Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110044008/sq3259sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110044008/sq3259Isup2.hkl |
CCDC reference: 809997
The title compound was prepared by adding a solution of palladium chloride (0.04 g, 0.25 mmol) in methanol (60 ml) to the hot solution of benzyl 3-(4-n-octyloxybenzylidene)dithiocarbazate (0.21 g, 0.5 mmol) in ethanol (20 ml). The resulting solution was kept under reflux for 30 min, after which time a brick-red precipitate appeared. The compound was filtered off, washed with hot ethanol, and recrystallized from a mixture of chloroform and ethanol (20:10 v/v) (yield 0.1 g, 40%; m.p. 417 K). In an attempt to grow single crystals, the product was dissolved in a solution of chloroform and toluene (20:5 v/v) and allowed to stand at room temperature. Red microcrystals unsuitable for X-ray study were obtained after 7 d. The compound was then dissolved in a mixture of chloroform and acetone (30:30 v/v) and allowed to stand at room temperature. Very fine flat orange–red crystals of (I) were obtained after 12 d that proved usable for analysis.
The octyloxy chain proved to be highly disordered. The part of the chain immediately attached to the arene ring (atoms O1 and C16–C18) was split over two positions, with refined occupancies of 0.568 (8):0.432 (8) and restraints on displacement parameters and bond distances (Sheldrick, 2008). The disordered non-H atoms at lower occupancy were treated isotropically. H atoms were included at calculated positions, with C—H = 0.93 (aromatic) or 0.97Å (alkyl), and with Uiso(H) = 1.2Ueq(C).
Data collection: XPRESS (MacScience, 2002); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Pd(C23H29N2OS2)2] | F(000) = 976 |
Mr = 933.60 | Dx = 1.298 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.586 (4) Å | Cell parameters from 258 reflections |
b = 14.082 (3) Å | θ = 2.4–23.1° |
c = 10.507 (2) Å | µ = 0.60 mm−1 |
β = 103.22 (3)° | T = 293 K |
V = 2389.0 (8) Å3 | Plate, orange |
Z = 2 | 0.40 × 0.35 × 0.12 mm |
Enraf–Nonius DIP1030 image-plate diffractometer | 4042 independent reflections |
Radiation source: fine-focus sealed tube | 1977 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
laser scanner | θmax = 25.0°, θmin = 2.5° |
Absorption correction: part of the refinement model (ΔF) (Parkin et al., 1995) | h = −19→19 |
Tmin = 0.742, Tmax = 0.932 | k = −16→16 |
27894 measured reflections | l = −12→12 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 0.77 | w = 1/[σ2(Fo2) + (0.0296P)2] where P = (Fo2 + 2Fc2)/3 |
