DOE OSTI2020
Pr6S3(OF4)2 crystallizes in the monoclinic Pm space group. The structure is three-dimensional. there are twelve inequivalent Pr3+ sites. In the first Pr3+ site, Pr3+ is bonded in a 5-coordinate geometry to four S2-, two equivalent O2-, and three F1- atoms. There are two shorter (3.07 Å) and two longer (3.16 Å) Pr–S bond lengths. Both Pr–O bond lengths are 2.45 Å. There are a spread of Pr–F bond distances ranging from 2.41–2.56 Å. In the second Pr3+ site, Pr3+ 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 (3.28 Å) Pr–S bond lengths. There are one shorter (2.41 Å) and two longer (2.42 Å) Pr–O bond lengths. There are one shorter (2.46 Å) and one longer (2.57 Å) Pr–F bond lengths. In the third Pr3+ site, Pr3+ is bonded in a 5-coordinate geometry to four S2-, two equivalent O2-, and three F1- atoms. There are two shorter (3.07 Å) and two longer (3.13 Å) Pr–S bond lengths. Both Pr–O bond lengths are 2.46 Å. There are a spread of Pr–F bond distances ranging from 2.42–2.54 Å. In the fourth Pr3+ site, Pr3+ is bonded in a 9-coordinate geometry to four S2-, one O2-, and four F1- atoms. There are two shorter (2.95 Å) and two longer (3.14 Å) Pr–S bond lengths. The Pr–O bond length is 2.41 Å. There are a spread of Pr–F bond distances ranging from 2.38–2.60 Å. In the fifth Pr3+ site, Pr3+ is bonded in a 5-coordinate geometry to four S2-, three O2-, and two F1- atoms. There are two shorter (3.15 Å) and two longer (3.25 Å) Pr–S bond lengths. All Pr–O bond lengths are 2.39 Å. There are one shorter (2.45 Å) and one longer (2.54 Å) Pr–F bond lengths. In the sixth Pr3+ site, Pr3+ is bonded in a 9-coordinate geometry to four S2-, one O2-, and four F1- atoms. There are two shorter (3.01 Å) and two longer (3.07 Å) Pr–S bond lengths. The Pr–O bond length is 2.41 Å. There are a spread of Pr–F bond distances ranging from 2.37–2.61 Å. In the seventh Pr3+ site, Pr3+ is bonded in a 7-coordinate geometry to two equivalent S2- and seven F1- atoms. Both Pr–S bond lengths are 3.00 Å. There are a spread of Pr–F bond distances ranging from 2.40–2.50 Å. In the eighth Pr3+ site, Pr3+ is bonded in a 7-coordinate geometry to two equivalent S2- and seven F1- atoms. Both Pr–S bond lengths are 2.98 Å. There are a spread of Pr–F bond distances ranging from 2.42–2.53 Å. In the ninth Pr3+ site, Pr3+ is bonded in a 7-coordinate geometry to two equivalent S2-, one O2-, and six F1- atoms. Both Pr–S bond lengths are 3.01 Å. The Pr–O bond length is 2.37 Å. There are a spread of Pr–F bond distances ranging from 2.46–2.52 Å. In the tenth Pr3+ site, Pr3+ is bonded in a 9-coordinate geometry to two equivalent S2-, one O2-, and six F1- atoms. Both Pr–S bond lengths are 3.03 Å. The Pr–O bond length is 2.40 Å. There are a spread of Pr–F bond distances ranging from 2.45–2.56 Å. In the eleventh Pr3+ site, Pr3+ is bonded in a 9-coordinate geometry to two equivalent S2-, one O2-, and six F1- atoms. Both Pr–S bond lengths are 2.98 Å. The Pr–O bond length is 2.40 Å. There are a spread of Pr–F bond distances ranging from 2.48–2.50 Å. In the twelfth Pr3+ site, Pr3+ is bonded in a 9-coordinate geometry to two equivalent S2-, one O2-, and six F1- atoms. Both Pr–S bond lengths are 2.99 Å. The Pr–O bond length is 2.35 Å. There are a spread of Pr–F bond distances ranging from 2.48–2.54 Å. There are six inequivalent S2- sites. In the first S2- site, S2- is bonded in a 8-coordinate geometry to six Pr3+, three O2-, and seven F1- atoms. There are two shorter (3.34 Å) and one longer (3.54 Å) S–O bond lengths. There are a spread of S–F bond distances ranging from 3.09–3.44 Å. In the second S2- site, S2- is bonded in a 8-coordinate geometry to six Pr3+, two equivalent O2-, and eight F1- atoms. Both S–O bond lengths are 3.30 Å. There are a spread of S–F bond distances ranging from 3.10–3.49 Å. In the third S2- site, S2- is bonded in a 6-coordinate geometry to six Pr3+, three O2-, and seven F1- atoms. There are two shorter (3.27 Å) and one longer (3.38 Å) S–O bond lengths. There are a spread of S–F bond distances ranging from 3.07–3.41 Å. In the fourth S2- site, S2- is bonded in a 8-coordinate geometry to six Pr3+, four O2-, and six F1- atoms. There are a spread of S–O bond distances ranging from 3.28–3.50 Å. There are a spread of S–F bond distances ranging from 3.13–3.42 Å. In the fifth S2- site, S2- is bonded in a 8-coordinate geometry to six Pr3+, two O2-, and eight F1- atoms. There are one shorter (3.40 Å) and one longer (3.43 Å) S–O bond lengths. There are a spread of S–F bond distances ranging from 3.15–3.24 Å. In the sixth S2- site, S2- is bonded in a 6-coordinate geometry to six Pr3+, two O2-, and eight F1- atoms. There are one shorter (3.35 Å) and one longer (3.41 Å) S–O bond lengths. There are a spread of S–F bond distances ranging from 3.17–3.28 