Bis(μ-N-methyl-N-phenyl­di­thio­carbamato)[bis(N-methyl-N-phenyl­di­thio­carbamato)­zinc(II)]

The Zn atom in the centrosymmetric title compound, [Zn₂(C₈H₈NS₂)₄], is almost symmetrically coordinated by one terminal bidentate N-phenyl-N-methyl­di­thio­carbamate ligand [Zn—S 2.348 (1) and 2.459 (1) Å] and non-symmetrically coordinated by a second bidentate bridging di­thio­carbamate ligand [Zn—S 2.316 (1) and 2.980 (1) Å]. The latter also uses its bridging S atom to coordinate the second Zn atom [Zn—S 2.378 (1) Å], thus forming a dimeric binuclear complex. Taking into account the long Zn...S distance, the Zn atom has a distorted trigonal–bipyramidal coordination.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.047
• wR factor = 0.114
• Data-to-parameter ratio = 21.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_702  Alert C Angle   Calc   130.86(3), Rep  130.90(10), Dev.      1.33 Sigma
                     S1   -ZN1  -S3      1.555   1.555   1.555

PLAT_702  Alert C Angle   Calc   107.65(3), Rep  107.70(10), Dev.      1.67 Sigma
                     S2   -ZN1  -S4      3.666   1.555   1.555

PLAT_732  Alert C Angle   Calc   130.86(3), Rep  130.90(10) ....       3.33 su-Ratio
                     S1   -ZN1  -S3      1.555   1.555   1.555

PLAT_732  Alert C Angle   Calc   112.23(3), Rep  112.20(10) ....       3.33 su-Ratio
                     S1   -ZN1  -S4      1.555   1.555   1.555

PLAT_732  Alert C Angle   Calc    76.13(3), Rep   76.10(10) ....       3.33 su-Ratio
                     S3   -ZN1  -S4      1.555   1.555   1.555


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 5 Alert Level C = Please check

---

S1. Comment

The crystal structures of a number of zinc(II) dithiocarbamates have been reported; such compounds exist as centrosymmetric dimers (Cox & Tiekink, 1997). We have previously described complexes with ethylisopropyldithiocarbamate (Baba et al., 2001a), as well as ethylbutyldithiocarbamate (Baba et al., 2001b) ligands.

In the title compound, (I) (Fig. 1), both dithiocarbamate groups chelate to the Zn atom. One of the dithiocarbamates represents a terminal bidentate ligand with comparable bond lengths [Zn1—S3 2.348 (1) Å and Zn1—S4 2.459 (1) Å]. Another dithiocarbamate coordinates the Zn atom in a bridging bidentate manner, forming two distinctly unequal Zn1—S1 and Zn1···S2 bonds [2.316 (1) and 2.980 (1) Å, respectively]. The C—S bonds in either of the ligands are delocalized and can hardly be distinguished formally as single or double bonds [C1—S3 1.732 (3), C1—S4 1.712 (3), C9—S1 1.717 (2) and C9—S2 1.742 (2) Å]. Atom S2, which forms longer C—S bond in the bridging ligand, interacts across the inversion center with an adjacent complex, forming a short S2—Zn1ⁱ bond [2.378 (1) Å; symmetry code: (i) 1 − x, 1 − y, 1 − z]. If the long Zn1···S2 interaction is taken into account, the coordination geometry of the Zn1 atom may be represented as a severely distorted trigonal bipyramid.

S2. Experimental

The title compound, (I), was synthesized from zinc dichloride (10 mmol), methylaniline (20 mmol) and carbon disulfide (20 mmol) in ethanol solution according to the procedure described for the synthesis of such compounds (Baba et al., 2001a,b). Crystals were obtained by the use of a dichloromethane–methanol (1/1) mixture. Elemental analysis, found (calculated): C 43.69 (44.70), H 3.75 (3.75), N 6.52 (7.52), S 29.82% (29.83%).

S3. Refinement

The H atoms were positioned geometrically and allowed to ride on their parent C atoms, with U_iso(H) = 1.2U_eq(C) for the methylene H atoms and 1.5U_eq(C) for the methyl H atoms.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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: SHELXL97.

Figures

Fig. 1. ORTEPII (Johnson, 1976) plot of (I), with ellipsoids at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.

