trans-Chlorido­(4-fluoro­benzene­thiol­ato-κS)bis­(tri­phenyl­phosphane-κP)palladium(II) methanol hemisolvate

Avila-Sorrosa, A.; Santacruz-Juárez, E.; Reyes-Arellano, A.; Reyes-Martínez, R.; Morales-Morales, D.

doi:10.1107/S1600536814002499

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 3| March 2014| Pages m92-m93

doi:10.1107/S1600536814002499

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trans-Chlorido(4-fluorobenzenethiolato-κS)bis(triphenylphosphane-κP)palladium(II) methanol hemisolvate

Alcives Avila-Sorrosa,^a ^* Ericka Santacruz-Juárez,^b Alicia Reyes-Arellano,^a Reyna Reyes-Martínez ^c and David Morales-Morales ^c

^aEscuela Nacional de Ciencias Biológicas, IPN, Departamento de Química Orgánica, Caprio y Plan de Ayala S/N, Colonia Santo Tomás, 11340 México DF, Mexico, ^bUniversidad Politécnica de Tlaxcala, Av. Universidad Politécnica de Tlaxcala No. 1, San Pedro Xalcaltzinco Municipio de Tepeyanco, Tlaxcala, CP 90180, Mexico, and ^cInstituto de Química, Universidad Nacional Autónoma de México, Circuito exterior, Ciudad Universitaria, México, DF 04510, Mexico
^*Correspondence e-mail: aavilas@ipn.mx

(Received 24 January 2014; accepted 3 February 2014; online 12 February 2014)

The title compound, [Pd(SC₆H₄F-p)Cl(PPh₃)₂]·0.5CH₃OH, features a Pd^II complex with two triphenylphosphane (PPh₃) ligands arranged in a trans conformation, with one chloride and one 4-fluorobenzenethiolate ligand completing the coordination sphere, giving rise to a slightly distorted square-planar geometry of the Pd^II ion. The methanol solvent molecule is disordered about an inversion centre with an occupancy of 0.25 for each molecule. In the crystal, weak C—H⋯Cl hydrogen-bonding interactions between the complex molecules generate chain frameworks parallel to [010].

CCDC reference: 984868

Related literature

For palladium complexes in catalysis, see: Frisch & Beller (2005 ); Yin & Liebscher (2007 ); Knochel & Singer (1993 ); Surry & Buchwald (2008 ). For related compounds, see: Jones et al. (2000 ); Alvarez-Larena et al. (1993 ).

Experimental

Crystal data

[Pd(C₆H₄FS)Cl(C₁₈H₁₅P)₂]·0.5CH₄O
M_r = 809.56
Monoclinic, P 2₁ /c
a = 18.9189 (16) Å
b = 9.6909 (8) Å
c = 21.6179 (18) Å
β = 106.212 (1)°
V = 3805.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ) T_min = 0.822, T_max = 0.947
30189 measured reflections
6950 independent reflections
5392 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.110
S = 1.02
6950 reflections
469 parameters
33 restraints
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C34—H34⋯Cl1ⁱ	0.93	2.99	3.631 (5)	127
C35—H35⋯Cl1ⁱ	0.93	2.97	3.616 (4)	128
Symmetry code: (i) x, y-1, z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 984868

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814002499/hp2065sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814002499/hp2065Isup2.hkl

checkCIF report

Introduction top

The high efficiency of palladium complexes in C—C cross coupling reactions is well known, for example in the Suzuki-Miyaura (Frisch & Beller, 2005), Mizoroki-Heck (Yin & Liebscher, 2007) and Negishi reactions (Knochel & Singer, 1993), as well as for the formation of C-Heteroatom bonds as in the Buchwald–Hartwig couplings (Surry & Buchwald, 2008). In this context, different research groups have devoted their research efforts to the synthesis of new palladium complexes with a variety of ligands. Therefore, in this opportunity we would like to report the crystal structure of the Pd^II complex trans-[Pd(SC₆H₄F-p)(Cl)(PPh₃)₂] ·0.5CH₃OH.

Experimental top

Synthesis and crystallization top

To a suspension consisting of PdCl₂ (0.072 g, 0.41 mmol) and Na₂CO₃ (0.050 g, 0.0471 mmol) in 15 mL of toluene was added dropwise under magnetic stirring a toluene solution (5 mL) of an isomeric mix of (3-ethenylbenzyl)(4-fluorophenyl)sulfane and (4-ethenylbenzyl)(4-fluorophenyl)sulfane (60:40) (0.100 g, 0.41 mmol). The resulting mixture was set to reflux for 4 hours. After this time the reaction mixture was allowed to cool down to room temperature, filtered and the solid product washed with CHCl₃. The insoluble reddish solid was then suspended in 15 mL of CHCl₃ and then treated with Ph₃P (0.215 g, 820 mmol). The reaction was allowed to proceed under stirring until the solid was completely dissolved. This solution was then filtered through a short plug of celite and CH₃OH was added to promote precipitation. Slow evaporation of the solvent at room temperature produced brown crystals for X-ray diffraction analysis of trans-[Pd(SC₆H₄F-p)(Cl)(PPh₃)₂] ·0.5CH₃OH.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were included in calculated positions (C—H = 0.93 Å for aromatic H) and refined using a riding model with U_iso(H) = 1.2 U_eq of carrier atoms. The CH₃OH solvent is disordered over two sets of sites in a 0.25 : 0.25 ratio.

