand.

The crystal structure of (I) is built of discrete molecules of the CuII complex (Fig. 1). The CuII ion is five-coordinated in a distorted square-pyramidal environment by one I atom in the apical position, two N atoms from the bipyridine ligand and two S atoms from the pyrrolidine-1-dithiocarboxylate ligand in the basal plane (Table 1).

Related literature top

For related literature, see: Englhardt et al. (1998); Fernández et al. (2000); Koh et al. (2003); Noro et al. (2000); Yaghi et al. (1998).

Experimental top

A mixture of Cu(Ac)2.H2O (0.08 g, 0.4 mmol), NaS2CNC4H8.2H2O (0.09 g, 0.4 mmol), 2,2'-bipyridine (0.06 g 0.4 mmol) and NaI.2H2O (0.07 g, 0.4 mmol) was stirred in DMF (15 ml). 2-PrOH was diffused into the resulting solution, yielding single crystals of (I).

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) or 0.97 Å (pyrrolidinyl), Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); 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
[Figure 1] Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).
(2,2'-Bipyridine-κ2N,N')iodido(pyrrolidine-1-dithiocarboxylato- κ2S,S')copper(II) top
Crystal data top
[Cu(C5H8NS2)I(C10H8N2)]F000 = 964
Mr = 492.87Dx = 1.883 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1823 reflections
a = 6.606 (3) Åθ = 2.5–27.5º
b = 16.212 (8) ŵ = 3.27 mm−1
c = 16.405 (8) ÅT = 293 (2) K
β = 98.399 (10)ºPrism, black
V = 1738.3 (15) Å30.20 × 0.20 × 0.10 mm
Z = 4
Data collection top
Rigaku Mercury CCD
diffractometer		3983 independent reflections
Radiation source: Sealed Tube3326 reflections with I > 2σ(I)
Monochromator: Graphite MonochromatorRint = 0.029
T = 293(2) Kθmax = 27.5º
ω scansθmin = 2.5º
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)		h = −8→8
Tmin = 0.722, Tmax = 1.000k = −20→21
13239 measured reflectionsl = −21→20
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.085  w = 1/[σ2(Fo2) + (0.041P)2 + 0.011P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
3983 reflectionsΔρmax = 0.54 e Å−3
199 parametersΔρmin = −0.63 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C5H8NS2)I(C10H8N2)]V = 1738.3 (15) Å3
Mr = 492.87Z = 4
Monoclinic, P21/cMo Kα
a = 6.606 (3) ŵ = 3.27 mm−1
b = 16.212 (8) ÅT = 293 (2) K
c = 16.405 (8) Å0.20 × 0.20 × 0.10 mm
β = 98.399 (10)º
Data collection top
Rigaku Mercury CCD
diffractometer		3983 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)		3326 reflections with I > 2σ(I)
Tmin = 0.722, Tmax = 1.000Rint = 0.029
13239 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034199 parameters
wR(F2) = 0.085H-atom parameters constrained
S = 1.07Δρmax = 0.54 e Å−3
3983 reflectionsΔρmin = −0.63 e Å−3
