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.

     

Synthesis and crystal structure of monoclinic Fe2(SeO4)3

Summary Crystals of monoclinic Fe₂(SeO₄)₃ were synthesized under hydrothermal conditions. The structure was determined by single crystal X-ray methods and refined in space group P2₁/n with 2 646 independent reflections (sin /<0.7 Å^–1) toR=0.033,R _w=0.037:a=8.530 (2) Å,b=8.888 (2) Å,c=11.952 (2) Å, =91.13 (1)°,V=906.0 ų,Z=4. The crystal structure is isotypic with the monoclinic modification of Fe₂(SO₄)₃, containing two different Fe(III) and three Se(VI) atomic positions. The FeO₆ and SeO₄ polyhedra are only slightly distorted, the mean Fe-O bond lengths are 1.986 Å and 2.004 Å, the average distances within the SeO₄ tetrahedra are each 1.628 Å. The isolated FeO₆ octahedra only share corners with SeO₄ tetrahedra to build a framework structure.

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Synthese und Kristallstruktur von monoklinem Fe₂(SeO₄)₃

Zusammenfassung Kristalle von monoklinem Fe₂(SeO₄)₃ wurden unter Hydrothermalbedingungen gezüchtet. Die Struktur wurde mit Einkristall-Röntgenmethoden bestimmt und in der Raumgruppe P2₁/n mit 2 646 unabhängigen Reflexen (sin /<0.7Å^–1) aufR=0.033,R _w=0.037 verfeinert:a=8.530(2) Å,b=8.888(2) Å,c=11.952(2) Å, =91.13(1)°,V=906.0 ų,Z=4. Die Kristallstruktur ist isotyp mit der monoklinen Modifikation von Fe₂(SO₄)₃, sie enthält zwei unterschiedliche Fe(III) und drei Se(VI) Atompositionen. Die FeO₆-Polyeder sind nur gering verzerrt, die mittleren Fe-O Bindungslängen sind 1.986 Å und 2.004 Å, die mittleren Abstände in den SeO₄-Tetraedern sind jeweils 1.628 Å. Die isolierten FeO₆-Oktaeder sind nur über gemeinsame Ecken mit SeO₄-Tetraedern verbunden, wobei eine Gerüststruktur entsteht.

     

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.

     

Cu2O(SO4), dolerophanite: Refinement of the crystal structure,with a comparison of [O Cu(II)4] tetrahedra in inorganic compounds

The refinement of the crystal structure of Cu₂O(SO₄), dolerophanite, [a=9.370 (1) Å,b=6.319 (1) Å,c=7.639 (1) Å, =122.34 (1)°; space group C 2/m;Z=4;R=0.035] confirmed the trigonal dipyramidal coordination of one Cu(II) atom (mean distance Cu-O=2.025 Å). One O atom is tetrahedrally surrounded by four Cu(II) atoms; the mean Cu(II)-O distance of 1.918 Å compares well to [O Cu(II)₄] tetrahedra found in inorganic crystal structures.de|Die Verfeinerung der Kristallstruktur von Cu₂O(SO₄), Dolerophanit, [a=9.370 (1) Å,b=6.319 (1) Å,c=7.639 (1) Å, =122.34 (1)°; Raumgruppe C 2/m;Z=4;R=0.035] bestätigte die trigonal dipyramidale Koordination des einen Cu(II)-Atoms (mittlerer Cu-O-Abstand=2.025 Å). Ein O-Atom ist tetraedrisch von vier Cu(II)-Atomen umgeben; der mittlere Cu(II)-O-Abstand von 1.918 Å entspricht den in ähnlichen [O Cu(II)₄]-Tetraedern von anorganischen Kristallstrukturen gefundenen Werten.

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Cu₂O(SO₄), Dolerophanit: Verfeinerung der Kristallstruktur mit einem Vergleich von [O Cu(II)₄]-Tetraedern in anorganischen Verbindungen

     

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.

     

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.

     

Na3Fe2S4, ein Thioferrat mit gemischt valenter sk∞/1[FeS2]-Kette

Na₃Fe₂S₄ has been prepared from Na₂S, S and Fe. It crystallizes in space group Pnma,a=6.6333 (5) Å,b=10.675 (1) Å,c=10.677 (2) Å,Z=4. The crystal structure, as determined from single crystal four-circle diffractometer data (R=2.8%), consists of sk/1[FeS₂]-chains formed by slightly distorted edge sharing [FeS₄]-tetrahedra, the iron atoms having a formal valency of +2.5. The sodium ions are approximately octahedrally coordinated. Exposed to air, Na₃Fe₂S₄ readily takes up water to form a hydrate by a pertially topochemical reaction.

