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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

trans-Di­chlorido­bis­­(4,8-di­methyl-2-phenyl-2-phosphabi­cyclo­[3.3.1]nonane-κP)platinum(II)

aSasol Technology Research and Development, 1 Klasie Havenga Road, Sasolburg 1947, South Africa, and bDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein 9300, South Africa
*Correspondence e-mail: fanie.otto@sasol.com

(Received 24 February 2011; accepted 8 April 2011; online 16 April 2011)

The crystal structure of the title compound, trans-[PtCl2(C16H23P)2], has been determined at 100 K. The Pt atom is located on a twofold axis and adopts a distorted square-planar coordination geometry. The structure is only the second example of a coordination complex containing a derivative of the 4,8-dimethyl-2-phosphabicyclo­[3.3.1]nona­ne (Lim) phosphine ligand family. The ligand contains four chiral C atoms, with the stereochemistry at three of these fixed during synthesis, therefore resulting in two possible ligand stereoisomers. The compound crystallizes in the chiral space group P43212 but is racemic, comprising an equimolar mixture of both stereoisomers disordered on a single ligand site. The effective cone angles for both isomers are the same at 146°.

Comment

Lim ligands (2-Q-4,8-dimethyl-2-phosphabicyclo­[3.3.1]non­ane) are derived from the radical addition reaction of the monoterpene R-(+)-limonene with a QPH2 mol­ecule, where Q = H or some other suitable monoanionic group such as alkyl or aryl, resulting in a racemic mixture of ligands being obtained. Although the phosphine Lim backbone contains four chiral C atoms, the stereochemistry at three of these sites is fixed, viz. C1 (R), C5 (R) and C8 (S), while C4 can have either an R or S configuration. This stereochemistry is a consequence of performing the synthesis with the optically pure terpene and the mechanism of addition to the P atom (Robertson et al., 2001[Robertson, A., Bradaric, C., Frampton, C. S., McNulty, J. & Capretta, A. (2001). Tetrahedron Lett. 42, 2609-2612.]).

Chiral phosphine ligands are of general inter­est in coordination chemistry and catalysis, and ligands of the Lim family have been shown to display exceptional qualities in the modified cobalt hydro­formyl­ation of alkenes to give alcohols directly (Steynberg et al., 2002[Steynberg, J. P., Govender, K. & Steynberg, P. J. (2002). Int. Patent WO2002014248.]; Crause et al., 2003[Crause, C., Bennie, L., Damoense, L., Dwyer, C. L., Grove, C., Grimmer, N., Janse van Rensburg, W., Kirk, M. M., Mokheseng, K. M., Otto, S. & Steynberg, P. J. (2003). Dalton Trans. pp. 2036-2042.]; Dwyer et al., 2004[Dwyer, C., Assumption, H., Coetzee, J., Crause, C., Damoense, L. & Kirk, M. (2004). Coord. Chem. Rev. 248, 653-670.]). The only other crystal structure in the open literature of a coordination compound containing a member of the Lim ligand family, [Co(CO)3(Lim-C18)]2 (Lim-C18 is the 4R isomer of 2-octa­decyl-4,8-dimethyl-2-phosphabicyclo­[3.3.1]non­a­ne), was obtained during such a study (Polas et al., 2003[Polas, A., Wilton-Ely, J. D. E. T., Slawin, A. M. Z., Foster, D. F., Steynberg, P. J., Green, M. J. & Cole-Hamilton, D. J. (2003). Dalton Trans. pp. 4669-4677.]).

In order to investigate further the coordination mode of these ligands, we prepared [PtCl2(Lim-Ph)2] by reaction of [PtCl2(COD)] (COD is cis,cis-cyclo­octa-1,5-diene) with two molar equivalents of a solution containing a mixture of both Lim-Ph isomers. Recrystallization as described in the Experimental section resulted in crystals of (I)[link] being obtained.

[Scheme 1]

Compound (I)[link] crystallizes with a distorted square-planar coordination geometry, with a twofold rotation axis passing through the Pt metal centre and bis­ecting the P2—Pt1—P2i and Cl1—Pt1—Cl1i angles [symmetry code: (i) y, x, −z] (Fig. 1[link]). The Lim-Ph ligands adopt a trans orientation, suggesting significant steric bulk, although cis isomers have been observed in solution using 31P NMR (vide infra). The coordination geometry deviates significantly from ideal square planar, with P2—Pt1—P2i and Cl1—Pt1—Cl1i angles of 170.97 (9) and 175.49 (8)°, respectively. Inter­estingly, the C11 methyl groups, which contribute significantly to the overall steric bulk of the Lim-Ph ligands, occupy the same side of the equatorial plane, with a closest contact of only 3.655 (13) Å between C11 and C11i. This inter­action manifests itself in the deviation of the P atoms below the equatorial plane. In addition, the presence of these two methyl substituents effectively blocks one apical position of the Pt atom, with Pt1⋯C11 contacts of only 3.563 (6) Å. The Pt1—P2 bond distance of 2.3088 (14) Å is within the expected range, while the Pt1—Cl1 distance of 2.3320 (13) Å is quite long. This elongation is probably a consequence of the steric repulsion of the two bulky phosphine ligands and the resulting distortion from square planarity. The deviations in the bond angles from the ideal value of 180° would impact negatively on the efficiency of the relevant orbital overlap between the atoms involved. Table 1[link] presents a comparison with related structures, also containing bulky ligands, taken from the open literature, to illustrate this effect.

