Acta Cryst. (2007). E63, m1670-m1671 [ doi:10.1107/S160053680702226X ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
2N,O)copper(II)The 100 K crystal structure of the title compound, [Cu(C3H4NO3)2(H2O)2], is composed of discrete [Cu(hipa)2(H2O)2] units (hipa = 2-hydroxyiminopropionate). The CuII atom lies on an inversion centre and exhibits a slightly distorted octahedral coordination geometry formed by two chelating bidentate hipa ligands occupying equatorial sites and two water molecules in axial positions. The hipa ligands are bound to the copper centre in a trans fashion, generating a planar {Cu(hipa)2} core with the six-membered chelate rings having Cu-O and Cu-N distances of 1.9421 (13) and 2.0488 (15) Å, respectively, and N-Cu-O bite angles of 80.70 (6)°. The bonding parameters agree with those of the 298 K crystal structure of the title compound, which has been deposited at the Cambridge Structural Database (refcode IGUZAL) [Holt (2002). Private communication to the Cambridge Structural Database. Cambridge Crystallographic Data Centre, Cambridge, England] but remained unpublished. In the title compound, each water molecule acts as both an intermolecular hydrogen-bond donor (to the carboxylate O atoms) or acceptor (of hydrogen from the hydroxyl oxygen), thus multiply linking neighbouring mononuclear units and forming polymeric hydrogen-bonded two-dimensional layers. They are further extended by means of weak intermolecular C-H
O hydrogen bonds between methyl groups and the hydroxyl O atoms of hipa. The shortest CuCu separations within these layers are equal to the unit-cell dimensions. The hipa ligands in the title compound are derived from a copper-promoted fragmentation of N-hydroxy-2,2'-iminodipropionic acid.
To a methanolic solution (5 ml) of Cu(NO3)2×2.5H2O (58 mg, 0.25 mmol) was added N-hydroxy-2,2'-iminodipropionic acid (44 mg, 0.25 mmol) with continuous stirring at room temperature. The reaction mixture was stirred overnight and then filtered. The filtrate was left in a vial to evaporate in air at ambient temperature. Green X-ray quality crystals were formed in several days and were collected and dried in air (yield 26%, based on copper nitrate). Analysis calculated for C6H12CuN2O8: C 23.73, H 3.98, N 9.22; found: C 23.77, H 4.10, N 8.84%. FT—IR, selected bands, cm-1: 3306 [s,br, ν(H2O)+ν(OH)], 2796 [w, ν(CH)], 1678 [s,br, νas(COO)+ν(C=N)], 1460 and 1361 [s, νs(COO)], 1386 [w, δ(CH3)], 1077 [s, ν(NO)].
The hydrogen atoms H1O, H4A and H4B were located from the difference Fourier map. The H1O atom was refined isotropically and but the H4A and H4B atoms but were constrained to ride on their parent atom, with Uiso = 1.5 Ueq(parent atom). Other H atoms were positioned geometrically and were also constrained to ride on their parent atoms, with C—H = 0.98 Å, and Uiso = 1.5 Ueq(parent atom). The highest peak is located 0.75 Å from atom C1 and the deepest hole is located 0.81 Å from atom Cu1.
Data collection: Collect (Bruker, 2004 or Nonius, 1998?); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97.
