Synthesis and Crystal Structure of the Europium(II) Hydride Oxide Iodide Eu5H2O2I4 Showing Blue-Green Luminescence.

As the first europium(II) hydride oxide iodide, dark red single crystals of Eu5H2O2I4 could be synthesized from oxygen-contaminated mixtures of EuH2 and EuI2. Its orthorhombic crystal structure (a = 1636.97(9) pm, b = 1369.54(8) pm, c = 604.36(4) pm, Z = 4) was determined via single-crystal X-ray diffraction in the space group Cmcm. Anion-centred tetrahedra [HEu4]7+ and [OEu4]6+ serve as central building blocks interconnected via common edges to infinite ribbons parallel to the c axis. These ribbons consist of four trans-edge connected (Eu2+)4 tetrahedra as repetition unit, two H--centred ones in the inner part, and two O2--centred ones representing the outer sides. They are positively charged, according to ∞1{[Eu5H2O2]4+}, to become interconnected and charge-balanced by iodide anions. Upon excitation with UV light, the compound shows blue-green luminescence with the shortest Eu2+ emission wavelength ever observed for a hydride derivative, peaking at 463 nm. The magnetic susceptibility of Eu5H2O2I4 follows the Curie-Weiss law down to 100 K, and exhibits a ferromagnetic ordering transition at about 10 K.

The Role of the Bi3+ Lone Pair Effect in Bi(H3O)(SO4)2, Bi(HSO4)3, and Bi2(SO4)3.

Three new members in the Bi2O3-SO3-H2O system are identified by single crystal X-ray diffraction and Rietveld refinement after a fundamental examination of this phase space. Bi(H3O)(SO4)2 crystallizes in space group P21/c (no. 14, a = 1203.5(4), b = 682.9(2), c = 821.2(2) pm, ß = 102.99(1)°, 861 independent reflections, 88 refined parameters, wR2 = 0.14) homeotypic with Nd(H3O)(SO4)2 featuring edge-sharing BiO9 polyhedra. Bi(HSO4)3 crystallizes in a new structure type in space group P1 (no. 2, a = 492.04(7), b = 910.8(1), c = 1040.8(2) pm, α = 85.443(5)°, ß = 86.897(5)°, γ = 74.542(4)°, 3227 independent reflections, 154 refined parameters, wR2 = 0.05) comprising dimers of edge-sharing BiO8 polyhedra. For Bi2(SO4)3, a new modification crystallizing in space group P21/n (no. 14, a = 1308.03(7), b = 473.25(3), c = 1452.61(8) pm, ß = 100.886(2)°, 3189 independent reflections, 155 refined parameters, wR2 = 0.03) isotypic to Sb2(SO4)3 with noncondensed BiO7 polyhedra is presented. The role of the Bi3+ lone pair effect as elucidated by density functional theory (DFT) calculations is discussed for all three compounds with respect to their structural and optical properties. Additionally, the Bi3+ lone pair activity is compared to the recently reported borosulfates Bi(H3O)[B(SO4)2]4 and Bi2[B2(SO4)6]. Geometrical calculations based on structural data are correlated with electron localization function (ELF) calculations to establish the origin of the direction and strength of the lone pair stereoactivity of Bi3+ in oxidic compounds. Finally, the thermal properties of the three compounds are reported.

The First Bismuth Borosulfates Comprising Oxonium and a Tectosilicate-Analogous Anion.

The first bismuth borosulfate (H3 O)Bi[B(SO4 )2 ]4 is only the second featuring a three-dimensional anion, the first tectosilicate-analogous borosulfate synthesised solvothermally without a precursor (from Bi(NO3 )3 ⋅5 H2 O and B(OH)3 in oleum); moreover, it is the first comprising two differently charged cations and crystallises in a new structure type in space group I 4 ‾ (no. 82) (a=11.857(1), c=8.149(1) Å, 1947 refl., 111 param., wR2=0.037), confirmed by a second harmonic generation (SHG) measurement. The B(SO4 )4 supertetrahedra are connected via all four sulfate tetrahedra resulting in a three-dimensional anion with both H3 O+ and Bi3+ cations in channels. Additionally, the crystal structure of a further bismuth borosulfate, Bi2 [B2 (SO4 )6 ], is elucidated crystallising isotypically to the rare-earth borosulfates R2 [B2 (SO4 )6 ] in space group C2/c (No. 15) (a=13.568(2), b=11.490(2), c=11.106(2) Å, 3127 refl., 155 param., wR2=0.035). Moreover, the optical and thermal properties of both compounds are discussed.

