Relative humidity as a driver of structural change in three new ferric-sulfate-tellurite hydrates: New minerals tamboite and metatamboite, and a lower-hydrate derivative, possibly involving direct uptake of atmospheric {H2O}4 clusters

2019 ◽  
Vol 57 (5) ◽  
pp. 605-635
Author(s):  
Mark A. Cooper ◽  
Frank C. Hawthorne ◽  
Yassir A. Abdu ◽  
Phillip C. Walford ◽  
Malcolm E. Back
Keyword(s):  
Hydrogen Bonds ◽  
Room Temperature ◽  
Direct Methods ◽  
Structural Formula ◽  
Ferric Sulfate ◽  
Index Of Refraction ◽  
Monoclinic Space Group ◽  
Calculated Density ◽  
Space Group ◽  
Cell Parameters

Abstract Tamboite (x = 3; y = 2) and metatamboite (x = 3; y = 0), Fe3+3(SO4)(Te4+O3)3(Te4+O(OH)2)(OH)(H2O)x{H2O}y, are new tellurite minerals from the Tambo mine, Coquimbo Province, Chile. The two minerals transform to each other reversibly with changes in ambient humidity. They occur as pale-yellow clusters of radiating fiber bundles on the surface of a compact aggregate of silicified tuff. Tamboite and metatamboite are optically biaxial, and their calculated mean index of refraction is greater than 1.80. The calculated densities are 3.648 g/cm3 for tamboite and 4.053 g/cm3 for metatamboite. Tamboite and metatamboite are monoclinic, space group P21/c, Z = 4. Unit-cell parameters for tamboite are a 16.879(10), b 7.310(4), c 16.666(9) Å, β 108.857(11)°, V 1958(3) Å3; for metatamboite they are a 14.395(5), b 7.296(4), c 16.411(6) Å, β 98.909(10)°, V 1703(2) Å3. Chemical analysis by electron microprobe gave the empirical cations [calculated on the basis of 22 anions pfu with OH = 3 and H2O = 5 pfu (tamboite) or H2O = 3 pfu (metatamboite)] as (Fe3+3.10Al0.15)Σ3.25(S6+0.75Se6+0.05)Σ0.80Te4+4.11. The seven strongest lines in the X-ray powder diffraction patterns [listed as d (Å), I, (hkl)] are as follows: metatamboite: 14.221, 100, (100); 2.874, 13, ; 3.140, 12, (221); 3.423, 11, ; 3.400, 11, (312); 3.012, 11, ; 4.054, 9, ; tamboite: 16.068, 100, (100); 3.425, 9, ; 2.999, 8, ; 3.171, 6, (221); 2.853, 5, ; 4.153, 4, ; 3.943, 4, (004). The crystal structures were solved by direct methods and refined to R1 indices of 4.3 and 3.0%. The structures consist of virtually identical ferric-sulfate-tellurite-hydrate slabs that are constructed from strands of ferric-sulfate-hydrate polyhedra linked by Te4+ cations. In metatamboite, the slabs are linked directly by hydrogen bonds whereas in tamboite, interslab linkage occurs by hydrogen bonds through interstitial {H2O}4 clusters known as Ci cyclic tetramers. Exposure of a crystal to a desiccant at room temperature resulted in a third variant (x = 2; y = 0) with the structural formula Fe3+2Fe2+(SO3(OH))(Te4+O3)3(Te4+O(OH)2)(OH)(H2O)x, space group P21/c, Z = 4, a 16.879(10), b 7.310(4), c 16.666(9) Å, β 108.857(11)°, V 1958(3) Å3, calculated density 4.176 g/cm3. This lower-hydrate variant has less cation-bonded (H2O) than metatamboite and tamboite, and the ferric-sulfate-tellurite-hydrate slabs are polymerized to form a framework structure. Attempts to transform the lower hydrate back to tamboite or metatamboite at room temperature and elevated humidity were unsuccessful.