Results and discussion top

The compound trans-[Pd(SC₆H₄F-p)(Cl)(PPh₃)₂] ·0.5CH₃OH crystallized in a monoclinic system including the complex trans-[Pd(SC₆H₄F-p)(Cl)(PPh₃)₂] and half molecule of methanol in the asymmetric unit. The Pd²⁺ ion exhibits a slightly distorted square-planar PdClSP₂ geometry, with one chloride and one p-fluorobenzenethiolate ligand and two molecules of triphenylphosphane in trans conformation completing the coordination sphere. The bond distances Pd—Cl and Pd—S are 2.3269 (11) and 2.2977 (11) Å, respectively, and the Pd—P distances are 2.3432 (11) and 2.3342 (11) Å. These distances are comparable to those found in the structures of the related compounds trans-[Pd(SC₆H₄Cl-p)(Cl)(PPh₃)₂] (Jones et al., 2000) and trans-[Pd(SC₆H₅)(Cl)(PPh₃)₂] (Alvarez-Larena et al., 1993).

The p-fluorobenzenethiolate presents an intramolecular π-π interaction with one phenyl ring of the tripehylphosphane ligand. The distance between centroids Cg(C1—C6)-Cg(C7—C12) is 3.677 (3) Å. The structure is stabilized by weak C—H···Cl hydrogen bonding interactions between the complex molecules generate chain frameworks parallel to [010]. The methanol molecule is disordered over two positions in a 0.25:0.25 ratio.

Related literature top

For palladium complexes in catalysis, see: Frisch & Beller (2005); Yin & Liebscher (2007); Knochel & Singer (1993); Surry & Buchwald (2008). For related compounds, see: Jones et al. (2000); Alvarez-Larena et al. (1993).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of the title compound showing the atom-labelling and displacement ellipsoids drawn at 40% probability level. The hydrogen atoms were omitted.
	Fig. 2. A portion of the crystal structure showing weak hydrogen bonds by dashed lines.

trans-Chlorido(4-fluorobenzenethiolato-κS)bis(triphenylphosphane-κP)palladium(II) methanol hemisolvate top

Crystal data top

[Pd(C₆H₄FS)Cl(C₁₈H₁₅P)₂]·0.5CH₄O	F(000) = 1652
M_r = 809.56	D_x = 1.413 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.9189 (16) Å	Cell parameters from 8442 reflections
b = 9.6909 (8) Å	θ = 2.3–25.1°
c = 21.6179 (18) Å	µ = 0.73 mm⁻¹
β = 106.212 (1)°	T = 298 K
V = 3805.8 (6) Å³	Plates, dark-pink
Z = 4	0.30 × 0.20 × 0.08 mm

