Metal-thiolate chemistry: The structure of the first adamantane-type cation, [(μ-SPh)6(HgPPh3)4]2+

1993 ◽  
Vol 71 (12) ◽  
pp. 2043-2050 ◽  
Author(s):  
JAGADESE J. Vittal ◽  
Philip A.W. Dean ◽  
Nicholas C. Payne
Keyword(s):  
Molecular Structures ◽  
X Ray Diffraction ◽  
Torsion Angles ◽  
Triclinic Space Group ◽  
X Ray ◽  
Perchlorate Ion ◽  
Cell Dimensions ◽  
Minimum Number ◽  
Counter Data ◽  
The Ideal

The cosmpound [(μ-SC6H5)6{HgP(C6H5)3}4][ClO4]2 crystallizes in the triclinic space group [Formula: see text] as a bis(chloroform) solvate with cell dimensions a = 15.799(4), b = 26.813(5), c = 15.040(5) Å, α = 96.35(2), β = 114.52(2), γ = 100.45(2)° and two formula units per cell. The crystal and molecular structures of this salt were solved by X-ray diffraction techniques using 9898 counter data with I > 2.5σ(I) recorded at −50(2) °C. Refinement of 477 variables by full-matrix least-squares converged at an agreement factor R = 0.046. The cation has adamantane-type stereochemistry with a (μ-SPh)6Hg4 cage and four terminal triphenylphosphine ligands. The S—Cα vectors of the bridging SC6H5 groups adopt the configuration [aae, aae, aee, aee] with the minimum number of two 1,3-axial, axial substituent interactions. There is a significant flattening of the two Hg3S3 rings with two axial substituents into an envelope conformation; each has two torsion angles less than 25°, instead of the ideal values of ±60° in adamantane. One perchlorate ion is doubly solvated by chloroform molecules in an unusual, weakly hydrogen bonded, [ClO4•2HCCl3]− complex.

Metal-selenolate chemistry: stereochemistry of adamantane-type clusters of formula [(μ-SePh)6(MSePh)4]2− (M = Zn and Cd)

1992 ◽  
Vol 70 (3) ◽  
pp. 792-801 ◽  
Author(s):  
Jagadese J. Vittal ◽  
Philip A. W. Dean ◽  
Nicholas C. Payne
Keyword(s):  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Bridging Ligands ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Space Groups ◽  
X Ray Crystallography ◽  
Cell Dimensions ◽  
Minimum Number

The structures of three tetramethylammonium salts containing anions of formula [(μ-SePh)6(MSePh)4]2− (M = Zn and Cd) were determined by single crystal X-ray diffraction techniques. The Zn salt crystallizes in different space groups depending upon the solvent combination used in the synthesis. Thus crystals of (Me4N)2[Zn4(SePh)10], 1, grown from a mixture of methanol, acetonitrile, and acetone are triclinic, space group [Formula: see text] with cell dimensions a = 13.214(2), b = 23.859(2), c = 13.072(1) Å, α = 91.134(8), β = 113.350(8), γ = 79.865(9)°, and Z = 2. In the absence of acetone, a solvated crystal (Me4N)2[Zn4(SePh)10]•CH3CN, 2, is formed, which belongs to the monoclinic space group P21/n with a = 14.248(1), b = 39.722(2), c = 13.408(1) Å, β = 97.132(5)°, and Z = 4. The Cd salt (Me4N)2[Cd4(SePh)10], 3, crystallizes in the monoclinic space group P21/c, with a = 20.830(2), b = 14.282(1), c = 25.872(1) Å, β = 99.626(6)°, and Z = 4. These three salts are the first examples of homoleptic, tetranuclear selenolatometal(II) anions with (μ-Se)6M4 cages of adamantane-type stereochemistry. In each case the phenyl substituents of the bridging ligands adopt the configuration [aae, aae, aee, aee], which has the minimum number of two 1,3-axial–axial non-bonding substituent interactions. Keywords: selenolate complexes, synthesis, X-ray crystallography, isomerism, adamantane stereochemistry.

