Na3LaHfSi2SO12 crystallizes in the monoclinic Cc space group. There are eight inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one O(1), one O(11), and one O(9) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. In the third Na site, Na(1) is bonded in a 3-coordinate geometry to one O(1), one O(11), and one O(9) atom. In the fourth Na site, Na(1) is bonded in a 3-coordinate geometry to one O(1), one O(11), and one O(9) atom. In the fifth Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. In the sixth Na site, Na(3) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(12), one O(8), and one O(9) atom. In the seventh Na site, Na(3) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(12), one O(8), and one O(9) atom. In the eighth Na site, Na(3) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(12), one O(8), and one O(9) atom. La(1) is bonded to one O(1), one O(2), one O(3), one O(7), one O(8), and one O(9) atom to form distorted LaO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form distorted HfO6 octahedra that share corners with two Si(1,1)O4 tetrahedra; corners with two equivalent Si(2)O4 tetrahedra; and corners with two equivalent S(1)O4 tetrahedra. In the second Hf site, Hf(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form distorted HfO6 octahedra that share corners with two Si(1,1)O4 tetrahedra; corners with two equivalent Si(2)O4 tetrahedra; and corners with two equivalent S(1)O4 tetrahedra. In the third Hf site, Hf(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form distorted HfO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent La(1)O6 octahedra and corners with two Hf(1,1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-44°. In the second Si site, Si(2) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent La(1)O6 octahedra and corners with two Hf(1,1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-42°. In the third Si site, Si(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent La(1)O6 octahedra and corners with two Hf(1,1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-44°. S(1) is bonded to one O(12), one O(3), one O(4), and one O(7) atom to form SO4 tetrahedra that share corners with two equivalent La(1)O6 octahedra and corners with two Hf(1,1)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-34°. There are thirty-five inequivalent O sites. In the first O site, O(6) is bonded in a distorted linear geometry to one Na(2), one Hf(1), and one Si(1) atom. In the second O site, O(7) is bonded in a 1-coordinate geometry to one Na(2), one La(1), and one S(1) atom. In the third O site, O(8) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one La(1), and one Si(2) atom. In the fourth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one La(1), and one Si(1) atom. In the fifth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one Si(1) atom. In the sixth O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Hf(1), and one Si(2) atom. In the seventh O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one S(1) atom. In the eighth O site, O(7) is bonded in a 1-coordinate geometry to one Na(2), one La(1), and one S(1) atom. In the ninth O site, O(8) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one La(1), and one Si(2) atom. In the tenth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one La(1), and one Si(1) atom. In the eleventh O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one Si(1) atom. In the twelfth O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Hf(1), and one Si(2) atom. In the thirteenth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one S(1) atom. In the fourteenth O site, O(7) is bonded in a 1-coordinate geometry to one Na(2), one La(1), and one S(1) atom. In the fifteenth O site, O(8) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one La(1), and one Si(2) atom. In the sixteenth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one La(1), and one Si(1) atom. In the seventeenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one Si(1) atom. In the eighteenth O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Hf(1), and one Si(2) atom. In the nineteenth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one S(1) atom. In the twentieth O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one La(1), and one Si(1) atom. In the twenty-first O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one La(1), and one Si(2) atom. In the twenty-second O site, O(3) is bonded in a bent 150 degrees geometry to one La(1) and one S(1) atom. In the twenty-third O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Hf(1), and one S(1) atom. In the twenty-fourth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Hf(1) and one Si(2) atom. In the twenty-fifth O site, O(6) is bonded in a distorted linear geometry to one Na(2), one Hf(1), and one Si(1) atom. In the twenty-sixth O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one La(1), and one Si(1) atom. In the twenty-seventh O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one La(1), and one Si(2) atom. In the twenty-eighth O site, O(3) is bonded in a bent 150 degrees geometry to one La(1) and one S(1) atom. In the twenty-ninth O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Hf(1), and one S(1) atom. In the thirtieth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Hf(1) and one Si(2) atom. In the thirty-first O site, O(6) is bonded in a distorted linear geometry to one Na(2), one Hf(1), and one Si(1) atom. In the thirty-second O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one La(1), and one Si(1) atom. In the thirty-third O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one La(1), and one Si(2) atom. In the thirty-fourth O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Hf(1), and one S(1) atom. In the thirty-fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Hf(1) and one Si(2) atom.
