Retracted: (Dihydroxyglyoxime-κ2N,N′)bis(1,10-phenanthroline-κ2N,N′)copper(II) dinitrate dihydrate
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028255/hk2273sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028255/hk2273Isup2.hkl |
CCDC reference: 1148885
Copper(II) dinitrate hexahydrate (296 mg, 1 mmol), phen (396 mg, 2 mmol) and dihydroxyglyoxime (120 mg, 1 mmol) were dissolved in ethanol (20 ml). The mixture was heated for 5 h under reflux with stirring. It was then filtered to give a clear solution, into which diethyl ether vapour was allowed to condense in a closed vessel. After being allowed to stand for a few days at room temperature, some blue single crystals suitable for X-ray diffraction analysis precipitated.
H atoms of the water molecules were located in a difference synthesis and refined isotropically [O—H = 0.84 (3)–0.86 (9) Å, Uiso(H) = 0.450 (8)–0.59 (5) Å2]. The remaining H atoms were positioned geometrically, with O—H = 0.82 Å (for OH) and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,O), where x = 1.2 for aromatic H atoms and x = 1.5 for OH H atoms.
In recent years, interest in the chemistry of metal-oxygen clusters has grown because of their applications in areas including catalysis, materials chemistry and biochemistry (Pope, 1983; Pope & Müller, 2001). π-π Stacking between aromatic rings is related to the electron-transfer process in some biological systems (Deisenhofer & Michel, 1989; Wall et al., 1999). Aromatic polycyclic compounds, such as phenanthroline, quinoline and benzimidazole, have commonly shown π-π stacking in metal complexes (Wu et al., 2003; Pan & Xu, 2004; Liu et al., 2004; Li et al., 2005). As a bidentate flexible ligand, dihydroxyglyoxime is also a good ligand with excellent coordination capabilities for generating mono-, bi- or trinuclear complexes, which are commonly used as precursors for the formation of supramolecular architectures (Chaudhuri et al., 1991; Cervera et al., 1997). We report here the crystal structure of the title compound, (I).
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The six N atoms of one dihydroxyglyoxime and two 1,10-phenanthroline (phen) ligands are coordinated to the Cu atom, in a distorted octahedral arrangement (Table 1). The dihydroxyglyoxime and two phen ligands are each planar, and the phen ligands are nearly perpendicular to each other, with a dihedral angle of 87.21 (5)°.
In the crystal structure, there is a three-dimensional framework (Fig. 2) formed by O—H···O and C—H···O hydrogen bonds (Table 2). There are π-π stacking interactions between adjacent phen ligands with a centroid-centroid distance of 3.543 (2) Å (symmetry code: 1 - x, 2 - y, 1 - z). These π-π stacking interactions and hydrogen bonds lead to a supramolecular network structure (Fig. 2).
For general background, see: Pope (1983); Pope & Müller (2001); Deisenhofer & Michel (1989); Wall et al. (1999); Allen et al. (1987). For related literature, see: Wu et al. (2003); Pan & Xu (2004); Liu et al. (2004); Li et al. (2005); Chaudhuri et al. (1991); Cervera et al. (1997).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.
