Water Superstructures within Organic Arrays; Hydrogen‐Bonded Water Sheets, Chains and Clusters

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Abstract
A strategy for encouraging the formation of extended water arrays is presented, in which molecules that contain a 1,4‐dihydroquinoxaline‐2,3‐dione core are used as supramolecular hosts for the accommodation of guest water molecules and arrays. These molecules were selected as they contain a hydrophilic oxalamide‐based “terminus” that allows water molecules to hydrogen‐bond to the host organic molecules as well as to each other. The host molecules also contain a hydrophobic “end” based upon an aromatic ring, which serves to encourage the formation of discrete water clusters in preference to three‐dimensional networks, as the water molecules cannot form strong hydrogen bonds with this part of the molecule. A systematic study of several hydrated structures of four organic molecules based on 1,4‐dihydroquinoxaline‐2,3‐dione (qd) is discussed. The organic molecules, qd, 6‐methyl‐1,4‐dihydroquinoxaline‐2,3‐dione (mqd), 6,7‐dimethyl‐1,4‐dihydroquinoxaline‐2,3‐dione (dmqd) and 1,4‐dihydrobenzo[g]quinoxaline‐2,3‐dione (Phqd), act as supramolecular crystal hosts for the clusters of water, with zero‐, one‐ and two‐dimensional arrays of water being observed. The hydrogen bonding in the structures, both within the water clusters and between the clusters and organic molecules, is examined. In particular, the structure of dmqd⋅6 H2O contains a two‐dimensional water sheet composed of pentagonal and octagonal units. Phqd⋅3 H2O forms a hydrophilic extended structure encouraging the formation of one‐dimensional chains consisting entirely of water. Both qd⋅2 H2O and dmqd⋅2 H2O can be considered to form one‐dimensional chains, but only by utilising bridging carbonyl groups of the oxalamide moieties to form the extended array; if only the water is considered, zero‐dimensional water tetramers are observed. The remaining hydrated structures, [Na+dmqd−]dmqd⋅H2O, dmqd⋅1/3H2O and mqd⋅1/2H2O, all contain discrete water molecules but do not form extended water structures.