Acta Cryst. (2007). E63, m1734 [ doi:10.1107/S1600536807024051 ]
The crystal structure of the title compound, [Cu(C5H5N)4]PF6, consists of discrete [Cu(C5H5N)4]+ and PF6- ions. Both the cations and the anions are located on 
axes. The pyridine ligands are bonded to the Cu+ ion in an almost perfectly tetrahedral coordination geometry, with Cu-N = 2.061 (3) Å and N-Cu-N angles of 110.00 (9) and 108.42 (17)°.
The title compound was obtained unintentionally while attempting to crystallize a coordination compound of copper(I) with a bisoxazoline ligand. Tetrakis(acetonitrile)copper(I) hexafluorophosphate(V) (10 mg) and bisoxazoline (20 mg) were dissolved in a mixture of pyridine and toluene (10 ml, 1:1) and heated to boiling. The resulting solution was cooled to room temperature and left to slowly evaporate. Colourless crystals of (I) were obtained after 4 days.
All H atoms were placed geometrically and included in the refinement in the riding-model approximation, with C—H distances 0.93 with Uiso = 1.2Ueq of the carrier atom.
Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST95 (Nardelli, 1995).
![[Figure 1]](./rk2014fig1thm.gif)
| Fig. 1. View of (I) with the atom labeling scheme. Displacement ellipsoids are shown at 20% probability. Hydrogen atoms are shown as spheres of arbitrary radius. |
![[Figure 2]](./rk2014fig2thm.gif)
| Fig. 2. Crystal packing of (I) viewed along the z axis. |
| [Cu(C5H5N)4]PF6 | Dx = 1.547 Mg m−3 |
| Mr = 524.91 | Mo Kα radiation, λ = 0.71073 Å |
| Tetragonal, I4 | Cell parameters from 1485 reflections |
| Hall symbol: I -4 | θ = 4.6–32.0° |
| a = 12.600 (2) Å | µ = 1.10 mm−1 |
| c = 7.0983 (14) Å | T = 295 K |
| V = 1126.9 (3) Å3 | Prism, colourless |
| Z = 2 | 0.39 × 0.19 × 0.14 mm |
| F(000) = 532 |
| Oxford Diffraction Xcalibur CCD area-detector diffractometer | 1212 independent reflections |
| Radiation source: fine–focus sealed tube | 1074 reflections with I > 2σ(I) |
| graphite | Rint = 0.041 |
| ω scans | θmax = 27.0°, θmin = 4.6° |
| Absorption correction: analytical (Alcock, 1970) | h = −16→16 |
| Tmin = 0.616, Tmax = 0.791 | k = −16→15 |
| 4610 measured reflections | l = −9→9 |
| Refinement on F2 | H-atom parameters constrained |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0713P)2] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.044 | (Δ/σ)max = 0.003 |
| wR(F2) = 0.118 | Δρmax = 0.23 e Å−3 |
| S = 1.09 | Δρmin = −0.21 e Å−3 |
| 1212 reflections | Absolute structure: Flack (1983), with 551 Friedel pairs |
| 73 parameters | Flack parameter: −0.01 (3) |
| 1 restraint |
| [Cu(C5H5N)4]PF6 | Z = 2 |
| Mr = 524.91 | Mo Kα radiation |
| Tetragonal, I4 | µ = 1.10 mm−1 |
| a = 12.600 (2) Å | T = 295 K |
| c = 7.0983 (14) Å | 0.39 × 0.19 × 0.14 mm |
| V = 1126.9 (3) Å3 |
| Oxford Diffraction Xcalibur CCD area-detector diffractometer | 1212 independent reflections |
| Absorption correction: analytical (Alcock, 1970) | 1074 reflections with I > 2σ(I) |
| Tmin = 0.616, Tmax = 0.791 | Rint = 0.041 |
| 4610 measured reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
| wR(F2) = 0.118 | Δρmax = 0.23 e Å−3 |
| S = 1.09 | Δρmin = −0.21 e Å−3 |
| 1212 reflections | Absolute structure: Flack (1983), with 551 Friedel pairs |
| 73 parameters | Flack parameter: −0.01 (3) |
| 1 restraint |
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. |
| x | y | z | Uiso*/Ueq | ||
| Cu1 | 0 | 0 | 0 | 0.0670 (3) | |
| P1 | 0.5 | 0 | 0.25 | 0.0556 (4) | |
| C5 | 0.0527 (3) | 0.2144 (3) | 0.1582 (6) | 0.0663 (9) | |
| H5 | 0.007 | 0.2382 | 0.0643 | 0.08* | |
| N1 | 0.0734 (2) | 0.1106 (2) | 0.1698 (4) | 0.0594 (7) | |
| C4 | 0.0961 (3) | 0.2872 (3) | 0.2790 (7) | 0.0770 (12) | |
| H4 | 0.0789 | 0.3587 | 0.2691 | 0.092* | |
