(Mn1−xPbx)Pb10+ySb12−yS26−yCl4+yO, a new oxy-chloro-sulfide with ∼2 nm-spaced (Mn,Pb)Cl4 single chains within a waffle-type crystal structure

The new oxy-chloro-sulfide (Mn_1−xPb_x)Pb_10+ySb_12−yS_26−yCl_4+yO (x ∈ [0.2-0.3]; y ∈ [0.3-1.6]) was synthesized by dry way at 500-600 °C. A single crystal ∼Mn_0.7Pb_11.0Sb_11.3S_25.3Cl_4.7O indicates a monoclinic symmetry, space group C2/m, with a = 37.480(8), b = 4.1178(8), c = 18.167(4) Å, β = 106.37(3)°, V = 2690.2(9) Å³, Z = 2. Its crystal structure was determined by X-ray single crystal diffraction, with a final R = 5.11%. Modular analysis of the crystal structure reveals a “waffle” architecture, where complex rods with lozenge section delimitate an internal channel filled by a single chain of (Mn_0.7Pb_0.3)Cl₆ octahedra connected by opposite edges. Minimal inter-chain distances are close to 18 Å. The rod wall, two-atom thick, presents, in alternation with S atoms, Pb or (Pb,Sb) cations with prismatic coordination in the internal atom layer, while the external atom layer is constituted exclusively by Sb cations with dissymmetric square pyramidal coordination. A (Pb,Sb)₂S₂ fragment connects two successive rods along (2 0 1) to form a waffle-type palissadic layer. The unique O position, half filled, presents the same environment than the isolated O positions in the oxy-sulfide Pb₁₄Sb₃₀S₅₄O₅, or oxy-chloro-sulfides Pb₁₈Sb₂₀S₄₆Cl₂O and (Cu,Ag)₂Pb₂₁Sb₂₃S₅₅ClO. This compound belongs to a pseudo-homologous series of chalcogenides with waffle structure, ordered according to the size of their lozenge shape channel. Such a complex senary compound of the oxy-chloro-sulfide type illustrates the structural competition between three cations, on one hand, and, on the other hand, three anions. This compound is of special interest regarding the 1D distribution of magnetic Mn²⁺ atoms at the ∼2 nm scale.     

Reaktionen von Oxiden der Elemente der V. Hauptgruppe mit Trithiazylchlorid Kristallstruktur von (S5N5)4[As8Cl28] · 2 S4N4

Reactions of Element Oxides of the Fifth Main Group with Trithiazyl Chloride. Crystal Structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ Whereas P₄O₁₀ does not react with (NSCl)₃, the oxides As₂O₃, Sb₂O₃, and Bi₂O₃ react under formation of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄, S₅N₅[SbCl₆] and a mixture of S₄N₅[BiCl₄] and S₄N₄Cl[BiCl₄], respectively. The products were characterized by their IR spectra. The crystal structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ was determined by means of X-ray diffraction (1168 independent observed reflexions, R = 0.059). Crystal data: tetragonal, space group P4 2₁c, Z = 2, a = 1596.6, c = 1520.1 pm. The compound consists of planar S₅N₅^⊕ cations, octameric anions [As₈Cl₂₈]^4? and S₄N₄ molecules. The S₅N₅^⊕ ions and the S₄N₄ molecules show positional disorder, which very probably is of dynamical type for the S₅N₅^⊕ ion. The [As₈Cl₂₈]^4? ions can be described as a (so far unknown) [As₄Cl₁₆]^4? ion with cubane-like structure (As? Cl bridging distances between 286 and 305 pm) to which four AsCl₃ molecules are attached via chloro bridges with As? Cl bond lengths between 314 and 328 pm.     

