Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021526/bq2012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021526/bq2012Isup2.hkl |
CCDC reference: 650590
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.009 Å
- R factor = 0.058
- wR factor = 0.125
- Data-to-parameter ratio = 14.2
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for S1 - C17 .. 9.83 su
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.81 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.07 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - O2 .. 6.12 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N3
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Pd1 (2) 1.97
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
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).
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.
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.
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 π—π interaction (Kubo et al., 2005) arranges the molecules in anti parallel fashion (Fig. 3). The Cg3—Cg3i [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).
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).
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.
[Pd(C14H13N2O2S)Cl(C3H7NO)] | F(000) = 980 |
Mr = 488.30 | Dx = 1.624 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3396 reflections |
a = 10.199 (3) Å | θ = 2.1–25.0° |
b = 10.811 (3) Å | µ = 1.19 mm−1 |
c = 18.579 (5) Å | T = 298 K |
β = 103.427 (4)° | Rod, pink |
V = 1992.5 (9) Å3 | 0.36 × 0.28 × 0.21 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3396 independent reflections |
Radiation source: fine-focus sealed tube | 3235 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
φ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.676, Tmax = 0.778 | k = −12→12 |
17353 measured reflections | l = −22→22 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-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 parameters | Δρmax = 0.65 e Å−3 |
0 restraints | Δρmin = −0.95 e Å−3 |
[Pd(C14H13N2O2S)Cl(C3H7NO)] | V = 1992.5 (9) Å3 |
Mr = 488.30 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.199 (3) Å | µ = 1.19 mm−1 |
b = 10.811 (3) Å | T = 298 K |
c = 18.579 (5) Å | 0.36 × 0.28 × 0.21 mm |
β = 103.427 (4)° |
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 = 0.778 | Rint = 0.040 |
17353 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.65 e Å−3 |
3396 reflections | Δρmin = −0.95 e Å−3 |
239 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.73827 (17) | −0.00332 (16) | 0.12741 (9) | 0.0585 (4) | |
C7 | 0.4027 (5) | 0.3422 (4) | −0.0256 (3) | 0.0337 (11) | |
N3 | 0.5275 (5) | 0.2477 (5) | 0.2563 (3) | 0.0501 (12) | |
