Powell Anthony V, Lees Rachel J E, Chippindale Ann M
Department of Chemistry, Heriot-Watt University, Edinburgh EH14 4AS, UK.
Inorg Chem. 2006 May 15;45(10):4261-7. doi: 10.1021/ic060263f.
A new family of antimony sulfides, incorporating the macrocyclic tetramine 1,4,8,11-tetraazacyclotetradecane (cyclam), has been prepared by a hydrothermal method. [C10N4H26][Sb4S7] (1), [Ni(C10N4H24)][Sb4S7] (2), and [Co(C10N4H24)]xC10N4H26[Sb4S7] (0.08 < or = x < or = 0.74) (3) have been characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetry, and analytical electron microscopy. All three materials possess the same novel three-dimensional Sb4S7(2-) framework, constructed from layers of parallel arrays of Sb4S8(4-) chains stacked at 90 degrees to one another. In 1, doubly protonated macrocyclic cations reside in the channel structure of the antimony-sulfide framework. In 2 and 3, the cyclam acts as a ligand, chelating the divalent transition-metal cation. Analytical and X-ray diffraction data indicate that the level of metal incorporation in 2 is effectively complete, whereas in 3, both metalated and nonmetalated forms of the macrocycle coexist within the structure.
通过水热法制备了一族新的含大环四胺1,4,8,11-四氮杂环十四烷（环胺）的锑硫化物。[C10N4H26][Sb4S7]（1）、[Ni(C10N4H24)][Sb4S7]（2）和[Co(C10N4H24)]x[C10N4H26](1 - x)[Sb4S7]（0.08 ≤ x ≤ 0.74）（3）已通过单晶X射线衍射、元素分析、热重分析和分析电子显微镜进行了表征。所有这三种材料都具有相同的新型三维Sb4S7(2-)骨架，该骨架由相互成90度堆叠的Sb4S8(4-)链的平行阵列层构成。在1中，双质子化的大环阳离子存在于锑硫化物骨架的通道结构中。在2和3中，环胺作为配体，螯合二价过渡金属阳离子。分析和X射线衍射数据表明，2中金属掺入水平实际上已完成，而在3中，大环的金属化和未金属化形式在结构中共存。
