trans-Chloro(2-nitro­benzene­thiolato-S)­bis­(tri­phenyl­phosphine-P)palladium(II) mono­acetone solvate

Molecules of the title compound, [PdCl(C₆H₄NO₂S)(PPh₃)₂]·­C₃H₆O, exhibit a slight distortion from exact planarity at the Pd atom towards tetrahedral, with P-Pd-P and Cl-Pd-S angles of 174.98 (3) and 174.19 (3)°, respectively. The Pd-Cl and Pd-S bonds are, respectively, long [2.3550 (11) Å] and short [2.3020 (12) Å] for their types; the S-C bond is also very short [1.744 (4) Å]. The solvating acetone mol­ecule is linked to one of the phosphine ligands by means of a C-H...O hydrogen bond.

S1. Comment

We have recently reported the structures of members of the 2-O₂NC₆H₄SX system containing the 2-nitrophenylthiolate group, in which the α-atom of fragment X can be C or N (Low, Storey et al., 2000) or S (Low, Glidewell & Wardell, 2000). In general, at the global energy minimum conformation, both the nitro group and the α-atom of group X are essentially coplanar with the aryl ring. When X is not in the plane of the aryl ring, rotation about the exocyclic C—S bond is associated with a disrotatory twist of the nitro group about the C—N bond; the occurrence of such conformations seems to depend on the presence in the structure of specific intermolecular interactions, such as C—H···O hydrogen bonds. Seeking to investigate the wider generality of this idea, we report here the structure of a further compound of type 2-O₂NC₆H₄SX, namely trans-chloro(2-nitrobenzenethiolato)bis(triphenylphosphine)palladium(II), (I), in which the α-atom of group X is Pd and which crystallizes from acetone as a 1:1 solvate.

Molecules of (I) lie in general positions (Fig. 1). Although no bond angle at Pd involving a pair of cis substituents deviates from 90° by more than 1.7°, nonetheless there a slight but significant distortion from planarity towards tetrahedral and both bond angles at Pd involving trans pairs of substituents are less than 175° (Table 1). The deviations (Å) of the ligating atoms from their best plane through Pd are: Cl −0.106 (1), S −0.105 (1), P1 0.105 (1) and P2 0.106 (1). In this respect, the configuration of the trans-PdClP₂S chromophore in (I) differs from those found in two analogous compounds retrieved from the Cambridge Structural Database (Allen & Kennard, 1993), containing trans-PdCl₂P₂ and trans-PdP₂S₂ chromophores. Molecules of trans-[PdCl₂(PPh₃)₂] are centrosymmetric both in the unsolvated compound (BISKIX; Ferguson et al., 1982) and in the bis-chloroform solvate (RAVYUI; Stark & Whitmire, 1997). Similarly, molecules of trans-[Pd{PH(C₆H₁₁)₂}₂(SPh)₂] (LETNON; Pasquali et al., 1993) lie across inversion centres. Hence, in all these complexes, palladium and its four ligating atoms are strictly coplanar.

The conformation of (I) is close to that expected (Low, Storey et al., 2000) for the global energy minimum. There is a slight rotation around the C—S bond away from coplanarity of the Pd atom, with the nitrated aryl ring and a disrotatory twist of the nitro group around the C—N bond. The dihedral angles between the nitrated aryl ring and the planes defined by C1—S1—Pd1—Cl1 and C6—NO₂ are 6.2 (2) and 16.3 (2)°, respectively. In centrosymmetric molecules of trans-[PdCl₂(PPh₃)₂] (Ferguson et al., 1982; Stark & Whitmire, 1997), the P—C bonds of the two phosphine ligands are necessarily exactly staggered. In contrast in (I), these P—C bonds are almost eclipsed, with a mean deviation of 5.9 (3)° from a fully eclipsed Ph₃P—Pd-PPh₃ fragment. Presumably, the rotational barriers about the Pd—P bonds are low.

The two independent Pd—P distances in (I) (Table 1) are both very similar to those reported for BISKIX [2.337 (2) Å] and RAVYUI [2.343 (2) Å]. However, the Pd—Cl distance in (I) is very much longer than the corresponding distances in BISKIX [2.291 (2) Å] and RAVYUI [2.293 (2) Å]. On the other hand, the Pd—S distance in (I) is much shorter than those reported for LETNON [2.3393 (16) and 2.3366 (19) Å in two independent molecules]. These observations can all be readily rationalized in terms of the trans influence, t(X), of a ligand X upon the properties of the metal–ligand bond trans to X, which arises from the competition for a common metal d orbital of the π type between ligands occupying trans sites. Ligands of high trans-influence render the metal–ligand bonds trans to themselves longer (Appleton et al., 1973), and ligands can thus be ranked in order of t(X). This is a static thermodynamic phenomenon which closely parallels the dynamic kinetic trans effect describing the influence on the rates of ligand substitution exerted by ligands in trans sites (Basolo & Pearson, 1962). The data for (I) and related compounds show that a Pd—S bond trans to Cl is much shorter than a Pd—S bond trans to another thiolate; hence, t(SR⁻) >> t(Cl⁻). Similarly, Pd—P bonds trans to another P are typically much shorter than Pd—P bonds trans to chloride. For example, in cis-[PdCl₂(Me₂N=CH)PPh₃] (McCrindle et al., 2000), the Pd—P distance is 2.2495 (7) Å, much shorter than the corresponding bonds in (I), BISKIX and RAVYUI. Likewise, in [PdCl₂(Me₂N=CH)PPh₃], the Pd—Cl bond trans to P is very much longer [2.3600 (7) Å] than those in BISKIX [2.291 (2) Å] and RAVYUI [2.293 (2) Å], so that t(PR₃) >> t(Cl⁻). The order of PR₃ and SR⁻ can be established by comparison of analogous cis- and trans-PdP₂S₂ chromophores, as for example in LETNON and [Pd(Ph₂PCH₂CH₂PPh₂)(SCH₂Ph)₂] (TERREN; Su et al., 1997). On moving form trans to cis geometry, the Pd—P bonds become shorter and the Pd—S bonds become longer, hence, t(PR₃) > t(SR⁻) and overall t(PR₃) > t(SR⁻) > t(Cl⁻).

