Two new supramolecular compounds based on arsenic vanadates formulated as H{sub 2}As{sub 6}V{sub 15}O{sub 42}(H{sub 2}O)Co(H{sub 2}O){sub 6}{sub 2}.2H{sub 2}O (1) and H{sub 2}As{sub 6}V{sub 15}O{sub 42}(H{sub 2}O)Ni(H{sub 2}O){sub 6}{sub 2}.2H{sub 2}O (2) have been prepared by reacting V{sub 2}O{sub 5}, H{sub 2}C{sub 2}O{sub 4}.2H{sub 2}O, As{sub 2}O{sub 3},.H{sub 2}SO{sub 4}, CoCl{sub 2}.6H{sub 2}O (NiSO{sub 4}.6H{sub 2}O) and enMe (enMe=1,2-diaminopropane) under mild hydrothermal conditions and characterized by elemental analyses, IR, ESR, XPS and single crystal X-ray diffraction analyses. Crystal structure analyses reveal that compounds 1 and 2 are isostructural and exhibit novel 2-D supramolecular layer structures constructed from arsenic-vanadium clusters and two different types of secondary building units (SBUs), respectively, the different SBUs are formed by joint of two adjacent Co(H{sub 2}O){sub 6}{sup 2+} cations in compounds 1 and Ni(H{sub 2}O){sub 6}{sup 2+} cations in 2, respectively. - Graphical abstract: Two novel hydrogen bond-supported supramolecular compounds H{sub 2}As{sub 6}V{sub 15}O{sub 42}(H{sub 2}O)Co(H{sub 2}O){sub 6}{sub 2}.2H{sub 2}O (1) and H{sub 2}As{sub 6}V{sub 15}O{sub 42}(H{sub 2}O)Ni (H{sub 2}O){sub 6}{sub 2}.2H{sub 2}O (2) have already been synthesized and characterized by X-ray diffraction analyses, they are isostructural and are constructed from arsenic-vanadium clusters and Co(H{sub 2}O){sub 6}{sup 2+} or Ni(H{sub 2}O){sub 6}{sup 2+} cations, respectively, Each of which exhibits novel 2-D supramolecular architecture.