Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030747/hb2407sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030747/hb2407Isup2.hkl |
CCDC reference: 654831
0.0705 g (0.3 mmol) Cu(NO3)2.6H2O, 0.0734 g diphenyl-2,2'-dicarboxyl acid) and 0.0473 g 2,2'-bipyridine were dissolved in 20 ml water, to obtain a blue solution. After about two weeks at room temperature, blue plates of (I) were obtained and filtered off.
The C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The water H atoms were located in a diference map and refined with a distance restraint of O—H = 0.85 (1) Å and the constraint Uiso(H) = 1.5Ueq(O). Due to the disorder of the water molecules the location of their H atoms should be regarded as less certain.
Binuclear copper(II) complexes have been intensely investigated owing to their potential application as magnetic materials and catalysts (Zhu et al., 2001). Here we present the synthesis and crystal structure of the title compound, (I), [Cu2(dpa)2(bipy)2].4H2O (dpa = the diphenyl-2,2'dicarboxylato dianion and bipy = 2,2'-bipyridine), which contains a centrosymmetric binuclear complex. The copper(II) atom adopts a distorted square geometry (Table 1, Fig. 1). The bipy ligand shows its classical bidentate coordination mode, albeit with a shorter mean Cu—N bond length than in the related complex [Cu2(C2O4)(C12H8N2)2(C3H7NO)2](ClO4)2 (Wang et al., 2006). The dpa ligand adopts a µ2-bridged coordination and the dihedral angle between its aromatic rings is 86.7 (2)°. As well as the short Cu—O bonds, two long (> 2.60 Å) Cu—O contacts that might be regarded as secondary bonds (He & Zhu, 2003) complete a distorted octahedron. The Cu···Cui (i = 1 - x, 1 - y, 1 - z) distance bridged by the dpa ligands is 5.6865 (16) Å.
The complex (I) is extended into one dimensional framework by O—H···O hydrogen bonds (Table 2, Fig.2).
For related literature, see: He & Zhu (2003); Wang et al. (2006); Zhu et al. (2001).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Cu2(C14H8O4)2(C10H8N2)2]·4H2O | F(000) = 1020 |
Mr = 991.92 | Dx = 1.496 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 15487 reflections |
a = 11.428 (3) Å | θ = 2.0–25° |
b = 9.816 (2) Å | µ = 1.04 mm−1 |
c = 19.774 (4) Å | T = 293 K |
β = 97.098 (4)° | Plate, blue |
V = 2201.2 (9) Å3 | 0.19 × 0.12 × 0.02 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 3875 independent reflections |
Radiation source: fine-focus sealed tube | 2635 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.091 |
ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.827, Tmax = 0.980 | k = −11→11 |