![[Figure 1]](./si2012fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing the atom-labeling scheme. The suffixes A correspond to the symmetry position (-x, -y, -z). Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary radii. |
![[Figure 2]](./si2012fig2thm.gif)
| Fig. 2. Ball-and-stick partial representation of the crystal packing of compound (I), viewed down the a (a) and c (b) axis, with hydrogen-bonding network (dashed lines). H atoms are omitted for clarity. Cu, green; N, blue; O, red; C, grey. |
| [Cu(C3H4NO3)2(H2O)2] | Z = 1 |
| Mr = 303.72 | F(000) = 155 |
| Triclinic, P1 | Dx = 1.903 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 4.8204 (3) Å | Cell parameters from 2320 reflections |
| b = 6.5447 (4) Å | θ = 3.9–27.4° |
| c = 8.7092 (6) Å | µ = 2.10 mm−1 |
| α = 87.413 (4)° | T = 100 K |
| β = 88.565 (5)° | Plate, pale green |
| γ = 74.939 (5)° | 0.37 × 0.14 × 0.07 mm |
| V = 265.02 (3) Å3 |
| Nonius KappaCCD diffractometer | 1207 independent reflections |
| Radiation source: fine-focus sealed tube | 1170 reflections with I > 2σ(I) |
| horizontally mounted graphite crystal | Rint = 0.015 |
| Detector resolution: 9 pixels mm-1 | θmax = 27.4°, θmin = 3.9° |
| φ scans and ω scans with κ offset | h = −6→6 |
| Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2001) | k = −8→8 |
| Tmin = 0.509, Tmax = 0.867 | l = −11→11 |
| 2320 measured reflections |
| 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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.10 | w = 1/[σ2(Fo2) + (0.0274P)2 + 0.2627P] where P = (Fo2 + 2Fc2)/3 |
| 1207 reflections | (Δ/σ)max < 0.001 |
| 85 parameters | Δρmax = 0.42 e Å−3 |
| 0 restraints | Δρmin = −0.56 e Å−3 |
| [Cu(C3H4NO3)2(H2O)2] | γ = 74.939 (5)° |
| Mr = 303.72 | V = 265.02 (3) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 4.8204 (3) Å | Mo Kα radiation |
| b = 6.5447 (4) Å | µ = 2.10 mm−1 |
| c = 8.7092 (6) Å | T = 100 K |
| α = 87.413 (4)° | 0.37 × 0.14 × 0.07 mm |
| β = 88.565 (5)° |
| Nonius KappaCCD diffractometer | 1207 independent reflections |
| Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2001) | 1170 reflections with I > 2σ(I) |
| Tmin = 0.509, Tmax = 0.867 | Rint = 0.015 |
| 2320 measured reflections | θmax = 27.4° |
| R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.064 | Δρmax = 0.42 e Å−3 |
| S = 1.10 | Δρmin = −0.56 e Å−3 |
| 1207 reflections | Absolute structure: ? |
| 85 parameters | Flack parameter: ? |
| 0 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 | 0.0000 | 0.0000 | 0.0000 | 0.01113 (12) | |
| O1 | −0.3635 (3) | −0.0415 (2) | 0.29803 (15) | 0.0142 (3) | |
| H1O | −0.430 (6) | −0.118 (4) | 0.235 (3) | 0.030 (7)* | |
| O2 | 0.1815 (3) | 0.4394 (2) | 0.24723 (16) | 0.0161 (3) | |
| O3 | 0.1601 (3) | 0.2297 (2) | 0.05499 (15) | 0.0128 (3) | |
| O4 | 0.3956 (3) | −0.2557 (2) | 0.11946 (15) | 0.0133 (3) | |
| N1 | −0.1846 (3) | 0.0563 (2) | 0.21363 (18) | 0.0106 (3) | |
| C1 | −0.1067 (4) | 0.1993 (3) | 0.2845 (2) | 0.0112 (3) | |
