metal-organic compounds
cis-Dichlorido(6,11-dihydrodibenzo[b,f][1,4]dithiocine-κ2S,S′)palladium(II)
aInstituto de Física, Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico, bDepartamento de Química, CINVESTAV, Av. Instituto Politécnico Nacional 2508, San Pedro Zacatenco, 07360 México D.F., Mexico, and cFacultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, 04510 México D.F., Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com
In the title compound, [PdCl2(C14H12S2)], the PdII atom features a square-planar coordination to the two S atoms of the dithiocine ligand and two Cl− ions. The dithiocine ligand forms a pair of metallacycle rings, with seven (C4S2Pd) and five (C2S2Pd) members, respectively. The benzylic part of the molecule is oriented away from the Pd atom, as a consequence of the boat conformation adopted by the chelating ligand. The geometry for both S-donor atoms is consistent with sp3 hybridization.
Keywords: crystal structure; palladium; chelate; dithiocine; bidentate ligand.
CCDC reference: 1481992
Structure description
Good quality crystals for X-ray 2(κ2-S2C14H12)] were obtained by slow diffusion of two concentrated solutions of the reactants in CH2Cl2 separated by a phase of pure CH2Cl2, at room temperature (293–298 K). In the complex (Fig. 1), the PdII atom lies at the centre of a slightly distorted square-planar [S2Cl2] donor set, with the 1,4-dithiocine ligand coordinating in a bidentate fashion. The asymmetric character of this ligand gives rise to a pair of metallacycle rings with five and seven members. The bond angles at S1 and S4 indicate that these atoms retain a quasi-tetrahedral The Pd—S bond lengths, 2.2638 (8) and 2.2749 (8) Å, are similar to comparable Pd—S distances found in other thioether complexes (e.g. Tiburcio et al., 2002). The 6,8,6 system of the dithiocine ligand adopts a boat-like conformation, allowing the formation of a weak intramolecular π–π interaction, the distance between the centroids of the benzene rings being 3.854 (2) Å. However, these rings are not parallel, and are inclined at a dihedral angle of 46.5 (2)°.
of the complex [PdClThe molecules are staggered in the triclinic crystal, so the Cl and S atoms of one molecule are rotated by 180° with respect to the neighbouring molecule, forming centrosymmetric pairs (Fig. 2). The resulting Pd⋯Pd distance is rather short, 3.2234 (5) Å, slightly shorter than twice the van der Waals radius of Pd (3.26 Å; Bondi, 1964). Such a short intermolecular contact is however not exceptional, and Pd⋯Pd separations around 3 Å without any formal σ-bond formation have been reported previously (e.g. Karhu et al., 2016; Pullen et al., 1998). The arrangement of the molecules in the crystal avoids the formation of intermolecular π-stacking in the solid state.
Synthesis and crystallization
Unfortunately the title complex is insoluble in all common solvents and decomposes with loss of the ligand in dimethylsulfoxide and dimethylformamide. Therefore, normal synthesis and recrystallization was not possible. In addition, the insolubility of the complex precluded its characterization by standard NMR techniques.
To overcome this difficulty, we used an alternative method based on the slow diffusion of CH2Cl2 solutions containing each of the reagents, and separated by a phase of pure CH2Cl2. The reaction involves the direct displacement of SMe2 from the complex [PdCl2(SMe2)2] (Jasper et al., 1994) with the chelating ligand S2C14H12 (Schroth et al., 1964).
