cis-[mu]-Chloro-[mu]-p-toluene­thiol­ato-bis­[chloro­(triethyl­phos­phine)­palladium]

The title compound, cis-[Pd₂Cl₃(C₇H₇S)(C₆H₁₅P)₂], has bridging chloro and aryl­thiol­ato groups, with the phosphines being trans to the bridging chloro group. The four-membered metallocyclic Pd₂ClS ring is unexpectedly non-planar, with a dihedral angle of 133.8 (1)° between the PdCl₂SP coordination planes. Principal dimensions include Pd-Cl_t 2.316 (3) and 2.329 (3), Pd-Cl_b 2.442 (3) and 2.432 (3), Pd-S 2.280 (3) and 2.282 (3), and Pd-P 2.233 (3) and 2.236 (3) Å (where Cl_t and Cl_b are terminal and bridging chloro ligands, respectively).

Computing details

Data collection: CAD-4-PC (Enraf-Nonius, 1992); cell refinement: SET4 and CELDIM (Enraf-Nonius, 1992); data reduction: DATRD2 in NRCVAX96 (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: NRCVAX96 and SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: NRCVAX96, SHELXL97 and WORDPERFECT macro PREP8 (Ferguson, 1998).

cis-µ-Chloro-µ-p-toluenethiolato-bis[chloro(triethylphosphine)palladium]

Crystal data

[Pd2Cl3(C7H7S)(C6H15P)2]	? #Insert any comments here.
Mr = 678.69	Dx = 1.680 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.8564 (7) Å	Cell parameters from 25 reflections
b = 17.4629 (16) Å	θ = 10.0–18.3°
c = 9.7865 (16) Å	µ = 1.84 mm^−1
β = 92.132 (9)°	T = 294 K
V = 1341.7 (3) Å^3	Plate, colouless
Z = 2	0.43 × 0.16 × 0.07 mm
F(000) = 680

Data collection

Enraf-Nonius CAD-4 diffractometer	1842 reflections with I > 2σ(I)
Radiation source: X-ray tube	Rint = 0.016
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
θ/2θ scans	h = −9→9
Absorption correction: gaussian (ABSO in NRCVAX; Gabe et al., 1989)	k = 0→20
Tmin = 0.746, Tmax = 0.883	l = 0→11
2652 measured reflections	3 standard reflections every 120 min
2457 independent reflections	intensity decay: no decay, variation 1.0%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.027P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
2457 reflections	Δρmax = 0.48 e Å^−3
245 parameters	Δρmin = −0.55 e Å^−3
1 restraint	Absolute structure: Flack (1983), no Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (5)

