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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 4| April 2012| Page m404
doi:10.1107/S1600536812010100

trans-Di­chloridobis[di­cyclo­hex­yl(phen­yl)phosphane-κP]palladium(II)

Andrew R. Burgoyne,a Reinout Meijbooma* and Hezron Ogutua

aResearch Centre for Synthesis and Catalysis, Department of Chemistry, University of Johannesburg, PO Box 524 Auckland Park, Johannesburg 2006, South Africa
*Correspondence e-mail: rmeijboom@uj.ac.za

(Received 21 February 2012; accepted 7 March 2012; online 10 March 2012)

The title compound, [PdCl2{P(C6H11)2(C6H5)}2], forms a monomeric complex with a trans-square-planar geometry. The Pd—P bond lengths are 2.3343 (5) Å, as the Pd atom lies on an inversion centre, while the Pd—Cl bond lengths are 2.3017 (4) Å. The observed structure was found to be closely related to [PdCl2{P(C6H11)3}2] [Grushin et al. (1994[Grushin, V. V., Bensimon, C. & Alper, H. (1994). Inorg. Chem. 33, 4804-4806.]). Inorg. Chem. 33, 4804–4806], [PdBr2{P(C6H11)3}2] [Clarke et al. (2003[Clarke, M. L., Orpen, A. G., Pringle, P. G. & Turley, E. (2003). Dalton Trans. pp. 4393-4394.]). Dalton Trans. pp. 4393–4394] and [PdCl2P(C6H11)2(C7H7)}2] [Vuoti et al. (2008[Vuoti, S., Autio, J., Laitila, M., Haukka, M. & Pursiainen, J. (2008). Eur. J. Inorg. Chem. pp. 397-407.]). Eur. J. Inorg. Chem. pp. 397–407] (C6H11 is cyclo­hexyl and C7H7 is o-tol­yl). One of the cyclo­hexyl rings is disordered with the phenyl ring in a 0.587 (9):413 (9) ratio. Five long-range C—H⋯Cl inter­actions were observed within the structure.

Related literature

For a review on related compounds, see: Spessard & Miessler (1996[Spessard, G. O. & Miessler, G. L. (1996). Organometallic Chemistry, pp. 131-135. Upper Saddle River, New Jersey: Prentice Hall.]). For the synthesis of the starting materials, see: Drew & Doyle (1990[Drew, D. & Doyle, J. R. (1990). Inorg. Synth. 28, 346-349.]). For similar R-P2PdCl2 compounds, see: Ogutu & Meijboom (2011[Ogutu, H. & Meijboom, R. (2011). Acta Cryst. E67, m1662.]); Muller & Meijboom (2010a[Muller, A. & Meijboom, R. (2010a). Acta Cryst. E66, m1420.],b[Muller, A. & Meijboom, R. (2010b). Acta Cryst. E66, m1463.]). For their applications, see: Bedford et al. (2004[Bedford, R. B., Cazin, C. S. J. & Holder, D. (2004). Coord. Chem. Rev. 248, 2283-2321.]).

[Scheme 1]

Experimental

Crystal data

  • [PdCl2(C18H27P)2]

  • Mr = 726.03

  • Triclinic, [P \overline 1]

  • a = 9.439 (4) Å

  • b = 10.095 (4) Å

  • c = 10.623 (5) Å

  • α = 113.115 (2)°

  • β = 107.321 (2)°

  • γ = 91.625 (2)°

  • V = 876.5 (7) Å3

  • Z = 1

  • Mo Kα radiation

  • μ = 0.80 mm−1

  • T = 100 K

  • 0.27 × 0.13 × 0.11 mm
Data collection

  • Bruker X8 APEXII 4K KappaCCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2007[Bruker (2007). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.885, Tmax = 0.918

  • 12144 measured reflections

  • 2931 independent reflections

  • 2891 reflections with I > 2σ(I)

  • Rint = 0.024
Refinement

  • R[F2 > 2σ(F2)] = 0.021

  • wR(F2) = 0.051

  • S = 1.19

  • 2931 reflections

  • 266 parameters

  • 12 restraints

  • H-atom parameters constrained

  • Δρmax = 0.37 e Å−3

  • Δρmin = −0.38 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C8—H8B⋯Cl1 0.97 2.91 3.559 (2) 125
C5—H5⋯Cl1i 0.93 2.94 3.619 (7) 131
C13—H13⋯Cl1ii 0.98 2.68 3.254 (11) 118
C18—H18B⋯Cl1ii 0.97 2.97 3.542 (13) 119
C15—H15A⋯Cl1iii 0.97 3.02 3.800 (8) 139
Symmetry codes: (i) -x+2, -y, -z+1; (ii) -x+2, -y, -z+2; (iii) x-1, y, z.