In an H-shaped vessel with the vertical glass tubes open at the upper-ends and connected with a horizontal tube, [PdCl2(SMe2)2] (150 mg, 0.5 mmol) dissolved in 25 ml of CH2Cl2 was placed in one vertical arm, and S2C14H12 (122 mg, 0.5 mmol) dissolved in 25 ml of CH2Cl2 in the other. The top level of both solutions was around 3 cm below the horizontal glass tube. Pure CH2Cl2 was then layered until the solvent level reached one cm above the horizontal glass tube. The system was left aside for 3 days, affording orange crystals suitable for structural studies. Analysis, found: C 39.6, H 2.3, S 15.6%; calculated for C14H12Cl2PdS2: C 39.9, H 2.9, S 15.2%. IR (ν, cm−1): 2944 (m), 1485 (m), 1460 (s), 1237 (m), 779 (s), 668 (s), 326 (s), 295 (m), 287(s).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 1Structural data
CCDC reference: 1481992
10.1107/S241431461600852X/sj4043sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S241431461600852X/sj4043Isup2.hkl
Data collection: XSCANS (Bruker, 1997); cell
XSCANS (Bruker, 1997); data reduction: XSCANS (Bruker, 1997); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).[PdCl2(C14H12S2)] | Z = 2 |
Mr = 421.66 | F(000) = 416 |
Triclinic, P1 | Dx = 1.849 Mg m−3 |
a = 8.1594 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.2419 (6) Å | Cell parameters from 78 reflections |
c = 10.4393 (7) Å | θ = 4.2–13.0° |
α = 82.454 (6)° | µ = 1.84 mm−1 |
β = 77.443 (6)° | T = 297 K |
γ = 82.281 (4)° | Prism, orange |
V = 757.16 (9) Å3 | 0.20 × 0.12 × 0.10 mm |
Bruker P4 diffractometer | 3154 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 29.0°, θmin = 2.0° |
ω scans | h = −11→1 |
Absorption correction: ψ scan (XSCANS; Bruker, 1997) | k = −12→12 |
Tmin = 0.304, Tmax = 0.337 | l = −14→14 |
4833 measured reflections | 3 standard reflections every 97 reflections |
4021 independent reflections | intensity decay: 1% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0264P)2 + 0.1995P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
4021 reflections | Δρmax = 0.48 e Å−3 |
173 parameters | Δρmin = −0.53 e Å−3 |
0 restraints | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.0065 (6) |
Primary atom site location: structure-invariant direct methods |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.35201 (3) | 0.13119 (2) | 0.53585 (2) | 0.03134 (9) | |
Cl1 | 0.53384 (11) | 0.19942 (9) | 0.65447 (8) | 0.04461 (19) | |
Cl2 | 0.22036 (11) | −0.02243 (9) | 0.71175 (7) | 0.04510 (19) | |
S1 | 0.16909 (9) | 0.09097 (8) | 0.41133 (7) | 0.03249 (16) | |
C2 | 0.2749 (4) | 0.1462 (3) | 0.2468 (3) | 0.0325 (6) | |
C3 | 0.3975 (4) | 0.2410 (3) | 0.2291 (3) | 0.0344 (6) | |
S4 | 0.44874 (10) | 0.30113 (8) | 0.36954 (7) | 0.03602 (17) | |
C5 | 0.2777 (4) | 0.4545 (3) | 0.4108 (3) | 0.0423 (7) | |
H5A | 0.2218 | 0.4351 | 0.5023 | 0.051* | |
H5B | 0.3294 | 0.5447 | 0.4024 | 0.051* | |
C6 | 0.1470 (4) | 0.4776 (3) | 0.3273 (3) | 0.0378 (7) | |
C7 | 0.1456 (5) | 0.6017 (4) | 0.2347 (4) | 0.0501 (8) | |
H7A | 0.2266 | 0.6661 | 0.2259 | 0.060* | |
C8 | 0.0265 (6) | 0.6306 (4) | 0.1563 (4) | 0.0635 (11) | |
H8A | 0.0262 | 0.7146 | 0.0965 | 0.076* | |
