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Acta Cryst. (2007). E63, m1983    [ doi:10.1107/S1600536807030115 ]

Bis(cis-1,4-diphenyl-1,4-diphosphacyclohexane-[kappa]2P,P')platinum(II) bis(tetrafluoridoborate)

T. S. Morey, S. M. Miller and M. L. Helm

Abstract top

The title complex, [Pt(C16H18P2)2](BF4)2, possesses a crystallographically imposed center of symmetry occupied by a PtII ion, which is coordinated by four P atoms from two 1,4-diphenyl-1,4-diphosphacyclohexane ligands in a distorted square-planar geometry.

Comment top

The crystal structure of (I) consists of [Pt(C16H18P2)2]2+ cations and BF4− anions (Fig. 1). The cation shows a distorted square planar geometry around the metal center with two non-coordinating BF4− anions. The P—Pt—P bite angle observed in the structure is 72.908 (13)°. Additionally, the phenyl substituents on the phosphorus atoms are arranged in a parallel fashion, with a distance between the center of the phenyl rings of 3.727 Å and a dihedral angle of 2.15 (4)° between the rings. The parallel arrangement of phenyl rings is not, however, repeated in the unit cell between individual molecules. The parallel arrangement of the phenyl rings within the molecule was also observed in the previously reported analogous PtII an Pd(II) chloride complexes (Mason et al., 2006).

Related literature top

The corresponding complexes with both PtII and PdII have been previously reported as chloride salts (Mason et al., 2006). For related literature, see: Brooks et al. (1989).

Experimental top

The synthesis of (I) was completed through reaction of the previously reported chloride salt with an excess of AgBF4, followed by filtration to remove the solid AgCl (Mason et al., 2006, Brooks et al., 1989). Crystals where grown by slow vapor diffusion of diethylether into a saturated chloroform solution of (I).

Refinement top

All H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C—H distances in the range of 0.93–0.97 Å, with Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids. H–atoms are drawn as spheres with arbitrary radius.
Bis(cis-1,4-diphenyl-1,4-diphosphacyclohexane-κ2P,P')platinum(II) bis(tetrafluoridoborate) top
Crystal data top
[Pt(C16H18P2)2](BF4)2Z = 4
Mr = 913.20F000 = 1792
Tetragonal, P41212Dx = 1.775 Mg m−3
Hall symbol: P 4abw 2nwMelting point: not measured K
a = 10.83270 (15) ÅMo Kα radiation
λ = 0.71073 Å
b = 10.83270 (15) ÅCell parameters from 8065 reflections
c = 29.1244 (6) Åθ = 2.3–33.2º
α = 90ºµ = 4.36 mm−1
β = 90ºT = 373 (2) K
γ = 90ºPrismatic, colorless
V = 3417.67 (10) Å30.47 × 0.25 × 0.10 mm
Data collection top
Bruker APEXII area-detector
diffractometer		6509 independent reflections
Radiation source: fine-focus sealed tube6151 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.028
T = 373(2) Kθmax = 33.2º
φ and ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −16→16
Tmin = 0.281, Tmax = 0.647k = −16→16
41078 measured reflectionsl = −44→44
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.016  w = 1/[σ2(Fo2) + (0.0084P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.033(Δ/σ)max = 0.003
S = 0.98Δρmax = 0.69 e Å−3
6509 reflectionsΔρmin = −0.87 e Å−3
213 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapFlack parameter: 0.007 (3)
Crystal data top
[Pt(C16H18P2)2](BF4)2γ = 90º
Mr = 913.20V = 3417.67 (10) Å3
Tetragonal, P41212Z = 4
a = 10.83270 (15) ÅMo Kα
b = 10.83270 (15) ŵ = 4.36 mm−1
c = 29.1244 (6) ÅT = 373 (2) K
α = 90º0.47 × 0.25 × 0.10 mm
β = 90º
Data collection top
Bruker APEXII area-detector
diffractometer		6509 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		6151 reflections with I > 2σ(I)
Tmin = 0.281, Tmax = 0.647Rint = 0.028
41078 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.016H-atom parameters constrained
wR(F2) = 0.033Δρmax = 0.69 e Å−3
S = 0.98Δρmin = −0.87 e Å−3
6509 reflectionsAbsolute structure: Flack (1983)
213 parametersFlack parameter: 0.007 (3)
Special details top

