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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 596 (1991), S. 89-92 
    ISSN: 0044-2313
    Keywords: Calcium oxychloride ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Oxychloride of Calcium: Ca4OCl6Ca4OCl6 (hexagonal, P63mc, Z = 2), a = 905.8(3), c = 686.3(4) pm, (R = 0.031) crystallizes as colourless needles from reducing melts (CaCl2, Ca) that contain small amounts of „oxygen“. It contains „isolated“ tetrahedral units [Ca4O] and is isotypic with e.g., Ba4OCl6, Yb4OCl6 and K6HgS4. Ca4OCl6 does not form in the dehydration process of, for example, CaCl2 · 6 H2O.
    Notes: Ca4OCl6 (hexagonal, P63mc, Z = 2, a = 905.8(3)); c = 686.3(4) pm, (R = 0,031) kristallisiert in Form farbloser Nadeln aus „reduzierenden Schmelzen“ (CaCl2, Ca), die wenig „Sauerstoff“ enthalten. Es enthält „isolierte“ tetraedrische [Ca4O]-Einheiten und ist isotyp mit z. B. Ba4OCl6, Yb4OCl6 oder K6HgS4. Ca4OCl6 entsteht nicht beim Entwässern von z. B. CaCl2 · 6 H2O.
    Additional Material: 1 Ill.
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  • 2
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Complex Cation [(AnH)3(H2O)2]3+ in Trianilinium-tri-μ-chloro-nonachloro-trirhenate(III)-dihydrate, (AnH)3[Re3(μ-Cl3)Cl9] · 2 H2ODark red single crystals of trianilinium-tri-μ-chloro-nonachloro-trirhenate(III)-dihydrate grow from hydrochloric acid solutions of “ReCl3 · 2 H2O” and anilinium hydrochloride. An important feature of the crystal structure (monoclinic, P21/a, Z = 4, a = 1595.98(12), b = 1594.53(11), c = 1319.65 (9) pm, β = 100.20(1)°, Vm = 497.68(1) cm3 mol-1) are complex cations of the composition [(AnH)3(H2O)2]3+. The N—O- and O—O-distances in the hydrogen bonded cation [(AnH)3(H2O)2]3+ are 281 to 289 pm and 287, respectively. The cationic layers build up corrugated layers parallel (010) and leave two channels in the [010] direction per unit cell into which the anionic clusters, [Re3Cl12]3-, are embedded.
    Notes: Dunkelrote Einkristalle von Trianilinium-tri-μ-chloro-nonachloro-tri-rhenat(III)-dihydrat erhält man aus salzsauren Lösungen von „ReCl3 · 2 H2O“ und Aniliniumhydrochlorid. In der Kristallstruktur (monoklin, P21/a, Z = 4, a = 1595,98(12), b = 1594,53(11), c = 1319,65(9) pm, β = 100,20(1)°, Vm = 497,68(1) cm3 mol-1) sind drei Aniliniumkationen und zwei Wassermoleküle über Wasserstoff-Brückenbindungen zu einem komplexen Kation [(AnH)3(H2O)2]3+ verbunden. Innerhalb dieser Baugruppe findet man N—O-Bindungsabstände zwischen 281 und 289 pm sowie einen O—O-Abstand von 287 pm. Die komplexen Kationen [(AnH)3(H2O)2]3+ sind parallel (010) zu gewellten Schichten angeordnet, die je Elementarzelle zwei Kanäle in Richtung [010] freilassen, in die die Anionen [Re3Cl12]3- eingebettet sind.
    Additional Material: 3 Ill.
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  • 3
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese, Molekül- und Kristallstruktur eines zweiten Hydrates des Rheniumtrichlorids: [Re3Cl9(H2O)3] · 10 H2ODas Dekahydrat von [Re3Cl9(H2O)3] erhält man aus der wäßrigen Lösung von ReCl3 bei Temperaturen von 0 bis -5°C. Die Kristallstruktur (orthorhombisch, Pnma, Z = 4; a = 1 125,16(3), b = 1 630,30(5), c = 1 378,84(5) pm) wurde aus Einkristall-Diffraktometer-Daten bestimmt. Die Moleküle [Re3Cl9(H2O)3] werden in Richtung [0 1 0] gestapelt und durch Kristallwasser voneinander getrennt. Gemeinsam mit dem „Koordinationswasser“ in den Molekülen bilden sie ein System starker Wasserstoffbrücken-Bindungen, wenn dies aus den kurzen Abständen d (O—O) = 277 pm alleine geschlossen werden darf.
