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Acta Cryst. (2007). E63, m2172    [ doi:10.1107/S1600536807026189 ]

Tetra-[mu]-acetato-[kappa]8O:O'-bis{[2-(phenylsulfanylmethyl)pyridine-[kappa]N]copper(II)}

H. Wang, H. Wang, C. Xie, L.-N. Zhou and W. Chen

Abstract top

The title compound, [Cu2(C2H3O2)4(C12H11NS)2], is a centrosymmetric dimer. The Cu centre presents a CuO4N square-pyramidal geometry arising from four syn-syn bridging acetate anions and a 2-(phenylsulfanylmethyl)pyridine ligand N-coordinated in the apical position. The Cu...Cu separation is 2.6309 (6) Å.

Comment top

In the preparation of CuII complex with the ligand, 2-(phenylsulfanyl)methylpyridine (L), we obtained the title compound, (I), (Fig. 1).

The complex consists of a centrosymmetric dicopper(II) core with four acetate anions bridging the two copper atoms and two monodentate L ligands. The intradimer Cu···Cui (i = -x, 1 - y, -z) distance is 2.6309 (6) Å, which is similar to that (2.63 Å) in [Cu(O2CPh)2(DMF)]2 (Del Sesto et al., 2000). The copper ion in (I) presents a nearly square pyramidal geometry with four oxygen atoms in a plane, at a mean distance of 1.971 (2) Å. The axial site is occupied by the pyridine N atom of a ligand molecule at 2.232 (2) Å. The CuII ion is displaced from the basal plane towards the apical N atom by 0.199 (2) A. The L ligand takes a gauche conformation with a C6—S1—C7—C8 torsion angle of 76.8 (2)° between the two aryl groups.

Related literature top

For a related structure and background, see: Del Sesto et al. (2000).

Experimental top

Thiophenol (630 mg, 5.7 mmol) was added to a stirred solution of KOH (320 mg, 5.7 mmol) in ethanol (30 ml). The mixture was refluxed for 30 min and a solution of 2-bromomethylpyridine (986 mg, 5.7 mmol) in ethanol (25 ml) was slowly added to it. The mixture was refluxed for 4 h more. The KBr precipitate was filtered off, and the filtrate was washed by water and evaporated to obtain ligand L as a brown oil in 40% yield. A solution (5.0 ml) of Cu(OAc)2 (0.1 mmol) and L (0.2 mmol) in methanol/chloroform (1:1 v/v) was stirred for 30 min at room temperature, and then filtered. Green single crystals of (I) were obtained from the filtrate.

Refinement top

The H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CrystalStructure (Rigaku, 2004).