Data collection top

Bruker SMART APEX CCD diffractometer	6950 independent reflections
Radiation source: fine-focus sealed tube	5392 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
Detector resolution: 8.333 pixels mm^-1	θ_max = 25.4°, θ_min = 2.0°
ω–scans	h = −22→22
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	k = −11→11
T_min = 0.822, T_max = 0.947	l = −26→26
30189 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)] = 0.043	Hydrogen site location: mixed
wR(F²) = 0.110	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0613P)²] where P = (F_o² + 2F_c²)/3
6950 reflections	(Δ/σ)_max < 0.001
469 parameters	Δρ_max = 0.57 e Å⁻³
33 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Pd(C₆H₄FS)Cl(C₁₈H₁₅P)₂]·0.5CH₄O	V = 3805.8 (6) Å³
M_r = 809.56	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.9189 (16) Å	µ = 0.73 mm⁻¹
b = 9.6909 (8) Å	T = 298 K
c = 21.6179 (18) Å	0.30 × 0.20 × 0.08 mm
β = 106.212 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	6950 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	5392 reflections with I > 2σ(I)
T_min = 0.822, T_max = 0.947	R_int = 0.052
30189 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	33 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.02	Δρ_max = 0.57 e Å⁻³
6950 reflections	Δρ_min = −0.28 e Å⁻³
469 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pd1	0.24393 (2)	0.02208 (3)	0.14849 (2)	0.04003 (11)
Cl1	0.19542 (6)	0.18164 (10)	0.06730 (5)	0.0558 (3)
S1	0.29295 (6)	−0.13516 (10)	0.22852 (5)	0.0519 (2)
P1	0.15593 (5)	0.09096 (10)	0.19997 (5)	0.0437 (2)
P2	0.33009 (5)	−0.06767 (10)	0.10028 (5)	0.0424 (2)
F1	0.44844 (17)	0.1686 (4)	0.46211 (14)	0.1094 (11)
C1	0.3380 (2)	−0.0375 (4)	0.29652 (19)	0.0517 (10)
C2	0.3650 (2)	0.0954 (5)	0.2943 (2)	0.0615 (11)
H2	0.3584	0.1383	0.2547	0.074*
C3	0.4012 (2)	0.1645 (5)	0.3494 (2)	0.0658 (12)
H3	0.4181	0.2540	0.3473	0.079*
C4	0.4120 (2)	0.1002 (6)	0.4074 (2)	0.0736 (13)
C5	0.3885 (3)	−0.0311 (6)	0.4122 (2)	0.0740 (13)
H5	0.3977	−0.0742	0.4521	0.089*
C6	0.3510 (2)	−0.0987 (5)	0.3569 (2)	0.0623 (11)
H6	0.3338	−0.1876	0.3599	0.075*
C7	0.1691 (2)	0.0487 (4)	0.28479 (19)	0.0495 (9)
C8	0.1943 (2)	0.1436 (5)	0.33324 (19)	0.0658 (12)
H8	0.2035	0.2338	0.3230	0.079*
C9	0.2059 (3)	0.1061 (7)	0.3973 (2)	0.0877 (16)
H9	0.2233	0.1714	0.4295	0.105*
C10	0.1924 (3)	−0.0239 (8)	0.4135 (3)	0.098 (2)
H10	0.2003	−0.0483	0.4565	0.117*
C11	0.1666 (3)	−0.1204 (6)	0.3652 (3)	0.0883 (16)
H11	0.1560	−0.2095	0.3759	0.106*
C12	0.1564 (2)	−0.0862 (5)	0.3015 (2)	0.0677 (12)
H12	0.1411	−0.1529	0.2696	0.081*
C13	0.1360 (2)	0.2754 (4)	0.19518 (17)	0.0507 (9)
C14	0.0647 (3)	0.3255 (5)	0.1726 (2)	0.0717 (13)
H14	0.0255	0.2641	0.1600	0.086*
C15	0.0516 (4)	0.4662 (6)	0.1687 (3)	0.1000 (19)
H15	0.0037	0.4986	0.1526	0.120*
C16	0.1081 (5)	0.5574 (6)	0.1883 (3)	0.099 (2)
H16	0.0987	0.6518	0.1858	0.119*
C17	0.1799 (4)	0.5098 (5)	0.2121 (3)	0.0893 (17)
H17	0.2186	0.5716	0.2266	0.107*
C18	0.1931 (3)	0.3675 (5)	0.2140 (2)	0.0670 (12)
