Ca2NaSiO4F crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(11), one O(13), one O(15), one F(2), and one F(4) atom. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(1), one O(16), one O(2), one F(1), and one F(3) atom. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(12), one O(15), one O(4), one O(7), one O(9), and one F(2) atom. In the fourth Na site, Na(4) is bonded in a rectangular see-saw-like geometry to one O(14), one O(3), one O(8), and one F(1) atom. There are eight inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(11), one O(15), one O(4), one O(6), one O(8), one O(9), and one F(4) atom to form distorted CaO6F pentagonal bipyramids that share  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  an edgeedge with one Si(1)O3F tetrahedra, and  an edgeedge with one Si(4)O4 tetrahedra. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(13), one O(4), one O(9), and one F(2) atom. In the third Ca site, Ca(3) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(14), one O(3), one O(5), one O(7), and one O(8) atom. In the fourth Ca site, Ca(4) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one F(2), and one F(4) atom. In the fifth Ca site, Ca(5) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(14), one O(16), and one F(1) atom. In the sixth Ca site, Ca(6) is bonded to one O(1), one O(10), one O(13), one O(16), one O(5), and one F(3) atom to form CaO5F octahedra that share  a cornercorner with one Si(1)O3F tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. In the seventh Ca site, Ca(7) is bonded in a 4-coordinate geometry to one O(11), one O(12), one O(6), and one F(1) atom. In the eighth Ca site, Ca(8) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(5), one O(9), and one F(4) atom. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(6), one O(7), one O(8), and one F(3) atom to form SiO3F tetrahedra that share  a cornercorner with one Ca(6)O5F octahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  an edgeedge with one Ca(1)O6F pentagonal bipyramid. The corner-sharing octahedral tilt angles are 63°. In the second Si site, Si(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(6)O5F octahedra,  a cornercorner with one Ca(1)O6F pentagonal bipyramid, and  a cornercorner with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. In the third Si site, Si(3) is bonded to one O(14), one O(15), one O(16), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(6)O5F octahedra,  a cornercorner with one Ca(1)O6F pentagonal bipyramid, and  a cornercorner with one Si(1)O3F tetrahedra. The corner-sharing octahedral tilt angles are 66°. In the fourth Si site, Si(4) is bonded to one O(11), one O(13), one O(2), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(6)O5F octahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  an edgeedge with one Ca(1)O6F pentagonal bipyramid. The corner-sharing octahedral tilt angles are 53°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(2), one Ca(2), one Ca(4), one Ca(6), and one Si(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Si(2), and one Si(4) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(4), one Ca(3), one Ca(4), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(3), one Ca(1), one Ca(2), one Ca(4), and one Si(2) atom. In the fifth O site, O(5) is bonded to one Ca(3), one Ca(4), one Ca(6), and one Ca(8) atom to form OCa4 tetrahedra that share  a cornercorner with one O(10)Ca4 trigonal pyramid,  a cornercorner with one O(13)NaCa2Si trigonal pyramid,  a cornercorner with one O(16)NaCa2Si trigonal pyramid, and  an edgeedge with one O(10)Ca4 trigonal pyramid. