metal-organic compounds
(Pentafluoropropionato-κO)tetrakis(trimethylphosphine oxide-κO)copper(II) pentafluoropropionate
aFaculty of Chemistry, Nicolaus Copernicus University, Gagarina 7,87-100 Toruń, Poland, bDepartment of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F - bus 2404, B-3001 Heverlee, Belgium, and cDepartment of Chemistry, University of Stellenbosch, Private Bag X1, Matieland, South Africa
*Correspondence e-mail: lianger@chem.kuleuven.be
The title compound, [Cu(C3F5O2)(C3H9OP)4](C3F5O2), comprises a cationic CuII 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 CuII complexes with a pentafluoropropionate ligand, see: Jiang et al. (1998); Zhang et al. (1999).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2001); cell 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.
Supporting information
10.1107/S1600536811031114/hp2011sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811031114/hp2011Isup2.hkl
(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 CuII complex suitable for X-ray studies were obtained after a few months, presumably upon slow oxidation by diffused air.
All H atoms were positioned geometrically, with C—H = 0.98 and constrained to ride on their parent atoms with Uiso(H) = 1.5Ueq(C). The counter-ion was found to be disordered and modeled in two positions.
included bond lengths restraints applied to the O8B—O7B, C17B—O7B and C17B—O8B as well as to ADPs of 'A' part.Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level; the other orientation of the disordered counter-ion has been omitted for clarity. |
[Cu(C3F5O2)(C3H9OP)4](C3F5O2) | Z = 2 |
Mr = 757.89 | F(000) = 774 |
Triclinic, P1 | Dx = 1.550 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5955 (8) Å | Cell parameters from 5155 reflections |
b = 12.2627 (11) Å | θ = 2.2–28.1° |
c = 14.1848 (12) Å | µ = 0.96 mm−1 |
α = 82.720 (2)° | T = 100 K |
β = 80.501 (1)° | Plate, colorless |
γ = 82.899 (2)° | 0.48 × 0.17 × 0.03 mm |
V = 1623.9 (2) Å3 |
Bruker APEX CCD area-detector diffractometer | 7148 independent reflections |
Radiation source: fine-focus sealed tube | 6207 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ω scans | θmax = 28.3°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −10→12 |
Tmin = 0.655, Tmax = 0.972 | k = −12→15 |
10254 measured reflections | l = −12→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0677P)2 + 1.8569P] where P = (Fo2 + 2Fc2)/3 |
7148 reflections | (Δ/σ)max = 0.004 |
416 parameters | Δρmax = 1.33 e Å−3 |
33 restraints | Δρmin = −0.64 e Å−3 |
[Cu(C3F5O2)(C3H9OP)4](C3F5O2) | γ = 82.899 (2)° |
Mr = 757.89 | V = 1623.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.5955 (8) Å | Mo Kα radiation |
b = 12.2627 (11) Å | µ = 0.96 mm−1 |