[Cu(C12H8N2)2(C2H4N2O4)](NO3)2·2H2O | F(000) = 1444 |
Mr = 704.07 | Dx = 1.534 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5663 reflections |
a = 13.9108 (7) Å | θ = 2.2–24.9° |
b = 12.011 (3) Å | µ = 0.79 mm−1 |
c = 18.338 (4) Å | T = 273 K |
β = 95.897 (5)° | Prism, blue |
V = 3047.8 (10) Å3 | 0.30 × 0.23 × 0.18 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 6028 independent reflections |
Radiation source: fine-focus sealed tube | 3118 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
φ and ω scans | θmax = 26.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→17 |
Tmin = 0.798, Tmax = 0.871 | k = −15→15 |
19706 measured reflections | l = −22→22 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.167 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0966P)2] where P = (Fo2 + 2Fc2)/3 |
6028 reflections | (Δ/σ)max = 0.005 |
444 parameters | Δρmax = 0.79 e Å−3 |
12 restraints | Δρmin = −0.61 e Å−3 |
[Cu(C12H8N2)2(C2H4N2O4)](NO3)2·2H2O | V = 3047.8 (10) Å3 |
Mr = 704.07 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.9108 (7) Å | µ = 0.79 mm−1 |
b = 12.011 (3) Å | T = 273 K |
c = 18.338 (4) Å | 0.30 × 0.23 × 0.18 mm |
β = 95.897 (5)° |
Bruker APEXII area-detector diffractometer | 6028 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3118 reflections with I > 2σ(I) |
Tmin = 0.798, Tmax = 0.871 | Rint = 0.041 |
19706 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 12 restraints |
wR(F2) = 0.167 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.79 e Å−3 |
6028 reflections | Δρmin = −0.61 e Å−3 |
444 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 | 0.77579 (4) | 0.75553 (5) | 0.03828 (3) | 0.0432 (2) | |
O1 | 0.7961 (3) | 0.9961 (3) | 0.04774 (18) | 0.0483 (9) | |
H1A | 0.8000 | 0.9954 | 0.0034 | 0.072* | |
O2 | 0.8338 (3) | 0.6031 (3) | 0.1481 (2) | 0.0563 (10) | |
H2A | 0.8712 | 0.5921 | 0.1850 | 0.085* | |
O3 | 0.9324 (4) | 0.7551 (5) | 0.2458 (3) | 0.1201 (19) | |
H3A | 0.9908 | 0.7545 | 0.2431 | 0.180* | |
O4 | 0.9039 (5) | 0.9954 (5) | 0.1835 (4) | 0.133 (2) | |
H4A | 0.9520 | 0.9796 | 0.2111 | 0.199* | |
O5 | 0.7739 (3) | 0.1302 (3) | 0.9096 (3) | 0.0814 (13) | |
O6 | 0.8930 (3) | 0.0159 (3) | 0.9283 (2) | 0.0641 (11) | |
O7 | 0.8887 (4) | 0.1343 (4) | 0.8437 (3) | 0.116 (2) | |
O8 | 0.7394 (6) | 0.8785 (7) | 0.2880 (4) | 0.166 (3) | |
O9 | 0.6158 (7) | 0.8835 (7) | 0.3358 (5) | 0.184 (3) | |
O10 | 0.6387 (9) | 1.0077 (7) | 0.2627 (6) | 0.345 (11) | |
O11 | 0.5584 (13) | 0.4277 (14) | 0.1452 (12) | 0.497 (14) | |
