Ca5As3O12F crystallizes in the triclinic P-1 space group. There are five inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one O(11), one O(12), one O(2), one O(5), one O(6), one O(7), one O(8), and one O(9) atom. In the second Ca site, Ca(2) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(2), one O(4), one O(6), one O(7), and one F(1) atom. In the third Ca site, Ca(3) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(3), one O(4), one O(5), one O(7), and one F(1) atom. In the fourth Ca site, Ca(4) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(12), one O(3), one O(5), one O(6), one O(8), and one O(9) atom. In the fifth Ca site, Ca(5) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(8), one O(9), and one F(1) atom. There are three inequivalent As sites. In the first As site, As(1) is bonded in a tetrahedral geometry to one O(1), one O(3), one O(6), and one O(9) atom. In the second As site, As(2) is bonded in a tetrahedral geometry to one O(11), one O(4), one O(7), and one O(8) atom. In the third As site, As(3) is bonded in a tetrahedral geometry to one O(10), one O(12), one O(2), and one O(5) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(3), one Ca(5), and one As(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(5), and one As(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(3), one Ca(4), one Ca(5), and one As(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(2), one Ca(3), and one As(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(3), one Ca(4), and one As(3) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(4), and one As(1) atom. In the seventh O site, O(7) is bonded to one Ca(1), one Ca(2), one Ca(3), and one As(2) atom to form a mixture of distorted corner and edge-sharing OCa3As tetrahedra. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(4), one Ca(5), and one As(2) atom. In the ninth O site, O(9) is bonded to one Ca(1), one Ca(4), one Ca(5), and one As(1) atom to form a mixture of distorted corner and edge-sharing OCa3As trigonal pyramids. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Ca(2), one Ca(4), one Ca(5), and one As(3) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(3), one Ca(4), and one As(2) atom. In the twelfth O site, O(12) is bonded to one Ca(1), one Ca(2), one Ca(4), and one As(3) atom to form distorted edge-sharing OCa3As trigonal pyramids. F(1) is bonded in a trigonal planar geometry to one Ca(2), one Ca(3), and one Ca(5) atom.
Ca5As3O12F crystallizes in the triclinic P-1 space group. There are five inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one O(11), one O(12), one O(2), one O(5), one O(6), one O(7), one O(8), and one O(9) atom. The Ca(1)-O(11) bond length is 2.76 Å. The Ca(1)-O(12) bond length is 2.50 Å. The Ca(1)-O(2) bond length is 2.73 Å. The Ca(1)-O(5) bond length is 2.43 Å. The Ca(1)-O(6) bond length is 2.43 Å. The Ca(1)-O(7) bond length is 2.60 Å. The Ca(1)-O(8) bond length is 2.36 Å. The Ca(1)-O(9) bond length is 2.45 Å. In the second Ca site, Ca(2) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(2), one O(4), one O(6), one O(7), and one F(1) atom. The Ca(2)-O(10) bond length is 2.38 Å. The Ca(2)-O(12) bond length is 2.46 Å. The Ca(2)-O(2) bond length is 2.38 Å. The Ca(2)-O(4) bond length is 2.42 Å. The Ca(2)-O(6) bond length is 2.88 Å. The Ca(2)-O(7) bond length is 2.60 Å. The Ca(2)-F(1) bond length is 2.39 Å. In the third Ca site, Ca(3) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(3), one O(4), one O(5), one O(7), and one F(1) atom. The Ca(3)-O(1) bond length is 2.41 Å. The Ca(3)-O(11) bond length is 2.44 Å. The Ca(3)-O(3) bond length is 2.63 Å. The Ca(3)-O(4) bond length is 2.35 Å. The Ca(3)-O(5) bond length is 2.79 Å. The Ca(3)-O(7) bond length is 2.38 Å. The Ca(3)-F(1) bond length is 2.36 Å. In the fourth Ca site, Ca(4) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(12), one O(3), one O(5), one O(6), one O(8), and one O(9) atom. The Ca(4)-O(10) bond length is 2.96 Å. The Ca(4)-O(11) bond length is 2.39 Å. The Ca(4)-O(12) bond length is 2.55 Å. The Ca(4)-O(3) bond length is 2.57 Å. The Ca(4)-O(5) bond length is 2.41 Å. The Ca(4)-O(6) bond length is 2.33 Å. The Ca(4)-O(8) bond length is 2.49 Å. The Ca(4)-O(9) bond length is 2.61 Å. In the fifth Ca site, Ca(5) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(8), one O(9), and one F(1) atom. The Ca(5)-O(1) bond length is 2.37 Å. The Ca(5)-O(10) bond length is 2.44 Å. The Ca(5)-O(2) bond length is 2.64 Å. The Ca(5)-O(3) bond length is 2.39 Å. The Ca(5)-O(8) bond length is 2.86 Å. The Ca(5)-O(9) bond length is 2.46 Å. The Ca(5)-F(1) bond length is 2.36 Å. There are three inequivalent As sites. In the first As site, As(1) is bonded in a tetrahedral geometry to one O(1), one O(3), one O(6), and one O(9) atom. The As(1)-O(1) bond length is 1.71 Å. The As(1)-O(3) bond length is 1.73 Å. The As(1)-O(6) bond length is 1.71 Å. The As(1)-O(9) bond length is 1.73 Å. In the second As site, As(2) is bonded in a tetrahedral geometry to one O(11), one O(4), one O(7), and one O(8) atom. The As(2)-O(11) bond length is 1.73 Å. The As(2)-O(4) bond length is 1.72 Å. The As(2)-O(7) bond length is 1.73 Å. The As(2)-O(8) bond length is 1.71 Å. In the third As site, As(3) is bonded in a tetrahedral geometry to one O(10), one O(12), one O(2), and one O(5) atom. The As(3)-O(10) bond length is 1.72 Å. The As(3)-O(12) bond length is 1.73 Å. The As(3)-O(2) bond length is 1.72 Å. The As(3)-O(5) bond length is 1.71 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(3), one Ca(5), and one As(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(5), and one As(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(3), one Ca(4), one Ca(5), and one As(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(2), one Ca(3), and one As(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(3), one Ca(4), and one As(3) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(4), and one As(1) atom. In the seventh O site, O(7) is bonded to one Ca(1), one Ca(2), one Ca(3), and one As(2) atom to form a mixture of distorted corner and edge-sharing OCa3As tetrahedra. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(4), one Ca(5), and one As(2) atom. In the ninth O site, O(9) is bonded to one Ca(1), one Ca(4), one Ca(5), and one As(1) atom to form a mixture of distorted corner and edge-sharing OCa3As trigonal pyramids. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Ca(2), one Ca(4), one Ca(5), and one As(3) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(3), one Ca(4), and one As(2) atom. In the twelfth O site, O(12) is bonded to one Ca(1), one Ca(2), one Ca(4), and one As(3) atom to form distorted edge-sharing OCa3As trigonal pyramids. F(1) is bonded in a trigonal planar geometry to one Ca(2), one Ca(3), and one Ca(5) atom.