Synthesis, Spectroscopy and Structure of the Cobalt(III) Complex of the Hexadentate Ligand 5-(4-Amino-2-thiabutyl)-5-methyl-3,7-dithianonane-1,9-diamine

1993 ◽  
Vol 46 (11) ◽  
pp. 1799 ◽  
Author(s):  
TM Donlevy ◽  
LR Gahan ◽  
TW Hambley ◽  
KL Mcmahon ◽  
R Stranger
Keyword(s):  
Crystal Structure ◽  
Progressive Increase ◽  
Ligand Field ◽  
Octahedral Symmetry ◽  
X Ray Diffraction ◽  
X Ray ◽  
Hexadentate Ligand ◽  
Symmetry Result ◽  
Ligand Field Parameters ◽  
Systematic Reduction

A revised synthesis of the hexadentate ligand 5-(4-amino-2-thiabutyl)-5-methyl-3,7-dithianon- ane-1,9-diamine (N3S3) is reported. Reaction between the sodium salt of 2-aminoethanethiol and 1,1,1-tris([( tolylsulfonyl )oxy]methyl)ethane in refluxing ethanol results in the formation of the hexadentate ligand N3S3. The preparation of the nickel(II) and cobalt(III) complexes is reported. The crystal structure of [Co(N3S3)](ClO4)3.H2O has been determined by X-ray diffraction methods and refined to a residual of 0.044 for 3696 independent observed reflections. The crystals are monoclinic, P21/n, a 9.314(4), b 15.581(6), c 17.026(3) Ǻ, β 90.30(4)°. Low temperature (c.10 K) absorption spectra are reported for [Co(N3S3)]3+ and the analogous encapsulated complex [Co(AMN3S3sarH)]4+ where both the spin-allowed 1A1g → 1T1g, 1T2g and spin-forbidden 1A1g → 3T1g, 3T2g were observed. Ligand -field calculations based on octahedral symmetry result in the ligand -field parameters B 461, C 3075, Dq 2303 cm-1, and B 462, C 3085, Dq 2266 cm-1 for the [Co(N3S3)]3+ and [Co(AMN3S3sarH)]4+ complexes, respectively. A systematic reduction occurs in the Racah B parameter of between 25 and 30 cm-1 for each additional thioether donor in the series of complexes N6-xSx (x = 0, 1, 2, 3). In addition, there is evidence for a progressive increase in the Racah C/B ratio with increasing number of thioether donors in this series.

Crystal Structure of Tris(1,10-phenanthroline)mercury(II) Trifluoromethanesulfonate

1979 ◽  
Vol 32 (10) ◽  
pp. 2195 ◽  
Author(s):  
GB Deacon ◽  
CL Raston ◽  
D Tunaley ◽  
AH White
Keyword(s):  
Crystal Structure ◽  
Aqueous Solution ◽  
Title Compound ◽  
Unit Cell Volume ◽  
Octahedral Symmetry ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ethanol Solvate ◽  
The Mean ◽  
Trigonal Prismatic

The crystal structure of the ethanol solvate of the title compound, [Hg(phen)3](CF3S03)2 (phen =1,10-phenanthroline), has been determined at 295(1) K by single-crystal X-ray diffraction and refined by least squares to a residual of 0�043 for 2939 'observed' reflections. Crystals are monoclinic: C2/c, a 25�25(1), b 10�960(4), c 18�949(6) �, β 129�32(2)�, Z 4. The cation is centred on a crystallographictwofold axis and has approximate D3 point symmetry. The deviation of the mercury(II) environment from octahedral symmetry toward the trigonal-prismatic limit is considerable, the mean trans N-Hg-N angle being 154�52�. <Hg-N> is 2�400 �. The unit cell volume is considerablydependent on crystallization solvent, being larger for the ethanol solvate than for solvent-free crystals obtained from aqueous solution.

Studies of β-Diketone Complexes of Rhenium. I. Trispentane-2,4-dionatorhenium(III) and Tris(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)rhenium(III)

1972 ◽  
Vol 50 (1) ◽  
pp. 8-17 ◽  
Author(s):  
W. D. Courrier ◽  
W. Forster ◽  
C. J. L. Lock ◽  
G. Turner
Keyword(s):  
Crystal Structure ◽  
Mass Spectrometry ◽  
Magnetic Susceptibility ◽  
Infrared Spectroscopy ◽  
Physical Properties ◽  
Ligand Field ◽  
X Ray Diffraction ◽  
Rhenium Atom ◽  
X Ray ◽  
Monoclinic Cell

Pure samples2 of Re(hfac)3 and Re(acac)3 have been prepared and their physical properties studied by ultraviolet–visible and infrared spectroscopy, mass spectrometry, magnetic susceptibility measurements, and X-ray diffraction. The compounds are monomeric and the physical properties may be explained if the rhenium atom sits in an essentially octahedral ligand field. Re(hfac)3 has a hexagonal unit cell and the acetyl-acetone complex adopts the monoclinic cell of the α-form of the three typical crystal structure types which Astbury (1) observed for trispentane-2,4-dionatometal(III) compounds. The properties observed for trispentane-2,4-dionatorhenium(III) differ from those reported previously (2, 3). The difficulties experienced in obtaining pure Re(C5H7O2)3 were caused by the ease with which the material is oxidized.

