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Acta Cryst. (2007). E63, m2546    [ doi:10.1107/S1600536807044510 ]

[1,2-Bis(phenylseleno)benzene]dichloridopalladium(II)

N. Takeda, T. Isobe, T. Sasamori and N. Tokitoh

Abstract top

In the title compound, [PdCl2{1,2-C6H4(SePh)2}], the two Cl atoms and the two Se atoms are arranged in a square-planar fashion around the Pd atom. The two phenyl groups are on the same side of the PdCl2Se2 plane. Intermolecular interactions between the Cl and Se atoms are suggested [Se...Cl = 3.4003 (4) and 3.4101 (4) Å].

Comment top

There are no reports on the synthesis of the title compound, [PdCl2{1,2-C6H4(SePh)2}] (1), although the synthesis and full characterization of the sulfur analog, [PdCl2{1,2-C6H4(SPh)2}] (2), has already been reported (Hartley et al., 1979; Takeda et al., 2005). This paper presents the first synthesis and X-ray structural analysis of (1).

Compound (1) was prepared by a method similar to that for the sulfur analog (2) (Takeda et al., 2005), i.e., the reaction of the ligand, 1,2-bis(phenylseleno)benzene with NaPdCl4. The X-ray structural analysis of (1) shows features similar to those of (2) (Takeda et al., 2005), e.g., a square planar arrangement of the two chlorine and two chalcogen atoms around the palladium center, and a conformation where the two terminal phenyl groups of the diselenoether ligand are on the same side of the PdCl2Ch2 plane (Fig. 1). The Pd—Cl bond lengths (Pd1—Cl1 2.3471 (4) and Pd1—Cl2 2.3282 (4) Å) are slightly longer than those of (2) (Pd1—Cl1 2.3159 (6) and Pd1—Cl2 2.3116 (5) Å), although these values are within the range of the reported values for tetracoordinate palladium(II) complexes (2.298–2.354 Å) (Orpen et al., 1989). This result suggests that the coordination of the Se atoms to the Pd center in (1) is slightly stronger than that of the S atoms in (2). The Pd—Se bond lengths (Pd1—Se1 2.38098 (19) and Pd1—Se2 2.3790 (2) Å) are similar to those of the reported cis-dichloropalladium(II) complexes with selenoether (2.36–2.40 Å) (Booth et al., 1997; Champness et al., 1995; Whitfield, 1970).

Intermolecular Se—Cl distances (Se1—Cl2 3.4003 (4) and Se2—Cl1 3.4101 (4) Å) are slightly shorter than the sum of the van der Waals radii of chlorine and selinium (3.65 Å) (Bondi, 1964) (Fig. 2). This result suggests there is an intermolecular interaction between the chlorine and selenium atoms as well as between the chlorine and sulfur observed in (2). In addition, there are intermolecular C9—H7—Cl1 (2.94 (2) Å) and C10—H8—Cl2 (3.11 (2) Å) distances, although it is thought that these are weaker than the corresponding interactions in (2).

Related literature top

For related literature, see: Bondi (1964); Booth et al. (1997); Champness et al. (1995); Gujadhur & Venkataraman (2003); Gulliver et al. (1984); Hartley et al. (1979); Nakanishi & Hayashi (2000); Orpen et al. (1989); Petragnari & Toscano (1970); Takeda et al. (2005); Whitfield (1970).

Experimental top

Sodium tetrachloropalladate (93.8 mg, 0.319 mmol) was added to a solution of 1,2-bis(phenylseleno)benzene, 1,2-C6H4(SePh)2, (100 mg, 0.258 mmol) (Gujadhur & Venkataraman, 2003; Nakanishi & Hayashi, 2000; Gulliver et al., 1984; Petragnari & Toscano, 1970) in chloroform (3 ml)/ethanol (20 ml) at room temperature. After stirring for 3 h, the mixture was filtered. The precipitates were washed with ethanol (5 ml × 3) and then extracted with dichloromethane(300 ml) and chloroform (300 ml). After filtration of the mixture, evaporation of the filtrate gave the title compound, [PdCl2{1,2-C6H4(SePh)2}] (1) (138.7 mg, 0.245 mmol, 95%). Further purification by recrystallization from chloroform/ethanol provided analytically pure (1) (m.p. 270 °C, decomposition. Analysis found: C 38.08, H 2.65%; C18H14Cl2PdSe2 requires: C 38.23, H 2.50%). Suitable crystals for X-ray crystallography were obtained by slow evaporation of a dichloromethane/chloroform solution.

