Twisted [(R3P)PdX] groups above dicarbaborane ligands: 4-dimethyl­sulfido-3-iodo-3-triphenyl­phosphine-closo-3-pallada-1,2-dicarbadodeca­borane and 3-dimethyl­phenyl­phos­phine-3-chloro-4-dimethyl­sulfido-closo-3-pallada-1,2-dicarbadodeca­borane

Ferguson, G.; Gallagher, J.F.; Kennedy, J.D.; O'Connell, D.P.; Patterson, J.C.; Spalding, T.R.

doi:10.1107/S0108270105022286

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 8| August 2005| Pages m393-m396

doi:10.1107/S0108270105022286

Twisted [(R₃P)PdX] groups above dicarbaborane ligands: 4-dimethylsulfido-3-iodo-3-triphenylphosphine-closo-3-pallada-1,2-dicarbadodecaborane and 3-dimethylphenylphosphine-3-chloro-4-dimethylsulfido-closo-3-pallada-1,2-dicarbadodecaborane

George Ferguson,^a John F. Gallagher,^b John D. Kennedy,^c Donnacha P. O'Connell,^d Jennifer C. Patterson ^e and Trevor R. Spalding ^d ^*

^aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, ^bSchool of Chemical Sciences, Dublin City University, Dublin 9, Ireland, ^cDepartment of Chemistry, University of Leeds, Leeds LS2 9JT, England, ^dDepartment of Chemistry, University College Cork, National University of Ireland, Cork, Ireland, and ^eIntel Ireland Ltd, Leixlip, Co. Kildare, Ireland
^*Correspondence e-mail: t.spalding@ucc.ie

(Received 7 July 2005; accepted 11 July 2005; online 23 July 2005)

The structural analyses of [3-(PPh₃)-3-I-4-(SMe₂)-closo-3,1,2-PdC₂B₉H₁₀] or [Pd(C₄H₁₆B₉S)I(C₁₈H₁₅P)], (I), and [3-(PPhMe₂)-3-Cl-4-(SMe₂)-closo-3,1,2-PdC₂B₉H₁₀] or [Pd(C₄H₁₆B₉S)Cl(C₈H₁₁P)], (II), show that in comparison with [3-(PR₃)₂-closo-3,1,2-PdC₂B₉H₁₁] the presence of the 4-SMe₂ group causes the [PdX(PR₃)] unit (X = halogen) to twist about an axis passing through the Pd atom and the directly opposite B atom of the carbaborane ligand. The halogen atoms are located almost directly above a C atom in the C₂B₃ face, and the conformations of the [PdX(PR₃)] units above the C₂B₃ faces are not those predicted from molecular orbital calculations of the closo-3,1,2-PdC₂B₉ system. The fact that the variation from the predicted conformation is greater in the case of (I) than in (II) may be ascribed to the greater steric interactions induced by the I atom in (I) compared with the Cl atom in (II).

Comment

The factors affecting the conformation of L—M—X units (L and X may be phosphines or other ligands) above the faces of 11-atom heteroborane ligands in metalloheteroborane clusters, such as [3,3-(PR₃)₂-closo-3,1,2-MC₂B₉H₁₁], (III) (M = Pd or Pt), have been subject to both experimental (O′Connell et al., 1995 , 1996 ) and theoretical (Mingos et al., 1978 ) studies. We have now continued these studies to obtain information about the effect that a substituent on a B atom in the C₂B₃ face adjacent to the Pd atom would have on the structure of the metalloheteroborane. We synthesized two palladium complexes with the [9-SMe₂-nido-7,8-C₂B₉H₁₀] dicarbaborane fragment as a ligand, namely [3-(PPh₃)-3-I-4-(SMe₂)-closo-3,1,2-PdC₂B₉H₁₀], (I), and [3-(PPhMe₂)-3-Cl-4-(SMe₂)-closo-3,1,2-PdC₂B₉H₁₀], (II), which are isoelectronic in cluster terms (Wade, 1976 ) with [3-(PR₃)₂-closo-3,1,2-PdC₂B₉H₁₁], (III). In complex (III), which is a [closo-3,1,2-MC₂B₉H₁₁] species that contains `C atoms adjacent' [nido-7,8-C₂B₉H₁₁] ligand fragments and no replacements of boron-bound exo H atoms by bulkier groups, the conformation of the P—Pd—P plane is aligned approximately parallel to the C—C vector in the C₂B₃ face to which the Pd atom is attached, as shown in the scheme (diagram 1a). This alignment is expected on the basis of the

results of molecular orbital calculations (Mingos et al., 1978

). The alternative `perpendicular' conformation is expected for [closo-2,1,7-MC₂B₉H₁₁] species that have `C atoms apart' [nido-7,9-C₂B₉H₁₁] fragments as ligands (see diagram 1b

) (Mingos et al., 1978

Compounds (I) and (II) have closo 12-vertex PdC₂B₉ geometries based on distorted icosahedra with the Pd and C atoms adjacent, as shown in Figs. 1 and 2. Selected interatomic distances and angles are given in Table 1. In both (I) and (II), the substitution of a BSMe₂ group for a BH(exo) unit causes marked twisting of the [PdX(PR₃)] group (X = I or Cl) above the C₂B₃ face (see diagram 1c). The orientations of the [PdI(PPh₃)] and [PdCl(PPhMe₂)] units above the C₂B₃ faces are clearly shown in Figs. 3 and 4. The conformations of the Pd—X and Pd—P vectors above the C₂B₃ faces have become more like the `perpendicular' conformation that is expected for [closo-2,1,7-MC₂B₉H₁₁] species. It is noticeable that the twisting of the X—Pd—PR₃ unit away from the SMe₂ ligand is somewhat greater in (I) than in (II), as can be seen in the angles between the X—Pd and B4—S1 vectors when they are projected onto the plane of the C₂B₃ face; these are 71.7 (2)° in (I) and 53.7 (2)° in (II). This difference is also seen in the comparison between the S1—B4—Pd3—X twist angle, which is larger in (I), at −48.5 (3)°, with a smaller corresponding angle in (II) of −29.16 (9)°. All these values would be expected to be close to zero in the absence of substitution at B4. The difference in these pairs of angles is probably due to the steric interactions in the X—Pd3—C1—B4—S1(Me₂) region and, in particular, the difference in the effective radii of I and Cl, although the differential bulk of the PPh₃ versus the PPhMe₂ ligands will also affect the conformations, as will the locations of the methyl groups of the SMe₂ ligand attached at atom B4.

The Pd—C distances of 2.274 (6) and 2.467 (6) Å in (I) are significantly different, with the Pd—C1 bond considerably shorter than the Pd—C2 bond. Atom C1 is adjacent to the SMe₂-substituted B4 atom, and the shorter Pd—C distance may be an artefact of this configuration if extra electron density due to the presence of the S atom is available in the Pd—B4—C1 region compared with the Pd—B7—C2 region. The Pd—C distances in (II), at 2.304 (2) and 2.478 (2) Å, are similar to those in (I). The Pd—C distances in (I) and (II) span those observed in the cation of [3-(η²,η²-C₈H₁₂)-4-SMe₂-closo-3,1,2-PdC₂B₉H₁₀]BF₄ [2.371 (4) and 2.434 (4) Å; Douek & Welch, 1993 ]. A search of the May 2005 release of the Cambridge Structural Database (CSD; Allen, 2002 ) for palladacarbaboranes resulted in 11 unique hits that yielded Pd—C distances in a wide range from 2.187 (5) Å in the 13-vertex bis(diphenylphosphino)ethane derivative [4-(dppe)-closo-4,1,6-PdC₂B₁₀H₁₂] (Alcock et al., 1987 ; CSD refcode FODFOT) to 2.634 (7) Å in [1-(5-MeC₄H₂S)-3,3-(PMe₂Ph)₂-closo-3,1,2-PdC₂B₉H₁₀] (Michaelidou et al., 1997 ; CSD refcode RUSWIL). It is noteworthy that, in the latter compound, which has a 5-methylthiophenyl substituent on atom C1, the conformation of the plane containing the P—Pd—P unit and the C—C vector is near to the `parallel' type; the angle between the C—C vector and the plane containing the P—Pd—P unit projected onto the B₃C₂ plane is 26° rather than 0°.

The SMe₂ group has slightly different orientations in (I) and (II), quantified by the values of the Pd3—B4—S1—C3 torsion angles [−85.0 (4)° in (I) and −54.19 (13)° in (II)]. Presumably, this difference arises from packing effects. Examination of the intermolecular distances shows that there are no π–π or C—H⋯π interactions in the crystal structures of (I) and (II). In (I), there is a weak intramolecular C16—H16⋯I1 interaction (see Table 2). In (II), there are no significant intramolecular interactions; the inversion-related shortest intermolecular interactions are shown in Fig. 5 with pairs of C—H⋯Cl interactions leading to a weakly linked dimer (see Table 2). Such attractive interactions are consistent with the well known greater polarity and H-atom acidic character of carbaborane cluster CH(exo) units.

Figure 1
A view of (I)

, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
A view of (II)

, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3
A view of the P—Pd—I unit above the C₂B₃ face with the SMe₂ ligand at B4 in (I)

Figure 4
A view of the P—Pd—Cl unit above the C₂B₃ face with the SMe₂ ligand at B4 in (II)

Figure 5
A view of a pair of molecules of (II)

, linked by weak C—H⋯Cl interactions. [Symmetry code: (i) 1 − x, 1 − y, −z.]

Experimental

Reactions were carried out under an inert atmosphere, and products were isolated and manipulated in air. The reagents Tl[9-SMe₂-7,8-nido-C₂B₉H₁₀] (Hamilton & Welch, 1991 ), [Pd(PPhMe₂)₂Cl₂] (Jenkins & Shaw, 1966 ) and [Pd(PPh₃)₂I₂] (Bailey & Mason, 1968 ) were prepared according to literature methods. For the synthesis of (I), a solution of [Pd(PPh₃)₂I₂] (0.044 g, 0.05 mmol) in CH₂Cl₂ (10 ml) was added to a solution of Tl[9-SMe₂-7,8-nido-C₂B₉H₁₀] (0.02 g, 0.05 mmol) in CH₂Cl₂ (10 ml). The mixture was heated at reflux temperature for 2.5 h. The dark-green solution was concentrated under reduced pressure (rotatory film evaporator, 298 K) and subjected to preparative thin-layer chromatography (TLC; CH₂Cl₂–hexane, 3:2). The major band was extracted into CH₂Cl₂ and recrystallized from CH₂Cl₂–hexane (3:2) as dark-green block-shaped crystals of (I) (0.028 g, 81.3%). Analysis found: C 38.4, H 5.0, I 18.1%; C₂₂H₃₁B₉IPPdS requires: C 38.35, H 4.5, I 18.4%. For the synthesis of (II), a solution of [Pd(PPhMe₂)₂Cl₂] (0.1365 g, 0.301 mmol) in toluene (20 ml) was added to a solution of Tl[9-SMe₂-7,8-nido-C₂B₉H₁₀] (0.121 g, 0.304 mmol) in toluene (30 ml). The mixture was stirred at room temperature for 20 h. The purple solution was concentrated under reduced pressure (rotatory film evaporator, 308 K) and subjected to preparative TLC (CH₂Cl₂–hexane, 4:1). The major band was extracted into CH₂Cl₂ and recrystallized from CH₂Cl₂–hexane (1:1), affording purple crystals of (II) (0.143 g, 75.9%). Analysis found: C 30.7, H 5.9, S 6.85%; C₁₂H₂₇B₉ClPPdS requires: C 30.4, H 5.8, S 6.8%. For details of the IR and NMR spectra for (I) and (II), see the archived CIF.

Compound (I)

Crystal data

[Pd(C₄H₁₆B₉S)I(C₁₈H₁₅P)]
M_r = 689.12
Orthorhombic, P b c a
a = 10.9576 (5) Å
b = 16.8316 (10) Å
c = 30.2015 (17) Å
V = 5570.2 (5) Å³
Z = 8
D_x = 1.643 Mg m⁻³
Mo Kα radiation
Cell parameters from 25 reflections
θ = 9.9–16.0°
μ = 1.92 mm⁻¹
T = 294 (1) K
Block, dark green
0.20 × 0.15 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
θ/2θ scans
Absorption correction: ψ scan(ABSCOR in NRCVAX; Gabe et al., 1989 )T_min = 0.708, T_max = 0.751
6057 measured reflections
6057 independent reflections
3546 reflections with I > 2σ(I)
R_int = 0.0
θ_max = 27.0°
h = 0 → 13
k = 0 → 21
l = 0 → 38
3 standard reflections every 250 reflections intensity decay: none

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.162
S = 1.00
6057 reflections
318 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.1025P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 1.29 e Å⁻³
Δρ_min = −1.93 e Å⁻³

Compound (II)

Crystal data

[Pd(C₄H₁₆B₉S)Cl(C₈H₁₁P)]
M_r = 473.54
Monoclinic, P 2₁ /n
a = 12.8117 (8) Å
b = 9.2670 (7) Å
c = 18.2948 (10) Å
β = 96.567 (5)°
V = 2157.8 (2) Å³
Z = 4
D_x = 1.458 Mg m⁻³
Mo Kα radiation
Cell parameters from 25 reflections
θ = 10.0–16.5°
μ = 1.15 mm⁻¹
T = 294 (1) K
Block, purple
0.33 × 0.25 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
θ/2θ scans
Absorption correction: ψ scan(ABSCOR in NRCVAX; Gabe et al., 1989)T_min = 0.684, T_max = 0.760
6506 measured reflections
6265 independent reflections
5023 reflections with I > 2σ(I)
R_int = 0.020
θ_max = 30.0°
h = 0 → 18
k = 0 → 13
l = −25 → 25
3 standard reflections every 250 reflections intensity decay: none

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.064
S = 1.03
6265 reflections
231 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0335P)² + 0.6303P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.51 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.00185 (18)

Table 1
Selected bond distances (Å) and angles (°) for compounds (I) and (II)

X = I1 in (I) and Cl1 in (II).

	(I)	(II)
Pd3—X	2.6739 (7)	2.3751 (5)
Pd3—P1	2.2507 (17)	2.2275 (5)
Pd3—C1	2.274 (6)	2.304 (2)
Pd3—C2	2.467 (6)	2.478 (2)
Pd3—B4	2.315 (7)	2.278 (2)
Pd3—B7	2.269 (8)	2.212 (2)
Pd3—B8	2.254 (7)	2.229 (2)
S1—B4	1.899 (7)	1.896 (2)
C1—C2	1.584 (9)	1.561 (2)
C1—B4	1.693 (8)	1.697 (3)
C2—B7	1.644 (10)	1.686 (3)
B4—B8	1.766 (10)	1.764 (3)

X—Pd3—P1	95.06 (5)	92.00 (2)
X—Pd3—C1	90.64 (16)	97.52 (5)
X—Pd3—C2	106.07 (16)	116.77 (5)
X—Pd3—B4	110.47 (16)	108.25 (5)
X—Pd3—B7	143.2 (2)	148.67 (6)
X—Pd3—B8	155.09 (19)	148.67 (6)
P1—Pd3—C1	169.28 (16)	163.51 (5)
P1—Pd3—C2	130.57 (16)	125.64 (4)
P1—Pd3—B4	140.80 (16)	144.32 (5)
P1—Pd3—B7	100.3 (2)	95.72 (6)
P1—Pd3—B8	102.97 (19)	103.23 (6)
Pd3—B4—S1	104.2 (3)	106.64 (9)

Table 2
Hydrogen bond parameters (Å, °) for compounds (I) and (II)

	D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
(I)	C16—H16⋯I1	0.86	2.98	3.831 (9)	153
(II)	C2—H2⋯Cl1ⁱ	0.86	2.60	3.540 (2)	142
Symmetry code: (i) 1-x, 1-y, -z.

Molecule (I) crystallized in the orthorhombic system; space group Pbca was assigned from the systematic absences. Molecule (II) crystallized in the monoclinic system; space group P2₁/n was assigned from the systematic absences. In both compounds, H atoms were treated as riding atoms, with C—H distances of 0.93, 0.96 and 1.10 Å, and B—H distances of 1.10 Å, and with U_iso(H) values set at 1.2U_eq(C,B) or 1.5U_eq(methyl C). The maxima and minima in the final difference maps for (I) were adjacent to the I atom.