Kristall- und Molekülstrukturen von zwei trans-1.2.4.5-Tetraza-3.6-diphospha-cyclohexan-3.6-disulfiden / Crystal and Molecular Structures of Two trans- 1,2,4,5-Tetraza-3,6-diphospha-cyclohexane-3,6-disulfides

1984 ◽  
Vol 39 (3) ◽  
pp. 269-274 ◽  
Author(s):  
Franz Dirschl ◽  
Heinrich Nöth
Keyword(s):  
Chair Conformation ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Monoclinic System ◽  
Torsion Angles ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Twist Conformation

The crystal and molecular structures of two trans-1,2,4,5-tetraza-diphospha-3,6-cyclohexane- 3,6-disulfides, 2 and 3, have been determined by X-ray diffraction methods. The 3,6-diphenyl- 1,2,4,5-tetramethyl-derivative 2 crystallizes in the monoclinic system, space group C He. Its P2N 4 heterocycle adopts a twist conformation. In contrast, the hexamethyl derivative 3 is triclinic, space group P1̅, and its ring shows chair conformation. Torsion angles in these two compounds and similar ones reveal less interaction between lone pairs of electrons on adjacent N-atoms in the chair conformation but stronger interaction of those bound to phosphorus. It is suggested that the latter interaction is responsible for the larger N -P -N bond angle (107°) as compared to the smaller one (101°) in the P2N4 rings present in twist conformation.

Gold-acetylide chemistry: the structure of the complex [Au2(μ-dppm) (C≡C—CMe3)2]

1995 ◽  
Vol 73 (1) ◽  
pp. 6-11 ◽  
Author(s):  
Nicholas C. Payne ◽  
Ravindranath Ramachandran ◽  
Richard J. Puddephatt
Keyword(s):  
Spectroscopic Properties ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
X Ray ◽  
X Ray Crystallography ◽  
Crystal And Molecular Structures ◽  
Cell Dimensions ◽  
Counter Data ◽  
Gold Acetylide

The complex [Au2(μ-dppm)(C≡Ct-Bu)2], 1, dppm=Ph2PCH2PPh2, is formed by reaction of [AuC≡Ct-Bu] with dppm. Compound 1, as an acetone solvate, crystallizes in the monoclinic space group P21/c with cell dimensions a = 14.047(1), b = 16.124(1), c = 17.140(3) Å, β = 103.17(2)° and four formula units per cell. The crystal and molecular structures of this salt were solved by X-ray diffraction techniques using 2634 counter data with I > 2σ(I). Refinement of 278 variables by full-matrix least squares converged at an agreement factor R = 0.023. Thermolysis of complex 1 in refluxing toluene led to intermolecular elimination of t-BuC≡CH, by combination of a t-BuC≡C ligand of one molecule of 1 with a proton from the CH2P2 group of a second, and formation of the stable tetragold(I) complex [Au4(μ3-Ph2PCHPPh2)(μ-dppm)(C≡Ct-Bu)3], 2, which was characterized by its spectroscopic properties. Keywords: acetylide complexes, gold complexes, X-ray crystallography, nmr spectroscopy, bis(diphenylphosphino)methane.

Synthesis, Crystal Structure and Magnetic Properties of a Copper(II) p-Formylbenzoate Complex

2012 ◽  
Vol 67 (11) ◽  
pp. 1185-1190 ◽  
Author(s):  
Jin-Li Qi ◽  
Wei Xu ◽  
Yue-Qing Zheng
Keyword(s):  
Room Temperature ◽  
Magnetic Measurements ◽  
X Ray Diffraction ◽  
Complex Molecules ◽  
Triclinic Space Group ◽  
X Ray ◽  
Cell Dimensions ◽  
Ferromagnetic Interactions ◽  
Aqueous Conditions ◽  
Discrete Complex

