Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803009498/na6229sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803009498/na62292sup2.hkl |
CCDC reference: 214771
DMDS (5.64 g, 0.06 mol) was added to a stirred mixture of mesitylene (1.2 g, 0.01 mol) and K10/ZnCl2 (5 wt% ZnCl2) (10 g) (Clark et al., 1994) in dichloroethane (40 ml). After heating the mixture under reflux for 18 h, the reaction mixture was cooled and the clay catalyst was removed by filtration. Evaporation of the dichloroethane, mesitylene and excess DMDS left a semi-solid residue which afforded colorless crystals of (2) on crystallization from ethanol [m.p. > 373 K (decomposition)].
The H atoms were located from a difference Fourier map and were included in the refinement at idealized positions with isotropic displacement parameters 1.5 (CH3) and 1.2 (CH2) times the equivalent displacement parameters of the atoms to which they were bonded, with C—H distances of 0.98 and 0.99 Å, respectively.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1994); program(s) used to solve structure: SAPI91 (Fan, 1991); 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) drawing of (2), with displacement ellipsoids plotted at the 50% probability level. |
[ZnCl2(C4H10S2)] | F(000) = 520 |
Mr = 258.51 | Dx = 1.779 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 7.3110 (14) Å | θ = 10.0–15.0° |
b = 17.5535 (15) Å | µ = 3.45 mm−1 |
c = 7.7836 (15) Å | T = 170 K |
β = 104.984 (14)° | Prism, colorless |
V = 964.9 (3) Å3 | 0.35 × 0.26 × 0.15 mm |
Z = 4 |
Rigaku AFC-6S diffractometer | 1123 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.066 |
Graphite monochromator | θmax = 25.0°, θmin = 3.1° |
ω/2θ scans | h = 0→8 |
Absorption correction: empirical (using intensity measurements) via ψ scans (North et al., 1968) | k = 0→20 |
Tmin = 0.378, Tmax = 0.625 | l = −9→8 |
1834 measured reflections | 3 standard reflections every 200 reflections |
1706 independent reflections | intensity decay: 4.9% |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.043P)2 + 1.42P] where P = (Fo2 + 2Fc2)/3 |
1706 reflections | (Δ/σ)max < 0.001 |
84 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.80 e Å−3 |
[ZnCl2(C4H10S2)] | V = 964.9 (3) Å3 |
Mr = 258.51 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.3110 (14) Å | µ = 3.45 mm−1 |
b = 17.5535 (15) Å | T = 170 K |
c = 7.7836 (15) Å | 0.35 × 0.26 × 0.15 mm |
β = 104.984 (14)° |
Rigaku AFC-6S diffractometer | 1123 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scans (North et al., 1968) | Rint = 0.066 |
Tmin = 0.378, Tmax = 0.625 | 3 standard reflections every 200 reflections |
1834 measured reflections | intensity decay: 4.9% |
1706 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.62 e Å−3 |
1706 reflections | Δρmin = −0.80 e Å−3 |
84 parameters |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.49297 (10) | 0.10748 (4) | 0.14492 (10) | 0.0251 (2) | |
Cl1 | 0.7031 (2) | 0.01441 (10) | 0.2145 (2) | 0.0315 (4) | |
Cl2 | 0.4900 (3) | 0.19138 (10) | −0.0663 (2) | 0.0363 (4) | |
S1 | 0.5219 (2) | 0.18123 (10) | 0.4192 (2) | 0.0278 (4) | |
S2 | 0.1813 (2) | 0.06779 (9) | 0.1484 (2) | 0.0227 (4) | |
C1 | 0.4511 (10) | 0.2766 (4) | 0.3401 (9) | 0.0339 (16) | |
H1A | 0.3419 | 0.2737 | 0.2362 | 0.051* | |
H1B | 0.5564 | 0.3019 | 0.3067 | 0.051* | |
