Bis(methyl xanthato)-κS;κS:S'-(triphenyl-phosphane-κP)palladium(II).

The title compound, [Pd(C(2)H(3)OS(2))(2)(C(18)H(15)P)], features a palladium complex with a triphenyl-phosphane ligand and two xanthate ligands, one of them coordinates in a bidentate and the other in a monodentate fashion, giving rise to a slightly distorted square-planar coordination of the Pd(II) ion. As a result of this difference in the coordination modes, the C-S bond lengths are different, viz. 1.687 (2) and 1.692 (2) Å in the bidentate ligand and 1.723 (2) Å in the monodentate ligand, whereas the non-coordinating S atom has a C-S distance of 1.649 (2) Å. The crystal packing is stabilized by C-H⋯O inter-actions.

Related literature

For background information on xanthates, see: Karlin (2005 ▶); Friebolin et al. (2005 ▶). For crystal engineering, see: Tiekink (2003 ▶). For bond-length data, see: Allen (2002 ▶).

Experimental

Crystal data

[Pd(C2H3OS2)2(C18H15P)]

M = 583.00

Triclinic,

a = 9.5595 (10) Å

b = 9.5883 (10) Å

c = 14.4661 (16) Å

α = 73.619 (1)°

β = 87.492 (2)°

γ = 69.617 (1)°

V = 1190.3 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.22 mm−1

T = 298 K

0.30 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: analytical (SADABS, Bruker, 1999 ▶) T min = 0.712, T max = 0.817

9954 measured reflections

4371 independent reflections

4021 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.064

S = 1.10

4371 reflections

274 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.42 e Å−3

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811040487/bt5655sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040487/bt5655Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Pd(C2H3OS2)2(C18H15P)]	Z = 2
Mr = 583.00	F(000) = 588
Triclinic, P1	Dx = 1.627 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5595 (10) Å	Cell parameters from 8044 reflections
b = 9.5883 (10) Å	θ = 2.3–25.4°
c = 14.4661 (16) Å	µ = 1.22 mm−1
α = 73.619 (1)°	T = 298 K
β = 87.492 (2)°	Prism, orange
γ = 69.617 (1)°	0.30 × 0.22 × 0.20 mm
V = 1190.3 (2) Å3

Bruker SMART APEX CCD area-detector diffractometer	4371 independent reflections
Radiation source: fine-focus sealed tube	4021 reflections with I > 2σ(I)
graphite	Rint = 0.025
Detector resolution: 0.83 pixels mm-1	θmax = 25.4°, θmin = 2.4°
ω scans	h = −11→11
Absorption correction: analytical (SADABS, Bruker, 1999)	k = −11→11
Tmin = 0.712, Tmax = 0.817	l = −17→17
9954 measured reflections

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)] = 0.025	H-atom parameters constrained
wR(F2) = 0.064	w = 1/[σ2(Fo2) + (0.0336P)2 + 0.178P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max = 0.001
4371 reflections	Δρmax = 0.32 e Å−3
274 parameters	Δρmin = −0.42 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0063 (7)

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.

