Bis­[(di­phenyl­sulfimido)­tri­phenyl­phospho­nium] di-μ-bromo-bis[di­bromo­palladate(II)]

Dale, S.H.; Elsegood, M.R.J.; Gilby, L.M.; Holmes, K.E.; Kelly, P.F.

doi:10.1107/S0108270104029464

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 1| January 2005| Pages m40-m42

doi:10.1107/S0108270104029464

Bis[(diphenylsulfimido)triphenylphosphonium] di-μ-bromo-bis[dibromopalladate(II)]

Sophie H. Dale,^a Mark R. J. Elsegood,^a Liam M. Gilby,^a Kathryn E. Holmes ^a and Paul F. Kelly ^a ^*

^aChemistry Department, Loughborough University, Leicestershire LE11 3TU, England
^*Correspondence e-mail: p.f.kelly@lboro.ac.uk

(Received 4 November 2004; accepted 12 November 2004; online 11 December 2004)

The title compound, (C₃₀H₂₅NPS)₂[Pd₂Br₆] or (Ph₃PNSPh₂)₂[Pd₂Br₆], was crystallized from the reaction of (Ph₃PNSPh₂)[BPh₄] with (PPh₄)₂[Pd₂Br₆], giving a salt rather than the intended coordination complex [PdBr₃(Ph₃PNSPh₂)]. The compound crystallizes in the non-centrosymmetric space group Cc with one complete formula unit in the asymmetric unit. One of the two independent cations is disordered. The geometry of the two cations is compared with that of the only previously crystallized example of this cation, viz. its [SbCl₆]⁻ salt [Reck et al. (1982 ). Chem. Ber. 115, 2981–2996]. The bond angles within the P—N—S triad in the two cations in the title compound are narrower than those observed in the literature example, while the S—N bond lengths are slightly longer in the title compound. The P—N bond length in the ordered cation shows excellent agreement with that determined by Reck and co-workers, but the P—N bond lengths are lengthened slightly in the disordered cation. Weak C—H⋯Br interactions create a three-dimensional network, with cations and anions alternating along the crystallographic c direction.

Comment

It has been known for some time that the bromosulfimide Ph₂SNBr is capable of undergoing oxidative addition to simple phosphines and sulfides to generate cations such as Ph₃PNSPh₂⁺ and Ph₂SNSPh₂⁺ (Furukawa et al., 1978 ). In recent work, we have demonstrated that such reactions may be extended to polyphosphines and selenides, and we have used X-ray crystallography to characterize the novel [1,4-(Ph₂PNSPh₂)₂(C₆H₄)]²⁺ and Ph₂SNSPh₂⁺ cations (Aucott et al., 2004 ). In the light of the relative ease of preparation and stability of such compounds, and given our ability to include a variety of main-group atoms within the basic X—N—Y core, the question of the ability of these cations to act as ligands becomes relevant. The presence of the three potential donor sites is offset by the fact that the units possess a positive charge, which may hamper their ability to coordinate to a metal centre. In order to start to address this question we have undertaken the reaction between (Ph₃PNSPh₂)[BPh₄] and (PPh₄)₂[Pd₂Br₆] in order to generate (Ph₃PNSPh₂)₂[Pd₂Br₆] as the initial product by metathesis. Previous work has shown that the [Pd₂Br₆]²⁻ anion is a very effective source of the coordinatively unsaturated [PdBr₃]⁻ unit, which can then coordinate to a range of main-group species (e.g. Kelly et al., 1995 ). If the Ph₃PNSPh₂⁺ cation is capable of acting as a reasonably effective ligand, then previous experience would indicate that subsequent formation of [PdBr₃(Ph₃PNSPh₂)] could be expected, the positive charge on the incoming unit being offset by the fact that the [PdBr₃]⁻ unit is negatively charged, thereby providing some electrostatic encouragement to the reaction.

Crystallization of the product of the reaction results in orange crystals for which X-ray crystallography reveals the structure (Ph₃PNSPh₂)₂[Pd₂Br₆], (I), i.e. the simple salt rather than the coordination complex [PdBr₃(Ph₃PNSPh₂)]. The asymmetric unit contains one complete formula unit of (I) (Fig. 1). One of the two independent Ph₃PNSPh₂⁺ cations was found to be disordered, and the S and N atoms and the two phenyl rings bonded to atom S2 were modelled as disordered over two sets of positions (see Experimental). The two cations have very similar geometries (Table 1), and compare well with the geometry of the same cation in the structure of (Ph₃PNSPh₂)[SbCl₆]·CH₂Cl₂ (Table 3) (Reck et al., 1982). There are small differences between the geometric parameters of the cations in (I) and those in Table 3; clearly the P—N—S bond angle is narrower in both cations present in (I) (including the disordered group) and the S—N bond lengths are slightly longer than that in the literature compound. The P—N bond lengths in the second (disordered) cation in (I) are lengthened compared with the ordered cation in (I) and the literature compound. It should be noted here that restraints were only applied to the geometries of the partially occupied phenyl components of the disordered group, but not to the P—N or S—N bond lengths or to the P—N—S geometry.

Owing to the large number of relatively acidic aryl CH groups, the presence of C—H⋯Br interactions (Table 2) is unsurprising. These interactions have C⋯Br distances in the range ∼3.8–3.9 Å and C—H⋯Br angles greater than 140°; these ranges compare well with the mean value of 3.75 (2) Å for C⋯Br contact distances in Csp²—H⋯Br interactions having C—H⋯Br angles greater than 140° (Desiraju & Steiner, 1999 ). These weak interactions create a three-dimensional network, with cations and anions alternating along the crystallographic c direction.

The fact that the cation has not broken into the structure of the bromo-bridged palladium dimer is indicative of the poor donor capabilities of the cation. Of course, this result does not entirely rule out coordination by such species and future work will investigate their reactivity towards other complexes bearing labile ligands. It may prove necessary to use low valent metal reagents such as Pt⁰, which could induce concomitant reduction of the cations and the formation of anionic species more conducive to coordination, in this case to the resulting Pt^II centre. Indeed, the question of the nature of the reduction products of such heteronuclear cations is intriguing, and work to assess this process is underway.

Figure 1
A view of the components of (I

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, and H atoms and the minor disorder component have been omitted for clarity.

Experimental

(Ph₃PNSPh₂)Br was prepared by the reaction of Ph₂SNBr with PPh₃ in toluene in the same manner as the bisphosphine reactions described by Aucott et al. (2004). (Ph₃PNSPh₂)[BPh₄] was then precipitated from a methanol solution of (Ph₃PNSPh₂)Br by addition of Na[BPh₄]. (Ph₃PNSPh₂)[BPh₄] and (PPh₄)₂[Pd₂Br₆] were reacted in MeCN, producing a precipitate of (PPh₄)[BPh₄]. The filtrate was evaporated to dryness and redissolved in dichloromethane, and the title product was crystallized by diffusion of diethyl ether into this solution.

Crystal data

(C₃₀H₂₅NPS)₂[Pd₂Br₆]
M_r = 1617.34
Monoclinic, Cc
a = 12.8250 (13) Å
b = 16.2000 (16) Å
c = 28.721 (3) Å
β = 97.318 (2)°
V = 5918.7 (10) Å³
Z = 4
D_x = 1.815 Mg m⁻³
Mo Kα radiation
Cell parameters from 12 077 reflections
θ = 2.2–28.5°
μ = 4.82 mm⁻¹
T = 150 (2) K
Block, dark orange
0.59 × 0.40 × 0.37 mm

Data collection

Bruker SMART 1000 CCD diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.104, T_max = 0.168
24 282 measured reflections
12 979 independent reflections
11 006 reflections with I > 2σ(I)
R_int = 0.032
θ_max = 27.5°
h = −16 → 16
k = −21 → 21
l = −37 → 36

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.082
S = 1.01
12 639 reflections
732 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.029P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 1.29 e Å⁻³
Δρ_min = −0.90 e Å⁻³
Absolute structure: Flack (1983 ), 5943 Friedel pairs
Flack parameter = 0.065 (6)

Table 1
Selected geometric parameters (Å, °)

Pd1—Br1	2.4102 (7)
Pd1—Br2	2.4086 (7)
Pd1—Br3	2.4550 (7)
Pd1—Br4	2.4437 (7)
Pd2—Br3	2.4505 (7)
Pd2—Br4	2.4455 (7)
Pd2—Br5	2.4180 (7)
Pd2—Br6	2.4109 (7)
S1—N1	1.616 (4)
S1—C1	1.778 (4)
S1—C7	1.796 (5)
P1—N1	1.609 (4)
P1—C13	1.808 (6)
P1—C19	1.786 (5)
P1—C25	1.787 (5)
P2—N2	1.622 (5)
P2—N2X	1.63 (3)
P2—C43	1.803 (5)
P2—C49	1.797 (6)
P2—C55	1.785 (5)
S2—N2	1.615 (5)
S2—C31	1.789 (5)
S2—C37	1.795 (5)