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(7), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(3), one Ca(3), one Si(1), and one Si(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(4), one Ca(1), one Ca(3), and one Si(1) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(3), one Ca(1), one Ca(2), one Ca(8), and one Si(4) atom. In the tenth O site, O(10) is bonded to one Ca(3), one Ca(5), one Ca(6), and one Ca(8) atom to form OCa4 trigonal pyramids that share  a cornercorner with one O(5)Ca4 tetrahedra,  a cornercorner with one F(1)Na2Ca2 tetrahedra,  a cornercorner with one O(13)NaCa2Si trigonal pyramid,  an edgeedge with one O(5)Ca4 tetrahedra, and  an edgeedge with one O(16)NaCa2Si trigonal pyramid. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Ca(7), and one Si(4) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Na(3), one Ca(2), one Ca(3), one Ca(5), and one Ca(7) atom. In the thirteenth O site, O(13) is bonded to one Na(1), one Ca(2), one Ca(6), and one Si(4) atom to form distorted ONaCa2Si trigonal pyramids that share  a cornercorner with one O(5)Ca4 tetrahedra,  a cornercorner with one O(10)Ca4 trigonal pyramid, and  a cornercorner with one O(16)NaCa2Si trigonal pyramid. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to one Na(4), one Ca(3), one Ca(5), one Ca(8), and one Si(3) atom. In the fifteenth O site, O(15) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(3), one Ca(1), and one Si(3) atom. In the sixteenth O site, O(16) is bonded to one Na(2), one Ca(5), one Ca(6), and one Si(3) atom to form distorted ONaCa2Si trigonal pyramids that share  a cornercorner with one O(5)Ca4 tetrahedra,  a cornercorner with one O(13)NaCa2Si trigonal pyramid,  an edgeedge with one F(1)Na2Ca2 tetrahedra, and  an edgeedge with one O(10)Ca4 trigonal pyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), one Na(4), one Ca(5), and one Ca(7) atom to form FNa2Ca2 tetrahedra that share  a cornercorner with one O(10)Ca4 trigonal pyramid and  an edgeedge with one O(16)NaCa2Si trigonal pyramid. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(3), one Ca(2), and one Ca(4) atom. In the third F site, F(3) is bonded in a 1-coordinate geometry to one Na(2), one Ca(6), and one Si(1) atom. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Ca(1), one Ca(4), and one Ca(8) atom.
Ca2NaSiO4F crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(11), one O(13), one O(15), one F(2), and one F(4) atom. The Na(1)-O(11) bond length is 2.75 Å. The Na(1)-O(13) bond length is 2.23 Å. The Na(1)-O(15) bond length is 2.28 Å. The Na(1)-F(2) bond length is 2.39 Å. The Na(1)-F(4) bond length is 2.35 Å. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(1), one O(16), one O(2), one F(1), and one F(3) atom. The Na(2)-O(1) bond length is 2.77 Å. The Na(2)-O(16) bond length is 2.30 Å. The Na(2)-O(2) bond length is 2.42 Å. The Na(2)-F(1) bond length is 2.25 Å. The Na(2)-F(3) bond length is 2.52 Å. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(12), one O(15), one O(4), one O(7), one O(9), and one F(2) atom. The Na(3)-O(12) bond length is 2.94 Å. The Na(3)-O(15) bond length is 2.42 Å. The Na(3)-O(4) bond length is 2.48 Å. The Na(3)-O(7) bond length is 2.36 Å. The Na(3)-O(9) bond length is 2.31 Å. The Na(3)-F(2) bond length is 2.33 Å. In the fourth Na site, Na(4) is bonded in a rectangular see-saw-like geometry to one O(14), one O(3), one O(8), and one F(1) atom. The Na(4)-O(14) bond length is 2.20 Å. The Na(4)-O(3) bond length is 2.23 Å. The Na(4)-O(8) bond length is 2.21 Å. The Na(4)-F(1) bond length is 2.20 Å. There are eight inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(11), one O(15), one O(4), one O(6), one O(8), one O(9), and one F(4) atom to form distorted CaO6F pentagonal bipyramids that share  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  an edgeedge with one Si(1)O3F tetrahedra, and  an edgeedge with