O12 | 0.701 (2) | 0.340 (2) | 0.2000 (12) | 0.59 (2) | |
N1 | 0.6533 (3) | 0.7801 (3) | 0.0767 (2) | 0.0376 (9) | |
N2 | 0.7067 (3) | 0.8187 (3) | −0.0534 (2) | 0.0355 (9) | |
N3 | 0.7384 (3) | 0.6056 (3) | 0.0042 (2) | 0.0396 (9) | |
N4 | 0.8936 (2) | 0.7245 (3) | −0.0073 (2) | 0.0343 (9) | |
N5 | 0.8376 (3) | 0.7047 (3) | 0.1298 (2) | 0.0391 (9) | |
N6 | 0.8219 (2) | 0.8937 (3) | 0.0767 (2) | 0.0350 (9) | |
N7 | 0.8515 (3) | 0.0921 (4) | 0.8922 (3) | 0.0569 (12) | |
N8 | 0.6658 (6) | 0.9287 (9) | 0.2899 (5) | 0.130 (4) | |
C1 | 0.6305 (4) | 0.7620 (4) | 0.1432 (3) | 0.0491 (13) | |
H1 | 0.6778 | 0.7368 | 0.1789 | 0.059* | |
C2 | 0.5357 (4) | 0.7800 (5) | 0.1620 (3) | 0.0604 (15) | |
H2 | 0.5213 | 0.7658 | 0.2095 | 0.072* | |
C3 | 0.4666 (4) | 0.8173 (4) | 0.1120 (3) | 0.0557 (15) | |
H3 | 0.4044 | 0.8291 | 0.1248 | 0.067* | |
C4 | 0.4874 (3) | 0.8387 (4) | 0.0409 (3) | 0.0461 (13) | |
C5 | 0.4204 (4) | 0.8802 (4) | −0.0169 (4) | 0.0583 (15) | |
H5 | 0.3566 | 0.8924 | −0.0081 | 0.070* | |
C6 | 0.4477 (4) | 0.9023 (4) | −0.0846 (4) | 0.0615 (16) | |
H6 | 0.4025 | 0.9298 | −0.1211 | 0.074* | |
C7 | 0.5462 (4) | 0.8834 (4) | −0.1004 (3) | 0.0497 (13) | |
C8 | 0.5808 (4) | 0.9063 (4) | −0.1659 (3) | 0.0594 (15) | |
H8 | 0.5398 | 0.9356 | −0.2044 | 0.071* | |
C9 | 0.6761 (5) | 0.8862 (4) | −0.1748 (3) | 0.0598 (15) | |
H9 | 0.7001 | 0.9030 | −0.2190 | 0.072* | |
C10 | 0.7367 (4) | 0.8403 (4) | −0.1171 (3) | 0.0464 (13) | |
H10 | 0.8006 | 0.8247 | −0.1242 | 0.056* | |
C11 | 0.6124 (3) | 0.8403 (3) | −0.0443 (3) | 0.0398 (12) | |
C12 | 0.5832 (3) | 0.8180 (3) | 0.0253 (3) | 0.0371 (11) | |
C13 | 0.6609 (4) | 0.5462 (4) | 0.0146 (3) | 0.0554 (14) | |
H13 | 0.6147 | 0.5761 | 0.0422 | 0.066* | |
C14 | 0.6468 (4) | 0.4405 (5) | −0.0147 (4) | 0.0681 (18) | |
H14 | 0.5913 | 0.4008 | −0.0069 | 0.082* | |
C15 | 0.7131 (4) | 0.3945 (4) | −0.0545 (3) | 0.0674 (17) | |
H15 | 0.7034 | 0.3235 | −0.0741 | 0.081* | |
C16 | 0.7968 (4) | 0.4544 (4) | −0.0662 (3) | 0.0447 (12) | |
C17 | 0.8721 (4) | 0.4155 (4) | −0.1062 (3) | 0.0511 (14) | |
H17 | 0.8655 | 0.3468 | −0.1296 | 0.061* | |
C18 | 0.9512 (4) | 0.4742 (4) | −0.1111 (3) | 0.0533 (14) | |
H18 | 0.9997 | 0.4447 | −0.1366 | 0.064* | |
C19 | 0.9650 (3) | 0.5830 (4) | −0.0780 (3) | 0.0415 (12) | |
C20 | 1.0481 (4) | 0.6512 (4) | −0.0796 (3) | 0.0487 (13) | |
H20 | 1.1003 | 0.6273 | −0.1034 | 0.058* | |
C21 | 1.0500 (3) | 0.7503 (4) | −0.0464 (3) | 0.0479 (12) | |
H21 | 1.1040 | 0.7957 | −0.0474 | 0.057* | |
