Two New Polyoxovanadate‐supported Transition Metal Complexes: [Zn(en)2][Zn(en)2(H2O)2][{Zn(en)(enMe)}As6V15O42(H2O)]·4H2O and [Zn2(enMe)2(en)3][{Zn(enMe)2}As6V15O42(H2O)]·4H2O

Two novel As‐V‐O cluster supported transition metal complexes, Zn(en)₂]Zn(en)₂(H₂O)₂]{Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 1 ) and Zn₂(enMe)₂(en)₃]{Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 2 ), have been hydrothermally synthesized. The single X‐ray diffraction studies reveal that both compounds consist of discrete noncentral polyoxoanions {Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]^4? or {Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]^4? cocrystallized with respective zinc coordination complexes. Interestingly, compounds 1 and 2 exhibit the first two polyoxovanadates containing As₈V₁₅O₄₂‐(H₂O)]^6? cluster decorated by only one transition metal complex. Crystal data: 1 , monoclinic, P2₁/n, a = 14.9037(4) Å, b = 18.1243(5) Å, c = 27.6103(7) Å, β = 105.376(6)°, Z = 4; 2 monoclinic, P2₁/n, a = 14.9786(7) Å, b = 33.0534(16) Å, c = 14.9811(5) Å, Z = 4.