M. Fettouhi et al., POLYMORPHISM AND RELATED MAGNETIC-BEHAVIOR IN DECAMETHYLFERROCENIUM SALTS OF TRANSITION-METAL MALEONITRILEDITHIOLATES, Inorganic chemistry, 34(16), 1995, pp. 4152-4159
Several decamethylferrocenium/transition-metal maleonitriledithiolate
compounds have been synthesized and structurally characterized. The co
mpounds [Fe(cp)(2)](x)[M(mnt)(2)](gamma)(CH3CN)(z) (M = Cu(II), Co(II
I), Fe(III)) crystallize in the triclinic space group P $($) over bar$
$ 1 (No. 2). For M = Co(III) two solid-state phases have been isolated
. alpha-[Fe(cp)(2)](2)[Co(mnt)(2)](2)(CH3CN)(2) (Fe(2)Co(2)A): a = 9.
894(4) Angstrom, b = 12.942(6) Angstrom, c = 15.056(6) Angstrom, alpha
= 110.13(3)degrees, beta = 981.41(4)degrees, gamma = 107.78(3)degrees
, V = 1657 Angstrom(3), M(r) = 1413,3, d(c) = 1.419 g/cm(3), Z = 1, an
d R = 0.061 for 2351 reflections with 1 greater than or equal to 3 sig
ma(1). beta-[Fe(cp)(2)](2)[Co(mnt)(2)](2) (Fe2Co2B): a = 9.576(8) Ang
strom, b = 12.849(4) Angstrom, c = 13.641(7) Angstrom, alpha = 108.13(
4)degrees, beta = 90.91(6)degrees, gamma = 103.54(4)degrees, V = 1544
Angstrom(3), M(r) = 1331.2, d(c) = 1.431 g/cm(3), Z = 1, and R = 0.043
for 2407 reflections with I greater than or equal to 3 sigma(1). The
isostructural. ct modification is observed for M = Fe(III). alpha-[Fe(
cp)(2)](2)[Fe(mnt)(2)](2)(CH3CN)(2) (Fe(2)Fe(2)A): a = 9.905(7) Angst
rom, b = 12.966(5) Angstrom, c = 15.142(3) Angstrom, alpha = 109.77(2)
degrees, beta = 98.64(4)degrees, gamma = 108.06(6)degrees, V = 1668 An
gstrom(3) M(r) = 1407.2, d(c) = 1.401 g/cm(3), Z = 1, and R = 0.063 fo
r 3125 reflections with 1 greater than or equal to 3 sigma(I). The dim
eric anionic species show a square pyramidal coordination for the meta
l (the apical M-S bonds are Co-S = 2.39, 2.35 Angstrom and Fe-S = 2.49
Angstrom). Orthogonal arrangement of adjacent cations is observed in
the decamethylferrocenium chains of the two a compounds, while a paral
lel packing exists in the beta modification. [Fe(cp)(2)]Cu-2(mnt)(2)
(Fe2Cu): a = 9.713(5) Angstrom, b = 11.407(4) Angstrom, c = 11.958(5)
Angstrom, alpha = 100.90(2)degrees, beta = 113.20(5)degrees, gamma = 9
2.66(3)degrees, V = 1185 Angstrom(3), M(r)= 996.5, d(c) = 1.396 g/cm(3
), Z = 1, and R = 0.041 for 2724 reflections with 1 greater than or eq
ual to 3 sigma(1). The dianion [Cu(mnt)(2)](2-) exhibits a planar mono
meric structure and the mixed anion-cation stacks adopt a...A(2-)D(+)D
(+)A(2-)D(+)D(+)A(2-)... arrangement with short anion-cation distances
: d(Fe-S) 5.54 Angstrom, and d(Fe-Cu) = 6.37 Angstrom. The magnetic pr
operties of all the compounds have been investigated. In both Fe(2)Co(
2)A and Fe2Co2B the decamethylferrocenium cations have been found to b
e magnetically isolated. In Fe(2)Fe(2)A, a strong antiferromagnetic in
teraction within the {[Fe(mnt)](2)}(2-) dimeric unit has been characte
rized. In Fe2Cu, finally, each [Cu(mnt)(2)](2-) is found to interact a
ntiferromagnetically with two adjacent [Fe(C-p)(2)](+) cations.