    Notes: The decahydrate of [Re3Cl9(H2O)3] is obtained from aqueous solutions of ReCl3 at zero to -5°C. The crystal structure (orthorhombic, Pnma, Z = 4; a = 1125.16(3), b = 1 630.30(5), c = 1 378.84(5) pm) has been determined from single-crystal X-ray diffractometer data. The [Re3Cl9(H2O)3] molecules are stacked in the [0 1 0] direction and the rows of such molecules are separated by the crystal water molecules. Together with the water ligands, these form a rather strong hydrogen bonding system judging from O—O distances (d = 277 pm) alone.
    Additional Material: 4 Ill.
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  • 4
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of Praseodymium(III)-monoacetatohexaaquo-dichloridemonohydrate, [Pr(CH3COO)(H2O)6]Cl2 · H2OSingle crystals of [Pr(CH3COO)(H2O)6]Cl2 · H2O (pale green) may be obtained from a solution of PrCl3 · 7 H2O in aqueous acetic acid by isothermic evaporation at room temperature. [Pr(CH3COO)(H2O)6]Cl2 · H2O crystallizes with the triclinic system, space group P1 (No. 2); a = 872.27(9) pm, b = 933.02(8) pm, c = 961.75(9) pm; α = 105.238(9)°, β = 107.913(9)°, γ = 110.568(8)°; R = 0.023, Rw = 0.022 (Z = 2). Pr3+ is nine-coordinated by O2- of six water molecules, one bidentate acetate group, and the bridging oxygen from another (formally monodentate) acetate anion. Centrosymmetric dimers {[Pr(CH3COO)(H2O)6]2}4+ are thus formed, held together by four “lone-some” Cl- anions and two “zeolithic” water molecules per dimer. The chloride ions are surrounded by five (Cl1) and six (Cl2) aquo ligands, respectively. The “zeolithic” water molecule (O9z) has four aquo ligands and two chloride ions (Cl1 and Cl2) as nearest neighbours.
    Notes: [Pr(CH3COO)(H2O)6]Cl2 · H2O wird in Form von blaßgrünen Einkristallen durch Eindunsten wäßriger, essigsaurer Lösungen von PrCl3 · 7 H2O erhalten. Die Verbindung kristallisiert triklin (Z = 2), Raumgruppe P1 (Nr. 2); a = 872,27(9) pm; b = 933,02(8) pm; c = 961,75(9) pm; α = 105,238(9)°; β = 107,913(9)°; γ = 110,568(8)°; R = 0,023; Rw = 0,022. Pr3+ ist von insgesamt neun Sauerstoffatomen umgeben: Sechs gehören zu „Hydratwasser“-Molekülen, zwei zu einer chelatartig angreifenden, das neunte zu einer einzähnig koordinierenden Acetatgruppe. Durch Verbrückung über Acetationen entstehen zentrosymmetrische Dimere {[Pr(CH3COO)(H2O)6]2}4+, die durch vier „einsame“ Cl--Ionen und zwei weitere Wassermoleküle pro Dimer zusammengehalten werden. Die Chloridionen sind von fünf (Cl1) bzw. sechs (Cl2) Wasserliganden umgeben, das „zeolithische“ Wasser (O9z) hat vier Wassermoleküle und zwei Chloridionen (Cl1 und Cl2) als nächste Nachbarn.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 585 (1990), S. 38-48 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ternary Bromides of Aluminium, Gallium, and Indium of the Formula Type AIMIIIBr4 (AI = Na, Ga, K, In, Rb). An OverviewThe fourteen possible bromides AIMIIIBr4 with AI = Na, Ga, K, In, Rb and MIII = Al, Ga, In are obtained from mixtures of the binary components, ABr and MBr3. Six different structure types are observed: NaGaBr4-, NaAlCl4-, GaCl2-, β-GaBr2-, KAlBr4-, and BaSO4-type. Singlecrystal data are reported for the examples of NaGaBr4, KGaBr4, and InGaBr4. Without exception, slightly distorted tetrahedra [MBr4]- occur. The structural variety must be sought in the adjustment of the coordinational needs of the counter cations A+ (coordination numbers between six and twelve).