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2007[Bruker (2007). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus and XPREP (Bruker, 2007[Bruker (2007). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg & Putz, 2005[Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812010100/zl2455sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812010100/zl2455Isup2.hkl

checkCIF report


Comment top

Complexes involving palladium metal centres are amongst some of the most popular catalytic precursors in organic synthesis due to their catalytic abilities. They are used in carbon-carbon bond formation reactions like the Heck, Stille and Suzuki reactions (Bedford et al., 2004).

[PdCl2(L)2] (L = tertiary phosphine, arsine or stibine) complexes can conveniently be prepared by the substitution of 1,5-cyclooctadiene (COD) from [PdCl2(COD)]. The title compound, trans-[PdCl2(C18H27P)2], crystallizes with the Pd atom on a center of symmetry and each pair of equivalent ligands in a mutually trans orientation. The geometry is, therefore, slightly distorted square planar and the Pd atom is not elevated out of the coordinating atom plane. All angles in the coordination polyhedron are close to the ideal value of 90°, with P—Pd—Cl = 89.296 (16)° and P—Pd—Cli = 90.704 (16)°. As required by the crystallographic symmetry, the P—Pd—Pi and Cl—Pd—Cli angles are 180°. The symmetry code used to define atoms through the inversion point is: (iv) 2 - x, -y, 2 - z.

One of the cyclohexyl rings, C13–C18, in the title compound is disordered with the phenyl ring, C1–C6, over the same positions in a 59:41 (9) occupancy ratio.

The title compound compares well with other closely related PdII complexes from the literature containing two chloro and two tertiary phosphine ligands in a trans geometry (Muller & Meijboom, 2010a, b). The title compound, having a Pd—Cl bond length of 2.3017 (4) Å and a Pd—P bond length of 2.3343 (5) Å, fits well into the typical range for complexes of this kind. Notably the title compound did not crystallize as a solvated complex; these type of PdII complexes have a tendency to crystallize as solvates (Ogutu & Meijboom, 2011).

Due to the disorder of the cyclohexyl ring and phenyl ring, the crystilline structure for the title compound forms an isostructure with a variety of [PdCl2(PR3)2] compounds (R = any combination of aryl and cylcohexyl rings). Notably, the title compound is quintessentially isostructural with: [PdCl2{P(C6H11)3}2] (Grushin et al., 1994); [PdBr2{P(C6H11)3}2] (Clarke et al., 2003); and [PdCl2{P(C6H11)2(C7H7)}2] (Vuoti et al., 2008) ((C6H11) = cyclohexyl, (C7H7) = o-tolyl). The Pd–P and Pd–X (X = Br and Cl) bond lengths were compared and it was observed that they were all within the same range of 2.3–2.4 Å. The angles between the bonds around the Pd atom were all observed to be approximately right angles.

A weak hydrogen bond exists between C13—H13···Cl1i (Symmetry code: -x + 2, -y, -z + 2) with the distance listed in Table 1. Four other longer range hydrogen interactions exist as shown in Table 1.

Related literature top

For a review on related compounds, see: Spessard & Miessler (1996). For the synthesis of the starting materials, see: Drew & Doyle (1990). For similar R-P2PdCl2 compounds, see: Ogutu & Meijboom (2011); Muller & Meijboom (2010a,b). For their applications, see: Bedford et al. (2004).

Experimental top

Dicyclohexylphenylphosphine (0.05 g, 0.35 mmol) was dissolved in acetone (5 cm3). A solution of [Pd(COD)Cl2] (0.05 g, 0.17 mmol) in acetone (5 cm3) was added to the phosphine solution. The mixture was stirred for 5 minutes, after which the solution was left to crystallize. Yellow crystals of the title compound were obtained. 1H NMR (CDCl3, 400 MHz, p.p.m.): 7.6–7.5 (m, 4H), 7.4 (m, 6H), 2.6 (t, 4H), 2.1 (d, 4H), 1.8–1.7 (m, 10H), 1.4–1.2 (m, 20H), 1.1–1.0 (m, 6H). 31P{H} NMR (CDCl3, 162.0 MHz, p.p.m.): 28.05. IR (cm-1): 2925, 2849, 2161, 2023, 1977, 1446, 1433, 1261, 1109, 1011, 848, 773, 700 and 690.

