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Three new inorganic-organic composite polyoxotungstates [Cu(2,2ˊ-bpy)2]5[α-PW11.5Cu0.5O40]·2H2O 1, [Co(2,2ˊ-bpy)2(N3)2]4H3[α-PW12O40]·3H2O 2 and [Cu(2,2ˊ-bpy)2(4,4ˊ-bpy)]2[α-GeW12O40]·4H2O 3 (2,2ˊ-bpy = 2,2ˊ-bipyridine, 4,4ˊ-bpy = 4,4ˊ-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the orthorhombic space group Pna21 with a = 27.847(3), b = 21.597(2), c = 20.1179(19) , V = 12099(2) 3, Z = 4, GOF = 1.038, R = 0.0427 and wR = 0.1035; 2 belongs to the triclinic space group P1 with a = 12.31150(10), b = 16.1954(4), c = 19.36290(10) , α = 99.366(11), β =105.168(8), γ = 111.836(8)°, V = 3309.98(9) 3, Z = 1, GOF = 1.024, R = 0.0739 and wR = 0.2216; and 3 crystallizes in the monoclinic space group P21/n with a = 12.858(4), b = 20.943(6), c = 15.598(5) , β = 102.338(5)°, V = 4103(2) 3, Z = 2, GOF = 1.026, R = 0.0557 and wR = 0.1316. The common structural features of 1～3 are that their molecular structures all consist of a saturated α-Keggin polyoxoanion and several discrete metal-organic moieties. Intriguingly, 2 and 3 are composed of metal-organic coordination moieties with two mixed ligands.
Three new inorganic-organic composite polyoxotungstates [Cu (2,2’-bpy) 2] 5 [α-PW11.5Cu0.5O40] · 2H2O 1 [Co (2,2’-bpy) 2 (N3) 2] -PW12O40] 3H2O 2 and [Cu (2,2’-bpy) 2 (4,4’-bpy)] 2 [α-GeW12O40] · 4H2O 3 (2,2’-bpy = 2,2’-bipyridine, 1 crystallizes in the orthorhombic space group Pna21 with a = 27.847 (3), b = 21.597 (2), c = 20.1179 19, V = 12099 (2) 3, Z = 4, GOF = 1.038, R = 0.0427 and wR = 0.1035; 2 belongs to the triclinic space group P1 with a = 12.31150 (10), b = 16.1954 (4), c = 19.36290 Α = 99.366 (11) β = 105.168 (8) γ = 111.836 (8) ° V = 3309.98 3 Z = 1 GOF = 1.024 R = 0.0739 and wR = 0.2216 ; and 3 crystallizes in the monoclinic space group P21 / n with a = 12.858 (4), b = 20.943 (6), c = 15.598 (5) β, β = 102.338 (5) °, V = 4103 3, Z = 2, GOF = 1.026, R = 0.0557 and wR = 0.1316. The common structural features of 1 to 3 are that their molecular structures all consist of a saturated α-Keggin polyoxoanion and several discrete metal-organic moieties. Intriguingly, 2 and 3 are composed of metal-organic coordination moieties with two mixed ligands.