Synthesis and crystal structure of the novel Pb5Sb2MnO11 compound

The new Pb₅Sb₂MnO₁₁ compound was synthesized using a solid-state reaction in an evacuated sealed silica tube at 650°C. The crystal structure was determined ab initio using a combination of X-ray powder diffraction, electron diffraction and high-resolution electron microscopy (a=9.0660(8)Å, b=11.489(1)Å, c=10.9426(9)Å, S.G. Cmcm, R_I=0.045, R_P=0.059). The Pb₅Sb₂MnO₁₁ crystal structure represents a new structure type and it can be considered as quasi-one-dimensional, built up of chains running along the c-axis and consisting of alternating Mn⁺²O₇ capped trigonal prisms and Sb₂O₁₀ pairs of edge sharing Sb⁺⁵O₆ octahedra. The chains are joined together by Pb atoms located between the chains. The Pb⁺² cations have virtually identical coordination environments with a clear influence of the lone electron pair occupying one vertex of the PbO₅E octahedra. Electronic structure calculations and electron localization function distribution analysis were performed to define the nature of the structural peculiarities. Pb₅Sb₂MnO₁₁ exhibits paramagnetic behavior down to T=5 K with Weiss constant being nearly equal to zero that implies lack of cooperative magnetic interactions.     

Die Anwendung von Zinnamalgam in der chemischen Analyse

Zusammenfassung Es wird die Verwendung eines neuen, des Sn-Amalgams in der chemischen Analyse beschrieben. Die Vorzüge des Sn-Amalgams bestehen in der großen Geschwindigkeit der Reduktion (5 Minuten) und dem niedrigen Säuregrad der Lösung (n-Salzsäure). Mit Hilfe von Sn-Amalgam können Fe^..., Cu^.., Hg^.., Hg^., Sb^..., SbV, As^..., AsV, Pb^.., Sn^...., Ag^. und MnO₄ -Ionen leicht bestimmt werden. Auch die in Wasser schwer löslichen Verbindungen: Hg₂Cl₂, AgCl, As₂O₃, PbSO₄ und MnO₂ lassen sich damit reduzieren.     

Darstellung und Kristallstruktur der ersten Vertreter des neuen Verbindungstyps Pb4[SiO4]X4 mit X = Cl,Br

Inhaltsübersicht. Die beiden silicathaltigen Blei(II)-oxidhalogenide Pb₄[SiO₄]Cl₄ und Pb₄[SiO₄]Br₄ wurden erstmals dargestellt und ihre Kristallstruktur an Einkristallen mit Röntgen-beugungsmethoden ermittelt. Die Verbindungen kristallisieren in der monoklinen Raumgruppe P2₁/c (No. 14) mit den Gitterparametern: Pb₄[SiO₄]Cl₄: A = 8,73(1) Å, b = 15,68(1) Å, c = 8,265(6) Å, β = 92,4(1)°, Z = 4 Pb₄[SiO₄]Br₄: A = 9,00(1) Å, b = 16,217(8) Å, c = 8,404(4) Å, β = 92,4(1)°, Z = 4 Im Gegensatz zu der “nichtstöchiometrischen” Verbindungsgruppe um Pb₈O₇Br₂ · SiO₂ konnten hier alle Atomlagen ermittelt werden. Es liegen einzelne SiO₄-Gruppen vor, die über Pb²⁺ zu leicht gewellten Netzen verbunden sind. Zwischenräume und Löcher der Netze werden von Halogenidionen aufgefüllt. Preparation and Crystal Structures of the First Two Members of a New Type of Lead (II) Oxyhalides, Pb₄[SiO₄]X₄ (X = Cl, Br) Both silicate-bearing lead(II) oxyhalides Pb₄[SiO₄]Cl₄ and Pb₄[SiO₄]Br₄ were prepared and studied for their crystal structure with X-ray single crystal methods for the first time. The compounds crystallize in the monoclinic space group P2₁/c (No. 14) with following lattice parameters: Pb₄[SiO₄]Cl₄: A = 8.73(1) Å, b = 15.68(1) Å, c = 8.205(6) Å, β = 92.4(1)°, Z = 4 Pb₄[SiO₄]Br₄: A = 9.00(1) Å, b = 16.217(8) Å, c = 8.404(4) Å, β = 92.4(1)°, Z = 4. In contrast with further works about the group of nonstoichiometric lead oxyhalides Pb₈O₇Br₂ · SiO₂ in the present work all atomic positions were determined. The crystal structure shows single SiO₄ groups linked only by Pb²⁺ ions to form slightly undulated nets. Holes and interspaces of these nets are stuffed with halide ions.     

