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Acta Cryst. (2007). E63, m2130    [ doi:10.1107/S1600536807033636 ]

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

V. Bagchi, P. Das and D. Bandyopadhyay

Abstract top

The title compound, [Pd(C13H10ClN2S)Cl], is the monoclinic form of a previously reported triclinic structure of the same compound. The bond distances and angles of the molecule in the monoclinic form deviate slightly from those for the triclinic form. The Pd atom in this compound is tetracoordinated by a benzene C, a diazene N, a Cl and an S atom in an approximately square-planar geometry. The intermolecular interactions are very similar in both polymorphs. The molecules are found to dimerize through a nonbonding S...S interaction [S...S = 3.438 (2) Å]. There are no hydrogen bonds and the crystal packing is stabilized by four intermolecular [pi]-[pi] interactions; the distances between the centroids of the six-membered rings are 3.620 (3), 3.841 (3), 3.619 (3) and 3.842 (3) Å, and the perpendicular distances are 3.482, 3.482, 3.536 and 3.519 Å.

Comment top

We recently reported the structure of a first triclinic polymorph of [Pd(C13H10ClN2S)Cl] in space group P1 (Bagchi et al., 2007). The title molecule, (I), was produced during a parallel crystallization process. The present crystal found to crystallize in monoclinic form with P21/c space group at room temperature. Herein we report the monoclinic 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 bond distances and bond angles of the molecule in the monoclinic form deviates slightly from those in the triclinic morphology (Bagchi et al., 2007). The molecules are found to dimerize through a nonbonded S···S interaction; having S···Si [Symmetry code: (i) -x, 2 - y, -z] distance of 3.438 (2) Å (Chattopadhyay et al., 1991) and is smaller than that in the triclinic crystal modification (Bagchi et al., 2007) (Fig. 3). Four intermolecular 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, -z; (iii) 1 - x, 1 - y, -z. Cg3 and Cg4 are the centroids of C1—C6 and C7—C12 rings, respectively] distances are 3.620 (3), 3.841 (3), 3.619 (3) and 3.842 (3) Å; the perpendicular distances are 3.482, 3.482, 3.536 and 3.519 Å, respectively, with no slippages; though the Cg···Cg distances are very close in both the polymorph but the perpendicular distances are greater in the monoclinic crystal modification.

Related literature top

For related literature, see: Bagchi & Bandyopadhyay (2007); Bagchi et al. (2007); Chattopadhyay et al. (1991); Kubo et al. (2005).

