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The dichloro­methane solvates of the isomers tetra­kis([mu]-1,3-benzothia­zole-2-thiol­ato)-[kappa]4N:S;[kappa]4S:N-dipalladium(II)(Pd-Pd), (I), and tetra­kis([mu]-1,3-benzothia­zole-2-thiol­ato)-[kappa]6N:S;[kappa]2S:N-dipalladium(II)(Pd-Pd), (II), both [Pd2(C7H4­NS2)4]·CH2Cl2, have been synthesized in the presence of (o-isopropyl­phen­yl)­diphenyl­phosphane and (o-methyl­phen­yl)­diphenyl­phosphane. Both isomers form a lantern-type structure, where isomer (I) displays a regular and symmetric coordination and isomer (II) an asymmetric and distorted structure. In (I), sitting on an centre of inversion, two 1,3-benzothia­zole-2-thiol­ate units are bonded by a Pd-N bond to one Pd atom and by a Pd-S bond to the other Pd atom, and the other two benzothia­zole­thiol­ate units are bonded to the same Pd atoms by, respectively, a Pd-S and a Pd-N bond. In (II), three benzothia­zole­thiol­ate units are bonded by a Pd-N bond to one Pd atom and by a Pd-S bond to the other Pd atom, and the fourth benzothia­zole­thiol­ate unit is bonded to the same Pd atoms by, respectively, a Pd-S bond and a Pd-N bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107052353/tr3019sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107052353/tr3019Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107052353/tr3019IIsup3.hkl
Contains datablock II

CCDC references: 610377; 610378

Comment top

The construction of supramolecular coordination complexes by self-assembly in the coordinative-bond approach is a well known method (Fujita, 1998; Holliday & Mirkin, 2001; Dinolfo & Hupp, 2001). The use of highly directional hydrogen bonds together with the coordinative bond approach as a means to control self-assembly in supramolecular systems has been recognized as a versatile tool in inorganic materials synthesis (Braga et al., 1998; Burrows et al., 1995).

The combination of an exocyclic thione group and a heterocyclic molecule, containing nitrogen, oxygen, sulfur or a combination of these, generates a group of compounds with considerable coordination potential. Molecules such as 2-mercaptopyridine, 2-mercaptobenzothiazole, 2-mercaptopyrimidine, 2-mercaptobenzimidazole and 2-mercaptothiazoline belong to this class of ligands, and they have shown a rich coordination chemistry (Raper, 1985). The deprotonation of these molecules has resulted in an interesting chemical behaviour and a high versatility as ligands. Several coordination modes are possible for pyridine-2-thiolate (S-coordinated, N,S-chelated, N,S-bridging and N,S-triply bridging) and benzothiazole-2-thiolate (double and triply bridging) and related compounds (Lizarraga et al., 1997). The square-planar platinum (Raper et al., 1987; Umakoshi et al., 1990) and palladium (Kubiak, 1985; Raper et al., 1989) complexes of such compounds exhibit a variety of intermolecular interactions, such as metal–metal or ligand–ligand interactions besides bidentate bonding.

We present here the structures of two isomers of the square-planar palladium complex Pd2(S2NC7H4)4, which contain the 2-mercaptobenzothiazole unit bonded in two different modes. Both complexes were obtained during unsuccessful attempts to prepare a palladium complex with a mixture of phosphane and 2-mercaptobenzothiazole ligands by the reaction of PdCl2(cod) (cod is cyclooctadiene) with 2-mercaptobenzothiazole in the presence of an ortho-alkylphenyldiphenylphosphane. It is possible that the formed Pd–phosphane complex catalyzes the formation of either complex (I) or (II), but it is impossible to rule out the possibility of a mixture of isomers being formed. However, only one isomer could be crystallized from each reaction mixture.

The dinuclear complex (I) (Fig. 1) has been described in the literature previously (Kubiak, 1985). An equivalent Pd–dimethylformamide solvate complex with an NH2-substituted mercaptobenzothiazole unit has also been reported (Tzeng et al., 2004). However, the compound presented here is a CH2Cl2 solvate. Despite the differences in solvent structure, there are no major differences between the structures of the earlier reported dinuclear Pd complexes and (I)·CH2Cl2. A corresponding Pt complex, crystallized as a dimethylformamide solvate, has also been reported (Raper et al., 1987). Again, the structure of the Pt complex is practically identical to that of (I)·CH2Cl2. Complex (I)·CH2Cl2 exhibits an N,S-bidentate bonding of the four 2-mercaptobenzothiazole units, with two Pd—N and two Pd—S bonds formed with each Pd atom, leading to a symmetric and regular lantern-type stucture. Complex (II)·CH2Cl2 (Fig. 2) exhibits an asymmetric and distorted lantern stucture, with three Pd—N and one Pd—S bonds formed with one Pd atom and three Pd—S and one Pd—N bonds with the other Pd atom. In (II)·CH2Cl2, the three 2-mercaptobenzothiazole units with a similar bonding mode point in the same direction in relation to the Pd—Pd axis, leaving the fourth 2-mercaptobenzothiazole unit alone on the other side of the axis. The lantern structure is highly distorted owing to steric stress between the three units on the same side of the Pd—Pd axis. Complex (II) is previously unknown in the literature.

