Composition and Crystal Structure of SmSb₂O₄Cl Revisited – and the Analogy of Sm_1.5Sb_1.5O₄Br

Abstract

The quaternary halide-containing samarium(III) oxidoantimonates(III) Sm 1.3 Sb 1.7 O 4 Cl and Sm 1.5 Sb 1.5 O 4 Br were synthesized through solid-state reactions from the binary components (Sm 2 O 3 , Sb 2 O 3 and SmX 3 , X = Cl and Br) at 750°C in evacuated fused silica ampoules. They crystallize tetragonally in the space group P4/mmm, like the basically isotypic bismuthate(III) compounds SmBi 2 O 4 Cl and SmBi 2 O 4 Br, but show larger molar volumes and therefore contradict an ideal composition of "SmSb 2 O 4 X" (X = Cl and Br). Both singlecrystal X-ray diffraction and quantitative electron-beam microprobe

The True Nature of SmSb2O4Cl: Syntheses and Crystal Structures of Sm2[Sb4O8]Cl2 and Eu2[Sb4O8]Cl2

“…The Cl À anion layers serve to compensate the charge the [Sb(LnO 4 )Sb] + layers, so without these, no stability for the whole crystal structure would be expected and this fact has again resemblance to the rest of the LnSb 2 O 4 Cl series with Ln = Gd-Lu [11] and YSb 2 O 4 Cl, [10] all crystallizing in the non-centrosymmetric space group P42 1 2 (Table 4). The distances of the Sb 3 + cations to the nearest, but not directly bonded, terminal oxygen atoms (O1') of adjacent rings (dotted green connections in Figure 3 3), they clearly show that Sb 3 + strives for a fourfold coordination, as it is already known for the LnBi 2 O 4 X representatives (Ln = La-Lu, X = Cl-I) [2][3][4] and Sm 1 + x Sb 2À x O 4 X (X = Cl and Br), [5] which might be due to the fact that there is a high-temperature phase present at the reaction temperatures, most likely crystallizing analogously to the P4/mmm-type LnBi 2 O 4 X representatives (Figure 6, top), if necessary stabilized by some Ln 3 + surplus. [5] A link between the quadruple and triple oxygen-atom coordination of antimony(III) is not yet known so far, but a new monoclinic modification of LaBi 2 O 4 Cl [24] exhibits an infinite strand from fused components of this mixed coordination (Figure 7).…”

“…The distances of the Sb 3 + cations to the nearest, but not directly bonded, terminal oxygen atoms (O1') of adjacent rings (dotted green connections in Figure 3 3), they clearly show that Sb 3 + strives for a fourfold coordination, as it is already known for the LnBi 2 O 4 X representatives (Ln = La-Lu, X = Cl-I) [2][3][4] and Sm 1 + x Sb 2À x O 4 X (X = Cl and Br), [5] which might be due to the fact that there is a high-temperature phase present at the reaction temperatures, most likely crystallizing analogously to the P4/mmm-type LnBi 2 O 4 X representatives (Figure 6, top), if necessary stabilized by some Ln 3 + surplus. [5] A link between the quadruple and triple oxygen-atom coordination of antimony(III) is not yet known so far, but a new monoclinic modification of LaBi 2 O 4 Cl [24] exhibits an infinite strand from fused components of this mixed coordination (Figure 7). The square y 1 a -pyramids [BiO 4 ] 5À form a meandering chain via cis-oriented oxygen atoms by corner-linkage according to 1 ∞ {[BiO v 2=2 O t 2=1 ] 3À }.…”

“…The distances of the Sb 3+ cations to the nearest, but not directly bonded, terminal oxygen atoms (O1′) of adjacent rings (dotted green connections in Figure 3) amount to d (Sb−O1′)=322 pm for EuSb 2 O 4 Cl and d (Sb−O1′)=328 pm for SmSb 2 O 4 Cl. Although they appear rather long in comparison to the covalently bonded ones ( d (Sb−O)=194–209 pm, Table 3), they clearly show that Sb 3+ strives for a fourfold coordination, as it is already known for the Ln Bi 2 O 4 X representatives ( Ln =La–Lu, X =Cl–I) [2–4] and Sm 1+ x Sb 2− x O 4 X ( X= Cl and Br), [5] which might be due to the fact that there is a high‐temperature phase present at the reaction temperatures, most likely crystallizing analogously to the P 4/ mmm ‐type Ln Bi 2 O 4 X representatives (Figure 6, top ), if necessary stabilized by some Ln 3+ surplus [5] …”

“…According to Figure 11, only the four elements europium at 12.8(2) % (ideal: 12.5 %), antimony at 25.8(2) % (ideal: 25.0 %), oxygen at 50.6(3) % (ideal: 50.0 %) and chlorine at 12.7(4) % (ideal: 12.5 %) are visible. The ratio of europium to antimony equals 1 : 2, which means that there is no mixed occupation in this compound as in the case of Sm 1.3 Sb 1.7 O 4 Cl, [5] for example. WDXS measurements were performed for SmSb 2 O 4 Cl as well and the following results emerged: samarium 11.9(5) % (ideal: 12.5 %), antimony 25.5(3) % (ideal: 25.0 %), oxygen 50.5(4) % (ideal: 50.0 %), chlorine 12.1(4) % (ideal: 12.5 %).…”

Flux Growth of Tungsten Oxychloride Li 23 CuW 10 O 40 Cl 5

“…Recently, it has been reported that incorporation of halides into oxides can strikingly change their electronic structures and modify the physical properties [7][8] . Several novel transition-metal oxychlorides have been reported to date, such as MnSb 4 O 6 Cl 2 [9] , PbCu 2 (SeO 3 ) 2 Cl 2 [10] , Cu 3 Bi(SeO 3 ) 2 O 2 Cl [ 11 ] , FeTe 2 O 5 X (X=Cl, Br) [ 1 2 ] , SrCu 2 (SeO 3 ) 2 Cl 2 [13] , SmSb 2 O 4 Cl [14] , and MSb 2 O 3 (OH)Cl (M=Co, Fe, Mn) [15] . Above-mentioned materials show novel structures and special magnetic properties due to their diversity structural which was more helpful to generate the magnetic ordering during low temperature.…”