The Lim-Ph ligand exhibits disorder in the orientation of the C10 methyl group, with components A and B corresponding to the 4R and 4S isomers, respectively (Fig. 1[link]). Refinement of the site occupancies for C10A and C10B yielded values that did not differ significantly from 0.5 and the occupancies were therefore constrained to 0.5 for subsequent refinement, corresponding to a true racemic mixture. Short inter­molecular contacts [C10A⋯C10Aii = 2.502 (16) Å; symmetry code: (ii) y − 1, x + 1, −z] preclude the simultaneous presence of C10A in neighbouring mol­ecules, but there are no constraints on the presence of C10B.

Describing the steric demand of phosphine ligands has been the topic of many studies and a variety of models have been developed (Bunten et al., 2002[Bunten, K. A., Chen, L., Fernandez, A. L. & Poē, A. J. (2002). Coord. Chem. Rev. 233-234, 41-51.]). In practice, the Tolman cone angle (Tolman, 1977[Tolman, C. A. (1977). Chem. Rev. 77, 313-348.]) is still the most commonly used model, due to its simplicity and ease of calculation. This principle has been further developed (Otto, 2001[Otto, S. (2001). Acta Cryst. C57, 793-795.]) into the concept of the `effective cone angle', where the crystallographically determined metal–P bond length is used in the calculations. Using the Pt1—P2 bond distance obtained in this study and calculating the cone to the outermost H atoms (H11A, H19A and H25A) on C11, C19 and C25 results in a value of 146°. In addition, the cone angle is independent of the orientation of C10.

31P NMR analysis of the reaction mixture indicated a number of species in solution corresponding to Pt complexes of both cis and trans geometry, as well as containing combinations of the different ligand isomers, i.e. (4R,4R), (4S,4S) and (4R,4S). Aside from the constraint observed for the inter­molecular contacts involving C10A, the refined 50% disorder in the orientation of the C10 Me group is consistent with any of these combinations. Redissolving some of the single crystals obtained and recollecting the 31P NMR spectrum confirmed that mixtures of this nature are indeed present in both the solid and solution states.

Based on high-pressure NMR experiments, it was previously shown that the 4R isomer coordinates preferentially during modified Co hydro­formyl­ation (Polas et al., 2003[Polas, A., Wilton-Ely, J. D. E. T., Slawin, A. M. Z., Foster, D. F., Steynberg, P. J., Green, M. J. & Cole-Hamilton, D. J. (2003). Dalton Trans. pp. 4669-4677.]; Dwyer et al., 2004[Dwyer, C., Assumption, H., Coetzee, J., Crause, C., Damoense, L. & Kirk, M. (2004). Coord. Chem. Rev. 248, 653-670.]), and this observation was supported by modelling studies (Crause et al., 2003[Crause, C., Bennie, L., Damoense, L., Dwyer, C. L., Grove, C., Grimmer, N., Janse van Rensburg, W., Kirk, M. M., Mokheseng, K. M., Otto, S. & Steynberg, P. J. (2003). Dalton Trans. pp. 2036-2042.]). Considering, however, that the two isomers are electronically and sterically (as shown here) very similar, this behaviour is currently not well understood and may warrant further investigation.

[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. [Symmetry code: (i) y, x, −z.]

Experimental

The Lim-Ph ligand (mixture of isomers) was prepared by adapting methods described previously (Bungu & Otto, 2007[Bungu, P. N. & Otto, S. (2007). J. Organomet. Chem. 692, 3370-3379.]). All manipulations involving the free ligand were performed using degassed solvents and working under a positive argon atmosphere to prevent oxidation. PtCl2(COD) (COD is cis,cis-cyclo­octa-1,5-diene) (200 mg, 0.53 mmol) was dissolved in dichloro­methane (10 ml) and a di­chloro­methane solution of the ligand mixture (1.49 ml, 753 mM, 1.12 mmol) was subsequently added. The resulting reaction mixture was stirred overnight and a portion was subjected to 31P NMR analysis. The spectra were quite complex, with both cis and trans PtII complexes present as mixtures of the two ligand isomers. Crystals of compound (I)[link] suitable for single-crystal diffraction studies were obtained by addition of acetone to the dichloro­methane reaction mixture followed by slow evaporation.

