Na4Al2Si6O24Cl crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(11), one O(14), one O(7), and one O(9) atom. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(10), one O(15), one O(17), one O(22), and one O(4) atom. In the third Na site, Na(3) is bonded in a distorted T-shaped geometry to one O(3), one O(4), and one O(9) atom. In the fourth Na site, Na(4) is bonded in a distorted rectangular see-saw-like geometry to one O(14), one O(16), one O(2), and one O(5) atom. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded in a 5-coordinate geometry to one O(1), one O(13), one O(19), one O(5), and one O(7) atom. In the second Al site, Al(2) is bonded to one O(1), one O(12), one O(20), and one O(24) atom to form AlO4 tetrahedra that share  a cornercorner with one Si(5)O4 tetrahedra,  a cornercorner with one Si(6)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. There are six inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(18), one O(20), and one O(3) atom to form distorted SiO4 tetrahedra that share  an edgeedge with one Al(2)O4 tetrahedra. In the second Si site, Si(2) is bonded to one O(11), one O(21), one O(4), and one Cl(1) atom to form edge-sharing SiClO3 tetrahedra. In the third Si site, Si(3) is bonded in an L-shaped geometry to one O(16) and one O(22) atom. In the fourth Si site, Si(4) is bonded to one O(13), one O(15), one O(6), and one O(9) atom to form corner-sharing SiO4 tetrahedra. In the fifth Si site, Si(5) is bonded to one O(12), one O(16), one O(19), and one O(22) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(2)O4 tetrahedra. In the sixth Si site, Si(6) is bonded to one O(11), one O(21), one O(24), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(2)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, and  an edgeedge with one Si(2)ClO3 tetrahedra. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Al(1), one Al(2), and one Si(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(4), one O(18), and one O(8) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Na(3) and one Si(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(2), one Na(3), and one Si(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(4), one Al(1), and one O(7) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Si(4) and one Si(6) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one O(5) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one O(10) and one O(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(3), and one Si(4) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Na(2) and one O(8) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one Na(1), one Si(2), and one Si(6) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Al(2) and one Si(5) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one Al(1) and one Si(4) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(4), and one O(20) atom. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one Na(2) and one Si(4) atom. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Na(4), one Si(3), and one Si(5) atom. In the seventeenth O site, O(17) is bonded in a water-like geometry to one Na(2) and one O(23) atom. In the eighteenth O site, O(18) is bonded in a distorted single-bond geometry to one Si(1) and one O(2) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one Al(1) and one Si(5) atom. In the twentieth O site, O(20) is bonded in a distorted water-like geometry to one Al(2), one Si(1), and one O(14) atom. In the twenty-first O site, O(21) is bonded in an L-shaped geometry to one Si(2) and one Si(6) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Na(2), one Si(3), and one Si(5) atom. In the twenty-third O site, O(23) is bonded in a single-bond geometry to one O(17) atom. In the twenty-fourth O site, O(24) is bonded in a bent 120 degrees geometry to one Al(2) and one Si(6) atom. Cl(1) is bonded in a single-bond geometry to one Si(2) atom.
Na4Al2Si6O24Cl crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(11), one O(14), one O(7), and one O(9) atom. The Na(1)-O(11) bond length is 2.31 Å. The Na(1)-O(14) bond length is 2.34 Å. The Na(1)-O(7) bond length is 2.34 Å. The Na(1)-O(9) bond length is 2.23 Å. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(10), one O(15), one O(17), one O(22), and one O(4) atom. The Na(2)-O(10) bond length is 2.52 Å. The Na(2)-O(15) bond length is 2.22 Å. The Na(2)-O(17) bond length is 2.81 Å. The Na(2)-O(22) bond length is 2.36 Å. The Na(2)-O(4) bond length is 2.25 Å. In the third Na site, Na(3) is bonded in a distorted T-shaped geometry to one O(3), one O(4), and one O(9) atom. The Na(3)-O(3) bond length is 2.17 Å. The Na(3)-O(4) bond length is 2.23 Å. The Na(3)-O(9) bond length is 2.22 Å. In the fourth Na site, Na(4) is bonded in a distorted rectangular see-saw-like geometry to one O(14), one O(16), one O(2), and one O(5) atom. The Na(4)-O(14) bond length is 2.36 Å. The Na(4)-O(16) bond length is 2.25 Å. The Na(4)-O(2) bond