supplementary materials


Acta Cryst. (2007). E63, m1614-m1615    [ doi:10.1107/S1600536807021526 ]

Chlorido(N,N-dimethylformamide-[kappa]O){2-(4-methylphenyldiazenyl)-3-(methylsulfonyl)phenyl-[kappa]2C,N}palladium(II)

V. Bagchi and D. Bandyopadhyay

Abstract top

In the title compound, [Pd(C14H13N2O2S)Cl(C3H7NO)], the Pd atom is tetracoordinated by a phenyl C, a diazene N, a Cl and a dimethylformamide O atom in an approximate square-planar geometry. There are intramolecular C-H...O, C-H...N and C-H...Cl interactions. The crystal packing is stabilized by weak intermolecular [pi]-[pi] interactions; the Cg-Cg distance is 3.920 (4) Å and the perpendicular distance is 3.302 Å with a slippage of 2.113 Å.

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 (Dupont et al., 2005 & Neogi et al., 2006) and few N,N-dimethyl formamide solvated metal complexes (Suzuki & Ishiguro, 2006) have been reported in literature, report of palladium complexes with solvent molecules as donor is relatively sparse (Yen et al., 2006). Against this background, we report here the crystal structure of (I).

The molecular structure of the title compound, (I), and its packing arrangement are shown in Fig. 1 and Fig. 2, respectively. The palladium atom along with donor set of four atoms lie in an almost plane.

Selected bond lengths, bond angles and torsion angles are listed in Table 1. The N=N bond length is typical of other cyclopalladated azoarenes (Neogi et al., 2006), unlike those of free azoarenes (Şahin et al., 2005a,b). The metal carbon bond length, 1.952 (5) Å, is slightly higher than the reported values of other ortho-palladated azoarenes (Ghedini et al., 1991).

The sulfur atom in methyl-sulfonyl group is nearly in tetrahedral geometry. Three nearly planar fragment in the molecular structure of (I) may be identified: the palladium atom, diazene unit and the ortho-palladated phenyl unit (A), the para-methyl phenyl group (B) and the N,N-dimethyl formamide molecule (C). The dihedral angles between the planes A/B, A/C & B/C are 26.60 (20)°, 20.61 (38)° & 24.78 (37)°, respectively. Actual geometry of the compound can be understood by the four torsion angles listed in Table 1. An weak inter molecular ππ interaction (Kubo et al., 2005) arranges the molecules in anti parallel fashion (Fig. 3). The Cg3Cg3i [Symmetry code: (i) 1 - x, 1 - y, -z. Cg3 is the centroid of C7—C12 ring.] distance is 3.920 (4)Å and the perpendicular distance is 3.302Å with a slippage of 2.113 Å. There are intra molecular C—H···O, C—H···N and C—H···Cl interactions (Table 2, Fig. 1) in compound (I).

Related literature top

For related literature, see: Dupont et al. (2005); Ghedini et al. (1991); Kubo et al. (2005); Neogi et al. (2006); Suzuki & Ishiguro (2006); Yen et al. (2006); Şahin et al. (2005a,b).

Experimental top

2-(Methyl sulfonyl)azo-p-toluene was synthesized by the over oxidation of corresponding thio-ether ligand using hydrogen peroxide. An ethanolic solution (15 ml) of the 2-(methyl sulfonyl)azo-p-toluene (0.21 mmol) was added drop wise to an ethanolic solution (15 ml) of Na2PdCl4 (0.27 mmol) under stirring condition. The orange-red colored solution was evaporated in air, the solid thus left was washed with water followed by washing with 50% aqueous ethanol (5x3 ml). The compound was then chromatographed over silica-gel column (1x50 cm) which was pre-equilibrated in dicholoromethane. The title compound (I) was eluted with methanol-dichloromethane (1:9 v/v) mixture. The solvent was evaporated in vacuum to obtain the pure product (yield: 0.065 g, 74.9%). Suitable crystals of (I) were grown from an N,N-dimethyl formamide solution by slow evaporation.

