cis-Bis(di­methyl sulfoxide-S)­dinitrato­palladium(II) and cis-dinitratobis(1,4-oxathiane-S)­palladium(II)

The Pd atom in each of the two title compounds, [Pd(NO₃)₂(C₂H₆OS)₂], (I), and [Pd(NO₃)₂(C₄H₈OS)₂], (II), coordinates two O atoms from two nitrate ligands and two S atoms from di­methyl sulfoxide (dmso) and thio­xane (systematic name: 1,4-oxathiane) ligands in a pseudo-square-planar cis-geometry. In the dmso complex, the distances to palladium are Pd-O 2.067 (2) and 2.072 (2) Å, and Pd-S 2.2307 (11) and 2.2530 (8) Å. The corresponding distances in the thio­xane complex are Pd-O 2.053 (3) and 2.076 (2) Å, and Pd-S 2.2595 (9) and 2.2627 (11) Å. Both compounds may be regarded as dimers with an inversion centre, where one of the coordinating nitrate O atoms in one mol­ecule also interacts with the Pd atom in the adjacent mol­ecule, with Pd-O distances of 2.849 (9) and 3.31 (3) Å in (I) and (II), respectively.

S1. Comment

Both dimethyl sulfoxide (dmso) and thioxane (tx) are ambivalent ligands since they possess two potential donor sites, i.e. the S and O atoms. Pd^II and Pt^II are soft acceptors and sulfur bonding is predominant. Tetrakis(dimethyl sulfoxide)palladium(II) contains two S-bonded and two O-bonded ligands in a cis-arrangement (Johnson et al., 1981; Johansson & Oskarsson, 2001), while tetrakis(thioxane)palladium contains four S-bonded ligands (Moullet et al., 1997; Johansson & Oskarsson, 2001). The same arrangements are found for the corresponding platinum compounds (Elding & Oskarsson, 1987; Burgarcic et al., 1991). The crystal structure of cis-bis(dimethyl sulfoxide)dinitratopalladium(II) has been published previously but as a preliminary report with no atomic coordinates (Langs et al., 1967); only the coordination geometry is given. It has been noticed that in Pt compounds the Pt—S distances in sulfoxides are shorter than in the corresponding thioether complexes (Bugarcic et al., 1993) and it has been shown that the origin of this difference is stronger bonding to sulfoxide S compared with thioether S (Kapoor et al., 1998). In order to explore if the same applies to for Pd complexes we have redetermined the structure of cis-bis(dimethyl sulfoxide)dinitratopalladium(I), cis-[Pd(NO₃)₂(dmso)₂], (I), and synthesized and determined the structure of cis-dinitratobis(1,4-thioxane)palladium(II), cis-[Pd(NO₃)₂(tx)₂], (II). The bonding was studied at the extended Hückel level using the program CACAO (Mealli & Proserpio, 1990). We have calculated the reduced overlap population (ROP) in the Pd–ligand bonds using the crystallographically observed geometries in the title complexes (Table 1).

In cis-[Pd(NO₃)₂(dmso)₂] (Fig. 1), the coordination around the Pd atom is pseudo-square planar, with angles ranging from 82.89 (9) to 95.64 (7)°. The nitrate ligands are oxygen coordinated, while dmso coordinates via sulfur. The coordination plane has a mean deviation of 0.0878 Å. The N—O distances with O coordinated to Pd are 1.322 (3) and 1.312 (3) Å, while the other N—O distances are in the range 1.208 (3)–1.225 (3) Å. The structure is composed of dimers where the two complexes are related via an inversion centre. The nitrate O4 atom of one complex interacts with the Pd atom of another complex and vice verse, forming a short intermolecular Pd···O4ⁱ distance of 2.849 (9) Å [symmetry code: (i) 2 - x, 1 - y, 2 - z].