Figures top
[Figure 1] Fig. 1. View of (I) with 30% probability displacement ellipsoids (arbitrary spheres of H atoms). Symmetry code: (i) -x, 1 - y, -z.
Tetra-µ-acetato-κ8O:O'-bis{[2-(phenylsulfanylmethyl)pyridine-κN]copper(II)} top
Crystal data top
[Cu2(C2H3O2)4(C12H11NS)2]Z = 1
Mr = 765.85F(000) = 394
Triclinic, P1Dx = 1.551 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.7587 (16) ÅCell parameters from 7557 reflections
b = 7.9690 (16) Åθ = 3.1–27.5°
c = 13.986 (3) ŵ = 1.48 mm−1
α = 102.51 (3)°T = 293 K
β = 101.86 (2)°Block, green
γ = 94.29 (3)°0.34 × 0.33 × 0.30 mm
V = 819.7 (3) Å3
Data collection top
Rigaku R-AXIS RAPID IP area-detector
diffractometer		3029 independent reflections
Radiation source: rotating anode2859 reflections with I > 2σ(I)
graphiteRint = 0.029
ω scansθmax = 25.5°, θmin = 3.1°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −9→9
Tmin = 0.622, Tmax = 0.652k = −9→8
6775 measured reflectionsl = −16→16
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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0382P)2 + 0.5716P]
where P = (Fo2 + 2Fc2)/3
3029 reflections(Δ/σ)max = 0.001
208 parametersΔρmax = 0.41 e Å−3
0 restraintsΔρmin = −0.37 e Å−3
Crystal data top
[Cu2(C2H3O2)4(C12H11NS)2]γ = 94.29 (3)°
Mr = 765.85V = 819.7 (3) Å3
Triclinic, P1Z = 1
a = 7.7587 (16) ÅMo Kα radiation
b = 7.9690 (16) ŵ = 1.48 mm−1
c = 13.986 (3) ÅT = 293 K
α = 102.51 (3)°0.34 × 0.33 × 0.30 mm
β = 101.86 (2)°
Data collection top
Rigaku R-AXIS RAPID IP area-detector
diffractometer		3029 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2859 reflections with I > 2σ(I)
Tmin = 0.622, Tmax = 0.652Rint = 0.029
6775 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.078Δρmax = 0.41 e Å−3
S = 1.05Δρmin = −0.37 e Å−3
3029 reflectionsAbsolute structure: ?
208 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
S10.15681 (7)1.02827 (7)0.41049 (4)0.02382 (14)
N10.3502 (2)0.7760 (2)0.18067 (12)0.0167 (3)
Cu10.12181 (3)0.60867 (3)0.069933 (16)0.01511 (10)
O1−0.0394 (2)0.78294 (19)0.04802 (11)0.0230 (3)
O2−0.2453 (2)0.59886 (19)−0.07185 (12)0.0271 (4)
O3−0.0150 (2)0.5378 (2)0.16144 (11)0.0245 (3)
O4−0.2209 (2)0.3513 (2)0.04359 (11)0.0259 (3)
C10.2586 (3)1.3074 (3)0.33349 (17)0.0296 (5)
H1A0.25901.22890.27370.036*
C20.3046 (4)1.4820 (3)0.34379 (19)0.0377 (6)
H2A0.33541.52050.29060.045*
C30.3055 (4)1.5996 (3)0.4319 (2)0.0416 (6)
H3A0.33861.71700.43880.050*
C40.2570 (5)1.5422 (4)0.5097 (2)0.0471 (7)
H4A0.25581.62160.56900.057*
C50.2101 (4)1.3675 (3)0.50064 (19)0.0375 (6)
H5A0.17761.32980.55360.045*
C60.2118 (3)1.2487 (3)0.41206 (16)0.0236 (5)
C70.1672 (3)0.9108 (3)0.28692 (15)0.0213 (4)
H7A0.10120.79680.27380.026*
H7B0.10660.96970.23850.026*
C80.3503 (3)0.8875 (3)0.26746 (15)0.0168 (4)
C90.5058 (3)0.9744 (3)0.33319 (16)0.0236 (5)
H9A0.50221.05130.39290.028*
C100.6667 (3)0.9446 (3)0.30849 (17)0.0275 (5)
H10A0.77271.00070.35170.033*
C110.6675 (3)0.8307 (3)0.21884 (18)0.0268 (5)
H11A0.77370.80970.20020.032*
C120.5073 (3)0.7486 (3)0.15746 (16)0.0224 (4)
