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Acta Cryst. (2007). E63, m1704    [ doi:10.1107/S1600536807024853 ]

Chlorido{4-chloro-1-[2-(methylsulfanyl)phenyldiazenyl]phenyl-[kappa]3C,N,S}palladium(II)

V. Bagchi, P. Das and D. Bandyopadhyay

Abstract top

The Pd atom in the title compound, [Pd(C13H10ClN2S)Cl], is tetracoordinated by a benzene C, a diazene N, a Cl and an S atom in an approximately square-planar geometry. The molecules are found to dimerize through a nonbonded S...S interaction [S...S = 3.5162 (17) Å]. There are no hydrogen bonds and the crystal packing is stabilized by four intermolecular [pi]-[pi] interactions; the centroid-centroid distances are 3.808 (2), 3.623 (2), 3.808 (2) and 3.623 (2) Å; the corresponding perpendicular distances are 3.462, 3.454, 3.402 and 3.402 Å with no slippages.

Comment top

Cyclopalladated compounds have numerous applications (Dupont et al., 2005) in organic synthesis, catalysis, photochemistry and metallomesogen chemistry. Although a number of cyclometallated complexes of palladium (Omae, 2004 & Neogi et al., 2006) have been reported in literature, report of palladium complexes with sulfur as an auxiliary donor is relatively sparse (Pal et al., 1992). Against this background, we report here the crystal structure of (I).

The molecular structure of the title compound, (I), is shown in Fig. 1, with the atom numbering scheme. The palladium atom along with donor set of four atoms lie in an almost plane. Selected bond lengths and bond angles are listed in Table 1. The packing arrangement of (I) is shown in Fig. 2. The N?N bond length is typical of other cyclopalladated azoarenes (Neogi et al., 2006), unlike that of other free azoarenes containing thioether moiety (Das et al., 2006). The metal carbon bond length, 1.977 (3) Å, is higher than the reported values of other ortho-palladated azoarenes (Bagchi & Bandyopadhyay, 2007). The molecules are found to dimerize through a nonbonded S···S interaction; having S···Si [symmetry code: (i) 1 - x, -y, 1 - z] distance of 3.5162 (17) Å (Chattopadhyay et al., 1991) (Fig. 3). Four inter molecular π—π interactions (Kubo et al., 2005 & Bagchi & Bandyopadhyay, 2007) arrange the molecules in anti parallel fashion (Fig. 4). The Cg3—Cg4ii, Cg3—Cg4iii, Cg4—Cg3ii, Cg4—Cg3iii, [symmetry codes: (ii) -x, 1 - y, 1 - z; (iii) 1 - x, 1 - y, 1-z. Cg3 and Cg4 are the centroids of C1—C6 and C7—C12 rings, respectively.] distances are 3.808 (2), 3.623 (2), 3.808 (2) and 3.623 (2) Å; the corresponding perpendicular distances are 3.462, 3.454, 3.402 and 3.402 Å with slippages of 3.402, 3.402, 3.462 and 3.454 Å, respectively.

Related literature top

For related literature, see: Bagchi & Bandyopadhyay (2007); Chattopadhyay et al. (1991); Das et al. (2006); Dupont et al. (2005); Kubo et al. (2005); Mahapatra et al. (1986); Neogi et al. (2006); Omae (2004); Pal et al. (1992).

Experimental top

2-(Methylsulfanyl)diazenyl-4-cholorobenzene was prepared by coupling 2-(methylsulfanyl)aniline with 4-nitrosochlorobenzene. The ligand thus obtained was reacted with Na2PdCl4 following a reported method (Mahapatra et al., 1986). The product was purified by coloumn chromatographic technique using silica gel column and methanol and dichloromethane (1: 9 v/v) mixture as eluant. The solvent was evaporated in vacuum to obtain the pure product (yield: 83.9%). Suitable crystals of (I) were grown from a dichloromethane-hexane solution by slow evaporation.

