Ca2Al3O6F crystallizes in the triclinic P-1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), two equivalent F(1), and two equivalent F(2) atoms. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one O(2), one O(4), one O(5), two equivalent O(10), two equivalent O(9), and one F(2) atom. In the third Ca site, Ca(3) is bonded in a 8-coordinate geometry to one O(3), one O(5), one O(6), two equivalent O(11), two equivalent O(7), and one F(1) atom. In the fourth Ca site, Ca(4) is bonded in a 9-coordinate geometry to one O(1), one O(4), one O(6), two equivalent O(12), two equivalent O(8), one F(1), and one F(2) atom. There are six inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(11), one O(2), one O(3), and one O(7) atom to form corner-sharing AlO4 tetrahedra. In the second Al site, Al(2) is bonded to one O(1), one O(12), one O(3), and one O(8) atom to form corner-sharing AlO4 tetrahedra. In the third Al site, Al(3) is bonded to one O(1), one O(10), one O(2), and one O(9) atom to form corner-sharing AlO4 tetrahedra. In the fourth Al site, Al(4) is bonded to one O(10), one O(4), one O(5), and one O(7) atom to form corner-sharing AlO4 tetrahedra. In the fifth Al site, Al(5) is bonded to one O(11), one O(5), one O(6), and one O(8) atom to form corner-sharing AlO4 tetrahedra. In the sixth Al site, Al(6) is bonded to one O(12), one O(4), one O(6), and one O(9) atom to form corner-sharing AlO4 tetrahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(4), one Al(2), and one Al(3) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Al(1), and one Al(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(3), one Al(1), and one Al(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(4), one Al(4), and one Al(6) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(3), one Al(4), and one Al(5) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(3), one Ca(4), one Al(5), and one Al(6) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Ca(3), one Al(1), and one Al(4) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to two equivalent Ca(4), one Al(2), and one Al(5) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to two equivalent Ca(2), one Al(3), and one Al(6) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to two equivalent Ca(2), one Al(3), and one Al(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to two equivalent Ca(3), one Al(1), and one Al(5) atom. In the twelfth O site, O(12) is bonded in a distorted bent 120 degrees geometry to two equivalent Ca(4), one Al(2), and one Al(6) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Ca(3), one Ca(4), and two equivalent Ca(1) atoms to form distorted edge-sharing FCa4 tetrahedra. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(4), and two equivalent Ca(1) atoms.
Ca2Al3O6F crystallizes in the triclinic P-1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), two equivalent F(1), and two equivalent F(2) atoms. The Ca(1)-O(1) bond length is 2.57 Å. The Ca(1)-O(2) bond length is 2.52 Å. The Ca(1)-O(3) bond length is 2.53 Å. There is one shorter (2.31 Å) and one longer (2.52 Å) Ca(1)-F(1) bond length. There is one shorter (2.31 Å) and one longer (2.49 Å) Ca(1)-F(2) bond length. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one O(2), one O(4), one O(5), two equivalent O(10), two equivalent O(9), and one F(2) atom. The Ca(2)-O(2) bond length is 2.70 Å. The Ca(2)-O(4) bond length is 2.60 Å. The Ca(2)-O(5) bond length is 2.37 Å. There is one shorter (2.57 Å) and one longer (2.72 Å) Ca(2)-O(10) bond length. There is one shorter (2.53 Å) and one longer (2.54 Å) Ca(2)-O(9) bond length. The Ca(2)-F(2) bond length is 2.30 Å. In the third Ca site, Ca(3) is bonded in a 8-coordinate geometry to one O(3), one O(5), one O(6), two equivalent O(11), two equivalent O(7), and one F(1) atom. The Ca(3)-O(3) bond length is 2.74 Å. The