Na2Al2Si3(HO3)4 crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(16), one O(21), one O(23), one O(24), and one O(8) atom to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Al(3)O4 tetrahedra,  a cornercorner with one Al(4)O4 tetrahedra,  a cornercorner with one Si(3)HO3 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  an edgeedge with one Si(6)O4 tetrahedra. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(14), one O(16), one O(2), one O(6), and one O(9) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(18), one O(22), one O(23), one O(4), one O(5), and one O(8) atom. In the fourth Na site, Na(4) is bonded in a 8-coordinate geometry to one H(7), one O(1), one O(14), one O(15), one O(18), one O(20), one O(24), and one O(3) atom. There are four inequivalent Al sites. In the first Al site, Al(1) is bonded in a 5-coordinate geometry to one H(1), one O(1), one O(11), one O(19), and one O(7) atom. In the second Al site, Al(2) is bonded in a 6-coordinate geometry to one H(1), one H(4), one O(12), one O(21), one O(22), and one O(7) atom. In the third Al site, Al(3) is bonded to one O(13), one O(17), one O(23), and one O(6) atom to form AlO4 tetrahedra that share  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra,  a cornercorner with one Si(6)O4 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. In the fourth Al site, Al(4) is bonded to one O(10), one O(20), one O(22), and one O(8) atom to form AlO4 tetrahedra that share  a cornercorner with one Si(5)O4 tetrahedra,  a cornercorner with one Si(6)O4 tetrahedra,  a cornercorner with one Si(1)O5 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. There are six inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(10), one O(12), one O(19), one O(5), and one O(9) atom to form distorted SiO5 tetrahedra that share  a cornercorner with one Al(4)O4 tetrahedra,  a cornercorner with one Si(3)HO3 tetrahedra, and  a cornercorner with one Si(5)O4 tetrahedra. In the second Si site, Si(2) is bonded to one H(2), one H(4), one O(1), one O(3), and one O(4) atom to form corner-sharing SiH2O3 trigonal bipyramids. In the third Si site, Si(3) is bonded to one H(3), one O(14), one O(16), and one O(19) atom to form SiHO3 tetrahedra that share  a cornercorner with one Si(6)O4 tetrahedra,  a cornercorner with one Si(1)O5 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. In the fourth Si site, Si(4) is bonded to one O(18), one O(2), one O(21), and one O(6) atom to form distorted SiO4 tetrahedra that share  a cornercorner with one Al(3)O4 tetrahedra and  a cornercorner with one Na(1)O5 trigonal bipyramid. In the fifth Si site, Si(5) is bonded to one O(20), one O(23), one O(3), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(3)O4 tetrahedra,  a cornercorner with one Al(4)O4 tetrahedra,  a cornercorner with one Si(1)O5 tetrahedra,  a cornercorner with one Na(1)O5 trigonal bipyramid, and  a cornercorner with one Si(2)H2O3 trigonal bipyramid. In the sixth Si site, Si(6) is bonded to one O(11), one O(16), one O(17), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(3)O4 tetrahedra,  a cornercorner with one Al(4)O4 tetrahedra,  a cornercorner with one Si(3)HO3 tetrahedra, and  an edgeedge with one Na(1)O5 trigonal bipyramid. There are eight inequivalent H sites. In the first H site, H(1) is bonded in a water-like geometry to one Al(1) and one Al(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one Si(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one Si(3) atom. In the fourth H site, H(4) is bonded in a bent 150 degrees geometry to one Al(2) and one Si(2) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(13) atom. In the sixth H site, H(6) is bonded in a distorted linear geometry to one O(13) and one O(24) atom. In the seventh H site, H(7) is bonded in a distorted single-bond geometry to one Na(4), one O(14), and one O(18) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(15) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), one Na(4), one Al(1), and one Si(2) atom to form distorted corner-sharing ONa2AlSi trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Si(4), and one O(4) atom. In the third O site, O(3) is bonded in a distorted linear geometry to one Na(4), one Si(2), and one Si(5) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(3), one Si(2), and one O(2) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Na(3), one Si(1), and one O(12) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Al(3), and one Si(4) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Al(1), one Al(2), and one O(24) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Al(4), and one Si(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(2), one Si(1), and one Si(5) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Al(4) and one Si(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Al(1), one Si(6), and one O(15) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Al(2), one Si(1), and one O(5) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one Al(3), one H(5), and one H(6) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Si(3), and one H(7) atom. In the fifteenth O site, O(15) is bonded