Na9U3Si4(O10F)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(10), and two equivalent O(6) atoms to form NaO6 octahedra that share corners with two equivalent U(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent U(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one O(7), one O(8), and one F(1) atom. In the third Na site, Na(3) is bonded to one O(1), one O(6), two equivalent O(10), and two equivalent O(8) atoms to form NaO6 octahedra that share corners with two equivalent U(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and edges with two equivalent U(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the fourth Na site, Na(4) is bonded to one O(2), one O(5), two equivalent O(9), and two equivalent F(1) atoms to form distorted NaO4F2 octahedra that share corners with four equivalent Na(5)O4F2 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, edges with two equivalent Na(4)O4F2 octahedra, edges with two equivalent Na(5)O4F2 octahedra, and edges with two equivalent U(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-31°. In the fifth Na site, Na(5) is bonded to one O(3), one O(7), two equivalent O(9), and two equivalent F(1) atoms to form distorted NaO4F2 octahedra that share corners with four equivalent Na(4)O4F2 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, edges with two equivalent Na(4)O4F2 octahedra, edges with two equivalent Na(5)O4F2 octahedra, and edges with two equivalent U(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-31°. There are two inequivalent U sites. In the first U site, U(1) is bonded to two equivalent O(1), two equivalent O(6), and two equivalent O(8) atoms to form UO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. In the second U site, U(2) is bonded to one O(10), one O(2), one O(3), one O(5), one O(7), and one O(9) atom to form UO6 octahedra that share  a cornercorner with one Na(1)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Na(4)O4F2 octahedra, and edges with two equivalent Na(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. There are two inequivalent Si sites. In the first Si site, Si(1) 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 Na(4)O4F2 octahedra,  a cornercorner with one Na(5)O4F2 octahedra,  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one U(1)O6 octahedra, corners with two equivalent U(2)O6 octahedra, and  a cornercorner with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-69°. In the second Si site, Si(2) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(4)O4F2 octahedra,  a cornercorner with one Na(5)O4F2 octahedra,  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one U(1)O6 octahedra, corners with two equivalent U(2)O6 octahedra, and  a cornercorner with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-69°. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), one U(1), and one Si(1) atom to form distorted ONa2USi tetrahedra that share corners with two equivalent O(1)Na2USi tetrahedra, corners with two equivalent O(8)Na3U tetrahedra, corners with three equivalent O(6)Na2USi tetrahedra,  an edgeedge with one O(6)Na2USi tetrahedra, and  an edgeedge with one O(8)Na3U tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one U(2), and one Si(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one U(2), and one Si(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one U(2), and one Si(2) atom. In the sixth O site, O(6) is bonded to one Na(1), one Na(3), one U(1), and one Si(2) atom to form distorted ONa2USi tetrahedra that share corners with two equivalent O(6)Na2USi tetrahedra, corners with two equivalent O(8)Na3U tetrahedra, corners with three equivalent O(1)Na2USi tetrahedra,  an edgeedge with one O(1)Na2USi tetrahedra, and  an edgeedge with one O(8)Na3U tetrahedra. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one U(2), and one Si(2) atom. In the eighth O site, O(8) is bonded to one Na(2), two equivalent Na(3), and one U(1) atom to form distorted ONa3U tetrahedra that share  a cornercorner with one F(1)Na5 square pyramid,  a cornercorner with one O(8)Na3U tetrahedra, corners with two equivalent O(1)Na2USi tetrahedra, corners with two equivalent O(6)Na2USi tetrahedra,  an edgeedge with one O(1)Na2USi tetrahedra,  an edgeedge with one O(6)Na2USi tetrahedra, and  an edgeedge with one O(8)Na3U tetrahedra. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to two equivalent Na(4), two equivalent Na(5), and one U(2) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Na(3), and one U(2) atom. F(1) is bonded to one Na(2), two equivalent Na(4), and two equivalent Na(5) atoms to form FNa5 square pyramids that share  a cornercorner with one O(8)Na3U tetrahedra and edges with two equivalent F(1)Na5 square pyramids.