4042 reflections | (Δ/σ)max < 0.001 |
277 parameters | Δρmax = 0.22 e Å−3 |
60 restraints | Δρmin = −0.27 e Å−3 |
[Pd(C23H29N2OS2)2] | V = 2389.0 (8) Å3 |
Mr = 933.60 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.586 (4) Å | µ = 0.60 mm−1 |
b = 14.082 (3) Å | T = 293 K |
c = 10.507 (2) Å | 0.40 × 0.35 × 0.12 mm |
β = 103.22 (3)° |
Enraf–Nonius DIP1030 image-plate diffractometer | 4042 independent reflections |
Absorption correction: part of the refinement model (ΔF) (Parkin et al., 1995) | 1977 reflections with I > 2σ(I) |
Tmin = 0.742, Tmax = 0.932 | Rint = 0.060 |
27894 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 60 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 0.77 | Δρmax = 0.22 e Å−3 |
4042 reflections | Δρmin = −0.27 e Å−3 |
277 parameters |
Experimental. Absorption correction:- Parkin S, Moezzi B & Hope H, (1995) J. Appl. Cryst. 28, 53–56 Quadratic fit to sin(theta)/lambda - 18 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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. Some atoms in the alkyl chain (O1/C16/C17/C18) were refined over two positions. C19—C23 show abnormally high displacement parameters due to the disorder, and all these atoms were refined with anisotropic displacement parameters, with a positive definite thermal tensor. The phenyl group shows a libration motion, while the ipso carbon atom C3 appears more stable. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pd1 | 0.0000 | 0.5000 | 0.0000 | 0.07133 (17) | |
S1 | 0.06976 (8) | 0.36189 (7) | −0.01275 (9) | 0.0895 (4) | |
S2 | 0.18528 (8) | 0.26015 (8) | 0.19090 (10) | 0.0958 (4) | |
N1 | 0.05344 (19) | 0.4883 (2) | 0.1939 (3) | 0.0693 (8) | |
N2 | 0.1090 (2) | 0.4152 (2) | 0.2412 (3) | 0.0728 (9) | |
C1 | 0.1183 (2) | 0.3565 (3) | 0.1517 (3) | 0.0737 (11) | |
C2 | 0.2379 (3) | 0.2837 (3) | 0.3569 (3) | 0.0928 (13) | |
H2A | 0.2496 | 0.3511 | 0.3678 | 0.111* | |
H2B | 0.2026 | 0.2659 | 0.4150 | 0.111* | |
C3 | 0.3173 (4) | 0.2288 (4) | 0.3920 (4) | 0.1002 (15) | |
C4 | 0.3827 (6) | 0.2573 (5) | 0.3463 (9) | 0.198 (3) | |
H4 | 0.3773 | 0.3107 | 0.2929 | 0.238* | |
C5 | 0.4594 (6) | 0.2086 (7) | 0.3766 (11) | 0.227 (4) | |
H5 | 0.5032 | 0.2242 | 0.3391 | 0.272* | |
C6 | 0.4636 (7) | 0.1397 (9) | 0.4618 (10) | 0.216 (5) | |
H6 | 0.5162 | 0.1162 | 0.4983 | 0.259* | |
C7 | 0.4000 (8) | 0.0991 (7) | 0.5026 (8) | 0.237 (6) | |
H7 | 0.4050 | 0.0431 | 0.5506 | 0.284* | |
C8 | 0.3239 (5) | 0.1512 (5) | 0.4642 (6) | 0.188 (3) | |
H8 | 0.2776 | 0.1294 | 0.4912 | 0.225* | |
C9 | 0.0403 (2) | 0.5473 (3) | 0.2838 (3) | 0.0738 (11) | |