C15 | 0.4787 (8) | 0.3729 (7) | 0.2414 (4) | 0.072 (2) | |
H15A | 0.5216 | 0.4102 | 0.2059 | 0.107* | |
H15B | 0.4992 | 0.4200 | 0.2864 | 0.107* | |
H15C | 0.3829 | 0.3716 | 0.2218 | 0.107* | |
C16 | 0.5317 (11) | 0.1970 (10) | 0.3296 (5) | 0.094 (3) | |
H16A | 0.4437 | 0.2025 | 0.3397 | 0.141* | |
H16B | 0.5948 | 0.2433 | 0.3661 | 0.141* | |
H16C | 0.5593 | 0.1120 | 0.3312 | 0.141* | |
O1 | 0.5559 (4) | 0.2239 (4) | 0.1413 (2) | 0.0505 (10) | |
Pd1 | 0.60269 (4) | 0.13137 (4) | 0.04867 (2) | 0.03753 (17) | |
S1 | 0.57175 (17) | 0.21103 (17) | −0.24762 (9) | 0.0535 (4) | |
C12 | 0.3833 (6) | 0.4436 (5) | −0.0730 (3) | 0.0387 (12) | |
H12 | 0.4294 | 0.4486 | −0.1106 | 0.046* | |
N2 | 0.4923 (4) | 0.2455 (4) | −0.0316 (2) | 0.0352 (10) | |
C2 | 0.6572 (5) | 0.0695 (5) | −0.0387 (3) | 0.0389 (12) | |
C8 | 0.3343 (6) | 0.3391 (6) | 0.0315 (3) | 0.0445 (14) | |
H8 | 0.3485 | 0.2739 | 0.0650 | 0.053* | |
N1 | 0.5120 (5) | 0.2341 (4) | −0.0962 (2) | 0.0397 (10) | |
C1 | 0.6010 (5) | 0.1385 (5) | −0.1014 (3) | 0.0376 (12) | |
C6 | 0.6283 (6) | 0.1130 (5) | −0.1701 (3) | 0.0433 (13) | |
C11 | 0.2968 (6) | 0.5358 (5) | −0.0644 (3) | 0.0438 (13) | |
H11 | 0.2844 | 0.6027 | −0.0967 | 0.053* | |
C10 | 0.2264 (6) | 0.5323 (5) | −0.0081 (3) | 0.0439 (13) | |
C5 | 0.7106 (6) | 0.0153 (6) | −0.1767 (4) | 0.0496 (15) | |
H5 | 0.7264 | −0.0053 | −0.2225 | 0.060* | |
O3 | 0.6033 (7) | 0.1501 (6) | −0.3099 (3) | 0.0905 (19) | |
C14 | 0.5605 (6) | 0.1832 (6) | 0.2041 (3) | 0.0489 (14) | |
H14 | 0.5892 | 0.1021 | 0.2145 | 0.059* | |
C4 | 0.7698 (7) | −0.0520 (6) | −0.1146 (4) | 0.0554 (16) | |
H4 | 0.8275 | −0.1168 | −0.1188 | 0.066* | |
C9 | 0.2460 (6) | 0.4323 (6) | 0.0382 (3) | 0.0473 (14) | |
H9 | 0.1984 | 0.4271 | 0.0751 | 0.057* | |
C3 | 0.7452 (6) | −0.0253 (6) | −0.0461 (4) | 0.0531 (15) | |
H3 | 0.7877 | −0.0710 | −0.0048 | 0.064* | |
C13 | 0.1332 (7) | 0.6366 (6) | 0.0003 (5) | 0.0669 (19) | |
H13A | 0.0802 | 0.6128 | 0.0345 | 0.100* | |
H13B | 0.0745 | 0.6548 | −0.0469 | 0.100* | |
H13C | 0.1853 | 0.7087 | 0.0186 | 0.100* | |
C17 | 0.6273 (6) | 0.3294 (5) | −0.2288 (3) | 0.0406 (13) | |
H17A | 0.7239 | 0.3239 | −0.2166 | 0.061* | |
H17B | 0.5973 | 0.3605 | −0.1870 | 0.061* | |
H17C | 0.5986 | 0.3844 | −0.2700 | 0.061* | |
O2 | 0.3937 (7) | 0.2197 (8) | −0.2636 (4) | 0.113 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0639 (10) | 0.0573 (9) | 0.0491 (9) | 0.0143 (8) | 0.0025 (7) | 0.0075 (7) |
C7 | 0.040 (3) | 0.026 (2) | 0.036 (3) | 0.000 (2) | 0.012 (2) | 0.006 (2) |
N3 | 0.051 (3) | 0.066 (3) | 0.036 (3) | −0.003 (3) | 0.015 (2) | −0.003 (2) |
C15 | 0.077 (5) | 0.080 (5) | 0.057 (4) | 0.015 (4) | 0.014 (4) | −0.015 (4) |