A new Cu(II) complex was prepared at room temperature from the reaction of p-formylbenzoic acid, phenanthroline, CuCl2⋅2H2O, and NaOH under ethanolic aqueous conditions. The complex has been characterized by X-ray diffraction, IR spectroscopy, TG-DTA analyses, and magnetic measurements. Single-crystal X-ray diffraction analysis indicated that the complex crystallizes in the triclinic space group P1̄ with the cell dimensions a=7.875(2), b=10.724(2), c=15.317(3) Å , α =102.65(3), β =93.71(3), γ =107:64(3)°. The Cu atoms are in the environment of distorted CuN2O3 tetragonal pyramids. These discrete complex molecules are packed through intermolecular π...π-stacking interactions and C-H...O hydrogen bonds forming a supramolecular structure. The title complex obeys the Curie-Weiss law with a Curie constant C=0:53 cm3 K mol-1 and a Weiss constant θ = -0:27 K. The shape of the xmT curve is characteristic of weak ferromagnetic interactions between the Cu(II) centers from 300 to 7 K, while there are weak antiferromagnetic interactions below 7 K.

scholarly journals Fogoite-(Y), Na3Ca2Y2Ti(Si2O7)2OF3, a Group I TS-block mineral from the Lagoa do Fogo, the Fogo volcano, São Miguel Island, the Azores: Description and crystal structure

2017 ◽  
Vol 81 (2) ◽  
pp. 369-381 ◽  
Author(s):  
F. Cámara ◽  
E. Sokolova ◽  
Y. A. Abdu ◽  
F. C. Hawthorne ◽  
T. Charrier ◽  
...  
Keyword(s):  
Crystal Structure ◽  
New Mineral ◽  
X Ray Diffraction ◽  
Titanium Silicate ◽  
Triclinic Space Group ◽  
X Ray ◽  
Group I ◽  
Mohs Hardness ◽  
Fogo Volcano ◽  
The Ideal

AbstractFogoite-(Y), Na3Ca2Y2Ti(Si2O7)2OF3, is a new mineral from the Lagoa do Fogo, São Miguel Island, the Azores. It occurs in cavities as highly elongated (on [001]) prisms, up to 2000 μm long and 50 μm× 50 μm in cross-section, associated with sanidine, astrophyllite, fluornatropyrochlore, ferrokentbrooksite, quartz and ferro-katophorite. Crystals are generally transparent and colourless, with vitreous lustre, occasionally creamy white. Fogoite-(Y) has a white streak, splintery fracture and very good {100} cleavage. Mohs hardness is ∼5. Dcalc. = 3.523 g/cm3. It is biaxial (+) with refractive indices (λ = 590 nm) α = 1.686(2), β = 1.690(2), γ = 1.702(5); 2Vmeas. = 57(1)° and 2Vcalc. = 60°. It is nonpleochroic. Fogoite-(Y) is triclinic, space group P1, a = 9.575(6), b = 5.685(4), c = 7.279(5) Å, α = 89.985(6), β = 100.933(4), γ = 101.300(5)°, V = 381.2 (7) Å3. The six strongest reflections in the powder X-ray diffraction data [d (Å), I, (hkl)] are: 2.954, 100, (1̄1̄2, 3̄10); 3.069, 42, (300, 01̄2); 2.486, 24, (310, 21̄2); 3.960, 23, (1̄1̄1, 2̄10); 2.626, 21, (2̄20); 1.820, 20, (1̄04). Electron microprobe analysis gave the following empirical formula calculated on 18 (O + F) (Na2.74Mn0.15)∑2.89Ca2[Y1.21(La0.01Ce0.03Nd0.03Sm0.02Gd0.08Dy0.08Er0.05Yb0.04Lu0.01)∑0.35Mn0.16Zr0.11Na0.09Fe0.072+Ca0.01]∑2(Ti0.76Nb0.23Ta0.01)∑1(Si4.03O14)O1.12F2.88, Z = 1. The crystal structure was refined on a twinnedcrystal to R1 = 2.81% on the basis of 2157 unique reflections (Fo > 4σFo) and is a framework of TS (Titanium Silicate) blocks, which consist of HOH sheets (H – heteropolyhedral, O – octahedral) parallel to (100). In the O sheet, the the [6]MO(1) site is occupied mainly by Ti, <MO(1)–ϕ> = 1.980 Å, and the [6]MO(2) and [6]MO(3) sites are occupied by Na and Na plus minor Mn, <MO(2)–ϕ>= 2.490 Å and <MO(3)–ϕ> = 2.378 Å. In the H sheet, the two [4]Si sites are occupied by Si, with <Si–O> = 1.623 Å; the [6]MH site is occupied by Y and rare-earth elements (Y > REE), with minor Mn, Zr, Na, Fe2+ and Ca, <MH–ϕ> = 2.271 Å and the [6]AP site is occupied by Ca, <AP–ϕ> = 2.416 Å. The MH and AP octahedra and Si2O7 groups constitute the H sheet. The ideal compositions of the O and two H sheets are Na3Ti(OF)F2 and Y2Ca2(Si2O7)2 apfu. Fogoite-(Y) is isostructural with götzenite and hainite. The mineral is named after the type locality, the Fogo volcano in the Azores.