Refinement top

H atoms were included at calculated positions as riding atoms with C–H set to 0.93Å for (aromatic) and 0.96Å for (CH3) H atoms, with Uiso(H) = 1.2Ueq(C) (1.5Ueq for methyl group). Some low-angle reflections were excluded from the refinement, as they were probably obscured by the beam stop.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXL97 (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. The intra molecular C—H···O, C—H···N and C—H···Cl interactions are shown by dotted lines.
[Figure 2] Fig. 2. The molecular arrangement of (I) in the ac plane.
[Figure 3] Fig. 3. The inter molecular ππ interaction for (I), indicated by the dotted line. [Symmetry code: (i) 1 - x, 1 - y, -z.]. Cg3 is the centroid of C7—C12 ring.
Chlorido(N,N-dimethylformamide-κO){2-(4-methylphenyldiazenyl)-\ 3-(methylsulfonyl)phenyl-κ2C,N}palladium(II) top
Crystal data top
[Pd(C14H13N2O2S)Cl(C3H7NO)]F(000) = 980
Mr = 488.30Dx = 1.624 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3396 reflections
a = 10.199 (3) Åθ = 2.1–25.0°
b = 10.811 (3) ŵ = 1.19 mm1
c = 18.579 (5) ÅT = 298 K
β = 103.427 (4)°Rod, pink
V = 1992.5 (9) Å30.36 × 0.28 × 0.21 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
3396 independent reflections
Radiation source: fine-focus sealed tube3235 reflections with I > 2σ(I)
graphiteRint = 0.040
φ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1212
Tmin = 0.676, Tmax = 0.778k = 1212
17353 measured reflectionsl = 2222
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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125H-atom parameters constrained
S = 1.19 w = 1/[σ2(Fo2) + (0.0456P)2 + 6.1689P]
where P = (Fo2 + 2Fc2)/3
3396 reflections(Δ/σ)max = 0.001
239 parametersΔρmax = 0.65 e Å3
0 restraintsΔρmin = 0.95 e Å3
Crystal data top
[Pd(C14H13N2O2S)Cl(C3H7NO)]V = 1992.5 (9) Å3
Mr = 488.30Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.199 (3) ŵ = 1.19 mm1
b = 10.811 (3) ÅT = 298 K
c = 18.579 (5) Å0.36 × 0.28 × 0.21 mm
β = 103.427 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3396 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3235 reflections with I > 2σ(I)
Tmin = 0.676, Tmax = 0.778Rint = 0.040
17353 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.125Δρmax = 0.65 e Å3
S = 1.19Δρmin = 0.95 e Å3
3396 reflectionsAbsolute structure: ?
239 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
Cl10.73827 (17)0.00332 (16)0.12741 (9)0.0585 (4)
C70.4027 (5)0.3422 (4)0.0256 (3)0.0337 (11)
N30.5275 (5)0.2477 (5)0.2563 (3)0.0501 (12)
