A novel series of fully reduced heteropolyoxovanadium(IV) compounds, [MV
IV6O
6{(OCH
2CH
2)
2N(CH
2CH
2OH)}
6]X(
1, M = Li, X = Cl·LiCl;
2, M = Na, X = Cl·H
2O;
3, M = Mg, X = 2Br·H
2O;
4, M = Mn, X = 2Cl;
5, M = Fe,X = 2Cl;
6, M = Co, X = 2Cl·H
2O;
7, M = Ni, X = 2Cl·H
2O), have been synthesized and characterized by FT-IRand UV-vis spectroscopies, thermogravimetric analysis, elemental analysis, manganometric titration, temperature-dependent magnetic susceptibility measurements, bond valence sum calculations, X-ray powder diffraction, andsingle-crystal X-ray diffraction analyses. The structures of the crystals are comprised of discrete units of fullyreduced cluster cations, [MV
IV6O
6{(OCH
2CH
2)
2N(CH
2CH
2OH)}
6]
n+, counterions (chloride or bromide), and water ofcrystallization (in the case of
2,
3,
6,
7). In each case the cluster ion is composed of a fully reduced cyclic {MV
6N
6O
18}(M = Li, Na, Mg, Mn, Fe, Co, Ni) framework decorated with six triethanolamine ligands. Two arms of eachtriethanolamine ligand are coordinated to the metallacycle, and the third arm pro
jects outward from the hexagonalring. The {MV
6N
6O
18} core adopts the Anderson-type structure. The cyclic core is comprised of a ring of sixedge-sharing {VO
5N} octahedra linked to a central {MO
6} unit. The hexametalate ring contains six d
1 ions {V
IV}and shows remarkable flexibility to encapsulate a variety of metal centers M
n+ (M
n+ = Li
+, Na
+, Mg
2+, Mn
2+, Fe
2+,Co
2+, Ni
2+) with different (d
n) spins. The compounds show good thermal stability and exhibit interesting magneticproperties that make these magnetic clusters promising building blocks for constructing supramolecular structuresand extended structure magnetic solids. Crystal data for
1; C
36H
78Cl
2N
6Li
2O
24V
6, trigonal space group
R![](/images/entities/thremacr.gif)
,
a =13.7185(3) Å,
c = 24.8899(8) Å,
Z = 3. Crystal data for
2: C
36H
80ClN
6NaO
25V
6, triclinic space group
P![](/images/entities/onemacr.gif)
,
a =11.1817(5) Å,
b = 12.1612(5) Å,
c = 21.5979(10) Å,
![](/images/gifchars/alpha.gif)
= 75.8210(10),
![](/images/gifchars/beta2.gif)
= 78.8270(10),
![](/images/gifchars/gamma.gif)
= 71.1400(10),
Z =2. Crystal data for
4: C
36H
78Cl
2N
6MnO
24V
6, monoclinic, space group
P2
1,
a =11.2208(5) Å,
b = 21.5041(9) Å,
c= 11.8126(5),
![](/images/gifchars/beta2.gif)
= 111.2680,
Z= 2. Crystal data for
5: C
36H
78Cl
2N
6FeO
24V
6, monoclinic, space group
P2
1,
a =11.3057(7) Å,
b = 21.4372(13) Å,
c = 11.8167(7) Å,
![](/images/gifchars/beta2.gif)
= 111.4170,
Z = 2.