in a single-bond geometry to one Na(4), one H(8), and one O(11) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Si(3), and one Si(6) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one Al(3) and one Si(6) atom. In the eighteenth O site, O(18) is bonded in a 2-coordinate geometry to one Na(3), one Na(4), one Si(4), and one H(7) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Al(1), one Si(1), and one Si(3) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal non-coplanar geometry to one Na(4), one Al(4), and one Si(5) atom. In the twenty-first O site, O(21) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Al(2), and one Si(4) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Na(3), one Al(2), and one Al(4) atom. In the twenty-third O site, O(23) is bonded to one Na(1), one Na(3), one Al(3), and one Si(5) atom to form distorted corner-sharing ONa2AlSi tetrahedra. In the twenty-fourth O site, O(24) is bonded in a distorted single-bond geometry to one Na(1), one Na(4), one H(6), and one O(7) atom.
Na2Al2Si3(HO3)4 crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(16), one O(21), one O(23), one O(24), and one O(8) atom to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Al(3)O4 tetrahedra,  a cornercorner with one Al(4)O4 tetrahedra,  a cornercorner with one Si(3)HO3 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  an edgeedge with one Si(6)O4 tetrahedra. The Na(1)-O(16) bond length is 2.46 Å. The Na(1)-O(21) bond length is 2.30 Å. The Na(1)-O(23) bond length is 2.34 Å. The Na(1)-O(24) bond length is 2.23 Å. The Na(1)-O(8) bond length is 2.55 Å. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(14), one O(16), one O(2), one O(6), and one O(9) atom. The Na(2)-O(14) bond length is 2.32 Å. The Na(2)-O(16) bond length is 2.56 Å. The Na(2)-O(2) bond length is 2.16 Å. The Na(2)-O(6) bond length is 2.35 Å. The Na(2)-O(9) bond length is 2.27 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(18), one O(22), one O(23), one O(4), one O(5), and one O(8) atom. The Na(3)-O(1) bond length is 2.35 Å. The Na(3)-O(18) bond length is 2.49 Å. The Na(3)-O(22) bond length is 2.35 Å. The Na(3)-O(23) bond length is 2.81 Å. The Na(3)-O(4) bond length is 2.56 Å. The Na(3)-O(5) bond length is 2.95 Å. The Na(3)-O(8) bond length is 2.61 Å. In the fourth Na site, Na(4) is bonded in a 8-coordinate geometry to one H(7), one O(1), one O(14), one O(15), one O(18), one O(20), one O(24), and one O(3) atom. The Na(4)-H(7) bond length is 2.22 Å. The Na(4)-O(1) bond length is 2.46 Å. The Na(4)-O(14) bond length is 2.29 Å. The Na(4)-O(15) bond length is 2.75 Å. The Na(4)-O(18) bond length is 2.29 Å. The Na(4)-O(20) bond length is 2.35 Å. The Na(4)-O(24) bond length is 2.36 Å. The Na(4)-O(3) bond length is 2.85 Å. There are four inequivalent Al sites. In the first Al site, Al(1) is bonded in a 5-coordinate geometry to one H(1), one O(1), one O(11), one O(19), and one O(7) atom. The Al(1)-H(1) bond length is 1.66 Å. The Al(1)-O(1) bond length is 1.79 Å. The Al(1)-O(11) bond length is 2.10 Å. The Al(1)-O(19) bond length is 2.28 Å. The Al(1)-O(7) bond length is 1.80 Å. In the second Al site, Al(2) is bonded in a 6-coordinate geometry to one H(1), one H(4), one O(12), one O(21), one O(22), and one O(7) atom. The Al(2)-H(1) bond length is 2.01 Å. The Al(2)-H(4) bond length is 1.73 Å. The Al(2)-O(12) bond length is 1.88 Å. The Al(2)-O(21) bond length is 1.79 Å. The Al(2)-O(22) bond length is 1.75 Å. The Al(2)-O(7) bond length is 2.32 Å. In the third Al site, Al(3) is bonded to one O(13), one O(17), one O(23), and one O(6) atom to form AlO4 tetrahedra that share  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra,  a cornercorner with one Si(6)O4 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. The Al(3)-O(13) bond length is 1.78 Å. The Al(3)-O(17) bond length is 1.76 Å. The Al(3)-O(23) bond length is 1.79 Å. The Al(3)-O(6) bond length is 1.79 Å. In the fourth Al site, Al(4) is bonded to one O(10), one O(20), one O(22), and one O(8) atom to form AlO4 tetrahedra that share  a cornercorner with one Si(5)O4 tetrahedra,  a cornercorner with one Si(6)O4 tetrahedra,  a cornercorner with one Si(1)O5 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. The Al(4)-O(10) bond length is 1.74 Å. The Al(4)-O(20) bond length is 1.78 Å. The Al(4)-O(22) bond length is 1.71 Å. The Al(4)-O(8) bond length is 1.78 Å. There are six inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(10), one O(12), one O(19), one O(5), and one O(9) atom to form distorted SiO5 tetrahedra that share  a cornercorner with one Al(4)O4 tetrahedra,  a cornercorner with one Si(3)HO3 tetrahedra, and  a cornercorner with one Si(5)O4 tetrahedra. The Si(1)-O(10) bond length is 1.62 Å. The Si(1)-O(12) bond length is 2.04 Å. The Si(1)-O(19) bond length is 1.73 Å. The Si(1)-O(5) bond length is 1.65 Å. The Si(1)-O(9) bond length is 1.67 Å. In the second Si site, Si(2) is bonded to one H(2), one H(4), one O(1), one O(3), and one O(4) atom to form corner-sharing SiH2O3 trigonal bipyramids. The Si(2)-H(2) bond length is 1.48 Å. The Si(2)-H(4) bond length is 1.65 Å. The Si(2)-O(1) bond length is 1.68 Å. The Si(2)-O(3) bond