Ein neuer Bautyp der Oxohalogenoferrate: Ba3 Fe2 O5 Cl2 und Ba3 Fe2 O5 Br2

New Structure Type of the Two Oxohalogenoferrites: Ba₃Fe₂O₅Cl₂ and Ba₃Fe₂O₅Br₂ The hitherto unknown compounds Ba₃Fe₂O₅Cl₂ (A) and Ba₃Fe₂O₅Br₂ (B) are pre-pared and examined by single crystal techniques. (A) and (B) crystallizes in the cubic space group I2₁ 3-T⁵; (A) a = 9.9705(3) and (B) a = 10.0039(8) Å, Z = 4. The new structure consists of 10 corner-shared tetrahedra which are connected to a two-dimensional ring system. The differences to the previously investigated compound Sr₃Fe₂O₅Cl₂ are discussed.     

Ein neues Oxohalogenoferrat: Sr3Fe2O5Cl2

About a New Oxohalogenoferrite: Sr₃Fe₂O₅Cl₂ The preparation and single crystal X-ray investigation of Sr₃Fe₂O₅Cl₂ are described. This compound belongs to the Sr₃Ti₂O₇ structure with a = 3.942(2) and c = 23.786(12) Å; space group D?I4/mmm. Sr₃Fe₂O₅Cl₂ shows an one-sided streched FeO₅Cl octahedron in respect to the Fe? Cl distances. This particularity is discussed in comparison to other K₂NiF₄-type compounds.     

Synthese und Strukturaufklärung von SrBeLa2O5

A new compound of the formula SrBeLa₂O₅ was prepared by high temperature technique. Single crystal X-ray investigations led to orthorhombic symmetry (a=9.730,b=7.377,c=6.687 Å, space group: D _2h ¹⁶ -Pnma,Z=4). SrBeLa₂O₅ shows a typical tunnel structure of a three-dimensional connection of Sr, La/O-prisms, related to a distortedKgomé-network. The tunnels are occupied by La³⁺- and Be²⁺-ions. A detailed discussion of the polyhedra, their connection, and the statistical distribution of Sr²⁺ and La³⁺ within the trigonal O^2–-prisms are given.

     

Über Oxocuprate,XXVI Synthese und Struktur eines Oxohalogenocuprat(I): Sr2CuO2Cl

Single crystals of Sr₂CuO₂Cl were prepared in a closed system of Ag- and quartz-tubes. The colorless crystals are extremly sensitive against moisture. X-ray investigation proves a trigonal symmetry (a=400.3;c-2767.9 pm, space group P3₁21-D ₃ ⁴ ). Sr²⁺ has a distorted octahedral coordination of 3 O^2– and 3 Cl^–. Cu⁺ shows a dumbbell like O^2– surrounding. The O-Cu-O bond angle (176.5°) differs from the usually value (180°).

     

Phase equilibria in the system La2O3-Na2O-P2O5

In the ternary system La₂O₃-P₂O₅-Na₂O the partial system La₂O₃-Na₄La₂P₄O₁₅-LaPO₄ has been examined by the thermal, dilatometric X-ray and microscopic analyses and its phase diagram provided. The lanthanum oxyphosphate La₃PO₇ melts incongruently at the 1590°C temperature and crystallizes in a monoclinic systema=11.20 Å,b=11.94 Å,c=7.01 Å,=93.79 andV=936.97 ų.

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Zusammenfassung Mittels Thermo- und dilatometrischer Analyse, Röntgendiffraktionsuntersuchungen und Mikroskopie wurde das Teilsystem La₂O₃ - Na₄La₂P₄O₁₅ - LaPO₄ des ternären Systemes La₂O₃ - P₂O₅ - Na₂O untersucht und ein Phasendiagramm entwickelt. Lanthanoxyphosphat La₃O₇ schmilzt inkongruent bei 1590°C und kristalliert in einem monoklinen System mita=11.20 Ä,b=11.94 Ä,c=7.01 Å,=93.79 undV=936.97 ų.

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The author thanks Mrs. B. Lagódka for the technical assistance (thermogravimetric analyses). The thermal study was supported by grant CPBP.     

