The First Coordination Polymers and Hydrogen Bonded Networks Containing Octahedral Nb6 Clusters and Alkaline Earth Metal Complexes
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- 作者：Zhihua Yan ; Cynthia S. Day ; and Abdessadek Lachgar
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：June 27, 2005
- 年：2005
- 卷：44
- 期：13
- 页码：4499 - 4505
- 全文大小：477K
- 年卷期：v.44,no.13(June 27, 2005)
- ISSN：1520-510X
文摘
Three novel coordination polymers built of octahedral niobium cyanochloride clusters [Nb6Cl12(CN)6] and alkalineearth metal complexes have been prepared by reaction of aqueous solutions of (Me4N)4Nb6Cl18 and KCN withsolutions of alkaline earth metal salts and 1,10-phenanthroline (phen) (1:2 molar ratio) in H2O/EtOH. The structuresof [Ca(phen)2(H2O)3]2[Nb6Cl12(CN)6]·(phen)(EtOH)1.6 (1), [Ca(phen)2(H2O)2]2[Nb6Cl12(CN)6]·(phen)2·4H2O (2), and[Ba(phen)2(H2O)]2[Nb6Cl12(CN)6] (3) were determined by single-crystal X-ray diffraction. The three compounds werefound to crystallize in the monoclinic system (space group Pn) with a = 11.5499(6) Å, b = 17.5305(8) Å, c =21.784(1) Å, 
= 100.877(1)
for 1; triclinic system (P
) with a = 12.609(4) Å, b = 13.262(4) Å, c = 16.645(5)Å, 
= 69.933(6), = 68.607(6), 
= 63.522(5) for 2; and a = 16.057(1) Å, b = 16.063(1) Å, c = 16.061(1)Å, = 86.830(1), = 64.380(1), = 67.803(1) for 3. Compounds 1 and 2 are built of cluster anions[Nb6Cl12(CN)6]4- trans-coordinated by two Ca2+ complexes via CN ligands to form neutral macromolecular units[Ca(phen)2(H2O)3]2[Nb6Cl12(CN)6] in 1 and [Ca(phen)2(H2O)2]2[Nb6Cl12(CN)6] in 2. Water of coordination and cyanideligands form hydrogen bonded 3D and 2D frameworks for 1 and 2, respectively. The structure of 3 consists of[Nb6Cl12(CN)6]4- cluster anions and [Ba(phen)2(H2O)]2+ complexes linked through bridging cyanide ligands to forma neutral three-dimensional framework in which each barium complex is bound to three neighboring Nb6 clustersand each Nb6 cluster is linked to six Ba complexes.
= 100.877(1) for 1; triclinic system (P) with a = 12.609(4) Å, b = 13.262(4) Å, c = 16.645(5)Å, = 69.933(6), = 68.607(6), = 63.522(5) for 2; and a = 16.057(1) Å, b = 16.063(1) Å, c = 16.061(1)Å, = 86.830(1), = 64.380(1), = 67.803(1) for 3. Compounds 1 and 2 are built of cluster anions[Nb6Cl12(CN)6]4- trans-coordinated by two Ca2+ complexes via CN ligands to form neutral macromolecular units[Ca(phen)2(H2O)3]2[Nb6Cl12(CN)6] in 1 and [Ca(phen)2(H2O)2]2[Nb6Cl12(CN)6] in 2. Water of coordination and cyanideligands form hydrogen bonded 3D and 2D frameworks for 1 and 2, respectively. The structure of 3 consists of[Nb6Cl12(CN)6]4- cluster anions and [Ba(phen)2(H2O)]2+ complexes linked through bridging cyanide ligands to forma neutral three-dimensional framework in which each barium complex is bound to three neighboring Nb6 clustersand each Nb6 cluster is linked to six Ba complexes.