31P (CDCl3): trans-[PtCl2(4R-Lim-Ph)2] −8.82 p.p.m. (t, 1JPt—P = 2378 Hz); trans-[PtCl2(4R-Lim-Ph)(4S-Lim-Ph)] −9.83 (4R, t, 1JPt—P = 2378 Hz) and −12.42 p.p.m. (4S, t, 1JPt—P = 2383 Hz); trans-[PtCl2(4S-Lim-Ph)2] −13.58 p.p.m. (t, 1JPt—P = 2384 Hz).

Crystal data
  • [PtCl2(C16H23P)2]

  • Mr = 758.62

  • Tetragonal, P 43 21 2

  • a = 9.5909 (1) Å

  • c = 33.2924 (9) Å

  • V = 3062.41 (9) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 4.88 mm−1

  • T = 100 K

  • 0.37 × 0.24 × 0.22 mm

Data collection
  • Bruker X8 APEXII 4K KappaCCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2008[Bruker (2008). SADABS and APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.273, Tmax = 0.364

  • 31409 measured reflections

  • 3782 independent reflections

  • 3209 reflections with I > 2σ(I)

  • Rint = 0.083

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.067

  • S = 1.15

  • 3782 reflections

  • 180 parameters

  • 2 restraints

  • H-atom parameters constrained

  • Δρmax = 1.19 e Å−3

  • Δρmin = −1.42 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 1505 Friedel pairs

  • Flack parameter: 0.010 (10)

Table 1
Comparative data for trans-[PtCl2(P)2] complexes

P Pt—P (Å) Pt—Cl (Å) Reference
PEt3 2.298 (18) 2.294 (9) (i)
PPh3 2.3164 (11) 2.2997 (11) (ii)
PBz3 2.3219 (12) 2.3092 (11) (iii)
  2.3019 (10) 2.3053 (10) (iii)
PCy3 2.337 (2) 2.317 (2) (iv)
PPh2Fc 2.318 (2) 2.301 (2) (v)
s-PhobPBu 2.3121 (11) 2.3059 (11) (vi)
a7PhobPBu 2.302 (4) 2.307 (4) (vi)
  2.321 (5) 2.318 (4) (vi)
1,2,6-tpp 2.3096 (12) 2.3118 (12) (vii)
References: (i) Messmer & Amma (1966[Messmer, G. G. & Amma, E. L. (1966). Inorg. Chem. 5, 1775-1781.]); (ii) Johansson & Otto (2000[Johansson, M. H. & Otto, S. (2000). Acta Cryst. C56, e12-e15.]); (iii) Johansson et al. (2002[Johansson, M. H., Otto, S. & Oskarsson, Å. (2002). Acta Cryst. B58, 244-250.]); (iv) Del Pra & Zanotti (1980[Del Pra, A. & Zanotti, G. (1980). Inorg. Chim. Acta, 39, 137-141.]); (v) Otto & Roodt (1997[Otto, S. & Roodt, A. (1997). Acta Cryst. C53, 1414-1416.]); (vi) Carreira et al. (2009[Carreira, M., Charernsuk, M., Eberhard, M., Fey, N., Van Ginkel, R., Hamilton, A., Mul, W. P., Orpen, A. G., Phetmung, H. & Pringle, P. G. (2009). J. Am. Chem. Soc. 131, 3078-3094.]); (vii) Doherty et al. (2006[Doherty, R., Haddow, M. F., Harrison, Z. A., Orpen, A. G., Pringle, P. G., Turner, A. & Wingad, R. L. (2006). Dalton Trans. pp. 4310-4320.]).

The disorder of the methyl substituent on C4 of the Lim-Ph ligand was modelled as two orientations with occupancies summing to unity. Occupancies of 0.493 (18) and 0.507 (18) were obtained for C10A and C10B, respectively. Since these values do not differ significantly from 0.5, they were constrained to 0.5 for further refinement. The C4—C10A and C4—C10B distances were tightly restrained to 1.530 (5) Å. H atoms were placed geometrically with C—H distances of 1.00 Å for CH (alk­yl), 0.95 Å for CH (ar­yl), 0.99 Å for CH2 and 0.98 Å for CH3, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) for CH and CH2 or 1.5Ueq(C) for CH3. For the methyl groups, rotation was permitted about the C—C bond.

Data collection: APEX2 (Bruker, 2008[Bruker (2008). SADABS and APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2004[Bruker (2004). SAINT-Plus and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus and XPREP (Bruker, 2004[Bruker (2004). SAINT-Plus and XPREP. 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, 2001[Brandenburg, K. (2001). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Lim ligands (2-Q-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane) are derived from the radical addition reaction of the monoterpene R-(+)-limonene with a QPH2 molecule, where Q = H or some other suitable monoanionic group such as alkyl or aryl, resulting in a racemic mixture of ligands being obtained. Although the phosphine Lim backbone contains four chiral C atoms, the stereochemistry at three of these sites is fixed, viz. C1 (R), C5 (R) and C8 (S), while C4 can have either an R or S configuration. This stereochemistry is a consequence of performing the synthesis with the optically pure terpene and the mechanism of addition to the P atom (Robertson et al., 2001).

