Isomere vierkernige Molybdän—Wolfram—Schwefelclusterdithiophosphinate / Isomeric Tetranuclear Molybdenum—Tungsten — Sulfurclusterdithiophosphinates

1988 ◽  
Vol 43 (12) ◽  
pp. 1541-1546 ◽  
Author(s):  
Axel Deeg ◽  
Helmut Keck ◽  
Andreas Kruse ◽  
Wilhelm Kuchen ◽  
Hartmut Wunderlich

Abstract A mixture of three isomeric clusters of composition Mo3WS4(Et2PS2)6 (3) is obtained by reacting equimolar quantities of Mo3S4(Et2PS2)4, W(CO)3(CH3CN)3 and [Et2P(S)]2S2 in toluene'. Some NMR-spectroscopic data and the magnetic properties of these isomers are reported. Isomer 3a consists of a distorted cubane Mo3WS4, each metal of which is coordinated by six S atoms: three of them belonging to the cubane, one to a bridging and two to a chelating ligand Et2PS2-. The crystal structure of isomer 3b is reported. In 3b only three of the metals in the core are coordinated in this manner while the fourth is surrounded by three S of the cubane and three S of bridging ligands. 3b crystallizes in the orthorhombic space group Pbca, Z = 8. lattice parameters a = 2184,4(8), b = 2264,4(9). c = 2388.2(8) pm. The crystal structure was refined to R = 0.05 using 5398 observed reflections. By HPLC 3b can be separated into two isomers. 3b1 and 3b2, both differing in the type of metal. Mo or W. bonded to the three bridging ligands

2017 ◽  
Vol 72 (12) ◽  
pp. 983-988 ◽  
Author(s):  
Martin K. Schmitt ◽  
Hubert Huppertz

Abstractβ-Y(BO2)3 was synthesized in a Walker-type multianvil module at 5.9 GPa/1000°C. The crystal structure has been elucidated through single-crystal X-ray diffraction. β-Y(BO2)3 crystallizes in the orthorhombic space group Pnma (no. 62) with the lattice parameters a=15.886(2), b=7.3860(6), and c=12.2119(9) Å. Its crystal structure will be discussed in the context of the isotypic lanthanide borates β-Ln(BO2)3 (Ln=Nd, Sm, Gd–Lu).


1990 ◽  
Vol 45 (4) ◽  
pp. 461-464 ◽  
Author(s):  
Helmut Keck ◽  
Andreas Kruse ◽  
Wilhelm Kuchen ◽  
Dietrich Mootz ◽  
René Wiskemann ◽  
...  

The cubane-type diamagnetic cluster Mo3SnS4(Et2PS2)6 (1) is obtained by reaction of the “incomplete” cubane Mo3S4(Et2PS2)4 either with tin powder and Et2P(S)—S—S—P(S)Et2 or with bis(diethyldithiophosphinato)tin(II). While the Sn atom and two of the Mo atoms in the core are chelated by Et2PS2⁻, the remaining Mo atom serves as a bridgehead for three dithiophosphinato-ligand bridges to the other metals. 1 crystallizes in the orthorhombic space group Pbca with Z = 8 and lattice parameters a = 2240( 1), b = 2261 ( 1), c = 2401 (1) pm.


2007 ◽  
Vol 353-358 ◽  
pp. 3043-3046 ◽  
Author(s):  
Ping Li Qin ◽  
Liang Qin Nong ◽  
Ji Liang Zhang ◽  
Hai Qing Qin ◽  
Jiang Ping Liao ◽  
...  

The crystal structure of a new compound NdFeSb3 has been determined by X-ray powder diffraction using the Rietveld method. The compound crystallizes in the orthorhombic, space group Pbcm (No.57) with the CeNiSb3 structure type and lattice parameters a=1.26828(2)nm, b=0.61666(2)nm, c=1.81867(4) nm, z=12 and Dcalc=7.917g/cm3.


1996 ◽  
Vol 51 (8) ◽  
pp. 1132-1136 ◽  
Author(s):  
Yalcin Elerman ◽  
Mehmet Kabak ◽  
Ingrid Svoboda ◽  
Hartmut Fuess ◽  
Klaus Griesar ◽  
...  

