Hydrothermal synthesis, structure characterization and catalytic property of a zigzag chain structural cluster compound built on the novel tetra-capped and centered by NiII

► A zigzag chain structural cluster compound, Ni0.5{[Ni(en)]2[Ni(en)(H2O)]2[H3NiMo6W6O40]}·3H2O 1 has been synthesized. ► Compound 1 exhibits an unusual Mo/W mixed NiII centered Keggin structure. ► Compound 1 shows high selectivity for benzaldehyde ca. 94.0%.