Crystal structures and vibrational spectra ofMSnF6·6H2O(M=Fe,Co, Ni)

Summary Single crystal X-ray structural data (atT=300 K) are reported for CoSnF₆·6H₂O (rhombohedral; R{ie61-1}-C _3i ² ;a=9.735(7) Å,c=10.095(7) Å, =120°;Z=3;R=0.047) and for NiSnF₆· 6H₂O (rhombohedral; R{ie61-2}-C _3i ² ;a=9.697(1)Å,c=10.021(1)Å, =120°;Z=3;R=0.038). The two compounds are isostructural to FeSnF₆·6H₂O. IR and Raman spectroscopic data (atT=300 and 75 K) are reported for hydrated and for partially deuterated samples ofMSnF₆·6H₂O (M=Fe, Co, Ni). Two rather similar (OD) stretching frequencies and one (HDO) bending frequency of isotopically dilute HDO molecules are observed for either of the three compounds, which is consistent with one crystallographically distinct water molecule forming two different, but rather similar O ... F hydrogen bonds.

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Kristallstrukturen und Schwingungsspektren vonMSnF₆·6H₂O (M=Fe, Co, Ni)

Zusammenfassung Die Kristallstrukturen von CoSnF₆·6H₂O (rhomboedrisch; R{ie61-3}-C _3i ² ;a=9.735(7) Å,c=10.095(7) Å, =120°;Z=3;R=0.047) und von NiSnF₆·6H₂O (rhomboedrisch; R{ie61-4}-C _3i ² ;a=9.697(1)Å,c=10.021(1)Å, =120°;Z=3;R=0.038) wurden mittels Röntgen-Einkristalldaten (beiT=300 K) bestimmt. Die beiden Verbindungen sind isostrukturell zu FeSnF₆·6H₂O. IR- und Raman-Spektren vonMSnF₆·6H₂O (M=Fe, Co, Ni) wurden von Proben mit unterschiedlichem Deuterierungsgrad gemessen (beiT=300 und 75 K). Bei allen drei Verbindungen findet man für isotopenverdünnte HDO Moleküle zwei nur geringfügig unterschiedliche (OD)-Valenzfrequenzen und eine (HDO)-Deformationsfrequenz, was mit der Existenz von nur einer Art von Wassermolekülen mit zwei verschiedenen, aber doch sehr ähnlichen O ... F Wasserstoffbrückenbindungen übereinstimmt.

     

Synthesis and X-ray structural analysis of a unique Co-crystallization complex of [NaSal]2DB24C8 and [KSal]2DB24C8

Sodium salicylate (NaSal where Sal=2-hydroxybenzoate), when mixed with dibenzo-24-crown-8 (DB24C8) yields a bimetallic complex [NaSal]₂DB24C8 in most polar organic media, while potassium salicylate (KSal) under similar conditions shows a tendency to yield 11 or 21 complexes depending upon medium or synthesis. However, the presence of both NaSal and KSal together results in a unique mixed cation complex of composition NaKSal₂DB24C8. This product melts sharply (190-92°C) without decomposition, displays IR spectral characteristics comparable to those of [Na(Sal)]₂DB24C8, and is stable in aqueous media as shown by the detectable cation effect on the UV absorption bands of Sal and DB24C8. Single crystal X-ray analysis of NaK(Sal)₂DB24C8 reveals that the system represents a co-crystallization complex of individual (KSal)₂DB24C8 and (NaSal)₂DB24C8 molecules. The crystals are monoclinic,P2₁/c,a=19.976(2) Å,b=9.031(1) Å,c=25.541(5) Å,=122.065(9)°, ų,T=298 K,Z=2+2, CuK =1.5418 Å, and 2 (2.5°–100°). FinalR factor for the 3012 observed reflections (F>3) is 0.092. Both the Na₂- and K₂-molecules possess crystallographic centers of symmetry with one metal and its associated anion on each side of the crown ring. However, the conformations of the crowns are very different in the two molecules, with the K₂-crown being nearly planar and the Na₂-crown being quite puckered. Four oxygen atoms from the DB24C8 (KO, 2.680–2.908 Å) and three carboxyl oxygen atoms (KO, 2.472–2.708 Å) from separate salicylate ions coordinate with each potassium. Three oxygens from the crown (NaO, 2.536–2.65 Å) and three carboxyl oxygens (NaO, 2.31–2.563 Å) coordinate with each sodium. The salicylate ions lie on opposite sides and nearly perpendicular (77.2°, Na₂-molecule; 82.7° K₂-molecule) to each crown but coordinate to both of the metal ions within a molecule. The K⁺K⁺ and Na⁺Na⁺ distances in the respective molecules are 3.95 and 3.34 Å. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82044 (18 pages).     