In summary, we have shown that two structurally different isomers of Pd2(S2NC7H4)4 can be formed in the reaction between PdCl2(cod) and 2-mercaptobenzothiazole in the presence of an ortho-alkylphenyldiphenyl phosphane depending on the bonding mode of the 2-mercaptobenzothiazole and the alkyl group of the phosphane.

Related literature top

For related literature, see: Dinolfo & Hupp (2001); Fujita (1998); Lizarraga et al. (1997); Raper (1985); Raper et al. (1989).

Experimental top

For the preparation of (I), 2-mercaptobenzothiazole (0.096 g, 0.58 mmol) and ortho-methylphenyldiphenylphosphane (0.105 g, 0.14 mmol) were added to a solution of PdCl2(cod) (0.110 g, 0.39 mmol) in dry diethyl ether (30 ml) and the mixture was left to react for 24 h. The solution was filtered, and the solid material washed three times with diethyl ether (20 ml) and once with dichloromethane (10 ml). The orange solid (0.049 g, 86.3% yield) was dried in vacuo. Analysis calculated for C28H16N4Pd2S8 (877.78): C 38.31, H 1.84, N 6.38%; found: C 37.88, H 1.69, N 6.02%. Mass spectrum (ESI+) [m/z, (%)]: 878 (9%) [M+]. Orange block crystals were grown by slow evaporation of a dichloromethane–hexane solvent mixture at room temperature.

Complex (II) was prepared by the reaction of 2-mercaptobenzothiazole (0.093 g, 0.58 mmol), ortho-isopropylphenyldiphenylphosphane (0.098 g, 0.12 mmol) and PdCl2(cod) (0.111 g, 0.39 mmol) in dry diethyl ether (30 ml) (orange solid, yield 0.036 g, 63.4%). Analysis calculated for C28H16N4Pd2S8(877.78): C 38.31, H 1.84, N 6.38%; found: C 37.83, H 1.70, N 6.11%. Mass spectrum (ESI+) [m/z, (%)]: 878 (8%) [M+]. Orange block crystals were grown following the same procedure as for complex (I).

Refinement top

In (I) the asymmetric unit contains half a molecule, the Pd atoms being located around an inversion center. The final structural models for (I) and (II) were refined without the the heavily disordered CH2Cl2 solvent molecules. The contribution of the disordered solvent to the calculated structure factors was taken into account with the BYPASS algorithm (van der Sluis & Spek, 1990), implemented as the SQUEEZE option in PLATON (Spek, 2003). The H atoms in (I) and (II) were positioned geometrically and allowed to ride on their parent atoms [C—H = 0.95 Å and Uiso(H) = 1.2Ueq(parent atom)]. In (I), the highest peak is located 0.06 Å from atom Cl9A and the deepest hole 0.66 Å from atom Cl9A. In (II), the highest peak is located 0.88 Å from atom Pd2 and the deepest hole 0.70 Å from atom Pd2.

