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In the title complex, [PdCl2(C12H22S3)]·0.8CH3CN, a potentially tridentate thio­ether ligand coordinates in a cis-bidentate manner to yield a square-planar environment for the PdII cation [mean deviation of the Pd from the Cl2S2 plane = 0.0406 (7) Å]. Each square-planar entity packs in an inverse face-to-face manner, giving pairs with plane-to-plane separations of 3.6225 (12) Å off-set by 1.1263 (19) Å, with a Pd...Pd separation of 3.8551 (8) Å. A partial aceto­nitrile solvent mol­ecule is present. The occupancy of this mol­ecule was allowed to refine, and converged to 0.794 (10). The synthesis of the previously unreported 3,6,9-tri­thiabi­cyclo­[9.3.1]penta­decane ligand is also outlined.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113015060/fn3138sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113015060/fn3138Isup2.hkl
Contains datablock I

CCDC reference: 957039

Comment top

Group 10 transition metal complexes, in the +2 oxidation state (d8), normally exhibit stable square-planar geometries, in compliance with the 16-electron rule. However, the presence of two non-bonding orbitals perpendicular to the coordination plane, i.e. the occupied dz2 and the empty pz, means that higher coordination numbers can be achieved, with the cation possessing the ability to act as either a Lewis base or Lewis acid, or in some reported cases, both (Aullón & Alvarez, 1996). Further, Allan et al. (2006) have reported the high-pressure (46 kbar; 1 bar = 100000 Pa) conversion of cis-dichloro-(1,4,7-trithiacyclononane-S,S')palladium from a square-planar mononuclear complex to a six-coordinate chain polymer via apical coordination to both the third S atom in the ligand and a meridionally coordinated S atom in another nominal monomeric Pd complex. The authors present their work as a route to novel metal stereochemistries.

In the title complex, (I), the thioether ligand has the potential for up to three metal binding sites, but it coordinates in a cis-bidentate manner via two adjacent S atoms to the Pd centre, yielding a five-membered chelate ring (Fig. 1). The overall coordination geometry at the metal is square planar, with the remaining coordination sites occupied by chloride ligands. Atom Pd1 deviates from the Cl2S2 mean plane by 0.0406 (7) Å. A survey of the Cambridge Structural Database (CSD, Version 5.34 with February 2013 update; Allen, 2002) for all cis-PdCl2S2-containing structures was performed, yielding 115 unique observations of Pd—Cl and Pd—S bond lengths, and Cl—Pd—Cl and S—Pd—S angles. Average distances of 2.32 (3) and 2.31 (14) Å were found for Pd—Cl and Pd—S, respectively, while for Cl—Pd—Cl and S—Pd—S average angles of 92 (4) and 89 (5)° were found. The results reported here for (I) are in agreement with these previous values.

The overall structure of (I) is similar to that reported by de Groot et al. (1991) using the 2,5,8-trithia(9)-m-benzeneophane ligand, but stands in contrast with the coordination mode exhibited by Pd with the 2,5,8-trithia(9)-o-benzeneophane ligand. In that complex, a cis-PdCl2S2 coordination motif was also reported (de Groot et al., 1991), but the third S atom was present at a distance of 3.076 (3) Å, indicating apical coordination to Pd. In the title complex, the intramolecular distance from Pd to the third S atom is 5.0721 (14) Å, while the closest intermolecular approach of a third S atom to Pd1 is 5.2031 (14) Å [for atom S2, generated by the symmetry operation (1/2 - x, -y, z - 1/2)], which far exceeds the sum of the van der Waals radii for Pd and S (3.43 Å; Standard reference?). Of note in (I) is that the square-planar PdCl2S2 surfaces, oriented away from the uncoordinated macrocyclic atoms, pack in a face-to-face manner across the inversion centres at Wyckoff position 4b (Fig. 2). Plane-to-plane separations for the PdCl2S2 pairs are 3.6225 (12) Å off-set by 1.1263 (19) Å, with Pd···Pd separations of 3.8551 (8) Å.

Related literature top

For related literature, see: Allan et al. (2006); Allen (2002); Aullón & Alvarez (1996); Groot et al. (1991); Sheldrick (2013).

Experimental top

All starting materials were obtained from the Aldrich Chemical Company and used without further purification. The 3,6,9-trithiabicyclo[9.3.1]pentadecane ligand was prepared in four steps (see Scheme 2). Analyses were performed by Canadian Microanalytical Service Ltd.

