Na2B2S5 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form a mixture of distorted edge, corner, and face-sharing NaS5 trigonal bipyramids. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one S(2), one S(3), and one S(5) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one S(1), one S(3), and one S(4) atom. There are five inequivalent S sites. In the first S site, S(5) is bonded in a distorted single-bond geometry to one B(1) atom. In the second S site, S(1) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one B(2) atom. In the third S site, S(2) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one B(1) atom. In the fourth S site, S(3) is bonded in a distorted water-like geometry to two equivalent Na(1), one B(1), and one B(2) atom. In the fifth S site, S(4) is bonded in a distorted single-bond geometry to one B(2) atom.
Na2B2S5 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form a mixture of distorted edge, corner, and face-sharing NaS5 trigonal bipyramids. The Na(1)-S(3) bond length is 3.16 Å. There is one shorter (2.83 Å) and one longer (2.90 Å) Na(1)-S(1) bond length. There is one shorter (2.97 Å) and one longer (3.02 Å) Na(1)-S(2) bond length. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one S(2), one S(3), and one S(5) atom. The B(1)-S(2) bond length is 1.77 Å. The B(1)-S(3) bond length is 1.83 Å. The B(1)-S(5) bond length is 1.80 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one S(1), one S(3), and one S(4) atom. The B(2)-S(1) bond length is 1.77 Å. The B(2)-S(3) bond length is 1.83 Å. The B(2)-S(4) bond length is 1.81 Å. There are five inequivalent S sites. In the first S site, S(5) is bonded in a distorted single-bond geometry to one B(1) atom. In the second S site, S(1) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one B(2) atom. In the third S site, S(2) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one B(1) atom. In the fourth S site, S(3) is bonded in a distorted water-like geometry to two equivalent Na(1), one B(1), and one B(2) atom. In the fifth S site, S(4) is bonded in a distorted single-bond geometry to one B(2) atom.