Tetra-μ-acetato-bis-[(1,3-benzothia-zole)copper(II)](Cu-Cu).

The title compound, [Cu(2)(CH(3)CO(2))(4)(C(7)H(5)NS)(2)] or [(C(7)H(5)NS)Cu](2)(μ-O(2)CCH(3))(4), crystallizes with one mol-ecule per unit cell. The coordination number of copper is six with four basal O atoms, one axial N atom and one axial Cu atom. Four acetate ligands act as bidentate linker and connect two Cu atoms, with a crystallographic inversion center located at the mid-point of the Cu-Cu bond. The acetate ligands form slightly distorted square planes around each metal ion, while the copper ions are displaced by 0.2089 (4) Å from these planes towards the N atoms. Thus, the Cu-Cu distance is elongated to 2.6378 (7) Å, compared with the 2.2180 (7) Å distance between the two basal planes. The angle between the basal plane and the Cu-N bond is 4.84 (6)°.

Related literature

The structural prototype of (LCu)2(μ-O2CCH3)4 complexes is the crystal structure of n class="Chemical">cupric acetate monohydrate (L = water), see: Van Niekerk & Schoening (1953 ▶); Ferguson & Glidewell (2003 ▶). For similar structures with L = benzimidazole, see: Bukowska-Strzyżewska et al. (1982) ▶ and L = 2-amino-benzothia­zole, see: Sun et al. (2007 ▶). For theoretical studies see: Rodríguez-Fortea et al. (2001) ▶ and for magnetic properties of dinuclear copper complexes, see: Tokii & Muto (1983 ▶). For FIR spectroscopic data and the magnetic moment of the complex with L = benzothia­zole, see: Ford et al. (1968 ▶).

Experimental

Crystal data

[Cu2(C2H3O2)4(C7H5NS)2]

M = 633.66

Triclinic,

a = 7.185 (1) Å

b = 8.1918 (12) Å

c = 11.8265 (16) Å

α = 106.516 (16)°

β = 106.429 (16)°

γ = 97.344 (17)°

V = 623.49 (18) Å3

Z = 1

Mo Kα radiation

μ = 1.92 mm−1

T = 293 K

0.3 × 0.2 × 0.1 mm

Data collection

Stoe IPDS I diffractometer

Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1999 ▶) T min = 0.575, T max = 0.840

7525 measured reflections

2784 independent reflections

2092 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.075

S = 0.97

2784 reflections

165 parameters

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.45 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2011 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811027140/hg5042sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027140/hg5042Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu2(C2H3O2)4(C7H5NS)2]	Z = 1
Mr = 633.66	F(000) = 322
Triclinic, P1	Dx = 1.688 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.185 (1) Å	Cell parameters from 1512 reflections
b = 8.1918 (12) Å	θ = 3.8–56.3°
c = 11.8265 (16) Å	µ = 1.92 mm−1
α = 106.516 (16)°	T = 293 K
β = 106.429 (16)°	Plate, green
γ = 97.344 (17)°	0.3 × 0.2 × 0.1 mm
V = 623.49 (18) Å3

Stoe IPDS I diffractometer	2784 independent reflections
Radiation source: fine-focus sealed tube	2092 reflections with I > 2σ(I)
graphite	Rint = 0.038
Detector resolution: 0 pixels mm-1	θmax = 28.1°, θmin = 2.7°
Oscillation scans	h = −8→8
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1999)	k = −10→10
Tmin = 0.575, Tmax = 0.840	l = −15→15
7525 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075	H-atom parameters constrained
S = 0.97	w = 1/[σ2(Fo2) + (0.0379P)2] where P = (Fo2 + 2Fc2)/3
2784 reflections	(Δ/σ)max = 0.013
165 parameters	Δρmax = 0.45 e Å−3
0 restraints	Δρmin = −0.45 e Å−3

Experimental. A single crystal suitable for X-ray diffraction was selected under a polarization microscope and sealed in a capillary tube. Complete scattering intensities data sets were collected with an imaging plate diffractometer (IPDS I, Stoe & Cie). The data were corrected for Lorentz and polarization effects. A numerical absorption correction based on crystal-shape optimization was applied for all data.

