Di-μ-chlorido-bis-{aqua-chlorido[2,2'-thio-bis(pyridine N-oxide)-κO]copper(II)}.

The crystal structure of the title compound, [Cu(2)Cl(4)(C(10)H(8)N(2)O(2)S)(2)(H(2)O)(2)], comprises neutral centrosymmetric μ-chloride-bridged dinuclear units. Each Cu(II) ion is penta-coordinated by three chloride ligands, a pyridine N-oxide O atom and a water mol-ecule. Intra- and inter-molecular O-H⋯O hydrogen bonds occur between the coordinated water mol-ecules and the uncoordinated and coordinated pyridine N-oxide groups of the 2,2'-thio-bis(pyridine N-oxide) ligands, respectively.

Related literature

For the potential of pyridine N-oxide-based building blocks in the construction of coordination polymers and crystal engin­eering, see: Sun et al. (2008 ▶) and references cited therein. For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For a copper-catalysed example of in situ S—S and S—Csp 2 bond cleavage and rearrangement of an related disulfide, see: Wang et al. (2007 ▶).

Experimental

Crystal data

[Cu2Cl4(C10H8N2O2S)2(H2O)2]

M = 745.40

Monoclinic,

a = 6.7552 (18) Å

b = 11.430 (3) Å

c = 17.375 (3) Å

β = 95.516 (17)°

V = 1335.4 (6) Å3

Z = 2

Mo Kα radiation

μ = 2.19 mm−1

T = 294 K

0.27 × 0.21 × 0.19 mm

Data collection

Siemens P4 four-circle diffractometer

Absorption correction: ψ scan (ABSPsiScan in PLATON; Spek, 2009 ▶) T min = 0.529, T max = 0.663

3316 measured reflections

2349 independent reflections

1736 reflections with I > 2(I)

R int = 0.058

3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.088

S = 1.02

2349 reflections

178 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.53 e Å−3

Data collection: XSCANS (Bruker, 1999 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011076/dn2439sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011076/dn2439Isup2.hkl

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

[Cu2Cl4(C10H8N2O2S)2(H2O)2]	F(000) = 748
Mr = 745.40	Dx = 1.854 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 6.7552 (18) Å	θ = 5.1–18.0°
b = 11.430 (3) Å	µ = 2.19 mm−1
c = 17.375 (3) Å	T = 294 K
β = 95.516 (17)°	Prism, dark-yellow
V = 1335.4 (6) Å3	0.27 × 0.21 × 0.19 mm
Z = 2

Siemens P4 four-circle diffractometer	1736 reflections with I > 2(I)
Radiation source: fine-focus sealed tube	Rint = 0.058
graphite	θmax = 25.0°, θmin = 2.1°
ω scans	h = −8→1
Absorption correction: ψ scan (ABSPsiScan in PLATON; Spek, 2009)	k = −1→13
Tmin = 0.529, Tmax = 0.663	l = −20→20
3316 measured reflections	3 standard reflections every 97 reflections
2349 independent reflections	intensity decay: none

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0347P)2] where P = (Fo2 + 2Fc2)/3
2349 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.40 e Å−3
2 restraints	Δρmin = −0.53 e Å−3

