COPPER AND CALCIUM COMPLEXES WITH THE ANIONIC O-2-DONOR -TERT-BUTYLACETYL-3-METHYL-1-PHENYLPYRAZOL-5-ONATO (Q(-)) - INFLUENCE OF HYDROGEN-BOND INTERACTIONS ON LATTICE ARCHITECTURE IN THE CRYSTAL-STRUCTURES OF [CUQ(2)(H2O)] AND [CAQ(2)(ETOH)(2)]

By interaction of 4-tert-butylacetyl-3-methyl-1-phenylpyrazol-5-one (H Q) with Cu(O2CCH3)(2). H2O in EtOH, the derivative [CuQ(2)(H2O)] 1 has been synthesized. It possesses a square-pyramidal structure with the asymmetric beta-diketonate ligands arranged in an ''anti'' configurati on to each other and with a molecule of H2O at the apex of polyhedron. Both protons of H2O are involved in an intermolecular hydrogen-bondin g network with pyridinic nitrogen atoms of Q donors belonging to two n eighbouring complexes. Compound 1 reacts with substituted phenanthroli nes (2,9-Me(2)Phen with 4,7-Ph(2)Phen) in Et2O to give [CuQ(2)(2,9-Me( 2)Phen)] and [CuQ(2)(4,7-Ph(2)Phen)] derivatives. During the reaction of 1 with an excess of 2,9-Me(2)Phen in EtOH reduction of copper(II) t o copper(I) was observed with formation of the ionic diamagnetic coppe r(I) derivative [Cu(2,9-Me(2)Phen)]Q. Ethylenediamine (en) reacted wit h 1 affording the ionic complex [Cu(en)(3)]Q(2). 2H(2)O. By interactio n of 1 with N-methylimidazole (N-MeIm) the compound [CuQ(2)(N-MeIm)(2) ] has been isolated. Finally the P-donors triphenylphosphine and tricy clohexylphosphine (PCy3) reduced copper(II) affording the copper(I) de rivatives [CuQ(PPh3)(2)] and [CuQ(PCy3)(2)]. The reaction between HQ a nd CaCl2 in basic (KOH) EtOH produced the derivative [CaQ(2)(EtOH)(2)] . It contains the calcium atom in an axially distorted octahedral envi ronment with the two beta-diketonate ligands in ''anti'' positions and the EtOH molecules trans to each other. The O-Ca-O axis is bent [172. 86(6)degrees]. The protons of the solvent molecules are involved in a hydrogen-bonding network with the nitrogen atoms of Q donors of other molecular units, and the structure is constituted of infinite chains. The derivatives [CaQ(2)(ROH)(2)] have been obtained in alcoholic ROH s olvents when R = Me, Et or Pr-i, whereas the [CaQ(2)(H2O)(2)] complex formed when R = Bu-t, HC=CCH2 or Pr-i(Bu-t)CH. The interaction between [CaQ(2)(EtOH)(2)] and 1,10-phenanthroline afforded the adduct [Ca(Q)( 2)(Phen)(2)].