c = 14.1848 (12) Å | T = 100 K |
α = 82.720 (2)° | 0.48 × 0.17 × 0.03 mm |
β = 80.501 (1)° |
Bruker APEX CCD area-detector diffractometer | 7148 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 6207 reflections with I > 2σ(I) |
Tmin = 0.655, Tmax = 0.972 | Rint = 0.016 |
10254 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 33 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.33 e Å−3 |
7148 reflections | Δρmin = −0.64 e Å−3 |
416 parameters |
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 > σ(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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.08108 (3) | 0.78725 (2) | 0.19051 (2) | 0.01610 (10) | |
P1 | 0.24449 (7) | 0.85300 (5) | −0.01852 (5) | 0.01593 (14) | |
F1 | −0.1350 (2) | 0.6864 (2) | −0.05341 (14) | 0.0504 (6) | |
O1 | 0.18617 (19) | 0.87540 (15) | 0.08413 (13) | 0.0192 (4) | |
C1 | 0.3916 (3) | 0.9301 (2) | −0.0631 (2) | 0.0219 (5) | |
H1B | 0.3621 | 1.0088 | −0.0583 | 0.033* | |
H1C | 0.4253 | 0.9186 | −0.1305 | 0.033* | |
H1A | 0.4683 | 0.9053 | −0.0251 | 0.033* | |
P2 | 0.25316 (7) | 0.53881 (6) | 0.24912 (5) | 0.02095 (16) | |
F2 | −0.3344 (2) | 0.76050 (17) | 0.0154 (2) | 0.0551 (7) | |
O2 | 0.2545 (2) | 0.65462 (16) | 0.20071 (14) | 0.0241 (4) | |
C2 | 0.1173 (3) | 0.8928 (2) | −0.09896 (19) | 0.0216 (5) | |
H2A | 0.0808 | 0.9706 | −0.0950 | 0.032* | |
H2C | 0.0386 | 0.8467 | −0.0810 | 0.032* | |
H2B | 0.1628 | 0.8829 | −0.1649 | 0.032* | |
P3 | 0.23148 (7) | 0.95789 (6) | 0.28343 (5) | 0.02113 (16) | |
F3 | −0.3038 (4) | 0.5932 (3) | 0.17037 (17) | 0.0865 (11) | |
O3 | 0.1153 (2) | 0.88590 (17) | 0.28130 (14) | 0.0239 (4) | |
C3 | 0.3067 (3) | 0.7111 (2) | −0.0298 (2) | 0.0241 (6) | |
H3B | 0.2287 | 0.6654 | −0.0061 | 0.036* | |
H3C | 0.3841 | 0.6884 | 0.0081 | 0.036* | |
H3A | 0.3416 | 0.7017 | −0.0975 | 0.036* | |
P4 | −0.15738 (7) | 0.75219 (6) | 0.37572 (5) | 0.02040 (16) | |
F4 | −0.3406 (2) | 0.54896 (16) | 0.03595 (14) | 0.0372 (4) | |
O4 | −0.0456 (2) | 0.71361 (15) | 0.29524 (14) | 0.0219 (4) | |
C4 | 0.4003 (3) | 0.4476 (3) | 0.2000 (2) | 0.0311 (7) | |
H4C | 0.4893 | 0.4776 | 0.2029 | 0.047* | |
H4A | 0.3931 | 0.4405 | 0.1330 | 0.047* | |
H4B | 0.3988 | 0.3747 | 0.2374 | 0.047* | |
F5 | −0.1333 (3) | 0.51630 (18) | 0.0786 (2) | 0.0734 (9) | |
O5 | −0.00828 (19) | 0.71780 (16) | 0.09965 (14) | 0.0210 (4) | |
C5 | 0.0986 (3) | 0.4756 (3) | 0.2401 (3) | 0.0339 (7) | |
H5A | 0.0134 | 0.5217 | 0.2659 | 0.051* | |
H5C | 0.1016 | 0.4023 | 0.2769 | 0.051* | |
H5B | 0.0959 | 0.4681 | 0.1724 | 0.051* | |
O6 | −0.1970 (2) | 0.84408 (17) | 0.12865 (17) | 0.0327 (5) | |
C6 | 0.2642 (4) | 0.5320 (3) | 0.3743 (2) | 0.0373 (8) | |
H6A | 0.1857 | 0.5805 | 0.4053 | 0.056* | |
H6B | 0.3548 | 0.5561 | 0.3822 | 0.056* | |
