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The crystal structure of Nd 2 BC, synthesized by arc melting of the element mixture, repeated in a high frequency furnace and subsequent annealing at 1070 K, has been determined from single crystal X-ray diffraction data. It crystallizes in a new structure type in the monoclinic space group  C 2/ m  ( a  = 12.732(2) Å,  b  = 3.6848(4) Å,  c  = 9.398(2) Å,  β  = 130.43(1)°,  R 1 = 0.038 ( wR 2 = 0.091) for 596 reflections with  I  o  &gt; 2 σ  ( I  o )). Characteristic building units are C—B—B—C entities with the distances  d  C—B  = 1.51(2) Å and  d  B—B  = 1.65(2) Å. These units are embedded in a framework of neodymium atoms resulting from the stacking of slightly corrugated two-dimensional square nets of Nd. Within the ionic limit Nd 2 BC can be described as (Nd 2+ ) 4 [C—B—B—C] 8–  or (Nd 3+ ) 4 [CBBC] 8–  · 4 e –  with [C=B—B=C] 8–  units, which are isoelectronic to 1,3-butadiene. The measured magnetic moment of 3.65 μ  B  per Nd atom in Nd 2 BC is in good agreement with the expected value of 3.62 μ  B  for 4f 3  configuration. LMTO band structure calculations show that Nd 2 BC is metallic and the extra electrons occupy mainly bonding Nd-5d and antibonding π* states within the C—B—B—C units.

Synthesis, structure and properties of Nd 2 BC containing the trans -dibora–(1,3)-butadiene [C=B–B=C] 8– -unit