Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021141/ya6142sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021141/ya6142Isup2.hkl |
CCDC reference: 202296
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%).
The H atoms were positioned geometrically and allowed to ride on their parent C atoms, with Uiso(H) = 1.2Ueq(C) for the methylene H atoms and 1.5Ueq(C) for the methyl H atoms.
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.
Fig. 1. ORTEPII (Johnson, 1976) plot of (I), with ellipsoids at the 50% probability level. H atoms are drawn as spheres of arbitrary radii. |
[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) Å3 | Block, colorless |
Z = 2 | 0.46 × 0.22 × 0.20 mm |
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 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0385P)2] where P = (Fo2 + 2Fc2)/3 |
4460 reflections | (Δ/σ)max < 0.001 |
210 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −1.12 e Å−3 |
[Zn2(C8H8NS2)4] | V = 1856.09 (3) Å3 |
Mr = 859.84 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.7276 (1) Å | µ = 1.77 mm−1 |
b = 6.6693 (1) Å | T = 298 K |
c = 22.2508 (1) Å | 0.46 × 0.22 × 0.20 mm |
β = 100.669 (1)° |
Bruker CCD area-detector diffractometer | 4460 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3383 reflections with I > 2σ(I) |
Tmin = 0.496, Tmax = 0.718 | Rint = 0.089 |
12082 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.56 e Å−3 |
4460 reflections | Δρmin = −1.12 e Å−3 |
210 parameters |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Zn1—S1 | 2.316 (1) | C11—C12 | 1.387 (4) |
Zn1—S2 | 2.980 (1) | C12—C13 | 1.391 (4) |
Zn1—S2i | 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—S2i | 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) |
S2i—Zn1—S3 | 117.7 (1) | N1—C2—H2a | 109.5 |
S2i—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—Zn1i | 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) |
S2i—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) |
S2i—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) |
S2i—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) | Zn1i—S2—C9—N2 | 85.2 (2) |
C3—N1—C1—S3 | 1.2 (4) | Zn1i—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. |
Experimental details
Crystal data | |
Chemical formula | [Zn2(C8H8NS2)4] |
Mr | 859.84 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 12.7276 (1), 6.6693 (1), 22.2508 (1) |
β (°) | 100.669 (1) |
V (Å3) | 1856.09 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.77 |
Crystal size (mm) | 0.46 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.496, 0.718 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12082, 4460, 3383 |
Rint | 0.089 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.114, 0.95 |
No. of reflections | 4460 |
No. of parameters | 210 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.56, −1.12 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Zn1—S1 | 2.316 (1) | Zn1—S3 | 2.348 (1) |
Zn1—S2 | 2.980 (1) | Zn1—S4 | 2.459 (1) |
Zn1—S2i | 2.378 (1) | ||
S1—Zn1—S2i | 105.9 (1) | S3—Zn1—S4 | 76.1 (1) |
S1—Zn1—S3 | 130.9 (1) | C9—S1—Zn1 | 96.8 (1) |
S1—Zn1—S4 | 112.2 (1) | C9—S2—Zn1i | 99.9 (1) |
S2i—Zn1—S3 | 117.7 (1) | C1—S3—Zn1 | 83.8 (1) |
S2i—Zn1—S4 | 107.7 (1) | C1—S4—Zn1 | 80.8 (1) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
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.