H6C | 0.2581 | 0.4558 | 0.4040 | 0.056* | |
C7 | 0.4043 (3) | 0.8860 (3) | 0.2605 (2) | 0.0337 (7) | |
H7B | 0.4105 | 0.8184 | 0.3052 | 0.050* | |
H7C | 0.4752 | 0.9333 | 0.2695 | 0.050* | |
H7A | 0.4224 | 0.8668 | 0.1943 | 0.050* | |
C8 | 0.2270 (3) | 1.0803 (2) | 0.2011 (2) | 0.0285 (6) | |
H8B | 0.1326 | 1.1216 | 0.2115 | 0.043* | |
H8A | 0.2473 | 1.0603 | 0.1351 | 0.043* | |
H8C | 0.2987 | 1.1262 | 0.2113 | 0.043* | |
C9 | 0.2105 (4) | 1.0049 (3) | 0.3994 (2) | 0.0371 (8) | |
H9B | 0.1156 | 1.0445 | 0.4138 | 0.056* | |
H9C | 0.2826 | 1.0547 | 0.4003 | 0.056* | |
H9A | 0.2218 | 0.9413 | 0.4479 | 0.056* | |
C10 | −0.2257 (3) | 0.8943 (3) | 0.3576 (2) | 0.0297 (6) | |
H10B | −0.1475 | 0.9407 | 0.3488 | 0.045* | |
H10C | −0.2944 | 0.9133 | 0.4138 | 0.045* | |
H10A | −0.2728 | 0.9067 | 0.3003 | 0.045* | |
C11 | −0.0891 (3) | 0.7320 (3) | 0.4869 (2) | 0.0317 (7) | |
H11A | −0.0069 | 0.7738 | 0.4812 | 0.048* | |
H11C | −0.0601 | 0.6532 | 0.5025 | 0.048* | |
H11B | −0.1629 | 0.7579 | 0.5379 | 0.048* | |
C12 | −0.3045 (3) | 0.6728 (3) | 0.3907 (2) | 0.0308 (7) | |
H12C | −0.2711 | 0.5940 | 0.4011 | 0.046* | |
H12A | −0.3503 | 0.6869 | 0.3329 | 0.046* | |
H12B | −0.3730 | 0.6938 | 0.4464 | 0.046* | |
C13 | −0.1330 (3) | 0.7628 (2) | 0.0938 (2) | 0.0221 (5) | |
C14 | −0.2120 (3) | 0.7015 (2) | 0.0332 (2) | 0.0238 (6) | |
C15 | −0.2495 (4) | 0.5889 (3) | 0.0808 (2) | 0.0369 (8) | |
O7A | 0.4474 (9) | 0.8498 (7) | 0.7251 (5) | 0.0477 (17) | 0.629 (5) |
O8A | 0.5882 (6) | 0.7691 (6) | 0.6074 (5) | 0.0323 (13) | 0.629 (5) |
C16A | 0.4755 (7) | 0.8008 (5) | 0.6533 (5) | 0.021 (2) | 0.629 (5) |
C17A | 0.3420 (5) | 0.7754 (4) | 0.6121 (4) | 0.0329 (9) | 0.629 (5) |
F6A | 0.2231 (3) | 0.8483 (2) | 0.6315 (2) | 0.0347 (8) | 0.629 (5) |
F7A | 0.3679 (4) | 0.7818 (4) | 0.5132 (2) | 0.0379 (9) | 0.629 (5) |
C18A | 0.2969 (6) | 0.6623 (4) | 0.6453 (4) | 0.0372 (10) | 0.629 (5) |
F8A | 0.2645 (6) | 0.6562 (5) | 0.7412 (3) | 0.0703 (16) | 0.629 (5) |
F9A | 0.1885 (4) | 0.6422 (4) | 0.6027 (4) | 0.0480 (12) | 0.629 (5) |
F10A | 0.3998 (4) | 0.5841 (3) | 0.6197 (4) | 0.0678 (16) | 0.629 (5) |
O7B | 0.4232 (16) | 0.8398 (13) | 0.7137 (9) | 0.052 (4)* | 0.371 (5) |
O8B | 0.5843 (13) | 0.8011 (11) | 0.5898 (11) | 0.071 (6) | 0.371 (5) |
C16B | 0.4611 (9) | 0.7981 (10) | 0.6411 (8) | 0.035 (6)* | 0.371 (5) |
C17B | 0.3690 (6) | 0.7217 (6) | 0.6021 (4) | 0.041 (2)* | 0.371 (5) |
F7B | 0.3527 (9) | 0.7481 (6) | 0.5070 (4) | 0.053 (3)* | 0.371 (5) |
F6B | 0.4318 (6) | 0.6141 (5) | 0.6041 (5) | 0.0376 (18)* | 0.371 (5) |
C18B | 0.2217 (7) | 0.7160 (6) | 0.6562 (4) | 0.046 (2)* | 0.371 (5) |
F8B | 0.1567 (7) | 0.8193 (4) | 0.6525 (4) | 0.0486 (17)* | 0.371 (5) |
F9B | 0.1530 (7) | 0.6463 (5) | 0.6187 (4) | 0.0319 (19)* | 0.371 (5) |