	x	y	z	Uiso*/Ueq
Pd	0.557109 (17)	0.946630 (17)	0.158062 (11)	0.03533 (8)
S1	0.62793 (7)	1.11131 (6)	0.02530 (4)	0.04484 (15)
S2	0.77698 (7)	0.78738 (7)	0.10997 (4)	0.04619 (15)
S3	0.34534 (7)	1.12011 (7)	0.20223 (4)	0.04483 (15)
S4	0.16108 (9)	1.44896 (8)	0.16359 (6)	0.0674 (2)
P	0.53719 (6)	0.75832 (6)	0.29129 (4)	0.03699 (14)
C1	0.6235 (2)	0.5585 (2)	0.28557 (16)	0.0402 (5)
C2	0.5382 (3)	0.4710 (3)	0.2782 (2)	0.0540 (6)
H2	0.4346	0.5130	0.2779	0.065*
C3	0.6064 (3)	0.3212 (3)	0.2714 (2)	0.0673 (8)
H3	0.5482	0.2633	0.2661	0.081*
C4	0.7577 (4)	0.2585 (3)	0.2723 (2)	0.0650 (8)
H4	0.8027	0.1579	0.2676	0.078*
C5	0.8448 (3)	0.3428 (3)	0.2801 (2)	0.0614 (7)
H5	0.9484	0.2992	0.2811	0.074*
C6	0.7775 (3)	0.4931 (3)	0.28646 (18)	0.0511 (6)
H6	0.8364	0.5503	0.2914	0.061*
C7	0.6282 (3)	0.7628 (3)	0.39762 (16)	0.0431 (5)
C8	0.6358 (3)	0.9006 (3)	0.40261 (19)	0.0527 (6)
H8	0.5990	0.9893	0.3507	0.063*
C9	0.6979 (3)	0.9080 (4)	0.4844 (2)	0.0683 (8)
H9	0.7010	1.0024	0.4876	0.082*
C10	0.7548 (3)	0.7795 (4)	0.5605 (2)	0.0745 (9)
H10	0.7967	0.7856	0.6154	0.089*
C11	0.7498 (4)	0.6417 (4)	0.5555 (2)	0.0845 (10)
H11	0.7905	0.5528	0.6067	0.101*
C12	0.6853 (4)	0.6327 (3)	0.4754 (2)	0.0739 (9)
H12	0.6801	0.5384	0.4735	0.089*
C13	0.3460 (2)	0.7770 (2)	0.32140 (16)	0.0409 (5)
C14	0.2973 (3)	0.7726 (3)	0.41336 (19)	0.0536 (6)
H14	0.3635	0.7585	0.4632	0.064*
C15	0.1497 (3)	0.7892 (4)	0.4307 (2)	0.0727 (9)
H15	0.1165	0.7875	0.4923	0.087*
C16	0.0524 (3)	0.8082 (4)	0.3579 (3)	0.0754 (9)
H16	−0.0466	0.8190	0.3701	0.090*
C17	0.1000 (3)	0.8112 (3)	0.2669 (2)	0.0656 (8)
H17	0.0340	0.8219	0.2179	0.079*
C18	0.2455 (3)	0.7983 (3)	0.24803 (18)	0.0521 (6)
H18	0.2766	0.8039	0.1857	0.063*
C19	0.7744 (2)	0.9505 (3)	0.02430 (16)	0.0398 (5)
O20	0.87376 (17)	0.95924 (18)	−0.03937 (12)	0.0483 (4)
C21	0.9931 (3)	0.8175 (3)	−0.0439 (2)	0.0579 (7)
H21A	1.0437	0.7637	0.0187	0.087*
H21B	1.0629	0.8431	−0.0894	0.087*
H21C	0.9516	0.7522	−0.0641	0.087*
C22	0.2955 (2)	1.3103 (3)	0.13247 (16)	0.0414 (5)
O23	0.3687 (2)	1.33360 (19)	0.05373 (13)	0.0590 (5)
C24	0.3206 (4)	1.4853 (3)	−0.0161 (2)	0.0767 (9)
H24A	0.2189	1.5127	−0.0385	0.115*
H24B	0.3835	1.4834	−0.0697	0.115*
H24C	0.3276	1.5606	0.0137	0.115*

