cis-[1,4-Bis(di­phenyl­phosphino)­butane](μ-tetra­thio­tungstato)­palladium(II) N,N′-di­methyl­form­amide hemisolvate hemihydrate

In the title compound, [1,4-bis(di­phenyl­phosphino)­butane-2κ²P,P′]­di-μ-thio-1:2κ⁴S-di­thio-1κ²S-palladium(II)­tung­sten(VI) N,N′-di­methyl­form­amide hemisolvate hemihydrate, [PdWS₄­(C₂₈H₂₈P₂)]·0.5C₃H₇NO·0.5H₂O, the Pd atom is coordinated by two S atoms from the distorted-tetrahedral [WS₄]²⁻ anion and two P atoms from the dppb mol­ecule [dppb is 1,4-bis(di­phenyl­phos­phino)­butane] in an approximately square-planar configuration. A puckered seven-membered ring is formed by the Pd atom and the dppb ligand.

S1. Comment

Over the past two decades, transition metal complexes with thiometalate anions, [MO_4-nS_n]²⁻ (M=Mo,W;n=2–4), have been widely researched (Müller et al., 1981; Sarkar et al., 1984; Hou et al., 1996). Many of these complexes play important roles in catalysis, new materials and medical chemistry (Holm & Berg, 1986; Howard et al., 1986; Burgess,1990; Munakata et al., 1995). Heterobimetallic thiometalate complexes containing dithiolato ligands, (Et₄N)₂WS₄Pd(S₂C₄N₂) (Long et al., 1997), [NEt₄][PdWS₄(S₂CNC₄H₈)] (Long et al., 1997), [N(C₂H₅)₄][NiWS₄(S₂CNC₄H₈)] (Long et al., 1998), have been structurally characterized. Recently, bidentate phosphine ligands, R₂P(CH₂)_nPR₂ (R=Ph; dppm, n=1; dppe, n=2; dppp, n=3), which have versatile coordination modes with transition metals, have attracted some attention (Fenske & Langetepe, 2001; Lemaitre et al., 2002; Saravanabharathi et al., 2002). However, only a few examples containing thiometalate and bidentate phosphines have been reported, such as (dppm)PtWS₄ (Potvin et al., 1987) and (dppe)PdWS₄ (Wu et al., 1997, hereafter nTWO). We sought to extend our investigations by using different diphosphine ligands to confirm whether the structure of the products was similar to those already reported, anticipating the formation of new cluster frameworks. For example, (dppm)₂Pd₄W₂S₈ (Zheng et al., 2000, hereafter nONE) has a windmill-shaped structure whereas (dppp)PdWS₄ (Zheng et al., 2000, hereafter nTHREE) has a so-called `linear' (binuclear) structure.

An X-ray crystallographic study of the title compound [(dppb)PdWS₄]·0.5DMF·0.5H₂O, (I) (nFOUR) shows that the bond lengths and angles all fall within normal ranges. The Pd atom has a cis-quasi-square-planar coordination geometry, with two P-donors from dppb and two S-donors from WS₄²⁻ (Fig. 1). The average deviation from the least-squares plane through atoms Pd1, P1, P2, S1 and S2 is 0.0533 (11) Å. The W···Pd separation [2.9457 (6) Å] is shorter than that found in the heteroselenometallic compound (Zhang et al., 2002) and is longer than that found in nTWO [2.887 (2) Å] and nTHREE [2.9259 (6) Å]. The corresponding increase in the W—S—Pd angles, viz. nTWO [mean 78.0 (2)°], nTHREE [mean 79.19 (7)°] and (I) [mean 80.27 (5)°], are in accordance with the trend, suggesting that the metal–metal interactions weaken when the alkyl chain length of the diphosphine increases.

The terminal W—S bond distances in (I) [mean 2.12 Å] are comparable to those reported in nTWO (mean 2.14 Å) and nTHREE (mean 2.15 Å). The bridge W—S (mean 2.21 Å) bond distances are also simlar to those found in nTWO (mean 2.23 Å) and nTHREE (mean 2.22 Å). The S_bridge—W—S_bridge angles are 105.7 (3), 104.88 (7) and 103.87 (7)° for nTWO, nTHREE and (I) respectively. These parameters suggest that the tetrathiotungstate anion structure is not perturbed significantly in any of these complexes.

