Hydrothermal Synthesis of New Organically Templated Beryllium Phosphite and Phosphate with 3,4‐connected Networks

Two organically templated beryllium phosphite and phosphate, [H 2 tmpda][Be 3 (HPO 3 ) 4 ] ( 1 ) and [H 2 ampy][Be 3 (HPO 4 ) 4 ] ( 2 ) [tmpda = N,N,N′,N′ ‐tetramethyl‐1,3‐propanediamine, ampy = 3‐(aminomethyl)pyridine], were synthesized and structurally characterized. Compound 1 exhibits a (3,4)‐connected layered structure with eight‐ring windows, and it has a 4 4 grid topology by regarding the heptameric [Be 3 (HPO 3 ) 4 ] group as a 4‐connected node in the layer. Compound 2 possesses a different (3,4)‐connected three‐dimensional framework with multidirectional 8‐ring channels and zigzag 12‐ring channels. This 3D architecture shows a pcu topology when the heptameric [Be 3 (HPO 4 ) 4 ] groups are regarded as 6‐connected secondary building units. Crystal data: 1 , monoclinic, P 21/ m , a = 8.0217(6) Å, b = 13.7969(5) Å, c = 8.6581(2) Å, β = 92.315(3)°, V = 957.45(8) Å 3 , Z = 2, R 1 = 0.0761, wR 2 = 0.1640; 2 , monoclinic, P 21/ n , a = 7.5292(5) Å, b = 14.0999(8) Å, c = 16.5910(3) Å, β = 95.740(3)°, V = 1752.49(16) Å 3 , Z = 4, R 1 = 0.0434, wR 2 = 0.1017.