    Notes: Die 14 möglichen Bromide AIMIIIBr4 (AI = Na, Ga, K, In, Rb; MIII = Al, Ga, In) erhält man aus Gemengen der binären Komponenten, ABr und MBr3. Es treten sechs unterschiedliche Strukturtypen auf: NaGaBr4-, NaAlCl4-, GaCl2-, β-GaBr2-, KAlBr4- bzw. BaSO4-Typ. Einkristalldaten werden für die Beispiele NaGaBr4, KGaBr4 und InGaBr4 mitgeteilt. Stets liegen (leicht verzerrte) Tetraeder [MBr4]- vor. Die strukturelle Vielfalt ist in der Anpassung an die Koordinationsbedürfnisse der Gegenkationen A+ (Koordinationszahlen zwischen 6 und 12) zu suchen.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 587 (1990), S. 197-207 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sulfate, Phosphate, and Arsenate as Tridentate Ligands. Synthesis and Crystal Structures of (NMe4)2[Re3Cl9O3SO], (NMe4)2(H7O3)[Re3Cl9O3PO] and (NMe4)2(H5O2)[Re3Cl9ODark red (NMe4)2[Re3Cl9O3SO] (1) (monoclinic, P21/c, a = 1129.77(6) pm, b = 1890.46(7) pm, c = 1290.09(9) pm, β = 97.29(1)°, Vm = 411.49(4) cm3/mol) is obtained by direct reaction of rhenium trichloride with NMe4Cl in hydrochloric acid solution in the presence of sulfuric acid. Dark red crystals of (NMe4)2(H7O3)[Re3Cl9O3PO] (2) (monoclinic, P21/c, a = 1249.3(1) pm, b = 1760.5(2) pm, c = 1335.1(1) pm, β = 91.71(1)°, Vm = 441.91(7) cm3/mol) and (NMe4)2(H5O2)[Re3Cl9O 3AsO] (3) (monoclinic, P21/c, a = 975.23(6) pm, b = 1838.6(1) pm, c = 1572.31(7) pm, β = 92.39(1)°, Vm = 424.10(4) cm3/mol) grow from the hydrochloric acid solution of NMe4Cl of the violet precipitate that is obtained previously by the reaction of ReCl3 and Ag3[MO4] (M = P, As) in acetone solution. Important features of the crystal structures of (1), (2), and (3) are anionic building units [Re3Cl9O3MO]n- (M = S, n = 2; M = P, As, n = 3), where the tetrahedral anions [MO4]n- act as tridentate ligands. In the structures of (2) and (3) the anions form a hydrogen bonding system together with the cations H7O3+ (2) and “H5O2+” (3).
    Notes: Tiefrotes (NMe4)2[Re3Cl9O3SO] (1) (monoklin; P21/c: a = 1129,77(6) pm; b = 1890,46(7) pm; c = 1290,09(9) pm; β = 97,29(1)°; Vm = 411,49(4) cm3/mol) ist durch direkte Umsetzung von Rheniumtrichlorid mit NMe4Cl in salzsaurer Lösung in Gegenwart von Schwefelsäure zugänglich. Tiefrote Kristalle von (NMe4)2(H7O3)[Re3Cl9O3PO] (2) (monoklin; P21/c; a = 1249,3(1) pm; b = 1760,5(2) pm; c = 1335,1(1) pm; β = 91,71(1)°; Vm = 441, 91(7) cm3/mol) und (NMe4)2(H5O2)[Re3Cl9O 3AsO] (3) (monoklin; P21/c; a = 975,23(6) pm; b = 1838,6(1) pm; c = 1572,31(7) pm; β = 92,39(1)°; Vm = 424,10(4) cm3/mol) erhält man durch Umsetzung von ReCl3 mit Ag3[MO4] (M = P, As) in Aceton und anschließende Umsetzung des gebildeten violetten Niederschlags beim Eindunsten salzsaurer Lösungen in Gegenwart von NMe4Cl. Hervorstechende Strukturmerkmale von (1), (2) und (3) sind anionische Baugruppen [Re3Cl9O3MO]n- (M = S, n = 2; M = P, As, n = 3), in denen die tetraedrischen Anionen [MO4]n- als dreizähnige Liganden fungieren. In (2) und (3) sind die Anionen mit den Kationen H7O3+ (2) bzw. „H5O2+“ (3) in ein ausgedehntes System von Wasserstoffbrücken-Bindungen eingebunden. 3AsO].
