trans-Bromido[4,5-difluoro-2-(trifluoro­methyl­sulfon­yloxy)phenyl-κC¹]bis(triphenyl­phosphine-κP)palladium(II)

The title compound, trans-[PdBr(C₇H₂F₅O₃S)(C₁₈H₁₅P)₂], was obtained in quanti­tative yield by oxidative addition of the electrophile 1-bromo-3,4-difluoro-2-(trifluoro­methyl­sulfon­yl­oxy)benzene to Pd(PPh₃)₄ in toluene, and was recrystallized from a mixture of tetra­hydro­furan and pentane. The structure was resolved by single-crystal X-ray diffraction and turned out to be one of the few known examples among complexes of general formula trans-[(PAr₃)₂Pd(X)Ar′] that exhibit double π–π stacking intra­molecular inter­actions (three aromatic rings are piled above each other).

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.030
• wR factor = 0.032
• Data-to-parameter ratio = 11.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT021_ALERT_1_C Ratio Unique / Expected Reflections too High ...       1.03
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Pd1    -   Br1     ..       7.08 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Pd1    -   C1      ..       7.51 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound was prepared in the course of a recently reported work about the role of phosphines in Suzuki cross-coupling (Espino et al., 2007).

The coordination geometry of the Pd atom in the title compound, (1) (Fig. 1), closely approximates to planarity; the deviation of the metal atom from the best-plane of four coordinated atoms is 0.044 (3) Å. The Pd1/Br1/C1/P1/P2 plane makes an angle of 73.7 (1)° with that of the coordinated phenyl ring. The PPh₃ ligands are in trans disposition, so it seems that isomerization of the cis isomer takes place after oxidative addition, since otherwise, the former disposition would be the most reasonable after the addition (see Fig.1). Furthermore, a weak intramolecular hydrogen bond between O3 and C27 is observed, which conditions the orientation of the trifluoromethanesulfonate group (see Table 2).

The Pd—C bond length (Table 1) is virtually identical to that reported for [PdBr(Ph)(PPh₃)₂] (2.012 (4) Å; Sundermeier et al., 2003) and [PdBr(p-C₆H₄CF₃)(PPh₃)₂] (1.995 (6) Å; Flemming et al., 1998). The Pd—Br bond length is significantly shorter than that observed for [PdBr(Ph)(PPh₃)₂] (2.532 (1) Å) and [PdBr(p-C₆H₄CF₃)(PPh₃)₂] (2.5244 (9) Å). Moreover, the two Pd—P bond lengths (Table 1) are very similar to each other, and are also very close to those found in [PdBr(Ph)(PPh₃)₂] and [PdBr(p-C₆H₄CF₃)(PPh₃)₂], which range between 2.322 (2) Å and 2.346 (2) Å.

Two intramolecular π–π stacking interactions are observed between the Pd-σ-coordinated aryl ligand and two phenyl groups of two different PPh₃ ligands (see Fig.2). As a consequence, the molecule adopts a sandwich type conformation which is observed in just a few of other similar complexes of general formula [(PAr₃)₂Pd(X)Ar'], while in most of these derivatives (Fletcher et al., 1996), according to our CSD search, the stacking (alignment) of three aryl rings is far from the ideal geometry.

Distances between centroids of the Pd-bonded aryl ring and each of the two phenyl rings are Cg1···Cg2 = 3.587 (5) Å and Cg1···Cg3 = 3.671 (5) Å, where Cg1, Cg2 and Cg3, respectively, are the centroids of the C1—C6 (A), C8—C13 (B) and C38—C43 (C) rings. The dihedral angles between the rings are: A/B = 16.99 (17)° and A/C = 18.92 (16)° (see Fig. 2). The angles formed between the centroid-centroid vectors (Cg1—Cg2 and Cg1—Cg3) and normal to the Pd-coordinated aryl ring are 21.9° and 20.8° respectively, meaning that according to the literature these parameters are into the range accepted for these type of interactions (Janiak, 2000).