(i) Step 1. Conversion of 1, 3-cyclohexanedicarboxylic acid to its dimethyl ester, (1). (±)-1, 3-Cyclohexanedicarboxylic acid (5.20 g, 30.2 mmol) was dissolved in methanol (150 ml) to which concentrated H2SO4 (1 ml) was then added. The solution was stirred under reflux for 24 h then cooled to room temperature and neutralized with aqueous NaOH (2 M), and the solvent was removed under reduced pressure. Water (100 ml) was added to the residue and the mixture extracted with ether (4 × 50 ml). The extract was dried over MgSO4 and filtered, and the ether was removed under reduced pressure to yield (1) as a pale-yellow oil in 99% yield. 1H NMR (Frequency?, TMS, δ, p.p.m.): 3.68 (6H), 2.20–2.40 (2H), 1.90–2.05 (2H), 1.70–1.80 (2H), 1.50–1.60 (2H), 1.30–1.40 (2H).

(ii) Step 2. Conversion of (1) to the corresponding diol, (2). Under an atmosphere of dry nitrogen, LiAlH4 (9.5 g, 0.25 mmol) was suspended in dry diethyl ether (250 ml). The temperature of the suspension was maintained with an ice bath and a solution of (1) (14.5 g, 72.5 mmol) in dry diethyl ether (150 ml) was added dropwise over a period of 4 h. The mixture was then stirred overnight and allowed to warm to room temperature. Ethyl acetate (150 ml) was added to quench the remaining LiAlH4, followed by dilute (10%) aqueous H2SO4 (~150 ml) to dissolve sodium and aluminium salts. The two-layered mixture was separated, the aqueous layer washed with diethyl ether (2 × 100 ml), and the washings and original organic layer combined and dried over MgSO4. After filtration, the solvent was removed under reduced pressure to yield (2) as a nearly colourless oil in 85% yield. 1H NMR (Frequency?, TMS, δ, p.p.m.): 3.89 (2H), 0.8–2.7 (14H).

(iii) Step 3. Conversion of (2) to the corresponding dibromide, (3). This procedure was carried out in dry solvents under a dry nitrogen atmosphere. PBr3 (6.0 ml, 63.8 mmol) was dissolved in dry benzene (15 ml). Pyridine (1.5 ml) was added dropwise over a period of 15 min. A mixture of (2) (7.2 g, 50 mmol) and pyridine (1.0 ml) was added dropwise over a period of 4 h while maintaining a temperature of 278 K with a cold-water bath. The reaction was allowed to warm slowly to room temperature while stirring overnight. Water (250 ml) was added slowly to quench the remaining PBr3. The mixture was extracted with CHCl3 (3 × 200 ml) and the combined extracts dried over CaCl2. The solution was filtered and volatiles removed under reduced pressure to give (3) as a pale-yellow oil in 70% yield. 1H NMR (Frequency?, TMS, δ, p.p.m.): 3.25–3.40 (two doublets; 4H), 2.10–2.70 (10H).

(iv) Step 4. Formation of 3,6,9-trithiabicyclo[9.3.1]pentadecane, (4). This procedure was carried out under nitrogen and anhydrous conditions in a three-necked round-bottomed flask fitted with two dropping funnels on top of condensers. Sodium (0.90 g, 40 mmol) was reacted with commercial absolute ethanol (500 ml) in the round-bottomed flask and a solution of bis(2-mercaptoethyl)sulfide (3.08 g, 20.0 mmol) in tetrahydrofuran (THF) (75 ml) was placed in one dropping funnel. In the other funnel was placed (3) (5.40 g, 20.0 mmol) in commercial absolute ethanol (150 ml). A portion (10 ml) of the THF solution was added dropwise over a period of 10 min with stirring under reflux. Both solutions were then admitted dropwise at a rate of 2:1 ethanol:THF over a period of 4 h, and the resulting mixture was refluxed for a further 24 h. Upon cooling to room temperature, the solvent was removed under reduced pressure and the residue suspended in CHCl3 (300 ml). The suspension was washed with water (3 × 200 ml), and the organic layer dried over CaCl2 and filtered. The filtrate was reduced in volume under reduced pressure to approximately 30 ml and hot commercial absolute ethanol (60 ml) added. The solution was filtered and placed in a freezer for 1 d, after which time white crystals of (4) (m.p. 363.45–365.65 K) had formed. These were separated by filtration in 30% yield. 1H NMR (Frequency?, TMS, δ, p.p.m.): 2.60–3.00 (12H), 0.80–2.20 (10H); 13C NMR (Frequency?, TMS, δ, p.p.m.): 21–42. 12 main peaks, some as doublets due to the presence of two diastereomers. Mass spectrum, calculated for (C12H22S3)+: m/z = 262; found: m/z = 262.

