Chlorido[2,3,5,6-tetra­kis­(tert-butyl­sulfanylmeth­yl)phenyl-κ3S2,C1,S6]palladium(II) dichloro­methane monosolvate

Paz-Morales, E.; Hernández-Ortega, S.; Morales-Morales, D.

doi:10.1107/S1600536813003036

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Pages m139-m140

doi:10.1107/S1600536813003036

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Chlorido[2,3,5,6-tetrakis(tert-butylsulfanylmethyl)phenyl-κ³S²,C¹,S⁶]palladium(II) dichloromethane monosolvate

Evelyn Paz-Morales,^a ^* Simón Hernández-Ortega ^a and David Morales-Morales ^a

^aInstituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, Coyoacan, CP 04510, México, DF, Mexico
^*Correspondence e-mail: evelynpm@unam.mx

(Received 25 January 2013; accepted 29 January 2013; online 6 February 2013)

The title compound, [Pd(C₂₆H₄₅S₄)Cl]·CH₂Cl₂, crystallizes with a disordered dichloromethane solvent molecule [occupancy ratio = 0.67 (4):0.33 (4)]. Two of the tert-butyl groups are also disordered [occupancy ratios = 0.70 (5):0.30 (5) and 0.63 (4):0.37 (4)]. Although the pincer ligand offers the possibility for coordination of two different metal atoms, the present structure shows only the coordination of a single Pd^II atom in a typical S—C—S tridentate pincer manner. The Pd^II atom is in a slightly distorted square-planar environment with the two tert-butylsulfanyl groups arranged in a trans conformation and with a chloride ligand trans to the σ-bonded aromatic C atom. The structure exhibits a durene-like ligand frame, forming a dihedral angle of 13.6 (4)° with the metal coordination (Pd/S/S/Cl/C) environment. It is noteworthy that the tert-butyl groups are found in a syn arrangement, this being different to that found previously by Loeb, Shimizu & Wisner [(1998). Organometallics, 17, 2324–2327].

Related literature

For background to pincer compounds, see: Arroyo et al., (2003 ); Errington, et al. (1980 ); Morales-Morales & Jensen (2007 ). For an isomeric structure, see: Loeb et al. (1998 ).

Experimental

Crystal data

[Pd(C₂₆H₄₅S₄)Cl]·CH₂Cl₂
M_r = 712.64
Monoclinic, P 2₁ /n
a = 15.917 (15) Å
b = 13.768 (13) Å
c = 17.808 (16) Å
β = 105.216 (15)°
V = 3766 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 298 K
0.27 × 0.22 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: integration (SADABS; Sheldrick, 1996 ) T_min = 0.593, T_max = 0.745
28207 measured reflections
6570 independent reflections
5144 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.110
S = 1.03
6570 reflections
406 parameters
291 restraints
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Selected bond lengths (Å)

Pd—C2	2.022 (4)
Pd—S1	2.326 (2)
Pd—S2	2.333 (2)
Pd—Cl1	2.441 (2)

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; 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, 2012 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813003036/pk2463sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813003036/pk2463Isup2.hkl

checkCIF report

Comment top

Pincer compounds have had a preponderant importance in chemistry, this being especially important in areas such as homogeneous catalysis, organometallic chemistry, the activation of unreactive or difficult to activate bonds and the activation of small molecules (Errington et al. 1980; Morales-Morales & Jensen, 2007). Among these species, those including sulfur as donor atom have been scarcely studied (Arroyo et al., 2003), mostly due to the well known tendency of sulfur to kill the activity of homogeneous catalysts. Thus, following our continuing interest in the synthesis of pincer compounds, we report here the crystal structure of the Pd(II) sulfur based pincer complex (1,2,4,5-tetrakis(tert-butylsulfanylmethyl)phenyl)-chloro-palladium (II) dichloromethane solvate (I).

The structure of (I) is shown in Fig. 1 with the numbering scheme. Compound (I) was crystallized as a dichloromethane solvate. Selected bond distances and angles are shown in Table 1. In agreement with the dihedral angles of the planes C7—C1—C2—C3—C8 and S1—Pd—S2—Cl1 (13.6 (4)°) the Pd atom is located in a slightly distorted square-planar geometry. Compound (I) is a geometric isomer of a previously described compound (Loeb et al. 1998). However, there are several noticeable differences in our compound (I), the tert-butyl substituents at the S are found in a syn fashion while those described in the previously reported compound are oriented in an anti fashion with respect to the square plane. The bond distances for Pd—S and Pd—C [2.326 (2) Å, 2.333 (2) Å and 2.022 (4) Å] are slightly larger than those of the anti isomer [2.297 (3) Å, 2.302 (3) Å and 1.994 (4) Å]. The Pd—Cl bond distance [2.441 (2) Å] is larger than of the anti isomer. While the uncoordinated tert-butylS groups are found in a similar geometry as those previously observed in the Loeb's species (Loeb et al. 1998). Finally, both the tert-butyl groups and the dichloromethane solvent molecule are disordered and were refined as disordered with two components.