Bis(µ-N-methyl-N-phenyldithiocarbamato)[bis(µ-N-methyl-N– phenyldithiocarbamato)zinc(II)]

Crystal data

[Zn2(C8H8NS2)4]	F(000) = 880
Mr = 859.84	Dx = 1.538 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.7276 (1) Å	Cell parameters from 8192 reflections
b = 6.6693 (1) Å	θ = 1.6–28.2°
c = 22.2508 (1) Å	µ = 1.77 mm^−1
β = 100.669 (1)°	T = 298 K
V = 1856.09 (3) Å^3	Block, colorless
Z = 2	0.46 × 0.22 × 0.20 mm

Data collection

Bruker CCD area-detector diffractometer	4460 independent reflections
Radiation source: fine-focus sealed tube	3383 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.089
Detector resolution: 0 pixels mm^-1	θmax = 28.2°, θmin = 1.6°
ω scans	h = −16→15
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −8→8
Tmin = 0.496, Tmax = 0.718	l = −29→24
12082 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0385P)^2] where P = (Fo^2 + 2Fc^2)/3
4460 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.56 e Å^−3
0 restraints	Δρmin = −1.12 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.38122 (2)	0.34366 (5)	0.51329 (1)	0.0407 (1)
S1	0.46543 (6)	0.3716 (1)	0.61451 (3)	0.0446 (2)
S2	0.48256 (5)	0.7436 (1)	0.54213 (3)	0.0353 (2)
S3	0.22693 (5)	0.5001 (1)	0.45933 (3)	0.0383 (2)
S4	0.24708 (6)	0.0742 (1)	0.49795 (4)	0.0485 (2)
N1	0.0754 (2)	0.2269 (4)	0.4245 (1)	0.045 (1)
N2	0.5953 (2)	0.6696 (3)	0.6542 (1)	0.032 (1)
C1	0.1732 (2)	0.2611 (4)	0.4577 (1)	0.037 (1)
C2	0.0269 (3)	0.0249 (5)	0.4183 (2)	0.079 (1)
C3	0.0142 (2)	0.3836 (4)	0.3891 (1)	0.041 (1)
C4	0.0389 (2)	0.4417 (5)	0.3342 (1)	0.048 (1)
C5	−0.0223 (3)	0.5854 (5)	0.2989 (2)	0.058 (1)
C6	−0.1083 (3)	0.6708 (5)	0.3189 (2)	0.062 (1)
C7	−0.1330 (3)	0.6116 (5)	0.3742 (2)	0.065 (1)
C8	−0.0721 (3)	0.4669 (5)	0.4098 (2)	0.057 (1)
C9	0.5231 (2)	0.6013 (4)	0.6080 (1)	0.030 (1)
C10	0.6462 (3)	0.8680 (4)	0.6545 (1)	0.047 (1)
C11	0.6323 (2)	0.5478 (4)	0.7080 (1)	0.033 (1)
C12	0.5937 (2)	0.5852 (4)	0.7612 (1)	0.042 (1)
C13	0.6317 (3)	0.4720 (5)	0.8132 (1)	0.049 (1)
C14	0.7074 (3)	0.3261 (4)	0.8121 (2)	0.051 (1)
C15	0.7460 (2)	0.2906 (5)	0.7585 (2)	0.052 (1)
C16	0.7084 (2)	0.4017 (4)	0.7061 (1)	0.041 (1)