Struktur‐Eigenschafts‐Beziehung von Cu5Pb6O3Cl11, einer gut Kupferionen leitenden Verbindung

Structure‐Behaviour‐Relation of Cu₅Pb₆O₃Cl₁₁, a Good Solid State Ionic Conductor for Cu⁺‐Ions A new compound within the group of coin metal lead(II) oxide halides is found and characterized by X‐ray single crystal structure determination in a temperature range from 120 K to 400 K. Cu₅Pb₆O₃Cl₁₁ shows a new crystal type structure with a = 21.098(4) Å, b = 10.233(2) Å, c = 12.224(2) Å, β = 124.08(3)°, Z = 4 and space group C 2/c (No. 15) at 120 K. There are found isolated oxidic chains built of OPb₄ tetrahedra beside columnar areas consisting of CuCl. In this halidic partial structure are a lot of empty and partially occupied Cl₄‐tetrahedra. This structural characteristic seems to be source of a very good conductivity of copper ions, like in microscopic and nanoscaled composites of Al₂O₃ and AgI.     

Zum System K2O/PbO. Zur Kenntnis von K2Pb2O3

On the System K₂O/PbO: The Crystal Structure of K₂Pb₂O₃ Orange-coloured single crystals of K₂Pb₂O₃ crystallize by means of 4-circle-Diffractometer data (237 of 238 possible hkl, R = 5.9₉%, MoKα) cubic with a = 8.41₉ Å, Z = 4, in space group I2₁3?T⁵, parameter see text. We find a superstructure of the perovskite type of structure, where, concerning the formula KPbO_3/2, half of the O^2? ions are omitted systematically, without loosing the 3-Dimensional arrangement of order. Pb²⁺ is surrounded by 3 K⁺ by 6 O^2? and O^2? by 2 Pb²⁺ and 4 K⁺. The Madelung Part of the Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, are calculated and discussed.     

The Rb7Bi3−3xSb3xCl16 Family: A Fully Inorganic Solid Solution with Room‐Temperature Luminescent Members

Low‐dimensional ns²‐metal halide compounds have received immense attention for applications in solid‐state lighting, optical thermometry and thermography, and scintillation. However, these are based primarily on the combination of organic cations with toxic Pb²⁺ or unstable Sn²⁺, and a stable inorganic luminescent material has yet to be found. Here, the zero‐dimensional Rb₇Sb₃Cl₁₆ phase, comprised of isolated [SbCl₆]^3? octahedra and edge‐sharing [Sb₂Cl₁₀]^4? dimers, shows room‐temperature photoluminescence (RT PL) centered at 560 nm with a quantum yield of 3.8±0.2 % at 296 K (99.4 % at 77 K). The temperature‐dependent PL lifetime rivals that of previous low‐dimensional materials with a specific temperature sensitivity above 0.06 K^?1 at RT, making it an excellent thermometric material. Utilizing both DFT and chemical substitution with Bi³⁺ in the Rb₇Bi_3?3xSb_3xCl₁₆ (x≤1) family, we present the edge‐shared [Sb₂Cl₁₀]^4? dimer as a design principle for Sb‐based luminescent materials.     

Aggregation Induced Emissive Luminogens for Sensing of Toxic Elements

The major findings in the growing field of aggregation induced emissive (AIE) active materials for the detection of environmental toxic pollutants have been summarized and discussed in this Review article. Owing to the underlying photophysical phenomenon, fluorescent AIE active molecules show more impact on sensing applications. The major focus in current research efforts is on the development of AIE active materials such as TPE based organic fluorescent molecules, metal organic framework, and polymers that can be employed for the detection of toxic pollutants such as CN⁻, NO₂⁻, Hg²⁺, Cd²⁺, As³⁺, As⁵⁺, F⁻, Pb²⁺, Sb³⁺ ions.     