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
Cu10.47246 (6)0.43996 (2)0.34106 (3)0.03678 (12)
I10.22688 (4)0.387568 (15)0.190445 (15)0.04821 (10)
S10.37645 (15)0.34944 (6)0.43793 (6)0.0475 (2)
S20.74152 (13)0.34585 (6)0.36071 (6)0.0419 (2)
N10.6415 (4)0.22460 (17)0.45729 (17)0.0400 (7)
N20.3012 (4)0.53917 (17)0.36333 (17)0.0383 (6)
N30.6083 (4)0.52693 (16)0.28057 (17)0.0368 (6)
C10.5952 (5)0.2977 (2)0.4244 (2)0.0364 (7)
C20.5177 (6)0.1803 (2)0.5103 (2)0.0485 (9)
H2A0.39080.16090.47890.058*
H2B0.48650.21520.55480.058*
C30.6532 (9)0.1087 (3)0.5431 (4)0.0826 (16)
H3A0.73370.12270.59550.099*
H3B0.57160.06030.55040.099*
C40.7884 (8)0.0936 (3)0.4791 (3)0.0711 (13)
H4A0.72350.05590.43730.085*
H4B0.91800.07010.50390.085*
C50.8212 (6)0.1769 (2)0.4417 (3)0.0512 (10)
H5A0.94690.20210.46820.061*
H5B0.82620.17210.38310.061*
C60.1427 (6)0.5395 (2)0.4055 (2)0.0497 (9)
H6A0.10790.49060.42970.060*
C70.0283 (7)0.6094 (3)0.4148 (2)0.0549 (11)
H7A−0.07930.60800.44550.066*
C80.0778 (6)0.6805 (3)0.3777 (2)0.0549 (11)
H8A0.00250.72830.38220.066*
C90.2389 (6)0.6810 (2)0.3336 (2)0.0501 (9)
H9A0.27300.72910.30790.060*
C100.3503 (5)0.60970 (19)0.3277 (2)0.0369 (7)
C110.5251 (5)0.60319 (19)0.2813 (2)0.0351 (7)
C120.6013 (6)0.6680 (2)0.2401 (2)0.0458 (9)
H12A0.54320.72020.24110.055*
C130.7627 (6)0.6551 (3)0.1978 (2)0.0522 (10)
H13A0.81670.69860.17080.063*
C140.8441 (6)0.5771 (2)0.1955 (2)0.0497 (9)
H14A0.95150.56670.16610.060*
C150.7631 (5)0.5149 (2)0.2378 (2)0.0428 (8)
H15A0.81830.46220.23650.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0405 (2)0.0267 (2)0.0451 (2)0.00447 (16)0.01283 (19)0.00300 (16)
I10.04930 (17)0.04100 (16)0.05259 (17)−0.00012 (10)0.00166 (12)−0.00718 (10)
S10.0485 (5)0.0420 (5)0.0574 (6)0.0155 (4)0.0255 (5)0.0126 (4)
S20.0394 (5)0.0381 (5)0.0508 (5)0.0054 (4)0.0154 (4)0.0079 (4)
N10.0428 (16)0.0355 (16)0.0437 (16)0.0073 (12)0.0125 (13)0.0047 (12)
N20.0435 (16)0.0343 (15)0.0379 (15)0.0081 (12)0.0084 (13)0.0008 (11)
N30.0400 (15)0.0280 (14)0.0430 (15)0.0001 (11)0.0076 (13)−0.0002 (11)
C10.0398 (17)0.0344 (18)0.0357 (17)0.0029 (14)0.0081 (15)−0.0011 (13)
C20.053 (2)0.045 (2)0.049 (2)0.0033 (17)0.0125 (18)0.0156 (16)
C30.094 (4)0.052 (3)0.107 (4)0.018 (3)0.030 (3)0.031 (3)
C40.095 (4)0.038 (2)0.083 (3)0.020 (2)0.021 (3)0.009 (2)
C50.049 (2)0.046 (2)0.061 (2)0.0199 (17)0.0170 (19)0.0053 (18)
C60.054 (2)0.050 (2)0.048 (2)0.0113 (18)0.0144 (18)0.0037 (17)
C70.055 (2)0.065 (3)0.047 (2)0.022 (2)0.0126 (19)−0.0027 (18)
C80.061 (2)0.048 (2)0.054 (2)0.023 (2)0.001 (2)−0.0090 (18)
C90.063 (2)0.034 (2)0.049 (2)0.0139 (17)−0.0024 (19)−0.0033 (16)
C100.0429 (18)0.0295 (17)0.0362 (17)0.0049 (13)−0.0008 (15)−0.0031 (13)