Special details

Experimental. ? #Insert any special details here.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Pd1	0.57138 (9)	0.00001 (4)	0.58569 (7)	0.0417 (2)
Pd2	0.41466 (10)	−0.09317 (4)	0.32653 (8)	0.0434 (2)
S1	0.3062 (3)	−0.01285 (15)	0.4850 (2)	0.0423 (6)
Cl1	0.8433 (3)	−0.0031 (3)	0.6854 (3)	0.0786 (9)
Cl2	0.5263 (4)	−0.1698 (2)	0.1568 (3)	0.0738 (9)
Cl12	0.6746 (3)	−0.01835 (15)	0.3557 (3)	0.0556 (8)
P1	0.4450 (4)	0.01369 (18)	0.7852 (3)	0.0515 (8)
P2	0.1798 (4)	−0.16526 (16)	0.3146 (3)	0.0498 (7)
C11	0.3036 (16)	0.0981 (8)	0.7788 (12)	0.075 (4)
C12	0.1981 (18)	0.1087 (9)	0.9010 (14)	0.109 (5)
C13	0.5725 (15)	0.0205 (7)	0.9409 (10)	0.070 (4)
C14	0.6676 (17)	0.0924 (8)	0.9655 (13)	0.095 (4)
C15	0.3101 (15)	−0.0677 (7)	0.8128 (12)	0.066 (4)
C16	0.4005 (16)	−0.1435 (7)	0.7913 (13)	0.077 (4)
C21	0.0698 (17)	−0.1543 (8)	0.1514 (12)	0.076 (4)
C22	0.0183 (15)	−0.0720 (8)	0.1187 (11)	0.083 (4)
C23	0.2310 (17)	−0.2660 (7)	0.3273 (14)	0.078 (4)
C24	0.3412 (18)	−0.2869 (7)	0.4485 (16)	0.103 (5)
C25	0.0273 (12)	−0.1479 (7)	0.4428 (11)	0.061 (3)
C26	−0.1285 (14)	−0.1997 (7)	0.4373 (12)	0.077 (4)
C31	0.2507 (13)	0.0716 (6)	0.3901 (10)	0.043 (3)
C32	0.3665 (15)	0.1158 (7)	0.3259 (11)	0.063 (4)
C33	0.3083 (17)	0.1825 (7)	0.2537 (12)	0.076 (4)
C34	0.140 (2)	0.1988 (9)	0.2418 (15)	0.082 (4)
C35	0.0285 (18)	0.1521 (9)	0.3015 (14)	0.083 (4)
C36	0.0801 (15)	0.0898 (7)	0.3773 (12)	0.072 (4)
C37	0.085 (2)	0.2698 (9)	0.1633 (15)	0.124 (6)
H11A	0.3729	0.1435	0.7679	0.090*
H11B	0.2281	0.0940	0.6984	0.090*
H12A	0.1287	0.1536	0.8890	0.163*
H12B	0.2713	0.1145	0.9810	0.163*
H12C	0.1263	0.0647	0.9115	0.163*
H13A	0.4984	0.0127	1.0168	0.084*
H13B	0.6537	−0.0213	0.9424	0.084*
H14A	0.7305	0.0891	1.0513	0.143*
H14B	0.5891	0.1345	0.9679	0.143*
H14C	0.7451	0.1003	0.8932	0.143*
H15A	0.2703	−0.0659	0.9054	0.079*
H15B	0.2113	−0.0647	0.7506	0.079*
H16A	0.3234	−0.1849	0.8072	0.116*
H16B	0.4971	−0.1472	0.8539	0.116*
H16C	0.4379	−0.1461	0.6992	0.116*
H21A	0.1425	−0.1728	0.0806	0.092*
H21B	−0.0317	−0.1859	0.1497	0.092*
H22A	−0.0396	−0.0701	0.0306	0.124*
H22B	0.1182	−0.0403	0.1179	0.124*
H22C	−0.0562	−0.0535	0.1870	0.124*
H23A	0.1256	−0.2949	0.3304	0.094*
H23B	0.2878	−0.2814	0.2453	0.094*
H24A	0.3626	−0.3410	0.4480	0.154*
H24B	0.2849	−0.2733	0.5305	0.154*
H24C	0.4473	−0.2597	0.4453	0.154*