Related literature top

For background to pincer compounds, see: Arroyo et al., (2003); Errington, et al. (1980); Morales-Morales & Jensen (2007). For an isomeric structure, see: Loeb et al. (1998). [The scheme should show the solvent]

Experimental top

The title compound was synthesized according to a published procedure (Loeb et al. 1998). Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution of the title compound (I) in CH₂Cl₂.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); 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, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 40% probability level. The H-atoms and the minor disorder components have been omitted to enhance clarity.

Chlorido[2,3,5,6-tetrakis(tert-butylsulfanylmethyl)phenyl-κ³S²,C¹,S⁶]palladium(II) dichloromethane monosolvate top

Crystal data top

[Pd(C₂₆H₄₅S₄)Cl]·CH₂Cl₂	F(000) = 1480
M_r = 712.64	D_x = 1.257 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8648 reflections
a = 15.917 (15) Å	θ = 2.4–24.8°
b = 13.768 (13) Å	µ = 0.94 mm⁻¹
c = 17.808 (16) Å	T = 298 K
β = 105.216 (15)°	Prism, colourless
V = 3766 (6) Å³	0.27 × 0.22 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	6570 independent reflections
Radiation source: fine-focus sealed tube	5144 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
Detector resolution: 0.83 pixels mm^-1	θ_max = 25.0°, θ_min = 2.0°
ω scans	h = −18→18
Absorption correction: integration (SADABS; Sheldrick, 1996)	k = −16→16
T_min = 0.593, T_max = 0.745	l = −20→20
28207 measured reflections

Refinement top

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.055P)²] where P = (F_o² + 2F_c²)/3
6570 reflections	(Δ/σ)_max = 0.002
406 parameters	Δρ_max = 0.64 e Å⁻³
291 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

[Pd(C₂₆H₄₅S₄)Cl]·CH₂Cl₂	V = 3766 (6) Å³
M_r = 712.64	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.917 (15) Å	µ = 0.94 mm⁻¹
b = 13.768 (13) Å	T = 298 K
c = 17.808 (16) Å	0.27 × 0.22 × 0.15 mm
β = 105.216 (15)°

