Sc2(MoO4)3 and Sc2(WO4)3: Halide Flux Growth of Single Crystals and 45Sc Solid-state NMR

2010 ◽  
Vol 65 (1) ◽  
pp. 13-17 ◽  
Author(s):  
Sarkarainadar Balamurugan ◽  
Ute Ch. Rodewald ◽  
Thomas Harmening ◽  
Leo van Wüllen ◽  
Daniel Mohr ◽  
...  
Keyword(s):  
Single Crystals ◽  
Solid State Nmr ◽  
Nmr Spectra ◽  
Three Dimensional ◽  
Mas Nmr ◽  
Flux Growth ◽  
Quadrupolar Interaction ◽  
X Ray ◽  
Dimensional Network ◽  
Good Agreement

Single crystals of Sc2(TO4)3 with T = Mo and W were synthesized from Sc2O3, MoO3, and WO3 at 1223 K in NaCl / KCl as solvent. Both structures were refined from X-ray diffractometer data: Pbcn, a = 1325.1(1), b = 954.9(1), c = 964.4(1) pm, wR2 = 0.0425, 2097 F2, 79 variables for Sc2(MoO4)3 and a = 1332.9(9), b = 959.4(7), c = 967.9(2) pm, wR2 = 0.0384, 1971 F2, 79 variables for Sc2(WO4)3. The structures consist of a three-dimensional network of corner-sharing ScO6/2 octahedra and two crystallographically independent TO4/2 tetrahedra. 45Sc MAS NMR spectra show sharp single resonances in accordance with the crystallographic data. The quadrupolar interaction parameters obtained from a simulation of the full 45Sc MAS NMR spectra are found to be in good agreement with those obtained from DFT calculations of the electric field gradient

PbO / PbF2 Flux Growth of YScO3 and LaScO3 Single Crystals – Structure and Solid-State NMR Spectroscopy

2010 ◽  
Vol 65 (10) ◽  
pp. 1199-1205 ◽  
Author(s):  
Sarkarainadar Balamurugan ◽  
Ute Ch. Rodewald ◽  
Thomas Harmening ◽  
Leo van Wüllen ◽  
Daniel Mohr ◽  
...  
Keyword(s):  
Rare Earth ◽  
Solid State ◽  
Single Crystals ◽  
Solid State Nmr ◽  
Magic Angle Spinning ◽  
Magic Angle ◽  
Flux Growth ◽  
Quadrupolar Interaction ◽  
Angle Spinning ◽  
Good Agreement

Well-shaped small single crystals of the orthorhombic perovskites YScO3 and LaScO3 were grown from mixtures of the corresponding sesquioxides RE2O3 in PbO/PbF2 fluxes. Both structures were refined from single-crystal diffractometer data: GdFeO3-type, Pnma, a = 570.68(7), b = 789.3(1), c = 542.44(7) pm, wR2 = 0.0363, 448 F2 values for Y0.96ScO2.94, and a = 579.68(9), b = 810.3(2), c = 568.3(1) pm, wR2 = 0.0387, 513 F2 values for La0.94ScO2.91, with 32 variables per refinement. The 4c rare-earth sites of both perovskites show small defects which are charge-compensated by defects on both oxygen sites, leading to the compositions La0.94ScO2.91 and Y0.96ScO2.94 for the investigated crystals. The rare-earth sites have been characterized by 89Y and 45Sc magic-angle spinning (MAS) NMR. The 45Sc quadrupolar interaction parameters extracted from these spectra by simulations are found to be in good agreement with those obtained from DFT calculations of the electric field gradient.

scholarly journals Synthesis, crystal structure and charge-distribution validation of a new alluaudite-type phosphate, Na2.22Mn0.87In1.68(PO4)3

2020 ◽  
Vol 76 (8) ◽  
pp. 1369-1372
Author(s):  
Abdessalem Badri ◽  
Inmaculada Alvarez-Serrano ◽  
María Luisa López ◽  
Mongi Ben Amara
Keyword(s):  
Crystal Structure ◽  
Single Crystals ◽  
Three Dimensional ◽  
Structure Type ◽  
X Ray Diffraction ◽  
Flux Method ◽  
X Ray ◽  
Coordination Numbers ◽  
Dimensional Network ◽  
Anionic Framework

