Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104028720/sq1177sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104028720/sq1177Isup2.hkl |
CCDC reference: 263031
A mixture of CuCl2·2H2O (0.168 g, 1 mmol) and H2L (0.244 g, 1 mmol) in water (30 ml) was refluxed for 20 min then filtered while hot. Dark-green crystals of (I) were obtained by evaporating the filtrate at room temperature for three weeks. The compound is insoluble in common organic solvents, and dissolves in water very slowly. Analysis found: C 40.1, H 3.2, N 8.0%; C12H12N2O7Cu requires: C 40.0, H 3.3, N 7.8%.
All H atoms on C atoms were generated geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms of the two solvate water molecules and the water ligand could not be located from the electron-density difference map, which may be ascribed to two factors, firstly that there are heavy metallic atoms (Cu) in the crystal structure, and secondly that the H atoms of the two solvate water molecules and the water ligand may be disordered.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990).
[Cu(C12H6N2O4)(H2O)]·2H2O | F(000) = 732 |
Mr = 359.78 | Dx = 1.861 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.7680 (9) Å | Cell parameters from 6856 reflections |
b = 19.989 (3) Å | θ = 3.2–25.5° |
c = 9.4923 (12) Å | µ = 1.77 mm−1 |
β = 90.717 (2)° | T = 293 K |
V = 1284.0 (3) Å3 | Prism, dark green |
Z = 4 | 0.24 × 0.23 × 0.11 mm |
Rigaku R-AXIS RAPID area-detector diffractometer | 2498 independent reflections |
Radiation source: fine-focus sealed tube | 1871 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 10.0 pixels mm-1 | θmax = 26.0°, θmin = 3.2° |
ω scans | h = −8→7 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −24→20 |
Tmin = 0.628, Tmax = 0.812 | l = −11→11 |
7065 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.048P)2] where P = (Fo2 + 2Fc2)/3 |
2498 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
[Cu(C12H6N2O4)(H2O)]·2H2O | V = 1284.0 (3) Å3 |
Mr = 359.78 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.7680 (9) Å | µ = 1.77 mm−1 |
b = 19.989 (3) Å | T = 293 K |
c = 9.4923 (12) Å | 0.24 × 0.23 × 0.11 mm |
β = 90.717 (2)° |
Rigaku R-AXIS RAPID area-detector diffractometer | 2498 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1871 reflections with I > 2σ(I) |
Tmin = 0.628, Tmax = 0.812 | Rint = 0.045 |
7065 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.47 e Å−3 |
2498 reflections | Δρmin = −0.31 e Å−3 |
199 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 | ||
C1 | 0.4347 (5) | 0.37862 (16) | 0.3719 (3) | 0.0293 (8) | |
H1 | 0.4442 | 0.4227 | 0.4025 | 0.035* | |
C2 | 0.4380 (5) | 0.36570 (17) | 0.2292 (4) | 0.0304 (8) | |
H2 | 0.4600 | 0.3998 | 0.1645 | 0.036* | |
C3 | 0.4075 (5) | 0.30097 (17) | 0.1857 (3) | 0.0277 (8) | |
H3 | 0.4035 | 0.2914 | 0.0898 | 0.033* | |
C4 | 0.3828 (5) | 0.25003 (16) | 0.2807 (3) | 0.0224 (7) | |