length is 1.64 Å. The Si(2)-O(4) bond length is 1.86 Å. In the third Si site, Si(3) is bonded to one H(3), one O(14), one O(16), and one O(19) atom to form SiHO3 tetrahedra that share  a cornercorner with one Si(6)O4 tetrahedra,  a cornercorner with one Si(1)O5 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. The Si(3)-H(3) bond length is 1.48 Å. The Si(3)-O(14) bond length is 1.58 Å. The Si(3)-O(16) bond length is 1.67 Å. The Si(3)-O(19) bond length is 1.68 Å. In the fourth Si site, Si(4) is bonded to one O(18), one O(2), one O(21), and one O(6) atom to form distorted SiO4 tetrahedra that share  a cornercorner with one Al(3)O4 tetrahedra and  a cornercorner with one Na(1)O5 trigonal bipyramid. The Si(4)-O(18) bond length is 1.65 Å. The Si(4)-O(2) bond length is 1.71 Å. The Si(4)-O(21) bond length is 1.61 Å. The Si(4)-O(6) bond length is 1.65 Å. In the fifth Si site, Si(5) is bonded to one O(20), one O(23), one O(3), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(3)O4 tetrahedra,  a cornercorner with one Al(4)O4 tetrahedra,  a cornercorner with one Si(1)O5 tetrahedra,  a cornercorner with one Na(1)O5 trigonal bipyramid, and  a cornercorner with one Si(2)H2O3 trigonal bipyramid. The Si(5)-O(20) bond length is 1.61 Å. The Si(5)-O(23) bond length is 1.65 Å. The Si(5)-O(3) bond length is 1.64 Å. The Si(5)-O(9) bond length is 1.66 Å. In the sixth Si site, Si(6) is bonded to one O(11), one O(16), one O(17), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(3)O4 tetrahedra,  a cornercorner with one Al(4)O4 tetrahedra,  a cornercorner with one Si(3)HO3 tetrahedra, and  an edgeedge with one Na(1)O5 trigonal bipyramid. The Si(6)-O(11) bond length is 1.78 Å. The Si(6)-O(16) bond length is 1.65 Å. The Si(6)-O(17) bond length is 1.59 Å. The Si(6)-O(8) bond length is 1.60 Å. There are eight inequivalent H sites. In the first H site, H(1) is bonded in a water-like geometry to one Al(1) and one Al(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one Si(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one Si(3) atom. In the fourth H site, H(4) is bonded in a bent 150 degrees geometry to one Al(2) and one Si(2) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(13) atom. The H(5)-O(13) bond length is 0.97 Å. In the sixth H site, H(6) is bonded in a distorted linear geometry to one O(13) and one O(24) atom. The H(6)-O(13) bond length is 1.37 Å. The H(6)-O(24) bond length is 1.07 Å. In the seventh H site, H(7) is bonded in a distorted single-bond geometry to one Na(4), one O(14), and one O(18) atom. The H(7)-O(14) bond length is 1.63 Å. The H(7)-O(18) bond length is 1.01 Å. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(15) atom. The H(8)-O(15) bond length is 1.01 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), one Na(4), one Al(1), and one Si(2) atom to form distorted corner-sharing ONa2AlSi trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Si(4), and one O(4) atom. The O(2)-O(4) bond length is 1.53 Å. In the third O site, O(3) is bonded in a distorted linear geometry to one Na(4), one Si(2), and one Si(5) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(3), one Si(2), and one O(2) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Na(3), one Si(1), and one O(12) atom. The O(5)-O(12) bond length is 1.54 Å. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Al(3), and one Si(4) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Al(1), one Al(2), and one O(24) atom. The O(7)-O(24) bond length is 1.48 Å. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Al(4), and one Si(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(2), one Si(1), and one Si(5) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Al(4) and one Si(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Al(1), one Si(6), and one O(15) atom. The O(11)-O(15) bond length is 1.50 Å. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Al(2), one Si(1), and one O(5) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one Al(3), one H(5), and one H(6) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Si(3), and one H(7) atom. In the fifteenth O site, O(15) is bonded in a single-bond geometry to one Na(4), one H(8), and one O(11) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Si(3), and one Si(6) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one Al(3) and one Si(6) atom. In the eighteenth O site, O(18) is bonded in a 2-coordinate geometry to one Na(3), one Na(4), one Si(4), and one H(7) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Al(1), one Si(1), and one Si(3) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal non-coplanar geometry to one Na(4), one Al(4), and one Si(5) atom. In the twenty-first O site, O(21) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Al(2), and one Si(4) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Na(3), one Al(2), and one Al(4) atom. In the twenty-third O site, O(23) is bonded to one Na(1), one Na(3), one Al(3), and one Si(5) atom to form distorted corner-sharing ONa2AlSi tetrahedra. In the twenty-fourth O site, O(24) is bonded in a distorted single-bond geometry to one Na(1), one Na(4), one H(6), and one O(7) atom.