Acta Cryst. (2009). E65, m412 [ doi:10.1107/S1600536809008976 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-biphenyl-2,2'-dicarboxylato)bis[(2,2'-bipyridine)copper(II)]The title compound, [Cu2(C14H8O4)2(C10H8N2)2], was obtained by solvothermal synthesis. The CuII atom is coordinated by one chelating 2,2'-bipyridine ligand and two carboxyl groups from different biphenyl-2,2'-dicarboxylate ligands, leading to a distorted octahedral environment. Each carboxylate group makes one short Cu-O bond [1.9608 (14) and 1.9701 (14) Å] and one longer Cu-O contact [2.4338 (17) and 2.5541 (17) Å] to each CuII atom. The biphenyl-2,2'-dicarboxylate ligands bridge between CuII atoms, forming a dinuclear complex around a crystallographic inversion centre.
A mixture of Cu(CH3COO)2.H2O (1 mmol), biphenyl-2,2'-dicarboxylic acid (1 mmol), and 2,2'-bipyridine (1 mmol) in 20 ml methanol/water (1:1) were placed in a 25 ml Teflon-lined stainless steel autoclave and kept at 453 K for five days. Blue crystals were obtained after cooling to room temperature.
All H atoms were placed in calculated positions with C—H = 0.93 Å and refined as riding with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bi2358fig1thm.gif)
| Fig. 1. Molecular structure drawn with 30% probability displacement ellipsoids for the non-H atoms. Unlabelled atoms are related to labelled atoms by the symmetry code 1 - x, 1 - y, 1 - z. |
| [Cu2(C14H8O4)2(C10H8N2)2] | F(000) = 940 |
| Mr = 919.86 | Dx = 1.562 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 3644 reflections |
| a = 11.220 (2) Å | θ = 2.1–25.5° |
| b = 13.350 (3) Å | µ = 1.15 mm−1 |
| c = 13.400 (3) Å | T = 296 K |
| β = 103.02 (3)° | Block, blue |
| V = 1955.5 (7) Å3 | 0.12 × 0.10 × 0.08 mm |
| Z = 2 |
| Bruker APEXII CCD diffractometer | 3644 independent reflections |
| Radiation source: fine-focus sealed tube | 3099 reflections with I > 2σ(I) |
| graphite | Rint = 0.019 |
| φ and ω scans | θmax = 25.5°, θmin = 2.1° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −13→13 |
| Tmin = 0.874, Tmax = 0.913 | k = −16→10 |
| 10453 measured reflections | l = −16→14 |
| 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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.088 | H-atom parameters not refined |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.063P)2 + 0.1P] where P = (Fo2 + 2Fc2)/3 |
| 3644 reflections | (Δ/σ)max = 0.031 |
| 280 parameters | Δρmax = 0.27 e Å−3 |
| 0 restraints | Δρmin = −0.29 e Å−3 |
| [Cu2(C14H8O4)2(C10H8N2)2] | V = 1955.5 (7) Å3 |
