Bis(μ-N,N-dimethyl­dithio­carbamato-κ3S,S′:S)bis­[(N,N-dimethyl­dithio­carbamato-κ2S,S′)copper(II)]

Fan, L.-Q.; Wu, J.-H.

doi:10.1107/S1600536809006230

metal-organic compounds

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Volume 65| Part 3| March 2009| Page m319

doi:10.1107/S1600536809006230

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Bis(μ-N,N-dimethyldithiocarbamato-κ³S,S′:S)bis[(N,N-dimethyldithiocarbamato-κ²S,S′)copper(II)]

Le-Qing Fan ^a ^* and Ji-Huai Wu ^a

^aInstitute of Materials Physical Chemistry and the Key Laboratory for Functional Materials of Fujian Higher Education, Huaqiao University, Quanzhou, Fujian 362021, People's Republic of China
^*Correspondence e-mail: lqfan@hqu.edu.cn

(Received 19 February 2009; accepted 20 February 2009; online 25 February 2009)

In the centrosymmetric dimeric title compound, [Cu₂(C₃H₆NS₂)₄], the Cu^II atom is five-coordinate in a square-pyramidal environment. The basal coordination positions are occupied by four S atoms from two dimethyldithiocarbamate ligands and the apical coordination position is occupied by an S atom also bonded to the other Cu atom.

Related literature

For the structural diversity and potential applications of transition metal complexes, see: Noro et al. (2000 ); Yaghi et al. (1998 ). For dialkyldithiocarbamates anions acting as monodentate, bidentate or bridging ligands, see: Engelhardt et al. (1988 ); Fernández et al. (2000 ); Koh et al. (2003 ).

Experimental

Crystal data

[Cu₂(C₃H₆NS₂)₄]
M_r = 607.91
Monoclinic, C 2/c
a = 8.068 (3) Å
b = 19.446 (7) Å
c = 15.108 (6) Å
β = 99.354 (6)°
V = 2338.7 (15) Å³
Z = 4
Mo Kα radiation
μ = 2.54 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.15 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ) T_min = 0.807, T_max = 1.000 (expected range = 0.552–0.683)
9796 measured reflections
2685 independent reflections
2423 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.141
S = 1.07
2685 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—S3	2.3072 (13)
Cu1—S4	2.3208 (13)
Cu1—S1	2.3240 (13)
Cu1—S2	2.3278 (13)
Cu1—S1ⁱ	2.8258 (14)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006230/ng2548sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006230/ng2548Isup2.hkl

checkCIF report

Comment top

Research into transition metal complexes has been rapidly expanding because of their fascinating structural diversity, as well as their potential applications as functional materials and enzymes (Noro et al., 2000; Yaghi et al., 1998). Dialkyldithiocarbamates anions, which are typical sulfur ligands, acting as monodentate, bidentate or bridging ligands, are often chosen for the preparation of a considerable structural variety of complexes (Engelhardt et al., 1988; Fernández et al., 2000; Koh, et al., 2003). We report here the crystal structure of the title copper(II) complex, (I), contanining a dimethyldithiocarbamate ligand.

The crystal structure of (I) is built up by dimeric entities of Cu^II complex (Fig. 1). The coordination geometry of Cu^II ion is described as a distorted square-pyramid. The basal coordination positions are occupied by four S atoms from two dimethyldithiocarbamate ligands. Each briding S atom simultaneously occupies an equatorial coordination site on one Cu^II ion and apical site on the other Cu^II. The axial Cu—S bond distance is longer than the equatorial Cu—S ones (Table 1).

Related literature top

For the structural diversity and potential applications of transition metal complexes, see: Noro et al. (2000); Yaghi et al. (1998). For dialkyldithiocarbamates anions acting as monodentate, bidentate or bridging ligands, see: Engelhardt et al. (1988); Fernández et al. (2000); Koh et al. (2003);

Experimental top

A mixture of Cu(Ac)₂.H₂O (0.04 g, 0.2 mmol) and NaS₂CNMe₂.2H₂O (0.04 g, 0.2 mmol) was stirred in DMF (15 ml) at 313 K. 2-PrOH was diffused into the resulting solution, yielding single crystals of (I).

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). [Symmetry code: A 1 - x, y, 1/2 - z.]

