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WB2 is hexagonal omega structure structured and crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. W6+ is bonded to twelve equivalent B3- atoms to form a mixture of edge and face-sharing WB12 cuboctahedra. All W–B bond lengths are 2.43 Å. B3- is bonded in a 3-coordinate geometry to six equivalent W6+ and three equivalent B3- atoms. All B–B bond lengths are 1.74 Å.
WB2 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. W6+ is bonded in a 10-coordinate geometry to ten B3- atoms. There are a spread of W–B bond distances ranging from 2.22–2.38 Å. There are three inequivalent B3- sites. In the first B3- site, B3- is bonded in a 9-coordinate geometry to six equivalent W6+ and three equivalent B3- atoms. All B–B bond lengths are 1.74 Å. In the second B3- site, B3- is bonded in a 9-coordinate geometry to six equivalent W6+ and three equivalent B3- atoms. In the third B3- site, B3- is bonded in a 7-coordinate geometry to four equivalent W6+ and three equivalent B3- atoms. All B–B bond lengths are 1.86 Å.