| Mr = 919.86 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 11.220 (2) Å | µ = 1.15 mm−1 |
| b = 13.350 (3) Å | T = 296 K |
| c = 13.400 (3) Å | 0.12 × 0.10 × 0.08 mm |
| β = 103.02 (3)° |
| Bruker APEXII CCD diffractometer | 3644 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3099 reflections with I > 2σ(I) |
| Tmin = 0.874, Tmax = 0.913 | Rint = 0.019 |
| 10453 measured reflections | θmax = 25.5° |
| R[F2 > 2σ(F2)] = 0.027 | H-atom parameters not refined |
| wR(F2) = 0.088 | Δρmax = 0.27 e Å−3 |
| S = 1.00 | Δρmin = −0.29 e Å−3 |
| 3644 reflections | Absolute structure: ? |
| 280 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 | ||
| C1 | 0.52301 (18) | 0.68894 (15) | 0.42300 (15) | 0.0295 (4) | |
| C2 | 0.28746 (17) | 0.57752 (15) | 0.60591 (15) | 0.0293 (4) | |
| C3 | 0.30695 (16) | 0.51522 (15) | 0.70154 (14) | 0.0270 (4) | |
| C4 | 0.33117 (18) | 0.56634 (16) | 0.79532 (15) | 0.0341 (5) | |
| H4 | 0.3274 | 0.6359 | 0.7960 | 0.041* | |
| C5 | 0.36046 (19) | 0.51453 (18) | 0.88649 (15) | 0.0393 (5) | |
| H5 | 0.3786 | 0.5489 | 0.9484 | 0.047* | |
| C6 | 0.3627 (2) | 0.41049 (18) | 0.88508 (16) | 0.0404 (5) | |
| H6 | 0.3821 | 0.3752 | 0.9464 | 0.048* | |
| C7 | 0.33624 (19) | 0.35926 (16) | 0.79356 (16) | 0.0344 (5) | |
| H7 | 0.3370 | 0.2896 | 0.7939 | 0.041* | |
| C8 | 0.30828 (16) | 0.41025 (15) | 0.70031 (14) | 0.0268 (4) | |
| C9 | 0.66065 (16) | 0.69929 (14) | 0.45025 (14) | 0.0270 (4) | |
| C10 | 0.71452 (18) | 0.75479 (16) | 0.53682 (16) | 0.0358 (5) | |
| H10 | 0.6646 | 0.7884 | 0.5725 | 0.043* | |
| C11 | 0.83990 (19) | 0.76120 (16) | 0.57103 (17) | 0.0388 (5) | |
| H11 | 0.8741 | 0.7992 | 0.6285 | 0.047* | |
| C12 | 0.91368 (18) | 0.71022 (17) | 0.51856 (17) | 0.0393 (5) | |
| H12 | 0.9983 | 0.7130 | 0.5410 | 0.047* | |
| C13 | 0.86141 (19) | 0.65506 (15) | 0.43273 (17) | 0.0339 (5) | |
| H13 | 0.9120 | 0.6208 | 0.3982 | 0.041* | |
| C14 | 0.73499 (18) | 0.64916 (13) | 0.39621 (15) | 0.0270 (4) | |
| C15 | 0.2751 (2) | 0.87802 (18) | 0.39294 (19) | 0.0426 (5) | |
| H15 | 0.3426 | 0.8868 | 0.4470 | 0.051* | |
| C16 | 0.2221 (2) | 0.96089 (18) | 0.3405 (2) | 0.0522 (7) | |
| H16 | 0.2509 | 1.0248 | 0.3605 | 0.063* | |
| C17 | 0.1257 (2) | 0.9477 (2) | 0.2579 (2) | 0.0557 (7) | |
| H17 | 0.0896 | 1.0026 | 0.2202 | 0.067* | |
| C18 | 0.0830 (2) | 0.85266 (19) | 0.2316 (2) | 0.0463 (6) | |
| H18 | 0.0188 | 0.8425 | 0.1751 | 0.056* | |
| C19 | 0.13647 (18) | 0.77206 (16) | 0.29011 (15) | 0.0320 (5) | |
| C20 | 0.09346 (18) | 0.66758 (16) | 0.27505 (16) | 0.0322 (5) | |
| C21 | −0.0050 (2) | 0.6365 (2) | 0.19990 (18) | 0.0442 (6) | |