Bis(µ-N,N-dimethyldithiocarbamato- κ³S,S':S)bis[(N,N- dimethyldithiocarbamato-κ²S,S')copper(II)] top

Crystal data top

[Cu₂(C₃H₆NS₂)₄]	F(000) = 1240
M_r = 607.91	D_x = 1.727 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3071 reflections
a = 8.068 (3) Å	θ = 2.5–27.5°
b = 19.446 (7) Å	µ = 2.54 mm⁻¹
c = 15.108 (6) Å	T = 293 K
β = 99.354 (6)°	Block, black
V = 2338.7 (15) Å³	0.25 × 0.20 × 0.15 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	2685 independent reflections
Radiation source: Sealed Tube	2423 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.048
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −9→10
T_min = 0.807, T_max = 1.000	k = −25→25
9796 measured reflections	l = −19→18

Refinement top

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0741P)² + 4.6176P] where P = (F_o² + 2F_c²)/3
2685 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Cu₂(C₃H₆NS₂)₄]	V = 2338.7 (15) Å³
M_r = 607.91	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 8.068 (3) Å	µ = 2.54 mm⁻¹
b = 19.446 (7) Å	T = 293 K
c = 15.108 (6) Å	0.25 × 0.20 × 0.15 mm
β = 99.354 (6)°

Data collection top

Rigaku Mercury CCD diffractometer	2685 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	2423 reflections with I > 2σ(I)
T_min = 0.807, T_max = 1.000	R_int = 0.048
9796 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.07	Δρ_max = 0.44 e Å⁻³
2685 reflections	Δρ_min = −0.58 e Å⁻³
118 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.58962 (6)	0.37634 (2)	0.36682 (3)	0.04294 (19)
S1	0.72601 (13)	0.39120 (5)	0.24400 (7)	0.0438 (3)
S2	0.66137 (15)	0.49238 (5)	0.37410 (7)	0.0493 (3)
S3	0.50794 (15)	0.35823 (5)	0.50440 (7)	0.0497 (3)
S4	0.56076 (14)	0.25771 (5)	0.37160 (7)	0.0478 (3)
N1	0.7709 (4)	0.52631 (17)	0.2215 (2)	0.0482 (8)
N2	0.4789 (4)	0.22341 (17)	0.5308 (2)	0.0451 (7)
C1	0.7268 (5)	0.47699 (19)	0.2734 (3)	0.0410 (8)
C2	0.8173 (7)	0.5106 (3)	0.1342 (3)	0.0660 (13)
H2A	0.8225	0.4616	0.1269	0.099*
H2B	0.9251	0.5303	0.1307	0.099*
H2C	0.7348	0.5295	0.0876	0.099*
C3	0.7562 (7)	0.5986 (2)	0.2445 (4)	0.0642 (13)
H3A	0.7251	0.6022	0.3030	0.096*
H3B	0.6717	0.6201	0.2011	0.096*
H3C	0.8620	0.6211	0.2444	0.096*
C4	0.5123 (5)	0.27279 (19)	0.4761 (2)	0.0396 (8)
C5	0.4841 (6)	0.1509 (2)	0.5072 (3)	0.0616 (12)
H5A	0.5085	0.1466	0.4473	0.092*
H5B	0.3773	0.1301	0.5103	0.092*
H5C	0.5699	0.1281	0.5483	0.092*
C6	0.4417 (6)	0.2385 (3)	0.6202 (3)	0.0631 (13)
H6A	0.4415	0.2874	0.6291	0.095*
H6B	0.5257	0.2178	0.6645	0.095*
H6C	0.3333	0.2202	0.6258	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0524 (3)	0.0380 (3)	0.0398 (3)	0.00016 (19)	0.0115 (2)	0.00059 (18)
S1	0.0478 (6)	0.0412 (5)	0.0442 (5)	0.0025 (4)	0.0125 (4)	−0.0010 (4)
S2	0.0613 (7)	0.0414 (5)	0.0462 (6)	−0.0044 (4)	0.0114 (5)	−0.0078 (4)
S3	0.0667 (7)	0.0447 (5)	0.0397 (5)	0.0014 (5)	0.0144 (5)	−0.0027 (4)
S4	0.0643 (7)	0.0385 (5)	0.0430 (6)	0.0041 (4)	0.0158 (5)	−0.0005 (4)
N1	0.0478 (19)	0.0466 (18)	0.0489 (19)	−0.0053 (15)	0.0041 (15)	0.0071 (15)
N2	0.0445 (18)	0.0467 (17)	0.0438 (18)	−0.0017 (14)	0.0063 (14)	0.0063 (14)
C1	0.0365 (18)	0.0425 (18)	0.041 (2)	−0.0001 (15)	−0.0015 (15)	0.0027 (15)
C2	0.069 (3)	0.072 (3)	0.059 (3)	−0.008 (2)	0.018 (2)	0.013 (2)
C3	0.076 (3)	0.042 (2)	0.071 (3)	−0.012 (2)	0.002 (2)	0.008 (2)
C4	0.0359 (18)	0.0454 (19)	0.0367 (18)	0.0026 (15)	0.0034 (14)	0.0051 (15)
C5	0.071 (3)	0.043 (2)	0.070 (3)	−0.002 (2)	0.009 (2)	0.013 (2)
C6	0.071 (3)	0.072 (3)	0.050 (3)	−0.005 (2)	0.021 (2)	0.016 (2)