H12A0.50800.67100.09740.027*
C13−0.1833 (3)0.7472 (3)−0.01779 (15)0.0185 (4)
C14−0.2888 (3)0.8945 (3)−0.03217 (19)0.0287 (5)
H14A−0.23220.99830.01670.043*
H14B−0.40670.8675−0.02380.043*
H14C−0.29480.9117−0.09860.043*
C15−0.1492 (3)0.4248 (3)0.13311 (15)0.0201 (4)
C16−0.2312 (4)0.3755 (3)0.21380 (18)0.0355 (6)
H16A−0.32400.28080.18370.053*
H16B−0.27960.47300.24710.053*
H16C−0.14190.34120.26180.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0221 (3)0.0269 (3)0.0200 (3)−0.0009 (2)0.0070 (2)−0.0002 (2)
N10.0151 (8)0.0168 (8)0.0174 (8)0.0000 (6)0.0027 (6)0.0037 (7)
Cu10.01397 (14)0.01466 (15)0.01485 (14)−0.00007 (9)0.00168 (9)0.00172 (10)
O10.0225 (8)0.0181 (7)0.0248 (8)0.0029 (6)0.0003 (6)0.0020 (6)
O20.0206 (8)0.0187 (8)0.0350 (9)0.0029 (6)−0.0038 (6)0.0006 (7)
O30.0280 (8)0.0255 (8)0.0175 (7)−0.0063 (6)0.0046 (6)0.0036 (6)
O40.0232 (8)0.0316 (9)0.0193 (7)−0.0075 (6)0.0058 (6)0.0011 (6)
C10.0370 (13)0.0312 (13)0.0189 (10)0.0094 (10)0.0038 (9)0.0031 (9)
C20.0503 (16)0.0350 (14)0.0304 (13)0.0098 (12)0.0052 (11)0.0156 (11)
C30.0603 (18)0.0260 (13)0.0348 (14)0.0091 (12)0.0001 (12)0.0083 (11)
C40.081 (2)0.0278 (14)0.0295 (13)0.0116 (13)0.0139 (14)−0.0016 (11)
C50.0564 (17)0.0329 (13)0.0252 (12)0.0099 (12)0.0141 (11)0.0049 (11)
C60.0198 (10)0.0258 (11)0.0218 (10)0.0062 (8)0.0000 (8)0.0020 (9)
C70.0146 (10)0.0241 (11)0.0201 (10)−0.0004 (8)0.0025 (8)−0.0037 (8)
C80.0144 (9)0.0170 (10)0.0177 (9)−0.0007 (7)0.0021 (7)0.0042 (8)
C90.0191 (10)0.0262 (11)0.0196 (10)0.0005 (8)0.0005 (8)−0.0026 (9)
C100.0134 (10)0.0337 (13)0.0296 (12)−0.0013 (9)−0.0013 (8)0.0021 (10)
C110.0147 (10)0.0329 (12)0.0315 (12)0.0028 (9)0.0060 (9)0.0040 (10)
C120.0177 (10)0.0248 (11)0.0233 (10)0.0024 (8)0.0050 (8)0.0023 (9)
C130.0186 (10)0.0187 (10)0.0214 (10)0.0041 (8)0.0091 (8)0.0067 (8)
C140.0270 (12)0.0231 (11)0.0358 (12)0.0074 (9)0.0037 (10)0.0088 (10)
C150.0235 (11)0.0178 (10)0.0209 (10)0.0040 (8)0.0081 (8)0.0054 (8)
C160.0446 (15)0.0380 (14)0.0252 (12)−0.0083 (11)0.0165 (11)0.0065 (10)
Geometric parameters (Å, °) top
S1—C61.771 (2)C4—C51.384 (4)
S1—C71.799 (2)C4—H4A0.9300
N1—C81.340 (3)C5—C61.390 (3)
N1—C121.345 (3)C5—H5A0.9300
Cu1—O31.9663 (15)C7—C81.517 (3)
Cu1—O11.9680 (16)C7—H7A0.9700
Cu1—N12.2227 (19)C7—H7B0.9700
Cu1—O4i1.9743 (16)C8—C91.387 (3)
Cu1—O2i1.9746 (16)C9—C101.385 (3)
Cu1—Cu1i2.6309 (13)C9—H9A0.9300
O1—C131.262 (3)C10—C111.381 (3)
O2—C131.257 (3)C10—H10A0.9300
O2—Cu1i1.9746 (16)C11—C121.381 (3)
O3—C151.260 (3)C11—H11A0.9300
O4—C151.252 (3)C12—H12A0.9300
O4—Cu1i1.9743 (16)C13—C141.505 (3)
C1—C21.379 (4)C14—H14A0.9600
C1—C61.385 (3)C14—H14B0.9600
C1—H1A0.9300C14—H14C0.9600
C2—C31.376 (4)C15—C161.511 (3)
C2—H2A0.9300C16—H16A0.9600
C3—C41.376 (4)C16—H16B0.9600
C3—H3A0.9300C16—H16C0.9600
C6—S1—C7104.84 (11)C1—C6—S1124.78 (17)
C8—N1—C12118.22 (17)C8—C7—S1117.10 (14)
C8—N1—Cu1128.57 (13)C8—C7—H7A108.0
C12—N1—Cu1113.04 (13)S1—C7—H7A108.0
O3—Cu1—O189.29 (7)C8—C7—H7B108.0
O3—Cu1—O4i168.33 (6)S1—C7—H7B108.0
O1—Cu1—O4i89.15 (7)H7A—C7—H7B107.3