Ca(3)-O(5) bond length is 2.60 Å. The Ca(3)-O(6) bond length is 2.35 Å. There is one shorter (2.53 Å) and one longer (2.71 Å) Ca(3)-O(11) bond length. There is one shorter (2.53 Å) and one longer (2.57 Å) Ca(3)-O(7) bond length. The Ca(3)-F(1) bond length is 2.34 Å. In the fourth Ca site, Ca(4) is bonded in a 9-coordinate geometry to one O(1), one O(4), one O(6), two equivalent O(12), two equivalent O(8), one F(1), and one F(2) atom. The Ca(4)-O(1) bond length is 2.62 Å. The Ca(4)-O(4) bond length is 2.38 Å. The Ca(4)-O(6) bond length is 2.61 Å. There is one shorter (2.61 Å) and one longer (2.78 Å) Ca(4)-O(12) bond length. There is one shorter (2.65 Å) and one longer (2.72 Å) Ca(4)-O(8) bond length. The Ca(4)-F(1) bond length is 2.71 Å. The Ca(4)-F(2) bond length is 2.75 Å. There are six inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(11), one O(2), one O(3), and one O(7) atom to form corner-sharing AlO4 tetrahedra. The Al(1)-O(11) bond length is 1.75 Å. The Al(1)-O(2) bond length is 1.77 Å. The Al(1)-O(3) bond length is 1.79 Å. The Al(1)-O(7) bond length is 1.77 Å. In the second Al site, Al(2) is bonded to one O(1), one O(12), one O(3), and one O(8) atom to form corner-sharing AlO4 tetrahedra. The Al(2)-O(1) bond length is 1.81 Å. The Al(2)-O(12) bond length is 1.76 Å. The Al(2)-O(3) bond length is 1.78 Å. The Al(2)-O(8) bond length is 1.76 Å. In the third Al site, Al(3) is bonded to one O(1), one O(10), one O(2), and one O(9) atom to form corner-sharing AlO4 tetrahedra. The Al(3)-O(1) bond length is 1.78 Å. The Al(3)-O(10) bond length is 1.76 Å. The Al(3)-O(2) bond length is 1.80 Å. The Al(3)-O(9) bond length is 1.77 Å. In the fourth Al site, Al(4) is bonded to one O(10), one O(4), one O(5), and one O(7) atom to form corner-sharing AlO4 tetrahedra. The Al(4)-O(10) bond length is 1.76 Å. The Al(4)-O(4) bond length is 1.76 Å. The Al(4)-O(5) bond length is 1.78 Å. The Al(4)-O(7) bond length is 1.76 Å. In the fifth Al site, Al(5) is bonded to one O(11), one O(5), one O(6), and one O(8) atom to form corner-sharing AlO4 tetrahedra. The Al(5)-O(11) bond length is 1.77 Å. The Al(5)-O(5) bond length is 1.77 Å. The Al(5)-O(6) bond length is 1.78 Å. The Al(5)-O(8) bond length is 1.76 Å. In the sixth Al site, Al(6) is bonded to one O(12), one O(4), one O(6), and one O(9) atom to form corner-sharing AlO4 tetrahedra. The Al(6)-O(12) bond length is 1.76 Å. The Al(6)-O(4) bond length is 1.77 Å. The Al(6)-O(6) bond length is 1.76 Å. The Al(6)-O(9) bond length is 1.77 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(4), one Al(2), and one Al(3) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Al(1), and one Al(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(3), one Al(1), and one Al(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(4), one Al(4), and one Al(6) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(3), one Al(4), and one Al(5) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(3), one Ca(4), one Al(5), and one Al(6) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Ca(3), one Al(1), and one Al(4) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to two equivalent Ca(4), one Al(2), and one Al(5) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to two equivalent Ca(2), one Al(3), and one Al(6) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to two equivalent Ca(2), one Al(3), and one Al(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to two equivalent Ca(3), one Al(1), and one Al(5) atom. In the twelfth O site, O(12) is bonded in a distorted bent 120 degrees geometry to two equivalent Ca(4), one Al(2), and one Al(6) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Ca(3), one Ca(4), and two equivalent Ca(1) atoms to form distorted edge-sharing FCa4 tetrahedra. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(4), and two equivalent Ca(1) atoms.