P1—N1—S1	118.1 (3)
P2—N2—S2	119.1 (3)

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯Br6ⁱ	0.95	3.13	3.909 (6)	140
C17—H17⋯Br2ⁱⁱ	0.95	2.97	3.900 (7)	167
C27—H27⋯Br3ⁱⁱⁱ	0.95	2.93	3.858 (6)	167
C39—H39⋯Br6^iv	0.95	2.92	3.827 (8)	161
C59—H59⋯Br4^v	0.95	2.93	3.830 (6)	158
Symmetry codes: (i) x-1,y,z; (ii) $[x-{\script{1\over 2}},{\script{3\over 2}}-y,z-{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}},{\script{1\over 2}}+y,z]$ ; (iv) x-1, $[1-y, {\script{1\over 2}}+z]$ ; (v) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Table 3
Selected bond lengths and angle (Å, °) for (Ph₂SNPPh₃)[SbCl₆]·CH₂Cl₂ (Reck et al., 1982)

S—N	1.596
P—N	1.608
S—C	1.755, 1.761
P—C	1.779, 1.788, 1.797

P—N—S	123.6

The data set for (I) was truncated at 2θ = 55°, as only statistically insignificant data were present above this limit. Atoms N2 and S2 and the phenyl substituents bonded to atom S2 were found to be disordered. These groups were modelled over two sets of positions, giving a refined major occupancy of 88.5 (3)%. The C atoms in the minor component of the disorder model were refined isotropically, with restraints applied to their displacement parameters. Atoms N2X and S2X were refined anisotropically, with restraints applied to their displacement parameters. Restraints were also applied to the geometries of the phenyl substituents in the disordered group. The largest ΔF residual lies 1.03 Å from atom Pd1. H atoms were positioned geometrically (C—H = 0.95 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270104029464/bm1597sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104029464/bm1597Isup2.hkl

Comment top

It has been known for some time that the bromosulfimide Ph₂SNBr is capable of undergoing oxidative addition to simple phosphines and sulfides to generate cations such as Ph₃PNSPh₂⁺ and Ph₂SNSPh₂⁺ (Furukawa et al., 1978). In recent work, we have demonstrated that such reactions may be extended to polyphosphines and to selenides, and we have used X-ray crystallography to characterize fully the novel [1,4-(Ph₂PNSPh₂)₂(C₆H₄)]²⁺ and [Ph₂SNSPh₂]⁺ cations (Aucott et al., 2004). In the light of the relative ease of preparation and stability of such compounds, and given our ability to include a variety of main-group atoms within the basic X—N—Y core, the question of their ability to act as ligands becomes relevant. The presence of the three potential donor sites is offset by the fact that the units possess a positive charge, which may hamper their ability to coordinate to a metal centre. In order to start to address this question we have undertaken the reaction between (Ph₃PNSPh₂)[BPh₄] and (PPh₄)₂[Pd₂Br₆] in order to generate (Ph₃PNSPh₂)₂[Pd₂Br₆] as the initial product by metathesis. Previous work has shown that the [Pd₂Br₆]²⁻ anion is a very effective source of the coordinatively unsaturated [PdBr₃]⁻ unit, which can then coordinate to a range of main-group species (e.g. Kelly et al., 1995). If the Ph₂SNSPh₂⁺ cation is capable of acting as a reasonably effective ligand then previous experience would indicate that subsequent formation of [PdBr₃(Ph₂SNSPh₂)] could be expected, with the positive charge on the incoming unit being offset by the fact that the [PdBr₃]⁻ unit is negatively charged, thereby providing some electrostatic encouragement to the reaction.

Crystallization of the product of the reaction results in orange crystals for which X-ray crystallography reveals the structure (Ph₃PNSPh₂)₂[Pd₂Br₆] or, (C₃₀H₂₅NPS)₂[Pd₂Br₆], (I), i.e. the simple salt rather than the coordination complex [PdBr₃(Ph₃PNSPh₂)]. The asymmetric unit contains one complete formula unit of (I) (Fig. 1). One of the two independent [Ph₃PNSPh₂]⁺ cations was found to be disordered, and the S and N atoms and the two phenyl rings bonded to atom S2 were modelled as disordered over two sets of positions (see Experimental). The two cations have very similar geometries (Table 1), and also compare well with the geometry of the same cation in the structure of [Ph₃PNSPh₂][SbCl₆]·CH₂Cl₂ (Table 3) (Reck et al., 1982). There are small differences in the geometries of the cations in (I) compared with those shown in Table 3; clearly the P—N—S bond angle is narrower in both cations present in (I) (including the disordered group) and the S—N bond lengths are slightly longer than seen in the literature compound. The P—N bond lengths in the second (disordered) cation in (I) are lengthened compared with the ordered cation in (I) and the literature compound. It should be noted here that restraints have only been applied to the geometries of the partially occupied Ph rings components of the disordered group, but not to the P—N or S—N bond lengths or to the P—N—S geometry.

Owing to the large number of relatively acidic aryl C—H groups, the presence of C—H···Br interactions (Table 2) is unsurprizing. These interactions have C···Br distances in the range 3.8–3.9 Å and C—H···Br angles greater than 140°; these ranges compare well with the mean value of 3.75 (2) Å for C···Br contact distances in Csp²—H···Br interactions having C—H···Br angles greater than 140° (Desiraju & Steiner, 1999). These weak interactions create a three-dimensional network, with cations and anions alternating along the crystallographic c direction.

The fact that the cation has not broken into the structure of the bromo-bridged palladium dimer is indicative of its poor donor capabilities. Of course this does not entirely rule out coordination by such species and future work will investigate their reactivity towards other complexes bearing labile ligands. ## AUTHOR: Please clarify the next sentence: It may prove necessary to use low valent metal reagents, which could induce concomitant reduction of the cations and the formation of anionic species more conducive to coordination. Indeed, the question of the nature of the reduction products of such heteronuclear cations is intriguing and work to assess this is underway.

Experimental top

(Ph₃PNSPh₂)Br was prepared by the reaction of Ph₂SNBr with PPh₃ in toluene in the same manner as the bisphosphine reactions (Aucott et al., 2004). (Ph₃PNSPh₂)[BPh₄] was then precipitated from a methanol solution of (Ph₃PNSPh₂)Br by addition of Na[BPh₄]. (Ph₃PNSPh₂)[BPh₄] and [PPh₄]₂[Pd₂Br₆] were reacted in MeCN, producing a precipitate of [PPh₄][BPh₄]. The filtrate was evaporated to dryness, redissolved in dichloromethane and the title product was crystallized by diethyl ether diffusion into this solution.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures top

Fig. 1. A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, and H atoms and the minor disorder component have been omitted for clarity.

(I) top

Crystal data top

(C₃₀H₂₅NPS)₂[Pd₂Br₆]	F(000) = 3152
M_r = 1617.34	D_x = 1.815 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 12077 reflections
a = 12.8250 (13) Å	θ = 2.2–28.5°
b = 16.2000 (16) Å	µ = 4.82 mm⁻¹
c = 28.721 (3) Å	T = 150 K
β = 97.318 (2)°	Block, dark orange
V = 5918.7 (10) Å³	0.59 × 0.40 × 0.37 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	12979 independent reflections
Radiation source: sealed tube	11006 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω rotation with narrow frames scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −16→16
T_min = 0.104, T_max = 0.168	k = −21→21
24282 measured reflections	l = −37→36

Refinement top

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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.029P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
12639 reflections	Δρ_max = 1.29 e Å⁻³
732 parameters	Δρ_min = −0.90 e Å⁻³
519 restraints	Absolute structure: Flack (1983), 5943 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.065 (6)

Crystal data top

(C₃₀H₂₅NPS)₂[Pd₂Br₆]	V = 5918.7 (10) Å³
M_r = 1617.34	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 12.8250 (13) Å	µ = 4.82 mm⁻¹
b = 16.2000 (16) Å	T = 150 K
c = 28.721 (3) Å	0.59 × 0.40 × 0.37 mm
β = 97.318 (2)°