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

     

Synthesis,spectroscopic and structural studies of tris(3-methyl-pyridinium)(3-ethylpyridinium)β-octamolybdate monohydrate

Summary Three isostructural compounds of general formula (3-MepyH) _x (3-EtpyH)_4–x [Mo₈O₂₆] (x=0, 2, 4) crystallize in the monoclinic system, space group P2₁/n, Z=2. Previously determined parameters for the compoundx=4 area=13.652(2),b=10.887(1),c=13.759(1) Å, =90.87(1)°,V=2044.8(4) ų,Dx=2.53,Do=2.54(1) mg m^–3,F(000)=1496. Slight differences in cell dimensions have been observed whenx=0 or 2. A nonisomorphous compound of formula (3-MepyH)₃(3-EtpyH)[Mo₈O₂₆]·H₂O crystallizes in the triclinic system, space group P2₁/n,Z=2,a=10.918(1),b=10.985(3),c=18.991(2) Å, =97.19(2), =91.45(2), =107.30(2)⁰,V=2152.8(7) ų,Dx=2.456,Do=2.456(5) mg m^–3,F(000)=1532. The distinguishing features of tris(3-methylpyridinium)(3-ethylpyridinium) -octamolybdate monohydrate are its non-centrosymmetric polyanion and its extensive hydrogen bonding. The asymmetric unit contains three independent 3-methylpyridinium and one 3-ethylpyridinium cations, one water molecule and the -octamolybdate anion. The planar cations are oriented to permit hydrogen bonds with either molybdate oxygen atoms or water oxygen atoms. Four different types of hydrogen bonds have been found: N–H...O (mono- and bifurcated); N–H...Ow (monofurcated); Ow–Hw...O (monofurcated); and C–H...O (monofurcated). The proposed hydrogen bonding interactions appear to stabilize the structure.     

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.

     

Kristallstruktur von Sulfamid,SO2(NH2)2

X-ray crystal structure analyses of sulfamide were carried out at 293 K and at 100 K:M=96.10, orthorhombic, Fdd2,Z=8,F(000)=400, Mo K, =0.71069 Å (graphite monochromator). A) 293 K:a=9.127 (1) Å,b=16.857 (5) Å,c=4.579 (1) Å,V=704.50 ų,d _x =1.812 Mgm^–3, =0.648 mm^–1,R=1.77%,R _w =1.94% (384 reflections, 33 parameters). B) 100K:a=9.059 (1) Å,b=16.780 (8) Å,c=4.517 (1) Å,V=686.63 ų,d _x =1.859 Mgm^–3, =0.665 mm^–1,R=1.78%,R _w =1.95% (404 reflections, 33 parameters). The sulfamide molecule shows at 293 K S-O and S-N distances of 1.429 (1) Å and 1.620 (1) Å, respectively, which are in agreement with IR data. Hydrogen positions could be determined from differenceFourier syntheses. Strong weakening of some intense low order reflections by extinction was observed, their anisotropy depends on the crystal and on temperature.

     

Hydrogen bonding in 2-hydroxy-benzhydrazide and 2-hydroxy-thiobenzhydrazide. Structural and spectroscopic study

