metal-organic compounds
(2,2′-Bipyridine-κ2N,N′)iodido(pyrrolidine-1-dithiocarboxylato-κ2S,S′)copper(II)
aInstitute of Materials Physical Chemistry and The Key Laboratory for Functional Materials of Fujian Higher Education, Huaqiao University, Quanzhou, Fujian 362021, People's Republic of China
*Correspondence e-mail: lqfan@hqu.edu.cn
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.
Related literature
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
Crystal data
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Data collection: CrystalClear (Rigaku, 2000); cell CrystalClear; data reduction: CrystalClear; 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
10.1107/S1600536808008945/at2555sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808008945/at2555Isup2.hkl
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).
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).
Data collection: CrystalClear (Rigaku, 2000); cell
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).Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). |
[Cu(C5H8NS2)I(C10H8N2)] | F(000) = 964 |
Mr = 492.87 | Dx = 1.883 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1823 reflections |
a = 6.606 (3) Å | θ = 2.5–27.5° |
b = 16.212 (8) Å | µ = 3.27 mm−1 |
c = 16.405 (8) Å | T = 293 K |
β = 98.399 (10)° | Prism, black |
V = 1738.3 (15) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 4 |
Rigaku Mercury CCD diffractometer | 3983 independent reflections |
Radiation source: Sealed Tube | 3326 reflections with I > 2σ(I) |
Graphite Monochromator monochromator | Rint = 0.029 |
ω scans | θmax = 27.5°, θmin = 2.5° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | h = −8→8 |
Tmin = 0.722, Tmax = 1.000 | k = −20→21 |
13239 measured reflections | l = −21→20 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.041P)2 + 0.011P] where P = (Fo2 + 2Fc2)/3 |
3983 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.63 e Å−3 |
[Cu(C5H8NS2)I(C10H8N2)] | V = 1738.3 (15) Å3 |
Mr = 492.87 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.606 (3) Å | µ = 3.27 mm−1 |
b = 16.212 (8) Å | T = 293 K |
c = 16.405 (8) Å | 0.20 × 0.20 × 0.10 mm |
β = 98.399 (10)° |
Rigaku Mercury CCD diffractometer | 3983 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | 3326 reflections with I > 2σ(I) |
Tmin = 0.722, Tmax = 1.000 | Rint = 0.029 |
13239 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.54 e Å−3 |
3983 reflections | Δρmin = −0.63 e Å−3 |
199 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 | ||