The cis-[Pd(NO₃)₂(tx)₂] (Fig. 2) complex is pseudo-square planar, with angles around palladium ranging from 87.09 (10) to 92.06 (3)°. The nitrate ligands are oxygen coordinated, while the thioxane ligand coordinates through the S atoms. The coordination plane has a mean deviation of 0.0911 Å. The N—O distances with O coordinated to Pd are 1.285 (4) and 1.305 (4) Å, while the other N—O distances are in the range 1.210 (5)–1.231 (4) Å. The structure is composed of dimers, similar to the arrangement found in cis-[Pd(NO₃)₂(dmso)₂], with the two complexes related via an inversion centre. The nitrate O6 atom of one complex interacts with Pd atom of a second complex and vice verse, forming a short intermolecular Pd···O6ⁱⁱ distance of 3.303 (3) Å [symmetry code: (i) 1 - x, 1 - y, 1 - z]. The thioxane ligands adopt a chair conformation and are centred around the coordination plane.

The dimers have ROP values of 0.011 and 0.000 for (I) and (II), respectively. An ROP value larger than zero indicates covalent interaction, while a value of zero indicates only van der Waals interaction. However, a value as small as 0.011 may not be significant. The `intermolecular oxygen' is in an approximate octahedral position in both complexes, resulting in O4—Pd—O4ⁱ and O6—Pd—O6ⁱⁱ angles of 76.56 (10) and 95.39 (10)° in the dmso and thioxane compound, respectively, i.e. the O atom in the thioxane complex is close to the perfect octahedral position. The Pd···Pd distance in the dimers is 3.8897 (4) Å in (I) and 3.7350 (3) Å in (II). Both nitrate ligands in the title compounds point away from the coordination plane and face the second complex in the dimer with Pd—O—N angles of 115.2 (2), 114.2 (2), 115.1 (3) and 114.9 (2)°. Potassium (tetranitrato)palladium(II) has a similar geometry, with Pd—O—N angles ranging from 116.0 (2) to 119.4 (2)° (Elding et al., 1986). The same type of dimeric structure is found for the isostructural dmso–platinum analogue (Boström et al., 1991).

The Pd—S and Pd—O distances in the title compounds are compared with those of related structures in the literature in Table 1. The Pd—S distances for (II) are shorter than in [Pd(tx)₄]²⁺ (Johansson & Oskarsson, 2001; Moullet et al., 1997), which is in agreement with the weaker trans influence of oxygen compared to sulfur. The corresponding dmso complex does not show this trend since the S atoms in [Pd(dmso)₄]²⁺ are trans to O atoms (Johnson et al., 1981). The Pd—S distances in [Pd(tx)₄]²⁺ (Johansson & Oskarsson, 2001; Moullet et al., 1997) are longer than in all structures listed in Table 1 with oxygen trans with respect to sulfur.

The Pd—O distances in the two title structures [range 2.053 (3)–2.076 (2) Å] are about the same as in [Pd(dmso)₄]²⁺ [2.049 (3)–2.065 (10) Å; Johnson et al., 1981], while the Pd—O distances in [Pd(NO₃)₄]^2- [1.995 (3)–2.010 (2) Å; Elding et al., 1986] are much shorter, in accordance with the trans influence series.

The Pd—S distances in palladium sulfoxide compounds are compared with distances in similar thioether compounds in Table 2. A l l palladium sulfoxide compounds (except complexes with more than one metal centre) found in the Cambridge Structural Database (CSD; Allen & Kennard, 1993) are included, while only thioethers with a similar arrangement (compared to the sulfoxides) around the Pd and S atoms are taken into account. The Pd—S distances are 0.02–0.05 Å shorter in the sulfoxide compounds than in the thioether compounds.

The ROP values for the two title compounds are given in Table 1; the value for Pd—S_dmso is larger than for Pd—S_thioxane. The Pd—S bond length in (I) must be increased to 2.30 Å to get the same ROP as in (II) and it was concluded that sulfoxides form stronger bonds with Pd^II than thioethers, i.e. the same situation as observed for Pt^II compounds (Kapoor et al., 1998).

