The crystal structure of ZnFe 2 3+ (SeO3)4

Summary The new synthetic compound ZnFe ₂ ³⁺ (SeO₃)₄ forms at low-hydrothermal conditions at 220 °C. It belongs to the monoclinic system; the structure was determined by single-crystal X-ray diffraction in the space group Pc. The unit cell data are:a=8.196(4) Å,b=7.997(4) Å,c=8.033(4) Å, =92.27(3)°,V=526.1 ų;Z=2. The structure of ZnFe ₂ ³⁺ (SeO₃)₄ contains two types of FeO₆ octahedra, one distorted ZnO₅ trigonal bipyramid, and four selenite groups. Formal clusters consisting of the ZnO₅ group, edge-linked with both FeO₆ groups and one SeO₃ pyramid, are connected by common corners, involving three further selenite groups to a framework structure.

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Die Kristallstruktur von ZnFe ₂ ³⁺ (SeO₃)₄

Zusammenfassung Die neue synthetische Verbindung ZnFe ₂ ³⁺ (SeO₃)₄ bildet sich bei niedrighydrothermalen Bedingungen (220°C). Die Kristallstruktur wurde mit Einkristallröntgenmethoden in der monoklinen Raumgruppe Pc gelöst. Die Zellparameter sind:a=8.196(4) Å,b=7.997(4) Å,c=8.033(4) Å, =92.27(3)°,V=526.1 ų;Z=2. Die Kristallstruktur von ZnFe ₂ ³⁺ (SeO₃)₄ weist zwei Arten von FeO₆-Oktaedern, eine verzerrte trigonale ZnO₅-Dipyramide sowie vier Selenitgruppen auf. Formal können Cluster, bestehend aus dem ZnO₅-Polyeder, kantenverknüpft mit den beiden FeO₆-Gruppen sowie einer SeO₃-Pyramide, beschrieben werden. Die Verknüpfung über Ecken zu einer Gerüststruktur erfolgt unter Beteiligung von drei weiteren Selenitgruppen.

     

The crystal structure of Fe(SeO2OH)(SeO4)·H2O

Summary The crystal structure of the hydrothermally synthesized compound Fe(SeO₂OH) (SeO₄) · H₂O was determined by single crystal diffraction methods:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 ų;Z=4, space group P2₁/c,R=0.029,R _w=0.027 for 2430 independent reflections (sin /0.76 Å^–1). Isolated FeO₅(H₂O)-octahedra share five corners with [SeO₂OH] and [SeO₄] groups to form sheets parallel to (100). These sheets are interconnected via hydrogen bonds only.

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Die Kristallstruktur von Fe(SeO₂OH)(SeO₄)·H₂O

Zusammenfassung Die Kristallstruktur der hydrothermal dargestellten Verbindung Fe(SeO₂OH) (SeO₄)·H₂O wurde mittels Einkristallbeugungsmethoden bestimmt:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 ų;Z=4, Raumgruppe P2₁/c,R=0.029,R _w=0.027 für 2 430 unabhängige Reflexe (sin / 0.76 Å^–1). Isolierte FeO₅(H₂O)-Oktaeder teilen fünf Ecken mit [SeO₂OH]- und [SeO₄]-Gruppen, wobei sie Schichten parallel (100) bilden. Diese Schichten sind nur über Wasserstoffbrücken miteinander verbunden.

     

Crystal structure of synthetic Cu3SeO4(OH)4

Summary The crystal structure of synthetic Cu₃SeO₄(OH)₄ was determined by single crystal X-ray methods:a=8.382 (2) Å,b=6.087 (1) Å,c=12.285 (2) Å,V=626.8 ų,Z=4, space group Pnma,R=0.026,R _w =0.021 for 1255 independent reflections (sin / 0.8 Å^–1). The crystal structure is isotypic to that of the mineral antlerite, Cu₃SO₄(OH)₄. The copper atoms are Jahn-Teller distorted with Cu^[4+2]O₆ polyhedra forming triple chains along [010]. These chains are linked via SeO₄ tetrahedra and weak hydrogen bonds to a framework structure.