F10B | 0.2208 (7) | 0.6733 (6) | 0.7469 (4) | 0.0378 (18)* | 0.371 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01510 (16) | 0.01617 (17) | 0.01697 (17) | −0.00428 (12) | −0.00109 (11) | −0.00082 (12) |
P1 | 0.0158 (3) | 0.0150 (3) | 0.0169 (3) | −0.0026 (2) | −0.0013 (2) | −0.0017 (2) |
F1 | 0.0599 (14) | 0.0691 (15) | 0.0299 (10) | −0.0364 (12) | −0.0006 (9) | −0.0139 (10) |
O1 | 0.0221 (9) | 0.0172 (9) | 0.0179 (9) | −0.0055 (7) | 0.0004 (7) | −0.0017 (7) |
C1 | 0.0181 (12) | 0.0232 (13) | 0.0236 (13) | −0.0048 (10) | −0.0008 (10) | −0.0002 (11) |
P2 | 0.0181 (3) | 0.0204 (3) | 0.0220 (3) | 0.0000 (3) | −0.0013 (2) | 0.0024 (3) |
F2 | 0.0481 (12) | 0.0329 (11) | 0.0966 (19) | 0.0074 (9) | −0.0504 (13) | −0.0130 (11) |
O2 | 0.0189 (9) | 0.0232 (10) | 0.0273 (10) | −0.0015 (8) | −0.0017 (8) | 0.0053 (8) |
C2 | 0.0213 (12) | 0.0226 (13) | 0.0213 (13) | −0.0041 (11) | −0.0044 (10) | −0.0008 (10) |
P3 | 0.0221 (3) | 0.0230 (4) | 0.0199 (3) | −0.0078 (3) | −0.0044 (3) | −0.0015 (3) |
F3 | 0.148 (3) | 0.096 (2) | 0.0307 (12) | −0.097 (2) | 0.0034 (15) | −0.0048 (13) |
O3 | 0.0256 (10) | 0.0268 (10) | 0.0204 (9) | −0.0106 (8) | 0.0011 (8) | −0.0057 (8) |
C3 | 0.0280 (14) | 0.0170 (13) | 0.0253 (14) | 0.0011 (11) | 0.0004 (11) | −0.0047 (10) |
P4 | 0.0184 (3) | 0.0224 (3) | 0.0199 (3) | −0.0047 (3) | 0.0007 (2) | −0.0025 (3) |
F4 | 0.0430 (11) | 0.0317 (10) | 0.0440 (11) | −0.0200 (9) | −0.0147 (9) | −0.0053 (8) |
O4 | 0.0207 (9) | 0.0191 (9) | 0.0235 (10) | −0.0036 (7) | 0.0035 (7) | −0.0007 (7) |
C4 | 0.0251 (14) | 0.0303 (16) | 0.0333 (16) | 0.0069 (12) | −0.0011 (12) | 0.0002 (13) |
F5 | 0.0782 (18) | 0.0247 (11) | 0.134 (3) | −0.0036 (11) | −0.0712 (19) | −0.0002 (13) |
O5 | 0.0186 (9) | 0.0223 (10) | 0.0232 (9) | −0.0063 (8) | −0.0033 (7) | −0.0020 (7) |
C5 | 0.0250 (14) | 0.0236 (15) | 0.054 (2) | −0.0052 (12) | −0.0060 (14) | −0.0057 (14) |
O6 | 0.0338 (11) | 0.0214 (10) | 0.0461 (13) | 0.0031 (9) | −0.0157 (10) | −0.0088 (9) |
C6 | 0.0400 (18) | 0.045 (2) | 0.0225 (15) | 0.0030 (15) | −0.0028 (13) | 0.0042 (13) |
C7 | 0.0243 (14) | 0.0352 (17) | 0.0403 (18) | −0.0036 (13) | −0.0085 (13) | 0.0055 (14) |
C8 | 0.0299 (15) | 0.0247 (15) | 0.0313 (15) | −0.0071 (12) | −0.0065 (12) | 0.0019 (12) |
C9 | 0.050 (2) | 0.0398 (18) | 0.0264 (16) | −0.0216 (16) | −0.0047 (14) | −0.0079 (13) |
C10 | 0.0279 (14) | 0.0259 (15) | 0.0324 (16) | 0.0015 (12) | 0.0018 (12) | −0.0050 (12) |
C11 | 0.0315 (15) | 0.0391 (18) | 0.0253 (15) | −0.0034 (13) | −0.0051 (12) | −0.0055 (13) |
C12 | 0.0236 (14) | 0.0383 (17) | 0.0307 (16) | −0.0140 (13) | 0.0073 (11) | −0.0090 (13) |
C13 | 0.0235 (13) | 0.0191 (13) | 0.0255 (14) | −0.0069 (11) | −0.0078 (10) | 0.0009 (10) |
C14 | 0.0246 (13) | 0.0229 (14) | 0.0261 (14) | −0.0043 (11) | −0.0096 (11) | −0.0013 (11) |
