Acta Cryst. (2007). E63, m1855 [ doi:10.1107/S1600536807027109 ]
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2N,O)copper(II) dinitrateThe title compound, [Cu(C7H8N2O)2(H2O)2](NO3)2, was prepared by the reaction of 2-cyano-3-methylpyridine with Cu(NO3)2·3H2O in a methanol/water solution. In the crystal structure, the CuII ion is located on an inversion centre and is coordinated by two 3-methylpyridine-2-carboxamide ligands in the equatorial plane and two water molecules in the axial positions, forming an elongated octahedral coordination geometry. The Cu-Oaxial bond distance of 2.4715 (18) Å is much longer than the Cu-Oequatorial bond distance of 1.9471 (17) Å, showing a Jahn-Teller distortion. The nitrate anions are linked with the CuII complex cation via O-H
O hydrogen bonding.
A methanol solution (5 ml) of 2-cyano-3-methylpyridine (0.2368 g, 0.20 mmol) was mixed with an aqueous solution (5 ml) of Cu(NO3)2·3H2O (0.0491, 0.20 mmol) in a round-bottomed flask. The solution was refluxed for 10 min and then cooled to room temperature. Single crystals of the title compound were obtained after 5 d.
The H atoms bonded to N2 and O5 were founded in a difference Fourier map and refined as riding in their as-found relative positions with Uiso(H) = 1.5Ueq(O,N). Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion angle was refined to fit the electron density, Uiso(H) = 1.5Ueq(C). Aromatic H atoms were placed in calculated positions with C—H = 0.93 Å and refined in riding mode with Uiso(H) = 1.2Ueq(C).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./xu2256fig1thm.gif)
| Fig. 1. A view of the molecular structure, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability lever and H atoms are shown as small spheres of arbitrary radii. |
| [Cu(C7H8N2O)2(H2O)2](NO3)2 | F000 = 510 |
| Mr = 495.9 | Dx = 1.683 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 7644 reflections |
| a = 6.656 (4) Å | θ = 3.2–27.0º |
| b = 11.874 (9) Å | µ = 1.19 mm−1 |
| c = 12.472 (6) Å | T = 293 (2) K |
| β = 96.97 (2)º | Prism, blue |
| V = 978.4 (10) Å3 | 0.20 × 0.14 × 0.10 mm |
| Z = 2 |
| Rigaku R-AXIS RAPID diffractometer | 2221 independent reflections |
| Radiation source: fine-focus sealed tube | 1853 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.026 |
| Detector resolution: 10.00 pixels mm-1 | θmax = 27.5º |
| T = 293(2) K | θmin = 3.3º |
| ω scans | h = −8→7 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −15→15 |
| Tmin = 0.840, Tmax = 0.885 | l = −14→16 |
| 9362 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0509P)2 + 0.2656P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.09 | (Δ/σ)max < 0.001 |
| 2221 reflections | Δρmax = 0.61 e Å−3 |
| 143 parameters | Δρmin = −0.25 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Cu(C7H8N2O)2(H2O)2](NO3)2 | V = 978.4 (10) Å3 |
| Mr = 495.9 | Z = 2 |
| Monoclinic, P21/n | Mo Kα |
| a = 6.656 (4) Å | µ = 1.19 mm−1 |
| b = 11.874 (9) Å | T = 293 (2) K |
| c = 12.472 (6) Å | 0.20 × 0.14 × 0.10 mm |
| β = 96.97 (2)º |
| Rigaku R-AXIS RAPID diffractometer | 2221 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1853 reflections with I > 2σ(I) |
| Tmin = 0.840, Tmax = 0.885 | Rint = 0.026 |
