KNb4Ag(PS10)2 crystallizes in the triclinic P1 space group. K(1) is bonded in a 8-coordinate geometry to one S(12), one S(15), one S(16), one S(17), one S(18), one S(2), one S(20), and one S(8) atom. There are four inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one S(1), one S(10), one S(13), one S(3), one S(5), one S(6), one S(7), and one S(9) atom to form distorted NbS8 hexagonal bipyramids that share  an edgeedge with one P(1)S4 tetrahedra,  a faceface with one Nb(2)S8 hexagonal bipyramid, and  a faceface with one Nb(3)S8 hexagonal bipyramid. In the second Nb site, Nb(2) is bonded to one S(10), one S(14), one S(2), one S(4), one S(5), one S(6), one S(8), and one S(9) atom to form distorted NbS8 hexagonal bipyramids that share  a cornercorner with one S(2)KNb2S trigonal pyramid,  an edgeedge with one P(2)S4 tetrahedra,  a faceface with one Nb(1)S8 hexagonal bipyramid, and  a faceface with one Nb(4)S8 hexagonal bipyramid. In the third Nb site, Nb(3) is bonded to one S(1), one S(15), one S(16), one S(17), one S(18), one S(19), one S(3), and one S(7) atom to form distorted NbS8 hexagonal bipyramids that share  an edgeedge with one P(1)S4 tetrahedra,  a faceface with one Nb(1)S8 hexagonal bipyramid, and  a faceface with one Nb(4)S8 hexagonal bipyramid. In the fourth Nb site, Nb(4) is bonded to one S(15), one S(16), one S(17), one S(18), one S(2), one S(20), one S(4), and one S(8) atom to form distorted NbS8 hexagonal bipyramids that share  a cornercorner with one S(2)KNb2S trigonal pyramid,  an edgeedge with one P(2)S4 tetrahedra,  a faceface with one Nb(2)S8 hexagonal bipyramid, and  a faceface with one Nb(3)S8 hexagonal bipyramid. Ag(1) is bonded in a 2-coordinate geometry to one S(10), one S(11), one S(12), and one S(9) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one S(11), one S(13), one S(19), and one S(3) atom to form PS4 tetrahedra that share  an edgeedge with one Nb(1)S8 hexagonal bipyramid and  an edgeedge with one Nb(3)S8 hexagonal bipyramid. In the second P site, P(2) is bonded to one S(12), one S(14), one S(20), and one S(4) atom to form PS4 tetrahedra that share  an edgeedge with one Nb(2)S8 hexagonal bipyramid and  an edgeedge with one Nb(4)S8 hexagonal bipyramid. There are twenty inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Nb(1), one Nb(3), and one S(7) atom. In the second S site, S(2) is bonded to one K(1), one Nb(2), one Nb(4), and one S(8) atom to form distorted SKNb2S trigonal pyramids that share  a cornercorner with one Nb(2)S8 hexagonal bipyramid and  a cornercorner with one Nb(4)S8 hexagonal bipyramid. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Nb(1), one Nb(3), and one P(1) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Nb(2), one Nb(4), and one P(2) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Nb(1), one Nb(2), and one S(9) atom. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Nb(1), one Nb(2), and one S(10) atom. In the seventh S site, S(7) is bonded in a 3-coordinate geometry to one Nb(1), one Nb(3), and one S(1) atom. In the eighth S site, S(8) is bonded in a 4-coordinate geometry to one K(1), one Nb(2), one Nb(4), and one S(2) atom. In the ninth S site, S(9) is bonded in a 4-coordinate geometry to one Nb(1), one Nb(2), one Ag(1), and one S(5) atom. In the tenth S site, S(10) is bonded in a 4-coordinate geometry to one Nb(1), one Nb(2), one Ag(1), and one S(6) atom. In the eleventh S site, S(11) is bonded in an L-shaped geometry to one Ag(1) and one P(1) atom. In the twelfth S site, S(12) is bonded in a distorted T-shaped geometry to one K(1), one Ag(1), and one P(2) atom. In the thirteenth S site, S(13) is bonded in an L-shaped geometry to one Nb(1) and one P(1) atom. In the fourteenth S site, S(14) is