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The asymmetric unit of the title compound, [Nd2(C6H5COO)5Cl(C4H8O2)]·2.5C4H8O2, consists of two NdIII ions bridged by one Cl ion, five benzoate ions and one coordinating 1,4-dioxane mol­ecule. One NdIII ion is nine-coordinate, with a very distorted monocapped square-anti­prismatic geometry. It is coordinated by two chelating carboxyl­ate groups, three monodentate carboxyl­ate groups, one chloride ion and one dioxane mol­ecule. A second independent NdIII ion is eight-coordinated in a distorted square-anti­prismatic geometry by one chelating carboxyl­ate group, five monodentate carboxyl­ate groups and one chloride ion. The chains of the extended structure are parallel to the crystallographic b axis. There is a small amount of void space which is filled with five disordered dioxane solvent mol­ecules per unit cell. The intensity contribution of the disordered solvent molecules was removed by applying the SQUEEZE procedure in PLATON [Spek (2009). Acta Cryst. D65, 148–155].
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