Strong Lewis and Brønsted Acidic Sites in the Borosulfate Mg3 [H2 O→B(SO4 )3 ]2.

Borosulfates provide fascinating structures and properties that go beyond a pure analogy to silicates. Mg3 [H2 O→B(SO4 )3 ]2 is the first borosulfate featuring a boron atom solely coordinated by three tetrahedra. Thus, the free Lewis acidic site forms a Lewis acid-base adduct with a water molecule. This is unprecedented for borosulfate chemistry and even for borates. Quantum chemical calculations on water exchange reactions with BF3 and B(C6 F5 )3 revealed a higher Lewis acidity for the borosulfate anion. Moreover, proton exchange reactions showed a higher Brønsted acidity than comparable silicates or phosphates. Additionally, Mg3 [H2 O→B(SO4 )3 ]2 was characterised by X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and density functional theory (DFT) calculations.

Biuret-A Crucial Reaction Intermediate for Understanding Urea Pyrolysis To Form Carbon Nitrides: Crystal-Structure Elucidation and In Situ Diffractometric, Vibrational and Thermal Characterisation.

The crystal structure of biuret was elucidated by means of XRD analysis of single crystals grown through slow evaporation from a solution in ethanol. It crystallises in its own structure type in space group C2/c (a=15.4135(8) Å, b=6.6042(3) Å, c=9.3055(4) Å, Z=8). Biuret decomposition was studied in situ by means of temperature-programmed powder XRD and FTIR spectroscopy, to identify a co-crystalline biuret-cyanuric acid phase as a previously unrecognised reaction intermediate. Extensive thermogravimetric studies of varying crucible geometry, heating rate and initial sample mass reveal that the concentration of reactive gases at the interface to the condensed sample residues is a crucial parameter for the prevailing decomposition pathway. Taking these findings into consideration, a study on the optimisation of carbon nitride synthesis from urea on the gram scale, with standard solid-state laboratory techniques, is presented. Finally, a serendipitously encountered self-coating of the crucible inner walls by graphite during repeated synthetic cycles, which prove to be highly beneficial for the obtained yields, is reported.

Synthesis-Controlled Polymorphism and Optical Properties of Phyllosilicate-Analogous Borosulfates M[B2 (SO4 )4 ] (M=Mg, Co).

Increased synthetic control in borosulfate chemistry leads to the access of various new compounds. Herein, the polymorphism of phyllosilicate-analogous borosulfates is unraveled by adjusting the oleum (65 % SO3 ) content. The new polymorphs ß-Mg[B2 (SO4 )4 ] and α-Co[B2 (SO4 )4 ] both consist of similar layers of alternating borate and sulfate tetrahedra, but differ in the position of octahedrally coordinated cations. The α-modification comprises cations between the layers, whereas in the ß-modification cations are embedded within the layers. With this new synthetic approach, phase-pure compounds of the respective polymorphs α-Mg[B2 (SO4 )4 ] and ß-Co[B2 (SO4 )4 ] were also achieved. Tanabe-Sugano analysis of the Co2+ polymorphs reveal weak ligand field splitting and give insights into the coordination behavior of the two-dimensional borosulfate anions for the first time. DFT calculations confirmed previous in silico experiments and enabled an assignment of the polymorphs by comparing the total electronic energies. The compounds are characterized by single-crystal XRD, PXRD, FTIR, and UV/Vis/NIR spectroscopy, thermogravimetric analysis (TGA), and density functional theory (DFT) calculations.