H9 | 0.0010 | 0.5935 | 0.2512 | 0.089* | |
C10 | 0.0740 (3) | 0.5552 (3) | 0.4224 (3) | 0.0746 (11) | |
C11 | 0.1285 (3) | 0.4936 (3) | 0.5022 (3) | 0.0908 (12) | |
H11 | 0.1463 | 0.4393 | 0.4662 | 0.109* | |
C12 | 0.1565 (3) | 0.5114 (3) | 0.6328 (4) | 0.0960 (13) | |
H12 | 0.1930 | 0.4690 | 0.6842 | 0.115* | |
C13 | 0.1319 (3) | 0.5902 (4) | 0.6890 (4) | 0.0931 (14) | |
C14 | 0.0750 (3) | 0.6510 (3) | 0.6135 (4) | 0.1031 (15) | |
H14 | 0.0555 | 0.7035 | 0.6511 | 0.124* | |
C15 | 0.0478 (3) | 0.6330 (3) | 0.4823 (4) | 0.0952 (14) | |
H15 | 0.0103 | 0.6748 | 0.4318 | 0.114* | |
O1 | 0.1739 (5) | 0.5983 (5) | 0.8183 (6) | 0.097 (3) | 0.568 (8) |
C16 | 0.1559 (6) | 0.6823 (6) | 0.8853 (8) | 0.109 (4) | 0.568 (8) |
H16A | 0.1034 | 0.6759 | 0.9103 | 0.130* | 0.568 (8) |
H16B | 0.1539 | 0.7380 | 0.8304 | 0.130* | 0.568 (8) |
C17 | 0.2294 (7) | 0.6897 (9) | 1.0096 (10) | 0.157 (5) | 0.568 (8) |
H17A | 0.2807 | 0.6904 | 0.9802 | 0.189* | 0.568 (8) |
H17B | 0.2250 | 0.7505 | 1.0508 | 0.189* | 0.568 (8) |
C18 | 0.2360 (13) | 0.6168 (13) | 1.1084 (11) | 0.197 (7) | 0.568 (8) |
H18A | 0.2518 | 0.5578 | 1.0730 | 0.236* | 0.568 (8) |
H18B | 0.1817 | 0.6072 | 1.1262 | 0.236* | 0.568 (8) |
C19 | 0.2992 (6) | 0.6372 (7) | 1.2413 (9) | 0.228 (4) | 0.568 (8) |
H19A | 0.3508 | 0.6553 | 1.2194 | 0.274* | |
H19B | 0.2791 | 0.6931 | 1.2781 | 0.274* | |
O1A | 0.1424 (8) | 0.6269 (10) | 0.8161 (14) | 0.118 (5)* | 0.432 (8) |
C16A | 0.2028 (7) | 0.5754 (8) | 0.8983 (12) | 0.104 (5)* | 0.432 (8) |
H16C | 0.2557 | 0.5813 | 0.8744 | 0.125* | 0.432 (8) |
H16D | 0.1880 | 0.5087 | 0.8986 | 0.125* | 0.432 (8) |
C17A | 0.2050 (9) | 0.6246 (11) | 1.0383 (13) | 0.103 (5)* | 0.432 (8) |
H17C | 0.2039 | 0.6934 | 1.0325 | 0.123* | 0.432 (8) |
H17D | 0.1601 | 0.6028 | 1.0759 | 0.123* | 0.432 (8) |
C18A | 0.2883 (14) | 0.588 (2) | 1.113 (2) | 0.283 (19)* | 0.432 (8) |
H18C | 0.2875 | 0.5196 | 1.1240 | 0.340* | 0.432 (8) |
H18D | 0.3320 | 0.6049 | 1.0701 | 0.340* | 0.432 (8) |
C19A | 0.2992 (6) | 0.6372 (7) | 1.2413 (9) | 0.228 (4) | 0.432 (8) |
C20 | 0.3193 (9) | 0.5721 (7) | 1.3412 (13) | 0.277 (5) | |
H20A | 0.3500 | 0.5214 | 1.3112 | 0.332* | |
H20B | 0.2679 | 0.5446 | 1.3530 | 0.332* | |
C21 | 0.3670 (10) | 0.6013 (10) | 1.4704 (17) | 0.368 (11) | |
H21A | 0.3384 | 0.6521 | 1.5043 | 0.442* | |
H21B | 0.4211 | 0.6244 | 1.4642 | 0.442* | |
C22 | 0.3763 (10) | 0.5173 (13) | 1.5595 (19) | 0.394 (11) | |
H22A | 0.3232 | 0.4887 | 1.5600 | 0.472* | |
H22B | 0.4126 | 0.4697 | 1.5359 | 0.472* | |
C23 | 0.4108 (8) | 0.5586 (10) | 1.6761 (13) | 0.376 (10) | |