| C2 | −0.1950 (4) | 0.2699 (3) | 0.4424 (2) | 0.0163 (4) | |
| H2A | −0.3498 | 0.2080 | 0.4798 | 0.025* | |
| H2B | −0.2630 | 0.4247 | 0.4406 | 0.025* | |
| H2C | −0.0302 | 0.2235 | 0.5109 | 0.025* | |
| C3 | 0.0944 (4) | 0.3002 (3) | 0.1904 (2) | 0.0112 (3) | |
| H4A | 0.5075 | −0.3129 | 0.0472 | 0.017* | |
| H4B | 0.3083 | −0.3461 | 0.1542 | 0.017* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.01162 (18) | 0.01280 (17) | 0.01097 (17) | −0.00651 (12) | 0.00254 (11) | −0.00354 (11) |
| O1 | 0.0156 (7) | 0.0183 (7) | 0.0128 (6) | −0.0118 (5) | 0.0037 (5) | −0.0022 (5) |
| O2 | 0.0209 (7) | 0.0152 (7) | 0.0158 (7) | −0.0105 (6) | 0.0016 (5) | −0.0044 (5) |
| O3 | 0.0136 (7) | 0.0149 (6) | 0.0119 (6) | −0.0072 (5) | 0.0027 (5) | −0.0034 (5) |
| O4 | 0.0127 (7) | 0.0140 (6) | 0.0148 (6) | −0.0065 (5) | 0.0027 (5) | −0.0019 (5) |
| N1 | 0.0090 (7) | 0.0126 (7) | 0.0109 (7) | −0.0045 (6) | 0.0013 (5) | −0.0006 (6) |
| C1 | 0.0102 (9) | 0.0117 (8) | 0.0117 (8) | −0.0028 (7) | 0.0002 (6) | −0.0012 (6) |
| C2 | 0.0192 (10) | 0.0186 (9) | 0.0129 (9) | −0.0076 (8) | 0.0034 (7) | −0.0054 (7) |
| C3 | 0.0100 (8) | 0.0108 (8) | 0.0127 (8) | −0.0023 (6) | −0.0003 (6) | −0.0007 (6) |
| Cu1—O3 | 1.9421 (13) | O3—C3 | 1.288 (2) |
| Cu1—O3i | 1.9421 (13) | O4—H4A | 0.8527 |
| Cu1—N1i | 2.0487 (15) | O4—H4B | 0.8519 |
| Cu1—N1 | 2.0488 (15) | N1—C1 | 1.282 (2) |
| Cu1—O4i | 2.4090 (14) | C1—C2 | 1.488 (2) |
| Cu1—O4 | 2.4090 (14) | C1—C3 | 1.514 (2) |
| O1—N1 | 1.3805 (19) | C2—H2A | 0.9800 |
| O1—H1O | 0.88 (3) | C2—H2B | 0.9800 |
| O2—C3 | 1.225 (2) | C2—H2C | 0.9800 |
| O3—Cu1—O3i | 180 | Cu1—O4—H4B | 99.7 |
| O3—Cu1—N1i | 99.31 (6) | H4A—O4—H4B | 107.3 |
| O3i—Cu1—N1i | 80.69 (6) | C1—N1—O1 | 114.50 (15) |
| O3—Cu1—N1 | 80.69 (6) | C1—N1—Cu1 | 114.06 (12) |
| O3i—Cu1—N1 | 99.31 (6) | O1—N1—Cu1 | 131.30 (11) |
| N1i—Cu1—N1 | 180 | N1—C1—C2 | 126.73 (17) |
| O3—Cu1—O4i | 89.28 (5) | N1—C1—C3 | 113.30 (15) |
| O3i—Cu1—O4i | 90.72 (5) | C2—C1—C3 | 119.97 (16) |
| N1i—Cu1—O4i | 88.44 (5) | C1—C2—H2A | 109.5 |
| N1—Cu1—O4i | 91.56 (5) | C1—C2—H2B | 109.5 |
| O3—Cu1—O4 | 90.72 (5) | H2A—C2—H2B | 109.5 |
| O3i—Cu1—O4 | 89.28 (5) | C1—C2—H2C | 109.5 |
| N1i—Cu1—O4 | 91.56 (5) | H2A—C2—H2C | 109.5 |
| N1—Cu1—O4 | 88.44 (5) | H2B—C2—H2C | 109.5 |
| O4i—Cu1—O4 | 180 | O2—C3—O3 | 125.38 (17) |
| N1—O1—H1O | 107.5 (19) | O2—C3—C1 | 118.66 (16) |
| C3—O3—Cu1 | 115.88 (11) | O3—C3—C1 | 115.96 (15) |
| Cu1—O4—H4A | 106.8 |
| Symmetry codes: (i) −x, −y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1O···O4ii | 0.88 (3) | 1.74 (3) | 2.6207 (19) | 173 (3) |
| O4—H4A···O3iii | 0.85 | 2.00 | 2.6319 (18) | 130 |
| O4—H4B···O2iv | 0.85 | 1.82 | 2.6638 (18) | 170 |
| C2—H2C···O1v | 0.98 | 2.57 | 3.535 (3) | 169 |
| Symmetry codes: (ii) x−1, y, z; (iii) −x+1, −y, −z; (iv) x, y−1, z; (v) −x, −y, −z+1. |
| Cu1—O3 | 1.9421 (13) | Cu1—O4 | 2.4090 (14) |
| Cu1—N1 | 2.0488 (15) | ||
| O3—Cu1—N1 | 80.69 (6) | N1—Cu1—O4 | 88.44 (5) |
