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accessBis[(1-vinyl-1H-imidazol-2-yl-κN3)methanamine-κN]copper(II) bis(hexafluoridophosphate)
aInstitute for Inorganic and Analytical Chemistry, Friedrich Schiller University, Humboldtstrasse 8, 07743 Jena, Germany, and bInstitut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), BCH-LCS, CH-1015 Lausanne, Switzerland
*Correspondence e-mail: alexander.schiller@uni-jena.de
In the title compound, [Cu(C6H9N3)2](PF6)2, the Cu atom is located on a crystallographic center of inversion. The coordination environment of the Cu atom is square-planar with two amino and two imidazole N atoms bonded to the metal in a trans configuration.
Related literature
For the title ligand as a building block for tripodal tetraamine ligands, see: Blackman (2005![[Blackman, A. G. (2005). Polyhedron, 24, 1-39.]](../../../../../../logos/arrows/e_arr.gif "Blackman, A. G. (2005). Polyhedron, 24, 1-39.")
). For of copper(II) complexes with similar mulidendate N-donor ligands, see: Schiller et al. (2005, 2006).
![[Scheme 1]](fi2116scheme1.gif)
Experimental
Crystal data
|
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; 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: ORTEP-3 (Farrugia, 1997).
Supporting information
contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811050100/fi2116sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811050100/fi2116Isup2.hkl
Synthesis of the metal complex. Anhydrous copper(II) chloride (25.0 mg, 0.186 mmol) was added to a solution of (1-vinyl-1H-imidazol-2-yl)-methylamine (45.8 mg, 0.372 mmol) in ethanol (4 ml). NH4PF6 (60.6 mg, 0.372 mmol) was added and pink crystals were formed after 2 h. The product was isolated, washed with ethanol, and dried in a vacuum (yield: 83.7 mg, 75%). IR: ν (cm-1) = 3368/3314/3205 (w, NH), 1652 (vs, CH=CH2), 822 (vs, PF6).
Hydrogen atoms have been placed in calculated positions with C–H distances of 0.99Å for the methylene group and 0.95Å for all other hydrogen atoms bonded to carbon and 0.92Å for the amino function. was performed using a riding model with Uiso(H) = 1.2 Ueq(C).
The described ligand has been used as a building block for the synthesis of the chelate ligand tris[(1-vinylimidazole-2-yl)methyl]amine (L). The complexes [Zn(L)Cl]PF6 and [Cu(L)Cl]PF6 were obtained upon reaction with L and immobilized by co-polymerization with ethylene glycol dimethacrylate. The supported complexes were found to be efficient heterogenous catalysts for the hydrolysis of bis(p-nitrophenyl)phosphate (Schiller et al., 2006).
The structure of the title compound feature Cu on an inversion centre (Wyckoff position 2a). Two ligands coordinate to it in a trans fashion (Fig. 1).
For the title ligand as a building block for tripodal tetraamine ligands, see: Blackman (2005). For of copper(II) complexes with similar mulidendate N-donor ligands, see: Schiller et al. (2005, 2006).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); 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: ORTEP-3 (Farrugia, 1997).
![[Figure 1]](./fi2116fig1thm.gif) | Fig. 1. Molecular structure of the title compound. Second ligand is created by (i): -x, -y, -z. Ellipsoids are depicted on the 50% probability level. |
