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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](N-C) = 0.005 Å
• R factor = 0.050
• wR factor = 0.141
• Data-to-parameter ratio = 22.8

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   293.000
            Value of melting point given =     0.000
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.68
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C2
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C3
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C5
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C6

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.683
            Tmax scaled      0.683 Tmin scaled      0.552
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 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
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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);

S2. Experimental

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).

S3. Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.96 Å, U_iso(H) = 1.5U_eq(C).

Computing details

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

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)]

Crystal data

[Cu2(C3H6NS2)4]	F(000) = 1240
Mr = 607.91	Dx = 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) Å^3	0.25 × 0.20 × 0.15 mm
Z = 4

Data collection

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

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.141	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0741P)^2 + 4.6176P] where P = (Fo^2 + 2Fc^2)/3
2685 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.58 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
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—S1^i	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—S1^i	100.81 (5)	H3A—C3—H3B	109.5
S4—Cu1—S1^i	91.99 (4)	N1—C3—H3C	109.5
S1—Cu1—S1^i	90.70 (4)	H3A—C3—H3C	109.5
S2—Cu1—S1^i	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.