| H21 | −0.0477 | 0.6818 | 0.1522 | 0.053* | |
| C22 | −0.0390 (2) | 0.5368 (2) | 0.19696 (18) | 0.0511 (7) | |
| H22 | −0.1050 | 0.5145 | 0.1468 | 0.061* | |
| C23 | 0.0242 (2) | 0.4706 (2) | 0.26769 (19) | 0.0481 (6) | |
| H23 | 0.0014 | 0.4036 | 0.2664 | 0.058* | |
| C24 | 0.1223 (2) | 0.50567 (17) | 0.34091 (17) | 0.0390 (5) | |
| H24 | 0.1658 | 0.4612 | 0.3890 | 0.047* | |
| Cu1 | 0.30127 (2) | 0.660694 (17) | 0.440302 (17) | 0.033 (2) | |
| N1 | 0.15643 (14) | 0.60194 (13) | 0.34444 (12) | 0.0304 (4) | |
| N2 | 0.23357 (15) | 0.78535 (13) | 0.36946 (12) | 0.0309 (4) | |
| O1 | 0.46909 (13) | 0.65650 (12) | 0.33944 (13) | 0.0462 (4) | |
| O2 | 0.46709 (12) | 0.71453 (11) | 0.49257 (10) | 0.0356 (3) | |
| O3 | 0.23951 (18) | 0.66102 (11) | 0.60315 (13) | 0.0510 (5) | |
| O4 | 0.32843 (13) | 0.54377 (10) | 0.53117 (10) | 0.0336 (3) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0289 (10) | 0.0228 (10) | 0.0359 (11) | −0.0009 (8) | 0.0052 (9) | −0.0015 (8) |
| C2 | 0.0303 (10) | 0.0261 (11) | 0.0293 (10) | −0.0008 (9) | 0.0020 (8) | −0.0012 (8) |
| C3 | 0.0237 (9) | 0.0287 (11) | 0.0276 (10) | 0.0006 (8) | 0.0037 (8) | −0.0014 (8) |
| C4 | 0.0347 (11) | 0.0317 (11) | 0.0353 (11) | −0.0009 (9) | 0.0066 (9) | −0.0056 (9) |
| C5 | 0.0389 (12) | 0.0508 (14) | 0.0255 (11) | 0.0029 (10) | 0.0017 (9) | −0.0075 (9) |
| C6 | 0.0429 (12) | 0.0495 (14) | 0.0281 (11) | 0.0081 (11) | 0.0064 (9) | 0.0077 (10) |
| C7 | 0.0384 (12) | 0.0307 (11) | 0.0345 (12) | 0.0044 (9) | 0.0092 (9) | 0.0057 (9) |
| C8 | 0.0242 (9) | 0.0282 (11) | 0.0285 (10) | 0.0001 (8) | 0.0070 (8) | 0.0000 (8) |
| C9 | 0.0272 (10) | 0.0219 (10) | 0.0306 (10) | −0.0026 (8) | 0.0037 (8) | −0.0006 (8) |
| C10 | 0.0384 (12) | 0.0289 (11) | 0.0410 (12) | −0.0041 (9) | 0.0112 (10) | −0.0089 (9) |
| C11 | 0.0411 (12) | 0.0324 (12) | 0.0389 (12) | −0.0111 (10) | 0.0006 (10) | −0.0098 (9) |
| C12 | 0.0273 (10) | 0.0399 (13) | 0.0474 (13) | −0.0093 (9) | 0.0017 (9) | −0.0005 (10) |
| C13 | 0.0294 (11) | 0.0344 (12) | 0.0386 (12) | −0.0011 (9) | 0.0094 (9) | −0.0025 (9) |
| C14 | 0.0285 (10) | 0.0207 (10) | 0.0302 (11) | −0.0030 (8) | 0.0035 (8) | 0.0037 (8) |
| C15 | 0.0469 (13) | 0.0349 (13) | 0.0462 (13) | 0.0000 (11) | 0.0107 (11) | 0.0032 (10) |
| C16 | 0.0572 (16) | 0.0295 (13) | 0.0745 (18) | 0.0032 (11) | 0.0246 (14) | 0.0086 (12) |
| C17 | 0.0516 (15) | 0.0475 (16) | 0.0698 (18) | 0.0163 (12) | 0.0177 (13) | 0.0268 (13) |
| C18 | 0.0385 (13) | 0.0495 (16) | 0.0488 (15) | 0.0134 (11) | 0.0053 (11) | 0.0158 (11) |