C150.4787 (8)0.3729 (7)0.2414 (4)0.072 (2)
H15A0.52160.41020.20590.107*
H15B0.49920.42000.28640.107*
H15C0.38290.37160.22180.107*
C160.5317 (11)0.1970 (10)0.3296 (5)0.094 (3)
H16A0.44370.20250.33970.141*
H16B0.59480.24330.36610.141*
H16C0.55930.11200.33120.141*
O10.5559 (4)0.2239 (4)0.1413 (2)0.0505 (10)
Pd10.60269 (4)0.13137 (4)0.04867 (2)0.03753 (17)
S10.57175 (17)0.21103 (17)0.24762 (9)0.0535 (4)
C120.3833 (6)0.4436 (5)0.0730 (3)0.0387 (12)
H120.42940.44860.11060.046*
N20.4923 (4)0.2455 (4)0.0316 (2)0.0352 (10)
C20.6572 (5)0.0695 (5)0.0387 (3)0.0389 (12)
C80.3343 (6)0.3391 (6)0.0315 (3)0.0445 (14)
H80.34850.27390.06500.053*
N10.5120 (5)0.2341 (4)0.0962 (2)0.0397 (10)
C10.6010 (5)0.1385 (5)0.1014 (3)0.0376 (12)
C60.6283 (6)0.1130 (5)0.1701 (3)0.0433 (13)
C110.2968 (6)0.5358 (5)0.0644 (3)0.0438 (13)
H110.28440.60270.09670.053*
C100.2264 (6)0.5323 (5)0.0081 (3)0.0439 (13)
C50.7106 (6)0.0153 (6)0.1767 (4)0.0496 (15)
H50.72640.00530.22250.060*
O30.6033 (7)0.1501 (6)0.3099 (3)0.0905 (19)
C140.5605 (6)0.1832 (6)0.2041 (3)0.0489 (14)
H140.58920.10210.21450.059*
C40.7698 (7)0.0520 (6)0.1146 (4)0.0554 (16)
H40.82750.11680.11880.066*
C90.2460 (6)0.4323 (6)0.0382 (3)0.0473 (14)
H90.19840.42710.07510.057*
C30.7452 (6)0.0253 (6)0.0461 (4)0.0531 (15)
H30.78770.07100.00480.064*
C130.1332 (7)0.6366 (6)0.0003 (5)0.0669 (19)
H13A0.08020.61280.03450.100*
H13B0.07450.65480.04690.100*
H13C0.18530.70870.01860.100*
C170.6273 (6)0.3294 (5)0.2288 (3)0.0406 (13)
H17A0.72390.32390.21660.061*
H17B0.59730.36050.18700.061*
H17C0.59860.38440.27000.061*
O20.3937 (7)0.2197 (8)0.2636 (4)0.113 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0639 (10)0.0573 (9)0.0491 (9)0.0143 (8)0.0025 (7)0.0075 (7)
C70.040 (3)0.026 (2)0.036 (3)0.000 (2)0.012 (2)0.006 (2)
N30.051 (3)0.066 (3)0.036 (3)0.003 (3)0.015 (2)0.003 (2)
C150.077 (5)0.080 (5)0.057 (4)0.015 (4)0.014 (4)0.015 (4)
C160.120 (8)0.113 (7)0.057 (5)0.010 (6)0.036 (5)0.017 (5)
O10.061 (3)0.055 (3)0.038 (2)0.008 (2)0.0163 (19)0.0042 (19)
Pd10.0418 (3)0.0362 (3)0.0351 (3)0.00051 (18)0.00993 (17)0.00318 (18)
S10.0621 (10)0.0628 (10)0.0408 (8)0.0054 (8)0.0222 (7)0.0065 (7)
C120.052 (3)0.036 (3)0.030 (3)0.001 (2)0.014 (2)0.013 (2)
N20.041 (2)0.033 (2)0.034 (2)0.0030 (19)0.0128 (19)0.0004 (18)
C20.039 (3)0.040 (3)0.039 (3)0.004 (2)0.012 (2)0.005 (2)
C80.047 (3)0.045 (3)0.044 (3)0.003 (3)0.014 (3)0.008 (3)
N10.043 (3)0.040 (3)0.037 (3)0.002 (2)0.011 (2)0.002 (2)
C10.041 (3)0.036 (3)0.038 (3)0.008 (2)0.014 (2)0.002 (2)