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. Hydrogen atoms were placed in idealized positions and constrained riding on their parent atoms [C–H = 0.93–0.96 Å with Uiso(H) = 1.2 Ueq(C)]. The last cycles of refinement included atomic positions for all atoms, anisotropic thermal parameters for all non-hydrogen atoms and isotropic thermal parameters for all hydrogen atoms.

	x	y	z	Uiso*/Ueq
Cu1	0.43471 (5)	0.46234 (4)	0.58527 (3)	0.02316 (11)
S1	0.04719 (13)	0.43274 (11)	0.83857 (7)	0.0430 (2)
N1	0.2932 (4)	0.4019 (3)	0.71570 (19)	0.0265 (5)
O3	0.6747 (3)	0.6371 (3)	0.70893 (18)	0.0428 (5)
O4	0.7826 (3)	0.7015 (3)	0.56499 (17)	0.0390 (5)
O1	0.5911 (3)	0.2831 (3)	0.56937 (19)	0.0374 (5)
C2	0.3612 (4)	0.3329 (3)	0.8112 (2)	0.0259 (6)
O2	0.6990 (4)	0.3443 (3)	0.4247 (2)	0.0427 (6)
C6	0.3008 (5)	0.2858 (4)	0.9930 (3)	0.0411 (8)
H6	0.2271	0.2953	1.0468	0.049*
C4	0.5758 (5)	0.2012 (4)	0.9319 (3)	0.0458 (8)
H4	0.6848	0.1503	0.9462	0.055*
C5	0.4659 (6)	0.2169 (4)	1.0127 (3)	0.0462 (9)
H5	0.5055	0.1798	1.0813	0.055*
C11	0.9534 (6)	0.8715 (4)	0.7759 (3)	0.0542 (10)
H11A	0.9499	0.8716	0.8564	0.081*
H11B	0.9337	0.9812	0.7663	0.081*
H11C	1.0803	0.8550	0.7693	0.081*
C9	0.7821 (5)	0.1025 (4)	0.4827 (3)	0.0415 (7)
H9A	0.9197	0.1415	0.4931	0.062*
H9C	0.7166	0.0146	0.4018	0.062*
H9B	0.7733	0.0542	0.5466	0.062*
C1	0.1335 (5)	0.4564 (4)	0.7205 (3)	0.0344 (7)
H1	0.0685	0.5058	0.6633	0.041*
C3	0.5264 (5)	0.2595 (4)	0.8310 (3)	0.0359 (7)
H3	0.6015	0.2501	0.7780	0.043*
C7	0.2462 (5)	0.3417 (3)	0.8892 (2)	0.0307 (6)
C10	0.7917 (4)	0.7261 (3)	0.6755 (2)	0.0288 (6)
C8	0.6835 (4)	0.2542 (3)	0.4930 (2)	0.0278 (6)

	U11	U22	U33	U12	U13	U23
Cu1	0.0256 (2)	0.02769 (17)	0.02156 (16)	0.00738 (12)	0.01074 (12)	0.01282 (12)
S1	0.0358 (5)	0.0654 (5)	0.0383 (4)	0.0139 (4)	0.0222 (4)	0.0223 (4)
N1	0.0267 (14)	0.0329 (12)	0.0228 (11)	0.0055 (9)	0.0097 (9)	0.0127 (9)
O3	0.0453 (15)	0.0499 (12)	0.0239 (10)	−0.0096 (10)	0.0076 (9)	0.0115 (9)
O4	0.0353 (13)	0.0522 (13)	0.0247 (10)	−0.0037 (10)	0.0095 (9)	0.0124 (9)
O1	0.0467 (14)	0.0429 (11)	0.0437 (12)	0.0252 (10)	0.0268 (10)	0.0275 (10)
C2	0.0283 (16)	0.0263 (12)	0.0203 (12)	−0.0001 (10)	0.0065 (10)	0.0082 (10)
O2	0.0588 (16)	0.0442 (12)	0.0552 (13)	0.0307 (11)	0.0389 (12)	0.0338 (11)
C6	0.061 (2)	0.0362 (16)	0.0259 (14)	−0.0033 (14)	0.0177 (14)	0.0124 (13)
C4	0.056 (2)	0.0381 (16)	0.0425 (18)	0.0160 (15)	0.0071 (16)	0.0191 (15)
C5	0.073 (3)	0.0337 (16)	0.0285 (15)	0.0051 (15)	0.0081 (15)	0.0182 (13)
C11	0.055 (2)	0.050 (2)	0.0364 (18)	−0.0127 (16)	0.0009 (16)	0.0081 (15)
C9	0.045 (2)	0.0338 (15)	0.056 (2)	0.0195 (14)	0.0224 (16)	0.0201 (15)
C1	0.0300 (18)	0.0488 (17)	0.0292 (14)	0.0109 (13)	0.0104 (12)	0.0188 (13)
C3	0.040 (2)	0.0374 (15)	0.0337 (15)	0.0099 (13)	0.0121 (13)	0.0175 (13)
C7	0.0354 (18)	0.0305 (14)	0.0236 (13)	−0.0010 (11)	0.0114 (11)	0.0074 (11)
C10	0.0269 (17)	0.0295 (14)	0.0261 (13)	0.0053 (11)	0.0031 (11)	0.0102 (11)
C8	0.0253 (16)	0.0263 (13)	0.0327 (14)	0.0073 (11)	0.0087 (11)	0.0115 (11)

