Tetra-μ-acetato-κ⁸O:O′-bis­{[2-(phenyl­sulfanylmeth­yl)pyridine-κN]copper(II)}

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.028
• wR factor = 0.078
• Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.81 Ratio
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.12 Ratio

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.10

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

In the preparation of Cu^II 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 Cu^II 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

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

S2. Experimental

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.

S3. Refinement

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

Computing details

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

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)}

Crystal data

[Cu2(C2H3O2)4(C12H11NS)2]	Z = 1
Mr = 765.85	F(000) = 394
Triclinic, P1	Dx = 1.551 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7587 (16) Å	Cell parameters from 7557 reflections
b = 7.9690 (16) Å	θ = 3.1–27.5°
c = 13.986 (3) Å	µ = 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) Å^3

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer	3029 independent reflections
Radiation source: rotating anode	2859 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 25.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
Tmin = 0.622, Tmax = 0.652	k = −9→8
6775 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0382P)^2 + 0.5716P] where P = (Fo^2 + 2Fc^2)/3
3029 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.15681 (7)	1.02827 (7)	0.41049 (4)	0.02382 (14)
N1	0.3502 (2)	0.7760 (2)	0.18067 (12)	0.0167 (3)
Cu1	0.12181 (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)
C1	0.2586 (3)	1.3074 (3)	0.33349 (17)	0.0296 (5)
H1A	0.2590	1.2289	0.2737	0.036*
C2	0.3046 (4)	1.4820 (3)	0.34379 (19)	0.0377 (6)
H2A	0.3354	1.5205	0.2906	0.045*
C3	0.3055 (4)	1.5996 (3)	0.4319 (2)	0.0416 (6)
H3A	0.3386	1.7170	0.4388	0.050*
C4	0.2570 (5)	1.5422 (4)	0.5097 (2)	0.0471 (7)
H4A	0.2558	1.6216	0.5690	0.057*
C5	0.2101 (4)	1.3675 (3)	0.50064 (19)	0.0375 (6)
H5A	0.1776	1.3298	0.5536	0.045*
C6	0.2118 (3)	1.2487 (3)	0.41206 (16)	0.0236 (5)
C7	0.1672 (3)	0.9108 (3)	0.28692 (15)	0.0213 (4)
H7A	0.1012	0.7968	0.2738	0.026*
H7B	0.1066	0.9697	0.2385	0.026*
C8	0.3503 (3)	0.8875 (3)	0.26746 (15)	0.0168 (4)
C9	0.5058 (3)	0.9744 (3)	0.33319 (16)	0.0236 (5)
H9A	0.5022	1.0513	0.3929	0.028*
C10	0.6667 (3)	0.9446 (3)	0.30849 (17)	0.0275 (5)
H10A	0.7727	1.0007	0.3517	0.033*
C11	0.6675 (3)	0.8307 (3)	0.21884 (18)	0.0268 (5)
H11A	0.7737	0.8097	0.2002	0.032*
C12	0.5073 (3)	0.7486 (3)	0.15746 (16)	0.0224 (4)
H12A	0.5080	0.6710	0.0974	0.027*
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	−0.2322	0.9983	0.0167	0.043*
H14B	−0.4067	0.8675	−0.0238	0.043*
H14C	−0.2948	0.9117	−0.0986	0.043*
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	−0.3240	0.2808	0.1837	0.053*
H16B	−0.2796	0.4730	0.2471	0.053*
H16C	−0.1419	0.3412	0.2618	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0221 (3)	0.0269 (3)	0.0200 (3)	−0.0009 (2)	0.0070 (2)	−0.0002 (2)
N1	0.0151 (8)	0.0168 (8)	0.0174 (8)	0.0000 (6)	0.0027 (6)	0.0037 (7)
Cu1	0.01397 (14)	0.01466 (15)	0.01485 (14)	−0.00007 (9)	0.00168 (9)	0.00172 (10)
O1	0.0225 (8)	0.0181 (7)	0.0248 (8)	0.0029 (6)	0.0003 (6)	0.0020 (6)
O2	0.0206 (8)	0.0187 (8)	0.0350 (9)	0.0029 (6)	−0.0038 (6)	0.0006 (7)
O3	0.0280 (8)	0.0255 (8)	0.0175 (7)	−0.0063 (6)	0.0046 (6)	0.0036 (6)
O4	0.0232 (8)	0.0316 (9)	0.0193 (7)	−0.0075 (6)	0.0058 (6)	0.0011 (6)
C1	0.0370 (13)	0.0312 (13)	0.0189 (10)	0.0094 (10)	0.0038 (9)	0.0031 (9)
C2	0.0503 (16)	0.0350 (14)	0.0304 (13)	0.0098 (12)	0.0052 (11)	0.0156 (11)
C3	0.0603 (18)	0.0260 (13)	0.0348 (14)	0.0091 (12)	0.0001 (12)	0.0083 (11)
C4	0.081 (2)	0.0278 (14)	0.0295 (13)	0.0116 (13)	0.0139 (14)	−0.0016 (11)
C5	0.0564 (17)	0.0329 (13)	0.0252 (12)	0.0099 (12)	0.0141 (11)	0.0049 (11)
C6	0.0198 (10)	0.0258 (11)	0.0218 (10)	0.0062 (8)	0.0000 (8)	0.0020 (9)
C7	0.0146 (10)	0.0241 (11)	0.0201 (10)	−0.0004 (8)	0.0025 (8)	−0.0037 (8)
C8	0.0144 (9)	0.0170 (10)	0.0177 (9)	−0.0007 (7)	0.0021 (7)	0.0042 (8)
C9	0.0191 (10)	0.0262 (11)	0.0196 (10)	0.0005 (8)	0.0005 (8)	−0.0026 (9)
C10	0.0134 (10)	0.0337 (13)	0.0296 (12)	−0.0013 (9)	−0.0013 (8)	0.0021 (10)
C11	0.0147 (10)	0.0329 (12)	0.0315 (12)	0.0028 (9)	0.0060 (9)	0.0040 (10)
C12	0.0177 (10)	0.0248 (11)	0.0233 (10)	0.0024 (8)	0.0050 (8)	0.0023 (9)
C13	0.0186 (10)	0.0187 (10)	0.0214 (10)	0.0041 (8)	0.0091 (8)	0.0067 (8)
C14	0.0270 (12)	0.0231 (11)	0.0358 (12)	0.0074 (9)	0.0037 (10)	0.0088 (10)
C15	0.0235 (11)	0.0178 (10)	0.0209 (10)	0.0040 (8)	0.0081 (8)	0.0054 (8)
C16	0.0446 (15)	0.0380 (14)	0.0252 (12)	−0.0083 (11)	0.0165 (11)	0.0065 (10)