(v) Preparation of the title complex, (I). Bis(acetonitrile)dichloropalladium(II) (0.39 g, 1.50 mmol) was dissolved in acetonitrile (80 ml) to give a yellow–orange solution. Likewise, (4) (0.40 g, 1.5 mmol) was dissolved in acetonitrile (80 ml) to give a colourless solution. The solutions were mixed at room temperature and stirred for 4 h, and then the volume was reduced in a rotary evaporator to ~15 ml. The resulting suspension was filtered at room temperature to yield orange crystals of (I) in 95% yield; these were dried in air. Analysis, calculated for C12H22Cl2PdS3.CH3CN: C 34.97, H 5.24, N 2.91, Cl 14.74%; found: C 35.23, H 5.82, N 3.02, Cl 14.15%.

Refinement top

H atoms were introduced into idealized positions and refined using the riding-atom formalism (idealized methyl refined as a rotating group.) The applied constraints were: Cmethine—Hmethine = 0.98 Å, Cmethylene—Hmethylene = 0.97 Å, Cmethyl—Hmethyl = 0.96 Å, and Uiso(Hmethine) = 1.2Ueq(Cmethine), Uiso(Hmethylene) = 1.2Ueq(Cmethylene), Uiso(Hmethyl) = 1.5Ueq(Cmethyl). A partial-occupancy acetonitrile solvent molecule was present. All atoms in this group (N1, C13 and C14) were constrained to have the same occupancy, which was allowed to refine freely (tied to the second free variable) and converged to 0.798 (10). A similarity restraint (the command SIMU within SHELXL-2013; Sheldrick, 2013) was applied to N1—C13—C14. Only reflections between 2θ = 5 and 53° were included (the command SHEL 8.146492 0.796384 within SHELXL-2013) in order to minimize beam-stop effects and weak intensity at higher angles.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Rigaku, 1998); cell refinement: MSC/AFC Diffractometer Control Software (Rigaku, 1998); data reduction: MSC/AFC Diffractometer Control Software (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: Mercury (Macrae et al., 2008) and ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram for (I), showing the close facial association of the square-planar PdCl2S2 fragments. Solvent acetonitrile molecules and H atoms have been omitted for clarity. [Symmetry codes: (i) -x, -y, -z+1; (ii) x, -y+1/2, z-1/2; (iii) -x, y+1/2, -z+1/2; (iv) x+1/2, -y+1/2, -z+1; (v) -x+1/2, y+1/2, z; (vi) x+1/2, y+1, -z+1/2; (vii) -x+1/2, -y+1, z-1/2; (viii) x+1, y+1, z; (ix) -x+1, -z+1, -z+1; (x) x+1, -y+1/2, z+1/2; (xi) -x+1, y+1/2, -z+3/2; (xii) x+1/2, y, -z+3/2; (xiii) -x+1/2, -y, z+1/2.]
cis-Dichlorido(3,6,9-trithiabicyclo[9.3.1]pentadecane-κ2S3,S6)palladium(II) acetonitrile 0.8-solvate top
Crystal data top
[PdCl2(C12H22S3)]·0.8C2H3NF(000) = 1917
Mr = 472.62Dx = 1.668 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ac 2abCell parameters from 16 reflections
a = 24.906 (4) Åθ = 10.1–13.1°
