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Eight spinel single-crystal samples belonging to the spinel sensu stricto-magnesiocoulsonite series (MgAl 2 O 4 -MgV 2 O 4 ) were synthesized and crystal-chemically characterized by X-ray diffraction, electron microprobe and optical absorption spectroscopy. Site populations show that the tetrahedrally coordinated site (T) is populated by Mg and minor Al for the spinel sensu stricto compositions, and only by Mg for the magnesiocoulsonite compositions, while the octahedrally coordinated site (M) is populated by Al, V 3+ , minor Mg, and very minor amounts of V 4+ . The latter occurs in appreciable amounts in the Al-free magnesium vanadate spinel,T(   Mg   )    M    (Mg    0  .  26V   1  .  48    3+V   0  .  26    4+)    O  4$^{\rm{T}}{\left( {{\rm{Mg}}} \right)^{\rm{M}}}\left( {{\rm{M}}{{\rm{g}}_{{\rm{0}}{\rm{.26}}}}{\rm{V}}_{{\rm{1}}{\rm{.48}}}^{{\rm{3 + }}}{\rm{V}}_{{\rm{0}}{\rm{.26}}}^{{\rm{4 + }}}} \right){{\rm{O}}_{\rm{4}}}$   , showing the presence of the inverse spinel VMg 2 O 4 . The studied samples are characterized by substitution of Al 3+  for V 3+  and (Mg 2+ +V 4+ ) for 2V 3+  described in the system MgAl 2 O 4 -MgV 2 O 4 -VMg 2 O 4 .

Crystal chemistry of spinels in the system MgAl 2 O 4 -MgV 2 O 4 -Mg 2 VO 4