DOE OSTI2020
Nd6N3S4Cl crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are six inequivalent Nd3+ sites. In the first Nd3+ site, Nd3+ is bonded in a 2-coordinate geometry to two equivalent N3-, three S2-, and two equivalent Cl1- atoms. Both Nd–N bond lengths are 2.49 Å. There are two shorter (2.89 Å) and one longer (2.92 Å) Nd–S bond lengths. There are one shorter (3.01 Å) and one longer (3.42 Å) Nd–Cl bond lengths. In the second Nd3+ site, Nd3+ is bonded in a 3-coordinate geometry to three equivalent N3- and four S2- atoms. There are one shorter (2.34 Å) and two longer (2.42 Å) Nd–N bond lengths. There are a spread of Nd–S bond distances ranging from 2.96–3.41 Å. In the third Nd3+ site, Nd3+ is bonded in a 6-coordinate geometry to two N3-, two equivalent S2-, and two equivalent Cl1- atoms. There are one shorter (2.37 Å) and one longer (2.38 Å) Nd–N bond lengths. Both Nd–S bond lengths are 2.73 Å. Both Nd–Cl bond lengths are 3.08 Å. In the fourth Nd3+ site, Nd3+ is bonded in a 6-coordinate geometry to two N3-, two equivalent S2-, and two equivalent Cl1- atoms. There are one shorter (2.26 Å) and one longer (2.36 Å) Nd–N bond lengths. Both Nd–S bond lengths are 2.84 Å. Both Nd–Cl bond lengths are 3.02 Å. In the fifth Nd3+ site, Nd3+ is bonded in a 1-coordinate geometry to one N3- and five S2- atoms. The Nd–N bond length is 2.20 Å. There are a spread of Nd–S bond distances ranging from 2.90–3.02 Å. In the sixth Nd3+ site, Nd3+ is bonded in a 2-coordinate geometry to two equivalent N3- and five S2- atoms. Both Nd–N bond lengths are 2.41 Å. There are a spread of Nd–S bond distances ranging from 2.80–3.37 Å. There are three inequivalent N3- sites. In the first N3- site, N3- is bonded to four Nd3+ atoms to form NNd4 tetrahedra that share corners with two equivalent NNd4 tetrahedra, corners with two equivalent SNd4 trigonal pyramids, edges with two equivalent NNd4 tetrahedra, and an edgeedge with one SNd4 trigonal pyramid. In the second N3- site, N3- is bonded to four Nd3+ atoms to form a mixture of corner and edge-sharing NNd4 tetrahedra. In the third N3- site, N3- is bonded to four Nd3+ atoms to form NNd4 tetrahedra that share corners with two equivalent NNd4 tetrahedra, corners with two equivalent SNd4 trigonal pyramids, an edgeedge with one NNd4 tetrahedra, and an edgeedge with one SNd4 trigonal pyramid. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded in a 6-coordinate geometry to six Nd3+ atoms. In the second S2- site, S2- is bonded in a 5-coordinate geometry to six Nd3+ atoms. In the third S2- site, S2- is bonded in a 5-coordinate geometry to five Nd3+ atoms. In the fourth S2- site, S2- is bonded to four Nd3+ atoms to form distorted SNd4 trigonal pyramids that share corners with four NNd4 tetrahedra, corners with two equivalent SNd4 trigonal pyramids, and edges with two NNd4 tetrahedra. Cl1- is bonded in a 5-coordinate geometry to six Nd3+ atoms.