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TcF6 is Tungsten structured and crystallizes in the cubic Im-3m space group. The structure is zero-dimensional and consists of two 13842-93-8 molecules. Tc6+ is bonded in an octahedral geometry to six equivalent F1- atoms. All Tc–F bond lengths are 1.86 Å. F1- is bonded in a single-bond geometry to one Tc6+ atom.
Cs2TcF6 crystallizes in the trigonal P-3m1 space group. The structure is three-dimensional. Cs1+ is bonded to twelve equivalent F1- atoms to form distorted CsF12 cuboctahedra that share corners with six equivalent CsF12 cuboctahedra, corners with three equivalent TcF6 octahedra, faces with eight equivalent CsF12 cuboctahedra, and faces with three equivalent TcF6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are a spread of Cs–F bond distances ranging from 3.22–3.32 Å. Tc4+ is bonded to six equivalent F1- atoms to form TcF6 octahedra that share corners with six equivalent CsF12 cuboctahedra and faces with six equivalent CsF12 cuboctahedra. All Tc–F bond lengths are 1.98 Å. F1- is bonded in a distorted single-bond geometry to four equivalent Cs1+ and one Tc4+ atom.
Na2TcF6 crystallizes in the trigonal P-3m1 space group. The structure is three-dimensional. Na1+ is bonded to twelve equivalent F1- atoms to form distorted NaF12 cuboctahedra that share corners with six equivalent NaF12 cuboctahedra, corners with three equivalent TcF6 octahedra, faces with eight equivalent NaF12 cuboctahedra, and faces with three equivalent TcF6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are a spread of Na–F bond distances ranging from 2.51–2.90 Å. Tc4+ is bonded to six equivalent F1- atoms to form TcF6 octahedra that share corners with six equivalent NaF12 cuboctahedra and faces with six equivalent NaF12 cuboctahedra. All Tc–F bond lengths are 1.97 Å. F1- is bonded in a 1-coordinate geometry to four equivalent Na1+ and one Tc4+ atom.
K2TcF6 crystallizes in the trigonal P-3m1 space group. The structure is three-dimensional. K1+ is bonded to twelve equivalent F1- atoms to form distorted KF12 cuboctahedra that share corners with six equivalent KF12 cuboctahedra, corners with three equivalent TcF6 octahedra, faces with eight equivalent KF12 cuboctahedra, and faces with three equivalent TcF6 octahedra. The corner-sharing octahedral tilt angles are 19°. There are a spread of K–F bond distances ranging from 2.84–3.04 Å. Tc4+ is bonded to six equivalent F1- atoms to form TcF6 octahedra that share corners with six equivalent KF12 cuboctahedra and faces with six equivalent KF12 cuboctahedra. All Tc–F bond lengths are 1.97 Å. F1- is bonded in a distorted single-bond geometry to four equivalent K1+ and one Tc4+ atom.