There is evidence of C—C bond fixation in the nitrated aryl ring, where the C—C distances range from 1.358 (6) to 1.414 (5) Å. This range is greater than is usual for compounds of this type (Low, Storey et al., 2000; Low, Glidewell & Wardell, 2000), although the C—N distance and the O—N—O angle are both entirely typical of their types, so ruling out any p-quinonoid-type bond fixation, as observed in 2-O₂NC₆H₄SCH=CHPh (Low, Storey et al., 2000). On the other hand, the C—S distance is significantly shorter than those observed in previous examples of 2-O₂NC₆H₄SX compounds. For comparison, the lower quartile value for a C(aryl)—S—C bond distance is 1.765 Å and, indeed, C(aryl)—S bonds as short as that in (I) are generally found only with four-coordinate S^VI (Allen et al., 1987). The short C—S bond and the extremely small C—C—C angles ipso to S are together consistent with significant electron donation from S into the adjacent ring (Domenicano & Murray-Rust, 1979).

The solvating acetone molecule is linked to a phenyl group in one of the phosphine ligands of (I) by a C—H···O hydrogen bond (Table 2).

S2. Experimental

The title compound was obtained from the reaction of trans-[PdCl₂(PPh₃)₂] and 2-O₂NC₆H₄SSnPh₃ in acetone solution. The compound was purified by column chromatography on silica using CHCl₃ as eluent. The compound obtained decomposed on heating, before melting at 478 K. Crystals suitable for single-crystal X-ray diffraction were obtained from an acetone solution.

S3. Refinement

Compound (I) crystallized in the monoclinic system as a monoacetone solvate; space group P2₁/n was assumed from the systematic absences. H atoms were treated as riding atoms with a C—H distance of 0.95 Å for aromatic H atoms and 0.98 Å for methyl H atoms. The acetone molecule was modelled with six-half occupancy H atoms in the methyl group defined by C7; the O and C atoms of the acetone molecule all had large displacement parameters. Examination of the refined structure with PLATON (Spek, 2000) showed there were no solvent-accessible voids in the structure, but that there were four symmetry-related voids, each with a volume of ca 11 ų, in the vicinity of the four solvent molecules in the unit cell. These may be associated with the large displacement parameters of the solvent molecule. The sites of maximum and minimum residual density are adjacent to the acetone and Pd atom, respectively.

Computing details

Data collection: CAD-4-PC Software (Enraf-Nonius, 1992) and FAST/MADNES (Pflugrath & Messerschmidt, 1989); cell refinement: CAD-4-PC Software and FAST/MADNES; data reduction: CAD-4-PC Software and FAST/MADNES; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: NRCVAX96 (Gabe et al., 1989) and SHELXL97 (Sheldrick, 1997); molecular graphics: NRCVAX96, ORTEPII (Johnson, 1976) and PLATON (Spek, 2000); software used to prepare material for publication: NRCVAX96, SHELXL97 and WORDPERFECT macro PREP8 (Ferguson, 1998).

Figures

Fig. 1. The asymmetric unit of (I)·(CH3)2CO showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms bonded to C7 have site-occupation factor 0.5.

trans-Chloro(2-nitrobenzenethiolato-S)bis(triphenylphosphine-P)palladium(II) monoacetone solvate

Crystal data

[PdCl(C6H4NO2S)(C18H15P)2]·C3H6O	F(000) = 1800
Mr = 878.63	Dx = 1.410 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 18.292 (7) Å	Cell parameters from 11315 reflections
b = 10.969 (3) Å	θ = 1.3–30.5°
c = 21.363 (8) Å	µ = 0.68 mm^−1
β = 105.0928 (17)°	T = 150 K
V = 4139 (2) Å^3	Block, orange
Z = 4	0.30 × 0.10 × 0.05 mm

Data collection

Enraf-Nonius diffractometer with FAST area-detector	11315 independent reflections
Radiation source: fine-focus sealed X-ray tube	5642 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.095
ϕ and ω scans with κ offsets	θmax = 30.1°, θmin = 1.3°
Absorption correction: multi-scan (FAST/MADNES; Pflugrath & Messerschmidt, 1989)	h = −25→25
Tmin = 0.822, Tmax = 0.967	k = −14→15
49325 measured reflections	l = −29→30