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	0.36057 (7)	0.52270 (5)	0.07537 (3)	0.02340 (16)
Cl1	0.42569 (17)	0.52142 (11)	0.20449 (6)	0.0365 (3)
Cl2	0.34708 (15)	0.57187 (10)	−0.05629 (6)	0.0273 (3)
S1	0.42443 (17)	0.79699 (11)	0.11518 (7)	0.0343 (3)
O1	0.1176 (4)	0.6210 (3)	0.07498 (15)	0.0272 (7)
O2	0.1784 (5)	0.3623 (3)	0.05848 (18)	0.0325 (8)
H2A	0.086 (5)	0.372 (4)	0.026 (2)	0.039*
H2B	0.231 (7)	0.305 (3)	0.040 (2)	0.039*
N1	0.0804 (5)	0.6857 (3)	0.13620 (19)	0.0250 (8)
C2	−0.0843 (6)	0.6616 (4)	0.1706 (2)	0.0290 (11)
H2	−0.1683	0.6013	0.1521	0.035*
C3	−0.1287 (7)	0.7269 (4)	0.2335 (3)	0.0378 (12)
H3	−0.2435	0.7108	0.2572	0.045*
C4	−0.0060 (7)	0.8142 (4)	0.2611 (3)	0.0386 (12)
H4	−0.0342	0.8569	0.3043	0.046*
C5	0.1619 (7)	0.8391 (4)	0.2242 (3)	0.0352 (11)
H5	0.2461	0.8996	0.2423	0.042*
C6	0.2049 (6)	0.7744 (4)	0.1606 (2)	0.0250 (10)
O11	0.6518 (4)	0.8360 (3)	0.00176 (19)	0.0412 (9)
N11	0.4647 (5)	0.8581 (3)	−0.0254 (2)	0.0315 (9)
C12	0.3202 (7)	0.8442 (4)	0.0239 (2)	0.0276 (11)
C13	0.1254 (6)	0.8656 (4)	−0.0018 (2)	0.0292 (11)
H13	0.0267	0.8566	0.0315	0.035*
C14	0.0761 (7)	0.9005 (4)	−0.0771 (3)	0.0378 (12)
H14	−0.0560	0.9141	−0.0951	0.045*
C15	0.2246 (8)	0.9151 (4)	−0.1254 (3)	0.0425 (13)
H15	0.1930	0.9400	−0.1761	0.051*
C16	0.4167 (8)	0.8932 (4)	−0.0992 (3)	0.0395 (13)
H16	0.5161	0.9024	−0.1322	0.047*

	U11	U22	U33	U12	U13	U23
Cu1	0.0210 (3)	0.0273 (3)	0.0224 (3)	0.0022 (3)	0.0041 (2)	−0.0021 (2)
Cl1	0.0376 (7)	0.0499 (7)	0.0224 (6)	0.0122 (6)	0.0045 (5)	0.0007 (5)
Cl2	0.0246 (6)	0.0331 (6)	0.0249 (6)	0.0063 (5)	0.0050 (4)	−0.0017 (5)
S1	0.0216 (6)	0.0443 (7)	0.0370 (7)	−0.0053 (6)	0.0028 (5)	0.0023 (6)
O1	0.0223 (16)	0.0342 (17)	0.0250 (16)	0.0056 (14)	0.0018 (13)	−0.0109 (14)
O2	0.0259 (19)	0.0323 (19)	0.038 (2)	−0.0022 (16)	−0.0030 (15)	−0.0023 (16)
N1	0.0210 (19)	0.029 (2)	0.0253 (19)	0.0026 (17)	0.0042 (16)	−0.0004 (17)
C2	0.021 (2)	0.031 (3)	0.036 (3)	−0.001 (2)	0.006 (2)	0.000 (2)
C3	0.029 (3)	0.053 (3)	0.033 (3)	0.006 (3)	0.008 (2)	−0.001 (2)
C4	0.046 (3)	0.042 (3)	0.030 (3)	0.008 (3)	0.011 (2)	−0.006 (2)
C5	0.041 (3)	0.028 (3)	0.037 (3)	−0.005 (2)	−0.001 (2)	−0.005 (2)
C6	0.019 (2)	0.030 (2)	0.027 (2)	0.001 (2)	0.0029 (19)	0.0001 (19)
O11	0.0196 (17)	0.047 (2)	0.059 (2)	−0.0015 (16)	0.0111 (16)	−0.0083 (17)
N11	0.023 (2)	0.026 (2)	0.047 (2)	−0.0057 (17)	0.0112 (18)	−0.0080 (19)
C12	0.028 (3)	0.022 (2)	0.035 (3)	−0.008 (2)	0.011 (2)	−0.007 (2)
C13	0.020 (2)	0.032 (3)	0.037 (3)	−0.002 (2)	0.012 (2)	−0.002 (2)
C14	0.037 (3)	0.037 (3)	0.040 (3)	−0.002 (2)	0.002 (2)	0.007 (2)
C15	0.048 (3)	0.049 (3)	0.030 (3)	−0.006 (3)	0.007 (2)	0.002 (2)
C16	0.049 (3)	0.045 (3)	0.028 (3)	−0.010 (3)	0.020 (2)	−0.004 (2)