15487 measured reflections | l = −23→23 |
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)] = 0.058 | Hydrogen site location: difmap and geom |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0523P)2] where P = (Fo2 + 2Fc2)/3 |
3875 reflections | (Δ/σ)max < 0.001 |
326 parameters | Δρmax = 0.40 e Å−3 |
9 restraints | Δρmin = −0.39 e Å−3 |
[Cu2(C14H8O4)2(C10H8N2)2]·4H2O | V = 2201.2 (9) Å3 |
Mr = 991.92 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.428 (3) Å | µ = 1.04 mm−1 |
b = 9.816 (2) Å | T = 293 K |
c = 19.774 (4) Å | 0.19 × 0.12 × 0.02 mm |
β = 97.098 (4)° |
Bruker SMART CCD area-detector diffractometer | 3875 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2635 reflections with I > 2σ(I) |
Tmin = 0.827, Tmax = 0.980 | Rint = 0.091 |
15487 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 9 restraints |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.40 e Å−3 |
3875 reflections | Δρmin = −0.39 e Å−3 |
326 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 | Occ. (<1) | |
O3 | −0.1297 (3) | −0.3198 (3) | −0.11357 (19) | 0.0617 (10) | |
C24 | −0.0584 (4) | −0.2244 (4) | −0.1138 (2) | 0.0349 (11) | |
O4 | −0.0740 (2) | −0.1116 (3) | −0.08590 (14) | 0.0358 (7) | |
O5 | −0.1362 (3) | 0.2058 (4) | −0.02708 (18) | 0.0670 (11) | |
O6 | −0.2335 (5) | −0.5841 (6) | −0.1210 (4) | 0.095 (3) | 0.703 (7) |
O6' | −0.1884 (17) | −0.515 (2) | −0.0306 (11) | 0.192 (11) | 0.297 (7) |
H6A | −0.201 (8) | −0.639 (4) | −0.091 (3) | 0.288* | 0.703 (7) |
H6B | −0.204 (8) | −0.505 (3) | −0.112 (5) | 0.288* | 0.703 (7) |
H6B' | −0.202 (6) | −0.53 (3) | −0.073 (3) | 0.288* | 0.297 (7) |
H6A' | −0.114 (3) | −0.51 (3) | −0.020 (5) | 0.288* | 0.297 (7) |
H5B | −0.066 (2) | 0.223 (9) | −0.036 (3) | 0.288* | |
H5A | −0.132 (6) | 0.170 (8) | 0.012 (2) | 0.288* | |
Cu1 | 0.21213 (4) | 0.14650 (5) | 0.03932 (2) | 0.03214 (16) | |
O2 | 0.2010 (2) | 0.0042 (3) | −0.07275 (14) | 0.0422 (8) | |
O1 | 0.1142 (2) | 0.1934 (3) | −0.04561 (14) | 0.0377 (7) | |
N2 | 0.3250 (3) | 0.0462 (3) | 0.10571 (16) | 0.0343 (9) | |
N1 | 0.3617 (3) | 0.2201 (3) | 0.01224 (16) | 0.0332 (9) | |
C18 | 0.1004 (3) | −0.1420 (4) | −0.1838 (2) | 0.0314 (10) | |
C11 | 0.1296 (3) | 0.0982 (4) | −0.0884 (2) | 0.0290 (10) | |
C5 | 0.4607 (3) | 0.1641 (4) | 0.0449 (2) | 0.0334 (10) | |
C12 | 0.0576 (3) | 0.1050 (4) | −0.15634 (19) | 0.0305 (10) | |
C17 | 0.0412 (3) | −0.0076 (4) | −0.1992 (2) | 0.0329 (10) | |
C23 | 0.0521 (3) | −0.2448 (4) | −0.1464 (2) | 0.0308 (10) | |
C6 | 0.4389 (3) | 0.0638 (4) | 0.0973 (2) | 0.0322 (10) | |
C8 | 0.4958 (4) | −0.0963 (5) | 0.1854 (2) | 0.0536 (14) | |