Summary X-ray structural data are reported for 2-hydroxy-benzhydrazide(monoclinic; P2₁/n-C _2h ⁵ ;a=10.569(2) Å,b=11.264(2) Å,c=6.074(1) Å, =98.80(1)°;Z=4;R=0.054) and 2-hydroxy-thiobenzhydrazide (monoclinic; P2₁/n-C _2h ⁵ ;a=14.598(6) Å,b=5.975(2) Å,c=9.286(4) Å, =107.80(3)°;Z=4;R=0.044). In both compounds the phenolic OH groups are intramolecularly hydrogen bonded to the (thio)carbonyl oxygens and sulfurs, respectively; the basic intermolecular association patterns consist of closed six-membered hydrogen bonded dimers which are connected via N-H ... NH₂ hydrogen bonds. The spectral characteristics of the intramolecular O-H...O/S hydrogen bonds (solid state (OH)=2800/2700 cm^–1, CCl₄ solution (OH)=3035/3100 cm^–1, CDCl₃ solution (OH)=11.62/10.56 ppm) are similar to those of corresponding primary and secondary amides. The solid state IR spectra are consistent with hydrogen bonded NH groups and free NH₂ groups, the solution IR spectra indicate free NH₂ as well as free NH groups.

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Wasserstoffbrückenbindung in 2-Hydroxy-benzhydrazid und 2-Hydroxy-thiobenzhydrazid. Strukturelle und spektroskopische Untersuchungen

Zusammenfassung Es werden Röntgenstrukturdaten für 2-Hydroxy-benzhydrazid (monoklin; P2₁/n- C _2h ⁵ ;a=10.569(2) Å,b=11.264(2)Å,c=6.074(1)Å, =98.80(1)°;Z=4;R=0.054) und 2-Hydroxy-thiobenzhydrazid (monoklin; P2₁/n - C _2h ⁵ ;a=14.598(6)Å,b=5.975(2)Å,c=9.286(4)Å, =107.80(3)°;Z=4;R=0.044) berichtet. In beiden Verbindungen bilden die phenolischen OH-Gruppen intramolekulare Wasserstoffbrücken mit den Carbonyl-Sauerstoff-, bzw. den Thiocarbonyl-Schwefel-Atomen. Das intermolekulare Assoziationsmuster wird durch N-H...NH₂ Wasserstoffbrücken bestimmt, die jeweils zwei Moleküle über sechszählige Ringe zu Dimeren verbinden. Die IR- und NMR-spektroskopischen Charakteristika der intramolekularen O-H...O/S Wasserstoffbrücken (kristallin: (OH)=2800/2700 cm^–1, CCl₄-Lösungen: (OH)=3035/3100 cm^–1, CDCl₃-Lösungen: (OH)=11.62/10.56 ppm) sind sehr ähnlich zu denen entsprechender primärer und sekundärer Amide. Die Festkörper-IR-Spektren stehen in Einklang mit assoziierten NH- und freien NH₂-Gruppen, während die Lösungs-IR-Spektren auch auf das Vorliegen freier NH-Gruppen schließen lassen.

     

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.

     

Diaqua[N,N-di(2-carboxyethyl)-o-anisidinato]copper(II) Dihydrate [Cu(o-Andp)(H2O)2] · 2H2O: Synthesis and Crystal Structure

Crystals of [Cu(o-Andp)(H₂O)₂] · 2H₂O (where o-Andp^2–is -anisidine-N,N-di-3-propionate) were synthesized and studied using X-ray diffraction analysis. The crystals are triclinic: a= 12.063(1) Å, b= 12.483(3) Å, c= 13.586(2) Å, = 91.29(1)°, = 111.67(1)°, = 104.00(1)°, V= 1830.5(5) ų, space group P , Z= 2, and R= 0.0528 for 5965 reflections with I2(I). The two crystallographically independent complexes are isostructural. The tetragonal–bipyramidal coordination of copper(III) involves three O atoms, the N atom of the tetradentate ligand o-Andp^2–, and two O atoms from water. The aminodipropionate group of the ligand (average Cu–O 1.939 Å and Cu–N 2.051 Å) and one of the coordinated water molecules (Cu–O(w) 1.991 Å) lie in the equatorial plane. The second water molecule (Cu–O(w) 2.32 Å) and the methoxy O atom of o-Andp^2–(Cu–O 2.37 Å) are in the apical positions of the bipyramid.     