Refinement top

All H atoms were refined isotropically, while all the other atoms were refined anisotropically.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. View of the molecule of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size.
[Figure 2] Fig. 2. The molecular packing as viewed down the a axis..
[1,2-Bis(phenylseleno)benzene]dichloridopalladium(II) top
Crystal data top
[PdCl2(C18H14Se2)]Z = 2
Mr = 565.51F000 = 540
Triclinic, P1Dx = 2.175 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71069 Å
a = 8.7008 (3) ÅCell parameters from 2442 reflections
b = 10.4873 (2) Åθ = 3.1–25.5º
c = 10.9779 (3) ŵ = 5.59 mm−1
α = 64.1072 (13)ºT = 103 (2) K
β = 78.4779 (12)ºPrism, orange
γ = 74.2744 (17)º0.08 × 0.08 × 0.02 mm
V = 863.58 (4) Å3
Data collection top
Rigaku VariMax Saturn
diffractometer		3057 reflections with I > 2σ(I)
Radiation source: rotating-anode X-ray tubeRint = 0.015
Monochromator: Confocalθmax = 25.5º
T = 103(2) Kθmin = 3.1º
ω scansh = −10→10
Absorption correction: multi-scan
(REQAB; Jacobson; 1998)		k = −12→12
Tmin = 0.663, Tmax = 0.896l = −13→13
7378 measured reflectionsStandard reflections: ?
3122 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.014All H-atom parameters refined
wR(F2) = 0.037  w = 1/[σ2(Fo2) + (0.0102P)2 + 0.541P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
3122 reflectionsΔρmax = 0.63 e Å−3
264 parametersΔρmin = −0.31 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[PdCl2(C18H14Se2)]γ = 74.2744 (17)º
Mr = 565.51V = 863.58 (4) Å3
Triclinic, P1Z = 2
a = 8.7008 (3) ÅMo Kα
b = 10.4873 (2) ŵ = 5.59 mm−1
c = 10.9779 (3) ÅT = 103 (2) K
α = 64.1072 (13)º0.08 × 0.08 × 0.02 mm
β = 78.4779 (12)º
Data collection top
Rigaku VariMax Saturn
diffractometer		3122 independent reflections
Absorption correction: multi-scan
(REQAB; Jacobson; 1998)		3057 reflections with I > 2σ(I)
Tmin = 0.663, Tmax = 0.896Rint = 0.015
7378 measured reflectionsStandard reflections: ?
Refinement top
R[F2 > 2σ(F2)] = 0.014264 parameters
wR(F2) = 0.037All H-atom parameters refined
S = 1.05Δρmax = 0.63 e Å−3
3122 reflectionsΔρmin = −0.31 e Å−3
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 > 2sigma(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
Pd10.646899 (14)0.363137 (13)0.003739 (12)0.01048 (5)
Cl10.78072 (5)0.46915 (5)−0.21221 (4)0.01566 (9)
Cl20.47187 (5)0.28911 (5)−0.07496 (4)0.01613 (9)