C16 | 0.120 (8) | 0.113 (7) | 0.057 (5) | 0.010 (6) | 0.036 (5) | 0.017 (5) |
O1 | 0.061 (3) | 0.055 (3) | 0.038 (2) | 0.008 (2) | 0.0163 (19) | 0.0042 (19) |
Pd1 | 0.0418 (3) | 0.0362 (3) | 0.0351 (3) | 0.00051 (18) | 0.00993 (17) | 0.00318 (18) |
S1 | 0.0621 (10) | 0.0628 (10) | 0.0408 (8) | 0.0054 (8) | 0.0222 (7) | 0.0065 (7) |
C12 | 0.052 (3) | 0.036 (3) | 0.030 (3) | −0.001 (2) | 0.014 (2) | 0.013 (2) |
N2 | 0.041 (2) | 0.033 (2) | 0.034 (2) | −0.0030 (19) | 0.0128 (19) | 0.0004 (18) |
C2 | 0.039 (3) | 0.040 (3) | 0.039 (3) | −0.004 (2) | 0.012 (2) | −0.005 (2) |
C8 | 0.047 (3) | 0.045 (3) | 0.044 (3) | 0.003 (3) | 0.014 (3) | 0.008 (3) |
N1 | 0.043 (3) | 0.040 (3) | 0.037 (3) | 0.002 (2) | 0.011 (2) | 0.002 (2) |
C1 | 0.041 (3) | 0.036 (3) | 0.038 (3) | −0.008 (2) | 0.014 (2) | −0.002 (2) |
C6 | 0.047 (3) | 0.036 (3) | 0.050 (3) | −0.006 (2) | 0.018 (3) | 0.001 (3) |
C11 | 0.051 (3) | 0.032 (3) | 0.045 (3) | 0.002 (2) | 0.004 (3) | 0.008 (2) |
C10 | 0.037 (3) | 0.044 (3) | 0.050 (3) | −0.002 (2) | 0.010 (2) | −0.008 (3) |
C5 | 0.052 (3) | 0.051 (4) | 0.052 (4) | 0.000 (3) | 0.024 (3) | −0.007 (3) |
O3 | 0.124 (5) | 0.113 (5) | 0.044 (3) | 0.044 (4) | 0.040 (3) | 0.011 (3) |
C14 | 0.052 (4) | 0.046 (3) | 0.050 (4) | 0.003 (3) | 0.014 (3) | 0.006 (3) |
C4 | 0.060 (4) | 0.043 (3) | 0.070 (4) | 0.014 (3) | 0.027 (3) | −0.001 (3) |
C9 | 0.042 (3) | 0.057 (4) | 0.047 (3) | 0.002 (3) | 0.018 (3) | 0.005 (3) |
C3 | 0.054 (4) | 0.047 (4) | 0.059 (4) | 0.007 (3) | 0.016 (3) | 0.006 (3) |
C13 | 0.060 (4) | 0.051 (4) | 0.092 (6) | 0.007 (3) | 0.021 (4) | −0.005 (4) |
C17 | 0.045 (3) | 0.035 (3) | 0.044 (3) | −0.008 (2) | 0.015 (2) | 0.020 (2) |
O2 | 0.094 (5) | 0.135 (6) | 0.107 (5) | 0.011 (4) | 0.020 (4) | 0.011 (5) |
Cl1—Pd1 | 2.2875 (16) | C2—C1 | 1.389 (8) |
C7—C12 | 1.391 (7) | C2—C3 | 1.391 (8) |
C7—C8 | 1.400 (8) | C8—C9 | 1.376 (8) |
C7—N2 | 1.409 (7) | C8—H8 | 0.9300 |
N3—C14 | 1.302 (8) | N1—C1 | 1.394 (7) |
N3—C15 | 1.446 (9) | C1—C6 | 1.396 (8) |
N3—C16 | 1.459 (9) | C6—C5 | 1.373 (8) |
C15—H15A | 0.9600 | C11—C10 | 1.399 (8) |
C15—H15B | 0.9600 | C11—H11 | 0.9300 |
C15—H15C | 0.9600 | C10—C9 | 1.367 (8) |
C16—H16A | 0.9600 | C10—C13 | 1.507 (8) |
C16—H16B | 0.9600 | C5—C4 | 1.379 (9) |
C16—H16C | 0.9600 | C5—H5 | 0.9300 |
O1—C14 | 1.238 (7) | C14—H14 | 0.9300 |
O1—Pd1 | 2.138 (4) | C4—C3 | 1.383 (9) |
Pd1—C2 | 1.952 (5) | C4—H4 | 0.9300 |
Pd1—N2 | 2.058 (4) | C9—H9 | 0.9300 |
S1—C17 | 1.410 (6) | C3—H3 | 0.9300 |
S1—O3 | 1.432 (5) | C13—H13A | 0.9600 |
S1—C6 | 1.773 (6) | C13—H13B | 0.9600 |
S1—O2 | 1.774 (7) | C13—H13C | 0.9600 |
C12—C11 | 1.365 (8) | C17—H17A | 0.9600 |
C12—H12 | 0.9300 | C17—H17B | 0.9600 |
