Yeni nitridoboratlar: M2[BN2]Br (M = Ca, Sr, Eu), Eu3[B3N6] and Li0.42Eu3[B3N6]: Sentezi, kristal yapıları ve fiziksel özellikleri

The isostructural compound series M2[BN2]Br (M = Ca, Sr, Eu) crystallize in the rhombohedral space group R3m (Pearson code hR6; Z = 3) with a = 3.86897(7)Å, c =25.8135(6)Å for Ca2[BN2]Br, a = 4.117 Å, c = 26.487 for Sr2[BN2]Br and a = 4.0728 Å,c = 26.5890 Å for Eu2[BN2]Br. The crystal structure can be interpreted as a as a filled variant of anti-NaCrS2 type of structure in which M at S positions, Br at Cr positions and B at Na positions. The structure is characterized by slabs of edge-sharing [N-B-N]@M6 and [Br]@M6 trigonal antiprisms which are alternately packed along [001]. The bond lengths for the strictly linear [BN2]3? anions vary only marginal: d(B-N) = 1.353(7) ? 1.355(4) Å and are directly comparable with those of the other well-known dinitrido borates and halides. Unlike the isostoichiometric dinitridoborate bromide series, Eu2[BN2]I crystallizes monoclinic (space group: P21/m (No:11) with a = 10.2548 Å, b = 4.1587 Å, c = 13.1234 Å, = 91.21, Z =4 , V = 559.54 Å3) and is isotypic to Sr2[BN2]I. The crystal structure consists of slightly corrugated layers of condensed I@Eu6 octahedra which are separated by isolated [BN2]3? anions. The bond lengths for the crystallographically distinct [BN2]3? moieties are: d(B1?N3) = 1.301(39) Å, d(B1?N4) = 1.352(36) Å, d(B2?N1) = 1.302(49) Å and d(B2?N2) = 1.348(48) Å, respectively. The bond angles differ significantly from the linearity: ?(N3?B1?N4) = 178.92(3)° and ?(N1?B2?N2) = 172.90°(4). Vibrational Spectra confirm the presence of the [N-B-N]3? units in all four nitridoborate halides. According to the magnetic susceptibility measurements the oxidation state of Eu in Eu2[BN2]X (X = Br, I) is +2. Eu3[B3N6] and Li0.42Eu3[B3N6] crystallize in the trigonal space group R3c (No:167) with a = 11.9559(2) Å, c = 6.814(2) Å and Z = 6 for Eu3[B3N6] and a = 12.0225(2) Å, c = 6.8556(2) Å and Z = 6 for Li0.42Eu3[B3N6]. Partial anionic structures are built up by isolated, planar cyclic [B3N6]9? units (d(B?N)exo = 1.466(2), d(B?N)endo = 1.475(4) ) which are surrounded by bi capped polyhedra of trivalent Eu for Eu3[B3N6] and mixed valent Eu3+/Eu2+ for Li0.42Eu3[B3N6], respectively. In Li0.42Eu3[B3N6], Li+ occupies statistically (42%) the sites 36f and is sandwiched between the [B3N6]9? anions. The oxidation state +3 for Eu in Eu3[B3N6] and mixed valance state (+2/+3) in Li0.42Eu3[B3N6] are verified by magnetic measurements, ESR and Mössbauer Spectroscopy.