TY - JOUR
T1 - Tritungsten(IV) cluster compounds with hydroxo ligands. Preparation and structure of [W3O2(O2CCH3)6(H2O)(OH)2]·16H2O and [W3O2(O2CCH3)6(H2O)(OH)2]·KBr·15H2O
AU - Bino, Avi
AU - Gibson, Dan
PY - 1985/11/1
Y1 - 1985/11/1
N2 - The trinuclear tritungsten(IV) cluster ion, [W3O2(OAc)6(H2O)3]2+ acts as a polyprotic acid in aqueous solution. If the pH of the solution is about 6, brown yellow crystals of [W3O2(OAc)6(H2O)·(OH)2]· 16H2O, 2, are obtained. In the presence of KBr, crystals of the double salt, [W3O2(OAc)6(H2O)(OH)2]· KBr·15H2O, 3, precipitate upon evaporation of the solution. X-ray structural analyses of the two compounds revealed that compound 2 is monoclinic, space group C2/m with a = 18.845(2) Å, b = 19.001(3) Å, c = 10.862(1) Å, β = 95.60(3)°, V = 3871(1) Å3 and Z = 4. Compound 3 is monoclinic, space group P21/c with a = 10.984(1) Å, b = 18.440(2) Å c = 19.305(2) Å, β = 95.63(2)° V = 3891(1) Å3 and Z = 4. The structures were refined by a full-matrix least-squares technique, using 2996 and 3871 reflections to R values of 3.7% and 4.6% respectively. In both structures the presence of the two hydroxo ligands in the cluster causes a considerable increase in the WW bond lengths relative to the triaqua complex. In 3, the potassium cation is bonded to two hydroxo oxygen atoms from neighbouring clusters, forming infinite chains of ··O(H)W3O(H)⋯K⋯O(H)W3O(H)⋯ units in the crystal.
AB - The trinuclear tritungsten(IV) cluster ion, [W3O2(OAc)6(H2O)3]2+ acts as a polyprotic acid in aqueous solution. If the pH of the solution is about 6, brown yellow crystals of [W3O2(OAc)6(H2O)·(OH)2]· 16H2O, 2, are obtained. In the presence of KBr, crystals of the double salt, [W3O2(OAc)6(H2O)(OH)2]· KBr·15H2O, 3, precipitate upon evaporation of the solution. X-ray structural analyses of the two compounds revealed that compound 2 is monoclinic, space group C2/m with a = 18.845(2) Å, b = 19.001(3) Å, c = 10.862(1) Å, β = 95.60(3)°, V = 3871(1) Å3 and Z = 4. Compound 3 is monoclinic, space group P21/c with a = 10.984(1) Å, b = 18.440(2) Å c = 19.305(2) Å, β = 95.63(2)° V = 3891(1) Å3 and Z = 4. The structures were refined by a full-matrix least-squares technique, using 2996 and 3871 reflections to R values of 3.7% and 4.6% respectively. In both structures the presence of the two hydroxo ligands in the cluster causes a considerable increase in the WW bond lengths relative to the triaqua complex. In 3, the potassium cation is bonded to two hydroxo oxygen atoms from neighbouring clusters, forming infinite chains of ··O(H)W3O(H)⋯K⋯O(H)W3O(H)⋯ units in the crystal.
UR - http://www.scopus.com/inward/record.url?scp=46549094439&partnerID=8YFLogxK
U2 - 10.1016/S0020-1693(00)86765-1
DO - 10.1016/S0020-1693(00)86765-1
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AN - SCOPUS:46549094439
SN - 0020-1693
VL - 104
SP - 155
EP - 160
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 3
ER -