As the alkyl chain length increases, the P—Pd—P angles increase from 86.1 (2)° for n=2, to 92.00 (5)° for n=3 and to 92.87 (7)° for n=4. Concomitant with the increasing P—Pd—P angle is a decrease in the S—Pd—S angle. Thus, correspondingly, the S—Pd—S angles are 98.3 (3), 96.98 (5) and 95.57 (7)°. Some puckering of the chains occurs as the less usual seven-membered chelate ring is formed. The Pd—P (mean 2.31 Å) and Pd—S (mean 2.35 Å) bond distances in (I) are within the range reported for [Pd(S₂CNEt₂){Ph₂P(CH₂)_nPPh₂}]⁺ (Exarchos et al., 2000) and (PPh₃)Pd(S₂C₄N₂) (Long et al., 1997), and similar to those found in nTWO and nTHREE.

There are only weak intermolecular hydrogen bonds between the (partially occupied) water and dimethylformamide molecules, and the neutral complex, namely C24—H24···O1 (2.48 Å) and O2—H2B···S4 (2.32 Å) (Table 2). Other noteworthy intermolecular close contacts are C3—H3···S3 (2.71 Å), C25—H25B···S4 (2.86 Å), C5—H5···O2 (2.47 Å) and (C6—H6···O2 (2.50 Å), with one intramolecular C8—H8···S1 (2.59 Å) close contact.

S2. Experimental

The title compound was obtained when (dppb)PdCl₂ (Steffen et al., 1976) and (NH₄)₂WS₄ [McDonald et al., 1983] were added to a solution (20 ml) of CH₂Cl₂ and CH₃CN (1:1, v/v) and the mixture was stirred for 20 h. After filtration, the solid product was washed with CH₂Cl₂, distilled water, anhydrous ethanol and ether, respectively. Single yellow crystals were obtained by diffusing ethyl ether into DMF solution·Analysis calculated for C_29.50H_32.50N_0.50OS₄P₂PdW: C 39.79, H 3.68, N 0.79%; found: C 39.75, H 3.65, N 0.76%.

S3. Refinement

The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses. H atoms were fixed geometrically and refined as riding, with C—H distances of 0.85–0.97 Å and U_iso values of 1.2U_eq of the parent atom.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig.1: The structure of the title compound, with displacement ellipsoids shown at the 30% probability level; the DMF and water molecules have been omitted for clarity.

Cis-{[1,4-(diphenylphosphine-P,P')butane] [µ-(tetrathiotungstate-S,S')]}Pd(II)0.5 N,N'-dimethylformamide 0.5hydrate

Crystal data

[PdWS4(C28H28P2)]·0.5C3H7NO·0.5H2O	F(000) = 1740
Mr = 890.49	Dx = 1.690 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 878 reflections
a = 9.178 (1) Å	θ = 2.3–18.5°
b = 19.566 (2) Å	µ = 4.15 mm^−1
c = 19.705 (2) Å	T = 293 K
β = 98.44 (1)°	Block, yellow
V = 3500.2 (6) Å^3	0.3 × 0.2 × 0.2 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	6153 independent reflections
Radiation source: sealed tube	4371 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan SADABS (Bruker, 2000)	h = −10→10
Tmin = 0.385, Tmax = 0.436	k = 0→23
17162 measured reflections	l = 0→23

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.06P)^2 + 1.99P] where P = (Fo^2 + 2Fc^2)/3
6153 reflections	(Δ/σ)max < 0.001
379 parameters	Δρmax = 0.68 e Å^−3
0 restraints	Δρmin = −0.68 e Å^−3

Special details

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 7.5178 (0.0036) x + 10.6432 (0.0103) y − 5.9180 (0.0118) z = 9.8903 (0.0089) * 0.0587 (0.0010) S1 * −0.0649 (0.0010) S2 * −0.0685 (0.0011) P1 * 0.0604 (0.0011) P2 * 0.0143 (0.0009) Pd1

