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The Pd atom in the title compound, [Pd(C3H5OS2)2], lies on an inversion center and adopts a square-planar coordination geometry defined by the four S atoms of the two dithiocarbonate (xanthate) ligands. In the solid state, the molecules aggregate into layers in which the rows of molecules alternate their orientation to allow each Pd atom to interact with two symmetry-equivalent S atoms of the xanthate ligands of adjacent molecules, generating a pseudo-octahedral environment around each Pd atom. This weak interaction of 3.3579 (7) Å can be classified as a closed-shell electrostatic intermolecular interaction.
Supporting information
CCDC reference: 214151
Compound (I) (yield 82%.; m.p. 424 K.) was prepared following the procedure described by Bulmer and Mann (1945), but using as starting materials [Zn(S2COEt)2] and [PdCl2(SC4H8)2]. Analysis; found: C 20.43, H 2.75, S 36.30%; calculated: C 20.67, H 2.87, S 36.71%.
Single crystals were obtained by slow diffusion of n-hexane into a dichloromethane solution of the complex at room temperature.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 2000); software used to prepare material for publication: XP in SHELXTL.
bis(
O-ethyl dithiocarbonato)palladium(II)
top
Crystal data top
[Pd(C3H5OS2)2] | Dx = 2.070 Mg m−3 |
Mr = 348.78 | Melting point: 424 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 2030 reflections |
a = 7.4958 (6) Å | θ = 3.9–27.6° |
b = 7.1942 (6) Å | µ = 2.37 mm−1 |
c = 20.7522 (18) Å | T = 100 K |
V = 1119.09 (16) Å3 | Plate, orange |
Z = 4 | 0.36 × 0.20 × 0.12 mm |
F(000) = 688 | |
Data collection top
Bruker SMART APEX CCD diffractometer | 1324 independent reflections |
Radiation source: fine-focus sealed tube | 992 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
Detector resolution: 8.26 pixels mm-1 | θmax = 28.3°, θmin = 2.0° |
ω rotation scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | k = −9→7 |
Tmin = 0.483, Tmax = 0.764 | l = −27→24 |
6401 measured reflections | |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.057 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0251P)2] where P = (Fo2 + 2Fc2)/3 |
1324 reflections | (Δ/σ)max < 0.001 |
61 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
Crystal data top
[Pd(C3H5OS2)2] | V = 1119.09 (16) Å3 |
Mr = 348.78 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.4958 (6) Å | µ = 2.37 mm−1 |
b = 7.1942 (6) Å | T = 100 K |
c = 20.7522 (18) Å | 0.36 × 0.20 × 0.12 mm |
Data collection top
Bruker SMART APEX CCD diffractometer | 1324 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 992 reflections with I > 2σ(I) |
Tmin = 0.483, Tmax = 0.764 | Rint = 0.048 |
6401 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.057 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.48 e Å−3 |
1324 reflections | Δρmin = −0.42 e Å−3 |
61 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 | Uiso*/Ueq | |
Pd | 0.5000 | 0.0000 | 0.5000 | 0.01919 (10) | |
S1 | 0.38861 (9) | 0.28725 (11) | 0.53224 (4) | 0.02173 (18) | |
S2 | 0.61448 (9) | 0.04312 (10) | 0.60364 (4) | 0.02177 (18) | |
O | 0.5053 (2) | 0.3577 (3) | 0.65159 (10) | 0.0213 (4) | |
C1 | 0.5020 (3) | 0.2483 (4) | 0.60151 (14) | 0.0194 (6) | |
C2 | 0.4117 (4) | 0.5357 (4) | 0.64662 (15) | 0.0223 (7) | |
H2A | 0.2829 | 0.5150 | 0.6391 | 0.027* | |
H2B | 0.4602 | 0.6096 | 0.6104 | 0.027* | |