Se10.832610 (19)0.422118 (17)0.093337 (16)0.01072 (5)
Se20.527966 (19)0.244530 (17)0.227340 (16)0.01141 (5)
C10.99842 (19)0.24472 (18)0.13286 (17)0.0128 (3)
C21.0948 (2)0.20103 (19)0.23691 (18)0.0153 (3)
H11.088 (2)0.254 (2)0.287 (2)0.011 (5)*
C31.2088 (2)0.0720 (2)0.26636 (18)0.0169 (4)
H21.275 (3)0.042 (2)0.335 (2)0.021 (5)*
C41.2279 (2)−0.0099 (2)0.19135 (18)0.0167 (4)
H31.302 (2)−0.097 (2)0.211 (2)0.017 (5)*
C51.1351 (2)0.03816 (19)0.08486 (18)0.0169 (4)
H41.152 (3)−0.019 (2)0.033 (2)0.022 (5)*
C61.0194 (2)0.16632 (19)0.05435 (17)0.0155 (3)
H50.961 (2)0.197 (2)−0.016 (2)0.017 (5)*
C70.7402 (2)0.38254 (18)0.27874 (16)0.0125 (3)
C80.8009 (2)0.42967 (19)0.35619 (18)0.0151 (3)
H60.888 (3)0.480 (2)0.319 (2)0.020 (5)*
C90.7332 (2)0.40479 (19)0.48820 (18)0.0172 (4)
H70.774 (3)0.434 (2)0.538 (2)0.023 (6)*
C100.6045 (2)0.33526 (19)0.54185 (18)0.0170 (4)
H80.557 (2)0.326 (2)0.624 (2)0.017 (5)*
C110.5435 (2)0.28864 (19)0.46451 (18)0.0161 (4)
H90.453 (3)0.240 (2)0.502 (2)0.024 (6)*
C120.6132 (2)0.31227 (18)0.33235 (17)0.0129 (3)
C130.6685 (2)0.05285 (18)0.27761 (17)0.0131 (3)
C140.7849 (2)0.00403 (19)0.36772 (17)0.0146 (3)
H100.799 (2)0.064 (2)0.4087 (19)0.010 (4)*
C150.8820 (2)−0.1332 (2)0.39744 (18)0.0171 (4)
H110.960 (3)−0.165 (2)0.458 (2)0.018 (5)*
C160.8626 (2)−0.2206 (2)0.33869 (18)0.0168 (4)
H120.928 (2)−0.315 (2)0.358 (2)0.020 (5)*
C170.7451 (2)−0.17168 (19)0.25014 (18)0.0154 (3)
H130.732 (2)−0.224 (2)0.207 (2)0.015 (5)*
C180.6474 (2)−0.03441 (19)0.21878 (17)0.0143 (3)
H140.574 (2)−0.002 (2)0.157 (2)0.018 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01126 (8)0.01039 (8)0.00946 (8)−0.00007 (5)−0.00263 (5)−0.00429 (6)
Cl10.0179 (2)0.0164 (2)0.01045 (19)−0.00168 (16)−0.00059 (15)−0.00487 (16)
Cl20.0167 (2)0.0168 (2)0.0175 (2)−0.00128 (17)−0.00698 (16)−0.00834 (17)
Se10.01120 (9)0.01027 (9)0.01034 (9)−0.00178 (7)−0.00084 (6)−0.00420 (7)
Se20.01043 (9)0.01092 (9)0.01232 (9)−0.00123 (7)−0.00143 (6)−0.00464 (7)
C10.0103 (8)0.0113 (8)0.0143 (8)−0.0022 (6)0.0020 (6)−0.0041 (7)
C20.0151 (8)0.0174 (9)0.0158 (8)−0.0049 (7)−0.0004 (7)−0.0085 (7)
C30.0132 (8)0.0180 (9)0.0168 (9)−0.0025 (7)−0.0040 (7)−0.0041 (7)
C40.0117 (8)0.0136 (9)0.0204 (9)0.0000 (7)0.0003 (7)−0.0052 (7)
C50.0180 (9)0.0150 (9)0.0175 (9)−0.0024 (7)0.0009 (7)−0.0080 (7)
C60.0153 (8)0.0172 (9)0.0124 (8)−0.0026 (7)−0.0020 (7)−0.0049 (7)
C70.0135 (8)0.0112 (8)0.0099 (8)0.0031 (6)−0.0021 (6)−0.0045 (7)