[Methylamino-(N,N′-1,3-propyl-disalicylaldiminato)-Ni(II)-bis-(N-methylsalicylaldiminato)- Ni(II)] was synthesized from the condensation of N,N′-1,3-propyl-disalicylaldimine, salicylaldehyde, methylaminohydrochloride, NaOH and Ni(CH3COO)2·H2O, and its crystal structure determined. [C34H37N5O4Ni2], orthorhombic, space group Pbca, a = 12.330( 1), b = 24.967(2), c = 20.616(2)Å, Z = 8. The dinuclear complex contains two octahedrally coordinated nickel atoms which are linked via three oxygen atoms with an average (Ni-O-Ni) angle of 87.2( 1)° and a Ni···Ni distance of 2.884(1)Å. The coordination is completed by three nitrogen atoms. The nickel(II) centers are ferromagnetically coupled (J = 11.5 cm-1) as derived from temperature-dependent magnetic susceptibility measurements in the range 5 - 280 K.


1993 ◽  
Vol 48 (5) ◽  
pp. 548-554 ◽  
Author(s):  
Hansjörg Diller ◽  
Helmut Keck ◽  
Andreas Kruse ◽  
Wilhelm Kuchen

The syntheses of tetranuclear complexes Mo,W2S4L6 3 and Mo2Co2S4L2(CO)2(CH3CN)2 4 (L = R2PS2⁻; a: R = Et, b: R = Pr) containing the cubane-type Mo2M2S4 core are reported. While in 4 both Mo atoms are chelated by L, the dithiophosphinato group acts as a chelating and bridging ligand in 3. It is shown that there exist four isomers of 3 which differ not only in the function of L but also in the kind of metals which are chelated and bridged. Magnetic and NMR spectroscopic data are given. The structure of a mixed crystal of the two β-isomers of 3a containing three bridging and three chelating ligands L is reported: orthorhombic space group Pbca, Z = 8, and lattice parameters a = 2186.6(7), b = 2264.0(7), and c = 2386.7(6) pm.


1981 ◽  
Vol 36 (2) ◽  
pp. 161-171 ◽  
Author(s):  
Joachim Fuchs ◽  
Axel Thiele ◽  
Rosemarie Palm

Abstract Dodecatungstosilicates free of crystal water were prepared for the first time by using tetraalkylammonium as cation. The crystal structure of the tetramethylammonium a-dodeeatungstosilicate [N(CH3)4]4SiW12O40 (1) and tetrabutylammonium) β-dodecatungstosilicate, [N(C4H9)4]4SiWi2040 (2) were solved by X-ray diffraction. (1) crystallizes tetragonal in the space group 14̅ with lattice parameters a = 14.642 Å; c= 12.706 Å; (2) orthorhombic, space group P212121 with a = 29.277 Å, b = 22.181 Å and c = 15.381 Å. The differences between the two isomeric heteropolyanions are discussed, especially the distances and angles between the tungsten atoms. Comparison of characteristic differences in the vibrational spectra permits the identification of the isomeric anions.


1985 ◽  
Vol 40 (11) ◽  
pp. 1437-1440 ◽  
Author(s):  
Martin Schabert ◽  
Gerhardt Pausewang

Crystals of Rb2VOF4 have been obtained under hydrothermal conditions. The crystal structure (orthorhombic, space group Pnma, a = 759.9(2) pm. b = 579.1(2) pm, c = 1193.8(4) pm, Z = 4, dc = 3.96 gcm-3, dm = 3.90 gcm-3, R = 0.019 for 655 independent reflections) shows infinite zig-­zag-chains of VOF5-octahedra along the b-axis, linked by cis-bridging F-atoms. Despite of orien­tational disorder, clear evidence for a trans-effect could be established: d(V−O) 165.8(2), d(V−Ftrans brjdge) 221.1(1), d(V−Fcis bridge) 203.6(1), d(V-Fterminal) 185.2(2), 187.8(2), 193.2(2) pm.


