Three-dimensional supramolecular architecture based on 4,4'-methylene-bis(benzenamine) and aromatic carboxylic acid guests:Synthons cooperation,robust motifs and structural diversity  

作　　者：WANG Lei ZHAO Lei LIU Meng LIU FaQian XIAO Qiang HU ZhiQiang 

机构地区：[1]College of Chemistry and Molecular Engineering,Qingdao University of Science and Technology,Qingdao 266042,China [2]Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces,Zhejiang Normal University,Jinhua 321004,China

出　　处：《Science China Chemistry》2012年第12期2523-2531,共9页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(20701023 and 21172127);the Natural Science Foundation of Shandong Province,China(BS2010NJ004, 2009ZRB019KH)

摘　　要：The two-component solid forms involving 4,4'-methylene-bis(benzenamine) included both salts and co-crystals,while 4,4'methylene-bis(benzenamine) crystallized exclusively as a salt,in agreement with the differences in the pK a values.Many of the crystal structures displayed either the neutral or the ionic form of the carboxylic acid-amino heterosynthon,and the similarity in crystal structures between the neutral and the ionized molecules makes the visual distinction between a salt and co-crystal dependent on the experimental location of the acidic proton.A variety of supramolecular hydrogen bonded motifs involving interactions between the aza molecules and carboxylic acid groups are observed rather than just the O-H···N/O-H···O motif.The motifs are identical in all the two compounds analyzed showing the robustness of these supramolecular synthons.In all adducts,recognition between the constituents is established through either N-H···O and/or O-H···O/O-H···N pairwise hydrogen bonds.In all adducts,COOH functional groups available on 1 and 2 interact with the N-donor compounds.The COOH moieties in 1 forms only single N-H···O hydrogen bonds,whereas in 2,it forms pairwise O-H···N/N-H···O hydrogen bonds.The supramolecular architectures are elegant and simple,with stacking of networks in 2,but a rather complex network with a threefold interpenetration pattern was found in 1.Thermal stability of these compounds has been investigated by thermogravimetric analysis(TGA) of mass loss.The two-component solid forms involving 4,4＇-methylene-bis（benzenamine） included both salts and co-crystals, while 4,4＇- methylene-bis（benzenamine） crystallized exclusively as a salt, in agreement with the differences in the pKa values. Many of the crystal structures displayed either the neutral or the ionic form of the carboxylic acid-amino heterosynthon, and the similarity in crystal structures between the neutral and the ionized molecules makes the visual distinction between a salt and co-crystal dependent on the experimental location of the acidic proton. A variety of supramolecular hydrogen bonded motifs involving interactions between the aza molecules and carboxylic acid groups are observed rather than just the O-H-..N/O-H...O motif. The motifs are identical in all the two compounds analyzed showing the robustness of these supramolecular synthons. In all adducts, recognition between the constituents is established through either N-H-＂O and/or O-H..-O/O-H---N pairwise hydro- gen bonds. In all adducts, COOH functional groups available on 1 and 2 interact with the N-donor compounds. The COOH moieties in 1 forms only single N-H...O hydrogen bonds, whereas in 2, it forms pairwise O-H..N/N-H-O hydrogen bonds. The supramolecular architectures are elegant and simple, with stacking of networks in 2, but a rather complex network with a threefold interpenetration pattern was found in 1. Thermal stability of these compounds has been investigated by thermogravimetric analysis （TGA） of mass loss.

关 键 词：crystal structure salt CO-CRYSTAL supramolecular synthons 4 4＇-methylene-bis（benzenamine） 

分 类 号：TQ244.1[化学工程—有机化工] S562.01[农业科学—作物学]