Syntheses and Structural Properties of Rare Earth Carbodiimides

Crystalline samples of rare earth carbodiimides were synthesized by solid-state metathesis reactions of rare earth
trichlorides with lithium cyanamide in sealed silica ampules. Two distinct structures were determined by single-crystal X-ray diffraction. The structure determined for Sm2(CN2)3 [C2/m, Z = 2, a = 14.534(2) Å, b = 3.8880(8) Å,
c = 5.2691(9) Å, β = 95.96(2)°, R1 = 0.0267, and wR2 = 0.0667] was assigned for RE2(CN2)3 compounds with
RE = Y, Pr, Nd, Sm, Gd, Tb, Dy, Ho, and Er, and the structure determined for Lu2(CN2)3 [R32, Z = 3, a =
6.2732(8) Å, c = 14.681(2) Å, R1 = 0.0208, and wR2 = 0.0526] was assigned for the smallest rare earth ions with
RE = Tm, Yb, and Lu by powder X-ray diffraction. Both types of crystal structures are characterized by layers of
[NCN]2- ions whose arrangements can be derived from the motif of a closest packed layer of sticks. These layers
alternate with layers of rare earth ions in a one-by-one sequence. Different tilting arrangements of the N−C−N-axes relative to the stacking directions (c) and different arrangements of RE3+ ions within metal atom layers account
for the two distinct structures in which Sm3+ and Lu3+ ions adopt the coordination numbers 7 and 6, respectively.