Related literature

For related literature, see: Allen & Kennard (1993); Boström et al. (1991); Burgarcic et al. (1991); Elding & Oskarsson (1987); Elding et al. (1986); Johansson & Oskarsson (2001); Johnson et al. (1981); Kapoor et al. (1998); Langs et al. (1967); Mealli & Proserpio (1990); Moullet et al. (1997).

S2. Experimental

For the preparation of cis-[Pd(NO₃)₂(dmso)₂], AgNO₃ (204 mg, 1.2 mmol) was added to an aqueous solution of PdCl₂(dmso)₂ (200 mg, 0.6 mmol). AgCl precipitates immediately and the mixure was stirred at room temperature for 1 h. AgCl was removed by filtration and orange crystals appear upon slow evaporation. For the preparation of cis-[Pd(NO₃)₂(tx)₂], AgNO₃ (204 mg,1.2 mmol) was added to an aqueous solution of PdCl₂(1,4-thioxane)₂ (200 mg, 0.6 mmol). AgCl precipitates immediately and the mixure was stirred at room temperature for 1 h. AgCl was removed by filtration and recrystallization from CH₂Cl₂ and CH₃NO₃ afforded orange crystals.

S3. Refinement

The thioxane compound has one residual density peak of 1.426 e^- Å^-3 in the final difference Fourier map that lies 0.80 Å from the Pd atom. No high residual density peak where found in the final difference Fourier map for the dmso compound.

Computing details

For both compounds, data collection: SMART (Bruker, 1995); cell refinement: SAINT (Bruker, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000). Software used to prepare material for publication: SHELXTL97 for (I); SHELXL97 for (II).

Figures

	Fig. 1. The dimer in cis-[Pd(NO3)2(dmso)2], (I), showing the numbering scheme and displacement ellipsoids at the 30% probability level (DIAMOND; Brandenburg, 2000).
	Fig. 2. The dimer in cis-[Pd(NO3)2(tx)2], (II), showing the numbering scheme and displacement ellipsoids at the 30% probability level (DIAMOND; Brandenburg, 2000).

(I) cis-bis(dimethyl sulphoxide)dinitratopalladium(II)

Crystal data

[Pd(NO3)2(C2H6OS)2]	F(000) = 768
Mr = 386.68	Dx = 2.104 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5671 reflections
a = 8.971 (2) Å	θ = 4–20°
b = 14.195 (3) Å	µ = 1.89 mm^−1
c = 10.358 (2) Å	T = 293 K
β = 112.24 (3)°	Prismatic, orange
V = 1221.0 (4) Å^3	0.14 × 0.08 × 0.07 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	3759 independent reflections
Radiation source: rotating anode	2898 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 512 pixels mm^-1	θmax = 31.8°, θmin = 2.6°
ω scans	h = −7→13
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −20→20
Tmin = 0.737, Tmax = 0.869	l = −15→13
10268 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0282P)^2] where P = (Fo^2 + 2Fc^2)/3
3759 reflections	(Δ/σ)max = 0.001
158 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.99 e Å^−3

Special details

Experimental. The intensity data sets were collected at 293 K with a Bruker SMART CCD system using ω-scans, -0.3° and 10 sec for cis-[Pd(NO₃)₂(dmso)₂] and 20 s for cis-[Pd(NO₃)₂(tx)₂] per frame (BrukerAXS, 1995). The detector distance was set to 4.0 cm. A rotating anode with Mo Kα radiation was used. Data is complete to 99.5% up to θ=29.8° for cis-[Pd(NO₃)₂(dmso)₂] and to 98.5% up to θ=27.5° for cis-[Pd(NO₃)₂(tx)₂]. Scattering factors, dispersion corrections and absorption coefficients were taken from International Tables for Crystallography, Vol. C. (1992), tables 6.1.1.4, 4.2.6.8 and 4.2.4.2 respectively. In both structures the first 50 frames were collected again at the end to check for decay. No decay was observed. All reflections were merged and integrated using SAINT (BrukerAXS, 1995). Both structures were solved by direct methods and refined by full matrix least-square calculations on F² using SHELXTL5.1 (Sheldrick, 1998). Non-H atoms were refined with anisotropic displacement parameters and the hydrogen atoms were constrained to parent sites, using a riding model.