C60.047 (3)0.036 (3)0.050 (3)0.006 (2)0.018 (3)0.001 (3)
C110.051 (3)0.032 (3)0.045 (3)0.002 (2)0.004 (3)0.008 (2)
C100.037 (3)0.044 (3)0.050 (3)0.002 (2)0.010 (2)0.008 (3)
C50.052 (3)0.051 (4)0.052 (4)0.000 (3)0.024 (3)0.007 (3)
O30.124 (5)0.113 (5)0.044 (3)0.044 (4)0.040 (3)0.011 (3)
C140.052 (4)0.046 (3)0.050 (4)0.003 (3)0.014 (3)0.006 (3)
C40.060 (4)0.043 (3)0.070 (4)0.014 (3)0.027 (3)0.001 (3)
C90.042 (3)0.057 (4)0.047 (3)0.002 (3)0.018 (3)0.005 (3)
C30.054 (4)0.047 (4)0.059 (4)0.007 (3)0.016 (3)0.006 (3)
C130.060 (4)0.051 (4)0.092 (6)0.007 (3)0.021 (4)0.005 (4)
C170.045 (3)0.035 (3)0.044 (3)0.008 (2)0.015 (2)0.020 (2)
O20.094 (5)0.135 (6)0.107 (5)0.011 (4)0.020 (4)0.011 (5)
Geometric parameters (Å, °) top
Cl1—Pd12.2875 (16)C2—C11.389 (8)
C7—C121.391 (7)C2—C31.391 (8)
C7—C81.400 (8)C8—C91.376 (8)
C7—N21.409 (7)C8—H80.9300
N3—C141.302 (8)N1—C11.394 (7)
N3—C151.446 (9)C1—C61.396 (8)
N3—C161.459 (9)C6—C51.373 (8)
C15—H15A0.9600C11—C101.399 (8)
C15—H15B0.9600C11—H110.9300
C15—H15C0.9600C10—C91.367 (8)
C16—H16A0.9600C10—C131.507 (8)
C16—H16B0.9600C5—C41.379 (9)
C16—H16C0.9600C5—H50.9300
O1—C141.238 (7)C14—H140.9300
O1—Pd12.138 (4)C4—C31.383 (9)
Pd1—C21.952 (5)C4—H40.9300
Pd1—N22.058 (4)C9—H90.9300
S1—C171.410 (6)C3—H30.9300
S1—O31.432 (5)C13—H13A0.9600
S1—C61.773 (6)C13—H13B0.9600
S1—O21.774 (7)C13—H13C0.9600
C12—C111.365 (8)C17—H17A0.9600
C12—H120.9300C17—H17B0.9600
N2—N11.270 (6)C17—H17C0.9600
C12—C7—C8118.4 (5)C7—C8—H8119.9
C12—C7—N2122.3 (5)N2—N1—C1112.7 (4)
C8—C7—N2119.2 (5)C2—C1—N1119.3 (5)
C14—N3—C15119.7 (6)C2—C1—C6122.0 (5)
C14—N3—C16122.5 (6)N1—C1—C6118.7 (5)
C15—N3—C16117.7 (6)C5—C6—C1119.3 (6)
N3—C15—H15A109.5C5—C6—S1118.5 (5)
N3—C15—H15B109.5C1—C6—S1122.0 (4)
H15A—C15—H15B109.5C12—C11—C10121.7 (5)
N3—C15—H15C109.5C12—C11—H11119.1
H15A—C15—H15C109.5C10—C11—H11119.1
H15B—C15—H15C109.5C9—C10—C11117.8 (5)
N3—C16—H16A109.5C9—C10—C13122.0 (6)
N3—C16—H16B109.5C11—C10—C13120.2 (6)
H16A—C16—H16B109.5C6—C5—C4119.3 (6)
N3—C16—H16C109.5C6—C5—H5120.4
H16A—C16—H16C109.5C4—C5—H5120.4
H16B—C16—H16C109.5O1—C14—N3123.5 (6)
C14—O1—Pd1128.7 (4)O1—C14—H14118.2
C2—Pd1—N279.4 (2)N3—C14—H14118.2
C2—Pd1—O1171.7 (2)C5—C4—C3121.5 (6)
N2—Pd1—O196.65 (16)C5—C4—H4119.2
C2—Pd1—Cl193.86 (17)C3—C4—H4119.2
N2—Pd1—Cl1173.19 (13)C10—C9—C8121.7 (6)
O1—Pd1—Cl189.87 (12)C10—C9—H9119.2
C17—S1—O3117.7 (4)C8—C9—H9119.2
C17—S1—C6107.7 (3)C4—C3—C2120.2 (6)
O3—S1—C6106.9 (3)C4—C3—H3119.9
C17—S1—O2109.3 (4)C2—C3—H3119.9
O3—S1—O2107.6 (4)C10—C13—H13A109.5
C6—S1—O2107.1 (3)C10—C13—H13B109.5