| [Cu(C6H9N3)2](PF6)2 | F(000) = 598 |
| Mr = 599.80 | Dx = 1.708 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 3520 reflections |
| a = 11.543 (2) Å | θ = 2.4–26.6° |
| b = 12.282 (2) Å | µ = 1.18 mm−1 |
| c = 8.2793 (14) Å | T = 140 K |
| β = 96.476 (15)° | Prismatic, pink |
| V = 1166.3 (4) Å3 | 0.24 × 0.20 × 0.16 mm |
| Z = 2 |
| Oxford Diffraction KM-4/Sapphire CCD diffractometer | 1955 independent reflections |
| Radiation source: fine-focus sealed tube | 1396 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.088 |
| φ and ω scans | θmax = 25.0°, θmin = 3.0° |
| Absorption correction: multi-scan (Blessing, 1995) | h = −13→13 |
| Tmin = 0.657, Tmax = 1.000 | k = −14→14 |
| 6439 measured reflections | l = −9→9 |
| 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) = 0.123 | H-atom parameters constrained |
| S = 0.97 | w = 1/[σ2(Fo2) + (0.0677P)2] where P = (Fo2 + 2Fc2)/3 |
| 1955 reflections | (Δ/σ)max < 0.001 |
| 151 parameters | Δρmax = 0.91 e Å−3 |
| 0 restraints | Δρmin = −0.46 e Å−3 |
| [Cu(C6H9N3)2](PF6)2 | V = 1166.3 (4) Å3 |
| Mr = 599.80 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 11.543 (2) Å | µ = 1.18 mm−1 |
| b = 12.282 (2) Å | T = 140 K |
| c = 8.2793 (14) Å | 0.24 × 0.20 × 0.16 mm |
| β = 96.476 (15)° |
| Oxford Diffraction KM-4/Sapphire CCD diffractometer | 1955 independent reflections |
| Absorption correction: multi-scan (Blessing, 1995) | 1396 reflections with I > 2σ(I) |
| Tmin = 0.657, Tmax = 1.000 | Rint = 0.088 |
| 6439 measured reflections |
| R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
| wR(F2) = 0.123 | H-atom parameters constrained |
| S = 0.97 | Δρmax = 0.91 e Å−3 |
| 1955 reflections | Δρmin = −0.46 e Å−3 |
| 151 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 | ||
| Cu1 | 0.0000 | 0.0000 | 0.0000 | 0.0228 (2) | |
| N1 | 0.1254 (3) | 0.1059 (2) | −0.0384 (4) | 0.0259 (8) | |
| N2 | 0.3038 (3) | 0.1375 (2) | −0.1192 (4) | 0.0274 (8) | |
| N3 | 0.1108 (3) | −0.1091 (2) | −0.0966 (4) | 0.0266 (8) | |
| H3A | 0.1138 | −0.1725 | −0.0370 | 0.032* | |
| H3B | 0.0811 | −0.1258 | −0.2015 | 0.032* | |
| C1 | 0.2219 (3) | 0.0595 (3) | −0.0873 (5) | 0.0222 (9) | |
| C2 | 0.2538 (4) | 0.2409 (3) | −0.0848 (6) | 0.0315 (11) | |
| H2 | 0.2886 | 0.3104 | −0.0940 | 0.038* | |
| C3 | 0.1460 (4) | 0.2200 (3) | −0.0360 (5) | 0.0296 (10) | |
| H3 | 0.0933 | 0.2736 | −0.0054 | 0.036* | |
| C4 | 0.4149 (4) | 0.1189 (3) | −0.1822 (5) | 0.0316 (10) | |
| H4 | 0.4311 | 0.0471 | −0.2160 | 0.038* | |
| C5 | 0.4952 (4) | 0.1947 (4) | −0.1960 (7) | 0.0474 (14) | |
| H5A | 0.4821 | 0.2675 | −0.1634 | 0.057* | |
| H5B | 0.5658 | 0.1763 | −0.2383 | 0.057* | |
| C6 | 0.2332 (3) | −0.0645 (3) | −0.0967 (5) | 0.0227 (9) | |
| H6A | 0.2661 | −0.0860 | −0.1974 | 0.027* | |
| H6B | 0.2847 | −0.0924 | −0.0021 | 0.027* | |
| P1 | 0.19988 (10) | 0.57233 (7) | 0.90769 (13) | 0.0244 (3) | |
| F1 | 0.0883 (2) | 0.51137 (19) | 0.8082 (3) | 0.0463 (8) | |
| F2 | 0.2875 (2) | 0.50369 (17) | 0.8029 (3) | 0.0392 (7) | |
| F3 | 0.1923 (3) | 0.66853 (17) | 0.7698 (3) | 0.0472 (8) | |