Geometric parameters (Å, º)

S1—C6	1.771 (2)	C4—C5	1.384 (4)
S1—C7	1.799 (2)	C4—H4A	0.9300
N1—C8	1.340 (3)	C5—C6	1.390 (3)
N1—C12	1.345 (3)	C5—H5A	0.9300
Cu1—O3	1.9663 (15)	C7—C8	1.517 (3)
Cu1—O1	1.9680 (16)	C7—H7A	0.9700
Cu1—N1	2.2227 (19)	C7—H7B	0.9700
Cu1—O4^i	1.9743 (16)	C8—C9	1.387 (3)
Cu1—O2^i	1.9746 (16)	C9—C10	1.385 (3)
Cu1—Cu1^i	2.6309 (13)	C9—H9A	0.9300
O1—C13	1.262 (3)	C10—C11	1.381 (3)
O2—C13	1.257 (3)	C10—H10A	0.9300
O2—Cu1^i	1.9746 (16)	C11—C12	1.381 (3)
O3—C15	1.260 (3)	C11—H11A	0.9300
O4—C15	1.252 (3)	C12—H12A	0.9300
O4—Cu1^i	1.9743 (16)	C13—C14	1.505 (3)
C1—C2	1.379 (4)	C14—H14A	0.9600
C1—C6	1.385 (3)	C14—H14B	0.9600
C1—H1A	0.9300	C14—H14C	0.9600
C2—C3	1.376 (4)	C15—C16	1.511 (3)
C2—H2A	0.9300	C16—H16A	0.9600
C3—C4	1.376 (4)	C16—H16B	0.9600
C3—H3A	0.9300	C16—H16C	0.9600
C6—S1—C7	104.84 (11)	C1—C6—S1	124.78 (17)
C8—N1—C12	118.22 (17)	C8—C7—S1	117.10 (14)
C8—N1—Cu1	128.57 (13)	C8—C7—H7A	108.0
C12—N1—Cu1	113.04 (13)	S1—C7—H7A	108.0
O3—Cu1—O1	89.29 (7)	C8—C7—H7B	108.0
O3—Cu1—O4^i	168.33 (6)	S1—C7—H7B	108.0
O1—Cu1—O4^i	89.15 (7)	H7A—C7—H7B	107.3
O3—Cu1—O2^i	88.87 (7)	N1—C8—C9	122.23 (18)
O1—Cu1—O2^i	168.47 (6)	N1—C8—C7	114.47 (17)
O4^i—Cu1—O2^i	90.36 (8)	C9—C8—C7	123.30 (18)
O3—Cu1—N1	100.28 (6)	C10—C9—C8	118.96 (19)
O1—Cu1—N1	100.09 (7)	C10—C9—H9A	120.5
O4^i—Cu1—N1	91.38 (6)	C8—C9—H9A	120.5
O2^i—Cu1—N1	91.44 (7)	C11—C10—C9	119.1 (2)
O3—Cu1—Cu1^i	83.62 (5)	C11—C10—H10A	120.4
O1—Cu1—Cu1^i	85.08 (5)	C9—C10—H10A	120.4
O4^i—Cu1—Cu1^i	84.73 (5)	C12—C11—C10	118.6 (2)
O2^i—Cu1—Cu1^i	83.41 (5)	C12—C11—H11A	120.7
N1—Cu1—Cu1^i	173.51 (5)	C10—C11—H11A	120.7
C13—O1—Cu1	122.22 (14)	N1—C12—C11	122.9 (2)
C13—O2—Cu1^i	124.00 (14)	N1—C12—H12A	118.6
C15—O3—Cu1	123.84 (14)	C11—C12—H12A	118.6
C15—O4—Cu1^i	122.33 (14)	O2—C13—O1	125.2 (2)
C2—C1—C6	120.1 (2)	O2—C13—C14	117.68 (19)
C2—C1—H1A	120.0	O1—C13—C14	117.14 (19)