Cu1 | 0.47246 (6) | 0.43996 (2) | 0.34106 (3) | 0.03678 (12) | |
I1 | 0.22688 (4) | 0.387568 (15) | 0.190445 (15) | 0.04821 (10) | |
S1 | 0.37645 (15) | 0.34944 (6) | 0.43793 (6) | 0.0475 (2) | |
S2 | 0.74152 (13) | 0.34585 (6) | 0.36071 (6) | 0.0419 (2) | |
N1 | 0.6415 (4) | 0.22460 (17) | 0.45729 (17) | 0.0400 (7) | |
N2 | 0.3012 (4) | 0.53917 (17) | 0.36333 (17) | 0.0383 (6) | |
N3 | 0.6083 (4) | 0.52693 (16) | 0.28057 (17) | 0.0368 (6) | |
C1 | 0.5952 (5) | 0.2977 (2) | 0.4244 (2) | 0.0364 (7) | |
C2 | 0.5177 (6) | 0.1803 (2) | 0.5103 (2) | 0.0485 (9) | |
H2A | 0.3908 | 0.1609 | 0.4789 | 0.058* | |
H2B | 0.4865 | 0.2152 | 0.5548 | 0.058* | |
C3 | 0.6532 (9) | 0.1087 (3) | 0.5431 (4) | 0.0826 (16) | |
H3A | 0.7337 | 0.1227 | 0.5955 | 0.099* | |
H3B | 0.5716 | 0.0603 | 0.5504 | 0.099* | |
C4 | 0.7884 (8) | 0.0936 (3) | 0.4791 (3) | 0.0711 (13) | |
H4A | 0.7235 | 0.0559 | 0.4373 | 0.085* | |
H4B | 0.9180 | 0.0701 | 0.5039 | 0.085* | |
C5 | 0.8212 (6) | 0.1769 (2) | 0.4417 (3) | 0.0512 (10) | |
H5A | 0.9469 | 0.2021 | 0.4682 | 0.061* | |
H5B | 0.8262 | 0.1721 | 0.3831 | 0.061* | |
C6 | 0.1427 (6) | 0.5395 (2) | 0.4055 (2) | 0.0497 (9) | |
H6A | 0.1079 | 0.4906 | 0.4297 | 0.060* | |
C7 | 0.0283 (7) | 0.6094 (3) | 0.4148 (2) | 0.0549 (11) | |
H7A | −0.0793 | 0.6080 | 0.4455 | 0.066* | |
C8 | 0.0778 (6) | 0.6805 (3) | 0.3777 (2) | 0.0549 (11) | |
H8A | 0.0025 | 0.7283 | 0.3822 | 0.066* | |
C9 | 0.2389 (6) | 0.6810 (2) | 0.3336 (2) | 0.0501 (9) | |
H9A | 0.2730 | 0.7291 | 0.3079 | 0.060* | |
C10 | 0.3503 (5) | 0.60970 (19) | 0.3277 (2) | 0.0369 (7) | |
C11 | 0.5251 (5) | 0.60319 (19) | 0.2813 (2) | 0.0351 (7) | |
C12 | 0.6013 (6) | 0.6680 (2) | 0.2401 (2) | 0.0458 (9) | |
H12A | 0.5432 | 0.7202 | 0.2411 | 0.055* | |
C13 | 0.7627 (6) | 0.6551 (3) | 0.1978 (2) | 0.0522 (10) | |
H13A | 0.8167 | 0.6986 | 0.1708 | 0.063* | |
C14 | 0.8441 (6) | 0.5771 (2) | 0.1955 (2) | 0.0497 (9) | |
H14A | 0.9515 | 0.5667 | 0.1661 | 0.060* | |
C15 | 0.7631 (5) | 0.5149 (2) | 0.2378 (2) | 0.0428 (8) | |
H15A | 0.8183 | 0.4622 | 0.2365 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0405 (2) | 0.0267 (2) | 0.0451 (2) | 0.00447 (16) | 0.01283 (19) | 0.00300 (16) |
I1 | 0.04930 (17) | 0.04100 (16) | 0.05259 (17) | −0.00012 (10) | 0.00166 (12) | −0.00718 (10) |
S1 | 0.0485 (5) | 0.0420 (5) | 0.0574 (6) | 0.0155 (4) | 0.0255 (5) | 0.0126 (4) |
S2 | 0.0394 (5) | 0.0381 (5) | 0.0508 (5) | 0.0054 (4) | 0.0154 (4) | 0.0079 (4) |