C5 | 0.4032 (4) | 0.26532 (15) | 0.4243 (3) | 0.0190 (7) | |
C6 | 0.4162 (4) | 0.21691 (15) | 0.5433 (3) | 0.0194 (7) | |
C7 | 0.4811 (4) | 0.15095 (14) | 0.5354 (3) | 0.0197 (7) | |
C8 | 0.4707 (5) | 0.11145 (16) | 0.6558 (3) | 0.0272 (8) | |
H8 | 0.4991 | 0.0660 | 0.6507 | 0.033* | |
C9 | 0.4184 (5) | 0.13941 (16) | 0.7821 (3) | 0.0281 (8) | |
H9 | 0.4119 | 0.1134 | 0.8632 | 0.034* | |
C10 | 0.3757 (5) | 0.20679 (16) | 0.7863 (3) | 0.0263 (7) | |
H10 | 0.3512 | 0.2268 | 0.8728 | 0.032* | |
C11 | 0.3162 (5) | 0.18230 (18) | 0.2237 (4) | 0.0302 (8) | |
C12 | 0.5904 (5) | 0.12067 (16) | 0.4126 (3) | 0.0248 (7) | |
Cu1 | 0.34847 (6) | 0.344115 (19) | 0.67357 (4) | 0.02614 (15) | |
O1 | 0.4024 (5) | 0.16084 (13) | 0.1177 (3) | 0.0509 (7) | |
N2 | 0.3685 (4) | 0.24435 (12) | 0.6690 (3) | 0.0204 (6) | |
O2 | 0.1714 (4) | 0.15582 (12) | 0.2837 (3) | 0.0393 (6) | |
O3 | 0.7141 (3) | 0.16050 (10) | 0.3558 (2) | 0.0249 (5) | |
N1 | 0.4184 (4) | 0.32980 (12) | 0.4680 (3) | 0.0227 (6) | |
O4 | 0.5636 (4) | 0.06164 (12) | 0.3844 (3) | 0.0453 (7) | |
O5W | 0.3439 (5) | 0.44308 (14) | 0.6675 (3) | 0.0611 (9) | |
O6W | 0.8128 (5) | 0.47346 (15) | 0.5847 (3) | 0.0671 (9) | |
O7W | 0.6416 (5) | 0.47782 (19) | 0.9044 (5) | 0.0927 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.037 (2) | 0.0206 (18) | 0.0301 (19) | 0.0020 (15) | 0.0042 (16) | 0.0053 (15) |
C2 | 0.038 (2) | 0.0268 (19) | 0.0267 (18) | 0.0036 (15) | 0.0037 (16) | 0.0106 (15) |
C3 | 0.0268 (19) | 0.036 (2) | 0.0198 (16) | 0.0058 (15) | −0.0026 (14) | 0.0030 (14) |
C4 | 0.0193 (17) | 0.0262 (17) | 0.0216 (16) | 0.0035 (13) | −0.0013 (14) | −0.0008 (14) |
C5 | 0.0171 (16) | 0.0212 (17) | 0.0187 (15) | 0.0011 (12) | 0.0013 (13) | −0.0013 (13) |
C6 | 0.0165 (16) | 0.0209 (17) | 0.0208 (16) | −0.0038 (12) | 0.0005 (13) | −0.0005 (13) |
C7 | 0.0187 (17) | 0.0183 (16) | 0.0222 (16) | −0.0033 (12) | 0.0019 (13) | 0.0006 (13) |
C8 | 0.0272 (19) | 0.0222 (18) | 0.0323 (19) | 0.0026 (14) | 0.0020 (15) | 0.0029 (14) |
C9 | 0.033 (2) | 0.030 (2) | 0.0216 (17) | 0.0003 (14) | 0.0012 (15) | 0.0080 (14) |
C10 | 0.0304 (19) | 0.0305 (19) | 0.0179 (16) | 0.0013 (15) | 0.0020 (14) | −0.0004 (14) |
C11 | 0.037 (2) | 0.0306 (19) | 0.0231 (18) | 0.0018 (16) | −0.0093 (16) | 0.0008 (15) |
C12 | 0.032 (2) | 0.0199 (18) | 0.0229 (17) | 0.0004 (14) | 0.0001 (15) | 0.0013 (14) |
Cu1 | 0.0377 (3) | 0.0196 (2) | 0.0213 (2) | −0.00045 (18) | 0.00766 (17) | −0.00103 (17) |
O1 | 0.085 (2) | 0.0390 (16) | 0.0286 (14) | −0.0057 (14) | 0.0101 (14) | −0.0126 (12) |
N2 | 0.0241 (15) | 0.0200 (14) | 0.0170 (13) | −0.0021 (10) | 0.0035 (11) | −0.0001 (11) |
O2 | 0.0378 (16) | 0.0362 (15) | 0.0438 (15) | −0.0078 (12) | −0.0089 (13) | −0.0001 (12) |
O3 | 0.0290 (13) | 0.0247 (13) | 0.0214 (11) | −0.0011 (10) | 0.0077 (10) | 0.0008 (9) |
N1 | 0.0256 (15) | 0.0199 (15) | 0.0227 (14) | 0.0008 (11) | 0.0015 (12) | 0.0009 (11) |
O4 | 0.0642 (19) | 0.0232 (14) | 0.0492 (16) | −0.0074 (12) | 0.0283 (15) | −0.0057 (12) |