Borosulfates-Synthesis and Structural Chemistry of Silicate Analogue Compounds.

Borosulfates are oxoanionic compounds consisting of condensed sulfur- and boron-centered tetrahedra. Hitherto, they were mostly achieved from solvothermal syntheses in SO3 -enriched sulfuric acid, or from reactions with the superacid H[B(HSO4 )4 ]. The crystal structures are very similar to those of the corresponding class of silicates and their substitution variants, especially regarding the typical structural motif of corner-sharing tetrahedra. However, the borosulfates are supposed to be even more versatile, because (BO3 ) units might also be part of the anionic network. The following article deals with detailed reports on the different synthesis strategies, the crystal chemistry of borosulfates in comparison to silicates, and their hitherto identified properties.

Sr[B2(SO4)3(S2O7)]: A Borosulfate with an Unprecedented Chain Structure Comprising Disulfate Groups.

Unconventional borosulfates containing S-O-S bridges are still rare. Sr[B2(SO4)3(S2O7)] was synthesized solvothermally in oleum (65% SO3) and crystallizes in a new structure type in space group P21/n (Z = 4, a = 747.0(2) pm, b = 1533.4(4) pm, c = 1222.0(3) pm, ß = 93.293(10)°). The structure features loop-branched vierer double chains, in which two terminal sulfate tetrahedra are condensed to a disulfate group. The resulting ratio between boron and sulfur of 2:5 was not yet found in borosulfate chemistry. The presence of S-O-S bridges was confirmed by FT-IR spectroscopy. Temperature-programmed X-ray powder diffraction in addition to thermogravimetric analysis revealed a transformation from chains containing S-O-S bridges in Sr[B2(SO4)3(S2O7)] to chains containing solely B-O-S bridges in Sr[B2(SO4)4] and to chains containing B-O-B bridges in Sr[B2O(SO4)3].

From S-O-S to B-O-S to B-O-B Bridges: Ba[B(S2O7)2]2 as a Model System for the Structural Diversity in Borosulfate Chemistry.

Various different possible connection patterns of sulfate and borate tetrahedra enable a vast structural diversity in borosulfates, a rather new class of silicate-analogous compounds. Here we unravel a direct relationship from S-O-S to B-O-S to B-O-B bridges for the first time in borosulfate chemistry. Solvothermal synthesis in pure oleum (65% SO3) yielded the first alkaline earth metal borosulfate comprising S-O-S bridges: Ba[B(S2O7)2]2 (I2/a, Z = 4, a = 1160.77(9) pm, b = 891.44(7) pm, c = 2130.26(19) pm, ß = 104.0341(17)°) contains molecular [B(S2O7)2]- anions of a central boron atom and two chelating disulfate groups. By using equal amounts of sulfuric acid and oleum solely B-O-S bridges were obtained in Ba[B2(SO4)4] (Pnna, Z = 4, a = 1279.08(18) pm, b = 1280.0(2) pm, c = 731.70(11) pm) featuring one-dimensional ∞1[B(SO4)4/2]- chains. The thermal analysis on Ba[B(S2O7)2]2 revealed the conversion from S-O-S bridges to B-O-S bridges in Ba[B2(SO4)4] and to B-O-B bridges in Ba[B2O(SO4)3] by a successive release of SO3. Thus, BaO-B2O3-SO3 is the first quaternary system for borosulfates uniting all three possible connection patterns enabling us to understand the fascinating but systematic chemistry in such systems. Both new compounds were also characterized by means of X-ray powder diffraction, electrostatic calculations, and infrared spectroscopy assisted by density functional theory (DFT).

Blue Excitement: The Lanthanide(III) Chloride Oxidomolybdates(VI) Ln3Cl3[MoO6] (Ln = La, Pr, and Nd) and Their Spectroscopic Properties.