Data collection top

Bruker SMART 1000 CCD diffractometer	12979 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	11006 reflections with I > 2σ(I)
T_min = 0.104, T_max = 0.168	R_int = 0.032
24282 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.082	Δρ_max = 1.29 e Å⁻³
S = 1.01	Δρ_min = −0.90 e Å⁻³
12639 reflections	Absolute structure: Flack (1983), 5943 Friedel pairs
732 parameters	Absolute structure parameter: 0.065 (6)
519 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pd1	1.00239 (4)	0.64390 (2)	0.433146 (18)	0.02103 (9)
Pd2	1.03280 (4)	0.61411 (2)	0.311737 (18)	0.01992 (9)
Br1	0.88771 (5)	0.58759 (4)	0.48539 (2)	0.03321 (14)
Br2	1.09863 (5)	0.72090 (4)	0.49632 (2)	0.03064 (14)
Br3	0.90823 (5)	0.57186 (3)	0.36521 (2)	0.02934 (14)
Br4	1.11786 (5)	0.69452 (4)	0.37800 (2)	0.03075 (14)
Br5	0.94835 (5)	0.52626 (3)	0.25007 (2)	0.02818 (13)
Br6	1.15656 (5)	0.66590 (4)	0.26231 (2)	0.02809 (13)
S1	0.68188 (10)	0.80902 (7)	0.23301 (5)	0.0185 (3)
P1	0.53982 (10)	0.68618 (8)	0.24768 (5)	0.0172 (3)
N1	0.6597 (3)	0.7177 (3)	0.25220 (15)	0.0219 (10)
C1	0.7563 (3)	0.8581 (2)	0.28172 (16)	0.0198 (11)
C2	0.7344 (3)	0.9409 (2)	0.28784 (16)	0.0213 (11)
H2	0.6830	0.9686	0.2667	0.026*
C3	0.7893 (4)	0.9827 (3)	0.32564 (17)	0.0274 (13)
H3	0.7744	1.0392	0.3308	0.033*
C4	0.8654 (4)	0.9421 (2)	0.35563 (18)	0.0277 (12)
H4	0.9039	0.9714	0.3809	0.033*
C5	0.8861 (4)	0.8593 (3)	0.34924 (17)	0.0280 (12)
H5	0.9388	0.8320	0.3699	0.034*
C6	0.8297 (4)	0.8160 (3)	0.31252 (16)	0.0233 (11)
H6	0.8412	0.7587	0.3086	0.028*
C7	0.7767 (4)	0.7900 (3)	0.19333 (19)	0.0218 (11)
C8	0.7604 (5)	0.8310 (4)	0.1512 (2)	0.0317 (13)
H8	0.7045	0.8696	0.1451	0.038*
C9	0.8266 (5)	0.8154 (4)	0.1179 (2)	0.0377 (15)
H9	0.8162	0.8429	0.0885	0.045*
C10	0.9085 (5)	0.7591 (4)	0.1275 (2)	0.0348 (14)
H10	0.9550	0.7487	0.1049	0.042*
C11	0.9217 (5)	0.7181 (4)	0.1705 (2)	0.0323 (14)
H11	0.9777	0.6797	0.1773	0.039*
C12	0.8556 (4)	0.7323 (3)	0.2028 (2)	0.0257 (12)
H12	0.8634	0.7028	0.2317	0.031*
C13	0.4656 (4)	0.7188 (3)	0.19303 (19)	0.0232 (12)
C14	0.3691 (5)	0.7560 (4)	0.1902 (2)	0.0305 (14)
H14	0.3335	0.7581	0.2173	0.037*
C15	0.3213 (6)	0.7913 (4)	0.1476 (3)	0.0452 (17)
H15	0.2541	0.8166	0.1456	0.054*
C16	0.3751 (6)	0.7877 (4)	0.1093 (2)	0.0475 (19)
H16	0.3452	0.8125	0.0807	0.057*
C17	0.4702 (6)	0.7496 (4)	0.1112 (2)	0.0471 (18)
H17	0.5049	0.7472	0.0839	0.057*
C18	0.5164 (5)	0.7146 (4)	0.1522 (2)	0.0333 (14)
H18	0.5824	0.6875	0.1532	0.040*
C19	0.5508 (4)	0.5763 (3)	0.25074 (18)	0.0204 (11)
C20	0.6478 (5)	0.5399 (3)	0.2658 (2)	0.0273 (13)
H20	0.7076	0.5734	0.2751	0.033*
C21	0.6565 (5)	0.4541 (3)	0.2670 (2)	0.0323 (14)
H21	0.7226	0.4292	0.2770	0.039*
C22	0.5698 (5)	0.4052 (4)	0.2539 (2)	0.0370 (15)
H22	0.5755	0.3467	0.2553	0.044*
C23	0.4754 (5)	0.4420 (4)	0.2387 (2)	0.0412 (17)
H23	0.4162	0.4082	0.2288	0.049*
C24	0.4637 (5)	0.5266 (3)	0.2375 (2)	0.0306 (14)
H24	0.3969	0.5506	0.2277	0.037*
C25	0.4716 (4)	0.7232 (3)	0.29402 (18)	0.0193 (11)
C26	0.4557 (4)	0.8084 (3)	0.2977 (2)	0.0239 (12)
H26	0.4767	0.8444	0.2746	0.029*
C27	0.4102 (4)	0.8402 (4)	0.3344 (2)	0.0288 (13)
H27	0.4017	0.8982	0.3369	0.035*
C28	0.3767 (4)	0.7887 (4)	0.3676 (2)	0.0295 (13)
H28	0.3434	0.8110	0.3925	0.035*
C29	0.3917 (4)	0.7038 (4)	0.3646 (2)	0.0283 (13)
H29	0.3693	0.6681	0.3876	0.034*
C30	0.4398 (4)	0.6716 (3)	0.32778 (19)	0.0221 (11)
H30	0.4508	0.6138	0.3258	0.027*
P2	0.49777 (10)	0.56828 (8)	0.51370 (5)	0.0202 (3)
S2	0.35427 (11)	0.44673 (8)	0.53211 (5)	0.0179 (4)	0.885 (3)
N2	0.3774 (4)	0.5403 (3)	0.51683 (18)	0.0206 (10)	0.885 (3)
C31	0.2813 (4)	0.4004 (3)	0.48158 (18)	0.0209 (11)	0.885 (3)
C32	0.2077 (5)	0.4452 (3)	0.4524 (2)	0.0249 (12)	0.885 (3)
H32	0.1963	0.5020	0.4581	0.030*	0.885 (3)
C33	0.1506 (5)	0.4049 (3)	0.4145 (2)	0.0273 (12)	0.885 (3)
H33	0.0999	0.4343	0.3938	0.033*	0.885 (3)
C34	0.1682 (5)	0.3221 (3)	0.4070 (2)	0.0275 (13)	0.885 (3)
H34	0.1284	0.2947	0.3814	0.033*	0.885 (3)
C35	0.2430 (5)	0.2783 (3)	0.4361 (2)	0.0272 (12)	0.885 (3)
H35	0.2544	0.2215	0.4304	0.033*	0.885 (3)
C36	0.3013 (4)	0.3177 (3)	0.47400 (19)	0.0226 (11)	0.885 (3)
H36	0.3534	0.2886	0.4941	0.027*	0.885 (3)
C37	0.2554 (4)	0.4619 (3)	0.57022 (17)	0.0202 (10)	0.885 (3)
C38	0.2680 (4)	0.4173 (4)	0.61164 (19)	0.0252 (11)	0.885 (3)
H38	0.3275	0.3827	0.6193	0.030*	0.885 (3)
C39	0.1916 (4)	0.4241 (4)	0.64185 (19)	0.0296 (12)	0.885 (3)
H39	0.1990	0.3945	0.6706	0.036*	0.885 (3)
C40	0.1047 (4)	0.4741 (4)	0.6298 (2)	0.0272 (12)	0.885 (3)
H40	0.0521	0.4775	0.6502	0.033*	0.885 (3)
C41	0.0936 (4)	0.5193 (4)	0.5885 (2)	0.0256 (11)	0.885 (3)
H41	0.0340	0.5538	0.5808	0.031*	0.885 (3)
C42	0.1703 (5)	0.5139 (3)	0.55836 (17)	0.0215 (11)	0.885 (3)
H42	0.1644	0.5452	0.5302	0.026*	0.885 (3)
S2X	0.2903 (8)	0.5220 (6)	0.5170 (4)	0.019 (2)	0.115 (3)
N2X	0.414 (3)	0.506 (2)	0.5342 (14)	0.018 (3)	0.115 (3)
C31X	0.246 (3)	0.431 (2)	0.4787 (13)	0.023 (2)*	0.115 (3)
C32X	0.172 (3)	0.4482 (17)	0.4407 (16)	0.026 (2)*	0.115 (3)
H32X	0.1460	0.5028	0.4353	0.031*	0.115 (3)
C33X	0.135 (3)	0.384 (2)	0.4108 (16)	0.027 (2)*	0.115 (3)
H33X	0.0773	0.3926	0.3871	0.032*	0.115 (3)
C34X	0.183 (4)	0.307 (2)	0.4157 (17)	0.0268 (17)*	0.115 (3)
H34X	0.1591	0.2640	0.3947	0.032*	0.115 (3)
C35X	0.265 (4)	0.2930 (19)	0.4509 (17)	0.025 (2)*	0.115 (3)
H35X	0.2999	0.2410	0.4530	0.030*	0.115 (3)
C36X	0.297 (3)	0.355 (3)	0.4832 (13)	0.023 (2)*	0.115 (3)
H36X	0.3528	0.3456	0.5078	0.027*	0.115 (3)
C37X	0.224 (3)	0.501 (3)	0.5665 (12)	0.0230 (13)*	0.115 (3)
C38X	0.276 (2)	0.450 (3)	0.6007 (15)	0.0232 (19)*	0.115 (3)
H38X	0.3430	0.4276	0.5973	0.028*	0.115 (3)
C39X	0.227 (3)	0.432 (3)	0.6403 (13)	0.027 (2)*	0.115 (3)
H39X	0.2646	0.4033	0.6661	0.032*	0.115 (3)
C40X	0.124 (3)	0.456 (3)	0.6416 (13)	0.028 (2)*	0.115 (3)
H40X	0.0872	0.4363	0.6662	0.033*	0.115 (3)
C41X	0.073 (2)	0.507 (3)	0.6074 (15)	0.0230 (13)*	0.115 (3)
H41X	0.0069	0.5302	0.6112	0.028*	0.115 (3)
C42X	0.121 (3)	0.525 (3)	0.5675 (13)	0.0230 (13)*	0.115 (3)
H42X	0.0828	0.5529	0.5416	0.028*	0.115 (3)
C43	0.4862 (4)	0.6792 (3)	0.51151 (19)	0.0226 (12)
C44	0.3890 (4)	0.7146 (3)	0.49680 (19)	0.0242 (12)
H44	0.3298	0.6807	0.4870	0.029*
C45	0.3789 (5)	0.7996 (3)	0.4966 (2)	0.0306 (13)
H45	0.3124	0.8243	0.4871	0.037*
C46	0.4656 (5)	0.8487 (3)	0.5102 (2)	0.0354 (15)
H46	0.4589	0.9071	0.5095	0.042*