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Die Kristallstruktur von synthetischem Cu₃SeO₄(OH)₄

Zusammenfassung Die Kristallstruktur von synthetischem Cu₃SeO₄(OH)₄ wurde mittels Einkristall-Röntgenmethoden ermittelt:a=8.382 (2) Å,b=6.087 (1) Å,c=12.285 (2) Å,V=626.8 ų,Z=4, Raumgruppe Pnma,R=0.026,R _w =0.021 für 1255 unabhängige Reflexe (sin / 0.8 Å^–1). Die Kristallstruktur ist isotyp mit der des Minerals Antlerit, Cu₃SO₄(OH)₄. Die Kupferatome sind Jahn-Teller-verzerrt, die Cu^[4+2]O₆ Polyeder bilden Dreierketten entlang [010]. Diese Ketten sind über SeO₄-Tetraeder und schwache Wasserstoffbrücken zu einer Gerüststruktur verbunden.

     

Crystal structure of Li2Cu3(SeO3)2(SeO4)2

Summary Single crystal X-ray data of the hydrothermally grown new phase Li₂Cu₃(SeO₃)₂(SeO₄)₂ were measured with a four-circle diffractometer up to sin /=0.81 Å^–1 [I2/a,Z=4,V=1175.5 ų,a=16.293(6),b=5.007(2),c=14.448(6) Å, = 94.21(1)°]. The structure was determined by direct and Fourier methods and refined toR=0.034,R _w =0.027 for 2 086 independent reflections.Cu(1)^[4+1]O₅ forms a tetragonal pyramid, Cu(2)^{[4 + 2]}O₆ is a strongly elongated octahedron. The Li atom is surrounded by four O atoms forming a distorted tetrahedron. Se(IV)O₃ and Se(VI)O₄ groups are in accordance to literature, mean Se-O bond lengths are 1.714 and 1.644 Å.

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Die Kristallstruktur von Li₂Cu₃(SeO₃)₂(SeO₄)₂

Zusammenfassung Einkristall-Röntgendaten der hydrothermal gezüchteten neuen Phase Li₂Cu₃(SeO₃)₂(SeO₄)₂ wurden mit einem Vierkreisdiffraktometer im Bereich bis zu sin /=0.81 Å^–1 gemessen [I2/a,Z=4,V=1175.5 ų,a=16.293(6),b=5.007(2),c=14.448(6) Å, =94.21(1)°]. Die Kristallstruktur wurde mittels direkter und Fourier-Methoden bestimmt und für 2 086 unabhängige Reflexe zuR=0.034,R _w =0.027 verfeinert.Cu(1)^[4+1]O₅ bildet eine tetragonale Pyramide, Cu(2)^[4+2]O₆ ist ein stark verlängertes Oktaeder. Das Li-Atom ist von vier O-Atomen in Gestalt eines verzerrten Tetraeders umgeben. Die Se(IV)O₃-und Se(VI)O₄-Gruppen entsprechen der Literatur, die mittleren Se-O-Abstände betragen 1.714 und 1.644 Å.

     

Crystal structure of anhydrous alum RbFe3+(SeO4)2

Summary The compound RbFe(SeO₄)₂ was prepared hydrothermally by reaction of Rb₂CO₃ and FeC₂O₄·2H₂O with H₂O and H₂SeO₄ at 490 K. Single crystal X-ray methods revealed isotypy with KAl(SO₄)₂. RbFe(SeO₄)₂ crystallizes in space group P321;Z=1;a=5.005(1)Å,c=8.548(2) Å,V=185.4 ų; 781 unique data up to 80 °2;R,R _w =0.045, 0.042. The structure is best described as sheets of [Fe(SeO₄)₂]^– parallel (001), interconnected by Rb⁺. FeO₆ trigonal prims and SeO₄ tetrahedra have bond lengths of 1.99 Å and 1.63 Å, respectively. The Rb atom is [6 + 6] coordinated with Rb-O distances of 3.04 Å and 3.48 Å.