Rms deviation of fitted atoms = 0.0569

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
W1	0.28249 (3)	0.815464 (16)	0.172102 (13)	0.04328 (12)
Pd1	0.41404 (6)	0.81484 (3)	0.31775 (2)	0.03682 (15)
P1	0.5635 (2)	0.73783 (10)	0.38316 (9)	0.0439 (5)
P2	0.39485 (19)	0.88448 (9)	0.41084 (8)	0.0374 (4)
S1	0.4477 (2)	0.74341 (10)	0.22455 (9)	0.0528 (5)
S2	0.2475 (2)	0.88932 (10)	0.25349 (9)	0.0509 (5)
S3	0.0860 (3)	0.76349 (17)	0.13437 (11)	0.0858 (9)
S4	0.3627 (3)	0.86325 (12)	0.08739 (10)	0.0640 (6)
C1	0.7310 (9)	0.7126 (5)	0.3490 (4)	0.060 (2)
C2	0.7943 (10)	0.7548 (6)	0.3042 (4)	0.079 (3)
H2	0.7461	0.7946	0.2876	0.095*
C3	0.9293 (10)	0.7378 (6)	0.2839 (5)	0.082 (3)
H3	0.9691	0.7653	0.2529	0.098*
C4	1.0044 (12)	0.6794 (6)	0.3102 (5)	0.087 (3)
H4	1.0968	0.6686	0.2993	0.105*
C5	0.9362 (10)	0.6377 (6)	0.3536 (5)	0.084 (3)
H5	0.9819	0.5970	0.3690	0.101*
C6	0.7963 (10)	0.6553 (6)	0.3758 (5)	0.079 (3)
H6	0.7546	0.6284	0.4067	0.094*
C7	0.4690 (9)	0.6596 (4)	0.3984 (4)	0.055 (2)
C8	0.4143 (10)	0.6201 (5)	0.3415 (5)	0.073 (3)
H8	0.4269	0.6346	0.2978	0.088*
C9	0.3407 (10)	0.5588 (5)	0.3496 (5)	0.076 (3)
H9	0.3054	0.5316	0.3120	0.091*
C10	0.3221 (10)	0.5398 (5)	0.4159 (5)	0.074 (3)
H10	0.2724	0.4995	0.4224	0.089*
C11	0.3760 (11)	0.5797 (5)	0.4728 (5)	0.079 (3)
H11	0.3644	0.5668	0.5171	0.095*
C12	0.4471 (10)	0.6389 (5)	0.4597 (5)	0.069 (2)
H12	0.4824	0.6666	0.4969	0.083*
C13	0.3134 (8)	0.8411 (4)	0.4764 (4)	0.052 (2)
C14	0.2235 (8)	0.7844 (4)	0.4584 (4)	0.054 (2)
H14	0.2105	0.7679	0.4136	0.064*
C15	0.1536 (9)	0.7530 (4)	0.5080 (4)	0.058 (2)
H15	0.0967	0.7142	0.4965	0.070*
C16	0.1665 (9)	0.7771 (4)	0.5712 (4)	0.055 (2)
H16	0.1129	0.7567	0.6022	0.067*
C17	0.2576 (9)	0.8321 (4)	0.5928 (4)	0.058 (2)
H17	0.2720	0.8461	0.6384	0.069*
C18	0.3267 (8)	0.8655 (4)	0.5435 (4)	0.055 (2)
H18	0.3823	0.9046	0.5556	0.066*
C19	0.2821 (9)	0.9613 (4)	0.3967 (4)	0.055 (2)
C20	0.1463 (9)	0.9654 (4)	0.4197 (4)	0.057 (2)
H20	0.1099	0.9290	0.4425	0.069*
C21	0.0665 (9)	1.0259 (4)	0.4074 (4)	0.059 (2)
H21	−0.0236	1.0291	0.4235	0.070*
C22	0.1123 (10)	1.0800 (4)	0.3736 (4)	0.060 (2)