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 (Ų)

	x	y	z	Uiso*/Ueq
Pd	0.99190 (2)	0.485088 (14)	0.81081 (2)	0.02024 (6)
S1	0.72881 (8)	0.48710 (5)	0.68114 (7)	0.02302 (13)
S2	1.01960 (9)	0.34960 (5)	0.70880 (7)	0.02764 (15)
O1	1.2342 (3)	0.49996 (15)	0.9334 (2)	0.0350 (5)
O2	1.4275 (3)	0.59695 (19)	0.9513 (3)	0.0527 (7)
O3	1.2864 (3)	0.5375 (2)	0.7500 (2)	0.0573 (7)
O4	0.9688 (3)	0.59799 (13)	0.9279 (2)	0.0303 (4)
O5	1.0613 (4)	0.73742 (17)	0.9924 (3)	0.0664 (8)
O6	1.0461 (4)	0.68552 (16)	0.7923 (3)	0.0543 (7)
O7	0.6956 (3)	0.47777 (16)	0.5316 (2)	0.0375 (5)
O8	0.8834 (3)	0.28462 (15)	0.6708 (2)	0.0398 (5)
N1	1.3195 (3)	0.54689 (19)	0.8750 (3)	0.0342 (6)
N2	1.0295 (3)	0.67702 (17)	0.9038 (3)	0.0337 (6)
C1	0.6427 (4)	0.5919 (2)	0.7123 (3)	0.0376 (7)
H1A	0.6582	0.5953	0.8091	0.056*
H1B	0.5295	0.5924	0.6562	0.056*
H1C	0.6934	0.6450	0.6885	0.056*
C2	0.6240 (4)	0.4010 (2)	0.7361 (3)	0.0369 (7)
H2A	0.6356	0.4137	0.8305	0.055*
H2B	0.6673	0.3399	0.7312	0.055*
H2C	0.5120	0.4026	0.6766	0.055*
C3	1.0622 (5)	0.3703 (3)	0.5579 (3)	0.0485 (9)
H3A	1.0856	0.3116	0.5236	0.073*
H3B	1.1535	0.4114	0.5807	0.073*
H3C	0.9705	0.3992	0.4875	0.073*
C4	1.1961 (4)	0.2925 (3)	0.8238 (4)	0.0493 (9)
H4A	1.1879	0.2832	0.9127	0.074*
H4B	1.2885	0.3308	0.8354	0.074*
H4C	1.2073	0.2325	0.7855	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd	0.02103 (10)	0.02061 (10)	0.01875 (10)	−0.00148 (8)	0.00715 (7)	−0.00111 (8)
S1	0.0217 (3)	0.0264 (3)	0.0201 (3)	−0.0014 (3)	0.0069 (3)	−0.0010 (2)
S2	0.0318 (4)	0.0241 (3)	0.0290 (4)	0.0014 (3)	0.0138 (3)	−0.0022 (3)
O1	0.0232 (10)	0.0476 (13)	0.0311 (11)	−0.0074 (9)	0.0067 (9)	0.0050 (9)
O2	0.0380 (14)	0.0620 (17)	0.0526 (15)	−0.0228 (12)	0.0108 (12)	−0.0068 (12)
O3	0.0548 (17)	0.090 (2)	0.0343 (13)	−0.0197 (15)	0.0248 (13)	−0.0100 (13)
O4	0.0409 (12)	0.0251 (10)	0.0290 (10)	−0.0052 (9)	0.0178 (9)	−0.0045 (8)
O5	0.096 (2)	0.0335 (14)	0.0597 (18)	−0.0121 (14)	0.0184 (17)	−0.0241 (12)
O6	0.087 (2)	0.0359 (13)	0.0596 (16)	−0.0009 (13)	0.0494 (16)	0.0086 (12)
O7	0.0330 (12)	0.0588 (14)	0.0194 (10)	0.0002 (10)	0.0084 (9)	−0.0021 (9)
O8	0.0442 (14)	0.0271 (11)	0.0508 (14)	−0.0060 (10)	0.0211 (12)	−0.0078 (10)
N1	0.0234 (13)	0.0431 (15)	0.0361 (14)	−0.0035 (11)	0.0112 (11)	−0.0026 (12)
N2	0.0369 (14)	0.0252 (13)	0.0362 (14)	0.0003 (10)	0.0107 (12)	−0.0021 (11)
C1	0.0302 (16)	0.0317 (16)	0.0454 (18)	0.0085 (12)	0.0081 (15)	−0.0002 (14)
C2	0.0337 (17)	0.0374 (18)	0.0443 (18)	−0.0105 (13)	0.0201 (15)	−0.0035 (13)
C3	0.070 (3)	0.050 (2)	0.0381 (18)	−0.0075 (19)	0.0345 (19)	−0.0091 (15)
C4	0.046 (2)	0.041 (2)	0.053 (2)	0.0182 (16)	0.0097 (18)	−0.0014 (16)

