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The title compound, (C21H33N2O)2[SmCl5(C4H8O)]·C7H8·C4H8O, has a layered structure in which each distorted octa­hedral [SmCl5(THF)]2− unit (THF is tetra­hydro­furan) is capped by two cations. The central metal SmIII atom of the [SmCl5(THF)]2− anionic unit is coordinated by five Cl atoms and one THF O atom, forming a distorted octa­hedral geometry. The crystal structure displays C—H...Cl and O—H...Cl hydrogen bonding. The structure exhibits disorder of the solvent.

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The anion of the title compound, C5H6N+·C5H2NO4S, is approximately planar, with the carboxyl­ate and nitro group planes forming dihedral angles of 7.5 (3) and 3.5 (3)°, respectively, with the thio­phene ring. In the crystal structure, the cations and anions are linked into a two-dimensional network parallel to (011) by N—H...O and C—H...O hydrogen bonds.
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