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Metronidazole(MTZ)is an important antibiotic,which has been widely applied to cure protozoal and bacterial diseases for human beings or animals.Herein,three novel drug supramolecular crystals constructed by MTZ with 2,5-dihydroxy-benzoic acid(2,5-DHBA)(1),2,6-dihydroxy-benzoic acid(2,6-DHBA)(2)and 3,5-dihydroxy-benzoic acid(3,5-DHBA)(3),respectively,have been discovered.The hydrogen bonds of N—H… O(O—H… N),C—H… O and O—H… O play important roles in the 3D supramolecular framework formation for crystals 1-3.Interestingly,due to the vary locations of the substituent groups,the two-dimensional layers in crystals 1 or 2 are constructed via intermolecular hydrogen bonds between MTZ and 2,5-DHBA or 2,6-DHBA,while in crystal 3 water molecules play a significant role except the intermolecular hydrogen bonds between MTZ and 3,5-DHBA.In addition,five synthons of Ⅰ R22(8),Ⅱ R33(9)in crystal 1,Ⅲ R21(4),Ⅳ R22(8)in crystal 2 and V R22(7)in crystal 3 formed through various hydrogen bonds are founded in this work.Systematic studies of syntheses,crystal structures and thermal analysis are reported.