Ba2CaCu3F14 crystallizes in the triclinic P1 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to one F(11), one F(18), one F(2), one F(22), one F(24), one F(27), one F(3), one F(5), one F(9), and two equivalent F(4) atoms. In the second Ba site, Ba(2) is bonded in a 11-coordinate geometry to one F(13), one F(14), one F(15), one F(16), one F(19), one F(21), one F(23), one F(7), one F(8), and two equivalent F(28) atoms. In the third Ba site, Ba(3) is bonded in a 11-coordinate geometry to one F(1), one F(13), one F(14), one F(16), one F(2), one F(20), one F(23), one F(25), one F(3), and two equivalent F(10) atoms. In the fourth Ba site, Ba(4) is bonded in a 11-coordinate geometry to one F(11), one F(17), one F(21), one F(22), one F(26), one F(27), one F(6), one F(7), one F(9), and two equivalent F(12) atoms. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one F(11), one F(18), one F(22), one F(26), one F(27), one F(5), one F(6), and one F(9) atom. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one F(1), one F(13), one F(14), one F(15), one F(16), one F(23), one F(25), and one F(8) atom. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(11), one F(12), one F(19), one F(26), one F(7), and one F(9) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 47-55°. In the second Cu site, Cu(2) is bonded to one F(14), one F(16), one F(17), one F(21), one F(28), and one F(8) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. In the third Cu site, Cu(3) is bonded to one F(1), one F(10), one F(13), one F(2), one F(23), and one F(24) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 44-56°. In the fourth Cu site, Cu(4) is bonded to one F(18), one F(20), one F(22), one F(27), one F(3), and one F(4) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. In the fifth Cu site, Cu(5) is bonded to one F(15), one F(17), one F(19), one F(21), one F(6), and one F(7) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. In the sixth Cu site, Cu(6) is bonded to one F(2), one F(20), one F(24), one F(25), one F(3), and one F(5) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. There are twenty-eight inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Ba(3), one Ca(2), and one Cu(3) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one Cu(3), and one Cu(6) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one Cu(4), and one Cu(6) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Cu(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ca(1), and one Cu(6) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Ba(4), one Ca(1), and one Cu(5) atom. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Ba(2), one Ba(4), one Cu(1), and one Cu(5) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Ba(2), one Ca(2), and one Cu(2) atom. In the ninth F site, F(9) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(4), one Ca(1), and one Cu(1) atom. In the tenth F site, F(10) is bonded in a distorted single-bond geometry to two equivalent Ba(3) and one Cu(3) atom. In the eleventh F site, F(11) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(4), one Ca(1), and one Cu(1) atom. In the twelfth F site, F(12) is bonded in a distorted single-bond geometry to two equivalent Ba(4) and one Cu(1) atom. In the thirteenth F site, F(13) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(3), one Ca(2), and one Cu(3) atom. In the fourteenth F site, F(14) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(3), one Ca(2), and one Cu(2) atom. In the fifteenth F site, F(15) is bonded in a distorted trigonal planar geometry to