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Die Kristallstruktur des wasserfreien Alauns RbFe³⁺(SeO₄)₂

Zusammenfassung Die Verbindung RbFe(SeO₄)₂ wurde hydrothermal dargestellt durch Reaktion von Rb₂CO₃ und FeC₂O₄·2H₂O mit H₂O und H₂SeO₄ bei 490K. Einkristallröntgenmethoden belegten die Isotypie mit KAl(SO₄)₂ RbFe(SeO₄)₂ kristallisiert in der Raumgruppe P321;Z=1;a=5.005(1) Å,c=8.548(2) Å,V=185.4 ų; 781 unabhängige Daten bis 80 °2;R,R _w =0.045, 0.042. Die Struktur läßt sich am besten als Schichten von [Fe(SeO₄)₂]^– parallel (001) beschreiben, die durch Rb⁺ verbunden sind. FeO₆ trigonale Prismen und SeO₄ Tetraeder weisen Bindungslängen von 1.99 Å bzw. 1.63 Å auf. Das Rb-Atom ist [6+6] koordiniert mit Rb-O Abständen von 3.04 Å und 3.48 Å.

     

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.

     

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.

     

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.

     

Crystal structures of Co3(SeO3)3·H2O and Ni3(SeO3)3·H2O,two new isotypic compounds

Summary The crystal structures of the new, hydrothermally synthesized, isotypic compounds Co₃(SeO₃)₃·H₂O and Ni₃(SeO₃)₃·H₂O were determined by direct and Fourier methods and refined toR _w=0.023, 0.032 using single crystal X-ray data up to sin/=0.81 Å^–1 [space group P ,a=8.102 (2), 7.986 (3) Å;b=8.219 (2), 8.133 (3) Å;c=8.572 (2), 8.422 (3) Å, =69.15 (1), 69.50 (1)°; =62.88 (1), 62.50 (1)°; =67.23 (1), 67.64 (1)°;Z=2]. The structures are built up from [Me ₅(SeO₃)₆·2H₂O]^2– sheets containing three crystallographically different types of octahedrally coordinatedMe ²⁺ and trigonal pyramidal coordinated Se⁴⁺ atoms, respectively. These sheets are linked only by a fourth type ofMe ^2+[6] atom. All coordination polyhedra deviate significantly from their ideal shapes, bond lengths within the extremly distortedMe(4)O₆ polyhedra range from 1.983 (2) Å to 2.403 (2) Å in Co₃(SeO₃)₃·H₂O and from 1.987 (4) Å to 2.301 (3) Å in the Ni compound, O-Se-O bond angles were found between 92.8 (2)° and 104.9 (1)°. Hydrogen bond lengths are 2.802 (3)Å and 2.600 (4)Å in the Co compound, and 2.762 (6) Å and 2.561 (6) Å in Ni₃(SeO₃)₃·H₂O. The latter is one of the shortest known hydrogen bonds donated by a water molecule.

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Die Kristallstrukturen von Co₃(SeO₃)₃·H₂O und Ni₃(SeO₃)₃·H₂O, zwei neue isotype Verbindungen

Zusammenfassung Die Kristallstrukturen der neuen, hydrothermal synthetisierten, isotypen Verbindungen Co₃(SeO₃)₃·H₂O und Ni₃(SeO₃)₃·H₂O wurden mit direkten und Fourier-Methoden bestimmt und unter Verwendung von Einkristallröntgendaten bis sin/=0.81 Å^–1 aufR _w-Werte von 0.023, 0.032 verfeinert [Raumgruppe P ,a=8.102 (2), 7.986 (3) Å;b=8.219 (2), 8.133 (3) Å;c=8.572 (2), 8.422 (3) Å, =69.15 (1), 69.50 (1)°; =62.88 (1), 62.50 (1)°; =67.23 (1), 67.64 (1)°;Z=2]. Die Strukturen werden von [Me ₅(SeO₃)₆·2H₂O]^2– Schichten aufgebaut, die je drei kristallographisch unterschiedliche Arten von oktaedrisch koordiniertenMe ²⁺ und trigonal pyramidal koordinierten Se⁴⁺ Atomen enthalten. Diese Schichten sind nur durch eine vierte Art vonMe ^2+[6] Atomen verknüpft. Alle Koordinationspolyeder weichen deutlich von ihren Idealformen ab, Bindungslängen in den extrem verzerrtenMe(4)O₆ Polyedern variieren zwischen 1.983 (2) Å und 2.403 (2) Å in Co₃(SeO₃)₃·H₂O und zwischen 1.987 (4) Å und 2.301 (3) Å in der Ni-Verbindung, O-Se-O-Bindungswinkel liegen zwischen 92.8 (2)° und 104.9 (1)°. Wasserstoffbrückenlängen sind 2.802 (3) Å und 2.600 (4) Å in der Co-Verbindung, und 2.762 (6) Å und 2.561 (6) Å in Ni₃(SeO₃)₃·H₂O. Letztere ist eine der kürzesten bekannten Wasserstoffbrücken eines Wassermoleküls.