Computing details top

For both compounds, data collection: Collect (Bruker–Nonius, 2004); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997). Program(s) used to solve structure: SIR2002 (Burla et al., 2003) for (I); SHELXS97 (Sheldrick, 1997) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Diamond (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labeling scheme. Only the asymmetric unit has been labelled. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by spheres with arbitary radii.
[Figure 2] Fig. 2. The molecular structure of (II), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by spheres with arbitary radii.
(I) tetrakis(µ-2,3-dihydro-1,3-benzothiazole-2-thiolato)-κ4N:S;κ4S:N- dipalladium(II)(Pd—Pd) dichloromethane solvate top
Crystal data top
[Pd2(C7H4NS2)4]·CH2Cl2Z = 1
Mr = 962.65F(000) = 474
Triclinic, P1Dx = 2.037 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4255 (4) ÅCell parameters from 11445 reflections
b = 10.1954 (9) Åθ = 3.8–26.4°
c = 11.1581 (9) ŵ = 1.88 mm1
α = 77.129 (3)°T = 100 K
β = 86.933 (5)°Block, orange
γ = 72.384 (5)°0.38 × 0.12 × 0.04 mm
V = 784.80 (10) Å3
Data collection top
Nonius KappaCCD
diffractometer
3137 independent reflections
Radiation source: fine-focus sealed tube2736 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromatorRint = 0.000
Detector resolution: 9 pixels mm-1θmax = 26.4°, θmin = 3.8°
ϕ scans and ω scans with κ offseth = 99
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
k = 1212
Tmin = 0.534, Tmax = 0.929l = 013
3137 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0328P)2 + 1.5712P]
where P = (Fo2 + 2Fc2)/3
3137 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 1.05 e Å3
0 restraintsΔρmin = 0.82 e Å3
Crystal data top
[Pd2(C7H4NS2)4]·CH2Cl2γ = 72.384 (5)°
Mr = 962.65V = 784.80 (10) Å3
Triclinic, P1Z = 1
a = 7.4255 (4) ÅMo Kα radiation
b = 10.1954 (9) ŵ = 1.88 mm1
c = 11.1581 (9) ÅT = 100 K
α = 77.129 (3)°0.38 × 0.12 × 0.04 mm
β = 86.933 (5)°
Data collection top
Nonius KappaCCD
diffractometer
3137 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
2736 reflections with I > 2σ(I)
Tmin = 0.534, Tmax = 0.929Rint = 0.000
3137 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.077H-atom parameters constrained
S = 1.07Δρmax = 1.05 e Å3
3137 reflectionsΔρmin = 0.82 e Å3
191 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
xyzUiso*/Ueq
Pd10.65068 (4)0.50426 (3)0.06436 (2)0.01824 (10)
S10.21107 (12)0.40889 (10)0.11108 (8)0.0232 (2)
S20.17536 (13)0.71859 (9)0.04811 (8)0.0232 (2)
S50.30623 (14)0.31432 (11)0.37445 (8)0.0293 (2)
S60.21958 (13)0.93606 (10)0.07313 (8)0.0241 (2)
N10.5268 (4)0.4202 (3)0.2246 (2)0.0186 (6)
N20.4937 (4)0.7090 (3)0.0752 (2)0.0176 (6)
C10.3670 (5)0.3893 (4)0.2267 (3)0.0232 (8)
C20.6115 (5)0.3871 (4)0.3401 (3)0.0249 (8)
C30.7801 (6)0.4077 (4)0.3670 (3)0.0313 (9)
H30.85410.44370.30360.038*
C40.8380 (6)0.3735 (5)0.4913 (4)0.0335 (9)
H40.95290.38650.51210.040*
C50.7290 (6)0.3209 (5)0.5838 (3)0.0358 (10)
H50.76900.30120.66700.043*
C60.5648 (6)0.2968 (5)0.5575 (4)0.0352 (9)
H60.49290.25870.62110.042*
C70.5067 (5)0.3299 (4)0.4351 (3)0.0277 (8)
C80.3175 (5)0.7719 (4)0.0350 (3)0.0215 (7)
C90.5635 (5)0.7916 (4)0.1331 (3)0.0219 (7)
C100.7471 (5)0.7577 (4)0.1792 (3)0.0261 (8)
H100.83990.67240.17160.031*
C110.7897 (6)0.8525 (4)0.2364 (3)0.0288 (8)
H110.91320.83100.26930.035*