C3 | 0.4402 (4) | 0.6353 (5) | 0.70905 (15) | 0.0301 (8) | |
H3A | 0.3791 | 0.7557 | 0.7078 | 0.045* | |
H3B | 0.5681 | 0.6550 | 0.7158 | 0.045* | |
H3C | 0.3918 | 0.5604 | 0.7444 | 0.045* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pd | 0.01655 (15) | 0.02276 (18) | 0.01827 (18) | 0.00076 (14) | −0.00097 (14) | 0.00178 (14) |
S1 | 0.0203 (3) | 0.0240 (4) | 0.0209 (4) | 0.0023 (3) | −0.0026 (3) | 0.0024 (3) |
S2 | 0.0199 (3) | 0.0250 (4) | 0.0204 (4) | 0.0034 (3) | −0.0024 (3) | 0.0019 (3) |
O | 0.0195 (9) | 0.0230 (11) | 0.0212 (12) | 0.0030 (9) | −0.0011 (9) | 0.0006 (9) |
C1 | 0.0124 (12) | 0.0258 (15) | 0.0198 (16) | −0.0041 (12) | 0.0018 (12) | 0.0039 (13) |
C2 | 0.0181 (14) | 0.0236 (16) | 0.0252 (17) | 0.0041 (13) | −0.0012 (13) | 0.0012 (13) |
C3 | 0.0316 (16) | 0.032 (2) | 0.0268 (19) | 0.0044 (14) | −0.0007 (14) | −0.0010 (16) |
Geometric parameters (Å, º) top
Pd—S1i | 2.3271 (8) | O—C2 | 1.463 (3) |
Pd—S1 | 2.3271 (8) | C2—C3 | 1.496 (4) |
Pd—S2 | 2.3363 (8) | C2—H2A | 0.9900 |
Pd—S2i | 2.3363 (8) | C2—H2B | 0.9900 |
S1—C1 | 1.693 (3) | C3—H3A | 0.9800 |
S2—C1 | 1.700 (3) | C3—H3B | 0.9800 |
O—C1 | 1.304 (3) | C3—H3C | 0.9800 |
| | | |
S1i—Pd—S1 | 180.00 (4) | O—C2—C3 | 106.8 (2) |
S1i—Pd—S2 | 104.53 (3) | O—C2—H2A | 110.4 |
S1—Pd—S2 | 75.47 (3) | C3—C2—H2A | 110.4 |
S1i—Pd—S2i | 75.47 (3) | O—C2—H2B | 110.4 |
S1—Pd—S2i | 104.53 (3) | C3—C2—H2B | 110.4 |
S2—Pd—S2i | 180.0 | H2A—C2—H2B | 108.6 |
C1—S1—Pd | 85.24 (11) | C2—C3—H3A | 109.5 |
C1—S2—Pd | 84.78 (10) | C2—C3—H3B | 109.5 |
C1—O—C2 | 117.6 (2) | H3A—C3—H3B | 109.5 |
O—C1—S1 | 125.9 (2) | C2—C3—H3C | 109.5 |
O—C1—S2 | 119.6 (2) | H3A—C3—H3C | 109.5 |
S1—C1—S2 | 114.50 (17) | H3B—C3—H3C | 109.5 |
| | | |
S2—Pd—S1—C1 | 0.10 (9) | Pd—S1—C1—O | −178.5 (2) |
S2i—Pd—S1—C1 | −179.90 (9) | Pd—S1—C1—S2 | −0.14 (13) |
S1i—Pd—S2—C1 | 179.91 (9) | Pd—S2—C1—O | 178.6 (2) |
S1—Pd—S2—C1 | −0.09 (9) | Pd—S2—C1—S1 | 0.14 (13) |
C2—O—C1—S1 | −3.8 (3) | C1—O—C2—C3 | −178.5 (2) |
C2—O—C1—S2 | 177.88 (18) | | |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Pd(C3H5OS2)2] |
Mr | 348.78 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 100 |
a, b, c (Å) | 7.4958 (6), 7.1942 (6), 20.7522 (18) |
V (Å3) | 1119.09 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.37 |
Crystal size (mm) | 0.36 × 0.20 × 0.12 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.483, 0.764 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6401, 1324, 992 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.667 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.057, 0.92 |
No. of reflections | 1324 |
No. of parameters | 61 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.42 |
Selected geometric parameters (Å, º) topPd—S1 | 2.3271 (8) | O—C1 | 1.304 (3) |
Pd—S2 | 2.3363 (8) | O—C2 | 1.463 (3) |
S1—C1 | 1.693 (3) | C2—C3 | 1.496 (4) |
S2—C1 | 1.700 (3) | | |
| | | |
S1i—Pd—S1 | 180.00 (4) | C1—S1—Pd | 85.24 (11) |
S1i—Pd—S2 | 104.53 (3) | C1—S2—Pd | 84.78 (10) |
S1—Pd—S2 | 75.47 (3) | C1—O—C2 | 117.6 (2) |
Symmetry code: (i) −x+1, −y, −z+1. |
