Copper K-edge X-ray absorption spectroscopic (XAS) measurements were recorded for the veterinary antiinflammatory Cu(II) complexes of indomethacin (1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid = IndoH), of the general formula [Cu-2(Indo)(4)L-2] (L = N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP), and water), and [Cu-2(OAc)(4)(OH2)(2)] at room temperature and 10 K. The bond lengths and bridging O-C-O angles of the dimeric Cu(II) cage (CU2O10C8) obtained from the multiplescattering (MS) fitting of the X-ray absorption fine structure (XAFS) using a centrosymmetric model of [Cu2- (Indo)(4)(DMF)(2)] gave Cu . . . Cu = 2.62(2) Angstrom, mean Cu-O-Ac = 1.95(7) Angstrom, Cu-O-L = 2.15(2) Angstrom, bridging O-C-O = 125(1)degrees, Cu displacement from plane 0.19 Angstrom compared with the XRD data Cu . . . Cu = 2.630(1) Angstrom, mean Cu-O-Ac = 1.959 Angstrom, Cu-O-L = 2.143(5) Angstrom, bridging O-C-O angles = 123.2(5)degrees, Cu displacement from plane 0.20 Angstrom. The excellent agreement between the XAFS- and XRD-derived data allowed the structures of related [Cu-2(Indo)(4)L-2] (L = DMA, NMP) complexes to be determined. All display a similar Cu2O10C8 coordination geometry, which is independent of the nature of the axial ligand. While XAFS analysis of [Cu-2(Indo)(4)(OH2)(2)] and [Cu-2(OAc)(4)(OH2)(2)] indicates a coordination geometry similar to that of [Cu-2(Indo)(4)L-2] (L = DMF, DMA, NMP), removal of symmetry restraints in the MS model is required to obtain axial bond lengths comparable to those derived in the XRD structures of the acetate complex. For the Indo complex, the fitted bond lengths with the lower symmetry model give a mean Cu-L-OH2 bond distance within experimental errors of the value for [Cu-2(Indo)(4)(DMSO)(2)] (2.16(2) Angstrom) (XRD). The difficulty in refining the Cu-O((OH2)) distance of [Cu-2(OAc)(4)(OH2)(2)] and [Cu-2(IndO)(4)(OH2)(2)] using a centrosymmetric MS model is attributed to a symmetry reduction due to hydrogenbonding effects characteristic of the aqua adducts, as is observed in the XRD structure of the acetate complex.