Chiral phosphine ligands are of general interest in coordination chemistry and catalysis, and ligands of the Lim family have been shown to display exceptional qualities in the modified cobalt hydroformylation of alkenes to give alcohols directly (Steynberg et al., 2002; Crause et al., 2003; Dwyer et al., 2004). The only other crystal structure in the open literature of a coordination compound containing a member of the Lim ligand family, [Co(CO)3(Lim-C18)]2 (Lim-C18 = 4R isomer of 2-octadecyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane), was obtained during such a study (Polas et al., 2003).

In order to investigate further the coordination mode of these ligands, we prepared [PtCl2(Lim-Ph)2] by reaction of [PtCl2(COD)] (COD = 1,5-cyclooctadiene) with two molar equivalents of a solution containing a mixture of both Lim-Ph isomers. Recrystallization as described in the Experimental section resulted in crystals of (I) being obtained.

Compound (I) crystallizes with a distorted square-planar coordination geometry, with a twofold rotation axis passing through the Pt metal centre and bisecting the P2—Pt1—P2i and Cl1—Pt1—Cl1i angles [symmetry code: (i) y, x, -z] (Fig. 1). The Lim-Ph ligands adopt a trans orientation, suggesting significant steric bulk, although cis isomers have been observed in solution using 31P NMR (vide infra). The coordination geometry deviates significantly from ideal square planar, with P2—Pt1—P2i and Cl1—Pt1—Cl1i angles of 170.97 (9) and 175.49 (8)°, respectively. Interestingly, the C11 methyl groups, which contribute significantly to the overall steric bulk of the Lim-Ph ligands, occupy the same side of the equatorial plane, with a closest contact of only 3.655 (13) Å between C11 and C11i. This interaction manifests itself in the deviation of the P atoms below the equatorial plane. In addition, the presence of these two methyl substituents effectively blocks one apical position of the Pt atom, with Pt1···C11 contacts of only 3.563 (6) Å. The Pt1—P2 bond distance of 2.3088 (14) Å is within the expected range, while the Pt1—Cl1 distance of 2.3320 (13) Å is quite long. This elongation is probably a consequence of the steric repulsion of the two bulky phosphine ligands and the resulting distortion from square planarity. The deviations in the bond angles from the ideal 180° would negatively impact on the efficiency of the relevant orbital overlap between the atoms involved. Table 1 presents a comparison with related structures, also containing bulky ligands, taken from the open literature, to illustrate this effect.

The Lim-Ph ligand exhibits disorder in the orientation of the C10 methyl group, with components A and B corresponding to the 4R and 4S isomers, respectively (Fig. 1). Refinement of the site occupancies for C10A and C10B yielded values that did not differ significantly from 0.5 and the occupancies were therefore constrained to 0.5 for subsequent refinement, corresponding to a true racemic mixture. Short intermolecular contacts [C10A···C10Aii = 2.502 (16) Å; symmetry code: (ii) -1 + y, 1 + x, -z] preclude the simultaneous presence of C10A in neighbouring molecules, but there are no constraints on the presence of C10B.

Describing the steric demand of phosphine ligands has been the topic of many studies and a variety of models have been developed (Bunten et al., 2002). In practice, the Tolman cone angle (Tolman, 1977) is still the most commonly used model, due to its simplicity and ease of calculation. This principle has been further developed (Otto, 2001) into the concept of the `effective cone angle', where the crystallographically determined metal–P bond length is used in the calculations. Using the Pt1—P2 bond distance obtained in this study and calculating the cone to the outermost H atoms (H11A, H19A and H25A) on C11, C19 and C25 results in a value of 146°. In addition, the cone angle is independent of the orientation of C10.

31P NMR analysis of the reaction mixture indicated a number of species in solution corresponding to Pt complexes of both cis and trans geometry as well as containing combinations of the different ligand isomers, i.e. (4R,4R), (4S,4S) and (4R,4S). Aside from the constraint observed for the intermolecular contacts involving C10A, the refined 50% disorder in the orientation of the C10 Me group is consistent with any of these combinations. Redissolving some of the single crystals obtained and recollecting the 31P NMR spectrum confirmed that mixtures of this nature are indeed present in both the solid and solution states.

Based on high-pressure NMR experiments it was previously shown that the 4R isomer coordinates preferentially during modified Co hydroformylation (Polas et al. 2003, Dwyer et al. 2004), and this observation was supported by modelling studies (Crause et al., 2003). Considering, however, that the two isomers are electronically and sterically (as shown here) very similar, this behaviour is currently not well understood and may warrant further investigation.