H23A | 0.4651 | 0.5815 | 1.6747 | 0.564* | |
H23B | 0.4148 | 0.5128 | 1.7449 | 0.564* | |
H23C | 0.3769 | 0.6108 | 1.6910 | 0.564* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0805 (3) | 0.0726 (3) | 0.0607 (2) | −0.0011 (3) | 0.0158 (2) | 0.0009 (2) |
S1 | 0.1121 (10) | 0.0856 (8) | 0.0662 (6) | 0.0168 (7) | 0.0112 (6) | −0.0039 (5) |
S2 | 0.1229 (11) | 0.0881 (8) | 0.0727 (7) | 0.0259 (8) | 0.0146 (6) | −0.0007 (6) |
N1 | 0.073 (2) | 0.070 (2) | 0.0635 (17) | −0.002 (2) | 0.0132 (15) | −0.0026 (17) |
N2 | 0.083 (3) | 0.071 (2) | 0.0651 (19) | 0.008 (2) | 0.0174 (17) | 0.0033 (17) |
C1 | 0.079 (3) | 0.072 (3) | 0.071 (2) | −0.001 (2) | 0.018 (2) | 0.003 (2) |
C2 | 0.097 (4) | 0.099 (3) | 0.081 (3) | 0.016 (3) | 0.015 (2) | 0.004 (2) |
C3 | 0.111 (5) | 0.095 (4) | 0.092 (3) | 0.023 (4) | 0.019 (3) | −0.001 (3) |
C4 | 0.110 (6) | 0.146 (6) | 0.335 (10) | 0.031 (5) | 0.044 (7) | 0.049 (6) |
C5 | 0.136 (8) | 0.200 (9) | 0.347 (12) | −0.003 (7) | 0.059 (8) | 0.010 (8) |
C6 | 0.177 (10) | 0.243 (11) | 0.195 (9) | 0.072 (8) | −0.022 (7) | 0.033 (8) |
C7 | 0.324 (15) | 0.238 (11) | 0.177 (7) | 0.169 (11) | 0.117 (8) | 0.088 (6) |
C8 | 0.246 (9) | 0.193 (7) | 0.151 (5) | 0.136 (6) | 0.103 (5) | 0.078 (5) |
C9 | 0.076 (3) | 0.074 (2) | 0.069 (2) | 0.004 (2) | 0.014 (2) | 0.004 (2) |
C10 | 0.083 (3) | 0.078 (3) | 0.063 (2) | −0.001 (2) | 0.017 (2) | −0.005 (2) |
C11 | 0.105 (3) | 0.101 (3) | 0.065 (2) | 0.011 (3) | 0.016 (2) | −0.005 (2) |
C12 | 0.114 (4) | 0.104 (3) | 0.061 (2) | 0.011 (3) | 0.004 (2) | 0.000 (3) |
C13 | 0.121 (4) | 0.095 (4) | 0.063 (3) | −0.014 (3) | 0.022 (3) | −0.017 (3) |
C14 | 0.143 (5) | 0.086 (3) | 0.079 (3) | 0.010 (3) | 0.022 (3) | −0.017 (3) |
C15 | 0.115 (4) | 0.093 (3) | 0.076 (3) | 0.012 (3) | 0.020 (3) | −0.009 (2) |
O1 | 0.116 (6) | 0.114 (6) | 0.051 (4) | 0.022 (5) | −0.002 (4) | −0.025 (3) |
C16 | 0.145 (9) | 0.098 (7) | 0.075 (5) | 0.009 (6) | 0.009 (5) | −0.025 (5) |
C17 | 0.205 (12) | 0.166 (10) | 0.119 (8) | −0.037 (9) | 0.074 (8) | −0.054 (7) |
C18 | 0.257 (16) | 0.230 (14) | 0.115 (9) | −0.125 (12) | 0.069 (10) | −0.077 (9) |
C19 | 0.222 (8) | 0.264 (9) | 0.170 (7) | −0.022 (7) | −0.013 (6) | −0.025 (7) |
C19A | 0.222 (8) | 0.264 (9) | 0.170 (7) | −0.022 (7) | −0.013 (6) | −0.025 (7) |
C20 | 0.328 (14) | 0.224 (10) | 0.305 (12) | −0.063 (10) | 0.124 (11) | −0.014 (10) |
C21 | 0.291 (15) | 0.301 (16) | 0.393 (19) | −0.080 (12) | −0.167 (14) | 0.053 (13) |
C22 | 0.210 (15) | 0.49 (3) | 0.47 (3) | −0.066 (18) | 0.064 (17) | −0.14 (2) |