C110.0372 (17)0.0292 (17)0.0363 (17)−0.0012 (13)−0.0031 (14)0.0011 (13)
C120.051 (2)0.0270 (18)0.057 (2)0.0008 (15)0.0004 (19)0.0038 (15)
C130.054 (2)0.044 (2)0.059 (2)−0.0094 (18)0.010 (2)0.0128 (17)
C140.052 (2)0.048 (2)0.052 (2)−0.0051 (18)0.0155 (18)0.0043 (17)
C150.0446 (19)0.037 (2)0.049 (2)−0.0012 (15)0.0147 (17)−0.0015 (15)
Geometric parameters (Å, °) top
Cu1—N32.010 (3)C4—H4A0.9700
Cu1—N22.030 (3)C4—H4B0.9700
Cu1—S12.3185 (12)C5—H5A0.9700
Cu1—S22.3289 (13)C5—H5B0.9700
Cu1—I12.8789 (11)C6—C71.382 (5)
S1—C11.713 (3)C6—H6A0.9300
S2—C11.712 (3)C7—C81.365 (6)
N1—C11.319 (4)C7—H7A0.9300
N1—C21.466 (4)C8—C91.371 (6)
N1—C51.471 (4)C8—H8A0.9300
N2—C61.337 (5)C9—C101.381 (5)
N2—C101.345 (4)C9—H9A0.9300
N3—C151.336 (4)C10—C111.476 (5)
N3—C111.354 (4)C11—C121.384 (5)
C2—C31.516 (5)C12—C131.371 (5)
C2—H2A0.9700C12—H12A0.9300
C2—H2B0.9700C13—C141.377 (6)
C3—C41.495 (7)C13—H13A0.9300
C3—H3A0.9700C14—C151.375 (5)
C3—H3B0.9700C14—H14A0.9300
C4—C51.511 (5)C15—H15A0.9300
N3—Cu1—N280.44 (12)C3—C4—H4B110.5
N3—Cu1—S1165.74 (8)C5—C4—H4B110.5
N2—Cu1—S199.36 (9)H4A—C4—H4B108.7
N3—Cu1—S298.11 (9)N1—C5—C4103.4 (3)
N2—Cu1—S2158.17 (8)N1—C5—H5A111.1
S1—Cu1—S276.71 (4)C4—C5—H5A111.1
N3—Cu1—I191.12 (8)N1—C5—H5B111.1
N2—Cu1—I197.42 (8)C4—C5—H5B111.1
S1—Cu1—I1103.02 (4)H5A—C5—H5B109.0
S2—Cu1—I1104.39 (4)N2—C6—C7122.9 (4)
C1—S1—Cu184.31 (12)N2—C6—H6A118.6
C1—S2—Cu184.01 (12)C7—C6—H6A118.6
C1—N1—C2124.5 (3)C8—C7—C6118.2 (4)
C1—N1—C5123.1 (3)C8—C7—H7A120.9
C2—N1—C5112.3 (3)C6—C7—H7A120.9
C6—N2—C10118.6 (3)C7—C8—C9119.7 (4)
C6—N2—Cu1126.6 (3)C7—C8—H8A120.2
C10—N2—Cu1114.8 (2)C9—C8—H8A120.2
C15—N3—C11118.7 (3)C8—C9—C10119.7 (4)
C15—N3—Cu1126.0 (2)C8—C9—H9A120.2
C11—N3—Cu1115.1 (2)C10—C9—H9A120.2
N1—C1—S2122.8 (3)N2—C10—C9121.0 (4)
N1—C1—S1122.4 (3)N2—C10—C11114.8 (3)
S2—C1—S1114.70 (19)C9—C10—C11124.1 (3)
N1—C2—C3103.5 (3)N3—C11—C12120.8 (3)
N1—C2—H2A111.1N3—C11—C10114.8 (3)
C3—C2—H2A111.1C12—C11—C10124.4 (3)
N1—C2—H2B111.1C13—C12—C11119.8 (3)
C3—C2—H2B111.1C13—C12—H12A120.1
H2A—C2—H2B109.0C11—C12—H12A120.1
C4—C3—C2105.0 (4)C12—C13—C14119.3 (4)
C4—C3—H3A110.8C12—C13—H13A120.3
C2—C3—H3A110.8C14—C13—H13A120.3
C4—C3—H3B110.8C15—C14—C13118.5 (4)
C2—C3—H3B110.8C15—C14—H14A120.7
H3A—C3—H3B108.8C13—C14—H14A120.7
C3—C4—C5105.9 (4)N3—C15—C14122.8 (4)
C3—C4—H4A110.5N3—C15—H15A118.6
C5—C4—H4A110.5C14—C15—H15A118.6
Acknowledgements top

This work was supported financially by the National Natural Science Foundation of China (Nos. 50572030, 50372022), the Research Fund of Huaqiao University (No. 06BS216) and the Young Talent Fund of Fujian Province (2007 F3060).

references
References top

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