C22 | 0.9725 (3) | 0.7865 (4) | −0.0103 (3) | 0.0429 (12) | |
H22 | 0.9758 | 0.8560 | 0.0122 | 0.051* | |
C23 | 0.8906 (3) | 0.6243 (4) | −0.0405 (2) | 0.0367 (11) | |
C24 | 0.8064 (3) | 0.5595 (4) | −0.0348 (2) | 0.0367 (11) | |
C25 | 0.8804 (3) | 0.7815 (4) | 0.1715 (3) | 0.0401 (11) | |
C26 | 0.8672 (3) | 0.8918 (4) | 0.1413 (3) | 0.0430 (12) | |
H11A | 0.514 (4) | 0.400 (3) | 0.116 (3) | 0.500 (16)* | |
H12A | 0.673 (10) | 0.286 (4) | 0.220 (6) | 0.59 (5)* | |
H11B | 0.557 (2) | 0.4964 (15) | 0.1531 (19) | 0.450 (8)* | |
H12B | 0.729 (3) | 0.317 (3) | 0.1644 (18) | 0.587 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0397 (4) | 0.0421 (4) | 0.0469 (4) | 0.0020 (3) | 0.0012 (3) | −0.0024 (3) |
O1 | 0.060 (2) | 0.0367 (18) | 0.047 (2) | 0.0085 (15) | 0.0012 (18) | −0.0016 (16) |
O2 | 0.059 (2) | 0.050 (2) | 0.057 (3) | 0.0037 (17) | −0.0072 (18) | 0.0168 (18) |
O3 | 0.106 (4) | 0.149 (5) | 0.097 (4) | 0.000 (4) | −0.027 (3) | 0.018 (3) |
O4 | 0.148 (6) | 0.112 (4) | 0.133 (6) | −0.017 (4) | −0.010 (4) | −0.042 (4) |
O5 | 0.059 (3) | 0.079 (3) | 0.107 (4) | 0.012 (2) | 0.016 (3) | 0.008 (3) |
O6 | 0.064 (2) | 0.051 (2) | 0.076 (3) | 0.0083 (19) | 0.004 (2) | 0.014 (2) |
O7 | 0.117 (4) | 0.116 (4) | 0.124 (5) | 0.031 (3) | 0.054 (4) | 0.053 (4) |
O8 | 0.149 (6) | 0.189 (8) | 0.158 (7) | −0.025 (6) | 0.007 (6) | −0.034 (5) |
O9 | 0.222 (10) | 0.186 (8) | 0.142 (7) | 0.006 (7) | 0.009 (6) | −0.017 (6) |
O10 | 0.49 (2) | 0.122 (7) | 0.349 (15) | −0.081 (8) | −0.327 (14) | 0.109 (8) |
O11 | 0.46 (3) | 0.62 (3) | 0.47 (3) | 0.05 (3) | 0.35 (3) | 0.10 (3) |
O12 | 0.48 (3) | 0.94 (6) | 0.34 (3) | −0.12 (3) | 0.01 (2) | −0.40 (3) |
N1 | 0.037 (2) | 0.034 (2) | 0.042 (3) | 0.0023 (16) | 0.0026 (18) | −0.0003 (18) |
N2 | 0.040 (2) | 0.030 (2) | 0.035 (3) | 0.0036 (16) | −0.0011 (18) | −0.0033 (18) |
N3 | 0.035 (2) | 0.034 (2) | 0.049 (3) | −0.0009 (17) | 0.0014 (19) | −0.0016 (19) |
N4 | 0.031 (2) | 0.031 (2) | 0.040 (2) | 0.0034 (15) | −0.0023 (16) | −0.0020 (17) |
N5 | 0.035 (2) | 0.040 (2) | 0.042 (3) | 0.0049 (18) | 0.0047 (18) | 0.006 (2) |
N6 | 0.034 (2) | 0.031 (2) | 0.040 (3) | 0.0020 (16) | 0.0013 (18) | −0.0020 (18) |
N7 | 0.051 (3) | 0.054 (3) | 0.067 (4) | −0.007 (2) | 0.011 (3) | 0.009 (3) |
N8 | 0.084 (6) | 0.195 (11) | 0.108 (7) | −0.026 (6) | 0.003 (5) | −0.081 (8) |
C1 | 0.043 (3) | 0.058 (3) | 0.046 (3) | 0.008 (2) | 0.005 (2) | 0.006 (3) |
C2 | 0.053 (3) | 0.070 (4) | 0.060 (4) | 0.001 (3) | 0.016 (3) | −0.002 (3) |
