Acta Cryst. (2012). E68, m275 [ doi:10.1107/S1600536812004564 ]
The title complex, [Cu(C13H10ClN2O)(H2O)]NO3·H2O, was obtained by the reaction of 5-chlorosalicylaldehyde, 2-(aminomethyl)pyridine and copper nitrate in methanol. The first reported polymorph of this complex was triclinic [Liang et al. (2010). Acta Cryst. E66, m40]. The present polymorph crystallized in the monoclinic space group P21/c. The CuII ion is in a square planar environment and is coordinated by one phenolate O, one imine N and one pyridine N atom of the tridentate Schiff base ligand and by one water O atom. In the crystal, molecules are linked through intermolecular O-H
O hydrogen bonds to form chains along the a axis.
To a solution of 5-chlorosalicylaldehyde (0.156 g, 1.0 mmol), 2-aminomethylpyridine (0.108 g, 1.0 mmol) in 30 ml me thanol was added slowly a solution of copper nitrate (0.241 g, 1.0 mmol) in methanol. The mixture was stirred for 2 h at room temperature to give a blue solution, which was filtered and the filtrate was left to stand at room temperature. Blue block crystals suitable for X-ray diffraction were obtained by slow evaporation.
The water H atoms were located in a difference map and refined with distances restraint of O—H = 0.85 (1) Å and H···H = 1.37 (2) Å. Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.
![[Figure 1]](./qm2051fig1thm.gif)
| Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. |
![[Figure 2]](./qm2051fig2thm.gif)
| Fig. 2. The packing of (I), viewed down the b axis. Hydrogen bonds are drawn as dashed lines. H atoms not involved in hydrogen bonding have been omitted. |
| [Cu(C13H10ClN2O)(H2O)]NO3·H2O | F(000) = 828 |
| Mr = 407.26 | Dx = 1.720 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.840 (2) Å | Cell parameters from 3984 reflections |
| b = 8.815 (3) Å | θ = 2.5–26.9° |
| c = 23.079 (3) Å | µ = 1.60 mm−1 |
| β = 99.680 (2)° | T = 298 K |
| V = 1572.4 (7) Å3 | Block, blue |
| Z = 4 | 0.22 × 0.20 × 0.19 mm |
| Bruker SMART 1K CCD area-detector diffractometer | 3410 independent reflections |
| Radiation source: fine-focus sealed tube | 2647 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.046 |
| ω scans | θmax = 27.0°, θmin = 2.5° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −9→9 |
| Tmin = 0.720, Tmax = 0.752 | k = −11→10 |
| 12290 measured reflections | l = −29→29 |
| 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0362P)2 + 0.669P] where P = (Fo2 + 2Fc2)/3 |
| 3410 reflections | (Δ/σ)max < 0.001 |
| 233 parameters | Δρmax = 0.39 e Å−3 |
| 3 restraints | Δρmin = −0.48 e Å−3 |
| [Cu(C13H10ClN2O)(H2O)]NO3·H2O | V = 1572.4 (7) Å3 |
| Mr = 407.26 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 7.840 (2) Å | µ = 1.60 mm−1 |
| b = 8.815 (3) Å | T = 298 K |
| c = 23.079 (3) Å | 0.22 × 0.20 × 0.19 mm |
| β = 99.680 (2)° |
| Bruker SMART 1K CCD area-detector diffractometer | 3410 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2647 reflections with I > 2σ(I) |
