Magneto-structural analysis of metal-orotato coordination complexes based on N-H•••O and O-H•••O supramolecular synthon

Two new supramolecular synthon induced single crystals of metal-orotato complexes of formula [Cu (Orotate).2H(2)O]2 (1), [Mn(Orotate)2.2H(2)O].2H(2)O] (2), have been engineefed and synthesized by self assembly of metal salts with orotic acid in presence of 25% ammonia solution. Although both complexes crystallize in similar crystal system and different coordination geometries [(square planar (1), octahedral (2)] but identical synthon patterns recur after complex formation. N-H center dot center dot center dot O, O-H center dot center dot center dot O synthons were the only artifact for both the hydrogen bonded metal-organic architecture. X-ray structural analysis, EPR, temperature independent paramagnetism (TIP) analysis, have been discussed. DFT calculation is used to rationalize the magnetic behavior of both the complexes. These calculations underline the pathway of magnetic exchange interactions through N-H center dot center dot center dot O, O-H center dot center dot center dot O supramolecular synthons and confirm, that the magnetic interactions propagate through such contacts in complex 1 and 2. (C) 2016 Elsevier Ltd. All rights reserved.