	U11	U22	U33	U12	U13	U23
Pd	0.03777 (12)	0.02838 (11)	0.03679 (11)	−0.01107 (8)	0.00156 (7)	−0.00519 (7)
S1	0.0442 (3)	0.0308 (3)	0.0494 (3)	−0.0087 (2)	0.0092 (3)	−0.0027 (2)
S2	0.0444 (3)	0.0313 (3)	0.0524 (3)	−0.0074 (2)	0.0049 (3)	−0.0038 (3)
S3	0.0462 (3)	0.0334 (3)	0.0465 (3)	−0.0086 (2)	0.0072 (3)	−0.0061 (2)
S4	0.0682 (5)	0.0440 (4)	0.0658 (4)	0.0038 (3)	0.0171 (4)	−0.0105 (3)
P	0.0415 (3)	0.0315 (3)	0.0367 (3)	−0.0151 (2)	−0.0002 (2)	−0.0046 (2)
C1	0.0460 (12)	0.0321 (11)	0.0396 (12)	−0.0144 (10)	0.0015 (9)	−0.0044 (9)
C2	0.0512 (14)	0.0393 (13)	0.0719 (17)	−0.0182 (11)	0.0005 (12)	−0.0130 (12)
C3	0.0733 (19)	0.0424 (15)	0.092 (2)	−0.0259 (14)	−0.0023 (16)	−0.0193 (15)
C4	0.079 (2)	0.0354 (14)	0.0713 (18)	−0.0102 (14)	0.0053 (15)	−0.0130 (13)
C5	0.0541 (15)	0.0444 (15)	0.0676 (17)	−0.0055 (12)	0.0035 (13)	−0.0033 (13)
C6	0.0478 (14)	0.0423 (14)	0.0576 (15)	−0.0166 (11)	−0.0018 (11)	−0.0038 (11)
C7	0.0448 (12)	0.0462 (13)	0.0390 (12)	−0.0183 (11)	0.0016 (9)	−0.0100 (10)
C8	0.0506 (14)	0.0484 (14)	0.0602 (15)	−0.0137 (12)	−0.0036 (12)	−0.0208 (12)
C9	0.0618 (17)	0.075 (2)	0.076 (2)	−0.0173 (15)	−0.0012 (15)	−0.0412 (17)
C10	0.0581 (17)	0.118 (3)	0.0530 (17)	−0.0248 (18)	0.0002 (13)	−0.0404 (19)
C11	0.113 (3)	0.084 (2)	0.0465 (16)	−0.032 (2)	−0.0208 (17)	−0.0012 (16)
C12	0.109 (2)	0.0577 (17)	0.0515 (16)	−0.0359 (18)	−0.0187 (16)	0.0022 (13)
C13	0.0447 (12)	0.0312 (11)	0.0446 (12)	−0.0152 (10)	0.0043 (10)	−0.0051 (9)
C14	0.0610 (16)	0.0489 (14)	0.0514 (14)	−0.0208 (13)	0.0104 (12)	−0.0142 (12)
C15	0.0672 (19)	0.075 (2)	0.0714 (19)	−0.0249 (16)	0.0293 (16)	−0.0181 (16)
C16	0.0468 (16)	0.069 (2)	0.099 (3)	−0.0192 (15)	0.0192 (17)	−0.0101 (18)
C17	0.0473 (15)	0.0649 (18)	0.075 (2)	−0.0190 (14)	−0.0063 (14)	−0.0050 (15)
C18	0.0465 (13)	0.0534 (15)	0.0492 (14)	−0.0169 (12)	0.0005 (11)	−0.0042 (12)
C19	0.0379 (11)	0.0373 (12)	0.0426 (12)	−0.0126 (10)	−0.0004 (9)	−0.0092 (10)
O20	0.0407 (9)	0.0436 (9)	0.0509 (9)	−0.0084 (7)	0.0091 (7)	−0.0080 (8)
C21	0.0419 (13)	0.0569 (16)	0.0669 (17)	−0.0056 (12)	0.0112 (12)	−0.0216 (14)
C22	0.0411 (12)	0.0374 (12)	0.0437 (12)	−0.0111 (10)	−0.0005 (10)	−0.0111 (10)
O23	0.0658 (11)	0.0359 (9)	0.0562 (10)	−0.0039 (8)	0.0164 (9)	−0.0036 (8)
C24	0.093 (2)	0.0384 (15)	0.0670 (19)	−0.0032 (15)	0.0225 (16)	0.0050 (13)

