We have performed a study of the structure and energetics of some chlorohydroxypyridines based on experimental calorimetry techniques and high level ab initio computational calculations. The standard (p degrees = 0.1 MPa) molar enthalpies of formation of 2-chloro-3-hydroxypyridine (2-Cl-3-OHPy), 2-chloro-6-hydroxypyridine (2-Cl-6-OHPy) and 3-chloro-5-hydroxypyridine (3-Cl-5-OHPy) in the crystalline phase, at T = 298.15 K, were derived from the respective standard massic energies of combustion measured by rotating-bomb combustion calorimetry, in oxygen, at T = 298.15 K. The standard molar enthalpies of sublimation, at T = 298.15 K, were measured by Calvet microcalorimetry. From these experimentally determined enthalpic parameters we have derived the standard molar enthalpies of formation of the three compounds in the gaseous phase, at T = 298.15 K: 2-Cl-3-OHPy, -(76.8 +/- 2.0) kJ . mol(-1); 2-Cl-6-OHPy, -(105.0 +/- 1.7) kJ . mol(-1), 3-Cl-5-OHPy -(61.2 +/- 2.4) kJ . mol(-1). These values were compared with estimates obtained from very accurate computational calculations using the G3(MP2)//B3LYP composite method and appropriately chosen reactions. These calculations have also been extended to the remaining chloro hydroxypyridine isomers that were not studied experimentally. Based on B3LYP/6-31G* optimized geometries and calculated G3(MP2)//B3LYP absolute enthalpies some structure-energy correlations were discussed. (c) 2013 Elsevier Ltd. All rights reserved.