C15 | 0.054 (2) | 0.0300 (17) | 0.0333 (17) | −0.0229 (16) | −0.0176 (15) | 0.0027 (13) |
O7A | 0.059 (4) | 0.062 (4) | 0.029 (3) | −0.007 (3) | −0.003 (2) | −0.032 (2) |
O8A | 0.030 (2) | 0.030 (4) | 0.036 (3) | −0.0178 (18) | 0.0070 (18) | −0.001 (2) |
C16A | 0.023 (3) | 0.028 (4) | 0.015 (3) | −0.0121 (19) | −0.003 (2) | −0.0083 (18) |
C17A | 0.038 (2) | 0.027 (2) | 0.0363 (18) | 0.0004 (15) | −0.007 (2) | −0.0156 (17) |
F6A | 0.0312 (16) | 0.0262 (15) | 0.0452 (17) | 0.0042 (12) | −0.0056 (13) | −0.0053 (13) |
F7A | 0.045 (2) | 0.049 (2) | 0.0245 (14) | −0.0102 (17) | −0.0080 (12) | −0.0096 (13) |
C18A | 0.036 (3) | 0.0291 (18) | 0.050 (2) | −0.0039 (18) | −0.016 (2) | −0.0034 (19) |
F8A | 0.058 (3) | 0.108 (4) | 0.0394 (17) | −0.005 (3) | −0.0178 (19) | 0.025 (2) |
F9A | 0.0239 (19) | 0.071 (3) | 0.055 (2) | −0.023 (2) | −0.0081 (18) | −0.007 (2) |
F10A | 0.046 (2) | 0.0196 (18) | 0.151 (5) | 0.0063 (18) | −0.048 (3) | −0.025 (2) |
O8B | 0.092 (9) | 0.038 (8) | 0.069 (9) | −0.038 (6) | 0.058 (7) | −0.016 (6) |
Cu1—O1 | 1.9535 (18) | O6—C13 | 1.220 (4) |
Cu1—O4 | 1.9582 (18) | C6—H6A | 0.9800 |
Cu1—O3 | 1.965 (2) | C6—H6B | 0.9800 |
Cu1—O5 | 1.9863 (19) | C6—H6C | 0.9800 |
Cu1—O2 | 2.1876 (19) | C7—H7B | 0.9800 |
P1—O1 | 1.5176 (19) | C7—H7C | 0.9800 |
P1—C1 | 1.780 (3) | C7—H7A | 0.9800 |
P1—C3 | 1.786 (3) | C8—H8B | 0.9800 |
P1—C2 | 1.789 (3) | C8—H8A | 0.9800 |
F1—C14 | 1.346 (4) | C8—H8C | 0.9800 |
C1—H1B | 0.9800 | C9—H9B | 0.9800 |
C1—H1C | 0.9800 | C9—H9C | 0.9800 |
C1—H1A | 0.9800 | C9—H9A | 0.9800 |
P2—O2 | 1.498 (2) | C10—H10B | 0.9800 |
P2—C5 | 1.786 (3) | C10—H10C | 0.9800 |
P2—C6 | 1.787 (3) | C10—H10A | 0.9800 |
P2—C4 | 1.792 (3) | C11—H11A | 0.9800 |
F2—C14 | 1.345 (3) | C11—H11C | 0.9800 |
C2—H2A | 0.9800 | C11—H11B | 0.9800 |
C2—H2C | 0.9800 | C12—H12C | 0.9800 |
C2—H2B | 0.9800 | C12—H12A | 0.9800 |
P3—O3 | 1.511 (2) | C12—H12B | 0.9800 |
P3—C7 | 1.779 (3) | C13—C14 | 1.549 (4) |
P3—C8 | 1.782 (3) | C14—C15 | 1.516 (4) |
P3—C9 | 1.784 (3) | O7A—C16A | 1.222 (8) |
F3—C15 | 1.296 (4) | O8A—C16A | 1.213 (9) |
C3—H3B | 0.9800 | C16A—C17A | 1.572 (8) |
C3—H3C | 0.9800 | C17A—F6A | 1.373 (6) |
C3—H3A | 0.9800 | C17A—F7A | 1.378 (6) |
P4—O4 | 1.5116 (19) | C17A—C18A | 1.499 (6) |
P4—C12 | 1.782 (3) | C18A—F10A | 1.328 (6) |
P4—C11 | 1.783 (3) | C18A—F9A | 1.348 (5) |
P4—C10 | 1.787 (3) | C18A—F8A | 1.339 (7) |
F4—C15 | 1.334 (4) | O7B—C16B | 1.191 (14) |
C4—H4C | 0.9800 | O8B—C16B | 1.285 (14) |
C4—H4A | 0.9800 | C16B—C17B | 1.569 (8) |
C4—H4B | 0.9800 | C17B—F6B | 1.379 (6) |
F5—C15 | 1.337 (5) | C17B—F7B | 1.378 (6) |
O5—C13 | 1.265 (3) | C17B—C18B | 1.498 (6) |
C5—H5A | 0.9800 | C18B—F10B | 1.325 (7) |
C5—H5C | 0.9800 | C18B—F9B | 1.349 (5) |