C47	0.5625 (5)	0.8128 (4)	0.5248 (2)	0.0391 (16)
H47	0.6219	0.8467	0.5342	0.047*
C48	0.5729 (5)	0.7282 (4)	0.5258 (2)	0.0328 (14)
H48	0.6390	0.7037	0.5363	0.039*
C49	0.5916 (4)	0.5367 (3)	0.56226 (18)	0.0211 (12)
C50	0.6936 (5)	0.5119 (4)	0.5565 (2)	0.0319 (14)
H50	0.7157	0.5128	0.5262	0.038*
C51	0.7624 (5)	0.4862 (4)	0.5946 (2)	0.0465 (17)
H51	0.8318	0.4700	0.5905	0.056*
C52	0.7305 (6)	0.4841 (4)	0.6385 (2)	0.0489 (19)
H52	0.7778	0.4663	0.6648	0.059*
C53	0.6307 (6)	0.5078 (4)	0.6444 (2)	0.0445 (17)
H53	0.6086	0.5053	0.6747	0.053*
C54	0.5619 (5)	0.5350 (4)	0.6068 (2)	0.0347 (14)
H54	0.4935	0.5529	0.6116	0.042*
C55	0.5522 (4)	0.5324 (3)	0.46318 (18)	0.0193 (11)
C56	0.5860 (4)	0.5853 (3)	0.4305 (2)	0.0244 (12)
H56	0.5753	0.6431	0.4330	0.029*
C57	0.6358 (4)	0.5541 (4)	0.39409 (19)	0.0264 (12)
H57	0.6582	0.5905	0.3714	0.032*
C58	0.6526 (4)	0.4711 (4)	0.3908 (2)	0.0290 (13)
H58	0.6877	0.4504	0.3661	0.035*
C59	0.6193 (4)	0.4171 (4)	0.4229 (2)	0.0282 (13)
H59	0.6314	0.3596	0.4203	0.034*
C60	0.5685 (4)	0.4469 (3)	0.45877 (19)	0.0237 (12)
H60	0.5444	0.4097	0.4806	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.01828 (19)	0.01824 (19)	0.0275 (2)	0.00010 (16)	0.00634 (16)	−0.00068 (16)
Pd2	0.01965 (19)	0.01595 (19)	0.0247 (2)	0.00061 (15)	0.00510 (16)	−0.00115 (16)
Br1	0.0308 (3)	0.0386 (3)	0.0307 (3)	−0.0066 (3)	0.0059 (3)	0.0097 (3)
Br2	0.0306 (3)	0.0325 (3)	0.0283 (3)	−0.0041 (3)	0.0018 (3)	−0.0011 (3)
Br3	0.0262 (3)	0.0292 (3)	0.0347 (3)	−0.0097 (2)	0.0120 (2)	−0.0092 (3)
Br4	0.0299 (3)	0.0310 (3)	0.0343 (3)	−0.0117 (2)	0.0159 (3)	−0.0126 (2)
Br5	0.0302 (3)	0.0251 (3)	0.0277 (3)	−0.0026 (2)	−0.0024 (2)	0.0005 (2)
Br6	0.0301 (3)	0.0293 (3)	0.0258 (3)	−0.0025 (2)	0.0074 (2)	0.0030 (2)
S1	0.0165 (6)	0.0151 (6)	0.0236 (7)	−0.0025 (5)	0.0017 (5)	0.0017 (5)
P1	0.0181 (6)	0.0155 (6)	0.0178 (7)	−0.0041 (5)	0.0018 (5)	0.0016 (5)
N1	0.024 (2)	0.016 (2)	0.026 (3)	−0.0037 (18)	0.0007 (19)	0.0031 (18)
C1	0.013 (2)	0.023 (3)	0.024 (3)	−0.005 (2)	0.007 (2)	0.002 (2)
C2	0.018 (2)	0.018 (3)	0.029 (3)	−0.004 (2)	0.005 (2)	−0.001 (2)
C3	0.028 (3)	0.021 (3)	0.036 (4)	−0.009 (2)	0.014 (3)	−0.005 (2)
C4	0.026 (3)	0.029 (3)	0.027 (3)	−0.004 (2)	0.000 (2)	−0.006 (2)
C5	0.025 (3)	0.032 (3)	0.025 (3)	0.001 (2)	−0.003 (2)	0.000 (2)
C6	0.026 (3)	0.020 (3)	0.023 (3)	0.002 (2)	0.001 (2)	0.001 (2)
C7	0.020 (3)	0.015 (2)	0.029 (3)	−0.003 (2)	−0.003 (2)	−0.001 (2)
C8	0.037 (3)	0.025 (3)	0.033 (4)	0.007 (3)	0.004 (3)	0.008 (2)
C9	0.047 (4)	0.042 (4)	0.026 (3)	0.006 (3)	0.014 (3)	0.018 (3)
C10	0.043 (4)	0.033 (3)	0.032 (4)	0.001 (3)	0.016 (3)	0.004 (3)
C11	0.033 (3)	0.035 (3)	0.028 (3)	0.008 (3)	0.001 (3)	0.002 (3)
C12	0.030 (3)	0.027 (3)	0.020 (3)	0.008 (2)	0.002 (2)	0.005 (2)
C13	0.022 (3)	0.024 (3)	0.022 (3)	−0.012 (2)	−0.001 (2)	0.000 (2)
C14	0.036 (3)	0.028 (3)	0.026 (3)	−0.007 (3)	−0.002 (3)	0.002 (2)
C15	0.048 (4)	0.039 (4)	0.044 (4)	0.003 (3)	−0.012 (3)	0.005 (3)
C16	0.072 (5)	0.040 (4)	0.026 (4)	−0.010 (4)	−0.013 (4)	0.018 (3)
C17	0.069 (5)	0.054 (4)	0.018 (4)	−0.028 (4)	0.004 (3)	0.001 (3)
C18	0.036 (3)	0.045 (4)	0.018 (3)	−0.012 (3)	−0.001 (3)	−0.005 (3)
C19	0.028 (3)	0.015 (2)	0.018 (3)	−0.005 (2)	0.003 (2)	−0.002 (2)
C20	0.039 (3)	0.022 (3)	0.020 (3)	−0.002 (2)	0.002 (2)	−0.001 (2)
C21	0.043 (4)	0.028 (3)	0.025 (3)	0.006 (3)	0.003 (3)	−0.003 (2)
C22	0.051 (4)	0.021 (3)	0.044 (4)	0.001 (3)	0.024 (3)	0.001 (3)
C23	0.043 (4)	0.027 (3)	0.058 (5)	−0.020 (3)	0.022 (3)	−0.007 (3)
C24	0.024 (3)	0.025 (3)	0.047 (4)	−0.007 (2)	0.019 (3)	−0.001 (3)
C25	0.018 (2)	0.022 (3)	0.017 (3)	0.001 (2)	−0.003 (2)	−0.001 (2)
C26	0.028 (3)	0.019 (3)	0.024 (3)	0.000 (2)	0.001 (2)	0.003 (2)
C27	0.028 (3)	0.025 (3)	0.031 (3)	0.002 (2)	−0.005 (3)	−0.003 (2)
C28	0.023 (3)	0.039 (3)	0.025 (3)	0.006 (2)	0.002 (2)	−0.009 (3)
C29	0.018 (3)	0.044 (3)	0.024 (3)	−0.004 (3)	0.008 (2)	0.005 (3)
C30	0.021 (3)	0.025 (3)	0.021 (3)	−0.002 (2)	0.001 (2)	0.003 (2)
P2	0.0189 (7)	0.0214 (7)	0.0213 (8)	−0.0077 (5)	0.0062 (5)	−0.0052 (5)
S2	0.0174 (7)	0.0141 (7)	0.0222 (8)	−0.0030 (5)	0.0018 (6)	0.0017 (5)
N2	0.021 (2)	0.016 (2)	0.025 (3)	−0.0028 (19)	0.002 (2)	0.006 (2)
C31	0.018 (2)	0.023 (2)	0.022 (2)	−0.0038 (18)	0.0041 (18)	0.0042 (18)
C32	0.025 (2)	0.025 (2)	0.025 (2)	−0.0028 (18)	0.003 (2)	0.0009 (18)
C33	0.028 (2)	0.029 (2)	0.025 (2)	−0.0016 (19)	−0.0001 (18)	−0.0008 (19)
C34	0.027 (2)	0.030 (2)	0.025 (2)	−0.002 (2)	0.0002 (19)	−0.002 (2)
C35	0.027 (2)	0.028 (2)	0.026 (2)	−0.0022 (19)	0.0020 (19)	−0.0039 (19)
C36	0.022 (2)	0.023 (2)	0.022 (2)	−0.0022 (19)	0.0048 (18)	−0.0020 (18)
C37	0.0193 (19)	0.021 (2)	0.020 (2)	−0.0029 (18)	−0.0001 (18)	0.0009 (18)
C38	0.025 (2)	0.026 (2)	0.025 (2)	−0.0014 (19)	0.0045 (19)	0.0060 (19)
C39	0.031 (2)	0.032 (2)	0.027 (2)	−0.001 (2)	0.007 (2)	0.0043 (19)
C40	0.026 (2)	0.029 (2)	0.028 (2)	−0.0040 (19)	0.007 (2)	0.0010 (19)
C41	0.025 (2)	0.025 (2)	0.026 (2)	−0.0018 (19)	0.0021 (19)	−0.0036 (19)
C42	0.023 (2)	0.020 (2)	0.021 (2)	−0.0040 (18)	0.0007 (19)	−0.0018 (18)
S2X	0.018 (4)	0.016 (4)	0.024 (5)	−0.002 (3)	0.004 (4)	0.004 (4)
N2X	0.017 (5)	0.016 (6)	0.023 (6)	−0.001 (5)	0.006 (5)	0.002 (6)
C43	0.025 (3)	0.024 (3)	0.021 (3)	−0.009 (2)	0.009 (2)	−0.007 (2)
C44	0.025 (3)	0.022 (3)	0.025 (3)	−0.010 (2)	0.001 (2)	−0.006 (2)
C45	0.033 (3)	0.027 (3)	0.032 (3)	−0.002 (2)	0.005 (3)	0.001 (2)
C46	0.050 (4)	0.016 (3)	0.045 (4)	−0.007 (3)	0.025 (3)	−0.003 (3)
C47	0.038 (3)	0.027 (3)	0.055 (4)	−0.020 (3)	0.015 (3)	−0.016 (3)
C48	0.027 (3)	0.032 (3)	0.042 (4)	−0.009 (2)	0.012 (3)	−0.012 (3)
C49	0.033 (3)	0.017 (3)	0.014 (3)	−0.010 (2)	0.007 (2)	−0.001 (2)
C50	0.026 (3)	0.050 (4)	0.018 (3)	−0.011 (3)	−0.002 (2)	0.001 (3)
C51	0.041 (4)	0.063 (5)	0.034 (4)	0.001 (3)	−0.003 (3)	0.004 (3)
C52	0.067 (5)	0.045 (4)	0.028 (4)	−0.012 (4)	−0.019 (3)	0.013 (3)
C53	0.074 (5)	0.044 (4)	0.016 (3)	0.000 (4)	0.007 (3)	0.002 (3)
C54	0.045 (4)	0.036 (3)	0.023 (3)	−0.003 (3)	0.005 (3)	0.000 (3)
C55	0.016 (2)	0.023 (3)	0.017 (3)	−0.004 (2)	−0.002 (2)	−0.006 (2)
C56	0.023 (3)	0.024 (3)	0.025 (3)	0.003 (2)	−0.003 (2)	0.000 (2)
C57	0.030 (3)	0.034 (3)	0.015 (3)	0.005 (2)	0.004 (2)	0.008 (2)
C58	0.024 (3)	0.047 (4)	0.016 (3)	0.006 (3)	0.004 (2)	−0.010 (3)
C59	0.033 (3)	0.027 (3)	0.024 (3)	−0.001 (2)	0.000 (2)	−0.005 (2)
C60	0.024 (3)	0.026 (3)	0.020 (3)	−0.003 (2)	0.003 (2)	0.003 (2)