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Xanthate ligands have been extensively studied for a wide variety of structural features. They can act as monodentate, bidentate or bridging ligands to two or even three metal centers, which leads to a variety of complexes. A structural feature of xanthates that is not very well represented in the literature is their involvement in intermolecular interactions. Such interactions are the basis for crystal engineering, their nature and strength determining their competitive importance in forming different crystal packings (Desiraju, 1995). The S atom, although weak, is a donor atom and can interact with acceptors to help define the crystal packing of the molecules (Xue et al., 2003). As far as metal xanthates are concerned, the intermolecular distances are long enough in most cases to preclude any kind of interaction (Eisenberg, 1970); other cases have not been explored?. In the title complex, (I), the intermolecular interactions are not negligible and contribute to the shaping of the supramolecular array. Although (I) was first synthesized in 1945 (Bulmer & Mann, 1945) and its structure is known to be square-planar, as in [Ni(S2COEt)2] or [Pt(S2COEt)2] (Watt & McCormick, 1965), a description of the crystal packing of (I) has not been reported to date.
The crystal structure of (I) shows that the Pd atom, which is located at a center of inversion, is coordinated by two equivalent xanthate groups, each group behaving as a bidentate ligand through two sulfur atoms. The two Pd—S distances are not significantly different and the S—C, C—O and O—C distances have the usual lengths (Table 1). The S1···S2 bite distance is 2.8542 (11) Å, which is somewhat longer than that found in other related complexes of group 10 metals, which range from 2.81 to 2.84 Å (Chen & Fackler, 1978, Chan et al., 1982). Considerable strain within the four membered 1,1-dithiolato chelate is evidenced by a significant deviation from ideal square-planar coordination, the bite angle of the xanthate being 75.47 (3)°. All non hydrogen atoms of the molecule [Pd(S2COEt)2] are in a plane (mean deviation is 0.01 Å).
The supramolecular structure of (I) consists of a two-dimensional array of molecules. In each layer, rows of molecules alternate their orientations and lie at an angle of 72.77 (2)° to each other. This allows each Pd atom to interact with two equivalent S1 atoms of neighboring centrosymmetrically related molecules, thereby giving an S1i···Pd···Sii [symmetry codes: (i) 0.5 − x, y − 0.5, z; (ii) 0.5 + x, 0.5 − y, 1 − z] angle of 180°. The Pd···S1i distance of 3.3579 (7) Å is considerably shorter than the sum of the van der Waals radii (3.8 Å; Whuler et al., 1980) of these atoms. Considering these Pd···S contacts, the Pd atom lies in a pseudo-octahedral coordination environment, with a heavy tetragonal distortion of four short and two long Pd—S distances. The S1—Pd···S1ii and S2—Pd···S1ii angles are 87.92 (1) and 78.72 (2)°, respectively. These intermolecular contacts can be classified as closed-shell electrostatic interactions rather than donor-acceptor interactions, because the distance is closer to the limit of the van der Waals contacts than to true Pd—S bond lengths and there is no significant distortion of the geometry of the formal complex (Bertolasi et al., 2001). The structure of (I) is comparable to that of the arylxanthate derivative, Pd(S2COC6H2-2,4,6-Me3)2 (Chen & Fackler, 1978). In both cases, the geometric parameters around the Pd atoms are very similar, but in the latter, the PdS4 groups form a plane to which the phenyl ring plane is perpendicular. This conformation precludes any intermolecular interactions, the nearest Pd—S distance being 5.834 Å.