Five ionic assemblies of octacoordinated cyano complexes of molybdenum and tungsten with protonated
cyclam (1,4,8,11-tetraazacyclotetradecane) and tmc (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetra-
decane) have been obtained: (cyclamH
4
)[Mo
IV
(CN)
8
]
1.5H
2
O(
1
), (cyclamH
2
)(cyclamH
4
)[W
V
(CN)
8
]
2
4H
2
O
(
2
), (cyclamH
4
)[W
V
(CN)
8
]Cl
4H
2
O(
3
), (tmcH
4
)(tmcH
2
)[W
V
(CN)
8
]
2
4H
2
O(
4
) and (cyclamH
4
)[W
IV
(CN)
6
-
(bpy)]
2
12H
2
O(
5
) (bpy = 2,2
0
-bipyridine). The presence of 3d metal cations as a template led to partly
protonated cyclams in
2
and
4
, where for the first time cyclam and tmc cations of different degree of pro-
tonation are encountered within one structure. Compounds
2
,
3
and
5
crystallise in triclinic system space
group
P
1, while
4
crystallises in monoclinic system space group
P
21/
c
. Compound
1
shows the highest
symmetry of the lattice: orthorombic system space group
I
41/
a
. Thermogravimetric analyses of
1
,
3
and
4
show the presence of stable anhydrous phase below 140° C.