     

On the crystal chemistry of three copper(II)-arsenates: Cu3(AsO4)2-III,Na4Cu(AsO4)2, and KCu4(AsO4)3

The three copper(II)-arsenates were synthesized under hydrothermal conditions; their crystal structures were determined by single-crystal X-ray diffraction methods:Cu₃(AsO₄)₂-III:a=5.046(2) Å,b=5.417(2) Å,c=6.354(2) Å, =70.61(2)°, =86.52(2)°, =68.43(2)°,Z=1, space group ,R=0.035 for 1674 reflections with sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a=4.882(2) Å,b=5.870(2) Å,c=6.958(3) Å, =98.51(2)°, =90.76(2)°, =105.97(2)°,Z=1, space group ,R=0.028 for 2157 reflections with sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a=12.234(5) Å,b=12.438(5) Å,c=7.307(3) Å, =118.17(2)°,Z=4, space group C2/c,R=0.029 for 1896 reflections with sin / 0.80 Å^–1.Within these three compounds the Cu atoms are square planar [4], tetragonal pyramidal [4+1], and tetragonal bipyramidal [4+2] coordinated by O atoms; an exception is the Cu(2)^[4+1] atom in Cu₃(AsO₄)₂-III: the coordination polyhedron is a representative for the transition from a tetragonal pyramid towards a trigonal bipyramid. In KCu₄(AsO₄)₃ the Cu(1)^[4]O₄ square and the As(1)O₄ tetrahedron share a common O—O edge of 2.428(5) Å, resulting in distortions of both the CuO₄ square and the AsO₄ tetrahedron. The two Na atoms in Na₄Cu(AsO₄)₂ are [6] coordinated, the K atom in KCu₄(AsO₄)₃ is [8] coordinated by O atoms.Die drei Kupfer(II)-Arsenate wurden unter Hydrothermalbedingungen gezüchtet und ihre Kristallstrukturen mittels Einkristall-Röntgenbeugungsmethoden ermittelt:Cu₃(AsO₄)₂-III:a = 5.046(2) Å,b = 5.417(2) Å,c = 6.354(2) Å, = 70.61 (2)°, = 86.52(2)°, = 68.43(2)°,Z = 1, Raumgruppe ,R = 0.035 für 1674 Reflexe mit sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a = 4.882(2) Å,b = 5.870(2) Å,c = 6.958(3) Å, = 98.51(2)°, = 90.76(2)°, = 105.97(2)°,Z = 1, Raumgruppe ,R = 0.028 für 2157 Reflexe mit sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a = 12.234(5) Å,b = 12.438(5) Å,c = 7.307(3) Å, = 118.17(2)°,Z = 4, Raumgruppe C2/c,R = 0.029 für 1896 Reflexe mit sin / 0.80 Å^–1.Die Cu-Atome in diesen drei Verbindungen sind durch O-Atome quadratisch planar [4], tetragonal pyramidal [4 + 1] und tetragonal dipyramidal [4 + 2]-koordiniert; eine Ausnahme ist das Cu(2)^{[4 + 1]}-Atom in Cu₃(AsO₄)₂-III: Das Koordinationspolyeder stellt einen Vertreter des Übergangs von einer tetragonalen Pyramide zu einer trigonalen Dipyramide dar. In KCu₄(AsO₄)₃ haben das Cu(1)^[4]O₄-Quadrat und das As(1)O₄-Tetraeder eine gemeinsame O—O-Kante von 2.428(5) Å, was eine Verzerrung der beiden Koordinationsfiguren CuO₄-Quadrat und AsO₄-Tetraeder bedingt. Die zwei Na-Atome in Na₄Cu(AsO₄)₃ sind durch O-Atome [6]-koordiniert, das K-Atom in KCu₄(AsO₄)₃ ist [8]-koordiniert.