N2—N1 | 1.270 (6) | C17—H17C | 0.9600 |
C12—C7—C8 | 118.4 (5) | C7—C8—H8 | 119.9 |
C12—C7—N2 | 122.3 (5) | N2—N1—C1 | 112.7 (4) |
C8—C7—N2 | 119.2 (5) | C2—C1—N1 | 119.3 (5) |
C14—N3—C15 | 119.7 (6) | C2—C1—C6 | 122.0 (5) |
C14—N3—C16 | 122.5 (6) | N1—C1—C6 | 118.7 (5) |
C15—N3—C16 | 117.7 (6) | C5—C6—C1 | 119.3 (6) |
N3—C15—H15A | 109.5 | C5—C6—S1 | 118.5 (5) |
N3—C15—H15B | 109.5 | C1—C6—S1 | 122.0 (4) |
H15A—C15—H15B | 109.5 | C12—C11—C10 | 121.7 (5) |
N3—C15—H15C | 109.5 | C12—C11—H11 | 119.1 |
H15A—C15—H15C | 109.5 | C10—C11—H11 | 119.1 |
H15B—C15—H15C | 109.5 | C9—C10—C11 | 117.8 (5) |
N3—C16—H16A | 109.5 | C9—C10—C13 | 122.0 (6) |
N3—C16—H16B | 109.5 | C11—C10—C13 | 120.2 (6) |
H16A—C16—H16B | 109.5 | C6—C5—C4 | 119.3 (6) |
N3—C16—H16C | 109.5 | C6—C5—H5 | 120.4 |
H16A—C16—H16C | 109.5 | C4—C5—H5 | 120.4 |
H16B—C16—H16C | 109.5 | O1—C14—N3 | 123.5 (6) |
C14—O1—Pd1 | 128.7 (4) | O1—C14—H14 | 118.2 |
C2—Pd1—N2 | 79.4 (2) | N3—C14—H14 | 118.2 |
C2—Pd1—O1 | 171.7 (2) | C5—C4—C3 | 121.5 (6) |
N2—Pd1—O1 | 96.65 (16) | C5—C4—H4 | 119.2 |
C2—Pd1—Cl1 | 93.86 (17) | C3—C4—H4 | 119.2 |
N2—Pd1—Cl1 | 173.19 (13) | C10—C9—C8 | 121.7 (6) |
O1—Pd1—Cl1 | 89.87 (12) | C10—C9—H9 | 119.2 |
C17—S1—O3 | 117.7 (4) | C8—C9—H9 | 119.2 |
C17—S1—C6 | 107.7 (3) | C4—C3—C2 | 120.2 (6) |
O3—S1—C6 | 106.9 (3) | C4—C3—H3 | 119.9 |
C17—S1—O2 | 109.3 (4) | C2—C3—H3 | 119.9 |
O3—S1—O2 | 107.6 (4) | C10—C13—H13A | 109.5 |
C6—S1—O2 | 107.1 (3) | C10—C13—H13B | 109.5 |
C11—C12—C7 | 120.1 (5) | H13A—C13—H13B | 109.5 |
C11—C12—H12 | 119.9 | C10—C13—H13C | 109.5 |
C7—C12—H12 | 119.9 | H13A—C13—H13C | 109.5 |
N1—N2—C7 | 113.2 (4) | H13B—C13—H13C | 109.5 |
N1—N2—Pd1 | 116.5 (3) | S1—C17—H17A | 109.5 |
C7—N2—Pd1 | 130.1 (3) | S1—C17—H17B | 109.5 |
C1—C2—C3 | 117.6 (5) | H17A—C17—H17B | 109.5 |
C1—C2—Pd1 | 111.8 (4) | S1—C17—H17C | 109.5 |
C3—C2—Pd1 | 130.5 (5) | H17A—C17—H17C | 109.5 |
C9—C8—C7 | 120.2 (5) | H17B—C17—H17C | 109.5 |
C9—C8—H8 | 119.9 | ||
C14—O1—Pd1—N2 | 158.0 (5) | C2—C1—C6—C5 | 1.5 (8) |
C14—O1—Pd1—Cl1 | −24.0 (5) | N1—C1—C6—C5 | −176.9 (5) |
C8—C7—C12—C11 | −1.5 (8) | C2—C1—C6—S1 | −172.9 (4) |
N2—C7—C12—C11 | −179.1 (5) | N1—C1—C6—S1 | 8.7 (7) |
C12—C7—N2—N1 | −25.2 (7) | C17—S1—C6—C5 | −115.2 (5) |
C8—C7—N2—N1 | 157.2 (5) | O3—S1—C6—C5 | 12.2 (6) |
C12—C7—N2—Pd1 | 150.1 (4) | O2—S1—C6—C5 | 127.3 (5) |
C8—C7—N2—Pd1 | −27.5 (7) | C17—S1—C6—C1 | 59.3 (6) |
C2—Pd1—N2—N1 | −4.4 (4) | O3—S1—C6—C1 | −173.3 (5) |
O1—Pd1—N2—N1 | 168.2 (4) | O2—S1—C6—C1 | −58.2 (6) |
C2—Pd1—N2—C7 | −179.6 (5) | C7—C12—C11—C10 | 0.5 (9) |
O1—Pd1—N2—C7 | −7.0 (4) | C12—C11—C10—C9 | −0.5 (9) |
N2—Pd1—C2—C1 | 3.7 (4) | C12—C11—C10—C13 | 179.2 (6) |
Cl1—Pd1—C2—C1 | −175.1 (4) | C1—C6—C5—C4 | −3.0 (9) |