The W2Cl4(NHCMe3)2(PR 3)2 molecules (R 3=Me3, Et3, Pr n 3, Me2Ph) I. Their isomeric forms,interconversion proeesses,crystalline forms,and detailed molecular structures

A thorough study of compounds with the formula W₂Cl₄(NHCMe₃)2(PR₃)₂, withR ₃=Me₃, Et₃, Prg ⁿ ₃ Me₂,Ph, is reported. In addition to the previously reported crystalline compounds, namely Ia,trans-W₂Cl₄(NHCMe₃)₂(PMe₃)₂ in space group Pmmn;3a,trans-W₂Cl₄(NHCM₃)₂(PEt₃)₂ in space group P2₁/^a (or P2₁/^c); and4,cis-W₂Cl₄(NHCMe₃)₂(PMe₂Ph)₂ in Pna2₁, we have obtained and structurally characterized the following new substances,1b,trans-W₂Cl₄,(NHCMe₃)₂(PMe₂)₂, space group P2₁/^c,a= 12.233 (4) Å,b= 12.872 (4) Å,c=17.095 (5) Å,=93.52 (2)°,Z=4,V=2687 (1) ų 2,cis-W₂Cl₄(NHCMe₃)₂(PMe₃)₂, P2₁/^c,a=9.673 (4) Å,b=17.249 (4) Å,c=16.244 (5) Å,=99.63 (3),Z = 4 ,V=2669 (1) Å.3b,trans-W₂Cl₄(NHCMe₃)₂(PEt₃)₂, Pl,a=16.850 (3) Å,b=17.797 (3) Å,c= 11.459 (2)Å,= 101.02 (1),= 103.13°, y=84.23 (1)°,Z=4,V= 3279 (1) Å5,trans-W₂Cl₄(NHCM₃)₂(PMe₂Ph)₂, Fdd2,a=39.563 (8) Å at 20°C; 39.325 (10) Å at -6O°C,b = 57.543 (17) Å at 20°C; 57.186 (16) Å at -60°C,c= 8.810 (1) Å at 20°C; 8.770 (1) Å at - 60°C ,Z=24,V=20057 (7) ų (20°C), 19723 (8) ų ( - 60°C) .6,trans-W₂Cl₄(NHCMe_{3 2}(PPrⁿ ₃)₂, Pl,a= 17.287 (2) Å (20°C); 17.077 (5) Å (-60°C),b= 19.119 (2) Å (20°C); 18.952 (6) Å (-60°C),c= 12.713 (1) Å (20°C); 12.668 (4) Å (-60°C),Z=4,V= 3980 (1) ų (20°C), 3898 (2) ,ų ( - 60°C). In addition, the structure of3a was re-determined and refined so that the disorder ratio was a refined parameter, leading to a value of 0.520:0.480 instead of being arbitrarily fixed at 0.50:0.50. In all of the structures the molecules are held in eclipsed (but very distorted) rotational conformations and the W-W distances are all within the range of 2.305-2.330 Å. As will be shown in a later paper, for all phosphines, thecis andtrans isomers are of similar stability and an equilibrium mixture exists in solution. It is also shown that1a and3a do not contain unexpectedly short W-N bonds as previously reported.     

[Cl3Cu(I)-As(III)O3]: Ein kristallchemisch neues Bauelement in der Struktur des Pb6Cu(AsO3)2Cl7

The synthetic compound Pb₆Cu(AsO₃)₂Cl₇ crystallizes in space group R witha ₀=9.8614(4),c ₀=17.089(2)Å,Z=3. The crystal structure, determined by single crystal X-ray work, is a typical layer structure. Complex Pb₆(AsO₃)₂Cl₆ layers are combined via monovalent Cu and Cl atoms. A novel element within the structure is a [Cl₃Cu(I)-As(III)O₃] group with the interatomic distances (Å): Cu-Cl=2.44 (3×), As-O=1.76 (3×), Cu-As=2.34 (1×).

     

Die Kristallstruktur von Tetrachloräthylencarbonat—Antimon(V)-chlorid,C2Cl4O2CO·SbCl5

Zusammenfassung Die Kristallstruktur des Adduktes Tetrachloräthylencarbonat—Antimon(V)-chlorid, C₂Cl₄O₂CO·SbCl₅ wurde mit Hilfe der Schweratom-Methode aus dreidimensionalen Röntgendaten bestimmt und nach der Methode der kleinsten Quadrate bis zu einemR-Wert von 13,1% verfeinert (Raumgruppe P2₁/n — Nr. 14;a=10,13,b=12,15 undc=12,55 Å, =108°40). Die Elementarzelle enthält 4 Moleküle C₂Cl₄O₂CO· SbCl₅. Das Antimonatom ist oktaedrisch von 5 Chloratomen und dem Carbonylsauerstoffatom des Tetrachloräthylencarbonats umgeben (Sb–Cl 2,28–2,33 und Sb–O 2,40 Å).