Photochemische Reaktionen von Übergangsmetall-Organyl-Komplexen mit Olefinen, XVI [1]: Photochemisch induzierte Cycloadditionen von Diphenylacetylen an Tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)mangan / Photochemical Reactions of Transition Metal Organyl Complexes with Olefins, XVI [1]: Photochemically Induced Cycloadditions of Diphenylacetylene to Tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)manganese

1996 ◽  
Vol 51 (10) ◽  
pp. 1473-1485 ◽  
Author(s):  
Cornelius G. Kreiter ◽  
Ernst-Christian Koch ◽  
Walter Frank ◽  
Guido J. Reiß
Keyword(s):  
Mass Spectra ◽  
Photochemical Reactions ◽  
Molecular Structures ◽  
Manganese Complexes ◽  
Formation Mechanisms ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray

Upon UV irradiation in THF at 208 K tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)- manganese (1) yields solvent stabilized, very reactive dicarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)(tetrahydrofuran)manganese (2), which reacts in situ with one or two molecules of diphenylacetylene (3) and yields four manganese complexes and 1,3-dimethyl-5,6-diphenyl-bicyclo[3.2.1]oct-2-ene-7-one (5), which were separated by HPL chromatography. In addition to tricarbonyl η5-4,6 -dimethyl-1,2-diphenyl-cyclohepta-2,4-dien-1-yl)manganese (4) formed by [5+2]cycloaddition and successive 1,4-H shift, tricarbonyl{ 1′,2′,5′-η-5-methyl-2,3 -diphenyl-5- (2′-methyl-4′,5′-diphenyl-penta-1′,4′-dien-1′,5′-diyl)cyclopent-2-en-1 -one-κ-O}manganese (6) is isolated with a ligand, formed from 2,4-dimethyl-2,4-pentadien-1-yl, two units of 3 and one carbon monoxide. The ligands of tricarbonyl{ 1-4,2′-η-4,6 -dimethyl-1,2-diphenyl-5-(E-1′,2′- diphenyl-vinylen)cyclohepta-1,3-diene}manganese (7), and tricarbonyl{η5-4,6 -dimethyl-1,2-diphenyl-7-(E-1′,2′-diphenyl-vinyl)cyclohepta-2,4-dien-1-yl}m anganese (8) are formed from 2,4-dimethyl-2,4-pentadien-1-yl and of two molecules of 3 each. The crystal and molecular structures of 5 and 6 have been determined by single crystal X-ray diffraction. 5 crystallizes in the triclinic space group P1̅ , a = 992.0(2) pm, b = 996.8(2) pm, c = 1021.0(2) pm, a = 77.67(3)°, β = 61.17(3)°, γ = 88.68(3)°. Complex 6 crystallizes also in the triclinic space group P1̅ ,a = 1023.2(2) pm, b - 1113.8(2) pm, c = 1567.9(3) pm, α = 82.88(3)°, β = 86.93(3)°, 7 = 63.53(3)°. The constitutions of 4, 7 and 8 were elucidated from the IR, NMR and mass spectra. Possible formation mechanisms for the compounds 4-8 are proposed. Complex 7 shows hindered rotations of two phenyl groups with different barriers of energy ΔG≠316 = 68.8 kJ/mol, „ΔH≠ = 67.9 ± 0.7 kJ/mol, ΔS≠ = -2 ± 2 J/mol · K and ΔG≠296 = 60.6 kJ/mol, ΔH≠ = 57.7 ± 1.0 kJ/mol, ΔS≠ = -10 ± 2 J/mol·K due to steric interactions.

