Christian-Albrechts-Universität zu Kiel, Institut für Anorganische Chemie, D-24098, Kiel, Germany.
Dalton Trans. 2012 Jan 28;41(4):1338-44. doi: 10.1039/c1dt11635e. Epub 2011 Dec 8.
Three new poloxovanadates were synthesized under solvothermal conditions and were structurally characterized. The two compounds with composition {Ni(dien)(2)}(3)[V(15)Sb(6)O(42)(H(2)O)]·nH(2)O (n = 12 and 8; dien = bis(2-aminoethyl)amine or diethylenetriamine) are pseudopolymorphs crystallizing in different space groups. The compounds were obtained by applying identical reaction slurries but using different reaction temperatures. Both compounds feature the V(15)Sb(6)O(42)(H(2)O) anion which is the antimony analogue to the single molecule magnet V(15)As(6)O(42)(H(2)O). Crystal data: 1 tetragonal space group P4, a = 46.9378(3), c = 16.51300(10) Å and V = 36380.7(4) Å(3). 2 rhombohedral space group R3c with a = 23.0517(4), c = 28.6216(5) Å and V = 13171.3(4) Å(3). In 1 several unusual short inter-cluster Sb···O contacts lead to the formation of three different super-clusters with composition V(60)Sb(24)O(168). The 12 unique {Ni(dien)(2)}(2+) complexes adopt all three possible configurations. In 2 the special arrangement of the {Ni(dien)(2)}(2+) complexes around the cluster anion prevents inter-cluster Sb···O contacts. The main structural motif of the third compound {Ni(dien)(2)}(4)[V(16)Sb(4)O(42)(H(2)O)] (3) is the V(16)Sb(4)O(42)(H(2)O) cluster anion consisting of two perpendicular eight-membered rings of VO(5) pyramids. Two additional VO(5) polyhedra are located on opposite sides. Crystal data: 3 triclinic space group P1 = 13.5159(4), b = 14.2497(5), c = 14.9419(4) Å, α = 98.322(2), β = 114.080(2), γ = 110.130(2)° and V = 2326.35(12) Å(3).
三种新的多钒酸盐在溶剂热条件下合成，并进行了结构表征。两种组成分别为{Ni(dien)(2)}(3)[V(15)Sb(6)O(42)(H(2)O)]·nH(2)O (n = 12 和 8; dien = 双(2-氨基乙基)胺或二乙三胺)的化合物是伪同晶物，结晶于不同的空间群中。这两种化合物是通过应用相同的反应混合物，但使用不同的反应温度而得到的。两种化合物均具有V(15)Sb(6)O(42)(H(2)O)阴离子，这是单分子磁体V(15)As(6)O(42)(H(2)O)的锑类似物。晶体数据：1 个四方晶系 P4，a = 46.9378(3)，c = 16.51300(10) Å，V = 36380.7(4) Å(3)。2 个三方晶系 R3c，a = 23.0517(4)，c = 28.6216(5) Å，V = 13171.3(4) Å(3)。在 1 中，几个不寻常的短簇间 Sb···O 接触导致形成了三个具有不同组成的 V(60)Sb(24)O(168)的超簇。12 个独特的{Ni(dien)(2)}(2+)复合物采用了所有三种可能的构型。在 2 中，{Ni(dien)(2)}(2+)复合物围绕簇阴离子的特殊排列阻止了簇间 Sb···O 接触。第三种化合物{Ni(dien)(2)}(4)[V(16)Sb(4)O(42)(H(2)O)] (3)的主要结构基元是V(16)Sb(4)O(42)(H(2)O)簇阴离子，它由两个垂直的八元环 VO(5)金字塔组成。另外两个 VO(5)多面体位于相对的两侧。晶体数据：3 个三斜晶系 P1 = 13.5159(4)，b = 14.2497(5)，c = 14.9419(4) Å，α = 98.322(2)，β = 114.080(2)，γ = 110.130(2)°，V = 2326.35(12) Å(3)。