H18	0.2412	0.3350	0.2281	0.080*
C19	0.0685 (2)	0.0080 (4)	0.1601 (2)	0.0574 (11)
C20	0.0565 (3)	−0.0437 (5)	0.0987 (2)	0.0761 (14)
H20	0.0931	−0.0360	0.0779	0.091*
C21	−0.0097 (3)	−0.1070 (7)	0.0675 (3)	0.103 (2)
H21	−0.0182	−0.1391	0.0255	0.123*
C22	−0.0624 (3)	−0.1214 (8)	0.0995 (3)	0.117 (2)
H22	−0.1064	−0.1657	0.0793	0.141*
C23	−0.0514 (3)	−0.0726 (8)	0.1596 (3)	0.116 (2)
H23	−0.0876	−0.0830	0.1808	0.139*
C24	0.0138 (3)	−0.0069 (6)	0.1899 (3)	0.0874 (17)
H24	0.0208	0.0278	0.2313	0.105*
C25	0.4207 (2)	−0.0086 (4)	0.14525 (19)	0.0488 (9)
C26	0.4425 (2)	0.1222 (4)	0.1350 (2)	0.0678 (12)
H26	0.4125	0.1769	0.1029	0.081*
C27	0.5096 (3)	0.1733 (5)	0.1729 (3)	0.0836 (15)
H27	0.5242	0.2621	0.1657	0.100*
C28	0.5541 (3)	0.0943 (6)	0.2205 (3)	0.0838 (16)
H28	0.5993	0.1287	0.2447	0.101*
C29	0.5330 (3)	−0.0320 (6)	0.2322 (2)	0.0754 (14)
H29	0.5628	−0.0841	0.2655	0.091*
C30	0.4664 (2)	−0.0865 (5)	0.1947 (2)	0.0625 (11)
H30	0.4525	−0.1752	0.2028	0.075*
C31	0.33212 (19)	−0.2558 (4)	0.09877 (16)	0.0434 (8)
C32	0.3926 (2)	−0.3279 (4)	0.09171 (19)	0.0536 (10)
H32	0.4351	−0.2801	0.0910	0.064*
C33	0.3907 (3)	−0.4696 (4)	0.0857 (2)	0.0641 (11)
H33	0.4318	−0.5175	0.0817	0.077*
C34	0.3277 (3)	−0.5392 (4)	0.0857 (2)	0.0674 (12)
H34	0.3263	−0.6347	0.0815	0.081*
C35	0.2672 (3)	−0.4707 (4)	0.0917 (2)	0.0601 (11)
H35	0.2246	−0.5193	0.0913	0.072*
C36	0.2691 (2)	−0.3287 (4)	0.09834 (18)	0.0530 (10)
H36	0.2278	−0.2819	0.1025	0.064*
C37	0.3254 (2)	−0.0314 (4)	0.01670 (19)	0.0487 (9)
C38	0.2591 (3)	−0.0288 (4)	−0.0293 (2)	0.0655 (12)
H38	0.2160	−0.0342	−0.0167	0.079*
C39	0.2546 (3)	−0.0181 (5)	−0.0945 (2)	0.0776 (14)
H39	0.2090	−0.0179	−0.1252	0.093*
C40	0.3169 (3)	−0.0081 (5)	−0.1131 (3)	0.0799 (15)
H40	0.3138	0.0013	−0.1566	0.096*
C41	0.3848 (3)	−0.0118 (6)	−0.0684 (3)	0.0891 (17)
H41	0.4274	−0.0064	−0.0817	0.107*
C42	0.3896 (3)	−0.0232 (5)	−0.0041 (2)	0.0780 (14)
H42	0.4356	−0.0257	0.0260	0.094*
O1	0.0542 (7)	1.0384 (15)	0.5041 (6)	0.077 (4)	0.25
H1	0.0112	1.0626	0.4896	0.115*	0.25
C43	0.0682 (13)	0.889 (3)	0.5018 (13)	0.071 (4)	0.25
H43A	0.0231	0.8397	0.4971	0.086*	0.25
H43B	0.1036	0.8617	0.5409	0.086*	0.25
H43C	0.0869	0.8698	0.4658	0.086*	0.25
O1B	0.0386 (8)	0.928 (2)	0.5026 (8)	0.084 (4)	0.25
H1B	0.0521	0.9888	0.4820	0.125*	0.25
C43B	0.0690 (11)	0.808 (2)	0.4885 (10)	0.079 (4)	0.25
H43D	0.0340	0.7605	0.4542	0.094*	0.25
H43E	0.0821	0.7499	0.5260	0.094*	0.25
H43F	0.1123	0.8284	0.4752	0.094*	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.04087 (17)	0.03949 (17)	0.03993 (17)	−0.00118 (12)	0.01160 (12)	−0.00155 (12)
Cl1	0.0686 (6)	0.0477 (6)	0.0503 (6)	0.0034 (5)	0.0151 (5)	0.0052 (4)
S1	0.0627 (6)	0.0458 (5)	0.0468 (6)	0.0065 (5)	0.0147 (5)	0.0020 (4)
P1	0.0414 (5)	0.0484 (6)	0.0416 (5)	−0.0008 (4)	0.0119 (4)	−0.0012 (4)
P2	0.0429 (5)	0.0412 (5)	0.0446 (5)	−0.0017 (4)	0.0147 (4)	−0.0026 (4)
F1	0.100 (2)	0.147 (3)	0.0691 (19)	−0.022 (2)	0.0042 (17)	−0.0266 (19)
C1	0.047 (2)	0.056 (2)	0.053 (2)	0.0114 (18)	0.0148 (18)	0.0026 (19)
