The crystal structure, the C-13 NMR spectroscopy and the complex impedance have been carried out on [Cd-3(SCN)(2)Br-6(C2H9N2)(2)](n). Crystal structure shows a 2D polymeric network built up of two crystallographically independent cadmium atoms with two different octahedral coordinations. This compound exhibits a phase transition at (T=355 +/- 2 K) which has been characterized by differential scanning calorimetry (DSC), X-rays powder diffraction, AC conductivity and dielectric measurements. Examination of C-13 CP/MAS line shapes shows indirect spin-spin coupling (N-14 and C-13) with a dipolar coupling constant of 1339 Hz. The AC conductivity of this compound has been carried out in the temperature range 325-376 K and the frequency range from 10(-2) Hz to 10 MHz. The impedance data were well fitted to two equivalent electrical circuits. The results of the modulus study reveal the presence of two distinct relaxation processes. One, at low frequency side, is thermally activated due to the ionic conduction of the crystal and the other, at higher frequency side, gradually disappears when temperature reaches 355 K which is attributed to the localized dipoles in the crystal. Moreover, the temperature dependence of DC-conductivity in both phases follows the Arrhenius law and the frequency dependence of sigma(omega,T) follows Jonscher's universal law. The near values of activation energies obtained from the conductivity data and impedance confirm that the transport is through the ion hopping mechanism. (C) 2013 Elsevier Ltd. All rights reserved.