Refinement top

The undisordered quintessential cyclohexyl ring, C7–C12, was used to model the disordered cyclohexyl ring, C1B–C6B, by restraining the two rings to have similar bond lengths and 1,3 atom distances within a standard deviation of 0.02 Å. (SAME command in Shelxtl, Sheldrick, 2008). Atoms C1 and C1B, the two ipso–carbons for the disordered phenyl and dicyclohexyl rings, were constrained to have identical ADPs. The phenyl ring has been constrained to resemble an ideal hexagon with C—C distances of 1.39 Å All hydrogen atoms were positioned geometrically with C—H = 0.98 Å for H atoms bonded to tertiary C atoms, 0.97 Å for methylene H atoms, and 0.93 Å for aromatic H atoms. . All hydrogen atoms were allowed to ride on their parent atoms with Uiso(H) = 1.2Ueq(C). The remaining highest electron peak was 0.37 at 0.95 Å from P1 and the deepest hole was -0.38 at 0.92 Å from Pd1.

Structure description top

Complexes involving palladium metal centres are amongst some of the most popular catalytic precursors in organic synthesis due to their catalytic abilities. They are used in carbon-carbon bond formation reactions like the Heck, Stille and Suzuki reactions (Bedford et al., 2004).

[PdCl2(L)2] (L = tertiary phosphine, arsine or stibine) complexes can conveniently be prepared by the substitution of 1,5-cyclooctadiene (COD) from [PdCl2(COD)]. The title compound, trans-[PdCl2(C18H27P)2], crystallizes with the Pd atom on a center of symmetry and each pair of equivalent ligands in a mutually trans orientation. The geometry is, therefore, slightly distorted square planar and the Pd atom is not elevated out of the coordinating atom plane. All angles in the coordination polyhedron are close to the ideal value of 90°, with P—Pd—Cl = 89.296 (16)° and P—Pd—Cli = 90.704 (16)°. As required by the crystallographic symmetry, the P—Pd—Pi and Cl—Pd—Cli angles are 180°. The symmetry code used to define atoms through the inversion point is: (iv) 2 - x, -y, 2 - z.

One of the cyclohexyl rings, C13–C18, in the title compound is disordered with the phenyl ring, C1–C6, over the same positions in a 59:41 (9) occupancy ratio.

The title compound compares well with other closely related PdII complexes from the literature containing two chloro and two tertiary phosphine ligands in a trans geometry (Muller & Meijboom, 2010a, b). The title compound, having a Pd—Cl bond length of 2.3017 (4) Å and a Pd—P bond length of 2.3343 (5) Å, fits well into the typical range for complexes of this kind. Notably the title compound did not crystallize as a solvated complex; these type of PdII complexes have a tendency to crystallize as solvates (Ogutu & Meijboom, 2011).

Due to the disorder of the cyclohexyl ring and phenyl ring, the crystilline structure for the title compound forms an isostructure with a variety of [PdCl2(PR3)2] compounds (R = any combination of aryl and cylcohexyl rings). Notably, the title compound is quintessentially isostructural with: [PdCl2{P(C6H11)3}2] (Grushin et al., 1994); [PdBr2{P(C6H11)3}2] (Clarke et al., 2003); and [PdCl2{P(C6H11)2(C7H7)}2] (Vuoti et al., 2008) ((C6H11) = cyclohexyl, (C7H7) = o-tolyl). The Pd–P and Pd–X (X = Br and Cl) bond lengths were compared and it was observed that they were all within the same range of 2.3–2.4 Å. The angles between the bonds around the Pd atom were all observed to be approximately right angles.

A weak hydrogen bond exists between C13—H13···Cl1i (Symmetry code: -x + 2, -y, -z + 2) with the distance listed in Table 1. Four other longer range hydrogen interactions exist as shown in Table 1.