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

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 > 2σ(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*/Ueq
Pt10.832348 (5)0.832348 (5)0.00000.01048 (2)
P10.84079 (4)1.00450 (4)0.045922 (11)0.01195 (6)
P20.84132 (4)0.64859 (3)−0.040032 (12)0.01251 (7)
C10.97255 (15)1.10328 (14)0.05191 (5)0.0148 (3)
C20.96273 (16)1.23257 (15)0.04781 (6)0.0184 (3)
H2A0.88721.26910.04110.022*
C31.06751 (18)1.30451 (16)0.05401 (6)0.0234 (4)
H3A1.06171.39000.05180.028*
C41.18032 (18)1.25058 (17)0.06340 (6)0.0247 (4)
H4A1.24971.29990.06760.030*
C51.19046 (15)1.12267 (17)0.06662 (6)0.0221 (3)
H5A1.26671.08650.07250.026*
C61.08678 (15)1.04949 (15)0.06097 (5)0.0180 (3)
H6A1.09340.96410.06320.022*
C70.80596 (14)0.94231 (14)0.10316 (5)0.0150 (3)
H7A0.87590.89500.11430.018*
H7B0.79121.00970.12440.018*
C80.70129 (14)1.09169 (15)0.03316 (5)0.0163 (3)
H8A0.68191.14690.05840.020*
H8B0.71301.14070.00560.020*
C90.85797 (14)0.68966 (14)−0.10070 (5)0.0158 (3)
H9A0.89500.6219−0.11760.019*
H9B0.77780.7074−0.11400.019*
C100.99765 (16)0.59454 (13)−0.02600 (5)0.0171 (3)
H10A1.00040.56690.00570.021*
H10B1.01920.5254−0.04560.021*
C110.73590 (14)0.52277 (14)−0.03228 (5)0.0152 (3)
C120.70222 (14)0.49227 (15)0.01255 (5)0.0158 (3)
H12A0.73750.53410.03710.019*
C130.61647 (15)0.40002 (15)0.02062 (5)0.0180 (3)
H13A0.59410.37990.05050.022*
C140.56379 (15)0.33727 (16)−0.01647 (6)0.0192 (3)
H14A0.50520.2762−0.01120.023*
C150.59824 (17)0.36542 (15)−0.06104 (6)0.0223 (4)
H15A0.56400.3220−0.08550.027*
C160.68378 (16)0.45819 (14)−0.06942 (5)0.0200 (3)
H16A0.70640.4775−0.09940.024*
B11.00964 (16)0.65886 (17)0.10947 (5)0.0167 (3)
F11.01041 (11)0.72699 (9)0.14989 (4)0.0289 (2)
F21.07033 (10)0.54795 (10)0.11657 (4)0.0334 (3)
F30.88695 (10)0.63397 (11)0.09696 (4)0.0319 (3)
F41.06599 (11)0.72618 (12)0.07492 (4)0.0350 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.01143 (2)0.01143 (2)0.00858 (3)0.00085 (3)0.00064 (2)−0.00064 (2)
P10.01367 (15)0.01235 (14)0.00981 (13)0.00177 (18)−0.00029 (13)−0.00078 (13)
P20.01565 (16)0.01150 (16)0.01038 (13)0.00070 (17)0.00073 (13)−0.00081 (12)
C10.0182 (7)0.0147 (7)0.0114 (6)−0.0019 (6)0.0002 (5)−0.0015 (5)
