Disulfonated azo dyes: metal coordination and ion-pair separation in twelve M II compounds of Ponceau Xylidine and Crystal Scarlet

The structures of seven divalent metal cation compounds of Ponceau Xylidine {PX; systematic name of dication: 4-[2-(3,4-dimethylphenyl)hydrazin-1-ylidene]-3-oxo-3,4-dihydronaphthalene-2,7-disulfonate}, also known as Acid Red 26, CI 16150, and of five divalent metal cation compounds of Crystal Scarlet {CS; systematic name of dication: 8-[2-(naphthalen-1-yl)hydrazin-1-ylidene]-7-oxo-7,8-dihydronaphthalene-1,3-disulfonate}, also known as Acid Red 44, CI 16250, are presented. These are hexaaquamagnesium(II) PX dimethylformamide (DMF) monosolvate, [Mg(H O) ](C H N O S )·C H NO, (I); heptaaquacalcium(II) PX 2.5-hydrate, [Ca(H O) ](C H N O S )·2.5H O, (II); catena-poly[aqua(μ-DMF)tris(DMF)bis(μ -PX)distrontium(II)], [Sr(C H N O S )(C H NO) (H O) ] , (III); the transition-metal series hexaaquametal(II) PX DMF monosolvate, [M(H O) ](C H N O S )·C H NO, where M (metal) = Co, (IV), Ni, (V), Cu, (VI), and Zn, (VII); heptaaquacalcium(II) CS monohydrate, [Ca(H O) ](C H N O S )·H O, (VIII); octaaquastrontium(II) CS monohydrate, [Sr(H O) ](C H N O S )·H O, (IX); catena-poly[[triaqua(DMF)barium(II)]-μ-CS], [Ba(C H N O S )(C H NO)(H O) ] , (X); tetrakis(DMF)(CS)copper(II) monohydrate, [Cu(C H N O S )(C H NO) ]·H O, (XI); and catena-poly[[[aquatris(DMF)zinc(III)]-μ-CS] diethyl ether hemisolvate], {[Zn(C H N O S )(C H NO) (H O)]·0.5C H O} , (XII). In all cases, the structures obtained were solvates with dimethylformamide (DMF) and/or water present. The disulfonated naphthalene-based azo anions adopt hydrazone tautomeric forms. The structures of the Mg salt and of four transition-metal forms (M = Co, Ni, Cu and Zn) of PX are found to form an isostructural series. All have solvent-separated ion-pair (SSIP) type structures and the formula [M(H O) ][PX]·DMF. The Ca salt of PX also has an SSIP structure, but has a higher hydration state, [Ca(H O) ][PX]·2.5H O. In contrast, the Sr salt of PX, [Sr(PX)(DMF) (H O) ] forms a one-dimensional coordination polymer. Both the Ca and the Sr salt of CS have an SSIP structure, namely [Ca(H O) ][CS]·H O and [Sr(H O) ][CS]·H O, whilst the heavier Ba analogue, [Ba(CS)(DMF)(H O) ] , forms a one-dimensional coordination polymer. Unlike PX, two CS structures containing transition metals are found to be coordination complexes, [Cu(CS)(DMF) ]·H O and {[Zn(CS)(DMF) (H O)]·0.5Et O} . This suggests that CS is a better ligand than PX for transition metals. The Cu complex forms discrete molecules with Cu in a square-pyramidal environment, whilst the Zn spe