bonded in an L-shaped geometry to one Nb(2) and one P(2) atom. In the fifteenth S site, S(15) is bonded in a 4-coordinate geometry to one K(1), one Nb(3), one Nb(4), and one S(17) atom. In the sixteenth S site, S(16) is bonded in a 4-coordinate geometry to one K(1), one Nb(3), one Nb(4), and one S(18) atom. In the seventeenth S site, S(17) is bonded in a 4-coordinate geometry to one K(1), one Nb(3), one Nb(4), and one S(15) atom. In the eighteenth S site, S(18) is bonded in a 4-coordinate geometry to one K(1), one Nb(3), one Nb(4), and one S(16) atom. In the nineteenth S site, S(19) is bonded in an L-shaped geometry to one Nb(3) and one P(1) atom. In the twentieth S site, S(20) is bonded in a 3-coordinate geometry to one K(1), one Nb(4), and one P(2) atom.
KNb4Ag(PS10)2 crystallizes in the triclinic P1 space group. K(1) is bonded in a 8-coordinate geometry to one S(12), one S(15), one S(16), one S(17), one S(18), one S(2), one S(20), and one S(8) atom. The K(1)-S(12) bond length is 3.29 Å. The K(1)-S(15) bond length is 3.65 Å. The K(1)-S(16) bond length is 3.54 Å. The K(1)-S(17) bond length is 3.63 Å. The K(1)-S(18) bond length is 3.73 Å. The K(1)-S(2) bond length is 3.43 Å. The K(1)-S(20) bond length is 3.41 Å. The K(1)-S(8) bond length is 3.55 Å. There are four inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one S(1), one S(10), one S(13), one S(3), one S(5), one S(6), one S(7), and one S(9) atom to form distorted NbS8 hexagonal bipyramids that share  an edgeedge with one P(1)S4 tetrahedra,  a faceface with one Nb(2)S8 hexagonal bipyramid, and  a faceface with one Nb(3)S8 hexagonal bipyramid. The Nb(1)-S(1) bond length is 2.60 Å. The Nb(1)-S(10) bond length is 2.52 Å. The Nb(1)-S(13) bond length is 2.59 Å. The Nb(1)-S(3) bond length is 2.64 Å. The Nb(1)-S(5) bond length is 2.52 Å. The Nb(1)-S(6) bond length is 2.52 Å. The Nb(1)-S(7) bond length is 2.58 Å. The Nb(1)-S(9) bond length is 2.51 Å. In the second Nb site, Nb(2) is bonded to one S(10), one S(14), one S(2), one S(4), one S(5), one S(6), one S(8), and one S(9) atom to form distorted NbS8 hexagonal bipyramids that share  a cornercorner with one S(2)KNb2S trigonal pyramid,  an edgeedge with one P(2)S4 tetrahedra,  a faceface with one Nb(1)S8 hexagonal bipyramid, and  a faceface with one Nb(4)S8 hexagonal bipyramid. The Nb(2)-S(10) bond length is 2.51 Å. The Nb(2)-S(14) bond length is 2.60 Å. The Nb(2)-S(2) bond length is 2.60 Å. The Nb(2)-S(4) bond length is 2.65 Å. The Nb(2)-S(5) bond length is 2.52 Å. The Nb(2)-S(6) bond length is 2.51 Å. The Nb(2)-S(8) bond length is 2.60 Å. The Nb(2)-S(9) bond length is 2.51 Å. In the third Nb site, Nb(3) is bonded to one S(1), one S(15), one S(16), one S(17), one S(18), one S(19), one S(3), and one S(7) atom to form distorted NbS8 hexagonal bipyramids that share  an edgeedge with one P(1)S4 tetrahedra,  a faceface with one Nb(1)S8 hexagonal bipyramid, and  a faceface with one Nb(4)S8 hexagonal bipyramid. The Nb(3)-S(1) bond length is 2.59 Å. The Nb(3)-S(15) bond length is 2.53 Å. The Nb(3)-S(16) bond length is 2.54 Å. The Nb(3)-S(17) bond length is 2.51 Å. The Nb(3)-S(18) bond length is 2.51 Å. The Nb(3)-S(19) bond length is 2.60 Å. The Nb(3)-S(3) bond length is 2.63 Å. The Nb(3)-S(7) bond length is 2.57 Å. In the fourth Nb site, Nb(4) is bonded to one S(15), one S(16), one S(17), one S(18), one S(2), one S(20), one S(4), and one S(8) atom to form distorted NbS8 hexagonal bipyramids that share  a cornercorner with one S(2)KNb2S trigonal pyramid,  an edgeedge with one P(2)S4 tetrahedra,  a faceface with one Nb(2)S8 hexagonal bipyramid, and  a faceface with one Nb(3)S8 hexagonal bipyramid. The Nb(4)-S(15) bond length is 2.53 Å. The Nb(4)-S(16) bond length is 2.52 Å. The Nb(4)-S(17) bond