Na2.22Mn0.87In1.68(PO4)3, sodium manganese indium tris(phosphate) (2.22/0.87/1.68), was obtained in the form of single crystals by a flux method and was structurally characterized by single-crystal X-ray diffraction. The compound belongs to the alluaudite structure type (space group C2/c) with general formula X(2)X(1)M(1)M(2)2(PO4)3. The X(2) and X(1) sites are partially occupied by sodium [occupancy 0.7676 (17) and 1/2] while the M(1) and M(2) sites are fully occupied within a mixed distribution of sodium/manganese(II) and manganese(II)/indium, respectively. The three-dimensional anionic framework is built up on the basis of M(2)2O10 dimers that share opposite edges with M(1)O6 octahedra, thus forming infinite chains extending parallel to [10\overline{1}]. The linkage between these chains is ensured by PO4 tetrahedra through common vertices. The three-dimensional network thus constructed delimits two types of hexagonal channels, resulting from the catenation of M(2)2O10 dimers, M(1)O6 octahedra and PO4 tetrahedra through edge- and corner-sharing. The channels are occupied by Na+ cations with coordination numbers of seven and eight.

Aluminiumphosphate mit nichtzentrosymmetrischen Schicht- und Raumnetzstrukturen aus topologisch verwandten Motiven: 2. KAl2(PO4)2(OH)·2H2O/Aluminum Phosphates with Non-Centrosymmetric Layer- and Framework-Structures of Topologically Related Motifs: 2. KAl2(PO4)2(OH)·2H2O

1997 ◽  
Vol 52 (12) ◽  
pp. 1447-1455 ◽  
Author(s):  
Stefan Dick ◽  
Gisbert Großmann ◽  
Gisela Ohms ◽  
Manfred Müller
Keyword(s):  
Nmr Spectra ◽  
Three Dimensional ◽  
Potassium Phosphate ◽  
Mas Nmr ◽  
Water Molecules ◽  
Phosphate Solution ◽  
Orthorhombic Space Group ◽  
X Ray ◽  
Aluminum Phosphates ◽  
Phosphate Groups

Abstract KAl2(PO4)2(OH)·2H2O was obtained by the reaction of gibbsite with a potassium-phosphate solution of pH = 5.5 at 373 K. A single crystal X-ray structure analysis showed that it is an ordered, F-free K-analog of the microporous compound AIPO4-CI2 . Crystal data: orthorhombic space group P212121, a = 920.5(1), b = 970.7(2), c = 982.8(2) pm, Z = 4. The structure consists of dimeric units of AIO6 octahedra and AIO5 trigonal bipyramids, bridged by an OH and two bidentate phosphate groups. The dimers are linked by phosphate to form corrugated layers which are topologically related to the layers in KAl2(PO4)2(OH)·4H2O and minyulite. The layers are connected by Al-O-P and hydrogen bonds to a three dimensional framework structure with K ions in channel-like cavities. A neutron powder scattering experiment with KAl2(PO4)2(OD)·2D2O showed that the bridging OD group and only one D of each water molecule are involved in hydrogen bonding.31P MAS NMR spectra show two isotropic lines at δiso = -6.9 and -18,7 ppm of the intensity ratio 1:1 and confirm the presence of two crystallographically independent P atoms in the unit cell. In the 1H MAS NMR spectra the water molecules and the bridging OH group show signals at 5.9 and 1.1 ppm, respectively.

23Na 2D 3QMAS NMR and 29Si, 27Al MAS NMR investigation of Laponite and synthetic saponites of variable interlayer charge

Clay Minerals ◽  
2003 ◽  
Vol 38 (1) ◽  
pp. 63-69 ◽  
Author(s):  
L. Delevoye ◽  
J . -L. Robert ◽  
J . Grandjean
Keyword(s):  
High Resolution ◽  
Chemical Shift ◽  
Chemical Analysis ◽  
Nmr Spectra ◽  
Mas Nmr ◽  
High Resolution Spectrum ◽  
Isotropic Chemical Shift ◽  
Quadrupolar Interaction ◽  
27Al Mas Nmr ◽  
Good Agreement

Abstract29Si, 27Al MAS NMR is used to characterize Laponite RD and synthetic saponites of variable interlayer charge. The Si/Al ratios are in good agreement with the calculated charge from chemical analysis except for the lowest-charged saponite. In contrast to the 29Si MAS NMR spectra in which resolved signals are detected, the 27Al MAS NMR spectra show one signal whose linewidth increases with the clay charge. The water content of the clay samples was obtained from 1H MAS NMR.The 2D MQMAS NMR technique is required to obtain a high-resolution spectrum of nuclei with strong quadrupolar interaction. This method was applied to the 23Na nucleus of clay counterions and to the 27Al structural nucleus. One well-defined 23Na NMR signal is observed for all the clays studied except the highest-charged saponite. Possible explanations for this different behaviour are discussed. The calculated isotropic chemical shift evolves progressively with the clay charge whereas the deduced quadrupolar interaction does not change significantly. The 27Al 2D 3QMAS technique was not able to resolve more than one signal.