     

Die Kristallstruktur von Ca2As2O7

The structure of Ca₂As₂O₇ (a ₀=7.05,b ₀=9.30,c ₀=4.89 Å; =101.3°; space groupC2/m-C _2h ³ ;Z=2) has been solved from 465 independent X-ray intensities collected on aWeissenberg-type diffractometer up to anR-factor of 2.4% for all intensities. The structure of Ca₂As₂O₇ represents a further Thortveitite structure type.

     

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.

     

Synthese,Kristallstruktur und Konformation von N2-Dibenzyl-N1-t-butoxycarbonylhydrazin

Summary The synthesis and the crystal structure of N²-dibenzyl-N¹-butoxycarbonyl hydrazine are reported. The compound was prepared from commercially availablet-butyl carbazate. It crystallizes in the triclinic space group P 1 witha=5.479(1) Å,b=9.559(1) Å,c=9.748(1) Å,a=63.81(1)°, =87.52(1)°, =74.07(1) Å,Z=1,D=1.18 g/cm³. The structure was solved by direct methods and refined toR=0.0329.

     

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.

     

Natural product chemistry,part 100: The structure of carissone,C15H24O2

Summary C₁₅H₂₄O₂,M=236.2, monoclinic, P 2₁,a=7.229(7),b=14.925 (9),c=6.235 (9) Å, =92.40 (9)°,V=672.1 ų,T=–133 °C,Z=2,D _x=1.17 g cm^–3. The X-ray diffraction analysis of this sesquiterpenoid fromCarissa opaca confirmed the previously proposed constitution of the isolate and, furthermore, allowed precise NMR assignment.

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Naturstoffchemie, 100. Mitt.: Die Struktur des Carissons, C₁₅H₂₄O₂

Zusammenfassung C₁₅H₂₄O₂,M=236.2, monoklin, P 2₁,a=7.229 (7),b=14.925 (9),c=6.235 (9) Å, =92.40 (9)°,V=672.1 ų,T=–133 °C,Z=2,D _x=1.17 g cm^–3. Die Röntgenstrukturanalyse dieses Sesquiterpenoids ausCarissa opaca bestätigte die bereits vorgeschlagene Struktur und erlaubte ferner eine genaue NMR-Zuordnung.

     

Untersuchungen der Hydroxylammonium-Fluorozirconate(IV)

Summary Hydroxylammonium fluorozirconates have been investigated. Two new microcristalline phases have been isolated from aqueous solutions: (NH₃OH)₂ZrF₆ (1) and (NH₃OH)₃ZrF₇ (2). The crystals were prepared by slow evaporation of the solution of NH₂OH, Zr, and HF. Different compositions of the crystals were achieved by varying the molar ratios of the components. They were characterized by thermal analysis, vibrational spectroscopy, and structure (single crystal x-ray methods). (NH₃OH)₂ZrF₆ (1) crystallizes triclinic, P (No.: 2),a=7.400(2),b=7.609(2),c=7.887(2) Å, =57.29(3)°, =62.16(3)°, =67.83(2)°. (NH₃OH)₃ZrF₇ (2) crystallizes triclinic, P (No.: 2),a=7.128(1),b=7.989(1),c=8.888(1) Å, =109.72(1)°, =91.01(1)°, =104.27(1)°.

     

Syntheses and crystal structures of NH4Ag2(AsS2)3 and (NH4)5Ag16(AsS4)7 with a discussion of (NH4)Sx polyhedra

Summary The atomic arrangements within the structures of NH₄Ag₂(AsS₂)₃ [a=9.557(2),b=7.414(2),c=16.29(1) Å; =91.30(5)°; space group P2₁/n;R(F)=0.042] and (NH₄)₅Ag₁₆(AsS₄)₇ [a=64.49(6),b=6.471(2),c=12.806(4) Å; =95.47(5)°; space group Cc;R(F)=0.073] were determined from single crystal X-ray data. In these two compounds the coordination spheres of the Ag atoms are quite different. In NH₄Ag₂(AsS₂)₃, the Ag atoms exhibit a [2+2]- and a [3+1]-coordination to S atoms up to 3.3 Å and with Ag atom neighbours at 2.93 Å and 3.05 Å respectively. In (NH₄)₅Ag₁₆(AsS₄)₇, the Ag atoms are — with one exception- [4] coordinated (Ag-S<3.3 Å) and the distances to further Ag atom neighbours are greater than 3.1 Å. NH₄Ag₂(AsS₂)₃ represents an ordered cyclo-thioarsenate(III) with three-membered As₃S₆ rings, (NH₄)₅Ag₁₆(AsS₄)₇ a neso-thioarsenate(V) with two split Ag atom positions. Both compounds were synthesized under moderate hydrothermal conditions.