Preparation and crystal structure of SbV1.50InIII0.50(PO4)3 and (SbV0.50InIII0.50)P2O7

2008 ◽  
Vol 23 (3) ◽  
pp. 232-240
Author(s):  
Abderrahim Aatiq ◽  
Rachid Bakri ◽  
Aaron Richard Sakulich
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Room Temperature ◽  
Rietveld Method ◽  
Monoclinic Space Group ◽  
Unit Cell Parameters ◽  
Orthorhombic System ◽  
Space Group ◽  
X Ray ◽  
Cell Parameters

Synthesis and structure of two phosphates belonging to the ternary Sb2O5–In2O3–P2O5 system are realized. Structures of SbV1.50InIII0.50(PO4)3 and (SbV0.50InIII0.50)P2O7 phases, obtained by solid state reaction in air at 950 °C, were determined at room temperature from X-ray powder diffraction using the Rietveld method. SbV1.50InIII0.50(PO4)3 have a monoclinic (space group P21/n) distortion of the Sc2(W O4)3-type framework. Its structure is constituted by corner-shared SbO6 or InO6 octahedra and PO4 tetrahedra. Monoclinic unit cell parameters are a=11.801(2) Å, b=8.623(1) Å, c=8.372(1) Å, and β=90.93(1)°. (Sb0.50In0.50)P2O7 is isotypic with (Sb0.50Fe0.50)P2O7 and crystallizes in orthorhombic system (space group Pna21) with a=7.9389(1) Å, b=16.0664(2) Å, and c=7.9777(1) Å. Its structure is built up from corner-shared SbO6 or InO6 octahedra and P2O7 groups (two group-types). Each P2O7 group shares its six vertices with three SbO6 and three InO6 octahedra, and each octahedron is connected to six P2O7 groups.

Synthese und Kristallstrukturen von N-[ω-(Dimethylammonio)alkyl]- N´,N´,N´´,N´´-tetramethylguanidinium-chlorid-tetraphenylboraten / Synthesis and Crystal Structures of N-[ω-(Dimethylammonio)alkyl]-N´,N´,N´´,N´´- tetramethylguanidinium Chloride Tetraphenylborates

2010 ◽  
Vol 65 (7) ◽  
pp. 907-916 ◽  
Author(s):  
Ioannis Tiritiris ◽  
Falk Lissner ◽  
Thomas Schleid ◽  
Willi Kantlehner
Keyword(s):  
Crystal Structure ◽  
Low Temperature ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Room Temperature ◽  
Chloride Ions ◽  
Monoclinic Space Group ◽  
Temperature Structure ◽  
Space Group ◽  
Temperature Modification

Dicationic N,N´,N´,N´´,N´´-pentasubstituted guanidinium dichlorides 4a, b are obtained from the chloroformamidinium salt 2 and diamines 3a, b. N-[2-(Dimethylammonio)ethyl]-N´,N´,N´´,N´´-tetramethylguanidinium chloride tetraphenylborate (5a) and N-[3-(dimethylammonio)propyl]-N´,N´,N´´,N´´-tetramethylguanidinium chloride tetraphenylborate (5b) were synthesized from 4a, b by anion metathesis with one equivalent of sodium tetraphenylborate. The thermal properties of the salts 5a, b were studied by means of DSC methods, and their crystal structures were determined by single-crystal X-ray diffraction analysis. For 5a a solid-solid phase transition is observed at −156 ◦C to a low-temperature structure. The room-temperature modification (α-5a) crystallizes in the centrosymmetric orthorhombic space group Pbca (a = 13.1844(4), b = 13.8007(4), c = 34.7537(11) A° ).The guanidinium ions are interconnected via chloride ions through bridging N-H· · ·Cl hydrogen bonds, providing isolated units. The tetraphenylborate ions show some dynamic disordering in the crystal structure. The low-temperature modification (β -5a) also crystallizes orthorhombically, but in the non-centrosymmetric space group Pna21 (a = 13.1099(4), b = 69.1810(11), c = 13.5847(5) A° ) and consists of four crystallographically independent cations and anions in the unit cell. Compared with the room-temperature structure, a similar N-H· · ·Cl hydrogen bond pattern is observed in the β -phase, but the tetraphenylborate ions are now completely ordered. 5b crystallizes in the monoclinic space group P21/c (a = 10.8010(3), b = 14.1502(5), c = 20.9867(9) A° , β = 94.322(1)◦). In the crystal structure the guanidinium ions are linked via chloride ions through N-H· · ·Cl hydrogen bonds, but in contrast to 5a two infinite strands are formed along the a axis with the tetraphenylborate ions interspersed between them for charge compensation.

scholarly journals Synthese und Struktur von Zn(HSO4)2(H2SO4)2 und Cd(HSO4)2 / Synthesis and Structure of Zn(HSO4)2(H2SO4)2 und Cd(HSO4)2

1996 ◽  
Vol 51 (1) ◽  
pp. 14-18 ◽  
Author(s):  
E. Kemnitz ◽  
C. Werner ◽  
A. Stiewe ◽  
H. Worzala ◽  
S. Trojanov
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Binary Systems ◽  
Monoclinic Space Group ◽  
Space Group ◽  
Cell Parameters ◽  
Medium Strength ◽  
Zinc Compound