N1 | 0.0428 (16) | 0.0355 (16) | 0.0437 (16) | 0.0073 (12) | 0.0125 (13) | 0.0047 (12) |
N2 | 0.0435 (16) | 0.0343 (15) | 0.0379 (15) | 0.0081 (12) | 0.0084 (13) | 0.0008 (11) |
N3 | 0.0400 (15) | 0.0280 (14) | 0.0430 (15) | 0.0001 (11) | 0.0076 (13) | −0.0002 (11) |
C1 | 0.0398 (17) | 0.0344 (18) | 0.0357 (17) | 0.0029 (14) | 0.0081 (15) | −0.0011 (13) |
C2 | 0.053 (2) | 0.045 (2) | 0.049 (2) | 0.0033 (17) | 0.0125 (18) | 0.0156 (16) |
C3 | 0.094 (4) | 0.052 (3) | 0.107 (4) | 0.018 (3) | 0.030 (3) | 0.031 (3) |
C4 | 0.095 (4) | 0.038 (2) | 0.083 (3) | 0.020 (2) | 0.021 (3) | 0.009 (2) |
C5 | 0.049 (2) | 0.046 (2) | 0.061 (2) | 0.0199 (17) | 0.0170 (19) | 0.0053 (18) |
C6 | 0.054 (2) | 0.050 (2) | 0.048 (2) | 0.0113 (18) | 0.0144 (18) | 0.0037 (17) |
C7 | 0.055 (2) | 0.065 (3) | 0.047 (2) | 0.022 (2) | 0.0126 (19) | −0.0027 (18) |
C8 | 0.061 (2) | 0.048 (2) | 0.054 (2) | 0.023 (2) | 0.001 (2) | −0.0090 (18) |
C9 | 0.063 (2) | 0.034 (2) | 0.049 (2) | 0.0139 (17) | −0.0024 (19) | −0.0033 (16) |
C10 | 0.0429 (18) | 0.0295 (17) | 0.0362 (17) | 0.0049 (13) | −0.0008 (15) | −0.0031 (13) |
C11 | 0.0372 (17) | 0.0292 (17) | 0.0363 (17) | −0.0012 (13) | −0.0031 (14) | 0.0011 (13) |
C12 | 0.051 (2) | 0.0270 (18) | 0.057 (2) | 0.0008 (15) | 0.0004 (19) | 0.0038 (15) |
C13 | 0.054 (2) | 0.044 (2) | 0.059 (2) | −0.0094 (18) | 0.010 (2) | 0.0128 (17) |
C14 | 0.052 (2) | 0.048 (2) | 0.052 (2) | −0.0051 (18) | 0.0155 (18) | 0.0043 (17) |
C15 | 0.0446 (19) | 0.037 (2) | 0.049 (2) | −0.0012 (15) | 0.0147 (17) | −0.0015 (15) |
Cu1—N3 | 2.010 (3) | C4—H4A | 0.9700 |
Cu1—N2 | 2.030 (3) | C4—H4B | 0.9700 |
Cu1—S1 | 2.3185 (12) | C5—H5A | 0.9700 |
Cu1—S2 | 2.3289 (13) | C5—H5B | 0.9700 |
Cu1—I1 | 2.8789 (11) | C6—C7 | 1.382 (5) |
S1—C1 | 1.713 (3) | C6—H6A | 0.9300 |
S2—C1 | 1.712 (3) | C7—C8 | 1.365 (6) |
N1—C1 | 1.319 (4) | C7—H7A | 0.9300 |
N1—C2 | 1.466 (4) | C8—C9 | 1.371 (6) |
N1—C5 | 1.471 (4) | C8—H8A | 0.9300 |
N2—C6 | 1.337 (5) | C9—C10 | 1.381 (5) |
N2—C10 | 1.345 (4) | C9—H9A | 0.9300 |
N3—C15 | 1.336 (4) | C10—C11 | 1.476 (5) |
N3—C11 | 1.354 (4) | C11—C12 | 1.384 (5) |
C2—C3 | 1.516 (5) | C12—C13 | 1.371 (5) |
C2—H2A | 0.9700 | C12—H12A | 0.9300 |
C2—H2B | 0.9700 | C13—C14 | 1.377 (6) |
C3—C4 | 1.495 (7) | C13—H13A | 0.9300 |
C3—H3A | 0.9700 | C14—C15 | 1.375 (5) |
C3—H3B | 0.9700 | C14—H14A | 0.9300 |
C4—C5 | 1.511 (5) | C15—H15A | 0.9300 |
N3—Cu1—N2 | 80.44 (12) | C3—C4—H4B | 110.5 |
N3—Cu1—S1 | 165.74 (8) | C5—C4—H4B | 110.5 |
N2—Cu1—S1 | 99.36 (9) | H4A—C4—H4B | 108.7 |