H8 | 0.5538 | −0.1442 | 0.2127 | 0.064* | |
C16 | −0.0338 (4) | 0.0043 (5) | −0.2599 (2) | 0.0385 (11) | |
H16 | −0.0467 | −0.0713 | −0.2882 | 0.046* | |
C22 | 0.1106 (4) | −0.3689 (5) | −0.1356 (2) | 0.0427 (12) | |
H22 | 0.0785 | −0.4369 | −0.1107 | 0.051* | |
C13 | 0.0006 (4) | 0.2268 (4) | −0.1761 (2) | 0.0375 (11) | |
H13 | 0.0111 | 0.3026 | −0.1479 | 0.045* | |
C15 | −0.0894 (4) | 0.1248 (5) | −0.2792 (2) | 0.0487 (13) | |
H15 | −0.1387 | 0.1307 | −0.3202 | 0.058* | |
C7 | 0.5268 (4) | −0.0085 (5) | 0.1364 (2) | 0.0441 (12) | |
H7 | 0.6054 | 0.0023 | 0.1297 | 0.053* | |
C19 | 0.2051 (4) | −0.1712 (4) | −0.2100 (2) | 0.0408 (12) | |
H19 | 0.2373 | −0.1056 | −0.2362 | 0.049* | |
C2 | 0.4777 (4) | 0.3556 (5) | −0.0524 (3) | 0.0559 (14) | |
H2 | 0.4817 | 0.4218 | −0.0857 | 0.067* | |
C20 | 0.2626 (4) | −0.2930 (5) | −0.1986 (2) | 0.0496 (13) | |
H20 | 0.3333 | −0.3082 | −0.2162 | 0.060* | |
C10 | 0.2967 (4) | −0.0408 (4) | 0.1524 (2) | 0.0430 (12) | |
H10 | 0.2174 | −0.0530 | 0.1572 | 0.052* | |
C4 | 0.5699 (4) | 0.2020 (5) | 0.0290 (2) | 0.0472 (13) | |
H4 | 0.6378 | 0.1623 | 0.0515 | 0.057* | |
C14 | −0.0716 (4) | 0.2355 (5) | −0.2377 (2) | 0.0460 (13) | |
H14 | −0.1082 | 0.3176 | −0.2508 | 0.055* | |
C1 | 0.3707 (4) | 0.3143 (5) | −0.0355 (2) | 0.0507 (13) | |
H1 | 0.3024 | 0.3529 | −0.0579 | 0.061* | |
C21 | 0.2161 (4) | −0.3922 (5) | −0.1615 (2) | 0.0492 (13) | |
H21 | 0.2550 | −0.4750 | −0.1536 | 0.059* | |
C3 | 0.5780 (4) | 0.2990 (5) | −0.0201 (3) | 0.0576 (15) | |
H3 | 0.6513 | 0.3257 | −0.0313 | 0.069* | |
C9 | 0.3793 (4) | −0.1136 (5) | 0.1939 (2) | 0.0520 (14) | |
H9 | 0.3571 | −0.1728 | 0.2267 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.057 (2) | 0.043 (2) | 0.090 (3) | −0.0187 (17) | 0.0289 (19) | −0.0131 (18) |
C24 | 0.036 (2) | 0.038 (3) | 0.029 (2) | −0.002 (2) | −0.0003 (19) | 0.008 (2) |
O4 | 0.0300 (15) | 0.0339 (17) | 0.0458 (18) | −0.0023 (13) | 0.0140 (14) | −0.0038 (14) |
O5 | 0.050 (2) | 0.088 (3) | 0.063 (2) | 0.015 (2) | 0.0054 (18) | 0.009 (2) |
O6 | 0.071 (4) | 0.060 (4) | 0.151 (7) | −0.010 (3) | −0.005 (4) | 0.038 (4) |
O6' | 0.24 (2) | 0.095 (15) | 0.28 (3) | 0.015 (15) | 0.16 (2) | 0.057 (16) |
Cu1 | 0.0225 (3) | 0.0413 (3) | 0.0322 (3) | 0.0016 (2) | 0.0020 (2) | 0.0023 (3) |
O2 | 0.0353 (17) | 0.0431 (18) | 0.0443 (19) | 0.0077 (14) | −0.0101 (14) | −0.0023 (15) |
O1 | 0.0327 (16) | 0.0478 (19) | 0.0311 (16) | 0.0110 (14) | −0.0023 (13) | −0.0057 (14) |
N2 | 0.0287 (19) | 0.044 (2) | 0.030 (2) | −0.0011 (16) | 0.0006 (15) | 0.0037 (17) |
N1 | 0.034 (2) | 0.036 (2) | 0.029 (2) | −0.0029 (16) | 0.0020 (16) | 0.0042 (16) |
