DOE OSTI2020
Sm4AlSi5(NO)7 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twelve inequivalent Sm3+ sites. In the first Sm3+ site, Sm3+ is bonded in a 7-coordinate geometry to four N3- and four O2- atoms. There are a spread of Sm–N bond distances ranging from 2.32–2.97 Å. There are a spread of Sm–O bond distances ranging from 2.30–3.06 Å. In the second Sm3+ site, Sm3+ is bonded in a 7-coordinate geometry to four N3- and three O2- atoms. There are a spread of Sm–N bond distances ranging from 2.31–2.67 Å. There are a spread of Sm–O bond distances ranging from 2.43–2.73 Å. In the third Sm3+ site, Sm3+ is bonded in a 6-coordinate geometry to four N3- and one O2- atom. There are a spread of Sm–N bond distances ranging from 2.20–2.55 Å. The Sm–O bond length is 2.70 Å. In the fourth Sm3+ site, Sm3+ is bonded in a 6-coordinate geometry to three N3- and three O2- atoms. There are a spread of Sm–N bond distances ranging from 2.28–2.63 Å. There are a spread of Sm–O bond distances ranging from 2.34–2.54 Å. In the fifth Sm3+ site, Sm3+ is bonded in a 7-coordinate geometry to three N3- and four O2- atoms. There are a spread of Sm–N bond distances ranging from 2.39–2.67 Å. There are a spread of Sm–O bond distances ranging from 2.25–2.77 Å. In the sixth Sm3+ site, Sm3+ is bonded in a 9-coordinate geometry to six N3- and three O2- atoms. There are a spread of Sm–N bond distances ranging from 2.46–2.86 Å. There are a spread of Sm–O bond distances ranging from 2.38–2.78 Å. In the seventh Sm3+ site, Sm3+ is bonded in a 6-coordinate geometry to three N3- and three O2- atoms. There are a spread of Sm–N bond distances ranging from 2.23–2.58 Å. There are a spread of Sm–O bond distances ranging from 2.31–2.53 Å. In the eighth Sm3+ site, Sm3+ is bonded in a 8-coordinate geometry to six N3- and two O2- atoms. There are a spread of Sm–N bond distances ranging from 2.49–2.85 Å. There are one shorter (2.32 Å) and one longer (2.38 Å) Sm–O bond lengths. In the ninth Sm3+ site, Sm3+ is bonded in a 4-coordinate geometry to six N3- and two O2- atoms. There are a spread of Sm–N bond distances ranging from 2.35–2.97 Å. There are one shorter (2.44 Å) and one longer (2.60 Å) Sm–O bond lengths. In the tenth Sm3+ site, Sm3+ is bonded in a 4-coordinate geometry to four N3- and one O2- atom. There are a spread of Sm–N bond distances ranging from 2.32–2.69 Å. The Sm–O bond length is 2.42 Å. In the eleventh Sm3+ site, Sm3+ is bonded in a 8-coordinate geometry to five N3- and two O2- atoms. There are a spread of Sm–N bond distances ranging from 2.38–2.69 Å. There are one shorter (2.27 Å) and one longer (2.80 Å) Sm–O bond lengths. In the twelfth Sm3+ site, Sm3+ is bonded in a 8-coordinate geometry to five N3- and three O2- atoms. There are a spread of Sm–N bond distances ranging from 2.44–2.58 Å. There are a spread of Sm–O bond distances ranging from 2.45–2.81 Å. There are three inequivalent Al3+ sites. In the first Al3+ site, Al3+ is bonded in a 5-coordinate geometry to one N3- and four O2- atoms. The Al–N bond length is 1.97 Å. There are a spread of Al–O bond distances ranging from 1.85–1.98 Å. In the second Al3+ site, Al3+ is bonded to three N3- and one O2- atom to form distorted AlN3O tetrahedra that share a cornercorner with one SiN2O2 tetrahedra. There are a spread of Al–N bond distances ranging from 1.87–2.01 Å. The Al–O bond length is 1.77 Å. In the third Al3+ site, Al3+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There are a spread of Al–O bond distances ranging from 1.82–1.87 Å. There are fifteen inequivalent Si4+ sites. In the first Si4+ site, Si4+ is bonded in a trigonal non-coplanar geometry to one N3- and two O2- atoms. The Si–N bond length is 1.77 Å. There is one shorter (1.69 Å) and one longer (1.70 Å) Si–O bond length. In the second Si4+ site, Si4+ is bonded in a