Na9U3Si4(O10F)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(10), and two equivalent O(6) atoms to form NaO6 octahedra that share corners with two equivalent U(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent U(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. Both Na(1)-O(1) bond lengths are 2.48 Å. Both Na(1)-O(10) bond lengths are 2.49 Å. Both Na(1)-O(6) bond lengths are 2.48 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one O(7), one O(8), and one F(1) atom. The Na(2)-O(2) bond length is 2.74 Å. The Na(2)-O(3) bond length is 2.68 Å. The Na(2)-O(5) bond length is 2.73 Å. The Na(2)-O(7) bond length is 2.67 Å. The Na(2)-O(8) bond length is 2.38 Å. The Na(2)-F(1) bond length is 2.23 Å. In the third Na site, Na(3) is bonded to one O(1), one O(6), two equivalent O(10), and two equivalent O(8) atoms to form NaO6 octahedra that share corners with two equivalent U(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and edges with two equivalent U(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Na(3)-O(1) bond length is 2.39 Å. The Na(3)-O(6) bond length is 2.39 Å. There is one shorter (2.52 Å) and one longer (2.53 Å) Na(3)-O(10) bond length. There is one shorter (2.59 Å) and one longer (2.60 Å) Na(3)-O(8) bond length. In the fourth Na site, Na(4) is bonded to one O(2), one O(5), two equivalent O(9), and two equivalent F(1) atoms to form distorted NaO4F2 octahedra that share corners with four equivalent Na(5)O4F2 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, edges with two equivalent Na(4)O4F2 octahedra, edges with two equivalent Na(5)O4F2 octahedra, and edges with two equivalent U(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-31°. The Na(4)-O(2) bond length is 2.49 Å. The Na(4)-O(5) bond length is 2.49 Å. There is one shorter (2.59 Å) and one longer (2.60 Å) Na(4)-O(9) bond length. Both Na(4)-F(1) bond lengths are 2.32 Å. In the fifth Na site, Na(5) is bonded to one O(3), one O(7), two equivalent O(9), and two equivalent F(1) atoms to form distorted NaO4F2 octahedra that share corners with four equivalent Na(4)O4F2 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, edges with two equivalent Na(4)O4F2 octahedra, edges with two equivalent Na(5)O4F2 octahedra, and edges with two equivalent U(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-31°. The Na(5)-O(3) bond length is 2.55 Å. The Na(5)-O(7) bond length is 2.55 Å. There is one shorter (2.58 Å) and one longer (2.59 Å) Na(5)-O(9) bond length. There is one shorter (2.31 Å) and one longer (2.32 Å) Na(5)-F(1) bond length. There are two inequivalent U sites. In the first U site, U(1) is bonded to two equivalent O(1), two equivalent O(6), and two equivalent O(8) atoms to form UO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. Both U(1)-O(1) bond lengths are 2.32 Å. Both U(1)-O(6) bond lengths are 2.32 Å. Both U(1)-O(8) bond lengths are 1.90 Å. In the second U site, U(2) is bonded to one O(10), one O(2), one O(3), one O(5), one O(7), and one O(9) atom to form UO6 octahedra that share  a cornercorner with one Na(1)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Na(4)O4F2 octahedra, and edges with two equivalent Na(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. The U(2)-O(10) bond length is 1.90 Å. The U(2)-O(2) bond length is 2.24 Å. The U(2)-O(3) bond length is 2.25 Å. The U(2)-O(5) bond length is 2.24 Å. The U(2)-O(7) bond length is 2.25 Å. The U(2)-O(9) bond length is 1.91 Å. There are two inequivalent Si sites. In the first Si site, Si(1) 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 Na(4)O4F2 octahedra,  a cornercorner with one Na(5)O4F2 octahedra,  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one U(1)O6 octahedra, corners with two equivalent U(2)O6 octahedra, and  a cornercorner with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-69°. The Si(1)-O(1) bond length is 1.64 Å. The Si(1)-O(2) bond length is 1.64 Å. The Si(1)-O(3) bond length is 1.64 Å. The Si(1)-O(4) bond length is 1.64 Å. In the second Si site, Si(2) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(4)O4F2 octahedra,  a cornercorner with one Na(5)O4F2 octahedra,  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one U(1)O6 octahedra, corners with two equivalent U(2)O6 octahedra, and  a cornercorner with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-69°. The Si(2)-O(4) bond length is 1.64 Å. The Si(2)-O(5) bond length is 1.64 Å. The Si(2)-O(6) bond length is 1.64 Å. The Si(2)-O(7) bond length is 1.64 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), one U(1), and one Si(1) atom to form distorted ONa2USi tetrahedra that share corners with two equivalent O(1)Na2USi tetrahedra, corners with two equivalent O(8)Na3U tetrahedra, corners with three equivalent O(6)Na2USi tetrahedra,  an edgeedge with one O(6)Na2USi tetrahedra, and  an edgeedge with one O(8)Na3U tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one U(2), and one Si(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one U(2), and one Si(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one U(2), and one Si(2) atom. In the sixth O site, O(6) is bonded to one Na(1), one Na(3), one U(1), and one Si(2) atom to form distorted ONa2USi tetrahedra that share corners with two equivalent O(6)Na2USi tetrahedra, corners with two equivalent O(8)Na3U tetrahedra, corners with three equivalent O(1)Na2USi tetrahedra,  an edgeedge with one O(1)Na2USi tetrahedra, and  an edgeedge with one O(8)Na3U tetrahedra. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one U(2), and one Si(2) atom. In the eighth O site, O(8) is bonded to one Na(2), two equivalent Na(3), and one U(1) atom to form distorted ONa3U tetrahedra that share  a cornercorner with one F(1)Na5 square pyramid,  a cornercorner with one O(8)Na3U tetrahedra, corners with two equivalent O(1)Na2USi tetrahedra, corners with two equivalent O(6)Na2USi tetrahedra,  an edgeedge with one O(1)Na2USi tetrahedra,  an edgeedge with one O(6)Na2USi tetrahedra, and  an edgeedge with one O(8)Na3U tetrahedra. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to two equivalent Na(4), two equivalent Na(5), and one U(2) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Na(3), and one U(2) atom. F(1) is bonded to one Na(2), two equivalent Na(4), and two equivalent Na(5) atoms to form FNa5 square pyramids that share  a cornercorner with one O(8)Na3U tetrahedra and edges with two equivalent F(1)Na5 square pyramids.