Trimer formation of 6-methyl-1,3,5-triazine-2,4-diamine in salt with organic and inorganic acids:analysis of supramolecular architecture  

作　　者：XIAO Zhen Yu WANG Wen Qiang XUE Rui Yu ZHAO Lei WANG Lei ZHANG YiHeng 

机构地区：[1]College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology

出　　处：《Science China Chemistry》2014年第12期1731-1737,1-2,共7页中国科学（化学英文版）

基　　金：financially supported by the National Natural Science Foundation of China(51372125,21176128,21203106);the Natural Science Foundation of Shandong Province(BS2010CL019,ZR2011BL015)

摘　　要：Although the numbers of co-crystals,salts,polymorphs,hydrates,and solvates are growing steadily,trimers that contain both inorganic and organic acids are still very rare in the Cambridge Structural Database(CSD).When 3,5-dihydroxybenzoic acid was crystallized readily with 6-methyl-1,3,5-triazine-2,4-diamine in a 4:3 ratio of ethanol and water by adding a few drops of nitric acid upon slow evaporation in ambient conditions,6-methyl-1,3,5-triazine-2,4-diamine and 3,5-dihydroxybenzoic acid with the nitric acid form of 1:1:1 an inorganic-organic salt formulated as[(C4H8N5+)·(NO3-)·(C7H6O4)].The supramolecular architecture,which is quite elegant and simple,appeared as stacking of a 3D network in adduct.Proton transfer from the HNO3to 6-methyl-1,3,5-triazine-2,4-diamine N acceptor(triazine N)occurred in the organic salt and led to the ionic heterosynthon in the structure.Cooperation among the–COOH,–OH,NO3–,and–NH–functional groups for the observed hydrogen bond synthon was examined in the structure.In adduct,recognition among the constituents is established through N–H···O,O–H···N,and O–H···O hydrogen bonds.The agomelatine molecules are linked through the intermolecular hydrogen bonding interactions(O–H···O)to form a 1D chain.In addition,the nitric acid anions and base cations act as donors and acceptors of hydrogen bonds and interlink,almost to co-planarity,the hydrogen-bonded chains through interchain N–H···O,O–H···N,as well as O–H···O interactions into a 2D sheet structure.Persistent N–H···O interactions were found to play an important role in the formation of the final 3D array.The salt was characterized by elemental analysis,IR,thermogravimetric analysis,and singlecrystal X-ray diffraction,to better understand how intermolecular interactions influence its supramolecular assembly.Although the numbers of co-crystals,salts,polymorphs,hydrates,and solvates are growing steadily,trimers that contain both inorganic and organic acids are still very rare in the Cambridge Structural Database（CSD）.When 3,5-dihydroxybenzoic acid was crystallized readily with 6-methyl-1,3,5-triazine-2,4-diamine in a 4：3 ratio of ethanol and water by adding a few drops of nitric acid upon slow evaporation in ambient conditions,6-methyl-1,3,5-triazine-2,4-diamine and 3,5-dihydroxybenzoic acid with the nitric acid form of 1：1：1 an inorganic-organic salt formulated as[（C4H8N5＋）·（NO3-）·（C7H6O4）].The supramolecular architecture,which is quite elegant and simple,appeared as stacking of a 3D network in adduct.Proton transfer from the HNO3to 6-methyl-1,3,5-triazine-2,4-diamine N acceptor（triazine N）occurred in the organic salt and led to the ionic heterosynthon in the structure.Cooperation among the–COOH,–OH,NO3–,and–NH–functional groups for the observed hydrogen bond synthon was examined in the structure.In adduct,recognition among the constituents is established through N–H···O,O–H···N,and O–H···O hydrogen bonds.The agomelatine molecules are linked through the intermolecular hydrogen bonding interactions（O–H···O）to form a 1D chain.In addition,the nitric acid anions and base cations act as donors and acceptors of hydrogen bonds and interlink,almost to co-planarity,the hydrogen-bonded chains through interchain N–H···O,O–H···N,as well as O–H···O interactions into a 2D sheet structure.Persistent N–H···O interactions were found to play an important role in the formation of the final 3D array.The salt was characterized by elemental analysis,IR,thermogravimetric analysis,and singlecrystal X-ray diffraction,to better understand how intermolecular interactions influence its supramolecular assembly.

关 键 词：SUPRAMOLECULAR hydrogen bonds crystal structure SALT 

分 类 号：O641.3[理学—物理化学]