Nd5(AsO3)4Cl3: The First Oxo‐Arsenate(III)‐Chloride of the Lanthanides

Single crystals of Nd₅(AsO₃)₄Cl₃ (monoclinic, P2/n, Z = 2, a = 1026.0(1), b = 543.35(3), c = 1400.2(1) pm, β = 93.48(1)°) were obtained from the reaction of Nd₂O₃, As₂O₃ and NaCl in a sealed silica ampoule. In the crystal structure the Nd³⁺ ions are linked by AsO₃^3? groups into layers that alternate with layers of Cl^? ions. Two of the three crystallographically different Nd³⁺ ions are coordinated by eight oxygen atoms, the third one has four oxygen and four chlorine atoms as neighbours.     

Ag2Pb8O7Cl4, Ein neues Blei(II)-oxidhalogenid mit Silber

Ag₂Pb₈O₇Cl₄, a New Member of Lead(II) Oxyhalides with Silver Ag₂Pb₈O₇Cl₄ is one among other products of the thermal decomposition of AgPb₄O₄Cl. Ag₂Pb₈O₇Cl₄ can be prepared directly by heating the binary components within a temperature range from 590°C to 620°C. The crystal structure was solved by single crystal X-ray methods. The compound crystallizes monoclinic with a = 12.411(4) Å, b = 17.99(3) Å, c = 14.785(4) Å, β = 147.01(2)°, Z = 4 with the space group P2₁/c. Ag₂Pb₈O₇Cl₄ shows remarkable structural features, e.g. silver tetrahedrally surrounded by chlorine.     

New Pyrochlore Pb[In0.5 Sb1.5]O6.5

From the study of the hypothetical series Pb[PbIn_c–2pSb_c]O_6+p (O ? p < 1; 0 ? c < 2), the existence of the cubic pyrochlore Pb₂^II[In_0.5Sb_1.5]O_6.5 has been established. This compound was obtained as an orange yellow powder, S.G. Fd4 m (No. 227), Z = 8, a = 10.5892(1) Å, V = 1187.38(3) ų, D_c = 8.48 M gm^?3. For Pb in 16(c) positions, In and Sb (1:3) randomly distributed in 16(d), oxygen atoms in 48(f) and in a half of the 8(a) sites, and oxygen positional parameter x = 0.429 (origin at center, 3 m), R = 0.062. The apparent interatomic distances (Å) are determined: Pb? O = 2.612; (In, Sb)? O = 2.019.     

Prediction and assignment of site occupation and energy levels for Pb ions in crystal hosts

The environmental factor h_e of the host was calculated quantitatively in Pb²⁺-doped 23 compounds based on the dielectric theory of chemical bond for complex crystals. The relationship between the A band energy E_A of Pb²⁺ and the environmental factor h_e was intensively studied. The results indicate that E_A of Pb²⁺ decreases linearly with increasing of h_e. A linear model was proposed which allows us to correctly predict and assign the site occupations and the position of A band for Pb²⁺-doped compounds if the crystal structure and the refraction index were known. Applied to SrGa₂O₄:Pb²⁺, CaAl₂B₂O₇:Pb²⁺ and SrAl₂B₂O₇:Pb²⁺, the theoretical predictions are in very good agreement with the experimental data. In SrGa₂O₄:Pb²⁺, the excitation spectrum of Pb²⁺ from two different cation sites was identified: the higher energy band of A (265 nm) from the site of Sr2, and the lower ones (280 nm) from the site of Sr1.     

Preparation and crystallographic investigation of the spinel series: Mn1 + 2sCr2 − 3sSbsO4 (0.05 ⩽ , s ⩽ 0.30)

Mn_{1 + 2s}Cr_{2 ? 3s}Sb_sO₄, a new series of spinels, have been prepared and studied using X-ray powder data. For s going from 0.05 to 0.30, a gradually increases from 8.441(1) to 8.472(1) Å, and u slightly decreases, from 0.262 to 0.258. Interatomic distances are given. The Mn_{1 + 2s}Cr_{2 ? 3s}Sb_sO₄ (0.05 < s < 0.30) series may be conceived as the result of partial substitution of Cr^{3 +} by 2/3Mn^{2 +} + 1/3Sb^{5 +} in the normal spinel, MnCr₂O ₄.     