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)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.147	w = 1/[σ^2(Fo^2) + (0.0686P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.94	(Δ/σ)max < 0.001
11315 reflections	Δρmax = 1.54 e Å^−3
489 parameters	Δρmin = −1.10 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0026 (2)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pd1	0.412423 (15)	−0.00059 (2)	0.213104 (13)	0.02071 (10)
Cl1	0.32845 (5)	−0.15334 (8)	0.22875 (5)	0.0284 (2)
S1	0.50238 (5)	0.13304 (8)	0.19609 (5)	0.0278 (2)
P1	0.46940 (5)	0.00014 (8)	0.32452 (4)	0.0210 (2)
P2	0.34622 (5)	0.00591 (8)	0.10405 (4)	0.0199 (2)
O1	0.61027 (18)	0.2968 (3)	0.18010 (17)	0.0551 (9)
O2	0.5886 (2)	0.4828 (3)	0.14727 (19)	0.0679 (11)
N1	0.5707 (2)	0.3889 (3)	0.17161 (18)	0.0429 (9)
C1	0.4673 (2)	0.2782 (3)	0.20464 (18)	0.0285 (9)
C2	0.3996 (2)	0.2942 (4)	0.22387 (19)	0.0318 (9)
C3	0.3684 (2)	0.4059 (4)	0.2299 (2)	0.0409 (11)
C4	0.4040 (3)	0.5111 (4)	0.2165 (2)	0.0435 (12)
C5	0.4686 (3)	0.5008 (4)	0.1969 (2)	0.0394 (11)
C6	0.5002 (2)	0.3880 (4)	0.19153 (19)	0.0318 (9)
C111	0.5321 (2)	0.1258 (3)	0.35935 (18)	0.0263 (9)
C112	0.6042 (2)	0.1299 (4)	0.34794 (19)	0.0346 (10)
C113	0.6536 (2)	0.2236 (4)	0.3721 (2)	0.0410 (11)
C114	0.6324 (2)	0.3149 (4)	0.4077 (2)	0.0447 (12)
C115	0.5618 (3)	0.3123 (4)	0.4195 (2)	0.0489 (13)
C116	0.5117 (2)	0.2175 (3)	0.3955 (2)	0.0357 (10)
C121	0.3976 (2)	0.0008 (3)	0.37015 (18)	0.0256 (8)
C122	0.4003 (2)	−0.0771 (3)	0.42209 (19)	0.0308 (9)
C123	0.3440 (2)	−0.0705 (4)	0.4550 (2)	0.0381 (11)
C124	0.2863 (2)	0.0132 (4)	0.4372 (2)	0.0389 (11)
C125	0.2834 (2)	0.0907 (4)	0.3855 (2)	0.0404 (11)
C126	0.3382 (2)	0.0832 (4)	0.3521 (2)	0.0333 (10)
C131	0.5289 (2)	−0.1325 (3)	0.35103 (18)	0.0256 (8)
C132	0.5247 (2)	−0.2343 (4)	0.3114 (2)	0.0341 (10)
C133	0.5743 (2)	−0.3318 (4)	0.3316 (2)	0.0443 (12)
C134	0.6273 (2)	−0.3276 (4)	0.3895 (2)	0.0439 (12)
C135	0.6316 (3)	−0.2283 (4)	0.4299 (2)	0.0464 (12)
C136	0.5823 (2)	−0.1322 (4)	0.4107 (2)	0.0391 (11)
C211	0.2452 (2)	0.0239 (3)	0.09887 (18)	0.0231 (8)
C212	0.1911 (2)	−0.0528 (4)	0.0615 (2)	0.0315 (9)
C213	0.1155 (2)	−0.0394 (4)	0.0604 (2)	0.0397 (11)
C214	0.0928 (2)	0.0497 (4)	0.0965 (2)	0.0376 (10)
C215	0.1468 (2)	0.1265 (4)	0.1347 (2)	0.0343 (10)
C216	0.2220 (2)	0.1133 (3)	0.13582 (19)	0.0320 (9)
C221	0.3684 (2)	0.1270 (3)	0.05327 (17)	0.0234 (8)
C222	0.4364 (2)	0.1183 (3)	0.03580 (19)	0.0309 (9)
C223	0.4562 (2)	0.2047 (4)	−0.0036 (2)	0.0401 (11)
C224	0.4091 (3)	0.3025 (4)	−0.0246 (2)	0.0457 (12)
C225	0.3421 (3)	0.3147 (4)	−0.0074 (2)	0.0434 (11)
C226	0.3222 (2)	0.2264 (3)	0.0322 (2)	0.0351 (10)
C231	0.3535 (2)	−0.1287 (3)	0.05621 (18)	0.0248 (8)
C232	0.3819 (2)	−0.2382 (3)	0.08609 (19)	0.0303 (9)
C233	0.3859 (2)	−0.3413 (3)	0.0485 (2)	0.0342 (10)
