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NpCl4 crystallizes in the tetragonal I4_1/amd space group. The structure is three-dimensional. Np4+ is bonded in a 8-coordinate geometry to eight equivalent Cl1- atoms. There are four shorter (2.64 Å) and four longer (2.90 Å) Np–Cl bond lengths. Cl1- is bonded in a distorted water-like geometry to two equivalent Np4+ atoms.
NpCl3 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. Np3+ is bonded in a 9-coordinate geometry to nine equivalent Cl1- atoms. There are six shorter (2.91 Å) and three longer (2.93 Å) Np–Cl bond lengths. Cl1- is bonded in a trigonal non-coplanar geometry to three equivalent Np3+ atoms.