C18 | 0.031 (2) | 0.034 (2) | 0.029 (2) | −0.0021 (19) | 0.0016 (18) | −0.004 (2) |
C11 | 0.021 (2) | 0.032 (2) | 0.034 (2) | −0.0012 (18) | 0.0039 (18) | 0.003 (2) |
C5 | 0.026 (2) | 0.036 (3) | 0.038 (3) | 0.0020 (19) | 0.0039 (19) | −0.010 (2) |
C12 | 0.027 (2) | 0.038 (3) | 0.026 (2) | −0.0052 (18) | 0.0019 (17) | 0.0020 (19) |
C17 | 0.029 (2) | 0.038 (3) | 0.033 (2) | −0.0057 (19) | 0.0098 (19) | 0.004 (2) |
C23 | 0.030 (2) | 0.036 (3) | 0.027 (2) | −0.0016 (19) | 0.0031 (19) | −0.0040 (19) |
C6 | 0.028 (2) | 0.036 (2) | 0.032 (2) | 0.0040 (19) | 0.0007 (18) | −0.006 (2) |
C8 | 0.051 (3) | 0.058 (3) | 0.047 (3) | 0.010 (2) | −0.011 (2) | 0.011 (3) |
C16 | 0.037 (3) | 0.045 (3) | 0.033 (3) | −0.002 (2) | −0.001 (2) | 0.002 (2) |
C22 | 0.047 (3) | 0.041 (3) | 0.040 (3) | 0.003 (2) | 0.006 (2) | −0.003 (2) |
C13 | 0.040 (3) | 0.035 (3) | 0.038 (3) | −0.001 (2) | 0.007 (2) | 0.007 (2) |
C15 | 0.042 (3) | 0.064 (3) | 0.036 (3) | −0.002 (2) | −0.008 (2) | 0.012 (2) |
C7 | 0.033 (3) | 0.058 (3) | 0.040 (3) | 0.003 (2) | −0.001 (2) | 0.000 (2) |
C19 | 0.035 (2) | 0.047 (3) | 0.041 (3) | 0.000 (2) | 0.008 (2) | 0.000 (2) |
C2 | 0.061 (3) | 0.051 (3) | 0.058 (3) | −0.011 (3) | 0.019 (3) | 0.016 (3) |
C20 | 0.036 (3) | 0.066 (3) | 0.049 (3) | 0.009 (2) | 0.012 (2) | −0.007 (3) |
C10 | 0.038 (3) | 0.043 (3) | 0.048 (3) | −0.002 (2) | 0.008 (2) | 0.003 (2) |
C4 | 0.032 (3) | 0.052 (3) | 0.057 (3) | 0.000 (2) | 0.007 (2) | 0.000 (3) |
C14 | 0.045 (3) | 0.045 (3) | 0.048 (3) | 0.008 (2) | 0.002 (2) | 0.015 (2) |
C1 | 0.048 (3) | 0.053 (3) | 0.051 (3) | −0.003 (2) | 0.008 (2) | 0.014 (3) |
C21 | 0.050 (3) | 0.046 (3) | 0.051 (3) | 0.018 (2) | 0.003 (2) | −0.006 (2) |
C3 | 0.045 (3) | 0.062 (3) | 0.069 (4) | −0.005 (3) | 0.023 (3) | 0.002 (3) |
C9 | 0.054 (3) | 0.051 (3) | 0.049 (3) | −0.001 (2) | 0.000 (2) | 0.019 (2) |
O3—C24 | 1.242 (5) | C23—C22 | 1.394 (6) |
C24—O4 | 1.260 (5) | C6—C7 | 1.385 (5) |
C24—C23 | 1.500 (6) | C8—C9 | 1.372 (6) |
C24—Cu1i | 2.545 (4) | C8—C7 | 1.375 (6) |
O4—Cu1i | 1.953 (3) | C8—H8 | 0.9300 |
O5—H5B | 0.855 (18) | C16—C15 | 1.375 (6) |
O5—H5A | 0.86 (2) | C16—H16 | 0.9300 |
O6—H6A | 0.85 (2) | C22—C21 | 1.386 (6) |
O6—H6B | 0.86 (2) | C22—H22 | 0.9300 |
O6—H6B' | 1.09 (8) | C13—C14 | 1.387 (6) |
O6'—H6B' | 0.85 (2) | C13—H13 | 0.9300 |
O6'—H6A' | 0.85 (2) | C15—C14 | 1.361 (6) |
Cu1—O4i | 1.953 (3) | C15—H15 | 0.9300 |
Cu1—O1 | 1.955 (3) | C7—H7 | 0.9300 |
Cu1—N2 | 1.984 (3) | C19—C20 | 1.369 (6) |
Cu1—N1 | 1.989 (3) | C19—H19 | 0.9300 |
O2—C11 | 1.245 (4) | C2—C3 | 1.360 (6) |
