Двойные молибдаты серебра и одновалентных металлов
Аннотация
Рентгенографически изучена система Ag2MoO4–Cs2MoO4, установлено образование нового двойного молибдата CsAg3(MoO4)2, получены кристаллы этого соединения и определено его строение. Установлена принадлежность CsAg3(MoO4)2 (пр. гр. P3¯, Z = 1, a = 5.9718(5), c = 7.6451(3) Å, R = 0.0149) к структурному типу Ag2BaMn(VO4)2. Основу структуры составляют глазеритоподобные слои из связанных кислородными вершинами чередующихся MoO4‑тетраэдров и Ag1O6-октаэдров, которые соединены в единый трехмерный каркас Ag2O4-тетраэдрами.
Необычная черта окружения атома Ag2 – расположение почти в центре кислородной грани Ag2O4-тетраэдра. Атомы цезия находятся в кубооктаэдрической координации (КЧ = 12).
Определены структуры полученного нами ранее двойного молибдата рубидия-серебра и кристалла из области твердого раствора на основе гексагональной модификации Tl2MoO4, которые принадлежат к типу глазерита K3Na(SO4)2 (пр. гр. P3¯m1). По данным РСА оба кристалла имеют нестехиометрические составы Rb2.81Ag1.19(MoO4)2 (a = 6.1541(2), c = 7.9267(5) Å, R = 0.0263) и Tl3.14Ag0.86(MoO4)2 (a = 6.0977(3), c = 7.8600(7) Å, R = 0.0174), причем в случае рубидиевой
фазы впервые в молибдатах выявлено расщепление позиции Rb/Ag. Основу обеих структур составляют слои из связанных кислородными вершинами чередующихся MoO4-тетраэдров и AgO6- или (Ag, Tl)O6-октаэдров. Координационные числа рубидия и таллия равны 12 и 10
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Литература
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