Geometric parameters (Å, º)

Pd—O4	2.067 (2)	S2—C3	1.768 (3)
Pd—O1	2.072 (2)	S2—C4	1.777 (3)
Pd—S1	2.2307 (11)	O1—N1	1.322 (3)
Pd—S2	2.2530 (8)	O2—N1	1.220 (3)
S1—O7	1.469 (2)	O3—N1	1.221 (3)
S1—C1	1.761 (3)	O4—N2	1.312 (3)
S1—C2	1.762 (3)	O5—N2	1.208 (3)
S2—O8	1.461 (2)	O6—N2	1.225 (3)
O4—Pd—O1	82.89 (9)	O8—S2—C4	109.6 (2)
O4—Pd—S1	91.43 (6)	C3—S2—C4	103.5 (2)
O1—Pd—S1	173.36 (6)	O8—S2—Pd	115.86 (9)
O4—Pd—S2	172.06 (6)	C3—S2—Pd	111.82 (13)
O1—Pd—S2	95.64 (7)	C4—S2—Pd	107.68 (12)
S1—Pd—S2	90.45 (3)	N1—O1—Pd	115.2 (2)
O7—S1—C1	109.96 (15)	N2—O4—Pd	114.2 (2)
O7—S1—C2	110.98 (14)	O2—N1—O3	124.4 (3)
C1—S1—C2	101.6 (2)	O2—N1—O1	116.9 (2)
O7—S1—Pd	112.33 (10)	O3—N1—O1	118.7 (3)
C1—S1—Pd	109.76 (11)	O5—N2—O6	124.6 (3)
C2—S1—Pd	111.65 (12)	O5—N2—O4	117.3 (3)
O8—S2—C3	107.8 (2)	O6—N2—O4	118.1 (2)

(II) cis-dinitratobistioxanepalladium(II)