The lanthanide(III) chloride oxidomolybdates(VI) with the empirical formula Ln3Cl3[MoO6] (Ln = La, Pr, and Nd) were synthesized by solid-state reactions utilizing the respective lanthanide trichloride, lanthanide sesquioxide (where available), and molybdenum trioxide together with lithium chloride as a fluxing agent. The title compounds crystallize in hexagonal space group P63/ m ( a = 942-926 pm, c = 542-533 pm, Z = 2). Besides tetracapped trigonal prismatically coordinated Ln3+ cations, noncondensed trigonal prismatic [MoO6]6- entities are found in the crystal structure. In addition to X-ray diffraction, the title compounds were also characterized by single-crystal Raman and infrared spectroscopy as well as measurements to determine their magnetic susceptibility and behavior at low temperatures. The most outstanding properties of the Ln3Cl3[MoO6] representatives (Ln = La, Pr, and Nd), however, are of an optical nature, because their band gaps, determined by diffuse reflectance spectroscopy, show a significant shift toward lower energies compared to those of other rare-earth metal chloride molybdates with a different polyhedral arrangement. This culminates in La3Cl3[MoO6]:Eu3+ exhibiting luminescence, which can be excited in the visible range of the electromagnetic spectrum by a blue light-emitting diode.

Synthesis and Characterization of the First Tin Fluoride Borate Sn3 [B3 O7 ]F with Second Harmonic Generation Response.

The new non-centrosymmetric tin fluoride borate Sn3 [B3 O7 ]F was synthesized hydrothermally, and was characterized by single-crystal and powder X-ray diffraction, vibrational spectroscopy, DFT calculations, second harmonic generation (SHG) measurements, thermogravimetry, and differential scanning calorimetry. Its SHG response is about 12 times that of quartz. The compound crystallizes in the non-centrosymmetric orthorhombic space group Pna21 with lattice parameters a=922.4(2), b=769.8(4), and c=1221.9(6) pm (Z=4). Characteristic for the structure are isolated B3 O7 moieties, consisting of two corner-sharing BO3 units and one BO4 tetrahedron. These occupy half of the octahedral voids of a slightly distorted hexagonal closest packing of Sn2+ atoms, with [SnF]+ units in the other half of the octahedral voids. Sn3 [B3 O7 ]F is transparent over a wide spectral range with a UV cut-off edge at about 263 nm.

The First Alkaline-Earth Fluorooxoborate Ba[B4 O6 F2 ]-Characterisation and Doping with Eu2.

The very first alkaline-earth fluorooxoborate Ba[B4 O6 F2 ] was synthesised by solid state methods starting from Ba(BF4 )2 , ß-BaB2 O4 , and B2 O3 . The crystal structure derived from single-crystal X-ray diffraction (P21 /n, a=6.6384(2) Å, b=7.6733(3) Å, c=11.3385(4) Å, ß=91.281(2)°, Z=4, Rint =0.0269, R1 =0.018, wR2 =0.034) comprises layers of BO3 F tetrahedra condensed through triangular BO3 units according to the descriptor 2Δ2□:<Δ2□>Δ. The extraordinary thirteen-fold coordination of barium by oxygen and fluorine leads to interesting optical properties of a sample doped with divalent europium, where a 4f→4f emission was recorded around 359 nm together with a broad emission band of a 5d→4f emission peaking at 366 nm. The compound is further characterised by IR-, Raman-, and solid-state NMR-spectroscopic methods. Moreover, DFT calculations as well as TGA and DSC measurements were performed.

Synthesis and Characterization of the First Borosulfates of Magnesium, Manganese, Cobalt, Nickel, and Zinc.

