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Acta Cryst. (2007). E63, m2314    [ doi:10.1107/S160053680703913X ]

catena-Poly[copper(I)-di-[mu]-chlorido-copper(I)-bis[[mu]-bis(pyrimidin-2-ylsulfanyl)methane-[kappa]2N:N']]

W.-J. Shi and Z.-Q. Gong

Abstract top

The flexible heterocyclic thioether ligand bis(pyrimidin-2-ylsulfanyl)methane in the centrosymmetric title compound, [Cu2Cl2(C9H8N4S2)2]n, links Cu2Cl2 dimers into a chain. The chains are linked into a three-dimensional network through C-H...Cl hydrogen bonds. The CuI atom is in a slightly distorted tetrahedral coordination environment.

Comment top

Heterocyclic flexible thioethers containing nitrogen and sulfur donors have attracted much attention because of the flexibility and conformational freedoms. Previously, a series of flexible thioethers were designed, and the investigations on the formation of Ag(I) complexes with these ligands have been reported (Bu et al., 2003; Hong et al., 2000; Zheng et al., 2003; Zheng et al., 2005), while those on the CuI complexes with heterocyclic flexible thioether ligands were much more sporadic (Peng et al., 2006; Song et al., 2005).

In the title compound, 1, Fig. 1, two chloride ions are each bound to two symmetry related CuI centers forming a Cu2Cl2 core. Within these cores the CuI centres are separated by a distance of 2.991 (3) Å. The dihedral angle between the two pyrimidyl rings is 83.9 (2) °, with interplanar angles between the S1—C1—S2 plane and the N1 and N3 pyrimidyl rings of the ligand 106.5 (2) ° and 73 (1) °, respectively.

There are weak intermolecular C—H···Cl interactions in the adjacent chain, furnishing a three-dimensional supramolecular array (Fig. 2).

Related literature top

For details of metal complexes of bis(pyrimidin-2-ylsulfanyl)methane, see: Hou et al. (2005); Zheng et al. (2003). For complexes of other flexible thioether ligands, see: Bu et al. (2003); Hong et al. (2000); Zheng et al. (2005). For those with heterocyclic components, see: Peng et al. (2006); Song et al. (2005).

For synthesis, see: Xu et al. (1997).

Experimental top

The ligand bis(pyrimidin-2-ylsulfanyl)methane was synthesized according to the reported procedure (Xu et al., 1997). Equimolar quantities (0.05 mmol) of solid CuCl (5.0 mg) was added to MeCN solution (7 ml) of the ligand (12.0 mg), the mixture was stirred until a small amount of precipitate was formed. The precipitate was filtered off, and the filtrate was allowed to stand at room temperature for two weeks, well shaped yellow crystals were obtained. Yield: 5.0 mg (30%).