Geometry and force constant determination from correlated wave functions for polyatomic molecules: Ground states of H2O and CH2

Ab initio calculations including electron correlation are reported for the water and methylene molecules as a function of geometry. A large contracted gaussian basis set is used and the multiconfiguration wave functions, optimized by the iterative natural orbital procedure, include 277 and 617 configurations for H₂O and CH₂ respectively. The method of selecting configurations, yielding first-order wave functions, is discussed in some detail. For H₂O, the SCF geometry is r=0,942 Å, =105,8°, the correlated result is r=0,968 Å, =103,2°, and the experimental r=0,957 Å, =104,5°. The water stretching force constants, in millidynes/Å, are 8,72 (SCF), 8,75 (CI), and 8,4 (experiment). Bending force constants are 0,88 (SCF), 0,83 (CI), and 0,76 (experiment). For methylene the SCF geometry is r=1,072 Å, =129,5°, while the result from first-order wave functions is r=1,088 Å, =134°. The predicted CH₂ force constants are 6,16 (SCF) and 6,13 (CI) for stretching and 0,44 (SCF) and 0,33 (CI) for bending.

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Zusammenfassung Es wird über ab intito-Rechnungen mit Berücksichtigung der Elektronenkorrelation berichtet, die an Wasser- und Methylenmolekülen als Funktion der Geometrie durchgeführt worden sind. Dazu benutzt man einen großen kontrahierten Gauß-Basissatz. Die Multikonfigurationswellenfunktionen, die unter Benutzung von natürlichen Orbitalen nach der iterativen Prozedur optimiert werden, enthalten für H₂O 277 Konfigurationen und für CH₂ 617. Die Auswahlmethode, die zu Wellenfunktionen 1. Ordnung führt, wird diskutiert. Im Falle des Wassers erhält man die SCF-Geometrie zu r=0,942 Å, =105,8°, das korrelierte Resultat ist: r=0,968 Å, =103,2° und das experimentelle r=0,957 Å, =104,5°. Für Wasser ergeben sich die Valenzkraftkonstanten (in Millidyn Å^–1) 8,72 (SCF), 8,75 (CI) und 8,4 (Experiment). Die Deformationskonstanten sind 0,88 (SCF), 0,83 (CI) und 0,76 (Experiment). Im Falle des Methylens ist die SCF-Geometrie r=1,072 Å, =129,5°, während man mit Wellenfunktionen 1. Ordnung r=1,088 Å und =134° erhält. Die CH₂-Kraftkonstanten werden für die Valenzschwingung zu 6,16 (SCF) und 6,13 (CI) bzw. für die Deformationsschwingung zu 0,44 (SCF) und 0,33 (CI) vorausgesagt.

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Work performed under the auspices of the U.S. Atomic Energy Commision.

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Supported by the grants from the Research Corporation and the University of California Committee on Research.     

Crystal structure of Ba(VUO<Subscript>6</Subscript>)<Subscript>2</Subscript>

The crystal structure of Ba(VUO₆)₂ was determined by X-ray diffraction at 243 K: monoclinic crystal system, space group P2₁/c, unit cell parameters a=6.4992(6) Å, b=8.3803(8) Å, c=10.4235(9) Å, =104.749(2) °, Z=2. The structure contains close-packed [VUO₆] ₂ ^- layers formed by the dimers of the flattened U₂O₁₂ pentagonal bipyramids and by the dimers of V₂O₈ square pyramids. The neighboring layers are bound by the statistically distributed barium atoms.Original Russian Text Copyright © 2004 by E. V. Alekseev, E. V. Suleimanov, E. V. Chuprunov, and G. K. FukinTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 544–548, May–June 2004.     

Cluster synthesis 44. The synthesis and structural characterization of an unusual new high nuclearity platinum-osmium cluster complex,Pt5Os6(CO)25

The reaction of Pt₂Os₄(CO)₁₈ (1) with H₂ in refluxing octane (125°C) yielded the new compound Pt₅Os₆(CO)₂₅ (2), 58%. Compound 2 was characterized by IR, elemental and single crystal X-ray diffraction analyses. Compound 2 contains 11 metal atoms. five platinum, and six osmium. The cluster can be viewed as two fused trigonal bipyramidal clusters that share one platinum vertex. These two clusters are also joined by three metal-metal bonds, and Os(CO)₄ groups bridge two of these three metal-metal bonds. Crystal data for 2·CH₂Cl₂: space group itP1¯ma=12.250(1) Å,b=17.476(4) Å,c=11.89(2) Å,=109.87(1)°,=112.66(1)°,=83.05(2)°,Z=2, 2986 reflections,R=0.033.     