| Tmin = 0.720, Tmax = 0.752 | Rint = 0.046 |
| 12290 measured reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.089 | Δρmax = 0.39 e Å−3 |
| S = 1.06 | Δρmin = −0.48 e Å−3 |
| 3410 reflections | Absolute structure: ? |
| 233 parameters | Flack parameter: ? |
| 3 restraints | Rogers parameter: ? |
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 | 0.31780 (4) | 0.86046 (4) | 0.441029 (14) | 0.03273 (12) | |
| Cl1 | 0.30943 (12) | 1.01565 (10) | 0.74737 (3) | 0.0561 (2) | |
| N1 | 0.2244 (3) | 1.0428 (2) | 0.46999 (9) | 0.0311 (5) | |
| N2 | 0.2433 (3) | 0.9578 (2) | 0.36353 (9) | 0.0341 (5) | |
| N3 | 0.0449 (3) | 0.5644 (3) | 0.39668 (10) | 0.0427 (6) | |
| O1 | 0.3889 (3) | 0.7778 (2) | 0.51693 (8) | 0.0387 (5) | |
| O2 | 0.4383 (4) | 0.6939 (3) | 0.40783 (11) | 0.0392 (5) | |
| O3 | 0.1648 (3) | 0.5200 (3) | 0.37200 (10) | 0.0539 (6) | |
| O4 | −0.0834 (3) | 0.4839 (3) | 0.39510 (12) | 0.0764 (8) | |
| O5 | 0.0556 (3) | 0.6892 (3) | 0.42285 (11) | 0.0595 (6) | |
| O6 | 0.6908 (3) | 0.5408 (3) | 0.47630 (10) | 0.0499 (5) | |
| C1 | 0.2878 (3) | 0.9799 (3) | 0.57295 (12) | 0.0315 (6) | |
| C2 | 0.3686 (3) | 0.8378 (3) | 0.56748 (11) | 0.0317 (6) | |
| C3 | 0.4316 (4) | 0.7585 (3) | 0.61943 (12) | 0.0388 (7) | |
| H3 | 0.4867 | 0.6658 | 0.6170 | 0.047* | |
| C4 | 0.4142 (4) | 0.8134 (3) | 0.67321 (12) | 0.0397 (7) | |
| H4 | 0.4573 | 0.7583 | 0.7069 | 0.048* | |
| C5 | 0.3323 (4) | 0.9515 (3) | 0.67803 (12) | 0.0383 (7) | |
| C6 | 0.2709 (4) | 1.0331 (3) | 0.62901 (12) | 0.0380 (7) | |
| H6 | 0.2169 | 1.1257 | 0.6327 | 0.046* | |
| C7 | 0.2211 (3) | 1.0744 (3) | 0.52380 (12) | 0.0339 (6) | |
| H7 | 0.1715 | 1.1663 | 0.5317 | 0.041* | |
| C8 | 0.1576 (4) | 1.1552 (3) | 0.42524 (12) | 0.0383 (7) | |
| H8A | 0.2252 | 1.2476 | 0.4318 | 0.046* | |
| H8B | 0.0385 | 1.1793 | 0.4279 | 0.046* | |
| C9 | 0.1674 (3) | 1.0935 (3) | 0.36544 (12) | 0.0323 (6) | |
| C10 | 0.1044 (4) | 1.1749 (3) | 0.31527 (13) | 0.0443 (7) | |
| H10 | 0.0529 | 1.2693 | 0.3177 | 0.053* | |
| C11 | 0.1198 (4) | 1.1132 (4) | 0.26167 (13) | 0.0486 (8) | |
| H11 | 0.0773 | 1.1651 | 0.2272 | 0.058* | |
| C12 | 0.1979 (4) | 0.9748 (4) | 0.25938 (13) | 0.0470 (8) | |
| H12 | 0.2096 | 0.9321 | 0.2234 | 0.056* | |
| C13 | 0.2586 (4) | 0.9002 (3) | 0.31071 (13) | 0.0420 (7) | |
| H13 | 0.3122 | 0.8066 | 0.3090 | 0.050* | |
| H6A | 0.773 (3) | 0.535 (3) | 0.4574 (12) | 0.045 (10)* | |
| H2A | 0.362 (5) | 0.633 (4) | 0.3958 (16) | 0.067 (14)* | |
| H2B | 0.502 (5) | 0.656 (4) | 0.4284 (15) | 0.047 (12)* | |
| H6B | 0.657 (5) | 0.452 (2) | 0.4820 (18) | 0.100 (16)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0389 (2) | 0.02223 (18) | 0.03751 (19) | 0.00418 (15) | 0.00787 (14) | −0.00095 (14) |
| Cl1 | 0.0715 (6) | 0.0575 (5) | 0.0400 (4) | −0.0038 (4) | 0.0120 (4) | −0.0117 (4) |
| N1 | 0.0343 (12) | 0.0188 (11) | 0.0396 (12) | 0.0034 (9) | 0.0045 (10) | 0.0015 (9) |
| N2 | 0.0384 (13) | 0.0257 (12) | 0.0381 (12) | −0.0011 (10) | 0.0063 (10) | 0.0001 (10) |