The first magnesium, manganese, cobalt, nickel, and zinc borosulfates were synthesized employing solvothermal conditions starting from the superacid H[B(HSO4)4] and the respective metal powders (Mg, Ni, Zn) or oxides (MnO2, CoO). α- M4[B2O(SO4)6] ( M = Mg, Mn, Co, Ni, Zn) crystallize isotypically in a new structure type in P3̅ (No. 147) with Z = 1, a = 793.59(4)-810.86(9) pm, and c = 743.98(4)-775.09(9) pm. The oligomeric anion comprises unprecedented dimeric open-branched quadruple tetrahedra { oB, 4 t}[B2O(SO4)6]8-, which are connected via M2O9 dimers to give a three-dimensional network. Upon mild heating, we observed a phase change from α-Mg4[B2O(SO4)6] to ß-Mg4[B2O(SO4)6], yielding a further new structure type in P3̅ (No. 147) with Z = 3, a = 1391.96(6) pm, and c = 748.54(3) pm. The reaction of MgB2 with SO3 yields Mg[B2(SO4)4] crystallizing in C2/ c with Z = 4, a = 1744.28(10) pm, b = 531.45(3) pm, c = 1429.06(8) pm, and ß = 126.323(2)° showing phyllosilicate topology. UV/vis spectroscopy on α- TM4[B2O(SO4)6] ( TM = Co, Ni) confirms the valence state of the TM and reveals that borosulfates are weakly coordinating host structures. Structure relationships between the presented crystal structures and similar borophosphates are shown. The results of vibrational spectroscopy as well as magnetic and thermal measurement investigations are discussed.

The Borosulfates K4[BS4O15(OH)], Ba[B2S3O13], and Gd2 [B2S6O24].

K4 [BS4 O15 (OH)], Ba[B2 S3 O13 ], and Gd2 [B2 S6 O24 ] were obtained by a new synthetic approach. The strategy involves initially synthesizing the complex acid H[B(HSO4 )4 ] which is subsequently reacted in an open system with anhydrous chlorides of K, Ba, and Gd to the respective borosulfates and a volatile molecule (HCl). Furthermore, protonated borosulfates should be accessible by appropriate stoichiometry of the starting materials, particularly in closed systems, which inhibit deprotonation of H[B(HSO4 )4 ] via condensation and dehydration. This approach led to the successful synthesis of the first divalent and trivalent metal borosulfates (Ba[B2 S3 O13 ] with band-silicate topology and Gd2 [B2 S6 O24 ] with cyclosilicate topology) and the first hydrogen borosulfate K4 [BS4 O15 (OH)].

The borosulfate story goes on--from alkali and oxonium salts to polyacids.

The structural principles of borosulfates derived from the B/S ratio are confirmed and extended to new representatives of this class showing novel motifs. According to the composition, Na[B(S2O7)2] (P2(1)/c; a=10.949(6), b=8.491(14), c=12.701(8) Å; ß=110.227(1)°; Z=4) and K[B(S2O7)2] (Cc; a=11.3368(6), b=14.662(14), c=13.6650(8) Å; ß=94.235(1)°; Z=8) contain isolated [B(S2O7)2](-) ions, in which the central BO4 tetrahedron is coordinated by two disulfate units. The alkali cations have coordination numbers of 7 (Na) and 8 (K), respectively. The structure of Cs[B(S2O7)(SO4)] (P2(1)/c; a=10.4525(6), b=11.3191(14), c=8.2760(8) Å; ß=103.206(1); Z=4) combines, for the first time, sulfate and disulfate units into a chain structure. Cs has a coordination number of 12. The same structural units were found in H[B(S2O7)(SO4)] (P2(1)/c; a=15.6974(6), b=11.4362(14), c=8.5557(8) Å; ß=90.334(3)°; Z=8). This compound represents the first example of a polyacid. The hydrogen atoms were located and connect the chains to form layers through hydrogen-bonding bridges. H3O[B(SO4)2] (P4/ncc; a=9.1377(6), c=7.3423(8) Å; Z=4) is the first oxonium compound of this type to be found. The BO4 tetrahedra are linked by SO4 tetrahedra to form linear chains similar to those in SiS2. The chains form a tetragonal rod packing structure with H3O(+) between the rods. The structures of borosulfates can be classified following the concept described by Liebau for silicates, which was extended to borophosphates by Kniep et al. In contrast to these structures, borosulfates do not comprise B-O-B bonds but instead contain S-O-S connections. All compounds were obtained as colourless, moisture-sensitive single crystals by reaction of B2O3 and the appropriate alkali salt in oleum.