Moreover, C(Ph)—P—Pd—C(σ-Ar) torsion angles, C1—Pd1—P1—C8 and C1—Pd1—P2—C38, are 1.98 (14) and 6.89 (14)°, respectively, close to zero. According to the Cambridge Structural Database (CSD, Version 5.26; Allen, 2002), the number of similar compounds which show both of these torsion angles under 8° is very limited and up to now, restricted to a couple of cases: [(PPh₃)₂Pd(F)Ph] (1.95° and 4.41°; Flemming et al., 1998) and [(PPh₃)₂Pd(Cl)Ph] (7.99° and 5.90°; Hwang et al., 2005). Two other complexes exhibit values around 10° are [(PPh₃)₂Pd(I)(C₆H₄I)] (9.07° and 9.11°; Gniewek et al., 2006) and [(PPh(o-C₆H₄CH₃)₂)₂Pd(Br)(p-Tol)] (10.84° and 10.80°; Hartwig et al., 1996).

In line with this, the Newman-type projections along the P1—P2 axis show an almost eclipsed conformation for both phosphine ligands, with a mean torsion angle for the Cⁱ—P—P—Cⁱ groups of 7.9° (see Fig. 3).

The weak π-π interactions could play a role in the stabilization of the trans isomer versus the cis isomer, along with the lower steric hindrance attributed to the first, and the trans effect, so explaining the isomerization process.

Related literature

For the role of phosphines in Suzuki cross-coupling, see: Espino et al. (2007). For the Cambridge Structural Database, see: Allen (2002). For related literature, see: Espino et al. (2007); Flemming et al. (1998); Fletcher et al. (1996); Gniewek et al. (2006); Hartwig et al. (1996); Hwang et al. (2005); Janiak (2000); Sundermeier et al. (2003); Prince (1982); Watkin (1994).

S2. Experimental

The title compound was synthesized under a nitrogen atmosphere by reacting Pd(PPh₃)₄ (0.1 g, 0.043 mmol), toluene (2 ml) and 3,4-difluoro-2-trifluoromethanesulfonyloxybromobenzene (0.03 g, 0.087 mmol) in a Schlenk tube (see scheme 2). The mixture was refluxed for ca 24 h. The original suspension of Pd(PPh₃)₄ in toluene became a solution after a couple of hours, but reflux was maintained overnight to ensure the completion of the reaction. The solvent was removed and the white solid residue was washed with pentane (3 × 8 ml) in order to eliminate the leaving PPh₃. Finally, the product was dried under vacuum, (0.069 gr, 0.071 mmol, 82%). The white solid turned out to be soluble in CDCl₃ and toluene but insoluble in pentane. ¹⁹F{¹H}-NMR (377 MHz): -75.24 p.p.m. (s, 3 F, CF₃); -138.88 p.p.m. (d, ³J_FF = 20.6 Hz, 1 F, C—F); -142.93 p.p.m. (d, ³J_FF = 20.6 Hz, 1 F, C—F). ³¹P{¹H}-NMR (162 MHz): 24.06 p.p.m. (s, 2P). ¹H-NMR (400 MHz): 6.48 p.p.m. (t, J=9.67, 9.67 Hz, 1H); 6.06 p.p.m. (dd, J=6.31, 10.83 Hz, 1H). ¹³C{¹H}-NMR (126 MHz): 149.24 (d, J=11.86 Hz); 147.24 (d, J=11.93 Hz); 145.97 (d, J=19.37 Hz); 134.83 (t, J=6.24, 6.24 Hz); 132.18 (d, J=9.96 Hz); 132.10 (s); 130.55 (t, J=24.05, 24.05 Hz); 130.42 (s, 1 C); 128.59 (d, J=12.14 Hz); 128.09 (t, J=5.17, Hz); 125.35 (s); 124.54 (d, J=15.84 Hz); 119.51 (s); 116.97 (s); 108.54 (d, J=20.68 Hz). MS: [M–Br+K]⁺=930; [M–Br]⁺=891. Analysis calculated for C₄₃H₃₂BrF₅O₃P₂PdS: C 53.13, H 3.32, S 3.30%; found: C 53.30, H 3.55, S 3.47%.

S3. Refinement

The H atoms were all located in a difference map, but were repositioned geometrically. They were initially refined with soft restraints on the bond lengths and angles to regularize their geometry, with C—H distances of 1.00 Å, and with U_iso(H) = 1.2–1.5 times U_eq of the parent C atom, after which the positions were refined with riding constraints.

Computing details

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006)'; software used to prepare material for publication: CRYSTALS.

