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This paper aims to review recent advances on synthesis, crystal structures, thermal, spectroscopic, phase transitions, optical, dielectric, and catalysis properties of hydrate and anhydrous alkylenediammonium halogenometallates materials (Metal: Bi, Sb, Halogen: Cl, Br, I). These hybrid materials present rich structural diversities based on octahedra forming infinite zero dimensional, 1-dimensional chains, 2-dimensional layers, discrete bioctahedra, and discrete tetramer units. The effect, contribution and importance of hydrogen bonding N–H ... X (X: Cl, Br, I) are reviewed in terms of solid state relationship. Particularly, a comparative study is made on hydrate and anyhdrous aliphatic chlorobismuthates with alkylenediammonium +NH3(CH2)nNH3+ based on structural data and V/Z variation with (CH2)n chains (n = 2–8, 12), and variation of BiCl63− Raman frequencies modes versus (CH2)n chains (n = 3–8). Hydrate salts with (n = 3, 12) consist of isolated BiCl63− anions and two water molecules, against others ones with isolated anionic chains [BiCl52−]n or Bi2Cl104− dimers, formed by distorted octahedra BiCl63− sharing corners, vices or edges. The reviewed optical and electronic band gaps suggested interesting compounds with band gaps (1.85–2.4 eV), as suitable materials in optoelectronic properties, photoactive layer in solution-processed photovoltaics, and bio-imaging or photovoltaic applications. It was concluded that iodobismuthate salts have generally the lowest bands gap, compared to that of bromo and chlorobismuthate slats. Catalysis proprieties are reviewed n fast (RhB) degradation under dark conditions for (C4N2H7)4Bi2Cl10, (C5H9N2)BiI4, and {(H-BPA)4·[(BiI6)I13]·2I3}n, and in organic salts synthesis under solvent-free conditions. Herein NH3(CH2)nNH3BiCl5 (n = 5–7) salts were used as highly efficient catalysts, which is a novel tendency in chlorobismuthate researchs in the green chemistry field. [ABSTRACT FROM AUTHOR]

C19H16CuN6O5, triclinic, P 1 ‾ (no. 2), a = 9.0143(3) Å, b = 9.2122(3) Å, c = 11.8205(4) Å, α = 82.900(3)°, β = 74.593(3)°, γ = 83.612(3), V = 935.90(5) Å3, Z = 2, Rgt(F) = 0.0284, wRref(F2) = 0.0684, T = 293 K. [ABSTRACT FROM AUTHOR]

C10H16Cl4MnN2, monoclinic, P21 (no. 4), a = 7.28276(7) Å, b = 13.22972(12) Å, c = 8.01007(7) Å, β = 97.5018(9)°, V = 765.155(12) Å3, Z = 2, Rgt(F) = 0.0165, wRref(F2) = 0.0392, T = 123(2) K. [ABSTRACT FROM AUTHOR]