For both compounds, data collection: DIFRAC (Gabe & White, 1993 ) with profile analysis; cell refinement: DIFRAC; data reduction: DATRD2 in NRCVAX94 (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) in WinGX (Version 1.70.01; Farrugia, 1999 ); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S0108270105022286/sk1861sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105022286/sk1861Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270105022286/sk1861IIsup3.hkl

Comment top

The factors affecting the conformation of (L—M—X) units (L and X may be phosphines or other ligands) above the faces of 11-atom heteroborane ligands in metallaheteroborane clusters such as [3,3-(PR₃)₂-closo-3,1,2-MC₂B₉H₁₁], (III) (M = Pd or Pt), have been subject to both experimental (O'Connell et al., 1995, 1996) and theoretical (Mingos et al., 1978) studies. We have now continued these studies to obtain information about the effect that a substituent on a B atom in the C₂B₃ face adjacent to the Pd atom would have on the structure of the metallaheteroborane. We synthesized two palladium complexes with the [9-SMe₂-nido-7,8-C₂B₉H₁₀] dicarbaborane fragment as a ligand, namely [3-(PPh₃)-3-I-4-(SMe₂)-closo-3,1,2-PdC₂B₉H₁₀], (I), and [3-(PPhMe₂)-3-Cl-4-(SMe₂)-closo-3,1,2-PdC₂B₉H₁₀], (II), which are isoelectronic in cluster terms (Wade, 1996) with [3-(PR₃)₂-closo-3,1,2-PdC₂B₉H₁₁], (III). In complex (III), which is a [closo-3,1,2-MC₂B₉H₁₁] species that contains `C atoms c-adjacent' [nido-7,8-C₂B₉H₁₁] ligand fragments and no replacements of boron-bound exo H atoms by bulkier groups, the conformation of the P—Pd—P plane is aligned approximately parallel to the C—C vector in the C₂B₃ face to which the Pd atom is attached, as shown in the first scheme below (1a). This alignment is expected on the basis of the results of molecular orbital calculations (Mingos et al., 1978). The alternative `perpendicular' conformation is expected for [closo-2,1,7-MC₂B₉H₁₁] species that have `C atoms c-apart' [nido-7,9-C₂B₉H₁₁] fragments as ligands (see diagram 1b) (Mingos et al., 1978).

Compounds (I) and (II) have closo 12-vertex PdC₂B₉ geometries based on distorted icosahedra with the Pd and C atoms adjacent, as shown in Figs. 1 and 2. Selected interatomic distances and angles are given in Table 1. In both [3-PPh₃-3-I-4-SMe₂-closo-3,1,2-PdC₂B₉H₁₀], (I), and [3-PPhMe₂-3-Cl-4-SMe₂-closo-3,1,2-PdC₂B₉H₁₀], (II) the substitution of a B-SMe₂ group for a BH(exo) unit causes marked twisting of the {PdX(PR₃)} [X = I or Cl] above the C₂B₃-face (see diagram 1c). The orientations of the {PdI(PPh₃)} and {PdCl(PPhMe₂)} units above the C₂B₃ faces are clearly shown in Figs. 3 and 4. The conformations of the Pd—X and Pd—P vectors above the C₂B₃ faces have become more like the `perpendicular' conformation that is expected for [closo-2,1,7-MC₂B₉H₁₁] species. It is noticeable that the twisting of the {X—Pd—PR₃} unit away from the SMe₂ ligand is somewhat greater in (I) than in (II), as can be seen in the angles made between the X—Pd and B4—S1 vectors when they are projected onto the plane of the C₂B₃ face; these are 71.7 (2)° in (I) and 53.7 (2)° in (II). This difference is also seen in the comparison between the S1—B4—Pd3—X twist angle in (I), which is larger at −48.5 (3)° with the smaller corresponding angle in (II) of −29.16 (9)°. All these values would be expected to be close to zero in the absence of substitution at B4. The difference in these pairs of angles is most probably due to the steric interactions in the X—Pd3—C1—B4—S1(Me₂) region and in particular the difference in the effective radii of I and Cl, although the differential bulk of the PPh₃ versus the PPhMe₂ ligands will also affect the conformations, as will the locations of the methyl groups of the SMe₂ ligand attached at atom B4.

The Pd—C distances of 2.274 (6) and 2.467 (6) Å in (I) are significantly different, with Pd—C1 considerably shorter than Pd—C2. Atom C1 is adjacent to the (SMe₂)-substituted B4 atom, and the shorter Pd—C distance may be an artefact of this configuration if extra electron density due to the presence of the S atom is available in the Pd—B4—C1 region compared with the Pd—B7—C2 region. The Pd—C distances in (II), at 2.304 (2) and 2.478 (2) Å, are similar to those in (I). The Pd—C distances in (I) and (II) span those observed in the cation of [3-(η²,η²-C₈H₁₂)-4-SMe₂-closo-3,1,2-PdC₂B₉H₁₀][BF₄] [2.371 (4) and 2.434 (4) Å; Douek & Welch, 1993]. A search of the May 2005 release of the Cambridge Structural Database (CSD; Allen, 2002) for palladacarbaboranes resulted in 11 unique hits that yielded Pd—C distances in a wide range from 2.187 (5) Å, in the 13-vertex bis(diphenylphosphino)ethane derivative [4-(dppe)-closo-4,1,6- PdC₂B₁₀H₁₂] (Alcock et al., 1987; CSD refcode FODFOT), to 2.634 (7) Å, in [1-(5-MeC₄H₂S)-3,3-(PMe₂Ph)₂-closo-3,1,2-PdC₂B₉H₁₀] (Michaelidou et al., 1997; CSD refcode RUSWIL). It is noteworthy that, in the latter compound, which has a 5-methylthiophenyl substituent on atom C1, the conformation of the plane containing the P—Pd—P unit and the C—C vector is near to the `parallel' type; the angle between the C—C vector and the plane containing the P—Pd—P unit projected onto the B₃C₂ plane is 26° rather than 0°.

The SMe₂ group has slightly different orientations in (I) and in (II), quantified by the values of the Pd3—B4—S1—C3 torsion angles [−85.0 (4)° in (I) and −54.19 (13)° in (II)]. Presumably, this difference arises from packing effects. Examination of the intermolecular distances shows that there are no π–π or C—H···π interactions in the crystal structures of (I) and (II). In (I), there is a weak intramolecular C16—H16···I1 interaction (see Table 2). In (II), there are no significant intramolecular interactions; the inversion-related shortest intermolecular interactions are shown in Fig. 5 with pairs of C—H···Cl interactions leading to a weakly linked dimer (see Table 2). Such attractive interactions are consistent with the well known greater polarity and H-atom acidic character of carbaborane cluster CH(exo) units.

Experimental top

Reactions were carried out under an inert atmosphere and products were isolated and manipulated in air. The reagents Tl[9-SMe₂-7,8-nido-C₂B₉H₁₀] (Hamilton & Welch, 1991), [Pd(PPhMe₂)₂Cl₂] (Jenkins & Shaw, 1966) and [Pd(PPh₃)₂I₂] (Bailey & Mason, 1968) were prepared according to literature methods. For the synthesis of (I), to a solution of Tl[9-SMe₂-7,8-nido-C₂B₉H₁₀] (0.02 g, 0.05 mmol) in CH₂Cl₂ (10 ml) was added a solution of [Pd(PPh₃)₂I₂] (0.044 g, 0.05 mmol) in CH₂Cl₂ (10 ml). The mixture was heated at the reflux temperature for 2.5 h. The dark-green solution was concentrated under reduced pressure (rotatory film evaporator, 298 K) and subjected to preparative thin-layer chromatography (CH₂Cl₂–hexane, 3:2). The major band was extracted into CH₂Cl₂ and recrystallized from CH₂Cl₂–hexane (3:2) as dark-green block-shaped crystals of (I) (0.028 g, 81.3%). Analysis found: C 38.4, H 5.0, I 18.1%; C₂₂H₃₁B₉IPPdS requires: C 38.35, H 4.5, I 18.4%. For details of IR and NMR spectra for (I), see the archived CIF. For the synthesis of (II), to a solution of Tl[9-SMe₂-7,8-nido-C₂B₉H₁₀] (0.121 g, 0.304 mmol) in toluene (30 ml) was added a solution of [Pd(PPhMe₂)₂Cl₂] (0.1365 g, 0.301 mmol) in toluene (20 ml). The mixture was stirred at room temperature for 20 h. The purple solution was concentrated under reduced pressure (rotatory film evaporator, 308 K) and subjected to preparative TLC (CH₂Cl₂–hexane, 4:1). The major band was extracted into CH₂Cl₂ and recrystallized from CH₂Cl₂–hexane (1:1), affording purple crystals of (II) (0.143 g, 75.9%). Analysis found: C 30.7, H 5.9, S 6.85%; C₁₂H₂₇ClB₉PPdS requires: C 30.4, H 5.8, S 6.8%. For details of IR and NMR spectra for (II), see the archived CIF.

Computing details top

For both compounds, data collection: DIFRAC (Gabe & White, 1993) with profile analysis; cell refinement: DIFRAC (Gabe & White, 1993); data reduction: DATRD2 in NRCVAX94 (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) in WinGX (Version 1.70.01; Farrugia, 1999); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of (II), with atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A view of the P—Pd—I unit above the C₂B₃ face with the SMe₂ ligand at B4 in (I).
	Fig. 4. A view of the P—Pd—Cl unit above the C₂B₃ face with the SMe₂ ligand at B4 in (II).
	Fig. 5. A view of a pair of molecules of (II), linked by weak C—H···Cl interactions. [Symmetry code: (i) 1 − x, 1 − y, −z.]

(I) 4-dimethylsulfido-3-iodo-3-triphenylphosphine-closo-3-pallada- 1,2-dicarbadodecaborane top

Crystal data top

[Pd(C₄H₁₆B₉S)I(C₁₈H₁₅P)]	F(000) = 2704
M_r = 689.12	D_x = 1.643 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 10.9576 (5) Å	θ = 9.9–16.0°
b = 16.8316 (10) Å	µ = 1.92 mm⁻¹
c = 30.2015 (17) Å	T = 294 K
V = 5570.2 (5) Å³	Block, dark green
Z = 8	0.20 × 0.15 × 0.15 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	3546 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	R_int = 0.0
Graphite monochromator	θ_max = 27.0°, θ_min = 2.3°
θ/2θ scans	h = 0→13
Absorption correction: ψ scan (ABSCOR in NRCVAX; Gabe et al., 1989)	k = 0→21
T_min = 0.708, T_max = 0.751	l = 0→38
6057 measured reflections	3 standard reflections every 250 reflections
6057 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1025P)²] where P = (F_o² + 2F_c²)/3
6057 reflections	(Δ/σ)_max = 0.001
318 parameters	Δρ_max = 1.29 e Å⁻³
0 restraints	Δρ_min = −1.93 e Å⁻³

Crystal data top

[Pd(C₄H₁₆B₉S)I(C₁₈H₁₅P)]	V = 5570.2 (5) Å³
M_r = 689.12	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.9576 (5) Å	µ = 1.92 mm⁻¹
b = 16.8316 (10) Å	T = 294 K
c = 30.2015 (17) Å	0.20 × 0.15 × 0.15 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	3546 reflections with I > 2σ(I)
Absorption correction: ψ scan (ABSCOR in NRCVAX; Gabe et al., 1989)	R_int = 0.0
T_min = 0.708, T_max = 0.751	3 standard reflections every 250 reflections
6057 measured reflections	intensity decay: none
6057 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.162	H-atom parameters constrained
S = 1.00	Δρ_max = 1.29 e Å⁻³
6057 reflections	Δρ_min = −1.93 e Å⁻³
318 parameters

Special details top

Experimental. Details of IR and NMR spectra for (I) are as follows:-

IR: ν_max(KBr disc) cm⁻¹ 2555(s) (BH), 2513(versus) (BH), 2499(versus,sh) (BH), 2480(s) (BH). ¹¹B and ¹H NMR data (CDCl₃ 294 K) ordered as δ(¹¹B) [δ(¹H) of directly attached proton]: +2.3 [+3.61], −2.8 [+2.65], −10.8 [+1.79], BH(4) ca −11.0 [SMe₂ +2.47, +2.91], −11.5 [+2.73], −14.8 [+1.20], −21.1 [+2.06], −21.1 [+1.03], −23.1 [+1.02]. Additional data, ¹³C (CDCl₃ 300 K) CH +3.07, +3.60 and ³¹P NMR δ+41.7 at 219 K.