| C19 | 0.0284 (10) | 0.0400 (12) | 0.0292 (10) | 0.0078 (9) | 0.0095 (8) | 0.0072 (9) |
| C20 | 0.0260 (10) | 0.0433 (13) | 0.0281 (11) | 0.0036 (9) | 0.0077 (8) | 0.0052 (9) |
| C21 | 0.0310 (11) | 0.0635 (17) | 0.0344 (12) | −0.0044 (11) | −0.0006 (9) | 0.0078 (11) |
| C22 | 0.0376 (13) | 0.0725 (19) | 0.0395 (14) | −0.0156 (12) | 0.0010 (11) | −0.0042 (12) |
| C23 | 0.0442 (13) | 0.0493 (15) | 0.0501 (15) | −0.0174 (11) | 0.0089 (11) | −0.0039 (12) |
| C24 | 0.0381 (11) | 0.0380 (13) | 0.0391 (12) | −0.0041 (10) | 0.0051 (10) | 0.0015 (10) |
| Cu1 | 0.045 (5) | 0.025 (4) | 0.028 (4) | −0.004 (4) | 0.002 (4) | 0.002 (3) |
| N1 | 0.0279 (8) | 0.0338 (10) | 0.0284 (9) | −0.0003 (7) | 0.0042 (7) | 0.0018 (7) |
| N2 | 0.0308 (9) | 0.0305 (10) | 0.0315 (9) | 0.0017 (7) | 0.0069 (7) | 0.0038 (7) |
| O1 | 0.0303 (8) | 0.0595 (11) | 0.0457 (10) | −0.0038 (7) | 0.0022 (7) | −0.0248 (8) |
| O2 | 0.0284 (7) | 0.0461 (10) | 0.0318 (8) | −0.0007 (6) | 0.0058 (6) | −0.0052 (6) |
| O3 | 0.0790 (13) | 0.0343 (10) | 0.0429 (10) | 0.0232 (8) | 0.0207 (9) | 0.0070 (7) |
| O4 | 0.0423 (8) | 0.0315 (8) | 0.0269 (7) | 0.0067 (6) | 0.0078 (6) | 0.0043 (6) |
| Cu1—O1 | 2.5541 (17) | C11—H11 | 0.930 |
| Cu1—O2 | 1.9701 (14) | C12—C13 | 1.380 (3) |
| Cu1—O3 | 2.4338 (17) | C12—H12 | 0.930 |
| Cu1—O4 | 1.9608 (14) | C13—C14 | 1.395 (3) |
| Cu1—N1 | 1.9914 (17) | C13—H13 | 0.930 |
| Cu1—N2 | 1.9806 (17) | C14—C8i | 1.502 (3) |
| C1—O1 | 1.226 (2) | C15—N2 | 1.334 (3) |
| C1—O2 | 1.282 (2) | C15—C16 | 1.372 (3) |
| C1—C9 | 1.511 (3) | C15—H15 | 0.930 |
| C2—O3 | 1.235 (2) | C16—C17 | 1.373 (4) |
| C2—O4 | 1.275 (2) | C16—H16 | 0.930 |
| C2—C3 | 1.502 (3) | C17—C18 | 1.374 (4) |
| C3—C8 | 1.402 (3) | C17—H17 | 0.930 |
| C3—C4 | 1.402 (3) | C18—C19 | 1.386 (3) |
| C4—C5 | 1.378 (3) | C18—H18 | 0.930 |
| C4—H4 | 0.930 | C19—N2 | 1.352 (3) |
| C5—C6 | 1.389 (3) | C19—C20 | 1.475 (3) |
| C5—H5 | 0.930 | C20—N1 | 1.355 (3) |
| C6—C7 | 1.377 (3) | C20—C21 | 1.381 (3) |
| C6—H6 | 0.930 | C21—C22 | 1.383 (4) |
| C7—C8 | 1.395 (3) | C21—H21 | 0.930 |
| C7—H7 | 0.930 | C22—C23 | 1.370 (4) |
| C8—C14i | 1.502 (3) | C22—H22 | 0.930 |
| C9—C14 | 1.393 (3) | C23—C24 | 1.381 (3) |
| C9—C10 | 1.394 (3) | C23—H23 | 0.9300 |
| C10—C11 | 1.381 (3) | C24—N1 | 1.339 (3) |
| C10—H10 | 0.930 | C24—H24 | 0.930 |
| C11—C12 | 1.380 (3) | ||
| O1—C1—O2 | 122.48 (18) | C17—C16—H16 | 120.6 |
| O1—C1—C9 | 121.35 (18) | C15—C16—H16 | 120.6 |
| O2—C1—C9 | 116.17 (17) | C16—C17—C18 | 119.4 (2) |
| O3—C2—O4 | 121.83 (18) | C16—C17—H17 | 120.3 |
| O3—C2—C3 | 120.29 (18) | C18—C17—H17 | 120.3 |