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Synthesen und Kristallstrukturen von NH₄Ag₂(AsS₂)₃ und (NH₄)₅Ag₁₆(AsS₄)₇ mit einer Diskussion über (NH₄)S_x Polyeder

Zusammenfassung Die Atomanordnungen in den Strukturen von NH₄Ag₂(AsS₂)₃ [a=9.557(2),b=7.414(2),c=16.29(1) Å; =91.30(5)°; Raumgruppe P2₁/n;R(F)=0.042] und (NH₄)₅Ag₁₆(AsS₄)₇ [a=64.49(6),b=6.471(2),c=12.806(4) Å; =95.47(5)°; Raumgruppe Cc;R(F)=0.073] wurden anhand von röntgenographischen Einkristalldaten bestimmt. In diesen beiden Verbindungen sind die Koordinationsverhältnisse um die Ag-Atome sehr unterschiedlich. In NH₄Ag₂(AsS₂)₃ besitzen die Ag-Atome bis 3.3 Å eine [2+2]- und [3+1]-Koordination durch S-Atome mit weiteren Ag-Atomen bei 2.93 Å und 3.05 Å. In (NH₄)₅Ag₁₆(AsS₄)₇ sind die Ag-Atome mit einer Ausnahme [4]-koordiniert (Ag-S < 3.3 Å), und die Abstände zu weiteren Ag-Atomen sind größer als 3.1 Å. NH₄Ag₂(AsS₂)₃ stellt ein geordnetes Cyclothioarsenat(III) mit dreigliedrigen As₃S₆-Ringen dar, (NH₄)₅Ag₁₆(AsS₄)₇ ein Nesothioarsenat (V) mit zwei aufgespaltenen Ag-Positionen. Beide Verbindungen wurden unter mäßigen Hydrothermalbedingungen synthetisiert.

     

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.

     

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.     

Die Phase La2U2N5

In the system U–La–N a new phase of composition La₂U₂N₅ was observed. The differaction pattern of this phase can be indexed with a tetragonal unit cell:a=8.43 Å,c=8.50 Å andc/a=1.008. The pseudocubic sub-cell withaca/2 is closely related to the CsCl-type.

Auszug aus der von der Technisch-Naturwissenschaftlichen Fakuktät der TU Wien approbierten Diplomarbait des Herrn Dipl.-Ing.J. Waldhart.     

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 structures and hydrogen bonding schemes in four benzamide derivatives (2-hydroxy-benzamide, 2-hydroxy-thiobenzamide, 2-hydroxy-N,N-dimethyl-benzamide,and 2-Hydroxy-N,N-dimethyl-thiobenzamide)

Summary 2-Hydroxy-benzamide, C₇H₇NO₂; monoclinic; I2/a-C _2h ⁶ ;a=12.901 (2),b=4.982 (1),c=20.987 (3) Å; =91.50 (2)°;Z=8. 2-Hydroxy-thiobenzamide, C₇H₇NOS; monoclinic; P2₁/n-C _2h ⁵ ;a=13.508 (5),b=6.780 (2),c=15.878 (6) Å; =93.74 (5)°;Z=8. 2-Hydroxy-N,N-dimethyl-benzamide, C₉H₁₁NO₂; orthorhombic; Pbca-D _2h ¹⁵ ;a=11.752 (2),b=16.680 (3),c=9.079 (2) Å;Z=8. 2-Hydroxy-N,N-dimethyl-thiobenzamide, C₉H₁₁NOS; monoclinic; P2₁/c-C _2h ⁵ ;a=6.983 (1),b=11.652 (3),c=11.704 (3) Å; =100.02 (2)°;Z=4. The crystal structures of these four compounds were determined (respectively refined: 2-hydroxy-benzamide) by single crystal X-ray data. The refinements of the structure parameters by least squares methods yielded in all casesR<0.056. The hydrogen atoms were located by means of difference Fourier summations. The O-H ... O distances are 2.513 (1) Å in 2-hydroxy-benzamide (intramolecular) and 2.625 (1) Å in 2-hydroxy-N,N-dimethyl-benzamide (intermolecular). The two O-H ... S distances in 2-hydroxy-thiobenzamide are 2.904 (2) Å and 2.918 (2) Å (intramolecular, two molecules in the asymmetric unit) and 3.228 (2) Å in 2-hydroxy-N,N-dimethyl-thiobenzamide (intermolecular). Clear N-H ... O hydrogen bonds with 2.926 (1) Å and 3.006 (1) Å occur only in the structure of 2-hydroxy-benzamide (intermolecular).