Molecular encapsulation of transition metal complexes in cyclodextrins. Part 2. Synthesis and crystal structures of 2:1 adducts between α-cyclodextrin and metallocenium hexafluorophosphates [η5-C5H5)2M]PF6(M = Fe,Co, Rh)

The title metallocenium salts form crystalline 2:1 host:guest inclusion compounds with-cyclodextrin, [(⁵-C₅H₅)₂M]PF₆ · 2-CD · 8H₂O (1, M = Fe;2, M = Co;3, M = Rh). The X-ray crystal structures of1 and3, and the lattice constants, crystal system and space group of2 have been determined. Crystal data: triclinic, space groupP1 (No. 1),Z = 1;1,a = 13.865 (2) Å,b = 13.839 (2) Å,c = 15.520 (2) Å, = 91.43 (2)°, = 85.81 (2)°, = 120.22 (2)°, andR _F = 0.089 for 4257 observed MoK reflections [I > 3(I)];2,a = 13.810 (2) Å,b = 13.872 (2) Å,c = 15.560 (2) Å, = 93.99 (2)°, = 87.06 (2)°, = 120.04 (2)°;3,a = 13.756 (1) Å,b = 13.863 (1) Å,c = 15.561 (2) Å, =94.39 (1)°, = 86.92 (1)°, = 119.89 (1)°, andR _F = 0.061 for 11142 observed MoK reflections [I > 3(I)]. In the crystals of1 and3, two -cyclodextrin molecules are arranged head-to-head to form a dimer by means of intermolecular hydrogen bonding across the secondary hydroxyl faces of adjacent -CD monomers. The dimers are stacked along the crystallographicc axis to form a channel-type structure. The metallocenium cation is encapsulated within the cavity of the dimer, while the PF ₆ ^– anion is located outside the cavity, being centered between the primary hydroxyl faces of adjacent dimers. Eight water molecules of hydration per asymmetric unit reside in the spaces between the -CD columns. In view of the almost identical crystal data for2 a similar structure can be assumed for the cobaltocenium adduct.     

Gold(I) Pyrazolate Clusters: The Structure and Luminescence of the Tetranuclear, Base-Stabilized [(dppm)2Au4(3,5-Ph2Pz)2](NO3)2 ⋅ H2O

The tetranuclear Au(I) pyrazolate complex, [(dppm)₂Au₄(3,5-Ph₂Pz)₂](NO₃)₂  H₂O, 1, has been synthesized and structurally characterized. It is the first tetranuclear pyrazolate of Au(I) to have been found, although the trinuclear pyrazolates of Au(I) are well known. Complex 1 exhibits luminescence at 77 K when excited at 333 nm with an emission maximum at 454 nm. The emission has been assigned to ligand to metal charge transfer, LMCT, based upon the vibronic structure that is observed. The complex crystallizes in the monoclinic space group P2₁/c, with a=19.33(3) Å, b=20.26(3) Å, c=19.80(3) Å, =106.74(2)°, V=7425(17) ų, Z=8, and R=0.058. The Au    Au distances are Au(1)    Au(4)=3.185(3) Å, Au(1)    Au(2)=3.230(3) Å, Au(2)    Au(3)=3.079(3) Å, and Au(3)    Au(4)=3.280(3) Å.     

The designed synthesis and crystallographic characterization of three novel heterotrimetallic linear complexes of [Et4N][(Ph3P)2{M′S2 MS2Fe}Cl2] (M=Mo,M′=Ag;M=W,M′=Cu,Ag)