C234	0.3618 (2)	−0.3344 (4)	−0.0183 (2)	0.0382 (11)
C235	0.3344 (2)	−0.2258 (4)	−0.0480 (2)	0.0357 (10)
C236	0.3303 (2)	−0.1239 (3)	−0.01082 (19)	0.0310 (9)
O3	0.2651 (3)	0.0434 (4)	−0.1423 (2)	0.0982 (15)
C7	0.3458 (5)	0.1230 (7)	−0.2021 (4)	0.146 (4)
C8	0.2880 (4)	0.0371 (6)	−0.1895 (3)	0.0751 (19)
C9	0.2630 (4)	−0.0568 (7)	−0.2386 (3)	0.106 (2)
H2	0.3742	0.2236	0.2331	0.038*
H3	0.3228	0.4114	0.2432	0.049*
H4	0.3834	0.5891	0.2210	0.052*
H5	0.4925	0.5723	0.1867	0.047*
H112	0.6191	0.0671	0.3232	0.042*
H113	0.7024	0.2250	0.3642	0.049*
H114	0.6663	0.3799	0.4242	0.054*
H115	0.5473	0.3755	0.4442	0.059*
H116	0.4633	0.2161	0.4041	0.043*
H122	0.4403	−0.1344	0.4350	0.037*
H123	0.3455	−0.1243	0.4901	0.046*
H124	0.2485	0.0177	0.4603	0.047*
H125	0.2438	0.1489	0.3732	0.048*
H126	0.3353	0.1353	0.3160	0.040*
H132	0.4882	−0.2374	0.2707	0.041*
H133	0.5709	−0.4016	0.3047	0.053*
H134	0.6616	−0.3936	0.4023	0.053*
H135	0.6682	−0.2261	0.4706	0.056*
H136	0.5849	−0.0643	0.4388	0.047*
H212	0.2059	−0.1151	0.0364	0.038*
H213	0.0788	−0.0923	0.0343	0.048*
H214	0.0409	0.0585	0.0954	0.045*
H215	0.1318	0.1882	0.1600	0.041*
H216	0.2586	0.1659	0.1622	0.038*
H222	0.4696	0.0520	0.0513	0.037*
H223	0.5021	0.1968	−0.0162	0.048*
H224	0.4231	0.3624	−0.0515	0.055*
H225	0.3098	0.3823	−0.0222	0.052*
H226	0.2764	0.2347	0.0448	0.042*
H232	0.3986	−0.2428	0.1320	0.036*
H233	0.4052	−0.4158	0.0689	0.041*
H234	0.3641	−0.4046	−0.0438	0.046*
H235	0.3183	−0.2211	−0.0940	0.043*
H236	0.3114	−0.0496	−0.0316	0.037*
H7A	0.3593	0.1827	−0.1669	0.219*	0.50
H7B	0.3250	0.1653	−0.2433	0.219*	0.50
H7C	0.3911	0.0772	−0.2044	0.219*	0.50
H7D	0.3576	0.1008	−0.2428	0.219*	0.50
H7E	0.3919	0.1182	−0.1664	0.219*	0.50
H7F	0.3259	0.2063	−0.2053	0.219*	0.50
H9A	0.2193	−0.0999	−0.2306	0.159*
H9B	0.3043	−0.1147	−0.2367	0.159*
H9C	0.2484	−0.0189	−0.2816	0.159*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.02289 (16)	0.01881 (15)	0.01983 (16)	−0.00052 (12)	0.00448 (11)	0.00098 (12)
Cl1	0.0317 (5)	0.0254 (5)	0.0278 (5)	−0.0046 (4)	0.0073 (4)	0.0022 (4)
S1	0.0273 (5)	0.0278 (5)	0.0288 (6)	−0.0031 (4)	0.0079 (4)	−0.0001 (4)
P1	0.0225 (5)	0.0201 (5)	0.0197 (5)	0.0007 (4)	0.0042 (4)	0.0006 (4)
P2	0.0203 (5)	0.0198 (5)	0.0195 (5)	−0.0014 (4)	0.0048 (4)	0.0006 (4)
O1	0.052 (2)	0.047 (2)	0.078 (3)	−0.0015 (17)	0.038 (2)	0.0035 (18)
O2	0.081 (3)	0.046 (2)	0.091 (3)	−0.0153 (18)	0.048 (2)	0.0146 (19)
N1	0.050 (2)	0.040 (2)	0.042 (2)	−0.010 (2)	0.020 (2)	−0.0010 (18)
C1	0.031 (2)	0.032 (2)	0.020 (2)	−0.0024 (18)	0.0031 (17)	−0.0002 (16)
C2	0.032 (2)	0.028 (2)	0.035 (2)	−0.0011 (18)	0.0068 (19)	0.0010 (18)
C3	0.037 (2)	0.037 (3)	0.047 (3)	0.003 (2)	0.009 (2)	−0.001 (2)
C4	0.056 (3)	0.026 (2)	0.047 (3)	0.003 (2)	0.012 (2)	0.0005 (19)
C5	0.054 (3)	0.026 (2)	0.037 (3)	−0.006 (2)	0.009 (2)	0.0041 (19)
