title: One-dimensional oxalato-bridged Cu(II), Co(II), and Zn(II) complexes with purine and adenine as terminal ligands.
abstract: The reaction of nucleobases (adenine or purine) with a metallic salt in the presence of potassium oxalate in an aqueous solution yields one-dimensional complexes of formulas [M(mu-ox)(H(2)O)(pur)](n) (pur = purine, ox = oxalato ligand (2-); M = Cu(II) [1], Co(II) [2], and Zn(II) [3]), [Co(mu-ox)(H(2)O)(pur)(0.76)(ade)(0.24)](n)(4) and ([M(mu-ox)(H(2)O)(ade)].2(ade).(H(2)O))(n) (ade = adenine; M = Co(II) [5] and Zn(II) [6]). Their X-ray single-crystal structures, variable-temperature magnetic measurements, thermal behavior, and FT-IR spectroscopy are reported. The complexes 1-4 crystallize in the monoclinic space group P2(1)/a (No. 14) with similar crystallographic parameters. The compounds 5 and 6 are also isomorphous but crystallize in the triclinic space group P (No. 2). All compounds contain one-dimensional chains in which cis-[M(H(2)O)(L)](2+) units are bridged by bis-bidentate oxalato ligands with M(.)M intrachain distances in the range 5.23-5.57 A. In all cases, the metal atoms are six-coordinated by four oxalato oxygen atoms, one water molecule, and one nitrogen atom from a terminal nucleobase, building distorted octahedral MO(4)O(w)N surroundings. The purine ligand is bound to the metal atom through the most basic imidazole N9 atom in 1-4, whereas in 5 and 6 the minor groove site N3 of the adenine nucleobase is the donor atom. The crystal packing of compounds 5 and 6 shows the presence of uncoordinated adenine and water crystallization molecules. The cohesiveness of the supramolecular 3D structure of the compounds is achieved by means of an extensive network of noncovalent interactions (hydrogen bonds and pi-pi stacking interactions). Variable-temperature magnetic susceptibility measurements of the Cu(II) and Co(II) complexes in the range 2-300 K show the occurrence of antiferromagnetic intrachain interactions.
authors.affiliation: Departamento de Química Inorgánica, Universidad del País Vasco, Apartado 644, E-48080 Bilbao, Spain.
authors.forename: Juan P
authors.initials: JP
authors.lastname: García-Terán
authors.forename: Oscar
authors.initials: O
authors.lastname: Castillo
authors.forename: Antonio
authors.initials: A
authors.lastname: Luque
authors.forename: Urko
authors.initials: U
authors.lastname: García-Couceiro
authors.forename: Pascual
authors.initials: P
authors.lastname: Román
authors.forename: Francesc
authors.initials: F
authors.lastname: Lloret
mesh_terms: D000225:Adenine / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D008024:Ligands; D019216:Metals, Heavy / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010070:Oxalates / Q000737:chemistry*; D011687:Purines / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry
chemical_list: D008024:Ligands; D019216:Metals, Heavy; D009942:Organometallic Compounds; D010070:Oxalates; D011687:Purines; D003035:Cobalt; D003300:Copper; D015032:Zinc; D000225:Adenine; C030985:purine