| O4—C2—C3 | 117.75 (17) | C19—C18—C17 | 119.4 (2) |
| C8—C3—C4 | 119.79 (18) | C19—C18—H18 | 120.3 |
| C8—C3—C2 | 122.93 (17) | C17—C18—H18 | 120.3 |
| C4—C3—C2 | 117.19 (18) | N2—C19—C18 | 120.8 (2) |
| C5—C4—C3 | 120.7 (2) | N2—C19—C20 | 114.37 (17) |
| C5—C4—H4 | 119.7 | C18—C19—C20 | 124.8 (2) |
| C3—C4—H4 | 119.7 | N1—C20—C21 | 121.0 (2) |
| C4—C5—C6 | 119.4 (2) | N1—C20—C19 | 114.45 (18) |
| C4—C5—H5 | 120.3 | C21—C20—C19 | 124.6 (2) |
| C6—C5—H5 | 120.3 | C20—C21—C22 | 118.7 (2) |
| C7—C6—C5 | 120.52 (19) | C20—C21—H21 | 120.7 |
| C7—C6—H6 | 119.7 | C22—C21—H21 | 120.7 |
| C5—C6—H6 | 119.7 | C23—C22—C21 | 120.3 (2) |
| C6—C7—C8 | 121.0 (2) | C23—C22—H22 | 119.9 |
| C6—C7—H7 | 119.5 | C21—C22—H22 | 119.9 |
| C8—C7—H7 | 119.5 | C22—C23—C24 | 118.6 (2) |
| C7—C8—C3 | 118.56 (18) | C22—C23—H23 | 120.7 |
| C7—C8—C14i | 118.53 (18) | C24—C23—H23 | 120.7 |
| C3—C8—C14i | 122.41 (17) | N1—C24—C23 | 121.8 (2) |
| C14—C9—C10 | 119.32 (18) | N1—C24—H24 | 119.1 |
| C14—C9—C1 | 121.98 (17) | C23—C24—H24 | 119.1 |
| C10—C9—C1 | 118.52 (17) | O4—Cu1—O2 | 93.87 (6) |
| C11—C10—C9 | 121.83 (19) | O4—Cu1—N2 | 162.88 (6) |
| C11—C10—H10 | 119.1 | O2—Cu1—N2 | 95.36 (7) |
| C9—C10—H10 | 119.1 | O4—Cu1—N1 | 94.42 (7) |
| C12—C11—C10 | 118.92 (19) | O2—Cu1—N1 | 160.23 (6) |
| C12—C11—H11 | 120.5 | N2—Cu1—N1 | 81.52 (7) |
| C10—C11—H11 | 120.5 | O4—Cu1—O3 | 58.70 (5) |
| C11—C12—C13 | 119.77 (19) | O2—Cu1—O3 | 96.74 (7) |
| C11—C12—H12 | 120.1 | N2—Cu1—O3 | 105.80 (6) |
| C13—C12—H12 | 120.1 | N1—Cu1—O3 | 102.90 (7) |
| C14—C13—C12 | 122.0 (2) | C24—N1—C20 | 119.72 (18) |
| C14—C13—H13 | 119.0 | C24—N1—Cu1 | 125.89 (14) |
| C12—C13—H13 | 119.0 | C20—N1—Cu1 | 114.30 (14) |
| C13—C14—C9 | 118.12 (18) | C15—N2—C19 | 118.94 (18) |
| C13—C14—C8i | 115.98 (17) | C15—N2—Cu1 | 126.17 (15) |
| C9—C14—C8i | 125.89 (17) | C19—N2—Cu1 | 114.89 (14) |
| N2—C15—C16 | 122.6 (2) | C1—O2—Cu1 | 102.82 (12) |
| N2—C15—H15 | 118.7 | C2—O3—Cu1 | 79.35 (12) |
| C16—C15—H15 | 118.7 | C2—O4—Cu1 | 99.98 (12) |
| C17—C16—C15 | 118.8 (2) |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
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Xu, X.-X., Lu, Y., Wang, E.-B., Ma, Y. & Bai, X.-L. (2006). Cryst. Growth Des. 6, 2029–2035.
Biphenyl-2,2'-dicarboxylic acid (H2dpa) has been demonstrated to be a good candidate for the construction of metal-organic frameworks, and some complexes based on 2,2'-dpa have been reported (Rueff et al., 2003; Xu et al., 2006; An & Niu, 2008). In this paper, we report a new metal complex constructed from dpa, 2,2-bipyridine and copper(II) (Figure 1).