Refinement top

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic and 0.97 Å, Uiso = 1.2Ueq (C) for CH2 atoms.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level, Only the asymmetric unit and one of the symmetry related copper atoms are labelled. [symmetry code: (I) 3/2 − x, 1/2 − y, 1 − z].
[Figure 2] Fig. 2. A view of title compound, showing the extended three-dimensional structure linked by C—H····Cl hydrogen interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level, and H atoms are drawn as spheres of arbitrary radii.
catena-Poly[copper(I)-di-µ-chlorido-copper(I)- bis[µ-bis(pyrimidin-2-ylsulfanyl)methane-κ2N:N']] top
Crystal data top
[Cu2Cl2(C9H8N4S2)2]F000 = 1344
Mr = 670.61Dx = 1.775 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1888 reflections
a = 12.3432 (13) Åθ = 2.5–23.6º
b = 13.2611 (14) ŵ = 2.27 mm−1
c = 15.5179 (17) ÅT = 293 (2) K
β = 98.992 (2)ºBlock, yellow
V = 2508.8 (5) Å30.20 × 0.18 × 0.15 mm
Z = 4
Data collection top
Bruker APEX area-detector
diffractometer		2422 independent reflections
Radiation source: fine-focus sealed tube2032 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.029
T = 293(2) Kθmax = 26.0º
φ and ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→13
Tmin = 0.660, Tmax = 0.727k = −16→16
6900 measured reflectionsl = −19→16
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)] = 0.041H-atom parameters constrained
wR(F2) = 0.101  w = 1/[σ2(Fo2) + (0.0493P)2 + 1.7815P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2422 reflectionsΔρmax = 0.53 e Å−3
154 parametersΔρmin = −0.32 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2Cl2(C9H8N4S2)2]V = 2508.8 (5) Å3
Mr = 670.61Z = 4
Monoclinic, C2/cMo Kα
a = 12.3432 (13) ŵ = 2.27 mm−1
b = 13.2611 (14) ÅT = 293 (2) K
c = 15.5179 (17) Å0.20 × 0.18 × 0.15 mm
β = 98.992 (2)º
Data collection top
Bruker APEX area-detector
diffractometer		2422 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2032 reflections with I > 2σ(I)
Tmin = 0.660, Tmax = 0.727Rint = 0.029
6900 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041154 parameters
wR(F2) = 0.101H-atom parameters constrained
S = 1.06Δρmax = 0.53 e Å−3
2422 reflectionsΔρmin = −0.32 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
Cu10.67661 (3)0.25183 (3)0.56808 (3)0.04173 (17)
S10.71478 (8)0.24875 (6)0.77139 (6)0.0457 (2)
Cl10.63766 (7)0.19728 (7)0.42107 (5)0.0492 (3)
N10.6667 (2)0.12565 (17)0.64085 (16)0.0339 (6)
C40.6342 (3)0.0371 (2)0.6037 (2)0.0403 (8)
H40.62620.03130.54330.048*
S20.57245 (7)0.22466 (6)0.91426 (6)0.0427 (2)
C30.6125 (3)−0.0448 (2)0.6519 (2)0.0462 (9)
H30.5881−0.10550.62560.055*
N20.6603 (2)0.0539 (2)0.78057 (18)0.0431 (7)
C20.6283 (3)−0.0331 (2)0.7404 (2)0.0487 (9)
H20.6163−0.08830.77470.058*
N30.6021 (2)0.4215 (2)0.8873 (2)0.0495 (7)
N40.4249 (2)0.36602 (19)0.90977 (16)0.0347 (6)
C10.6763 (2)0.1290 (2)0.7280 (2)0.0335 (7)
C50.7080 (3)0.2308 (3)0.8853 (2)0.0419 (8)
H5B0.74730.28570.91770.050*
H5A0.74630.16880.90420.050*
C60.5306 (3)0.3511 (2)0.9025 (2)0.0372 (7)
C70.3891 (3)0.4610 (2)0.8990 (2)0.0440 (8)
H70.31650.47500.90400.053*
C80.4552 (3)0.5384 (3)0.8808 (3)0.0555 (10)
H80.42860.60370.87160.067*
C90.5628 (3)0.5152 (3)0.8768 (3)0.0580 (10)
H90.61010.56680.86650.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0473 (3)0.0431 (3)0.0374 (3)−0.00333 (17)0.0148 (2)0.00048 (16)
S10.0600 (6)0.0452 (5)0.0334 (5)−0.0081 (4)0.0119 (4)−0.0025 (3)
Cl10.0425 (5)0.0745 (6)0.0324 (4)−0.0175 (4)0.0111 (4)−0.0133 (4)
N10.0332 (14)0.0363 (13)0.0333 (14)−0.0018 (10)0.0089 (11)0.0012 (11)