Abstract From the binary systems M2SO4/H2SO4 (M = Zn, Cd), two new hydrogen sulfates, (Zn(HSO4)2(H2SO4)2 and Cd(HSO4)2, have been synthesized and structurally characterized. Both compounds crystallize in the monoclinic space group P21/c with cell parameters a = 5.047(2), b = 15.430(4), c = 7.958(3) Å and β = 104.16(4)° (Z= 2) for Zn(HSO4)2(H2SO4)2 and a = 5.339(1), b = 13.351(3), c = 8.508(2) Å and β = 92.22(3)° (Z = 4) for Cd(HSO4)2. In the zinc compound there are slightly distorted centrosymmetric ZnO6 octahedra with Zn-O distances of 2.05-2.13 A which are sharing corners with SO4 tetrahedra. HSO4 and H2SO4 tetrahedra are linked via hydrogen bonds to form layers perpendicular to the c-axis. In the crystal structure of Cd(HSO4)2 there exist two crystallographically different HSO4 tetrahedra. The CdO6 octahedra with Cd-O distances between 2.24 and 2.31 A are strongly angle-distorted. Besides hydrogen bonds of medium strength (do···o = 2.66 Å) there are also much more weaker ones (do···o = 3.04 Å). Considering these latter ones zigzag chains in z-direction can be recognized. The relatively low stability of Cd(HSO4)2 in comparison with other metal-II-hydrogen sulfates is discussed with respect to its structural pecularities.

scholarly journals Tetra-n-butylammoniumdicyanoaurat(I), (n-C4H9)4NAu(CN)2 / Tetra-n-butylammonium Dicyanoaurate(I), (n-C4H9)4NAu(CN)2

1990 ◽  
Vol 45 (8) ◽  
pp. 1118-1122 ◽  
Author(s):  
R. J. Schubert ◽  
K.-J. Range
Keyword(s):  
Least Squares ◽  
Single Crystals ◽  
Direct Methods ◽  
Monoclinic Space Group ◽  
Calculated Density ◽  
Space Group ◽  
Computer Controlled ◽  
R Factors ◽  
Measured Density

Single crystals of (n-C4H9)4NAu(CN)2 were obtained by crystallization using the temperature decreasing method in a newly developed computer-controlled apparatus. The colourless crystals are monoclinic, space group A2/n, with a = 20.216(2) Å, b = 13.130(1) Å, c = 9.328(1) Å, and β = 109.69(1)°. The measured density is 1.45 g/cm3, which agrees with the calculated density of 1.40 g/cm3 for Ζ = 4. The structure was solved by Direct Methods using 674 independent reflections and refined by least-squares procedures to conventional and weighted R factors of 0.068 and 0.058, respectively. The nearly linear [Au(CN)2]--anions form pseudohexagonal layers, in which they are arranged parallel to each other. The shortest Au—Au distance is 8.05 A. The stacking of the layers produces pseudo-trigonal channels, occupied by the cations. The tetra-n-butylammonium cation has four ordered trans chains with idealized D2d symmetry (4̄2 m).

Die Kristallstrukturen von 1,4-Dimethylpiperazinium-tetrabromocobaltat(II) und -zinkat(II), (dmpipzH2) [MIIBr4] (M = Co, Zn) / The Crystal Structures of 1,4-Dimethylpiperazinium Tetrabromocobaltate(II) and -Zincate(II), (dmpipzH2) [MIIBr4] (M = Co, Zn)

1996 ◽  
Vol 51 (1) ◽  
pp. 9-13 ◽  
Author(s):  
Michael Feist ◽  
Sergej Trojanov ◽  
Erhard Kemnitz
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Room Temperature ◽  
Mirror Plane ◽  
Monoclinic Space Group ◽  
Chair Form ◽  
Space Group

Abstract The compounds (dmpipzH2)[MIIBr4] (M = Co, Zn) crystallize at room temperature from equimolar solutions of 1,4-dimethylpiperazine and MBr2 · n H2O in 3M HBr. (dmpipzH2)[CoBr4] is isotypic with the homologous chlorometalates of Co and Zn and crystallizes in the mono­ clinic space group P21/m with a = 6.424(3), b = 14.588(6), c = 7.102(6) Å, β = 90.87(6)°, Z = 2. (dmpipzH2)[ZnBr4], however, crystallizes in the monoclinic space group P21/c with a = 7,605(5), b = 13,760(9), c = 13,286(7) Å, β = 93,03(6)°, Z = 4. Both structures contain centrosymmetric cations (dmpipzH2)2+ in the chair form and slightly distorted tetrahedra [MBr4]2- with a mirror plane in the case of M = Co. Several distances N···Br in both structures are interpreted in terms of N-H···Br hydrogen bonds which are favoured by the packing in the case of M = Zn.

