Role of Chains in the Formation of Extended Framework Tin(II) Phosphates and Related Materials

Abstract

The reactions of tin(II) chloride with phosphonic and phosphinic acids under hydrothermal conditions result in structures with varying dimensionalities. The synthesis and characterization of eight new structures is described. SnCl(HPhPO 2 ), I, triclinic, P 1̄ (No. 2), has lattice parameters a = 5.4767(6) Å, b = 8.8106(9) Å, c = 9.5219(10) Å, α = 104.564(2)°, β = 95.440(2)°, γ = 99.349(2)°, and V = 434.34(8) Å 3 . (SnCl) 2 MePO 3, II, triclinic, P 1̄ (No. 2), has a = 4.7275(17) Å, b = 6.152(2) Å, c = 13.632(5) Å, α = 81.299(7)°, β = 89.052(7)°, γ = 89.781(7)°, and V = 391.8(3) Å 3 . Sn 2 Cl(EtPO 3 )EtPO 2 OH, III, monoclinic, P 2 1 / m (No. 11), has a = 4.814(4) Å, b = 8.530(4) Å, c = 15.214(8) Å, β = 99.09(10)°, and V = 616.9(7) Å 3 . β-SnEtPO 3, IV, monoclinic, Cc (No. 9), has a = 4.6415(13) Å, b = 18.695(5) Å, c = 6.4964(18) Å, β = 99.907(4)°, and V = 555.3(3) Å 3 . SnMePO 3, V, monoclinic, P 2 1 / c (No. 14), has a = 4.5998(7) Å, b = 15.430(2) Å, c = 6.5861(10) Å, β = 100.719(3)°, and V = 459.30(12) Å 3 . Sn 2 (O 3 P(CH 2 ) 2 PO 3 ), VI, monoclinic, P 2 1 / c (no. 14), has a = 4.6435(6) Å, b = 13.4512(16) Å, c = 6.4767(8) Å, β = 100.258(2)°, and V = 398.07(9) Å 3 . SnPO 3 CH 2 COOH, VII, monoclinic, P 2 1 / n (No. 14), has a = 5.490(2) Å, b = 4.890(2) Å, c = 21.884(9) Å, β = 90.505(7)°, and V = 587.4(4) Å 3 . (NH 4 ) 2 Sn(O 3 PCH 2 PO 3 ), VIII, orthorhombic, Pbca (No. 61), has a = 10.3417(10) Å, b = 10.0475(10) Å, c = 16.9927(17) Å, and V = 1765.7(3) Å 3 . For the first time, a three-ring (3R) phosphonate chain and an open-chain (i.e., no rings) phosphinate “wire” have been isolated. The phosphate analogues of these structures serve as key structural motifs in tin(II), zinc(II), and cobalt(II) phosphates, underscoring their role in the formation of framework phosphates. We propose that metal phosphate wires could play an important role in the formation of open-framework materials.