H2a	0.0536	−0.0523	0.4543	0.118*
H2b	0.0449	−0.0407	0.3831	0.118*
H2c	−0.0494	0.0365	0.4134	0.118*
H4	0.0969	0.3843	0.3207	0.057*
H5	−0.0054	0.6244	0.2617	0.070*
H6	−0.1495	0.7676	0.2953	0.074*
H7	−0.1910	0.6693	0.3877	0.078*
H8	−0.0891	0.4268	0.4469	0.069*
H10a	0.6150	0.9401	0.6183	0.070*
H10b	0.7214	0.8515	0.6555	0.070*
H10c	0.6354	0.9416	0.6899	0.070*
H12	0.5429	0.6848	0.7621	0.050*
H13	0.6057	0.4954	0.8489	0.059*
H14	0.7327	0.2512	0.8470	0.061*
H15	0.7973	0.1918	0.7578	0.062*
H16	0.7343	0.3779	0.6703	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0332 (2)	0.0588 (2)	0.0266 (2)	−0.0073 (1)	−0.0032 (1)	0.0010 (1)
S1	0.0580 (4)	0.0439 (4)	0.0262 (3)	−0.0205 (3)	−0.0072 (3)	0.0070 (3)
S2	0.0362 (3)	0.0378 (3)	0.0292 (3)	0.0029 (3)	−0.0014 (3)	0.0058 (3)
S3	0.0332 (3)	0.0369 (3)	0.0405 (4)	−0.0085 (3)	−0.0045 (3)	−0.0025 (3)
S4	0.0478 (4)	0.0418 (4)	0.0511 (5)	−0.0109 (3)	−0.0033 (3)	0.0070 (3)
N1	0.037 (1)	0.044 (1)	0.049 (1)	−0.015 (1)	−0.004 (1)	−0.005 (1)
N2	0.038 (1)	0.028 (1)	0.028 (1)	−0.002 (1)	−0.003 (1)	−0.001 (1)
C1	0.035 (1)	0.041 (1)	0.034 (1)	−0.009 (1)	0.002 (1)	−0.005 (1)
C2	0.068 (2)	0.057 (2)	0.098 (3)	−0.033 (2)	−0.021 (2)	0.000 (2)
C3	0.029 (1)	0.046 (2)	0.042 (2)	−0.010 (1)	−0.006 (1)	−0.010 (1)
C4	0.037 (2)	0.058 (2)	0.043 (2)	−0.003 (1)	−0.002 (1)	−0.008 (1)
C5	0.061 (2)	0.061 (2)	0.048 (2)	−0.009 (2)	−0.004 (2)	0.000 (2)
C6	0.048 (2)	0.055 (2)	0.073 (3)	−0.002 (2)	−0.017 (2)	−0.014 (2)
C7	0.036 (2)	0.063 (2)	0.090 (3)	0.000 (2)	−0.002 (2)	−0.029 (2)
C8	0.044 (2)	0.067 (2)	0.059 (2)	−0.015 (2)	0.009 (2)	−0.018 (2)
C9	0.031 (1)	0.032 (1)	0.026 (1)	0.000 (1)	0.001 (1)	−0.002 (1)
C10	0.056 (2)	0.034 (1)	0.045 (2)	−0.011 (1)	−0.006 (1)	−0.003 (1)
C11	0.035 (1)	0.032 (1)	0.026 (1)	−0.001 (1)	−0.008 (1)	−0.002 (1)
C12	0.052 (2)	0.041 (1)	0.030 (1)	0.011 (1)	−0.001 (1)	−0.002 (1)
C13	0.065 (2)	0.050 (2)	0.030 (2)	0.005 (1)	0.002 (1)	0.001 (1)
C14	0.057 (2)	0.045 (2)	0.042 (2)	0.005 (1)	−0.015 (1)	0.009 (1)
C15	0.044 (2)	0.044 (2)	0.061 (2)	0.015 (1)	−0.006 (1)	0.003 (1)
C16	0.039 (1)	0.041 (2)	0.041 (2)	0.005 (1)	0.004 (1)	−0.003 (1)