C20.0240 (8)0.0171 (7)0.0143 (7)0.0012 (7)0.0012 (6)0.0002 (6)
C30.0348 (9)0.0178 (8)0.0177 (7)−0.0063 (8)0.0012 (7)−0.0003 (6)
C40.0259 (9)0.0275 (8)0.0208 (7)−0.0122 (8)0.0007 (7)−0.0016 (6)
C50.0172 (8)0.0300 (8)0.0190 (7)−0.0040 (7)−0.0025 (6)−0.0013 (6)
C60.0197 (7)0.0180 (7)0.0165 (7)0.0010 (7)−0.0025 (6)−0.0010 (6)
C70.0180 (7)0.0175 (7)0.0094 (6)0.0006 (6)−0.0012 (5)−0.0007 (5)
C80.0183 (7)0.0147 (6)0.0158 (7)0.0039 (6)−0.0004 (5)−0.0013 (5)
C90.0192 (7)0.0165 (7)0.0116 (6)−0.0016 (6)−0.0002 (5)−0.0010 (5)
C100.0197 (7)0.0142 (6)0.0174 (6)0.0037 (7)−0.0004 (6)0.0008 (5)
C110.0186 (7)0.0125 (7)0.0145 (6)0.0016 (6)0.0003 (5)−0.0006 (5)
C120.0210 (7)0.0154 (6)0.0111 (5)0.0010 (7)−0.0018 (5)−0.0008 (5)
C130.0216 (8)0.0157 (7)0.0168 (6)0.0002 (6)0.0004 (6)0.0037 (6)
C140.0212 (7)0.0143 (6)0.0222 (7)−0.0010 (7)−0.0016 (6)0.0014 (6)
C150.0280 (8)0.0193 (7)0.0196 (7)−0.0043 (7)−0.0037 (6)−0.0041 (6)
C160.0257 (8)0.0188 (7)0.0154 (6)−0.0020 (7)−0.0001 (6)−0.0014 (5)
B10.0159 (7)0.0186 (8)0.0157 (6)−0.0001 (7)0.0008 (6)−0.0001 (6)
F10.0368 (6)0.0281 (5)0.0220 (5)0.0017 (6)0.0052 (5)−0.0078 (4)
F20.0316 (6)0.0203 (5)0.0484 (7)0.0082 (5)−0.0111 (5)−0.0084 (5)
F30.0193 (5)0.0343 (6)0.0422 (7)−0.0048 (5)−0.0082 (5)0.0085 (5)
F40.0357 (6)0.0486 (7)0.0208 (5)−0.0118 (6)0.0064 (5)0.0078 (5)
Geometric parameters (Å, °) top
Pt1—P12.2967 (4)C8—C10i1.555 (2)
Pt1—P1i2.2967 (4)C8—H8A0.9700
Pt1—P22.3089 (3)C8—H8B0.9700
Pt1—P2i2.3089 (3)C9—C7i1.558 (2)
P1—C11.7924 (16)C9—H9A0.9700
P1—C81.8204 (16)C9—H9B0.9700
P1—C71.8372 (15)C10—C8i1.555 (2)
P2—C111.7924 (16)C10—H10A0.9700
P2—C91.8309 (15)C10—H10B0.9700
P2—C101.8379 (17)C11—C121.395 (2)
C1—C61.393 (2)C11—C161.407 (2)
C1—C21.410 (2)C12—C131.384 (2)
C2—C31.389 (2)C12—H12A0.9300
C2—H2A0.9300C13—C141.398 (2)
C3—C41.382 (3)C13—H13A0.9300
C3—H3A0.9300C14—C151.384 (2)
C4—C51.393 (3)C14—H14A0.9300
C4—H4A0.9300C15—C161.389 (2)
C5—C61.385 (2)C15—H15A0.9300
C5—H5A0.9300C16—H16A0.9300
C6—H6A0.9300B1—F41.3845 (19)
C7—C9i1.558 (2)B1—F21.385 (2)
C7—H7A0.9700B1—F11.3894 (18)
C7—H7B0.9700B1—F31.404 (2)
P1—Pt1—P1i105.93 (2)C10i—C8—P1107.75 (11)
P1—Pt1—P2172.928 (14)C10i—C8—H8A110.2
P1i—Pt1—P272.908 (13)P1—C8—H8A110.2