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 589 (1990), S. 96-100 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Addition and Substitution of Sodium to/into Cerium(III) Chloride: Na0.38(Na0.19Ce0.81)Cl3The action of sodium on CeCl3 (sealed tantalum ampoule, 750°C, 7 d) yields single crystals of the composition Na0,38(2)(Na0.193(3)Ce0.808(3))Cl3 (hexagonal, P63/m, Z = 2; a = 757.07(4); c = 431.56(3) pm, single-crystal data). The crystal structure may be viewed at as a substitution (Na0,19Ce0,81) plus addition (Na0,38) variant of CeCl3 (UCl3 type of structure).
    Notes: Bei der Einwirkung von Natrium auf CeCl3 (verschweißte Ta-Ampulle, 750°C, 7 d) erhält man Einkristalle der Zusammensetzung Na0,38(2)(Na0,193(3)Ce0,808(3))Cl3 (hexagonal, P63/m, Z = 2; a = 757,07(4); c = 431,56(3) pm, Einkristalldaten). Es liegt eine Substitutions-(Na0,19Ce0,81) und Additionsvariante (Na0,38) des CeCl3 (UCl3-Typ) vor.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 590 (1990), S. 103-110 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The System NazGdClHx/S. I. Crystal Structure of NaGdCl4NaGdCl4 is obtained together with Gd2S3 through oxidation of Na0.25GdClH0.75 with sulfur (sealed tantalum container, 850°C, 7 d) as colourless single crystals or as a white powder by thermal decomposition of (NH4)2NaGdCl6 (320°C). The crystal structure (triclinic, P1, a = 702.81(6), b = 676.25(5), c = 666.72(5) pm, α = 100.852(7), β = 91.702(7), γ = 89.760(7)°, R = 0.040, Rw = 0.032) may be derived from the fluorite type although both Na+ and Gd3+ have coordination numbers (C.N.) of seven (monocapped trigonal prism). The structure may also be described as a layer structure where puckered layers are stacked along [100] in the sequence Cl2GdCl2NaCl2GdCl2 with Cl3 and Cl4 in four-fold cationic coordination and Cl1 and Cl2 with C.N. 3.
    Notes: NaGdCl4 entsteht neben Gd2S3 bei der Oxydation von Na0,25GdClH0,75 mit Schwefel (Tantal-Ampulle, 850°C, 7 d) in Form von farblosen, derben Einkristallen oder durch thermischen Abbau von (NH4)2NaGdCl6 (320°C) als weißes Pulver. Die Kristallstruktur (triklin, P1; a = 702,81(6); b = 676,25(5); c = 666,72(5) pm; α = 100,852(7); β = 91,702(7); γ = 89,760(7)°; R = 0,040; Rw = 0,032) leitet sich vom Fluorit-Typ ab, jedoch weisen Na+ und Gd3+ jeweils die Koordinationszahl 7 (bekapptes trigonales Prisma) auf. Sie kann auch als Schichtstruktur beschrieben werden: Gewellte Schichten werden gemäß Cl2GdCl2NaCl2GdCl2 längs [100] gestapelt, wobei Cl1 und Cl2 C.N. 3, Cl3 und Cl4 aber C.N. 4 aufweisen.