H22	0.0537	1.1187	0.3655	0.071*
C23	0.2452 (10)	1.0766 (4)	0.3518 (4)	0.056 (2)
H23	0.2800	1.1140	0.3298	0.067*
C24	0.3303 (9)	1.0174 (4)	0.3620 (4)	0.054 (2)
H24	0.4201	1.0152	0.3455	0.065*
C25	0.6404 (8)	0.7653 (4)	0.4697 (4)	0.055 (2)
H25A	0.5613	0.7823	0.4927	0.066*
H25B	0.6833	0.7260	0.4953	0.066*
C26	0.7590 (9)	0.8213 (4)	0.4708 (4)	0.060 (2)
H26A	0.7931	0.8336	0.5182	0.072*
H26B	0.8423	0.8024	0.4521	0.072*
C27	0.7107 (8)	0.8846 (4)	0.4323 (4)	0.056 (2)
H27A	0.6946	0.8734	0.3838	0.068*
H27B	0.7912	0.9171	0.4396	0.068*
C28	0.5715 (8)	0.9205 (4)	0.4493 (4)	0.056 (2)
H28A	0.5748	0.9679	0.4351	0.068*
H28B	0.5750	0.9202	0.4988	0.068*
C29	0.632 (3)	0.9769 (13)	0.2556 (15)	0.092 (7)	0.50
H29	0.5368	0.9615	0.2420	0.111*	0.50
C30	0.748 (2)	0.9269 (13)	0.1660 (13)	0.108 (8)	0.50
H30A	0.6867	0.8869	0.1640	0.129*	0.50
H30B	0.8495	0.9136	0.1743	0.129*	0.50
H30C	0.7282	0.9511	0.1232	0.129*	0.50
C31	0.861 (3)	0.9842 (13)	0.2487 (12)	0.106 (8)	0.50
H31A	0.8662	1.0113	0.2895	0.127*	0.50
H31B	0.9052	1.0087	0.2147	0.127*	0.50
H31C	0.9131	0.9420	0.2592	0.127*	0.50
N1	0.737 (2)	0.9641 (10)	0.2181 (10)	0.082 (5)	0.50
O1	0.6613 (17)	1.0066 (8)	0.3035 (8)	0.090 (5)	0.50
O2	0.9361 (15)	0.5574 (7)	0.4831 (8)	0.108 (5)	0.50
H2A	1.0125	0.5539	0.5130	0.161*	0.50
H2B	0.8597	0.5544	0.5027	0.161*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.0514 (2)	0.0510 (2)	0.02597 (16)	−0.00122 (16)	0.00078 (12)	−0.00632 (14)
Pd1	0.0458 (3)	0.0396 (3)	0.0239 (3)	−0.0009 (3)	0.0009 (2)	−0.0045 (2)
P1	0.0494 (11)	0.0514 (12)	0.0296 (9)	0.0011 (9)	0.0019 (8)	−0.0039 (8)
P2	0.0430 (10)	0.0398 (10)	0.0291 (9)	−0.0039 (8)	0.0041 (7)	−0.0050 (8)
S1	0.0729 (14)	0.0548 (12)	0.0289 (9)	0.0087 (10)	0.0009 (9)	−0.0080 (9)
S2	0.0619 (12)	0.0569 (12)	0.0312 (9)	0.0128 (10)	−0.0020 (8)	−0.0067 (9)
S3	0.0778 (17)	0.141 (3)	0.0375 (12)	−0.0344 (17)	0.0059 (11)	−0.0186 (14)
S4	0.0789 (15)	0.0746 (15)	0.0389 (11)	−0.0089 (13)	0.0103 (10)	0.0012 (11)
C1	0.058 (5)	0.077 (6)	0.043 (5)	0.016 (5)	0.000 (4)	−0.011 (4)
C2	0.071 (6)	0.116 (9)	0.049 (5)	0.003 (6)	0.007 (5)	−0.013 (6)