Data collection top

Bruker SMART APEX CCD diffractometer	6570 independent reflections
Absorption correction: integration (SADABS; Sheldrick, 1996)	5144 reflections with I > 2σ(I)
T_min = 0.593, T_max = 0.745	R_int = 0.066
28207 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	291 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.03	Δρ_max = 0.64 e Å⁻³
6570 reflections	Δρ_min = −0.24 e Å⁻³
406 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pd	0.386615 (17)	1.08106 (2)	0.319516 (16)	0.04396 (12)
Cl1	0.37582 (7)	1.23743 (9)	0.25300 (8)	0.0792 (4)
S1	0.53435 (6)	1.06823 (7)	0.32714 (6)	0.0491 (2)
S2	0.24590 (6)	1.07447 (7)	0.33560 (5)	0.0476 (2)
S3	0.23346 (7)	0.83956 (10)	0.53990 (7)	0.0700 (3)
S4	0.62344 (7)	0.72277 (8)	0.41972 (6)	0.0623 (3)
C1	0.4886 (2)	0.9199 (3)	0.41609 (19)	0.0418 (8)
C2	0.4033 (2)	0.9564 (3)	0.38174 (19)	0.0393 (8)
C3	0.3296 (2)	0.9071 (3)	0.3951 (2)	0.0428 (9)
C4	0.3422 (2)	0.8228 (3)	0.4436 (2)	0.0437 (9)
C5	0.4270 (2)	0.7883 (3)	0.4761 (2)	0.0466 (9)
H5	0.4347	0.7332	0.5073	0.056*
C6	0.5011 (2)	0.8349 (3)	0.46264 (19)	0.0440 (9)
C7	0.5669 (2)	0.9770 (3)	0.4048 (2)	0.0469 (9)
H7A	0.6081	0.9323	0.3920	0.056*
H7B	0.5957	1.0092	0.4532	0.056*
C8	0.2386 (2)	0.9439 (3)	0.3549 (2)	0.0522 (10)
H8A	0.1997	0.9333	0.3880	0.063*
H8B	0.2157	0.9092	0.3064	0.063*
C9	0.5909 (2)	0.7917 (3)	0.4969 (2)	0.0492 (9)
H9A	0.5896	0.7488	0.5398	0.059*
H9B	0.6326	0.8430	0.5165	0.059*
C10	0.2641 (2)	0.7715 (3)	0.4616 (2)	0.0532 (10)
H10A	0.2795	0.7053	0.4781	0.064*
H10B	0.2156	0.7698	0.4154	0.064*
C11	0.5483 (3)	1.0033 (3)	0.2379 (2)	0.0626 (11)
C12	0.5103 (4)	1.0728 (4)	0.1686 (3)	0.0945 (17)
H12A	0.5158	1.0434	0.1212	0.142*
H12B	0.5418	1.1330	0.1768	0.142*
H12C	0.4500	1.0848	0.1650	0.142*
C13	0.4989 (3)	0.9058 (4)	0.2249 (3)	0.0851 (16)
H13A	0.4376	0.9176	0.2159	0.128*
H13B	0.5188	0.8656	0.2702	0.128*
H13C	0.5096	0.8735	0.1805	0.128*
C14	0.6471 (3)	0.9881 (4)	0.2493 (3)	0.0868 (16)
H14A	0.6683	0.9415	0.2900	0.130*
H14B	0.6769	1.0487	0.2632	0.130*
H14C	0.6574	0.9646	0.2017	0.130*
C15	0.1526 (2)	1.0958 (3)	0.2465 (2)	0.0613 (11)
C16	0.1716 (3)	1.0506 (4)	0.1738 (3)	0.0981 (18)
H16A	0.1257	1.0671	0.1288	0.147*
H16B	0.1751	0.9812	0.1795	0.147*
H16C	0.2259	1.0752	0.1678	0.147*
C17	0.1440 (3)	1.2083 (4)	0.2396 (3)	0.0865 (15)
H17A	0.1006	1.2249	0.1929	0.130*
H17B	0.1989	1.2358	0.2380	0.130*
H17C	0.1272	1.2335	0.2838	0.130*
C18	0.0705 (3)	1.0526 (4)	0.2631 (3)	0.0928 (17)
H18A	0.0656	1.0749	0.3128	0.139*
H18B	0.0742	0.9830	0.2634	0.139*
H18C	0.0202	1.0729	0.2233	0.139*
C19	0.1205 (3)	0.7963 (4)	0.5345 (3)	0.1000 (16)
C20	0.1243 (12)	0.6833 (5)	0.5442 (11)	0.113 (3)	0.70 (5)
H20A	0.1444	0.6548	0.5029	0.170*	0.70 (5)
H20B	0.0672	0.6591	0.5423	0.170*	0.70 (5)
H20C	0.1635	0.6668	0.5934	0.170*	0.70 (5)
C21	0.0584 (8)	0.8249 (16)	0.4531 (7)	0.112 (4)	0.70 (5)