| 9362 measured reflections |
| R[F2 > 2σ(F2)] = 0.033 | 143 parameters |
| wR(F2) = 0.092 | H-atom parameters constrained |
| S = 1.09 | Δρmax = 0.61 e Å−3 |
| 2221 reflections | Δρmin = −0.25 e Å−3 |
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 | 0.5000 | 0.5000 | 0.03437 (13) | |
| N1 | −0.0100 (2) | 0.33946 (13) | 0.46298 (13) | 0.0350 (3) | |
| N2 | 0.4421 (3) | 0.38605 (17) | 0.34147 (17) | 0.0527 (5) | |
| N3 | 0.1397 (3) | 0.67879 (16) | 0.84496 (14) | 0.0448 (4) | |
| O1 | 0.2432 (2) | 0.49394 (11) | 0.42776 (14) | 0.0445 (4) | |
| O2 | 0.2770 (3) | 0.71509 (18) | 0.79573 (17) | 0.0717 (5) | |
| H2A | 0.4694 | 0.3264 | 0.3106 | 0.108* | |
| H2B | 0.5352 | 0.4471 | 0.3450 | 0.108* | |
| O3 | 0.0465 (3) | 0.74715 (19) | 0.89250 (18) | 0.0798 (6) | |
| O4 | 0.0982 (5) | 0.57935 (18) | 0.8442 (2) | 0.1048 (9) | |
| O5 | 0.2239 (2) | 0.46062 (14) | 0.66877 (12) | 0.0495 (4) | |
| H5A | 0.2408 | 0.3924 | 0.6774 | 0.074* | |
| H5B | 0.1896 | 0.4927 | 0.7231 | 0.074* | |
| C1 | 0.1385 (3) | 0.30383 (16) | 0.40762 (14) | 0.0344 (4) | |
| C2 | 0.1543 (3) | 0.19255 (17) | 0.37466 (16) | 0.0415 (5) | |
| C3 | 0.0070 (4) | 0.11950 (18) | 0.40420 (19) | 0.0513 (6) | |
| H3 | 0.0105 | 0.0442 | 0.3842 | 0.062* | |
| C4 | −0.1453 (4) | 0.15636 (18) | 0.46297 (19) | 0.0499 (5) | |
| H4 | −0.2427 | 0.1071 | 0.4830 | 0.060* | |
| C5 | −0.1461 (3) | 0.26862 (17) | 0.49020 (16) | 0.0408 (4) | |
| H5 | −0.2468 | 0.2952 | 0.5293 | 0.049* | |
| C6 | 0.3131 (4) | 0.1473 (2) | 0.3118 (3) | 0.0694 (8) | |
| H6A | 0.2827 | 0.0704 | 0.2925 | 0.104* | |
| H6B | 0.4426 | 0.1512 | 0.3549 | 0.104* | |
| H6C | 0.3163 | 0.1913 | 0.2474 | 0.104* | |
| C7 | 0.2820 (3) | 0.40018 (17) | 0.39072 (15) | 0.0366 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0337 (2) | 0.02471 (18) | 0.0487 (2) | −0.00089 (12) | 0.02154 (14) | −0.00463 (12) |
| N1 | 0.0358 (9) | 0.0301 (8) | 0.0401 (8) | 0.0013 (6) | 0.0092 (6) | −0.0021 (6) |
| N2 | 0.0418 (10) | 0.0568 (11) | 0.0642 (12) | 0.0062 (9) | 0.0262 (9) | −0.0048 (9) |
| N3 | 0.0458 (10) | 0.0465 (11) | 0.0425 (9) | 0.0032 (8) | 0.0074 (8) | −0.0063 (7) |
| O1 | 0.0420 (8) | 0.0365 (8) | 0.0597 (9) | −0.0018 (6) | 0.0257 (7) | −0.0037 (6) |
| O2 | 0.0623 (11) | 0.0767 (13) | 0.0827 (13) | −0.0073 (10) | 0.0361 (10) | −0.0132 (10) |
| O3 | 0.0647 (12) | 0.0893 (15) | 0.0897 (14) | 0.0180 (11) | 0.0272 (10) | −0.0272 (11) |
| O4 | 0.166 (3) | 0.0532 (13) | 0.1063 (18) | −0.0334 (14) | 0.0600 (18) | −0.0137 (11) |
| O5 | 0.0574 (10) | 0.0401 (8) | 0.0512 (9) | 0.0044 (7) | 0.0076 (7) | 0.0009 (7) |
| C1 | 0.0331 (9) | 0.0347 (10) | 0.0347 (9) | 0.0086 (7) | 0.0006 (7) | −0.0046 (7) |
| C2 | 0.0424 (11) | 0.0361 (11) | 0.0436 (10) | 0.0110 (8) | −0.0048 (8) | −0.0084 (8) |
| C3 | 0.0623 (15) | 0.0307 (10) | 0.0570 (13) | 0.0035 (10) | −0.0085 (11) | −0.0053 (9) |
| C4 | 0.0535 (13) | 0.0361 (11) | 0.0573 (12) | −0.0113 (9) | −0.0045 (10) | 0.0086 (9) |
| C5 | 0.0435 (11) | 0.0367 (11) | 0.0427 (10) | −0.0017 (8) | 0.0079 (8) | 0.0028 (8) |
| C6 | 0.0615 (16) | 0.0604 (17) | 0.0868 (19) | 0.0161 (13) | 0.0112 (14) | −0.0331 (14) |
| C7 | 0.0343 (10) | 0.0385 (10) | 0.0380 (9) | 0.0075 (8) | 0.0084 (8) | −0.0016 (7) |
