Kiriukhina Galina V, Yakubovich Olga V, Shvanskaya Larisa V, Kochetkova Ekaterina M, Dimitrova Olga V, Volkov Anatoliy S, Simonov Sergey V
M.V. Lomonosov Moscow State University, Leninskye Gory 1, Moscow 119991, Russian Federation.
The Institute of Solid State Physics RAS, Akademika Osip`yana st 2, Chernogolovka, Moscow region 142432, Russian Federation.
Acta Crystallogr C Struct Chem. 2020 Mar 1;76(Pt 3):302-310. doi: 10.1107/S2053229620002466. Epub 2020 Feb 25.
Two novel K/Mn phosphate hydrates, namely, dipotassium trimanganese dipyrophosphate dihydrate, KMn(HO)[PO], (I), and potassium manganese dialuminium triphosphate dihydrate, KMn(HO)[Al(PO)], (II), were obtained in the form of single crystals during a single hydrothermal synthesis experiment. Their crystal structures were studied by X-ray diffraction. Both new compounds are members of the morphotropic series of phosphates with the following formulae: AM(HO)[PO], where A = K, NH, Rb or Na and M = Mn, Fe, Co or Ni, and AM(HO)[M(PO)], where A = Cs, Rb, K, NH or (HO); M = Mn, Fe, Co or Ni; and M = Al, Ga or Fe. A detailed crystal chemical analysis revealed correlations between the unit-cell parameters of the members of the series, their structural features and the sizes of the cations. It has been shown that a mixed type anionic framework is formed in (II) by aluminophosphate [(AlO)(PO)] layers, with a cationic topology similar to the Si/Al-topology of the crystal structures of feldspars. A study of the magnetic susceptibility of (II) demonstrates a paramagnetic behaviour of the compound.
在一次水热合成实验中，获得了两种新型钾/锰磷酸盐水合物单晶，即焦磷酸二氢三锰二钾水合物K₂Mn₃(PO₄)₂(OH)₂·2H₂O (I)和磷酸二氢铝锰钾水合物KMnAl₂(PO₄)₂(OH)₂·2H₂O (II)。通过X射线衍射研究了它们的晶体结构。这两种新化合物都是同构系列磷酸盐的成员，其通式如下：AM(OH)₂[PO₄]，其中A = K、NH₄、Rb或Na，M = Mn、Fe、Co或Ni；以及AM(OH)₂[M′(PO₄)₂]，其中A = Cs、Rb、K、NH₄或(HO)₃⁺；M = Mn、Fe、Co或Ni；M′ = Al、Ga或Fe。详细的晶体化学分析揭示了该系列成员的晶胞参数、结构特征与阳离子尺寸之间的相关性。结果表明，在(II)中由磷酸铝[(AlO₂)(PO₄)]层形成了一种混合型阴离子骨架，其阳离子拓扑结构类似于长石晶体结构的Si/Al拓扑结构。对(II)的磁化率研究表明该化合物具有顺磁性。