N2—Pd1—C2—C3 | −179.7 (6) | S1—C6—C5—C4 | 171.5 (5) |
Cl1—Pd1—C2—C3 | 1.4 (6) | Pd1—O1—C14—N3 | −178.8 (4) |
C12—C7—C8—C9 | 2.6 (9) | C15—N3—C14—O1 | 1.8 (10) |
N2—C7—C8—C9 | −179.8 (5) | C16—N3—C14—O1 | 179.0 (7) |
C7—N2—N1—C1 | 179.8 (4) | C6—C5—C4—C3 | 1.7 (10) |
Pd1—N2—N1—C1 | 3.8 (6) | C11—C10—C9—C8 | 1.6 (9) |
C3—C2—C1—N1 | 179.8 (5) | C13—C10—C9—C8 | −178.1 (6) |
Pd1—C2—C1—N1 | −3.2 (6) | C7—C8—C9—C10 | −2.7 (9) |
C3—C2—C1—C6 | 1.5 (8) | C5—C4—C3—C2 | 1.3 (10) |
Pd1—C2—C1—C6 | 178.5 (4) | C1—C2—C3—C4 | −2.8 (9) |
N2—N1—C1—C2 | −0.5 (7) | Pd1—C2—C3—C4 | −179.2 (5) |
N2—N1—C1—C6 | 177.9 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl1 | 0.93 | 2.72 | 3.250 (7) | 117 |
C5—H5···O3 | 0.93 | 2.47 | 2.862 (9) | 106 |
C8—H8···O1 | 0.93 | 2.32 | 2.947 (7) | 124 |
C14—H14···Cl1 | 0.93 | 2.72 | 3.253 (7) | 118 |
C17—H17B···N1 | 0.96 | 2.48 | 3.140 (8) | 126 |
Experimental details
Crystal data | |
Chemical formula | [Pd(C14H13N2O2S)Cl(C3H7NO)] |
Mr | 488.30 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 10.199 (3), 10.811 (3), 18.579 (5) |
β (°) | 103.427 (4) |
V (Å3) | 1992.5 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.19 |
Crystal size (mm) | 0.36 × 0.28 × 0.21 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.676, 0.778 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17353, 3396, 3235 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.125, 1.19 |
No. of reflections | 3396 |
No. of parameters | 239 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.95 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2000), SAINT, SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Cl1—Pd1 | 2.2875 (16) | S1—O3 | 1.432 (5) |
C7—N2 | 1.409 (7) | S1—C6 | 1.773 (6) |
O1—Pd1 | 2.138 (4) | S1—O2 | 1.774 (7) |
Pd1—C2 | 1.952 (5) | N2—N1 | 1.270 (6) |
Pd1—N2 | 2.058 (4) | N1—C1 | 1.394 (7) |
S1—C17 | 1.410 (6) | ||
C14—O1—Pd1 | 128.7 (4) | C2—Pd1—Cl1 | 93.86 (17) |
C2—Pd1—N2 | 79.4 (2) | O1—Pd1—Cl1 | 89.87 (12) |
N2—Pd1—O1 | 96.65 (16) | C17—S1—C6 | 107.7 (3) |
C14—O1—Pd1—Cl1 | −24.0 (5) | C7—N2—N1—C1 | 179.8 (4) |
C12—C7—N2—N1 | −25.2 (7) | C17—S1—C6—C1 | 59.3 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl1 | 0.93 | 2.72 | 3.250 (7) | 117 |
C5—H5···O3 | 0.93 | 2.47 | 2.862 (9) | 106 |
C8—H8···O1 | 0.93 | 2.32 | 2.947 (7) | 124 |
C14—H14···Cl1 | 0.93 | 2.72 | 3.253 (7) | 118 |
C17—H17B···N1 | 0.96 | 2.48 | 3.140 (8) | 126 |
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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 π—π interaction (Kubo et al., 2005) arranges the molecules in anti parallel fashion (Fig. 3). The Cg3—Cg3i [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).