Refinement top

H atoms were included at calculated positions as riding atoms with C–H set to 0.93 Å for (aromatic) and 0.96 Å for (CH3) H atoms, with Uiso(H) = 1.2Ueq(C) (1.5Ueq for methyl group).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. The molecular arrangement of (I) in the unitcell.
[Figure 3] Fig. 3. The intermolecular S···S interaction for (I), indicated by dotted line [symmetry code: (i) 1 - x, -y, 1 - z].
[Figure 4] Fig. 4. The intermolecular π—π interactions for (I), indicated by the blue and green dotted lines. [Symmetry codes: (ii) - x, 1 - y, 1 - z; (iii) 1 - x, 1 - y, 1 - z.]. Cg3 and Cg4 are centroids of C1—C6 and C7—C12 rings, respectively.
Chlorido{4-chloro-1-[2-(methylsulfanyl)phenyldiazenyl]phenyl -κ3C,N,S}palladium(II) top
Crystal data top
[Pd(C13H10ClN2S)Cl]Z = 2
Mr = 403.59F(000) = 396
Triclinic, P1Dx = 1.952 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.413 (2) ÅCell parameters from 3745 reflections
b = 8.768 (3) Åθ = 2.4–28.0°
c = 11.051 (3) ŵ = 1.88 mm−1
α = 105.330 (4)°T = 298 K
β = 92.875 (5)°Block, red
γ = 95.995 (5)°0.43 × 0.28 × 0.19 mm
V = 686.7 (4) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		2416 independent reflections
Radiation source: fine-focus sealed tube2308 reflections with I > 2σ(I)
graphiteRint = 0.035
φ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.538, Tmax = 0.701k = −10→10
6579 measured reflectionsl = −13→13
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0218P)2 + 0.4766P]
where P = (Fo2 + 2Fc2)/3
2416 reflections(Δ/σ)max < 0.001
173 parametersΔρmax = 0.37 e Å−3
0 restraintsΔρmin = −0.43 e Å−3
Crystal data top
[Pd(C13H10ClN2S)Cl]γ = 95.995 (5)°
Mr = 403.59V = 686.7 (4) Å3
Triclinic, P1Z = 2
a = 7.413 (2) ÅMo Kα radiation
b = 8.768 (3) ŵ = 1.88 mm−1
c = 11.051 (3) ÅT = 298 K
α = 105.330 (4)°0.43 × 0.28 × 0.19 mm
β = 92.875 (5)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2416 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2308 reflections with I > 2σ(I)
Tmin = 0.538, Tmax = 0.701Rint = 0.035
6579 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.069Δρmax = 0.37 e Å−3
S = 1.13Δρmin = −0.43 e Å−3
2416 reflectionsAbsolute structure: ?
173 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
C80.1472 (5)0.7783 (4)0.6873 (4)0.0399 (8)
H80.14020.85140.64020.048*
C130.2318 (6)−0.0523 (4)0.3667 (4)0.0547 (10)
H13A0.2241−0.11120.42860.082*
H13B0.2717−0.11730.29090.082*
H13C0.1143−0.02270.34900.082*
C40.3860 (5)0.2481 (5)0.0990 (4)0.0524 (10)
H40.40780.20220.01590.063*
C120.2017 (4)0.5121 (4)0.6990 (3)0.0324 (7)
C110.1687 (5)0.5551 (4)0.8249 (3)0.0373 (8)
H110.17430.48280.87280.045*