C120.6548 (6)0.9788 (4)0.2466 (4)0.0330 (9)
H120.68711.04110.28750.040*
C130.4771 (6)1.0141 (4)0.1986 (4)0.0305 (9)
H130.38621.10100.20420.037*
C140.4321 (5)0.9201 (4)0.1414 (3)0.0237 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01635 (15)0.02228 (15)0.01666 (15)0.00696 (10)0.00022 (9)0.00368 (10)
S10.0192 (5)0.0327 (5)0.0197 (4)0.0119 (4)0.0014 (3)0.0044 (4)
S20.0195 (5)0.0255 (5)0.0255 (5)0.0059 (4)0.0039 (3)0.0075 (4)
S50.0280 (5)0.0420 (6)0.0208 (5)0.0180 (4)0.0040 (4)0.0032 (4)
S60.0236 (5)0.0245 (5)0.0246 (5)0.0059 (4)0.0018 (3)0.0070 (4)
N10.0166 (15)0.0215 (15)0.0175 (14)0.0059 (11)0.0008 (11)0.0031 (11)
N20.0164 (15)0.0206 (15)0.0165 (14)0.0072 (11)0.0010 (11)0.0032 (11)
C10.025 (2)0.0233 (18)0.0198 (17)0.0070 (15)0.0033 (14)0.0032 (14)
C20.0220 (19)0.031 (2)0.0189 (17)0.0067 (15)0.0018 (14)0.0018 (15)
C30.026 (2)0.042 (2)0.0231 (19)0.0098 (17)0.0025 (15)0.0033 (17)
C40.025 (2)0.049 (3)0.026 (2)0.0104 (18)0.0024 (15)0.0082 (18)
C50.034 (2)0.051 (3)0.0174 (18)0.0097 (19)0.0040 (16)0.0007 (17)
C60.030 (2)0.048 (3)0.024 (2)0.0117 (19)0.0007 (16)0.0011 (18)
C70.025 (2)0.037 (2)0.0216 (18)0.0108 (16)0.0004 (14)0.0028 (16)
C80.0238 (19)0.0231 (18)0.0180 (17)0.0092 (15)0.0013 (13)0.0024 (14)
C90.024 (2)0.0268 (19)0.0179 (17)0.0137 (15)0.0007 (13)0.0024 (14)
C100.026 (2)0.029 (2)0.0216 (18)0.0095 (16)0.0004 (14)0.0020 (15)
C110.030 (2)0.036 (2)0.0255 (19)0.0187 (17)0.0028 (15)0.0046 (16)
C120.040 (2)0.037 (2)0.030 (2)0.0215 (19)0.0012 (17)0.0109 (17)
C130.036 (2)0.030 (2)0.028 (2)0.0137 (17)0.0010 (16)0.0052 (16)
C140.025 (2)0.031 (2)0.0178 (17)0.0134 (16)0.0005 (14)0.0040 (14)
Geometric parameters (Å, º) top
Pd1—N22.087 (3)C3—C41.410 (5)
Pd1—N12.097 (3)C3—H30.9500
Pd1—S1i2.2877 (9)C4—C51.391 (6)
Pd1—S2i2.2904 (9)C4—H40.9500
Pd1—Pd1i2.7559 (5)C5—C61.372 (6)
S1—C11.718 (4)C5—H50.9500
S1—Pd1i2.2876 (9)C6—C71.391 (5)
S2—C81.717 (4)C6—H60.9500
S2—Pd1i2.2904 (10)C9—C141.396 (5)
S5—C71.732 (4)C9—C101.398 (5)
S5—C11.753 (3)C10—C111.386 (5)
S6—C141.737 (4)C10—H100.9500
S6—C81.749 (4)C11—C121.396 (6)
N1—C11.314 (5)C11—H110.9500
N1—C21.391 (4)C12—C131.363 (6)
N2—C81.323 (5)C12—H120.9500
N2—C91.392 (4)C13—C141.387 (5)
C2—C31.389 (6)C13—H130.9500
C2—C71.407 (5)
N2—Pd1—N191.17 (11)C3—C4—H4119.6
N2—Pd1—S1i90.07 (8)C6—C5—C4121.5 (4)
N1—Pd1—S1i178.75 (8)C6—C5—H5119.2
N2—Pd1—S2i178.73 (8)C4—C5—H5119.2
N1—Pd1—S2i90.06 (8)C5—C6—C7118.1 (4)
S1i—Pd1—S2i88.70 (3)C5—C6—H6120.9
N2—Pd1—Pd1i87.25 (8)C7—C6—H6120.9
N1—Pd1—Pd1i87.36 (8)C6—C7—C2121.5 (4)
S1i—Pd1—Pd1i92.54 (3)C6—C7—S5128.6 (3)
S2i—Pd1—Pd1i92.50 (3)C2—C7—S5109.9 (3)
C1—S1—Pd1i104.37 (12)N2—C8—S2130.3 (3)
C8—S2—Pd1i104.60 (13)N2—C8—S6113.2 (3)
C7—S5—C190.25 (18)S2—C8—S6116.5 (2)
C14—S6—C890.27 (18)N2—C9—C14114.0 (3)
C1—N1—C2113.3 (3)N2—C9—C10126.2 (3)
C1—N1—Pd1124.3 (2)C14—C9—C10119.8 (3)
C2—N1—Pd1122.3 (2)C11—C10—C9118.0 (4)
C8—N2—C9112.7 (3)C11—C10—H10121.0
C8—N2—Pd1125.1 (2)C9—C10—H10121.0
C9—N2—Pd1122.2 (2)C10—C11—C12121.3 (4)
N1—C1—S1131.3 (3)C10—C11—H11119.3
N1—C1—S5113.2 (3)C12—C11—H11119.3
S1—C1—S5115.5 (2)C13—C12—C11120.9 (4)
C3—C2—N1126.6 (3)C13—C12—H12119.6
C3—C2—C7120.1 (3)C11—C12—H12119.6
N1—C2—C7113.4 (3)C12—C13—C14118.5 (4)
C2—C3—C4118.0 (4)C12—C13—H13120.8
C2—C3—H3121.0C14—C13—H13120.8
C4—C3—H3121.0C13—C14—C9121.5 (3)
C5—C4—C3120.7 (4)C13—C14—S6128.7 (3)
C5—C4—H4119.6C9—C14—S6109.8 (3)