length is 2.45 Å. The Na(4)-O(5) bond length is 2.36 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded in a 5-coordinate geometry to one O(1), one O(13), one O(19), one O(5), and one O(7) atom. The Al(1)-O(1) bond length is 1.84 Å. The Al(1)-O(13) bond length is 1.72 Å. The Al(1)-O(19) bond length is 1.74 Å. The Al(1)-O(5) bond length is 1.90 Å. The Al(1)-O(7) bond length is 1.93 Å. In the second Al site, Al(2) is bonded to one O(1), one O(12), one O(20), and one O(24) atom to form AlO4 tetrahedra that share  a cornercorner with one Si(5)O4 tetrahedra,  a cornercorner with one Si(6)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The Al(2)-O(1) bond length is 1.83 Å. The Al(2)-O(12) bond length is 1.71 Å. The Al(2)-O(20) bond length is 1.86 Å. The Al(2)-O(24) bond length is 1.70 Å. There are six inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(18), one O(20), and one O(3) atom to form distorted SiO4 tetrahedra that share  an edgeedge with one Al(2)O4 tetrahedra. The Si(1)-O(1) bond length is 1.70 Å. The Si(1)-O(18) bond length is 1.72 Å. The Si(1)-O(20) bond length is 1.74 Å. The Si(1)-O(3) bond length is 1.54 Å. In the second Si site, Si(2) is bonded to one O(11), one O(21), one O(4), and one Cl(1) atom to form edge-sharing SiClO3 tetrahedra. The Si(2)-O(11) bond length is 1.69 Å. The Si(2)-O(21) bond length is 1.69 Å. The Si(2)-O(4) bond length is 1.57 Å. The Si(2)-Cl(1) bond length is 2.08 Å. In the third Si site, Si(3) is bonded in an L-shaped geometry to one O(16) and one O(22) atom. The Si(3)-O(16) bond length is 1.71 Å. The Si(3)-O(22) bond length is 1.74 Å. In the fourth Si site, Si(4) is bonded to one O(13), one O(15), one O(6), and one O(9) atom to form corner-sharing SiO4 tetrahedra. The Si(4)-O(13) bond length is 1.63 Å. The Si(4)-O(15) bond length is 1.64 Å. The Si(4)-O(6) bond length is 1.68 Å. The Si(4)-O(9) bond length is 1.61 Å. In the fifth Si site, Si(5) is bonded to one O(12), one O(16), one O(19), and one O(22) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(2)O4 tetrahedra. The Si(5)-O(12) bond length is 1.61 Å. The Si(5)-O(16) bond length is 1.71 Å. The Si(5)-O(19) bond length is 1.59 Å. The Si(5)-O(22) bond length is 1.70 Å. In the sixth Si site, Si(6) is bonded to one O(11), one O(21), one O(24), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(2)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, and  an edgeedge with one Si(2)ClO3 tetrahedra. The Si(6)-O(11) bond length is 1.70 Å. The Si(6)-O(21) bond length is 1.68 Å. The Si(6)-O(24) bond length is 1.61 Å. The Si(6)-O(6) bond length is 1.59 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Al(1), one Al(2), and one Si(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(4), one O(18), and one O(8) atom. The O(2)-O(18) bond length is 1.39 Å. The O(2)-O(8) bond length is 1.96 Å. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Na(3) and one Si(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(2), one Na(3), and one Si(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(4), one Al(1), and one O(7) atom. The O(5)-O(7) bond length is 1.40 Å. In the sixth O site, O(6) is bonded in a linear geometry to one Si(4) and one Si(6) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one O(5) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one O(10) and one O(2) atom. The O(8)-O(10) bond length is 1.23 Å. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(3), and one Si(4) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Na(2) and one O(8) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one Na(1), one Si(2), and one Si(6) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Al(2) and one Si(5) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one Al(1) and one Si(4) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(4), and one O(20) atom. The O(14)-O(20) bond length is 1.44 Å. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one Na(2) and one Si(4) atom. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Na(4), one Si(3), and one Si(5) atom. In the seventeenth O site, O(17) is bonded in a water-like geometry to one Na(2) and one O(23) atom. The O(17)-O(23) bond length is 1.23 Å. In the eighteenth O site, O(18) is bonded in a distorted single-bond geometry to one Si(1) and one O(2) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one Al(1) and one Si(5) atom. In the twentieth O site, O(20) is bonded in a distorted water-like geometry to one Al(2), one Si(1), and one O(14) atom. In the twenty-first O site, O(21) is bonded in an L-shaped geometry to one Si(2) and one Si(6) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Na(2), one Si(3), and one Si(5) atom. In the twenty-third O site, O(23) is bonded in a single-bond geometry to one O(17) atom. In the twenty-fourth O site, O(24) is bonded in a bent 120 degrees geometry to one Al(2) and one Si(6) atom. Cl(1) is bonded in a single-bond geometry to one Si(2) atom.