O1—C11 | 1.287 (5) | C2—C1 | 1.368 (6) |
N2—C10 | 1.326 (5) | C2—H2 | 0.9300 |
N2—C6 | 1.343 (5) | C20—C21 | 1.366 (6) |
N1—C1 | 1.334 (5) | C20—H20 | 0.9300 |
N1—C5 | 1.348 (5) | C10—C9 | 1.373 (6) |
C18—C19 | 1.392 (5) | C10—H10 | 0.9300 |
C18—C23 | 1.404 (6) | C4—C3 | 1.371 (6) |
C18—C17 | 1.496 (5) | C4—H4 | 0.9300 |
C11—C12 | 1.488 (5) | C14—H14 | 0.9300 |
C5—C4 | 1.376 (6) | C1—H1 | 0.9300 |
C5—C6 | 1.474 (6) | C21—H21 | 0.9300 |
C12—C17 | 1.391 (5) | C3—H3 | 0.9300 |
C12—C13 | 1.394 (6) | C9—H9 | 0.9300 |
C17—C16 | 1.392 (5) | ||
O3—C24—O4 | 122.2 (4) | C7—C6—C5 | 124.1 (4) |
O3—C24—C23 | 119.2 (4) | C9—C8—C7 | 120.2 (4) |
O4—C24—C23 | 118.5 (4) | C9—C8—H8 | 119.9 |
O3—C24—Cu1i | 74.0 (3) | C7—C8—H8 | 119.9 |
O4—C24—Cu1i | 48.49 (19) | C15—C16—C17 | 121.8 (4) |
C23—C24—Cu1i | 165.1 (3) | C15—C16—H16 | 119.1 |
C24—O4—Cu1i | 102.6 (2) | C17—C16—H16 | 119.1 |
H5B—O5—H5A | 109 (3) | C21—C22—C23 | 120.7 (4) |
H6A—O6—H6B | 108 (3) | C21—C22—H22 | 119.7 |
H6A—O6—H6B' | 68 (10) | C23—C22—H22 | 119.7 |
H6B—O6—H6B' | 48 (10) | C14—C13—C12 | 120.4 (4) |
H6B'—O6'—H6A' | 109 (4) | C14—C13—H13 | 119.8 |
O4i—Cu1—O1 | 92.09 (12) | C12—C13—H13 | 119.8 |
O4i—Cu1—N2 | 95.61 (13) | C14—C15—C16 | 119.3 (4) |
O1—Cu1—N2 | 160.33 (13) | C14—C15—H15 | 120.3 |
O4i—Cu1—N1 | 164.13 (13) | C16—C15—H15 | 120.3 |
O1—Cu1—N1 | 95.89 (12) | C8—C7—C6 | 118.8 (4) |
N2—Cu1—N1 | 81.29 (13) | C8—C7—H7 | 120.6 |
O4i—Cu1—C24i | 28.88 (12) | C6—C7—H7 | 120.6 |
O1—Cu1—C24i | 93.65 (12) | C20—C19—C18 | 122.4 (4) |
N2—Cu1—C24i | 101.82 (13) | C20—C19—H19 | 118.8 |
N1—Cu1—C24i | 136.39 (14) | C18—C19—H19 | 118.8 |
C11—O1—Cu1 | 106.5 (2) | C3—C2—C1 | 119.4 (5) |
C10—N2—C6 | 119.5 (4) | C3—C2—H2 | 120.3 |
C10—N2—Cu1 | 125.8 (3) | C1—C2—H2 | 120.3 |
C6—N2—Cu1 | 114.5 (3) | C21—C20—C19 | 120.0 (4) |
C1—N1—C5 | 119.2 (4) | C21—C20—H20 | 120.0 |
C1—N1—Cu1 | 125.9 (3) | C19—C20—H20 | 120.0 |
C5—N1—Cu1 | 114.9 (3) | N2—C10—C9 | 122.8 (4) |
C19—C18—C23 | 117.4 (4) | N2—C10—H10 | 118.6 |
C19—C18—C17 | 119.6 (4) | C9—C10—H10 | 118.6 |
C23—C18—C17 | 122.9 (4) | C3—C4—C5 | 119.4 (4) |
O2—C11—O1 | 120.9 (4) | C3—C4—H4 | 120.3 |
O2—C11—C12 | 122.0 (4) | C5—C4—H4 | 120.3 |
O1—C11—C12 | 117.1 (3) | C15—C14—C13 | 120.6 (4) |
N1—C5—C4 | 120.8 (4) | C15—C14—H14 | 119.7 |
N1—C5—C6 | 113.9 (3) | C13—C14—H14 | 119.7 |
C4—C5—C6 | 125.3 (4) | N1—C1—C2 | 121.9 (5) |
C17—C12—C13 | 119.2 (4) | N1—C1—H1 | 119.1 |
C17—C12—C11 | 122.1 (4) | C2—C1—H1 | 119.1 |
C13—C12—C11 | 118.6 (4) | C20—C21—C22 | 119.7 (4) |
C12—C17—C16 | 118.7 (4) | C20—C21—H21 | 120.2 |
C12—C17—C18 | 123.6 (4) | C22—C21—H21 | 120.2 |