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

	x	y	z	U_iso*/U_eq
I1	0.67262 (4)	0.13753 (3)	0.099786 (17)	0.04633 (17)
Pd3	0.42963 (4)	0.15203 (3)	0.098863 (17)	0.03107 (15)
S1	0.45758 (14)	0.21805 (9)	−0.00477 (6)	0.0329 (4)
P1	0.42053 (16)	0.22895 (10)	0.15973 (6)	0.0333 (4)
C1	0.4157 (6)	0.0587 (3)	0.0446 (2)	0.0317 (13)
C2	0.3485 (6)	0.0176 (4)	0.0850 (2)	0.0365 (15)
C3	0.3814 (7)	0.3096 (4)	0.0053 (3)	0.0452 (17)
C4	0.4252 (8)	0.2060 (4)	−0.0628 (2)	0.0499 (19)
C11	0.4356 (6)	0.1706 (4)	0.2107 (2)	0.0381 (15)
C12	0.3601 (9)	0.1814 (6)	0.2467 (3)	0.073 (3)
C13	0.3749 (11)	0.1359 (8)	0.2846 (4)	0.097 (4)
C14	0.4652 (11)	0.0819 (6)	0.2876 (3)	0.076 (3)
C15	0.5408 (11)	0.0711 (6)	0.2522 (3)	0.091 (4)
C16	0.5270 (10)	0.1144 (6)	0.2144 (3)	0.078 (3)
C21	0.5438 (6)	0.3024 (4)	0.1601 (2)	0.0347 (14)
C22	0.5621 (7)	0.3470 (4)	0.1222 (3)	0.0463 (18)
C23	0.6509 (8)	0.4044 (5)	0.1212 (3)	0.055 (2)
C24	0.7221 (8)	0.4185 (5)	0.1569 (3)	0.059 (2)
C25	0.7057 (9)	0.3744 (5)	0.1956 (3)	0.066 (3)
C26	0.6156 (8)	0.3164 (5)	0.1970 (2)	0.0503 (19)
C31	0.2850 (7)	0.2901 (4)	0.1695 (2)	0.0418 (16)
C32	0.1686 (7)	0.2570 (5)	0.1664 (3)	0.053 (2)
C33	0.0657 (8)	0.3030 (6)	0.1748 (3)	0.065 (2)
C34	0.0754 (8)	0.3810 (6)	0.1850 (3)	0.063 (2)
C35	0.1904 (8)	0.4141 (5)	0.1878 (3)	0.067 (3)
C36	0.2938 (8)	0.3702 (4)	0.1795 (3)	0.052 (2)
B4	0.3567 (6)	0.1462 (4)	0.0270 (2)	0.0253 (13)
B5	0.3181 (6)	0.0597 (4)	−0.0017 (3)	0.0359 (17)
B6	0.3143 (7)	−0.0223 (4)	0.0355 (3)	0.0405 (19)
B7	0.2531 (7)	0.0828 (5)	0.1061 (3)	0.0382 (17)
B8	0.2460 (7)	0.1715 (4)	0.0671 (2)	0.0331 (15)
B9	0.2051 (7)	0.1283 (4)	0.0143 (3)	0.0346 (17)
B10	0.1770 (7)	0.0262 (4)	0.0198 (3)	0.042 (2)
B11	0.2024 (8)	−0.0022 (5)	0.0751 (3)	0.044 (2)
B12	0.1376 (7)	0.0934 (5)	0.0644 (3)	0.0425 (19)
H1	0.5139	0.0471	0.0406	0.038*
H2	0.3949	−0.0254	0.1066	0.044*
H3A	0.4158	0.3503	−0.0132	0.068*
H3B	0.3911	0.3242	0.0358	0.068*
H3C	0.2962	0.3039	−0.0013	0.068*
H4A	0.3388	0.2095	−0.0676	0.075*
H4B	0.4541	0.1551	−0.0726	0.075*
H4C	0.4656	0.2471	−0.0793	0.075*
H12A	0.2987	0.2195	0.2455	0.087*
H13	0.3218	0.1429	0.3083	0.117*
H14	0.4758	0.0525	0.3134	0.092*
H15	0.6028	0.0336	0.2539	0.110*
H16	0.5798	0.1060	0.1908	0.093*
H22	0.5140	0.3381	0.0974	0.056*
H23	0.6624	0.4340	0.0955	0.067*
H24	0.7820	0.4576	0.1557	0.071*
H25	0.7546	0.3837	0.2202	0.080*
H26	0.6036	0.2871	0.2227	0.060*
H32	0.1597	0.2038	0.1587	0.064*
H33	−0.0112	0.2797	0.1733	0.078*
H34	0.0061	0.4117	0.1900	0.075*
H35	0.1982	0.4673	0.1955	0.080*
H36	0.3700	0.3945	0.1805	0.063*
H5	0.3460	0.0504	−0.0363	0.043*
H6	0.3386	−0.0827	0.0247	0.049*
H7	0.2347	0.0846	0.1419	0.046*
H8	0.2175	0.2324	0.0754	0.040*
H9	0.1544	0.1631	−0.0105	0.041*
H10	0.1079	−0.0033	−0.0008	0.051*
H11	0.1491	−0.0504	0.0902	0.053*
H12	0.0430	0.1074	0.0737	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0296 (2)	0.0626 (3)	0.0468 (3)	0.0010 (2)	−0.0013 (2)	−0.0074 (2)
Pd3	0.0265 (2)	0.0361 (3)	0.0307 (3)	0.00015 (19)	0.0011 (2)	−0.0016 (2)
S1	0.0296 (8)	0.0316 (7)	0.0376 (9)	0.0003 (6)	0.0013 (7)	0.0024 (7)
P1	0.0325 (9)	0.0364 (8)	0.0310 (9)	−0.0001 (7)	0.0024 (7)	−0.0012 (7)
C1	0.027 (3)	0.025 (3)	0.043 (4)	0.004 (2)	0.001 (3)	−0.001 (3)
C2	0.034 (3)	0.031 (3)	0.045 (4)	−0.002 (3)	0.002 (3)	0.008 (3)
C3	0.053 (5)	0.030 (3)	0.052 (4)	0.003 (3)	0.003 (4)	0.003 (3)
C4	0.067 (5)	0.051 (4)	0.032 (4)	−0.003 (4)	0.005 (4)	−0.001 (3)
C11	0.041 (4)	0.043 (4)	0.030 (3)	−0.010 (3)	0.002 (3)	0.001 (3)
C12	0.062 (6)	0.098 (7)	0.058 (6)	0.020 (5)	0.027 (5)	0.020 (6)
C13	0.087 (8)	0.143 (11)	0.062 (7)	0.015 (8)	0.033 (6)	0.044 (7)
C14	0.101 (8)	0.081 (7)	0.048 (6)	−0.028 (6)	−0.012 (6)	0.028 (5)
C15	0.127 (10)	0.090 (7)	0.057 (6)	0.045 (7)	0.007 (6)	0.030 (6)
C16	0.102 (8)	0.095 (7)	0.035 (5)	0.047 (6)	0.011 (5)	0.018 (5)
C21	0.032 (3)	0.033 (3)	0.038 (4)	0.003 (3)	0.004 (3)	−0.002 (3)
C22	0.051 (5)	0.050 (4)	0.037 (4)	−0.004 (4)	−0.007 (3)	0.004 (3)
C23	0.056 (5)	0.044 (4)	0.067 (6)	−0.007 (4)	0.020 (4)	0.013 (4)
C24	0.047 (5)	0.059 (5)	0.071 (6)	−0.022 (4)	0.005 (4)	−0.008 (4)
C25	0.067 (6)	0.088 (6)	0.044 (5)	−0.033 (5)	−0.018 (4)	0.008 (4)
C26	0.065 (5)	0.054 (4)	0.031 (4)	−0.013 (4)	−0.001 (4)	0.006 (3)
C31	0.042 (4)	0.052 (4)	0.031 (4)	0.006 (3)	0.007 (3)	0.000 (3)
C32	0.044 (4)	0.067 (5)	0.048 (5)	0.004 (4)	0.003 (4)	−0.014 (4)
C33	0.042 (5)	0.091 (7)	0.063 (6)	0.013 (5)	0.010 (4)	−0.007 (5)
C34	0.053 (5)	0.084 (6)	0.051 (5)	0.032 (5)	0.014 (4)	0.009 (5)
C35	0.060 (5)	0.055 (5)	0.085 (7)	0.018 (4)	0.016 (5)	0.008 (5)
C36	0.053 (5)	0.050 (4)	0.054 (5)	0.002 (4)	0.009 (4)	0.004 (4)
B4	0.023 (3)	0.022 (3)	0.030 (4)	0.001 (2)	0.005 (3)	0.002 (3)
B5	0.029 (4)	0.026 (3)	0.054 (5)	0.003 (3)	−0.006 (3)	−0.011 (3)
B6	0.037 (4)	0.025 (3)	0.059 (6)	−0.007 (3)	−0.004 (4)	−0.001 (3)
B7	0.036 (4)	0.040 (4)	0.039 (4)	0.000 (3)	0.000 (4)	0.002 (3)
B8	0.031 (4)	0.034 (4)	0.035 (4)	0.003 (3)	−0.001 (3)	−0.004 (3)
B9	0.023 (3)	0.029 (3)	0.051 (5)	0.002 (3)	−0.004 (3)	−0.004 (3)
B10	0.026 (4)	0.030 (4)	0.071 (6)	−0.002 (3)	−0.004 (4)	−0.003 (4)
B11	0.037 (4)	0.038 (4)	0.058 (6)	−0.009 (3)	0.004 (4)	0.005 (4)
B12	0.029 (4)	0.046 (4)	0.053 (5)	0.001 (3)	0.007 (4)	−0.006 (4)

Geometric parameters (Å, º) top

I1—Pd3	2.6739 (7)	C23—H23	0.93
Pd3—P1	2.2507 (17)	C24—C25	1.396 (12)
Pd3—B8	2.254 (7)	C24—H24	0.93
Pd3—B7	2.269 (8)	C25—C26	1.388 (11)
Pd3—C1	2.274 (6)	C25—H25	0.93
Pd3—B4	2.315 (7)	C26—H26	0.93
Pd3—C2	2.467 (6)	C31—C36	1.384 (10)
S1—C3	1.779 (7)	C31—C32	1.396 (10)
S1—C4	1.801 (7)	C32—C33	1.391 (11)
S1—B4	1.899 (7)	C32—H32	0.93
P1—C21	1.831 (7)	C33—C34	1.353 (13)
P1—C31	1.831 (7)	C33—H33	0.93
P1—C11	1.834 (7)	C34—C35	1.381 (13)
C1—C2	1.584 (9)	C34—H34	0.93
C1—B4	1.693 (8)	C35—C36	1.375 (11)
C1—B5	1.761 (10)	C35—H35	0.93
C1—B6	1.781 (9)	C36—H36	0.93
C1—H1	1.10	B4—B9	1.731 (10)
C2—B7	1.644 (10)	B4—B5	1.745 (9)
C2—B11	1.663 (10)	B4—B8	1.766 (10)
C2—B6	1.681 (10)	B5—B9	1.759 (10)
C2—H2	1.10	B5—B10	1.769 (11)
C3—H3A	0.96	B5—B6	1.781 (11)
C3—H3B	0.96	B5—H5	1.10
C3—H3C	0.96	B6—B11	1.745 (12)
C4—H4A	0.96	B6—B10	1.776 (10)
C4—H4B	0.96	B6—H6	1.10
C4—H4C	0.96	B7—B12	1.795 (12)
C11—C12	1.378 (10)	B7—B11	1.798 (11)
C11—C16	1.381 (11)	B7—B8	1.903 (11)
C12—C13	1.388 (13)	B7—H7	1.10
C12—H12A	0.93	B8—B12	1.774 (11)
C13—C14	1.346 (15)	B8—B9	1.809 (11)
C13—H13	0.93	B8—H8	1.10
C14—C15	1.366 (14)	B9—B10	1.754 (10)
C14—H14	0.93	B9—B12	1.783 (12)
C15—C16	1.361 (12)	B9—H9	1.10
C15—H15	0.93	B10—B11	1.757 (13)
C16—H16	0.93	B10—B12	1.809 (12)
C21—C22	1.383 (10)	B10—H10	1.10
C21—C26	1.385 (10)	B11—B12	1.787 (12)
C22—C23	1.371 (10)	B11—H11	1.10
C22—H22	0.93	B12—H12	1.10
C23—C24	1.352 (12)

P1—Pd3—B8	102.97 (19)	B5—B4—B8	112.0 (5)
P1—Pd3—B7	100.3 (2)	C1—B4—S1	119.3 (4)
B8—Pd3—B7	49.8 (3)	B9—B4—S1	123.8 (5)
P1—Pd3—C1	169.28 (16)	B5—B4—S1	114.9 (5)
B8—Pd3—C1	74.6 (2)	B8—B4—S1	126.3 (4)
B7—Pd3—C1	70.0 (3)	C1—B4—Pd3	67.1 (3)
P1—Pd3—B4	140.80 (16)	B9—B4—Pd3	123.2 (5)
B8—Pd3—B4	45.5 (2)	B5—B4—Pd3	125.8 (4)
B7—Pd3—B4	76.9 (3)	B8—B4—Pd3	65.4 (3)
C1—Pd3—B4	43.3 (2)	S1—B4—Pd3	104.2 (3)
P1—Pd3—C2	130.57 (16)	B4—B5—B9	59.2 (4)
B8—Pd3—C2	74.9 (2)	B4—B5—C1	57.7 (4)
B7—Pd3—C2	40.4 (2)	B9—B5—C1	102.5 (5)
C1—Pd3—C2	38.8 (2)	B4—B5—B10	107.2 (5)
B4—Pd3—C2	71.2 (2)	B9—B5—B10	59.6 (4)
P1—Pd3—I1	95.06 (5)	C1—B5—B10	103.7 (6)
B8—Pd3—I1	155.09 (19)	B4—B5—B6	109.8 (6)
B7—Pd3—I1	143.2 (2)	B9—B5—B6	108.7 (6)
C1—Pd3—I1	90.64 (16)	C1—B5—B6	60.4 (4)
B4—Pd3—I1	110.47 (16)	B10—B5—B6	60.1 (4)
C2—Pd3—I1	106.07 (16)	B4—B5—H5	121.5
C3—S1—C4	99.9 (4)	B9—B5—H5	123.3
C3—S1—B4	101.1 (3)	C1—B5—H5	125.7
C4—S1—B4	107.8 (3)	B10—B5—H5	123.1
C21—P1—C31	102.6 (3)	B6—B5—H5	119.7
C21—P1—C11	106.9 (3)	C2—B6—B11	58.0 (5)
C31—P1—C11	103.9 (3)	C2—B6—B10	104.0 (6)
C21—P1—Pd3	111.1 (2)	B11—B6—B10	59.9 (5)
C31—P1—Pd3	119.4 (2)	C2—B6—B5	104.2 (5)
C11—P1—Pd3	111.9 (2)	B11—B6—B5	107.3 (6)
C2—C1—B4	116.4 (5)	B10—B6—B5	59.7 (4)
C2—C1—B5	109.4 (5)	C2—B6—C1	54.4 (4)
B4—C1—B5	60.7 (4)	B11—B6—C1	100.6 (5)
C2—C1—B6	59.6 (4)	B10—B6—C1	102.6 (5)
B4—C1—B6	112.3 (5)	B5—B6—C1	59.3 (4)
B5—C1—B6	60.4 (4)	C2—B6—H6	125.3
C2—C1—Pd3	77.2 (3)	B11—B6—H6	123.5
B4—C1—Pd3	69.6 (3)	B10—B6—H6	123.4
B5—C1—Pd3	127.3 (4)	B5—B6—H6	121.6
B6—C1—Pd3	133.0 (4)	C1—B6—H6	127.1
C2—C1—H1	117.5	C2—B7—B12	104.0 (6)
B4—C1—H1	119.6	C2—B7—B11	57.6 (4)
B5—C1—H1	120.5	B12—B7—B11	59.7 (5)
B6—C1—H1	117.2	C2—B7—B8	108.1 (5)
Pd3—C1—H1	97.9	B12—B7—B8	57.2 (4)
C1—C2—B7	107.6 (5)	B11—B7—B8	106.8 (5)
C1—C2—B11	113.3 (6)	C2—B7—Pd3	76.3 (4)
B7—C2—B11	65.9 (5)	B12—B7—Pd3	118.9 (5)
C1—C2—B6	66.0 (4)	B11—B7—Pd3	128.5 (5)
B7—C2—B6	118.0 (6)	B8—B7—Pd3	64.7 (3)
B11—C2—B6	62.9 (5)	C2—B7—H7	121.1
C1—C2—Pd3	64.0 (3)	B12—B7—H7	123.9
B7—C2—Pd3	63.3 (3)	B11—B7—H7	118.5
B11—C2—Pd3	124.1 (4)	B8—B7—H7	125.4
B6—C2—Pd3	126.7 (4)	Pd3—B7—H7	103.7
C1—C2—H2	122.0	B4—B8—B12	104.4 (5)
B7—C2—H2	120.2	B4—B8—B9	57.9 (4)
B11—C2—H2	114.8	B12—B8—B9	59.7 (4)
B6—C2—H2	111.6	B4—B8—B7	101.9 (5)
Pd3—C2—H2	109.7	B12—B8—B7	58.3 (4)
S1—C3—H3A	109.5	B9—B8—B7	103.9 (5)
S1—C3—H3B	109.5	B4—B8—Pd3	69.1 (3)
H3A—C3—H3B	109.5	B12—B8—Pd3	120.6 (5)
S1—C3—H3C	109.5	B9—B8—Pd3	122.5 (4)
H3A—C3—H3C	109.5	B7—B8—Pd3	65.5 (3)
H3B—C3—H3C	109.5	B4—B8—H8	125.2
S1—C4—H4A	109.5	B12—B8—H8	120.8
S1—C4—H4B	109.5	B9—B8—H8	120.4
H4A—C4—H4B	109.5	B7—B8—H8	126.9
S1—C4—H4C	109.5	Pd3—B8—H8	106.9
H4A—C4—H4C	109.5	B4—B9—B10	108.5 (5)
H4B—C4—H4C	109.5	B4—B9—B5	60.0 (4)
C12—C11—C16	117.5 (7)	B10—B9—B5	60.5 (4)
C12—C11—P1	122.5 (6)	B4—B9—B12	105.5 (6)
C16—C11—P1	120.0 (6)	B10—B9—B12	61.5 (5)
C11—C12—C13	120.5 (9)	B5—B9—B12	107.9 (6)
C11—C12—H12A	119.7	B4—B9—B8	59.8 (4)
C13—C12—H12A	119.7	B10—B9—B8	110.7 (6)
C14—C13—C12	120.9 (10)	B5—B9—B8	109.3 (5)
C14—C13—H13	119.6	B12—B9—B8	59.2 (5)
C12—C13—H13	119.6	B4—B9—H9	122.9
C13—C14—C15	118.9 (9)	B10—B9—H9	119.8
C13—C14—H14	120.6	B5—B9—H9	121.2
C15—C14—H14	120.6	B12—B9—H9	122.8
C16—C15—C14	121.2 (10)	B8—B9—H9	120.7
C16—C15—H15	119.4	B9—B10—B11	109.2 (6)
C14—C15—H15	119.4	B9—B10—B5	59.9 (4)
C15—C16—C11	121.0 (9)	B11—B10—B5	107.3 (6)
C15—C16—H16	119.5	B9—B10—B6	109.1 (5)
C11—C16—H16	119.5	B11—B10—B6	59.2 (5)
C22—C21—C26	119.3 (6)	B5—B10—B6	60.3 (4)
C22—C21—P1	118.0 (5)	B9—B10—B12	60.1 (5)
C26—C21—P1	122.6 (5)	B11—B10—B12	60.1 (5)
C23—C22—C21	120.3 (7)	B5—B10—B12	106.4 (5)
C23—C22—H22	119.8	B6—B10—B12	106.9 (6)
C21—C22—H22	119.8	B9—B10—H10	120.6
C24—C23—C22	121.0 (8)	B11—B10—H10	121.6
C24—C23—H23	119.5	B5—B10—H10	122.5
C22—C23—H23	119.5	B6—B10—H10	121.8
C23—C24—C25	120.0 (7)	B12—B10—H10	122.7
C23—C24—H24	120.0	C2—B11—B6	59.0 (4)
C25—C24—H24	120.0	C2—B11—B10	105.6 (6)
C26—C25—C24	119.4 (8)	B6—B11—B10	61.0 (5)
C26—C25—H25	120.3	C2—B11—B12	103.6 (5)
C24—C25—H25	120.3	B6—B11—B12	109.3 (6)
C21—C26—C25	120.0 (7)	B10—B11—B12	61.4 (5)
C21—C26—H26	120.0	C2—B11—B7	56.6 (4)
C25—C26—H26	120.0	B6—B11—B7	107.1 (5)
C36—C31—C32	117.9 (7)	B10—B11—B7	109.1 (5)
C36—C31—P1	121.7 (6)	B12—B11—B7	60.1 (5)
C32—C31—P1	120.4 (6)	C2—B11—H11	125.7
C33—C32—C31	120.4 (8)	B6—B11—H11	121.0
C33—C32—H32	119.8	B10—B11—H11	120.8
C31—C32—H32	119.8	B12—B11—H11	121.9
C34—C33—C32	121.2 (9)	B7—B11—H11	122.3
C34—C33—H33	119.4	B8—B12—B9	61.1 (4)
C32—C33—H33	119.4	B8—B12—B11	113.1 (6)
C33—C34—C35	118.5 (8)	B9—B12—B11	106.6 (6)
C33—C34—H34	120.8	B8—B12—B7	64.5 (5)
C35—C34—H34	120.8	B9—B12—B7	109.6 (6)
C36—C35—C34	121.6 (9)	B11—B12—B7	60.3 (5)
C36—C35—H35	119.2	B8—B12—B10	109.8 (5)
C34—C35—H35	119.2	B9—B12—B10	58.4 (4)
C35—C36—C31	120.3 (8)	B11—B12—B10	58.5 (5)
C35—C36—H36	119.8	B7—B12—B10	107.0 (5)
C31—C36—H36	119.8	B8—B12—H12	117.4
C1—B4—B9	106.6 (5)	B9—B12—H12	122.6
C1—B4—B5	61.6 (4)	B11—B12—H12	121.4
B9—B4—B5	60.8 (4)	B7—B12—H12	120.3
C1—B4—B8	104.9 (5)	B10—B12—H12	123.4
B9—B4—B8	62.3 (4)