N3—Cu1—S2 | 98.11 (9) | N1—C5—C4 | 103.4 (3) |
N2—Cu1—S2 | 158.17 (8) | N1—C5—H5A | 111.1 |
S1—Cu1—S2 | 76.71 (4) | C4—C5—H5A | 111.1 |
N3—Cu1—I1 | 91.12 (8) | N1—C5—H5B | 111.1 |
N2—Cu1—I1 | 97.42 (8) | C4—C5—H5B | 111.1 |
S1—Cu1—I1 | 103.02 (4) | H5A—C5—H5B | 109.0 |
S2—Cu1—I1 | 104.39 (4) | N2—C6—C7 | 122.9 (4) |
C1—S1—Cu1 | 84.31 (12) | N2—C6—H6A | 118.6 |
C1—S2—Cu1 | 84.01 (12) | C7—C6—H6A | 118.6 |
C1—N1—C2 | 124.5 (3) | C8—C7—C6 | 118.2 (4) |
C1—N1—C5 | 123.1 (3) | C8—C7—H7A | 120.9 |
C2—N1—C5 | 112.3 (3) | C6—C7—H7A | 120.9 |
C6—N2—C10 | 118.6 (3) | C7—C8—C9 | 119.7 (4) |
C6—N2—Cu1 | 126.6 (3) | C7—C8—H8A | 120.2 |
C10—N2—Cu1 | 114.8 (2) | C9—C8—H8A | 120.2 |
C15—N3—C11 | 118.7 (3) | C8—C9—C10 | 119.7 (4) |
C15—N3—Cu1 | 126.0 (2) | C8—C9—H9A | 120.2 |
C11—N3—Cu1 | 115.1 (2) | C10—C9—H9A | 120.2 |
N1—C1—S2 | 122.8 (3) | N2—C10—C9 | 121.0 (4) |
N1—C1—S1 | 122.4 (3) | N2—C10—C11 | 114.8 (3) |
S2—C1—S1 | 114.70 (19) | C9—C10—C11 | 124.1 (3) |
N1—C2—C3 | 103.5 (3) | N3—C11—C12 | 120.8 (3) |
N1—C2—H2A | 111.1 | N3—C11—C10 | 114.8 (3) |
C3—C2—H2A | 111.1 | C12—C11—C10 | 124.4 (3) |
N1—C2—H2B | 111.1 | C13—C12—C11 | 119.8 (3) |
C3—C2—H2B | 111.1 | C13—C12—H12A | 120.1 |
H2A—C2—H2B | 109.0 | C11—C12—H12A | 120.1 |
C4—C3—C2 | 105.0 (4) | C12—C13—C14 | 119.3 (4) |
C4—C3—H3A | 110.8 | C12—C13—H13A | 120.3 |
C2—C3—H3A | 110.8 | C14—C13—H13A | 120.3 |
C4—C3—H3B | 110.8 | C15—C14—C13 | 118.5 (4) |
C2—C3—H3B | 110.8 | C15—C14—H14A | 120.7 |
H3A—C3—H3B | 108.8 | C13—C14—H14A | 120.7 |
C3—C4—C5 | 105.9 (4) | N3—C15—C14 | 122.8 (4) |
C3—C4—H4A | 110.5 | N3—C15—H15A | 118.6 |
C5—C4—H4A | 110.5 | C14—C15—H15A | 118.6 |
Experimental details
Crystal data | |
Chemical formula | [Cu(C5H8NS2)I(C10H8N2)] |
Mr | 492.87 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.606 (3), 16.212 (8), 16.405 (8) |
β (°) | 98.399 (10) |
V (Å3) | 1738.3 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.27 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury CCD diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2000) |
Tmin, Tmax | 0.722, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13239, 3983, 3326 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.085, 1.07 |
No. of reflections | 3983 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.63 |
Computer programs: CrystalClear (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
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
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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).