Jm. Dominguezvera et al., DINUCLEAR COPPER(II) COMPLEXES CONTAINING NITROSO-OXIMATO BRIDGES - 2DIFFERENT COPPER(II)-BRIDGING ENTITIES FROM THE SAME PRECURSOR, Polyhedron, 16(2), 1997, pp. 281-289
The complexes [Cu(mu-L)Cu(bipy)(EtOH)](ClO4)(2) 2a and [Cu(mu-(1)L)Cu(
bipy)(H2O)](ClO4)(2) . H2O 2b [where H(2)L = pyrimidine-2,4-(1H,3H)-di
on-6-yl)propylenediamine; H(2)(1)L arises from H(2)L by elimination of
a CO molecule from one of the pyrimidine rings] have been obtained fr
om the reaction of the precursor [Cu(mu-HL)Cu(H2O)(2)(CH3CH2OH)](ClO4)
(3) 1 with bipy and Cu(ClO4)(2) . 6H(2)O, respectively. The structures
of 2a and 2b have been solved by X-ray crystallographic methods. The
structure of 2a is made up of [Cu(mu-L)Cu(bipy)(EtOH)](2+) cations and
two semi coordinated perchlorate anions. The [Cu(1)L] fragment coordi
nates to the external Cu(2) ion through the two deprotonated oximate o
xygens to afford a dinuclear structure with double syn-syn mitroso-oxi
mate bridge and an intramolecular Cu-Cu distance of 3.731(1) Angstrom.
The Cu(1) exhibits a CuN4O2 pseudoctahedral coordination polyhedron w
hereas the geometry around the Cu(2) ion is distorted square-pyramidal
CuN2O2O. The structure of 2b consists of [Cu(mu-(1)L)Cu(bipy)(H2O)](2
+) cations, two perchlorate anions and one lattice water molecule. The
coordination of the [Cu((1)L)] unit to the external Cu(2) ion takes p
lace through the two nitroso-oximate groups, one of them disordered on
two sets of crystallographic positions, one with a 63% occupancy and
the other with a 37% occupancy. The intramolecular Cu(1)-Cu(2) distanc
e is 3.655(3) Angstrom. The Cu(1) occupying the inner site of the (1)L
(2-) ligand exhibits a 4+1 CuN4O (63%) [CuN3O2 (37%)] coordination env
ironment whereas the Cu(2) atom is in a distorted square-pyramidal CuN
2O3 (63%) [CuN3O2 (37%)] environment. The dinuclear fragments of 2a an
d 2b are almost planar with dihedral angles between the mean basal coo
rdination planes of 4.1(2)degrees and 4.6 degrees, respectively. Both
2a and 2b are diamagnetic at room temperature, so that J < -1000 cm(-1
). The structural and magnetic data for these complexes have been comp
ared with those of similar compounds, but no correlation between the m
agnitude of the exchange interaction and the degree of deviation from
planarity is evident. In view of this and to rationalize the influence
of the distortion from planarity on the magnetic properties in oximat
e-bridged complexes, MO Extended Huckel calculations have been perform
ed. Copyright (C) 1996 Elsevier Science Ltd