C23 | 0.319 (17) | 0.45 (2) | 0.295 (15) | −0.132 (14) | −0.066 (12) | 0.067 (14) |
Pd1—N1i | 2.034 (3) | C14—H14 | 0.9300 |
Pd1—N1 | 2.034 (3) | C15—H15 | 0.9300 |
Pd1—S1i | 2.2825 (11) | O1—C16 | 1.442 (11) |
Pd1—S1 | 2.2825 (11) | C16—C17 | 1.572 (11) |
S1—C1 | 1.732 (4) | C16—H16A | 0.9700 |
S2—C1 | 1.743 (4) | C16—H16B | 0.9700 |
S2—C2 | 1.794 (4) | C17—C18 | 1.447 (14) |
N1—C9 | 1.312 (4) | C17—H17A | 0.9700 |
N1—N2 | 1.396 (4) | C17—H17B | 0.9700 |
N2—C1 | 1.287 (4) | C18—C19 | 1.568 (13) |
C2—C3 | 1.499 (6) | C18—H18A | 0.9700 |
C2—H2A | 0.9700 | C18—H18B | 0.9700 |
C2—H2B | 0.9700 | C19—C20 | 1.376 (9) |
C3—C8 | 1.321 (7) | C19—H19A | 0.9700 |
C3—C4 | 1.343 (8) | C19—H19B | 0.9700 |
C4—C5 | 1.416 (9) | O1A—C16A | 1.372 (14) |
C4—H4 | 0.9300 | C16A—C17A | 1.619 (14) |
C5—C6 | 1.310 (10) | C16A—H16C | 0.9700 |
C5—H5 | 0.9300 | C16A—H16D | 0.9700 |
C6—C7 | 1.353 (11) | C17A—C18A | 1.516 (18) |
C6—H6 | 0.9300 | C17A—H17C | 0.9700 |
C7—C8 | 1.434 (10) | C17A—H17D | 0.9700 |
C7—H7 | 0.9300 | C18A—H18C | 0.9700 |
C8—H8 | 0.9300 | C18A—H18D | 0.9700 |
C9—C10 | 1.440 (5) | C20—C21 | 1.465 (13) |
C9—H9 | 0.9300 | C20—H20A | 0.9700 |
C10—C15 | 1.382 (5) | C20—H20B | 0.9700 |
C10—C11 | 1.387 (5) | C21—C22 | 1.495 (16) |
C11—C12 | 1.368 (5) | C21—H21A | 0.9700 |
C11—H11 | 0.9300 | C21—H21B | 0.9700 |
C12—C13 | 1.363 (5) | C22—C23 | 1.359 (13) |
C12—H12 | 0.9300 | C22—H22A | 0.9700 |
C13—C14 | 1.382 (6) | C22—H22B | 0.9700 |
C13—O1 | 1.383 (8) | C23—H23A | 0.9600 |
C13—O1A | 1.405 (14) | C23—H23B | 0.9600 |
C14—C15 | 1.372 (5) | C23—H23C | 0.9600 |
N1i—Pd1—N1 | 180.0 | C14—C15—H15 | 118.7 |
N1i—Pd1—S1i | 83.08 (10) | C10—C15—H15 | 118.7 |
N1—Pd1—S1i | 96.92 (10) | C13—O1—C16 | 115.7 (7) |
N1i—Pd1—S1 | 96.92 (10) | O1—C16—C17 | 104.6 (7) |
N1—Pd1—S1 | 83.08 (10) | O1—C16—H16A | 110.8 |
S1i—Pd1—S1 | 180.0 | C17—C16—H16A | 110.8 |
C1—S1—Pd1 | 96.01 (13) | O1—C16—H16B | 110.8 |
C1—S2—C2 | 103.20 (19) | C17—C16—H16B | 110.8 |
C9—N1—N2 | 114.5 (3) | H16A—C16—H16B | 108.9 |
C9—N1—Pd1 | 124.3 (3) | C18—C17—C16 | 117.8 (12) |
N2—N1—Pd1 | 121.1 (2) | C18—C17—H17A | 107.9 |
C1—N2—N1 | 113.1 (3) | C16—C17—H17A | 107.9 |
N2—C1—S1 | 126.5 (3) | C18—C17—H17B | 107.9 |
N2—C1—S2 | 120.2 (3) | C16—C17—H17B | 107.9 |
S1—C1—S2 | 113.3 (2) | H17A—C17—H17B | 107.2 |
C3—C2—S2 | 110.4 (3) | C17—C18—C19 | 115.7 (12) |
C3—C2—H2A | 109.6 | C17—C18—H18A | 108.3 |
S2—C2—H2A | 109.6 | C19—C18—H18A | 108.3 |
C3—C2—H2B | 109.6 | C17—C18—H18B | 108.3 |
S2—C2—H2B | 109.6 | C19—C18—H18B | 108.3 |
H2A—C2—H2B | 108.1 | H18A—C18—H18B | 107.4 |