length is 2.51 Å. The Nb(4)-S(18) bond length is 2.51 Å. The Nb(4)-S(2) bond length is 2.62 Å. The Nb(4)-S(20) bond length is 2.62 Å. The Nb(4)-S(4) bond length is 2.65 Å. The Nb(4)-S(8) bond length is 2.58 Å. Ag(1) is bonded in a 2-coordinate geometry to one S(10), one S(11), one S(12), and one S(9) atom. The Ag(1)-S(10) bond length is 3.20 Å. The Ag(1)-S(11) bond length is 2.44 Å. The Ag(1)-S(12) bond length is 2.45 Å. The Ag(1)-S(9) bond length is 3.12 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one S(11), one S(13), one S(19), and one S(3) atom to form PS4 tetrahedra that share  an edgeedge with one Nb(1)S8 hexagonal bipyramid and  an edgeedge with one Nb(3)S8 hexagonal bipyramid. The P(1)-S(11) bond length is 1.99 Å. The P(1)-S(13) bond length is 2.04 Å. The P(1)-S(19) bond length is 2.05 Å. The P(1)-S(3) bond length is 2.08 Å. In the second P site, P(2) is bonded to one S(12), one S(14), one S(20), and one S(4) atom to form PS4 tetrahedra that share  an edgeedge with one Nb(2)S8 hexagonal bipyramid and  an edgeedge with one Nb(4)S8 hexagonal bipyramid. The P(2)-S(12) bond length is 2.00 Å. The P(2)-S(14) bond length is 2.03 Å. The P(2)-S(20) bond length is 2.05 Å. The P(2)-S(4) bond length is 2.07 Å. There are twenty inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Nb(1), one Nb(3), and one S(7) atom. The S(1)-S(7) bond length is 2.04 Å. In the second S site, S(2) is bonded to one K(1), one Nb(2), one Nb(4), and one S(8) atom to form distorted SKNb2S trigonal pyramids that share  a cornercorner with one Nb(2)S8 hexagonal bipyramid and  a cornercorner with one Nb(4)S8 hexagonal bipyramid. The S(2)-S(8) bond length is 2.04 Å. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Nb(1), one Nb(3), and one P(1) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Nb(2), one Nb(4), and one P(2) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Nb(1), one Nb(2), and one S(9) atom. The S(5)-S(9) bond length is 2.03 Å. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Nb(1), one Nb(2), and one S(10) atom. The S(6)-S(10) bond length is 2.03 Å. In the seventh S site, S(7) is bonded in a 3-coordinate geometry to one Nb(1), one Nb(3), and one S(1) atom. In the eighth S site, S(8) is bonded in a 4-coordinate geometry to one K(1), one Nb(2), one Nb(4), and one S(2) atom. In the ninth S site, S(9) is bonded in a 4-coordinate geometry to one Nb(1), one Nb(2), one Ag(1), and one S(5) atom. In the tenth S site, S(10) is bonded in a 4-coordinate geometry to one Nb(1), one Nb(2), one Ag(1), and one S(6) atom. In the eleventh S site, S(11) is bonded in an L-shaped geometry to one Ag(1) and one P(1) atom. In the twelfth S site, S(12) is bonded in a distorted T-shaped geometry to one K(1), one Ag(1), and one P(2) atom. In the thirteenth S site, S(13) is bonded in an L-shaped geometry to one Nb(1) and one P(1) atom. In the fourteenth S site, S(14) is bonded in an L-shaped geometry to one Nb(2) and one P(2) atom. In the fifteenth S site, S(15) is bonded in a 4-coordinate geometry to one K(1), one Nb(3), one Nb(4), and one S(17) atom. The S(15)-S(17) bond length is 2.03 Å. In the sixteenth S site, S(16) is bonded in a 4-coordinate geometry to one K(1), one Nb(3), one Nb(4), and one S(18) atom. The S(16)-S(18) bond length is 2.03 Å. In the seventeenth S site, S(17) is bonded in a 4-coordinate geometry to one K(1), one Nb(3), one Nb(4), and one S(15) atom. In the eighteenth S site, S(18) is bonded in a 4-coordinate geometry to one K(1), one Nb(3), one Nb(4), and one S(16) atom. In the nineteenth S site, S(19) is bonded in an L-shaped geometry to one Nb(3) and one P(1) atom. In the twentieth S site, S(20) is bonded in a 3-coordinate geometry to one K(1), one Nb(4), and one P(2) atom.