Die Kristallstruktur des Spirophosphorans (HOCH2 · C6H3 · CH2O)2PPh.

1976 ◽  
Vol 31 (7) ◽  
pp. 948-952 ◽  
Author(s):  
D. Hellwinkel ◽  
W. Krapp ◽  
D. Schomburg ◽  
W. S. Sheldrick
Keyword(s):  
Hydrogen Bonds ◽  
Dihedral Angle ◽  
Equatorial Plane ◽  
Title Compound ◽  
Direct Methods ◽  
Monoclinic Space Group ◽  
Phenyl Substituent ◽  
Space Group ◽  
Trigonal Bipyramidal Geometry ◽  
Trigonal Bipyramidal

The title compound crystallises in the monoclinic space group, Cc, Z = 4, with a = 12.370(1), b = 19.447(1), c = 7.786(1) Å, β = 90.82(1)°.The structure was solved by direct methods and refined to R = 0.070 for 2163 independent reflections.Trigonal-bipyramidal geometry is observed at phosphorus with the ring oxygens occupying the axial sites. The plane of the phenyl substituent makes a dihedral angle of 20.2° with the equatorial plane. The molecules are linked into infinite chains in the [010] plane through (CH2)O ••• H—O(CH2) hydrogen bonds of length 2.77 A.

scholarly journals Crystal structures ofN-(pyridin-2-ylmethyl)pyrazine-2-carboxamide (monoclinic polymorph) andN-(pyridin-4-ylmethyl)pyrazine-2-carboxamide

2014 ◽  
Vol 70 (7) ◽  
pp. 18-22 ◽  
Author(s):  
Dilovan S. Cati ◽  
Helen Stoeckli-Evans
Keyword(s):  
Hydrogen Bonds ◽  
Room Temperature ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Monoclinic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
Three Dimensional Structure ◽  
Π Interactions ◽  
Centroid Distance

The title compounds, C11H10N4O (HL1) and C11H10N4O (HL2), are pyridine 2-ylmethyl and 4-ylmethyl derivatives, respectively, of pyrazine-2-carboxamide. HL1 was measured at 153 K and crystallized in the monoclinic space groupP21/cwithZ= 4. There has been a report of the same structure measured at room temperature but assumed to crystallize in the triclinic space groupP-1 withZ= 4 [Sasanet al.(2008).Monatsh. Chem.139, 773–780]. In HL1, the pyridine ring is inclined to the pyrazine ring by 61.34 (6)°, while in HL2 this dihedral angle is 84.33 (12)°. In both molecules, there is a short N—H...N interaction involving the pyrazine carboxamide unit. In the crystal of HL1, molecules are linked by N—H...N hydrogen bonds, forming inversion dimers with anR22(10) ring motif. The dimers are linkedviabifurcated-acceptor C—H...O hydrogen bonds, forming sheets lying parallel to (102). The sheets are linkedviaC—H...N hydrogen bonds, forming a three-dimensional structure. In the crystal of HL2, molecules are linked by N—H...N and C—H...N hydrogen bonds to form chains propagating along [010]. The chains are linkedviaC—H...O hydrogen bonds, forming sheets lying parallel to (100). Within the sheets there are π–π interactions involving neighbouring pyrazine rings [inter-centroid distance = 3.711 (15) Å]. Adjacent sheets are linkedviaparallel slipped π–π interactions involving inversion-related pyridine rings [inter-centroid distance = 3.6395 (17) Å], forming a three-dimensional structure.

Description and crystal structure of bobkingite, a new mineral from New Cliffe Hill Quarry, Stanton-under-Bardon, Leicestershire, UK

2002 ◽  
Vol 66 (2) ◽  
pp. 301-311 ◽  
Author(s):  
F. C. Hawthorne ◽  
M. A. Cooper ◽  
J. D. Grice ◽  
A. C. Roberts ◽  
N. Hubbard
Keyword(s):  
Crystal Structure ◽  
Direct Methods ◽  
Crystal Structure Analysis ◽  
New Mineral ◽  
Monoclinic Space Group ◽  
X Rays ◽  
Calculated Density ◽  
International Mineralogical Association ◽  
Cell Parameters ◽  
Conchoidal Fracture