b = 18.144 (2) ŵ = 1.59 mm1
c = 8.328 (2) ÅT = 299 K
V = 3763.4 (12) Å3Irregular, yellow
Z = 80.30 × 0.20 × 0.10 mm
Data collection top
Rigaku AFC6S
diffractometer
Rint = 0.000
Radiation source: fine-focus sealed tubeθmax = 26.4°, θmin = 2.8°
ω–2θ scansh = 032
Absorption correction: ψ scan
(North et al., 1968)
k = 023
Tmin = 0.715, Tmax = 0.853l = 100
4892 measured reflections3 standard reflections every 150 reflections
3850 independent reflections intensity decay: 5.8%
2488 reflections with I > 2σ(I)
Refinement top
Refinement on F2Primary atom site location: heavy-atom method
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.109 w = 1/[σ2(Fo2) + (0.0435P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
3850 reflectionsΔρmax = 0.46 e Å3
192 parametersΔρmin = 0.58 e Å3
12 restraints
Crystal data top
[PdCl2(C12H22S3)]·0.8C2H3NV = 3763.4 (12) Å3
Mr = 472.62Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 24.906 (4) ŵ = 1.59 mm1
b = 18.144 (2) ÅT = 299 K
c = 8.328 (2) Å0.30 × 0.20 × 0.10 mm
Data collection top
Rigaku AFC6S
diffractometer
2488 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.000
Tmin = 0.715, Tmax = 0.8533 standard reflections every 150 reflections
4892 measured reflections intensity decay: 5.8%
3850 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03812 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 0.99Δρmax = 0.46 e Å3
3850 reflectionsΔρmin = 0.58 e Å3
192 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Pd10.07275 (2)0.03067 (2)0.45790 (4)0.03345 (12)
Cl10.06611 (6)0.12759 (7)0.27642 (17)0.0558 (4)
Cl20.08395 (5)0.05430 (7)0.25322 (16)0.0495 (3)
S10.05690 (5)0.11118 (7)0.66059 (16)0.0417 (3)
S20.25544 (5)0.07024 (7)0.61307 (15)0.0416 (3)
S30.07756 (5)0.06267 (7)0.63987 (15)0.0400 (3)
N10.3855 (4)0.2380 (6)0.3889 (16)0.148 (5)0.794 (10)
C130.4218 (4)0.2337 (5)0.4601 (17)0.095 (4)0.794 (10)
C140.4692 (4)0.2286 (5)0.5518 (16)0.117 (5)0.794 (10)
H14A0.49710.20660.48810.176*0.794 (10)
H14B0.46270.19870.64490.176*0.794 (10)
H14C0.48020.27700.58490.176*0.794 (10)
C10.1071 (2)0.1845 (3)0.6590 (7)0.0461 (13)
H1A0.10670.20660.55290.055*
H1B0.09530.22210.73390.055*
C20.16499 (18)0.1666 (2)0.6989 (6)0.0371 (10)
H20.16660.15100.81140.045*
C30.1987 (2)0.2373 (3)0.6809 (7)0.0464 (13)
H3A0.19640.25500.57120.056*
H3B0.18460.27530.75110.056*
C40.2573 (2)0.2223 (3)0.7233 (7)0.0509 (13)
H4A0.27830.26620.70100.061*
H4B0.25990.21230.83750.061*
C50.2810 (2)0.1579 (3)0.6312 (7)0.0477 (12)
H5A0.31700.14810.67010.057*
H5B0.28350.17060.51830.057*
C60.24677 (18)0.0882 (2)0.6497 (6)0.0356 (10)
H60.24570.07530.76400.043*
C70.18938 (18)0.1054 (2)0.5957 (6)0.0378 (11)
H7A0.16750.06130.60440.045*
H7B0.18960.12060.48400.045*
C80.27251 (19)0.0237 (3)0.5589 (6)0.0394 (11)
H8A0.31110.02880.56930.047*