C16—C17—C18 | 117.7 (4) | C2—C3—C4 | 119.3 (5) |
C22—C23—C18 | 119.8 (4) | C2—C3—H3 | 120.3 |
C22—C23—C24 | 117.7 (4) | C4—C3—H3 | 120.3 |
C18—C23—C24 | 122.5 (4) | C8—C9—C10 | 117.9 (4) |
N2—C6—C7 | 120.8 (4) | C8—C9—H9 | 121.1 |
N2—C6—C5 | 115.1 (3) | C10—C9—H9 | 121.1 |
O3—C24—O4—Cu1i | 7.1 (5) | C17—C18—C23—C24 | −5.0 (6) |
C23—C24—O4—Cu1i | −170.9 (3) | O3—C24—C23—C22 | −40.9 (6) |
O4i—Cu1—O1—C11 | −111.8 (2) | O4—C24—C23—C22 | 137.2 (4) |
N2—Cu1—O1—C11 | 1.4 (5) | Cu1i—C24—C23—C22 | 109.9 (11) |
N1—Cu1—O1—C11 | 81.9 (3) | O3—C24—C23—C18 | 142.3 (4) |
C24i—Cu1—O1—C11 | −140.7 (3) | O4—C24—C23—C18 | −39.6 (6) |
O4i—Cu1—N2—C10 | 15.1 (4) | Cu1i—C24—C23—C18 | −66.9 (12) |
O1—Cu1—N2—C10 | −97.5 (5) | C10—N2—C6—C7 | 0.5 (6) |
N1—Cu1—N2—C10 | 179.4 (4) | Cu1—N2—C6—C7 | −174.8 (3) |
C24i—Cu1—N2—C10 | 43.7 (4) | C10—N2—C6—C5 | −179.2 (4) |
O4i—Cu1—N2—C6 | −170.0 (3) | Cu1—N2—C6—C5 | 5.6 (5) |
O1—Cu1—N2—C6 | 77.4 (5) | N1—C5—C6—N2 | −1.6 (5) |
N1—Cu1—N2—C6 | −5.7 (3) | C4—C5—C6—N2 | 177.8 (4) |
C24i—Cu1—N2—C6 | −141.4 (3) | N1—C5—C6—C7 | 178.8 (4) |
O4i—Cu1—N1—C1 | −97.5 (6) | C4—C5—C6—C7 | −1.8 (7) |
O1—Cu1—N1—C1 | 22.3 (4) | C12—C17—C16—C15 | 1.6 (6) |
N2—Cu1—N1—C1 | −177.3 (4) | C18—C17—C16—C15 | −178.2 (4) |
C24i—Cu1—N1—C1 | −79.3 (4) | C18—C23—C22—C21 | −0.1 (6) |
O4i—Cu1—N1—C5 | 84.6 (6) | C24—C23—C22—C21 | −177.0 (4) |
O1—Cu1—N1—C5 | −155.6 (3) | C17—C12—C13—C14 | 0.1 (6) |
N2—Cu1—N1—C5 | 4.8 (3) | C11—C12—C13—C14 | −177.1 (4) |
C24i—Cu1—N1—C5 | 102.8 (3) | C17—C16—C15—C14 | −0.5 (7) |
Cu1—O1—C11—O2 | −3.4 (4) | C9—C8—C7—C6 | 1.4 (7) |
Cu1—O1—C11—C12 | 175.8 (3) | N2—C6—C7—C8 | −1.6 (7) |
C1—N1—C5—C4 | −0.6 (6) | C5—C6—C7—C8 | 178.0 (4) |
Cu1—N1—C5—C4 | 177.4 (3) | C23—C18—C19—C20 | −2.0 (6) |
C1—N1—C5—C6 | 178.8 (4) | C17—C18—C19—C20 | −179.0 (4) |
Cu1—N1—C5—C6 | −3.2 (4) | C18—C19—C20—C21 | 1.3 (7) |
O2—C11—C12—C17 | 17.5 (6) | C6—N2—C10—C9 | 0.9 (7) |
O1—C11—C12—C17 | −161.7 (4) | Cu1—N2—C10—C9 | 175.6 (3) |
O2—C11—C12—C13 | −165.4 (4) | N1—C5—C4—C3 | 0.6 (7) |
O1—C11—C12—C13 | 15.3 (5) | C6—C5—C4—C3 | −178.7 (4) |
C13—C12—C17—C16 | −1.4 (6) | C16—C15—C14—C13 | −0.8 (7) |
C11—C12—C17—C16 | 175.7 (4) | C12—C13—C14—C15 | 1.1 (7) |
C13—C12—C17—C18 | 178.4 (4) | C5—N1—C1—C2 | 0.1 (7) |
C11—C12—C17—C18 | −4.5 (6) | Cu1—N1—C1—C2 | −177.7 (4) |
C19—C18—C17—C12 | −94.7 (5) | C3—C2—C1—N1 | 0.4 (8) |
C23—C18—C17—C12 | 88.5 (5) | C19—C20—C21—C22 | 0.1 (7) |
C19—C18—C17—C16 | 85.1 (5) | C23—C22—C21—C20 | −0.7 (7) |
C23—C18—C17—C16 | −91.8 (5) | C1—C2—C3—C4 | −0.4 (8) |
C19—C18—C23—C22 | 1.4 (6) | C5—C4—C3—C2 | −0.1 (8) |
C17—C18—C23—C22 | 178.3 (4) | C7—C8—C9—C10 | −0.1 (7) |