Geometric parameters (Å, º) top

Pd1—Br1	2.4102 (7)	C31—C36	1.386 (4)
Pd1—Br2	2.4086 (7)	C32—C33	1.395 (4)
Pd1—Br3	2.4550 (7)	C32—H32	0.9500
Pd1—Br4	2.4437 (7)	C33—C34	1.383 (4)
Pd2—Br3	2.4505 (7)	C33—H33	0.9500
Pd2—Br4	2.4455 (7)	C34—C35	1.385 (4)
Pd2—Br5	2.4180 (7)	C34—H34	0.9500
Pd2—Br6	2.4109 (7)	C35—C36	1.393 (4)
S1—N1	1.616 (4)	C35—H35	0.9500
S1—C1	1.778 (4)	C36—H36	0.9500
S1—C7	1.796 (5)	C37—C38	1.384 (4)
P1—N1	1.609 (4)	C37—C42	1.385 (4)
P1—C13	1.808 (6)	C38—C39	1.393 (4)
P1—C19	1.786 (5)	C38—H38	0.9500
P1—C25	1.787 (5)	C39—C40	1.385 (4)
C1—C6	1.385 (4)	C39—H39	0.9500
C1—C2	1.388 (4)	C40—C41	1.386 (4)
C2—C3	1.392 (4)	C40—H40	0.9500
C2—H2	0.9500	C41—C42	1.394 (4)
C3—C4	1.383 (4)	C41—H41	0.9500
C3—H3	0.9500	C42—H42	0.9500
C4—C5	1.385 (4)	S2X—N2X	1.62 (4)
C4—H4	0.9500	S2X—C37X	1.78 (3)
C5—C6	1.390 (4)	S2X—C31X	1.89 (3)
C5—H5	0.9500	C31X—C36X	1.386 (5)
C6—H6	0.9500	C31X—C32X	1.386 (5)
C7—C8	1.373 (8)	C32X—C33X	1.393 (5)
C7—C12	1.379 (7)	C32X—H32X	0.9500
C8—C9	1.381 (8)	C33X—C34X	1.385 (5)
C8—H8	0.9500	C33X—H33X	0.9500
C9—C10	1.391 (8)	C34X—C35X	1.385 (5)
C9—H9	0.9500	C34X—H34X	0.9500
C10—C11	1.395 (8)	C35X—C36X	1.393 (5)
C10—H10	0.9500	C35X—H35X	0.9500
C11—C12	1.354 (8)	C36X—H36X	0.9500
C11—H11	0.9500	C37X—C42X	1.386 (5)
C12—H12	0.9500	C37X—C38X	1.386 (5)
C13—C14	1.370 (8)	C38X—C39X	1.393 (5)
C13—C18	1.413 (8)	C38X—H38X	0.9500
C14—C15	1.418 (9)	C39X—C40X	1.385 (5)
C14—H14	0.9500	C39X—H39X	0.9500
C15—C16	1.373 (10)	C40X—C41X	1.385 (5)
C15—H15	0.9500	C40X—H40X	0.9500
C16—C17	1.362 (10)	C41X—C42X	1.394 (5)
C16—H16	0.9500	C41X—H41X	0.9500
C17—C18	1.373 (9)	C42X—H42X	0.9500
C17—H17	0.9500	C43—C48	1.386 (7)
C18—H18	0.9500	C43—C44	1.389 (8)
C19—C24	1.392 (7)	C44—C45	1.384 (7)
C19—C20	1.394 (8)	C44—H44	0.9500
C20—C21	1.395 (8)	C45—C46	1.382 (8)
C20—H20	0.9500	C45—H45	0.9500
C21—C22	1.378 (9)	C46—C47	1.388 (9)
C21—H21	0.9500	C46—H46	0.9500
C22—C23	1.370 (9)	C47—C48	1.376 (8)
C22—H22	0.9500	C47—H47	0.9500
C23—C24	1.378 (8)	C48—H48	0.9500
C23—H23	0.9500	C49—C54	1.382 (8)
C24—H24	0.9500	C49—C50	1.398 (8)
C25—C30	1.381 (7)	C50—C51	1.379 (9)
C25—C26	1.400 (7)	C50—H50	0.9500
C26—C27	1.367 (8)	C51—C52	1.375 (10)
C26—H26	0.9500	C51—H51	0.9500
C27—C28	1.377 (8)	C52—C53	1.366 (10)
C27—H27	0.9500	C52—H52	0.9500
C28—C29	1.393 (8)	C53—C54	1.377 (9)
C28—H28	0.9500	C53—H53	0.9500
C29—C30	1.392 (8)	C54—H54	0.9500
C29—H29	0.9500	C55—C56	1.381 (7)
C30—H30	0.9500	C55—C60	1.409 (7)
P2—N2	1.622 (5)	C56—C57	1.389 (8)
P2—N2X	1.63 (3)	C56—H56	0.9500
P2—C43	1.803 (5)	C57—C58	1.366 (8)
P2—C49	1.797 (6)	C57—H57	0.9500
P2—C55	1.785 (5)	C58—C59	1.378 (8)
S2—N2	1.615 (5)	C58—H58	0.9500
S2—C31	1.789 (5)	C59—C60	1.373 (8)
S2—C37	1.795 (5)	C59—H59	0.9500
C31—C32	1.385 (4)	C60—H60	0.9500

Br2—Pd1—Br1	91.25 (3)	C36—C31—S2	116.4 (4)
Br2—Pd1—Br4	91.13 (2)	C31—C32—C33	118.5 (4)
Br1—Pd1—Br4	177.15 (3)	C31—C32—H32	120.8
Br2—Pd1—Br3	176.30 (3)	C33—C32—H32	120.8
Br1—Pd1—Br3	92.15 (2)	C34—C33—C32	119.7 (4)
Br4—Pd1—Br3	85.51 (2)	C34—C33—H33	120.1
Br6—Pd2—Br5	92.33 (3)	C32—C33—H33	120.1
Br6—Pd2—Br4	90.63 (2)	C33—C34—C35	121.1 (4)
Br5—Pd2—Br4	175.85 (3)	C33—C34—H34	119.5
Br6—Pd2—Br3	175.51 (3)	C35—C34—H34	119.5
Br5—Pd2—Br3	91.59 (2)	C34—C35—C36	120.0 (4)
Br4—Pd2—Br3	85.57 (2)	C34—C35—H35	120.0
Pd2—Br3—Pd1	94.09 (2)	C36—C35—H35	120.0
Pd1—Br4—Pd2	94.51 (2)	C31—C36—C35	118.2 (4)
N1—S1—C1	103.9 (2)	C31—C36—H36	120.9
N1—S1—C7	102.8 (2)	C35—C36—H36	120.9
C1—S1—C7	103.7 (2)	C38—C37—C42	122.1 (4)
N1—P1—C19	104.1 (2)	C38—C37—S2	116.0 (4)
N1—P1—C25	112.7 (2)	C42—C37—S2	121.9 (4)
C19—P1—C25	110.0 (2)	C37—C38—C39	118.6 (4)
N1—P1—C13	111.6 (2)	C37—C38—H38	120.7
C19—P1—C13	111.3 (2)	C39—C38—H38	120.7
C25—P1—C13	107.2 (2)	C40—C39—C38	119.9 (4)
P1—N1—S1	118.1 (3)	C40—C39—H39	120.1
C6—C1—C2	121.8 (4)	C38—C39—H39	120.1
C6—C1—S1	122.4 (3)	C39—C40—C41	120.9 (4)
C2—C1—S1	115.8 (3)	C39—C40—H40	119.5
C1—C2—C3	118.6 (3)	C41—C40—H40	119.5
C1—C2—H2	120.7	C40—C41—C42	119.7 (4)
C3—C2—H2	120.7	C40—C41—H41	120.2