B8—Pd3—P1—C21	−122.0 (3)	B4—Pd3—B7—B11	50.2 (6)
B7—Pd3—P1—C21	−172.9 (3)	C2—Pd3—B7—B11	−26.0 (5)
C1—Pd3—P1—C21	162.5 (9)	I1—Pd3—B7—B11	−56.6 (8)
B4—Pd3—P1—C21	−90.9 (3)	P1—Pd3—B7—B8	98.3 (3)
C2—Pd3—P1—C21	156.9 (3)	C1—Pd3—B7—B8	−86.4 (3)
I1—Pd3—P1—C21	40.7 (2)	B4—Pd3—B7—B8	−41.7 (3)
B8—Pd3—P1—C31	−3.0 (3)	C2—Pd3—B7—B8	−117.9 (5)
B7—Pd3—P1—C31	−53.8 (3)	I1—Pd3—B7—B8	−148.5 (3)
C1—Pd3—P1—C31	−78.5 (9)	C1—B4—B8—B12	−62.1 (6)
B4—Pd3—P1—C31	28.1 (4)	B9—B4—B8—B12	39.1 (5)
C2—Pd3—P1—C31	−84.1 (3)	B5—B4—B8—B12	2.9 (7)
I1—Pd3—P1—C31	159.7 (3)	S1—B4—B8—B12	152.3 (5)
B8—Pd3—P1—C11	118.6 (3)	Pd3—B4—B8—B12	−117.7 (5)
B7—Pd3—P1—C11	67.7 (3)	C1—B4—B8—B9	−101.2 (5)
C1—Pd3—P1—C11	43.1 (9)	B5—B4—B8—B9	−36.2 (5)
B4—Pd3—P1—C11	149.7 (3)	S1—B4—B8—B9	113.2 (6)
C2—Pd3—P1—C11	37.5 (3)	Pd3—B4—B8—B9	−156.8 (4)
I1—Pd3—P1—C11	−78.7 (2)	C1—B4—B8—B7	−2.1 (6)
P1—Pd3—C1—C2	−6.8 (11)	B9—B4—B8—B7	99.1 (5)
B8—Pd3—C1—C2	−85.0 (4)	B5—B4—B8—B7	62.8 (6)
B7—Pd3—C1—C2	−32.7 (4)	S1—B4—B8—B7	−147.7 (5)
B4—Pd3—C1—C2	−124.8 (5)	Pd3—B4—B8—B7	−57.7 (4)
I1—Pd3—C1—C2	115.3 (3)	C1—B4—B8—Pd3	55.6 (4)
P1—Pd3—C1—B4	117.9 (8)	B9—B4—B8—Pd3	156.8 (4)
B8—Pd3—C1—B4	39.8 (3)	B5—B4—B8—Pd3	120.6 (5)
B7—Pd3—C1—B4	92.0 (4)	S1—B4—B8—Pd3	−90.0 (5)
C2—Pd3—C1—B4	124.8 (5)	C2—B7—B8—B4	−4.3 (6)
I1—Pd3—C1—B4	−119.9 (3)	B12—B7—B8—B4	−99.7 (5)
P1—Pd3—C1—B5	98.0 (9)	B11—B7—B8—B4	−64.9 (6)
B8—Pd3—C1—B5	19.9 (5)	Pd3—B7—B8—B4	60.2 (4)
B7—Pd3—C1—B5	72.1 (5)	C2—B7—B8—B12	95.4 (6)
B4—Pd3—C1—B5	−19.9 (5)	B11—B7—B8—B12	34.8 (5)
C2—Pd3—C1—B5	104.8 (6)	Pd3—B7—B8—B12	159.9 (5)
I1—Pd3—C1—B5	−139.8 (5)	C2—B7—B8—B9	55.2 (6)
P1—Pd3—C1—B6	16.0 (13)	B12—B7—B8—B9	−40.2 (5)
B8—Pd3—C1—B6	−62.1 (6)	B11—B7—B8—B9	−5.4 (6)
B7—Pd3—C1—B6	−9.9 (5)	Pd3—B7—B8—B9	119.7 (4)
B4—Pd3—C1—B6	−101.9 (6)	C2—B7—B8—Pd3	−64.6 (4)
C2—Pd3—C1—B6	22.9 (5)	B12—B7—B8—Pd3	−159.9 (5)
I1—Pd3—C1—B6	138.2 (5)	B11—B7—B8—Pd3	−125.2 (5)
B4—C1—C2—B7	−11.9 (7)	P1—Pd3—B8—B4	152.8 (3)
B5—C1—C2—B7	−78.1 (6)	B7—Pd3—B8—B4	−114.6 (4)
B6—C1—C2—B7	−113.5 (6)	C1—Pd3—B8—B4	−38.0 (3)
Pd3—C1—C2—B7	47.3 (4)	C2—Pd3—B8—B4	−78.3 (3)
B4—C1—C2—B11	58.8 (7)	I1—Pd3—B8—B4	17.4 (6)
B5—C1—C2—B11	−7.4 (7)	P1—Pd3—B8—B12	−112.5 (5)
B6—C1—C2—B11	−42.8 (5)	B7—Pd3—B8—B12	−19.8 (5)
Pd3—C1—C2—B11	118.0 (5)	C1—Pd3—B8—B12	56.8 (5)
B4—C1—C2—B6	101.5 (6)	B4—Pd3—B8—B12	94.8 (6)
B5—C1—C2—B6	35.4 (5)	C2—Pd3—B8—B12	16.5 (5)
Pd3—C1—C2—B6	160.8 (4)	I1—Pd3—B8—B12	112.2 (6)
B4—C1—C2—Pd3	−59.3 (4)	P1—Pd3—B8—B9	176.1 (5)
B5—C1—C2—Pd3	−125.4 (4)	B7—Pd3—B8—B9	−91.3 (6)
B6—C1—C2—Pd3	−160.8 (4)	C1—Pd3—B8—B9	−14.7 (5)
P1—Pd3—C2—C1	178.3 (3)	B4—Pd3—B8—B9	23.3 (4)
B8—Pd3—C2—C1	84.0 (4)	C2—Pd3—B8—B9	−54.9 (5)
B7—Pd3—C2—C1	128.4 (5)	I1—Pd3—B8—B9	40.8 (8)
B4—Pd3—C2—C1	36.5 (3)	P1—Pd3—B8—B7	−92.6 (3)
I1—Pd3—C2—C1	−70.1 (3)	C1—Pd3—B8—B7	76.6 (3)
P1—Pd3—C2—B7	50.0 (4)	B4—Pd3—B8—B7	114.6 (4)
B8—Pd3—C2—B7	−44.3 (4)	C2—Pd3—B8—B7	36.4 (3)
C1—Pd3—C2—B7	−128.4 (5)	I1—Pd3—B8—B7	132.1 (4)
B4—Pd3—C2—B7	−91.8 (4)	C1—B4—B9—B10	−5.2 (7)
I1—Pd3—C2—B7	161.5 (3)	B5—B4—B9—B10	37.5 (6)
P1—Pd3—C2—B11	76.6 (6)	B8—B4—B9—B10	−103.6 (6)
B8—Pd3—C2—B11	−17.7 (6)	S1—B4—B9—B10	139.4 (5)
B7—Pd3—C2—B11	26.7 (6)	Pd3—B4—B9—B10	−78.3 (6)
C1—Pd3—C2—B11	−101.7 (7)	C1—B4—B9—B5	−42.7 (5)
B4—Pd3—C2—B11	−65.2 (6)	B8—B4—B9—B5	−141.1 (6)
I1—Pd3—C2—B11	−171.8 (5)	S1—B4—B9—B5	101.9 (6)
P1—Pd3—C2—B6	156.3 (5)	Pd3—B4—B9—B5	−115.8 (5)
B8—Pd3—C2—B6	62.0 (6)	C1—B4—B9—B12	59.4 (6)
B7—Pd3—C2—B6	106.3 (7)	B5—B4—B9—B12	102.1 (6)
C1—Pd3—C2—B6	−22.1 (5)	B8—B4—B9—B12	−39.1 (5)
B4—Pd3—C2—B6	14.5 (5)	S1—B4—B9—B12	−156.0 (5)
I1—Pd3—C2—B6	−92.2 (5)	Pd3—B4—B9—B12	−13.7 (6)
C21—P1—C11—C12	103.9 (7)	C1—B4—B9—B8	98.4 (5)
C31—P1—C11—C12	−4.1 (8)	B5—B4—B9—B8	141.1 (6)
Pd3—P1—C11—C12	−134.3 (7)	S1—B4—B9—B8	−117.0 (6)
C21—P1—C11—C16	−74.8 (8)	Pd3—B4—B9—B8	25.3 (4)
C31—P1—C11—C16	177.2 (8)	C1—B5—B9—B4	39.8 (4)
Pd3—P1—C11—C16	47.1 (8)	B10—B5—B9—B4	138.4 (6)
C16—C11—C12—C13	−1.3 (15)	B6—B5—B9—B4	102.4 (6)
P1—C11—C12—C13	−179.9 (9)	B4—B5—B9—B10	−138.4 (6)
C11—C12—C13—C14	1.8 (19)	C1—B5—B9—B10	−98.7 (6)
C12—C13—C14—C15	−1.5 (19)	B6—B5—B9—B10	−36.0 (6)
C13—C14—C15—C16	0.7 (18)	B4—B5—B9—B12	−97.9 (6)
C14—C15—C16—C11	−0.2 (19)	C1—B5—B9—B12	−58.1 (6)
C12—C11—C16—C15	0.5 (16)	B10—B5—B9—B12	40.6 (6)
P1—C11—C16—C15	179.1 (9)	B6—B5—B9—B12	4.6 (7)
C31—P1—C21—C22	−79.5 (6)	B4—B5—B9—B8	−35.1 (5)
C11—P1—C21—C22	171.6 (5)	C1—B5—B9—B8	4.7 (7)
Pd3—P1—C21—C22	49.2 (6)	B10—B5—B9—B8	103.4 (6)
C31—P1—C21—C26	98.3 (7)	B6—B5—B9—B8	67.3 (6)
C11—P1—C21—C26	−10.7 (7)	B12—B8—B9—B4	−135.0 (5)
Pd3—P1—C21—C26	−133.0 (6)	B7—B8—B9—B4	−95.5 (5)
C26—C21—C22—C23	0.3 (11)	Pd3—B8—B9—B4	−25.9 (5)
P1—C21—C22—C23	178.1 (6)	B4—B8—B9—B10	100.0 (5)
C21—C22—C23—C24	0.0 (12)	B12—B8—B9—B10	−35.0 (5)
C22—C23—C24—C25	0.0 (14)	B7—B8—B9—B10	4.5 (7)
C23—C24—C25—C26	−0.3 (15)	Pd3—B8—B9—B10	74.1 (6)
C22—C21—C26—C25	−0.6 (12)	B4—B8—B9—B5	35.2 (5)
P1—C21—C26—C25	−178.3 (7)	B12—B8—B9—B5	−99.8 (6)
C24—C25—C26—C21	0.6 (14)	B7—B8—B9—B5	−60.3 (6)
C21—P1—C31—C36	−6.7 (7)	Pd3—B8—B9—B5	9.3 (7)
C11—P1—C31—C36	104.5 (7)	B4—B8—B9—B12	135.0 (5)
Pd3—P1—C31—C36	−130.0 (6)	B7—B8—B9—B12	39.5 (5)
C21—P1—C31—C32	172.4 (6)	Pd3—B8—B9—B12	109.1 (6)
C11—P1—C31—C32	−76.4 (7)	B4—B9—B10—B11	62.0 (7)
Pd3—P1—C31—C32	49.1 (7)	B5—B9—B10—B11	99.3 (6)
C36—C31—C32—C33	−2.3 (12)	B12—B9—B10—B11	−36.0 (5)
P1—C31—C32—C33	178.5 (7)	B8—B9—B10—B11	−1.9 (7)
C31—C32—C33—C34	1.7 (14)	B4—B9—B10—B5	−37.3 (5)
C32—C33—C34—C35	−1.3 (14)	B12—B9—B10—B5	−135.2 (6)
C33—C34—C35—C36	1.6 (14)	B8—B9—B10—B5	−101.1 (6)
C34—C35—C36—C31	−2.4 (14)	B4—B9—B10—B6	−1.1 (8)
C32—C31—C36—C35	2.7 (12)	B5—B9—B10—B6	36.2 (6)
P1—C31—C36—C35	−178.2 (7)	B12—B9—B10—B6	−99.0 (7)
C2—C1—B4—B9	−56.2 (7)	B8—B9—B10—B6	−64.9 (7)
B5—C1—B4—B9	42.3 (5)	B4—B9—B10—B12	98.0 (6)
B6—C1—B4—B9	9.7 (7)	B5—B9—B10—B12	135.2 (6)
Pd3—C1—B4—B9	−119.6 (5)	B8—B9—B10—B12	34.1 (5)
C2—C1—B4—B5	−98.5 (6)	B4—B5—B10—B9	36.6 (5)
B6—C1—B4—B5	−32.5 (5)	C1—B5—B10—B9	96.6 (5)
Pd3—C1—B4—B5	−161.9 (4)	B6—B5—B10—B9	140.0 (6)
C2—C1—B4—B8	8.8 (7)	B4—B5—B10—B11	−66.0 (6)
B5—C1—B4—B8	107.3 (5)	B9—B5—B10—B11	−102.6 (6)
B6—C1—B4—B8	74.7 (6)	C1—B5—B10—B11	−6.0 (6)
Pd3—C1—B4—B8	−54.6 (4)	B6—B5—B10—B11	37.4 (5)
C2—C1—B4—S1	157.3 (5)	B4—B5—B10—B6	−103.4 (6)
B5—C1—B4—S1	−104.2 (5)	B9—B5—B10—B6	−140.0 (6)
B6—C1—B4—S1	−136.7 (5)	C1—B5—B10—B6	−43.3 (5)
Pd3—C1—B4—S1	93.9 (4)	B4—B5—B10—B12	−2.9 (7)
C2—C1—B4—Pd3	63.4 (5)	B9—B5—B10—B12	−39.5 (5)
B5—C1—B4—Pd3	161.9 (4)	C1—B5—B10—B12	57.1 (6)
B6—C1—B4—Pd3	129.3 (5)	B6—B5—B10—B12	100.5 (6)
C3—S1—B4—C1	−156.5 (5)	C2—B6—B10—B9	62.4 (7)
C4—S1—B4—C1	99.2 (5)	B11—B6—B10—B9	101.5 (7)
C3—S1—B4—B9	63.1 (6)	B5—B6—B10—B9	−36.1 (6)
C4—S1—B4—B9	−41.2 (6)	C1—B6—B10—B9	6.4 (8)
C3—S1—B4—B5	133.5 (5)	C2—B6—B10—B11	−39.1 (5)
C4—S1—B4—B5	29.2 (5)	B5—B6—B10—B11	−137.6 (6)
C3—S1—B4—B8	−15.3 (6)	C1—B6—B10—B11	−95.1 (6)
C4—S1—B4—B8	−119.5 (6)	C2—B6—B10—B5	98.5 (5)
C3—S1—B4—Pd3	−85.0 (3)	B11—B6—B10—B5	137.6 (6)
C4—S1—B4—Pd3	170.7 (3)	C1—B6—B10—B5	42.5 (5)
P1—Pd3—B4—C1	−164.9 (2)	C2—B6—B10—B12	−1.1 (7)
B8—Pd3—B4—C1	−120.0 (4)	B11—B6—B10—B12	38.0 (5)
B7—Pd3—B4—C1	−74.6 (3)	B5—B6—B10—B12	−99.5 (6)
C2—Pd3—B4—C1	−32.9 (3)	C1—B6—B10—B12	−57.0 (7)
I1—Pd3—B4—C1	67.7 (3)	C1—C2—B11—B6	44.2 (5)
P1—Pd3—B4—B9	−69.5 (5)	B7—C2—B11—B6	143.8 (6)
B8—Pd3—B4—B9	−24.6 (4)	Pd3—C2—B11—B6	117.7 (6)
B7—Pd3—B4—B9	20.8 (5)	C1—C2—B11—B10	3.2 (7)
C1—Pd3—B4—B9	95.4 (5)	B7—C2—B11—B10	102.9 (6)
C2—Pd3—B4—B9	62.5 (5)	B6—C2—B11—B10	−40.9 (5)
I1—Pd3—B4—B9	163.1 (4)	Pd3—C2—B11—B10	76.8 (7)
P1—Pd3—B4—B5	−145.2 (4)	C1—C2—B11—B12	−60.4 (7)
B8—Pd3—B4—B5	−100.3 (6)	B7—C2—B11—B12	39.2 (5)
B7—Pd3—B4—B5	−54.9 (5)	B6—C2—B11—B12	−104.5 (6)
C1—Pd3—B4—B5	19.7 (5)	Pd3—C2—B11—B12	13.2 (8)
C2—Pd3—B4—B5	−13.2 (5)	C1—C2—B11—B7	−99.6 (6)
I1—Pd3—B4—B5	87.4 (5)	B6—C2—B11—B7	−143.8 (6)
P1—Pd3—B4—B8	−44.9 (4)	Pd3—C2—B11—B7	−26.1 (5)
B7—Pd3—B4—B8	45.4 (4)	B10—B6—B11—C2	−133.8 (5)
C1—Pd3—B4—B8	120.0 (4)	B5—B6—B11—C2	−96.3 (5)
C2—Pd3—B4—B8	87.1 (3)	C1—B6—B11—C2	−35.4 (4)
I1—Pd3—B4—B8	−172.3 (3)	C2—B6—B11—B10	133.8 (5)
P1—Pd3—B4—S1	78.9 (4)	B5—B6—B11—B10	37.6 (5)
B8—Pd3—B4—S1	123.8 (4)	C1—B6—B11—B10	98.5 (5)
B7—Pd3—B4—S1	169.2 (3)	C2—B6—B11—B12	94.6 (6)
C1—Pd3—B4—S1	−116.2 (4)	B10—B6—B11—B12	−39.2 (5)
C2—Pd3—B4—S1	−149.1 (3)	B5—B6—B11—B12	−1.6 (7)
I1—Pd3—B4—S1	−48.5 (3)	C1—B6—B11—B12	59.3 (7)
C1—B4—B5—B9	132.4 (6)	C2—B6—B11—B7	31.1 (5)
B8—B4—B5—B9	36.8 (5)	B10—B6—B11—B7	−102.8 (6)
S1—B4—B5—B9	−116.3 (5)	B5—B6—B11—B7	−65.2 (7)
Pd3—B4—B5—B9	111.7 (6)	C1—B6—B11—B7	−4.3 (7)
B9—B4—B5—C1	−132.4 (6)	B9—B10—B11—C2	−61.3 (7)
B8—B4—B5—C1	−95.6 (5)	B5—B10—B11—C2	2.1 (7)
S1—B4—B5—C1	111.3 (5)	B6—B10—B11—C2	40.0 (5)
Pd3—B4—B5—C1	−20.7 (5)	B12—B10—B11—C2	−97.2 (6)
C1—B4—B5—B10	95.6 (6)	B9—B10—B11—B6	−101.3 (6)
B9—B4—B5—B10	−36.8 (5)	B5—B10—B11—B6	−37.8 (5)
B8—B4—B5—B10	0.0 (7)	B12—B10—B11—B6	−137.2 (5)
S1—B4—B5—B10	−153.1 (5)	B9—B10—B11—B12	35.9 (5)
Pd3—B4—B5—B10	74.9 (6)	B5—B10—B11—B12	99.3 (6)
C1—B4—B5—B6	31.9 (5)	B6—B10—B11—B12	137.2 (5)
B9—B4—B5—B6	−100.4 (6)	B9—B10—B11—B7	−1.8 (7)
B8—B4—B5—B6	−63.6 (7)	B5—B10—B11—B7	61.6 (7)
S1—B4—B5—B6	143.2 (5)	B6—B10—B11—B7	99.4 (6)
Pd3—B4—B5—B6	11.3 (7)	B12—B10—B11—B7	−37.8 (5)
C2—C1—B5—B4	110.0 (5)	B12—B7—B11—C2	134.8 (6)
B6—C1—B5—B4	145.1 (5)	B8—B7—B11—C2	101.1 (6)
Pd3—C1—B5—B4	21.5 (5)	Pd3—B7—B11—C2	30.3 (6)
C2—C1—B5—B9	69.5 (6)	C2—B7—B11—B6	−32.0 (5)
B4—C1—B5—B9	−40.5 (5)	B12—B7—B11—B6	102.8 (6)
B6—C1—B5—B9	104.5 (6)	B8—B7—B11—B6	69.0 (7)
Pd3—C1—B5—B9	−19.0 (7)	Pd3—B7—B11—B6	−1.7 (9)
C2—C1—B5—B10	8.1 (6)	C2—B7—B11—B10	−96.5 (6)
B4—C1—B5—B10	−101.9 (5)	B12—B7—B11—B10	38.3 (5)
B6—C1—B5—B10	43.2 (5)	B8—B7—B11—B10	4.6 (7)
Pd3—C1—B5—B10	−80.4 (6)	Pd3—B7—B11—B10	−66.2 (7)
C2—C1—B5—B6	−35.1 (5)	C2—B7—B11—B12	−134.8 (6)
B4—C1—B5—B6	−145.1 (5)	B8—B7—B11—B12	−33.8 (5)
Pd3—C1—B5—B6	−123.6 (6)	Pd3—B7—B11—B12	−104.5 (6)
C1—C2—B6—B11	−135.6 (5)	B4—B8—B12—B9	−38.2 (5)
B7—C2—B6—B11	−37.6 (6)	B7—B8—B12—B9	−133.5 (5)
Pd3—C2—B6—B11	−113.9 (6)	Pd3—B8—B12—B9	−112.2 (5)
C1—C2—B6—B10	−95.6 (5)	B4—B8—B12—B11	58.6 (7)
B7—C2—B6—B10	2.4 (7)	B9—B8—B12—B11	96.8 (6)
B11—C2—B6—B10	40.0 (5)	B7—B8—B12—B11	−36.7 (6)
Pd3—C2—B6—B10	−73.9 (6)	Pd3—B8—B12—B11	−15.4 (8)
C1—C2—B6—B5	−33.9 (5)	B4—B8—B12—B7	95.3 (5)
B7—C2—B6—B5	64.1 (7)	B9—B8—B12—B7	133.5 (5)
B11—C2—B6—B5	101.7 (6)	Pd3—B8—B12—B7	21.3 (5)
Pd3—C2—B6—B5	−12.2 (7)	B4—B8—B12—B10	−4.6 (7)
B7—C2—B6—C1	97.9 (6)	B9—B8—B12—B10	33.6 (5)
B11—C2—B6—C1	135.6 (5)	B7—B8—B12—B10	−99.9 (6)
Pd3—C2—B6—C1	21.7 (5)	Pd3—B8—B12—B10	−78.6 (7)
B4—B5—B6—C2	0.8 (7)	B4—B9—B12—B8	39.4 (5)
B9—B5—B6—C2	−62.3 (6)	B10—B9—B12—B8	142.3 (6)
C1—B5—B6—C2	31.8 (5)	B5—B9—B12—B8	102.3 (6)
B10—B5—B6—C2	−98.1 (6)	B4—B9—B12—B11	−68.3 (6)
B4—B5—B6—B11	61.3 (7)	B10—B9—B12—B11	34.7 (5)
B9—B5—B6—B11	−1.8 (7)	B5—B9—B12—B11	−5.4 (7)
C1—B5—B6—B11	92.2 (6)	B8—B9—B12—B11	−107.7 (6)
B10—B5—B6—B11	−37.7 (5)	B4—B9—B12—B7	−4.6 (7)
B4—B5—B6—B10	98.9 (6)	B10—B9—B12—B7	98.3 (6)
B9—B5—B6—B10	35.8 (5)	B5—B9—B12—B7	58.2 (7)
C1—B5—B6—B10	129.9 (6)	B8—B9—B12—B7	−44.0 (5)
B4—B5—B6—C1	−31.0 (5)	B4—B9—B12—B10	−103.0 (5)
B9—B5—B6—C1	−94.1 (5)	B5—B9—B12—B10	−40.1 (5)
B10—B5—B6—C1	−129.9 (6)	B8—B9—B12—B10	−142.3 (6)
B4—C1—B6—C2	−108.4 (6)	C2—B11—B12—B8	0.8 (8)
B5—C1—B6—C2	−141.1 (6)	B6—B11—B12—B8	−60.8 (8)
Pd3—C1—B6—C2	−26.0 (6)	B10—B11—B12—B8	−99.8 (6)
C2—C1—B6—B11	37.2 (5)	B7—B11—B12—B8	38.4 (6)
B4—C1—B6—B11	−71.3 (6)	C2—B11—B12—B9	66.0 (7)
B5—C1—B6—B11	−103.9 (6)	B6—B11—B12—B9	4.4 (8)
Pd3—C1—B6—B11	11.1 (8)	B10—B11—B12—B9	−34.6 (5)
C2—C1—B6—B10	98.4 (6)	B7—B11—B12—B9	103.5 (6)
B4—C1—B6—B10	−10.1 (7)	C2—B11—B12—B7	−37.5 (5)
B5—C1—B6—B10	−42.7 (5)	B6—B11—B12—B7	−99.1 (6)
Pd3—C1—B6—B10	72.3 (7)	B10—B11—B12—B7	−138.1 (6)
C2—C1—B6—B5	141.1 (6)	C2—B11—B12—B10	100.6 (6)
B4—C1—B6—B5	32.6 (5)	B6—B11—B12—B10	39.0 (5)
Pd3—C1—B6—B5	115.0 (6)	B7—B11—B12—B10	138.1 (6)
C1—C2—B7—B12	69.1 (6)	C2—B7—B12—B8	−102.7 (5)
B11—C2—B7—B12	−39.1 (5)	B11—B7—B12—B8	−140.8 (6)
B6—C2—B7—B12	−2.6 (7)	Pd3—B7—B12—B8	−20.8 (5)
Pd3—C2—B7—B12	116.8 (5)	C2—B7—B12—B9	−60.2 (7)
C1—C2—B7—B11	108.3 (6)	B11—B7—B12—B9	−98.3 (6)
B6—C2—B7—B11	36.6 (6)	B8—B7—B12—B9	42.4 (5)
Pd3—C2—B7—B11	156.0 (5)	Pd3—B7—B12—B9	21.7 (7)
C1—C2—B7—B8	9.5 (7)	C2—B7—B12—B11	38.1 (5)
B11—C2—B7—B8	−98.8 (6)	B8—B7—B12—B11	140.8 (6)
B6—C2—B7—B8	−62.2 (7)	Pd3—B7—B12—B11	120.0 (6)
Pd3—C2—B7—B8	57.2 (4)	C2—B7—B12—B10	1.6 (7)
C1—C2—B7—Pd3	−47.7 (4)	B11—B7—B12—B10	−36.5 (5)
B11—C2—B7—Pd3	−156.0 (5)	B8—B7—B12—B10	104.3 (6)
B6—C2—B7—Pd3	−119.4 (5)	Pd3—B7—B12—B10	83.5 (6)
P1—Pd3—B7—C2	−143.8 (3)	B9—B10—B12—B8	−34.7 (5)
B8—Pd3—B7—C2	117.9 (5)	B11—B10—B12—B8	105.6 (6)
C1—Pd3—B7—C2	31.5 (3)	B5—B10—B12—B8	4.8 (8)
B4—Pd3—B7—C2	76.2 (4)	B6—B10—B12—B8	68.0 (7)
I1—Pd3—B7—C2	−30.6 (5)	B11—B10—B12—B9	140.3 (6)
P1—Pd3—B7—B12	117.6 (5)	B5—B10—B12—B9	39.4 (5)
B8—Pd3—B7—B12	19.3 (5)	B6—B10—B12—B9	102.7 (6)
C1—Pd3—B7—B12	−67.2 (5)	B9—B10—B12—B11	−140.3 (6)
B4—Pd3—B7—B12	−22.4 (5)	B5—B10—B12—B11	−100.8 (6)
C2—Pd3—B7—B12	−98.7 (6)	B6—B10—B12—B11	−37.6 (5)
I1—Pd3—B7—B12	−129.3 (4)	B9—B10—B12—B7	−103.0 (6)
P1—Pd3—B7—B11	−169.8 (6)	B11—B10—B12—B7	37.3 (5)
B8—Pd3—B7—B11	91.9 (7)	B5—B10—B12—B7	−63.5 (7)
C1—Pd3—B7—B11	5.5 (6)	B6—B10—B12—B7	−0.3 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···I1	0.93	2.98	3.831 (9)	153