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Die Kristallstrukturen und Wasserstoffbrücken-Bindungsschemata in vier Benzamid-Derivaten

Zusammenfassung 2-Hydroxy-benzamid, C₇H₇NO₂; monoklin; I2/a-C _2h ⁶ ;a=12.901 (2),b=4.982 (1),c=20.987 (3) Å; =91.50 (2)°;Z=8. 2-Hydroxy-thiobenzamid, C₇H₇NOS; monoklin; P2₁/n-C _2h ⁵ ;a=13.508 (5),b=6.780 (2),c=15.878 (6) Å; =93.74 (5)°;Z=8. 2-Hydroxy-N,N-dimethyl-benzamid, C₉H₁₁NO₂; orthorhombisch; Pbca-D _2h ¹⁵ ;a=11.752 (2),b=16.680 (3),c=9.079 (2) Å;Z=8. 2-Hydroxy-N,N-dimethyl-thiobenzamid, C₉H₁₁NOS; monoklin; P2₁/c-C _2h ⁵ ;a=6.983 (1),b=11.652 (3),c=11.704 (3) Å; =100.02 (2)°;Z=4. Die Kristallstrukturen dieser vier Verbindungen wurden mittels Röntgen-Einkristalldaten bestimmt (bzw. verfeinert: 2-Hydroxy-benzamid). Die Verfeinerungen der Strukturparameter nach der Methode der kleinsten Quadrate ergab in allen FällenR<0.056. Die Wasserstoffatome konnten anhand von Differenz-Fourier-Summationen belegt werden. Die O-H ... O-Abstände haben folgende Werte: 2.513(1)Å in 2-Hydroxy-benzamid (intramolekular) und 2.625(1) Å in 2-Hydroxy-N,N-dimethyl-benzamid (intermolekular). Die zwei O-H ... S-Abstände sind in 2-Hydroxy-thiobenzamid 2.904(2)Å und 2.918(2)Å (intramolekular, zwei moleküle in der asymmetrischen Einheit) und 3.228(2)Å in 2-Hydroxy-N,N-dimethyl-thiobenzamid(intermollekular). Klar zuzuordnende N-H ... O-Wasserstoffbrücken mit 2.926(1)Å und 3.006(1)Å treten lediglich in der Struktur des 2-Hydroxy-benzamid auf (intermolekular).

     

Crystal structure and spectra of the Ni(II) complex of pyridine-2,6-dithio-carbomethylamide

The crystal structure of the paramagnetic bis(pyridine-2,6-dithiocarbomethylamide) nickel(II) nitrate (NiPDTA) is described: C₁₈H₂₂N₆S₄·(NO₃)₂·(H₂O)_1,5, monoclinic, C2/c,Z=4,a=14.705 (3) Å,b=23.254 (8) Å,c=8.383 (3) A, =98.18 (2)°,d _x=1.55 gcm^–3,d _m=1.53 gcm^–3. The structure was solved withPatterson and differenceFourier techniques and refined to a residual ofR=0.053. The nickel is surrounded by a square bipyramidal coordination of four thioamide sulfur atoms and two pyridine nitrogen atoms. Vibrational and electronic band positions for this compound are discussed.

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Kristallstruktur und Spektren des Pyridin-2,6-dithiocarbomethylamid Nickel(II)-Komplexes

Zusammenfassung Die Kristallstruktur des paramagnetischen bis(Pyridin-2,6-dithiocarbomethylamid) Nickel(II)-nitrats (NiPDTA) wurde bestimmt. C₁₈H₂₂N₆S₄Ni·(NO₃)₂·(H₂O)_1,5, monoklin, C2/c,Z=4,a=14,705 (3) Å,b=23,254 (8) Å,c=8,383 (3) A, =98,18 (2)°,d _x=1,55gcm^–3,d _m=1,53gcm^–3. Das Phasenproblem wurde mittelsPatterson-und Differenz-Fourier-Synthese bestimmt und die Struktur bis zu einem kristallographischenR-Faktor vonR=0.053 verfeinert. Das Nickel-Atom ist von vier Thioamid-Schwefelatomen und zwei Pyridin-Stickstoffatomen in quadratisch-bipyramidaler Anordnung umgeben. Schwingungsspektren und Anregungsspektren des Komplexes werden diskutiert.