| F4 | 0.3113 (2) | 0.6338 (2) | 1.0077 (3) | 0.0531 (8) | |
| F5 | 0.1112 (2) | 0.64221 (17) | 1.0131 (3) | 0.0396 (7) | |
| F6 | 0.2065 (2) | 0.47717 (17) | 1.0447 (3) | 0.0365 (7) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0264 (4) | 0.0165 (3) | 0.0261 (5) | 0.0009 (3) | 0.0056 (3) | 0.0002 (3) |
| N1 | 0.029 (2) | 0.0210 (15) | 0.028 (2) | 0.0045 (14) | 0.0070 (16) | −0.0020 (14) |
| N2 | 0.0282 (19) | 0.0216 (16) | 0.034 (2) | −0.0003 (14) | 0.0092 (17) | −0.0042 (14) |
| N3 | 0.031 (2) | 0.0185 (15) | 0.031 (2) | −0.0002 (14) | 0.0089 (17) | 0.0000 (14) |
| C1 | 0.025 (2) | 0.0223 (19) | 0.020 (2) | −0.0004 (16) | 0.0026 (19) | 0.0021 (16) |
| C2 | 0.037 (3) | 0.0180 (19) | 0.041 (3) | −0.0049 (17) | 0.010 (2) | −0.0024 (18) |
| C3 | 0.033 (2) | 0.0182 (18) | 0.039 (3) | 0.0005 (17) | 0.010 (2) | −0.0044 (17) |
| C4 | 0.029 (2) | 0.032 (2) | 0.035 (3) | 0.0010 (19) | 0.009 (2) | −0.0055 (19) |
| C5 | 0.031 (3) | 0.043 (3) | 0.070 (4) | −0.001 (2) | 0.016 (3) | −0.008 (3) |
| C6 | 0.024 (2) | 0.0181 (19) | 0.027 (2) | 0.0029 (15) | 0.0081 (19) | 0.0022 (16) |
| P1 | 0.0330 (6) | 0.0177 (5) | 0.0230 (6) | −0.0002 (4) | 0.0053 (5) | −0.0003 (4) |
| F1 | 0.0429 (17) | 0.0558 (17) | 0.0388 (18) | −0.0141 (13) | −0.0018 (14) | −0.0081 (13) |
| F2 | 0.0548 (18) | 0.0329 (13) | 0.0336 (16) | 0.0120 (12) | 0.0212 (14) | −0.0019 (11) |
| F3 | 0.084 (2) | 0.0240 (12) | 0.0376 (17) | 0.0114 (13) | 0.0255 (15) | 0.0086 (11) |
| F4 | 0.0495 (17) | 0.0613 (17) | 0.050 (2) | −0.0274 (14) | 0.0112 (15) | −0.0192 (14) |
| F5 | 0.0579 (17) | 0.0311 (12) | 0.0329 (16) | 0.0117 (12) | 0.0193 (13) | −0.0003 (11) |
| F6 | 0.0568 (18) | 0.0257 (12) | 0.0277 (15) | 0.0051 (11) | 0.0080 (14) | 0.0052 (10) |
| Cu1—N1 | 1.998 (3) | C2—H2 | 0.9500 |
| Cu1—N1i | 1.998 (3) | C3—H3 | 0.9500 |
| Cu1—N3 | 2.074 (3) | C4—C5 | 1.328 (6) |
| Cu1—N3i | 2.074 (3) | C4—H4 | 0.9500 |
| N1—C1 | 1.352 (5) | C5—H5A | 0.9500 |
| N1—C3 | 1.421 (4) | C5—H5B | 0.9500 |
| N2—C1 | 1.392 (5) | C6—H6A | 0.9900 |
| N2—C2 | 1.436 (5) | C6—H6B | 0.9900 |
| N2—C4 | 1.456 (5) | P1—F6 | 1.625 (2) |
| N3—C6 | 1.516 (5) | P1—F1 | 1.631 (3) |
| N3—H3A | 0.9200 | P1—F4 | 1.634 (3) |
| N3—H3B | 0.9200 | P1—F2 | 1.638 (3) |
| C1—C6 | 1.531 (5) | P1—F3 | 1.638 (3) |
| C2—C3 | 1.375 (6) | P1—F5 | 1.658 (3) |
| N1—Cu1—N1i | 180.00 (13) | C5—C4—N2 | 124.9 (4) |
| N1—Cu1—N3 | 82.53 (13) | C5—C4—H4 | 117.6 |
| N1i—Cu1—N3 | 97.47 (13) | N2—C4—H4 | 117.6 |
| N1—Cu1—N3i | 97.47 (13) | C4—C5—H5A | 120.0 |
| N1i—Cu1—N3i | 82.53 (13) | C4—C5—H5B | 120.0 |
| N3—Cu1—N3i | 180.0 | H5A—C5—H5B | 120.0 |
| C1—N1—C3 | 106.1 (3) | N3—C6—C1 | 106.0 (3) |
| C1—N1—Cu1 | 114.2 (2) | N3—C6—H6A | 110.5 |
| C3—N1—Cu1 | 139.7 (3) | C1—C6—H6A | 110.5 |
| C1—N2—C2 | 105.9 (3) | N3—C6—H6B | 110.5 |
| C1—N2—C4 | 127.2 (3) | C1—C6—H6B | 110.5 |
| C2—N2—C4 | 126.8 (3) | H6A—C6—H6B | 108.7 |
| C6—N3—Cu1 | 112.4 (2) | F6—P1—F1 | 89.70 (14) |
| C6—N3—H3A | 109.1 | F6—P1—F4 | 90.34 (15) |
| Cu1—N3—H3A | 109.1 | F1—P1—F4 | 179.76 (17) |
| C6—N3—H3B | 109.1 | F6—P1—F2 | 90.94 (13) |
| Cu1—N3—H3B | 109.1 | F1—P1—F2 | 89.76 (15) |
| H3A—N3—H3B | 107.8 | F4—P1—F2 | 90.48 (15) |