Geometric parameters (Å, º)

Zn1—S1	2.316 (1)	C11—C12	1.387 (4)
Zn1—S2	2.980 (1)	C12—C13	1.391 (4)
Zn1—S2^i	2.378 (1)	C13—C14	1.372 (4)
Zn1—S3	2.348 (1)	C14—C15	1.390 (5)
Zn1—S4	2.459 (1)	C15—C16	1.389 (4)
S1—C9	1.717 (2)	C2—H2a	0.9600
S2—C9	1.742 (2)	C2—H2b	0.9600
S3—C1	1.732 (3)	C2—H2c	0.9600
S4—C1	1.712 (3)	C4—H4	0.9300
N1—C1	1.345 (3)	C5—H5	0.9300
N1—C3	1.446 (4)	C6—H6	0.9300
N1—C2	1.478 (4)	C7—H7	0.9300
N2—C9	1.327 (3)	C8—H8	0.9300
N2—C11	1.450 (3)	C10—H10a	0.9600
N2—C10	1.473 (3)	C10—H10b	0.9600
C3—C4	1.373 (4)	C10—H10c	0.9600
C3—C8	1.383 (4)	C12—H12	0.9300
C4—C5	1.384 (5)	C13—H13	0.9300
C5—C6	1.379 (5)	C14—H14	0.9300
C6—C7	1.383 (6)	C15—H15	0.9300
C7—C8	1.391 (5)	C16—H16	0.9300
C11—C16	1.380 (4)
S1—Zn1—S2^i	105.9 (1)	C13—C14—C15	119.7 (3)
S1—Zn1—S3	130.9 (1)	C16—C15—C14	120.5 (3)
S1—Zn1—S4	112.2 (1)	C11—C16—C15	119.1 (3)
S2^i—Zn1—S3	117.7 (1)	N1—C2—H2a	109.5
S2^i—Zn1—S4	107.7 (1)	N1—C2—H2b	109.5
S3—Zn1—S4	76.1 (1)	H2a—C2—H2b	109.5
C9—S1—Zn1	96.8 (1)	N1—C2—H2c	109.5
C9—S2—Zn1^i	99.9 (1)	H2a—C2—H2c	109.5
C1—S3—Zn1	83.8 (1)	H2b—C2—H2c	109.5
C1—S4—Zn1	80.8 (1)	C3—C4—H4	119.9
C1—N1—C3	121.8 (2)	C5—C4—H4	119.9
C1—N1—C2	122.3 (3)	C6—C5—H5	120.0
C3—N1—C2	115.7 (2)	C4—C5—H5	120.0
C9—N2—C11	121.3 (2)	C5—C6—H6	120.2
C9—N2—C10	123.6 (2)	C7—C6—H6	120.2
C11—N2—C10	115.1 (2)	C6—C7—H7	119.6
N1—C1—S4	121.8 (2)	C8—C7—H7	119.6
N1—C1—S3	119.3 (2)	C3—C8—H8	120.6
S4—C1—S3	118.9 (2)	C7—C8—H8	120.6
C4—C3—C8	120.6 (3)	N2—C10—H10a	109.5
C4—C3—N1	120.0 (3)	N2—C10—H10b	109.5
C8—C3—N1	119.3 (3)	H10a—C10—H10b	109.5
C3—C4—C5	120.2 (3)	N2—C10—H10c	109.5
C6—C5—C4	120.0 (4)	H10a—C10—H10c	109.5
C5—C6—C7	119.6 (4)	H10b—C10—H10c	109.5
C6—C7—C8	120.7 (3)	C11—C12—H12	120.4
C3—C8—C7	118.8 (4)	C13—C12—H12	120.4
N2—C9—S1	119.1 (2)	C14—C13—H13	119.7
N2—C9—S2	121.4 (2)	C12—C13—H13	119.7
S1—C9—S2	119.5 (1)	C13—C14—H14	120.1
C16—C11—C12	120.9 (2)	C15—C14—H14	120.1
C16—C11—N2	119.6 (2)	C16—C15—H15	119.8
C12—C11—N2	119.4 (2)	C14—C15—H15	119.8
C11—C12—C13	119.3 (3)	C11—C16—H16	120.4
C14—C13—C12	120.5 (3)	C15—C16—H16	120.4
S3—Zn1—S1—C9	−75.6 (1)	C5—C6—C7—C8	−0.1 (5)
S2^i—Zn1—S1—C9	76.6 (1)	C4—C3—C8—C7	−0.4 (4)
S4—Zn1—S1—C9	−166.3 (1)	N1—C3—C8—C7	−177.4 (3)
S1—Zn1—S3—C1	−111.5 (1)	C6—C7—C8—C3	0.3 (5)
S2^i—Zn1—S3—C1	99.0 (1)	C11—N2—C9—S1	4.9 (3)
S4—Zn1—S3—C1	−4.0 (1)	C10—N2—C9—S1	−177.3 (2)
S1—Zn1—S4—C1	132.9 (1)	C11—N2—C9—S2	−177.4 (2)
S3—Zn1—S4—C1	4.0 (1)	C10—N2—C9—S2	0.5 (4)
S2^i—Zn1—S4—C1	−111.0 (1)	Zn1—S1—C9—N2	−169.8 (2)
C3—N1—C1—S4	−178.3 (2)	Zn1—S1—C9—S2	12.4 (2)
C2—N1—C1—S4	−2.8 (4)	Zn1^i—S2—C9—N2	85.2 (2)
C3—N1—C1—S3	1.2 (4)	Zn1^i—S2—C9—S1	−97.0 (1)
C2—N1—C1—S3	176.7 (3)	C9—N2—C11—C16	79.7 (3)
Zn1—S4—C1—N1	173.4 (2)	C10—N2—C11—C16	−98.3 (3)
Zn1—S4—C1—S3	−6.1 (1)	C9—N2—C11—C12	−102.8 (3)
Zn1—S3—C1—N1	−173.1 (2)	C10—N2—C11—C12	79.2 (3)
Zn1—S3—C1—S4	6.3 (2)	C16—C11—C12—C13	−0.6 (4)
C1—N1—C3—C4	77.1 (4)	N2—C11—C12—C13	−178.1 (3)
C2—N1—C3—C4	−98.7 (3)	C11—C12—C13—C14	0.6 (5)
C1—N1—C3—C8	−105.9 (3)	C12—C13—C14—C15	−0.3 (5)
C2—N1—C3—C8	78.3 (4)	C13—C14—C15—C16	0.0 (5)
C8—C3—C4—C5	0.2 (4)	C12—C11—C16—C15	0.3 (4)
N1—C3—C4—C5	177.2 (3)	N2—C11—C16—C15	177.8 (3)
C3—C4—C5—C6	0.1 (5)	C14—C15—C16—C11	0.0 (5)
C4—C5—C6—C7	−0.1 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.