C6	0.038 (2)	0.029 (2)	0.029 (2)	−0.0065 (19)	0.0096 (19)	−0.0015 (17)
C111	0.032 (2)	0.0209 (19)	0.023 (2)	−0.0022 (17)	0.0008 (17)	0.0038 (16)
C112	0.035 (2)	0.040 (2)	0.027 (2)	−0.006 (2)	0.0056 (19)	−0.0053 (19)
C113	0.034 (2)	0.044 (3)	0.045 (3)	−0.009 (2)	0.009 (2)	0.000 (2)
C114	0.037 (3)	0.028 (2)	0.060 (3)	−0.009 (2)	−0.002 (2)	0.000 (2)
C115	0.047 (3)	0.027 (2)	0.070 (4)	0.003 (2)	0.009 (3)	−0.016 (2)
C116	0.028 (2)	0.031 (2)	0.044 (3)	0.0015 (18)	0.002 (2)	−0.008 (2)
C121	0.028 (2)	0.0252 (19)	0.023 (2)	−0.0044 (18)	0.0067 (16)	−0.0055 (17)
C122	0.037 (2)	0.025 (2)	0.030 (2)	0.0011 (18)	0.0073 (19)	0.0004 (17)
C123	0.048 (3)	0.039 (3)	0.031 (3)	−0.006 (2)	0.018 (2)	0.0029 (19)
C124	0.035 (2)	0.050 (3)	0.037 (3)	−0.006 (2)	0.019 (2)	−0.005 (2)
C125	0.036 (2)	0.046 (3)	0.040 (3)	0.004 (2)	0.011 (2)	−0.001 (2)
C126	0.032 (2)	0.038 (2)	0.029 (2)	0.004 (2)	0.0076 (19)	0.0048 (18)
C131	0.025 (2)	0.026 (2)	0.025 (2)	0.0034 (17)	0.0073 (17)	0.0041 (16)
C132	0.030 (2)	0.037 (2)	0.032 (2)	0.0030 (19)	0.0031 (19)	−0.0026 (19)
C133	0.042 (3)	0.033 (2)	0.054 (3)	0.007 (2)	0.005 (2)	−0.005 (2)
C134	0.035 (3)	0.033 (2)	0.059 (3)	0.009 (2)	0.004 (2)	0.009 (2)
C135	0.048 (3)	0.036 (2)	0.044 (3)	0.006 (2)	−0.008 (2)	0.004 (2)
C136	0.050 (3)	0.031 (2)	0.029 (2)	0.006 (2)	−0.004 (2)	0.0034 (19)
C211	0.0250 (19)	0.023 (2)	0.021 (2)	0.0001 (15)	0.0066 (16)	0.0034 (15)
C212	0.029 (2)	0.030 (2)	0.036 (3)	0.0000 (18)	0.008 (2)	−0.0069 (18)
C213	0.029 (2)	0.044 (2)	0.045 (3)	−0.009 (2)	0.006 (2)	−0.008 (2)
C214	0.028 (2)	0.043 (2)	0.044 (3)	0.000 (2)	0.015 (2)	0.002 (2)
C215	0.036 (2)	0.036 (2)	0.033 (2)	0.0046 (19)	0.014 (2)	−0.0054 (19)
C216	0.032 (2)	0.032 (2)	0.033 (2)	−0.0015 (18)	0.0100 (19)	−0.0059 (18)
C221	0.025 (2)	0.0233 (19)	0.019 (2)	−0.0038 (16)	0.0009 (16)	0.0003 (15)
C222	0.031 (2)	0.030 (2)	0.032 (2)	0.0023 (18)	0.0100 (19)	0.0083 (18)
C223	0.034 (2)	0.042 (3)	0.048 (3)	0.000 (2)	0.019 (2)	0.005 (2)
C224	0.055 (3)	0.034 (2)	0.054 (3)	−0.007 (2)	0.026 (3)	0.014 (2)
C225	0.051 (3)	0.031 (2)	0.051 (3)	0.007 (2)	0.018 (2)	0.013 (2)
C226	0.036 (2)	0.033 (2)	0.039 (3)	0.0032 (19)	0.014 (2)	0.0082 (19)
C231	0.0231 (19)	0.026 (2)	0.026 (2)	−0.0035 (16)	0.0080 (17)	−0.0026 (16)
C232	0.040 (2)	0.025 (2)	0.029 (2)	−0.0039 (18)	0.016 (2)	0.0014 (17)
C233	0.040 (2)	0.025 (2)	0.043 (3)	−0.0013 (19)	0.022 (2)	0.0024 (18)
C234	0.041 (3)	0.034 (2)	0.046 (3)	−0.010 (2)	0.023 (2)	−0.010 (2)
C235	0.037 (2)	0.043 (3)	0.029 (2)	−0.004 (2)	0.010 (2)	−0.0075 (19)
C236	0.032 (2)	0.030 (2)	0.032 (2)	−0.0022 (18)	0.0093 (19)	−0.0025 (18)
O3	0.128 (4)	0.106 (3)	0.079 (3)	0.048 (3)	0.059 (3)	0.028 (3)
C7	0.190 (9)	0.082 (5)	0.216 (11)	0.001 (6)	0.141 (8)	−0.002 (6)
C8	0.097 (5)	0.077 (4)	0.070 (4)	0.044 (4)	0.054 (4)	0.024 (3)
C9	0.088 (5)	0.137 (6)	0.099 (6)	0.025 (5)	0.034 (5)	−0.024 (5)

