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N2PbCl6 is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is zero-dimensional and consists of eight ammonia molecules and four PbCl6 clusters. In each PbCl6 cluster, Pb4+ is bonded in an octahedral geometry to six equivalent Cl1- atoms. All Pb–Cl bond lengths are 2.57 Å. Cl1- is bonded in a single-bond geometry to one Pb4+ atom.
Pb2NCl5 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are two inequivalent Pb4+ sites. In the first Pb4+ site, Pb4+ is bonded in a 8-coordinate geometry to eight Cl1- atoms. There are a spread of Pb–Cl bond distances ranging from 2.93–3.23 Å. In the second Pb4+ site, Pb4+ is bonded to seven Cl1- atoms to form distorted edge-sharing PbCl7 pentagonal bipyramids. There are a spread of Pb–Cl bond distances ranging from 2.77–3.09 Å. N3- is bonded in a 9-coordinate geometry to eight Cl1- atoms. There are a spread of N–Cl bond distances ranging from 3.25–3.63 Å. There are five inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a distorted water-like geometry to two equivalent Pb4+ and two equivalent N3- atoms. In the second Cl1- site, Cl1- is bonded to four Pb4+ atoms to form a mixture of distorted edge and corner-sharing ClPb4 trigonal pyramids. In the third Cl1- site, Cl1- is bonded in a 2-coordinate geometry to three Pb4+ and two equivalent N3- atoms. In the fourth Cl1- site, Cl1- is bonded in a 5-coordinate geometry to three Pb4+ and two equivalent N3- atoms. In the fifth Cl1- site, Cl1- is bonded in a 3-coordinate geometry to three Pb4+ and two equivalent N3- atoms.