Figures

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 2. A spacefill representation of π–π stacking interactions between the aryl ligand and two phenyl groups belonging to two different PPh3 ligands, showing distances (Å) between centroids and interplane angles (°).
	Fig. 3. A Newman-type projection along the P1–P2 axis, showing the eclipsed conformation for both PPh3 ligands.
	Fig. 4. The reaction scheme for the formation of (1).

trans-Bromido[4,5-difluoro-2-(trifluoromethylsulfonyloxy)phenyl- κC¹)bis(triphenylphosphine-κP)palladium(II)

Crystal data

[PdBr(C7H2F5O3S)(C18H15P)2]	F(000) = 1944
Mr = 972.03	Dx = 1.640 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 29420 reflections
a = 14.4320 (2) Å	θ = 5–28°
b = 14.3157 (3) Å	µ = 1.69 mm^−1
c = 19.5504 (3) Å	T = 150 K
β = 103.0167 (9)°	Block, pale yellow
V = 3935.41 (12) Å^3	0.12 × 0.08 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	5917 reflections with I > 3.0σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 27.5°, θmin = 5.1°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −18→18
Tmin = 0.87, Tmax = 0.87	k = −18→18
29420 measured reflections	l = −24→25
9258 independent reflections

Refinement

Refinement on F	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.032	w = [1-(Fo-Fc)^2/36σ^2(F)]^2/ [0.323T0(x) + 0.164E-01T1(x) + 0.115T2(x)] where Ti are Chebychev polynomials and x = Fc/Fmax (Watkin, 1994; Prince, 1982)
S = 1.10	(Δ/σ)max = 0.002
5917 reflections	Δρmax = 0.43 e Å^−3
505 parameters	Δρmin = −0.69 e Å^−3
0 restraints