The complexes [Et₄N][(Ph₃P)₂{MS₂ MS₂Fe}Cl₂] (M=Mo,M=Ag;M=W,M=Cu, Ag) have been obtained by reaction of [Et₄N]₂[S₂ MS₂FeCl₂] (M=Mo, W) with Cu(PPh₃)₃Cl or Ag(PPh₃)₃NO₃ in MeCN/CH₂Cl₂, respectively. Crystal data for [Et₄N][(PPh₃)₂ {AgS₂MoS₂Fe}Cl₂] (I): triclinic, P (No. 2),Z=2,a=13.41(1)Å,b=15.54(1)Å,c=12.30(1)Å, =105.24(6)°, =94.63(7)°, =101.38(6)°, andV=2399(4)ų. The bond lengths of Mo-Fe bond and the Mo-Ag distance are 2.756(2)Å and 3.033(2)Å, respectively. Crystal data for [Et₄N][(PPh₃)₂ {AgS₂WS₂Fe}Cl₂] (II): triclinic, P (No. 2),Z=2,a=13.457(5))Å,b=15.601(6)Å,c=12.338(4)Å, =105.20(3)°, =94.61(4)°, =101.43(4)°, andV=2426(2)ų. The bond length of W-Fe bond and the W-Ag distance are 2.786(2)Å and 3.076(1)Å, respectively. Crystal data for [Et₄N][(PPh₃)₂ {CuS₂WS₂Fe}Cl₂] (III): triclinic, P (No. 2),Z=2,a=13.498(5)Å,b=15.372(4)Å,c=12.340(4)Å, =105.54(2)°, =93.32(3)°, =101.40(3)°, andV=2401(1)ų. The bond lengths of W-Fe bond and the W-Cu bond are 2.800(1)Å and 2.851(1)Å, respectively.     

Syntheses,crystal structures,and characterizations of two novel cubane-like and double cubane-like molybdenum-copper-sulphur clusters {MoCu3S3(S2COEt)}(O)(Ph3P)3 and {Mo2Cu6S6(SCMe3)2}(O)2(Ph3P)4

Two novel heterometallic cubane-like and double cubane-like clusters, {MoCu₃S₃(S₂COEt)}(O)(Ph₃P)₃ I and {Mo₂Cu₆S₆(SCMe₃)₂}(O)₂(Ph₃P)₄ II, were synthesized by reaction of {MoCu₂S₃}(O)(Ph₃P)₃ with CuS₂COEt and CuSCMe₃, respectively. ClusterI crystallized in the triclinic space group (2) witha=12.766(6) Å,b=22.904(5) Å,c=10.522(3) Å, =99.86(2)°, =109.68(2)°, =86.84(3)°,V=2854(2) ų,Z=2,R=0.049 for 6622 observed reflections (I>5(I)) and 410 variables. ClusterII crystallized in the triclinic space group (2) with dimensionsa=14.212(4) Å,b=14.725(5) Å,c=12.396(8) Å, =110.32(4)°, =90.40(5)°, =62.88(2)°,V=2129(2) ų,Z=1,R=0.039 for 6020 observed reflections (I>3(I)) and 461 variables. ClusterI consists of a neutral cubane-like molecule with the core {MoCu₃S₃(S₂COEt)}²⁺, in which one corner of the cubane-like core is a novel triply bridging bidentate 1,1-dithiolato (xanthate, S₂COEt^–) ligand. ClusterII is a double cubane-like one, in which two cubane-like cores {MoCu₃S₃(SCMe₃)}²⁺ are connected by two Cu-S bonds of the triply bridging monothiolato (SCMe ₃ ^– ) ligand. Two different pathways of unit construction from a small heterometallic cluster {MoCu₂S₃}(O)(Ph₃P)₃ have been outlined. Comparisons of the selected bond lengths and bond angles for the cubane-like core {MoCu₃S₃ X} (X=Cl^–, Br^–, S₂COEt^–, SCMe ₃ ^– ) are given. Spectroscopic properties of the title clusters are also reported.     

Synthesis and X-ray structures of dinitrato-bis[2-(2′-thienyl)-1-(2′-thienylmethyl)benzimidazole]copper(II) and dichloro-bis-[2-(2′-thienyl)-benzimidazole]copper(II)-ethanol

