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The asymmetric unit of title co-crystal, C14H16N4S22+·2C7H3N2O6·4C7H4N2O6, comprises a centrosymmetric dipyridinium dication, a 2,6-di­nitro­benzoate anion and two independent 2,6-di­nitro­benzoic acid mol­ecules. The pyridin­ium rings are each approximately perpendicular to the central di­thio­amide unit [dihedral angle = 80.67 (12)°]. The carboxyl­ate/carb­oxy­lic acid groups are approximately perpendicular to the benzene ring to which they are attached [dihedral angles = 78.85 (16), 81.46 (19) and 71.28 (15)°]. By contrast, the major twist exhibited by a nitro group is manifested in a dihedral angle of 32.66 (17)°. The most prominent feature of the crystal packing is linear supra­molecular chains along [1-10], featuring O—H...O(carboxyl­ate) and pyridinium-N—H...O hydrogen bonds. These are consolidated into a three-dimensional architecture by thio­amide–nitro N—H...O, C—H...O and π–π [inter-centroid distance = 3.524 (2) Å] inter­actions. One of the nitro O atoms was refined over two sites; the major site was 0.65 (7) occupied.

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In the title compound, C20H27N5O3, the central piperazine ring adopts a chair conformation, with the N-bound carboxyl­ate and methyl­ene substituents occupying bis­ectional and equatorial orientations, respectively. A twist is evident between the aromatic rings [dihedral angle = 25.61 (9)°] but an intra­molecular O—H...N hydrogen bond persists between these. Supra­molecular tapes along [1-10] are formed in the crystal packing through N(amino)—H...O(hydrox­yl) and N(amino)—H...N(pyrimidin­yl) hydrogen bonds, and these are linked into layers in the ab plane by π–π inter­actions [inter-centroid distance between pyrimidinyl rings = 3.5919 (9) Å].
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