tetrahedral geometry to two N3- and two O2- atoms. There is one shorter (1.67 Å) and one longer (1.75 Å) Si–N bond length. There is one shorter (1.67 Å) and one longer (1.69 Å) Si–O bond length. In the third Si4+ site, Si4+ is bonded in a T-shaped geometry to one N3- and two O2- atoms. The Si–N bond length is 2.01 Å. There is one shorter (1.73 Å) and one longer (1.82 Å) Si–O bond length. In the fourth Si4+ site, Si4+ is bonded in a 5-coordinate geometry to two N3- and three O2- atoms. There is one shorter (1.80 Å) and one longer (1.82 Å) Si–N bond length. There are a spread of Si–O bond distances ranging from 1.69–2.20 Å. In the fifth Si4+ site, Si4+ is bonded in a bent 120 degrees geometry to one N3- and one O2- atom. The Si–N bond length is 1.83 Å. The Si–O bond length is 1.65 Å. In the sixth Si4+ site, Si4+ is bonded in a trigonal non-coplanar geometry to two N3- and one O2- atom. There is one shorter (1.76 Å) and one longer (1.80 Å) Si–N bond length. The Si–O bond length is 1.64 Å. In the seventh Si4+ site, Si4+ is bonded in a distorted trigonal non-coplanar geometry to two N3- and one O2- atom. There is one shorter (1.75 Å) and one longer (1.85 Å) Si–N bond length. The Si–O bond length is 1.68 Å. In the eighth Si4+ site, Si4+ is bonded in a T-shaped geometry to two N3- and one O2- atom. There is one shorter (1.79 Å) and one longer (1.82 Å) Si–N bond length. The Si–O bond length is 1.72 Å. In the ninth Si4+ site, Si4+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There are a spread of Si–O bond distances ranging from 1.67–1.73 Å. In the tenth Si4+ site, Si4+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. There are a spread of Si–O bond distances ranging from 1.64–1.68 Å. In the eleventh Si4+ site, Si4+ is bonded in a see-saw-like geometry to two N3- and two O2- atoms. There is one shorter (1.74 Å) and one longer (1.85 Å) Si–N bond length. There is one shorter (1.72 Å) and one longer (1.77 Å) Si–O bond length. In the twelfth Si4+ site, Si4+ is bonded in a trigonal non-coplanar geometry to one N3- and two O2- atoms. The Si–N bond length is 1.71 Å. There is one shorter (1.66 Å) and one longer (1.70 Å) Si–O bond length. In the thirteenth Si4+ site, Si4+ is bonded to two N3- and two O2- atoms to form corner-sharing SiN2O2 trigonal pyramids. There is one shorter (1.74 Å) and one longer (1.78 Å) Si–N bond length. There is one shorter (1.80 Å) and one longer (1.94 Å) Si–O bond length. In the fourteenth Si4+ site, Si4+ is bonded in a tetrahedral geometry to two N3- and two O2- atoms. There is one shorter (1.71 Å) and one longer (1.78 Å) Si–N bond length. There is one shorter (1.65 Å) and one longer (1.72 Å) Si–O bond length. In the fifteenth Si4+ site, Si4+ is bonded to two N3- and two O2- atoms to form SiN2O2 tetrahedra that share a cornercorner with one AlN3O tetrahedra and a cornercorner with one SiN2O2 trigonal pyramid. There is one shorter (1.70 Å) and one longer (1.77 Å) Si–N bond length. There is one shorter (1.67 Å) and one longer (1.69 Å) Si–O bond length. There are twenty-one inequivalent N3- sites. In the first N3- site, N3- is bonded in a 1-coordinate geometry to four Sm3+ and one Si4+ atom. In the second N3- site, N3- is bonded in a 1-coordinate geometry to four Sm3+ and one Al3+ atom. In the third N3- site, N3- is bonded in a distorted bent 120 degrees geometry to two Sm3+ and two Si4+ atoms. In the fourth N3- site, N3- is bonded in a 1-coordinate geometry to two Sm3+, one Si4+, and one N3- atom. The N–N bond length is 1.49 Å. In the fifth N3- site, N3- is bonded in a 2-coordinate geometry to two Sm3+ and two Si4+ atoms. In the sixth N3- site, N3- is bonded in a 1-coordinate geometry to three Sm3+, one Si4+, and one N3- atom. In the seventh N3- site, N3- is bonded in a 1-coordinate geometry to two Sm3+, one Si4+, and one