Geometric parameters (Å, º) top

Cu1—S3	2.3072 (13)	N2—C5	1.457 (5)
Cu1—S4	2.3208 (13)	C2—H2A	0.9600
Cu1—S1	2.3240 (13)	C2—H2B	0.9600
Cu1—S2	2.3278 (13)	C2—H2C	0.9600
Cu1—S1ⁱ	2.8258 (14)	C3—H3A	0.9600
S1—C1	1.726 (4)	C3—H3B	0.9600
S2—C1	1.715 (4)	C3—H3C	0.9600
S3—C4	1.717 (4)	C5—H5A	0.9600
S4—C4	1.713 (4)	C5—H5B	0.9600
N1—C1	1.324 (5)	C5—H5C	0.9600
N1—C2	1.461 (6)	C6—H6A	0.9600
N1—C3	1.457 (6)	C6—H6B	0.9600
N2—C4	1.323 (5)	C6—H6C	0.9600
N2—C6	1.460 (5)

S3—Cu1—S4	77.03 (4)	H2A—C2—H2B	109.5
S3—Cu1—S1	168.48 (5)	N1—C2—H2C	109.5
S4—Cu1—S1	102.20 (4)	H2A—C2—H2C	109.5
S3—Cu1—S2	102.16 (4)	H2B—C2—H2C	109.5
S4—Cu1—S2	170.94 (5)	N1—C3—H3A	109.5
S1—Cu1—S2	76.75 (4)	N1—C3—H3B	109.5
S3—Cu1—S1ⁱ	100.81 (5)	H3A—C3—H3B	109.5
S4—Cu1—S1ⁱ	91.99 (4)	N1—C3—H3C	109.5
S1—Cu1—S1ⁱ	90.70 (4)	H3A—C3—H3C	109.5
S2—Cu1—S1ⁱ	97.01 (4)	H3B—C3—H3C	109.5
C1—S1—Cu1	84.09 (14)	N2—C4—S3	122.2 (3)
C1—S2—Cu1	84.21 (13)	N2—C4—S4	123.5 (3)
C4—S3—Cu1	84.45 (13)	S3—C4—S4	114.3 (2)
C4—S4—Cu1	84.12 (13)	N2—C5—H5A	109.5
C1—N1—C2	121.1 (4)	N2—C5—H5B	109.5
C1—N1—C3	121.2 (4)	H5A—C5—H5B	109.5
C2—N1—C3	117.3 (4)	N2—C5—H5C	109.5
C4—N2—C6	121.7 (4)	H5A—C5—H5C	109.5
C4—N2—C5	122.2 (4)	H5B—C5—H5C	109.5
C6—N2—C5	116.1 (4)	N2—C6—H6A	109.5
N1—C1—S2	123.4 (3)	N2—C6—H6B	109.5
N1—C1—S1	122.5 (3)	H6A—C6—H6B	109.5
S2—C1—S1	114.1 (2)	N2—C6—H6C	109.5
N1—C2—H2A	109.5	H6A—C6—H6C	109.5
N1—C2—H2B	109.5	H6B—C6—H6C	109.5

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₃H₆NS₂)₄]
M_r	607.91
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	8.068 (3), 19.446 (7), 15.108 (6)
β (°)	99.354 (6)
V (Å³)	2338.7 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.54
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2007)
T_min, T_max	0.807, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9796, 2685, 2423
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.141, 1.07
No. of reflections	2685
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.58

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—S3	2.3072 (13)	Cu1—S2	2.3278 (13)
Cu1—S4	2.3208 (13)	Cu1—S1ⁱ	2.8258 (14)
Cu1—S1	2.3240 (13)

Symmetry code: (i) −x+1, y, −z+1/2.

Acknowledgements

This work was supported financially by the Research Fund of Huaqiao University (No. 06BS216) and the Young Talent Fund of Fujian Province (No. 2007 F3060).

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