C2	0.055 (2)	0.069 (3)	0.060 (3)	0.003 (2)	0.016 (2)	0.006 (2)
C3	0.054 (3)	0.076 (3)	0.064 (3)	−0.011 (2)	0.011 (2)	−0.008 (2)
C4	0.058 (3)	0.102 (4)	0.053 (3)	−0.002 (3)	0.002 (2)	−0.016 (3)
C5	0.072 (3)	0.095 (4)	0.049 (3)	0.017 (3)	0.008 (2)	0.007 (3)
C6	0.069 (3)	0.066 (3)	0.052 (3)	0.011 (2)	0.018 (2)	0.005 (2)
C7	0.046 (2)	0.059 (3)	0.046 (2)	0.0070 (18)	0.0166 (18)	0.0041 (19)
C8	0.074 (3)	0.078 (3)	0.045 (2)	0.021 (2)	0.015 (2)	−0.005 (2)
C9	0.089 (4)	0.118 (5)	0.054 (3)	0.032 (3)	0.015 (3)	−0.008 (3)
C10	0.099 (4)	0.146 (6)	0.051 (3)	0.033 (4)	0.027 (3)	0.027 (4)
C11	0.090 (4)	0.102 (4)	0.077 (4)	0.008 (3)	0.029 (3)	0.038 (3)
C12	0.068 (3)	0.077 (3)	0.057 (3)	0.000 (2)	0.017 (2)	0.007 (2)
C13	0.064 (3)	0.052 (2)	0.041 (2)	0.006 (2)	0.0214 (19)	−0.0009 (18)
C14	0.075 (3)	0.068 (3)	0.070 (3)	0.021 (2)	0.016 (2)	0.001 (2)
C15	0.123 (5)	0.085 (4)	0.088 (4)	0.049 (4)	0.024 (4)	0.004 (3)
C16	0.171 (7)	0.058 (3)	0.076 (4)	0.031 (4)	0.045 (4)	0.009 (3)
C17	0.134 (5)	0.067 (4)	0.076 (4)	−0.018 (3)	0.045 (4)	−0.008 (3)
C18	0.078 (3)	0.055 (3)	0.073 (3)	−0.003 (2)	0.029 (3)	0.000 (2)
C19	0.048 (2)	0.069 (3)	0.052 (3)	−0.0102 (19)	0.010 (2)	0.003 (2)
C20	0.067 (3)	0.094 (4)	0.064 (3)	−0.030 (3)	0.013 (2)	−0.005 (3)
C21	0.093 (4)	0.137 (5)	0.068 (3)	−0.055 (4)	0.005 (3)	−0.010 (3)
C22	0.084 (4)	0.173 (7)	0.083 (4)	−0.069 (4)	0.002 (3)	0.009 (4)
C23	0.054 (3)	0.208 (7)	0.083 (4)	−0.041 (4)	0.013 (3)	0.023 (5)
C24	0.053 (3)	0.145 (5)	0.063 (3)	−0.022 (3)	0.014 (2)	−0.003 (3)
C25	0.050 (2)	0.044 (2)	0.054 (2)	−0.0033 (17)	0.0162 (19)	−0.0112 (18)
C26	0.060 (3)	0.052 (3)	0.095 (3)	−0.006 (2)	0.027 (2)	−0.005 (2)
C27	0.078 (3)	0.062 (3)	0.118 (5)	−0.028 (3)	0.039 (3)	−0.026 (3)
C28	0.052 (3)	0.093 (4)	0.104 (4)	−0.022 (3)	0.019 (3)	−0.046 (4)
C29	0.060 (3)	0.095 (4)	0.066 (3)	−0.010 (3)	0.008 (2)	−0.022 (3)
C30	0.057 (3)	0.069 (3)	0.057 (3)	−0.011 (2)	0.009 (2)	−0.009 (2)
C31	0.048 (2)	0.042 (2)	0.039 (2)	−0.0035 (16)	0.0102 (16)	−0.0041 (16)
C32	0.047 (2)	0.053 (2)	0.061 (3)	0.0034 (18)	0.0162 (19)	0.001 (2)
C33	0.068 (3)	0.053 (3)	0.072 (3)	0.016 (2)	0.020 (2)	0.000 (2)
C34	0.089 (4)	0.042 (2)	0.071 (3)	0.001 (2)	0.023 (3)	−0.002 (2)
C35	0.070 (3)	0.046 (2)	0.067 (3)	−0.018 (2)	0.025 (2)	−0.006 (2)
C36	0.051 (2)	0.053 (2)	0.060 (3)	−0.0027 (18)	0.022 (2)	−0.0062 (19)
C37	0.057 (2)	0.042 (2)	0.049 (2)	0.0004 (18)	0.019 (2)	0.0006 (17)
C38	0.067 (3)	0.070 (3)	0.061 (3)	−0.004 (2)	0.019 (2)	−0.007 (2)
C39	0.081 (3)	0.093 (4)	0.053 (3)	0.010 (3)	0.008 (3)	−0.001 (2)
C40	0.109 (4)	0.080 (4)	0.056 (3)	0.009 (3)	0.031 (3)	0.007 (2)
C41	0.086 (4)	0.126 (5)	0.067 (3)	0.007 (3)	0.040 (3)	0.013 (3)
C42	0.061 (3)	0.112 (4)	0.064 (3)	0.004 (3)	0.021 (2)	0.007 (3)
O1	0.051 (6)	0.131 (10)	0.048 (5)	−0.026 (7)	0.014 (5)	0.006 (7)
C43	0.040 (7)	0.134 (10)	0.045 (6)	−0.025 (9)	0.020 (7)	0.000 (8)
O1B	0.055 (7)	0.153 (11)	0.048 (5)	−0.042 (8)	0.023 (6)	0.003 (7)
C43B	0.051 (7)	0.141 (12)	0.045 (8)	−0.036 (9)	0.016 (6)	0.022 (9)