C40.0369 (18)0.0428 (18)0.0419 (19)0.0027 (14)0.0082 (15)−0.0042 (14)
S20.0347 (5)0.0452 (5)0.0500 (5)0.0051 (3)0.0119 (4)0.0040 (4)
C30.048 (2)0.0329 (17)0.058 (2)−0.0022 (14)0.0113 (18)−0.0005 (15)
N20.0436 (16)0.0449 (15)0.0419 (16)0.0064 (12)0.0099 (13)0.0107 (12)
C20.049 (2)0.0370 (18)0.062 (3)0.0052 (15)0.0137 (18)0.0173 (16)
N30.0385 (16)0.0484 (17)0.065 (2)−0.0026 (13)0.0179 (15)−0.0011 (14)
N40.0308 (14)0.0413 (14)0.0326 (14)0.0009 (11)0.0064 (11)−0.0012 (11)
C10.0253 (15)0.0404 (16)0.0357 (18)0.0039 (12)0.0077 (13)0.0033 (13)
C50.0334 (18)0.057 (2)0.0353 (18)0.0070 (14)0.0064 (14)−0.0054 (15)
C60.0362 (18)0.0459 (18)0.0303 (16)−0.0006 (14)0.0074 (14)−0.0042 (13)
C70.0339 (18)0.051 (2)0.049 (2)0.0063 (15)0.0096 (16)0.0011 (16)
C80.054 (2)0.0432 (19)0.070 (3)0.0049 (17)0.0126 (19)0.0068 (18)
C90.051 (2)0.051 (2)0.075 (3)−0.0079 (17)0.020 (2)0.0051 (19)
Geometric parameters (Å, °) top
Cu1—N4i2.029 (3)N2—C11.322 (4)
Cu1—N12.033 (2)N2—C21.341 (4)
Cu1—Cl12.3698 (9)C2—H20.9300
Cu1—Cl1ii2.3704 (10)N3—C61.331 (4)
Cu1—Cu1ii2.9909 (9)N3—C91.334 (4)
S1—C11.760 (3)N4—C71.337 (4)
S1—C51.799 (3)N4—C61.343 (4)
Cl1—Cu1ii2.3704 (10)N4—Cu1i2.029 (3)
N1—C11.339 (4)C5—H5B0.9700
N1—C41.341 (4)C5—H5A0.9700
C4—C31.369 (4)C7—C81.368 (5)
C4—H40.9300C7—H70.9300
S2—C61.755 (3)C8—C91.373 (5)
S2—C51.801 (3)C8—H80.9300
C3—C21.367 (5)C9—H90.9300
C3—H30.9300
N4i—Cu1—N1115.34 (10)C6—N3—C9115.9 (3)
N4i—Cu1—Cl1110.69 (7)C7—N4—C6115.8 (3)
N1—Cu1—Cl1105.24 (7)C7—N4—Cu1i121.6 (2)
N4i—Cu1—Cl1ii113.04 (7)C6—N4—Cu1i122.6 (2)
N1—Cu1—Cl1ii109.65 (7)N2—C1—N1126.9 (3)
Cl1—Cu1—Cl1ii101.76 (3)N2—C1—S1120.0 (2)
N4i—Cu1—Cu1ii126.16 (7)N1—C1—S1113.1 (2)
N1—Cu1—Cu1ii118.34 (7)S1—C5—S2116.02 (18)
Cl1—Cu1—Cu1ii50.89 (2)S1—C5—H5B108.3
Cl1ii—Cu1—Cu1ii50.87 (2)S2—C5—H5B108.3
C1—S1—C5101.88 (15)S1—C5—H5A108.3
Cu1—Cl1—Cu1ii78.24 (3)S2—C5—H5A108.3
C1—N1—C4115.9 (3)H5B—C5—H5A107.4
C1—N1—Cu1121.97 (19)N3—C6—N4126.3 (3)
C4—N1—Cu1121.4 (2)N3—C6—S2119.8 (2)
N1—C4—C3122.1 (3)N4—C6—S2114.0 (2)
N1—C4—H4118.9N4—C7—C8122.5 (3)
C3—C4—H4118.9N4—C7—H7118.8
C6—S2—C5101.55 (15)C8—C7—H7118.8
C2—C3—C4116.6 (3)C7—C8—C9117.0 (3)
C2—C3—H3121.7C7—C8—H8121.5
C4—C3—H3121.7C9—C8—H8121.5
C1—N2—C2115.0 (3)N3—C9—C8122.6 (3)
N2—C2—C3123.4 (3)N3—C9—H9118.7
N2—C2—H2118.3C8—C9—H9118.7
C3—C2—H2118.3
N4i—Cu1—Cl1—Cu1ii120.39 (8)C4—N1—C1—S1−178.0 (2)
N1—Cu1—Cl1—Cu1ii−114.37 (8)Cu1—N1—C1—S1−7.5 (3)
Cl1ii—Cu1—Cl1—Cu1ii0.0C5—S1—C1—N2−5.1 (3)
N4i—Cu1—N1—C1−52.8 (2)C5—S1—C1—N1175.0 (2)
Cl1—Cu1—N1—C1−175.1 (2)C1—S1—C5—S2−74.1 (2)
Cl1ii—Cu1—N1—C176.1 (2)C6—S2—C5—S1−72.9 (2)
Cu1ii—Cu1—N1—C1131.5 (2)C9—N3—C6—N4−1.3 (5)
N4i—Cu1—N1—C4117.2 (2)C9—N3—C6—S2178.2 (3)
Cl1—Cu1—N1—C4−5.1 (2)C7—N4—C6—N31.2 (5)
Cl1ii—Cu1—N1—C4−113.9 (2)Cu1i—N4—C6—N3179.4 (3)
Cu1ii—Cu1—N1—C4−58.5 (2)C7—N4—C6—S2−178.4 (2)
C1—N1—C4—C3−0.2 (4)Cu1i—N4—C6—S2−0.2 (3)
Cu1—N1—C4—C3−170.7 (2)C5—S2—C6—N3−7.6 (3)
N1—C4—C3—C2−1.7 (5)C5—S2—C6—N4172.0 (2)
C1—N2—C2—C3−0.3 (5)C6—N4—C7—C80.6 (5)
C4—C3—C2—N22.0 (5)Cu1i—N4—C7—C8−177.5 (3)
C2—N2—C1—N1−1.9 (5)N4—C7—C8—C9−2.2 (6)
C2—N2—C1—S1178.2 (2)C6—N3—C9—C8−0.4 (6)
C4—N1—C1—N22.1 (4)C7—C8—C9—N32.1 (6)
Cu1—N1—C1—N2172.6 (2)
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+3/2, −y+1/2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl1iii0.932.673.537 (4)155
Symmetry codes: (iii) x, −y, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl1i0.932.673.537 (4)155
Symmetry codes: (i) x, −y, z+1/2.
Acknowledgements top

We thank Jiangxi Science and Technology Normal University for supporting this study.

references
References top

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