Lead-flux Growth of Eu4Ir8As7 Crystals

2013 ◽  
Vol 68 (11) ◽  
pp. 1185-1190 ◽  
Author(s):  
Ulrike Pfannenschmidt ◽  
Rainer Pöttgen
Keyword(s):  
Single Crystal ◽  
Single Crystals ◽  
Three Dimensional ◽  
Flux Growth ◽  
Tetrahedral Coordination ◽  
X Ray ◽  
Coordination Numbers ◽  
Covalently Bonded ◽  
The Eu

Single crystals of the new arsenide Eu4Ir8As7 were grown from a lead flux. The structure was refined on the basis of single-crystal X-ray diffractometer data: Ca4Ir8P7 type, P21=m, a=1311.3(1), b = 408:4(1), c = 1360:3(1) pm, β = 98:45(1)°, wR2=0.0640, 1985 F2 values, 95 variables. The iridium and arsenic atoms in the Eu4Ir8As7 structure build up a complex three-dimensional, covalently bonded [Ir8As7] network with Ir-As distances ranging from 239 to 260 pm. Each iridium atom has three or four arsenic neighbors in slightly distorted trigonal-planar or tetrahedral coordination. The four crystallographically independent europium atoms fill cavities of coordination numbers 12, 13, and 15 (2) within the [Ir8As7] network. Parts of the Eu4Ir8As7 structure resemble known simpler structure types, and one can describe the Eu4Ir8As7 structure as an intergrowth variant of CaBe2Ge2-, TiNiSi- and AlB2-related slabs.

scholarly journals Single-crystal Structure and Solid-state NMR of Ga2–xScxO3 (x = 0.83)

2011 ◽  
Vol 66 (1) ◽  
pp. 14-20
Author(s):  
Hamdi Ben Yahia ◽  
Leo van Wüllen ◽  
Sarkarainadar Balamurugan ◽  
Ute Ch. Rodewald ◽  
Hellmut Eckert ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Crystal Growth ◽  
Solid State ◽  
Single Crystal ◽  
Solid State Nmr ◽  
Nmr Spectra ◽  
Three Dimensional ◽  
Crystal Data ◽  
X Ray ◽  
Nmr Data

Colorless needles of Ga2−xScxO3 (x = 0.83) were isolated during the crystal growth of La3Ga3Sc2O12 in a K2WO4 flux. The structure was refined from X-ray single-crystal data: β -Ga2O3 type,C2/m, Z = 4, a = 12.716(4), b = 3.1566(6), c = 5.928(5) Å , β = 102.57(3)◦,V = 232.2 Å3, wR2 = 0.0618, 429 F2 values, 32 variables. The structure is based on infinite double chains of edge-sharing Sc/GaO6 octahedra running along the b axis. The GaO4 tetrahedra connect these chains by sharing corners and form a three-dimensional framework. The oxygen atoms form a distorted ccp pattern. The 45Sc NMR spectra confirm the presence of a single scandium site, while 71Ga NMR data clearly prove the partial occupancy of the scandium site by gallium atoms. The nuclear electric quadrupolar parameters of 45Sc and 71Ga are discussed in relation to the crystallographic atomic environments

scholarly journals Synthesis, crystal structure and vibrational spectra of Sr0.5Zr2(AsO4)3

2009 ◽  
Vol 24 (3) ◽  
pp. 200-204 ◽  
Author(s):  
A. Jrifi ◽  
A. El Jazouli ◽  
J. P. Chaminade ◽  
M. Couzi
Keyword(s):  
Rietveld Method ◽  
Group Analysis ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
Bending Vibrations ◽  
Space Group ◽  
X Ray ◽  
Cell Parameters ◽  
Dimensional Network ◽  
Good Agreement

Sr0.5Zr2(AsO4)3 arsenate was prepared and structurally characterized by powder X-ray diffraction and by Raman and infrared spectroscopies. Its structure, which belongs to the Nasicon-type family, was refined by the Rietveld method in the R-3 space group, from X-ray powder diffraction data. The hexagonal unit-cell parameters were determined to be ah=8.965(2) Å, ch=23.955(6) Å, V=1667.43(6) Å3, and Z=6. The structure is formed by an ionic three-dimensional network of AsO4 tetrahedra and ZrO6 octahedra linked by corners with Sr2+ ions occupying half of the M1 sites in an ordered manner. Raman and infrared spectra were recorded and assignments of the stretching and bending vibrations of the AsO43− tetrahedra were made. The number of the peaks observed is in good agreement with that predicted by the factor-group analysis of the R-3 space group.