C19—C18—C23—C24 | 178.1 (4) | N2—C10—C9—C8 | −1.1 (7) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O2i | 0.85 (5) | 2.29 (7) | 3.009 (5) | 144 (6) |
O5—H5B···O1 | 0.86 (3) | 2.11 (3) | 2.932 (4) | 160 (8) |
O6—H6A···O5ii | 0.85 (6) | 2.06 (5) | 2.903 (8) | 171 (7) |
O6—H6B···O3 | 0.86 (5) | 2.01 (5) | 2.849 (7) | 167 (9) |
Symmetry codes: (i) −x, −y, −z; (ii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C14H8O4)2(C10H8N2)2]·4H2O |
Mr | 991.92 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.428 (3), 9.816 (2), 19.774 (4) |
β (°) | 97.098 (4) |
V (Å3) | 2201.2 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.04 |
Crystal size (mm) | 0.19 × 0.12 × 0.02 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.827, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15487, 3875, 2635 |
Rint | 0.091 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.132, 1.02 |
No. of reflections | 3875 |
No. of parameters | 326 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.39 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
Cu1—O4i | 1.953 (3) | Cu1—N2 | 1.984 (3) |
Cu1—O1 | 1.955 (3) | Cu1—N1 | 1.989 (3) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O2i | 0.85 (5) | 2.29 (7) | 3.009 (5) | 144 (6) |
O5—H5B···O1 | 0.86 (3) | 2.11 (3) | 2.932 (4) | 160 (8) |
O6—H6A···O5ii | 0.85 (6) | 2.06 (5) | 2.903 (8) | 171 (7) |
O6—H6B···O3 | 0.86 (5) | 2.01 (5) | 2.849 (7) | 167 (9) |
Symmetry codes: (i) −x, −y, −z; (ii) x, y−1, z. |
Binuclear copper(II) complexes have been intensely investigated owing to their potential application as magnetic materials and catalysts (Zhu et al., 2001). Here we present the synthesis and crystal structure of the title compound, (I), [Cu2(dpa)2(bipy)2].4H2O (dpa = the diphenyl-2,2'dicarboxylato dianion and bipy = 2,2'-bipyridine), which contains a centrosymmetric binuclear complex. The copper(II) atom adopts a distorted square geometry (Table 1, Fig. 1). The bipy ligand shows its classical bidentate coordination mode, albeit with a shorter mean Cu—N bond length than in the related complex [Cu2(C2O4)(C12H8N2)2(C3H7NO)2](ClO4)2 (Wang et al., 2006). The dpa ligand adopts a µ2-bridged coordination and the dihedral angle between its aromatic rings is 86.7 (2)°. As well as the short Cu—O bonds, two long (> 2.60 Å) Cu—O contacts that might be regarded as secondary bonds (He & Zhu, 2003) complete a distorted octahedron. The Cu···Cui (i = 1 - x, 1 - y, 1 - z) distance bridged by the dpa ligands is 5.6865 (16) Å.
The complex (I) is extended into one dimensional framework by O—H···O hydrogen bonds (Table 2, Fig.2).