C9 | −0.0912 (5) | 0.5350 (4) | 0.1669 (4) | 0.0631 (11) | |
H9A | −0.1700 | 0.5533 | 0.1127 | 0.076* | |
C10 | −0.0943 (4) | 0.4115 (4) | 0.2574 (4) | 0.0497 (8) | |
H10A | −0.1753 | 0.3478 | 0.2634 | 0.060* | |
C11 | 0.0223 (4) | 0.3809 (3) | 0.3400 (3) | 0.0370 (6) | |
C12 | 0.0040 (4) | 0.2501 (3) | 0.4414 (3) | 0.0382 (7) | |
H12A | −0.1054 | 0.2169 | 0.4469 | 0.046* | |
H12B | 0.0045 | 0.2812 | 0.5265 | 0.046* | |
C13 | 0.2340 (5) | 0.0954 (4) | 0.1402 (3) | 0.0434 (7) | |
H13A | 0.1516 | 0.0316 | 0.1526 | 0.052* | |
C14 | 0.3192 (5) | 0.1420 (4) | 0.0135 (3) | 0.0530 (9) | |
H14A | 0.2939 | 0.1088 | −0.0595 | 0.064* | |
C15 | 0.4399 (5) | 0.2364 (5) | −0.0035 (3) | 0.0564 (10) | |
H15A | 0.4953 | 0.2669 | −0.0885 | 0.068* | |
C16 | 0.4815 (5) | 0.2877 (4) | 0.1032 (3) | 0.0483 (8) | |
H16A | 0.5636 | 0.3518 | 0.0906 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.03337 (13) | 0.03475 (13) | 0.02738 (12) | −0.00566 (9) | −0.00776 (8) | −0.00404 (8) |
Cl1 | 0.0515 (5) | 0.0503 (4) | 0.0394 (4) | −0.0137 (4) | −0.0192 (4) | −0.0062 (3) |
Cl2 | 0.0531 (5) | 0.0495 (4) | 0.0346 (4) | −0.0177 (4) | −0.0102 (3) | 0.0033 (3) |
S1 | 0.0341 (4) | 0.0341 (3) | 0.0307 (3) | −0.0084 (3) | −0.0069 (3) | −0.0035 (3) |
C2 | 0.0301 (14) | 0.0380 (14) | 0.0283 (13) | 0.0034 (12) | −0.0066 (11) | −0.0060 (11) |
C3 | 0.0327 (15) | 0.0390 (15) | 0.0293 (13) | 0.0003 (12) | −0.0039 (12) | −0.0034 (11) |
S4 | 0.0319 (4) | 0.0434 (4) | 0.0340 (4) | −0.0104 (3) | −0.0071 (3) | −0.0017 (3) |
C5 | 0.0458 (19) | 0.0360 (15) | 0.0486 (18) | −0.0084 (14) | −0.0117 (15) | −0.0101 (13) |
C6 | 0.0365 (16) | 0.0370 (15) | 0.0393 (15) | −0.0033 (13) | −0.0041 (13) | −0.0081 (12) |
C7 | 0.052 (2) | 0.0377 (17) | 0.059 (2) | −0.0087 (16) | −0.0092 (17) | 0.0014 (15) |
C8 | 0.072 (3) | 0.050 (2) | 0.068 (3) | −0.001 (2) | −0.027 (2) | 0.0104 (19) |
C9 | 0.058 (2) | 0.059 (2) | 0.075 (3) | 0.000 (2) | −0.031 (2) | 0.007 (2) |
C10 | 0.0361 (17) | 0.0513 (19) | 0.065 (2) | −0.0034 (15) | −0.0160 (16) | −0.0080 (17) |
C11 | 0.0316 (15) | 0.0366 (15) | 0.0426 (16) | −0.0010 (12) | −0.0059 (13) | −0.0087 (12) |
C12 | 0.0276 (15) | 0.0435 (16) | 0.0426 (16) | −0.0077 (13) | 0.0001 (13) | −0.0093 (13) |
C13 | 0.0475 (19) | 0.0481 (17) | 0.0381 (16) | −0.0024 (15) | −0.0134 (14) | −0.0124 (14) |
C14 | 0.060 (2) | 0.068 (2) | 0.0325 (16) | 0.005 (2) | −0.0153 (16) | −0.0127 (16) |
C15 | 0.057 (2) | 0.080 (3) | 0.0262 (15) | −0.002 (2) | −0.0005 (15) | −0.0045 (16) |
C16 | 0.0433 (19) | 0.064 (2) | 0.0342 (16) | −0.0081 (17) | −0.0020 (14) | 0.0008 (15) |
Pd1—S4 | 2.2638 (8) | C7—H7A | 0.9300 |
Pd1—S1 | 2.2749 (8) | C8—C9 | 1.367 (6) |
Pd1—Cl1 | 2.3211 (8) | C8—H8A | 0.9300 |
Pd1—Cl2 | 2.3257 (8) | C9—C10 | 1.382 (5) |
Pd1—Pd1i | 3.2234 (5) | C9—H9A | 0.9300 |
S1—C2 | 1.789 (3) | C10—C11 | 1.396 (5) |
S1—C12 | 1.866 (3) | C10—H10A | 0.9300 |
C2—C13 | 1.383 (4) | C11—C12 | 1.499 (4) |
C2—C3 | 1.384 (4) | C12—H12A | 0.9700 |
C3—C16 | 1.386 (4) | C12—H12B | 0.9700 |
C3—S4 | 1.782 (3) | C13—C14 | 1.395 (5) |
S4—C5 | 1.873 (3) | C13—H13A | 0.9300 |
C5—C6 | 1.495 (5) | C14—C15 | 1.371 (5) |
C5—H5A | 0.9700 | C14—H14A | 0.9300 |
C5—H5B | 0.9700 | C15—C16 | 1.388 (5) |