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The crystal structure of tetrachloroethylene carbonate antimony(V) chloride, C₂Cl₄O₂CO·SbCl₅

The crystal structure of the adduct tetrachloroethylene carbonate antimony(V)-chloride, C₂Cl₄O₂CO·SbCl₅, has been determined by the heavy-atom method from three-dimensional X-ray data. The refinement of the parameters was carried out by least-squares resulting anR-value of 13.1% (space group P2₁/n — No. 14;a=10.13,b=12.15 andc=12.55 Å, =108°40). The unit cell contains 4 discrete molecules C₂Cl₄O₂CO·SbCl₅. The antimony atom is coordinated octahedrally by 5 chlorine atoms and the carbonyl oxygen atom of tetrachloroethylene carbonate (Sb–Cl 2.28–2.33 and Sb–O 2.40 Å).

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Mit 2 Abbildungen     

Synthese und Strukturuntersuchung von Zn3Ta2O8

Zn₃Ta₂O₈ was prepared by high temperature solid state reaction (CO₂-Lasertechnique). X-ray investigations of single crystals yield monoclinic symmetry (a=9.499;b=8.411;c=8.881 Å; =116.03°, space group C _2h ⁶ —C2/c). There is no relationship between Zn₃Ta₂O₈ and Zn₃Nb₂O₈. Zn₃Ta₂O₈ shows a characteristic structure type with octahedral coordination of Ta⁵⁺ and tetrahedral coordination of Zn²⁺.

     

The Enantioselective Role of the [N(C5H11)4]+Organic Cation in the Structure of the Molecular Magnet [N(C5H11)4][MnIIFeIII(C2O4)3]

A crystal of [N(C₅H₁₁)₄][Mn^IIFe^III(C₂O₄)₃] was studied by X-ray diffraction analysis: space group C222₁, a= 9.653(2) Å, b= 16.201(2) Å, c= 20.193(4) Å. The arrangement of the cations predetermines the formation of the crystal structure from anionic layers of the same chirality. The presence of two types of organic cation does not contradict the formation of crystals with left and right chirality and accounts for the data of Mössbauer spectroscopy, indicating two states of iron.     

Eine neue Verbindung vom M5TiB2O10-Typ mit geordneter Metallverteilung: Ni5SnB2O10

Summary The unknown compound Ni₅SnB₂O₁₀, prepared by using a flux of excess B₂O₃, was investigated by single crystal X-ray technique. It crystallizes with orthorhombic symmetry, space group D _2h ¹⁶ — Pnma witha=9.302,b=6.089,c=12.280 Å,Z=4. The mean result of this investigation is a hitherto unobserved strictly ordered metal distribution. Ni₅SnB₂O₁₀ is not isotypic but related to Ni₅TiB₂O₁₀.

     

Die Kristallstrukturen der Kupfer(II)-oxo-selenite Cu2O(SeO3) (kubisch und monoklin) und Cu4O(SeO3)3 (monoklin und triklin)

Syntheses within the system CuO-SeO₂-H₂O revealed four copper(II)-oxo-selenites. The crystal structures of these compounds were determined by single crystal X-ray techniques. Chemical formulae, lattice parameters and space groups are: Cu₂O(SeO₃)-I [a=8.925 (1) Å, P2₁3], Cu₂O(SeO₃)-II [a=6.987 (5) Å,b=5.953 (4) Å,c=8.429 (6) Å, =92.17 (3)°, P2₁/n], Cu₄O(SeO₃)₃-I [a=15.990 (8) Å,b=13.518 (8) Å,c=17.745 (12) Å, =90.49 (5)°, P2₁/a], and Cu₄O(SeO₃)₃-II [a=7.992 (6) Å,b=8.141 (6) Å,c=8.391 (6) Å, =77.34 (3)°, =65.56 (3)°, =81.36 (3)°, ].All the Cu atoms are-with one exception-[4], [4+1], and [4+2] coordinated by O atoms. The four nearest O atoms are more or less distorted square planar arranged. Within the CuO₄ squares the Cu-O bond lengths are significantly shorter for the [4] coordinated O atoms as compared with those of the [4+1] and [4+2] coordinated Cu atoms. The exception in the coordination of the Cu atoms is the Cu(1) atom in Cu₂O(SeO₃)-I with the site symmetry 3, which is trigonal dipyramidal [5] coordinated. A common feature of these four crystal structures is, that O atoms outside the SeO₃ groups are tetrahedrally coordinated by four Cu(II) atoms. The Se atoms are as usual [3] coordinated, building up SeO₃ pyramids. In all these four compounds the copper-oxygen polyhedra are combined to a three-dimensional network.

