Polymeric chains of tetranuclear hydroxo-o-phthalatocuprate(II) units and silver(I)–aromatic interactions in the crystal structure of Ag[Cu2(C8H4O4)2(OH)].5H2O

Abstract

The crystal structure of Ag[Cu2(C~H404)~(OH)I.5H20, CI6H9AgCu209.5H20, has been determined from diffractometer data by Patterson and Fourier methods and refined to R = 0.079 for 2359 counter reflections: a = 11.388 (11), b = 11.772 (12), c = 7.875 (9) A, ,~ = 100.3 (1), fl = 80.2 (1), y = 102.2 (1) °, space group P i , Z = 2. The structure consists of centrosymmetric tetranuclear [ C u 2 ( C s H 4 0 4 ) 2 ( O H ) ] 2 2 anions (linked in polymeric chains by bridging ophthalate anions), Ag ~ cations and water molecules. The tetranuclear hydroxo-o-phthalatocuprate(II) anions contain two independent Cu atoms linked by triplybridging hydroxo O atoms and by carboxylate bridges from o-phthalate anions. The coordination polyhedron of Cu(1) is a trigonal bipyramid whose equatorial plane is tbrmed by three O atoms from three bridging carboxylates [ C u O = 2.049 (10), 2.101 (10), 2.233 (12) A], the axial positions being occupied by an O atom from an OHion [ C u O = 1.911 (11) A] and by an O atom from a monodentate carboxylate group [ C u O = 1.923 (11) AI. The coordination of Cu(2) is square pyramidal, the basal plane comprising two O atoms from OHions [ C u O = 1.955 (9), 1-949 (9) /k] and two O atoms from two bridging carboxylates [ C u O = 1-924(10), 1.928(10) AI. Another O atom from a bridging carboxylate is at the apex of the pyramid [ C u O = 2.352 (13) /k]. The Ag I ion is linked to this last O atom [ A g O = 2.264 (12) ,~,1 and to two water molecules [ A g O w = 2.328 (25), 2.536 (26) AI, and interacts with a benzene C C bond [ A g (midpoint of C C ) = 2.431 (16) ,~1, so that Ag-aromatic complexes, in a distorted tetrahedral configuration, are present.