C8—C3—C4 | 119.0 (6) | C20—C19—C18 | 123.6 (11) |
C8—C3—C2 | 121.4 (6) | C20—C19—H19A | 106.4 |
C4—C3—C2 | 119.6 (6) | C18—C19—H19A | 106.4 |
C3—C4—C5 | 122.1 (8) | C20—C19—H19B | 106.4 |
C3—C4—H4 | 118.9 | C18—C19—H19B | 106.4 |
C5—C4—H4 | 118.9 | H19A—C19—H19B | 106.5 |
C6—C5—C4 | 114.7 (10) | C16A—O1A—C13 | 108.5 (11) |
C6—C5—H5 | 122.7 | O1A—C16A—C17A | 101.9 (10) |
C4—C5—H5 | 122.7 | O1A—C16A—H16C | 111.4 |
C5—C6—C7 | 127.2 (12) | C17A—C16A—H16C | 111.4 |
C5—C6—H6 | 116.4 | O1A—C16A—H16D | 111.4 |
C7—C6—H6 | 116.4 | C17A—C16A—H16D | 111.4 |
C6—C7—C8 | 113.2 (9) | H16C—C16A—H16D | 109.2 |
C6—C7—H7 | 123.4 | C18A—C17A—C16A | 99.0 (11) |
C8—C7—H7 | 123.4 | C18A—C17A—H17C | 112.0 |
C3—C8—C7 | 122.5 (7) | C16A—C17A—H17C | 112.0 |
C3—C8—H8 | 118.8 | C18A—C17A—H17D | 112.0 |
C7—C8—H8 | 118.8 | C16A—C17A—H17D | 112.0 |
N1—C9—C10 | 133.4 (4) | H17C—C17A—H17D | 109.7 |
N1—C9—H9 | 113.3 | C17A—C18A—H18C | 111.2 |
C10—C9—H9 | 113.3 | C17A—C18A—H18D | 111.2 |
C15—C10—C11 | 116.7 (3) | H18C—C18A—H18D | 109.1 |
C15—C10—C9 | 115.6 (4) | C19—C20—C21 | 120.3 (11) |
C11—C10—C9 | 127.7 (4) | C19—C20—H20A | 107.2 |
C12—C11—C10 | 121.1 (4) | C21—C20—H20A | 107.2 |
C12—C11—H11 | 119.4 | C19—C20—H20B | 107.2 |
C10—C11—H11 | 119.4 | C21—C20—H20B | 107.2 |
C13—C12—C11 | 121.1 (4) | H20A—C20—H20B | 106.9 |
C13—C12—H12 | 119.4 | C20—C21—C22 | 108.3 (14) |
C11—C12—H12 | 119.4 | C20—C21—H21A | 110.0 |
C12—C13—C14 | 119.3 (4) | C22—C21—H21A | 110.0 |
C12—C13—O1 | 111.1 (5) | C20—C21—H21B | 110.0 |
C14—C13—O1 | 129.6 (5) | C22—C21—H21B | 110.0 |
C12—C13—O1A | 136.6 (6) | H21A—C21—H21B | 108.4 |
C14—C13—O1A | 103.7 (6) | C23—C22—C21 | 100.8 (17) |
O1—C13—O1A | 27.2 (5) | C23—C22—H22A | 111.6 |
C15—C14—C13 | 119.1 (4) | C21—C22—H22A | 111.6 |
C15—C14—H14 | 120.5 | C23—C22—H22B | 111.6 |
C13—C14—H14 | 120.5 | C21—C22—H22B | 111.6 |
C14—C15—C10 | 122.6 (4) | H22A—C22—H22B | 109.4 |
N1i—Pd1—S1—C1 | 177.41 (15) | N1—C9—C10—C15 | 175.4 (4) |
N1—Pd1—S1—C1 | −2.59 (15) | N1—C9—C10—C11 | −5.4 (7) |
S1i—Pd1—S1—C1 | −123 (18) | C15—C10—C11—C12 | −2.0 (6) |
N1i—Pd1—N1—C9 | 175 (100) | C9—C10—C11—C12 | 178.8 (4) |
S1i—Pd1—N1—C9 | 2.9 (3) | C10—C11—C12—C13 | −0.1 (7) |
S1—Pd1—N1—C9 | −177.1 (3) | C11—C12—C13—C14 | 2.7 (7) |
N1i—Pd1—N1—N2 | −5 (100) | C11—C12—C13—O1 | −174.2 (5) |
S1i—Pd1—N1—N2 | −176.4 (2) | C11—C12—C13—O1A | 174.4 (10) |
S1—Pd1—N1—N2 | 3.6 (2) | C12—C13—C14—C15 | −3.1 (7) |
C9—N1—N2—C1 | 177.5 (3) | O1—C13—C14—C15 | 173.0 (6) |
Pd1—N1—N2—C1 | −3.1 (4) | O1A—C13—C14—C15 | −177.3 (7) |
N1—N2—C1—S1 | 0.0 (5) | C13—C14—C15—C10 | 1.1 (7) |