C3	0.056 (6)	0.126 (10)	0.065 (6)	0.004 (6)	0.016 (5)	−0.019 (6)
C4	0.066 (6)	0.127 (10)	0.070 (7)	0.009 (7)	0.015 (5)	−0.015 (7)
C5	0.063 (6)	0.120 (9)	0.066 (6)	0.014 (6)	0.003 (5)	−0.022 (6)
C6	0.059 (6)	0.122 (9)	0.056 (6)	0.011 (6)	0.012 (4)	−0.017 (6)
C7	0.067 (5)	0.054 (5)	0.042 (4)	−0.005 (4)	0.001 (4)	−0.002 (4)
C8	0.087 (7)	0.060 (6)	0.068 (6)	−0.015 (5)	−0.006 (5)	0.002 (5)
C9	0.089 (7)	0.072 (7)	0.062 (6)	−0.014 (6)	0.001 (5)	−0.007 (5)
C10	0.080 (6)	0.060 (6)	0.081 (7)	−0.009 (5)	0.005 (5)	0.004 (5)
C11	0.102 (8)	0.061 (6)	0.074 (6)	−0.017 (6)	0.010 (6)	0.001 (5)
C12	0.090 (7)	0.058 (6)	0.060 (6)	−0.009 (5)	0.011 (5)	0.000 (5)
C13	0.049 (5)	0.064 (5)	0.047 (5)	0.006 (4)	0.013 (4)	0.002 (4)
C14	0.052 (5)	0.063 (5)	0.048 (5)	0.007 (4)	0.017 (4)	0.001 (4)
C15	0.055 (5)	0.069 (6)	0.053 (5)	0.003 (4)	0.014 (4)	−0.001 (4)
C16	0.055 (5)	0.067 (6)	0.049 (5)	0.009 (4)	0.021 (4)	0.005 (4)
C17	0.058 (5)	0.067 (6)	0.049 (5)	0.013 (4)	0.010 (4)	0.002 (4)
C18	0.053 (5)	0.066 (6)	0.047 (5)	0.013 (4)	0.013 (4)	0.003 (4)
C19	0.073 (6)	0.047 (5)	0.045 (4)	0.007 (4)	0.011 (4)	−0.002 (4)
C20	0.068 (5)	0.046 (5)	0.057 (5)	0.010 (4)	0.007 (4)	−0.002 (4)
C21	0.069 (6)	0.054 (5)	0.054 (5)	0.011 (4)	0.010 (4)	−0.004 (4)
C22	0.077 (6)	0.046 (5)	0.056 (5)	0.008 (4)	0.012 (4)	−0.003 (4)
C23	0.078 (6)	0.043 (5)	0.047 (4)	0.003 (4)	0.007 (4)	−0.007 (4)
C24	0.068 (5)	0.046 (5)	0.048 (4)	0.006 (4)	0.006 (4)	−0.007 (4)
C25	0.050 (5)	0.062 (5)	0.047 (4)	0.003 (4)	−0.009 (4)	−0.003 (4)
C26	0.054 (5)	0.068 (6)	0.053 (5)	0.001 (4)	−0.004 (4)	−0.007 (4)
C27	0.055 (5)	0.062 (5)	0.049 (5)	−0.013 (4)	0.000 (4)	−0.007 (4)
C28	0.057 (5)	0.063 (5)	0.046 (5)	0.001 (4)	−0.001 (4)	−0.007 (4)
C29	0.063 (15)	0.089 (18)	0.12 (2)	−0.010 (13)	0.002 (16)	0.022 (16)
C30	0.094 (17)	0.098 (19)	0.12 (2)	−0.029 (14)	−0.004 (16)	0.029 (17)
C31	0.101 (19)	0.100 (19)	0.12 (2)	−0.002 (15)	0.026 (17)	0.007 (15)
N1	0.089 (14)	0.080 (13)	0.075 (12)	−0.011 (11)	0.010 (11)	0.006 (10)
O1	0.088 (11)	0.098 (12)	0.086 (10)	−0.002 (9)	0.025 (9)	0.016 (9)
O2	0.094 (10)	0.098 (11)	0.125 (13)	−0.029 (9)	−0.004 (9)	0.029 (9)