C3 | 0.037 (3) | 0.056 (3) | 0.077 (5) | −0.002 (2) | 0.016 (3) | −0.016 (3) |
C4 | 0.037 (3) | 0.032 (3) | 0.068 (4) | −0.002 (2) | −0.002 (3) | −0.009 (3) |
C5 | 0.036 (3) | 0.050 (3) | 0.087 (5) | 0.004 (2) | −0.003 (3) | −0.006 (3) |
C6 | 0.051 (3) | 0.045 (3) | 0.084 (5) | 0.010 (3) | −0.020 (3) | −0.007 (3) |
C7 | 0.053 (3) | 0.038 (3) | 0.054 (4) | 0.001 (2) | −0.014 (3) | −0.006 (3) |
C8 | 0.075 (4) | 0.048 (3) | 0.050 (4) | 0.011 (3) | −0.016 (3) | −0.001 (3) |
C9 | 0.092 (5) | 0.045 (3) | 0.040 (4) | −0.003 (3) | −0.004 (3) | −0.001 (3) |
C10 | 0.060 (3) | 0.041 (3) | 0.038 (3) | 0.004 (2) | 0.003 (3) | −0.005 (2) |
C11 | 0.043 (3) | 0.027 (2) | 0.047 (3) | 0.002 (2) | −0.009 (2) | −0.001 (2) |
C12 | 0.034 (3) | 0.030 (2) | 0.047 (3) | 0.0008 (19) | 0.000 (2) | −0.005 (2) |
C13 | 0.043 (3) | 0.045 (3) | 0.079 (4) | −0.004 (2) | 0.008 (3) | −0.005 (3) |
C14 | 0.053 (4) | 0.045 (3) | 0.107 (5) | −0.013 (3) | 0.007 (3) | −0.011 (3) |
C15 | 0.070 (4) | 0.035 (3) | 0.093 (5) | −0.009 (3) | −0.008 (4) | −0.012 (3) |
C16 | 0.052 (3) | 0.033 (3) | 0.046 (3) | 0.006 (2) | −0.010 (2) | −0.001 (2) |
C17 | 0.072 (4) | 0.037 (3) | 0.042 (3) | 0.009 (3) | −0.003 (3) | −0.007 (2) |
C18 | 0.075 (4) | 0.051 (3) | 0.033 (3) | 0.031 (3) | 0.001 (3) | −0.006 (3) |
C19 | 0.046 (3) | 0.047 (3) | 0.031 (3) | 0.013 (2) | −0.002 (2) | 0.004 (2) |
C20 | 0.043 (3) | 0.063 (4) | 0.041 (3) | 0.013 (3) | 0.008 (2) | 0.005 (3) |
C21 | 0.037 (3) | 0.060 (3) | 0.047 (3) | −0.003 (3) | 0.004 (2) | 0.003 (3) |
C22 | 0.042 (3) | 0.039 (3) | 0.047 (3) | 0.003 (2) | 0.000 (2) | −0.003 (2) |
C23 | 0.038 (3) | 0.038 (3) | 0.033 (3) | 0.007 (2) | −0.005 (2) | 0.002 (2) |
C24 | 0.042 (3) | 0.032 (2) | 0.034 (3) | 0.005 (2) | −0.004 (2) | 0.000 (2) |
C25 | 0.039 (3) | 0.049 (3) | 0.032 (3) | 0.002 (2) | 0.001 (2) | 0.002 (2) |
C26 | 0.042 (3) | 0.043 (3) | 0.043 (3) | −0.002 (2) | 0.005 (2) | −0.013 (2) |
Cu1—N1 | 1.933 (4) | C3—C4 | 1.388 (7) |
Cu1—N2 | 1.999 (4) | C3—H3 | 0.9300 |
Cu1—N3 | 1.959 (4) | C4—C12 | 1.414 (6) |
Cu1—N4 | 1.950 (3) | C4—C5 | 1.428 (7) |
Cu1—N5 | 1.906 (4) | C5—C6 | 1.361 (8) |
Cu1—N6 | 1.889 (4) | C5—H5 | 0.9300 |
O1—N6 | 1.372 (4) | C6—C7 | 1.448 (7) |
O1—H1A | 0.8200 | C6—H6 | 0.9300 |
O2—N5 | 1.269 (5) | C7—C8 | 1.365 (7) |
O2—H2A | 0.8200 | C7—C11 | 1.408 (7) |
O3—C25 | 1.509 (6) | C8—C9 | 1.374 (7) |
O3—H3A | 0.8200 | C8—H8 | 0.9300 |
O4—C26 | 1.525 (6) | C9—C10 | 1.397 (7) |
O4—H4A | 0.8200 | C9—H9 | 0.9300 |
O5—N7 | 1.244 (5) | C10—H10 | 0.9300 |
O6—N7 | 1.237 (5) | C11—C12 | 1.403 (6) |