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Zur Kristallchemie dreier Kupfer (II)-Arsenate: Cu₃(AsO₄)₂-III, Na₄Cu(AsO₄)₂ und KCu₄(AsO₄)₃

     

Crystal structure of LiFe3+(SeO3)2

Summary Single crystals of LiFe³⁺(SeO₃)₂ were prepared by hydrothermal synthesis. The crystal structure of LiFe³⁺(SeO₃)₂ is reported: tetragonal, space group I 2d,a=10.649(2) Å,c=9.959(2) Å,V=1129.4 ų,Z=8, 1268 unique reflections,R=0.037. The structure contains LiFeO₈ groups, built up by FeO₆ octahedra edgesharing with strongly distorted LiO₄ tetrahedra. These LiFeO₈ groups share corners with trigonal pyramidal SeO₃ groups to form a three dimensional network. The mean bondlengths are 1.994 Å, 2.006 Å and 1.699 Å for Li-O, Fe-O and Se(IV)-O, respectively.

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Die Kristallstruktur von LiFe³⁺(SeO₃)₂

Zusammenfassung Einkristalle von LiFe³⁺(SeO₃)₂ wurden auf hydrothermalem Weg dargestellt und ihre Kristallstruktur bestimmt: tetragonal, Raumgruppe I 2d,a=10.649(2) Å,c=9.959(2) Å,V=1129.4 ų,Z=8, 1268 unabhängige Reflexe,R=0.037. Kennzeichnend für die Atomanordnung sind LiFeO₈ Gruppen, die aus FeO₆ Oktaedern und mit ihnen kantenverknüpften, stark verzerrten LiO₄ Tetraedern aufgebaut sind. Diese LiFeO₈ Baueinheiten bilden, mit trigonal pyramidalen SeO₃ Gruppen über Ecken verbunden, ein dreidimensionales Netzwerk. Die Mittelwerte der Li-O, Fe-O and Se(IV)-O Abstände sind 1.994 Å, 2.006 Å und 1.699 Å.

     

Darstellung und Kristallstruktur von Pb2(NO2)(NO3)(SeO3)

Crystals of Pb₂(NO₂)(NO₃)(SeO₃) were synthesized by partial reduction of nitrate ions with native copper under hydrothermal conditions. The crystal structure [a=5.529 (2) Å,b=10.357 (3) Å,c=6.811 (2) Å, space group Pmn2₁,Z=2] was determined from 1 707 independent X-ray data up to sin /=0.81 Å^–1 and was refined toR _w =0.028. The Pb(1) atom is ten coordinated to O atoms [Pb(1)-O from 2.51 Å to 2.96 Å], the Pb(2) atom has three nearest O atoms [Pb(2)-O=2.41 Å (1 ×) and 2.45 Å (2 ×)] and six next-nearest O atoms [Pb(2)-O from 2.80 Å to 3.22 Å].

Herrn Prof. Dr.K. Komarek zum 60. Geburtstag gewidmet.     

Kristallstruktur von Monosilber(I)amidosulfat,AgSO3NH2

A crystal structure analysis of the colourless AgSO₃NH₂ was carried out at room temperature:M=203.95, orthorhombic, Pcab,a=7.809 (2) Å,b=8.067 (2) Å,c=11.682 (3) Å,V=735.9 ų,Z=8,d _x=3.681 Mgm^–3,F(000)=760, Mo K, =0.71069 Å (graphite monochromator), =5.77 mm^–1,R=4.36% (509 reflections, 56 parameters). The ionic structure shows approximate trigonal bipyramidal coordination around the Ag⁺-ions.

     

Untersuchungen des Hydroxylammonium-Fluorogallats

Summary Crystals of (NH₃OH)₃GaF₆ have been isolated from aqueous solution. The compound crystallizes triclinic, with cell parametersa=6.539(5) Å,b=6.924(5) Å,c=9.403(1) Å, =87.01(9)°, =83.98(8)°, =70.28(8)°. The thermal decomposition was studied by TG and DSC analysis.