Geometric parameters (Å, º)

W1—S1	2.212 (2)	C15—H15	0.9300
W1—S2	2.2170 (18)	C16—C17	1.391 (11)
W1—S3	2.109 (2)	C16—H16	0.9300
W1—S4	2.136 (2)	C17—C18	1.398 (10)
Pd1—P1	2.301 (2)	C17—H17	0.9300
Pd1—P2	2.3126 (18)	C18—H18	0.9300
Pd1—S2	2.344 (2)	C19—C20	1.389 (11)
Pd1—S1	2.3637 (19)	C19—C24	1.399 (10)
P1—C7	1.806 (9)	C20—C21	1.394 (10)
P1—C25	1.828 (7)	C20—H20	0.9300
P1—C1	1.834 (9)	C21—C22	1.350 (11)
P2—C13	1.797 (8)	C21—H21	0.9300
P2—C19	1.823 (8)	C22—C23	1.353 (11)
P2—C28	1.827 (7)	C22—H22	0.9300
C1—C6	1.341 (13)	C23—C24	1.396 (10)
C1—C2	1.398 (12)	C23—H23	0.9300
C2—C3	1.397 (12)	C24—H24	0.9300
C2—H2	0.9300	C25—C26	1.543 (11)
C3—C4	1.395 (13)	C25—H25A	0.9700
C3—H3	0.9300	C25—H25B	0.9700
C4—C5	1.393 (14)	C26—C27	1.485 (10)
C4—H4	0.9300	C26—H26A	0.9700
C5—C6	1.457 (12)	C26—H26B	0.9700
C5—H5	0.9300	C27—C28	1.538 (10)
C6—H6	0.9300	C27—H27A	0.9700
C7—C12	1.318 (11)	C27—H27B	0.9700
C7—C8	1.393 (11)	C28—H28A	0.9700
C8—C9	1.396 (12)	C28—H28B	0.9700
C8—H8	0.9300	C29—O1	1.11 (3)
C9—C10	1.392 (12)	C29—N1	1.32 (3)
C9—H9	0.9300	C29—H29	0.9300
C10—C11	1.395 (12)	C30—N1	1.27 (3)
C10—H10	0.9300	C30—H30A	0.9601
C11—C12	1.373 (11)	C30—H30B	0.9600
C11—H11	0.9300	C30—H30C	0.9601
C12—H12	0.9300	C31—N1	1.27 (2)
C13—C18	1.395 (10)	C31—H31A	0.9600
C13—C14	1.396 (11)	C31—H31B	0.9600
C14—C15	1.389 (10)	C31—H31C	0.9601
C14—H14	0.9300	O2—H2A	0.8501
C15—C16	1.320 (10)	O2—H2B	0.8501
S3—W1—S4	108.09 (9)	C13—C14—H14	120.3
S3—W1—S1	110.46 (11)	C16—C15—C14	121.2 (8)
S4—W1—S1	110.67 (9)	C16—C15—H15	119.4
S3—W1—S2	111.23 (9)	C14—C15—H15	119.4
S4—W1—S2	112.53 (9)	C15—C16—C17	122.1 (8)
S1—W1—S2	103.87 (7)	C15—C16—H16	118.9
S3—W1—Pd1	123.27 (7)	C17—C16—H16	118.9
S4—W1—Pd1	128.63 (6)	C16—C17—C18	117.6 (8)
S1—W1—Pd1	52.22 (5)	C16—C17—H17	121.2
S2—W1—Pd1	51.70 (5)	C18—C17—H17	121.2
P1—Pd1—P2	92.87 (7)	C13—C18—C17	120.8 (8)
P1—Pd1—S2	175.97 (8)	C13—C18—H18	119.6
P2—Pd1—S2	86.71 (6)	C17—C18—H18	119.6
P1—Pd1—S1	85.01 (7)	C20—C19—C24	118.5 (7)
P2—Pd1—S1	176.87 (7)	C20—C19—P2	120.9 (6)
S2—Pd1—S1	95.57 (7)	C24—C19—P2	120.5 (6)
P1—Pd1—W1	132.37 (5)	C19—C20—C21	117.8 (8)
P2—Pd1—W1	134.61 (5)	C19—C20—H20	121.1
S2—Pd1—W1	47.91 (5)	C21—C20—H20	121.1
S1—Pd1—W1	47.71 (5)	C22—C21—C20	123.8 (8)
C7—P1—C25	102.9 (4)	C22—C21—H21	118.1