O7—N7 | 1.188 (6) | C13—C14 | 1.384 (7) |
O8—N8 | 1.192 (9) | C13—H13 | 0.9300 |
O9—N8 | 1.268 (9) | C14—C15 | 1.353 (7) |
O10—N8 | 1.119 (10) | C14—H14 | 0.9300 |
O11—H11A | 0.84 (5) | C15—C16 | 1.403 (7) |
O11—H11B | 0.84 (3) | C15—H15 | 0.9300 |
O12—H12A | 0.86 (9) | C16—C24 | 1.389 (6) |
O12—H12B | 0.84 (4) | C16—C17 | 1.419 (7) |
N1—C1 | 1.309 (6) | C17—C18 | 1.317 (7) |
N1—C12 | 1.363 (6) | C17—H17 | 0.9300 |
N2—C10 | 1.305 (6) | C18—C19 | 1.445 (7) |
N2—C11 | 1.365 (5) | C18—H18 | 0.9300 |
N3—C13 | 1.323 (6) | C19—C23 | 1.391 (6) |
N3—C24 | 1.360 (5) | C19—C20 | 1.419 (7) |
N4—C22 | 1.332 (6) | C20—C21 | 1.336 (6) |
N4—C23 | 1.348 (5) | C20—H20 | 0.9300 |
N5—C25 | 1.302 (6) | C21—C22 | 1.392 (6) |
N6—C26 | 1.284 (6) | C21—H21 | 0.9300 |
C1—C2 | 1.414 (7) | C22—H22 | 0.9300 |
C1—H1 | 0.9300 | C23—C24 | 1.419 (6) |
C2—C3 | 1.336 (8) | C25—C26 | 1.440 (6) |
C2—H2 | 0.9300 | ||
N1—Cu1—N2 | 83.30 (16) | C7—C6—H6 | 119.6 |
N1—Cu1—N3 | 92.39 (15) | C8—C7—C11 | 117.0 (5) |
N1—Cu1—N4 | 175.33 (15) | C8—C7—C6 | 124.8 (5) |
N1—Cu1—N5 | 93.57 (16) | C11—C7—C6 | 118.2 (5) |
N1—Cu1—N6 | 90.45 (15) | C7—C8—C9 | 120.0 (5) |
N2—Cu1—N3 | 89.54 (15) | C7—C8—H8 | 120.0 |
N2—Cu1—N4 | 93.71 (15) | C9—C8—H8 | 120.0 |
N2—Cu1—N5 | 175.49 (15) | C8—C9—C10 | 119.6 (5) |
N2—Cu1—N6 | 95.51 (15) | C8—C9—H9 | 120.2 |
N3—Cu1—N4 | 83.97 (15) | C10—C9—H9 | 120.2 |
N3—Cu1—N5 | 93.86 (17) | N2—C10—C9 | 122.1 (5) |
N3—Cu1—N6 | 174.47 (16) | N2—C10—H10 | 118.9 |
N4—Cu1—N5 | 89.60 (15) | C9—C10—H10 | 118.9 |
N4—Cu1—N6 | 93.42 (15) | N2—C11—C12 | 116.5 (4) |
N5—Cu1—N6 | 81.23 (17) | N2—C11—C7 | 123.0 (5) |
N6—O1—H1A | 109.5 | C12—C11—C7 | 120.5 (5) |
N5—O2—H2A | 109.5 | N1—C12—C11 | 116.1 (4) |
C25—O3—H3A | 109.5 | N1—C12—C4 | 122.7 (5) |
C26—O4—H4A | 109.5 | C11—C12—C4 | 121.1 (4) |
H11A—O11—H11B | 118 (3) | N3—C13—C14 | 121.6 (5) |
H12A—O12—H12B | 111 (7) | N3—C13—H13 | 119.2 |
C1—N1—C12 | 118.4 (4) | C14—C13—H13 | 119.2 |
C1—N1—Cu1 | 128.4 (3) | C15—C14—C13 | 120.4 (5) |
C12—N1—Cu1 | 113.1 (3) | C15—C14—H14 | 119.8 |
C10—N2—C11 | 118.2 (4) | C13—C14—H14 | 119.8 |
C10—N2—Cu1 | 131.1 (3) | C14—C15—C16 | 119.7 (5) |
C11—N2—Cu1 | 110.7 (3) | C14—C15—H15 | 120.1 |
C13—N3—C24 | 118.5 (4) | C16—C15—H15 | 120.1 |
C13—N3—Cu1 | 130.1 (3) | C24—C16—C15 | 116.7 (5) |
C24—N3—Cu1 | 111.4 (3) | C24—C16—C17 | 118.0 (5) |
C22—N4—C23 | 117.9 (4) | C15—C16—C17 | 125.3 (5) |
C22—N4—Cu1 | 130.0 (3) | C18—C17—C16 | 121.6 (5) |
C23—N4—Cu1 | 112.1 (3) | C18—C17—H17 | 119.2 |
O2—N5—C25 | 123.7 (4) | C16—C17—H17 | 119.2 |