Cyclopentadienyl-Ruthenium and -Osmium Chemistry. XL. X-Ray Crystal Structures of MBr (PPh3)2(η-C5H5).CH2Cl2 (M = Ru, Os)

1995 ◽  
Vol 48 (11) ◽  
pp. 1887 ◽  
Author(s):  
MI Bruce ◽  
PJ Low ◽  
BW Skelton ◽  
ERT Tiekink ◽  
A Werth ◽  
...  
Keyword(s):  
Structural Parameters ◽  
Molecular Structures ◽  
Coordination Geometry ◽  
Chloro Complexes ◽  
Triclinic Space Group ◽  
Full Matrix ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Cell Dimensions ◽  
Unit Cell Dimensions

The crystal and molecular structures of MBr (PPh3)2(η-C5H5).CH2Cl2 (M = Ru and Os) have been determined. A revised synthesis of the bromo osmium complex is given. The coordination geometry about the metal atom is based on a distorted octahedron with one face being occupied by the cyclopentadienyl group [average Ru -C(Cp) 2.214(3), Os-C(Cp) 2.177(3)Ǻ] and the other by the bromide [ Ru -Br 2.5683(8), Os-Br 2.5438(9)Ǻ] and the two phosphorus atoms [ Ru -P 2.323(2), 2.329(1); Os-P 2.290(2), 2.297(2)Ǻ]. Structural parameters are compared with those of the corresponding chloro complexes and differ only minimally. Crystals of MBr (PPh3)2(η-C5H5).CH2Cl2 are triclinic, space group Pī , with unit cell dimensions ( Ru [Os]): a 14.374(5) [14.276(4)], b 14.057(4) [13.959(3)], c 10.012(5) [9.903(3)]Ǻ, α 99.43(3) [99.79(2)], β 105.60(3) [105.74(2)], γ 100.42(3) [100.39(2)]°, V 1868(1) [1817.7(9)] Ǻ3, Z 2. The structures were refined by a full-matrix least-squares procedure to R 0.050 [0.036] for 7365 [5108] reflections with I ≥ 3σ(I).

Cluster Chemistry. XLVII. X-Ray Crystal Structure of OsPt2(μ-CO)3(CO)2(PPh3)3

1986 ◽  
Vol 39 (12) ◽  
pp. 2145 ◽  
Author(s):  
MI Bruce ◽  
MR Snow ◽  
ERT Tiekink
Keyword(s):  
Crystal Structure ◽  
X Ray Diffraction ◽  
Cluster Chemistry ◽  
Triclinic Space Group ◽  
X Ray ◽  
Metal Atoms ◽  
Metal Metal ◽  
Cell Dimensions ◽  
Unit Cell Dimensions ◽  
Triphenylphosphine Ligand

The crystal structure of OsPt2(μ-CO)3(CO)2(PPh3)3 has been determined by single-crystal X-ray diffraction techniques. Crystals are triclinic, space group Pī with unit cell dimensions a 13.593(4), b 15.839(4), c 12.633(8) Ǻ, α 102.97(3), β 108.18(2), γ 84.86(3)° with Z2. The structure was refined by a full-matrix least-squares procedure on 5896 reflections [I ≥ 2.5σ(I)] to final R 0.028 and Rw 0.034. A triphenylphosphine ligand binds each of the metal atoms disposed at the corners of a triangle. Each metal-metal bond is spanned by a bridging carbonyl group. The coordination about the osmium atom is completed by two terminal carbonyl groups.