AbstractBobkingite, ideally is a new mineral from the New Cliffe Hill Quarry, Stantonunder-Bardon, Leicestershire, England. It occurs as very thin (⩽5 µm) transparent plates up to 0.2 mm across, perched on a compact fibrous crust of malachite and crystalline azurite attached to massive cuprite. Crystals are tabular on {001} with dominant {001} and minor {100} and {110}. Bobkingite is a soft pale blue colour with a pale-blue streak, vitreous lustre and no observable fluorescence under ultraviolet light. It has perfect {001} and fair {100} cleavages, no observable parting, conchoidal fracture, and is brittle. Its Mohs' hardness is 3 and the calculated density is 3.254 g/cm3. Bobkingite is biaxial negative with α = 1.724(2), β = 1.745(2), γ = 1.750(2), 2Vγmeas = 33(6)°, 2Vcalc = 52°, pleochroism distinct, X = very pale blue, Z = pale greenish blue, X^a = 22° (in β obtuse), Y = c, Z = b. Bobkingite is monoclinic, space group C2/m, unit-cell parameters (refined from powder data): a = 10.301(8), b = 6.758(3), c = 8.835(7)Å, β = 111.53(6)°, V = 572.1(7)Å3, Z = 2. The seven strongest lines in the X-ray powder-diffraction pattern are [d (Å), I, (hkl)]: 8.199, 100, (001); 5.502, 100, (110); 5.029, 40, (2̄01); 2.883, 80, (310); 2.693, 40, (1̄13); 2.263, 40, (113), (4̄03); 2.188, 50, (2̄23). Chemical analysis by electron microprobe and crystal-structure solution and refinement gave CuO 70.46, Cl 12.71, H2O 19.19, O≡Cl –2.87, sum 99.49 wt.%, where the amount of H2O was determined by crystal-structure analysis. The resulting empirical formula on the basis of 12 anions (including 8 (OH) and 2H2O) is Cu4.99Cl2.02O10H12. The crystal structure was solved by direct methods and refined to an R index of 2.6% for 638 observed reflections measured with X-rays on a single crystal. Three distinct (Cuϕ6) (ϕ = unspecified anion) octahedra share edges to form a framework that is related to the structures of paratacamite and the Cu2(OH)3Cl polymorphs, atacamite and clinoatacamite. The mineral is named for Robert King, formerly of the Department of Geology, Leicester University, prominent mineral collector and founding member of the Russell Society. The mineral and its name have been approved by the Commission on New Minerals and Mineral Names of the International Mineralogical Association.

Two lithium tricyanomethanide compounds: syntheses and single-crystal structure determination of LiK[C(CN)3]2 and Li[C(CN)3]·½ (H3C)2CO

2015 ◽  
Vol 70 (3) ◽  
pp. 191-196 ◽  
Author(s):  
Olaf Reckeweg ◽  
Francis J. DiSalvo
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Single Crystals ◽  
Structure Determination ◽  
Monoclinic Space Group ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
Cell Parameters ◽  
New Compounds

AbstractThe new compounds LiK[C(CN)3]2 and Li[C(CN)3]·½ (H3C)2CO were synthesized and their crystal structures were determined. Li[C(CN)3]·½ (H3C)2CO crystallizes in the orthorhombic space group Ima2 (no. 46) with the cell parameters a=794.97(14), b=1165.1(2) and c=1485.4(3) pm, while LiK[C(CN)3]2 adopts the monoclinic space group P21/c (no. 14) with the cell parameters a=1265.7(2), b=1068.0(2) and c=778.36(12) pm and the angle β=95.775(7)°. Single crystals of K[C(CN)3] were also acquired, and the crystal structure was refined more precisely than before corroborating earlier results.

Structure of 3α,4α:5β,6β-Diepoxyandrostan-17-one

1983 ◽  
Vol 36 (11) ◽  
pp. 2333 ◽  
Author(s):  
B Kamenar ◽  
RA Pauptit ◽  
JM Waters
Keyword(s):  
Crystal Structure ◽  
Title Compound ◽  
Direct Methods ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray

The X-ray crystal structure of 3α,4α:5β,6β-diepoxyandrostan-17-one has been determined. Crystals of the title compound (C19H26O3)are monoclinic, space group P21, with a 9.208(2), b 9.620(4), c 9.312(3) �, β 99.14(2)�, V 814.5 Ǻ3 and Z 2. The structure was solved by direct methods and refined to R 0.039 for 887 observed reflexions. The 3α,4α:5β,6β configuration of the epoxide rings confirms the assignment based on proton n.m.r. studies.

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