O2—N5—Cu1 | 120.9 (3) | C17—C18—C19 | 122.2 (5) |
C25—N5—Cu1 | 115.3 (3) | C17—C18—H18 | 118.9 |
C26—N6—O1 | 117.2 (4) | C19—C18—H18 | 118.9 |
C26—N6—Cu1 | 116.4 (3) | C23—C19—C20 | 117.0 (5) |
O1—N6—Cu1 | 125.3 (3) | C23—C19—C18 | 117.1 (5) |
O7—N7—O6 | 120.1 (5) | C20—C19—C18 | 125.9 (5) |
O7—N7—O5 | 119.4 (5) | C21—C20—C19 | 118.9 (5) |
O6—N7—O5 | 120.3 (5) | C21—C20—H20 | 120.6 |
O10—N8—O8 | 131.8 (13) | C19—C20—H20 | 120.6 |
O10—N8—O9 | 118.5 (11) | C20—C21—C22 | 121.0 (5) |
O8—N8—O9 | 109.5 (11) | C20—C21—H21 | 119.5 |
N1—C1—C2 | 121.5 (5) | C22—C21—H21 | 119.5 |
N1—C1—H1 | 119.2 | N4—C22—C21 | 121.8 (4) |
C2—C1—H1 | 119.2 | N4—C22—H22 | 119.1 |
C3—C2—C1 | 120.4 (5) | C21—C22—H22 | 119.1 |
C3—C2—H2 | 119.8 | N4—C23—C19 | 123.5 (4) |
C1—C2—H2 | 119.8 | N4—C23—C24 | 116.3 (4) |
C2—C3—C4 | 120.2 (5) | C19—C23—C24 | 120.2 (4) |
C2—C3—H3 | 119.9 | N3—C24—C16 | 123.1 (4) |
C4—C3—H3 | 119.9 | N3—C24—C23 | 116.1 (4) |
C3—C4—C12 | 116.7 (5) | C16—C24—C23 | 120.8 (4) |
C3—C4—C5 | 125.3 (5) | N5—C25—C26 | 113.1 (4) |
C12—C4—C5 | 117.9 (5) | N5—C25—O3 | 121.9 (5) |
C6—C5—C4 | 121.5 (5) | C26—C25—O3 | 124.8 (5) |
C6—C5—H5 | 119.2 | N6—C26—C25 | 113.8 (4) |
C4—C5—H5 | 119.2 | N6—C26—O4 | 124.0 (5) |
C5—C6—C7 | 120.7 (5) | C25—C26—O4 | 122.2 (5) |
C5—C6—H6 | 119.6 |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···O6i | 0.93 | 2.55 | 3.289 (6) | 137 |
C18—H18···O2ii | 0.93 | 2.42 | 3.269 (7) | 152 |
C5—H5···O1iii | 0.93 | 2.55 | 3.354 (6) | 145 |
C3—H3···O5iv | 0.93 | 2.54 | 3.387 (7) | 151 |
O1—H1A···O6v | 0.82 | 2.00 | 2.697 (5) | 143 |
O1—H1A···O5v | 0.82 | 2.36 | 2.991 (5) | 134 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iii) −x+1, −y+2, −z; (iv) −x+1, −y+1, −z+1; (v) x, y+1, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C12H8N2)2(C2H4N2O4)](NO3)2·2H2O |
Mr | 704.07 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 273 |
a, b, c (Å) | 13.9108 (7), 12.011 (3), 18.338 (4) |
β (°) | 95.897 (5) |
V (Å3) | 3047.8 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.79 |
Crystal size (mm) | 0.30 × 0.23 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.798, 0.871 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19706, 6028, 3118 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.167, 1.00 |
No. of reflections | 6028 |
No. of parameters | 444 |
No. of restraints | 12 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.79, −0.61 |
Computer programs: APEX2 (Bruker, 2005), APEX2, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL.