Pd10.28010 (3)0.31568 (3)0.59178 (2)0.03148 (10)
S0.39237 (12)0.12483 (10)0.42611 (8)0.0373 (2)
Cl10.29394 (16)0.18486 (11)0.74538 (9)0.0551 (3)
Cl20.08874 (16)0.76042 (13)1.03770 (9)0.0599 (3)
N10.2693 (4)0.4451 (3)0.4709 (3)0.0317 (6)
N20.2272 (4)0.5860 (3)0.5041 (3)0.0352 (6)
C10.3113 (4)0.3831 (4)0.3433 (3)0.0326 (7)
C90.1155 (5)0.8202 (4)0.8127 (4)0.0417 (8)
H90.08690.92140.85170.050*
C100.1271 (5)0.7082 (4)0.8789 (3)0.0396 (8)
C60.3623 (4)0.2299 (4)0.3102 (3)0.0344 (7)
C70.1897 (4)0.6260 (4)0.6309 (3)0.0333 (7)
C20.3014 (5)0.4691 (4)0.2552 (3)0.0412 (8)
H20.26900.57190.27790.049*
C50.4002 (5)0.1628 (5)0.1866 (3)0.0451 (9)
H50.43480.06080.16330.054*
C30.3400 (5)0.4010 (5)0.1337 (4)0.0494 (10)
H30.33490.45870.07440.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C80.043 (2)0.0319 (18)0.047 (2)0.0092 (15)0.0064 (16)0.0120 (16)
C130.069 (3)0.036 (2)0.054 (3)−0.0035 (19)−0.008 (2)0.0078 (18)
C40.053 (2)0.072 (3)0.0292 (19)0.004 (2)0.0054 (17)0.0081 (19)
C120.0320 (17)0.0282 (16)0.0347 (18)0.0041 (13)0.0034 (14)0.0045 (14)
C110.044 (2)0.0313 (18)0.0349 (19)0.0031 (15)0.0039 (15)0.0058 (15)
Pd10.04049 (17)0.02465 (15)0.02860 (16)0.00572 (10)0.00310 (11)0.00526 (10)
S0.0452 (5)0.0335 (4)0.0320 (5)0.0116 (4)0.0017 (4)0.0046 (4)
Cl10.0936 (8)0.0372 (5)0.0413 (5)0.0175 (5)0.0143 (5)0.0174 (4)
Cl20.0818 (7)0.0539 (6)0.0375 (5)0.0141 (5)0.0122 (5)−0.0027 (4)
N10.0318 (15)0.0316 (15)0.0318 (15)0.0033 (11)0.0015 (11)0.0094 (12)
N20.0383 (16)0.0286 (14)0.0390 (16)0.0056 (12)0.0035 (12)0.0090 (12)
C10.0292 (17)0.0379 (18)0.0287 (17)0.0019 (14)0.0013 (13)0.0065 (14)
C90.040 (2)0.0311 (18)0.051 (2)0.0086 (15)0.0070 (17)0.0035 (16)
C100.0392 (19)0.0378 (19)0.0348 (19)0.0017 (15)0.0077 (15)−0.0018 (15)
C60.0315 (17)0.0387 (18)0.0316 (18)0.0051 (14)0.0024 (14)0.0067 (15)
C70.0335 (18)0.0297 (17)0.0350 (18)0.0043 (13)0.0044 (14)0.0055 (14)
C20.041 (2)0.044 (2)0.041 (2)0.0051 (16)0.0013 (16)0.0153 (17)
C50.046 (2)0.047 (2)0.040 (2)0.0095 (17)0.0063 (16)0.0044 (17)
C30.048 (2)0.065 (3)0.039 (2)0.0063 (19)0.0028 (17)0.020 (2)
Geometric parameters (Å, °) top
C8—C91.376 (5)Pd1—Cl12.2900 (11)
C8—C71.392 (5)Pd1—S2.3810 (10)
C8—H80.9300S—C61.783 (3)
C13—S1.805 (4)Cl2—C101.739 (4)
C13—H13A0.9600N1—N21.270 (4)
C13—H13B0.9600N1—C11.433 (4)
C13—H13C0.9600N2—C71.401 (4)
C4—C51.377 (6)C1—C21.384 (5)
C4—C31.378 (6)C1—C61.393 (5)
C4—H40.9300C9—C101.377 (5)
C12—C111.383 (5)C9—H90.9300
C12—C71.407 (5)C6—C51.392 (5)
C12—Pd11.977 (3)C2—C31.375 (5)
C11—C101.391 (5)C2—H20.9300
C11—H110.9300C5—H50.9300
Pd1—N11.972 (3)C3—H30.9300
C9—C8—C7119.8 (3)N2—N1—Pd1121.0 (2)
C9—C8—H8120.1C1—N1—Pd1120.8 (2)
C7—C8—H8120.1N1—N2—C7110.3 (3)
S—C13—H13A109.5C2—C1—C6120.5 (3)