Geometric parameters (Å, º) top

Pd1—S1	2.2976 (10)	C21—H21	0.9300
Pd1—Cl1	2.3269 (10)	C22—C23	1.345 (8)
Pd1—P2	2.3342 (10)	C22—H22	0.9300
Pd1—P1	2.3432 (10)	C23—C24	1.380 (7)
S1—C1	1.756 (4)	C23—H23	0.9300
P1—C13	1.824 (4)	C24—H24	0.9300
P1—C19	1.825 (4)	C25—C26	1.369 (5)
P1—C7	1.827 (4)	C25—C30	1.394 (6)
P2—C25	1.812 (4)	C26—C27	1.396 (6)
P2—C37	1.818 (4)	C26—H26	0.9300
P2—C31	1.824 (4)	C27—C28	1.368 (7)
F1—C4	1.364 (5)	C27—H27	0.9300
C1—C2	1.391 (6)	C28—C29	1.333 (7)
C1—C6	1.392 (6)	C28—H28	0.9300
C2—C3	1.371 (6)	C29—C30	1.398 (6)
C2—H2	0.9300	C29—H29	0.9300
C3—C4	1.362 (6)	C30—H30	0.9300
C3—H3	0.9300	C31—C36	1.384 (5)
C4—C5	1.362 (7)	C31—C32	1.385 (5)
C5—C6	1.374 (6)	C32—C33	1.380 (5)
C5—H5	0.9300	C32—H32	0.9300
C6—H6	0.9300	C33—C34	1.368 (6)
C7—C8	1.375 (6)	C33—H33	0.9300
C7—C12	1.394 (6)	C34—C35	1.362 (6)
C8—C9	1.389 (6)	C34—H34	0.9300
C8—H8	0.9300	C35—C36	1.384 (5)
C9—C10	1.351 (8)	C35—H35	0.9300
C9—H9	0.9300	C36—H36	0.9300
C10—C11	1.386 (8)	C37—C38	1.366 (6)
C10—H10	0.9300	C37—C42	1.410 (6)
C11—C12	1.376 (6)	C38—C39	1.394 (6)
C11—H11	0.9300	C38—H38	0.9300
C12—H12	0.9300	C39—C40	1.349 (7)
C13—C18	1.372 (6)	C39—H39	0.9300
C13—C14	1.388 (6)	C40—C41	1.376 (7)
C14—C15	1.384 (7)	C40—H40	0.9300
C14—H14	0.9300	C41—C42	1.371 (7)
C15—C16	1.361 (9)	C41—H41	0.9300
C15—H15	0.9300	C42—H42	0.9300
C16—C17	1.390 (9)	O1—C43	1.47 (2)
C16—H16	0.9300	O1—H1	0.8200
C17—C18	1.400 (7)	C43—H43A	0.9600
C17—H17	0.9300	C43—H43B	0.9600
C18—H18	0.9300	C43—H43C	0.9600
C19—C24	1.370 (6)	O1B—C43B	1.37 (2)
C19—C20	1.376 (6)	O1B—H1B	0.8199
C20—C21	1.389 (6)	C43B—H43D	0.9600
C20—H20	0.9300	C43B—H43E	0.9600
C21—C22	1.368 (8)	C43B—H43F	0.9600