For a review on related compounds, see: Spessard & Miessler (1996). For the synthesis of the starting materials, see: Drew & Doyle (1990). For similar R-P2PdCl2 compounds, see: Ogutu & Meijboom (2011); Muller & Meijboom (2010a,b). For their applications, see: Bedford et al. (2004).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus and XPREP (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The structure of the trans-dichlorobis (dicyclohexylphenylphosphine)palladium(II) showing 50% probability displacement ellipsoids. Symmetry code to generate molecule through inversiont point: (iv) 2 - x, -y, 2 - z. Disordered and hydrogen atoms were omitted for clarity.
[Figure 2] Fig. 2. The structure of the disordered cyclohexyl and phenyl rings in trans-dichlorobis(dicyclohexylphenylphosphine)palladium(II), with the lower occupancy atoms shown in blue.
trans-Dichloridobis[dicyclohexyl(phenyl)phosphane- κP]palladium(II) top
Crystal data top
[PdCl2(C18H27P)2]Z = 1
Mr = 726.03F(000) = 380
Triclinic, P1Dx = 1.375 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 9.439 (4) ÅCell parameters from 9929 reflections
b = 10.095 (4) Åθ = 2.2–24.9°
c = 10.623 (5) ŵ = 0.80 mm−1
α = 113.115 (2)°T = 100 K
β = 107.321 (2)°Conical, yellow
γ = 91.625 (2)°0.27 × 0.13 × 0.11 mm
V = 876.5 (7) Å3
Data collection top
Bruker X8 APEXII 4K KappaCCD
diffractometer		2931 independent reflections
Radiation source: fine-focus sealed tube2891 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
φ and ω scansθmax = 24.9°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)		h = −10→11
Tmin = 0.885, Tmax = 0.918k = −11→11
12144 measured reflectionsl = −11→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.051H-atom parameters constrained
S = 1.19 w = 1/[σ2(Fo2) + (0.0125P)2 + 0.5911P]
where P = (Fo2 + 2Fc2)/3
2931 reflections(Δ/σ)max = 0.001
266 parametersΔρmax = 0.37 e Å−3
12 restraintsΔρmin = −0.38 e Å−3
Crystal data top
[PdCl2(C18H27P)2]γ = 91.625 (2)°
Mr = 726.03V = 876.5 (7) Å3
Triclinic, P1Z = 1
a = 9.439 (4) ÅMo Kα radiation
b = 10.095 (4) ŵ = 0.80 mm−1
c = 10.623 (5) ÅT = 100 K
α = 113.115 (2)°0.27 × 0.13 × 0.11 mm
β = 107.321 (2)°
Data collection top
Bruker X8 APEXII 4K KappaCCD
diffractometer		2931 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)		2891 reflections with I > 2σ(I)
Tmin = 0.885, Tmax = 0.918Rint = 0.024
12144 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02112 restraints
wR(F2) = 0.051H-atom parameters constrained
S = 1.19Δρmax = 0.37 e Å−3
2931 reflectionsΔρmin = −0.38 e Å−3
266 parameters
Special details top