     

Synthesis,characterization and x-ray structure of V3(μ3-O)(μ-Cl)Cl6(μ-η1-η1-PhNHNH2)2(PhNHNH2)2(THF) · 6THF: A new binding mode for phenylhydrazine

Addition of phenylhydrazine to a mixture of VCl₃ · THF/N,N-propyl-bis (salicyladimine) and sodium hydride yielded a trinuclear vanadium complex, V₃(₃-O)(-Cl)Cl₆(-¹-¹PhNHNH₂)₂(PhNHN H₂)₂(THF), containing two bridging and two terminal phenylhydrazine ligands. The product has been crystallographically characterized (P2₁/n, a=12.949(2) Å,b=24.061(4) Å,c=22.504(4) Å, =107.22(1) deg.,V=6697(2) ų withZ=4) and was found to contain the first example of bridging monosubstituted hydrazine (phenylhydrazine) ligands.     

Synthese und Strukturanalyse von Na3SbSe3·3Sb2O3·0,5Sb(OH)3

Investigations in the system Sb-Se-NaOH-H₂O, hydrothermal conditions, yielded crystals of the compound Na₃SbSe₃·3Sb₂O₃·0,5Sb(OH)₃. The structure of this compound (a=14.40 Å,c=5.568 Å; space group P 6₃-C ₆ ⁶ ;Z=2) was determined from 985 independent X-ray intensities — collected on an automaticWeissenberg type diffractometer — by thePatterson method and refined by the least squares method toR=8.3% (with -weighting 5.9%). The structure consists of SbO₃ pyramids which are connected via common oxygen corners to tubes parallel [001]. These tubes and SbSe₃ pyramids are combined by Na atoms to a framework. The Sb(OH)₃ groups are statistically located within the channels of the tubes.

     

Tetracarbonyliron adducts of Cp2Cr2(CO)4(μ-η2-P2). Syntheses and crystal structures of Cp2Cr2(CO)4P2[Fe(CO)4] m (m=1 and 2)

Cp₂Cr₂(CO)₄( - ² - P₂), 1, reacts with one molar equivalent of Fe₂(CO)₉ in THF to yield the mono- and di-iron complexes, Cp₂Cr₂(CO)₄P₂[Fe(CO)₄], 2, (16.5% yield) and Cp₂Cr₂(CO)₄P₂[Fe(CO)₄]₂, 3, (16.9% yield), as dark magenta brown and dark greenish brown crystals, respectively. Both complexes were characterized by single-crystal X-ray diffraction analysis. Crystal data –2: space group =P2₁/c,a=17.024(1) Å,b=8.180(1) Å,c=30.891(2) Å, =100.953(5)°,V=4223.4(7)ų,Z=8, 3743 observed reflections,R _F=0.033; 3: space group P1,a=10.209(2) Å,b=10.212(2) Å,c=15.989(3) Å, =106.93(1)°, =91.87(1)°, =119.50(1)°,V=1356.5(4) ų,Z=2, 3489 observed reflections,R _F=0.029.     

The crystal structure of the molybdenum cementite Mo12Fe22C10 (ξ-phase)

The crystal structure of molybdenum cementite Mo₁₂Fe₂₂C₁₀ (-phase) has been determined by means of a single crystal x-ray diffraction study of crystal fragments. The lattice parameters were found to be:a=10.865 (3),b=7.767 (2),c=6.559 (2) Å and =120.13 (2)°, space group C2/m;Z=1. From the analysis ofPatterson maps and differenceFourier analysis the atomic parameters were derived, yielding a residual ofR=0.059. The crystal structure contains octahedral and triangular prismatic groups which accommodate the carbon atoms in their voids, as is usually found in interstitial compounds. The octahedral building group consists of four Mo- and two Fe-atoms, the triangular prism is built up by four Fe-and two Mo-atoms. The mode of filling of the metal polyhedra is discussed.

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Die Kristallstruktur von Molybdän-Zementit, Mo₁₂Fe₂₂C₁₀ (-Phase)

Zusammenfassung Die Kristallstruktur von Molybdän-Zementit, Mo₁₂Fe₂₂C₁₀ (-Phase) wird auf Grund von Einkristall-Beugungsaufnahmen unter Anwendung vonPatterson-and DifferentialFourier-Analysen bestimmt. In der monoklinen Elementarzelle (a=1.870;b=7.67;c=6.563 Å, =120.1°) Raumgruppe C 2/m befindet sich eine Formeleinheit Mo₁₂Fe₂₂C₁₀ (oderZ=2, Mo₆Fe₁₁C₅). DerR-Wert von 6% für 1200 Reflexe unterstreicht die Richtigkeit der Struktur, die aus oktaedrischen und trigonal prismatischen Gruppen aufgebaut ist. Die Oktaedergruppe besteht aus 4 Mo- und 2-Fe-Atomen, die trigonal prismatische Gruppe aus 4 Fe- und 2 Mo-Atomen. Die Kohlenstoffatome füllen die Lücken dieser Bauelemente, wie es für typische Einlagerungscarbide (Komplexcarbide) erwartet werden kann.