(II) 3-dimethylphenylphosphine- 3-chloro-4-dimethylsulfido-closo-3-pallada-1,2-dicarbadodecaborane top

Crystal data top

[Pd(C₄H₁₆B₉S)Cl(C₈H₁₁P)]	F(000) = 952
M_r = 473.54	D_x = 1.458 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 12.8117 (8) Å	θ = 10.0–16.5°
b = 9.2670 (7) Å	µ = 1.15 mm⁻¹
c = 18.2948 (10) Å	T = 294 K
β = 96.567 (5)°	Block, purple
V = 2157.8 (2) Å³	0.33 × 0.25 × 0.25 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	5023 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	R_int = 0.020
Graphite monochromator	θ_max = 30.0°, θ_min = 1.9°
θ/2θ scans	h = 0→18
Absorption correction: ψ scan (ABSCOR in NRCVAX; Gabe et al., 1989)	k = 0→13
T_min = 0.684, T_max = 0.760	l = −25→25
6506 measured reflections	3 standard reflections every 250 reflections
6265 independent reflections	intensity decay: none

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)] = 0.024	H-atom parameters constrained
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.0335P)² + 0.6303P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
6265 reflections	Δρ_max = 0.70 e Å⁻³
231 parameters	Δρ_min = −0.51 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00185 (18)

Crystal data top

[Pd(C₄H₁₆B₉S)Cl(C₈H₁₁P)]	V = 2157.8 (2) Å³
M_r = 473.54	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.8117 (8) Å	µ = 1.15 mm⁻¹
b = 9.2670 (7) Å	T = 294 K
c = 18.2948 (10) Å	0.33 × 0.25 × 0.25 mm
β = 96.567 (5)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	5023 reflections with I > 2σ(I)
Absorption correction: ψ scan (ABSCOR in NRCVAX; Gabe et al., 1989)	R_int = 0.020
T_min = 0.684, T_max = 0.760	3 standard reflections every 250 reflections
6506 measured reflections	intensity decay: none
6265 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.03	Δρ_max = 0.70 e Å⁻³
6265 reflections	Δρ_min = −0.51 e Å⁻³
231 parameters

Special details top

Experimental. Details of IR and NMR spectra for (II) are as follows:- IR: ν_max(KBr disc) cm⁻¹ 2602(m,sh) (BH), 2561(m,sh) (BH), 2537(versus) (BH), 2497(m,sh) (BH). ¹¹B and ¹H NMR data (CDCl₃ 294 K) ordered as δ(¹¹B) [δ(¹H) of directly attached proton]: −3.5 [+2.6], −5.6 [+2.8], BH(4) −10.0 [SMe₂ +2.47, +2.66], −12.5 [+2.1], −14.2 [+2.4], −17.3 [+1.4], −21.7 [+2.0], −23.9 [+0.8], −26.0 [+0.8]. Additional data, ¹H (CDCl₃ 294 K) P-methyl resonances at +1.99, +1.96, +1.93 and +1.89; ³¹P (CDCl₃ 229 K) δ +15.96.

