K4Mo6Se2O33 crystallizes in the triclinic P1 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 4-coordinate geometry to one O(11), one O(14), one O(24), one O(25), and one O(26) atom. In the second K site, K(2) is bonded in a distorted square co-planar geometry to one O(12), one O(13), one O(25), and one O(26) atom. In the third K site, K(3) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(17), one O(19), one O(2), one O(20), one O(21), one O(22), and one O(27) atom. In the fourth K site, K(4) is bonded in a 5-coordinate geometry to one O(18), one O(28), one O(3), one O(4), and one O(9) atom. There are six inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 6-coordinate geometry to one O(13), one O(16), one O(3), one O(31), one O(5), and one O(7) atom. In the second Mo site, Mo(2) is bonded in a 6-coordinate geometry to one O(14), one O(16), one O(32), one O(4), one O(6), and one O(8) atom. In the third Mo site, Mo(3) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(15), one O(29), one O(5), and one O(7) atom. In the fourth Mo site, Mo(4) is bonded in a 6-coordinate geometry to one O(12), one O(15), one O(2), one O(30), one O(6), and one O(8) atom. In the fifth Mo site, Mo(5) is bonded in a 6-coordinate geometry to one O(16), one O(18), one O(26), one O(28), one O(7), and one O(8) atom. In the sixth Mo site, Mo(6) is bonded in a 6-coordinate geometry to one O(15), one O(17), one O(25), one O(27), one O(5), and one O(6) atom. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a tetrahedral geometry to one O(10), one O(13), one O(14), and one O(18) atom. In the second Se site, Se(2) is bonded in a tetrahedral geometry to one O(11), one O(12), one O(17), and one O(9) atom. There are thirty-three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one K(3) and one Mo(3) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one K(3) and one Mo(4) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one K(4) and one Mo(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one K(4) and one Mo(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(3), and one Mo(6) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Mo(2), one Mo(4), and one Mo(6) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(3), and one Mo(5) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Mo(2), one Mo(4), and one Mo(5) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one K(4) and one Se(2) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one K(3) and one Se(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one K(1), one Mo(3), and one Se(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one K(2), one Mo(4), and one Se(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one K(2), one Mo(1), and one Se(1) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one K(1), one Mo(2), and one Se(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Mo(3), one Mo(4), and one Mo(6) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(2), and one Mo(5) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one K(3), one Mo(6), and one Se(2) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one K(4), one Mo(5), and one Se(1) atom. In the nineteenth O site, O(19) is bonded in a bent 120 degrees geometry to one K(3), one O(22), and one O(23) atom. In the twentieth O site, O(20) is bonded in a distorted L-shaped geometry to one K(3) and one O(21) atom. In the twenty-first O site, O(21) is bonded in a distorted single-bond geometry to one K(3) and one O(20) atom. In the twenty-second O site, O(22) is bonded in a distorted single-bond geometry to one K(3) and one O(19) atom. In the twenty-third O site, O(23) is bonded in a single-bond geometry to one O(19) atom. In the twenty-fourth O site, O(24) is bonded in a distorted single-bond geometry to one K(1) and one O(33) atom. In the twenty-fifth O site, O(25) is bonded in a distorted trigonal planar geometry to one K(1), one K(2), and one Mo(6) atom. In the twenty-sixth O site, O(26) is bonded in a distorted trigonal planar geometry to one K(1), one K(2), and one Mo(5) atom. In the