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

	x	y	z	Uiso*/Ueq
Pd1	0.329188 (16)	0.324809 (16)	0.601732 (12)	0.0171
Br1	0.34657 (2)	0.25546 (2)	0.720712 (17)	0.0263
C1	0.3092 (2)	0.3810 (2)	0.50513 (16)	0.0211
C2	0.3638 (2)	0.4559 (2)	0.48901 (17)	0.0236
C3	0.3449 (2)	0.4939 (2)	0.42243 (18)	0.0275
C4	0.2725 (3)	0.4591 (3)	0.37014 (17)	0.0307
C5	0.2185 (2)	0.3853 (3)	0.38228 (18)	0.0292
C6	0.2389 (2)	0.3490 (2)	0.45023 (16)	0.0223
F1	0.39784 (16)	0.56600 (15)	0.40802 (12)	0.0400
F2	0.25560 (16)	0.49941 (18)	0.30544 (11)	0.0440
O1	0.18666 (16)	0.26748 (16)	0.46369 (12)	0.0273
S1	0.07900 (6)	0.26758 (7)	0.46216 (5)	0.0326
O2	0.03476 (19)	0.3504 (2)	0.43190 (16)	0.0479
O3	0.0657 (2)	0.2320 (2)	0.52674 (15)	0.0472
C7	0.0455 (3)	0.1723 (4)	0.3980 (2)	0.0506
F3	−0.0461 (2)	0.1579 (3)	0.38763 (17)	0.0851
F4	0.0915 (2)	0.0951 (2)	0.42243 (16)	0.0699
F5	0.0676 (2)	0.1954 (2)	0.33823 (13)	0.0643
P1	0.26893 (5)	0.46045 (5)	0.64151 (4)	0.0186
C8	0.2361 (2)	0.5534 (2)	0.57685 (17)	0.0224
C9	0.1532 (2)	0.5402 (2)	0.52444 (18)	0.0277
C10	0.1291 (3)	0.6030 (3)	0.46960 (19)	0.0381
C11	0.1871 (3)	0.6800 (3)	0.4666 (2)	0.0432
C12	0.2677 (3)	0.6936 (3)	0.5184 (2)	0.0410
C13	0.2925 (3)	0.6312 (2)	0.57362 (18)	0.0299
C14	0.3633 (2)	0.5113 (2)	0.70937 (16)	0.0214
C15	0.4573 (2)	0.4921 (2)	0.70651 (18)	0.0265
C16	0.5327 (2)	0.5294 (3)	0.7558 (2)	0.0327
C17	0.5145 (3)	0.5856 (3)	0.80912 (18)	0.0323
C18	0.4220 (3)	0.6051 (3)	0.81227 (18)	0.0313
C19	0.3462 (2)	0.5684 (2)	0.76294 (18)	0.0289
C20	0.1609 (2)	0.4516 (2)	0.67506 (15)	0.0205
C21	0.1219 (2)	0.3642 (2)	0.68444 (18)	0.0262
C22	0.0368 (2)	0.3604 (3)	0.7063 (2)	0.0324
C23	−0.0085 (2)	0.4412 (3)	0.71997 (19)	0.0322
C24	0.0308 (2)	0.5272 (2)	0.71130 (17)	0.0284
C25	0.1149 (2)	0.5329 (2)	0.68816 (17)	0.0242
P2	0.40604 (5)	0.19609 (5)	0.56595 (4)	0.0187
C26	0.3561 (2)	0.0843 (2)	0.58363 (15)	0.0213
C27	0.2581 (2)	0.0795 (2)	0.5773 (2)	0.0294
C28	0.2150 (3)	−0.0047 (3)	0.5866 (2)	0.0364
C29	0.2686 (3)	−0.0843 (2)	0.6040 (2)	0.0344
C30	0.3662 (3)	−0.0799 (2)	0.6113 (2)	0.0355
C31	0.4099 (2)	0.0037 (2)	0.60090 (19)	0.0284
C32	0.5332 (2)	0.1896 (2)	0.60660 (16)	0.0215
C33	0.5688 (2)	0.2357 (2)	0.66937 (17)	0.0259
C34	0.6651 (2)	0.2283 (3)	0.70215 (18)	0.0325
C35	0.7246 (2)	0.1736 (3)	0.6724 (2)	0.0325
C36	0.6900 (2)	0.1285 (2)	0.6093 (2)	0.0315
C37	0.5944 (2)	0.1359 (2)	0.57637 (18)	0.0267
C38	0.4036 (2)	0.1914 (2)	0.47197 (16)	0.0210
C39	0.4543 (2)	0.2595 (2)	0.44329 (17)	0.0249
C40	0.4446 (2)	0.2662 (3)	0.37136 (18)	0.0301
C41	0.3848 (3)	0.2034 (3)	0.32734 (18)	0.0326
C42	0.3373 (3)	0.1350 (3)	0.35490 (17)	0.0317
C43	0.3459 (2)	0.1290 (2)	0.42744 (17)	0.0275
H21	0.4168	0.4817	0.5262	0.0290*