H8B0.26400.02990.44610.047*
C90.18580 (18)0.0813 (3)0.5521 (6)0.0398 (11)
H9A0.17710.04500.47050.048*
H9B0.18080.12990.50590.048*
C100.14825 (19)0.0717 (3)0.6949 (6)0.0471 (12)
H10A0.15900.02820.75440.057*
H10B0.15220.11390.76550.057*
C110.0531 (2)0.0193 (3)0.8234 (6)0.0442 (12)
H11A0.01410.01980.82290.053*
H11B0.06510.04790.91510.053*
C120.0723 (2)0.0593 (3)0.8418 (6)0.0476 (13)
H12A0.11080.05980.86060.057*
H12B0.05480.08200.93340.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.03253 (19)0.0364 (2)0.03140 (19)0.00201 (14)0.00319 (16)0.00041 (16)
Cl10.0715 (9)0.0464 (7)0.0494 (8)0.0079 (6)0.0103 (7)0.0135 (6)
Cl20.0517 (7)0.0559 (7)0.0408 (6)0.0035 (6)0.0045 (6)0.0131 (6)
S10.0364 (6)0.0443 (7)0.0443 (7)0.0013 (5)0.0016 (5)0.0072 (6)
S20.0415 (7)0.0424 (7)0.0409 (6)0.0107 (5)0.0042 (6)0.0022 (6)
S30.0401 (6)0.0411 (6)0.0389 (6)0.0051 (5)0.0020 (5)0.0051 (5)
N10.103 (7)0.145 (10)0.196 (12)0.018 (7)0.039 (9)0.036 (9)
C130.071 (6)0.064 (6)0.151 (11)0.006 (5)0.016 (7)0.005 (6)
C140.109 (9)0.078 (7)0.165 (13)0.011 (6)0.002 (9)0.005 (8)
C10.048 (3)0.031 (2)0.060 (3)0.006 (2)0.001 (3)0.012 (2)
C20.038 (2)0.030 (2)0.044 (3)0.0032 (19)0.002 (2)0.005 (2)
C30.052 (3)0.029 (2)0.057 (3)0.007 (2)0.004 (3)0.003 (2)
C40.049 (3)0.040 (3)0.064 (3)0.014 (2)0.013 (3)0.004 (3)
C50.041 (3)0.049 (3)0.054 (3)0.005 (2)0.003 (3)0.007 (3)
C60.038 (2)0.036 (2)0.033 (2)0.0014 (19)0.000 (2)0.003 (2)
C70.036 (2)0.036 (2)0.042 (3)0.002 (2)0.004 (2)0.009 (2)
C80.036 (2)0.048 (3)0.034 (2)0.004 (2)0.001 (2)0.002 (2)
C90.044 (3)0.038 (2)0.037 (3)0.003 (2)0.002 (2)0.001 (2)
C100.044 (3)0.054 (3)0.044 (3)0.008 (2)0.002 (2)0.011 (2)
C110.041 (3)0.061 (3)0.031 (2)0.010 (2)0.003 (2)0.002 (2)
C120.049 (3)0.064 (3)0.029 (2)0.001 (3)0.006 (2)0.008 (2)
Geometric parameters (Å, º) top
Pd1—Cl12.3246 (13)C4—H4A0.9700
Pd1—Cl22.3154 (13)C4—H4B0.9700
Pd1—S12.2669 (13)C4—C51.518 (7)
Pd1—S32.2759 (13)C5—H5A0.9700
S1—C11.827 (5)C5—H5B0.9700
S1—C121.820 (5)C5—C61.532 (6)
S2—C81.814 (5)C6—H60.9800
S2—C91.818 (5)C6—C71.531 (6)
S3—C101.827 (5)C6—C81.533 (6)
S3—C111.824 (5)C7—H7A0.9700
N1—C131.085 (13)C7—H7B0.9700
C13—C141.410 (15)C8—H8A0.9700
C14—H14A0.9600C8—H8B0.9700
C14—H14B0.9600C9—H9A0.9700
C14—H14C0.9600C9—H9B0.9700
C1—H1A0.9700C9—C101.523 (6)
C1—H1B0.9700C10—H10A0.9700
C1—C21.514 (6)C10—H10B0.9700
C2—H20.9800C11—H11A0.9700
C2—C31.540 (6)C11—H11B0.9700
C2—C71.531 (6)C11—C121.512 (7)
C3—H3A0.9700C12—H12A0.9700
C3—H3B0.9700C12—H12B0.9700
C3—C41.525 (7)
Cl2—Pd1—Cl191.92 (5)C4—C5—C6111.6 (4)
S1—Pd1—Cl189.11 (5)H5A—C5—H5B108.0
S1—Pd1—Cl2176.65 (5)C6—C5—H5A109.3
S1—Pd1—S389.59 (5)C6—C5—H5B109.3
S3—Pd1—Cl1178.45 (5)C5—C6—H6108.0
S3—Pd1—Cl289.33 (5)C5—C6—C8110.3 (4)
C1—S1—Pd1110.16 (18)C7—C6—C5108.8 (4)
C12—S1—Pd1104.33 (17)C7—C6—H6108.0