Na3LaHfSi2SO12 crystallizes in the monoclinic Cc space group. There are eight inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one O(1), one O(11), and one O(9) atom. The Na(1)-O(1) bond length is 2.28 Å. The Na(1)-O(11) bond length is 2.45 Å. The Na(1)-O(9) bond length is 2.33 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. The Na(2)-O(10) bond length is 2.45 Å. The Na(2)-O(12) bond length is 2.85 Å. The Na(2)-O(2) bond length is 2.50 Å. The Na(2)-O(4) bond length is 2.86 Å. The Na(2)-O(6) bond length is 2.87 Å. The Na(2)-O(7) bond length is 2.46 Å. The Na(2)-O(8) bond length is 2.57 Å. In the third Na site, Na(1) is bonded in a 3-coordinate geometry to one O(1), one O(11), and one O(9) atom. The Na(1)-O(1) bond length is 2.27 Å. The Na(1)-O(11) bond length is 2.45 Å. The Na(1)-O(9) bond length is 2.33 Å. In the fourth Na site, Na(1) is bonded in a 3-coordinate geometry to one O(1), one O(11), and one O(9) atom. The Na(1)-O(1) bond length is 2.28 Å. The Na(1)-O(11) bond length is 2.45 Å. The Na(1)-O(9) bond length is 2.33 Å. In the fifth Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. The Na(2)-O(10) bond length is 2.45 Å. The Na(2)-O(12) bond length is 2.85 Å. The Na(2)-O(2) bond length is 2.50 Å. The Na(2)-O(4) bond length is 2.85 Å. The Na(2)-O(6) bond length is 2.87 Å. The Na(2)-O(7) bond length is 2.46 Å. The Na(2)-O(8) bond length is 2.57 Å. In the sixth Na site, Na(3) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(12), one O(8), and one O(9) atom. The Na(3)-O(10) bond length is 2.45 Å. The Na(3)-O(11) bond length is 2.73 Å. The Na(3)-O(12) bond length is 2.75 Å. The Na(3)-O(8) bond length is 2.49 Å. The Na(3)-O(9) bond length is 2.57 Å. In the seventh Na site, Na(3) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(12), one O(8), and one O(9) atom. The Na(3)-O(10) bond length is 2.45 Å. The Na(3)-O(11) bond length is 2.73 Å. The Na(3)-O(12) bond length is 2.74 Å. The Na(3)-O(8) bond length is 2.50 Å. The Na(3)-O(9) bond length is 2.58 Å. In the eighth Na site, Na(3) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(12), one O(8), and one O(9) atom. The Na(3)-O(10) bond length is 2.45 Å. The Na(3)-O(11) bond length is 2.73 Å. The Na(3)-O(12) bond length is 2.74 Å. The Na(3)-O(8) bond length is 2.50 Å. The Na(3)-O(9) bond length is 2.58 Å. La(1) is bonded to one O(1), one O(2), one O(3), one O(7), one O(8), and one O(9) atom to form distorted LaO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The La(1)-O(1) bond length is 2.28 Å. The La(1)-O(2) bond length is 2.28 Å. The La(1)-O(3) bond length is 2.31 Å. The La(1)-O(7) bond length is 2.50 Å. The La(1)-O(8) bond length is 2.38 Å. The La(1)-O(9) bond length is 2.34 Å. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form distorted HfO6 octahedra that share corners with two Si(1,1)O4 tetrahedra; corners with two equivalent Si(2)O4 tetrahedra; and corners with two equivalent S(1)O4 tetrahedra. The Hf(1)-O(10) bond length is 2.13 Å. The Hf(1)-O(11) bond length is 2.00 Å. The Hf(1)-O(12) bond length is 2.31 Å. The Hf(1)-O(4) bond length is 2.52 Å. The Hf(1)-O(5) bond length is 2.00 Å. The Hf(1)-O(6) bond length is 2.04 Å. In the second Hf site, Hf(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form distorted HfO6 octahedra that share corners with two Si(1,1)O4 tetrahedra; corners with two equivalent Si(2)O4 tetrahedra; and corners with two equivalent S(1)O4 tetrahedra. The Hf(1)-O(10) bond length is 2.13 Å. The Hf(1)-O(11) bond length is 2.00 Å. The Hf(1)-O(12) bond length is 2.31 Å. The Hf(1)-O(4) bond length is 2.52 Å. The Hf(1)-O(5) bond length is 2.00 Å. The Hf(1)-O(6) bond length is 2.04 Å. In the third Hf site, Hf(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form distorted HfO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The Hf(1)-O(10) bond length is 2.13 Å. The Hf(1)-O(11) bond length is 2.00 Å. The Hf(1)-O(12) bond length is 2.31 Å. The Hf(1)-O(4) bond length is 2.52 Å. The Hf(1)-O(5) bond length is 2.00 Å. The Hf(1)-O(6) bond length is 2.04 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent La(1)O6 octahedra and corners with two Hf(1,1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-44°. The Si(1)-O(1) bond length is 1.61 Å. The Si(1)-O(10) bond length is 1.68 Å. The Si(1)-O(6) bond length is 1.70 Å. The Si(1)-O(9) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent La(1)O6 octahedra and corners with two Hf(1,1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-42°. The Si(2)-O(11) bond length is 1.68 Å. The Si(2)-O(2) bond length is 1.61 Å. The Si(2)-O(5) bond length is 1.70 Å. The Si(2)-O(8) bond length is 1.62 Å. In the third Si site, Si(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent La(1)O6 octahedra and corners with two Hf(1,1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-44°. The Si(1)-O(1) bond length is 1.61 Å. The Si(1)-O(10) bond length is 1.68 Å. The Si(1)-O(6) bond length