one Si(4)O4 tetrahedra. The Ca(1)-O(11) bond length is 2.51 Å. The Ca(1)-O(15) bond length is 2.29 Å. The Ca(1)-O(4) bond length is 2.62 Å. The Ca(1)-O(6) bond length is 2.50 Å. The Ca(1)-O(8) bond length is 2.47 Å. The Ca(1)-O(9) bond length is 2.62 Å. The Ca(1)-F(4) bond length is 2.47 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(13), one O(4), one O(9), and one F(2) atom. The Ca(2)-O(1) bond length is 2.36 Å. The Ca(2)-O(12) bond length is 2.23 Å. The Ca(2)-O(13) bond length is 2.35 Å. The Ca(2)-O(4) bond length is 2.66 Å. The Ca(2)-O(9) bond length is 2.88 Å. The Ca(2)-F(2) bond length is 2.31 Å. In the third Ca site, Ca(3) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(14), one O(3), one O(5), one O(7), and one O(8) atom. The Ca(3)-O(10) bond length is 2.20 Å. The Ca(3)-O(12) bond length is 2.89 Å. The Ca(3)-O(14) bond length is 2.74 Å. The Ca(3)-O(3) bond length is 2.38 Å. The Ca(3)-O(5) bond length is 2.25 Å. The Ca(3)-O(7) bond length is 2.71 Å. The Ca(3)-O(8) bond length is 2.47 Å. In the fourth Ca site, Ca(4) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one F(2), and one F(4) atom. The Ca(4)-O(1) bond length is 2.95 Å. The Ca(4)-O(3) bond length is 2.44 Å. The Ca(4)-O(4) bond length is 2.55 Å. The Ca(4)-O(5) bond length is 2.21 Å. The Ca(4)-F(2) bond length is 2.26 Å. The Ca(4)-F(4) bond length is 2.45 Å. In the fifth Ca site, Ca(5) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(14), one O(16), and one F(1) atom. The Ca(5)-O(10) bond length is 2.20 Å. The Ca(5)-O(12) bond length is 2.26 Å. The Ca(5)-O(14) bond length is 2.55 Å. The Ca(5)-O(16) bond length is 2.39 Å. The Ca(5)-F(1) bond length is 2.34 Å. In the sixth Ca site, Ca(6) is bonded to one O(1), one O(10), one O(13), one O(16), one O(5), and one F(3) atom to form CaO5F octahedra that share  a cornercorner with one Si(1)O3F tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The Ca(6)-O(1) bond length is 2.52 Å. The Ca(6)-O(10) bond length is 2.25 Å. The Ca(6)-O(13) bond length is 2.34 Å. The Ca(6)-O(16) bond length is 2.42 Å. The Ca(6)-O(5) bond length is 2.30 Å. The Ca(6)-F(3) bond length is 2.75 Å. In the seventh Ca site, Ca(7) is bonded in a 4-coordinate geometry to one O(11), one O(12), one O(6), and one F(1) atom. The Ca(7)-O(11) bond length is 2.26 Å. The Ca(7)-O(12) bond length is 2.25 Å. The Ca(7)-O(6) bond length is 2.33 Å. The Ca(7)-F(1) bond length is 2.23 Å. In the eighth Ca site, Ca(8) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(5), one O(9), and one F(4) atom. The Ca(8)-O(10) bond length is 2.26 Å. The Ca(8)-O(14) bond length is 2.52 Å. The Ca(8)-O(5) bond length is 2.25 Å. The Ca(8)-O(9) bond length is 2.35 Å. The Ca(8)-F(4) bond length is 2.53 Å. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(6), one O(7), one O(8), and one F(3) atom to form SiO3F tetrahedra that share  a cornercorner with one Ca(6)O5F octahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  an edgeedge with one Ca(1)O6F pentagonal bipyramid. The corner-sharing octahedral tilt angles are 63°. The Si(1)-O(6) bond length is 1.61 Å. The Si(1)-O(7) bond length is 1.63 Å. The Si(1)-O(8) bond length is 1.62 Å. The Si(1)-F(3) bond length is 1.70 Å. In the second Si site, Si(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(6)O5F octahedra,  a cornercorner with one Ca(1)O6F pentagonal bipyramid, and  a cornercorner with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. The Si(2)-O(1) bond length is 1.66 Å. The Si(2)-O(2) bond length is 1.70 Å. The Si(2)-O(3) bond length is 1.63 Å. The Si(2)-O(4) bond length is 1.65 Å. In the third Si site, Si(3) is bonded to one O(14), one O(15), one O(16), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(6)O5F octahedra,  a cornercorner with one Ca(1)O6F pentagonal