C11—C12—C7120.1 (5)H13A—C13—H13B109.5
C11—C12—H12119.9C10—C13—H13C109.5
C7—C12—H12119.9H13A—C13—H13C109.5
N1—N2—C7113.2 (4)H13B—C13—H13C109.5
N1—N2—Pd1116.5 (3)S1—C17—H17A109.5
C7—N2—Pd1130.1 (3)S1—C17—H17B109.5
C1—C2—C3117.6 (5)H17A—C17—H17B109.5
C1—C2—Pd1111.8 (4)S1—C17—H17C109.5
C3—C2—Pd1130.5 (5)H17A—C17—H17C109.5
C9—C8—C7120.2 (5)H17B—C17—H17C109.5
C9—C8—H8119.9
C14—O1—Pd1—N2158.0 (5)C2—C1—C6—C51.5 (8)
C14—O1—Pd1—Cl124.0 (5)N1—C1—C6—C5176.9 (5)
C8—C7—C12—C111.5 (8)C2—C1—C6—S1172.9 (4)
N2—C7—C12—C11179.1 (5)N1—C1—C6—S18.7 (7)
C12—C7—N2—N125.2 (7)C17—S1—C6—C5115.2 (5)
C8—C7—N2—N1157.2 (5)O3—S1—C6—C512.2 (6)
C12—C7—N2—Pd1150.1 (4)O2—S1—C6—C5127.3 (5)
C8—C7—N2—Pd127.5 (7)C17—S1—C6—C159.3 (6)
C2—Pd1—N2—N14.4 (4)O3—S1—C6—C1173.3 (5)
O1—Pd1—N2—N1168.2 (4)O2—S1—C6—C158.2 (6)
C2—Pd1—N2—C7179.6 (5)C7—C12—C11—C100.5 (9)
O1—Pd1—N2—C77.0 (4)C12—C11—C10—C90.5 (9)
N2—Pd1—C2—C13.7 (4)C12—C11—C10—C13179.2 (6)
Cl1—Pd1—C2—C1175.1 (4)C1—C6—C5—C43.0 (9)
N2—Pd1—C2—C3179.7 (6)S1—C6—C5—C4171.5 (5)
Cl1—Pd1—C2—C31.4 (6)Pd1—O1—C14—N3178.8 (4)
C12—C7—C8—C92.6 (9)C15—N3—C14—O11.8 (10)
N2—C7—C8—C9179.8 (5)C16—N3—C14—O1179.0 (7)
C7—N2—N1—C1179.8 (4)C6—C5—C4—C31.7 (10)
Pd1—N2—N1—C13.8 (6)C11—C10—C9—C81.6 (9)
C3—C2—C1—N1179.8 (5)C13—C10—C9—C8178.1 (6)
Pd1—C2—C1—N13.2 (6)C7—C8—C9—C102.7 (9)
C3—C2—C1—C61.5 (8)C5—C4—C3—C21.3 (10)
Pd1—C2—C1—C6178.5 (4)C1—C2—C3—C42.8 (9)
N2—N1—C1—C20.5 (7)Pd1—C2—C3—C4179.2 (5)
N2—N1—C1—C6177.9 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···Cl10.932.723.250 (7)117
C5—H5···O30.932.472.862 (9)106
C8—H8···O10.932.322.947 (7)124
C14—H14···Cl10.932.723.253 (7)118
C17—H17B···N10.962.483.140 (8)126
Table 1
Selected geometric parameters (Å, °)
top
Cl1—Pd12.2875 (16)S1—O31.432 (5)
C7—N21.409 (7)S1—C61.773 (6)
O1—Pd12.138 (4)S1—O21.774 (7)
Pd1—C21.952 (5)N2—N11.270 (6)
Pd1—N22.058 (4)N1—C11.394 (7)
S1—C171.410 (6)
C14—O1—Pd1128.7 (4)C2—Pd1—Cl193.86 (17)
C2—Pd1—N279.4 (2)O1—Pd1—Cl189.87 (12)
N2—Pd1—O196.65 (16)C17—S1—C6107.7 (3)
C14—O1—Pd1—Cl124.0 (5)C7—N2—N1—C1179.8 (4)
C12—C7—N2—N125.2 (7)C17—S1—C6—C159.3 (6)
Table 2
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
C3—H3···Cl10.932.723.250 (7)117
C5—H5···O30.932.472.862 (9)106
C8—H8···O10.932.322.947 (7)124
C14—H14···Cl10.932.723.253 (7)118
C17—H17B···N10.962.483.140 (8)126
Acknowledgements top

We thank the Department of Science and Technology (Project No. SR/S1/IC-11/2002) for funding and the CSIR for a fellowship to VB.

references
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