(Penta­fluoro­propionato-κO)tetra­kis­(trimethyl­phosphine oxide-κO)copper(II) penta­fluoro­propionate

Iwona B Szymańska; Liliana Dobrzańska

doi:10.1107/S1600536811031114

. 2011 Aug 11;67(Pt 9):m1225–m1226. doi: 10.1107/S1600536811031114

(Pentafluoropropionato-κO)tetrakis(trimethylphosphine oxide-κO)copper(II) pentafluoropropionate

Iwona B Szymańska ^a, Liliana Dobrzańska ^b,^c,^*

PMCID: PMC3200869 PMID: 22064902

Abstract

The title compound, [Cu(C₃F₅O₂)(C₃H₉OP)₄](C₃F₅O₂), comprises a cationic Cu^II complex and a disordered pentafluoropropionate counter-ion. The metal atom has a distorted square-pyramidal coordination environment formed by four O atoms originating from trimethylphosphine oxide molecules and the remaining one belonging to the monodentate pentafluoropropionate anion, which is situated in the basal plane of the pyramid. The molecules are held together in the crystal by a net of weak C—H⋯O and C—H⋯F hydrogen bonds. The counter anion is disordered over two sets of sites in a 0.629 (5):0.371 (5) ratio.

Related literature

For our previous studies on metal complexes suitable for chemical vapour deposition (CVD), see: Szymańska et al. (2007 ▶, 2009 ▶); Piszczek et al. (2008 ▶). For crystal structures of metal complexes with trimethylphosphine oxide ligands involving metal ions from the first transition series, see: Hill et al. (2003 ▶) for Sc(III); Johnson & Bergman (2001 ▶) for Ti(III); Veige et al. (2003 ▶) for V(III); Cotton et al. (1991 ▶) for Fe(II); Edelmann & Behrens (1986 ▶) for Co(II); Klein et al. (1999 ▶) for Ni(II); Hlavinka & Hagadorn (2005 ▶) for Zn(II). For crystallographic data on Cu^II complexes with a pentafluoropropionate ligand, see: Jiang et al. (1998 ▶); Zhang et al. (1999 ▶).

Experimental

Crystal data

[Cu(C₃F₅O₂)(C₃H₉OP)₄](C₃F₅O₂)
M _r = 757.89
Triclinic,
a = 9.5955 (8) Å
b = 12.2627 (11) Å
c = 14.1848 (12) Å
α = 82.720 (2)°
β = 80.501 (1)°
γ = 82.899 (2)°
V = 1623.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.96 mm⁻¹
T = 100 K
0.48 × 0.17 × 0.03 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T _min = 0.655, T _max = 0.972
10254 measured reflections
7148 independent reflections
6207 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.124
S = 1.07
7148 reflections
416 parameters
33 restraints
H-atom parameters constrained
Δρ_max = 1.33 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811031114/hp2011sup1.cif

e-67-m1225-sup1.cif^{(28.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031114/hp2011Isup2.hkl

e-67-m1225-Isup2.hkl^{(349.7KB, hkl)}

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

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

Cu1—O1	1.9535 (18)
Cu1—O4	1.9582 (18)
Cu1—O3	1.965 (2)
Cu1—O5	1.9863 (19)
Cu1—O2	2.1876 (19)

Open in a new tab

O1—Cu1—O4	172.44 (8)
O1—Cu1—O3	90.48 (8)
O4—Cu1—O3	88.42 (8)
O1—Cu1—O5	91.12 (8)
O4—Cu1—O5	87.71 (8)
O3—Cu1—O5	162.51 (8)
O1—Cu1—O2	94.54 (7)
O4—Cu1—O2	92.99 (7)
O3—Cu1—O2	102.55 (8)
O5—Cu1—O2	94.69 (8)

Open in a new tab

Table 2. Geometry of selected hydrogen bonds (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯O5	0.98	2.57	3.265 (3)	128
C5—H5A⋯O4	0.98	2.42	3.204 (4)	136
C10—H10B⋯O3	0.98	2.58	3.266 (4)	127
C1—H1A⋯F2ⁱ	0.98	2.52	3.392 (3)	149
C1—H1B⋯O6ⁱⁱ	0.98	2.47	3.265 (3)	138
C4—H4A⋯F4ⁱⁱⁱ	0.98	2.51	3.482 (3)	170
C4—H4C⋯F3ⁱ	0.98	2.53	3.478 (5)	163
C9—H9A⋯F7A	0.98	2.44	3.322 (6)	150
C11—H11B⋯O8A^iv	0.98	2.42	3.289 (7)	147
C12—H12B⋯O8A^iv	0.98	2.52	3.388 (8)	147

Open in a new tab

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

Acknowledgments

IBSz thanks the Ministry of Science and High Education for grant N N204 546539. LD thanks the Research Foundation Flanders (FWO) for financial support.

supplementary crystallographic information

Comment

During our ongoing studies on metal complexes with tertiary phosphines (Szymańska et al., 2007) and perfluorinated carboxylates (Piszczek et al., 2008; Szymańska et al., 2009) suitable for chemical vapour deposition (CVD), the title compound was accidentally isolated. It is the first report on the crystal structure of a Cu complex with trimethylphosphine oxides. There is however some literature on coordination compounds of trimethylphosphine oxide ligands with other metals from the first transition series such as: Sc(III) (Hill et al., 2003), Ti(III) (Johnson & Bergman, 2001), V(III) (Veige et al., 2003), Fe(II) (Cotton et al., 1991), Co(II) (Edelmann & Behrens, 1986), Ni(II) (Klein et al., 1999), Zn(II) (Hlavinka & Hagadorn, 2005).

Furthermore, there are also only two reports on crystal structures of Cu^II complexes containing coordinating pentafluoropropionate ions (Jiang et al., 1998; Zhang et al., 1999).

The title compound has one monocationic Cu^II complex and one pentafluoropropionate counter-ion present in the asymmetric unit (Fig.1). The geometry around the Cu^II ion is a distorted square-pyramid formed by four O atoms originating from trimethylphosphine oxide molecules and one from the monodentate pentafluoropropionate ion, which is located in the base plane of the pyramid. The corresponding bond lengths and angles are presented in Table 1. The geometrical features of the ligands are in good agreement with reported values. The counter-ion is disordered over two positions with refined site occupancies of 0.629 (5):0.371 (5). There are weak intramolecular C—H···O interactions between the methyl groups of three distinct trimethylphosphine oxides (P1, P2 and P4) involving the atoms C3, C5 and C10, that act as donors, and O5 (from the counter-ion), as well as O4 and O3 (from the oxide ligands), that act as acceptors, respectively (Table 2). The C9 methyl group from P3 however, interacts with the counter-ion by weak C9—H9A···F7A hydrogen bonding with a C···F distance of 3.322 (6) Å, and a C—H—F angle of 150°. The packing is further stabilized by numerous weak intermolecular C—H···O and C—H···F interactions.

Experimental

(C₂F₅COO)₂Cu (1.04 mmol) was placed in a Schlenk tube, dissolved in 25 ml of freshly distilled acetonitrile, and copper powder (5 mmol) was added. The obtained suspension was stirred until the solution was pale yellow. Then PMe₃ (2.1 ml of a 1 M THF solution) was added and the reaction mixture was stirred for 18 h at ambient temperature, and filtered. The solvent was evaporated under reduced pressure, yielding [Cu₂(PMe₃)₂(µ–C₂F₅CO₂)₂] as a pale yellow, viscous oil. Crystals of the title Cu^II complex suitable for X-ray studies were obtained after a few months, presumably upon slow oxidation by diffused air.