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

	x	y	z	U_iso*/U_eq
Pd3	0.379261 (10)	0.335664 (14)	0.101576 (7)	0.03293 (5)
S1	0.53335 (4)	0.04233 (5)	0.12176 (3)	0.03873 (10)
P1	0.20666 (4)	0.36995 (5)	0.07755 (3)	0.03981 (11)
Cl1	0.39537 (4)	0.27972 (7)	−0.02333 (3)	0.05485 (13)
C1	0.55550 (13)	0.36598 (18)	0.14010 (9)	0.0329 (3)
H1	0.5867	0.3636	0.0865	0.039*
C2	0.50663 (14)	0.51148 (19)	0.16241 (10)	0.0375 (4)
H2	0.5099	0.6092	0.1286	0.045*
C3	0.40912 (19)	−0.0446 (3)	0.10041 (15)	0.0622 (6)
H3A	0.4197	−0.1400	0.0822	0.093*
H3B	0.3668	0.0101	0.0636	0.093*
H3C	0.3741	−0.0506	0.1440	0.093*
C4	0.5948 (2)	−0.0794 (2)	0.18996 (13)	0.0562 (6)
H4A	0.5492	−0.0946	0.2274	0.084*
H4B	0.6600	−0.0387	0.2117	0.084*
H4C	0.6081	−0.1699	0.1672	0.084*
C11	0.18008 (14)	0.5338 (2)	0.02529 (10)	0.0393 (4)
C12	0.1707 (2)	0.6645 (2)	0.06040 (12)	0.0531 (5)
H12	0.1725	0.6674	0.1113	0.064*
C13	0.1586 (2)	0.7905 (3)	0.02020 (15)	0.0676 (7)
H13	0.1524	0.8779	0.0443	0.081*
C14	0.1555 (2)	0.7883 (3)	−0.05508 (15)	0.0673 (7)
H14	0.1477	0.8737	−0.0818	0.081*
C15	0.1640 (2)	0.6597 (3)	−0.09035 (13)	0.0670 (7)
H15	0.1614	0.6578	−0.1414	0.080*
C16	0.17644 (19)	0.5322 (3)	−0.05101 (12)	0.0578 (6)
H16	0.1824	0.4453	−0.0756	0.069*
C17	0.1412 (2)	0.2262 (3)	0.02328 (18)	0.0750 (8)
H17A	0.1448	0.1388	0.0517	0.113*
H17B	0.1752	0.2116	−0.0203	0.113*
H17C	0.0690	0.2517	0.0096	0.113*
C18	0.13252 (18)	0.3838 (3)	0.15605 (14)	0.0593 (6)
H18A	0.1616	0.4591	0.1881	0.089*
H18B	0.1362	0.2938	0.1822	0.089*
H18C	0.0605	0.4057	0.1393	0.089*
B4	0.50616 (16)	0.2128 (2)	0.17366 (11)	0.0335 (4)
B5	0.62480 (18)	0.2841 (2)	0.21582 (12)	0.0401 (4)
H5	0.6990	0.2246	0.2154	0.048*
B6	0.62427 (18)	0.4761 (2)	0.20917 (12)	0.0431 (5)
H6	0.6966	0.5386	0.2058	0.052*
B7	0.39869 (18)	0.4687 (2)	0.20263 (12)	0.0421 (5)
H7	0.3282	0.5374	0.1959	0.050*
B8	0.39851 (18)	0.2672 (2)	0.21915 (11)	0.0396 (4)
H8	0.3308	0.1991	0.2281	0.048*
B9	0.52454 (19)	0.2306 (2)	0.26969 (12)	0.0425 (5)
H9	0.5347	0.1384	0.3077	0.051*
B10	0.5951 (2)	0.3929 (3)	0.29088 (12)	0.0491 (5)
H10	0.6484	0.4034	0.3422	0.059*
B11	0.5189 (2)	0.5382 (2)	0.25307 (12)	0.0466 (5)
H11	0.5217	0.6441	0.2803	0.056*
B12	0.4533 (2)	0.3886 (3)	0.28837 (12)	0.0483 (5)
H12A	0.4128	0.3999	0.3380	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd3	0.03533 (7)	0.03033 (7)	0.03383 (7)	0.00362 (5)	0.00693 (5)	0.00116 (5)
S1	0.0453 (2)	0.0300 (2)	0.0402 (2)	0.00383 (18)	0.00193 (18)	−0.00286 (17)
P1	0.0349 (2)	0.0340 (2)	0.0511 (3)	−0.00032 (18)	0.0071 (2)	−0.0008 (2)
Cl1	0.0621 (3)	0.0670 (3)	0.0361 (2)	0.0092 (3)	0.0086 (2)	−0.0039 (2)
C1	0.0353 (8)	0.0301 (8)	0.0330 (8)	−0.0020 (6)	0.0030 (6)	0.0012 (6)
C2	0.0467 (10)	0.0253 (8)	0.0406 (9)	−0.0021 (7)	0.0052 (7)	0.0012 (7)
C3	0.0541 (12)	0.0404 (12)	0.0885 (18)	−0.0046 (10)	−0.0081 (12)	−0.0166 (11)
C4	0.0739 (15)	0.0351 (10)	0.0554 (12)	0.0121 (10)	−0.0102 (11)	0.0006 (9)
C11	0.0315 (8)	0.0438 (10)	0.0419 (9)	0.0032 (7)	0.0020 (7)	0.0006 (8)
C12	0.0734 (15)	0.0431 (11)	0.0424 (10)	0.0035 (10)	0.0043 (10)	0.0031 (9)
C13	0.093 (2)	0.0432 (12)	0.0659 (16)	0.0046 (13)	0.0067 (14)	0.0081 (11)
C14	0.0652 (15)	0.0699 (17)	0.0670 (16)	0.0078 (13)	0.0083 (12)	0.0317 (14)
C15	0.0629 (14)	0.096 (2)	0.0430 (11)	0.0205 (14)	0.0087 (10)	0.0167 (13)
C16	0.0604 (13)	0.0687 (16)	0.0436 (11)	0.0172 (12)	0.0032 (9)	−0.0029 (10)
C17	0.0578 (14)	0.0527 (15)	0.114 (2)	−0.0154 (12)	0.0059 (14)	−0.0247 (15)
C18	0.0481 (12)	0.0626 (14)	0.0719 (15)	0.0041 (11)	0.0272 (11)	0.0157 (12)
B4	0.0403 (10)	0.0258 (8)	0.0344 (9)	−0.0004 (7)	0.0043 (7)	0.0021 (7)
B5	0.0449 (11)	0.0355 (10)	0.0382 (10)	−0.0009 (9)	−0.0022 (8)	0.0016 (8)
B6	0.0485 (12)	0.0352 (11)	0.0440 (11)	−0.0098 (9)	−0.0016 (9)	−0.0011 (9)
B7	0.0499 (12)	0.0347 (11)	0.0432 (11)	0.0048 (9)	0.0123 (9)	−0.0025 (8)
B8	0.0481 (11)	0.0343 (10)	0.0380 (10)	−0.0022 (9)	0.0115 (8)	0.0028 (8)
B9	0.0590 (13)	0.0345 (11)	0.0337 (10)	−0.0025 (9)	0.0038 (9)	0.0043 (8)
B10	0.0677 (15)	0.0412 (12)	0.0356 (10)	−0.0049 (11)	−0.0054 (10)	−0.0031 (9)
B11	0.0660 (14)	0.0327 (11)	0.0412 (11)	−0.0034 (10)	0.0061 (10)	−0.0052 (9)
B12	0.0692 (15)	0.0432 (12)	0.0347 (10)	−0.0007 (11)	0.0153 (10)	−0.0023 (9)

Geometric parameters (Å, º) top

Pd3—B7	2.212 (2)	C15—C16	1.383 (4)
Pd3—P1	2.2275 (5)	C15—H15	0.93
Pd3—B8	2.229 (2)	C16—H16	0.93
Pd3—B4	2.278 (2)	C17—H17A	0.96
Pd3—C1	2.304 (2)	C17—H17B	0.96
Pd3—Cl1	2.3751 (5)	C17—H17C	0.96
Pd3—C2	2.478 (2)	C18—H18A	0.96
S1—C3	1.787 (2)	C18—H18B	0.96
S1—C4	1.796 (2)	C18—H18C	0.96
S1—B4	1.896 (2)	B4—B5	1.753 (3)
P1—C11	1.806 (2)	B4—B9	1.754 (3)
P1—C17	1.809 (2)	B4—B8	1.764 (3)
P1—C18	1.815 (2)	B5—B9	1.777 (3)
C1—C2	1.561 (2)	B5—B10	1.780 (3)
C1—B4	1.697 (3)	B5—B6	1.783 (3)
C1—B5	1.733 (3)	B5—H5	1.10
C1—B6	1.778 (3)	B6—B11	1.745 (3)
C1—H1	1.10	B6—B10	1.759 (3)
C2—B11	1.667 (3)	B6—H6	1.10
C2—B6	1.678 (3)	B7—B12	1.802 (3)
C2—B7	1.686 (3)	B7—B11	1.820 (3)
C2—H2	1.10	B7—B8	1.891 (3)
C3—H3A	0.96	B7—H7	1.10
C3—H3B	0.96	B8—B12	1.777 (3)
C3—H3C	0.96	B8—B9	1.799 (3)
C4—H4A	0.96	B8—H8	1.10
C4—H4B	0.96	B9—B10	1.775 (3)
C4—H4C	0.96	B9—B12	1.779 (3)
C11—C12	1.382 (3)	B9—H9	1.10
C11—C16	1.391 (3)	B10—B11	1.757 (4)
C12—C13	1.380 (3)	B10—B12	1.813 (4)
C12—H12	0.93	B10—H10	1.10
C13—C14	1.374 (4)	B11—B12	1.781 (3)
C13—H13	0.93	B11—H11	1.10
C14—C15	1.365 (4)	B12—H12A	1.10
C14—H14	0.93

B7—Pd3—P1	95.72 (6)	B4—B5—B9	59.57 (12)
B7—Pd3—B8	50.40 (8)	C1—B5—B10	103.51 (16)
P1—Pd3—B8	103.23 (6)	B4—B5—B10	107.59 (16)
B7—Pd3—B4	77.88 (8)	B9—B5—B10	59.88 (13)
P1—Pd3—B4	144.32 (5)	C1—B5—B6	60.72 (12)
B8—Pd3—B4	46.07 (8)	B4—B5—B6	110.47 (15)
B7—Pd3—C1	70.36 (7)	B9—B5—B6	108.59 (16)
P1—Pd3—C1	163.51 (5)	B10—B5—B6	59.19 (13)
B8—Pd3—C1	75.12 (7)	C1—B5—H5	125.3
B4—Pd3—C1	43.48 (6)	B4—B5—H5	121.0
B7—Pd3—Cl1	155.75 (6)	B9—B5—H5	123.0
P1—Pd3—Cl1	92.00 (2)	B10—B5—H5	123.4
B8—Pd3—Cl1	148.67 (6)	B6—B5—H5	119.8
B4—Pd3—Cl1	108.25 (5)	C2—B6—B11	58.23 (13)
C1—Pd3—Cl1	97.52 (5)	C2—B6—B10	104.67 (17)
B7—Pd3—C2	41.66 (7)	B11—B6—B10	60.19 (14)
P1—Pd3—C2	125.64 (4)	C2—B6—C1	53.60 (10)
B8—Pd3—C2	76.06 (7)	B11—B6—C1	99.78 (15)
B4—Pd3—C2	71.27 (7)	B10—B6—C1	102.50 (15)
C1—Pd3—C2	37.87 (6)	C2—B6—B5	103.06 (14)
Cl1—Pd3—C2	116.77 (5)	B11—B6—B5	107.14 (16)
C3—S1—C4	100.24 (12)	B10—B6—B5	60.30 (13)
C3—S1—B4	105.96 (10)	C1—B6—B5	58.23 (11)
C4—S1—B4	105.45 (10)	C2—B6—H6	125.6
C11—P1—C17	106.33 (12)	B11—B6—H6	123.6
C11—P1—C18	106.00 (10)	B10—B6—H6	122.7
C17—P1—C18	103.57 (14)	C1—B6—H6	127.9
C11—P1—Pd3	110.32 (6)	B5—B6—H6	122.2
C17—P1—Pd3	112.98 (10)	C2—B7—B12	102.75 (16)
C18—P1—Pd3	116.84 (9)	C2—B7—B11	56.59 (12)
C2—C1—B4	116.80 (14)	B12—B7—B11	58.87 (13)
C2—C1—B5	110.70 (14)	C2—B7—B8	108.53 (14)
B4—C1—B5	61.48 (11)	B12—B7—B8	57.45 (12)
C2—C1—B6	59.94 (12)	B11—B7—B8	106.53 (16)
B4—C1—B6	113.44 (14)	C2—B7—Pd3	77.63 (10)
B5—C1—B6	61.05 (12)	B12—B7—Pd3	119.55 (13)
C2—C1—Pd3	77.11 (9)	B11—B7—Pd3	128.94 (14)
B4—C1—Pd3	67.43 (9)	B8—B7—Pd3	65.25 (9)
B5—C1—Pd3	125.86 (11)	C2—B7—H7	121.2
B6—C1—Pd3	132.54 (12)	B12—B7—H7	124.6
C2—C1—H1	116.6	B11—B7—H7	119.2
B4—C1—H1	119.6	B8—B7—H7	125.0
B5—C1—H1	119.9	Pd3—B7—H7	102.5
B6—C1—H1	116.4	B4—B8—B12	104.54 (16)
Pd3—C1—H1	99.7	B4—B8—B9	58.96 (12)
C1—C2—B11	113.17 (15)	B12—B8—B9	59.68 (13)
C1—C2—B6	66.46 (12)	B4—B8—B7	101.05 (14)
B11—C2—B6	62.90 (13)	B12—B8—B7	58.76 (13)
C1—C2—B7	106.53 (14)	B9—B8—B7	104.53 (15)
B11—C2—B7	65.77 (14)	B4—B8—Pd3	68.42 (9)
B6—C2—B7	117.72 (15)	B12—B8—Pd3	119.91 (13)
C1—C2—Pd3	65.02 (9)	B9—B8—Pd3	122.92 (13)
B11—C2—Pd3	121.81 (12)	B7—B8—Pd3	64.34 (9)
B6—C2—Pd3	127.40 (12)	B4—B8—H8	125.3
B7—C2—Pd3	60.70 (9)	B12—B8—H8	120.7
C1—C2—H2	121.5	B9—B8—H8	119.5
B11—C2—H2	115.6	B7—B8—H8	127.3
B6—C2—H2	110.9	Pd3—B8—H8	107.7
B7—C2—H2	121.7	B4—B9—B10	107.79 (15)
Pd3—C2—H2	110.8	B4—B9—B5	59.55 (12)
S1—C3—H3A	109.5	B10—B9—B5	60.14 (13)
S1—C3—H3B	109.5	B4—B9—B12	104.89 (15)
H3A—C3—H3B	109.5	B10—B9—B12	61.36 (14)
S1—C3—H3C	109.5	B5—B9—B12	107.25 (16)
H3A—C3—H3C	109.5	B4—B9—B8	59.54 (11)
H3B—C3—H3C	109.5	B10—B9—B8	110.95 (16)
S1—C4—H4A	109.5	B5—B9—B8	109.01 (14)
S1—C4—H4B	109.5	B12—B9—B8	59.55 (13)
H4A—C4—H4B	109.5	B4—B9—H9	123.5
S1—C4—H4C	109.5	B10—B9—H9	120.0
H4A—C4—H4C	109.5	B5—B9—H9	121.7
H4B—C4—H4C	109.5	B12—B9—H9	123.0
C12—C11—C16	118.7 (2)	B8—B9—H9	120.4
C12—C11—P1	120.77 (15)	B11—B10—B6	59.50 (14)
C16—C11—P1	120.34 (17)	B11—B10—B9	108.47 (17)
C13—C12—C11	120.3 (2)	B6—B10—B9	109.75 (15)
C13—C12—H12	119.9	B11—B10—B5	106.76 (16)
C11—C12—H12	119.9	B6—B10—B5	60.51 (13)
C14—C13—C12	120.7 (3)	B9—B10—B5	59.98 (13)
C14—C13—H13	119.7	B11—B10—B12	59.79 (14)
C12—C13—H13	119.7	B6—B10—B12	107.31 (17)
C15—C14—C13	119.5 (2)	B9—B10—B12	59.44 (14)
C15—C14—H14	120.2	B5—B10—B12	105.66 (16)
C13—C14—H14	120.2	B11—B10—H10	122.1
C14—C15—C16	120.7 (2)	B6—B10—H10	121.0
C14—C15—H15	119.7	B9—B10—H10	120.8
C16—C15—H15	119.7	B5—B10—H10	122.8
C15—C16—C11	120.1 (2)	B12—B10—H10	123.1
C15—C16—H16	119.9	C2—B11—B6	58.87 (12)
C11—C16—H16	119.9	C2—B11—B10	105.25 (16)
P1—C17—H17A	109.5	B6—B11—B10	60.31 (14)
P1—C17—H17B	109.5	C2—B11—B12	104.51 (15)
H17A—C17—H17B	109.5	B6—B11—B12	109.43 (17)
P1—C17—H17C	109.5	B10—B11—B12	61.66 (15)
H17A—C17—H17C	109.5	C2—B11—B7	57.64 (12)
H17B—C17—H17C	109.5	B6—B11—B7	107.71 (15)
P1—C18—H18A	109.5	B10—B11—B7	109.17 (16)
P1—C18—H18B	109.5	B12—B11—B7	60.06 (13)
H18A—C18—H18B	109.5	C2—B11—H11	125.3
P1—C18—H18C	109.5	B6—B11—H11	121.1
H18A—C18—H18C	109.5	B10—B11—H11	121.2
H18B—C18—H18C	109.5	B12—B11—H11	121.5
C1—B4—B5	60.25 (11)	B7—B11—H11	121.8
C1—B4—B9	105.70 (14)	B8—B12—B9	60.77 (13)
B5—B4—B9	60.88 (12)	B8—B12—B11	113.50 (15)
C1—B4—B8	105.96 (14)	B9—B12—B11	107.26 (17)
B5—B4—B8	111.70 (15)	B8—B12—B7	63.79 (13)
B9—B4—B8	61.51 (13)	B9—B12—B7	109.16 (15)
C1—B4—S1	114.73 (12)	B11—B12—B7	61.07 (13)
B5—B4—S1	109.56 (13)	B8—B12—B10	110.17 (16)
B9—B4—S1	124.69 (13)	B9—B12—B10	59.20 (14)
B8—B4—S1	132.30 (14)	B11—B12—B10	58.54 (14)
C1—B4—Pd3	69.09 (9)	B7—B12—B10	107.51 (16)
B5—B4—Pd3	126.28 (12)	B8—B12—H12A	117.6
B9—B4—Pd3	122.55 (13)	B9—B12—H12A	122.5
B8—B4—Pd3	65.51 (10)	B11—B12—H12A	120.8
S1—B4—Pd3	106.64 (9)	B7—B12—H12A	120.4
C1—B5—B4	58.27 (11)	B10—B12—H12A	122.8
C1—B5—B9	103.23 (15)

