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
N1 - Funding Information:
K.H. thanks the Syracuse University and the Universität des Saarlandes for the possibility of spending 5 months as a visiting scholar at Syracuse. Financial support by the Fonds der Chemischen Industrie for K.H. is gratefully acknowledged. The work at Syracuse University was also supported by NSF grant CHE 9987471.
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 -