DOE OSTI2020
Nd6S3(OF4)2 crystallizes in the monoclinic Pm space group. The structure is three-dimensional. there are twelve inequivalent Nd3+ sites. In the first Nd3+ site, Nd3+ is bonded in a 7-coordinate geometry to two equivalent S2- and seven F1- atoms. Both Nd–S bond lengths are 2.97 Å. There are a spread of Nd–F bond distances ranging from 2.37–2.48 Å. In the second Nd3+ site, Nd3+ is bonded in a 7-coordinate geometry to two equivalent S2- and seven F1- atoms. Both Nd–S bond lengths are 2.95 Å. There are a spread of Nd–F bond distances ranging from 2.39–2.50 Å. In the third Nd3+ site, Nd3+ is bonded in a 7-coordinate geometry to two equivalent S2-, one O2-, and six F1- atoms. Both Nd–S bond lengths are 2.98 Å. The Nd–O bond length is 2.35 Å. There are a spread of Nd–F bond distances ranging from 2.44–2.50 Å. In the fourth Nd3+ site, Nd3+ is bonded in a 9-coordinate geometry to two equivalent S2-, one O2-, and six F1- atoms. Both Nd–S bond lengths are 3.00 Å. The Nd–O bond length is 2.38 Å. There are a spread of Nd–F bond distances ranging from 2.42–2.53 Å. In the fifth Nd3+ site, Nd3+ is bonded in a 9-coordinate geometry to two equivalent S2-, one O2-, and six F1- atoms. Both Nd–S bond lengths are 2.96 Å. The Nd–O bond length is 2.38 Å. There are a spread of Nd–F bond distances ranging from 2.45–2.47 Å. In the sixth Nd3+ site, Nd3+ is bonded in a 9-coordinate geometry to two equivalent S2-, one O2-, and six F1- atoms. Both Nd–S bond lengths are 2.96 Å. The Nd–O bond length is 2.32 Å. There are a spread of Nd–F bond distances ranging from 2.45–2.52 Å. In the seventh Nd3+ site, Nd3+ is bonded in a 5-coordinate geometry to four S2-, two equivalent O2-, and three F1- atoms. There are two shorter (3.04 Å) and two longer (3.12 Å) Nd–S bond lengths. Both Nd–O bond lengths are 2.42 Å. There are a spread of Nd–F bond distances ranging from 2.39–2.53 Å. In the eighth Nd3+ site, Nd3+ is bonded in a 5-coordinate geometry to four S2-, three O2-, and two F1- atoms. There are two shorter (3.07 Å) and two longer (3.25 Å) Nd–S bond lengths. There are one shorter (2.38 Å) and two longer (2.39 Å) Nd–O bond lengths. There are one shorter (2.45 Å) and one longer (2.55 Å) Nd–F bond lengths. In the ninth Nd3+ site, Nd3+ is bonded in a 5-coordinate geometry to four S2-, two equivalent O2-, and three F1- atoms. There are two shorter (3.04 Å) and two longer (3.10 Å) Nd–S bond lengths. Both Nd–O bond lengths are 2.44 Å. There are a spread of Nd–F bond distances ranging from 2.40–2.52 Å. In the tenth Nd3+ site, Nd3+ is bonded in a 9-coordinate geometry to four S2-, one O2-, and four F1- atoms. There are two shorter (2.92 Å) and two longer (3.11 Å) Nd–S bond lengths. The Nd–O bond length is 2.39 Å. There are a spread of Nd–F bond distances ranging from 2.36–2.57 Å. In the eleventh Nd3+ site, Nd3+ is bonded in a 5-coordinate geometry to four S2-, three O2-, and two F1- atoms. There are two shorter (3.11 Å) and two longer (3.22 Å) Nd–S bond lengths. There are two shorter (2.36 Å) and one longer (2.37 Å) Nd–O bond lengths. There are one shorter (2.43 Å) and one longer (2.51 Å) Nd–F bond lengths. In the twelfth Nd3+ site, Nd3+ is bonded in a 9-coordinate geometry to four S2-, one O2-, and four F1- atoms. There