H1C | 0.4167 | 0.3057 | 0.4345 | 0.051* | |
C2 | 0.3094 (9) | 0.1454 (4) | 0.4745 (8) | 0.0267 (14) | |
H2A | 0.3411 | 0.0967 | 0.5396 | 0.032* | |
H2B | 0.2722 | 0.1821 | 0.5558 | 0.032* | |
C3 | 0.1402 (9) | 0.1322 (4) | 0.3160 (8) | 0.0293 (15) | |
H3A | 0.0993 | 0.1820 | 0.2591 | 0.035* | |
H3B | 0.0345 | 0.1119 | 0.3603 | 0.035* | |
C4 | 0.2174 (10) | −0.0219 (4) | 0.2648 (10) | 0.0329 (16) | |
H4A | 0.3023 | −0.0145 | 0.3836 | 0.049* | |
H4B | 0.2741 | −0.0584 | 0.1984 | 0.049* | |
H4C | 0.0955 | −0.0416 | 0.2757 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0216 (4) | 0.0266 (4) | 0.0279 (4) | 0.0007 (3) | 0.0078 (3) | 0.0033 (3) |
Cl1 | 0.0241 (8) | 0.0334 (9) | 0.0363 (9) | 0.0076 (7) | 0.0067 (7) | 0.0015 (7) |
Cl2 | 0.0448 (10) | 0.0335 (10) | 0.0300 (8) | −0.0118 (8) | 0.0085 (7) | 0.0050 (8) |
S1 | 0.0221 (8) | 0.0297 (9) | 0.0263 (8) | −0.0002 (7) | −0.0032 (6) | −0.0022 (7) |
S2 | 0.0201 (8) | 0.0232 (8) | 0.0230 (7) | −0.0011 (6) | 0.0023 (6) | −0.0010 (7) |
C1 | 0.033 (4) | 0.026 (4) | 0.040 (4) | −0.001 (3) | 0.005 (3) | −0.005 (3) |
C2 | 0.028 (3) | 0.028 (4) | 0.024 (3) | −0.003 (3) | 0.006 (3) | −0.002 (3) |
C3 | 0.025 (3) | 0.037 (4) | 0.026 (3) | −0.002 (3) | 0.007 (3) | −0.004 (3) |
C4 | 0.028 (4) | 0.025 (4) | 0.044 (4) | −0.001 (3) | 0.005 (3) | 0.005 (3) |
Zn1—Cl2 | 2.203 (2) | C1—H1C | 0.9800 |
Zn1—Cl1 | 2.212 (2) | C2—C3 | 1.522 (9) |
Zn1—S2 | 2.390 (2) | C2—H2A | 0.9900 |
Zn1—S1 | 2.459 (2) | C2—H2B | 0.9900 |
S1—C1 | 1.813 (7) | C3—H3A | 0.9900 |
S1—C2 | 1.828 (6) | C3—H3B | 0.9900 |
S2—C4 | 1.801 (7) | C4—H4A | 0.9800 |
S2—C3 | 1.809 (7) | C4—H4B | 0.9800 |
C1—H1A | 0.9800 | C4—H4C | 0.9800 |
C1—H1B | 0.9800 | ||
Cl2—Zn1—Cl1 | 123.28 (7) | C3—C2—S1 | 115.1 (4) |
Cl2—Zn1—S2 | 112.21 (7) | C3—C2—H2A | 108.5 |
Cl1—Zn1—S2 | 112.69 (7) | S1—C2—H2A | 108.5 |
Cl2—Zn1—S1 | 106.14 (7) | C3—C2—H2B | 108.5 |
Cl1—Zn1—S1 | 106.13 (6) | S1—C2—H2B | 108.5 |
S2—Zn1—S1 | 90.68 (6) | H2A—C2—H2B | 107.5 |
C1—S1—C2 | 102.3 (3) | C2—C3—S2 | 115.3 (5) |
C1—S1—Zn1 | 103.8 (2) | C2—C3—H3A | 108.4 |
C2—S1—Zn1 | 97.8 (2) | S2—C3—H3A | 108.4 |
C4—S2—C3 | 102.3 (3) | C2—C3—H3B | 108.4 |
C4—S2—Zn1 | 104.1 (2) | S2—C3—H3B | 108.4 |
C3—S2—Zn1 | 99.4 (2) | H3A—C3—H3B | 107.5 |
S1—C1—H1A | 109.5 | S2—C4—H4A | 109.5 |
S1—C1—H1B | 109.5 | S2—C4—H4B | 109.5 |
H1A—C1—H1B | 109.5 | H4A—C4—H4B | 109.5 |
S1—C1—H1C | 109.5 | S2—C4—H4C | 109.5 |
H1A—C1—H1C | 109.5 | H4A—C4—H4C | 109.5 |
H1B—C1—H1C | 109.5 | H4B—C4—H4C | 109.5 |
Cl2—Zn1—S1—C1 | 18.6 (3) | Cl2—Zn1—S2—C3 | −95.5 (2) |
Cl1—Zn1—S1—C1 | 151.3 (2) | Cl1—Zn1—S2—C3 | 120.1 (2) |
S2—Zn1—S1—C1 | −94.8 (2) | S1—Zn1—S2—C3 | 12.3 (2) |
Cl2—Zn1—S1—C2 | 123.3 (2) | C1—S1—C2—C3 | 68.4 (6) |
Cl1—Zn1—S1—C2 | −103.9 (2) | Zn1—S1—C2—C3 | −37.6 (5) |
S2—Zn1—S1—C2 | 10.0 (2) | S1—C2—C3—S2 | 57.0 (7) |
Cl2—Zn1—S2—C4 | 159.2 (3) | C4—S2—C3—C2 | 66.7 (6) |
Cl1—Zn1—S2—C4 | 14.8 (3) | Zn1—S2—C3—C2 | −40.1 (5) |
S1—Zn1—S2—C4 | −93.1 (3) |
Experimental details
Crystal data | |
Chemical formula | [ZnCl2(C4H10S2)] |
Mr | 258.51 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 170 |
a, b, c (Å) | 7.3110 (14), 17.5535 (15), 7.7836 (15) |
β (°) | 104.984 (14) |
V (Å3) | 964.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.45 |
Crystal size (mm) | 0.35 × 0.26 × 0.15 |
Data collection | |
Diffractometer | Rigaku AFC-6S diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scans (North et al., 1968) |