H25A	0.0841	−0.1535	0.5319	0.073*
H25B	−0.0109	−0.0952	0.4346	0.073*
H26A	−0.2022	−0.1861	0.5094	0.115*
H26B	−0.0932	−0.2520	0.4483	0.115*
H26C	−0.1883	−0.1937	0.3506	0.115*
H32	0.4814	0.1027	0.3290	0.075*
H33	0.3867	0.2150	0.2146	0.091*
H35	−0.0873	0.1625	0.2908	0.100*
H36	0.0000	0.0599	0.4201	0.087*
H37A	0.1630	0.2795	0.0922	0.186*
H37B	0.0840	0.3128	0.2244	0.186*
H37C	−0.0274	0.2622	0.1236	0.186*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0316 (4)	0.0482 (5)	0.0453 (4)	−0.0003 (4)	0.0000 (3)	0.0007 (4)
Pd2	0.0402 (4)	0.0490 (5)	0.0409 (4)	0.0037 (5)	−0.0015 (3)	−0.0032 (4)
S1	0.0341 (13)	0.0462 (17)	0.0464 (14)	−0.0041 (12)	0.0003 (11)	−0.0027 (12)
Cl1	0.0396 (15)	0.121 (3)	0.0737 (19)	0.008 (2)	−0.0120 (13)	−0.011 (2)
Cl2	0.072 (2)	0.090 (2)	0.0595 (19)	0.0133 (19)	0.0061 (16)	−0.0229 (18)
Cl12	0.0419 (15)	0.067 (2)	0.0590 (16)	−0.0009 (14)	0.0112 (12)	−0.0023 (14)
P1	0.0532 (17)	0.058 (2)	0.0430 (15)	0.0028 (16)	0.0003 (12)	−0.0022 (15)
P2	0.0487 (18)	0.0538 (18)	0.0464 (17)	−0.0060 (15)	−0.0045 (14)	−0.0057 (14)
C11	0.082 (9)	0.082 (9)	0.063 (8)	0.021 (8)	0.015 (7)	−0.017 (7)
C12	0.094 (11)	0.113 (13)	0.118 (13)	0.040 (10)	0.007 (10)	−0.021 (10)
C13	0.068 (8)	0.087 (10)	0.056 (7)	−0.005 (7)	−0.004 (6)	0.017 (7)
C14	0.106 (12)	0.083 (10)	0.097 (11)	−0.011 (10)	−0.010 (9)	−0.008 (9)
C15	0.062 (8)	0.082 (9)	0.056 (7)	−0.001 (7)	0.019 (6)	−0.007 (6)
C16	0.094 (11)	0.053 (8)	0.085 (10)	−0.019 (8)	0.022 (8)	−0.004 (7)
C21	0.073 (9)	0.097 (11)	0.058 (8)	−0.031 (9)	−0.010 (7)	−0.009 (7)
C22	0.072 (9)	0.134 (13)	0.041 (6)	0.036 (9)	−0.005 (6)	0.014 (7)
C23	0.083 (10)	0.059 (8)	0.092 (10)	−0.008 (7)	−0.015 (8)	−0.016 (8)
C24	0.125 (13)	0.053 (9)	0.129 (15)	0.025 (10)	−0.021 (12)	0.016 (8)
C25	0.035 (6)	0.070 (8)	0.078 (9)	−0.009 (6)	−0.001 (6)	0.008 (7)
C26	0.060 (8)	0.076 (9)	0.095 (10)	−0.015 (7)	0.009 (7)	0.008 (8)
C31	0.039 (6)	0.049 (7)	0.040 (6)	−0.007 (5)	−0.004 (5)	−0.017 (5)
C32	0.057 (8)	0.088 (9)	0.043 (6)	−0.016 (7)	−0.005 (6)	0.010 (7)
C33	0.084 (10)	0.083 (10)	0.060 (8)	0.018 (8)	−0.011 (8)	0.023 (8)
C34	0.085 (11)	0.095 (11)	0.063 (9)	0.035 (10)	−0.016 (9)	−0.001 (7)
C35	0.055 (9)	0.104 (12)	0.089 (11)	0.037 (9)	−0.017 (8)	−0.013 (9)
C36	0.048 (7)	0.077 (9)	0.091 (9)	0.031 (7)	−0.007 (7)	−0.006 (7)
C37	0.155 (16)	0.116 (13)	0.099 (11)	0.080 (12)	−0.002 (11)	0.051 (10)