1993 ◽  
Vol 57 (387) ◽  
pp. 329-336 ◽  
Author(s):  
M. A. Hoyos ◽  
T. Calderon ◽  
I. Vergara ◽  
J. Garcia-Solé

AbstractX-ray diffraction refinement of the crystal structure of eosphorite has been carried out with reference to the orthorhombic space group Cmca. The structure is similar to that previously described by Hanson (1960), but the standard deviations are improved. Optical absorption and photoluminescence have also been studied for this mineral. Two sharp emission lines, denoted as R1 and R2, superimposed to a broad band (630-750 nm) have been related to the presence of Cr3+ ions. The excitation spectrum of these emissions confirms that the absorption (excitation) bands centred at 431 nm and 585 are related to with 4A2 → 4T1 and 4A2 → 4T2 spin allowed transitions of this ion.


2017 ◽  
Vol 72 (2) ◽  
pp. 159-165 ◽  
Author(s):  
Olaf Reckeweg ◽  
Robert E. Dinnebier ◽  
Armin Schulz ◽  
Björn Blaschkowski ◽  
Christof Schneck ◽  
...  

AbstractLight-yellow microcrystalline samples of Cu[dca] ([dca]−≡[N(CN)2]−≡dicyanamide anion) were obtained by blending an in-situ generated aqueous Cu+ brine with stoichiometric amounts of Na[dca] dissolved in water. The crystal structure of Cu[dca] was solved and refined from powder X-ray diffraction (PXRD) data. Cu[dca] crystallizes in the orthorhombic space group Cmcm (no. 63) with the lattice parameters of a=356.28(3), b=611.10(9) and c=1525.87(10) pm. The crystal structure contains undulated chains of alternating Cu+ and boomerang-shaped [N≡C–N–C≡N]− ions with C2v symmetry running along [100]. It is closely related to that of Ag[dca] crystallizing in space group Pnma (no. 62). The vibrational spectra for Cu[dca] and Cu[dca]2 were recorded exhibiting modes typical for the dicyanamide anion. Comparative DSC/TG measurements were performed for both copper dicyanamides and the cyanide Cu[CN].


2021 ◽  
Vol 18 (38) ◽  
pp. 85-99
Author(s):  
Gerzon E. DELGADO ◽  
Pilar DELGADO-NIÑO ◽  
Eugenio QUINTERO

Background: Quaternary compounds bellowing to the I2-II-IV-VI4 system are of considerable technological interest due to their possible use in the preparation of solar cell and thermoelectric materials devices. In recent years, considerable attention has been focused on the detailed study of quaternary chalcogenide compounds related to the chalcopyrite compounds, particularly AgInSe2, which has emerged as a leading material for the preparation of photovoltaic devices due to their potential applications in solar cell technology. Aims: This work focuses on synthesis, chemical analysis, thermal study, magnetism measurement, and crystal structural characterization of the quaternary semiconductor Ag2FeGeSe4, an essential member of the family I2-II-IV-VI4. Methods: This material was synthesized by the melt and anneal technique. The chemical analysis was carried out by scanning electron microscopy (SEM) and differential thermal analysis (DTA). Magnetic susceptibility () as a function of temperature and magnetization as a function of the magnetic field were also performed, and crystal structure analysis was made employing the Rietveld method with powder X-ray diffraction data. Results and Discussion: The preparation confirms the formation of the quaternary compound with stoichiometric 2:1:1:4 according to the chemical analysis. This quaternary compound melt at 1015 K, and show an antiferromagnetic behavior with Neel temperature TN of 240 K. The Debye temperature (D) estimated for this compound was 194 K. The quaternary chalcogenide compound Ag2FeGeSe4 crystallizes in the orthorhombic space group Pmn21, Z = 4, with unit cell parameters: a = 7.6478(1) Å, b = 6.5071(1) Å, c = 6.4260(1) Å, and V = 319.79(1) Å3, in a wurtzite-stannite arrangement with a Cu2CdGeS4-type structure, which is characterized by a three-dimensional arrangement of slightly distorted AgSe4, FeSe4, and GeSe4 tetrahedra connected by corners. In this structure, each Se atom is coordinated by four cations located at the corners of a slightly distorted tetrahedron, and each cation is tetrahedrally bonded to four anions. Conclusions: The melt and anneal method remains effective for preparing compounds chalcogenides as the quaternary Ag2FeGeSe4, a new member of I2-II-IV-VI4 family of semiconductors, which crystallizes in the non-centrosymmetric space group Pmn21 with diamond-like structure. The crystal structure information of this compound allows explaining their magnetic properties, which in combination with its semiconductor properties make this material a potential aspirant for different applications, mainly in solar cells.


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