N1—N2—C1—S2 | 179.9 (2) | C11—C10—C15—C14 | 1.5 (6) |
Pd1—S1—C1—N2 | 2.3 (4) | C9—C10—C15—C14 | −179.3 (4) |
Pd1—S1—C1—S2 | −177.53 (18) | C12—C13—O1—C16 | 176.7 (6) |
C2—S2—C1—N2 | −9.0 (4) | C14—C13—O1—C16 | 0.3 (10) |
C2—S2—C1—S1 | 170.9 (2) | O1A—C13—O1—C16 | −20.5 (15) |
C1—S2—C2—C3 | −160.0 (4) | C13—O1—C16—C17 | −162.7 (8) |
S2—C2—C3—C8 | −103.1 (5) | O1—C16—C17—C18 | −66.6 (14) |
S2—C2—C3—C4 | 74.9 (6) | C16—C17—C18—C19 | −168.8 (11) |
C8—C3—C4—C5 | −2.2 (12) | C17—C18—C19—C20 | −173.5 (13) |
C2—C3—C4—C5 | 179.7 (7) | C12—C13—O1A—C16A | 11.8 (17) |
C3—C4—C5—C6 | −6.1 (14) | C14—C13—O1A—C16A | −175.6 (9) |
C4—C5—C6—C7 | 14.0 (18) | O1—C13—O1A—C16A | −12.0 (11) |
C5—C6—C7—C8 | −12.3 (18) | C13—O1A—C16A—C17A | −178.6 (10) |
C4—C3—C8—C7 | 4.0 (11) | O1A—C16A—C17A—C18A | −162.7 (17) |
C2—C3—C8—C7 | −178.0 (6) | C18—C19—C20—C21 | −169.0 (15) |
C6—C7—C8—C3 | 2.5 (14) | C19—C20—C21—C22 | 177.7 (13) |
N2—N1—C9—C10 | 3.2 (6) | C20—C21—C22—C23 | −172.1 (13) |
Pd1—N1—C9—C10 | −176.2 (3) |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Pd(C23H29N2OS2)2] |
Mr | 933.60 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 16.586 (4), 14.082 (3), 10.507 (2) |
β (°) | 103.22 (3) |
V (Å3) | 2389.0 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.60 |
Crystal size (mm) | 0.40 × 0.35 × 0.12 |
Data collection | |
Diffractometer | Enraf–Nonius DIP1030 image-plate diffractometer |
Absorption correction | Part of the refinement model (ΔF) (Parkin et al., 1995) |
Tmin, Tmax | 0.742, 0.932 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27894, 4042, 1977 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.083, 0.77 |
No. of reflections | 4042 |
No. of parameters | 277 |
No. of restraints | 60 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.27 |
Computer programs: XPRESS (MacScience, 2002), DENZO (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Pd1—N1 | 2.034 (3) | N1—N2 | 1.396 (4) |
Pd1—S1 | 2.2825 (11) | N2—C1 | 1.287 (4) |
N1—C9 | 1.312 (4) | ||
N1—Pd1—S1 | 83.08 (10) |
Metal chelates of S-alkyl/arylesters of dithiocarbazate (SBDTC) and their Schiff bases have attracted the interest of researchers for their coordination chemistry and also for their potential use as anticancer compounds (How et al. 2008; Crouse et al., 2004; Tarafder et al., 2002, 2001; Ali et al., 1992). As a continuation of our interest in N,S-donor ligands and their complexes, we have isolated a novel Schiff base of SBDTC, benzyl-3-[(4-n-octyloxyphenyl)methylene]dithiocarbazate, and its bis(bidentate) palladium(II) complex, the title compound, (I).