     

Mo2(O2CPh)6(PEt3)2, the second example of bridging Y11-02CR for dimolybdenum (III) compounds

From the reaction or Mo₂Cl₆(THF)₃ with excess of NaO₂CPh and PEt₃ in THF three types of crystals have been obtained and recrystallized in CH₂Cl₂. They are brown compound Mo₂(O₂CPh)₆(PEt₃)2·2CH₂Cl₂ (1), yellow-Mo₂(O₂CPb)₄ (2), and black Mo₄O₆(O₂CPh)₆(PEt₃)₂.CH₂Cl₂ (3). When a strict ratio of MO₂Cl₆(THF)₃:NaO₂CPh = 1:2 was applied, Mo₂(O₂CPh)₄(THF)₂, (4) was the only compound separated from the THF reaction mixture. Their structures have been determined by X-ray crystallography. There are three coordination modes of benzoate in 1: bridging ²-O₂CPh, bridging ¹-O₂CPh and terminal O₂CPh groups. Compound 2 is chemically well known, but was found to pack differently from the previously reported structure. Mo₄O₆(O₂CPh)₆(PEt₃)₂·CH₂C1₂ (3) is a mixed-valence Mo (IV, V) tetranuclear compound in a butterfly arrangement. A molecule of 4 is actually a MO₂(O₂CPh)₄ molecule with two THIF molecules axially coordinating to the molybdenum atoms. The crystallographic data for these compounds are as follows: 1, triclinicPl witha = 11.612(3) Å, b = 11.970(2) Å,c=12.135(3) Å,=95.55(2)°,=117.51(2)°,98.84(2)°,V=l450.8(7) ų,Z=1,R=0.0673, and R _w ,=0.0936; 2, monoclinicP2₁/n witha = 14,437(2) Å,b=5.6168(7) Å,c=15.979(3) Å,=93,93(l)°,V=1292.7(4) ų,Z=2,R=0.0217, and R_w=0.0352; 3, trigonal (hexagonal setting)R3¯ witha=28.83(4) Å,c=44.98(2) Å,V=323570(10) ų,Z=18,R=0.067, andwR2=0203; 4 monoclinicP2₁/c witha=9.456(4) Å,b=17.757(8) Å,c=10.887(3) Å,=109.63(2)°,V=1722(2)ų Z=2,R=0.0330, andR _w = 0.0451.     

Kristallstruktur von Trimethylisocyanursäure, (CH3NCO)3, und von Trichlorisocyanursäure-1/2-Ethylenchlorid, (ClNCO)3·1/2C2H4Cl2

X-ray crystal structure analyses of (CH₃NCO)₃ (M) and (ClNCO)₃·1/2C₂H₄Cl₂ (C) were carried out at room temperature (MoK, graphite monochromator, =0.71069 Å): 1.M=171.16, monochlinic, P2₁/c,a=14.848 (1) Å,b=13.400 (2) Å,c=8.149 (1) Å, =100.87 (1)°,V=1 592.3 ų,Z=8,F(000)=720,d _x =1.428 Mgm^–3, =76m^–1,R=6.51%,R _w =7.01% (964 reflections, 218 parameters). 2.M=281.89, monochlinic, P 2₁/c,a=9.416 (3) Å,b=5.728 (1) Å,c=18.199 (8) Å, =98.64 (2)°,V=970.4 Å₃,Z=4,F(000)=556,d _x =1.929 Mgm^–3, =1.11 mm^–1,R=3.96%,R _w =3.44% (605 reflections, 132 parameters). The ring systems together with the C atoms of the methyl groups in (M) and with the Cl atoms in (C) are planar and have D_3h-symmetry. Bond lengths and bond angles are discussed with regard to¹⁴N-NQR,³⁵Cl-NQR and vibrational spectroscopic data.

     

PbCu3(OH)(NO3)(SeO3)3·1/2H2O und Pb2Cu3O2(NO3)2(SeO3)2: Synthese und Kristallstrukturuntersuchung

Crystals of PbCu₃(OH)(NO₃)(SeO₃)₃·1/2H₂O [a=7.761(3)Å,b=9.478(4)Å,c=9.514(4)Å, =66.94(2)°, =69.83(2)°, =81.83(2)°, space group P ,Z=2] and Pb₂Cu₃O₂(NO₃)₂(SeO₃)₂ [a=5.884(2)Å,b=12.186(3)Å,c=19.371(4)Å, space group Cmc2₁,Z=4] were synthesized under hydrothermal conditions. Their crystal structures were refined with three-dimensional X-ray data toR _w=0.033 resp. 0.055. In PbCu₃(OH)(NO₃)(SeO₃)₃·1/2H₂O the Cu atoms are [4+1] and [4+2] coordinated and via SeO₃ groups a three-dimensional atomic arrangement is built up. In Pb₂Cu₃O₂(NO₃)₂(SeO₃)₂ there are sheets, which are connected only via Pb-O bonds ranging from 2.98 Å to 3.16 Å.

