Template Syntheses of Two Open‐framework Zinc Phosphites

Two new open‐framework zincophosphites, Zn(H₆C₄N₂S)(HPO₃) (TJPU‐4) and [C₆N₂H₁₄]·[Zn₃(HPO₃)₄] (TJPU‐5) have been hydrothermally synthesized by using 2‐mercapto‐1‐methylimidazole [MMI] and 1,4‐diazabicyclo[2.2.2]octane [DABCO] as templates. TJPU‐4 crystallizes in monoclinic space group P2₁/c with the cell parameters a = 8.787(4) Å, b = 9.732(4) Å, c = 10.515(4) Å, β = 105.316(6)°, V = 867.3(6) ų. The structure of TJPU‐4 is constructed by ZnO₃S tetrahedron and HPO₃ pseudo‐pyramid to generate a layer of 4, 8‐network in bc plane. The organic template locates on the both sides of the 8‐membered rings and bonds to zinc atom through Zn–S bond. TJPU‐5 crystallizes in the triclinic space group with cell parameters a = 9.294 (5) Å, b = 9.976 (5) Å, c = 9.986 (5) Å, α = 85.692 (7)°, β = 82.010 (7)° and γ = 80.184 (7)°, V = 902.1 (8) ų. A novel 4⁴8⁸ cage is found in TJPU‐5. The connections of Zn(1)O₄, Zn(3)O₄ and HPO₃ groups give rise to an infinite corner‐shared four‐ring chain. Using Zn(2)O₄ as four connected bridges, linkages of these chains produce a 3‐D framework with intersecting 8‐ring channels running along [100], [010], [001], [011] and [111] directions.