Geometric parameters (Å, º)

Pd1—P1	2.236 (3)	C21—C22	1.524 (18)
Pd1—S1	2.282 (3)	C21—H21A	0.97
Pd1—Cl1	2.316 (3)	C21—H21B	0.97
Pd1—Cl12	2.442 (3)	C22—H22A	0.96
Pd2—P2	2.233 (3)	C22—H22B	0.96
Pd2—S1	2.280 (3)	C22—H22C	0.96
Pd2—Cl2	2.329 (3)	C23—C24	1.488 (16)
Pd2—Cl12	2.432 (3)	C23—H23A	0.97
S1—C31	1.788 (11)	C23—H23B	0.97
P1—C13	1.796 (10)	C24—H24A	0.96
P1—C15	1.799 (11)	C24—H24B	0.96
P1—C11	1.845 (12)	C24—H24C	0.96
P2—C25	1.793 (11)	C25—C26	1.521 (13)
P2—C21	1.797 (11)	C25—H25A	0.97
P2—C23	1.809 (12)	C25—H25B	0.97
C11—C12	1.492 (16)	C26—H26A	0.96
C11—H11A	0.97	C26—H26B	0.96
C11—H11B	0.97	C26—H26C	0.96
C12—H12A	0.96	C31—C32	1.364 (14)
C12—H12B	0.96	C31—C36	1.379 (13)
C12—H12C	0.96	C32—C33	1.430 (15)
C13—C14	1.476 (15)	C32—H32	0.93
C13—H13A	0.97	C33—C34	1.353 (16)
C13—H13B	0.97	C33—H33	0.93
C14—H14A	0.96	C34—C35	1.346 (18)
C14—H14B	0.96	C34—C37	1.513 (17)
C14—H14C	0.96	C35—C36	1.369 (17)
C15—C16	1.520 (15)	C35—H35	0.93
C15—H15A	0.97	C36—H36	0.93
C15—H15B	0.97	C37—H37A	0.96
C16—H16A	0.96	C37—H37B	0.96
C16—H16B	0.96	C37—H37C	0.96
C16—H16C	0.96
P1—Pd1—S1	87.69 (10)	H16A—C16—H16C	109.5
P1—Pd1—Cl1	93.84 (10)	H16B—C16—H16C	109.5
S1—Pd1—Cl1	172.99 (14)	C22—C21—P2	113.7 (9)
P1—Pd1—Cl12	172.96 (10)	C22—C21—H21A	108.8
S1—Pd1—Cl12	85.31 (9)	P2—C21—H21A	108.8
Cl1—Pd1—Cl12	93.02 (10)	C22—C21—H21B	108.8
P2—Pd2—S1	93.07 (10)	P2—C21—H21B	108.8
P2—Pd2—Cl2	88.36 (12)	H21A—C21—H21B	107.7
S1—Pd2—Cl2	176.97 (12)	C21—C22—H22A	109.5
P2—Pd2—Cl12	175.93 (11)	C21—C22—H22B	109.5
S1—Pd2—Cl12	85.59 (9)	H22A—C22—H22B	109.5
Cl2—Pd2—Cl12	93.16 (11)	C21—C22—H22C	109.5
C31—S1—Pd2	104.1 (3)	H22A—C22—H22C	109.5
C31—S1—Pd1	110.1 (3)	H22B—C22—H22C	109.5
Pd2—S1—Pd1	89.78 (9)	C24—C23—P2	114.5 (9)
Pd2—Cl12—Pd1	82.67 (8)	C24—C23—H23A	108.6
C13—P1—C15	103.8 (6)	P2—C23—H23A	108.6
C13—P1—C11	107.0 (6)	C24—C23—H23B	108.6
C15—P1—C11	106.2 (6)	P2—C23—H23B	108.6
C13—P1—Pd1	119.7 (4)	H23A—C23—H23B	107.6
C15—P1—Pd1	109.3 (4)	C23—C24—H24A	109.5
C11—P1—Pd1	110.0 (4)	C23—C24—H24B	109.5
C25—P2—C21	106.9 (6)	H24A—C24—H24B	109.5
C25—P2—C23	105.6 (6)	C23—C24—H24C	109.5
C21—P2—C23	105.3 (6)	H24A—C24—H24C	109.5
C25—P2—Pd2	116.2 (4)	H24B—C24—H24C	109.5
C21—P2—Pd2	110.8 (4)	C26—C25—P2	115.6 (8)
C23—P2—Pd2	111.4 (4)	C26—C25—H25A	108.4
C12—C11—P1	115.0 (10)	P2—C25—H25A	108.4
C12—C11—H11A	108.5	C26—C25—H25B	108.4
P1—C11—H11A	108.5	P2—C25—H25B	108.4
C12—C11—H11B	108.5	H25A—C25—H25B	107.4
P1—C11—H11B	108.5	C25—C26—H26A	109.5
H11A—C11—H11B	107.5	C25—C26—H26B	109.5
C11—C12—H12A	109.5	H26A—C26—H26B	109.5
C11—C12—H12B	109.5	C25—C26—H26C	109.5
H12A—C12—H12B	109.5	H26A—C26—H26C	109.5
C11—C12—H12C	109.5	H26B—C26—H26C	109.5
H12A—C12—H12C	109.5	C32—C31—C36	119.3 (11)
H12B—C12—H12C	109.5	C32—C31—S1	123.5 (9)
C14—C13—P1	117.2 (9)	C36—C31—S1	117.1 (9)
C14—C13—H13A	108.0	C31—C32—C33	118.8 (12)