Related literature top

For related literature, see: Bungu & Otto (2007); Bunten et al. (2002); Crause et al. (2003); Dwyer et al. (2004); Otto (2001); Polas et al. (2003); Robertson et al. (2001); Steynberg et al. (2002); Tolman (1977).

Experimental top

The Lim-Ph ligand (mixture of isomers) was prepared by adapting the methods described previously (Bungu & Otto, 2007). All manipulations involving the free ligand were performed using degassed solvents and working under a positive argon atmosphere to prevent oxidation. PtCl2(COD) (COD = cis,cis-1,5-cyclooctadiene) (200 mg, 0.53 mmol) was dissolved in dichloromethane (10 ml) and a dichloromethane solution of the ligand mixture (1.49 ml, 753 mM, 1.12 mmol) was subsequently added. The resulting reaction mixture was stirred overnight and a portion was subjected to 31P NMR analysis. The spectra could be quite complex with both cis and trans PtII complexes present as mixtures of the two ligand isomers. Crystals of compound (I) suitable for single-crystal diffraction studies were obtained by addition of acetone to the dichloromethane reaction mixture followed by slow evaporation.

31P (CDCl3): trans-[PtCl2(4R-Lim-Ph)2] -8.82 p.p.m. (t, 1JPt—P = 2378 Hz); trans-[PtCl2(4R-Lim-Ph)(4S-Lim-Ph)] -9.83 p.p.m. (4R, t, 1JPt—P = 2378 Hz) and -12.42 p.p.m. (4S, t, 1JPt—P = 2383 Hz); trans-[PtCl2(4S-Lim-Ph)2] -13.58 p.p.m. (t, 1JPt—P = 2384 Hz).

Refinement top

The disorder of the Me substituent on C4 of the Lim-Ph ligand was modelled as two orientations with occupancies summing to unity. Occupancies of 0.493 (18) and 0.507 (18) were obtained for C10A and C10B, respectively. Since these values do not differ significantly from 0.5, they were constrained to 0.5 for further refinement. The C4—C10A and C4—C10B distances were tightly restrained to 1.530 (5) Å. H atoms were placed geometrically with C—H distances of 1.00 Å for CH (alkyl), 0.95 Å for CH (aryl), 0.99 Å for CH2 or 0.98 Å for CH3, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) for CH and CH2 or 1.5Ueq(C) for CH3. For the methyl groups, rotation was permitted about the C—C bond.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are omitted for clarity. Symmetry code: (i) y, x, -z.
trans-Dichloridobis(4,8-dimethyl-2-phenyl-2- phosphabicyclo[3.3.1]nonane-κP)platinum(II) top
Crystal data top
[PtCl2(C16H23P)2]Dx = 1.645 Mg m3
Mr = 758.62Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212Cell parameters from 6453 reflections
Hall symbol: P 4nw 2abwθ = 2.5–23.0°
a = 9.5909 (1) ŵ = 4.88 mm1
c = 33.2924 (9) ÅT = 100 K
V = 3062.41 (9) Å3Block, yellow
Z = 40.37 × 0.24 × 0.22 mm
F(000) = 1520
Data collection top
Bruker X8 APEXII 4K Kappa CCD
diffractometer
3782 independent reflections
Radiation source: fine-focus sealed tube3209 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.083
Detector resolution: 8.4 pixels mm-1θmax = 28.3°, θmin = 3.5°
ϕ and ω scansh = 1210
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
k = 812
Tmin = 0.273, Tmax = 0.364l = 4334
31409 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.067 w = 1/[σ2(Fo2) + (0.P)2 + 6.9783P]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max < 0.001
3782 reflectionsΔρmax = 1.19 e Å3
180 parametersΔρmin = 1.42 e Å3
2 restraintsAbsolute structure: Flack (1983), 1505 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.010 (10)
Crystal data top
[PtCl2(C16H23P)2]Z = 4
Mr = 758.62Mo Kα radiation
Tetragonal, P43212µ = 4.88 mm1
a = 9.5909 (1) ÅT = 100 K
c = 33.2924 (9) Å0.37 × 0.24 × 0.22 mm
V = 3062.41 (9) Å3
Data collection top
Bruker X8 APEXII 4K Kappa CCD
diffractometer
3782 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
3209 reflections with I > 2σ(I)
Tmin = 0.273, Tmax = 0.364Rint = 0.083
31409 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.067Δρmax = 1.19 e Å3
S = 1.15Δρmin = 1.42 e Å3
3782 reflectionsAbsolute structure: Flack (1983), 1505 Friedel pairs
180 parametersAbsolute structure parameter: 0.010 (10)
2 restraints
Special details top

Experimental. The intensity data were collected on a Bruker X8 ApexII 4K Kappa CCD diffractometer using an exposure time of 20 s/frame with a frame width of 0.5°, a total of 949 frames were collected.