H51	0.1670	0.3586	0.3444	0.0352*
H91	0.1113	0.4852	0.5267	0.0343*
H101	0.0701	0.5932	0.4321	0.0459*
H111	0.1700	0.7254	0.4269	0.0534*
H121	0.3089	0.7491	0.5162	0.0512*
H131	0.3511	0.6422	0.6112	0.0371*
H151	0.4704	0.4509	0.6685	0.0328*
H161	0.5997	0.5159	0.7528	0.0393*
H171	0.5685	0.6120	0.8453	0.0381*
H181	0.4093	0.6460	0.8506	0.0373*
H191	0.2795	0.5831	0.7658	0.0350*
H211	0.1548	0.3055	0.6755	0.0319*
H221	0.0078	0.2983	0.7123	0.0405*
H231	−0.0695	0.4374	0.7361	0.0404*
H241	−0.0015	0.5856	0.7217	0.0348*
H251	0.1423	0.5954	0.6809	0.0295*
H271	0.2185	0.1371	0.5660	0.0360*
H281	0.1444	−0.0076	0.5806	0.0451*
H291	0.2374	−0.1447	0.6113	0.0426*
H301	0.4055	−0.1375	0.6241	0.0421*
H311	0.4804	0.0058	0.6059	0.0341*
H331	0.5254	0.2744	0.6912	0.0314*
H341	0.6909	0.2624	0.7470	0.0378*
H351	0.7931	0.1667	0.6967	0.0382*
H361	0.7337	0.0905	0.5873	0.0381*
H371	0.5692	0.1028	0.5309	0.0324*
H391	0.4977	0.3033	0.4752	0.0301*
H401	0.4798	0.3153	0.3511	0.0377*
H411	0.3767	0.2084	0.2753	0.0397*
H421	0.2964	0.0894	0.3230	0.0371*
H431	0.3104	0.0797	0.4472	0.0328*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.01936 (11)	0.01532 (10)	0.01728 (11)	0.00154 (9)	0.00543 (8)	0.00046 (9)
Br1	0.03054 (17)	0.02712 (16)	0.02220 (15)	0.00269 (13)	0.00787 (13)	0.00649 (13)
C1	0.0205 (15)	0.0175 (14)	0.0274 (16)	0.0036 (12)	0.0100 (12)	−0.0031 (12)
C2	0.0220 (15)	0.0234 (16)	0.0270 (16)	0.0047 (12)	0.0092 (13)	0.0001 (13)
C3	0.0279 (17)	0.0274 (17)	0.0322 (18)	0.0032 (13)	0.0170 (15)	0.0060 (14)
C4	0.0370 (19)	0.0377 (19)	0.0207 (16)	0.0141 (16)	0.0133 (14)	0.0110 (14)
C5	0.0302 (18)	0.0332 (18)	0.0247 (16)	0.0079 (15)	0.0070 (14)	0.0007 (14)
C6	0.0244 (15)	0.0216 (15)	0.0212 (15)	0.0040 (12)	0.0056 (12)	0.0022 (12)
F1	0.0416 (12)	0.0365 (12)	0.0470 (13)	−0.0025 (10)	0.0209 (10)	0.0164 (10)
F2	0.0467 (13)	0.0616 (15)	0.0256 (11)	0.0122 (11)	0.0122 (10)	0.0203 (10)
O1	0.0242 (12)	0.0246 (12)	0.0315 (12)	−0.0043 (9)	0.0029 (10)	0.0002 (10)
S1	0.0241 (4)	0.0417 (5)	0.0318 (5)	0.0032 (4)	0.0063 (3)	0.0100 (4)
O2	0.0287 (14)	0.0540 (18)	0.0621 (19)	0.0158 (12)	0.0126 (13)	0.0246 (15)
O3	0.0430 (16)	0.064 (2)	0.0386 (15)	0.0112 (14)	0.0178 (13)	0.0201 (14)
C7	0.044 (2)	0.061 (3)	0.039 (2)	−0.025 (2)	−0.0057 (18)	0.004 (2)
F3	0.0478 (16)	0.121 (3)	0.074 (2)	−0.0506 (18)	−0.0132 (14)	0.0256 (19)
F4	0.087 (2)	0.0438 (16)	0.0671 (18)	−0.0166 (15)	−0.0074 (16)	−0.0074 (14)
F5	0.0681 (18)	0.088 (2)	0.0324 (12)	−0.0339 (16)	0.0027 (12)	−0.0090 (13)
P1	0.0206 (4)	0.0165 (4)	0.0200 (4)	0.0019 (3)	0.0071 (3)	−0.0007 (3)
C8	0.0263 (16)	0.0185 (15)	0.0247 (16)	0.0056 (12)	0.0104 (13)	−0.0007 (12)
C9	0.0311 (17)	0.0266 (17)	0.0280 (17)	0.0053 (14)	0.0120 (14)	0.0028 (14)