Pd—P	2.2924 (6)	C9—H9	0.9300
Pd—S3	2.3267 (6)	C10—C11	1.361 (5)
Pd—S2	2.3386 (6)	C10—H10	0.9300
Pd—S1	2.3581 (6)	C11—C12	1.373 (4)
S1—C19	1.687 (2)	C11—H11	0.9300
S2—C19	1.692 (2)	C12—H12	0.9300
S3—C22	1.723 (2)	C13—C14	1.384 (3)
S4—C22	1.649 (2)	C13—C18	1.386 (3)
P—C7	1.818 (2)	C14—C15	1.384 (4)
P—C13	1.819 (2)	C14—H14	0.9300
P—C1	1.827 (2)	C15—C16	1.367 (5)
C1—C2	1.383 (3)	C15—H15	0.9300
C1—C6	1.384 (3)	C16—C17	1.369 (4)
C2—C3	1.386 (4)	C16—H16	0.9300
C2—H2	0.9300	C17—C18	1.375 (4)
C3—C4	1.359 (4)	C17—H17	0.9300
C3—H3	0.9300	C18—H18	0.9300
C4—C5	1.373 (4)	C19—O20	1.301 (3)
C4—H4	0.9300	O20—C21	1.455 (3)
C5—C6	1.387 (4)	C21—H21A	0.9600
C5—H5	0.9300	C21—H21B	0.9600
C6—H6	0.9300	C21—H21C	0.9600
C7—C8	1.371 (3)	C22—O23	1.316 (3)
C7—C12	1.381 (3)	O23—C24	1.447 (3)
C8—C9	1.377 (4)	C24—H24A	0.9600
C8—H8	0.9300	C24—H24B	0.9600
C9—C10	1.359 (4)	C24—H24C	0.9600
P—Pd—S3	88.08 (2)	C10—C11—C12	120.6 (3)
P—Pd—S2	95.32 (2)	C10—C11—H11	119.7
S3—Pd—S2	175.72 (2)	C12—C11—H11	119.7
P—Pd—S1	168.78 (2)	C11—C12—C7	120.3 (3)
S3—Pd—S1	101.78 (2)	C11—C12—H12	119.8
S2—Pd—S1	74.60 (2)	C7—C12—H12	119.8
C19—S1—Pd	85.06 (8)	C14—C13—C18	119.3 (2)
C19—S2—Pd	85.56 (8)	C14—C13—P	122.88 (19)
C22—S3—Pd	115.44 (8)	C18—C13—P	117.85 (18)
C7—P—C13	105.95 (10)	C15—C14—C13	119.7 (3)
C7—P—C1	104.63 (10)	C15—C14—H14	120.2
C13—P—C1	104.52 (10)	C13—C14—H14	120.2
C7—P—Pd	110.69 (8)	C16—C15—C14	120.4 (3)
C13—P—Pd	114.35 (7)	C16—C15—H15	119.8
C1—P—Pd	115.78 (7)	C14—C15—H15	119.8
C2—C1—C6	118.7 (2)	C15—C16—C17	120.3 (3)
C2—C1—P	121.55 (18)	C15—C16—H16	119.9
C6—C1—P	119.78 (18)	C17—C16—H16	119.9
C1—C2—C3	120.4 (2)	C16—C17—C18	120.0 (3)
C1—C2—H2	119.8	C16—C17—H17	120.0
C3—C2—H2	119.8	C18—C17—H17	120.0
C4—C3—C2	120.3 (3)	C17—C18—C13	120.3 (3)
C4—C3—H3	119.9	C17—C18—H18	119.8
C2—C3—H3	119.9	C13—C18—H18	119.8
C3—C4—C5	120.4 (3)	O20—C19—S1	119.69 (17)
C3—C4—H4	119.8	O20—C19—S2	125.54 (17)
C5—C4—H4	119.8	S1—C19—S2	114.77 (13)
C4—C5—C6	119.7 (3)	C19—O20—C21	118.96 (19)
C4—C5—H5	120.2	O20—C21—H21A	109.5
C6—C5—H5	120.2	O20—C21—H21B	109.5
C1—C6—C5	120.6 (2)	H21A—C21—H21B	109.5
C1—C6—H6	119.7	O20—C21—H21C	109.5
C5—C6—H6	119.7	H21A—C21—H21C	109.5
C8—C7—C12	118.7 (2)	H21B—C21—H21C	109.5