S1—Pd1—Cl1	179.44 (4)	C22—C21—H21	120.5
S1—Pd1—P2	84.47 (4)	C20—C21—H21	120.5
Cl1—Pd1—P2	95.07 (4)	C23—C22—C21	121.0 (5)
S1—Pd1—P1	91.28 (4)	C23—C22—H22	119.5
Cl1—Pd1—P1	89.20 (4)	C21—C22—H22	119.5
P2—Pd1—P1	174.61 (4)	C22—C23—C24	119.8 (5)
C1—S1—Pd1	105.81 (14)	C22—C23—H23	120.1
C13—P1—C19	105.03 (19)	C24—C23—H23	120.1
C13—P1—C7	104.19 (17)	C19—C24—C23	121.2 (5)
C19—P1—C7	103.12 (19)	C19—C24—H24	119.4
C13—P1—Pd1	114.53 (12)	C23—C24—H24	119.4
C19—P1—Pd1	108.71 (14)	C26—C25—C30	118.4 (4)
C7—P1—Pd1	119.79 (12)	C26—C25—P2	119.2 (3)
C25—P2—C37	104.38 (18)	C30—C25—P2	122.1 (3)
C25—P2—C31	107.68 (17)	C25—C26—C27	119.9 (5)
C37—P2—C31	99.83 (16)	C25—C26—H26	120.1
C25—P2—Pd1	108.49 (12)	C27—C26—H26	120.1
C37—P2—Pd1	121.69 (13)	C28—C27—C26	120.7 (5)
C31—P2—Pd1	113.66 (12)	C28—C27—H27	119.6
C2—C1—C6	117.1 (4)	C26—C27—H27	119.6
C2—C1—S1	124.6 (3)	C29—C28—C27	120.1 (4)
C6—C1—S1	118.2 (3)	C29—C28—H28	119.9
C3—C2—C1	121.4 (4)	C27—C28—H28	119.9
C3—C2—H2	119.3	C28—C29—C30	120.4 (5)
C1—C2—H2	119.3	C28—C29—H29	119.8
C4—C3—C2	119.1 (4)	C30—C29—H29	119.8
C4—C3—H3	120.5	C25—C30—C29	120.4 (4)
C2—C3—H3	120.5	C25—C30—H30	119.8
C5—C4—C3	122.0 (4)	C29—C30—H30	119.8
C5—C4—F1	119.0 (5)	C36—C31—C32	118.6 (3)
C3—C4—F1	119.0 (5)	C36—C31—P2	119.2 (3)
C4—C5—C6	118.6 (4)	C32—C31—P2	121.9 (3)
C4—C5—H5	120.7	C33—C32—C31	120.7 (4)
C6—C5—H5	120.7	C33—C32—H32	119.6
C5—C6—C1	121.7 (4)	C31—C32—H32	119.6
C5—C6—H6	119.1	C34—C33—C32	119.4 (4)
C1—C6—H6	119.1	C34—C33—H33	120.3
C8—C7—C12	118.5 (4)	C32—C33—H33	120.3
C8—C7—P1	122.4 (3)	C35—C34—C33	121.0 (4)
C12—C7—P1	119.0 (3)	C35—C34—H34	119.5
C7—C8—C9	120.6 (5)	C33—C34—H34	119.5
C7—C8—H8	119.7	C34—C35—C36	119.8 (4)
C9—C8—H8	119.7	C34—C35—H35	120.1
C10—C9—C8	120.9 (5)	C36—C35—H35	120.1
C10—C9—H9	119.6	C35—C36—C31	120.4 (4)
C8—C9—H9	119.6	C35—C36—H36	119.8
C9—C10—C11	119.1 (5)	C31—C36—H36	119.8
C9—C10—H10	120.4	C38—C37—C42	117.7 (4)
C11—C10—H10	120.4	C38—C37—P2	120.4 (3)
C12—C11—C10	120.8 (5)	C42—C37—P2	121.3 (3)
C12—C11—H11	119.6	C37—C38—C39	121.4 (4)
C10—C11—H11	119.6	C37—C38—H38	119.3
C11—C12—C7	119.9 (5)	C39—C38—H38	119.3
C11—C12—H12	120.0	C40—C39—C38	119.7 (5)
C7—C12—H12	120.0	C40—C39—H39	120.1
C18—C13—C14	119.0 (4)	C38—C39—H39	120.1
C18—C13—P1	119.2 (3)	C39—C40—C41	120.7 (5)
C14—C13—P1	121.8 (3)	C39—C40—H40	119.7
C15—C14—C13	120.4 (5)	C41—C40—H40	119.7
C15—C14—H14	119.8	C42—C41—C40	119.9 (5)
C13—C14—H14	119.8	C42—C41—H41	120.0
C16—C15—C14	120.6 (6)	C40—C41—H41	120.0
C16—C15—H15	119.7	C41—C42—C37	120.5 (5)
C14—C15—H15	119.7	C41—C42—H42	119.7
C15—C16—C17	120.1 (5)	C37—C42—H42	119.7
C15—C16—H16	120.0	C43—O1—H1	115.9
C17—C16—H16	120.0	O1—C43—H43A	109.5
C16—C17—C18	119.0 (6)	O1—C43—H43B	109.5
C16—C17—H17	120.5	H43A—C43—H43B	109.5
C18—C17—H17	120.5	O1—C43—H43C	109.5
C13—C18—C17	120.9 (5)	H43A—C43—H43C	109.5
C13—C18—H18	119.6	H43B—C43—H43C	109.5
C17—C18—H18	119.6	C43B—O1B—H1B	106.1
C24—C19—C20	118.1 (4)	O1B—C43B—H43D	109.5
C24—C19—P1	121.9 (3)	O1B—C43B—H43E	109.5
C20—C19—P1	120.0 (3)	H43D—C43B—H43E	109.5
C19—C20—C21	120.9 (5)	O1B—C43B—H43F	109.5
C19—C20—H20	119.6	H43D—C43B—H43F	109.5
C21—C20—H20	119.6	H43E—C43B—H43F	109.5
C22—C21—C20	119.0 (5)