C10	0.042 (2)	0.042 (2)	0.0309 (19)	0.0152 (18)	0.0095 (16)	0.0100 (17)
C11	0.063 (3)	0.036 (2)	0.035 (2)	0.019 (2)	0.0195 (19)	0.0153 (17)
C12	0.062 (3)	0.0226 (18)	0.044 (2)	0.0010 (17)	0.023 (2)	0.0078 (16)
C13	0.043 (2)	0.0191 (16)	0.0310 (18)	−0.0010 (14)	0.0146 (16)	0.0012 (13)
C14	0.0255 (16)	0.0173 (14)	0.0215 (15)	−0.0001 (12)	0.0058 (12)	−0.0005 (12)
C15	0.0242 (16)	0.0246 (16)	0.0332 (18)	0.0015 (13)	0.0122 (14)	−0.0003 (14)
C16	0.0212 (16)	0.037 (2)	0.040 (2)	−0.0009 (14)	0.0073 (14)	−0.0012 (16)
C17	0.0334 (19)	0.0314 (18)	0.0306 (18)	−0.0083 (15)	0.0038 (15)	−0.0033 (15)
C18	0.0356 (19)	0.0298 (18)	0.0278 (17)	−0.0022 (15)	0.0058 (14)	−0.0079 (14)
C19	0.0289 (17)	0.0286 (17)	0.0299 (17)	0.0033 (14)	0.0081 (14)	−0.0065 (14)
C20	0.0227 (15)	0.0221 (15)	0.0178 (14)	0.0007 (12)	0.0068 (12)	−0.0006 (12)
C21	0.0249 (16)	0.0254 (16)	0.0295 (17)	0.0021 (13)	0.0088 (14)	0.0007 (13)
C22	0.0282 (18)	0.0302 (18)	0.043 (2)	0.0004 (14)	0.0165 (16)	0.0047 (16)
C23	0.0264 (17)	0.040 (2)	0.0343 (19)	0.0024 (15)	0.0157 (15)	0.0051 (16)
C24	0.0289 (17)	0.0321 (18)	0.0260 (17)	0.0069 (14)	0.0104 (14)	0.0017 (14)
C25	0.0247 (16)	0.0235 (16)	0.0256 (16)	0.0020 (13)	0.0081 (13)	−0.0001 (13)
P2	0.0200 (4)	0.0173 (4)	0.0187 (4)	0.0021 (3)	0.0038 (3)	−0.0009 (3)
C26	0.0268 (16)	0.0194 (14)	0.0177 (14)	0.0002 (12)	0.0048 (12)	−0.0009 (12)
C27	0.0254 (17)	0.0216 (16)	0.043 (2)	0.0033 (13)	0.0112 (15)	0.0040 (15)
C28	0.0315 (19)	0.0263 (18)	0.055 (2)	−0.0045 (15)	0.0174 (18)	−0.0019 (17)
C29	0.040 (2)	0.0210 (16)	0.045 (2)	−0.0044 (15)	0.0168 (17)	−0.0013 (15)
C30	0.040 (2)	0.0188 (16)	0.046 (2)	0.0048 (15)	0.0068 (17)	0.0014 (15)
C31	0.0283 (17)	0.0222 (16)	0.0348 (18)	0.0037 (13)	0.0070 (14)	−0.0004 (14)
C32	0.0198 (14)	0.0228 (15)	0.0212 (15)	0.0026 (12)	0.0033 (12)	0.0040 (12)
C33	0.0231 (16)	0.0287 (17)	0.0268 (16)	−0.0005 (13)	0.0074 (13)	0.0010 (14)
C34	0.0256 (17)	0.043 (2)	0.0256 (17)	−0.0035 (15)	−0.0005 (13)	−0.0023 (15)
C35	0.0199 (15)	0.0355 (18)	0.0400 (19)	0.0024 (15)	0.0022 (14)	0.0024 (17)
C36	0.0264 (17)	0.0271 (18)	0.042 (2)	0.0055 (14)	0.0093 (15)	0.0031 (15)
C37	0.0276 (17)	0.0246 (16)	0.0288 (17)	0.0015 (13)	0.0080 (14)	−0.0030 (13)
C38	0.0208 (14)	0.0196 (15)	0.0230 (15)	0.0044 (12)	0.0059 (12)	−0.0027 (12)
C39	0.0226 (16)	0.0250 (16)	0.0277 (16)	0.0059 (13)	0.0071 (13)	0.0012 (13)
C40	0.0285 (17)	0.0353 (19)	0.0304 (18)	0.0109 (15)	0.0146 (14)	0.0086 (15)
C41	0.0330 (19)	0.044 (2)	0.0227 (17)	0.0158 (16)	0.0094 (14)	0.0010 (15)
C42	0.0348 (19)	0.0369 (19)	0.0211 (16)	0.0065 (15)	0.0012 (14)	−0.0069 (14)
C43	0.0306 (18)	0.0245 (17)	0.0269 (17)	0.0054 (13)	0.0050 (14)	−0.0003 (13)