are two shorter (2.98 Å) and two longer (3.03 Å) Nd–S bond lengths. The Nd–O bond length is 2.38 Å. There are a spread of Nd–F bond distances ranging from 2.35–2.58 Å. There are six inequivalent S2- sites. In the first S2- site, S2- is bonded in a 8-coordinate geometry to six Nd3+, three O2-, and seven F1- atoms. There are two shorter (3.30 Å) and one longer (3.50 Å) S–O bond lengths. There are a spread of S–F bond distances ranging from 3.06–3.40 Å. In the second S2- site, S2- is bonded in a 8-coordinate geometry to six Nd3+, two equivalent O2-, and eight F1- atoms. Both S–O bond lengths are 3.26 Å. There are a spread of S–F bond distances ranging from 3.06–3.45 Å. In the third S2- site, S2- is bonded in a 6-coordinate geometry to six Nd3+, three O2-, and seven F1- atoms. There are two shorter (3.24 Å) and one longer (3.34 Å) S–O bond lengths. There are a spread of S–F bond distances ranging from 3.04–3.37 Å. In the fourth S2- site, S2- is bonded in a 8-coordinate geometry to six Nd3+, four O2-, and six F1- atoms. There are a spread of S–O bond distances ranging from 3.25–3.46 Å. There are a spread of S–F bond distances ranging from 3.09–3.39 Å. In the fifth S2- site, S2- is bonded in a 8-coordinate geometry to six Nd3+, two O2-, and eight F1- atoms. There are one shorter (3.37 Å) and one longer (3.40 Å) S–O bond lengths. There are a spread of S–F bond distances ranging from 3.11–3.21 Å. In the sixth S2- site, S2- is bonded in a 6-coordinate geometry to six Nd3+, two O2-, and eight F1- atoms. There are one shorter (3.31 Å) and one longer (3.38 Å) S–O bond lengths. There are a spread of S–F bond distances ranging from 3.13–3.25 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded to four Nd3+ and four S2- atoms to form ONd4S4 tetrahedra that share corners with four ONd4S4 tetrahedra, corners with seven FNd4S3 tetrahedra, an edgeedge with one FNd4S3 tetrahedra, edges with two equivalent ONd4S4 tetrahedra, faces with two equivalent ONd4S4 tetrahedra, and faces with three FNd4S3 tetrahedra. In the second O2- site, O2- is bonded to four Nd3+ and four S2- atoms to form ONd4S4 tetrahedra that share corners with four ONd4S4 tetrahedra, corners with seven FNd4S3 tetrahedra, an edgeedge with one FNd4S3 tetrahedra, edges with two equivalent ONd4S4 tetrahedra, and faces with five FNd4S3 tetrahedra. In the third O2- site, O2- is bonded to four Nd3+ and four S2- atoms to form ONd4S4 tetrahedra that share corners with four ONd4S4 tetrahedra, corners with seven FNd4S3 tetrahedra, an edgeedge with one FNd4S3 tetrahedra, edges with two equivalent ONd4S4 tetrahedra, and faces with five FNd4S3 tetrahedra. In the fourth O2- site, O2- is bonded to four Nd3+ and four S2- atoms to form distorted ONd4S4 tetrahedra that share corners with two ONd4S4 tetrahedra, corners with nine FNd4S3 tetrahedra, an edgeedge with one FNd4S3 tetrahedra, edges with two equivalent ONd4S4 tetrahedra, faces with two equivalent ONd4S4 tetrahedra, and faces with three FNd4S3 tetrahedra. There are sixteen inequivalent F1- sites. In the first F1- site, F1- is bonded in a trigonal planar geometry to three Nd3+ and six S2- atoms. In the second F1- site, F1- is bonded in a distorted trigonal planar geometry to three Nd3+ and