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TmCo3B2 crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Tm3+ is bonded in a hexagonal planar geometry to six equivalent B3- atoms. All Tm–B bond lengths are 2.86 Å. Co1+ is bonded in a square co-planar geometry to four equivalent B3- atoms. All Co–B bond lengths are 2.08 Å. B3- is bonded in a 6-coordinate geometry to three equivalent Tm3+ and six equivalent Co1+ atoms.
Tm(Co2B)6 crystallizes in the trigonal R-3m space group. The structure is three-dimensional. Tm3+ is bonded in a hexagonal planar geometry to six equivalent B3- atoms. All Tm–B bond lengths are 3.03 Å. There are two inequivalent Co+1.25+ sites. In the first Co+1.25+ site, Co+1.25+ is bonded in a T-shaped geometry to three equivalent B3- atoms. All Co–B bond lengths are 2.10 Å. In the second Co+1.25+ site, Co+1.25+ is bonded to four equivalent B3- atoms to form a mixture of distorted edge and corner-sharing CoB4 trigonal pyramids. There are two shorter (2.02 Å) and two longer (2.04 Å) Co–B bond lengths. B3- is bonded in a 7-coordinate geometry to one Tm3+ and seven Co+1.25+ atoms.
Tm4CoB13 crystallizes in the tetragonal P4/mnc space group. The structure is three-dimensional. Tm3+ is bonded in a 6-coordinate geometry to fifteen B+1.15- atoms. There are a spread of Tm–B bond distances ranging from 2.54–2.88 Å. Co3+ is bonded in a 8-coordinate geometry to eight equivalent B+1.15- atoms. All Co–B bond lengths are 2.15 Å. There are three inequivalent B+1.15- sites. In the first B+1.15- site, B+1.15- is bonded in a cuboctahedral geometry to four equivalent Tm3+ and eight equivalent B+1.15- atoms. All B–B bond lengths are 2.10 Å. In the second B+1.15- site, B+1.15- is bonded in a 3-coordinate geometry to six equivalent Tm3+ and three B+1.15- atoms. There is two shorter (1.77 Å) and one longer (1.85 Å) B–B bond length. In the third B+1.15- site, B+1.15- is bonded in a 9-coordinate geometry to four equivalent Tm3+, one Co3+, and four B+1.15- atoms. Both B–B bond lengths are 1.79 Å.
TmCoB4 crystallizes in the orthorhombic Pbam space group. The structure is three-dimensional. Tm3+ is bonded in a 4-coordinate geometry to fourteen B+1.50- atoms. There are a spread of Tm–B bond distances ranging from 2.55–2.69 Å. Co3+ is bonded in a 10-coordinate geometry to ten B+1.50- atoms. There are a spread of Co–B bond distances ranging from 2.18–2.28 Å. There are four inequivalent B+1.50- sites. In the first B+1.50- site, B+1.50- is bonded in a 9-coordinate geometry to two equivalent Tm3+, four equivalent Co3+, and three B+1.50- atoms. There are a spread of B–B bond distances ranging from 1.68–1.73 Å. In the second B+1.50- site, B+1.50- is bonded in a 9-coordinate geometry to four equivalent Tm3+, two equivalent Co3+, and three B+1.50- atoms. There is one shorter (1.78 Å) and one longer (1.80 Å) B–B bond length. In the third B+1.50- site, B+1.50- is bonded in a 9-coordinate geometry to four equivalent Tm3+, two equivalent Co3+, and three B+1.50- atoms. Both B–B bond lengths are 1.80 Å. In the fourth B+1.50- site, B+1.50- is bonded in a 9-coordinate geometry to four equivalent Tm3+, two equivalent Co3+, and three B+1.50- atoms.
Tm2Co7B3 crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. there are three inequivalent Tm sites. In the first Tm site, Tm is bonded in a 6-coordinate geometry to six equivalent Co atoms. All Tm–Co bond lengths are 2.88 Å. In the second Tm site, Tm is bonded in a 12-coordinate geometry to two equivalent Tm, twelve equivalent Co, and six equivalent B atoms. Both Tm–Tm bond lengths are 3.07 Å. All Tm–Co bond lengths are 2.90 Å. All Tm–B bond lengths are 2.88 Å. In the third Tm site, Tm is bonded in a 12-coordinate geometry to one Tm, twelve Co, and six equivalent B atoms. There are six shorter (2.85 Å) and six longer (2.96 Å) Tm–Co bond lengths. All Tm–B bond lengths are 2.89 Å. There are three inequivalent Co sites. In the first Co site, Co is bonded in a 12-coordinate geometry to three equivalent Tm and six equivalent Co atoms. All Co–Co bond lengths are 2.45 Å. In the second Co site, Co is bonded in a distorted L-shaped geometry to two equivalent Tm, two equivalent Co, and two equivalent B atoms. Both Co–B bond lengths are 2.05 Å. In the third Co site, Co is bonded in a distorted square co-planar geometry to four Tm and four B atoms. There are two shorter (2.07 Å) and two longer (2.08 Å) Co–B bond lengths. There are two inequivalent B sites. In the first B site, B is bonded in a 6-coordinate geometry to three equivalent Tm and six equivalent Co atoms. In the second B site, B is bonded in a 6-coordinate geometry to three equivalent Tm and six Co atoms.