Pd1—S1—C1—C2	−24.8 (4)	C19—C20—C21—C22	−2.0 (9)
Pd1—S1—C1—C6	158.4 (3)	C20—C21—C22—C23	1.5 (11)
C6—C1—C2—C3	−1.6 (6)	C21—C22—C23—C24	−0.1 (12)
S1—C1—C2—C3	−178.5 (3)	C20—C19—C24—C23	0.4 (8)
C1—C2—C3—C4	1.3 (6)	P1—C19—C24—C23	−178.6 (5)
C2—C3—C4—C5	0.6 (7)	C22—C23—C24—C19	−0.9 (10)
C2—C3—C4—F1	179.5 (4)	C37—P2—C25—C26	51.5 (4)
C3—C4—C5—C6	−1.9 (7)	C31—P2—C25—C26	156.9 (3)
F1—C4—C5—C6	179.2 (4)	Pd1—P2—C25—C26	−79.6 (3)
C4—C5—C6—C1	1.5 (7)	C37—P2—C25—C30	−135.2 (3)
C2—C1—C6—C5	0.3 (6)	C31—P2—C25—C30	−29.8 (4)
S1—C1—C6—C5	177.4 (3)	Pd1—P2—C25—C30	93.7 (3)
C13—P1—C7—C8	−28.2 (4)	C30—C25—C26—C27	1.2 (6)
C19—P1—C7—C8	−137.7 (3)	P2—C25—C26—C27	174.8 (3)
Pd1—P1—C7—C8	101.5 (3)	C25—C26—C27—C28	−0.2 (7)
C13—P1—C7—C12	154.7 (3)	C26—C27—C28—C29	−1.5 (8)
C19—P1—C7—C12	45.2 (4)	C27—C28—C29—C30	2.1 (8)
Pd1—P1—C7—C12	−75.6 (3)	C26—C25—C30—C29	−0.7 (6)
C12—C7—C8—C9	−0.7 (6)	P2—C25—C30—C29	−174.0 (3)
P1—C7—C8—C9	−177.8 (3)	C28—C29—C30—C25	−1.0 (7)
C7—C8—C9—C10	−0.5 (7)	C25—P2—C31—C36	147.5 (3)
C8—C9—C10—C11	0.0 (8)	C37—P2—C31—C36	−103.8 (3)
C9—C10—C11—C12	1.6 (8)	Pd1—P2—C31—C36	27.3 (3)
C10—C11—C12—C7	−2.8 (7)	C25—P2—C31—C32	−38.9 (4)
C8—C7—C12—C11	2.3 (6)	C37—P2—C31—C32	69.7 (3)
P1—C7—C12—C11	179.5 (4)	Pd1—P2—C31—C32	−159.1 (3)
C19—P1—C13—C18	−171.9 (3)	C36—C31—C32—C33	−1.3 (6)
C7—P1—C13—C18	80.0 (3)	P2—C31—C32—C33	−174.9 (3)
Pd1—P1—C13—C18	−52.7 (3)	C31—C32—C33—C34	1.1 (7)
C19—P1—C13—C14	7.6 (4)	C32—C33—C34—C35	−0.3 (7)
C7—P1—C13—C14	−100.4 (3)	C33—C34—C35—C36	−0.4 (7)
Pd1—P1—C13—C14	126.8 (3)	C34—C35—C36—C31	0.1 (6)
C18—C13—C14—C15	0.4 (7)	C32—C31—C36—C35	0.7 (6)
P1—C13—C14—C15	−179.1 (4)	P2—C31—C36—C35	174.5 (3)
C13—C14—C15—C16	−1.5 (8)	C25—P2—C37—C38	−162.9 (3)
C14—C15—C16—C17	0.4 (9)	C31—P2—C37—C38	85.9 (4)
C15—C16—C17—C18	1.6 (8)	Pd1—P2—C37—C38	−40.0 (4)
C14—C13—C18—C17	1.6 (6)	C25—P2—C37—C42	25.5 (4)
P1—C13—C18—C17	−178.8 (3)	C31—P2—C37—C42	−85.7 (4)
C16—C17—C18—C13	−2.7 (7)	Pd1—P2—C37—C42	148.4 (3)
C13—P1—C19—C24	−77.5 (4)	C42—C37—C38—C39	−0.1 (6)
C7—P1—C19—C24	31.4 (4)	P2—C37—C38—C39	−172.0 (4)
Pd1—P1—C19—C24	159.5 (4)	C37—C38—C39—C40	−1.0 (7)
C13—P1—C19—C20	103.6 (4)	C38—C39—C40—C41	1.6 (8)
C7—P1—C19—C20	−147.6 (4)	C39—C40—C41—C42	−1.1 (8)
Pd1—P1—C19—C20	−19.4 (4)	C40—C41—C42—C37	0.0 (8)
C24—C19—C20—C21	1.1 (8)	C38—C37—C42—C41	0.6 (7)
P1—C19—C20—C21	−179.9 (4)	P2—C37—C42—C41	172.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C34—H34···Cl1ⁱ	0.93	2.99	3.631 (5)	127
C35—H35···Cl1ⁱ	0.93	2.97	3.616 (4)	128

Symmetry code: (i) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C34—H34···Cl1ⁱ	0.93	2.99	3.631 (5)	127
C35—H35···Cl1ⁱ	0.93	2.97	3.616 (4)	128

Symmetry code: (i) x, y−1, z.

Acknowledgements

ESJ thanks PROMEP "Apoyo a perfil deseable". Financial support of this research by CONACYT (grant No. CB2010–154732) and PAPIIT (grant No. IN201711–3) is gratefully acknowledged. RRM and DMM thank Dr Ruben A. Toscano for technical assistance.

References

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Volume 70| Part 3| March 2014| Pages m92-m93

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

trans-Chlorido­(4-fluoro­benzene­thiol­ato-κS)bis­­(tri­phenyl­phosphane-κP)palladium(II) methanol hemisolvate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

trans-Chlorido(4-fluorobenzenethiolato-κS)bis(triphenylphosphane-κP)palladium(II) methanol hemisolvate