twenty-seventh O site, O(27) is bonded in a distorted bent 120 degrees geometry to one K(3) and one Mo(6) atom. In the twenty-eighth O site, O(28) is bonded in a distorted bent 120 degrees geometry to one K(4) and one Mo(5) atom. In the twenty-ninth O site, O(29) is bonded in a single-bond geometry to one Mo(3) atom. In the thirtieth O site, O(30) is bonded in a single-bond geometry to one Mo(4) atom. In the thirty-first O site, O(31) is bonded in a single-bond geometry to one Mo(1) atom. In the thirty-second O site, O(32) is bonded in a single-bond geometry to one Mo(2) atom. In the thirty-third O site, O(33) is bonded in a single-bond geometry to one O(24) atom.
K4Mo6Se2O33 crystallizes in the triclinic P1 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 4-coordinate geometry to one O(11), one O(14), one O(24), one O(25), and one O(26) atom. The K(1)-O(11) bond length is 2.82 Å. The K(1)-O(14) bond length is 2.80 Å. The K(1)-O(24) bond length is 3.37 Å. The K(1)-O(25) bond length is 2.84 Å. The K(1)-O(26) bond length is 2.81 Å. In the second K site, K(2) is bonded in a distorted square co-planar geometry to one O(12), one O(13), one O(25), and one O(26) atom. The K(2)-O(12) bond length is 2.81 Å. The K(2)-O(13) bond length is 2.82 Å. The K(2)-O(25) bond length is 2.81 Å. The K(2)-O(26) bond length is 2.86 Å. In the third K site, K(3) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(17), one O(19), one O(2), one O(20), one O(21), one O(22), and one O(27) atom. The K(3)-O(1) bond length is 2.75 Å. The K(3)-O(10) bond length is 2.82 Å. The K(3)-O(17) bond length is 3.03 Å. The K(3)-O(19) bond length is 3.44 Å. The K(3)-O(2) bond length is 2.73 Å. The K(3)-O(20) bond length is 3.19 Å. The K(3)-O(21) bond length is 3.32 Å. The K(3)-O(22) bond length is 3.30 Å. The K(3)-O(27) bond length is 2.77 Å. In the fourth K site, K(4) is bonded in a 5-coordinate geometry to one O(18), one O(28), one O(3), one O(4), and one O(9) atom. The K(4)-O(18) bond length is 3.04 Å. The K(4)-O(28) bond length is 2.79 Å. The K(4)-O(3) bond length is 2.80 Å. The K(4)-O(4) bond length is 2.74 Å. The K(4)-O(9) bond length is 2.79 Å. There are six inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 6-coordinate geometry to one O(13), one O(16), one O(3), one O(31), one O(5), and one O(7) atom. The Mo(1)-O(13) bond length is 2.36 Å. The Mo(1)-O(16) bond length is 1.99 Å. The Mo(1)-O(3) bond length is 1.73 Å. The Mo(1)-O(31) bond length is 1.73 Å. The Mo(1)-O(5) bond length is 1.98 Å. The Mo(1)-O(7) bond length is 2.40 Å. In the second Mo site, Mo(2) is bonded in a 6-coordinate geometry to one O(14), one O(16), one O(32), one O(4), one O(6), and one O(8) atom. The Mo(2)-O(14) bond length is 2.39 Å. The Mo(2)-O(16) bond length is 1.98 Å. The Mo(2)-O(32) bond length is 1.73 Å. The Mo(2)-O(4) bond length is 1.73 Å. The Mo(2)-O(6) bond length is 1.98 Å. The Mo(2)-O(8) bond length is 2.36 Å. In the third Mo site, Mo(3) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(15), one O(29), one O(5), and one O(7) atom. The Mo(3)-O(1) bond length is 1.73 Å. The Mo(3)-O(11) bond length is 2.36 Å. The Mo(3)-O(15) bond length is 1.99 Å. The Mo(3)-O(29) bond length is 1.73 Å. The Mo(3)-O(5) bond length is 2.39 Å. The Mo(3)-O(7) bond length is 1.98 Å. In the fourth Mo site, Mo(4) is bonded in a 6-coordinate geometry to one O(12), one O(15), one O(2), one O(30), one O(6), and one O(8) atom. The Mo(4)-O(12) bond length is 2.39 Å. The Mo(4)-O(15) bond length is 1.99 Å. The Mo(4)-O(2) bond length is 1.73 Å. The Mo(4)-O(30) bond length is 1.73 Å. The Mo(4)-O(6) bond length is 2.36 Å. The Mo(4)-O(8) bond length is 1.98 Å. In the fifth Mo site, Mo(5) is bonded in a 6-coordinate geometry to one O(16), one O(18), one O(26), one O(28), one O(7), and one O(8) atom. The Mo(5)-O(16) bond length is 2.35 Å. The Mo(5)-O(18) bond length is 2.24 Å. The Mo(5)-O(26) bond length is 1.75 Å. The Mo(5)-O(28) bond length is 1.72 Å. The Mo(5)-O(7) bond length is 1.99 Å. The Mo(5)-O(8) bond length is 1.99 Å. In the sixth Mo site, Mo(6) is bonded in a 6-coordinate geometry to one O(15), one O(17), one O(25), one O(27), one O(5), and one O(6) atom. The Mo(6)-O(15) bond length is 2.34 Å. The Mo(6)-O(17) bond length is 2.24 Å. The Mo(6)-O(25) bond length is 1.75 Å. The Mo(6)-O(27) bond length is 1.72 Å. The Mo(6)-O(5) bond length is 1.99 Å. The Mo(6)-O(6) bond length is 1.99 Å. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a tetrahedral geometry to one O(10), one O(13), one O(14), and one O(18) atom. The Se(1)-O(10) bond length is 1.64 Å. The Se(1)-O(13) bond length is 1.69 Å. The Se(1)-O(14) bond length is 1.69 Å. The Se(1)-O(18) bond length is 1.70 Å. In the second Se site, Se(2) is bonded in a tetrahedral geometry to one O(11), one O(12), one O(17), and one O(9) atom. The Se(2)-O(11) bond length is 1.69 Å. The Se(2)-O(12) bond length is 1.69 Å. The Se(2)-O(17) bond length is 1.70 Å. The Se(2)-O(9) bond length is 1.64 Å. There are thirty-three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one K(3) and one Mo(3) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one K(3) and one Mo(4) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one K(4) and one Mo(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one K(4) and one Mo(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(3), and one Mo(6) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Mo(2), one Mo(4), and one Mo(6) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(3), and one Mo(5) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Mo(2), one Mo(4), and one Mo(5) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one K(4) and one Se(2) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one K(3) and one Se(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one K(1), one Mo(3), and one Se(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one K(2), one Mo(4), and one Se(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one K(2), one Mo(1), and one Se(1) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one K(1), one Mo(2), and one Se(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Mo(3), one Mo(4), and one Mo(6) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Mo(1), one Mo(2), and one Mo(5) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one K(3), one Mo(6), and one Se(2) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one K(4), one Mo(5), and one Se(1) atom. In the nineteenth O site, O(19) is bonded in a bent 120 degrees geometry to one K(3), one O(22), and one O(23) atom. The O(19)-O(22) bond length is 1.29 Å. The O(19)-O(23) bond length is 1.28 Å. In the twentieth O site, O(20) is bonded in a distorted L-shaped geometry to one K(3) and one O(21) atom. The O(20)-O(21) bond length is 1.24 Å. In the twenty-first O site, O(21) is bonded in a distorted single-bond geometry to one K(3) and one O(20) atom. In the twenty-second O site, O(22) is bonded in a distorted single-bond geometry to one K(3) and one O(19) atom. In the twenty-third O site, O(23) is bonded in a single-bond geometry to one O(19) atom. In the twenty-fourth O site, O(24) is bonded in a distorted single-bond geometry to one K(1) and one O(33) atom. The O(24)-O(33) bond length is 1.23 Å. In the twenty-fifth O site, O(25) is bonded in a distorted trigonal planar geometry to one K(1), one K(2), and one Mo(6) atom. In the twenty-sixth O site, O(26) is bonded in a distorted trigonal planar geometry to one K(1), one K(2), and one Mo(5) atom. In the twenty-seventh O site, O(27) is bonded in a distorted bent 120 degrees geometry to one K(3) and one Mo(6) atom. In the twenty-eighth O site, O(28) is bonded in a distorted bent 120 degrees geometry to one K(4) and one Mo(5) atom. In the twenty-ninth O site, O(29) is bonded in a single-bond geometry to one Mo(3) atom. In the thirtieth O site, O(30) is bonded in a single-bond geometry to one Mo(4) atom. In the thirty-first O site, O(31) is bonded in a single-bond geometry to one Mo(1) atom. In the thirty-second O site, O(32) is bonded in a single-bond geometry to one Mo(2) atom. In the thirty-third O site, O(33) is bonded in a single-bond geometry to one O(24) atom.