The borophosphate family incorporates compounds with crystal structures ranging from densely packed to microporous.We have synthesized several transition metal borophosphates with alkali-metal cations and determined their crystal structures using single-crystal X-ray diffraction at 100 K. Crystal chemical interpretations of studied phases in correlation with literature data has allowed us to reveal some new features in title group of compounds. One among them presents a tendency of subsistence of phosphate archetypes for borophosphate phases. The borato-phosphate mineral seamanite, Mn3(OH)2[B(OH)4][PO4] has a synthetic phosphate analogue, Na2Fe3(OH)2[PO4][PO4]. We found a novel structural type of cubic microporous borophosphates that realizes in the framework of two compositions: KNi5[P6B6O23(OH)13] (an ordered phase) and Na0.45K(Mg,Ni,Al)Ni2(Ni,Al,Mg2)2[P6B6O24(OH)12] (a disordered phase having isomorphous and vacancy defects). We have shown that these borophosphates are topologically related to the cyclophosphates Cs3M3(PO3)12 (M = V or In) and NaM(PO3)3 (M = Zn or Mg) as parent structures. A zeolite-type material “CZP” - Na[Zn(PO4)](H2O) is also known as archetype for some borophosphates, namely, A+xM(H2O)2(BP2O8)(H2O), (A = Na, K, Ca, and M = Zn, Co, Ni, Fe, Mn, Cd, Sc, In). In connection with compounds having general formula A+{M3+[BP2O8(OH)]} (A: K, NH4, Rb Cs; octahedral position M: Al, Ga, Fe, Sc, In) we showed that the polymorphism of the [BP2O8(OH)]4- anion has a morphotropic nature and is related to substitutions both in the cationic part of the structure and in the octahedral position of mixed anionic framework.
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