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Ti3As crystallizes in the cubic Pm-3n space group. The structure is three-dimensional. Ti is bonded in a 6-coordinate geometry to two equivalent Ti and four equivalent As atoms. Both Ti–Ti bond lengths are 2.51 Å. All Ti–As bond lengths are 2.81 Å. As is bonded to twelve equivalent Ti atoms to form a mixture of face and edge-sharing AsTi12 cuboctahedra.
TiAs is Molybdenum Carbide MAX Phase-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Ti3+ is bonded to six equivalent As3- atoms to form a mixture of distorted corner and edge-sharing TiAs6 pentagonal pyramids. All Ti–As bond lengths are 2.61 Å. As3- is bonded to six equivalent Ti3+ atoms to form a mixture of corner, edge, and face-sharing AsTi6 octahedra. The corner-sharing octahedral tilt angles are 47°.