Experimental. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD diffractometer using an exposure time of 10 s/frame. A collection frame width of 0.5° covering up to θ = 24.9° resulted in 97% completeness accomplished.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.8288 (11)−0.1156 (10)0.6237 (7)0.0215 (7)0.587 (9)
C20.9177 (12)−0.2245 (12)0.6081 (9)0.025 (3)0.587 (9)
H20.9665−0.24410.68740.030*0.587 (9)
C30.9336 (9)−0.3042 (9)0.4741 (10)0.030 (3)0.587 (9)
H30.9931−0.37700.46370.036*0.587 (9)
C40.8606 (8)−0.2749 (8)0.3556 (8)0.038 (2)0.587 (9)
H40.8713−0.32820.26600.045*0.587 (9)
C50.7718 (9)−0.1660 (9)0.3712 (7)0.040 (4)0.587 (9)
H50.7229−0.14650.29200.048*0.587 (9)
C60.7558 (7)−0.0864 (7)0.5053 (8)0.0294 (15)0.587 (9)
H60.6964−0.01350.51570.035*0.587 (9)
C1B0.8337 (16)−0.1023 (17)0.6235 (11)0.0215 (7)0.413 (9)
H1B0.9155−0.03240.63420.026*0.413 (9)
C2B0.892 (2)−0.2484 (19)0.5907 (14)0.021 (3)0.413 (9)
H2BA0.8132−0.32330.57480.025*0.413 (9)
H2BB0.9771−0.23970.67320.025*0.413 (9)
C3B0.9388 (17)−0.2926 (17)0.4549 (15)0.027 (3)0.413 (9)
H3BA1.0238−0.22230.47470.033*0.413 (9)
H3BB0.9705−0.38730.43270.033*0.413 (9)
C4B0.8129 (12)−0.2994 (11)0.3271 (10)0.023 (2)0.413 (9)
H4BA0.7318−0.37650.30120.027*0.413 (9)
H4BB0.8477−0.32280.24480.027*0.413 (9)
C5B0.7549 (14)−0.1569 (12)0.3589 (11)0.023 (3)0.413 (9)
H5BA0.6712−0.16550.27510.028*0.413 (9)
H5BB0.8337−0.08110.37730.028*0.413 (9)
C6B0.7032 (10)−0.1141 (10)0.4917 (11)0.0224 (18)0.413 (9)
H6BA0.6677−0.02120.51180.027*0.413 (9)
H6BB0.6207−0.18710.47180.027*0.413 (9)
C70.7420 (2)0.1499 (2)0.8114 (2)0.0247 (4)
H70.64980.13000.72920.030*
C80.8584 (3)0.2478 (2)0.8001 (2)0.0335 (5)
H8A0.87720.19760.70930.040*
H8B0.95220.26900.87920.040*
C90.8040 (3)0.3903 (2)0.8064 (2)0.0355 (5)
H9A0.88160.45290.80340.043*
H9B0.71520.36970.72240.043*
C100.7666 (3)0.4687 (2)0.9438 (2)0.0353 (5)
H10A0.85790.49881.02750.042*
H10B0.72670.55580.94240.042*
C110.6531 (3)0.3725 (2)0.9585 (3)0.0365 (5)
H11A0.55770.35310.88180.044*
H11B0.63780.42361.05080.044*
C120.7038 (2)0.2278 (2)0.9498 (2)0.0288 (4)
H12A0.62420.16580.95090.035*
H12B0.79160.24591.03390.035*
C130.6240 (7)−0.1337 (11)0.7724 (14)0.017 (2)0.587 (9)
H130.6085−0.09580.86670.020*0.587 (9)
C140.4830 (6)−0.1221 (6)0.6629 (6)0.0260 (12)0.587 (9)
H14A0.4726−0.02020.68980.031*0.587 (9)
H14B0.4928−0.16110.56720.031*0.587 (9)
C150.3432 (8)−0.2058 (7)0.6579 (13)0.038 (2)0.587 (9)
H15A0.3289−0.16170.75150.046*0.587 (9)
H15B0.2557−0.19940.58550.046*0.587 (9)
C160.3565 (8)−0.3654 (7)0.6210 (8)0.0311 (14)0.587 (9)
H16A0.2694−0.41430.62550.037*0.587 (9)
H16B0.3591−0.41280.52280.037*0.587 (9)
C170.4985 (10)−0.3777 (10)0.7268 (16)0.029 (2)0.587 (9)
H17A0.5083−0.47980.69850.035*0.587 (9)
H17B0.4903−0.33970.82320.035*0.587 (9)
C180.6381 (8)−0.2948 (9)0.7318 (17)0.023 (3)0.587 (9)
H18A0.6513−0.33730.63770.028*0.587 (9)
H18B0.7258−0.30270.80290.028*0.587 (9)
C13B0.6193 (7)−0.1534 (11)0.7533 (16)0.027 (5)0.413 (9)
C14B0.4787 (8)−0.1111 (7)0.7229 (11)0.0331 (19)0.413 (9)
H14C0.4707−0.01760.72830.040*0.413 (9)
C15B0.3501 (7)−0.2087 (9)0.6846 (13)0.045 (5)0.413 (9)
H15C0.2560−0.18040.66420.054*0.413 (9)
C16B0.3620 (11)−0.3485 (8)0.6766 (10)0.033 (2)0.413 (9)
H16C0.2760−0.41370.65090.040*0.413 (9)
C17B0.5026 (14)−0.3907 (9)0.7070 (17)0.035 (5)0.413 (9)
H17C0.5106−0.48430.70160.042*0.413 (9)
C18B0.6312 (10)−0.2932 (14)0.745 (2)0.032 (6)0.413 (9)
H18C0.7253−0.32150.76570.038*0.413 (9)
P10.79648 (5)−0.02795 (5)0.79688 (5)0.01688 (11)
Cl11.15978 (5)0.06458 (5)0.89925 (5)0.02496 (11)
Pd11.00000.00001.00000.01502 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0227 (11)0.0238 (17)0.0172 (9)0.0024 (11)0.0065 (8)0.0079 (9)