Summary The reactions of Cu(NO₃)₂ · 3 H₂O with 2- (2-thienyl)-1-(2-thienylmethyl)benzimidazole (L) and of CuCl₂ · 2H₂O with 2-(2-thienyl)benzimidazole (L) have been carried out. The crystal structure of two isolated complexes,(1) and(2), have been determined by single-crystal x-ray diffraction methods. Crystals of(1) are monoclinic, space groupP2₁ /c, witha=9.884(4),b=9.892(4),c=18.732(8) Å, =114.89(2)°,Z=2;R=0.068 for 1909 observed reflections. Crystals of (2) are orthorhombic, space groupPbcn, witha=14.835(1),b=8.193(1),c=20.493(1) Å,Z=4;R=0.086 for 415 observed reflections. In the complex (1) the copper co-ordination is tetragonal (compressed octahedral) and involves a nitrogen atom of the organic ligand [Cu-N 1.970(6) Å] and two oxygen atoms of the nitrate group [Cu-O 2.318(7) and 2.246(9) Å] which appears to coordinate nearly symmetrically to the metal; however it has unusually large thermal motion which suggests a fluxional behaviour. In the complex (2) the co-ordination is square planar and involves an imidazole nitrogen [Cu-N 1.95(3) Å] and a chlorine atom [Cu-Cl 2.27(1) Å]. A long interaction Cu-S=3.37(2) Å completes the co-ordination polyhedron to a very elongated distorted tetragonal bipyramid. In both compounds a thiophene ring is disordered.     

Low-temperature structural phase transition in SrMo6S8 studied by X-ray powder diffraction

Lattice parameters as a function of temperature for, and atomic coordinates of the low-temperature phase of, SrMo₆S₈ are reported from X-ray powder diffraction. The structure transforms atT ₁=135(3) K from the rhombohedral high-temperature modification (R ,a _rh=6.5630 (3) Å, _rh=88.9982(2)°,V _rh=282.55(5)ų at 298 K) into the triclinic low-temperature modification (P ,a _tr=6.481(1)Å,b _tr=6.572(1)Å,c _tr=6.611(1)Å, _tr=89.246(4)°, _tr=89.304(4)°, _tr=88.169(4)°,V _tr=281.4(2)ų at 20K). The triclinic distortion is larger than in the Ca analogue, and similar to the Ba and Eu analogues.

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Untersuchung des Tieftemperatur-Phasenübergangs von SrMo₆S₈ mittels Röntgenpulverdiffraktometrie (Kurze Mitt.)

Zusammenfassung Die Temperaturabhängigkeit der Gitterparameter und die Atomlagen der Tieftemperaturphase von SrMo₆S₈ wurden mittels Röntgenpulverdiffraktometrie bestimmt. Die rhomboedrische Hochtemperaturmodifikation (R ,a _rh=6.5630(3)Å, _rh=88.9982(2)°,V _rh=282.55(5)ų,T=298 K) wandelt beiT ₁=135(3) K in die trikline Tieftemperaturmodifikation (P ,a _tr=6.481(1)Å,b _tr=6.572(1)Å,c _tr=6.611(1)Å, _tr=89.246(4)°, _tr=89.304(4)°, _tr=88.169(4)°,V _tr=281.4(2)ų,T=20 K) um. Die trikline Deformation ist stärker ausgeprägt als in der Ca-Verbindung und ähnlich jener der Ba- and Eu-Verbindung.

     

The crystal and molecular structure of the β-cyclodextrin inclusion complex with aspirin and salicylic acid

The crystal structure of the -cyclodextrin (-CyD) molecular complex with aspirin (acetylsalicylic acid), salicylic acid, and water, (C₄₂H₇₀O₃₅)₂ (C₉H₈O₄)₂ (C₇H₆O₃) 23.3H₂O, was determined by X-ray structure analysis. The crystal data is space group Pl, a=19.777(5), b=15.247(3), c=15.475(4) Å, =102.63(2)°, =116.96(2)°, =104.12(2)°, V=3729(2) ų, D_m=1.409(2) g/cm³, D_X=1.419 g/cm³, and Z=1. The two -CyDs form a dimer unit with hydrogen bond networks among the secondary hydroxyl groups of both -CyDs. This -CyD dimer includes three guest molecules of two different types in its hydrophobic cavity. Two of them are aspirin, which are separately included in each cavity of the -CyD unit, with their hydrophobic benzene rings protruding into the hydrophobic cavities of the host -CyDs. The remaining guest molecule is the hydrolyzed product of an aspirin, that is salicylic acid, which is sandwiched in the space constructed by the -CyD dimer formation, and is statistically disordered at three sites.     

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.