H21A	0.0764	0.7916	0.4126	0.167*	0.70 (5)
H21B	0.0613	0.8938	0.4457	0.167*	0.70 (5)
H21C	−0.0003	0.8069	0.4515	0.167*	0.70 (5)
C22	0.0923 (15)	0.8477 (12)	0.6022 (10)	0.142 (4)	0.70 (5)
H22A	0.0890	0.9165	0.5933	0.213*	0.70 (5)
H22B	0.1343	0.8343	0.6506	0.213*	0.70 (5)
H22C	0.0363	0.8238	0.6044	0.213*	0.70 (5)
C20A	0.101 (3)	0.6851 (9)	0.522 (2)	0.119 (6)	0.30 (5)
H20D	0.1409	0.6493	0.5629	0.179*	0.30 (5)
H20E	0.1090	0.6656	0.4728	0.179*	0.30 (5)
H20F	0.0426	0.6721	0.5239	0.179*	0.30 (5)
C21A	0.0545 (19)	0.858 (3)	0.473 (2)	0.120 (6)	0.30 (5)
H21D	0.0563	0.8385	0.4213	0.180*	0.30 (5)
H21E	0.0698	0.9257	0.4798	0.180*	0.30 (5)
H21F	−0.0032	0.8488	0.4784	0.180*	0.30 (5)
C22A	0.122 (3)	0.828 (3)	0.6194 (11)	0.125 (6)	0.30 (5)
H22D	0.1622	0.7884	0.6561	0.188*	0.30 (5)
H22E	0.0645	0.8204	0.6270	0.188*	0.30 (5)
H22F	0.1390	0.8949	0.6270	0.188*	0.30 (5)
C23	0.7421 (3)	0.7020 (3)	0.4609 (3)	0.0885 (14)
C24	0.7840 (11)	0.8059 (7)	0.4636 (12)	0.097 (3)	0.63 (4)
H24A	0.7718	0.8320	0.4119	0.145*	0.63 (4)
H24B	0.8459	0.8012	0.4850	0.145*	0.63 (4)
H24C	0.7600	0.8479	0.4957	0.145*	0.63 (4)
C25	0.7747 (14)	0.6346 (11)	0.4031 (11)	0.120 (4)	0.63 (4)
H25A	0.7607	0.6638	0.3524	0.180*	0.63 (4)
H25B	0.7468	0.5724	0.4002	0.180*	0.63 (4)
H25C	0.8367	0.6264	0.4214	0.180*	0.63 (4)
C26	0.7646 (13)	0.6563 (17)	0.5444 (7)	0.118 (4)	0.63 (4)
H26A	0.7395	0.5925	0.5418	0.177*	0.63 (4)
H26B	0.7413	0.6964	0.5781	0.177*	0.63 (4)
H26C	0.8266	0.6518	0.5643	0.177*	0.63 (4)
C24A	0.8068 (18)	0.7877 (18)	0.4898 (18)	0.112 (5)	0.37 (4)
H24D	0.8018	0.8339	0.4485	0.169*	0.37 (4)
H24E	0.8652	0.7631	0.5054	0.169*	0.37 (4)
H24F	0.7930	0.8189	0.5334	0.169*	0.37 (4)
C25A	0.759 (2)	0.653 (2)	0.3868 (13)	0.108 (5)	0.37 (4)
H25D	0.7200	0.5991	0.3711	0.162*	0.37 (4)
H25E	0.8183	0.6293	0.3988	0.162*	0.37 (4)
H25F	0.7504	0.6991	0.3454	0.162*	0.37 (4)
C26A	0.747 (2)	0.6253 (19)	0.5270 (14)	0.108 (5)	0.37 (4)
H26D	0.7079	0.5727	0.5073	0.162*	0.37 (4)
H26E	0.7310	0.6554	0.5698	0.162*	0.37 (4)
H26F	0.8054	0.6007	0.5444	0.162*	0.37 (4)
Cl2	0.8993 (11)	0.9229 (8)	0.1142 (5)	0.148 (3)	0.67 (4)
Cl3	0.8721 (9)	0.8710 (11)	0.2647 (7)	0.176 (3)	0.67 (4)
C27	0.9079 (19)	0.8314 (12)	0.1845 (13)	0.113 (5)	0.67 (4)
H27A	0.9682	0.8108	0.2023	0.135*	0.67 (4)
H27B	0.8736	0.7758	0.1610	0.135*	0.67 (4)
Cl2A	0.875 (2)	0.9294 (16)	0.1197 (14)	0.172 (7)	0.33 (4)
Cl3A	0.841 (2)	0.835 (3)	0.2547 (12)	0.185 (6)	0.33 (4)
C27A	0.890 (4)	0.824 (2)	0.177 (2)	0.104 (6)	0.33 (4)
H27C	0.9513	0.8112	0.1972	0.125*	0.33 (4)
H27D	0.8640	0.7690	0.1446	0.125*	0.33 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd	0.04006 (17)	0.0427 (2)	0.04995 (18)	−0.00192 (13)	0.01323 (13)	0.00124 (14)
Cl1	0.0618 (7)	0.0613 (8)	0.1110 (9)	0.0010 (6)	0.0164 (6)	0.0313 (7)
S1	0.0453 (5)	0.0476 (6)	0.0576 (6)	−0.0058 (4)	0.0191 (5)	0.0012 (5)