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)
Pt10.02824 (2)0.02824 (2)0.00000.02014 (9)
Cl10.13895 (16)0.06895 (16)0.05573 (4)0.0277 (4)
P20.11680 (16)0.14649 (16)0.04363 (4)0.0214 (3)
C10.0416 (7)0.2564 (6)0.08386 (15)0.0242 (14)
H10.01140.19360.10230.029*
C30.2444 (6)0.2641 (6)0.02059 (17)0.0304 (14)
H3A0.19450.32560.00150.036*
H3B0.31070.20710.00480.036*
C40.3287 (7)0.3562 (7)0.04924 (19)0.0400 (17)
H4A0.39020.28830.06360.048*0.50
H4B0.35920.43620.03210.048*0.50
C50.2461 (7)0.4254 (7)0.0834 (2)0.0341 (17)
H50.31590.46890.10180.041*
C60.1484 (7)0.5413 (8)0.0697 (2)0.0386 (17)
H6A0.20000.60300.05110.046*
H6B0.12210.59760.09340.046*
C70.0161 (6)0.4933 (6)0.04896 (18)0.0329 (16)
H7A0.04850.57340.04680.039*
H7B0.03960.46300.02140.039*
C80.0588 (7)0.3739 (7)0.07044 (18)0.0283 (17)
H80.09760.41480.09570.034*
C90.1633 (7)0.3203 (7)0.10820 (18)0.0305 (16)
H9A0.22630.24480.11730.037*
H9B0.12560.36730.13240.037*
C10A0.4311 (11)0.4562 (11)0.0298 (3)0.041 (3)0.50
H10A0.49480.40390.01230.062*0.50
H10B0.37990.52490.01370.062*0.50
H10C0.48480.50420.05060.062*0.50
C10B0.4639 (11)0.2847 (15)0.0608 (4)0.047 (4)0.50
H10D0.44530.21490.08170.071*0.50
H10E0.50380.23880.03720.071*0.50
H10F0.52980.35410.07110.071*0.50
C110.1822 (7)0.3252 (7)0.04652 (18)0.0326 (16)
H11A0.15160.29760.01960.049*
H11B0.22530.24530.06000.049*
H11C0.25030.40110.04440.049*
C210.2189 (6)0.0173 (7)0.07102 (16)0.0239 (14)
C220.1751 (6)0.0430 (7)0.10688 (16)0.0237 (13)
H220.08960.01300.11850.028*
C230.2508 (7)0.1438 (7)0.12603 (18)0.0288 (15)
H230.21830.18180.15070.035*
C240.3737 (7)0.1902 (7)0.1098 (2)0.0307 (16)
H240.42730.25920.12320.037*
C250.4184 (9)0.1361 (8)0.0740 (2)0.047 (2)
H250.50290.16830.06230.057*
C260.3409 (8)0.0350 (9)0.0548 (2)0.051 (2)
H260.37230.00020.02960.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.02319 (11)0.02319 (11)0.01406 (12)0.00274 (14)0.00116 (9)0.00116 (9)
Cl10.0303 (9)0.0402 (11)0.0127 (6)0.0100 (7)0.0031 (6)0.0069 (6)
P20.0231 (10)0.0261 (10)0.0151 (7)0.0033 (6)0.0014 (6)0.0018 (6)
C10.032 (4)0.031 (4)0.010 (3)0.002 (3)0.001 (3)0.003 (2)
C30.031 (4)0.029 (4)0.031 (3)0.003 (3)0.007 (3)0.001 (3)
C40.037 (5)0.033 (5)0.051 (4)0.007 (3)0.011 (3)0.014 (3)
C50.036 (4)0.025 (4)0.042 (4)0.001 (3)0.003 (3)0.009 (3)
C60.044 (4)0.032 (4)0.040 (4)0.008 (4)0.007 (3)0.002 (4)
C70.037 (4)0.030 (4)0.031 (3)0.011 (3)0.006 (3)0.003 (2)
C80.032 (4)0.030 (4)0.023 (3)0.015 (3)0.004 (3)0.001 (3)
C90.035 (4)0.027 (4)0.029 (3)0.006 (3)0.012 (3)0.008 (3)
C10A0.025 (7)0.037 (8)0.062 (8)0.009 (5)0.009 (6)0.023 (7)
C10B0.034 (8)0.072 (11)0.035 (8)0.001 (9)0.010 (8)0.016 (7)
C110.027 (4)0.044 (5)0.027 (3)0.010 (3)0.003 (3)0.002 (3)
C210.025 (3)0.028 (4)0.019 (3)0.003 (3)0.002 (2)0.005 (3)
C220.019 (3)0.027 (4)0.026 (3)0.005 (3)0.008 (2)0.000 (3)
C230.029 (4)0.027 (4)0.030 (3)0.005 (3)0.008 (3)0.004 (3)
C240.032 (4)0.023 (4)0.037 (4)0.002 (3)0.014 (3)0.002 (3)
C250.043 (5)0.049 (5)0.050 (5)0.027 (4)0.015 (4)0.007 (4)
C260.056 (5)0.054 (5)0.043 (4)0.029 (5)0.018 (4)0.015 (4)
Geometric parameters (Å, º) top
Pt1—P2i2.3088 (14)C7—H7B0.990
Pt1—P22.3088 (14)C8—C111.501 (9)
Pt1—Cl1i2.3320 (13)C8—H81.000
Pt1—Cl12.3320 (13)C9—H9A0.990
P2—C211.824 (6)C9—H9B0.990
P2—C31.833 (5)C10A—H10A0.980
P2—C11.851 (6)C10A—H10B0.980
C1—C91.548 (8)C10A—H10C0.980
