Bis(1-{bis­[2-(diphenyl­phosphino­yl)eth­yl]phosphan­yl}-2-(diphenyl­phosphan­yl)ethane)dinitratoplatinum(II) methanol tetra­solvate

Timo Paul Rieckborn; Emine Karakoc; Marc Heinrich Prosenc

doi:10.1107/S160053680801533X

. 2008 Jun 7;64(Pt 7):m898–m899. doi: 10.1107/S160053680801533X

Bis(1-{bis[2-(diphenylphosphinoyl)ethyl]phosphanyl}-2-(diphenylphosphanyl)ethane)dinitratoplatinum(II) methanol tetrasolvate

Timo Paul Rieckborn ^a, Emine Karakoc ^a, Marc Heinrich Prosenc ^a,^*

PMCID: PMC2961811 PMID: 21202764

Abstract

In the title compound, [Pt(NO₃)₂(C₄₂H₄₂O₂P₄)₂]·4CH₃OH, the Pt atom positioned on a crystallographic centre of inversion. The two symmetry-equivalent nitrate anions are weakly coordinated to the Pt^II ion, creating, together with four P ligand atoms, a distorted octahedral coordination environment. In addition, several close C—H⋯O contacts between the nitrate O atoms and phenyl H atoms are found. Hydrogen bonds from two methanol solvent molecules to one of the O—P groups complete the crystal structure.

Related literature

For related literature on Pt^II complexes, see: Brüggeller et al. (1992 ▶). For a structure of a related Pt^II nitrato complex, see: Fernandez et al. (2001 ▶).

Experimental

Crystal data

[Pt(NO₃)₂(C₄₂H₄₂O₂P₄)₂]·4CH₄O
M _r = 1852.64
Triclinic,
a = 9.9905 (9) Å
b = 14.3346 (13) Å
c = 16.9916 (15) Å
α = 66.200 (1)°
β = 77.479 (1)°
γ = 88.477 (1)°
V = 2168.4 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.83 mm⁻¹
T = 153 (2) K
0.48 × 0.10 × 0.03 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ▶) T _min = 0.474, T _max = 0.947
25181 measured reflections
9347 independent reflections
8160 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.068
S = 0.91
9347 reflections
512 parameters
H-atom parameters constrained
Δρ_max = 1.31 e Å⁻³
Δρ_min = −1.37 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801533X/si2089sup1.cif

e-64-0m898-sup1.cif^{(29.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680801533X/si2089Isup2.hkl

e-64-0m898-Isup2.hkl^{(457.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Pt1—P2	2.3236 (9)
Pt1—P1	2.3399 (9)
Pt1—O4	3.524 (3)

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P2—Pt1—P1	83.40 (3)
P2—Pt1—O4	99.77 (5)
P1—Pt1—O4	104.36 (5)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6C⋯O2	0.84	2.32	3.160 (9)	174
O7—H7A⋯O2	0.84	1.95	2.777 (4)	170
C12—H12A⋯O4	0.95	2.29	3.132 (4)	147
C6—H6B⋯O4	0.99	2.53	3.294 (4)	134
C1—H1B⋯O5ⁱ	0.99	2.42	3.289 (5)	146
C1—H1C⋯O5ⁱⁱ	0.99	2.44	3.399 (5)	162
C8—H8A⋯O3ⁱ	0.95	2.58	3.376 (5)	142
C14—H14A⋯O4ⁱⁱ	0.95	2.56	3.317 (5)	137
C27—H27A⋯O6ⁱⁱⁱ	0.95	2.50	3.338 (11)	147
C28—H28A⋯O2ⁱⁱⁱ	0.95	2.60	3.385 (5)	141

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

Financial support by the Deutsche Forschungsgemeinschaft (DFG) (grant No. PR 654/1–1) is gratefully acknowlegded. TPR thanks the Studienstiftung des deutschen Volkes for a fellowship.

supplementary crystallographic information

Comment

The title compound, [Pt(L)₂]²⁺ (NO₃^-)₂ (L = (P1,P1-bis(2-(diphenylphosphinoxid)ethyl)-P2,P2-diphenylethane -1,2-diphosphine), crystallizes as a packing of a discrete dication and two nitrate anions with the Pt-atom positioned on a centre of inversion. The two symmetry equivalent ligands molecules L are coordinated to the Pt-center by two phosphine donor atoms P1 and P2 with Pt—P distances (d(Pt—P1) = 2.3399 (9) Å, d(Pt—P2) = 2.3236 (9) Å) (Table 1) creating a square planar coordination environment in accord with previously reported Pt^II tetraphosphine complexes (Brüggeller et al., 1992). The two additional phosphor oxide groups of the ligands are not coordinated to the metal centre in the solid state. A long distance of d(Pt1—O4) = 3.524 (3) Å, angles of P1—Pt—O4 of 104.36 (5) ° and P2—Pt—O4 of 99.77 (5) ° are indicative of a weak Pt—NO₃^- interaction which is much weaker than a previously reported Pt^II—NO₃^- distance of 2.116 Å in a related complex (Fernandez et al., 2001). The nitrate anion is packed within a cavity created by the coordinated phosphine ligand atoms above and due to symmetry below the square plane spanned by the four phosphor ligand atoms creating a distorted octahedral coordination environment around the Pt^II ion. In addition several close C—H···O contacts between 2.30 and 2.70 Å were found between ortho-phenyl protons and methylene protons with nitrate oxygen atoms. Two methanol molecules with O—H···O hydrogen bonds to one of the O—P groups (Table 2) complete the crystal packing. The second P—O1 fragment exhibits weak hydrogen bond interactions with d(O1—H17A) of 2.997 Å and d(O1—H18A) of 2.991 Å to one of the adjacent phenyl group hydrogen atoms.

Experimental

All reactions were carried out under an atmosphere of dry nitrogen using standard Schlenk techniques. Solvents were dried and stored under nitrogen. Platinum(II)nitrate was purchased from ChemPur and Tris(2-(diphenylphosphino)ethyl)-phosphine was obtained from Acros Organics.

150 mg (0.47 mmol) Platinum(II)nitrate was dissolved in 50 ml water and 50 ml e thanol was added. 315 mg (0.47 mmol) Tris(2-(diphenylphosphino)ethyl)- phosphine (PP3) was dissolved in dichlormethane and added to the reaction mixture. The suspension was stirred at room temperature for 3 days. Afterwards the mixture was concentrated to small volume and a yellow solid precipitated. The precipitate was filtered and dried in vacuo. Single crystals were received by gas phase diffusion of diethyl ether into a solution of the yellow product in methanol.