Ji, Bao-Ming Deng, Dong-Sheng Ma, Ning Miao, Shao-Bin Yang, Xiao-Gang Ji, Li-Guo Du, Miao Multicomponent Hydrogen-Bonding Salts Constructed from Tris(2-benzimidazylmethyl)amine and Various Carboxylic Acids: Role of Benzimidazolium-Carboxylate Supramolecular Heterosynthons on Network Assembly A survey of the Cambridge Structural Database (CSD) indicates that 79% of complexes that contain both imidazole and carboxyl groups generate imidazolium-carboxylate supramolecular heterosynthons rather than carboxyl or imidazole supramolecular homosynthons. In the absence of other competing factors, the occurrence of such heterosynthons is increased to 100%. This observation is further supported by the crystal structures of seven new complexes that contain tris(2-benzimidazylmethyl)amine (TBMA) and a variety of carboxylic acids, including benzoic acid (HBA), <i>p</i>-methoxybenzoic acid (HPMBA), phthalic acid (H<sub>2</sub>PA), terephthalic acid (H<sub>2</sub>TPA), isophthalic acid (H<sub>2</sub>PIA), trimesic acid (H<sub>3</sub>TMA), and pyromellitic acid (H<sub>4</sub>PMA). In all seven complexes, (H<sub>2</sub>TBMA)·(BA)<sub>2</sub>·DMF (<b>1</b>), (HTBMA)·(PMBA)·(TBMA)·(HPMBA)<sub>2</sub>·2DMF·H<sub>2</sub>O (<b>2</b>), (HTBMA)·(H<sub>2</sub>TBMA)·(HPA)·(PA)·3DMF·H<sub>2</sub>O (<b>3</b>), (HTBMA)<sub>2</sub>·(TPA)·2DMF (<b>4</b>), (HTBMA)<sub>2</sub>·(PIA)·2DMF (<b>5</b>), (H<sub>2</sub>TBMA)·(HTMA)·0.5DMF·H<sub>2</sub>O (<b>6</b>), and (HTBMA)<sub>2</sub>·(H<sub>2</sub>PMA)·2DMF·H<sub>2</sub>O (<b>7</b>), proton transfer occurs from acid to aromatic nitrogen of benzimidazole (partial proton transfer for <b>3</b>, <b>6</b>, and <b>7</b>). Analysis of the H-bonding synthons and their effect on crystal packing is also presented in the context of crystal engineering and host−guest chemistry. In the structure of <b>1</b>, discrete acid/base hexamers are formed via synthons <b>III</b>, <b>V</b>, and <b>VI</b>, while in <b>2</b>−<b>5</b>, self-recognition via synthons <b>IV</b>, <b>V</b>, and <b>VI</b> results in one-dimensional (1-D) chains, and these structures are extended to high-dimensional architectures (two-dimensional (2-D) structures in <b>3</b> and three-dimensional (3-D) structures in <b>2</b>, <b>4</b>, and <b>5</b>) via additional C−H···O, C−H···π and π···π interactions. Interestingly, salts <b>6</b> and <b>7</b> display the 3-D supramolecular networks via synthons <b>III</b>, <b>IV</b>, <b>V</b>, and <b>VI</b>, which have 1-D channels that are occupied by DMF guests. synthons III;Various Carboxylic Acids;Network AssemblyA survey;H 2TPA isophthalic acid;H 2PIA trimesic acid;3TMA;imidazole supramolecular homosynthons;HBA;HPMBA;H 2PA terephthalic acid;CSD;TBMA;DMF;4PMA;HTBMA;2TBMA;VI;IV;Cambridge Structural Database 2010-07-07
    https://acs.figshare.com/articles/dataset/Multicomponent_Hydrogen_Bonding_Salts_Constructed_from_Tris_2_benzimidazylmethyl_amine_and_Various_Carboxylic_Acids_Role_of_Benzimidazolium_Carboxylate_Supramolecular_Heterosynthons_on_Network_Assembly/2754499
10.1021/cg100177n.s006