Symmetry code: (i) x+1, y+1, z.
(II) tetrakis(µ-2,3-dihydro-1,3-benzothiazole-2-thiolato)-κ6N:S;κ2S:N- dipalladium(II)(Pd—Pd) dichloromethane solvate top
Crystal data top
[Pd2(C7H4NS2)4]·CH2Cl2F(000) = 3456
Mr = 877.73Dx = 1.995 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 53120 reflections
a = 17.2484 (2) Åθ = 3.9–26.0°
b = 18.0383 (3) ŵ = 1.83 mm1
c = 18.7816 (3) ÅT = 100 K
V = 5843.55 (15) Å3Block, orange
Z = 80.23 × 0.13 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer
5722 independent reflections
Radiation source: fine-focus sealed tube4870 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromatorRint = 0.054
Detector resolution: 9 pixels mm-1θmax = 26.0°, θmin = 3.9°
ϕ scans and ω scans with κ offseth = 2121
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
k = 2222
Tmin = 0.682, Tmax = 0.838l = 1923
53120 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0366P)2 + 22.171P]
where P = (Fo2 + 2Fc2)/3
5722 reflections(Δ/σ)max = 0.002
379 parametersΔρmax = 1.51 e Å3
0 restraintsΔρmin = 1.43 e Å3
Crystal data top
[Pd2(C7H4NS2)4]·CH2Cl2V = 5843.55 (15) Å3
Mr = 877.73Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 17.2484 (2) ŵ = 1.83 mm1
b = 18.0383 (3) ÅT = 100 K
c = 18.7816 (3) Å0.23 × 0.13 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer
5722 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
4870 reflections with I > 2σ(I)
Tmin = 0.682, Tmax = 0.838Rint = 0.054
53120 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.095H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0366P)2 + 22.171P]
where P = (Fo2 + 2Fc2)/3
5722 reflectionsΔρmax = 1.51 e Å3
379 parametersΔρmin = 1.43 e Å3
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
xyzUiso*/Ueq
Pd10.623652 (18)0.181556 (18)0.227860 (18)0.02474 (10)
Pd20.64332 (2)0.15685 (2)0.370137 (19)0.03215 (11)
S10.61248 (9)0.03308 (7)0.35021 (7)0.0441 (3)
S20.77192 (7)0.13114 (9)0.35159 (7)0.0460 (3)
S30.67582 (8)0.27974 (8)0.38842 (7)0.0408 (3)
S40.50867 (6)0.24285 (6)0.24990 (6)0.0297 (2)
S50.52197 (8)0.05076 (7)0.24408 (8)0.0405 (3)
S60.86445 (7)0.07096 (8)0.23344 (7)0.0384 (3)
S70.75699 (8)0.38830 (7)0.29752 (8)0.0436 (3)
S80.40174 (7)0.26098 (7)0.37189 (7)0.0353 (3)
N10.5647 (2)0.08305 (19)0.2189 (2)0.0254 (8)
N20.7298 (2)0.1260 (2)0.2106 (2)0.0274 (8)
N30.6835 (2)0.2790 (2)0.2408 (2)0.0338 (9)
N40.5292 (2)0.1876 (2)0.3847 (2)0.0303 (8)
C10.5683 (3)0.0316 (3)0.2691 (3)0.0331 (10)
C20.5211 (3)0.0632 (3)0.1608 (3)0.0316 (10)
C30.5007 (3)0.1082 (3)0.1038 (3)0.0351 (11)
H30.51860.15790.10110.042*
C40.4534 (3)0.0788 (3)0.0507 (3)0.0442 (12)
H40.43880.10880.01140.053*
C50.4275 (3)0.0062 (3)0.0546 (3)0.0497 (14)
H50.39570.01270.01740.060*
C60.4465 (3)0.0395 (3)0.1109 (3)0.0471 (14)
H60.42790.08910.11340.057*
C70.4934 (3)0.0107 (3)0.1635 (3)0.0388 (11)
C80.7785 (3)0.1125 (3)0.2621 (3)0.0339 (10)
C90.7575 (3)0.1041 (3)0.1431 (3)0.0314 (10)
C100.7197 (3)0.1097 (3)0.0774 (3)0.0349 (11)
H100.66910.13020.07400.042*
C110.7579 (3)0.0849 (3)0.0180 (3)0.0372 (11)
H110.73280.08860.02690.045*
C120.8322 (3)0.0543 (3)0.0210 (3)0.0426 (12)
H120.85660.03790.02150.051*
C130.8703 (3)0.0477 (3)0.0853 (3)0.0416 (12)
H130.92080.02670.08810.050*
C140.8323 (3)0.0729 (3)0.1459 (3)0.0334 (10)
C150.7013 (3)0.3086 (3)0.3046 (3)0.0366 (11)
C160.7111 (3)0.3177 (3)0.1855 (3)0.0341 (11)
C170.6997 (3)0.3027 (3)0.1130 (3)0.0373 (11)