C5—H5B | 0.9800 | C18B—F8B | 1.339 (7) |
O1—Cu1—O4 | 172.44 (8) | P3—C7—H7A | 109.5 |
O1—Cu1—O3 | 90.48 (8) | H7B—C7—H7A | 109.5 |
O4—Cu1—O3 | 88.42 (8) | H7C—C7—H7A | 109.5 |
O1—Cu1—O5 | 91.12 (8) | P3—C8—H8B | 109.5 |
O4—Cu1—O5 | 87.71 (8) | P3—C8—H8A | 109.5 |
O3—Cu1—O5 | 162.51 (8) | H8B—C8—H8A | 109.5 |
O1—Cu1—O2 | 94.54 (7) | P3—C8—H8C | 109.5 |
O4—Cu1—O2 | 92.99 (7) | H8B—C8—H8C | 109.5 |
O3—Cu1—O2 | 102.55 (8) | H8A—C8—H8C | 109.5 |
O5—Cu1—O2 | 94.69 (8) | P3—C9—H9B | 109.5 |
O1—P1—C1 | 109.87 (12) | P3—C9—H9C | 109.5 |
O1—P1—C3 | 113.30 (12) | H9B—C9—H9C | 109.5 |
C1—P1—C3 | 106.69 (13) | P3—C9—H9A | 109.5 |
O1—P1—C2 | 112.92 (12) | H9B—C9—H9A | 109.5 |
C1—P1—C2 | 106.63 (13) | H9C—C9—H9A | 109.5 |
C3—P1—C2 | 107.03 (14) | P4—C10—H10B | 109.5 |
P1—O1—Cu1 | 131.81 (11) | P4—C10—H10C | 109.5 |
P1—C1—H1B | 109.5 | H10B—C10—H10C | 109.5 |
P1—C1—H1C | 109.5 | P4—C10—H10A | 109.5 |
H1B—C1—H1C | 109.5 | H10B—C10—H10A | 109.5 |
P1—C1—H1A | 109.5 | H10C—C10—H10A | 109.5 |
H1B—C1—H1A | 109.5 | P4—C11—H11A | 109.5 |
H1C—C1—H1A | 109.5 | P4—C11—H11C | 109.5 |
O2—P2—C5 | 113.83 (14) | H11A—C11—H11C | 109.5 |
O2—P2—C6 | 111.92 (15) | P4—C11—H11B | 109.5 |
C5—P2—C6 | 106.86 (17) | H11A—C11—H11B | 109.5 |
O2—P2—C4 | 112.71 (13) | H11C—C11—H11B | 109.5 |
C5—P2—C4 | 105.21 (16) | P4—C12—H12C | 109.5 |
C6—P2—C4 | 105.69 (16) | P4—C12—H12A | 109.5 |
P2—O2—Cu1 | 130.30 (11) | H12C—C12—H12A | 109.5 |
P1—C2—H2A | 109.5 | P4—C12—H12B | 109.5 |
P1—C2—H2C | 109.5 | H12C—C12—H12B | 109.5 |
H2A—C2—H2C | 109.5 | H12A—C12—H12B | 109.5 |
P1—C2—H2B | 109.5 | O6—C13—O5 | 129.8 (3) |
H2A—C2—H2B | 109.5 | O6—C13—C14 | 117.6 (2) |
H2C—C2—H2B | 109.5 | O5—C13—C14 | 112.6 (2) |
O3—P3—C7 | 112.50 (14) | F2—C14—F1 | 105.9 (3) |
O3—P3—C8 | 114.19 (13) | F2—C14—C15 | 106.8 (3) |
C7—P3—C8 | 107.45 (15) | F1—C14—C15 | 107.2 (3) |
O3—P3—C9 | 109.04 (14) | F2—C14—C13 | 111.1 (2) |
C7—P3—C9 | 108.03 (18) | F1—C14—C13 | 111.7 (2) |
C8—P3—C9 | 105.23 (16) | C15—C14—C13 | 113.7 (2) |
P3—O3—Cu1 | 133.98 (12) | F3—C15—F4 | 109.1 (3) |
P1—C3—H3B | 109.5 | F3—C15—F5 | 107.2 (3) |
P1—C3—H3C | 109.5 | F4—C15—F5 | 107.2 (3) |
H3B—C3—H3C | 109.5 | F3—C15—C14 | 111.1 (3) |
P1—C3—H3A | 109.5 | F4—C15—C14 | 111.5 (3) |
H3B—C3—H3A | 109.5 | F5—C15—C14 | 110.6 (3) |
H3C—C3—H3A | 109.5 | O8A—C16A—O7A | 131.6 (7) |
O4—P4—C12 | 109.79 (13) | O8A—C16A—C17A | 114.0 (6) |
O4—P4—C11 | 110.73 (13) | O7A—C16A—C17A | 114.5 (6) |
C12—P4—C11 | 107.01 (16) | F6A—C17A—F7A | 104.2 (4) |
O4—P4—C10 | 114.59 (13) | F6A—C17A—C18A | 106.1 (4) |
C12—P4—C10 | 107.08 (16) | F7A—C17A—C18A | 105.5 (4) |
C11—P4—C10 | 107.30 (16) | F6A—C17A—C16A | 114.6 (4) |
P4—O4—Cu1 | 134.85 (12) | F7A—C17A—C16A | 111.0 (4) |
P2—C4—H4C | 109.5 | C18A—C17A—C16A | 114.4 (4) |