B7—Pd3—P1—C11	86.05 (9)	B5—B4—B8—B9	−35.70 (14)
B8—Pd3—P1—C11	136.67 (9)	S1—B4—B8—B9	112.43 (19)
B4—Pd3—P1—C11	163.22 (11)	Pd3—B4—B8—B9	−156.93 (13)
C1—Pd3—P1—C11	54.47 (17)	C1—B4—B8—B7	0.92 (17)
Cl1—Pd3—P1—C11	−70.94 (7)	B5—B4—B8—B7	64.71 (17)
C2—Pd3—P1—C11	54.48 (9)	B9—B4—B8—B7	100.42 (15)
B7—Pd3—P1—C17	−155.09 (13)	S1—B4—B8—B7	−147.15 (15)
B8—Pd3—P1—C17	−104.47 (13)	Pd3—B4—B8—B7	−56.52 (11)
B4—Pd3—P1—C17	−77.92 (15)	C1—B4—B8—Pd3	57.44 (11)
C1—Pd3—P1—C17	173.33 (19)	B5—B4—B8—Pd3	121.23 (14)
Cl1—Pd3—P1—C17	47.93 (12)	B9—B4—B8—Pd3	156.93 (13)
C2—Pd3—P1—C17	173.35 (13)	S1—B4—B8—Pd3	−90.63 (16)
B7—Pd3—P1—C18	−35.07 (11)	C2—B7—B8—B4	−6.85 (19)
B8—Pd3—P1—C18	15.55 (11)	B12—B7—B8—B4	−100.42 (17)
B4—Pd3—P1—C18	42.10 (13)	B11—B7—B8—B4	−66.44 (17)
C1—Pd3—P1—C18	−66.65 (18)	Pd3—B7—B8—B4	59.37 (11)
Cl1—Pd3—P1—C18	167.95 (10)	C2—B7—B8—B12	93.57 (17)
C2—Pd3—P1—C18	−66.63 (11)	B11—B7—B8—B12	33.98 (15)
B7—Pd3—C1—C2	−33.57 (10)	Pd3—B7—B8—B12	159.79 (14)
P1—Pd3—C1—C2	0.0 (2)	C2—B7—B8—B9	53.67 (18)
B8—Pd3—C1—C2	−86.32 (10)	B12—B7—B8—B9	−39.90 (15)
B4—Pd3—C1—C2	−126.59 (13)	B11—B7—B8—B9	−5.92 (18)
Cl1—Pd3—C1—C2	124.77 (9)	Pd3—B7—B8—B9	119.89 (13)
B7—Pd3—C1—B4	93.01 (11)	C2—B7—B8—Pd3	−66.22 (12)
P1—Pd3—C1—B4	126.61 (15)	B12—B7—B8—Pd3	−159.79 (14)
B8—Pd3—C1—B4	40.27 (10)	B11—B7—B8—Pd3	−125.81 (14)
Cl1—Pd3—C1—B4	−108.64 (9)	B7—Pd3—B8—B4	−114.75 (14)
C2—Pd3—C1—B4	126.59 (13)	P1—Pd3—B8—B4	158.78 (8)
B7—Pd3—C1—B5	72.81 (15)	C1—Pd3—B8—B4	−38.14 (9)
P1—Pd3—C1—B5	106.40 (18)	Cl1—Pd3—B8—B4	41.72 (16)
B8—Pd3—C1—B5	20.06 (15)	C2—Pd3—B8—B4	−77.28 (10)
B4—Pd3—C1—B5	−20.21 (13)	B7—Pd3—B8—B12	−19.93 (15)
Cl1—Pd3—C1—B5	−128.85 (14)	P1—Pd3—B8—B12	−106.40 (15)
C2—Pd3—C1—B5	106.38 (17)	B4—Pd3—B8—B12	94.82 (18)
B7—Pd3—C1—B6	−8.72 (15)	C1—Pd3—B8—B12	56.68 (16)
P1—Pd3—C1—B6	24.9 (3)	Cl1—Pd3—B8—B12	136.54 (13)
B8—Pd3—C1—B6	−61.46 (16)	C2—Pd3—B8—B12	17.54 (15)
B4—Pd3—C1—B6	−101.73 (18)	B7—Pd3—B8—B9	−91.18 (17)
Cl1—Pd3—C1—B6	149.62 (15)	P1—Pd3—B8—B9	−177.65 (14)
C2—Pd3—C1—B6	24.85 (14)	B4—Pd3—B8—B9	23.57 (13)
B4—C1—C2—B11	59.5 (2)	C1—Pd3—B8—B9	−14.57 (14)
B5—C1—C2—B11	−8.1 (2)	Cl1—Pd3—B8—B9	65.3 (2)
B6—C1—C2—B11	−43.37 (15)	C2—Pd3—B8—B9	−53.71 (15)
Pd3—C1—C2—B11	115.66 (14)	P1—Pd3—B8—B7	−86.47 (9)
B4—C1—C2—B6	102.86 (16)	B4—Pd3—B8—B7	114.75 (14)
B5—C1—C2—B6	35.26 (15)	C1—Pd3—B8—B7	76.61 (10)
Pd3—C1—C2—B6	159.03 (11)	Cl1—Pd3—B8—B7	156.47 (10)
B4—C1—C2—B7	−10.7 (2)	C2—Pd3—B8—B7	37.47 (10)
B5—C1—C2—B7	−78.32 (17)	C1—B4—B9—B10	−4.4 (2)
B6—C1—C2—B7	−113.57 (16)	B5—B4—B9—B10	37.34 (16)
Pd3—C1—C2—B7	45.46 (12)	B8—B4—B9—B10	−104.29 (18)
B4—C1—C2—Pd3	−56.17 (12)	S1—B4—B9—B10	131.95 (16)
B5—C1—C2—Pd3	−123.78 (13)	Pd3—B4—B9—B10	−79.27 (19)
B6—C1—C2—Pd3	−159.03 (11)	C1—B4—B9—B5	−41.70 (14)
B7—Pd3—C2—C1	128.42 (14)	B8—B4—B9—B5	−141.63 (16)
P1—Pd3—C2—C1	−179.99 (7)	S1—B4—B9—B5	94.61 (17)
B8—Pd3—C2—C1	83.57 (10)	Pd3—B4—B9—B5	−116.61 (16)
B4—Pd3—C2—C1	35.69 (10)	C1—B4—B9—B12	59.82 (18)
Cl1—Pd3—C2—C1	−65.81 (10)	B5—B4—B9—B12	101.52 (17)
B7—Pd3—C2—B11	25.60 (15)	B8—B4—B9—B12	−40.11 (15)
P1—Pd3—C2—B11	77.19 (15)	S1—B4—B9—B12	−163.87 (15)
B8—Pd3—C2—B11	−19.25 (15)	Pd3—B4—B9—B12	−15.1 (2)
B4—Pd3—C2—B11	−67.13 (15)	C1—B4—B9—B8	99.93 (15)
C1—Pd3—C2—B11	−102.82 (17)	B5—B4—B9—B8	141.63 (16)
Cl1—Pd3—C2—B11	−168.63 (13)	S1—B4—B9—B8	−123.75 (17)
B7—Pd3—C2—B6	104.03 (18)	Pd3—B4—B9—B8	25.02 (13)
P1—Pd3—C2—B6	155.62 (13)	C1—B5—B9—B4	40.13 (13)
B8—Pd3—C2—B6	59.18 (16)	B10—B5—B9—B4	138.24 (17)
B4—Pd3—C2—B6	11.30 (15)	B6—B5—B9—B4	103.32 (16)
C1—Pd3—C2—B6	−24.39 (14)	C1—B5—B9—B10	−98.12 (16)
Cl1—Pd3—C2—B6	−90.20 (15)	B4—B5—B9—B10	−138.24 (17)
P1—Pd3—C2—B7	51.59 (11)	B6—B5—B9—B10	−34.92 (15)
B8—Pd3—C2—B7	−44.85 (11)	C1—B5—B9—B12	−57.32 (18)
B4—Pd3—C2—B7	−92.73 (11)	B4—B5—B9—B12	−97.44 (16)
C1—Pd3—C2—B7	−128.42 (14)	B10—B5—B9—B12	40.80 (16)
Cl1—Pd3—C2—B7	165.78 (10)	B6—B5—B9—B12	5.9 (2)
C17—P1—C11—C12	147.65 (19)	C1—B5—B9—B8	5.67 (19)
C18—P1—C11—C12	37.9 (2)	B4—B5—B9—B8	−34.46 (14)
Pd3—P1—C11—C12	−89.51 (17)	B10—B5—B9—B8	103.78 (17)
C17—P1—C11—C16	−37.1 (2)	B6—B5—B9—B8	68.86 (18)
C18—P1—C11—C16	−146.89 (18)	B12—B8—B9—B4	−133.76 (15)
Pd3—P1—C11—C16	85.73 (17)	B7—B8—B9—B4	−94.31 (14)
C16—C11—C12—C13	−0.4 (4)	Pd3—B8—B9—B4	−25.72 (14)
P1—C11—C12—C13	174.9 (2)	B4—B8—B9—B10	98.88 (17)
C11—C12—C13—C14	0.1 (4)	B12—B8—B9—B10	−34.88 (16)
C12—C13—C14—C15	0.3 (4)	B7—B8—B9—B10	4.57 (19)
C13—C14—C15—C16	−0.5 (4)	Pd3—B8—B9—B10	73.15 (19)
C14—C15—C16—C11	0.2 (4)	B4—B8—B9—B5	34.47 (14)
C12—C11—C16—C15	0.2 (3)	B12—B8—B9—B5	−99.29 (17)
P1—C11—C16—C15	−175.09 (19)	B7—B8—B9—B5	−59.84 (18)
C2—C1—B4—B5	−100.15 (17)	Pd3—B8—B9—B5	8.7 (2)
B6—C1—B4—B5	−33.26 (15)	B4—B8—B9—B12	133.76 (15)
Pd3—C1—B4—B5	−161.42 (12)	B7—B8—B9—B12	39.45 (14)
C2—C1—B4—B9	−58.13 (19)	Pd3—B8—B9—B12	108.03 (17)
B5—C1—B4—B9	42.02 (14)	C2—B6—B10—B11	−38.99 (15)
B6—C1—B4—B9	8.8 (2)	C1—B6—B10—B11	−94.22 (16)
Pd3—C1—B4—B9	−119.40 (13)	B5—B6—B10—B11	−135.86 (17)
C2—C1—B4—B8	6.1 (2)	C2—B6—B10—B9	61.3 (2)
B5—C1—B4—B8	106.23 (16)	B11—B6—B10—B9	100.32 (19)
B6—C1—B4—B8	72.97 (18)	C1—B6—B10—B9	6.1 (2)
Pd3—C1—B4—B8	−55.19 (11)	B5—B6—B10—B9	−35.54 (16)
C2—C1—B4—S1	160.58 (13)	C2—B6—B10—B5	96.87 (16)
B5—C1—B4—S1	−99.28 (15)	B11—B6—B10—B5	135.86 (17)
B6—C1—B4—S1	−132.54 (14)	C1—B6—B10—B5	41.64 (14)
Pd3—C1—B4—S1	99.30 (11)	C2—B6—B10—B12	−1.7 (2)
C2—C1—B4—Pd3	61.27 (13)	B11—B6—B10—B12	37.32 (16)
B5—C1—B4—Pd3	161.42 (12)	C1—B6—B10—B12	−56.90 (19)
B6—C1—B4—Pd3	128.16 (14)	B5—B6—B10—B12	−98.54 (17)
C3—S1—B4—C1	−128.38 (15)	B4—B9—B10—B11	62.0 (2)
C4—S1—B4—C1	125.91 (14)	B5—B9—B10—B11	99.10 (17)
C3—S1—B4—B5	166.21 (14)	B12—B9—B10—B11	−35.58 (16)
C4—S1—B4—B5	60.50 (15)	B8—B9—B10—B11	−1.4 (2)
C3—S1—B4—B9	98.68 (18)	B4—B9—B10—B6	−1.3 (2)
C4—S1—B4—B9	−7.03 (19)	B5—B9—B10—B6	35.75 (16)
C3—S1—B4—B8	17.6 (2)	B12—B9—B10—B6	−98.93 (19)
C4—S1—B4—B8	−88.1 (2)	B8—B9—B10—B6	−64.8 (2)
C3—S1—B4—Pd3	−54.19 (12)	B4—B9—B10—B5	−37.08 (15)
C4—S1—B4—Pd3	−159.90 (11)	B12—B9—B10—B5	−134.68 (16)
B7—Pd3—B4—C1	−74.14 (10)	B8—B9—B10—B5	−100.51 (16)
P1—Pd3—B4—C1	−157.01 (7)	B4—B9—B10—B12	97.60 (17)
B8—Pd3—B4—C1	−119.84 (13)	B5—B9—B10—B12	134.68 (16)
Cl1—Pd3—B4—C1	81.53 (9)	B8—B9—B10—B12	34.17 (15)
C2—Pd3—B4—C1	−31.36 (8)	C1—B5—B10—B11	−4.4 (2)
B7—Pd3—B4—B5	−54.07 (16)	B4—B5—B10—B11	−65.0 (2)
P1—Pd3—B4—B5	−136.94 (12)	B9—B5—B10—B11	−102.01 (19)
B8—Pd3—B4—B5	−99.77 (18)	B6—B5—B10—B11	38.81 (16)
C1—Pd3—B4—B5	20.07 (13)	C1—B5—B10—B6	−43.20 (14)
Cl1—Pd3—B4—B5	101.60 (15)	B4—B5—B10—B6	−103.78 (17)
C2—Pd3—B4—B5	−11.29 (14)	B9—B5—B10—B6	−140.82 (17)
B7—Pd3—B4—B9	21.59 (15)	C1—B5—B10—B9	97.62 (16)
P1—Pd3—B4—B9	−61.28 (18)	B4—B5—B10—B9	37.04 (15)
B8—Pd3—B4—B9	−24.11 (14)	B6—B5—B10—B9	140.82 (17)
C1—Pd3—B4—B9	95.73 (17)	C1—B5—B10—B12	58.14 (19)
Cl1—Pd3—B4—B9	177.26 (13)	B4—B5—B10—B12	−2.4 (2)
C2—Pd3—B4—B9	64.37 (14)	B9—B5—B10—B12	−39.48 (15)
B7—Pd3—B4—B8	45.70 (11)	B6—B5—B10—B12	101.34 (18)
P1—Pd3—B4—B8	−37.17 (14)	C1—C2—B11—B6	45.01 (15)
C1—Pd3—B4—B8	119.84 (13)	B7—C2—B11—B6	143.45 (16)
Cl1—Pd3—B4—B8	−158.63 (9)	Pd3—C2—B11—B6	119.04 (15)
C2—Pd3—B4—B8	88.48 (10)	C1—C2—B11—B10	4.9 (2)
B7—Pd3—B4—S1	175.18 (11)	B6—C2—B11—B10	−40.14 (16)
P1—Pd3—B4—S1	92.31 (11)	B7—C2—B11—B10	103.31 (17)
B8—Pd3—B4—S1	129.47 (14)	Pd3—C2—B11—B10	78.90 (19)
C1—Pd3—B4—S1	−110.68 (12)	C1—C2—B11—B12	−59.2 (2)
Cl1—Pd3—B4—S1	−29.16 (9)	B6—C2—B11—B12	−104.19 (18)
C2—Pd3—B4—S1	−142.05 (10)	B7—C2—B11—B12	39.26 (16)
C2—C1—B5—B4	110.08 (15)	Pd3—C2—B11—B12	14.9 (2)
B6—C1—B5—B4	144.89 (16)	C1—C2—B11—B7	−98.44 (16)
Pd3—C1—B5—B4	21.29 (14)	B6—C2—B11—B7	−143.45 (16)
C2—C1—B5—B9	69.28 (17)	Pd3—C2—B11—B7	−24.41 (13)
B4—C1—B5—B9	−40.79 (13)	B10—B6—B11—C2	−134.27 (16)
B6—C1—B5—B9	104.10 (16)	C1—B6—B11—C2	−35.39 (12)
Pd3—C1—B5—B9	−19.5 (2)	B5—B6—B11—C2	−95.00 (15)
C2—C1—B5—B10	7.56 (19)	C2—B6—B11—B10	134.27 (16)
B4—C1—B5—B10	−102.52 (16)	C1—B6—B11—B10	98.88 (15)
B6—C1—B5—B10	42.38 (15)	B5—B6—B11—B10	39.28 (15)
Pd3—C1—B5—B10	−81.23 (17)	C2—B6—B11—B12	95.58 (17)
C2—C1—B5—B6	−34.82 (15)	B10—B6—B11—B12	−38.69 (16)
B4—C1—B5—B6	−144.89 (16)	C1—B6—B11—B12	60.19 (19)
Pd3—C1—B5—B6	−123.61 (15)	B5—B6—B11—B12	0.6 (2)
B9—B4—B5—C1	−132.47 (15)	C2—B6—B11—B7	31.88 (14)
B8—B4—B5—C1	−96.52 (15)	B10—B6—B11—B7	−102.40 (17)
S1—B4—B5—C1	107.96 (13)	C1—B6—B11—B7	−3.52 (18)
Pd3—B4—B5—C1	−21.67 (14)	B5—B6—B11—B7	−63.12 (19)
C1—B4—B5—B9	132.47 (15)	B6—B10—B11—C2	39.44 (14)
B8—B4—B5—B9	35.95 (15)	B9—B10—B11—C2	−63.1 (2)
S1—B4—B5—B9	−119.57 (14)	B5—B10—B11—C2	0.2 (2)
Pd3—B4—B5—B9	110.80 (16)	B12—B10—B11—C2	−98.51 (17)
C1—B4—B5—B10	95.29 (16)	B9—B10—B11—B6	−102.52 (17)
B9—B4—B5—B10	−37.18 (15)	B5—B10—B11—B6	−39.28 (16)
B8—B4—B5—B10	−1.2 (2)	B12—B10—B11—B6	−137.95 (16)
S1—B4—B5—B10	−156.75 (13)	B6—B10—B11—B12	137.95 (16)
Pd3—B4—B5—B10	73.63 (19)	B9—B10—B11—B12	35.43 (15)
C1—B4—B5—B6	32.37 (14)	B5—B10—B11—B12	98.67 (18)
B9—B4—B5—B6	−100.10 (18)	B6—B10—B11—B7	99.93 (17)
B8—B4—B5—B6	−64.14 (19)	B9—B10—B11—B7	−2.6 (2)
S1—B4—B5—B6	140.33 (14)	B5—B10—B11—B7	60.7 (2)
Pd3—B4—B5—B6	10.7 (2)	B12—B10—B11—B7	−38.02 (15)
C1—C2—B6—B11	−134.83 (15)	B12—B7—B11—C2	135.01 (16)
B7—C2—B6—B11	−37.84 (16)	B8—B7—B11—C2	101.62 (15)
Pd3—C2—B6—B11	−110.74 (16)	Pd3—B7—B11—C2	30.37 (16)
C1—C2—B6—B10	−94.88 (16)	C2—B7—B11—B6	−32.36 (14)
B11—C2—B6—B10	39.96 (15)	B12—B7—B11—B6	102.65 (18)
B7—C2—B6—B10	2.1 (2)	B8—B7—B11—B6	69.26 (18)
Pd3—C2—B6—B10	−70.78 (19)	Pd3—B7—B11—B6	−2.0 (2)
B11—C2—B6—C1	134.83 (15)	C2—B7—B11—B10	−96.28 (18)
B7—C2—B6—C1	96.99 (16)	B12—B7—B11—B10	38.73 (16)
Pd3—C2—B6—C1	24.10 (13)	B8—B7—B11—B10	5.3 (2)
C1—C2—B6—B5	−32.59 (14)	Pd3—B7—B11—B10	−65.9 (2)
B11—C2—B6—B5	102.25 (17)	C2—B7—B11—B12	−135.01 (16)
B7—C2—B6—B5	64.4 (2)	B8—B7—B11—B12	−33.39 (14)
Pd3—C2—B6—B5	−8.5 (2)	Pd3—B7—B11—B12	−104.63 (19)
B4—C1—B6—C2	−108.48 (16)	B4—B8—B12—B9	−39.74 (14)
B5—C1—B6—C2	−141.89 (16)	B7—B8—B12—B9	−134.00 (16)
Pd3—C1—B6—C2	−28.26 (15)	Pd3—B8—B12—B9	−112.94 (16)
C2—C1—B6—B11	37.72 (13)	B4—B8—B12—B11	57.6 (2)
B4—C1—B6—B11	−70.76 (18)	B9—B8—B12—B11	97.32 (19)
B5—C1—B6—B11	−104.18 (16)	B7—B8—B12—B11	−36.68 (17)
Pd3—C1—B6—B11	9.5 (2)	Pd3—B8—B12—B11	−15.6 (2)
C2—C1—B6—B10	99.13 (17)	B4—B8—B12—B7	94.26 (15)
B4—C1—B6—B10	−9.3 (2)	B9—B8—B12—B7	134.00 (16)
B5—C1—B6—B10	−42.76 (15)	Pd3—B8—B12—B7	21.06 (15)
Pd3—C1—B6—B10	70.9 (2)	B4—B8—B12—B10	−5.9 (2)
C2—C1—B6—B5	141.89 (16)	B9—B8—B12—B10	33.84 (15)
B4—C1—B6—B5	33.42 (15)	B7—B8—B12—B10	−100.16 (17)
Pd3—C1—B6—B5	113.64 (17)	Pd3—B8—B12—B10	−79.1 (2)
C1—B5—B6—C2	30.66 (13)	B4—B9—B12—B8	40.11 (14)
B4—B5—B6—C2	−0.8 (2)	B10—B9—B12—B8	142.52 (16)
B9—B5—B6—C2	−64.40 (18)	B5—B9—B12—B8	102.30 (16)
B10—B5—B6—C2	−99.61 (17)	B4—B9—B12—B11	−67.63 (19)
C1—B5—B6—B11	91.04 (16)	B10—B9—B12—B11	34.78 (15)
B4—B5—B6—B11	59.6 (2)	B5—B9—B12—B11	−5.4 (2)
B9—B5—B6—B11	−4.0 (2)	B8—B9—B12—B11	−107.74 (17)
B10—B5—B6—B11	−39.23 (16)	B4—B9—B12—B7	−3.0 (2)
C1—B5—B6—B10	130.27 (16)	B10—B9—B12—B7	99.42 (18)
B4—B5—B6—B10	98.79 (18)	B5—B9—B12—B7	59.2 (2)
B9—B5—B6—B10	35.21 (16)	B8—B9—B12—B7	−43.10 (15)
B4—B5—B6—C1	−31.47 (14)	B4—B9—B12—B10	−102.41 (16)
B9—B5—B6—C1	−95.06 (15)	B5—B9—B12—B10	−40.22 (15)
B10—B5—B6—C1	−130.27 (16)	B8—B9—B12—B10	−142.52 (16)
C1—C2—B7—B12	70.10 (17)	C2—B11—B12—B8	−0.3 (2)
B11—C2—B7—B12	−38.35 (15)	B6—B11—B12—B8	−62.0 (2)
B6—C2—B7—B12	−1.6 (2)	B10—B11—B12—B8	−100.07 (19)
Pd3—C2—B7—B12	117.90 (14)	B7—B11—B12—B8	37.76 (17)
C1—C2—B7—B11	108.45 (16)	C2—B11—B12—B9	64.7 (2)
B6—C2—B7—B11	36.79 (16)	B6—B11—B12—B9	3.0 (2)
Pd3—C2—B7—B11	156.26 (13)	B10—B11—B12—B9	−35.06 (15)
C1—C2—B7—B8	10.50 (19)	B7—B11—B12—B9	102.77 (17)
B11—C2—B7—B8	−97.96 (17)	C2—B11—B12—B7	−38.09 (14)
B6—C2—B7—B8	−61.2 (2)	B6—B11—B12—B7	−99.73 (17)
Pd3—C2—B7—B8	58.30 (11)	B10—B11—B12—B7	−137.83 (16)
C1—C2—B7—Pd3	−47.80 (12)	C2—B11—B12—B10	99.74 (17)
B11—C2—B7—Pd3	−156.26 (13)	B6—B11—B12—B10	38.09 (15)
B6—C2—B7—Pd3	−119.47 (14)	B7—B11—B12—B10	137.83 (16)
P1—Pd3—B7—C2	−140.21 (9)	C2—B7—B12—B8	−104.01 (15)
B8—Pd3—B7—C2	117.34 (14)	B11—B7—B12—B8	−141.25 (16)
B4—Pd3—B7—C2	75.36 (10)	Pd3—B7—B12—B8	−21.14 (15)
C1—Pd3—B7—C2	30.71 (9)	C2—B7—B12—B9	−62.36 (19)
Cl1—Pd3—B7—C2	−32.3 (2)	B11—B7—B12—B9	−99.60 (18)
P1—Pd3—B7—B12	122.00 (15)	B8—B7—B12—B9	41.65 (15)
B8—Pd3—B7—B12	19.56 (14)	Pd3—B7—B12—B9	20.5 (2)
B4—Pd3—B7—B12	−22.43 (15)	C2—B7—B12—B11	37.24 (14)
C1—Pd3—B7—B12	−67.08 (16)	B8—B7—B12—B11	141.25 (16)
Cl1—Pd3—B7—B12	−130.07 (15)	Pd3—B7—B12—B11	120.11 (17)
C2—Pd3—B7—B12	−97.79 (19)	C2—B7—B12—B10	0.3 (2)
P1—Pd3—B7—B11	−165.81 (16)	B11—B7—B12—B10	−36.91 (15)
B8—Pd3—B7—B11	91.74 (19)	B8—B7—B12—B10	104.34 (17)
B4—Pd3—B7—B11	49.76 (17)	Pd3—B7—B12—B10	83.20 (19)
C1—Pd3—B7—B11	5.11 (16)	B11—B10—B12—B8	105.86 (17)
Cl1—Pd3—B7—B11	−57.9 (3)	B6—B10—B12—B8	68.7 (2)
C2—Pd3—B7—B11	−25.60 (14)	B9—B10—B12—B8	−34.45 (15)
P1—Pd3—B7—B8	102.45 (9)	B5—B10—B12—B8	5.3 (2)
B4—Pd3—B7—B8	−41.98 (10)	B11—B10—B12—B9	140.31 (16)
C1—Pd3—B7—B8	−86.63 (10)	B6—B10—B12—B9	103.12 (17)
Cl1—Pd3—B7—B8	−149.63 (13)	B5—B10—B12—B9	39.74 (15)
C2—Pd3—B7—B8	−117.34 (14)	B6—B10—B12—B11	−37.19 (15)
C1—B4—B8—B12	−59.40 (17)	B9—B10—B12—B11	−140.31 (16)
B5—B4—B8—B12	4.40 (19)	B5—B10—B12—B11	−100.57 (17)
B9—B4—B8—B12	40.10 (14)	B11—B10—B12—B7	38.04 (15)
S1—B4—B8—B12	152.54 (16)	B6—B10—B12—B7	0.8 (2)
Pd3—B4—B8—B12	−116.83 (14)	B9—B10—B12—B7	−102.28 (17)
C1—B4—B8—B9	−99.50 (15)	B5—B10—B12—B7	−62.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl1ⁱ	1.10	2.60	3.540 (2)	142