Tmin, Tmax | 0.378, 0.625 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1834, 1706, 1123 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.117, 1.10 |
No. of reflections | 1706 |
No. of parameters | 84 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −0.80 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1994), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Zn1—Cl2 | 2.203 (2) | S1—C1 | 1.813 (7) |
Zn1—Cl1 | 2.212 (2) | S1—C2 | 1.828 (6) |
Zn1—S2 | 2.390 (2) | S2—C4 | 1.801 (7) |
Zn1—S1 | 2.459 (2) | S2—C3 | 1.809 (7) |
Cl2—Zn1—Cl1 | 123.28 (7) | C1—S1—C2 | 102.3 (3) |
Cl2—Zn1—S2 | 112.21 (7) | C1—S1—Zn1 | 103.8 (2) |
Cl1—Zn1—S2 | 112.69 (7) | C2—S1—Zn1 | 97.8 (2) |
Cl2—Zn1—S1 | 106.14 (7) | C4—S2—C3 | 102.3 (3) |
Cl1—Zn1—S1 | 106.13 (6) | C4—S2—Zn1 | 104.1 (2) |
S2—Zn1—S1 | 90.68 (6) | C3—S2—Zn1 | 99.4 (2) |
Dithio compounds are of considerable interest with respect to their use in preparing conducting materials from organic substrates and for chelation of metal species. In this paper, we report a rather unusual preparation of [1,2-bis(methylthio)ethane]dichlorozinc(II), (2), from the commonly available solvent 1,2-dichloroethane and dimethyl disulfide (DMDS), using a ZnCl2-impregnated montmorillonite clay. Previously (Clark et al., 1996), we have reported the use of such clay materials to catalyze the electrophilic substitution of aromatics by –SMe groups. The mechanism of those reactions likely occurs by coordination of one S atom of DMDS to the ZnCl2 adsorbed on the clay surface, rendering the other S atom of DMDS electrophilic, followed by attack of the aromatic at that electrophilic sulfur. In the present case of the formation of (2), it is probable that the Cl of the dichloroethane solvent coordinates at the ZnCl2 adsorbed at the clay surface followed by attack of DMDS at the now electrophilic carbon bonded to the adsorbed Cl. A repeat of this process at the second C—Cl center results in the dithio compound (1), which then is able to chelate the ZnCl2 to form complex (2).
The crystal structure is composed of discrete monomeric molecules of (2) (Fig. 1) separated by normal van der Waals distances. The Zn atom is coordinated to two Cl and two S atoms, with Zn—Cl distances of 2.203 (2) and 2.212 (2) Å, and Zn—S distances of 2.390 (2) and 2.459 (2) Å. The angles Cl—Zn—Cl and S—Zn—S are 123.28 (7) and 90.68 (6)°, respectively, while the angles Cl—Zn—S are in the range 106.13 (6)–112.69 (7)°. The geometry around the Zn atom is distorted tetrahedral. A similar distorted tetrahedral geometry has been reported for the structures of (N,N'-dimethyldithiooxamide)dichlorozinc(II) (Antolini et al., 1987), trans-[2,3-bis(methylthio)hexane-S,S']dichlorozinc(II) (Parvez et al., 1997), trans-[1,2-bis(methylthio)cyclohexane-S,S']dichlorozinc(II) (Parvez et al., 1997) and cis-[5,6-bis(methylthio)-1,3-cycloheptadiene-S,S']dichlorozinc(II) (Parvez et al., 1997).
The S—C distances in (2) range between 1.801 (7) and 1.828 (6) Å, which are in agreement with the reported values (Orpen et al., 1994). The Zn1/S1/S2/C2/C3 five-membered ring adopts a C3-envelope conformation with C3 0.587 (9) Å out of the plane formed by the rest of the atoms in the ring; the maximum deviation of any atom from the mean plane is 0.098 (2) Å.