C4—C3—C2	120.1 (4)	C42—C41—H41	120.2
C4—C3—H3	120.0	C37—C42—C41	118.8 (4)
C2—C3—H3	120.0	C37—C42—H42	120.6
C3—C4—C5	120.7 (4)	C41—C42—H42	120.6
C3—C4—H4	119.7	N2X—S2X—C37X	106 (2)
C5—C4—H4	119.7	N2X—S2X—C31X	105.2 (18)
C4—C5—C6	119.9 (4)	C37X—S2X—C31X	100 (2)
C4—C5—H5	120.0	P2—N2X—S2X	117 (2)
C6—C5—H5	120.0	C36X—C31X—C32X	121.8 (7)
C1—C6—C5	118.8 (4)	C36X—C31X—S2X	122 (3)
C1—C6—H6	120.6	C32X—C31X—S2X	115 (3)
C5—C6—H6	120.6	C31X—C32X—C33X	118.4 (6)
C8—C7—C12	121.9 (5)	C31X—C32X—H32X	120.8
C8—C7—S1	115.9 (4)	C33X—C32X—H32X	120.8
C12—C7—S1	122.0 (4)	C34X—C33X—C32X	119.8 (6)
C7—C8—C9	118.9 (5)	C34X—C33X—H33X	120.1
C7—C8—H8	120.6	C32X—C33X—H33X	120.1
C9—C8—H8	120.6	C35X—C34X—C33X	120.8 (6)
C8—C9—C10	119.9 (5)	C35X—C34X—H34X	119.6
C8—C9—H9	120.1	C33X—C34X—H34X	119.6
C10—C9—H9	120.1	C34X—C35X—C36X	119.9 (5)
C9—C10—C11	119.4 (5)	C34X—C35X—H35X	120.1
C9—C10—H10	120.3	C36X—C35X—H35X	120.1
C11—C10—H10	120.3	C31X—C36X—C35X	118.6 (5)
C12—C11—C10	120.7 (5)	C31X—C36X—H36X	120.7
C12—C11—H11	119.7	C35X—C36X—H36X	120.7
C10—C11—H11	119.7	C42X—C37X—C38X	121.9 (7)
C11—C12—C7	119.2 (5)	C42X—C37X—S2X	121 (3)
C11—C12—H12	120.4	C38X—C37X—S2X	116 (3)
C7—C12—H12	120.4	C37X—C38X—C39X	118.5 (6)
C14—C13—C18	118.8 (5)	C37X—C38X—H38X	120.7
C14—C13—P1	123.4 (4)	C39X—C38X—H38X	120.7
C18—C13—P1	117.3 (4)	C40X—C39X—C38X	119.6 (6)
C13—C14—C15	121.0 (6)	C40X—C39X—H39X	120.2
C13—C14—H14	119.5	C38X—C39X—H39X	120.2
C15—C14—H14	119.5	C39X—C40X—C41X	120.7 (7)
C16—C15—C14	118.0 (6)	C39X—C40X—H40X	119.7
C16—C15—H15	121.0	C41X—C40X—H40X	119.7
C14—C15—H15	121.0	C40X—C41X—C42X	119.7 (6)
C17—C16—C15	121.7 (6)	C40X—C41X—H41X	120.1
C17—C16—H16	119.1	C42X—C41X—H41X	120.1
C15—C16—H16	119.1	C37X—C42X—C41X	118.3 (6)
C16—C17—C18	120.6 (6)	C37X—C42X—H42X	120.9
C16—C17—H17	119.7	C41X—C42X—H42X	120.8
C18—C17—H17	119.7	C48—C43—C44	120.5 (5)
C17—C18—C13	119.9 (6)	C48—C43—P2	120.1 (4)
C17—C18—H18	120.1	C44—C43—P2	119.3 (4)
C13—C18—H18	120.1	C45—C44—C43	119.5 (5)
C24—C19—C20	119.5 (5)	C45—C44—H44	120.2
C24—C19—P1	120.5 (4)	C43—C44—H44	120.2
C20—C19—P1	119.9 (4)	C46—C45—C44	120.0 (5)
C19—C20—C21	119.7 (5)	C46—C45—H45	120.0
C19—C20—H20	120.2	C44—C45—H45	120.0
C21—C20—H20	120.2	C45—C46—C47	120.0 (5)
C22—C21—C20	120.5 (6)	C45—C46—H46	120.0
C22—C21—H21	119.8	C47—C46—H46	120.0
C20—C21—H21	119.8	C48—C47—C46	120.3 (5)
C23—C22—C21	119.1 (5)	C48—C47—H47	119.8
C23—C22—H22	120.5	C46—C47—H47	119.8
C21—C22—H22	120.5	C47—C48—C43	119.5 (6)
C22—C23—C24	122.0 (6)	C47—C48—H48	120.2
C22—C23—H23	119.0	C43—C48—H48	120.2
C24—C23—H23	119.0	C54—C49—C50	118.4 (5)
C23—C24—C19	119.2 (6)	C54—C49—P2	119.2 (4)
C23—C24—H24	120.4	C50—C49—P2	122.3 (4)
C19—C24—H24	120.4	C51—C50—C49	120.4 (6)
C30—C25—C26	118.9 (5)	C51—C50—H50	119.8
C30—C25—P1	122.4 (4)	C49—C50—H50	119.8
C26—C25—P1	118.5 (4)	C52—C51—C50	120.0 (7)
C27—C26—C25	120.8 (5)	C52—C51—H51	120.0
C27—C26—H26	119.6	C50—C51—H51	120.0
C25—C26—H26	119.6	C53—C52—C51	119.9 (6)
C26—C27—C28	120.4 (5)	C53—C52—H52	120.0
C26—C27—H27	119.8	C51—C52—H52	120.0
C28—C27—H27	119.8	C52—C53—C54	120.7 (6)
C27—C28—C29	119.9 (5)	C52—C53—H53	119.7
C27—C28—H28	120.0	C54—C53—H53	119.7
C29—C28—H28	120.0	C53—C54—C49	120.5 (6)
C28—C29—C30	119.6 (5)	C53—C54—H54	119.8
C28—C29—H29	120.2	C49—C54—H54	119.8
C30—C29—H29	120.2	C56—C55—C60	119.1 (5)
C25—C30—C29	120.4 (5)	C56—C55—P2	122.6 (4)
C25—C30—H30	119.8	C60—C55—P2	118.1 (4)
C29—C30—H30	119.8	C55—C56—C57	120.0 (5)
N2—P2—C55	115.3 (3)	C55—C56—H56	120.0
N2X—P2—C55	115.7 (13)	C57—C56—H56	120.0
N2—P2—C49	115.2 (3)	C58—C57—C56	120.1 (5)
N2X—P2—C49	87.1 (15)	C58—C57—H57	119.9
C55—P2—C49	104.2 (2)	C56—C57—H57	119.9
N2—P2—C43	101.9 (2)	C57—C58—C59	120.9 (5)
N2X—P2—C43	124.8 (13)	C57—C58—H58	119.6
C55—P2—C43	109.6 (2)	C59—C58—H58	119.6
C49—P2—C43	110.8 (2)	C60—C59—C58	119.7 (5)
N2—S2—C31	105.6 (3)	C60—C59—H59	120.1
N2—S2—C37	101.9 (3)	C58—C59—H59	120.1
C31—S2—C37	102.4 (3)	C59—C60—C55	120.2 (5)
P2—N2—S2	119.1 (3)	C59—C60—H60	119.9
C32—C31—C36	122.5 (4)	C55—C60—H60	119.9
C32—C31—S2	121.1 (4)

