Symmetry and topology code of the cluster self-assembly of framework MT structures of alumophosphates AlPO4(H2O)2 (metavariscite and variscite) and Al2(PO4)2(H2O)3 (APC)

The supramolecular chemistry of alumophosphates, which form framework 3D MT structures from polyhedral AlО 4 (Н 2 О) 2 clusters with octahedral O coordination (of M polyhedra) and PO 4 and AlO 4 with tetrahedral O coordination (of T polyhedra), is considered. A combinatorial–topological modeling of the formation of possible types of linear (six types) and ring (two types) tetrapolyhedral cluster precursors М 2 Т 2 from MT monomers is carried out. Different versions of chain formation from linked (MT) 2 rings (six types) are considered. The model, which has a universal character, has been used to simulate the cluster selfassembly of the crystal structure of AlPO 4 (H 2 O) 2 minerals (metavariscite, m -VAR, and variscite, VAR) and zeolite [Al 2 (P O4 ) 2 (H 2 O) 2 ] · H 2 O (APC). A tetrapolyhedral linear precursor is established for m -VAR and a ring precursor (MT) 2 is established for VAR and APC. The symmetry and topology code of the processes of crystal structure self-assembly from cluster precursors is completely reconstructed. The functional role of the O–H···O hydrogen bonds is considered for the first time. The cluster self-assembly model explains the specific features of the morphogenesis of single crystals: m -VAR prisms, flattened VAR octahedra, and needleshaped APC square-base prisms.