C1—C81.548 (8)C10B—H10D0.980
C1—H11.000C10B—H10E0.980
C3—C41.530 (8)C10B—H10F0.980
C3—H3A0.990C11—H11A0.980
C3—H3B0.990C11—H11B0.980
C4—C10B1.517 (5)C11—H11C0.980
C4—C10A1.519 (5)C21—C261.383 (8)
C4—C51.535 (9)C21—C221.391 (8)
C4—H4A1.000C22—C231.368 (8)
C4—H4B1.000C22—H220.950
C5—C61.524 (9)C23—C241.371 (9)
C5—C91.526 (9)C23—H230.950
C5—H51.000C24—C251.368 (10)
C6—C71.515 (9)C24—H240.950
C6—H6A0.990C25—C261.379 (10)
C6—H6B0.990C25—H250.950
C7—C81.529 (8)C26—H260.950
C7—H7A0.990
P2i—Pt1—P2170.97 (9)C8—C7—H7A108.7
P2i—Pt1—Cl1i88.29 (5)C6—C7—H7B108.7
P2—Pt1—Cl1i92.06 (5)C8—C7—H7B108.7
P2i—Pt1—Cl192.06 (5)H7A—C7—H7B107.6
P2—Pt1—Cl188.29 (5)C11—C8—C7110.8 (5)
Cl1i—Pt1—Cl1175.49 (8)C11—C8—C1114.7 (5)
C21—P2—C3105.6 (3)C7—C8—C1112.8 (5)
C21—P2—C1103.6 (3)C11—C8—H8105.9
C3—P2—C1102.3 (3)C7—C8—H8105.9
C21—P2—Pt1107.7 (2)C1—C8—H8105.9
C3—P2—Pt1116.20 (19)C5—C9—C1111.7 (5)
C1—P2—Pt1120.0 (2)C5—C9—H9A109.3
C9—C1—C8109.4 (5)C1—C9—H9A109.3
C9—C1—P2108.1 (4)C5—C9—H9B109.3
C8—C1—P2116.6 (4)C1—C9—H9B109.3
C9—C1—H1107.5H9A—C9—H9B107.9
C8—C1—H1107.5C4—C10A—H10A109.5
P2—C1—H1107.5C4—C10A—H10B109.5
C4—C3—P2116.5 (4)C4—C10A—H10C109.5
C4—C3—H3A108.2C4—C10B—H10D109.5
P2—C3—H3A108.2C4—C10B—H10E109.5
C4—C3—H3B108.2H10D—C10B—H10E109.5
P2—C3—H3B108.2C4—C10B—H10F109.5
H3A—C3—H3B107.3H10D—C10B—H10F109.5
C10B—C4—C3110.4 (7)H10E—C10B—H10F109.5
C10A—C4—C3116.1 (6)C8—C11—H11A109.5
C10B—C4—C5116.6 (7)C8—C11—H11B109.5
C10A—C4—C5112.1 (6)H11A—C11—H11B109.5
C3—C4—C5116.0 (5)C8—C11—H11C109.5
C10A—C4—H4A103.5H11A—C11—H11C109.5
C3—C4—H4A103.5H11B—C11—H11C109.5
C5—C4—H4A103.5C26—C21—C22116.1 (6)
C10B—C4—H4B104.0C26—C21—P2120.3 (5)
C3—C4—H4B104.0C22—C21—P2123.3 (4)
C5—C4—H4B104.0C23—C22—C21122.2 (6)
H4A—C4—H4B126.8C23—C22—H22118.9
C6—C5—C9108.9 (6)C21—C22—H22118.9
C6—C5—C4114.3 (6)C22—C23—C24120.1 (6)
C9—C5—C4112.6 (5)C22—C23—H23119.9
C6—C5—H5106.9C24—C23—H23119.9
C9—C5—H5106.9C25—C24—C23119.3 (6)
C4—C5—H5106.9C25—C24—H24120.3
C7—C6—C5115.4 (6)C23—C24—H24120.3
C7—C6—H6A108.4C24—C25—C26120.1 (7)
C5—C6—H6A108.4C24—C25—H25119.9
C7—C6—H6B108.4C26—C25—H25119.9
C5—C6—H6B108.4C25—C26—C21122.0 (7)
H6A—C6—H6B107.5C25—C26—H26119.0
C6—C7—C8114.1 (5)C21—C26—H26119.0
C6—C7—H7A108.7
Cl1i—Pt1—P2—C21120.39 (19)C5—C6—C7—C846.0 (7)
Cl1—Pt1—P2—C2164.10 (19)C6—C7—C8—C11175.7 (5)
Cl1i—Pt1—P2—C32.2 (3)C6—C7—C8—C145.6 (7)
Cl1—Pt1—P2—C3177.8 (3)C9—C1—C8—C11179.9 (5)
Cl1i—Pt1—P2—C1121.7 (2)P2—C1—C8—C1157.1 (7)
Cl1—Pt1—P2—C153.9 (2)C9—C1—C8—C752.0 (6)
C21—P2—C1—C959.4 (4)P2—C1—C8—C771.0 (6)
C3—P2—C1—C950.2 (4)C6—C5—C9—C159.1 (7)
Pt1—P2—C1—C9179.5 (3)C4—C5—C9—C168.7 (7)
C21—P2—C1—C8176.9 (5)C8—C1—C9—C560.2 (7)
C3—P2—C1—C873.5 (6)P2—C1—C9—C567.8 (6)
Pt1—P2—C1—C856.9 (6)C3—P2—C21—C2639.5 (7)
C21—P2—C3—C468.0 (6)C1—P2—C21—C26146.6 (6)
C1—P2—C3—C440.1 (6)Pt1—P2—C21—C2685.3 (6)
Pt1—P2—C3—C4172.7 (4)C3—P2—C21—C22146.2 (5)
P2—C3—C4—C10B92.1 (8)C1—P2—C21—C2239.1 (6)
P2—C3—C4—C10A178.3 (7)Pt1—P2—C21—C2289.0 (5)
P2—C3—C4—C543.4 (8)C26—C21—C22—C232.7 (9)
C10B—C4—C5—C6156.6 (8)P2—C21—C22—C23177.3 (5)
C10A—C4—C5—C665.9 (9)C21—C22—C23—C240.8 (9)
C3—C4—C5—C670.7 (8)C22—C23—C24—C251.0 (10)
C10B—C4—C5—C978.6 (9)C23—C24—C25—C260.6 (12)
C10A—C4—C5—C9169.3 (7)C24—C25—C26—C211.5 (13)
C3—C4—C5—C954.1 (8)C22—C21—C26—C253.1 (11)
C9—C5—C6—C751.8 (7)P2—C21—C26—C25177.8 (7)
C4—C5—C6—C775.0 (7)
Symmetry code: (i) y, x, z.

