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The title compounds Sr 2 [BN 2 ]Br ( 1 ), Eu 2 [BN 2 ]Br ( 2 ) and Eu 2 [BN 2 ]I ( 3 ) were obtained from reactions of mixtures of Sr 3 [BN 2 ] 2  and SrBr 2  ( 1 ) and the binaries EuN, h-BN and Eu X  2  ( X  = Br, I) ( 2 ,  3 ), respectively. The crystal structure of Sr 2 [BN 2 ]Br was solved from X-ray powder diffraction data and those of the europium compounds from X-ray single crystal data. Sr 2 [BN 2 ]Br and Eu 2 [BN 2 ]Br are isotypic crystallizing in the rhombohedral space group  R -3 m  (No. 166, Pearson code:  hR 18;  Z  = 3;  a  = 4.11692(2) Å,  c  = 26.4611(2) Å ( 1 );  a  = 4.0728(3) Å,  c  = 26.589(3) Å ( 2 )). The crystal structures are built up by layers of condensed edge-sharing [B—N—B]@Eu 6  and [Br]@Eu 6  trigonal antiprisms, which are alternately stacked along [001]. Eu 2 [BN 2 ]I – isotypic to Sr 2 [BN 2 ]I – crystallizes in the monoclinic space group  P 2 1 / m  (No. 11, Pearson code:  mP 24;  Z  = 4;  a  = 10.2548(6) Å,  b  = 4.1587(3) Å,  c  = 13.1234(9) Å,  β  = 91.215(4)°). The crystal structure is characterized by slightly puckered layers formed by condensed edge sharing I@Eu 6  octahedra which are separated by isolated [BN 2 ] 3–  units. The bond lengths for the strictly linear [BN 2 ] 3–  anions in  (1)  and  (2)  are  d (B—N) = 1.351(4) Å and 1.356(8) Å, respectively. In Eu 2 [BN 2 ]I two crystallograhically distinct [BN 2 ] 3–  anions are present with  d (B1—N) = 1.32(4) Å, 1.37(4) Å and  d (B2—N) = 1.30(4) Å, 1.34(4) Å, respectively. Their bond angles vary slightly: ∠(N—B1—N) = 179(3)° and ∠(N—B2—N) = 177(3)°. The magnetic susceptibility data of the europium compounds ( 2 ) and ( 3 ) indicate that the Eu ions are divalent with 4 f  7  configuration. Vibrational spectra were measured and interpreted based on the  D  ∞ h   symmetry of the discrete linear [N—B—N] 3–  moieties, considering the site symmetry reduction and the presence of two distinct [BN 2 ] 3–  groups in ( 3 ).

zeitschrift für kristallographie

Syntheses, crystal structures, magnetic properties and vibrational spectra of nitridoborate-halide compounds Sr 2 [BN 2 ]Br and Eu 2 [BN 2 ] X  ( X  = Br, I) with isolated [BN 2 ] 3–  units