O5W | 0.087 (2) | 0.0387 (17) | 0.0580 (19) | −0.0001 (15) | 0.0238 (17) | −0.0012 (14) |
O6W | 0.085 (2) | 0.052 (2) | 0.064 (2) | 0.0123 (17) | −0.0070 (18) | 0.0086 (16) |
O7W | 0.067 (3) | 0.079 (3) | 0.131 (3) | 0.0248 (19) | −0.016 (2) | −0.044 (2) |
C1—N1 | 1.341 (4) | C8—H8 | 0.9300 |
C1—C2 | 1.379 (5) | C9—C10 | 1.378 (4) |
C1—H1 | 0.9300 | C9—H9 | 0.9300 |
C2—C3 | 1.373 (5) | C10—N2 | 1.344 (4) |
C2—H2 | 0.9300 | C10—H10 | 0.9300 |
C3—C4 | 1.372 (4) | C11—O1 | 1.246 (4) |
C3—H3 | 0.9300 | C11—O2 | 1.256 (4) |
C4—C5 | 1.402 (4) | C12—O4 | 1.223 (4) |
C4—C11 | 1.524 (5) | C12—O3 | 1.280 (4) |
C5—N1 | 1.357 (4) | Cu1—O3i | 1.966 (2) |
C5—C6 | 1.489 (4) | Cu1—O5W | 1.979 (3) |
C6—N2 | 1.355 (4) | Cu1—N2 | 1.999 (3) |
C6—C7 | 1.392 (4) | Cu1—N1 | 2.034 (3) |
C7—C8 | 1.392 (4) | Cu1—O2ii | 2.411 (2) |
C7—C12 | 1.514 (4) | O2—Cu1iii | 2.411 (2) |
C8—C9 | 1.373 (4) | O3—Cu1iv | 1.966 (2) |
N1—C1—C2 | 122.3 (3) | N2—C10—C9 | 121.8 (3) |
N1—C1—H1 | 118.9 | N2—C10—H10 | 119.1 |
C2—C1—H1 | 118.9 | C9—C10—H10 | 119.1 |
C3—C2—C1 | 117.9 (3) | O1—C11—O2 | 126.6 (3) |
C3—C2—H2 | 121.1 | O1—C11—C4 | 117.0 (3) |
C1—C2—H2 | 121.1 | O2—C11—C4 | 116.3 (3) |
C4—C3—C2 | 121.4 (3) | O4—C12—O3 | 127.1 (3) |
C4—C3—H3 | 119.3 | O4—C12—C7 | 118.8 (3) |
C2—C3—H3 | 119.3 | O3—C12—C7 | 113.9 (3) |
C3—C4—C5 | 117.8 (3) | O3i—Cu1—O5W | 93.74 (10) |
C3—C4—C11 | 117.6 (3) | O3i—Cu1—N2 | 90.27 (9) |
C5—C4—C11 | 124.3 (3) | O5W—Cu1—N2 | 175.79 (11) |
N1—C5—C4 | 120.7 (3) | O3i—Cu1—N1 | 162.38 (10) |
N1—C5—C6 | 112.5 (2) | O5W—Cu1—N1 | 96.68 (11) |
C4—C5—C6 | 126.9 (3) | N2—Cu1—N1 | 79.75 (10) |
N2—C6—C7 | 120.6 (3) | O3i—Cu1—O2ii | 92.60 (9) |
N2—C6—C5 | 113.1 (3) | O5W—Cu1—O2ii | 91.49 (11) |
C7—C6—C5 | 126.2 (3) | N2—Cu1—O2ii | 87.05 (9) |
C8—C7—C6 | 118.3 (3) | N1—Cu1—O2ii | 101.27 (10) |
C8—C7—C12 | 115.8 (3) | C10—N2—C6 | 119.8 (3) |
C6—C7—C12 | 125.3 (3) | C10—N2—Cu1 | 122.8 (2) |
C9—C8—C7 | 120.2 (3) | C6—N2—Cu1 | 116.09 (19) |
C9—C8—H8 | 119.9 | C11—O2—Cu1iii | 120.7 (2) |
C7—C8—H8 | 119.9 | C12—O3—Cu1iv | 130.8 (2) |
C8—C9—C10 | 118.6 (3) | C1—N1—C5 | 119.3 (3) |
C8—C9—H9 | 120.7 | C1—N1—Cu1 | 124.9 (2) |
C10—C9—H9 | 120.7 | C5—N1—Cu1 | 114.13 (19) |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C12H6N2O4)(H2O)]·2H2O |
Mr | 359.78 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 6.7680 (9), 19.989 (3), 9.4923 (12) |
β (°) | 90.717 (2) |
V (Å3) | 1284.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.77 |
Crystal size (mm) | 0.24 × 0.23 × 0.11 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID area-detector diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.628, 0.812 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7065, 2498, 1871 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.094, 0.95 |
No. of reflections | 2498 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.31 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990).