Cu1—O1	1.988 (3)	C3—H3	0.9300
Cu1—O2	2.212 (3)	C4—C5	1.386 (6)
Cu1—Cl1	2.2443 (12)	C4—H4	0.9300
Cu1—Cl2i	2.3031 (12)	C5—C6	1.384 (6)
Cu1—Cl2	2.3489 (12)	C5—H5	0.9300
Cl2—Cu1i	2.3031 (12)	O11—N11	1.331 (5)
S1—C12	1.758 (5)	N11—C16	1.353 (6)
S1—C6	1.764 (4)	N11—C12	1.369 (5)
O1—N1	1.339 (4)	C12—C13	1.370 (6)
O2—H2A	0.81 (2)	C13—C14	1.378 (6)
O2—H2B	0.82 (2)	C13—H13	0.9300
N1—C2	1.341 (5)	C14—C15	1.379 (6)
N1—C6	1.359 (5)	C14—H14	0.9300
C2—C3	1.381 (6)	C15—C16	1.357 (7)
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.355 (7)	C16—H16	0.9300
O1—Cu1—O2	91.10 (12)	C3—C4—H4	120.4
O1—Cu1—Cl1	95.13 (8)	C5—C4—H4	120.4
O2—Cu1—Cl1	100.39 (9)	C6—C5—C4	120.3 (4)
O1—Cu1—Cl2i	169.61 (9)	C6—C5—H5	119.9
O2—Cu1—Cl2i	93.77 (9)	C4—C5—H5	119.9
Cl1—Cu1—Cl2i	93.00 (4)	N1—C6—C5	118.5 (4)
O1—Cu1—Cl2	84.65 (8)	N1—C6—S1	119.4 (3)
O2—Cu1—Cl2	95.75 (9)	C5—C6—S1	121.9 (3)
Cl1—Cu1—Cl2	163.86 (5)	O11—N11—C16	121.7 (4)
Cl2i—Cu1—Cl2	85.74 (4)	O11—N11—C12	117.8 (4)
Cu1i—Cl2—Cu1	94.26 (4)	C16—N11—C12	120.5 (4)
C12—S1—C6	99.6 (2)	N11—C12—C13	119.7 (4)
N1—O1—Cu1	121.8 (2)	N11—C12—S1	110.7 (3)
Cu1—O2—H2A	111 (4)	C13—C12—S1	129.6 (3)
Cu1—O2—H2B	117 (3)	C12—C13—C14	119.9 (4)
H2A—O2—H2B	100 (5)	C12—C13—H13	120.1
O1—N1—C2	117.9 (4)	C14—C13—H13	120.1
O1—N1—C6	120.1 (3)	C13—C14—C15	119.3 (5)
C2—N1—C6	122.0 (4)	C13—C14—H14	120.3
N1—C2—C3	119.6 (4)	C15—C14—H14	120.3
N1—C2—H2	120.2	C16—C15—C14	120.1 (5)
C3—C2—H2	120.2	C16—C15—H15	120.0
C4—C3—C2	120.4 (4)	C14—C15—H15	120.0
C4—C3—H3	119.8	N11—C16—C15	120.5 (4)
C2—C3—H3	119.8	N11—C16—H16	119.7
C3—C4—C5	119.2 (4)	C15—C16—H16	119.7

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ii	0.81 (2)	2.13 (2)	2.919 (4)	167 (5)
O2—H2B···O11i	0.82 (2)	1.97 (2)	2.789 (5)	177 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1i	0.81 (2)	2.13 (2)	2.919 (4)	167 (5)
O2—H2B⋯O11ii	0.82 (2)	1.97 (2)	2.789 (5)	177 (5)

Symmetry codes: (i) ; (ii) .