Na3GaF6 – A crystal chemical and solid state NMR spectroscopic study

2018 ◽  
Vol 233 (7) ◽  
pp. 479-487 ◽  
Author(s):  
David Böhnisch ◽  
Stefan Seidel ◽  
Christopher Benndorf ◽  
Thomas Jansen ◽  
Lena Funke ◽  
...  
Keyword(s):  
Solid State Nmr ◽  
Nmr Spectra ◽  
Chemical Exchange ◽  
Center Of Mass ◽  
Mas Nmr ◽  
X Ray Diffraction ◽  
X Ray ◽  
Exchange Effects ◽  
Distorted Octahedral ◽  
Motional Narrowing

Abstract Na3GaF6 and Na3GaF6:Mn4+ samples were obtained from NaNO3 and Ga(NO3)3·9H2O in hydrofluoric acid using K2MnF6 or NaMnO4 as manganese sources. The structure of Na3GaF6 was studied by single crystal X-ray diffraction at 90, 293, 440 and 500 K, confirming the monoclinic cryolite type structure, space group P21/c. The gallium atoms show slightly distorted octahedral coordination by fluorine atoms, similar to the Na1 atoms. Coordination number 8 is observed for Na2. Both sodium sites are clearly distinguished by 23Na MAS-NMR spectroscopy. Above 400 K the spectra reveal distinct chemical exchange effects, signifying sodium ion hopping between these two sites. At the same time static 19F NMR spectra indicate pronounced motional narrowing effects in this temperature region. The nearly invariant 69Ga MAS-NMR spectra suggest that any reorientational motion involving the GaF63− ions (if present) occurs with preservation of the center of mass of these octahedra.

New Intermetallic Zinc Compounds with Ordering Variants of the KHg2 and LT-SrZn5 Type

2014 ◽  
Vol 69 (6) ◽  
pp. 674-680 ◽  
Author(s):  
Christian Schwickert ◽  
Rainer Pöttgen
Keyword(s):  
Transition Metal ◽  
Single Crystal ◽  
Single Crystals ◽  
Coordination Number ◽  
Induction Furnace ◽  
Three Dimensional ◽  
Zinc Compounds ◽  
Space Group ◽  
X Ray ◽  
Dimensional Network

The intermetallic zinc compounds CaAuZn, SrPdZn, SrPtZn, SrAuZn, BaPd1.57 Zn3.43, and BaAu1.41Zn3.59 were synthesized from the elements in sealed niobium ampoules in an induction furnace. The equiatomic compounds crystallize with the orthorhombic TiNiSi-type structure, space group Pnma. Single-crystal X-ray data exhibited small degrees of Au=Zn mixing within the three-dimensional [AuZn] networks and resulted in the compositions CaAu1.02Zn0.98 and SrAu1.03Zn0.97 for two investigated single crystals. BaPd1.57 Zn3.43 and BaAu1.41 Zn3.59 adopt partially ordered versions of the LT-SrZn5 type, space group Pnma. Both structures were refined on the basis of X-ray single-crystal diffractometer data. a=1331.13(6), b=531.45(3), c=682.20(4) pm, wR=0.0245, 1138 F2 values, 39 variables for BaPd1.57Zn3.43 and a=1344.35(2), b=537.47(2), c=691.22(4) pm, wR=0.0441, 931 F2 values, 37 refined variables for BaAu1.41Zn3.59. The transition metal and zinc atoms form a complex three-dimensional network of (T, Zn)4 tetrahedra which are condensed via common corners and T/Zn-T/Zn bonds. Large cavities within these networks are filled by the barium atoms which have coordination number 19, i. e. Ba@(T, Zn)17Ba2.

Three-dimensional visualization of the inner structure of single crystals by step-scanning white X-ray section topography

2006 ◽  
Vol 13 (6) ◽  
pp. 484-488 ◽  
Author(s):  
Taihei Mukaide ◽  
Kentaro Kajiwara ◽  
Takashi Noma ◽  
Kazuhiro Takada
Keyword(s):  
Single Crystals ◽  
Three Dimensional ◽  
X Ray ◽  
Section Topography
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