is 1.70 Å. The Si(1)-O(9) bond length is 1.63 Å. S(1) is bonded to one O(12), one O(3), one O(4), and one O(7) atom to form SO4 tetrahedra that share corners with two equivalent La(1)O6 octahedra and corners with two Hf(1,1)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-34°. The S(1)-O(12) bond length is 1.49 Å. The S(1)-O(3) bond length is 1.48 Å. The S(1)-O(4) bond length is 1.49 Å. The S(1)-O(7) bond length is 1.48 Å. There are thirty-five inequivalent O sites. In the first O site, O(6) is bonded in a distorted linear geometry to one Na(2), one Hf(1), and one Si(1) atom. The O(6)-Si(1) bond length is 1.70 Å. In the second O site, O(7) is bonded in a 1-coordinate geometry to one Na(2), one La(1), and one S(1) atom. The O(7)-S(1) bond length is 1.48 Å. In the third O site, O(8) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one La(1), and one Si(2) atom. The O(8)-Si(2) bond length is 1.62 Å. In the fourth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one La(1), and one Si(1) atom. The O(9)-Si(1) bond length is 1.63 Å. In the fifth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one Si(1) atom. The O(10)-Na(2) bond length is 2.45 Å. In the sixth O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Hf(1), and one Si(2) atom. The O(11)-Si(2) bond length is 1.68 Å. In the seventh O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one S(1) atom. The O(12)-Na(2) bond length is 2.85 Å. The O(12)-S(1) bond length is 1.49 Å. In the eighth O site, O(7) is bonded in a 1-coordinate geometry to one Na(2), one La(1), and one S(1) atom. The O(7)-La(1) bond length is 2.50 Å. In the ninth O site, O(8) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one La(1), and one Si(2) atom. The O(8)-La(1) bond length is 2.38 Å. In the tenth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one La(1), and one Si(1) atom. The O(9)-La(1) bond length is 2.34 Å. In the eleventh O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one Si(1) atom. The O(10)-Si(1) bond length is 1.68 Å. In the twelfth O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Hf(1), and one Si(2) atom. The O(11)-Si(2) bond length is 1.68 Å. In the thirteenth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one S(1) atom. The O(12)-S(1) bond length is 1.49 Å. In the fourteenth O site, O(7) is bonded in a 1-coordinate geometry to one Na(2), one La(1), and one S(1) atom. The O(7)-Na(2) bond length is 2.46 Å. The O(7)-La(1) bond length is 2.50 Å. The O(7)-S(1) bond length is 1.48 Å. In the fifteenth O site, O(8) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one La(1), and one Si(2) atom. The O(8)-Na(2) bond length is 2.57 Å. The O(8)-La(1) bond length is 2.38 Å. The O(8)-Si(2) bond length is 1.62 Å. In the sixteenth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one La(1), and one Si(1) atom. The O(9)-La(1) bond length is 2.34 Å. In the seventeenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one Si(1) atom. In the eighteenth O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Hf(1), and one Si(2) atom. In the nineteenth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one S(1) atom. In the twentieth O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one La(1), and one Si(1) atom. In the twenty-first O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one La(1), and one Si(2) atom. In the twenty-second O site, O(3) is bonded in a bent 150 degrees geometry to one La(1) and one S(1) atom. In the twenty-third O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Hf(1), and one S(1) atom. The O(4)-Na(2) bond length is 2.86 Å. In the twenty-fourth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Hf(1) and one Si(2) atom. In the twenty-fifth O site, O(6) is bonded in a distorted linear geometry to one Na(2), one Hf(1), and one Si(1) atom. In the twenty-sixth O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one La(1), and one Si(1) atom. The O(1)-La(1) bond length is 2.28 Å. In the twenty-seventh O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one La(1), and one Si(2) atom. The O(2)-La(1) bond length is 2.28 Å. The O(2)-Si(2) bond length is 1.61 Å. In the twenty-eighth O site, O(3) is bonded in a bent 150 degrees geometry to one La(1) and one S(1) atom. The O(3)-La(1) bond length is 2.31 Å. The O(3)-S(1) bond length is 1.48 Å. In the twenty-ninth O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Hf(1), and one S(1) atom. The O(4)-S(1) bond length is 1.49 Å. In the thirtieth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Hf(1) and one Si(2) atom. The O(5)-Si(2) bond length is 1.70 Å. In the thirty-first O site, O(6) is bonded in a distorted linear geometry to one Na(2), one Hf(1), and one Si(1) atom. The O(6)-Na(2) bond length is 2.87 Å. In the thirty-second O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one La(1), and one Si(1) atom. The O(1)-La(1) bond length is 2.28 Å. The O(1)-Si(1) bond length is 1.61 Å. In the thirty-third O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one La(1), and one Si(2) atom. The O(2)-Na(2) bond length is 2.50 Å. The O(2)-La(1) bond length is 2.28 Å. The O(2)-Si(2) bond length is 1.61 Å. In the thirty-fourth O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Hf(1), and one S(1) atom. The O(4)-S(1) bond length is 1.49 Å. In the thirty-fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Hf(1) and one Si(2) atom. The O(5)-Si(2) bond length is 1.70 Å.