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Hydrogen‐bonded assemblies in the molecular crystals of 2,2′‐thiodiacetic acid with ethylenediamine and o ‐phenylenediamine
Author(s) -
Gomathi V.,
Theivarasu C.
Publication year - 2017
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s2053229617000559
Subject(s) - supramolecular chemistry , hydrogen bond , ethylenediamine , chemistry , crystallography , crystal engineering , crystal structure , carboxylate , ligand (biochemistry) , stereochemistry , molecule , inorganic chemistry , organic chemistry , biochemistry , receptor
Carboxylate molecular crystals have been of interest due to the presence of hydrogen bonding, which plays a significant role in chemical and crystal engineering, as well as in supramolecular chemistry. Acid–base adducts possess hydrogen bonds which increase the thermal and mechanical stability of the crystal. 2,2′‐Thiodiacetic acid (Tda) is a versatile ligand that has been widely explored, employing its multidendate and chelating coordination abilities with many metals; however, charge‐transfer complexes of thiodiacetic acid have not been reported. Two salts, namely ethylenediaminium 2,2′‐thiodiacetate, C 2 H 10 N 2 2+ ·C 4 H 4 O 4 S 2 2− , denoted Tdaen, and 2‐aminoanilinium 2‐(carboxymethylsulfanyl)acetate, C 6 H 9 N 2 + ·C 4 H 5 O 4 S − , denoted Tdaophen, were synthesized and characterized by IR, 1 H and 13 C NMR spectroscopies, and single‐crystal X‐ray diffraction. In these salts, Tda reacts with the aliphatic (ethylenediamine) and aromatic ( o ‐phenylenediamine) diamines, and deprotonates them to form anions with different valencies and different supramolecular networks. In Tdaen, the divalent Tda 2− anions form one‐dimensional linear supramolecular chains and these are extended into a three‐dimensional sandwich‐type supramolecular network by interaction with the ethylenediaminium cations. However, in Tdaophen, the monovalent Tda − anions form one‐dimensional zigzag supramolecular chains, which are extended into a three‐dimensional supramolecular network by interaction with the 2‐aminoanilinium cations. Thus, both three‐dimensional structures display different ring motifs. The structures of these diamines, which are influenced by hydrogen‐bonded assemblies in the molecular crystals, are discussed in detail.