one Ba(2), one Ca(2), and one Cu(5) atom. In the sixteenth F site, F(16) is bonded to one Ba(2), one Ba(3), one Ca(2), and one Cu(2) atom to form distorted corner-sharing FBa2CaCu tetrahedra. In the seventeenth F site, F(17) is bonded in a distorted bent 150 degrees geometry to one Ba(4), one Cu(2), and one Cu(5) atom. In the eighteenth F site, F(18) is bonded in a 3-coordinate geometry to one Ba(1), one Ca(1), and one Cu(4) atom. In the nineteenth F site, F(19) is bonded in a 2-coordinate geometry to one Ba(2), one Cu(1), and one Cu(5) atom. In the twentieth F site, F(20) is bonded in a distorted bent 150 degrees geometry to one Ba(3), one Cu(4), and one Cu(6) atom. In the twenty-first F site, F(21) is bonded in a 4-coordinate geometry to one Ba(2), one Ba(4), one Cu(2), and one Cu(5) atom. In the twenty-second F site, F(22) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(4), one Ca(1), and one Cu(4) atom. In the twenty-third F site, F(23) is bonded to one Ba(2), one Ba(3), one Ca(2), and one Cu(3) atom to form distorted corner-sharing FBa2CaCu tetrahedra. In the twenty-fourth F site, F(24) is bonded in a 2-coordinate geometry to one Ba(1), one Cu(3), and one Cu(6) atom. In the twenty-fifth F site, F(25) is bonded in a distorted trigonal planar geometry to one Ba(3), one Ca(2), and one Cu(6) atom. In the twenty-sixth F site, F(26) is bonded in a 3-coordinate geometry to one Ba(4), one Ca(1), and one Cu(1) atom. In the twenty-seventh F site, F(27) is bonded in a distorted tetrahedral geometry to one Ba(1), one Ba(4), one Ca(1), and one Cu(4) atom. In the twenty-eighth F site, F(28) is bonded in a distorted single-bond geometry to two equivalent Ba(2) and one Cu(2) atom.
Ba2CaCu3F14 crystallizes in the triclinic P1 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to one F(11), one F(18), one F(2), one F(22), one F(24), one F(27), one F(3), one F(5), one F(9), and two equivalent F(4) atoms. The Ba(1)-F(11) bond length is 3.01 Å. The Ba(1)-F(18) bond length is 2.68 Å. The Ba(1)-F(2) bond length is 2.80 Å. The Ba(1)-F(22) bond length is 3.19 Å. The Ba(1)-F(24) bond length is 2.99 Å. The Ba(1)-F(27) bond length is 2.80 Å. The Ba(1)-F(3) bond length is 2.87 Å. The Ba(1)-F(5) bond length is 2.81 Å. The Ba(1)-F(9) bond length is 2.78 Å. There is one shorter (2.75 Å) and one longer (2.93 Å) Ba(1)-F(4) bond length. In the second Ba site, Ba(2) is bonded in a 11-coordinate geometry to one F(13), one F(14), one F(15), one F(16), one F(19), one F(21), one F(23), one F(7), one F(8), and two equivalent F(28) atoms. The Ba(2)-F(13) bond length is 2.99 Å. The Ba(2)-F(14) bond length is 3.15 Å. The Ba(2)-F(15) bond length is 2.79 Å. The Ba(2)-F(16) bond length is 2.78 Å. The Ba(2)-F(19) bond length is 2.96 Å. The Ba(2)-F(21) bond length is 2.90 Å. The Ba(2)-F(23) bond length is 2.76 Å. The Ba(2)-F(7) bond length is 2.85 Å. The Ba(2)-F(8) bond length is 2.71 Å. There is one shorter (2.76 Å) and one longer (2.95 Å) Ba(2)-F(28) bond length. In the third Ba site, Ba(3) is bonded in a 11-coordinate geometry to one F(1), one F(13), one F(14), one F(16), one F(2), one F(20), one F(23), one F(25), one F(3), and two equivalent F(10) atoms. The Ba(3)-F(1) bond length is 2.68 Å. The Ba(3)-F(13) bond length is 3.17 Å. The Ba(3)-F(14) bond length is 2.98 Å. The Ba(3)-F(16) bond length is 2.75 Å. The Ba(3)-F(2) bond length is 2.88 Å. The Ba(3)-F(20) bond length is 3.02 Å. The Ba(3)-F(23) bond length is 2.81 Å. The Ba(3)-F(25) bond length is 2.81 Å. The Ba(3)-F(3) bond length is 2.81 Å. There is one shorter (2.75 Å) and one