S2	0.0428 (5)	0.0499 (6)	0.0497 (5)	0.0032 (4)	0.0116 (4)	−0.0025 (5)
S3	0.0543 (6)	0.0934 (10)	0.0689 (7)	−0.0112 (6)	0.0282 (6)	−0.0068 (6)
S4	0.0554 (6)	0.0693 (8)	0.0635 (6)	0.0091 (6)	0.0181 (5)	−0.0143 (6)
C1	0.0394 (19)	0.051 (2)	0.0380 (18)	−0.0016 (18)	0.0147 (15)	−0.0026 (17)
C2	0.042 (2)	0.041 (2)	0.0371 (18)	0.0014 (17)	0.0144 (15)	−0.0010 (16)
C3	0.0387 (19)	0.045 (2)	0.047 (2)	0.0026 (17)	0.0145 (16)	−0.0026 (17)
C4	0.041 (2)	0.047 (2)	0.046 (2)	−0.0024 (17)	0.0163 (16)	−0.0029 (18)
C5	0.051 (2)	0.048 (2)	0.046 (2)	0.0025 (19)	0.0205 (18)	0.0046 (18)
C6	0.043 (2)	0.051 (2)	0.0412 (19)	0.0037 (18)	0.0162 (16)	−0.0054 (17)
C7	0.0375 (19)	0.058 (3)	0.046 (2)	0.0004 (18)	0.0125 (16)	−0.0029 (18)
C8	0.043 (2)	0.052 (3)	0.063 (2)	−0.0019 (18)	0.0161 (19)	0.008 (2)
C9	0.046 (2)	0.056 (3)	0.047 (2)	0.0067 (19)	0.0146 (17)	0.0025 (18)
C10	0.051 (2)	0.053 (3)	0.058 (2)	−0.0036 (19)	0.0172 (19)	0.010 (2)
C11	0.065 (3)	0.076 (3)	0.055 (2)	−0.004 (2)	0.029 (2)	0.002 (2)
C12	0.100 (4)	0.123 (5)	0.068 (3)	0.011 (3)	0.037 (3)	0.017 (3)
C13	0.099 (4)	0.094 (4)	0.072 (3)	−0.018 (3)	0.039 (3)	−0.024 (3)
C14	0.072 (3)	0.116 (4)	0.090 (4)	0.008 (3)	0.052 (3)	0.002 (3)
C15	0.040 (2)	0.075 (3)	0.063 (3)	0.009 (2)	0.0042 (19)	0.009 (2)
C16	0.102 (4)	0.129 (5)	0.054 (3)	0.018 (4)	0.005 (3)	−0.009 (3)
C17	0.066 (3)	0.084 (4)	0.104 (4)	0.019 (3)	0.011 (3)	0.020 (3)
C18	0.046 (3)	0.112 (5)	0.111 (4)	0.000 (3)	0.003 (3)	0.020 (3)
C19	0.062 (3)	0.157 (4)	0.096 (3)	−0.022 (3)	0.047 (2)	−0.006 (3)
C20	0.091 (8)	0.157 (5)	0.096 (7)	−0.070 (5)	0.033 (6)	0.008 (4)
C21	0.045 (4)	0.178 (9)	0.117 (5)	0.006 (5)	0.030 (4)	−0.012 (6)
C22	0.083 (9)	0.241 (9)	0.125 (6)	−0.008 (7)	0.067 (6)	−0.030 (7)
C20A	0.094 (13)	0.165 (6)	0.088 (11)	−0.055 (9)	0.005 (11)	0.011 (8)
C21A	0.069 (10)	0.176 (11)	0.128 (9)	0.008 (10)	0.047 (9)	−0.006 (10)
C22A	0.070 (13)	0.215 (13)	0.114 (6)	−0.018 (10)	0.065 (8)	−0.024 (8)
C23	0.051 (3)	0.121 (4)	0.100 (3)	0.018 (2)	0.030 (3)	−0.023 (3)
C24	0.028 (6)	0.155 (5)	0.107 (8)	−0.014 (5)	0.017 (6)	−0.038 (5)
C25	0.081 (8)	0.147 (7)	0.144 (7)	0.045 (7)	0.050 (7)	−0.033 (7)
C26	0.087 (8)	0.144 (9)	0.103 (5)	0.041 (7)	−0.011 (6)	−0.008 (6)
C24A	0.043 (10)	0.168 (9)	0.115 (12)	−0.001 (7)	0.002 (9)	−0.038 (8)
C25A	0.073 (10)	0.135 (11)	0.125 (8)	0.041 (9)	0.043 (9)	−0.036 (7)
C26A	0.082 (11)	0.129 (10)	0.089 (8)	0.042 (8)	−0.019 (8)	−0.013 (7)
Cl2	0.184 (7)	0.102 (3)	0.134 (3)	0.001 (4)	0.001 (4)	−0.036 (3)
Cl3	0.126 (5)	0.218 (7)	0.196 (4)	−0.003 (5)	0.060 (4)	−0.015 (4)
C27	0.069 (12)	0.082 (5)	0.165 (6)	0.015 (6)	−0.008 (7)	−0.026 (5)
Cl2A	0.190 (14)	0.102 (7)	0.178 (10)	0.041 (7)	−0.035 (7)	0.010 (7)
Cl3A	0.122 (11)	0.254 (16)	0.191 (7)	0.042 (9)	0.062 (8)	−0.039 (9)
C27A	0.072 (16)	0.085 (8)	0.145 (8)	0.012 (9)	0.011 (10)	−0.018 (7)