C8—C7—P	119.16 (18)	O23—C22—S4	123.92 (17)
C12—C7—P	122.1 (2)	O23—C22—S3	115.46 (16)
C7—C8—C9	120.1 (3)	S4—C22—S3	120.60 (14)
C7—C8—H8	120.0	C22—O23—C24	119.4 (2)
C9—C8—H8	120.0	O23—C24—H24A	109.5
C10—C9—C8	121.1 (3)	O23—C24—H24B	109.5
C10—C9—H9	119.5	H24A—C24—H24B	109.5
C8—C9—H9	119.5	O23—C24—H24C	109.5
C9—C10—C11	119.2 (3)	H24A—C24—H24C	109.5
C9—C10—H10	120.4	H24B—C24—H24C	109.5
C11—C10—H10	120.4
P—Pd—S1—C19	26.14 (14)	C13—P—C7—C12	81.9 (3)
S3—Pd—S1—C19	177.19 (8)	C1—P—C7—C12	−28.2 (3)
S2—Pd—S1—C19	−0.47 (8)	Pd—P—C7—C12	−153.6 (2)
P—Pd—S2—C19	−174.52 (8)	C12—C7—C8—C9	−0.8 (4)
S3—Pd—S2—C19	−32.0 (3)	P—C7—C8—C9	176.9 (2)
S1—Pd—S2—C19	0.46 (8)	C7—C8—C9—C10	1.2 (4)
P—Pd—S3—C22	174.99 (9)	C8—C9—C10—C11	−0.1 (5)
S2—Pd—S3—C22	32.3 (3)	C9—C10—C11—C12	−1.4 (5)
S1—Pd—S3—C22	0.40 (9)	C10—C11—C12—C7	1.8 (6)
S3—Pd—P—C7	−85.16 (8)	C8—C7—C12—C11	−0.7 (5)
S2—Pd—P—C7	92.24 (8)	P—C7—C12—C11	−178.3 (3)
S1—Pd—P—C7	66.54 (14)	C7—P—C13—C14	−7.9 (2)
S3—Pd—P—C13	34.40 (8)	C1—P—C13—C14	102.3 (2)
S2—Pd—P—C13	−148.20 (8)	Pd—P—C13—C14	−130.10 (18)
S1—Pd—P—C13	−173.90 (12)	C7—P—C13—C18	171.35 (18)
S3—Pd—P—C1	156.01 (8)	C1—P—C13—C18	−78.4 (2)
S2—Pd—P—C1	−26.60 (8)	Pd—P—C13—C18	49.2 (2)
S1—Pd—P—C1	−52.30 (14)	C18—C13—C14—C15	0.1 (4)
C7—P—C1—C2	127.6 (2)	P—C13—C14—C15	179.3 (2)
C13—P—C1—C2	16.5 (2)	C13—C14—C15—C16	0.8 (4)
Pd—P—C1—C2	−110.26 (19)	C14—C15—C16—C17	−0.2 (5)
C7—P—C1—C6	−53.8 (2)	C15—C16—C17—C18	−1.3 (5)
C13—P—C1—C6	−164.93 (19)	C16—C17—C18—C13	2.2 (4)
Pd—P—C1—C6	68.3 (2)	C14—C13—C18—C17	−1.5 (4)
C6—C1—C2—C3	−0.4 (4)	P—C13—C18—C17	179.2 (2)
P—C1—C2—C3	178.2 (2)	Pd—S1—C19—O20	−179.27 (18)
C1—C2—C3—C4	0.3 (5)	Pd—S1—C19—S2	0.68 (11)
C2—C3—C4—C5	0.1 (5)	Pd—S2—C19—O20	179.3 (2)
C3—C4—C5—C6	−0.4 (5)	Pd—S2—C19—S1	−0.69 (11)
C2—C1—C6—C5	0.0 (4)	S1—C19—O20—C21	−175.44 (16)
P—C1—C6—C5	−178.6 (2)	S2—C19—O20—C21	4.6 (3)
C4—C5—C6—C1	0.4 (4)	Pd—S3—C22—O23	9.4 (2)
C13—P—C7—C8	−95.7 (2)	Pd—S3—C22—S4	−172.25 (10)
C1—P—C7—C8	154.22 (19)	S4—C22—O23—C24	−6.8 (4)
Pd—P—C7—C8	28.8 (2)	S3—C22—O23—C24	171.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O20i	0.93	2.64	3.211	120.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18⋯O20i	0.93	2.64	3.211	120

Symmetry code: (i) .