Cu1—O3i | 1.966 (2) | Cu1—N1 | 2.034 (3) |
Cu1—O5W | 1.979 (3) | Cu1—O2ii | 2.411 (2) |
Cu1—N2 | 1.999 (3) | ||
O3i—Cu1—O5W | 93.74 (10) | N2—Cu1—N1 | 79.75 (10) |
O3i—Cu1—N2 | 90.27 (9) | O3i—Cu1—O2ii | 92.60 (9) |
O5W—Cu1—N2 | 175.79 (11) | O5W—Cu1—O2ii | 91.49 (11) |
O3i—Cu1—N1 | 162.38 (10) | N2—Cu1—O2ii | 87.05 (9) |
O5W—Cu1—N1 | 96.68 (11) | N1—Cu1—O2ii | 101.27 (10) |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) x+1/2, −y+1/2, z+1/2. |
In recent years, research on coordination polymers has been rapidly expanding, because of their fascinating structural diversity and potential application as functional materials (Batten & Robson, 1998; Moulton & Zaworotko, 2001). To date, a number of one-, two- and three-dimensional infinite frameworks have been generated with linear N,N'-bidentate spacers (Tong et al., 2002). Much of the work has so far been focused on coordination polymers with rigid ligands, such as 4,4'-bipyridine, and pyrazine and its analogues. However, flexible ligands such as 2,2'-bipyridyl-3,3'-dicarboxylic acid (H2L) have not been explored as much and only a few examples have been reported to date (Goddard et al., 1990; Kovalev et al., 1989; Memon et al., 1997; Perkovic, 2000; Xie et al., 1999, 2000; Yoo et al., 1997; Zhang et al., 2002, 2003; Zhong et al., 1994). In these known structures based on the 2,2'-bipyridyl-3,3'-dicarboxylate anion, most are one-dimensional polymeric chains, such as [M(C12H6N2O4)(H2O)2]n (M is Co, Cu or Mn) and {[Ni(C12H6N2O4)(H2O)3]·H2O}n. These one-dimensional chains extend into two-dimensional sheets via O···H—O hydrogen-bonding interactions. Two- or three-dimensional structures of this type based on covalent linkages are rare. In the present work, we report the preparation and crystal structure of the title novel two-dimensional coordination polymer, (I), formulated as {[CuL(H2O)]·2H2O}n. \sch
Single-crystal X-ray diffraction reveals that the molecules of (I) form an extended two-dimensional network involving coordination frameworks of (4,4) topology. In these layers, all metal centres are five-coordinated. As shown in Fig. 1, each CuII atom is coordinated by two N atoms of an L ligand, two O atoms of two carboxyl groups from another two L ligands and one O atom of a water molecule, to give a square-pyramidal geometry (Table 1). An additional carboxyl O atom occupies the sixth coordination site at a distance [Cu1···O1 3.060 (1) Å] which is beyond the sum of the van der Waals radii of Cu and O (1.40 Å for Cu and 1.52 Å for O) and which is therefore too long to be considered a significant interaction.
Each L moiety, acting as a tetradentate ligand, coordinates to three CuII atoms. As a result, three CuII centres are bridged by three L ligands to form a grid (Fig. 2). Within this grid, the Cu···Cu distances are 6.767 (5), 6.908 (5) and 6.967 (1) Å. One Cu atom with one organic ligand constructs a node and these nodes connect to each other to form an extended layer structure with (4,4) topology in the ac plane. As illustrated in Fig. 3, the water molecules occupy channels formed by parallel stacking of two layers.
There are a number of significant contacts between the oxo groups of the two-dimensional layers and the water molecules. These include OW5···O4 2.819 (5), OW6···O1 2.769 (4), OW7···O2 2.915 (5), OW7···O4 2.971 (4) and Ow7···O7 2.800 (6) Å. Therefore, the extended structure of (I) has the metal-organic layers and the inorganic water layers arranged alternately along the b axis.