    Additional Material: 3 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 591 (1990), S. 77-86 
    ISSN: 0044-2313
    Keywords: Diammonium Diaquapentanitrato Praseodymate(III) Dihydrate ; Crystal Structure ; TG/DTA-MS ; HRTEM ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (NH4)2[Pr(NO3)5(H2O)2] · 2 H2O, Crystal Structure and Thermal BehaviorIn the crystal structure of (NH4)2[Pr(NO3)5(H2O)2] · 2 H2O (monoclinic, C2/c, Z = 4; a = 1104.7(5); b = 892.8(3); c = 1787.5(8) pm; β = 101.78(7)°) Pr3+ exhibits a coordination number of twelve (five bidentate nitrate and two water molecules as ligands). The structure may be viewed at as a layer structure: Slabs of the composition [Pr(NO3)5]2- and [(NH4)2(H2O)2(H2O)2]2+ are stacked in the [100] direction. The thermal decomposition consists of six steps where (NH4)2(Pr(NO3)5(H2O)2, (NH4)2[Pr(NO3)5], (NH4)[Pr(NO3)4], Pr(NO3)3, and PrONO3 are formed as intermediates judging from simultaneous TG/DTA-MS investigations. The final product is PrO2-x (CaF2-type). High Resolution Transmission Electron Microscopy shows that it is produced as highly ordered agglomerates of crystallites of the size 10-50 nm.
    Notes: In der Kristallstruktur von (NH4)2[Pr(NO3)5(H2O)2] · 2 H2O (monoklin), C2/c, Z = 4; a = 1104,7(5), b = 892,8(3); c = 1787,5(8) pm; β = 101,78(7)(°) hat Pr3+ die Koordinationszahl zwölf (fünf zweizähnige NO3-, zwei H2O als Liganden). Sie kann als Schichtstruktur aufgefaßt werden: Schichtpakete der Zusammensetzung [Pr(NO3)5]2- bzw. [(NH4)2(H2O)2(H2O)2]2+ sind längs [100] gestapelt. Der thermische Abbau verläuft in sechs Stufen, wobei simultane TG/DTA-MS-Untersuchungen als Zwischenstufen (NH4)2[Pr(NO3)5(H2O)2], [NH4] Pr[NO3)4], Pr(NO3)3 sowie PrONO3 nahelegen. Das Endprodukt ist PrO2-x (CaF2-Typ), das nach Ausweis von HRTEM-Aufnahmen in Form hochgeordneter, miteinander verwachsener Mikrokristalle von der Größe 10-50 nm entsteht.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 593 (1991), S. 185-192 
    ISSN: 0044-2313
    Keywords: Calciumcarbide Chloride ; Synthesis ; Crystal Structure ; Allylenide Ion ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of a Calciumcarbide Chloride Containing a C34- Unit, Ca3Cl2C3Ca3Cl2C3 was prepared from calcium, CaCl2 and graphite in sealed tantalum capsules. Red, transparent crystals were obtained from heating the mixture to 900°C (for one day) and annealing afterwards at 780°C for three days. The compound forms a layered structure (Cmcm, Z = 4, a = 384.24(9) pm, b = 1340.7(3) pm, c = 1152.6(3) pm, R = RW = 0.036 for 481 independent intensities) with alternating stacks of double layers of Ca2+ and monolayers of Cl-. The double layers of calcium contain allylenide ions, C34-. The latter exhibit C2v symmetry, a bond angle (C—C—C) of 169.0(6)° and a C—C separation of 134.6(4) pm.
    Notes: Ca3Cl2C3 entsteht aus Calcium, CaCl2 und Graphit in verschweißten Tantal-Kapseln in Form roter, transparenter Kristalle durch Erhitzen des Reaktionsgemenges auf 900°C (1 Tag) und anschließendes dreitägiges Tempern bei 780°C. Die Verbindung kristallisiert in einer Schichtstruktur (Cmcm, Z = 4, a = 384,24(9) pm, b = 1 340,7(3) pm, c = 1 152,6(3) pm, R = RW = 0,036 für 481 unabhängige Intensitäten) mit einer alternierenden Anordnung von Doppelschichten aus Ca2+ und Schichten aus Cl-. In den Calcium-Doppelschichten liegen die Allylenidionen, C34-. Sie zeigen C2v-Symmetrie mit einem Bindungswinkel (C—C—C) von 169,0(6)° und dem C—C-Bindungsabstand von 134,6(4) pm.
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