| Cu1—O1 | 1.9471 (17) | O5—H5A | 0.8237 |
| Cu1—O1i | 1.9471 (17) | O5—H5B | 0.8332 |
| Cu1—O5 | 2.4715 (18) | C1—C2 | 1.392 (3) |
| Cu1—O5i | 2.4715 (18) | C1—C7 | 1.521 (3) |
| Cu1—N1 | 1.961 (2) | C2—C3 | 1.392 (3) |
| Cu1—N1i | 1.961 (2) | C2—C6 | 1.490 (3) |
| N1—C5 | 1.311 (3) | C3—C4 | 1.392 (4) |
| N1—C1 | 1.341 (2) | C3—H3 | 0.9300 |
| N2—C7 | 1.304 (3) | C4—C5 | 1.376 (3) |
| N2—H2A | 0.8365 | C4—H4 | 0.9300 |
| N2—H2B | 0.9519 | C5—H5 | 0.9300 |
| N3—O4 | 1.213 (3) | C6—H6A | 0.9600 |
| N3—O3 | 1.218 (2) | C6—H6B | 0.9600 |
| N3—O2 | 1.239 (2) | C6—H6C | 0.9600 |
| O1—C7 | 1.244 (2) | ||
| O1—Cu1—O1i | 180.0 | C1—C2—C6 | 125.6 (2) |
| O1—Cu1—N1 | 82.04 (6) | C3—C2—C6 | 118.8 (2) |
| O1i—Cu1—N1 | 97.96 (6) | C4—C3—C2 | 121.7 (2) |
| O1—Cu1—N1i | 97.96 (6) | C4—C3—H3 | 119.2 |
| O1i—Cu1—N1i | 82.04 (6) | C2—C3—H3 | 119.2 |
| N1—Cu1—N1i | 180.0 | C5—C4—C3 | 117.4 (2) |
| C5—N1—C1 | 120.44 (18) | C5—C4—H4 | 121.3 |
| C5—N1—Cu1 | 124.59 (14) | C3—C4—H4 | 121.3 |
| C1—N1—Cu1 | 114.95 (13) | N1—C5—C4 | 122.3 (2) |
| C7—N2—H2A | 124.2 | N1—C5—H5 | 118.9 |
| C7—N2—H2B | 116.4 | C4—C5—H5 | 118.9 |
| H2A—N2—H2B | 119.3 | C2—C6—H6A | 109.5 |
| O4—N3—O3 | 121.6 (2) | C2—C6—H6B | 109.5 |
| O4—N3—O2 | 121.1 (2) | H6A—C6—H6B | 109.5 |
| O3—N3—O2 | 117.3 (2) | C2—C6—H6C | 109.5 |
| C7—O1—Cu1 | 115.23 (13) | H6A—C6—H6C | 109.5 |
| H5A—O5—H5B | 112.9 | H6B—C6—H6C | 109.5 |
| N1—C1—C2 | 122.58 (19) | O1—C7—N2 | 120.5 (2) |
| N1—C1—C7 | 110.39 (16) | O1—C7—C1 | 117.36 (17) |
| C2—C1—C7 | 127.01 (18) | N2—C7—C1 | 122.08 (18) |
| C1—C2—C3 | 115.63 (19) |
| Symmetry codes: (i) −x, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O2ii | 0.84 | 2.32 | 2.940 (4) | 131 |
| N2—H2B···O5ii | 0.95 | 1.97 | 2.886 (3) | 163 |
| O5—H5A···O2iii | 0.82 | 2.14 | 2.949 (4) | 169 |
| O5—H5A···O3iii | 0.82 | 2.46 | 3.103 (4) | 136 |
| O5—H5B···O4 | 0.83 | 1.98 | 2.814 (4) | 175 |
| Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1/2, y−1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O2i | 0.84 | 2.32 | 2.940 (4) | 131 |
| N2—H2B···O5i | 0.95 | 1.97 | 2.886 (3) | 163 |
| O5—H5A···O2ii | 0.82 | 2.14 | 2.949 (4) | 169 |
| O5—H5A···O3ii | 0.82 | 2.46 | 3.103 (4) | 136 |
| O5—H5B···O4 | 0.83 | 1.98 | 2.814 (4) | 175 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+3/2. |
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The title compound is shown in Fig. 1. The pyridine ring, methyl and amide substituent groups are almost coplanar, and their bond lengths and angles are normal. The CuII atom is coordinated by two N and two O atoms in the equatorial plane, and two O atoms at the apical positions of elongated octahedron (Table 1). The nitrate ion does not connect CuII atom directly but likes with the CuII complex cation via O—H···O hydrogen bonding (Table 2).
Further analysis of the short contacts present in (I) shows that there are O5—H5B···O2, O5—H5B···O4, O5—H5A···O3ii, O5—H5A···O2ii, [symmetry code: (ii)-x + 1/2,+y − 1/2,-z + 1/2 + 1], N2—H2A···O2iii, and N2—H2B···O5iii [symmetry code:(iii)-x + 1,-y + 1,-z + 1] interactions. All these contacts can be regarded as hydrogen bonds, which hold the complex cations and nitrate anions together.