Br5—Pd2—Br3—Pd1	172.73 (2)	C32—C31—C36—C35	−1.6 (9)
Br4—Pd2—Br3—Pd1	−4.23 (2)	S2—C31—C36—C35	177.4 (5)
Br1—Pd1—Br3—Pd2	−174.12 (2)	C34—C35—C36—C31	0.8 (10)
Br4—Pd1—Br3—Pd2	4.24 (2)	N2—S2—C37—C38	−135.6 (5)
Br2—Pd1—Br4—Pd2	177.31 (2)	C31—S2—C37—C38	115.3 (5)
Br3—Pd1—Br4—Pd2	−4.25 (2)	N2—S2—C37—C42	45.8 (5)
Br6—Pd2—Br4—Pd1	−178.14 (2)	C31—S2—C37—C42	−63.3 (5)
Br3—Pd2—Br4—Pd1	4.26 (2)	C42—C37—C38—C39	1.0 (9)
C19—P1—N1—S1	158.7 (3)	S2—C37—C38—C39	−177.6 (5)
C25—P1—N1—S1	−82.1 (3)	C37—C38—C39—C40	0.7 (10)
C13—P1—N1—S1	38.5 (4)	C38—C39—C40—C41	−1.5 (11)
C1—S1—N1—P1	126.0 (3)	C39—C40—C41—C42	0.6 (10)
C7—S1—N1—P1	−126.1 (3)	C38—C37—C42—C41	−1.9 (9)
N1—S1—C1—C6	36.1 (5)	S2—C37—C42—C41	176.6 (5)
C7—S1—C1—C6	−71.1 (5)	C40—C41—C42—C37	1.1 (9)
N1—S1—C1—C2	−142.2 (4)	C37X—S2X—N2X—P2	−143 (3)
C7—S1—C1—C2	110.6 (4)	C31X—S2X—N2X—P2	111 (3)
C6—C1—C2—C3	1.1 (7)	N2—P2—N2X—S2X	1.1 (6)
S1—C1—C2—C3	179.4 (4)	C55—P2—N2X—S2X	−95 (2)
C1—C2—C3—C4	1.3 (7)	C49—P2—N2X—S2X	160 (2)
C2—C3—C4—C5	−1.7 (8)	C43—P2—N2X—S2X	47 (3)
C3—C4—C5—C6	−0.3 (9)	N2X—S2X—C31X—C36X	25 (5)
C2—C1—C6—C5	−3.0 (8)	C37X—S2X—C31X—C36X	−85 (4)
S1—C1—C6—C5	178.8 (4)	N2X—S2X—C31X—C32X	−145 (3)
C4—C5—C6—C1	2.6 (8)	C37X—S2X—C31X—C32X	106 (4)
N1—S1—C7—C8	136.2 (4)	C36X—C31X—C32X—C33X	11 (7)
C1—S1—C7—C8	−115.8 (4)	S2X—C31X—C32X—C33X	−180 (4)
N1—S1—C7—C12	−38.3 (5)	C31X—C32X—C33X—C34X	−8 (7)
C1—S1—C7—C12	69.8 (5)	C32X—C33X—C34X—C35X	2 (9)
C12—C7—C8—C9	−1.6 (9)	C33X—C34X—C35X—C36X	3 (9)
S1—C7—C8—C9	−176.0 (5)	C32X—C31X—C36X—C35X	−6 (7)
C7—C8—C9—C10	−0.4 (9)	S2X—C31X—C36X—C35X	−175 (4)
C8—C9—C10—C11	1.0 (10)	C34X—C35X—C36X—C31X	−1 (8)
C9—C10—C11—C12	0.2 (9)	N2X—S2X—C37X—C42X	166 (4)
C10—C11—C12—C7	−2.1 (9)	C31X—S2X—C37X—C42X	−85 (4)
C8—C7—C12—C11	2.9 (9)	N2X—S2X—C37X—C38X	−22 (4)
S1—C7—C12—C11	177.0 (4)	C31X—S2X—C37X—C38X	87 (4)
N1—P1—C13—C14	−131.0 (4)	C42X—C37X—C38X—C39X	−9 (6)
C19—P1—C13—C14	113.1 (5)	S2X—C37X—C38X—C39X	180 (4)
C25—P1—C13—C14	−7.1 (5)	C37X—C38X—C39X—C40X	8 (7)
N1—P1—C13—C18	41.0 (5)	C38X—C39X—C40X—C41X	−9 (7)
C19—P1—C13—C18	−74.8 (5)	C39X—C40X—C41X—C42X	10 (7)
C25—P1—C13—C18	164.9 (4)	C38X—C37X—C42X—C41X	9 (6)
C18—C13—C14—C15	−1.4 (8)	S2X—C37X—C42X—C41X	−179 (4)
P1—C13—C14—C15	170.6 (5)	C40X—C41X—C42X—C37X	−10 (6)
C13—C14—C15—C16	−0.5 (9)	N2—P2—C43—C48	156.0 (5)
C14—C15—C16—C17	1.9 (10)	N2X—P2—C43—C48	134.5 (18)
C15—C16—C17—C18	−1.3 (10)	C55—P2—C43—C48	−81.4 (5)
C16—C17—C18—C13	−0.7 (9)	C49—P2—C43—C48	33.0 (5)
C14—C13—C18—C17	2.0 (8)	N2—P2—C43—C44	−21.9 (5)
P1—C13—C18—C17	−170.5 (5)	N2X—P2—C43—C44	−43.4 (19)
N1—P1—C19—C24	−165.3 (4)	C55—P2—C43—C44	100.7 (5)
C25—P1—C19—C24	73.7 (5)	C49—P2—C43—C44	−144.9 (4)
C13—P1—C19—C24	−44.9 (5)	C48—C43—C44—C45	−0.1 (8)
N1—P1—C19—C20	13.6 (5)	P2—C43—C44—C45	177.8 (4)
C25—P1—C19—C20	−107.4 (5)	C43—C44—C45—C46	1.1 (9)
C13—P1—C19—C20	134.0 (4)	C44—C45—C46—C47	−1.1 (9)
C24—C19—C20—C21	0.5 (8)	C45—C46—C47—C48	0.1 (10)
P1—C19—C20—C21	−178.5 (4)	C46—C47—C48—C43	0.9 (10)
C19—C20—C21—C22	−0.5 (9)	C44—C43—C48—C47	−0.9 (9)
C20—C21—C22—C23	1.2 (9)	P2—C43—C48—C47	−178.8 (5)
C21—C22—C23—C24	−1.8 (10)	N2—P2—C49—C54	−35.8 (5)
C22—C23—C24—C19	1.8 (10)	N2X—P2—C49—C54	−47.2 (14)
C20—C19—C24—C23	−1.1 (8)	C55—P2—C49—C54	−163.0 (4)
P1—C19—C24—C23	177.8 (5)	C43—P2—C49—C54	79.2 (5)
N1—P1—C25—C30	−112.1 (4)	N2—P2—C49—C50	142.9 (5)
C19—P1—C25—C30	3.5 (5)	N2X—P2—C49—C50	131.5 (14)
C13—P1—C25—C30	124.7 (4)	C55—P2—C49—C50	15.6 (5)
N1—P1—C25—C26	63.9 (5)	C43—P2—C49—C50	−102.1 (5)
C19—P1—C25—C26	179.6 (4)	C54—C49—C50—C51	0.2 (9)
C13—P1—C25—C26	−59.3 (5)	P2—C49—C50—C51	−178.4 (5)
C30—C25—C26—C27	0.6 (8)	C49—C50—C51—C52	0.6 (10)
P1—C25—C26—C27	−175.6 (4)	C50—C51—C52—C53	−0.2 (11)
C25—C26—C27—C28	−1.7 (8)	C51—C52—C53—C54	−1.1 (11)
C26—C27—C28—C29	1.7 (8)	C52—C53—C54—C49	1.9 (10)
C27—C28—C29—C30	−0.5 (8)	C50—C49—C54—C53	−1.5 (9)
C26—C25—C30—C29	0.6 (8)	P2—C49—C54—C53	177.2 (5)
P1—C25—C30—C29	176.7 (4)	N2—P2—C55—C56	118.7 (4)
C28—C29—C30—C25	−0.6 (8)	N2X—P2—C55—C56	152.1 (17)
C31—S2—N2—P2	−114.2 (4)	C49—P2—C55—C56	−114.1 (5)
C37—S2—N2—P2	139.1 (3)	C43—P2—C55—C56	4.5 (5)
N2X—P2—N2—S2	−22 (3)	N2—P2—C55—C60	−66.5 (5)
C55—P2—N2—S2	76.2 (4)	N2X—P2—C55—C60	−33.1 (17)
C49—P2—N2—S2	−45.2 (4)	C49—P2—C55—C60	60.7 (4)
C43—P2—N2—S2	−165.2 (3)	C43—P2—C55—C60	179.3 (4)
N2—S2—C31—C32	−36.9 (6)	C60—C55—C56—C57	−0.2 (8)
C37—S2—C31—C32	69.4 (5)	P2—C55—C56—C57	174.6 (4)
N2—S2—C31—C36	144.2 (4)	C55—C56—C57—C58	−0.9 (8)
C37—S2—C31—C36	−109.5 (5)	C56—C57—C58—C59	1.0 (8)
C36—C31—C32—C33	1.0 (9)	C57—C58—C59—C60	0.0 (8)
S2—C31—C32—C33	−177.8 (5)	C58—C59—C60—C55	−1.1 (8)
C31—C32—C33—C34	0.3 (10)	C56—C55—C60—C59	1.2 (8)
C32—C33—C34—C35	−1.0 (12)	P2—C55—C60—C59	−173.8 (4)
C33—C34—C35—C36	0.5 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···Br6ⁱ	0.95	3.13	3.909 (6)	140
C17—H17···Br2ⁱⁱ	0.95	2.97	3.900 (7)	167
C27—H27···Br3ⁱⁱⁱ	0.95	2.93	3.858 (6)	167
C39—H39···Br6^iv	0.95	2.92	3.827 (8)	161
C59—H59···Br4^v	0.95	2.93	3.830 (6)	158

Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, z−1/2; (iii) x−1/2, y+1/2, z; (iv) x−1, −y+1, z+1/2; (v) x−1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	(C₃₀H₂₅NPS)₂[Pd₂Br₆]
M_r	1617.34
Crystal system, space group	Monoclinic, Cc
Temperature (K)	150
a, b, c (Å)	12.8250 (13), 16.2000 (16), 28.721 (3)
β (°)	97.318 (2)
V (Å³)	5918.7 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.82
Crystal size (mm)	0.59 × 0.40 × 0.37

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.104, 0.168
No. of measured, independent and observed [I > 2σ(I)] reflections	24282, 12979, 11006
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.082, 1.01
No. of reflections	12639
No. of parameters	732
No. of restraints	519
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.29, −0.90
Absolute structure	Flack (1983), 5943 Friedel pairs
Absolute structure parameter	0.065 (6)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2000), SHELXTL and local programs.

Selected geometric parameters (Å, º) top

Pd1—Br1	2.4102 (7)	P1—C19	1.786 (5)
Pd1—Br2	2.4086 (7)	P1—C25	1.787 (5)
Pd1—Br3	2.4550 (7)	P2—N2	1.622 (5)
Pd1—Br4	2.4437 (7)	P2—N2X	1.63 (3)
Pd2—Br3	2.4505 (7)	P2—C43	1.803 (5)
Pd2—Br4	2.4455 (7)	P2—C49	1.797 (6)
Pd2—Br5	2.4180 (7)	P2—C55	1.785 (5)
Pd2—Br6	2.4109 (7)	S2—N2	1.615 (5)
S1—N1	1.616 (4)	S2—C31	1.789 (5)
S1—C1	1.778 (4)	S2—C37	1.795 (5)
S1—C7	1.796 (5)	S2X—N2X	1.62 (4)
P1—N1	1.609 (4)	S2X—C37X	1.78 (3)
P1—C13	1.808 (6)	S2X—C31X	1.89 (3)

P1—N1—S1	118.1 (3)	P2—N2X—S2X	117 (2)
P2—N2—S2	119.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···Br6ⁱ	0.95	3.13	3.909 (6)	140
C17—H17···Br2ⁱⁱ	0.95	2.97	3.900 (7)	167
C27—H27···Br3ⁱⁱⁱ	0.95	2.93	3.858 (6)	167
C39—H39···Br6^iv	0.95	2.92	3.827 (8)	161
C59—H59···Br4^v	0.95	2.93	3.830 (6)	158

Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, z−1/2; (iii) x−1/2, y+1/2, z; (iv) x−1, −y+1, z+1/2; (v) x−1/2, y−1/2, z.

Selected bond lengths and angle (Å, °) taken from [Ph₂SNPPh₃][SbCl₆]·CH₂Cl₂ (Reck et al., 1982). top

S—N	1.596
P—N	1.608
S—C	1.755, 1.761
P—C	1.779, 1.788, 1.797
P—N—S	123.6

Acknowledgements

The authors acknowledge the EPSRC for postdoctoral support (LMG) and Johnson Matthey for loans of precious metals.

References

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