longer (2.94 Å) Ba(3)-F(10) bond length. In the fourth Ba site, Ba(4) is bonded in a 11-coordinate geometry to one F(11), one F(17), one F(21), one F(22), one F(26), one F(27), one F(6), one F(7), one F(9), and two equivalent F(12) atoms. The Ba(4)-F(11) bond length is 3.16 Å. The Ba(4)-F(17) bond length is 3.01 Å. The Ba(4)-F(21) bond length is 2.81 Å. The Ba(4)-F(22) bond length is 2.99 Å. The Ba(4)-F(26) bond length is 2.68 Å. The Ba(4)-F(27) bond length is 2.77 Å. The Ba(4)-F(6) bond length is 2.80 Å. The Ba(4)-F(7) bond length is 2.92 Å. The Ba(4)-F(9) bond length is 2.81 Å. There is one shorter (2.75 Å) and one longer (2.95 Å) Ba(4)-F(12) bond length. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one F(11), one F(18), one F(22), one F(26), one F(27), one F(5), one F(6), and one F(9) atom. The Ca(1)-F(11) bond length is 2.38 Å. The Ca(1)-F(18) bond length is 2.35 Å. The Ca(1)-F(22) bond length is 2.37 Å. The Ca(1)-F(26) bond length is 2.36 Å. The Ca(1)-F(27) bond length is 2.50 Å. The Ca(1)-F(5) bond length is 2.31 Å. The Ca(1)-F(6) bond length is 2.30 Å. The Ca(1)-F(9) bond length is 2.52 Å. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one F(1), one F(13), one F(14), one F(15), one F(16), one F(23), one F(25), and one F(8) atom. The Ca(2)-F(1) bond length is 2.36 Å. The Ca(2)-F(13) bond length is 2.37 Å. The Ca(2)-F(14) bond length is 2.36 Å. The Ca(2)-F(15) bond length is 2.31 Å. The Ca(2)-F(16) bond length is 2.49 Å. The Ca(2)-F(23) bond length is 2.53 Å. The Ca(2)-F(25) bond length is 2.31 Å. The Ca(2)-F(8) bond length is 2.37 Å. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(11), one F(12), one F(19), one F(26), one F(7), and one F(9) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 47-55°. The Cu(1)-F(11) bond length is 1.94 Å. The Cu(1)-F(12) bond length is 1.90 Å. The Cu(1)-F(19) bond length is 1.97 Å. The Cu(1)-F(26) bond length is 1.90 Å. The Cu(1)-F(7) bond length is 1.96 Å. The Cu(1)-F(9) bond length is 1.97 Å. In the second Cu site, Cu(2) is bonded to one F(14), one F(16), one F(17), one F(21), one F(28), and one F(8) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. The Cu(2)-F(14) bond length is 1.96 Å. The Cu(2)-F(16) bond length is 2.02 Å. The Cu(2)-F(17) bond length is 1.98 Å. The Cu(2)-F(21) bond length is 1.97 Å. The Cu(2)-F(28) bond length is 1.87 Å. The Cu(2)-F(8) bond length is 1.88 Å. In the third Cu site, Cu(3) is bonded to one F(1), one F(10), one F(13), one F(2), one F(23), and one F(24) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 44-56°. The Cu(3)-F(1) bond length is 1.91 Å. The Cu(3)-F(10) bond length is 1.90 Å. The Cu(3)-F(13) bond length is 1.94 Å. The Cu(3)-F(2) bond length is 1.94 Å. The Cu(3)-F(23) bond length is 1.98 Å. The Cu(3)-F(24) bond length is 1.97 Å. In the fourth Cu site, Cu(4) is bonded to one F(18), one F(20), one F(22), one F(27), one F(3), and one F(4) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. The Cu(4)-F(18) bond length is 1.91 Å. The Cu(4)-F(20) bond length is 1.97 Å. The Cu(4)-F(22) bond length is 1.94 Å. The Cu(4)-F(27) bond length is 1.99 Å. The Cu(4)-F(3) bond length is 1.94 Å. The Cu(4)-F(4) bond length is 1.90 Å. In the fifth Cu site, Cu(5) is bonded to one F(15), one F(17), one F(19), one F(21), one F(6), and one F(7) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. The Cu(5)-F(15) bond length is 1.89 Å. The Cu(5)-F(17) bond length is 1.91 Å. The Cu(5)-F(19) bond length is 1.95 Å. The Cu(5)-F(21) bond length is 2.31 Å. The Cu(5)-F(6) bond length is 1.87 Å. The Cu(5)-F(7) bond length is 2.28 