The first non-centrosymmetric polyoxometallate with organic cations and the beta-isomer of Anderson-type POM clusters, (C7H12N2)(7)[beta-SbMo6O24](2)center dot 8H(2)O (1), has been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, infrared, ultraviolet spectroscopy and cyclic voltammetry. This compound crystallized in the monoclinic system, space group P2(1), with a = 12.4806(4) angstrom, b = 22.9845(6) angstrom, c = 17.2853(5) angstrom, beta = 110.6(degrees) and Z = 2. The crystal structures of the compounds exhibit three-dimensional supramolecular assembly based on the extensive hydrogen bonding interactions between organic cations, water molecules and Anderson polyoxoanions. The infrared spectrum fully confirms the X-ray crystal structure and the UV spectrum of the title compound exhibits two absorption peaks at 196 nm and 260 nm. Hirshfeld surface analyses, especially d(norm) surface and fingerprint plots were used for decoding intermolecular interactions in the crystal network. (C) 2018 Elsevier B.V. All rights reserved.