P1—C13—H13A	108.0	C31—C32—H32	120.6
C14—C13—H13B	108.0	C33—C32—H32	120.6
P1—C13—H13B	108.0	C34—C33—C32	120.5 (13)
H13A—C13—H13B	107.2	C34—C33—H33	119.7
C13—C14—H14A	109.5	C32—C33—H33	119.7
C13—C14—H14B	109.5	C35—C34—C33	119.0 (14)
H14A—C14—H14B	109.5	C35—C34—C37	122.6 (14)
C13—C14—H14C	109.5	C33—C34—C37	118.4 (15)
H14A—C14—H14C	109.5	C34—C35—C36	122.2 (13)
H14B—C14—H14C	109.5	C34—C35—H35	118.9
C16—C15—P1	112.7 (8)	C36—C35—H35	118.9
C16—C15—H15A	109.0	C35—C36—C31	120.0 (13)
P1—C15—H15A	109.0	C35—C36—H36	120.0
C16—C15—H15B	109.0	C31—C36—H36	120.0
P1—C15—H15B	109.0	C34—C37—H37A	109.5
H15A—C15—H15B	107.8	C34—C37—H37B	109.5
C15—C16—H16A	109.5	H37A—C37—H37B	109.5
C15—C16—H16B	109.5	C34—C37—H37C	109.5
H16A—C16—H16B	109.5	H37A—C37—H37C	109.5
C15—C16—H16C	109.5	H37B—C37—H37C	109.5
P1—Pd1—Pd2—P2	−6.80 (15)	Pd1—Pd2—P2—C25	20.2 (5)
S1—Pd1—Pd2—P2	−46.80 (14)	S1—Pd2—P2—C21	111.4 (5)
Cl1—Pd1—Pd2—P2	126.70 (16)	Cl2—Pd2—P2—C21	−66.0 (5)
Cl12—Pd1—Pd2—P2	176.56 (15)	Pd1—Pd2—P2—C21	142.5 (5)
P1—Pd1—Pd2—S1	40.00 (14)	S1—Pd2—P2—C23	−131.8 (5)
Cl1—Pd1—Pd2—S1	173.50 (17)	Cl2—Pd2—P2—C23	50.8 (5)
Cl12—Pd1—Pd2—S1	−136.64 (13)	Pd1—Pd2—P2—C23	−100.7 (5)
P1—Pd1—Pd2—Cl2	−144.26 (16)	C13—P1—C11—C12	−54.5 (11)
S1—Pd1—Pd2—Cl2	175.74 (17)	C15—P1—C11—C12	55.8 (11)
Cl1—Pd1—Pd2—Cl2	−10.76 (19)	Pd1—P1—C11—C12	173.9 (9)
Cl12—Pd1—Pd2—Cl2	39.10 (15)	C15—P1—C13—C14	−165.5 (10)
P1—Pd1—Pd2—Cl12	176.63 (14)	C11—P1—C13—C14	−53.4 (11)
S1—Pd1—Pd2—Cl12	136.64 (13)	Pd1—P1—C13—C14	72.5 (11)
Cl1—Pd1—Pd2—Cl12	−49.86 (16)	C13—P1—C15—C16	−79.4 (10)
P2—Pd2—S1—C31	−104.3 (3)	C11—P1—C15—C16	168.0 (9)
Cl12—Pd2—S1—C31	79.5 (3)	Pd1—P1—C15—C16	49.4 (10)
Pd1—Pd2—S1—C31	110.7 (3)	C25—P2—C21—C22	69.4 (11)
P2—Pd2—S1—Pd1	144.94 (10)	C23—P2—C21—C22	−178.6 (10)
Cl12—Pd2—S1—Pd1	−31.21 (9)	Pd2—P2—C21—C22	−58.1 (11)
P1—Pd1—S1—C31	106.8 (3)	C25—P2—C23—C24	−73.9 (12)
Cl12—Pd1—S1—C31	−73.9 (3)	C21—P2—C23—C24	173.2 (11)
Pd2—Pd1—S1—C31	−105.0 (3)	Pd2—P2—C23—C24	53.0 (12)
P1—Pd1—S1—Pd2	−148.17 (11)	C21—P2—C25—C26	58.2 (10)
Cl12—Pd1—S1—Pd2	31.08 (9)	C23—P2—C25—C26	−53.5 (10)
S1—Pd2—Cl12—Pd1	29.22 (9)	Pd2—P2—C25—C26	−177.5 (7)
Cl2—Pd2—Cl12—Pd1	−153.54 (10)	Pd2—S1—C31—C32	−62.6 (9)
S1—Pd1—Cl12—Pd2	−29.20 (9)	Pd1—S1—C31—C32	32.5 (10)
Cl1—Pd1—Cl12—Pd2	143.97 (13)	Pd2—S1—C31—C36	114.3 (8)
S1—Pd1—P1—C13	174.9 (5)	Pd1—S1—C31—C36	−150.6 (7)
Cl1—Pd1—P1—C13	1.8 (5)	C36—C31—C32—C33	3.7 (16)
Pd2—Pd1—P1—C13	147.8 (5)	S1—C31—C32—C33	−179.4 (8)
S1—Pd1—P1—C15	55.6 (4)	C31—C32—C33—C34	−4.3 (18)
Cl1—Pd1—P1—C15	−117.5 (4)	C32—C33—C34—C35	1 (2)
Pd2—Pd1—P1—C15	28.5 (4)	C32—C33—C34—C37	−179.5 (13)
S1—Pd1—P1—C11	−60.6 (5)	C33—C34—C35—C36	2 (2)
Cl1—Pd1—P1—C11	126.3 (5)	C37—C34—C35—C36	−177.1 (13)
Pd2—Pd1—P1—C11	−87.7 (5)	C34—C35—C36—C31	−3 (2)
S1—Pd2—P2—C25	−10.9 (4)	C32—C31—C36—C35	−0.5 (17)
Cl2—Pd2—P2—C25	171.7 (4)	S1—C31—C36—C35	−177.5 (9)