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For the first time, large single crystals of lithium divanadate spinel, LiV2O4, showing heavy-fermion behavior down to 20 K, have been grown by a flux method using an effective LiCl–Li2MoO4–LiBO2 solvent system. LiV2O4 belongs to the normal spinel structure type. The V atoms (16d) have octa­hedral coordination [V—O = 1.9709 (7) Å] and are arranged in a pyrochlore-type sublattice [V...V = 2.9147 (4) Å]. The Li atoms (8a) have tetra­hedral coordination [Li—O = 1.9487 (5) Å] and are located in channels running parallel to [110].
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