Crystal data

[Pd(NO3)2(C4H8OS)2]	F(000) = 880
Mr = 438.75	Dx = 1.919 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5939 reflections
a = 8.9697 (18) Å	θ = 3–30°
b = 9.3263 (19) Å	µ = 1.53 mm^−1
c = 18.317 (4) Å	T = 293 K
β = 97.56 (3)°	Triangular, orange
V = 1518.9 (5) Å^3	0.19 × 0.16 × 0.06 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	4651 independent reflections
Radiation source: rotating anode	3370 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: 512 pixels mm^-1	θmax = 31.6°, θmin = 2.2°
ω scans	h = −13→7
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −13→13
Tmin = 0.742, Tmax = 0.912	l = −26→23
12387 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0364P)^2 + 0.7265P] where P = (Fo^2 + 2Fc^2)/3
4651 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 1.43 e Å^−3
0 restraints	Δρmin = −1.02 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Pd	0.55526 (3)	0.44420 (2)	0.597731 (13)	0.02864 (8)
S1	0.59228 (9)	0.22105 (8)	0.55557 (4)	0.02995 (17)
S2	0.79726 (10)	0.46150 (8)	0.65052 (5)	0.03518 (19)
O1	0.8366 (3)	−0.0176 (3)	0.56660 (17)	0.0536 (7)
O2	0.9904 (3)	0.7128 (3)	0.72287 (15)	0.0518 (7)
O3	0.5172 (3)	0.6565 (3)	0.61834 (15)	0.0472 (6)
O4	0.3916 (5)	0.8020 (4)	0.6768 (3)	0.1117 (16)
O5	0.3936 (4)	0.5773 (5)	0.70336 (18)	0.0804 (11)
O6	0.3300 (3)	0.4313 (3)	0.55423 (14)	0.0390 (6)
O7	0.1151 (3)	0.3385 (4)	0.56921 (17)	0.0676 (9)
O8	0.3172 (3)	0.2510 (3)	0.62980 (18)	0.0657 (9)
N1	0.4316 (4)	0.6800 (4)	0.6681 (2)	0.0563 (10)
N2	0.2518 (3)	0.3371 (4)	0.58577 (17)	0.0418 (7)
C1	0.6554 (4)	0.1080 (4)	0.63319 (19)	0.0392 (8)
H1A	0.7355	0.1555	0.6650	0.047*
H1B	0.5731	0.0903	0.6614	0.047*
C2	0.7122 (5)	−0.0330 (4)	0.6064 (2)	0.0509 (10)
H2A	0.7411	−0.0947	0.6485	0.061*
H2B	0.6309	−0.0798	0.5751	0.061*
C3	0.7990 (5)	0.0585 (4)	0.4999 (2)	0.0525 (10)
H3A	0.7129	0.0132	0.4714	0.063*
H3B	0.8826	0.0536	0.4714	0.063*
C4	0.7626 (4)	0.2133 (4)	0.5129 (2)	0.0397 (8)
H4A	0.7489	0.2648	0.4665	0.048*
H4B	0.8447	0.2577	0.5448	0.048*
C5	0.8777 (4)	0.6095 (4)	0.6064 (2)	0.0416 (8)
H5A	0.9018	0.5794	0.5587	0.050*
H5B	0.8050	0.6868	0.5988	0.050*
C6	1.0177 (5)	0.6624 (5)	0.6526 (2)	0.0530 (10)
H6A	1.0906	0.5851	0.6592	0.064*
H6B	1.0609	0.7395	0.6266	0.064*
C7	0.9444 (5)	0.6033 (5)	0.7679 (2)	0.0476 (9)
H7A	0.9430	0.6405	0.8173	0.057*
H7B	1.0170	0.5257	0.7708	0.057*
C8	0.7903 (5)	0.5452 (4)	0.73928 (19)	0.0452 (9)
H8A	0.7174	0.6226	0.7344	0.054*
H8B	0.7596	0.4755	0.7737	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd	0.02394 (12)	0.02669 (13)	0.03392 (13)	0.00104 (10)	−0.00133 (9)	−0.00131 (10)
S1	0.0259 (4)	0.0293 (4)	0.0332 (4)	0.0006 (3)	−0.0016 (3)	−0.0038 (3)
S2	0.0287 (4)	0.0267 (4)	0.0469 (5)	−0.0014 (3)	−0.0068 (4)	−0.0026 (3)
O1	0.0504 (17)	0.0431 (15)	0.0655 (19)	0.0173 (13)	0.0009 (15)	−0.0019 (13)
O2	0.0523 (16)	0.0490 (16)	0.0539 (15)	−0.0220 (13)	0.0056 (14)	−0.0171 (13)
O3	0.0446 (15)	0.0371 (14)	0.0598 (16)	0.0060 (12)	0.0061 (13)	−0.0067 (12)
O4	0.090 (3)	0.086 (3)	0.157 (4)	0.039 (2)	0.010 (3)	−0.065 (3)
O5	0.074 (2)	0.122 (3)	0.0476 (19)	0.008 (2)	0.0197 (18)	−0.008 (2)
O6	0.0269 (12)	0.0449 (14)	0.0430 (13)	−0.0011 (11)	−0.0041 (10)	0.0059 (11)
O7	0.0241 (13)	0.107 (3)	0.0707 (19)	−0.0086 (16)	0.0028 (14)	0.0080 (19)
O8	0.0478 (17)	0.073 (2)	0.078 (2)	0.0044 (16)	0.0165 (17)	0.0325 (18)
N1	0.0423 (19)	0.069 (2)	0.054 (2)	0.0165 (19)	−0.0076 (17)	−0.0245 (19)
N2	0.0303 (15)	0.0544 (19)	0.0412 (16)	−0.0018 (15)	0.0060 (13)	−0.0010 (15)
C1	0.043 (2)	0.0347 (17)	0.0384 (18)	−0.0003 (16)	0.0010 (16)	0.0052 (14)
C2	0.063 (3)	0.0275 (19)	0.060 (2)	0.0005 (17)	−0.002 (2)	0.0046 (16)
C3	0.048 (2)	0.060 (3)	0.049 (2)	0.021 (2)	0.0054 (19)	−0.010 (2)
C4	0.0321 (18)	0.048 (2)	0.0398 (18)	0.0074 (16)	0.0076 (16)	0.0028 (15)
C5	0.0395 (19)	0.045 (2)	0.0409 (19)	−0.0055 (17)	0.0068 (16)	−0.0029 (16)
C6	0.041 (2)	0.061 (3)	0.059 (2)	−0.018 (2)	0.0138 (19)	−0.013 (2)
C7	0.044 (2)	0.056 (2)	0.040 (2)	−0.0041 (19)	−0.0069 (17)	−0.0080 (18)
C8	0.042 (2)	0.059 (2)	0.0330 (18)	−0.0127 (18)	0.0015 (16)	0.0038 (16)