C7—P1—C1	106.3 (4)	C20—C21—H21	118.1
C25—P1—C1	101.0 (4)	C21—C22—C23	118.6 (8)
C7—P1—Pd1	112.7 (3)	C21—C22—H22	120.7
C25—P1—Pd1	116.6 (3)	C23—C22—H22	120.7
C1—P1—Pd1	115.7 (3)	C22—C23—C24	120.4 (8)
C13—P2—C19	102.3 (4)	C22—C23—H23	119.8
C13—P2—C28	108.7 (4)	C24—C23—H23	119.8
C19—P2—C28	101.2 (4)	C23—C24—C19	120.7 (8)
C13—P2—Pd1	112.3 (3)	C23—C24—H24	119.6
C19—P2—Pd1	118.2 (2)	C19—C24—H24	119.6
C28—P2—Pd1	113.0 (3)	C26—C25—P1	113.4 (6)
W1—S1—Pd1	80.07 (7)	C26—C25—H25A	108.9
W1—S2—Pd1	80.40 (6)	P1—C25—H25A	108.9
C6—C1—C2	122.7 (9)	C26—C25—H25B	108.9
C6—C1—P1	115.5 (7)	P1—C25—H25B	108.9
C2—C1—P1	121.4 (7)	H25A—C25—H25B	107.7
C3—C2—C1	120.5 (10)	C27—C26—C25	115.3 (7)
C3—C2—H2	119.8	C27—C26—H26A	108.4
C1—C2—H2	119.8	C25—C26—H26A	108.4
C4—C3—C2	120.0 (10)	C27—C26—H26B	108.4
C4—C3—H3	120.0	C25—C26—H26B	108.4
C2—C3—H3	120.0	H26A—C26—H26B	107.5
C5—C4—C3	117.7 (10)	C26—C27—C28	117.7 (7)
C5—C4—H4	121.1	C26—C27—H27A	107.9
C3—C4—H4	121.1	C28—C27—H27A	107.9
C4—C5—C6	122.8 (11)	C26—C27—H27B	107.9
C4—C5—H5	118.6	C28—C27—H27B	107.9
C6—C5—H5	118.6	H27A—C27—H27B	107.2
C1—C6—C5	116.2 (10)	C27—C28—P2	116.6 (5)
C1—C6—H6	121.9	C27—C28—H28A	108.1
C5—C6—H6	121.9	P2—C28—H28A	108.1
C12—C7—C8	118.8 (9)	C27—C28—H28B	108.1
C12—C7—P1	123.6 (7)	P2—C28—H28B	108.1
C8—C7—P1	117.5 (7)	H28A—C28—H28B	107.3
C7—C8—C9	120.5 (9)	O1—C29—N1	118 (2)
C7—C8—H8	119.7	O1—C29—H29	120.8
C9—C8—H8	119.7	N1—C29—H29	120.8
C10—C9—C8	117.6 (9)	N1—C30—H30A	112.6
C10—C9—H9	121.2	N1—C30—H30B	101.9
C8—C9—H9	121.2	H30A—C30—H30B	109.5
C9—C10—C11	121.8 (9)	N1—C30—H30C	113.6
C9—C10—H10	119.1	H30A—C30—H30C	109.5
C11—C10—H10	119.1	H30B—C30—H30C	109.5
C12—C11—C10	116.3 (9)	N1—C31—H31A	119.9
C12—C11—H11	121.8	N1—C31—H31B	105.3
C10—C11—H11	121.8	H31A—C31—H31B	109.5
C7—C12—C11	124.9 (9)	N1—C31—H31C	102.7
C7—C12—H12	117.6	H31A—C31—H31C	109.5
C11—C12—H12	117.6	H31B—C31—H31C	109.5
C18—C13—C14	118.6 (7)	C31—N1—C30	113 (2)
C18—C13—P2	122.1 (7)	C31—N1—C29	111 (2)
C14—C13—P2	119.0 (6)	C30—N1—C29	135 (2)
C15—C14—C13	119.3 (7)	H2A—O2—H2B	109.5
C15—C14—H14	120.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···S4^i	0.85	2.32	2.737 (16)	111
C24—H24···O1	0.93	2.48	3.410 (17)	179

Symmetry code: (i) x+1/2, −y+3/2, z+1/2.