New alkaline-earth amidosulfates and their unexpected decomposition to S4N4.

The amidosulphates Mg(NH2SO3)2·4H2O (P21/c), Mg(NH2SO3)2·3H2O (P1̄), Ca(NH2SO3)2·4H2O (C2/c), Ca(NH2SO3)2·H2O (P212121), Sr(NH2SO3)2·4H2O (C2/c), Sr(NH2SO3)2·H2O (P21/c) and Ba(NH2SO3)2 (Pna21) could be obtained as cm-sized crystals from aqueous solutions of the corresponding metal carbonates, hydroxides and amidosulphonic acid, respectively, by careful control of the crystallisation conditions. ß-Sr(NH2SO3)2 (Pc) and α-Sr(NH2SO3)2 (P21) could be obtained by careful thermal dehydration of Sr(NH2SO3)2·H2O. Their crystal structures were determined by single-crystal XRD and revealed a rich structural diversity with a significant tendency to form non-centrosymmetric crystals. The compounds were characterised by powder XRD, FT-IR, Raman and UV/vis spectroscopy and thermogravimetry. Temperature programmed single-crystal XRD, powder XRD and Raman spectroscopy, as well as DFT calculations were employed to aid the interpretation of vibrational and thermal properties. For the first time, SHG measurements were performed on metal amidosulphates, revealing the SHG intensities of ß-Sr(NH2SO3)2 and Ba(NH2SO3)2 that were comparable to quartz and KDP. Thermal decomposition was additionally studied by the preparation of reaction intermediates, serendipitously revealing the formation of S4N4 as the decomposition product. This unprecedented reaction represents the first sulphur nitride synthesis process that neither employs a sulphur halide nor elemental sulphur.

Cd[B2(SO4)4] and H2[B2(SO4)4] - a phyllosilicate-analogous borosulfate and its homeotypic heteropolyacid.

Borosulfates consist of heteropolyanionic networks of corner-shared (SO4)- and (BO4)-tetrahedra charge compensated by metal or non-metal cations. The anionic substructures differ significantly, depending on the different branching of the silicate-analogous borosulfate building blocks. However, only one acid has been characterized by single crystal X-ray diffraction so far. Herein, we present H2[B2(SO4)4] as the first phyllosilicate analogue representative, together with the homeotypic representative Cd[B2(SO4)4]. The latter can be considered the cadmium salt of the former. Their crystal structures and crystallographic relationship are elucidated. For H2[B2(SO4)4], the bonding situation is examined using Hirshfeld-surface analysis. Further, the optical and thermal properties of Cd[B2(SO4)4] are investigated by FTIR and UV-Vis spectroscopy, thermogravimetry, as well as temperature-programmed powder X-ray diffraction.

Polymorphism and optical, magnetic and thermal properties of the either phyllo- or inosilicate-analogous borosulfate Cu[B2(SO4)4].

Two polymorphs of the borosulfate Cu[B2(SO4)4] can be selectively prepared by solvothermal syntheses. The crystal structures of inosilicate-analogous α-Cu[B2(SO4)4] (P1̄, no. 2, a = 5.2636(2), b = 7.1449(2), c = 7.9352(2) Å, α = 73.698(2)°, ß = 70.737(2)°, γ = 86.677(2)°, 65 parameters, RBragg = 0.0052) and the new phyllosilicate-analogous polymorph ß-Cu[B2(SO4)4] (P21/n, no. 14, a = 7.712(3), b = 8.149(3), c = 9.092(3) Å, ß = 111.22(1)°, 3829 independent reflections, 106 parameters, wR2 = 0.054) are discussed. Further, the optical, magnetic and thermal properties of both polymorphs are investigated with focus on the role of the Cu2+ cation and its Jahn-Teller effect. The findings are confirmed by DFT calculations yielding insights in the stability of the synthesised polymorphs as well as a predicted γ-modification. Additionally, the crystal structures of two polymorphs of copper hydrogensulfate Cu(HSO4)2-I (P21/n, no. 14, a = 4.7530(2), b = 8.5325(4), c = 7.3719(3) Å, ß = 100.063(1)°, 1063 independent reflections, 55 parameters, wR2 = 0.052) and Cu(HSO4)2-II (P1̄, no. 2, a = 4.79.88(8), b = 7.857(1), c = 8.057(1) Å, α = 77.86(1)°, ß = 87.02(1)°, γ = 89.82(1)°, 1044 independent reflections, 109 parameters, wR2 = 0.132) as well as that of Cu[S2O7] (C2/c, no. 15, a = 6.6341(4), b = 8.7302(5), c = 9.0555(8) Å, ß = 104.763(3)°, 1117 independent reflections, 48 parameters, wR2 = 0.049) are presented and the cyclosilicate-analogous borosulfate Cu[B(SO4)2(HSO4)] is fully characterised with respect to its optical and thermal properties.

