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

Zeitschrift fur Kristallographie, ISSN: 0044-2968, Vol: 226, Issue: 8, Page: 633-639
2011
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The title compounds Sr[BN]Br (1), Eu [BN]Br (2) and Eu[BN]I (3) were obtained from reactions of mixtures of Sr[BN] and SrBr (1) and the binaries EuN, h-BN and EuX (X = Br, I) (2, 3), respectively. The crystal structure of Sr [BN]Br was solved from X-ray powder diffraction data and those of the europium compounds from X-ray single crystal data. Sr [BN]Br and Eu[BN]Br are isotypic crystallizing in the rhombohedral space group R3̄m (No. 166, Pearson code: hR18; 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 and [Br]@Eu trigonal antiprisms, which are alternately stacked along [001]. Eu [BN]I - isotypic to Sr[BN]I - crystallizes in the monoclinic space group P2/m (No. 11, Pearson code: mP24; 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 octahedra which are separated by isolated [BN] units. The bond lengths for the strictly linear [BN] anions in (1) and (2) are d(B-N) = 1.351(4) Å and 1.356(8) Å, respectively. In Eu[BN]I two crystallo-grahically distinct [BN ] anions are present with d(B1-N)=1.32(4)Å, 1.37(4)Å and d(B-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 4f configuration. Vibrational spectra were measured and interpreted based on the D symmetry of the discrete linear [N-B-N] moieties, considering the site symmetry reduction and the presence of two distinct [BN] groups in (3). © by Oldenbourg Wissenschaftsverlag, München.

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