The Rb7Bi3−3xSb3xCl16 Family: A Fully Inorganic Solid Solution with Room-Temperature Luminescent Members

Low-dimensional ns²-metal halide compounds have received immense attention for applications in solid-state lighting, optical thermometry and thermography, and scintillation. However, these are based primarily on the combination of organic cations with toxic Pb²⁺ or unstable Sn²⁺, and a stable inorganic luminescent material has yet to be found. Here, the zero-dimensional Rb₇Sb₃Cl₁₆ phase, comprised of isolated [SbCl₆]³⁻ octahedra and edge-sharing [Sb₂Cl₁₀]⁴⁻ dimers, shows room-temperature photoluminescence (RT PL) centered at 560 nm with a quantum yield of 3.8±0.2 % at 296 K (99.4 % at 77 K). The temperature-dependent PL lifetime rivals that of previous low-dimensional materials with a specific temperature sensitivity above 0.06 K⁻¹ at RT, making it an excellent thermometric material. Utilizing both DFT and chemical substitution with Bi³⁺ in the Rb₇Bi_3−3xSb_3xCl₁₆ (x≤1) family, we present the edge-shared [Sb₂Cl₁₀]⁴⁻ dimer as a design principle for Sb-based luminescent materials.     

A 3D Hybrid Praseodymium–Antimony–Oxochloride Compound: Single‐Crystal‐to‐Single‐Crystal Transformation and Photocatalytic Properties

A 3D organic–inorganic hybrid compound, (2‐MepyH)₃ [{Fe(1,10‐phen)₃}₃][{Pr₄Sb₁₂O₁₈(OH) Cl_11.5}(TDC)_4.5({Pr₄Sb₁₂O₁₈(OH)Cl_9.5} Cl)] ? 3 (2‐Mepy) ? 28 H₂O ( 1 ; 2‐Mepy=2‐methylpyridine, 1,10‐phen=1,10‐phenanthroline, H₂TDC=thiophene‐2,5‐dicarboxylic acid), was hydrothermally synthesized and structurally characterized. Unusually, two kinds of high‐nuclearity clusters, namely [(Pr₄Sb₁₂O₁₈ (OH)Cl₁₁)(COO)₅]^5? and [(Pr₄Sb₁₂O₁₈ (OH)Cl₉)Cl(COO)₅]^4?, coexist in the structure of compound 1 ; two of the latter clusters are doubly bridged by two μ₂‐Cl^? moieties to form a new centrosymmetric dimeric cluster. An unprecedented spontaneous and reversible single‐crystal‐to‐single‐crystal transformation was observed, which simultaneously involved a notable organic‐ligand movement between the metal ions and an alteration of the bridging ion in the dimeric cluster, induced by guest‐release/re‐adsorption, thereby giving rise to the interconversion between compound 1 and the compound (2‐MepyH)₃[{Fe(1,10‐phen)₃}₃][{Pr₄Sb₁₂O₁₈(OH)Cl_11.5}(TDC)₄({Pr₄Sb₁₂O₁₈Cl_10.5(TDC)_0.5(H₂O)_1.5}O_0.5)] ? 25 H₂O ( 1′ ). The mechanism of this transformation has also been discussed in great detail. Photocatalytic H₂‐evolution activity was observed for compound 1′ under UV light with Pt as a co‐catalyst and MeOH as a sacrificial electron donor.     

Potassium oxoaluminate ­antimonate(III), K2[Al2Sb2O7]

Dipotassium dialuminium diantimonate, K₂[Al₂Sb₂O₇], crystallizes in the trigonal space group . The structure is isotypic with K₂Pb₂Ge₂O₇ and consists of [Al₂Sb₂O₇]^2? layers containing Al³⁺ in a nearly regular tetrahedral and Sb³⁺ in a Ψ‐tetrahedral environment of O ligands.     