P2—C4—H4A | 109.5 | F10A—C18A—F9A | 103.9 (4) |
H4C—C4—H4A | 109.5 | F10A—C18A—F8A | 110.5 (5) |
P2—C4—H4B | 109.5 | F9A—C18A—F8A | 112.9 (5) |
H4C—C4—H4B | 109.5 | F10A—C18A—C17A | 111.3 (5) |
H4A—C4—H4B | 109.5 | F9A—C18A—C17A | 111.9 (4) |
C13—O5—Cu1 | 111.38 (18) | F8A—C18A—C17A | 106.5 (5) |
P2—C5—H5A | 109.5 | O7B—C16B—O8B | 125.4 (8) |
P2—C5—H5C | 109.5 | O7B—C16B—C17B | 123.0 (9) |
H5A—C5—H5C | 109.5 | O8B—C16B—C17B | 111.4 (9) |
P2—C5—H5B | 109.5 | F6B—C17B—F7B | 102.7 (4) |
H5A—C5—H5B | 109.5 | F6B—C17B—C18B | 106.1 (5) |
H5C—C5—H5B | 109.5 | F7B—C17B—C18B | 105.6 (5) |
P2—C6—H6A | 109.5 | F6B—C17B—C16B | 111.5 (5) |
P2—C6—H6B | 109.5 | F7B—C17B—C16B | 115.0 (5) |
H6A—C6—H6B | 109.5 | C18B—C17B—C16B | 114.9 (4) |
P2—C6—H6C | 109.5 | F10B—C18B—F9B | 103.9 (5) |
H6A—C6—H6C | 109.5 | F10B—C18B—F8B | 110.0 (5) |
H6B—C6—H6C | 109.5 | F9B—C18B—F8B | 112.8 (5) |
P3—C7—H7B | 109.5 | F10B—C18B—C17B | 112.6 (5) |
P3—C7—H7C | 109.5 | F9B—C18B—C17B | 110.3 (4) |
H7B—C7—H7C | 109.5 | F8B—C18B—C17B | 107.3 (5) |
C1—P1—O1—Cu1 | −154.13 (15) | F1—C14—C15—F3 | 169.7 (3) |
C3—P1—O1—Cu1 | −34.9 (2) | C13—C14—C15—F3 | 45.8 (4) |
C2—P1—O1—Cu1 | 86.98 (17) | F2—C14—C15—F4 | 44.8 (4) |
O3—Cu1—O1—P1 | 166.61 (16) | F1—C14—C15—F4 | −68.4 (4) |
O5—Cu1—O1—P1 | −30.81 (16) | C13—C14—C15—F4 | 167.7 (3) |
O2—Cu1—O1—P1 | 63.98 (16) | F2—C14—C15—F5 | 164.0 (3) |
C5—P2—O2—Cu1 | 37.4 (2) | F1—C14—C15—F5 | 50.8 (3) |
C6—P2—O2—Cu1 | −83.9 (2) | C13—C14—C15—F5 | −73.1 (3) |
C4—P2—O2—Cu1 | 157.08 (16) | O8A—C16A—C17A—F6A | −151.9 (6) |
O1—Cu1—O2—P2 | −163.26 (16) | O7A—C16A—C17A—F6A | 27.5 (8) |
O4—Cu1—O2—P2 | 16.18 (17) | O8A—C16A—C17A—F7A | −34.2 (7) |
O3—Cu1—O2—P2 | 105.23 (16) | O7A—C16A—C17A—F7A | 145.2 (7) |
O5—Cu1—O2—P2 | −71.76 (17) | O8A—C16A—C17A—C18A | 85.1 (7) |
C7—P3—O3—Cu1 | −49.3 (2) | O7A—C16A—C17A—C18A | −95.4 (7) |
C8—P3—O3—Cu1 | 73.5 (2) | F6A—C17A—C18A—F10A | 172.6 (4) |
C9—P3—O3—Cu1 | −169.11 (19) | F7A—C17A—C18A—F10A | 62.4 (5) |
O1—Cu1—O3—P3 | −28.23 (18) | C16A—C17A—C18A—F10A | −60.0 (6) |
O4—Cu1—O3—P3 | 159.25 (18) | F6A—C17A—C18A—F9A | 56.9 (6) |
O5—Cu1—O3—P3 | −123.5 (2) | F7A—C17A—C18A—F9A | −53.3 (6) |
O2—Cu1—O3—P3 | 66.53 (18) | C16A—C17A—C18A—F9A | −175.7 (5) |
C12—P4—O4—Cu1 | 140.10 (18) | F6A—C17A—C18A—F8A | −66.8 (5) |
C11—P4—O4—Cu1 | −102.0 (2) | F7A—C17A—C18A—F8A | −177.1 (4) |
C10—P4—O4—Cu1 | 19.6 (2) | C16A—C17A—C18A—F8A | 60.5 (6) |
O3—Cu1—O4—P4 | 41.48 (18) | O7B—C16B—C17B—F6B | −113.4 (14) |
O5—Cu1—O4—P4 | −121.46 (18) | O8B—C16B—C17B—F6B | 61.0 (11) |
O2—Cu1—O4—P4 | 143.97 (17) | O7B—C16B—C17B—F7B | 130.3 (14) |
O1—Cu1—O5—C13 | −99.79 (18) | O8B—C16B—C17B—F7B | −55.4 (12) |
O4—Cu1—O5—C13 | 72.74 (18) | O7B—C16B—C17B—C18B | 7.4 (16) |
O3—Cu1—O5—C13 | −4.6 (4) | O8B—C16B—C17B—C18B | −178.3 (10) |