The Preparation, Spectroscopic Characterization and X-Ray Structure of the Salt [Pt(η1 -C6H9)(Cy2PCH2CH2PCy2)(PPh3)]HCO3·3H2O Containing the Discrete, Uncoordinated, Hydrogen-Bonded Dimeric Bicarbonate Dianion [(HCO3)(H2O)3]22-

1999 ◽  
Vol 52 (10) ◽  
pp. 949 ◽  
Author(s):  
Martin A. Bennett ◽  
Glen B. Robertson ◽  
Pramesh N. Kapoor
Keyword(s):  
Low Temperature ◽  
Spectroscopic Characterization ◽  
Coordination Geometry ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
X Ray ◽  
Cell Dimensions ◽  
R Value ◽  
Unit Cell Dimensions ◽  
Hydrogen Bonded

Reaction of the cyclohexyne–platinum(0) complex [Pt(η2-C6H8)(Cy2PCH2CH2PCy2)]* with water and CO2 in the presence of triphenylphosphine gives the bicarbonate salt of the (η1-cyclohexenyl)platinum(II) cation, [Pt(η1-C6H9)(Cy2PCH2CH2 PCy2)(PPh3)] [HCO3] · 3H2O, which has been characterized by n.m.r. spectroscopy and single-crystal X-ray diffraction at low temperature. Crystals are triclinic, space group P1– with unit cell dimensions a 20.315(2), b 12.782(1), c 10.694(1) Å, α 66.61(1), β 104.73(1), γ 102.11(1)˚, and Z 2. The structure was refined to a final R value of 0.036 with use of 7553 reflections [I > 3σ(I)]. The cation has the expected, somewhat distorted planar coordination geometry; the anion consists of discrete, hydrogen-bonded dimers [(HCO3)(H2O)3]22-.

Gold(I) dimers. The synthesis and reactions of [tert-BuC≡CAu(dmpm—P)], and the crystal and molecular structures of [Au2(µ-dmpm)2]X2•2H2O, X = Cl, I

1988 ◽  
Vol 66 (12) ◽  
pp. 3176-3183 ◽  
Author(s):  
N. C. Payne ◽  
R. J. Puddephatt ◽  
R. Ravindranath ◽  
I. Treurnicht
Keyword(s):  
Chlorinated Solvents ◽  
Chloride Ion ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Crystal And Molecular Structures ◽  
Cell Dimensions ◽  
Network Of Hydrogen Bonds ◽  
Final Agreement ◽  
Unit Cell Dimensions

Acetylide complexes of formula [tert-BuC≡CAu(R2PCH2PR2)], R = CH3 (6a) and C6H5 (6b), have been prepared, and characterized by spectroscopic methods. These complexes undergo a fluxional process involving a three-coordinate Au(I) centre. Complex 6a dimerizes by a first-order process in chlorinated solvents, with substitution of the acetylide ligand by chloride ion, to form [Au2(µ-dmpm)2]Cl2•2H2O (7a). The crystal and molecular structures of 7a and the iodide salt 7b have been determined by single crystal X-ray diffraction methods. Both crystallize in the triclinic space group [Formula: see text] with Z = 1; unit cell dimensions are a = 7.962(1), b = 9.987(1), c = 7.895(1) Å, α = 90.11, β = 109.13(1), and γ = 112.84(1)° for 7a; a = 8.243(1), b = 9.057(1), c = 8.167(1) Å, α = 90.23, β = 110.33(1), and γ = 89.92(1)° for 7b. The analyses refined to final agreement factors on F of R = 0.035 based on 3225 unique reflections with I > 3σ (I) for 7a, and R = 0.030 based on 2971 unique reflections with I > 3σ(I) for 7b. The structures are closely related, with the cations containing an eight-membered centrosymmetric ring formed by the Au(I) centres and the bridging dmpm ligands. The Au … Au′ distances are 3.014(1) and 3.019(1) Å in 7a and 7b, respectively. In the solid state, the halide ions bridge the two Au centres, and, together with the water molecules, form a network of hydrogen bonds running at an angle of 104° to the eight-membered Au2P4C2 rings.

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