| N3 | 0.0444 (16) | 0.0418 (16) | 0.0400 (13) | −0.0038 (13) | 0.0014 (11) | 0.0011 (12) |
| O1 | 0.0533 (12) | 0.0250 (10) | 0.0385 (10) | 0.0094 (9) | 0.0100 (9) | −0.0021 (8) |
| O2 | 0.0399 (14) | 0.0312 (12) | 0.0468 (13) | 0.0071 (11) | 0.0079 (11) | −0.0014 (11) |
| O3 | 0.0568 (14) | 0.0522 (14) | 0.0567 (13) | −0.0071 (11) | 0.0214 (11) | −0.0186 (11) |
| O4 | 0.0560 (16) | 0.082 (2) | 0.095 (2) | −0.0297 (15) | 0.0250 (14) | −0.0259 (16) |
| O5 | 0.0533 (14) | 0.0371 (13) | 0.0913 (17) | 0.0026 (11) | 0.0211 (13) | −0.0148 (13) |
| O6 | 0.0554 (15) | 0.0354 (13) | 0.0579 (14) | 0.0075 (11) | 0.0067 (12) | −0.0017 (11) |
| C1 | 0.0319 (15) | 0.0227 (13) | 0.0401 (14) | −0.0018 (11) | 0.0063 (12) | −0.0035 (11) |
| C2 | 0.0319 (15) | 0.0252 (14) | 0.0382 (14) | −0.0022 (11) | 0.0064 (11) | −0.0022 (11) |
| C3 | 0.0438 (17) | 0.0255 (15) | 0.0464 (16) | 0.0020 (13) | 0.0057 (13) | 0.0011 (12) |
| C4 | 0.0437 (18) | 0.0359 (16) | 0.0385 (15) | −0.0040 (13) | 0.0042 (13) | 0.0042 (13) |
| C5 | 0.0402 (17) | 0.0370 (17) | 0.0390 (15) | −0.0085 (13) | 0.0099 (12) | −0.0094 (13) |
| C6 | 0.0402 (17) | 0.0297 (15) | 0.0451 (16) | 0.0001 (13) | 0.0099 (13) | −0.0076 (13) |
| C7 | 0.0329 (15) | 0.0230 (13) | 0.0460 (16) | 0.0026 (12) | 0.0073 (12) | −0.0037 (12) |
| C8 | 0.0460 (17) | 0.0240 (14) | 0.0438 (15) | 0.0078 (13) | 0.0040 (13) | 0.0021 (12) |
| C9 | 0.0283 (14) | 0.0245 (13) | 0.0429 (15) | −0.0029 (11) | 0.0021 (12) | −0.0002 (12) |
| C10 | 0.0478 (19) | 0.0321 (16) | 0.0468 (17) | 0.0032 (14) | −0.0100 (14) | 0.0017 (13) |
| C11 | 0.056 (2) | 0.0434 (19) | 0.0400 (16) | −0.0029 (16) | −0.0088 (14) | 0.0048 (14) |
| C12 | 0.053 (2) | 0.0446 (19) | 0.0403 (16) | −0.0076 (16) | −0.0013 (14) | −0.0066 (14) |
| C13 | 0.0471 (18) | 0.0327 (16) | 0.0459 (17) | 0.0002 (13) | 0.0074 (14) | −0.0042 (13) |
| Cu1—O1 | 1.8925 (18) | C2—C3 | 1.404 (4) |
| Cu1—N1 | 1.932 (2) | C3—C4 | 1.360 (4) |
| Cu1—O2 | 1.970 (2) | C3—H3 | 0.9300 |
| Cu1—N2 | 1.981 (2) | C4—C5 | 1.389 (4) |
| Cl1—C5 | 1.735 (3) | C4—H4 | 0.9300 |
| N1—C7 | 1.277 (3) | C5—C6 | 1.359 (4) |
| N1—C8 | 1.463 (3) | C6—H6 | 0.9300 |
| N2—C9 | 1.340 (3) | C7—H7 | 0.9300 |
| N2—C13 | 1.345 (3) | C8—C9 | 1.497 (4) |
| N3—O4 | 1.227 (3) | C8—H8A | 0.9700 |
| N3—O3 | 1.241 (3) | C8—H8B | 0.9700 |
| N3—O5 | 1.251 (3) | C9—C10 | 1.381 (4) |
| O1—C2 | 1.314 (3) | C10—C11 | 1.375 (4) |
| O2—H2A | 0.81 (4) | C10—H10 | 0.9300 |
| O2—H2B | 0.71 (4) | C11—C12 | 1.371 (4) |
| O6—H6A | 0.839 (10) | C11—H11 | 0.9300 |
| O6—H6B | 0.845 (10) | C12—C13 | 1.368 (4) |
| C1—C6 | 1.403 (4) | C12—H12 | 0.9300 |
| C1—C2 | 1.419 (3) | C13—H13 | 0.9300 |
| C1—C7 | 1.434 (4) | ||
| O1—Cu1—N1 | 94.00 (8) | C5—C4—H4 | 119.9 |
| O1—Cu1—O2 | 89.27 (9) | C6—C5—C4 | 120.1 (3) |
| N1—Cu1—O2 | 171.71 (10) | C6—C5—Cl1 | 121.2 (2) |
| O1—Cu1—N2 | 176.94 (8) | C4—C5—Cl1 | 118.7 (2) |
| N1—Cu1—N2 | 83.13 (9) | C5—C6—C1 | 121.0 (3) |
| O2—Cu1—N2 | 93.43 (10) | C5—C6—H6 | 119.5 |