Geometric parameters (Å, º)

Pd1—S1	2.3020 (11)	C133—H133	0.9500
Pd1—P1	2.3366 (13)	C134—C135	1.379 (6)
Pd1—P2	2.3303 (12)	C134—H134	0.9500
Pd1—Cl1	2.3550 (11)	C135—C136	1.378 (5)
S1—C1	1.744 (4)	C135—H135	0.9500
P1—C111	1.824 (4)	C136—H136	0.9500
P1—C121	1.828 (4)	C211—C212	1.384 (5)
P1—C131	1.817 (4)	C211—C216	1.392 (5)
P2—C211	1.833 (4)	C212—C213	1.385 (5)
P2—C221	1.826 (4)	C212—H212	0.9500
P2—C231	1.821 (4)	C213—C214	1.374 (6)
O1—N1	1.228 (4)	C213—H213	0.9500
O2—N1	1.237 (4)	C214—C215	1.389 (5)
N1—C6	1.458 (5)	C214—H214	0.9500
C1—C6	1.407 (5)	C215—C216	1.378 (5)
C1—C2	1.414 (5)	C215—H215	0.9500
C2—C3	1.371 (5)	C216—H216	0.9500
C2—H2	0.9500	C221—C222	1.393 (5)
C3—C4	1.391 (6)	C221—C226	1.380 (5)
C3—H3	0.9500	C222—C223	1.377 (5)
C4—C5	1.358 (6)	C222—H222	0.9500
C4—H4	0.9500	C223—C224	1.376 (6)
C5—C6	1.383 (5)	C223—H223	0.9500
C5—H5	0.9500	C224—C225	1.376 (6)
C111—C112	1.403 (5)	C224—H224	0.9500
C111—C116	1.377 (5)	C225—C226	1.394 (5)
C112—C113	1.378 (5)	C225—H225	0.9500
C112—H112	0.9500	C226—H226	0.9500
C113—C114	1.374 (6)	C231—C232	1.395 (5)
C113—H113	0.9500	C231—C236	1.384 (5)
C114—C115	1.378 (6)	C232—C233	1.400 (5)
C114—H114	0.9500	C232—H232	0.9500
C115—C116	1.393 (5)	C233—C234	1.381 (6)
C115—H115	0.9500	C233—H233	0.9500
C116—H116	0.9500	C234—C235	1.381 (6)
C121—C122	1.391 (5)	C234—H234	0.9500
C121—C126	1.388 (5)	C235—C236	1.385 (5)
C122—C123	1.390 (5)	C235—H235	0.9500
C122—H122	0.9500	C236—H236	0.9500
C123—C124	1.376 (6)	O3—C8	1.192 (6)
C123—H123	0.9500	C7—C8	1.491 (9)
C124—C125	1.383 (6)	C7—H7A	0.9800
C124—H124	0.9500	C7—H7B	0.9800
C125—C126	1.377 (6)	C7—H7C	0.9800
C125—H125	0.9500	C7—H7D	0.9800
C126—H126	0.9500	C7—H7E	0.9800
C131—C132	1.391 (5)	C7—H7F	0.9800
C131—C136	1.390 (5)	C8—C9	1.456 (9)
C132—C133	1.395 (5)	C9—H9A	0.9800
C132—H132	0.9500	C9—H9B	0.9800
C133—C134	1.359 (6)	C9—H9C	0.9800
Cl1—Pd1—P1	89.56 (4)	C136—C135—H135	120.3
Cl1—Pd1—P2	88.59 (4)	C134—C135—H135	120.3
S1—Pd1—P1	90.63 (4)	C135—C136—C131	121.4 (4)
S1—Pd1—P2	91.69 (4)	C135—C136—H136	119.3
Cl1—Pd1—S1	174.19 (3)	C131—C136—H136	119.3
P1—Pd1—P2	174.98 (3)	C212—C211—C216	118.6 (4)
C1—S1—Pd1	105.52 (14)	C212—C211—P2	121.8 (3)
C131—P1—C111	102.51 (17)	C216—C211—P2	119.5 (3)
C131—P1—C121	106.98 (17)	C211—C212—C213	120.4 (4)
C111—P1—C121	104.01 (17)	C211—C212—H212	119.8
C131—P1—Pd1	112.75 (13)	C213—C212—H212	119.8
C111—P1—Pd1	118.99 (12)	C214—C213—C212	120.8 (4)
C121—P1—Pd1	110.57 (12)	C214—C213—H213	119.6
C231—P2—C221	101.35 (17)	C212—C213—H213	119.6
C231—P2—C211	105.87 (17)	C213—C214—C215	119.3 (4)
C221—P2—C211	105.18 (16)	C213—C214—H214	120.4
C231—P2—Pd1	116.20 (13)	C215—C214—H214	120.4
C221—P2—Pd1	118.57 (12)	C216—C215—C214	120.0 (4)
C211—P2—Pd1	108.48 (12)	C216—C215—H215	120.0
O1—N1—O2	122.4 (4)	C214—C215—H215	120.0
O1—N1—C6	118.9 (3)	C215—C216—C211	121.0 (4)
O2—N1—C6	118.6 (4)	C215—C216—H216	119.5
C2—C1—C6	113.8 (4)	C211—C216—H216	119.5
C2—C1—S1	121.2 (3)	C226—C221—C222	118.7 (3)