     

Synthesis, Characterization, and Physical Properties of Two Trinuclear, Mixed-Valence Species of Type [μ3-OMnIIMnIII 2(O2CCF3)6(R)3] (R=H2O, CH3COOH)

The preparation and characterization of two new mixed-valence, trinuclear species, [Mn₃O(O₂CCF₃)₆(H₂O)₃]CF₃COOH4/3H₂O (1) and [Mn₃O(O₂CCF₃)₆(CH₃COOH)₃] (2), is reported. Compound 1 crystallizes in the triclinic space group, P¯1 (No. 2), with the parameters, a=12.3131(9) Å, b=12.4427(9) Å, c=12.965(1) Å, =72.593(4)°, =73.453(5)°, =68.345(4)°, V=1727.2(2) ų, and Z=2. A total of 14060 reflections were collected in the range 1.6827.52°. The final weighted and non-weighted agreement indices, R1=0.0589 and wR2=0.1445 were based on a total of 6953 unique reflections with an R _int value of 0.0542. Compound 2 crystallizes in the monoclinic space group, P2₁/n (No. 14), with the parameters, a=12.876(3) Å, b=12.212(4) Å, c=17.732(4) Å, =100.40(3)°, V=3640.4(1) ų, and Z=4. A total of 32197 reflections were collected in the range 1.7227.13°. The final weighted and non-weighted agreement factors, R1=0.0647 and wR2=0.1609 were based on a total of 8018 unique reflections with an R _int value of 0.0462. An investigation of the physical properties revealed that both compounds display an intermediate ground state of S=3/2 as a consequence of intramolecular antiferromagnetic coupling. The magnetic data for compound 1 was best fit to the parameters g=2.09, J=–5.5 cm^–1, J=–3.4 cm^–1, and D _Mn(III)=–4.5 cm^–1; the data for compound 2 was best fit to the parameters g=2.10, J=–2.9 cm^–1, J=–5.5 cm^–1, and D _Mn(III)=–4.5 cm^–1.     

Comparison of the crystal structures of Co2(X 2O7)·2H2O,X=P and As

Summary Crystals of Co₂(X ₂O₇)·2H₂O,X=P/As were synthesized under hydrothermal conditions. Their crystal structures were determined by single crystal X-ray diffraction:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2)Å, =94.77(2)/94.74(2)°, space group P2₁/n,R=0.032/0.046,R _w=0.028/0.034 for 2423/2042 reflections and 131/119 variables. Within the twoXO₄ tetrahedra connected via a common corner to anX ₂O₇ group the average P-O bond lengths are approximately equal (1.540 and 1.543 Å), but As-O differs significantly (1.685 and 1.696 Å). A comparison with the isotypic Mn and Mg pyrophosphates shows a correlation between the ratio Me-O/X-O and the angle O-X-O.

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Vergleich der Kristallstrukturen von Co₂(X ₂O₇)·2H₂O,X=P und As

Zusammenfassung Kristalle von Co₂(X ₂O₇)·2H₂O,X=P/As wurden unter Hydrothermalbedingungen synthetisiert. Ihre Kristallstrukturen wurden mittels Röntgenbeugung an Einkristallen bestimmt:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2) Å, =94.77(2)/97.74(2)°, Raumgruppe P2₁/n,R=0.032/0.046,R _w=0.028/0.034 für 2423/2042 Reflexe und 131/119 Variable. In den beiden über eine gemeinsame Ecke zuX ₂O₇-Gruppen verknüpftenXO₄-Tetraedern sind die mittleren P-O-Abstände ungefähr gleich (1.540 und 1.543 Å), hingegen differiert As-O signifikant (1.685 und 1.696 Å). Ein Vergleich mit den isotypen Mn- und Mg-Pyrophosphaten zeigt eine Korrelation zwischen dem Quotienten Me-O/X-O und dem WinkelX-O-X.