C20.022 (4)0.026 (4)0.022 (3)−0.002 (3)0.004 (3)0.006 (3)
C30.024 (3)0.030 (3)0.027 (4)0.001 (2)0.006 (3)0.005 (3)
C40.032 (5)0.046 (4)0.025 (4)−0.004 (3)0.017 (3)0.001 (3)
C50.040 (5)0.059 (7)0.024 (4)0.000 (4)0.009 (3)0.022 (4)
C60.030 (4)0.033 (3)0.029 (3)0.005 (3)0.012 (3)0.015 (2)
C1B0.0227 (11)0.0238 (17)0.0172 (9)0.0024 (11)0.0065 (8)0.0079 (9)
C2B0.022 (5)0.020 (5)0.016 (4)0.005 (5)0.004 (3)0.006 (3)
C3B0.036 (6)0.034 (5)0.018 (5)0.015 (4)0.016 (4)0.012 (4)
C4B0.027 (5)0.026 (4)0.015 (3)0.001 (4)0.007 (4)0.009 (3)
C5B0.033 (5)0.023 (5)0.012 (4)0.008 (4)0.007 (3)0.006 (4)
C6B0.023 (5)0.026 (4)0.016 (3)0.003 (3)0.002 (4)0.010 (3)
C70.0291 (10)0.0221 (9)0.0232 (9)0.0069 (8)0.0079 (8)0.0102 (8)
C80.0487 (13)0.0264 (10)0.0347 (11)0.0097 (9)0.0222 (10)0.0158 (9)
C90.0496 (14)0.0271 (10)0.0358 (12)0.0089 (9)0.0148 (10)0.0187 (9)
C100.0481 (14)0.0232 (10)0.0356 (11)0.0112 (9)0.0138 (10)0.0130 (9)
C110.0446 (13)0.0268 (10)0.0399 (12)0.0117 (9)0.0209 (11)0.0106 (9)
C120.0359 (11)0.0230 (9)0.0298 (10)0.0055 (8)0.0158 (9)0.0098 (8)
C130.023 (4)0.013 (2)0.013 (3)0.0053 (19)0.002 (2)0.007 (2)
C140.024 (2)0.029 (2)0.028 (3)0.0036 (15)0.007 (2)0.017 (2)
C150.033 (4)0.026 (4)0.054 (3)0.008 (3)0.009 (3)0.019 (3)
C160.027 (2)0.031 (2)0.034 (4)−0.0029 (17)0.008 (3)0.016 (2)
C170.025 (5)0.025 (4)0.043 (4)0.003 (3)0.013 (3)0.019 (3)
C180.019 (4)0.020 (5)0.031 (4)−0.004 (3)0.008 (3)0.011 (3)
C13B0.020 (5)0.033 (8)0.021 (6)−0.005 (4)0.010 (4)0.004 (4)
C14B0.034 (3)0.026 (3)0.044 (5)0.007 (2)0.018 (4)0.015 (4)
C15B0.011 (5)0.063 (9)0.065 (8)0.003 (4)0.011 (4)0.034 (5)
C16B0.036 (4)0.036 (4)0.029 (5)−0.003 (3)0.014 (4)0.012 (4)
C17B0.043 (9)0.023 (6)0.039 (7)0.001 (5)0.015 (5)0.011 (4)
C18B0.041 (9)0.031 (8)0.034 (7)0.020 (6)0.017 (6)0.020 (6)
P10.0191 (2)0.0180 (2)0.0148 (2)0.00359 (17)0.00545 (18)0.00827 (17)
Cl10.0231 (2)0.0357 (2)0.0193 (2)0.00003 (18)0.00788 (18)0.01451 (19)
Pd10.01700 (11)0.01711 (11)0.01244 (10)0.00288 (7)0.00508 (7)0.00760 (7)
Geometric parameters (Å, º) top
C1—C21.3900C10—H10A0.9700
C1—C61.3900C10—H10B0.9700
C1—P11.825 (7)C11—C121.527 (3)
C2—C31.3900C11—H11A0.9700
C2—H20.9300C11—H11B0.9700
C3—C41.3900C12—H12A0.9700
C3—H30.9300C12—H12B0.9700
C4—C51.3900C13—C141.528 (8)
C4—H40.9300C13—C181.531 (9)
C5—C61.3900C13—P11.813 (7)
C5—H50.9300C13—H130.9800
C6—H60.9300C14—C151.523 (8)
C1B—C6B1.524 (10)C14—H14A0.9700
C1B—C2B1.534 (9)C14—H14B0.9700
C1B—P11.843 (10)C15—C161.519 (7)
C1B—H1B0.9800C15—H15A0.9700
C2B—C3B1.538 (11)C15—H15B0.9700
C2B—H2BA0.9700C16—C171.516 (10)
C2B—H2BB0.9700C16—H16A0.9700
C3B—C4B1.491 (12)C16—H16B0.9700
C3B—H3BA0.9700C17—C181.517 (8)
C3B—H3BB0.9700C17—H17A0.9700
C4B—C5B1.503 (10)C17—H17B0.9700
C4B—H4BA0.9700C18—H18A0.9700
C4B—H4BB0.9700C18—H18B0.9700
C5B—C6B1.536 (9)C13B—C14B1.3900
C5B—H5BA0.9700C13B—C18B1.3900
C5B—H5BB0.9700C13B—P11.891 (7)
C6B—H6BA0.9700C14B—C15B1.3900
C6B—H6BB0.9700C14B—H14C0.9300
C7—C81.520 (3)C15B—C16B1.3900
C7—C121.528 (3)C15B—H15C0.9300
C7—P11.8421 (19)C16B—C17B1.3900
C7—H70.9800C16B—H16C0.9300
C8—C91.524 (3)C17B—C18B1.3900
C8—H8A0.9700C17B—H17C0.9300
C8—H8B0.9700C18B—H18C0.9300
C9—C101.516 (3)P1—Pd12.3343 (5)
C9—H9A0.9700Cl1—Pd12.3017 (4)
C9—H9B0.9700Pd1—Cl1i2.3017 (4)
C10—C111.507 (3)Pd1—P1i2.3343 (5)
C2—C1—C6120.0C12—C11—H11B109.2
C2—C1—P1117.9 (5)H11A—C11—H11B107.9
C6—C1—P1121.8 (5)C11—C12—C7110.85 (17)
C1—C2—C3120.0C11—C12—H12A109.5
C1—C2—H2120.0C7—C12—H12A109.5
C3—C2—H2120.0C11—C12—H12B109.5
C4—C3—C2120.0C7—C12—H12B109.5
C4—C3—H3120.0H12A—C12—H12B108.1
C2—C3—H3120.0C14—C13—C18109.4 (6)
C3—C4—C5120.0C14—C13—P1114.9 (5)
C3—C4—H4120.0C18—C13—P1111.5 (5)