| O3—Cu1—O4 | 90.72 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1O···O4i | 0.88 (3) | 1.74 (3) | 2.6207 (19) | 173 (3) |
| O4—H4A···O3ii | 0.85 | 2.00 | 2.6319 (18) | 130 |
| O4—H4B···O2iii | 0.85 | 1.82 | 2.6638 (18) | 170 |
| C2—H2C···O1iv | 0.98 | 2.57 | 3.535 (3) | 169 |
| Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z; (iii) x, y−1, z; (iv) −x, −y, −z+1. |
This work has been partially supported by the FCT, Portugal, the FCT POCI 2010 programme (FEDER funded), by the Human Resources and Mobility Marie Curie Research Training Network (AQUACHEM project, CMTN-CT-2003–503864) and by the Academy of Finland.
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The N-hydroxy-2,2'-iminodipropionic acid (H3hidpa), HON(CH(CH3)COOH2, constitutes, in its basic form hidpa3-, the ligand in Amavadine (Berry et al., 1999), a natural bare vanadium(IV) complex [V(hidpa)2]2- which is present in some Amanita fungi and has been applied as an efficient catalyst in various alkane functionalization reactions (Reis et al., 2005). Hence, in pursuit of these and other studies, namely focusing on the self-assembly synthesis of copper(II) complexes with various N,O-ligands and their application in catalysis (Kirillov et al., 2006; Nesterov et al., 2006), we have attempted the preparation of the copper compound structurally related to Amavadine. However, the reaction of Cu(NO3)2×2.5H2O with H3hidpa in methanol and at room temperature resulted in the formation of the title compound, (I), due to the fragmentation of H3hidpa to give 2-hydroxyiminopropionate, HON=C(CH3)COO- (hipa). Such a type of fragmentation is unusual or even unknown, although other examples of H3hidpa fragmentations promoted by Re or Mo centres have already been described (Harben et al., 1997; Kirillov, Haukka et al., 2005). Herein we report the synthesis of compound (I) and its characterization by IR spectroscopy, elemental and low-temperature (100 K) single-crystal X-ray diffraction analyses.
The crystal structure of (I) (Fig. 1) is composed of discrete monomeric units, with a slightly distorted centrosymmetric octahedral geometry formed by two bidentate hipa ligands occupying equatorial sites and two water molecules in apical positions. Most of the bonding parameters in (I) (Table 1) agree with those of the related copper compounds (Malek et al., 2004; Dobosz et al., 1999) bearing hipa or derived moieties.
In (I), each water oxygen atom (O4) acts as both an intermolecular hydrogen-bond donor (to the carboxylate oxygen atoms O2 and O3) or acceptor (of hydrogen from the hydroxo oxygen O1) (Table 2), thus multiply linking the neighbouring mononuclear units and forming polymeric H-bonded chains (if seen along the a or b axis, Fig. 2a) or two-dimensional layers (if seen along the c axis, Fig. 2 b). These chains and layers are further extended by means of the weak intermolecular C2—H2C···O1 interactions resulting in a three-dimensional hydrogen bonded network.