C6—C7 | 1.400 (4) | C15—H15A | 0.9300 |
C6—C11 | 1.416 (4) | C16—H16A | 0.9300 |
C7—C8 | 1.380 (5) | ||
S4—Pd1—S1 | 86.69 (3) | C8—C7—H7A | 119.3 |
S4—Pd1—Cl1 | 88.30 (3) | C6—C7—H7A | 119.3 |
S1—Pd1—Cl1 | 173.68 (3) | C9—C8—C7 | 119.7 (3) |
S4—Pd1—Cl2 | 172.50 (3) | C9—C8—H8A | 120.2 |
S1—Pd1—Cl2 | 90.62 (3) | C7—C8—H8A | 120.2 |
Cl1—Pd1—Cl2 | 93.88 (3) | C8—C9—C10 | 120.6 (4) |
S4—Pd1—Pd1i | 97.81 (2) | C8—C9—H9A | 119.7 |
S1—Pd1—Pd1i | 100.64 (2) | C10—C9—H9A | 119.7 |
Cl1—Pd1—Pd1i | 83.85 (2) | C9—C10—C11 | 121.1 (4) |
Cl2—Pd1—Pd1i | 89.56 (2) | C9—C10—H10A | 119.5 |
C2—S1—C12 | 100.75 (13) | C11—C10—H10A | 119.5 |
C2—S1—Pd1 | 103.05 (10) | C10—C11—C6 | 118.6 (3) |
C12—S1—Pd1 | 101.42 (10) | C10—C11—C12 | 117.9 (3) |
C13—C2—C3 | 121.1 (3) | C6—C11—C12 | 123.5 (3) |
C13—C2—S1 | 120.4 (2) | C11—C12—S1 | 115.9 (2) |
C3—C2—S1 | 118.5 (2) | C11—C12—H12A | 108.3 |
C2—C3—C16 | 120.4 (3) | S1—C12—H12A | 108.3 |
C2—C3—S4 | 119.5 (2) | C11—C12—H12B | 108.3 |
C16—C3—S4 | 120.1 (3) | S1—C12—H12B | 108.3 |
C3—S4—C5 | 102.25 (14) | H12A—C12—H12B | 107.4 |
C3—S4—Pd1 | 103.28 (10) | C2—C13—C14 | 118.5 (3) |
C5—S4—Pd1 | 98.12 (11) | C2—C13—H13A | 120.8 |
C6—C5—S4 | 115.1 (2) | C14—C13—H13A | 120.8 |
C6—C5—H5A | 108.5 | C15—C14—C13 | 120.2 (3) |
S4—C5—H5A | 108.5 | C15—C14—H14A | 119.9 |
C6—C5—H5B | 108.5 | C13—C14—H14A | 119.9 |
S4—C5—H5B | 108.5 | C14—C15—C16 | 121.5 (3) |
H5A—C5—H5B | 107.5 | C14—C15—H15A | 119.3 |
C7—C6—C11 | 118.6 (3) | C16—C15—H15A | 119.3 |
C7—C6—C5 | 118.6 (3) | C3—C16—C15 | 118.3 (3) |
C11—C6—C5 | 122.7 (3) | C3—C16—H16A | 120.8 |
C8—C7—C6 | 121.4 (3) | C15—C16—H16A | 120.8 |
C12—S1—C2—C13 | −96.8 (3) | C7—C8—C9—C10 | 1.4 (7) |
Pd1—S1—C2—C13 | 158.7 (2) | C8—C9—C10—C11 | −0.1 (6) |
C12—S1—C2—C3 | 82.9 (2) | C9—C10—C11—C6 | −1.4 (5) |
Pd1—S1—C2—C3 | −21.6 (2) | C9—C10—C11—C12 | 176.2 (3) |
C13—C2—C3—C16 | 0.3 (5) | C7—C6—C11—C10 | 1.6 (5) |
S1—C2—C3—C16 | −179.4 (2) | C5—C6—C11—C10 | −179.9 (3) |
C13—C2—C3—S4 | −178.9 (2) | C7—C6—C11—C12 | −175.9 (3) |
S1—C2—C3—S4 | 1.4 (3) | C5—C6—C11—C12 | 2.7 (5) |
C2—C3—S4—C5 | −81.8 (3) | C10—C11—C12—S1 | 109.4 (3) |
C16—C3—S4—C5 | 99.0 (3) | C6—C11—C12—S1 | −73.1 (3) |
C2—C3—S4—Pd1 | 19.7 (3) | C2—S1—C12—C11 | −10.0 (3) |
C16—C3—S4—Pd1 | −159.5 (2) | Pd1—S1—C12—C11 | 95.8 (2) |
C3—S4—C5—C6 | 3.7 (3) | C3—C2—C13—C14 | −0.1 (5) |
Pd1—S4—C5—C6 | −101.9 (2) | S1—C2—C13—C14 | 179.7 (2) |
S4—C5—C6—C7 | −108.3 (3) | C2—C13—C14—C15 | −0.3 (5) |
S4—C5—C6—C11 | 73.2 (4) | C13—C14—C15—C16 | 0.3 (6) |
C11—C6—C7—C8 | −0.3 (5) | C2—C3—C16—C15 | −0.3 (5) |
C5—C6—C7—C8 | −178.9 (3) | S4—C3—C16—C15 | 178.9 (3) |
C6—C7—C8—C9 | −1.2 (6) | C14—C15—C16—C3 | 0.0 (6) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5B···Cl1ii | 0.97 | 2.69 | 3.654 (3) | 172 |
C12—H12A···Cl2iii | 0.97 | 2.96 | 3.678 (3) | 132 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x, −y, −z+1. |
Acknowledgements
JT and HT are grateful for the assistance of DGAPA–UNAM, project IN-202314, and CONACYT, project CB-2012–147498. SB acknowledges support by the Instituto de Física Luis Rivera Terrazas (Puebla, Mexico).
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