The compound
[Cu(cyclam)(TCNQ)2](TCNQ) (cyclam =
1,4,8,11-tetraazacyclotetradecane, TCNQ = 7,7,8,8-tetracyanoquinodimethane) has been obtained in two different
crystallographic forms, isomers 1 and 2.
Crystal
data for isomer 1: triclinic, P1̄,
a = 7.855(6) Å, b = 10.267(2) Å,
c = 14.424(3) Å, α = 95.42(2)°, β =
102.18(5)°, γ = 109.74(3)°, Z = 1. Crystal data
for isomer 2: triclinic, P1̄, a
= 8.165(1) Å, b = 9.918(3) Å, c
=
13.278(3) Å, α = 83.91(2)°, β = 78.31(2)°,
γ = 79.22(2)°, Z = 1. Both isomers show
the same copper environment
and oxidation states in the TCNQ molecules, and the only difference is
observed in the stacking of the latter
groups. The main common feature is the presence of parallel chains
of copper macrocycle units linked by dimeric
(TCNQ)2
2-, which coordinates to
the metal. These chains are joined in isomer 1 by one
neutral TCNQ molecule
oriented parallel to the anionic TCNQ dimers and overlapping with two
of them creating a bidimensional network.
In contrast, the neutral TCNQ in isomer 2 is rotated
about 70° relative to the anionic dimers and overlaps
with
four different chains, extending the interaction in a tridimensional
way. The spectral and solid state conductivity
data show electronic localization on the dimers
(TCNQ)2
2- in both isomers with a
weak semiconducting behavior.
The magnetic behavior of both isomers can be interpreted as the
sum of contributions from the metal and a
thermally activated triplet state for the dimerized anions. The
latter contribution is favored by the π overlap of
the neutral TCNQ molecules, since the analogous derivative
[Cu(cyclam)(TCNQ)2], only with anionic
dimers,
shows a strong antiferromagnetic coupling inside the dimers and no
appreciable contribution to the bulk magnetic
susceptibility is observed.