Geometric parameters (Å, º) top

Pd—C2	2.022 (4)	C19—C21A	1.563 (7)
Pd—S1	2.326 (2)	C19—C20	1.564 (6)
Pd—S2	2.333 (2)	C19—C20A	1.565 (8)
Pd—Cl1	2.441 (2)	C19—C22A	1.570 (7)
S1—C7	1.839 (4)	C19—C21	1.574 (6)
S1—C11	1.887 (4)	C20—H20A	0.9600
S2—C8	1.839 (4)	C20—H20B	0.9600
S2—C15	1.890 (4)	C20—H20C	0.9600
S3—C10	1.849 (4)	C21—H21A	0.9600
S3—C19	1.873 (5)	C21—H21B	0.9600
S4—C9	1.852 (4)	C21—H21C	0.9600
S4—C23	1.861 (5)	C22—H22A	0.9600
C1—C6	1.418 (5)	C22—H22B	0.9600
C1—C2	1.427 (5)	C22—H22C	0.9600
C1—C7	1.530 (5)	C20A—H20D	0.9600
C2—C3	1.428 (5)	C20A—H20E	0.9600
C3—C4	1.429 (5)	C20A—H20F	0.9600
C3—C8	1.525 (5)	C21A—H21D	0.9600
C4—C5	1.405 (5)	C21A—H21E	0.9600
C4—C10	1.534 (5)	C21A—H21F	0.9600
C5—C6	1.418 (5)	C22A—H22D	0.9600
C5—H5	0.9300	C22A—H22E	0.9600
C6—C9	1.521 (5)	C22A—H22F	0.9600
C7—H7A	0.9700	C23—C24A	1.561 (7)
C7—H7B	0.9700	C23—C26	1.566 (7)
C8—H8A	0.9700	C23—C26A	1.567 (7)
C8—H8B	0.9700	C23—C25A	1.572 (7)
C9—H9A	0.9700	C23—C25	1.572 (6)
C9—H9B	0.9700	C23—C24	1.574 (6)
C10—H10A	0.9700	C24—H24A	0.9600
C10—H10B	0.9700	C24—H24B	0.9600
C11—C13	1.542 (6)	C24—H24C	0.9600
C11—C14	1.546 (6)	C25—H25A	0.9600
C11—C12	1.553 (6)	C25—H25B	0.9600
C12—H12A	0.9600	C25—H25C	0.9600
C12—H12B	0.9600	C26—H26A	0.9600
C12—H12C	0.9600	C26—H26B	0.9600
C13—H13A	0.9600	C26—H26C	0.9600
C13—H13B	0.9600	C24A—H24D	0.9600
C13—H13C	0.9600	C24A—H24E	0.9600
C14—H14A	0.9600	C24A—H24F	0.9600
C14—H14B	0.9600	C25A—H25D	0.9600
C14—H14C	0.9600	C25A—H25E	0.9600
C15—C18	1.534 (6)	C25A—H25F	0.9600
C15—C16	1.536 (6)	C26A—H26D	0.9600
C15—C17	1.557 (6)	C26A—H26E	0.9600
C16—H16A	0.9600	C26A—H26F	0.9600
C16—H16B	0.9600	Cl2—C27	1.755 (8)
C16—H16C	0.9600	Cl3—C27	1.759 (8)
C17—H17A	0.9600	C27—H27A	0.9700
C17—H17B	0.9600	C27—H27B	0.9700
C17—H17C	0.9600	Cl2A—C27A	1.755 (10)
C18—H18A	0.9600	Cl3A—C27A	1.757 (10)
C18—H18B	0.9600	C27A—H27C	0.9700
C18—H18C	0.9600	C27A—H27D	0.9700
C19—C22	1.562 (6)