N3- atom. The N–N bond length is 1.48 Å. In the eighth N3- site, N3- is bonded in a 2-coordinate geometry to one Sm3+, two Si4+, and one N3- atom. The N–N bond length is 1.48 Å. In the ninth N3- site, N3- is bonded in a 5-coordinate geometry to three Sm3+, one Al3+, and one N3- atom. In the tenth N3- site, N3- is bonded in a distorted single-bond geometry to three Sm3+, one Si4+, and one N3- atom. The N–N bond length is 1.54 Å. In the eleventh N3- site, N3- is bonded in a 4-coordinate geometry to three Sm3+ and one N3- atom. The N–N bond length is 1.45 Å. In the twelfth N3- site, N3- is bonded in a 2-coordinate geometry to one Sm3+, two Si4+, and one N3- atom. In the thirteenth N3- site, N3- is bonded in a 1-coordinate geometry to three Sm3+, one Si4+, and one N3- atom. In the fourteenth N3- site, N3- is bonded in a 2-coordinate geometry to two Sm3+, one Al3+, one Si4+, and one N3- atom. The N–N bond length is 1.49 Å. In the fifteenth N3- site, N3- is bonded in a 1-coordinate geometry to three Sm3+, one Si4+, and one N3- atom. The N–N bond length is 1.50 Å. In the sixteenth N3- site, N3- is bonded in a 4-coordinate geometry to two Sm3+, one Al3+, and one N3- atom. In the seventeenth N3- site, N3- is bonded in a 1-coordinate geometry to two Sm3+, one Si4+, and one N3- atom. In the eighteenth N3- site, N3- is bonded in a 1-coordinate geometry to three Sm3+, one Si4+, and one N3- atom. In the nineteenth N3- site, N3- is bonded in a distorted trigonal pyramidal geometry to three Sm3+ and one Si4+ atom. In the twentieth N3- site, N3- is bonded in a 4-coordinate geometry to three Sm3+ and one Si4+ atom. In the twenty-first N3- site, N3- is bonded in a 2-coordinate geometry to two Sm3+ and two Si4+ atoms. There are twenty-one inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to three Sm3+ and one Al3+ atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to two Sm3+ and one Si4+ atom. In the third O2- site, O2- is bonded in a 1-coordinate geometry to three Sm3+ and one Si4+ atom. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to two Sm3+ and two Si4+ atoms. In the fifth O2- site, O2- is bonded in a 1-coordinate geometry to three Sm3+ and one Si4+ atom. In the sixth O2- site, O2- is bonded in a distorted T-shaped geometry to one Sm3+ and two Si4+ atoms. In the seventh O2- site, O2- is bonded in a 2-coordinate geometry to one Sm3+ and two Si4+ atoms. In the eighth O2- site, O2- is bonded in a 1-coordinate geometry to three Sm3+ and one Si4+ atom. In the ninth O2- site, O2- is bonded in a 1-coordinate geometry to two Sm3+ and one Si4+ atom. In the tenth O2- site, O2- is bonded in a 3-coordinate geometry to one Sm3+ and two Si4+ atoms. In the eleventh O2- site, O2- is bonded in a distorted T-shaped geometry to one Sm3+, one Al3+, and one Si4+ atom. In the twelfth O2- site, O2- is bonded in a distorted water-like geometry to one Sm3+ and two Si4+ atoms. In the thirteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Sm3+, one Al3+, and one Si4+ atom. In the fourteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Sm3+, one Al3+, and one Si4+ atom. In the fifteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Sm3+ and two Si4+ atoms. In the sixteenth O2- site, O2- is bonded in a bent 150 degrees geometry to two Si4+ atoms. In the seventeenth O2- site, O2- is bonded in a 2-coordinate geometry to one Sm3+, one Al3+, and one Si4+ atom. In the eighteenth O2- site, O2- is bonded in a 2-coordinate geometry to one Sm3+ and two Si4+ atoms. In the nineteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Sm3+, one Al3+, and one Si4+ atom. In the twentieth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Sm3+, one Al3+, and one Si4+ atom. In the twenty-first O2- site, O2- is bonded in a 2-coordinate geometry to one Sm3+, one Al3+, and two Si4+ atoms.