SYNTHESIS, CRYSTAL-STRUCTURE AND MAGNETIC-PROPERTIES OF THE TRIPLY BRIDGED ONE-DIMENSIONAL POLYMERS ([CU-2(CLO4)(OAC)(2)(BPPZ)(H2O)(2)](CLO4)(H2O))(N) AND ([CU-2(OBZ)(3)(BPPZ)](CLO4)(H2O)(2))(N), BPPZ=2,5-BIS(2-PYRIDYL)PYRAZINE
A. Neels et al., SYNTHESIS, CRYSTAL-STRUCTURE AND MAGNETIC-PROPERTIES OF THE TRIPLY BRIDGED ONE-DIMENSIONAL POLYMERS ([CU-2(CLO4)(OAC)(2)(BPPZ)(H2O)(2)](CLO4)(H2O))(N) AND ([CU-2(OBZ)(3)(BPPZ)](CLO4)(H2O)(2))(N), BPPZ=2,5-BIS(2-PYRIDYL)PYRAZINE, Inorganica Chimica Acta, 260(2), 1997, pp. 189-198
Compounds {[Cu-2(ClO4)(OAc)(2)(bppz)(H2O)(2)](ClO4)(H2O)}(n) (1) and {
[Cu-2(OBz)(3)(bppz)](ClO4)(H2O)(2)}(n) (2), where bppz is 2,5-bis(2-py
ridyl)pyrazine, OAc acetate and OBz benzoate, have been synthesized an
d characterized crystallographically. Polymer 1 crystallized in the mo
noclinic system, space group P2(1)/m, a = 8.305(1), b = 10.747(2), c =
15.320(2) Angstrom, beta = 101.02(1)degrees Z = 2, R1 for 1837 observ
ed reflections [I>2 sigma(I)], measured at 213 K, was 0.0374. The stru
cture consists of centrosymmetric dinuclear copper bppz units bridged
by two acetate groups and a perchlorate anion, so forming a zig-zag on
e-dimensional polymer. A mirror plane bisects the three bridging group
s. The copper atoms have a distorted square bipyramidal geometry. The
one-dimensional polymer 2 crystallized in the triclinic system, space
group P (1) over bar, a = 10.505(4), b = 11.666(3), c = 16.780(5) Angs
trom, alpha = 91.87(3)degrees, beta = 102.85(4)degrees, gamma = 113.60
(2)degrees, Z = 2, R1 for 3742 observed reflections [I>2 sigma(T(I)],
measured at 213 K, was 0.0636. The structure is made up of two crystal
lographically different centrosymmetric binuclear copper bppz units br
idged by three benzoate groups; two coordinate in a syn-syn manner, th
e third in a monodentate manner. One copper atom possesses a distorted
square pyramidal geometry the other a distorted square bipyramidal ge
ometry. Magnetic measurements for 1 and 2 show different but significa
nt antiferromagnetic coupling with J = - 88.1 cm(-1), g = 2.18 for 1 a
nd J = - 26.4 cm(-1), g = 2.19 for 2. The magnetic behavior may be cor
related to the structural parameters.