C12—S1—C1103.8 (3)C7—C6—C8113.6 (4)
C8—S2—C9104.9 (2)C8—C6—H6108.0
C10—S3—Pd1106.55 (17)C2—C7—H7A109.5
C11—S3—Pd1102.68 (17)C2—C7—H7B109.5
C11—S3—C1098.7 (2)C6—C7—C2110.7 (4)
N1—C13—C14179.6 (16)C6—C7—H7A109.5
C13—C14—H14A109.5C6—C7—H7B109.5
C13—C14—H14B109.5H7A—C7—H7B108.1
C13—C14—H14C109.5S2—C8—H8A107.4
H14A—C14—H14B109.5S2—C8—H8B107.4
H14A—C14—H14C109.5C6—C8—S2119.8 (3)
H14B—C14—H14C109.5C6—C8—H8A107.4
S1—C1—H1A107.4C6—C8—H8B107.4
S1—C1—H1B107.4H8A—C8—H8B106.9
H1A—C1—H1B106.9S2—C9—H9A109.5
C2—C1—S1119.6 (3)S2—C9—H9B109.5
C2—C1—H1A107.4H9A—C9—H9B108.1
C2—C1—H1B107.4C10—C9—S2110.8 (3)
C1—C2—H2108.1C10—C9—H9A109.5
C1—C2—C3108.6 (4)C10—C9—H9B109.5
C1—C2—C7114.2 (4)S3—C10—H10A108.8
C3—C2—H2108.1S3—C10—H10B108.8
C7—C2—H2108.1C9—C10—S3114.0 (3)
C7—C2—C3109.5 (4)C9—C10—H10A108.8
C2—C3—H3A109.5C9—C10—H10B108.8
C2—C3—H3B109.5H10A—C10—H10B107.7
H3A—C3—H3B108.1S3—C11—H11A109.1
C4—C3—C2110.5 (4)S3—C11—H11B109.1
C4—C3—H3A109.5H11A—C11—H11B107.8
C4—C3—H3B109.5C12—C11—S3112.7 (3)
C3—C4—H4A109.0C12—C11—H11A109.1
C3—C4—H4B109.0C12—C11—H11B109.1
H4A—C4—H4B107.8S1—C12—H12A109.7
C5—C4—C3113.1 (4)S1—C12—H12B109.7
C5—C4—H4A109.0C11—C12—S1109.7 (3)
C5—C4—H4B109.0C11—C12—H12A109.7
C4—C5—H5A109.3C11—C12—H12B109.7
C4—C5—H5B109.3H12A—C12—H12B108.2
Pd1—S1—C1—C267.6 (5)C3—C4—C5—C653.7 (6)
Pd1—S1—C12—C1138.8 (4)C4—C5—C6—C756.2 (6)
Pd1—S3—C10—C953.7 (4)C4—C5—C6—C8178.6 (4)
Pd1—S3—C11—C1238.7 (4)C5—C6—C7—C260.5 (5)
S1—C1—C2—C3177.4 (4)C5—C6—C8—S2158.7 (4)
S1—C1—C2—C754.9 (6)C7—C2—C3—C455.8 (6)
S2—C9—C10—S3167.9 (3)C7—C6—C8—S278.9 (5)
S3—C11—C12—S152.3 (5)C8—S2—C9—C1098.9 (4)
C1—S1—C12—C11154.2 (3)C8—C6—C7—C2176.2 (4)
C1—C2—C3—C4178.8 (5)C9—S2—C8—C668.7 (4)
C1—C2—C7—C6177.1 (4)C10—S3—C11—C1270.5 (4)
C2—C3—C4—C553.1 (6)C11—S3—C10—C9159.7 (4)
C3—C2—C7—C660.9 (5)C12—S1—C1—C243.6 (5)

Experimental details

Crystal data
Chemical formula[PdCl2(C12H22S3)]·0.8C2H3N
Mr472.62
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)299
a, b, c (Å)24.906 (4), 18.144 (2), 8.328 (2)
V3)3763.4 (12)
Z8
Radiation typeMo Kα
µ (mm1)1.59
Crystal size (mm)0.30 × 0.20 × 0.10
Data collection
DiffractometerRigaku AFC6S
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.715, 0.853
No. of measured, independent and
observed [I > 2σ(I)] reflections
4892, 3850, 2488
Rint0.000
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.109, 0.99
No. of reflections3850
No. of parameters192
No. of restraints12
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.46, 0.58

Computer programs: MSC/AFC Diffractometer Control Software (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2013), Mercury (Macrae et al., 2008) and ORTEP-3 (Farrugia, 2012), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

 

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