C6—C1—H1A	120.0	C13—C14—H14A	109.5
C1—C2—C3	120.7 (2)	C13—C14—H14B	109.5
C1—C2—H2A	119.7	H14A—C14—H14B	109.5
C3—C2—H2A	119.7	C13—C14—H14C	109.5
C4—C3—C2	119.5 (3)	H14A—C14—H14C	109.5
C4—C3—H3A	120.3	H14B—C14—H14C	109.5
C2—C3—H3A	120.3	O4—C15—O3	125.3 (2)
C3—C4—C5	120.7 (2)	O4—C15—C16	117.43 (19)
C3—C4—H4A	119.7	O3—C15—C16	117.25 (19)
C5—C4—H4A	119.7	C15—C16—H16A	109.5
C4—C5—C6	119.7 (2)	C15—C16—H16B	109.5
C4—C5—H5A	120.1	H16A—C16—H16B	109.5
C6—C5—H5A	120.1	C15—C16—H16C	109.5
C5—C6—C1	119.4 (2)	H16A—C16—H16C	109.5
C5—C6—S1	115.81 (19)	H16B—C16—H16C	109.5
C8—N1—Cu1—O3	−38.69 (18)	C2—C1—C6—S1	−177.9 (2)
C12—N1—Cu1—O3	136.51 (15)	C7—S1—C6—C5	179.03 (18)
C8—N1—Cu1—O1	52.42 (18)	C7—S1—C6—C1	−2.4 (2)
C12—N1—Cu1—O1	−132.38 (15)	C6—S1—C7—C8	76.80 (19)
C8—N1—Cu1—O4^i	141.80 (18)	C12—N1—C8—C9	0.0 (3)
C12—N1—Cu1—O4^i	−43.00 (16)	Cu1—N1—C8—C9	175.01 (15)
C8—N1—Cu1—O2^i	−127.81 (18)	C12—N1—C8—C7	179.67 (19)
C12—N1—Cu1—O2^i	47.39 (16)	Cu1—N1—C8—C7	−5.3 (3)
O3—Cu1—O1—C13	−86.13 (16)	S1—C7—C8—N1	169.58 (15)
O4^i—Cu1—O1—C13	82.31 (16)	S1—C7—C8—C9	−10.8 (3)
O2^i—Cu1—O1—C13	−5.3 (4)	N1—C8—C9—C10	−0.2 (3)
N1—Cu1—O1—C13	173.56 (15)	C7—C8—C9—C10	−179.8 (2)
Cu1^i—Cu1—O1—C13	−2.47 (15)	C8—C9—C10—C11	0.6 (4)
O1—Cu1—O3—C15	88.00 (18)	C9—C10—C11—C12	−0.8 (4)
O4^i—Cu1—O3—C15	5.7 (4)	C8—N1—C12—C11	−0.3 (3)
O2^i—Cu1—O3—C15	−80.62 (18)	Cu1—N1—C12—C11	−176.01 (18)
N1—Cu1—O3—C15	−171.88 (17)	C10—C11—C12—N1	0.7 (4)
Cu1^i—Cu1—O3—C15	2.87 (17)	Cu1^i—O2—C13—O1	−3.6 (3)
C6—C1—C2—C3	0.3 (4)	Cu1^i—O2—C13—C14	176.56 (15)
C1—C2—C3—C4	−1.1 (4)	Cu1—O1—C13—O2	4.3 (3)
C2—C3—C4—C5	0.9 (5)	Cu1—O1—C13—C14	−175.83 (14)
C3—C4—C5—C6	0.0 (5)	Cu1^i—O4—C15—O3	4.3 (3)
C4—C5—C6—C1	−0.7 (4)	Cu1^i—O4—C15—C16	−176.35 (16)
C4—C5—C6—S1	177.9 (2)	Cu1—O3—C15—O4	−5.1 (3)
C2—C1—C6—C5	0.6 (4)	Cu1—O3—C15—C16	175.48 (16)

Symmetry code: (i) −x, −y+1, −z.