Hydrothermal Synthesis and Structure of a Dinuclear Molybdenum(III) Hydroxy Squarate with a Mo–Mo Bond

The
reaction of molybdenum­(II) and chromium­(II) acetates with squaric
acid in degassed and deionized water under hydrothermal conditions
at 150 °C is described. The products have been formulated as
M2(μ-OH)2(μ-C4O4)2(H2O)4·2H2O, where
M = Cr (1) and Mo (2), based on combustion
elemental analysis, infrared spectroscopy, magic angle spinning (MAS)
solid-state carbon-13 nuclear magnetic resonance (NMR), and single-crystal
X-ray diffraction. The edge-shared bioctahedral structures involve
doubly bridging hydroxide ligands and μ-squarate ligands. The
chromium compound lacks a direct metal–metal-bonding interaction,
while in contrast the molybdenum compound contains a Mo–Mo
bond [2.491(2) Å]. The nature of the Mo–Mo-bonding interaction
is compared with that of other similar d3–d3 dimers.