| N1—C1—N2 | 111.5 (3) | F6—P1—F3 | 179.61 (16) |
| N1—C1—C6 | 120.8 (3) | F1—P1—F3 | 90.11 (15) |
| N2—C1—C6 | 127.7 (3) | F4—P1—F3 | 89.84 (15) |
| C3—C2—N2 | 106.8 (3) | F2—P1—F3 | 89.41 (13) |
| C3—C2—H2 | 126.6 | F6—P1—F5 | 89.31 (13) |
| N2—C2—H2 | 126.6 | F1—P1—F5 | 90.23 (15) |
| C2—C3—N1 | 109.6 (4) | F4—P1—F5 | 89.53 (14) |
| C2—C3—H3 | 125.2 | F2—P1—F5 | 179.75 (14) |
| N1—C3—H3 | 125.2 | F3—P1—F5 | 90.34 (13) |
| N1i—Cu1—N1—C1 | −64.0 (4) | C4—N2—C1—N1 | −176.5 (4) |
| N3—Cu1—N1—C1 | −6.8 (3) | C2—N2—C1—C6 | −177.1 (4) |
| N3i—Cu1—N1—C1 | 173.2 (3) | C4—N2—C1—C6 | 5.6 (6) |
| N1i—Cu1—N1—C3 | 113.2 (6) | C1—N2—C2—C3 | −0.4 (4) |
| N3—Cu1—N1—C3 | 170.4 (4) | C4—N2—C2—C3 | 176.9 (4) |
| N3i—Cu1—N1—C3 | −9.6 (4) | N2—C2—C3—N1 | −0.1 (5) |
| N1—Cu1—N3—C6 | 16.6 (3) | C1—N1—C3—C2 | 0.6 (5) |
| N1i—Cu1—N3—C6 | −163.4 (3) | Cu1—N1—C3—C2 | −176.8 (3) |
| N3i—Cu1—N3—C6 | −41 (3) | C1—N2—C4—C5 | −173.1 (4) |
| C3—N1—C1—N2 | −0.9 (4) | C2—N2—C4—C5 | 10.1 (7) |
| Cu1—N1—C1—N2 | 177.2 (2) | Cu1—N3—C6—C1 | −21.4 (4) |
| C3—N1—C1—C6 | 177.2 (3) | N1—C1—C6—N3 | 17.6 (5) |
| Cu1—N1—C1—C6 | −4.7 (5) | N2—C1—C6—N3 | −164.7 (4) |
| C2—N2—C1—N1 | 0.8 (4) |
| Symmetry code: (i) −x, −y, −z. |
Experimental details
| Crystal data | |
| Chemical formula | [Cu(C6H9N3)2](PF6)2 |
| Mr | 599.80 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 140 |
| a, b, c (Å) | 11.543 (2), 12.282 (2), 8.2793 (14) |
| β (°) | 96.476 (15) |
| V (Å3) | 1166.3 (4) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 1.18 |
| Crystal size (mm) | 0.24 × 0.20 × 0.16 |
| Data collection | |
| Diffractometer | Oxford Diffraction KM-4/Sapphire CCD |
| Absorption correction | Multi-scan (Blessing, 1995) |
| Tmin, Tmax | 0.657, 1.000 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6439, 1955, 1396 |
| Rint | 0.088 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.123, 0.97 |
| No. of reflections | 1955 |
| No. of parameters | 151 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.91, −0.46 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).
Acknowledgements
AS thanks the Carl–Zeiss foundation for a Junior Professor Fellowship.
References
Blackman, A. G. (2005). Polyhedron, 24, 1–39. Web of Science CrossRef CAS Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Schiller, A., Scopelliti, R., Benmelouka, M. & Severin, K. (2005). Inorg. Chem. 44, 6482–6492. Web of Science CSD CrossRef PubMed CAS Google Scholar
Schiller, A., Scopelliti, R. & Severin, K. (2006). Dalton Trans. pp. 3858–3867. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
The described ligand has been used as a building block for the synthesis of the chelate ligand tris[(1-vinylimidazole-2-yl)methyl]amine (L). The complexes [Zn(L)Cl]PF6 and [Cu(L)Cl]PF6 were obtained upon reaction with L and immobilized by co-polymerization with ethylene glycol dimethacrylate. The supported complexes were found to be efficient heterogenous catalysts for the hydrolysis of bis(p-nitrophenyl)phosphate (Schiller et al., 2006).
The structure of the title compound feature Cu on an inversion centre (Wyckoff position 2a). Two ligands coordinate to it in a trans fashion (Fig. 1).