Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702226X/si2012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702226X/si2012Isup2.hkl |
CCDC reference: 650677
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.
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.
For general background, see: Berry et al. (1999); Reis et al. (2005); Kirillov et al. (2006); Nesterov et al. (2006). For related structures, see: Malek et al. (2004); Dobosz et al. (1999). For examples of the fragmentation of N-hydroxy-2,2'-iminodipropionic acid, see: Kirillov et al. (2005); Harben et al. (1997). Further details are given as supplementary material (see Comment).
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.
[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 monochromator | 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 |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.42 e Å−3 |
1207 reflections | Δρmin = −0.56 e Å−3 |
85 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 | 0.01113 (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 code: (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. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C3H4NO3)2(H2O)2] |
Mr | 303.72 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 4.8204 (3), 6.5447 (4), 8.7092 (6) |
α, β, γ (°) | 87.413 (4), 88.565 (5), 74.939 (5) |
V (Å3) | 265.02 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.10 |
Crystal size (mm) | 0.37 × 0.14 × 0.07 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (XPREP in SHELXTL; Sheldrick, 2001) |
Tmin, Tmax | 0.509, 0.867 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2320, 1207, 1170 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.064, 1.10 |
No. of reflections | 1207 |
No. of parameters | 85 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.42, −0.56 |
Computer programs: Collect (Bruker, 2004 or Nonius, 1998?), DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2006), SHELXL97.
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) | 169.2 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z; (iii) x, y−1, z; (iv) −x, −y, −z+1. |
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.