bipyramid, and  a cornercorner with one Si(1)O3F tetrahedra. The corner-sharing octahedral tilt angles are 66°. The Si(3)-O(14) bond length is 1.64 Å. The Si(3)-O(15) bond length is 1.62 Å. The Si(3)-O(16) bond length is 1.63 Å. The Si(3)-O(7) bond length is 1.73 Å. In the fourth Si site, Si(4) is bonded to one O(11), one O(13), one O(2), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(6)O5F octahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  an edgeedge with one Ca(1)O6F pentagonal bipyramid. The corner-sharing octahedral tilt angles are 53°. The Si(4)-O(11) bond length is 1.64 Å. The Si(4)-O(13) bond length is 1.62 Å. The Si(4)-O(2) bond length is 1.68 Å. The Si(4)-O(9) bond length is 1.64 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(2), one Ca(2), one Ca(4), one Ca(6), and one Si(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Si(2), and one Si(4) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(4), one Ca(3), one Ca(4), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(3), one Ca(1), one Ca(2), one Ca(4), and one Si(2) atom. In the fifth O site, O(5) is bonded to one Ca(3), one Ca(4), one Ca(6), and one Ca(8) atom to form OCa4 tetrahedra that share  a cornercorner with one O(10)Ca4 trigonal pyramid,  a cornercorner with one O(13)NaCa2Si trigonal pyramid,  a cornercorner with one O(16)NaCa2Si trigonal pyramid, and  an edgeedge with one O(10)Ca4 trigonal pyramid. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(7), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(3), one Ca(3), one Si(1), and one Si(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(4), one Ca(1), one Ca(3), and one Si(1) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(3), one Ca(1), one Ca(2), one Ca(8), and one Si(4) atom. In the tenth O site, O(10) is bonded to one Ca(3), one Ca(5), one Ca(6), and one Ca(8) atom to form OCa4 trigonal pyramids that share  a cornercorner with one O(5)Ca4 tetrahedra,  a cornercorner with one F(1)Na2Ca2 tetrahedra,  a cornercorner with one O(13)NaCa2Si trigonal pyramid,  an edgeedge with one O(5)Ca4 tetrahedra, and  an edgeedge with one O(16)NaCa2Si trigonal pyramid. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Ca(7), and one Si(4) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Na(3), one Ca(2), one Ca(3), one Ca(5), and one Ca(7) atom. In the thirteenth O site, O(13) is bonded to one Na(1), one Ca(2), one Ca(6), and one Si(4) atom to form distorted ONaCa2Si trigonal pyramids that share  a cornercorner with one O(5)Ca4 tetrahedra,  a cornercorner with one O(10)Ca4 trigonal pyramid, and  a cornercorner with one O(16)NaCa2Si trigonal pyramid. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to one Na(4), one Ca(3), one Ca(5), one Ca(8), and one Si(3) atom. In the fifteenth O site, O(15) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(3), one Ca(1), and one Si(3) atom. In the sixteenth O site, O(16) is bonded to one Na(2), one Ca(5), one Ca(6), and one Si(3) atom to form distorted ONaCa2Si trigonal pyramids that share  a cornercorner with one O(5)Ca4 tetrahedra,  a cornercorner with one O(13)NaCa2Si trigonal pyramid,  an edgeedge with one F(1)Na2Ca2 tetrahedra, and  an edgeedge with one O(10)Ca4 trigonal pyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), one Na(4), one Ca(5), and one Ca(7) atom to form FNa2Ca2 tetrahedra that share  a cornercorner with one O(10)Ca4 trigonal pyramid and  an edgeedge with one O(16)NaCa2Si trigonal pyramid. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(3), one Ca(2), and one Ca(4) atom. In the third F site, F(3) is bonded in a 1-coordinate geometry to one Na(2), one Ca(6), and one Si(1) atom. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Ca(1), one Ca(4), and one Ca(8) atom.