Experimental top

The title compound (I) was prepared following a method reported in an earlier communication (Bagchi et al., 2007). 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 bc plane.
[Figure 3] Fig. 3. The intermolecular S···S interaction for (I), indicated by dotted line [Symmetry code: (i) -x, 2 - y, -z].
[Figure 4] Fig. 4. The intermolecular π—π interactions for (I), indicated by the blue and green dotted lines. [Symmetry code: (ii) -x, 1 - y, -z; (iii) 1 - x, 1 - y, -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]F(000) = 792
Mr = 403.59Dx = 1.955 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2420 reflections
a = 7.3978 (10) Åθ = 2.0–25.0°
b = 8.8652 (12) ŵ = 1.88 mm−1
c = 20.978 (3) ÅT = 295 K
β = 94.668 (2)°Block, red
V = 1371.2 (3) Å30.42 × 0.30 × 0.19 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		2420 independent reflections
Radiation source: fine-focus sealed tube2346 reflections with I > 2σ(I)
graphiteRint = 0.036
φ and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.510, Tmax = 0.703k = −10→10
12718 measured reflectionsl = −24→24
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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H-atom parameters constrained
S = 1.31 w = 1/[σ2(Fo2) + (0.0356P)2 + 3.6827P]
where P = (Fo2 + 2Fc2)/3
2420 reflections(Δ/σ)max = 0.001
173 parametersΔρmax = 0.86 e Å−3
0 restraintsΔρmin = −0.79 e Å−3
Crystal data top
[Pd(C13H10ClN2S)Cl]V = 1371.2 (3) Å3
Mr = 403.59Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.3978 (10) ŵ = 1.88 mm−1
b = 8.8652 (12) ÅT = 295 K
c = 20.978 (3) Å0.42 × 0.30 × 0.19 mm
β = 94.668 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2420 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2346 reflections with I > 2σ(I)
Tmin = 0.510, Tmax = 0.703Rint = 0.036
12718 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.103Δρmax = 0.86 e Å−3
S = 1.31Δρmin = −0.79 e Å−3
2420 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
C50.3885 (8)1.2353 (6)0.3486 (3)0.0398 (14)
H50.41741.32560.32930.048*
C130.2475 (9)0.4991 (7)0.5732 (3)0.0496 (16)
H13A0.36820.53700.58280.074*
H13B0.24990.41900.54250.074*
H13C0.20140.46150.61160.074*
Cl10.2324 (3)0.60867 (17)0.38218 (7)0.0542 (5)
Cl20.4171 (3)1.10947 (19)0.23353 (7)0.0532 (4)
Pd10.22575 (6)0.79235 (4)0.458724 (19)0.03074 (16)
S10.1026 (2)0.64961 (16)0.54057 (7)0.0363 (3)
N20.2277 (6)0.9604 (5)0.5206 (2)0.0303 (10)
C70.1844 (7)0.9369 (6)0.5847 (3)0.0314 (12)
C20.3027 (7)0.9594 (6)0.4043 (2)0.0303 (12)
N10.2704 (6)1.0932 (5)0.5040 (2)0.0342 (10)
C10.3119 (7)1.0953 (6)0.4398 (3)0.0302 (12)