C2—Pd—S1	85.33 (10)	C22—C19—C21	111.0 (5)
C2—Pd—S2	83.78 (10)	C20—C19—C21	110.4 (5)
S1—Pd—S2	168.00 (4)	C20A—C19—C21	93.8 (13)
C2—Pd—Cl1	175.31 (10)	C22A—C19—C21	131.5 (13)
S1—Pd—Cl1	92.10 (4)	C22—C19—S3	106.4 (8)
S2—Pd—Cl1	98.41 (4)	C21A—C19—S3	108.7 (14)
C7—S1—C11	103.7 (2)	C20—C19—S3	107.6 (7)
C7—S1—Pd	100.17 (11)	C20A—C19—S3	117.9 (17)
C11—S1—Pd	109.11 (14)	C22A—C19—S3	95.3 (13)
C8—S2—C15	103.53 (19)	C21—C19—S3	109.3 (6)
C8—S2—Pd	99.85 (12)	C19—C20—H20A	109.5
C15—S2—Pd	117.30 (14)	C19—C20—H20B	109.5
C10—S3—C19	103.9 (2)	H20A—C20—H20B	109.5
C9—S4—C23	103.79 (18)	C19—C20—H20C	109.5
C6—C1—C2	120.9 (3)	H20A—C20—H20C	109.5
C6—C1—C7	120.4 (3)	H20B—C20—H20C	109.5
C2—C1—C7	118.6 (3)	C19—C21—H21A	109.5
C1—C2—C3	119.5 (3)	C19—C21—H21B	109.5
C1—C2—Pd	120.4 (3)	H21A—C21—H21B	109.5
C3—C2—Pd	120.0 (3)	C19—C21—H21C	109.5
C2—C3—C4	119.7 (3)	H21A—C21—H21C	109.5
C2—C3—C8	119.0 (3)	H21B—C21—H21C	109.5
C4—C3—C8	121.3 (3)	C19—C22—H22A	109.5
C5—C4—C3	119.4 (3)	C19—C22—H22B	109.5
C5—C4—C10	120.1 (3)	H22A—C22—H22B	109.5
C3—C4—C10	120.5 (3)	C19—C22—H22C	109.5
C4—C5—C6	122.0 (3)	H22A—C22—H22C	109.5
C4—C5—H5	119.0	H22B—C22—H22C	109.5
C6—C5—H5	119.0	C19—C20A—H20D	109.5
C1—C6—C5	118.5 (3)	C19—C20A—H20E	109.5
C1—C6—C9	122.1 (3)	H20D—C20A—H20E	109.5
C5—C6—C9	119.4 (3)	C19—C20A—H20F	109.5
C1—C7—S1	111.8 (2)	H20D—C20A—H20F	109.5
C1—C7—H7A	109.3	H20E—C20A—H20F	109.5
S1—C7—H7A	109.3	C19—C21A—H21D	109.5
C1—C7—H7B	109.3	C19—C21A—H21E	109.5
S1—C7—H7B	109.3	H21D—C21A—H21E	109.5
H7A—C7—H7B	107.9	C19—C21A—H21F	109.5
C3—C8—S2	108.3 (3)	H21D—C21A—H21F	109.5
C3—C8—H8A	110.0	H21E—C21A—H21F	109.5
S2—C8—H8A	110.0	C19—C22A—H22D	109.5
C3—C8—H8B	110.0	C19—C22A—H22E	109.5
S2—C8—H8B	110.0	H22D—C22A—H22E	109.5
H8A—C8—H8B	108.4	C19—C22A—H22F	109.5
C6—C9—S4	108.6 (2)	H22D—C22A—H22F	109.5
C6—C9—H9A	110.0	H22E—C22A—H22F	109.5
S4—C9—H9A	110.0	C24A—C23—C26	91.4 (10)
C6—C9—H9B	110.0	C24A—C23—C26A	111.3 (6)
S4—C9—H9B	110.0	C24A—C23—C25A	111.0 (6)
H9A—C9—H9B	108.4	C26—C23—C25A	125.2 (15)
C4—C10—S3	108.2 (3)	C26A—C23—C25A	110.7 (6)
C4—C10—H10A	110.1	C24A—C23—C25	111.1 (16)
S3—C10—H10A	110.1	C26—C23—C25	110.6 (5)
C4—C10—H10B	110.1	C26A—C23—C25	97.7 (14)
S3—C10—H10B	110.1	C26—C23—C24	110.3 (5)
H10A—C10—H10B	108.4	C26A—C23—C24	130.7 (10)
C13—C11—C14	111.3 (4)	C25A—C23—C24	104.7 (14)
C13—C11—C12	109.9 (4)	C25—C23—C24	110.3 (5)
C14—C11—C12	111.0 (4)	C24A—C23—S4	121.8 (14)
C13—C11—S1	111.8 (3)	C26—C23—S4	113.0 (8)
C14—C11—S1	107.1 (3)	C26A—C23—S4	104.2 (12)
C12—C11—S1	105.7 (3)	C25A—C23—S4	96.8 (13)
C11—C12—H12A	109.5	C25—C23—S4	107.9 (9)
C11—C12—H12B	109.5	C24—C23—S4	104.5 (8)
H12A—C12—H12B	109.5	C23—C24—H24A	109.5
C11—C12—H12C	109.5	C23—C24—H24B	109.5
H12A—C12—H12C	109.5	H24A—C24—H24B	109.5
H12B—C12—H12C	109.5	C23—C24—H24C	109.5
C11—C13—H13A	109.5	H24A—C24—H24C	109.5
C11—C13—H13B	109.5	H24B—C24—H24C	109.5
H13A—C13—H13B	109.5	C23—C25—H25A	109.5
C11—C13—H13C	109.5	C23—C25—H25B	109.5
H13A—C13—H13C	109.5	H25A—C25—H25B	109.5
H13B—C13—H13C	109.5	C23—C25—H25C	109.5
C11—C14—H14A	109.5	H25A—C25—H25C	109.5
C11—C14—H14B	109.5	H25B—C25—H25C	109.5
H14A—C14—H14B	109.5	C23—C26—H26A	109.5
C11—C14—H14C	109.5	C23—C26—H26B	109.5
H14A—C14—H14C	109.5	H26A—C26—H26B	109.5
H14B—C14—H14C	109.5	C23—C26—H26C	109.5
C18—C15—C16	111.8 (4)	H26A—C26—H26C	109.5
C18—C15—C17	109.8 (4)	H26B—C26—H26C	109.5
C16—C15—C17	111.7 (4)	C23—C24A—H24D	109.5
C18—C15—S2	107.4 (3)	C23—C24A—H24E	109.5
C16—C15—S2	111.1 (3)	H24D—C24A—H24E	109.5
C17—C15—S2	104.7 (3)	C23—C24A—H24F	109.5
C15—C16—H16A	109.5	H24D—C24A—H24F	109.5
C15—C16—H16B	109.5	H24E—C24A—H24F	109.5
H16A—C16—H16B	109.5	C23—C25A—H25D	109.5
C15—C16—H16C	109.5	C23—C25A—H25E	109.5
H16A—C16—H16C	109.5	H25D—C25A—H25E	109.5
H16B—C16—H16C	109.5	C23—C25A—H25F	109.5
C15—C17—H17A	109.5	H25D—C25A—H25F	109.5
C15—C17—H17B	109.5	H25E—C25A—H25F	109.5
H17A—C17—H17B	109.5	C23—C26A—H26D	109.5
C15—C17—H17C	109.5	C23—C26A—H26E	109.5
H17A—C17—H17C	109.5	H26D—C26A—H26E	109.5
H17B—C17—H17C	109.5	C23—C26A—H26F	109.5
C15—C18—H18A	109.5	H26D—C26A—H26F	109.5
C15—C18—H18B	109.5	H26E—C26A—H26F	109.5
H18A—C18—H18B	109.5	Cl2—C27—Cl3	112.1 (5)
C15—C18—H18C	109.5	Cl2—C27—H27A	109.2
H18A—C18—H18C	109.5	Cl3—C27—H27A	109.2
H18B—C18—H18C	109.5	Cl2—C27—H27B	109.2
C22—C19—C21A	91.2 (13)	Cl3—C27—H27B	109.2
C22—C19—C20	112.0 (5)	H27A—C27—H27B	107.9
C21A—C19—C20	128.4 (15)	Cl2A—C27A—Cl3A	111.7 (7)
C22—C19—C20A	117.7 (19)	Cl2A—C27A—H27C	109.3
C21A—C19—C20A	111.5 (7)	Cl3A—C27A—H27C	109.3
C21A—C19—C22A	111.3 (7)	Cl2A—C27A—H27D	109.3
C20—C19—C22A	100.4 (16)	Cl3A—C27A—H27D	109.3
C20A—C19—C22A	111.0 (7)	H27C—C27A—H27D	107.9