C5—C4—H4120.0C14—C13—H13106.9
C6—C5—C4120.0C18—C13—H13106.9
C6—C5—H5120.0P1—C13—H13106.9
C4—C5—H5120.0C15—C14—C13110.9 (6)
C5—C6—C1120.0C15—C14—H14A109.5
C5—C6—H6120.0C13—C14—H14A109.5
C1—C6—H6120.0C15—C14—H14B109.5
C6B—C1B—C2B109.7 (7)C13—C14—H14B109.5
C6B—C1B—P1114.9 (8)H14A—C14—H14B108.0
C2B—C1B—P1113.6 (8)C16—C15—C14111.4 (5)
C6B—C1B—H1B106.0C16—C15—H15A109.4
C2B—C1B—H1B106.0C14—C15—H15A109.4
P1—C1B—H1B106.0C16—C15—H15B109.4
C1B—C2B—C3B110.2 (6)C14—C15—H15B109.4
C1B—C2B—H2BA109.6H15A—C15—H15B108.0
C3B—C2B—H2BA109.6C17—C16—C15110.2 (6)
C1B—C2B—H2BB109.6C17—C16—H16A109.6
C3B—C2B—H2BB109.6C15—C16—H16A109.6
H2BA—C2B—H2BB108.1C17—C16—H16B109.6
C4B—C3B—C2B111.5 (7)C15—C16—H16B109.6
C4B—C3B—H3BA109.3H16A—C16—H16B108.1
C2B—C3B—H3BA109.3C16—C17—C18112.1 (6)
C4B—C3B—H3BB109.3C16—C17—H17A109.2
C2B—C3B—H3BB109.3C18—C17—H17A109.2
H3BA—C3B—H3BB108.0C16—C17—H17B109.2
C3B—C4B—C5B111.3 (8)C18—C17—H17B109.2
C3B—C4B—H4BA109.4H17A—C17—H17B107.9
C5B—C4B—H4BA109.4C17—C18—C13110.4 (6)
C3B—C4B—H4BB109.4C17—C18—H18A109.6
C5B—C4B—H4BB109.4C13—C18—H18A109.6
H4BA—C4B—H4BB108.0C17—C18—H18B109.6
C4B—C5B—C6B110.8 (7)C13—C18—H18B109.6
C4B—C5B—H5BA109.5H18A—C18—H18B108.1
C6B—C5B—H5BA109.5C14B—C13B—C18B120.0
C4B—C5B—H5BB109.5C14B—C13B—P1121.5 (5)
C6B—C5B—H5BB109.5C18B—C13B—P1118.4 (5)
H5BA—C5B—H5BB108.1C15B—C14B—C13B120.0
C1B—C6B—C5B109.8 (8)C15B—C14B—H14C120.0
C1B—C6B—H6BA109.7C13B—C14B—H14C120.0
C5B—C6B—H6BA109.7C16B—C15B—C14B120.0
C1B—C6B—H6BB109.7C16B—C15B—H15C120.0
C5B—C6B—H6BB109.7C14B—C15B—H15C120.0
H6BA—C6B—H6BB108.2C15B—C16B—C17B120.0
C8—C7—C12111.13 (16)C15B—C16B—H16C120.0
C8—C7—P1113.28 (14)C17B—C16B—H16C120.0
C12—C7—P1111.08 (13)C18B—C17B—C16B120.0
C8—C7—H7107.0C18B—C17B—H17C120.0
C12—C7—H7107.0C16B—C17B—H17C120.0
P1—C7—H7107.0C17B—C18B—C13B120.0
C7—C8—C9110.74 (18)C17B—C18B—H18C120.0
C7—C8—H8A109.5C13B—C18B—H18C120.0
C9—C8—H8A109.5C13—P1—C1104.6 (6)
C7—C8—H8B109.5C13—P1—C7103.3 (3)
C9—C8—H8B109.5C1—P1—C7107.4 (3)
H8A—C8—H8B108.1C13—P1—C1B108.0 (6)
C10—C9—C8111.03 (17)C7—P1—C1B103.5 (5)
C10—C9—H9A109.4C1—P1—C13B98.7 (5)
C8—C9—H9A109.4C7—P1—C13B106.9 (3)
C10—C9—H9B109.4C1B—P1—C13B102.1 (7)
C8—C9—H9B109.4C13—P1—Pd1115.0 (3)
H9A—C9—H9B108.0C1—P1—Pd1114.7 (3)
C11—C10—C9111.58 (18)C7—P1—Pd1110.95 (6)
C11—C10—H10A109.3C1B—P1—Pd1114.8 (4)
C9—C10—H10A109.3C13B—P1—Pd1117.3 (4)
C11—C10—H10B109.3Cl1—Pd1—Cl1i180.0
C9—C10—H10B109.3Cl1—Pd1—P189.296 (16)
H10A—C10—H10B108.0Cl1i—Pd1—P190.704 (16)
C10—C11—C12112.03 (18)Cl1—Pd1—P1i90.704 (16)
C10—C11—H11A109.2Cl1i—Pd1—P1i89.296 (16)
C12—C11—H11A109.2P1—Pd1—P1i180.0
C10—C11—H11B109.2
Symmetry code: (i) −x+2, −y, −z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8B···Cl10.972.913.559 (2)125
C5—H5···Cl1ii0.932.943.619 (7)131
C13—H13···Cl1i0.982.683.254 (11)118
C18—H18B···Cl1i0.972.973.542 (13)119
C15—H15A···Cl1iii0.973.023.800 (8)139
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, −y, −z+1; (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula[PdCl2(C18H27P)2]
Mr726.03
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)9.439 (4), 10.095 (4), 10.623 (5)
α, β, γ (°)113.115 (2), 107.321 (2), 91.625 (2)
V (Å3)876.5 (7)
Z1
Radiation typeMo Kα
µ (mm−1)0.80
Crystal size (mm)0.27 × 0.13 × 0.11
Data collection
DiffractometerBruker X8 APEXII 4K KappaCCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.885, 0.918
No. of measured, independent and
observed [I > 2σ(I)] reflections		12144, 2931, 2891
Rint0.024
(sin θ/λ)max (Å−1)0.591
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.021, 0.051, 1.19
No. of reflections2931
No. of parameters266
No. of restraints12
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.37, −0.38