H170.66890.26180.09850.045*
C180.7339 (3)0.3486 (3)0.0626 (3)0.0421 (12)
H180.72670.33820.01340.050*
C190.7785 (3)0.4091 (3)0.0825 (3)0.0463 (14)
H190.80230.43890.04690.056*
C200.7886 (3)0.4267 (3)0.1537 (3)0.0438 (13)
H200.81810.46890.16720.053*
C210.7549 (3)0.3818 (3)0.2048 (3)0.0390 (12)
C220.4885 (3)0.2240 (2)0.3380 (2)0.0305 (10)
C230.4953 (3)0.1875 (3)0.4526 (3)0.0334 (10)
C240.5258 (3)0.1541 (3)0.5142 (3)0.0393 (11)
H240.57270.12660.51180.047*
C250.4872 (3)0.1616 (3)0.5779 (3)0.0406 (12)
H250.50810.14050.62010.049*
C260.4166 (3)0.2006 (3)0.5800 (3)0.0451 (13)
H260.38980.20500.62400.054*
C270.3849 (3)0.2329 (3)0.5196 (3)0.0384 (11)
H270.33710.25900.52190.046*
C280.4246 (3)0.2262 (3)0.4564 (3)0.0352 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.02300 (17)0.02420 (17)0.02703 (18)0.00119 (12)0.00240 (13)0.00145 (13)
Pd20.03188 (19)0.0374 (2)0.02722 (19)0.00833 (15)0.00420 (14)0.00243 (15)
S10.0598 (8)0.0361 (7)0.0363 (7)0.0105 (6)0.0050 (6)0.0062 (5)
S20.0340 (6)0.0700 (9)0.0339 (7)0.0173 (6)0.0083 (5)0.0108 (6)
S30.0401 (7)0.0444 (7)0.0379 (7)0.0013 (6)0.0048 (5)0.0088 (6)
S40.0289 (5)0.0307 (6)0.0294 (6)0.0063 (5)0.0004 (4)0.0020 (5)
S50.0446 (7)0.0265 (6)0.0504 (8)0.0014 (5)0.0095 (6)0.0017 (5)
S60.0265 (6)0.0461 (7)0.0426 (7)0.0080 (5)0.0023 (5)0.0063 (6)
S70.0412 (7)0.0367 (7)0.0529 (8)0.0088 (5)0.0100 (6)0.0037 (6)
S80.0298 (6)0.0393 (7)0.0370 (7)0.0054 (5)0.0033 (5)0.0020 (5)
N10.0219 (17)0.0233 (18)0.0310 (19)0.0028 (14)0.0032 (15)0.0054 (15)
N20.0221 (18)0.0280 (19)0.032 (2)0.0009 (15)0.0010 (15)0.0073 (16)
N30.0260 (19)0.037 (2)0.038 (2)0.0032 (17)0.0077 (17)0.0139 (18)
N40.031 (2)0.032 (2)0.028 (2)0.0003 (16)0.0016 (16)0.0021 (16)
C10.032 (2)0.028 (2)0.040 (3)0.0048 (19)0.007 (2)0.000 (2)
C20.027 (2)0.031 (2)0.037 (3)0.0003 (18)0.0043 (19)0.003 (2)
C30.032 (2)0.037 (3)0.036 (3)0.002 (2)0.001 (2)0.006 (2)
C40.041 (3)0.052 (3)0.040 (3)0.002 (2)0.009 (2)0.006 (2)
C50.037 (3)0.056 (3)0.056 (4)0.006 (3)0.007 (3)0.019 (3)
C60.043 (3)0.043 (3)0.056 (4)0.014 (2)0.007 (3)0.014 (3)
C70.033 (2)0.033 (3)0.050 (3)0.005 (2)0.008 (2)0.006 (2)
C80.031 (2)0.032 (2)0.039 (3)0.0028 (19)0.000 (2)0.001 (2)
C90.030 (2)0.029 (2)0.035 (3)0.0035 (19)0.0015 (19)0.0014 (19)
C100.035 (2)0.032 (2)0.038 (3)0.003 (2)0.001 (2)0.000 (2)
C110.043 (3)0.033 (3)0.035 (3)0.004 (2)0.000 (2)0.000 (2)
C120.053 (3)0.040 (3)0.035 (3)0.007 (2)0.014 (2)0.008 (2)
C130.037 (3)0.039 (3)0.049 (3)0.006 (2)0.011 (2)0.007 (2)
C140.030 (2)0.032 (2)0.039 (3)0.0003 (19)0.005 (2)0.003 (2)
C150.028 (2)0.035 (3)0.046 (3)0.002 (2)0.004 (2)0.009 (2)
C160.026 (2)0.027 (2)0.049 (3)0.0044 (18)0.010 (2)0.005 (2)
C170.032 (2)0.035 (3)0.045 (3)0.003 (2)0.002 (2)0.003 (2)
C180.038 (3)0.047 (3)0.040 (3)0.002 (2)0.002 (2)0.008 (2)
C190.035 (3)0.043 (3)0.062 (4)0.000 (2)0.002 (2)0.019 (3)
C200.036 (3)0.028 (2)0.067 (4)0.001 (2)0.009 (3)0.007 (2)
C210.031 (2)0.031 (2)0.055 (3)0.003 (2)0.006 (2)0.002 (2)
C220.031 (2)0.028 (2)0.032 (2)0.0027 (18)0.0028 (19)0.0031 (19)
C230.033 (2)0.035 (2)0.032 (2)0.007 (2)0.002 (2)0.004 (2)
C240.039 (3)0.045 (3)0.034 (3)0.004 (2)0.004 (2)0.001 (2)
C250.049 (3)0.047 (3)0.026 (2)0.008 (2)0.001 (2)0.002 (2)
C260.044 (3)0.056 (3)0.035 (3)0.014 (3)0.008 (2)0.009 (2)
C270.031 (2)0.048 (3)0.036 (3)0.005 (2)0.007 (2)0.006 (2)
C280.034 (2)0.035 (3)0.036 (3)0.004 (2)0.000 (2)0.004 (2)
