Structure, Single Crystal EPR Spectra, and Exchange Interactions in [Cu(L-proline)(2)](2).5H(2)O and Cu(D,L-proline)(2).2H(2)O.
A new copper(II) compound, [Cu(L-proline)(2)](2).5H(2)O (C(20)Cu(2)H(42)N(4)O(13)) (called compound I) was synthesized and crystallized, and its structure was solved using X-ray methods. It is monoclinic, space group P2(1), with a = 11.187(1) Å, b = 12.172(3) Å, c = 11.661(1) Å, beta = 114.96(1) degrees, and Z = 2. There are two chemically different copper molecules (labeled A and B), both with the copper atom in a N(2)O(2) square planar coordination. Molecule type A has one water molecule in an apical position. Molecule B has water molecules in each of the two apical positions. Single-crystal EPR measurements have been performed in I and also in Cu(D,L-proline)(2).2H(2)O (compound II). From the similar angular variations of the position of the single resonance observed in both compounds, we evaluated the molecular g tensors. Interpretation of the molecular g tensors resulted in d(x)()()2(-)(y)()()2 orbital ground states. From the angular variations of the line width we calculated the magnitude of the exchange interactions coupling neighbor copper ions in each compound. In I copper ions type A at 7.25 Å are arranged in chains coupled through axial-equatorial bonds. The exchange coupling within these chains is |J/k| = 118 mK. The coupling between copper ions type B is weaker. However, the interactions between copper ions type A and B generate a three-dimensional magnetic network. Our data in compound II indicate that a superexchange pathway containing a weak hydrogen bond C-H- - -O is the path for an exchange interaction with |J'/k| = 48 mK between coppers in neighbor layers at 9.75 Å.
Sartoris
R. P.
RP
Departamento de Física, Facultad de Ciencias Exactas, Universidad Nacional de La Plata and Programa PROFIMO (CONICET), C.C. 67, 1900 La Plata, Argentina.
Ortigoza
L.
L
Casado
N. M. C.
NM
Calvo
R.
R
Castellano
E. E.
EE
Piro
O. E.
OE