S—C13—H13B109.5C2—C1—N1122.4 (3)
H13A—C13—H13B109.5C6—C1—N1117.1 (3)
S—C13—H13C109.5C8—C9—C10118.2 (3)
H13A—C13—H13C109.5C8—C9—H9120.9
H13B—C13—H13C109.5C10—C9—H9120.9
C5—C4—C3120.5 (4)C9—C10—C11123.2 (3)
C5—C4—H4119.8C9—C10—Cl2118.6 (3)
C3—C4—H4119.8C11—C10—Cl2118.2 (3)
C11—C12—C7118.0 (3)C5—C6—C1119.3 (3)
C11—C12—Pd1131.4 (3)C5—C6—S119.9 (3)
C7—C12—Pd1110.4 (2)C1—C6—S120.6 (3)
C12—C11—C10119.0 (3)C8—C7—N2119.4 (3)
C12—C11—H11120.5C8—C7—C12121.7 (3)
C10—C11—H11120.5N2—C7—C12118.9 (3)
N1—Pd1—C1279.36 (13)C3—C2—C1119.3 (4)
N1—Pd1—Cl1175.20 (8)C3—C2—H2120.3
C12—Pd1—Cl196.12 (10)C1—C2—H2120.3
N1—Pd1—S85.42 (9)C4—C5—C6119.7 (4)
C12—Pd1—S164.33 (10)C4—C5—H5120.2
Cl1—Pd1—S98.98 (4)C6—C5—H5120.2
C6—S—C13102.51 (17)C2—C3—C4120.7 (4)
C6—S—Pd195.55 (11)C2—C3—H3119.7
C13—S—Pd1112.06 (15)C4—C3—H3119.7
N2—N1—C1118.2 (3)
C7—C12—C11—C10−0.6 (5)C8—C9—C10—Cl2179.6 (3)
Pd1—C12—C11—C10175.3 (2)C12—C11—C10—C90.5 (5)
C11—C12—Pd1—N1−177.7 (3)C12—C11—C10—Cl2−179.3 (2)
C7—C12—Pd1—N1−1.7 (2)C2—C1—C6—C5−1.2 (5)
C11—C12—Pd1—Cl10.6 (3)N1—C1—C6—C5178.4 (3)
C7—C12—Pd1—Cl1176.7 (2)C2—C1—C6—S175.1 (3)
C11—C12—Pd1—S−163.8 (2)N1—C1—C6—S−5.3 (4)
C7—C12—Pd1—S12.3 (5)C13—S—C6—C5−62.4 (3)
N1—Pd1—S—C6−5.55 (13)Pd1—S—C6—C5−176.4 (3)
C12—Pd1—S—C6−19.3 (4)C13—S—C6—C1121.4 (3)
Cl1—Pd1—S—C6176.39 (11)Pd1—S—C6—C17.3 (3)
N1—Pd1—S—C13−111.46 (17)C9—C8—C7—N2−178.1 (3)
C12—Pd1—S—C13−125.2 (4)C9—C8—C7—C120.0 (5)
Cl1—Pd1—S—C1370.47 (15)N1—N2—C7—C8177.6 (3)
C12—Pd1—N1—N21.7 (2)N1—N2—C7—C12−0.5 (4)
S—Pd1—N1—N2−174.5 (2)C11—C12—C7—C80.3 (5)
C12—Pd1—N1—C1−179.1 (2)Pd1—C12—C7—C8−176.3 (3)
S—Pd1—N1—C14.6 (2)C11—C12—C7—N2178.4 (3)
C1—N1—N2—C7179.7 (3)Pd1—C12—C7—N21.7 (4)
Pd1—N1—N2—C7−1.2 (3)C6—C1—C2—C30.9 (5)
N2—N1—C1—C2−2.2 (5)N1—C1—C2—C3−178.7 (3)
Pd1—N1—C1—C2178.6 (2)C3—C4—C5—C61.9 (6)
N2—N1—C1—C6178.2 (3)C1—C6—C5—C4−0.3 (5)
Pd1—N1—C1—C6−1.0 (4)S—C6—C5—C4−176.5 (3)
C7—C8—C9—C100.0 (5)C1—C2—C3—C40.7 (6)
C8—C9—C10—C11−0.2 (5)C5—C4—C3—C2−2.2 (6)
Table 1
Selected geometric parameters (Å, °) top
C13—S1.805 (4)S—C61.783 (3)
C12—Pd11.977 (3)Cl2—C101.739 (4)
Pd1—N11.972 (3)N1—N21.270 (4)
Pd1—Cl12.2900 (11)N1—C11.433 (4)
Pd1—S2.3810 (10)N2—C71.401 (4)
N1—Pd1—C1279.36 (13)C6—S—C13102.51 (17)
C12—Pd1—Cl196.12 (10)N2—N1—C1118.2 (3)
N1—Pd1—S85.42 (9)N1—N2—C7110.3 (3)
Cl1—Pd1—S98.98 (4)
C13—S—C6—C1121.4 (3)Pd1—S—C6—C17.3 (3)
Acknowledgements top

We thank the Department of Science and Technology (project No. SR/S1/IC-11/2002) for funding and CSIR for the fellowship to VB and PD. The single-crystal X-ray diffractometer facility provided by IITD is gratefully acknowledged.

references
References top

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