NbNiAs2 crystallizes in the orthorhombic Pnma space group. Nb(1) is bonded in a 7-coordinate geometry to three equivalent As(2) and four equivalent As(1) atoms. Ni(1) is bonded in a 5-coordinate geometry to two equivalent As(1) and three equivalent As(2) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded to four equivalent Nb(1) and two equivalent Ni(1) atoms to form a mixture of distorted corner, edge, and face-sharing AsNb4Ni2 pentagonal pyramids. In the second As site, As(2) is bonded in a 6-coordinate geometry to three equivalent Nb(1) and three equivalent Ni(1) atoms.
NbNiAs2 crystallizes in the orthorhombic Pnma space group. Nb(1) is bonded in a 7-coordinate geometry to three equivalent As(2) and four equivalent As(1) atoms. There are two shorter (2.70 Å) and one longer (2.84 Å) Nb(1)-As(2) bond length. There are two shorter (2.62 Å) and two longer (2.63 Å) Nb(1)-As(1) bond lengths. Ni(1) is bonded in a 5-coordinate geometry to two equivalent As(1) and three equivalent As(2) atoms. Both Ni(1)-As(1) bond lengths are 2.37 Å. There is one shorter (2.40 Å) and two longer (2.44 Å) Ni(1)-As(2) bond lengths. There are two inequivalent As sites. In the first As site, As(1) is bonded to four equivalent Nb(1) and two equivalent Ni(1) atoms to form a mixture of distorted corner, edge, and face-sharing AsNb4Ni2 pentagonal pyramids. In the second As site, As(2) is bonded in a 6-coordinate geometry to three equivalent Nb(1) and three equivalent Ni(1) atoms.