Inorganic−Organic Framework Structures; M(II) Ethylenediphosphonates (M = Co, Ni, Mn) and a Mn(II) Ethylenediphosphonato-phenanthroline

The reaction of nickel, cobalt, and manganese with 1,2-ethylenediphosphonic acid or 1,2-ethylenediphosphonic
acid and 1,10-phenanthroline under hydrothermal conditions resulted in the pillared layered structures Co2(H2O)2(O3PC2H4PO3) (I) and Ni2(H2O)2(O3PC2H4PO3) (II), which are isostructural to a zinc phase that has previously been
characterized by X-ray powder methods. In addition, a 1D chain structure, Mn(HO3P(CH2)2PO3H)(H2O)2(C12H8N2)
(III), and a pillared layered structure, Mn(HO3P(CH2)2PO3H) (IV), were obtained. The structures of these phases
were solved by single-crystal X-ray diffraction methods. The crystallographic data are as follows:  compound I
P21/n (No. 14), a = 5.6500(11) Å, b = 4.7800(10) Å, c = 15.330(3) Å, β = 98.50(3)°, V = 409.47(14) Å3, Z =
2; compound II P21/n (No. 14), a = 5.5807(11) Å, b = 4.7205(9) Å, c = 15.250(3) Å, β = 98.55(3)° , V =
397.28(13) Å3, Z = 2; compound III C2/c (No. 15), a = 12.109(2) Å, b = 15.328(3) Å, c = 9.848(2) Å, β =
108.88(3)°, V = 1729.5(6) Å3, Z = 4; compound IV P1̄ (No. 2), a = 5.498(5) Å, b = 7.715(6) Å, c = 8.093(7)
Å, α = 82.986(12)°, β = 75.565(12)°, γ = 80.582(12)°, V = 326.7(5) Å3, Z = 2. Magnetic measurements show
antiferromagnetic behavior below TN = 7 K for I and 13 K for II.