Geometric parameters (Å, º)

Pd1—Br1	2.4892 (4)	C20—C21	1.401 (4)
Pd1—C1	2.013 (3)	C20—C25	1.392 (4)
Pd1—P1	2.3315 (8)	C21—C22	1.389 (5)
Pd1—P2	2.3377 (8)	C21—H211	1.00
C1—C2	1.407 (4)	C22—C23	1.385 (5)
C1—C6	1.379 (4)	C22—H221	1.00
C2—C3	1.380 (5)	C23—C24	1.382 (5)
C2—H21	1.00	C23—H231	1.00
C3—C4	1.379 (5)	C24—C25	1.390 (4)
C3—F1	1.351 (4)	C24—H241	1.00
C4—C5	1.365 (5)	C25—H251	1.00
C4—F2	1.361 (4)	P2—C26	1.819 (3)
C5—C6	1.395 (4)	P2—C32	1.831 (3)
C5—H51	1.00	P2—C38	1.831 (3)
C6—O1	1.445 (4)	C26—C27	1.395 (5)
O1—S1	1.547 (2)	C26—C31	1.390 (4)
S1—O2	1.412 (3)	C27—C28	1.386 (5)
S1—O3	1.414 (3)	C27—H271	1.00
S1—C7	1.842 (5)	C28—C29	1.377 (5)
C7—F3	1.307 (5)	C28—H281	1.00
C7—F4	1.322 (6)	C29—C30	1.384 (5)
C7—F5	1.322 (5)	C29—H291	1.00
P1—C8	1.823 (3)	C30—C31	1.389 (5)
P1—C14	1.825 (3)	C30—H301	1.00
P1—C20	1.827 (3)	C31—H311	1.00
C8—C9	1.402 (5)	C32—C33	1.386 (5)
C8—C13	1.390 (5)	C32—C37	1.397 (4)
C9—C10	1.382 (5)	C33—C34	1.398 (5)
C9—H91	1.00	C33—H331	1.00
C10—C11	1.394 (6)	C34—C35	1.383 (5)
C10—H101	1.00	C34—H341	1.00
C11—C12	1.372 (6)	C35—C36	1.384 (5)
C11—H111	1.00	C35—H351	1.00
C12—C13	1.385 (5)	C36—C37	1.389 (5)
C12—H121	1.00	C36—H361	1.00
C13—H131	1.00	C37—H371	1.00
C14—C15	1.397 (4)	C38—C39	1.407 (4)
C14—C19	1.394 (4)	C38—C43	1.387 (5)
C15—C16	1.388 (5)	C39—C40	1.385 (5)
C15—H151	1.00	C39—H391	1.00
C16—C17	1.389 (5)	C40—C41	1.400 (5)
C16—H161	1.00	C40—H401	1.00
C17—C18	1.380 (5)	C41—C42	1.373 (5)
C17—H171	1.00	C41—H411	1.00
C18—C19	1.387 (5)	C42—C43	1.398 (5)
C18—H181	1.00	C42—H421	1.00
C19—H191	1.00	C43—H431	1.00
Br1—Pd1—C1	177.59 (9)	P1—C20—C21	120.6 (2)
Br1—Pd1—P1	89.26 (2)	P1—C20—C25	119.3 (2)
C1—Pd1—P1	89.68 (8)	C21—C20—C25	120.0 (3)
Br1—Pd1—P2	90.60 (2)	C20—C21—C22	119.0 (3)
C1—Pd1—P2	90.68 (8)	C20—C21—H211	120.5
P1—Pd1—P2	173.75 (3)	C22—C21—H211	120.5
Pd1—C1—C2	123.0 (2)	C21—C22—C23	121.0 (3)
Pd1—C1—C6	121.5 (2)	C21—C22—H221	119.5
C2—C1—C6	115.5 (3)	C23—C22—H221	119.5
C1—C2—C3	120.6 (3)	C22—C23—C24	119.8 (3)
C1—C2—H21	119.7	C22—C23—H231	120.1
C3—C2—H21	119.7	C24—C23—H231	120.1
C2—C3—C4	120.8 (3)	C23—C24—C25	120.3 (3)
C2—C3—F1	119.8 (3)	C23—C24—H241	119.8
C4—C3—F1	119.4 (3)	C25—C24—H241	119.8
C3—C4—C5	121.1 (3)	C20—C25—C24	119.9 (3)
C3—C4—F2	118.9 (3)	C20—C25—H251	120.1
C5—C4—F2	120.0 (3)	C24—C25—H251	120.1
C4—C5—C6	116.6 (3)	Pd1—P2—C26	113.67 (10)
C4—C5—H51	121.7	Pd1—P2—C32	114.03 (10)
C6—C5—H51	121.7	C26—P2—C32	105.88 (14)
C5—C6—C1	125.3 (3)	Pd1—P2—C38	115.21 (10)