Experimental details

Crystal data
Chemical formula[PtCl2(C16H23P)2]
Mr758.62
Crystal system, space groupTetragonal, P43212
Temperature (K)100
a, c (Å)9.5909 (1), 33.2924 (9)
V3)3062.41 (9)
Z4
Radiation typeMo Kα
µ (mm1)4.88
Crystal size (mm)0.37 × 0.24 × 0.22
Data collection
DiffractometerBruker X8 APEXII 4K Kappa CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.273, 0.364
No. of measured, independent and
observed [I > 2σ(I)] reflections
31409, 3782, 3209
Rint0.083
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.067, 1.15
No. of reflections3782
No. of parameters180
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.19, 1.42
Absolute structureFlack (1983), 1505 Friedel pairs
Absolute structure parameter0.010 (10)

Computer programs: APEX2 (Bruker, 2008), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2001).

Comparative data for trans-[Pt(Cl)2(P)2] complexes. top
PPt-P (Å)Pt-Cl (Å)Footnote
PEt32.298 (18)2.294 (9)(i)
PPh32.3164 (11)2.2997 (11)(ii)
PBz32.3219 (12)2.3092 (11)(iii)
2.3019 (10)2.3053 (10)(iii)
PCy32.337 (2)2.317 (2)(iv)
PPh2Fc2.318 (2)2.301 (2)(v)
s-PhobPBu2.3121 (11)2.3059 (11)(vi)
a7PhobPBu2.302 (4)2.307 (4)(vi)
2.321 (5)2.318 (4)(vi)
1,2,6-tpp2.3096 (12)2.3118 (12)(vii)
(i) Messmer & Amma (1966); (ii) Johansson & Otto (2000); (iii) Johansson et al. (2002); (iv) Del Pra & Zanotti (1980); (v) Otto & Roodt (1997); (vi) Carreira et al. (2009); (vii) Doherty et al. (2006).
 

Acknowledgements

Cytec is thanked for generously supplying the Lim-H ligand precursor. Financial support from Sasol Technology Research and Development and from the research fund of the University of the Free State is gratefully acknowledged. Part of this material is based on work supported by the South African National Research Foundation (NRF) under grant No. GUN 2053397. Any opinion, finding and conclusions or recommendations in this material are those of the authors and do not necessarily reflect the views of the NRF.

References

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