| C3 | 0.1657 (4) | 0.2524 (4) | 0.4157 (7) | 0.0828 (12) | |
| H3 | 0.1956 | 0.2998 | 0.501 | 0.099* | |
| C2 | 0.1896 (5) | 0.1477 (4) | 0.4225 (7) | 0.0879 (13) | |
| H2 | 0.2386 | 0.1225 | 0.5096 | 0.105* | |
| C1 | 0.1414 (3) | 0.0798 (3) | 0.3012 (6) | 0.0702 (10) | |
| H1 | 0.1569 | 0.0079 | 0.3109 | 0.084* | |
| F2 | 0.5 | 0 | 0.4688 (6) | 0.156 (2) | |
| F1 | 0.3816 (3) | −0.0255 (6) | 0.2479 (10) | 0.196 (3) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0591 (4) | 0.0591 (4) | 0.0828 (6) | 0 | 0 | 0 |
| P1 | 0.0555 (6) | 0.0555 (6) | 0.0558 (9) | 0 | 0 | 0 |
| C5 | 0.061 (2) | 0.0560 (19) | 0.082 (2) | 0.0073 (17) | −0.0066 (18) | −0.0021 (18) |
| N1 | 0.0593 (16) | 0.0497 (14) | 0.0694 (16) | −0.0001 (12) | 0.0014 (13) | 0.0025 (12) |
| C4 | 0.078 (3) | 0.058 (2) | 0.095 (3) | −0.0017 (19) | 0.010 (2) | −0.012 (2) |
| C3 | 0.085 (3) | 0.083 (3) | 0.080 (2) | −0.016 (2) | −0.001 (2) | −0.024 (2) |
| C2 | 0.101 (3) | 0.091 (3) | 0.072 (2) | −0.010 (3) | −0.020 (2) | −0.001 (2) |
| C1 | 0.078 (2) | 0.059 (2) | 0.074 (2) | −0.0019 (19) | −0.0111 (18) | 0.0089 (17) |
| F2 | 0.178 (6) | 0.227 (7) | 0.062 (3) | −0.019 (5) | 0 | 0 |
| F1 | 0.0681 (19) | 0.323 (8) | 0.198 (5) | −0.030 (3) | −0.012 (3) | −0.014 (5) |
| Cu1—N1 | 2.061 (3) | C5—C4 | 1.369 (6) |
| Cu1—N1i | 2.061 (3) | C5—H5 | 0.93 |
| Cu1—N1ii | 2.061 (3) | N1—C1 | 1.324 (5) |
| Cu1—N1iii | 2.061 (3) | C4—C3 | 1.379 (7) |
| P1—F1iv | 1.526 (4) | C4—H4 | 0.93 |
| P1—F1 | 1.526 (4) | C3—C2 | 1.354 (7) |
| P1—F1v | 1.526 (4) | C3—H3 | 0.93 |
| P1—F1vi | 1.526 (4) | C2—C1 | 1.357 (7) |
| P1—F2iv | 1.553 (5) | C2—H2 | 0.93 |
| P1—F2 | 1.553 (5) | C1—H1 | 0.93 |
| C5—N1 | 1.337 (5) | ||
| N1—Cu1—N1i | 110.00 (9) | F2iv—P1—F2 | 180 |
| N1—Cu1—N1ii | 110.00 (9) | N1—C5—C4 | 122.6 (4) |
| N1i—Cu1—N1ii | 108.42 (17) | N1—C5—H5 | 118.7 |
| N1—Cu1—N1iii | 108.42 (17) | C4—C5—H5 | 118.7 |
| N1i—Cu1—N1iii | 110.00 (9) | C1—N1—C5 | 117.1 (3) |
| N1ii—Cu1—N1iii | 110.00 (9) | C1—N1—Cu1 | 120.3 (2) |
| F1iv—P1—F1 | 90.006 (6) | C5—N1—Cu1 | 122.6 (3) |
| F1iv—P1—F1v | 90.006 (6) | C5—C4—C3 | 118.8 (4) |
| F1—P1—F1v | 178.9 (6) | C5—C4—H4 | 120.6 |
| F1iv—P1—F1vi | 178.9 (6) | C3—C4—H4 | 120.6 |
| F1—P1—F1vi | 90.006 (6) | C2—C3—C4 | 118.4 (4) |
| F1v—P1—F1vi | 90.006 (6) | C2—C3—H3 | 120.8 |
| F1iv—P1—F2iv | 90.6 (3) | C4—C3—H3 | 120.8 |
| F1—P1—F2iv | 89.4 (3) | C3—C2—C1 | 119.5 (5) |
| F1v—P1—F2iv | 89.4 (3) | C3—C2—H2 | 120.3 |
| F1vi—P1—F2iv | 90.6 (3) | C1—C2—H2 | 120.3 |
| F1iv—P1—F2 | 89.4 (3) | N1—C1—C2 | 123.5 (4) |
| F1—P1—F2 | 90.6 (3) | N1—C1—H1 | 118.2 |
| F1v—P1—F2 | 90.6 (3) | C2—C1—H1 | 118.2 |
| F1vi—P1—F2 | 89.4 (3) |
| Symmetry codes: (i) −y, x, −z; (ii) y, −x, −z; (iii) −x, −y, z; (iv) y+1/2, −x+1/2, −z+1/2; (v) −x+1, −y, z; (vi) −y+1/2, x−1/2, −z+1/2. |
The authors thank the Ministry of Science, Education and Sport, Republic of Croatia, for financial support of this work through grant Nos. 119–1193079-3069, 119–1191342-2960 and 098–0982914-2935.
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The crystal structure of (I) consists of discrete tetrakis(pyridine)copper(I) and hexafluorophosphate(V) ions. The copper and phosphorus atoms are placed in 2a and 2c special positions of the space group respectively. The coordination of copper is almost perfectly tetrahedral with N—Cu—N angles 110.00 (9)° and 108.42 (17)°. The planes of the pyridine rings are at angles of 79.38° and 65.93°.
The hexafluorophosphate anions are octahedral and slightly elongated along z axes with F—P—F angles in the range 89.4 (3)° - 90.6 (3)° and P—F bond lengths 1.527 (4) Å and 1.553 (5) Å.
The shortest intermolecular distance is a C—H···F contact of 3.445 Å