Geometric parameters (Å, º) top
Pd1—N32.052 (4)C5—C61.381 (9)
Pd1—N12.054 (4)C5—H50.9500
Pd1—N22.112 (4)C6—C71.378 (8)
Pd1—S42.3080 (11)C6—H60.9500
Pd1—Pd22.7302 (5)C9—C101.400 (7)
Pd2—N42.064 (4)C9—C141.408 (7)
Pd2—S22.2927 (13)C10—C111.370 (7)
Pd2—S32.3121 (14)C10—H100.9500
Pd2—S12.3255 (14)C11—C121.396 (8)
S1—C11.703 (5)C11—H110.9500
S2—C81.718 (5)C12—C131.381 (8)
S3—C151.715 (6)C12—H120.9500
S4—C221.724 (5)C13—C141.390 (7)
S5—C71.749 (6)C13—H130.9500
S5—C11.751 (5)C16—C171.403 (7)
S6—C141.736 (5)C16—C211.427 (7)
S6—C81.746 (5)C17—C181.389 (7)
S7—C151.734 (5)C17—H170.9500
S7—C211.747 (6)C18—C191.386 (8)
S8—C281.751 (5)C18—H180.9500
S8—C221.758 (5)C19—C201.386 (9)
N1—C11.325 (6)C19—H190.9500
N1—C21.374 (6)C20—C211.383 (8)
N2—C81.303 (6)C20—H200.9500
N2—C91.412 (6)C23—C241.406 (7)
N3—C161.339 (7)C23—C281.407 (7)
N3—C151.349 (6)C24—C251.376 (7)
N4—C221.301 (6)C24—H240.9500
N4—C231.402 (6)C25—C261.408 (8)
C2—C31.389 (7)C25—H250.9500
C2—C71.417 (7)C26—C271.386 (8)
C3—C41.394 (7)C26—H260.9500
C3—H30.9500C27—C281.377 (7)
C4—C51.386 (8)C27—H270.9500
C4—H40.9500
N3—Pd1—N1177.79 (16)N2—C8—S6113.5 (4)
N3—Pd1—N289.34 (14)S2—C8—S6116.2 (3)
N1—Pd1—N290.32 (14)C10—C9—C14119.2 (4)
N3—Pd1—S490.05 (11)C10—C9—N2127.9 (4)
N1—Pd1—S490.23 (10)C14—C9—N2112.9 (4)
N2—Pd1—S4178.42 (11)C11—C10—C9118.0 (5)
N3—Pd1—Pd287.79 (12)C11—C10—H10121.0
N1—Pd1—Pd290.01 (10)C9—C10—H10121.0
N2—Pd1—Pd287.98 (10)C10—C11—C12122.6 (5)
S4—Pd1—Pd290.54 (3)C10—C11—H11118.7
N4—Pd2—S2175.95 (12)C12—C11—H11118.7
N4—Pd2—S387.35 (11)C13—C12—C11120.4 (5)
S2—Pd2—S388.96 (5)C13—C12—H12119.8
N4—Pd2—S193.52 (11)C11—C12—H12119.8
S2—Pd2—S190.15 (6)C12—C13—C14117.6 (5)
S3—Pd2—S1178.94 (5)C12—C13—H13121.2
N4—Pd2—Pd188.14 (11)C14—C13—H13121.2
S2—Pd2—Pd190.26 (4)C13—C14—C9122.2 (5)
S3—Pd2—Pd191.09 (4)C13—C14—S6128.2 (4)
S1—Pd2—Pd188.32 (4)C9—C14—S6109.6 (3)
C1—S1—Pd2105.15 (17)N3—C15—S3129.6 (4)
C8—S2—Pd2104.58 (17)N3—C15—S7112.7 (4)
C15—S3—Pd2102.54 (17)S3—C15—S7117.7 (3)
C22—S4—Pd1104.53 (16)N3—C16—C17127.0 (4)
C7—S5—C190.6 (2)N3—C16—C21114.5 (5)
C14—S6—C890.7 (2)C17—C16—C21118.4 (5)
C15—S7—C2190.6 (2)C18—C17—C16119.1 (5)
C28—S8—C2290.0 (2)C18—C17—H17120.4
C1—N1—C2114.1 (4)C16—C17—H17120.4
C1—N1—Pd1121.7 (3)C19—C18—C17121.4 (5)
C2—N1—Pd1124.1 (3)C19—C18—H18119.3
C8—N2—C9113.3 (4)C17—C18—H18119.3
C8—N2—Pd1122.3 (3)C20—C19—C18120.7 (5)
C9—N2—Pd1124.3 (3)C20—C19—H19119.7
C16—N3—C15113.6 (4)C18—C19—H19119.7
C16—N3—Pd1122.3 (3)C21—C20—C19118.8 (5)
C15—N3—Pd1124.0 (4)C21—C20—H20120.6
C22—N4—C23113.0 (4)C19—C20—H20120.6
C22—N4—Pd2124.1 (3)C20—C21—C16121.4 (5)
C23—N4—Pd2121.2 (3)C20—C21—S7130.0 (4)
N1—C1—S1130.3 (4)C16—C21—S7108.5 (4)
N1—C1—S5112.5 (4)N4—C22—S4129.7 (4)
S1—C1—S5117.3 (3)N4—C22—S8113.9 (3)
N1—C2—C3126.8 (4)S4—C22—S8116.4 (3)
N1—C2—C7113.7 (4)N4—C23—C24126.3 (4)
C3—C2—C7119.4 (5)N4—C23—C28114.0 (4)
C2—C3—C4118.5 (5)C24—C23—C28119.7 (5)
C2—C3—H3120.8C25—C24—C23119.5 (5)
C4—C3—H3120.8C25—C24—H24120.2
C5—C4—C3120.8 (5)C23—C24—H24120.2
C5—C4—H4119.6C24—C25—C26119.4 (5)
C3—C4—H4119.6C24—C25—H25120.3
C6—C5—C4121.9 (5)C26—C25—H25120.3
C6—C5—H5119.1C27—C26—C25121.9 (5)
C4—C5—H5119.1C27—C26—H26119.0
C7—C6—C5117.5 (5)C25—C26—H26119.0
C7—C6—H6121.2C28—C27—C26118.2 (5)
C5—C6—H6121.2C28—C27—H27120.9
C6—C7—C2121.9 (5)C26—C27—H27120.9
C6—C7—S5129.0 (4)C27—C28—C23121.2 (5)
C2—C7—S5108.9 (4)C27—C28—S8129.7 (4)
N2—C8—S2130.3 (4)C23—C28—S8109.1 (4)

