Thermodynamic nature of the magnetic transitions of a cyano-bridged W(V)-Cu(II) compound of [W(CN)(8)](4)[Cu(pn)H(2)O](4)[Cu(pn)](2) 2 5H(2)O is studied by low-temperature heat capacity measurements Distinct thermal anomalies were observed in the temperature dependence of the heat capacity at 7 8 K for chiral compound (S-enantiomer) and 7 2 K for racemic compound They are associated with the antiferromagnetic transitions reported by the previous magnetization measurements In the case of S-enantiomer a shoulder structure of C(p)/T has been observed just below the main peak of the antiferromagnetic transition temperature at 0 T The shoulder grows to a sharp anomaly with a first order character by applying magnetic field of about 1 T in the b-axis direction On the other hand just a broadening of the peak was observed for racemic compound which means that the complicated behavior under magnetic field is derived from the crystallographic chirality We also studied the behavior of S-enantiomer with magnetic fields applied parallel to the c-axis and found that the first order transition is not induced Appearance of the complicated peak structure including the first order character specific in the b-direction is ascribed to peculiar magnetic ordering derived from crystallographic chirality related to the Dzyaloshinskii-Moriya (DM) interaction (C) 2010 Elsevier B V All rights reserved