cis-Di­chlorido­(6,11-di­hydro­dibenzo[b,f][1,4]di­thio­cine-κ2S,S′)palladium(II)

Bernès, S.; Tiburcio, J.; Torrens, H.

doi:10.1107/S241431461600852X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160852

doi:10.1107/S241431461600852X

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cis-Dichlorido(6,11-dihydrodibenzo[b,f][1,4]dithiocine-κ²S,S′)palladium(II)

Sylvain Bernès,^a ^* Jorge Tiburcio ^b and Hugo Torrens ^c

^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

Edited by J. Simpson, University of Otago, New Zealand (Received 25 May 2016; accepted 26 May 2016; online 3 June 2016)

In the title compound, [PdCl₂(C₁₄H₁₂S₂)], the Pd^II 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 diffraction analysis of the complex [PdCl₂(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 Pd^II 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 hybridization. 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)°.

Figure 1
The structure of the title compound, with displacement ellipsoids for non-H atoms at the 30% probability level.

The 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.

Figure 2
Part of the crystal structure, emphasizing short Pd⋯Pd distances (dashed lines). H atoms are omitted for clarity [symmetry code: (i) 1 − x, −y, 1 − z].

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 refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	[PdCl₂(C₁₄H₁₂S₂)]
M_r	421.66
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	297
a, b, c (Å)	8.1594 (6), 9.2419 (6), 10.4393 (7)
α, β, γ (°)	82.454 (6), 77.443 (6), 82.281 (4)
V (Å³)	757.16 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.84
Crystal size (mm)	0.20 × 0.12 × 0.10

Data collection
Diffractometer	Bruker P4
Absorption correction	ψ scan (XSCANS; Bruker, 1997 )
T_min, T_max	0.304, 0.337
No. of measured, independent and observed [I > 2σ(I)] reflections	4833, 4021, 3154
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.076, 1.03
No. of reflections	4021
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.53
Computer programs: XSCANS (Bruker, 1997), SHELXS2013 and SHELXTL (Sheldrick, 2008 ) and SHELXL2014 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1481992

Crystal structure: contains datablock I. DOI: 10.1107/S241431461600852X/sj4043sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S241431461600852X/sj4043Isup2.hkl

checkCIF report

Computing details top

Data collection: XSCANS (Bruker, 1997); cell refinement: 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).

cis-Dichlorido(6,11-dihydrodibenzo[b,f][1,4]dithiocine-κ²S,S')palladium(II) top

Crystal data top

[PdCl₂(C₁₄H₁₂S₂)]	Z = 2
M_r = 421.66	F(000) = 416
Triclinic, P1	D_x = 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

Data collection top

Bruker P4 diffractometer	3154 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 29.0°, θ_min = 2.0°
ω scans	h = −11→1
Absorption correction: ψ scan (XSCANS; Bruker, 1997)	k = −12→12
T_min = 0.304, T_max = 0.337	l = −14→14
4833 measured reflections	3 standard reflections every 97 reflections
4021 independent reflections	intensity decay: 1%

Refinement top

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(F_o²) + (0.0264P)² + 0.1995P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4021 reflections	Δρ_max = 0.48 e Å⁻³
173 parameters	Δρ_min = −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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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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