P1—Pt1—P2i72.908 (13)C10i—C8—H8B110.2
P1i—Pt1—P2i172.928 (13)P1—C8—H8B110.2
P2—Pt1—P2i109.12 (2)H8A—C8—H8B108.5
C1—P1—C8111.79 (7)C7i—C9—P2107.38 (10)
C1—P1—C7107.11 (7)C7i—C9—H9A110.2
C8—P1—C7101.83 (7)P2—C9—H9A110.2
C1—P1—Pt1124.97 (5)C7i—C9—H9B110.2
C8—P1—Pt1105.63 (5)P2—C9—H9B110.2
C7—P1—Pt1102.85 (5)H9A—C9—H9B108.5
C11—P2—C9111.66 (7)C8i—C10—P2109.69 (10)
C11—P2—C10108.47 (7)C8i—C10—H10A109.7
C9—P2—C10101.61 (7)P2—C10—H10A109.7
C11—P2—Pt1124.41 (5)C8i—C10—H10B109.7
C9—P2—Pt1106.38 (5)P2—C10—H10B109.7
C10—P2—Pt1101.61 (5)H10A—C10—H10B108.2
C6—C1—C2119.91 (16)C12—C11—C16119.80 (14)
C6—C1—P1118.43 (12)C12—C11—P2117.68 (12)
C2—C1—P1121.66 (13)C16—C11—P2122.48 (12)
C3—C2—C1119.01 (16)C13—C12—C11120.34 (14)
C3—C2—H2A120.5C13—C12—H12A119.8
C1—C2—H2A120.5C11—C12—H12A119.8
C4—C3—C2120.76 (16)C12—C13—C14119.59 (14)
C4—C3—H3A119.6C12—C13—H13A120.2
C2—C3—H3A119.6C14—C13—H13A120.2
C3—C4—C5120.23 (17)C15—C14—C13120.48 (15)
C3—C4—H4A119.9C15—C14—H14A119.8
C5—C4—H4A119.9C13—C14—H14A119.8
C6—C5—C4119.84 (17)C14—C15—C16120.28 (15)
C6—C5—H5A120.1C14—C15—H15A119.9
C4—C5—H5A120.1C16—C15—H15A119.9
C5—C6—C1120.24 (15)C15—C16—C11119.50 (15)
C5—C6—H6A119.9C15—C16—H16A120.2
C1—C6—H6A119.9C11—C16—H16A120.2
C9i—C7—P1109.84 (10)F4—B1—F2110.86 (14)
C9i—C7—H7A109.7F4—B1—F1109.47 (14)
P1—C7—H7A109.7F2—B1—F1109.35 (12)
C9i—C7—H7B109.7F4—B1—F3109.26 (13)
P1—C7—H7B109.7F2—B1—F3108.75 (14)
H7A—C7—H7B108.2F1—B1—F3109.12 (13)
Symmetry codes: (i) y, x, −z.
Acknowledgements top

We thank the American Chemical Society Petroleum Research Fund (42268–GB3) for funding that supported this research.

references
References top

Brooks, P. J., Gallagher, M. J., Sarroff, A. & Bowyer, M. (1989). Phosphorus Sulfur Silicon Relat. Elem. 44, 235–247.

Bruker (2000). SHELXTL (Version 6.14) and SADABS (Version 2.10). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2006). APEX2 (Version 2.0-2). Bruker AXS Inc., Madison, Wisconsin, USA. Not in text?

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Mason, L. J., Perrault, E. M., Miller, S. M. & Helm, M. L. (2006). Inorg. Chem. Commun. 9, 946–948.

Sheldrick, G. M. (1997). SHELX97. University of Göttingen, Germany.