The structure of (I) shows the PdII ion in the expected square-planar donor environment (Fig. 1), with the metal on a centre of inversion and the asymmetric unit therefore constituted by half of the molecule. Each of the ligands is coordinated to the metal as a bidentate chelating agent bonding via the thiolate S and azomethine N atoms, yielding two five-membered chelate rings. The Pd—N and Pd—S bond lengths (Table 1) are sligthly shorter and longer, respectively, than those observed in Pd complexes containing bis-chelating dithiocarbazato-N,S ligands, which fall in the ranges 2.067–2.111 and 2.253–2.268 Å, respectively, as retrieved from the Cambridge Structural Database (CSD, Version 5.31 of November 2009; Allen, 2002). Inside the C—N—N—C group, the bond distances follow the trend found in the other Pd complexes retrieved, indicating that C9—N1 and N2—C1 are double bonds and N1—N2 is a single bond. As described in the Experimental section, the octyloxyl chain is disordered over two positions, leading to absolute O1—C17—C18—C19 torsion angles of 66.6 (14) and 162.7 (17)° for the two arrangements, corresponding to synclinal and antiperiplanar conformations, respectively. The former is close to that found in the octyloxybenzaldehyde thiosemicarbazone ligand (Islam et al., 2010).
A key interest in bis(N,S-bidentate) complexes of Ni triad metals is the adoption of cis versus trans geometries. A CSD search for the fragment M[SC(S)NN]2 (where M = Ni, Pd or Pt) indicates that Ni complexes with chelating dithiocarbazato-N,S groups adopt either a cis (12 entries) or a trans geometry (12 entries) with equal probability. By contrast, five out of six Pd complexes have a cis configuration, while all five Pt complexes adopt a trans arrangement. The unique reported Pd complex with a trans geometry is notable in that the S-benzyldithiocarbazate ligand has an NH2 group (Tampouris et al. 2007) as the coordinating N atom, rather than an alkyl- or alkylidene-substituted N atom.
Although the Pd and Pt dithiocarbazate complexes are fewer in number, there is a fair indication that these metals prefer a cis (Pd) or a trans (Pt) geometry, although it should be noted that a broader search of Pd complexes of bis(bidentate) ligands with N—C—C—S (nine cis versus five trans) or N—N—C—S (10 cis versus 17 trans) linkages shows no clear preference. Thus, we can say that (I) represents a rare example of a bis(dithiocarbazato)palladium(II) ion in a trans-planar coordination geometry (see second scheme), likely assumed in order to avoid steric clashes between the substituents on the ligand. The (ferrocenyl)ethylidene (Duan et al., 1998) and diazafluorene–dithiocarbazate (Zhou et al., 2007) derivatives, which have bulky groups on the ligand and a cis configuration, appear to be stabilized by intramolecular stacking interactions between the cyclopentadienyl planes from different Fe atoms and between the diazafluorene rings, respectively. Since no stacking interaction between phenyl rings is detected in (I), intermolecular packing forces favouring the trans geometry appear to be excluded. In the absence of such effects, the stabilization of one configuration over the other may result from the different trans influence exerted by the N and S atoms, induced by the electronic and steric effects of substituent groups on the ligand, which lead to different Pd—N and Pd—S bond energies.