Geometric parameters (Å, º)

Pd—O3	2.053 (3)	O2—C6	1.422 (5)
Pd—O6	2.076 (2)	O3—N1	1.285 (4)
Pd—S1	2.2595 (9)	O4—N1	1.210 (5)
Pd—S2	2.2627 (11)	O5—N1	1.229 (5)
S1—C1	1.801 (3)	O6—N2	1.305 (4)
S1—C4	1.807 (4)	O7—N2	1.224 (4)
S2—C5	1.798 (4)	O8—N2	1.231 (4)
S2—C8	1.812 (4)	C1—C2	1.515 (5)
O1—C3	1.414 (5)	C3—C4	1.507 (5)
O1—C2	1.418 (5)	C5—C6	1.502 (5)
O2—C7	1.408 (5)	C7—C8	1.513 (5)
O3—Pd—O6	87.09 (10)	N2—O6—Pd	114.92 (19)
O3—Pd—S1	170.68 (8)	O4—N1—O5	123.8 (4)
O6—Pd—S1	89.71 (7)	O4—N1—O3	118.0 (5)
O3—Pd—S2	91.50 (8)	O5—N1—O3	118.3 (4)
O6—Pd—S2	177.17 (7)	O7—N2—O8	123.0 (3)
S1—Pd—S2	92.06 (3)	O7—N2—O6	117.5 (3)
C1—S1—C4	96.99 (17)	O8—N2—O6	119.5 (3)
C1—S1—Pd	108.34 (12)	C2—C1—S1	109.7 (3)
C4—S1—Pd	110.80 (13)	O1—C2—C1	113.5 (3)
C5—S2—C8	97.79 (17)	O1—C3—C4	112.1 (3)
C5—S2—Pd	106.38 (13)	C3—C4—S1	108.6 (3)
C8—S2—Pd	105.64 (14)	C6—C5—S2	110.8 (3)
C3—O1—C2	112.4 (3)	O2—C6—C5	112.8 (3)
C7—O2—C6	112.9 (3)	O2—C7—C8	112.4 (3)
N1—O3—Pd	115.1 (3)	C7—C8—S2	109.1 (3)