An investigation of microporous cetineite-type phases A6[B12O18][CX3]2[Dx(H2O,OH,O)6−y] I. The cetineite structure field

Hydrothermal syntheses between 120 and 200 °C have been performed to determine the chemical variability of semiconducting microporous materials with cetineite structure. The syntheses were based on the general formula A₆[B₁₂O₁₈][CX₃]₂[D_x(H₂O,OH,O)_6−y], (0≤×≤2; 0≤y≤6), which was derived from X-ray crystal structure refinements. A = Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Tl⁺, NH₄⁺, Ca²⁺, Sr²⁺, and Ba²⁺ were introduced as hydroxides, in some cases as carbonates, B = C = As³⁺, Sb³⁺, and Bi³⁺, and X = S²⁻, Se²⁻, and Te²⁻ as elements. Only syntheses with B = C = Sb³⁺ and X = S²⁻ and Se²⁻ were successfull. Known cetineite-type phases now include the element combinations A/Sb³⁺/S²⁻ with A = Na⁺ and K⁺, and A/Sb³⁺/Se²⁻ with A = Na⁺, K⁺, Rb⁺, Sr²⁺, Ba²⁺, and probably Tl⁺. Variable amounts of Na⁺, Sb³⁺ and C⁴⁺ were found to occupy the D position of the cetineite-type structure. The chemical variability can be described by the coupled substitutions A⁺ + H₂OA²⁺ + OH⁻ mH₂OD^m+ + mOH, and nOH⁻Dⁿ⁺ + nO²⁻. The crystals obtained are orange to dark red, in agreement with their semiconducting properties.     

Prediction of New $$\rm{A^+B^{3+}X_2^{+5}O_7}$$ Compounds

Hitherto unprepared compounds of composition ABX₂O₇ (where A⁺ and B³⁺ are different cations; and X = P⁵⁺, V⁵⁺, As⁵⁺, Nb⁵⁺, Sb⁵⁺, or Ta⁵⁺) are predicted. Criteria are found to predict the possibility for these compounds to crystalize in one of the crystal structure types (KAlP₂O₇, weberite, NaAlP₂O₇, LiFeP₂O₇, or pyrochlore) at room temperature and atmospheric pressure. The prediction is based only on the properties of elements and simple oxides. The average prediction accuracy is at least 88%. The calculations use an information-analytical system (IAS) comprising precedent-based pattern recognition software.     

Synthesis and crystal structure of the salt of the protonated thiamine cation with the palladium(II) tetrachloride anion [HTA]2[PdCl4]Cl2 · 2H2O

The reaction of thiamine chloride hydrochloride with a solution of palladium chloride in hydrochloric acid gave a protonated thiamine salt [HTA]₂[PdCl₄]Cl₂ · 2H₂O (I) (TA is 4-methyl-3-[(2??-methyl-4??-amino-3??,4??-dihydropyrimidinyl-5??)methyl]-5-(2-hydroxyethyl)thiazolium cation, C₁₂H₁₆N₃O₂S). The crystal structure of I was determined by X-ray diffraction. The crystals are triclinic: a = 11.459(8) ?, b = 12.239(8) ?, c = 6.910(1) ?, ?? = 103.24(3)°, ?? = 76.95(3)°, ?? = 106.04(3)°, Z = 2, space group P $\bar 1$ . The structural units of I are doubly charged [HTA]²⁺ cations, [PdCl₄]^2? and Cl^? anions, and crystallization water molecules combined by hydrogen bonds and electrostatic interactions. The planar thiazolium and pyrimidine rings are in the F conformation, ??_t = 1.0°, ??_p = ?86.6°, and the dihedral angle between the planes is 85.5°. The torsion angles of the hydroxyethyl group are as follows: C(9)C(10)C(11)O(1), 175.6°; S(1)C(9)C(10)C(11), 33.2°; it is involved in the hydrogen bond with the free Cl^? anion. The sulfur atom forms a short (3.052 ?) intermolecular S-Cl contact with the chlorine atom of the [PdCl₄]^2? anion, which forms supramolecular chains.