Cu1—N1 | 1.933 (4) | Cu1—N4 | 1.950 (3) |
Cu1—N2 | 1.999 (4) | Cu1—N5 | 1.906 (4) |
Cu1—N3 | 1.959 (4) | Cu1—N6 | 1.889 (4) |
N1—Cu1—N2 | 83.30 (16) | N2—Cu1—N6 | 95.51 (15) |
N1—Cu1—N3 | 92.39 (15) | N3—Cu1—N4 | 83.97 (15) |
N1—Cu1—N4 | 175.33 (15) | N3—Cu1—N5 | 93.86 (17) |
N1—Cu1—N5 | 93.57 (16) | N3—Cu1—N6 | 174.47 (16) |
N1—Cu1—N6 | 90.45 (15) | N4—Cu1—N5 | 89.60 (15) |
N2—Cu1—N3 | 89.54 (15) | N4—Cu1—N6 | 93.42 (15) |
N2—Cu1—N4 | 93.71 (15) | N5—Cu1—N6 | 81.23 (17) |
N2—Cu1—N5 | 175.49 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···O6i | 0.93 | 2.55 | 3.289 (6) | 137 |
C18—H18···O2ii | 0.93 | 2.42 | 3.269 (7) | 152 |
C5—H5···O1iii | 0.93 | 2.55 | 3.354 (6) | 145 |
C3—H3···O5iv | 0.93 | 2.54 | 3.387 (7) | 151 |
O1—H1A···O6v | 0.82 | 2.00 | 2.697 (5) | 143 |
O1—H1A···O5v | 0.82 | 2.36 | 2.991 (5) | 134 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iii) −x+1, −y+2, −z; (iv) −x+1, −y+1, −z+1; (v) x, y+1, z−1. |
In recent years, interest in the chemistry of metal-oxygen clusters has grown because of their applications in areas including catalysis, materials chemistry and biochemistry (Pope, 1983; Pope & Müller, 2001). π-π Stacking between aromatic rings is related to the electron-transfer process in some biological systems (Deisenhofer & Michel, 1989; Wall et al., 1999). Aromatic polycyclic compounds, such as phenanthroline, quinoline and benzimidazole, have commonly shown π-π stacking in metal complexes (Wu et al., 2003; Pan & Xu, 2004; Liu et al., 2004; Li et al., 2005). As a bidentate flexible ligand, dihydroxyglyoxime is also a good ligand with excellent coordination capabilities for generating mono-, bi- or trinuclear complexes, which are commonly used as precursors for the formation of supramolecular architectures (Chaudhuri et al., 1991; Cervera et al., 1997). We report here the crystal structure of the title compound, (I).
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The six N atoms of one dihydroxyglyoxime and two 1,10-phenanthroline (phen) ligands are coordinated to the Cu atom, in a distorted octahedral arrangement (Table 1). The dihydroxyglyoxime and two phen ligands are each planar, and the phen ligands are nearly perpendicular to each other, with a dihedral angle of 87.21 (5)°.
In the crystal structure, there is a three-dimensional framework (Fig. 2) formed by O—H···O and C—H···O hydrogen bonds (Table 2). There are π-π stacking interactions between adjacent phen ligands with a centroid-centroid distance of 3.543 (2) Å (symmetry code: 1 - x, 2 - y, 1 - z). These π-π stacking interactions and hydrogen bonds lead to a supramolecular network structure (Fig. 2).