Cu1—O1	1.9589 (19)	C6—C5	1.367 (5)
Cu1—O2i	1.9689 (19)	C6—C7	1.401 (3)
Cu1—O3	1.978 (2)	C6—H6	0.9300
Cu1—O4i	1.984 (2)	C4—C3	1.381 (4)
Cu1—N1	2.203 (2)	C4—C5	1.391 (5)
Cu1—Cu1i	2.6378 (7)	C4—H4	0.9300
S1—C1	1.727 (3)	C5—H5	0.9300
S1—C7	1.732 (3)	C11—C10	1.497 (4)
N1—C1	1.293 (4)	C11—H11A	0.9600
N1—C2	1.398 (3)	C11—H11B	0.9600
O3—C10	1.261 (3)	C11—H11C	0.9600
O4—C10	1.246 (3)	C9—C8	1.500 (4)
O4—Cu1i	1.984 (2)	C9—H9A	0.9600
O1—C8	1.253 (3)	C9—H9C	0.9600
C2—C3	1.390 (4)	C9—H9B	0.9600
C2—C7	1.396 (4)	C1—H1	0.9300
O2—C8	1.256 (3)	C3—H3	0.9300
O2—Cu1i	1.9689 (19)
O1—Cu1—O2i	167.71 (7)	C5—C4—H4	119.3
O1—Cu1—O3	90.12 (10)	C6—C5—C4	121.3 (2)
O2i—Cu1—O3	88.37 (10)	C6—C5—H5	119.4
O1—Cu1—O4i	88.25 (10)	C4—C5—H5	119.4
O2i—Cu1—O4i	90.67 (10)	C10—C11—H11A	109.5
O3—Cu1—O4i	167.89 (8)	C10—C11—H11B	109.5
O1—Cu1—N1	100.05 (8)	H11A—C11—H11B	109.5
O2i—Cu1—N1	92.24 (8)	C10—C11—H11C	109.5
O3—Cu1—N1	98.77 (8)	H11A—C11—H11C	109.5
O4i—Cu1—N1	93.33 (8)	H11B—C11—H11C	109.5
O1—Cu1—Cu1i	84.48 (6)	C8—C9—H9A	109.5
O2i—Cu1—Cu1i	83.24 (6)	C8—C9—H9C	109.5
O3—Cu1—Cu1i	85.57 (6)	H9A—C9—H9C	109.5
O4i—Cu1—Cu1i	82.33 (6)	C8—C9—H9B	109.5
N1—Cu1—Cu1i	173.67 (6)	H9A—C9—H9B	109.5
C1—S1—C7	88.85 (13)	H9C—C9—H9B	109.5
C1—N1—C2	110.6 (2)	N1—C1—S1	116.61 (19)
C1—N1—Cu1	118.25 (16)	N1—C1—H1	121.7
C2—N1—Cu1	130.51 (18)	S1—C1—H1	121.7
C10—O3—Cu1	121.50 (17)	C4—C3—C2	118.0 (3)
C10—O4—Cu1i	125.44 (19)	C4—C3—H3	121.0
C8—O1—Cu1	123.50 (15)	C2—C3—H3	121.0
C3—C2—C7	120.5 (2)	C2—C7—C6	120.8 (3)
C3—C2—N1	125.5 (2)	C2—C7—S1	109.93 (18)
C7—C2—N1	114.0 (2)	C6—C7—S1	129.2 (2)
C8—O2—Cu1i	124.42 (18)	O4—C10—O3	124.7 (3)
C5—C6—C7	117.9 (3)	O4—C10—C11	117.7 (3)
C5—C6—H6	121.0	O3—C10—C11	117.6 (2)
C7—C6—H6	121.0	O1—C8—O2	124.2 (2)
C3—C4—C5	121.4 (3)	O1—C8—C9	117.9 (2)
C3—C4—H4	119.3	O2—C8—C9	118.0 (3)