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Pd(C₄H₁₆B₉S)I(C₁₈H₁₅P)]	[Pd(C₄H₁₆B₉S)Cl(C₈H₁₁P)]
M_r	689.12	473.54
Crystal system, space group	Orthorhombic, Pbca	Monoclinic, P2₁/n
Temperature (K)	294	294
a, b, c (Å)	10.9576 (5), 16.8316 (10), 30.2015 (17)	12.8117 (8), 9.2670 (7), 18.2948 (10)
α, β, γ (°)	90, 90, 90	90, 96.567 (5), 90
V (Å³)	5570.2 (5)	2157.8 (2)
Z	8	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	1.92	1.15
Crystal size (mm)	0.20 × 0.15 × 0.15	0.33 × 0.25 × 0.25

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (ABSCOR in NRCVAX; Gabe et al., 1989)	ψ scan (ABSCOR in NRCVAX; Gabe et al., 1989)
T_min, T_max	0.708, 0.751	0.684, 0.760
No. of measured, independent and observed [I > 2σ(I)] reflections	6057, 6057, 3546	6506, 6265, 5023
R_int	0.0	0.020
(sin θ/λ)_max (Å⁻¹)	0.638	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.162, 1.00	0.024, 0.064, 1.03
No. of reflections	6057	6265
No. of parameters	318	231
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.29, −1.93	0.70, −0.51

Computer programs: DIFRAC (Gabe & White, 1993) with profile analysis, DIFRAC (Gabe & White, 1993), DATRD2 in NRCVAX94 (Gabe et al., 1989), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997) in WinGX (Version 1.70.01; Farrugia, 1999), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected bond distances (Å) and angles (°) for compounds (I) and (II). X = I1 in (I) and Cl1 in (II) top

Parameter	(I)	(II)
Pd3-X	2.6739 (7)	2.3751 (5)
Pd3-P1	2.2507 (17)	2.2275 (5)
Pd3-C1	2.274 (6)	2.304 (2)
Pd3-C2	2.467 (6)	2.478 (2)
Pd3-B4	2.315 (7)	2.278 (2)
Pd3-B7	2.269 (8)	2.212 (2)
Pd3-B8	2.254 (7)	2.229 (2)
S1-B4	1.899 (7)	1.896 (2)
C1-C2	1.584 (9)	1.561 (2)
C1-B4	1.693 (8)	1.697 (3)
C2-B7	1.644 (10)	1.686 (3)
B4-B8	1.766 (10)	1.764 (3)
X-Pd3-P1	95.06 (5)	92.00 (2)
X-Pd3-C1	90.64 (16)	97.52 (5)
X-Pd3-C2	106.07 (16)	116.77 (5)
X-Pd3-B4	110.47 (16)	108.25 (5)
X-Pd3-B7	143.2 (2)	148.67 (6)
X-Pd3-B8	155.09 (19)	148.67 (6)
P1-Pd3-C1	169.28 (16)	163.51 (5)
P1-Pd3-C2	130.57 (16)	125.64 (4)
P1-Pd3-B4	140.80 (16)	144.32 (5)
P1-Pd3-B7	100.3 (2)	95.72 (6)
P1-Pd3-B8	102.97 (19)	103.23 (6)
Pd3-B4-S1	104.2 (3)	106.64 (9)

Hydrogen bond parameters (Å, °) for compounds (I) and (II) top

Compound	D—H···A	D—H	H···A	D···A	D—H···A
(I)	C16-H16···I1	0.86	2.98	3.831 (9)	153
(II)	C2-H2···Cl1ⁱ	0.86	2.60	3.540 (2)	142

Symmetry code: (i) 1 − x, 1 − y, −z.

Acknowledgements

JDK thanks the UK EPSRC for instrument support, and Dr B. Stibr for his friendly interest and for a sample of Tl[9-SMe₂-7,8-nido-C₂B₉H₁₀].

References

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ISSN: 2053-2296

Volume 61| Part 8| August 2005| Pages m393-m396

doi:10.1107/S0108270105022286

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