Experimental details

Crystal data
Chemical formula	[Pd(C₂₆H₄₅S₄)Cl]·CH₂Cl₂
M_r	712.64
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	15.917 (15), 13.768 (13), 17.808 (16)
β (°)	105.216 (15)
V (Å³)	3766 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.94
Crystal size (mm)	0.27 × 0.22 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Integration (SADABS; Sheldrick, 1996)
T_min, T_max	0.593, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	28207, 6570, 5144
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.110, 1.03
No. of reflections	6570
No. of parameters	406
No. of restraints	291
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.24

Computer programs: SMART (Bruker, 1999), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Pd—C2	2.022 (4)	Pd—S2	2.333 (2)
Pd—S1	2.326 (2)	Pd—Cl1	2.441 (2)

Acknowledgements

EPM would like to thank CONACYT for a postdoctoral scholarship (postdoctoral agreement No. 290662 UNAM). The financial support of this research by CONACYT (CB2010–154732) and DGAPA-UNAM (IN201711) is gratefully acknowledged. SHO would like to thank the Consejo Superior de Investigaciones Científicas (CSIC) of Spain for the award of a licence for the use of the Cambridge Structural Database.

References

Arroyo, M., Cervantes, R., Gómez-Benitez, V., López, P., Morales-Morales, D., Torrens, H. & Toscano, R. A. (2003). Synthesis, pp. 1565–1568. Web of Science CSD CrossRef Google Scholar
Bruker (1999). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Errington, J., McDonald, W. S. & Shaw, B. L. (1980). J. Chem. Soc. Dalton Trans. pp. 2312–2314. CSD CrossRef Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Loeb, S. J., Shimizu, K. H. G. & Wisner, J. A. (1998). Organometallics, 17, 2324–2327. Web of Science CSD CrossRef CAS Google Scholar
Morales-Morales, D. & Jensen, C. M. (2007). In The Chemistry of Pincer Compounds. Amsterdam: Elsevier. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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