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded to four Pr3+ and four S2- atoms to form OPr4S4 tetrahedra that share corners with four OPr4S4 tetrahedra, corners with seven FPr4S4 tetrahedra, an edgeedge with one FPr4S3 tetrahedra, edges with two equivalent OPr4S4 tetrahedra, faces with two equivalent OPr4S4 tetrahedra, and faces with three FPr4S3 tetrahedra. In the second O2- site, O2- is bonded to four Pr3+ and four S2- atoms to form OPr4S4 tetrahedra that share corners with four OPr4S4 tetrahedra, corners with seven FPr4S3 tetrahedra, an edgeedge with one FPr4S3 tetrahedra, edges with two equivalent OPr4S4 tetrahedra, and faces with five FPr4S4 tetrahedra. In the third O2- site, O2- is bonded to four Pr3+ and four S2- atoms to form OPr4S4 tetrahedra that share corners with four OPr4S4 tetrahedra, corners with seven FPr4S3 tetrahedra, an edgeedge with one FPr4S3 tetrahedra, edges with two equivalent OPr4S4 tetrahedra, and faces with five FPr4S3 tetrahedra. In the fourth O2- site, O2- is bonded to four Pr3+ and four S2- atoms to form distorted OPr4S4 tetrahedra that share corners with two OPr4S4 tetrahedra, corners with nine FPr4S3 tetrahedra, an edgeedge with one FPr4S3 tetrahedra, edges with two equivalent OPr4S4 tetrahedra, faces with two equivalent OPr4S4 tetrahedra, and faces with three FPr4S3 tetrahedra. There are sixteen inequivalent F1- sites. In the first F1- site, F1- is bonded in a distorted trigonal non-coplanar geometry to three Pr3+ and one S2- atom. In the second F1- site, F1- is bonded in a distorted trigonal non-coplanar geometry to three Pr3+ and one S2- atom. In the third F1- site, F1- is bonded in a trigonal non-coplanar geometry to three Pr3+ and one S2- atom. In the fourth F1- site, F1- is bonded in a distorted trigonal non-coplanar geometry to three Pr3+ and one S2- atom. In the fifth F1- site, F1- is bonded in a trigonal non-coplanar geometry to three Pr3+ and one S2- atom. In the sixth F1- site, F1- is bonded in a trigonal non-coplanar geometry to three Pr3+ and one S2- atom. In the seventh F1- site, F1- is bonded to four Pr3+ and three S2- atoms to form distorted FPr4S3 tetrahedra that share corners with two equivalent FPr4S4 tetrahedra, corners with three OPr4S4 tetrahedra, edges with seven FPr4S3 tetrahedra, a faceface with one FPr4S4 tetrahedra, and faces with two equivalent OPr4S4 tetrahedra. In the eighth F1- site, F1- is bonded to four Pr3+ and three S2- atoms to form distorted FPr4S3 tetrahedra that share corners with two equivalent OPr4S4 tetrahedra, corners with three FPr4S4 tetrahedra, an edgeedge with one OPr4S4 tetrahedra, edges with six FPr4S3 tetrahedra, a faceface with one FPr4S4 tetrahedra, and faces with two equivalent OPr4S4 tetrahedra. In the ninth F1- site, F1- is bonded to four Pr3+ and three S2- atoms to form FPr4S3 tetrahedra that share a cornercorner with one FPr4S4 tetrahedra, corners with four OPr4S4 tetrahedra, edges with seven FPr4S3 tetrahedra, and faces with three OPr4S4 tetrahedra. In the tenth F1- site, F1- is bonded to four Pr3+ and three S2- atoms to form FPr4S3 tetrahedra that share corners with two equivalent FPr4S4 tetrahedra, corners with three OPr4S4 tetrahedra, an edgeedge with one OPr4S4 tetrahedra, edges with six FPr4S3 tetrahedra, a faceface with one OPr4S4 tetrahedra, and faces with two equivalent FPr4S4 tetrahedra. In the eleventh F1- site, F1- is bonded to four Pr3+ and three S2- atoms to form distorted FPr4S3 tetrahedra that share corners with two equivalent FPr4S4 tetrahedra, corners with three OPr4S4 tetrahedra, an edgeedge with one OPr4S4 tetrahedra, edges with six FPr4S3 tetrahedra, and faces with three OPr4S4 tetrahedra. In the twelfth F1- site, F1- is bonded to four Pr3+ and three S2- atoms to form distorted FPr4S3 tetrahedra that share corners with five OPr4S4 tetrahedra, an edgeedge with one OPr4S4 tetrahedra, edges with six FPr4S3 tetrahedra, a faceface with one OPr4S4 tetrahedra, and faces with two equivalent FPr4S4 tetrahedra. In the thirteenth F1- site, F1- is bonded in a trigonal planar geometry to three Pr3+ and six S2- atoms. In the fourteenth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Pr3+ and six S2- atoms. In the fifteenth F1- site, F1- is bonded to four Pr3+ and four S2- atoms to form FPr4S4 tetrahedra that share corners with five OPr4S4 tetrahedra, corners with six FPr4S4 tetrahedra, edges with three FPr4S4 tetrahedra, faces with two equivalent OPr4S4 tetrahedra, and faces with three FPr4S3 tetrahedra. In the sixteenth F1- site, F1- is bonded to four Pr3+ and four S2- atoms to form FPr4S4 tetrahedra that share corners with five OPr4S4 tetrahedra, corners with six FPr4S3 tetrahedra, edges with three FPr4S4 tetrahedra, faces with two equivalent OPr4S4 tetrahedra, and faces with three FPr4S3 tetrahedra.