C5—C6—O1	117.9 (3)	C26—P2—C38	103.88 (14)
C1—C6—O1	116.7 (3)	C32—P2—C38	102.96 (14)
C6—O1—S1	124.0 (2)	P2—C26—C27	117.7 (2)
O1—S1—O2	111.48 (15)	P2—C26—C31	123.6 (2)
O1—S1—O3	108.66 (15)	C27—C26—C31	118.7 (3)
O2—S1—O3	122.49 (18)	C26—C27—C28	120.5 (3)
O1—S1—C7	96.96 (18)	C26—C27—H271	119.7
O2—S1—C7	108.2 (2)	C28—C27—H271	119.7
O3—S1—C7	105.9 (2)	C27—C28—C29	120.5 (3)
S1—C7—F3	108.9 (4)	C27—C28—H281	119.7
S1—C7—F4	109.9 (3)	C29—C28—H281	119.7
F3—C7—F4	109.4 (4)	C28—C29—C30	119.3 (3)
S1—C7—F5	109.8 (3)	C28—C29—H291	120.3
F3—C7—F5	109.8 (3)	C30—C29—H291	120.3
F4—C7—F5	109.0 (4)	C29—C30—C31	120.6 (3)
Pd1—P1—C8	115.78 (10)	C29—C30—H301	119.7
Pd1—P1—C14	107.51 (10)	C31—C30—H301	119.7
C8—P1—C14	104.37 (14)	C26—C31—C30	120.2 (3)
Pd1—P1—C20	118.35 (10)	C26—C31—H311	119.9
C8—P1—C20	100.94 (14)	C30—C31—H311	119.9
C14—P1—C20	108.91 (14)	P2—C32—C33	119.7 (2)
P1—C8—C9	117.0 (2)	P2—C32—C37	120.7 (2)
P1—C8—C13	123.6 (3)	C33—C32—C37	119.6 (3)
C9—C8—C13	119.1 (3)	C32—C33—C34	120.1 (3)
C8—C9—C10	120.2 (3)	C32—C33—H331	120.0
C8—C9—H91	119.9	C34—C33—H331	120.0
C10—C9—H91	119.9	C33—C34—C35	119.9 (3)
C9—C10—C11	119.9 (4)	C33—C34—H341	120.0
C9—C10—H101	120.1	C35—C34—H341	120.0
C11—C10—H101	120.1	C34—C35—C36	120.3 (3)
C10—C11—C12	119.9 (3)	C34—C35—H351	119.8
C10—C11—H111	120.0	C36—C35—H351	119.8
C12—C11—H111	120.0	C35—C36—C37	119.9 (3)
C11—C12—C13	120.7 (4)	C35—C36—H361	120.0
C11—C12—H121	119.6	C37—C36—H361	120.0
C13—C12—H121	119.6	C32—C37—C36	120.2 (3)
C8—C13—C12	120.1 (3)	C32—C37—H371	119.9
C8—C13—H131	120.0	C36—C37—H371	119.9
C12—C13—H131	120.0	P2—C38—C39	118.7 (2)
P1—C14—C15	117.7 (2)	P2—C38—C43	121.7 (2)
P1—C14—C19	123.4 (2)	C39—C38—C43	119.2 (3)
C15—C14—C19	118.9 (3)	C38—C39—C40	120.7 (3)
C14—C15—C16	120.9 (3)	C38—C39—H391	119.7
C14—C15—H151	119.5	C40—C39—H391	119.7
C16—C15—H151	119.5	C39—C40—C41	119.1 (3)
C15—C16—C17	119.5 (3)	C39—C40—H401	120.4
C15—C16—H161	120.2	C41—C40—H401	120.4
C17—C16—H161	120.2	C40—C41—C42	120.7 (3)
C16—C17—C18	120.0 (3)	C40—C41—H411	119.7
C16—C17—H171	120.0	C42—C41—H411	119.7
C18—C17—H171	120.0	C41—C42—C43	120.3 (3)
C17—C18—C19	120.8 (3)	C41—C42—H421	119.9
C17—C18—H181	119.6	C43—C42—H421	119.9
C19—C18—H181	119.6	C42—C43—C38	120.0 (3)
C14—C19—C18	119.9 (3)	C42—C43—H431	120.0
C14—C19—H191	120.0	C38—C43—H431	120.0
C18—C19—H191	120.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C21—H211···Br1	1.00	2.80	3.522 (3)	129
C27—H271···O3	1.00	2.56	3.495 (4)	156
C33—H331···Br1	1.00	2.78	3.581 (3)	137