(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)copper(II) bis-[O,O'-(o-phenyl-ene)dithio-phosphate].

In the title compound, [Cu(C(16)H(36)N(4))](C(6)H(4)O(2)PS(2))(2), the Cu(II) cation lies on an inversion center and is chelated by the macrocyclic tetra-amine ligand in a slightly distorted CuN(4) square-planar geometry. The axial positions are occupied by two O,O'-(o-phenyl-ene)dithio-phosphate anions with long Cu⋯S distances of 3.0940 (7) Å. Inter-molecular N-H⋯S and C-H⋯O hydrogen bonding is present between the anions and the cation and helps to stabilize the crystal structure.

(meso-5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetra-azacyclo-tetra-deca-4,11-diene)copper(II) bis-[O,O'-bis-(4-methyl-phen-yl) dithio-phosphate].

The title compound, [Cu(C(16)H(32)N(4))](C(14)H(14)O(2)PS(2))(2) or [Cu(trans[14]dien)][S(2)P(OC(6)H(4)Me-4)(2)](2), where trans[14]dien is meso-5,7,7,12,14,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-deca-4,11-diene, was obtained by the reaction of [Cu(trans[14]dien)](ClO(4))(2) and [(C(2)H(5))(2)NH](2) [S(2)P(OC(6)H(4)Me-4)(2)](2). The Cu(II) atom lies on a centre of inversion and possesses a relatively undistorted square-planar coordination arrangement with four N atoms of the macrocyclic tetra-mine trans[14]dien [Cu-N = 1.9716 (19) and 2.0075 (19) Å]. The two uncoordinated [(4-MeC(6)H(4)O)(2)PS(2)](-) groups act as counter-ions to balance the charge and inter-act with the [Cu(trans[14]dien)](2+ )complex cation through N-H⋯S hydrogen bonds.

(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)nickel(II) bis-[O,O'-bis-(4-methyl-phen-yl) thio-phosphate].

In the centrosymmetric title complex, [Ni(C(16)H(36)N(4))](C(14)H(14)O(3)PS)(2), the Ni(II) ion is coordinated by four N atoms and two O atoms within a slightly distorted NiN(4)O(2) octa-hedral geometry. The asymmetric unit consits of one Ni(II) ion that is located on a center of inversion, half of the macrocylic ligand and one anion occupying general positions. Intra-molecular N-H⋯O and N-H⋯S hydrogen bonding is found between the macrocyclic ligand and the monothio-phosphate anion.

{N'-[(E)-(5-Bromo-2-oxidophen-yl)(phen-yl)methyl-ene]benzohydrazidato}pyridine-copper(II).

The asymmetric unit of title complex, [Cu(C(20)H(13)BrN(2)O(2))(C(5)H(5)N)], contains two independent mol-ecules. In each mol-ecule, the central Cu(II) atom has a square-planar environment formed by the tridentate hydrazone and the monodentate pyridine ligands, with the N atoms in a trans arrangement about the Cu(II) atom.

(meso-5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetra-azacyclo-tetra-deca-4,11-diene)nickel(II) bis-[O,O'-bis(4-methyl-phen-yl) dithio-phosphate].

In the title compound, [Ni(C(16)H(32)N(4))](C(14)H(14)O(2)PS(2))(2) or [Ni(trans[14]dien)][S(2)P(OC(6)H(4)Me-4)(2)](2), where trans[14]dien is meso-5,7,7,12,14,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-deca-4,11-diene, the Ni(II) ion lies across a centre of inversion and is four-coordinated in a relatively undistorted square-planar arrangement by the four N atoms of the macrocyclic ligand trans[14]dien. The two O,O'-di(4-methyl-phen-yl)dithio-phos-phates act as counter-ions to balance the charge. Important geometric data include Ni-N = 1.9135 (16) and 1.9364 (15) Å.

{N'-[(E)-1-(5-Bromo-2-oxidophen-yl)ethyl-idene]-4-chloro-benzohydrazidato}pyridinenickel(II).

The title complex, [Ni(C(15)H(10)BrClN(2)O(2))(C(5)H(5)N)], displays a square-planar coordination geometry around the Ni(II) ion, formed by the tridentate hydrazone and monodentate pyridine ligands, with the N atoms in a trans arrangement about the Ni center.