Å. In the sixth Cu site, Cu(6) is bonded to one F(2), one F(20), one F(24), one F(25), one F(3), and one F(5) atom to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. The Cu(6)-F(2) bond length is 2.35 Å. The Cu(6)-F(20) bond length is 1.92 Å. The Cu(6)-F(24) bond length is 1.92 Å. The Cu(6)-F(25) bond length is 1.86 Å. The Cu(6)-F(3) bond length is 2.36 Å. The Cu(6)-F(5) bond length is 1.87 Å. There are twenty-eight inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Ba(3), one Ca(2), and one Cu(3) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one Cu(3), and one Cu(6) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one Cu(4), and one Cu(6) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Cu(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ca(1), and one Cu(6) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Ba(4), one Ca(1), and one Cu(5) atom. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Ba(2), one Ba(4), one Cu(1), and one Cu(5) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Ba(2), one Ca(2), and one Cu(2) atom. In the ninth F site, F(9) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(4), one Ca(1), and one Cu(1) atom. In the tenth F site, F(10) is bonded in a distorted single-bond geometry to two equivalent Ba(3) and one Cu(3) atom. In the eleventh F site, F(11) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(4), one Ca(1), and one Cu(1) atom. In the twelfth F site, F(12) is bonded in a distorted single-bond geometry to two equivalent Ba(4) and one Cu(1) atom. In the thirteenth F site, F(13) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(3), one Ca(2), and one Cu(3) atom. In the fourteenth F site, F(14) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(3), one Ca(2), and one Cu(2) atom. In the fifteenth F site, F(15) is bonded in a distorted trigonal planar geometry to one Ba(2), one Ca(2), and one Cu(5) atom. In the sixteenth F site, F(16) is bonded to one Ba(2), one Ba(3), one Ca(2), and one Cu(2) atom to form distorted corner-sharing FBa2CaCu tetrahedra. In the seventeenth F site, F(17) is bonded in a distorted bent 150 degrees geometry to one Ba(4), one Cu(2), and one Cu(5) atom. In the eighteenth F site, F(18) is bonded in a 3-coordinate geometry to one Ba(1), one Ca(1), and one Cu(4) atom. In the nineteenth F site, F(19) is bonded in a 2-coordinate geometry to one Ba(2), one Cu(1), and one Cu(5) atom. In the twentieth F site, F(20) is bonded in a distorted bent 150 degrees geometry to one Ba(3), one Cu(4), and one Cu(6) atom. In the twenty-first F site, F(21) is bonded in a 4-coordinate geometry to one Ba(2), one Ba(4), one Cu(2), and one Cu(5) atom. In the twenty-second F site, F(22) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(4), one Ca(1), and one Cu(4) atom. In the twenty-third F site, F(23) is bonded to one Ba(2), one Ba(3), one Ca(2), and one Cu(3) atom to form distorted corner-sharing FBa2CaCu tetrahedra. In the twenty-fourth F site, F(24) is bonded in a 2-coordinate geometry to one Ba(1), one Cu(3), and one Cu(6) atom. In the twenty-fifth F site, F(25) is bonded in a distorted trigonal planar geometry to one Ba(3), one Ca(2), and one Cu(6) atom. In the twenty-sixth F site, F(26) is bonded in a 3-coordinate geometry to one Ba(4), one Ca(1), and one Cu(1) atom. In the twenty-seventh F site, F(27) is bonded in a distorted tetrahedral geometry to one Ba(1), one Ba(4), one Ca(1), and one Cu(4) atom. In the twenty-eighth F site, F(28) is bonded in a distorted single-bond geometry to two equivalent Ba(2) and one Cu(2) atom.