O2—Cu1—O5—C13 | 165.56 (18) | F6B—C17B—C18B—F10B | 60.9 (6) |
Cu1—O5—C13—O6 | 6.3 (4) | F7B—C17B—C18B—F10B | 169.4 (6) |
Cu1—O5—C13—C14 | −173.07 (17) | C16B—C17B—C18B—F10B | −62.8 (8) |
O6—C13—C14—F2 | 10.4 (4) | F6B—C17B—C18B—F9B | −54.7 (6) |
O5—C13—C14—F2 | −170.1 (2) | F7B—C17B—C18B—F9B | 53.8 (7) |
O6—C13—C14—F1 | 128.4 (3) | C16B—C17B—C18B—F9B | −178.4 (6) |
O5—C13—C14—F1 | −52.1 (3) | F6B—C17B—C18B—F8B | −177.9 (5) |
O6—C13—C14—C15 | −110.1 (3) | F7B—C17B—C18B—F8B | −69.4 (6) |
O5—C13—C14—C15 | 69.4 (3) | C16B—C17B—C18B—F8B | 58.4 (7) |
F2—C14—C15—F3 | −77.1 (4) |
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···O8Aiv | 0.98 | 2.42 | 3.289 (7) | 147 |
C12—H12B···O8Aiv | 0.98 | 2.52 | 3.388 (8) | 147 |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+2, −z; (iii) −x, −y+1, −z; (iv) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C3F5O2)(C3H9OP)4](C3F5O2) |
Mr | 757.89 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 9.5955 (8), 12.2627 (11), 14.1848 (12) |
α, β, γ (°) | 82.720 (2), 80.501 (1), 82.899 (2) |
V (Å3) | 1623.9 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.96 |
Crystal size (mm) | 0.48 × 0.17 × 0.03 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.655, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10254, 7148, 6207 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.124, 1.07 |
No. of reflections | 7148 |
No. of parameters | 416 |
No. of restraints | 33 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.33, −0.64 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008).
Cu1—O1 | 1.9535 (18) | Cu1—O5 | 1.9863 (19) |
Cu1—O4 | 1.9582 (18) | Cu1—O2 | 2.1876 (19) |
Cu1—O3 | 1.965 (2) | ||
O1—Cu1—O4 | 172.44 (8) | O3—Cu1—O5 | 162.51 (8) |
O1—Cu1—O3 | 90.48 (8) | O1—Cu1—O2 | 94.54 (7) |
O4—Cu1—O3 | 88.42 (8) | O4—Cu1—O2 | 92.99 (7) |
O1—Cu1—O5 | 91.12 (8) | O3—Cu1—O2 | 102.55 (8) |
O4—Cu1—O5 | 87.71 (8) | O5—Cu1—O2 | 94.69 (8) |
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···O8Aiv | 0.98 | 2.42 | 3.289 (7) | 147 |
C12—H12B···O8Aiv | 0.98 | 2.52 | 3.388 (8) | 147 |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+2, −z; (iii) −x, −y+1, −z; (iv) x−1, y, z. |
Acknowledgements
IBSz thanks the Ministry of Science and High Education for grant N N204 546539. LD thanks the Research Foundation Flanders (FWO) for financial support.
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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 CuII complexes containing coordinating pentafluoropropionate ions (Jiang et al., 1998; Zhang et al., 1999).
The title compound has one monocationic CuII complex and one pentafluoropropionate counter-ion present in the asymmetric unit (Fig.1). The geometry around the CuII 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.