Abstract
The solid-state structures of the Na+, Li+, and NH4+ salts of the 4,5-di-hydroxy-benzene-1,3-di-sulfonate (tiron) dianion are reported, namely disodium 4,5-di-hydroxy-benzene-1,3-di-sulfonate, 2Na+·C6H4O8S22-, μ-4,5-di-hydroxy-benzene-1,3-di-sulfonato-bis-[aqua-lithium(I)] hemihydrate, [Li2(C6H4O8S2)(H2O)2]·0.5H2O, and di-ammonium 4,5-di-hydroxy-benzene-1,3-di-sulfonate monohydrate, 2NH4+·C6H4O8S22-·H2O. Inter-molecular inter-actions vary with the size of the cation, and the asymmetric unit cell, and the macromolecular features are also affected. The sodium in Na2(tiron) is coordinated in a distorted octa-hedral environment through the sulfonate oxygen and hydroxyl oxygen donors on tiron, as well as an inter-stitial water mol-ecule. Lithium, with its smaller ionic radius, is coordinated in a distorted tetra-hedral environment by sulfonic and phenolic O atoms, as well as water in Li2(tiron). The surrounding tiron anions coordinating to sodium or lithium in Na2(tiron) and Li2(tiron), respectively, result in a three-dimensional network held together by the coordinate bonds to the alkali metal cations. The formation of such a three-dimensional network for tiron salts is relatively rare and has not been observed with monovalent cations. Finally, (NH4)2(tiron) exhibits extensive hydrogen-bonding arrays between NH4+ and the surrounding tiron anions and inter-stitial water mol-ecules. This series of structures may be valuable for understanding charge transfer in a putative solid-state fuel cell utilizing tiron.
Highlights
Catechols play important roles across many areas of chemistry and biology
Catechols are key to the function of some marine bioadhesives (Lee et al, 2011); in one recent example, a protein in sessile marine organisms uses a cooperation between surface residues containing 3,4-dihydroxyphenylalanine (DOPA) and lysine to bind strongly to mineral surfaces (Rapp et al, 2016)
Tiron molecules can form a network through coordination of the counter-cation to the sulfonate or protonated or deprotonated hydroxide of the tiron (Cote & Shimizu, 2001, 2003; Sheriff et al, 2003; Guan & Wang, 2016, 2017). These networks can range from onedimensional networks, which form a linear polymer (Cote & Shimizu, 2003; Sheriff et al, 2003), to three-dimensional networks in which each tiron anion is coordinated to a metal cation and forms an interconnected lattice among all tiron anions in the crystal (Cote & Shimizu, 2001, 2003; Guan & Wang, 2016)
Summary
Catechols play important roles across many areas of chemistry and biology. Their rich coordination chemistry with metal ions (Pierpont & Lange, 1994; Sever & Wilker, 2004) emerges for example in siderophores (Boukhalfa & Crumbliss, 2002; Raymond et al, 2015; Springer & Butler, 2016). Tiron molecules can form a network through coordination of the counter-cation to the sulfonate or protonated or deprotonated hydroxide of the tiron (Cote & Shimizu, 2001, 2003; Sheriff et al, 2003; Guan & Wang, 2016, 2017) These networks can range from onedimensional networks, which form a linear polymer (Cote & Shimizu, 2003; Sheriff et al, 2003), to three-dimensional networks in which each tiron anion is coordinated to a metal cation and forms an interconnected lattice among all tiron anions in the crystal (Cote & Shimizu, 2001, 2003; Guan & Wang, 2016). This species is the first tiron salt which utilizes a counter-cation capable of hydrogen bond (H-bond) donation to allow for a complex H-bonding network
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