C80.0140 (8)0.0119 (8)0.0190 (9)0.0024 (7)−0.0049 (7)−0.0076 (7)
C90.0187 (9)0.0159 (9)0.0180 (9)0.0059 (7)−0.0080 (7)−0.0106 (8)
C100.0205 (9)0.0138 (9)0.0108 (8)0.0069 (7)−0.0020 (7)−0.0055 (7)
C110.0159 (9)0.0120 (9)0.0159 (8)0.0016 (7)−0.0006 (7)−0.0045 (7)
C120.0162 (8)0.0097 (8)0.0124 (8)0.0021 (7)−0.0042 (7)−0.0057 (7)
C130.0122 (8)0.0117 (8)0.0128 (8)−0.0026 (7)0.0019 (6)−0.0039 (7)
C140.0161 (8)0.0136 (9)0.0143 (8)−0.0035 (7)−0.0002 (7)−0.0060 (7)
C150.0166 (9)0.0172 (9)0.0157 (8)−0.0027 (7)−0.0047 (7)−0.0040 (7)
C160.0163 (9)0.0114 (9)0.0188 (9)−0.0006 (7)0.0002 (7)−0.0048 (7)
C170.0169 (8)0.0144 (9)0.0168 (8)−0.0052 (7)0.0021 (7)−0.0085 (7)
C180.0129 (8)0.0173 (9)0.0127 (8)−0.0049 (7)−0.0004 (7)−0.0055 (7)
Geometric parameters (Å, °) top
Pd1—Cl22.3282 (4)C7—C81.391 (2)
Pd1—Cl12.3471 (4)C8—C91.388 (3)
Pd1—Se22.3790 (2)C8—H60.96 (2)
Pd1—Se12.38098 (19)C9—C101.392 (3)
Se1—C71.9367 (16)C9—H70.89 (2)
Se1—C11.9547 (17)C10—C111.388 (3)
Se2—C121.9301 (16)C10—H80.89 (2)
Se2—C131.9515 (17)C11—C121.396 (2)
C1—C61.388 (2)C11—H90.97 (2)
C1—C21.391 (2)C13—C141.394 (2)
C2—C31.392 (3)C13—C181.394 (2)
C2—H10.92 (2)C14—C151.391 (3)
C3—C41.389 (3)C14—H100.96 (2)
C3—H20.93 (2)C15—C161.389 (3)
C4—C51.384 (3)C15—H110.94 (2)
C4—H30.92 (2)C16—C171.389 (3)
C5—C61.393 (2)C16—H120.95 (2)
C5—H40.96 (2)C17—C181.391 (3)
C6—H50.90 (2)C17—H130.91 (2)
C7—C121.383 (2)C18—H140.91 (2)
Cl2—Pd1—Cl194.066 (15)C9—C8—C7119.29 (17)
Cl2—Pd1—Se287.714 (12)C9—C8—H6120.0 (13)
Cl1—Pd1—Se2176.116 (12)C7—C8—H6120.7 (13)
Cl2—Pd1—Se1176.146 (12)C8—C9—C10120.37 (16)
Cl1—Pd1—Se187.742 (11)C8—C9—H7118.7 (14)
Se2—Pd1—Se190.279 (7)C10—C9—H7121.0 (14)
C7—Se1—C197.24 (7)C11—C10—C9120.38 (17)
C7—Se1—Pd1102.52 (5)C11—C10—H8119.7 (13)
C1—Se1—Pd199.60 (5)C9—C10—H8119.8 (13)
C12—Se2—C1398.11 (7)C10—C11—C12119.08 (17)
C12—Se2—Pd1102.46 (5)C10—C11—H9120.4 (13)
C13—Se2—Pd199.58 (5)C12—C11—H9120.5 (13)
C6—C1—C2121.35 (16)C7—C12—C11120.48 (15)
C6—C1—Se1119.04 (13)C7—C12—Se2121.14 (12)
C2—C1—Se1119.59 (13)C11—C12—Se2118.38 (13)
C1—C2—C3118.74 (16)C14—C13—C18120.97 (16)
C1—C2—H1123.1 (12)C14—C13—Se2122.29 (13)
C3—C2—H1118.2 (12)C18—C13—Se2116.74 (12)
C4—C3—C2120.52 (16)C15—C14—C13119.05 (16)
C4—C3—H2119.8 (13)C15—C14—H10120.2 (11)
C2—C3—H2119.6 (13)C13—C14—H10120.8 (11)
C5—C4—C3119.89 (17)C16—C15—C14120.42 (16)
C5—C4—H3119.0 (12)C16—C15—H11121.0 (13)
C3—C4—H3121.1 (12)C14—C15—H11118.5 (12)
C4—C5—C6120.53 (16)C15—C16—C17120.13 (17)