six S2- atoms. In the third F1- site, F1- is bonded in a distorted trigonal non-coplanar geometry to three Nd3+ and one S2- atom. In the fourth F1- site, F1- is bonded in a distorted trigonal non-coplanar geometry to three Nd3+ and one S2- atom. In the fifth F1- site, F1- is bonded in a trigonal non-coplanar geometry to three Nd3+ and one S2- atom. In the sixth F1- site, F1- is bonded in a trigonal non-coplanar geometry to three Nd3+ and one S2- atom. In the seventh F1- site, F1- is bonded in a trigonal non-coplanar geometry to three Nd3+ and one S2- atom. In the eighth F1- site, F1- is bonded in a trigonal non-coplanar geometry to three Nd3+ and one S2- atom. In the ninth F1- site, F1- is bonded to four Nd3+ and three S2- atoms to form distorted FNd4S3 tetrahedra that share corners with two equivalent FNd4S4 tetrahedra, corners with three ONd4S4 tetrahedra, edges with seven FNd4S3 tetrahedra, a faceface with one FNd4S4 tetrahedra, and faces with two equivalent ONd4S4 tetrahedra. In the tenth F1- site, F1- is bonded to four Nd3+ and three S2- atoms to form distorted FNd4S3 tetrahedra that share corners with two equivalent ONd4S4 tetrahedra, corners with three FNd4S4 tetrahedra, an edgeedge with one ONd4S4 tetrahedra, edges with six FNd4S3 tetrahedra, a faceface with one FNd4S4 tetrahedra, and faces with two equivalent ONd4S4 tetrahedra. In the eleventh F1- site, F1- is bonded to four Nd3+ and three S2- atoms to form FNd4S3 tetrahedra that share a cornercorner with one FNd4S4 tetrahedra, corners with four ONd4S4 tetrahedra, edges with seven FNd4S3 tetrahedra, and faces with three ONd4S4 tetrahedra. In the twelfth F1- site, F1- is bonded to four Nd3+ and three S2- atoms to form FNd4S3 tetrahedra that share corners with two equivalent FNd4S4 tetrahedra, corners with three ONd4S4 tetrahedra, an edgeedge with one ONd4S4 tetrahedra, edges with six FNd4S3 tetrahedra, a faceface with one ONd4S4 tetrahedra, and faces with two equivalent FNd4S4 tetrahedra. In the thirteenth F1- site, F1- is bonded to four Nd3+ and three S2- atoms to form distorted FNd4S3 tetrahedra that share corners with two equivalent FNd4S4 tetrahedra, corners with three ONd4S4 tetrahedra, an edgeedge with one ONd4S4 tetrahedra, edges with six FNd4S3 tetrahedra, and faces with three ONd4S4 tetrahedra. In the fourteenth F1- site, F1- is bonded to four Nd3+ and three S2- atoms to form distorted FNd4S3 tetrahedra that share corners with five ONd4S4 tetrahedra, an edgeedge with one ONd4S4 tetrahedra, edges with six FNd4S3 tetrahedra, a faceface with one ONd4S4 tetrahedra, and faces with two equivalent FNd4S4 tetrahedra. In the fifteenth F1- site, F1- is bonded to four Nd3+ and four S2- atoms to form FNd4S4 tetrahedra that share corners with five ONd4S4 tetrahedra, corners with six FNd4S3 tetrahedra, edges with three FNd4S3 tetrahedra, faces with two equivalent ONd4S4 tetrahedra, and faces with three FNd4S3 tetrahedra. In the sixteenth F1- site, F1- is bonded to four Nd3+ and four S2- atoms to form distorted FNd4S4 tetrahedra that share corners with five ONd4S4 tetrahedra, corners with six FNd4S3 tetrahedra, edges with three FNd4S4 tetrahedra, faces with two equivalent ONd4S4 tetrahedra, and faces with three FNd4S3 tetrahedra.