Some substituted urea and thiourea complexes of Co(II), Mn(II), and Cr(III)

1969 ◽  
Vol 47 (12) ◽  
pp. 2275-2282 ◽  
Author(s):  
Pakinam Askalani ◽  
R. A. Bailey
Keyword(s):  
Magnetic Susceptibility ◽  
Ligand Field ◽  
X Ray Diffraction ◽  
Visible Spectroscopy ◽  
X Ray ◽  
Ligand Field Parameters ◽  
Substituted Urea

Complexes of Co(II), Mn(II), and Cr(III) with N-butylurea, N-methylthiourea, and N,N′-dimethylthiourea, and Cl−, Br−, NO3−, and ClO4− anions were prepared and characterized using infrared and visible spectroscopy, and magnetic susceptibility. The urea is bonded through oxygen, and the thioureas through sulfur in all cases. The Co–N-butylurea compounds are octahedral, mostly with CoL6X2 stoichiometries, but some compounds involving coordinated anions and possibly bridging butylurea ligands were found. The Co–thioureas are tetrahedral. Octahedral Cr(III) compounds of the type CrL3X3 and CrL6(ClO4)3 were prepared, and the CrS6 chromophore characterized. Mn(II)–butylureas are octahedral, while the thioureas show MnL6X2 and MnL4X2 stoichiometries. X-ray diffraction established some of the latter to be isostructural with the analogous tetrahedral Co(II) compounds. Ligand field parameters Dq and B have been evaluated for the Co(II) and Cr(III) compounds.

Crystal structure of ethylenediammonium hexaaquanickel(II) sulfate: a variation on the Tutton salts

1984 ◽  
Vol 37 (5) ◽  
pp. 1105 ◽  
Author(s):  
PC Healy ◽  
JM Patrick ◽  
AH White
Keyword(s):  
Crystal Structure ◽  
Title Complex ◽  
Attractive Alternative ◽  
Water Molecules ◽  
Octahedral Symmetry ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
Tutton Salts ◽  
X Ray ◽  
Organic Species

The crystal structure of the title complex, [H3NCH2CH2NH3] [Ni(H2O)6] [SO4]2, has been determined by single-crystal X-ray diffraction methods at 295 K, being refined by full matrix least squares to a residual of 0.032 for 2532 independent 'observed' reflections. Crystals are monoclinic, P21/n, a 13.148(3), b 7.119(3), c 8.245(2) �, β 100.97(4)�, Z = 2. Both cations are disposed about crystallographic centres of symmetry. The organic species has a necessarily planar non-hydrogen atom skeleton [C-C, 1.513(3); C-N, 1.485(4) �]. In the hexaaquanickel(11) species, the Ni-O distances are very similar [2.060(2), 2.064(2), 2.066(2) �], although there is a significant departure from octahedral symmetry among the angles [89.71(8), 86.87(8), 90.00(8)�]. The oxygen atoms of the water molecules are bonded pseudo-tetrahedrally. The centrosymmetric metal atom environment is more regular than that in the corresponding Tutton salts, to which complexes of the present type may present an attractive alternative.

Crystal structure of an inclusion complex between chiral monoaza-15-crown-5 and S(–)-1-phenyl-ethyl ammonium percholorate

2003 ◽  
Vol 218 (5) ◽  
Author(s):  
Süheyla Özbey ◽  
F. B. Kaynak ◽  
M. Toğrul ◽  
N. Demirel ◽  
H. Hoşgören
Keyword(s):  
Crystal Structure ◽  
Inclusion Complex ◽  
Single Crystal ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
New Type

AbstractA new type of inclusion complex, S(–)-1 phenyl ethyl ammonium percholorate complex of R-(–)-2-ethyl - N - benzyl - 4, 7, 10, 13 - tetraoxa -1- azacyclopentadecane, has been prepared and studied by NMR, IR and single crystal X-ray diffraction techniques. The compound crystallizes in space group