C6—C1—S1	125.0 (3)	C226—C221—P2	123.9 (3)
C3—C2—C1	123.7 (4)	C222—C221—P2	117.5 (3)
C3—C2—H2	118.1	C223—C222—C221	120.8 (4)
C1—C2—H2	118.1	C223—C222—H222	119.6
C2—C3—C4	119.6 (4)	C221—C222—H222	119.6
C2—C3—H3	120.2	C224—C223—C222	119.6 (4)
C4—C3—H3	120.2	C224—C223—H223	120.2
C5—C4—C3	119.1 (4)	C222—C223—H223	120.2
C5—C4—H4	120.5	C225—C224—C223	120.9 (4)
C3—C4—H4	120.5	C225—C224—H224	119.5
C4—C5—C6	121.1 (4)	C223—C224—H224	119.5
C4—C5—H5	119.5	C224—C225—C226	119.1 (4)
C6—C5—H5	119.5	C224—C225—H225	120.5
C1—C6—C5	122.7 (4)	C226—C225—H225	120.5
C1—C6—N1	121.3 (4)	C221—C226—C225	120.9 (4)
C5—C6—N1	116.0 (4)	C221—C226—H226	119.6
C116—C111—C112	118.6 (4)	C225—C226—H226	119.6
C116—C111—P1	123.2 (3)	C236—C231—C232	118.9 (3)
C112—C111—P1	118.2 (3)	C236—C231—P2	120.2 (3)
C113—C112—C111	120.9 (4)	C232—C231—P2	120.9 (3)
C113—C112—H112	119.5	C231—C232—C233	120.1 (4)
C111—C112—H112	119.5	C231—C232—H232	120.0
C114—C113—C112	119.9 (4)	C233—C232—H232	120.0
C114—C113—H113	120.1	C234—C233—C232	119.9 (4)
C112—C113—H113	120.1	C234—C233—H233	120.0
C113—C114—C115	120.0 (4)	C232—C233—H233	120.0
C113—C114—H114	120.0	C233—C234—C235	120.1 (4)
C115—C114—H114	120.0	C233—C234—H234	119.9
C114—C115—C116	120.4 (4)	C235—C234—H234	119.9
C114—C115—H115	119.8	C234—C235—C236	119.9 (4)
C116—C115—H115	119.8	C234—C235—H235	120.0
C111—C116—C115	120.2 (4)	C236—C235—H235	120.0
C111—C116—H116	119.9	C231—C236—C235	121.0 (4)
C115—C116—H116	119.9	C231—C236—H236	119.5
C126—C121—C122	118.9 (4)	C235—C236—H236	119.5
C126—C121—P1	118.2 (3)	C8—C7—H7A	109.5
C122—C121—P1	122.8 (3)	C8—C7—H7B	109.5
C123—C122—C121	119.6 (4)	H7A—C7—H7B	109.5
C123—C122—H122	120.2	C8—C7—H7C	109.5
C121—C122—H122	120.2	H7A—C7—H7C	109.5
C124—C123—C122	120.7 (4)	H7B—C7—H7C	109.5
C124—C123—H123	119.6	C8—C7—H7D	109.5
C122—C123—H123	119.6	H7A—C7—H7D	141.1
C123—C124—C125	119.9 (4)	H7B—C7—H7D	56.3
C123—C124—H124	120.1	H7C—C7—H7D	56.3
C125—C124—H124	120.1	C8—C7—H7E	109.5
C126—C125—C124	119.7 (4)	H7A—C7—H7E	56.3
C126—C125—H125	120.2	H7B—C7—H7E	141.1
C124—C125—H125	120.2	H7C—C7—H7E	56.3
C125—C126—C121	121.2 (4)	H7D—C7—H7E	109.5
C125—C126—H126	119.4	C8—C7—H7F	109.5
C121—C126—H126	119.4	H7A—C7—H7F	56.3
C136—C131—C132	118.3 (3)	H7B—C7—H7F	56.3
C136—C131—P1	120.3 (3)	H7C—C7—H7F	141.1
C132—C131—P1	121.3 (3)	H7D—C7—H7F	109.5
C131—C132—C133	119.9 (4)	H7E—C7—H7F	109.5
C131—C132—H132	120.0	O3—C8—C9	122.5 (7)
C133—C132—H132	120.0	O3—C8—C7	122.6 (7)
C134—C133—C132	120.5 (4)	C9—C8—C7	114.9 (6)
C134—C133—H133	119.7	C8—C9—H9A	109.5
C132—C133—H133	119.7	C8—C9—H9B	109.5
C133—C134—C135	120.4 (4)	H9A—C9—H9B	109.5
C133—C134—H134	119.8	C8—C9—H9C	109.5
C135—C134—H134	119.8	H9A—C9—H9C	109.5
C136—C135—C134	119.4 (4)	H9B—C9—H9C	109.5
P2—Pd1—S1—C1	87.58 (13)	P1—C121—C126—C125	−178.2 (3)
P1—Pd1—S1—C1	−87.97 (13)	C111—P1—C131—C136	33.4 (4)
S1—Pd1—P1—C131	−100.03 (13)	C121—P1—C131—C136	−75.6 (3)
S1—Pd1—P1—C111	20.03 (15)	Pd1—P1—C131—C136	162.6 (3)
Cl1—Pd1—P1—C111	−165.77 (15)	C111—P1—C131—C132	−143.6 (3)
