Long-range magnetic order in Mn[N(CN)(2)](2)(pyz) {pyz = pyrazine} susceptibility, magnetization, specific heat, and neutron diffraction measurementsand electronic structure calculations
Jl. Manson et al., Long-range magnetic order in Mn[N(CN)(2)](2)(pyz) {pyz = pyrazine} susceptibility, magnetization, specific heat, and neutron diffraction measurementsand electronic structure calculations, J AM CHEM S, 123(1), 2001, pp. 162-172
Using de magnetization, ac susceptibility, specific heat, and neutron diffr
action, we have studied the magnetic properties of Mn[N(CN)(2)](2)(pyz) {py
z pyrazine} in detail. The material crystallizes in the monoclinic space gr
oup P2(1)/n with a = 7.3238(2), b = 16.7369(4), and c = 8.7905 (2) Angstrom
, beta = 89.596 (2)degrees, V = 1077.65(7) Angstrom (3), and Z = 4, as dete
rmined by Rietveld refinement of neutron powder diffraction data at 1.35 K.
The 5 K neutron powder diffraction data reflect very little variation in t
he crystal structure. Interpenetrating ReO3-like networks are formed from a
xially elongated Mn2+ octahedra and edges made up of mu -bonded [N(CN)(2)](
-) anions and neutral pyz ligands. A three-dimensional antiferromagnetic or
dering occurs below T-N = 2.53(2) K. The magnetic unit cell is double the n
uclear one along the a- and c-axes, giving the (1/2, 0, 1/2) superstructure
. The crystallographic and antiferromagnetic structures are commensurate an
d consist of collinear Mn2+ moments, each with a magnitude of 4.15(6) mu (B
) aligned parallel to the a-direction (Mn-pyz-Mn chains). Electronic struct
ure calculations indicate that the exchange interaction is much stronger al
ong the Mn-pyz-Mn chain axis than along the Mn-NCNCN-Mn axes by a factor of
approximately 40, giving rise to a predominantly one-dimensional magnetic
system. Thus, the variable-temperature magnetic susceptibility data are wel
l described by a Heisenberg antiferromagnetic chain model, giving g = 2.01(
1) and J/k(B) = -0.27(1) K. Owing to single-ion anisotropy of the Mn2+ ion,
field-induced phenomena ascribed to spin-flop and paramagnetic transitions
are observed at 0.43 and 2.83 T, respectively.