     

Das erste gemischte Erdalkalimetall-Oxomercurat: Ba0.75Sr0.25HgO2

Summary Ba_0.75Sr_0.25HgO₂ was prepared for the first time by an oxygen high-pressure technique. Single cystal X-ray investigations lead to hexagonal symmetry, space group D ₆ ⁶ -P6₃22;a=6.897;c=11.986 Å;Z=6. Hg²⁺-ions show a dumbbell-like coordination by two O^2–-ions. The alkaline earth ions Ba²⁺ and Sr²⁺ are surrounded by deformed trigonal O^2–-prisms. Only one of the two Ba²⁺ point positions of the BaHgO₂-type can be substituted by Sr²⁺. Polyhedra size and deformation are discussed in respect to the exchange of Ba²⁺ by Sr²⁺.

     

Ein neues Oxochromat: SrNi2Cr8O15 vom Strukturtyp BaV10O15

Summary A new quaternary oxochromate(III) was prepared by solid state reaction. Single crystal X-ray investigations of SrNi₂Cr₈O₁₅ show that this compound belongs to the BaV₁₀O₁₅ type. [Space group D _2h ¹⁸ - Ccmb,a=10.042;b=11.413;c=9.260 Å;Z=4.] Ni²⁺ and Cr³⁺ occupy the octahedrally coordinated point positions statistically. The surrounding of Sr²⁺ is similar to the iso- and heteropolyacids.

     

Crystal structures of the novel hydrated borates Ba2B5O9(OH), Sr2B5O9(OH) and Li2Sr8B22O41(OH)2

Three novel hydrated borates Ba₂B₅O₉(OH) (1), Sr₂B₅O₉(OH) (2) and Li₂Sr₈B₂₂O₄₁(OH)₂ (3) have been synthesized hydrothermally and their structures determined. Compounds (1) and (2) are isostructural, crystallizing in space group P2₁/c and having lattice parameters of a=6.6330(13) Å, b=8.6250(17) Å, c=14.680(3) Å, β=93.46(3)° and a=6.4970(13) Å, b=8.4180(17) Å, c=14.177(3) Å, β=94.35(3)°, respectively. Compound (3) crystallizes in P-1 with lattice parameters of a=6.4684(13) Å, b=8.4513(17) Å, c=14.881(3) Å, α=101.21(3)°, β=93.96(3)°, γ=90.67(3)°. While similar in their axis lengths, (3) differs greatly in structure and formulation from (1) and (2). The structure of (1) and (2) is contrasted to that of the well-known mineral hilgardite (Ca₂B₅O₉Cl·H₂O).     

Die Kristallstruktur von TlFeSe2 und TlFeS2

TlFeSe₂ is monoclinic, space groupC2/m–C _2h ³ ,a=11.973 Å,b=5.490 Å,c=7.110 Å, =118.2°,Z=4.TlFeS₂ is isotypic witha=11.636 Å,b=5.304 Å,c=6.799 Å, =116.7°.The crystal structure of TlFeSe₂ has been determined from single crystal diffractometer data. Isotypy of the sulfide has been confirmed from powder diffraction data. The crystal structure containing infinite linear chains of edgesharing FeX ₄-tetrahedra, and its relationship to the thio- and selenoferrates of the alkali metals are discussed. The mineral raguinite is very probably isotypic to synthetic TlFeS₂.

     

Untersuchungen der Hydroxylammonium-Aluminate

Summary Two microcristalline phases have been isolated from aqueous solutions: (NH₃OH)₂AlF₅(A) and (NH₃OH)AlF₄·H₂O(B). They crystallize in the orthorhombic system with cell parameters for A:a=6.475 (3) Å,b=7.295 (3) Å,c=10.827 (5) Å, and for B:a=7.003 (3) Å,b=8.489 (4) Å,c=10.745 (5) Å. The Hydroxylammonium-aluminates were characterized by vibrational spectroscopy and their thermal decomposition studied by DSC and TG analysis.