Experimental details

(I)(II)
Crystal data
Chemical formula[Pd2(C7H4NS2)4]·CH2Cl2[Pd2(C7H4NS2)4]·CH2Cl2
Mr962.65877.73
Crystal system, space groupTriclinic, P1Orthorhombic, Pbca
Temperature (K)100100
a, b, c (Å)7.4255 (4), 10.1954 (9), 11.1581 (9)17.2484 (2), 18.0383 (3), 18.7816 (3)
α, β, γ (°)77.129 (3), 86.933 (5), 72.384 (5)90, 90, 90
V3)784.80 (10)5843.55 (15)
Z18
Radiation typeMo KαMo Kα
µ (mm1)1.881.83
Crystal size (mm)0.38 × 0.12 × 0.040.23 × 0.13 × 0.10
Data collection
DiffractometerNonius KappaCCD
diffractometer
Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Multi-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.534, 0.9290.682, 0.838
No. of measured, independent and
observed [I > 2σ(I)] reflections
3137, 3137, 2736 53120, 5722, 4870
Rint0.0000.054
(sin θ/λ)max1)0.6250.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.077, 1.07 0.036, 0.095, 1.11
No. of reflections31375722
No. of parameters191379
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0328P)2 + 1.5712P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0366P)2 + 22.171P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.05, 0.821.51, 1.43

Computer programs: Collect (Bruker–Nonius, 2004), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR2002 (Burla et al., 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Diamond (Brandenburg, 2006).

Selected bond lengths (Å) for (I) top
Pd1—N22.087 (3)S5—C11.753 (3)
Pd1—N12.097 (3)S6—C141.737 (4)
Pd1—S1i2.2877 (9)S6—C81.749 (4)
Pd1—S2i2.2904 (9)N1—C11.314 (5)
Pd1—Pd1i2.7559 (5)N1—C21.391 (4)
S1—C11.718 (4)N2—C81.323 (5)
S2—C81.717 (4)N2—C91.392 (4)
S5—C71.732 (4)
Symmetry code: (i) x+1, y+1, z.
Selected bond lengths (Å) for (II) top
Pd1—N32.052 (4)S3—C151.715 (6)
Pd1—N12.054 (4)S4—C221.724 (5)
Pd1—N22.112 (4)S5—C71.749 (6)
Pd1—S42.3080 (11)S5—C11.751 (5)
Pd1—Pd22.7302 (5)S6—C141.736 (5)
Pd2—N42.064 (4)S6—C81.746 (5)
Pd2—S22.2927 (13)S7—C151.734 (5)
Pd2—S32.3121 (14)S7—C211.747 (6)
Pd2—S12.3255 (14)S8—C281.751 (5)
S1—C11.703 (5)S8—C221.758 (5)
S2—C81.718 (5)
 

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