| C7—N1—C8 | 118.4 (2) | C1—C6—H6 | 119.5 |
| C7—N1—Cu1 | 126.06 (19) | N1—C7—C1 | 125.3 (2) |
| C8—N1—Cu1 | 115.50 (16) | N1—C7—H7 | 117.3 |
| C9—N2—C13 | 118.3 (2) | C1—C7—H7 | 117.3 |
| C9—N2—Cu1 | 114.98 (18) | N1—C8—C9 | 109.7 (2) |
| C13—N2—Cu1 | 126.67 (19) | N1—C8—H8A | 109.7 |
| O4—N3—O3 | 118.9 (3) | C9—C8—H8A | 109.7 |
| O4—N3—O5 | 120.7 (3) | N1—C8—H8B | 109.7 |
| O3—N3—O5 | 120.3 (3) | C9—C8—H8B | 109.7 |
| C2—O1—Cu1 | 127.32 (17) | H8A—C8—H8B | 108.2 |
| Cu1—O2—H2A | 105 (3) | N2—C9—C10 | 122.3 (3) |
| Cu1—O2—H2B | 115 (3) | N2—C9—C8 | 116.5 (2) |
| H2A—O2—H2B | 108 (4) | C10—C9—C8 | 121.2 (2) |
| H6A—O6—H6B | 109 (2) | C11—C10—C9 | 118.4 (3) |
| C6—C1—C2 | 119.3 (2) | C11—C10—H10 | 120.8 |
| C6—C1—C7 | 117.2 (2) | C9—C10—H10 | 120.8 |
| C2—C1—C7 | 123.5 (2) | C12—C11—C10 | 119.6 (3) |
| O1—C2—C3 | 118.7 (2) | C12—C11—H11 | 120.2 |
| O1—C2—C1 | 123.8 (2) | C10—C11—H11 | 120.2 |
| C3—C2—C1 | 117.5 (2) | C13—C12—C11 | 119.1 (3) |
| C4—C3—C2 | 121.8 (3) | C13—C12—H12 | 120.4 |
| C4—C3—H3 | 119.1 | C11—C12—H12 | 120.4 |
| C2—C3—H3 | 119.1 | N2—C13—C12 | 122.2 (3) |
| C3—C4—C5 | 120.2 (3) | N2—C13—H13 | 118.9 |
| C3—C4—H4 | 119.9 | C12—C13—H13 | 118.9 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O6—H6B···O1i | 0.85 (1) | 2.06 (1) | 2.887 (3) | 167 (3) |
| O2—H2B···O6 | 0.71 (4) | 1.98 (4) | 2.681 (4) | 172 (4) |
| O2—H2A···O5 | 0.81 (4) | 2.63 (4) | 3.078 (3) | 116 (3) |
| O2—H2A···O3 | 0.81 (4) | 1.85 (4) | 2.652 (4) | 170 (4) |
| O6—H6A···O4ii | 0.84 (1) | 2.02 (1) | 2.831 (3) | 162 (3) |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O6—H6B···O1i | 0.845 (10) | 2.058 (14) | 2.887 (3) | 167 (3) |
| O2—H2B···O6 | 0.71 (4) | 1.98 (4) | 2.681 (4) | 172 (4) |
| O2—H2A···O5 | 0.81 (4) | 2.63 (4) | 3.078 (3) | 116 (3) |
| O2—H2A···O3 | 0.81 (4) | 1.85 (4) | 2.652 (4) | 170 (4) |
| O6—H6A···O4ii | 0.839 (10) | 2.020 (14) | 2.831 (3) | 162 (3) |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z. |
The College of Biological and Chemical Sciences Engineering at Jiaxing University is acknowledged for the provision of facilities to prepare and characterize the compound.
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Schiff base copper(II) complexes have been received much attention due to their interesting structures and biological properties (Patel et al., 2011; Creaven et al., 2010; Osowole et al., 2008). The title complex was first reported as triclinic space group P-1 (Liang et al., 2010). We report herein a monoclinic polymorph in space group P21/c.
The title complex, (I) (Fig. 1), contains a mononuclear copper complex cation, a nitrate anion, and a water molecule. The Cu atom is coordinated by one phenolate O, one imine N, and one pyridine N of the Schiff base ligand, and one water O atom, forming a square planar coordination. The bond lengths (Table 1) are within the normal range. In the crystal, molecules are linked through intermolecular O—H···O hydrogen bonds (Table 2), to form chains along the a axis, Fig. 2.