O3—Cu1—O2i88.87 (7)N1—C8—C9122.23 (18)
O1—Cu1—O2i168.47 (6)N1—C8—C7114.47 (17)
O4i—Cu1—O2i90.36 (8)C9—C8—C7123.30 (18)
O3—Cu1—N1100.28 (6)C10—C9—C8118.96 (19)
O1—Cu1—N1100.09 (7)C10—C9—H9A120.5
O4i—Cu1—N191.38 (6)C8—C9—H9A120.5
O2i—Cu1—N191.44 (7)C11—C10—C9119.1 (2)
O3—Cu1—Cu1i83.62 (5)C11—C10—H10A120.4
O1—Cu1—Cu1i85.08 (5)C9—C10—H10A120.4
O4i—Cu1—Cu1i84.73 (5)C12—C11—C10118.6 (2)
O2i—Cu1—Cu1i83.41 (5)C12—C11—H11A120.7
N1—Cu1—Cu1i173.51 (5)C10—C11—H11A120.7
C13—O1—Cu1122.22 (14)N1—C12—C11122.9 (2)
C13—O2—Cu1i124.00 (14)N1—C12—H12A118.6
C15—O3—Cu1123.84 (14)C11—C12—H12A118.6
C15—O4—Cu1i122.33 (14)O2—C13—O1125.2 (2)
C2—C1—C6120.1 (2)O2—C13—C14117.68 (19)
C2—C1—H1A120.0O1—C13—C14117.14 (19)
C6—C1—H1A120.0C13—C14—H14A109.5
C1—C2—C3120.7 (2)C13—C14—H14B109.5
C1—C2—H2A119.7H14A—C14—H14B109.5
C3—C2—H2A119.7C13—C14—H14C109.5
C4—C3—C2119.5 (3)H14A—C14—H14C109.5
C4—C3—H3A120.3H14B—C14—H14C109.5
C2—C3—H3A120.3O4—C15—O3125.3 (2)
C3—C4—C5120.7 (2)O4—C15—C16117.43 (19)
C3—C4—H4A119.7O3—C15—C16117.25 (19)
C5—C4—H4A119.7C15—C16—H16A109.5
C4—C5—C6119.7 (2)C15—C16—H16B109.5
C4—C5—H5A120.1H16A—C16—H16B109.5
C6—C5—H5A120.1C15—C16—H16C109.5
C5—C6—C1119.4 (2)H16A—C16—H16C109.5
C5—C6—S1115.81 (19)H16B—C16—H16C109.5
C8—N1—Cu1—O3−38.69 (18)C2—C1—C6—S1−177.9 (2)
C12—N1—Cu1—O3136.51 (15)C7—S1—C6—C5179.03 (18)
C8—N1—Cu1—O152.42 (18)C7—S1—C6—C1−2.4 (2)
C12—N1—Cu1—O1−132.38 (15)C6—S1—C7—C876.80 (19)
C8—N1—Cu1—O4i141.80 (18)C12—N1—C8—C90.0 (3)
C12—N1—Cu1—O4i−43.00 (16)Cu1—N1—C8—C9175.01 (15)
C8—N1—Cu1—O2i−127.81 (18)C12—N1—C8—C7179.67 (19)
C12—N1—Cu1—O2i47.39 (16)Cu1—N1—C8—C7−5.3 (3)
O3—Cu1—O1—C13−86.13 (16)S1—C7—C8—N1169.58 (15)
O4i—Cu1—O1—C1382.31 (16)S1—C7—C8—C9−10.8 (3)
O2i—Cu1—O1—C13−5.3 (4)N1—C8—C9—C10−0.2 (3)
N1—Cu1—O1—C13173.56 (15)C7—C8—C9—C10−179.8 (2)
Cu1i—Cu1—O1—C13−2.47 (15)C8—C9—C10—C110.6 (4)
O1—Cu1—O3—C1588.00 (18)C9—C10—C11—C12−0.8 (4)
O4i—Cu1—O3—C155.7 (4)C8—N1—C12—C11−0.3 (3)
O2i—Cu1—O3—C15−80.62 (18)Cu1—N1—C12—C11−176.01 (18)
N1—Cu1—O3—C15−171.88 (17)C10—C11—C12—N10.7 (4)
Cu1i—Cu1—O3—C152.87 (17)Cu1i—O2—C13—O1−3.6 (3)
C6—C1—C2—C30.3 (4)Cu1i—O2—C13—C14176.56 (15)
C1—C2—C3—C4−1.1 (4)Cu1—O1—C13—O24.3 (3)
C2—C3—C4—C50.9 (5)Cu1—O1—C13—C14−175.83 (14)
C3—C4—C5—C60.0 (5)Cu1i—O4—C15—O34.3 (3)
C4—C5—C6—C1−0.7 (4)Cu1i—O4—C15—C16−176.35 (16)
C4—C5—C6—S1177.9 (2)Cu1—O3—C15—O4−5.1 (3)
C2—C1—C6—C50.6 (4)Cu1—O3—C15—C16175.48 (16)
Symmetry codes: (i) −x, −y+1, −z.
Table 1
Selected geometric parameters (Å) top
Cu1—O31.9663 (15)Cu1—N12.2227 (19)
Cu1—O11.9680 (16)
Acknowledgements top

The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (grant No. 20576089) and from Tianjin Natural Science Foundation (grant Nos. 05YFJZJC02000 and 05YFGHHZ01100).

references
References top

Del Sesto, R. E., Arif, A. M. & Miller, J. S. (2000). Inorg. Chem. 39, 4894–4902.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.

Rigaku (2004). RAPID-AUTO and CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

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