C80.1314 (8)0.7914 (7)0.6008 (3)0.0360 (13)
C60.3554 (8)1.2324 (6)0.4122 (3)0.0390 (13)
H60.36191.32040.43640.047*
C90.0915 (8)0.7616 (7)0.6630 (3)0.0444 (15)
H90.05470.66550.67410.053*
C120.1965 (8)1.0512 (7)0.6304 (3)0.0398 (14)
H120.23021.14820.61940.048*
C40.3786 (7)1.1036 (6)0.3140 (3)0.0344 (12)
C30.3360 (7)0.9653 (6)0.3406 (3)0.0365 (13)
H30.33010.87830.31580.044*
C110.1579 (9)1.0191 (8)0.6921 (3)0.0481 (16)
H110.16621.09450.72300.058*
C100.1065 (8)0.8739 (8)0.7082 (3)0.0490 (16)
H100.08200.85270.75010.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C50.047 (3)0.028 (3)0.045 (3)−0.003 (3)0.009 (3)0.009 (3)
C130.062 (4)0.036 (3)0.049 (4)0.002 (3)−0.006 (3)0.004 (3)
Cl10.0972 (13)0.0283 (7)0.0391 (8)−0.0041 (8)0.0176 (8)−0.0051 (6)
Cl20.0783 (12)0.0464 (9)0.0363 (8)−0.0009 (8)0.0131 (8)0.0081 (7)
Pd10.0413 (3)0.0231 (2)0.0281 (2)−0.00143 (18)0.00396 (17)0.00059 (17)
S10.0453 (8)0.0322 (7)0.0308 (7)−0.0094 (6)0.0002 (6)0.0013 (6)
N20.033 (2)0.027 (2)0.031 (2)−0.0004 (19)0.0008 (19)−0.0012 (19)
C70.027 (3)0.032 (3)0.035 (3)0.000 (2)−0.001 (2)−0.001 (2)
C20.032 (3)0.028 (3)0.031 (3)0.006 (2)0.002 (2)0.005 (2)
N10.034 (2)0.030 (2)0.038 (3)−0.001 (2)0.006 (2)−0.003 (2)
C10.028 (3)0.027 (3)0.036 (3)0.004 (2)0.001 (2)0.000 (2)
C80.036 (3)0.041 (3)0.031 (3)−0.004 (3)0.003 (2)−0.001 (3)
C60.043 (3)0.026 (3)0.047 (4)−0.004 (2)0.005 (3)−0.001 (3)
C90.049 (4)0.047 (4)0.038 (3)−0.004 (3)0.007 (3)0.004 (3)
C120.042 (3)0.034 (3)0.043 (3)0.002 (3)0.003 (3)−0.011 (3)
C40.034 (3)0.037 (3)0.032 (3)0.002 (2)0.003 (2)0.007 (2)
C30.039 (3)0.033 (3)0.038 (3)0.000 (2)0.003 (3)0.001 (3)
C110.054 (4)0.055 (4)0.035 (3)−0.003 (3)0.003 (3)−0.014 (3)
C100.049 (4)0.066 (5)0.032 (3)−0.002 (3)0.008 (3)0.002 (3)
Geometric parameters (Å, °) top
C5—C41.374 (8)C7—C81.397 (8)
C5—C61.375 (8)C2—C31.380 (8)
C5—H50.9300C2—C11.415 (7)
C13—S11.810 (6)N1—C11.406 (7)
C13—H13A0.9600C1—C61.395 (8)
C13—H13B0.9600C8—C91.386 (8)
C13—H13C0.9600C6—H60.9300
Cl1—Pd12.2904 (15)C9—C101.374 (9)
Cl2—C41.736 (6)C9—H90.9300
Pd1—N21.975 (4)C12—C111.378 (9)
Pd1—C21.981 (5)C12—H120.9300
Pd1—S12.3735 (15)C4—C31.394 (8)
S1—C81.783 (6)C3—H30.9300
N2—N11.274 (6)C11—C101.392 (10)
N2—C71.424 (7)C11—H110.9300
C7—C121.393 (8)C10—H100.9300
C4—C5—C6119.3 (5)C6—C1—N1119.1 (5)
C4—C5—H5120.3C6—C1—C2121.7 (5)
C6—C5—H5120.3N1—C1—C2119.2 (5)
S1—C13—H13A109.5C9—C8—C7119.3 (5)
S1—C13—H13B109.5C9—C8—S1120.7 (5)
H13A—C13—H13B109.5C7—C8—S1119.9 (4)
S1—C13—H13C109.5C5—C6—C1119.0 (5)
H13A—C13—H13C109.5C5—C6—H6120.5
H13B—C13—H13C109.5C1—C6—H6120.5
N2—Pd1—C280.1 (2)C10—C9—C8120.0 (6)
N2—Pd1—Cl1176.01 (14)C10—C9—H9120.0