C4—C5—H4118.4 (13)C15—C16—H12121.4 (12)
C6—C5—H4121.1 (13)C17—C16—H12118.5 (12)
C1—C6—C5118.88 (16)C16—C17—C18120.24 (16)
C1—C6—H5121.8 (13)C16—C17—H13122.3 (13)
C5—C6—H5119.3 (13)C18—C17—H13117.4 (13)
C12—C7—C8120.39 (15)C17—C18—C13119.20 (16)
C12—C7—Se1120.80 (12)C17—C18—H14119.2 (13)
C8—C7—Se1118.78 (13)C13—C18—H14121.5 (13)
Cl1—Pd1—Se1—C7169.73 (5)C7—C8—C9—C10−0.9 (3)
Se2—Pd1—Se1—C7−13.61 (5)C8—C9—C10—C110.7 (3)
Cl1—Pd1—Se1—C1−90.57 (5)C9—C10—C11—C120.1 (3)
Se2—Pd1—Se1—C186.08 (5)C8—C7—C12—C110.5 (2)
Cl2—Pd1—Se2—C12−168.85 (5)Se1—C7—C12—C11−177.73 (13)
Se1—Pd1—Se2—C1214.44 (5)C8—C7—C12—Se2−179.51 (12)
Cl2—Pd1—Se2—C1390.55 (5)Se1—C7—C12—Se22.30 (19)
Se1—Pd1—Se2—C13−86.16 (5)C10—C11—C12—C7−0.7 (2)
C7—Se1—C1—C6133.28 (14)C10—C11—C12—Se2179.29 (13)
Pd1—Se1—C1—C629.21 (14)C13—Se2—C12—C788.59 (14)
C7—Se1—C1—C2−47.93 (14)Pd1—Se2—C12—C7−13.16 (14)
Pd1—Se1—C1—C2−152.00 (13)C13—Se2—C12—C11−91.38 (14)
C6—C1—C2—C3−3.3 (3)Pd1—Se2—C12—C11166.87 (12)
Se1—C1—C2—C3177.98 (13)C12—Se2—C13—C141.13 (15)
C1—C2—C3—C41.3 (3)Pd1—Se2—C13—C14105.32 (14)
C2—C3—C4—C51.2 (3)C12—Se2—C13—C18−178.82 (13)
C3—C4—C5—C6−1.7 (3)Pd1—Se2—C13—C18−74.64 (13)
C2—C1—C6—C52.7 (3)C18—C13—C14—C150.7 (2)
Se1—C1—C6—C5−178.49 (13)Se2—C13—C14—C15−179.21 (13)
C4—C5—C6—C1−0.2 (3)C13—C14—C15—C16−0.3 (3)
C1—Se1—C7—C12−91.70 (14)C14—C15—C16—C17−0.4 (3)
Pd1—Se1—C7—C129.85 (14)C15—C16—C17—C180.6 (3)
C1—Se1—C7—C890.07 (14)C16—C17—C18—C13−0.2 (3)
Pd1—Se1—C7—C8−168.37 (12)C14—C13—C18—C17−0.5 (2)
C12—C7—C8—C90.3 (2)Se2—C13—C18—C17179.49 (12)
Se1—C7—C8—C9178.56 (12)
Selected geometric parameters (Å, °) top
Pd1—Cl22.3282 (4)Se1—C71.9367 (16)
Pd1—Cl12.3471 (4)Se1—C11.9547 (17)
Pd1—Se22.3790 (2)Se2—C121.9301 (16)
Pd1—Se12.38098 (19)Se2—C131.9515 (17)
Cl2—Pd1—Cl194.066 (15)C7—Se1—C197.24 (7)
Cl2—Pd1—Se287.714 (12)C7—Se1—Pd1102.52 (5)
Cl1—Pd1—Se2176.116 (12)C1—Se1—Pd199.60 (5)
Cl2—Pd1—Se1176.146 (12)C12—Se2—C1398.11 (7)
Cl1—Pd1—Se187.742 (11)C12—Se2—Pd1102.46 (5)
Se2—Pd1—Se190.279 (7)C13—Se2—Pd199.58 (5)
Acknowledgements top

This work was partially supported by Grants-in-Aid for COE Research on Elements Science (No. 12CE2005), Creative Scientific Research (17GS0270), Young Scientists (B) (No. 15750031), and the 21s t Century COE Program of Kyoto University Alliance for Chemistry, from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

references
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