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SAINT-Plus and XPREP (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8B···Cl10.972.913.559 (2)125.3
C5—H5···Cl1i0.932.943.619 (7)131.1
C13—H13···Cl1ii0.982.683.254 (11)117.8
C18—H18B···Cl1ii0.972.973.542 (13)119.1
C15—H15A···Cl1iii0.973.023.800 (8)138.5
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y, −z+2; (iii) x−1, y, z.
 

Acknowledgements

ARB thanks the University of Johannesburg and the South African National Research Foundation for financial support.

References

First citationBedford, R. B., Cazin, C. S. J. & Holder, D. (2004). Coord. Chem. Rev. 248, 2283–2321.  Web of Science CrossRef CAS Google Scholar
 First citationBrandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
 First citationBruker (2007). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationClarke, M. L., Orpen, A. G., Pringle, P. G. & Turley, E. (2003). Dalton Trans. pp. 4393–4394.  Web of Science CSD CrossRef Google Scholar
 First citationDrew, D. & Doyle, J. R. (1990). Inorg. Synth. 28, 346–349.  CrossRef CAS Web of Science Google Scholar
 First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
 First citationGrushin, V. V., Bensimon, C. & Alper, H. (1994). Inorg. Chem. 33, 4804–4806.  CSD CrossRef CAS Web of Science Google Scholar
 First citationMuller, A. & Meijboom, R. (2010a). Acta Cryst. E66, m1420.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationMuller, A. & Meijboom, R. (2010b). Acta Cryst. E66, m1463.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationOgutu, H. & Meijboom, R. (2011). Acta Cryst. E67, m1662.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSpessard, G. O. & Miessler, G. L. (1996). Organometallic Chemistry, pp. 131–135. Upper Saddle River, New Jersey: Prentice Hall.  Google Scholar
 First citationVuoti, S., Autio, J., Laitila, M., Haukka, M. & Pursiainen, J. (2008). Eur. J. Inorg. Chem. pp. 397–407.  Web of Science CSD CrossRef Google Scholar

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ISSN: 2056-9890
Volume 68| Part 4| April 2012| Page m404
doi:10.1107/S1600536812010100
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