C2—Pd1—Cl195.98 (16)C8—C9—H9120.0
N2—Pd1—S184.81 (13)C11—C12—C7119.3 (6)
C2—Pd1—S1163.81 (16)C11—C12—H12120.3
Cl1—Pd1—S199.18 (6)C7—C12—H12120.3
C8—S1—C13102.6 (3)C5—C4—C3122.7 (5)
C8—S1—Pd196.11 (19)C5—C4—Cl2118.8 (4)
C13—S1—Pd1114.6 (2)C3—C4—Cl2118.4 (4)
N1—N2—C7118.2 (4)C2—C3—C4119.0 (5)
N1—N2—Pd1120.4 (4)C2—C3—H3120.5
C7—N2—Pd1121.3 (3)C4—C3—H3120.5
C12—C7—C8120.6 (5)C12—C11—C10120.0 (6)
C12—C7—N2122.5 (5)C12—C11—H11120.0
C8—C7—N2116.9 (5)C10—C11—H11120.0
C3—C2—C1118.2 (5)C9—C10—C11120.8 (6)
C3—C2—Pd1131.9 (4)C9—C10—H10119.6
C1—C2—Pd1109.7 (4)C11—C10—H10119.6
N2—N1—C1110.6 (4)
N2—Pd1—S1—C8−7.4 (2)C3—C2—C1—N1177.1 (5)
C2—Pd1—S1—C8−28.3 (6)Pd1—C2—C1—N10.7 (6)
Cl1—Pd1—S1—C8172.5 (2)C12—C7—C8—C9−0.3 (8)
N2—Pd1—S1—C13−114.3 (3)N2—C7—C8—C9178.6 (5)
C2—Pd1—S1—C13−135.2 (6)C12—C7—C8—S1176.0 (4)
Cl1—Pd1—S1—C1365.6 (2)N2—C7—C8—S1−5.1 (7)
C2—Pd1—N2—N10.4 (4)C13—S1—C8—C9−58.1 (6)
S1—Pd1—N2—N1−173.8 (4)Pd1—S1—C8—C9−175.0 (5)
C2—Pd1—N2—C7−178.6 (4)C13—S1—C8—C7125.7 (5)
S1—Pd1—N2—C77.1 (4)Pd1—S1—C8—C78.8 (5)
N1—N2—C7—C12−3.5 (7)C4—C5—C6—C1−0.2 (9)
Pd1—N2—C7—C12175.6 (4)N1—C1—C6—C5−177.3 (5)
N1—N2—C7—C8177.6 (5)C2—C1—C6—C50.6 (9)
Pd1—N2—C7—C8−3.3 (6)C7—C8—C9—C10−0.8 (9)
N2—Pd1—C2—C3−176.3 (6)S1—C8—C9—C10−177.0 (5)
Cl1—Pd1—C2—C34.2 (5)C8—C7—C12—C110.9 (9)
S1—Pd1—C2—C3−155.2 (4)N2—C7—C12—C11−178.0 (5)
N2—Pd1—C2—C1−0.6 (4)C6—C5—C4—C30.0 (9)
Cl1—Pd1—C2—C1180.0 (3)C6—C5—C4—Cl2179.0 (5)
S1—Pd1—C2—C120.6 (8)C1—C2—C3—C40.6 (8)
C7—N2—N1—C1178.9 (4)Pd1—C2—C3—C4176.1 (4)
Pd1—N2—N1—C1−0.2 (6)C5—C4—C3—C2−0.2 (9)
N2—N1—C1—C6177.6 (5)Cl2—C4—C3—C2−179.2 (4)
N2—N1—C1—C2−0.4 (7)C7—C12—C11—C10−0.4 (9)
C3—C2—C1—C6−0.8 (8)C8—C9—C10—C111.3 (10)
Pd1—C2—C1—C6−177.3 (4)C12—C11—C10—C9−0.7 (10)
Table 1
Selected geometric parameters (Å, °) top
Cl1—Pd12.2904 (15)Pd1—C21.981 (5)
Pd1—N21.975 (4)Pd1—S12.3735 (15)
N2—Pd1—C280.1 (2)N2—Pd1—S184.81 (13)
C2—Pd1—Cl195.98 (16)Cl1—Pd1—S199.18 (6)
Acknowledgements top

We thank the Department of Science and Technology for funding and CSIR for the fellowshipsto VB and PD. The single-crystal X-ray diffractometer facility provided by IITD is gratefully acknowledged.

references
References top

Bagchi, V. & Bandyopadhyay, D. (2007). Acta Cryst. E63, m1614–m1615.

Bagchi, V., Das, P. & Bandyopadhyay, D. (2007). Acta Cryst. E63, m1704–?.

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Chattopadhyay, S., Sinha, C., Basu, P. & Chakravorty, A. (1991). Organometallics, 10, 1135–1139.

Kubo, K., Matsumoto, T., Mori, A., Takahashi, H. & Takechi, H. (2005). Acta Cryst. E61, o3056–o3058.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.