S1—Pd1—P1—C121	140.26 (12)	C121—P1—C131—C132	107.3 (3)
Cl1—Pd1—P1—C121	−45.54 (13)	Pd1—P1—C131—C132	−14.4 (4)
Cl1—Pd1—P1—C131	74.17 (13)	C136—C131—C132—C133	−0.9 (6)
S1—Pd1—P2—C231	106.54 (13)	P1—C131—C132—C133	176.2 (3)
Cl1—Pd1—P2—C211	51.41 (12)	C131—C132—C133—C134	−0.8 (7)
S1—Pd1—P2—C221	−14.64 (14)	C132—C133—C134—C135	1.7 (7)
Cl1—Pd1—P2—C221	171.16 (14)	C133—C134—C135—C136	−0.9 (7)
S1—Pd1—P2—C211	−134.39 (12)	C134—C135—C136—C131	−0.8 (7)
Cl1—Pd1—P2—C231	−67.66 (13)	C132—C131—C136—C135	1.7 (6)
Pd1—S1—C1—C6	−172.9 (3)	P1—C131—C136—C135	−175.4 (4)
Pd1—S1—C1—C2	4.8 (3)	C231—P2—C211—C212	−2.9 (4)
C6—C1—C2—C3	−0.5 (6)	C221—P2—C211—C212	103.9 (3)
S1—C1—C2—C3	−178.4 (3)	Pd1—P2—C211—C212	−128.3 (3)
C1—C2—C3—C4	0.2 (6)	C231—P2—C211—C216	174.0 (3)
C2—C3—C4—C5	0.8 (6)	C221—P2—C211—C216	−79.2 (3)
C3—C4—C5—C6	−1.5 (7)	Pd1—P2—C211—C216	48.6 (3)
C4—C5—C6—C1	1.2 (7)	C216—C211—C212—C213	0.9 (6)
C4—C5—C6—N1	−178.5 (4)	P2—C211—C212—C213	177.7 (3)
C2—C1—C6—C5	−0.2 (6)	C211—C212—C213—C214	−0.3 (7)
S1—C1—C6—C5	177.6 (3)	C212—C213—C214—C215	−0.2 (7)
C2—C1—C6—N1	179.5 (3)	C213—C214—C215—C216	0.2 (7)
S1—C1—C6—N1	−2.7 (6)	C214—C215—C216—C211	0.3 (6)
O1—N1—C6—C5	163.5 (4)	C212—C211—C216—C215	−0.9 (6)
O2—N1—C6—C5	−15.9 (6)	P2—C211—C216—C215	−177.8 (3)
O1—N1—C6—C1	−16.2 (6)	C231—P2—C221—C226	125.7 (3)
O2—N1—C6—C1	164.4 (4)	C211—P2—C221—C226	15.6 (4)
C131—P1—C111—C116	−129.4 (3)	Pd1—P2—C221—C226	−105.8 (3)
C121—P1—C111—C116	−18.1 (4)	C231—P2—C221—C222	−55.1 (3)
Pd1—P1—C111—C116	105.4 (3)	C211—P2—C221—C222	−165.2 (3)
C131—P1—C111—C112	51.4 (3)	Pd1—P2—C221—C222	73.4 (3)
C121—P1—C111—C112	162.7 (3)	C226—C221—C222—C223	−2.2 (6)
Pd1—P1—C111—C112	−73.7 (3)	P2—C221—C222—C223	178.5 (3)
C116—C111—C112—C113	−0.2 (6)	C221—C222—C223—C224	1.6 (7)
P1—C111—C112—C113	179.0 (3)	C222—C223—C224—C225	−0.6 (7)
C111—C112—C113—C114	−0.3 (6)	C223—C224—C225—C226	0.2 (7)
C112—C113—C114—C115	0.4 (7)	C222—C221—C226—C225	1.8 (6)
C113—C114—C115—C116	−0.1 (7)	P2—C221—C226—C225	−179.0 (3)
C112—C111—C116—C115	0.5 (6)	C224—C225—C226—C221	−0.8 (7)
P1—C111—C116—C115	−178.6 (3)	C221—P2—C231—C236	−36.0 (3)
C114—C115—C116—C111	−0.4 (7)	C211—P2—C231—C236	73.5 (3)
C131—P1—C121—C126	−170.7 (3)	Pd1—P2—C231—C236	−166.0 (3)
C111—P1—C121—C126	81.3 (3)	C221—P2—C231—C232	144.3 (3)
Pd1—P1—C121—C126	−47.5 (3)	C211—P2—C231—C232	−106.2 (3)
C131—P1—C121—C122	9.6 (4)	Pd1—P2—C231—C232	14.3 (4)
C111—P1—C121—C122	−98.5 (3)	C236—C231—C232—C233	−0.8 (6)
Pd1—P1—C121—C122	132.7 (3)	P2—C231—C232—C233	179.0 (3)
C126—C121—C122—C123	−0.4 (6)	C231—C232—C233—C234	0.1 (6)
P1—C121—C122—C123	179.3 (3)	C232—C233—C234—C235	0.6 (6)
C121—C122—C123—C124	−0.8 (6)	C233—C234—C235—C236	−0.7 (6)
C122—C123—C124—C125	0.8 (6)	C232—C231—C236—C235	0.7 (6)
C123—C124—C125—C126	0.3 (7)	P2—C231—C236—C235	−179.0 (3)
C124—C125—C126—C121	−1.5 (6)	C234—C235—C236—C231	0.0 (6)
C122—C121—C126—C125	1.6 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C236—H236···O3	0.95	2.51	3.307 (6)	141