DOE OSTI2020
Zr13S2Zr2SZr25S24 crystallizes in the trigonal P3m1 space group. The structure is two-dimensional and consists of one Zr13S2 sheet oriented in the (0, 0, 1) direction; one Zr25S24 sheet oriented in the (0, 0, 1) direction; and one Zr2S sheet oriented in the (0, 0, 1) direction. In the Zr13S2 sheet, there are eleven inequivalent Zr sites. In the first Zr site, Zr is bonded in a 3-coordinate geometry to three equivalent S atoms. All Zr–S bond lengths are 2.65 Å. In the second Zr site, Zr is bonded in a 3-coordinate geometry to one Zr and three equivalent S atoms. The Zr–Zr bond length is 3.39 Å. All Zr–S bond lengths are 2.66 Å. In the third Zr site, Zr is bonded to eight Zr atoms to form ZrZr8 hexagonal bipyramids that share corners with seven ZrZr8 hexagonal bipyramids, corners with three equivalent SZr6 pentagonal pyramids, and edges with eighteen ZrZr8 hexagonal bipyramids. There are one shorter (3.36 Å) and six longer (3.39 Å) Zr–Zr bond lengths. In the fourth Zr site, Zr is bonded to eight Zr atoms to form a mixture of corner and edge-sharing ZrZr8 hexagonal bipyramids. There are six shorter (3.39 Å) and one longer (3.43 Å) Zr–Zr bond lengths. In the fifth Zr site, Zr is bonded to eight Zr atoms to form a mixture of corner and edge-sharing ZrZr8 hexagonal bipyramids. There are six shorter (3.39 Å) and one longer (3.45 Å) Zr–Zr bond lengths. In the sixth Zr site, Zr is bonded to eight Zr atoms to form a mixture of corner and edge-sharing ZrZr8 hexagonal bipyramids. There are six shorter (3.39 Å) and one longer (3.45 Å) Zr–Zr bond lengths. In the seventh Zr site, Zr is bonded to eight Zr atoms to form a mixture of corner and edge-sharing ZrZr8 hexagonal bipyramids. There are six shorter (3.39 Å) and one longer (3.45 Å) Zr–Zr bond lengths. In the eighth Zr site, Zr is bonded to eight Zr atoms to form a mixture of corner and edge-sharing ZrZr8 hexagonal bipyramids. There are six shorter (3.39 Å) and one longer (3.45 Å) Zr–Zr bond lengths. In the ninth Zr site, Zr is bonded in a 3-coordinate geometry to one Zr and three equivalent S atoms. The Zr–Zr bond length is 3.40 Å. All Zr–S bond lengths are 2.67 Å. In the tenth Zr site, Zr is bonded in a 3-coordinate geometry to three equivalent S atoms. All Zr–S bond lengths are 2.66 Å. In the eleventh Zr site, Zr is bonded to eight Zr atoms to form ZrZr8 hexagonal bipyramids that share corners with seven ZrZr8 hexagonal bipyramids, corners with three equivalent SZr6 pentagonal pyramids, and edges with eighteen ZrZr8 hexagonal bipyramids. There are one shorter (3.36 Å) and six longer (3.39 Å) Zr–Zr bond lengths. There are two inequivalent S sites. In the first S site, S is bonded to six Zr atoms to form distorted SZr6 pentagonal pyramids that share corners with three equivalent ZrZr8 hexagonal bipyramids and edges with six equivalent SZr6 pentagonal pyramids. In the second S site, S is bonded to six Zr atoms to form distorted SZr6 pentagonal pyramids that share corners with three equivalent ZrZr8 hexagonal bipyramids and edges with six equivalent SZr6 pentagonal pyramids. In the Zr25S24 sheet, there are six inequivalent Zr sites. In the first Zr site, Zr is bonded in a 3-coordinate geometry to three equivalent S atoms. All Zr–S bond lengths are 2.63 Å. In the second Zr site, Zr is bonded to six S atoms to form a mixture of distorted corner, edge, and face-sharing ZrS6 pentagonal pyramids. All Zr–S bond lengths are 2.63 Å. In the third Zr site, Zr is bonded to six S atoms to form a mixture of distorted corner, edge, and face-sharing ZrS6 pentagonal pyramids. All Zr–S bond lengths are 2.62 Å. In the fourth Zr site, Zr is bonded to six S atoms to form a mixture of distorted corner, edge, and face-sharing ZrS6 pentagonal pyramids. All Zr–S bond lengths are 2.61 Å. In the fifth Zr site, Zr is bonded to six equivalent S atoms to form a mixture of distorted corner, edge, and face-sharing ZrS6 pentagonal pyramids. All Zr–S bond lengths are 2.61 Å. In the sixth Zr site, Zr is bonded to six S atoms to form a mixture of distorted corner, edge, and face-sharing ZrS6 pentagonal pyramids. All Zr–S bond lengths are 2.61 Å. There are five inequivalent S sites. In the first S site, S is bonded to six Zr atoms to form a mixture of distorted corner, edge, and face-sharing SZr6 pentagonal pyramids. In the second S site, S is bonded to six Zr atoms to form a mixture of distorted corner, edge, and face-sharing SZr6 pentagonal pyramids. In the third S site, S is bonded to six Zr atoms to form a mixture of distorted corner, edge, and face-sharing SZr6 pentagonal pyramids. In the fourth S site, S is bonded to six Zr atoms to form a mixture of distorted corner, edge, and face-sharing SZr6 pentagonal pyramids. In the fifth S site, S is bonded to six equivalent Zr atoms to form a mixture of distorted corner, edge, and face-sharing SZr6 pentagonal pyramids. In the Zr2S sheet, there are two inequivalent Zr sites. In the first Zr site, Zr is bonded in a 3-coordinate geometry to three equivalent S atoms. All Zr–S bond lengths are 2.64 Å. In the second Zr site, Zr is bonded in a 3-coordinate geometry to three equivalent S atoms. All Zr–S bond lengths are 2.64 Å. S is bonded to six Zr atoms to form distorted edge-sharing SZr6 pentagonal pyramids.