Synthesis, crystal structures and spectroscopic properties of pure YSb2O4Br and YSb2O4Cl as well as Eu3+- and Tb3+-doped samples.

The quaternary halide-containing yttrium(iii) oxidoantimonates(iii) YSb2O4Cl and YSb2O4Br were synthesised through solid-state reactions from the binary components (Y2O3, Sb2O3 and YX3, X = Cl and Br) at 750 °C in evacuated fused silica ampoules with eutectic mixtures of NaX and CsX (X = Cl and Br) as fluxing agents. YSb2O4Cl crystallizes tetragonally in the non-centrosymmetric space group P4212 with unit-cell parameters of a = 773.56(4) pm and c = 878.91(6) pm, whereas YSb2O4Br is monoclinic (space group: P21/c) with a = 896.54(6) pm, b = 780.23(5) pm, c = 779.61(5) pm and ß = 91.398(3)°, both for Z = 4. The two new YSb2O4X compounds contain [YO8]13- polyhedra, which are connected via four common edges to form layers (d(Y3+-O2-) = 225-254 pm) without any Y3+⋯X- bonds (d(Y3+⋯X-) > 400 pm). Moreover, all oxygen atoms belong to ψ1-tetrahedral [SbO3]3- units, which are either connected to four-membered rings [Sb4O8]4- in the chloride (Y2[Sb4O8]Cl2 for Z = 2) or endless chains in the bromide (Y1/2(SbO2)Br1/2 for Z = 8) by common vertices. With distances of 307 pm in YSb2O4Cl and 326 pm in YSb2O4Br there are not even substantial bonding Sb3+⋯X- (X = Cl and Br) interactions at work. Luminescence spectroscopy on samples doped with trivalent europium and terbium showed an energy transfer from the oxidoantimonate(iii) moieties as the sensitizer in the host structure onto the lanthanoid activators.

The tin sulfates Sn(SO4)2 and Sn2(SO4)3: crystal structures, optical and thermal properties.

We report the crystal structures of two tin(IV) sulfate polymorphs Sn(SO4)2-I (P21/c (no. 14), a = 504.34(3), b = 1065.43(6), c = 1065.47(6) pm, ß = 91.991(2)°, 4617 independent reflections, 104 refined parameters, wR2 = 0.096) and Sn(SO4)2-II (P21/n (no. 14), a = 753.90(3), b = 802.39(3), c = 914.47(3) pm, ß = 92.496(2)°, 3970 independent reflections, 101 refined parameters, wR2 = 0.033). Moreover, the first heterovalent tin sulfate Sn2(SO4)3 is reported which adopts space group P1̄ (no. 2) (a = 483.78(9), b = 809.9(2), c = 1210.7(2) pm, α = 89.007(7)°, ß = 86.381(7)°, γ = 73.344(7)°, 1602 independent reflections, 152 refined parameters, wR2 = 0.059). Finally, SnSO4 - the only tin sulfate with known crystal structure - was revised and information complemented. The optical and thermal properties of all tin sulfates are investigated by FTIR, UV-vis, luminescence and 119Sn Mössbauer spectroscopy as well as thermogravimetry and compared.