TY - JOUR
T1 - Surface complexation of [Nb6O19]8- with NiII
T2 - Solvothermal synthesis and X-ray structural characterization of two novel heterometallic Ni-Nb-polyoxometalates
AU - Hegetschweiler, Kaspar
AU - Finn, Robert C.
AU - Rarig, Randy S.
AU - Sander, Jürgen
AU - Steinhauser, Stefan
AU - Wörle, Michael
AU - Zubieta, Jon
PY - 2002/9/26
Y1 - 2002/9/26
N2 - Solvothermal reaction of NiCl2, Nb(OEt)5 and 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) in a 1:1:1 ratio under alkaline conditions (NaOH) resulted in the formation of two new Nb-Ni heteropolyoxometalate complexes. [Ni(taci)2]2{trans-[Nb6O19][Ni (taci)]2}·26H2O (1) and [Na(H2O)6]2{cis-[H2Nb 6O19][Ni(taci)]2}·18H2O (2), were characterized by single crystal X-ray analysis. In both compounds, two [Ni(taci)]2+ entities are each bonded to three Nb-O-Nb bridges of a central Nb6O19 unit, resulting in the formation of an approximately C3v symmetric NiN3O3 coordination geometry. The mononuclear analogue [Ni(taci)(H2O)3]2+ was crystallized as the sulfate and structurally characterized for comparison. The two isolated anions {trans-[Nb6O19][Ni(taci)]2}4- and {cis-[H2Nb6O19][Ni(taci)]2} 2- have approximate D3d and C2v symmetry, respectively. Compound 2 crystallized, however, in the cubic space group Pn3̄m (No. 224) with the two Ni centers equally distributed over four symmetry equivalent sites. In this structure, the [Na(H2O)6]+ cations and the {cis-[H2Nb6O19][Ni(taci)]2} 2- anions represent linearly and tetrahedrally connecting building blocks in a hydrogen bonded supramolecular architecture which can be described in terms of two independent but interpenetrating diamond-type nets.
AB - Solvothermal reaction of NiCl2, Nb(OEt)5 and 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) in a 1:1:1 ratio under alkaline conditions (NaOH) resulted in the formation of two new Nb-Ni heteropolyoxometalate complexes. [Ni(taci)2]2{trans-[Nb6O19][Ni (taci)]2}·26H2O (1) and [Na(H2O)6]2{cis-[H2Nb 6O19][Ni(taci)]2}·18H2O (2), were characterized by single crystal X-ray analysis. In both compounds, two [Ni(taci)]2+ entities are each bonded to three Nb-O-Nb bridges of a central Nb6O19 unit, resulting in the formation of an approximately C3v symmetric NiN3O3 coordination geometry. The mononuclear analogue [Ni(taci)(H2O)3]2+ was crystallized as the sulfate and structurally characterized for comparison. The two isolated anions {trans-[Nb6O19][Ni(taci)]2}4- and {cis-[H2Nb6O19][Ni(taci)]2} 2- have approximate D3d and C2v symmetry, respectively. Compound 2 crystallized, however, in the cubic space group Pn3̄m (No. 224) with the two Ni centers equally distributed over four symmetry equivalent sites. In this structure, the [Na(H2O)6]+ cations and the {cis-[H2Nb6O19][Ni(taci)]2} 2- anions represent linearly and tetrahedrally connecting building blocks in a hydrogen bonded supramolecular architecture which can be described in terms of two independent but interpenetrating diamond-type nets.
KW - Hexaniobates
KW - Hydrogen bonding
KW - Nickel complexes
KW - Solvothermal synthesis
KW - Supramolecular structures
UR - http://www.scopus.com/inward/record.url?scp=0037179986&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0037179986&partnerID=8YFLogxK
U2 - 10.1016/S0020-1693(02)00991-X
DO - 10.1016/S0020-1693(02)00991-X
M3 - Article
AN - SCOPUS:0037179986
VL - 337
SP - 39
EP - 47
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
ER -