Crystal Forms of Semisynthetic Ergot Alkaloid Terguride

2002 ◽  
Vol 67 (4) ◽  
pp. 479-489 ◽  
Author(s):  
Michal Hušák ◽  
Bohumil Kratochvíl ◽  
Ivana Císařová ◽  
Ladislav Cvak ◽  
Alexandr Jegorov ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Ergot Alkaloid ◽  
Simplified Model ◽  
Quantum Mechanical ◽  
Quantum Mechanical Calculations ◽  
X Ray Diffraction ◽  
Torsion Angles ◽  
Crystal Forms ◽  
X Ray ◽  
Independent Molecules

Two new structures of semisynthetic ergot alkaloid terguride created by unusual number of symmetry-independent molecules were determined by X-ray diffraction methods at 150 K. Form A (monoclinic, P212121, Z = 12) contains three symmetry-independent terguride molecules and two molecules of water in the asymmetric part of the unit cell. The form CA (monoclinic, P21, Z = 8) is an anhydrate remarkable by the presence of four symmetry-independent molecules in the crystal structure. Conformations of twelve symmetry-independent molecules that were found in four already described terguride structures are compared with torsion angles obtained by ab initio quantum-mechanical calculations for the simplified model of N-cyclohexyl-N'-diethylurea.

scholarly journals High-pressure synthesis and crystal structure of the mixed-cation borate Ga4In4B15O33(OH)3

2019 ◽  
Vol 74 (4) ◽  
pp. 357-363
Author(s):  
Daniela Vitzthum ◽  
Hubert Huppertz
Keyword(s):  
Crystal Structure ◽  
High Pressure ◽  
High Temperature ◽  
Diffraction Data ◽  
X Ray Diffraction ◽  
Synthesis And Crystal Structure ◽  
X Ray ◽  
Mixed Cation ◽  
High Pressure High Temperature ◽  
Pressure Synthesis

AbstractThe mixed cation triel borate Ga4In4B15O33(OH)3 was synthesized in a Walker-type multianvil apparatus at high-pressure/high-temperature conditions of 12.5 GPa and 1300°C. Although the product could not be reproduced in further experiments, its crystal structure could be reliably determined via single-crystal X-ray diffraction data. Ga4In4B15O33(OH)3 crystallizes in the tetragonal space group I41/a (origin choice 2) with the lattice parameters a = 11.382(2), c = 15.244(2) Å, and V = 1974.9(4) Å3. The structure of the quaternary triel borate consists of a complex network of BO4 tetrahedra, edge-sharing InO6 octahedra in dinuclear units, and very dense edge-sharing GaO6 octahedra in tetranuclear units.

The Coordination Chemistry of Phosphoryl Compounds Containing the — N(CH3)2 Group, Part VIII

1972 ◽  
Vol 27 (7) ◽  
pp. 759-763 ◽  
Author(s):  
M. W. G. De Bolster ◽  
W. L. Groeneveld
Keyword(s):  
Coordination Chemistry ◽  
General Formula ◽  
Ligand Field ◽  
Chemical Analyses ◽  
X Ray ◽  
Physical Measurements ◽  
Ligand Field Spectra ◽  
Chloride Adduct ◽  
Ligand Field Parameters ◽  
Group Part

A number of new solvates and adducts containing bisphenyldimethylaminophosphine oxide is reported. The solvates have the general formula M[(C6H5)2P(O)N(CH3)2]42+(anion-)2, in which M = Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn and Cd, and the anions are ClO4- and BF4-. The adducts have the general formula M[(C6H5)2P(O)N(CH3)2]2Cl2, where M stands for the same series of metals.The compounds are characterized and identified by chemical analyses and physical measurements.Ligand-field and vibrational spectra have been investigated; values for the ligand-field parameters are reported. It is concluded that coordination takes place via the oxygen atom of the ligand.X-ray powder patterns were used in combination with ligand-field spectra to deduce the coordination around the metal ions.The interesting behaviour of the nickel (II) chloride adduct upon heating is discussed and it is shown that both a square pyramidal and a tetrahedral modification exists.

Crystal structure determination of the conformation of two bicyclo[3.3.1]nonan-ones

1985 ◽  
Vol 63 (6) ◽  
pp. 1166-1169 ◽  
Author(s):  
John F. Richardson ◽  
Ted S. Sorensen
Keyword(s):  
Crystal Structure ◽  
Direct Methods ◽  
Chair Conformation ◽  
Molecular Structures ◽  
Boat Conformation ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
Final Agreement

The molecular structures of exo-7-methylbicyclo[3.3.1]nonan-3-one, 3, and the endo-7-methyl isomer, 4, have been determined using X-ray-diffraction techniques. Compound 3 crystallizes in the space group [Formula: see text] with a = 15.115(1), c = 7.677(2) Å, and Z = 8 while 4 crystallizes in the space group P21 with a = 6.446(1), b = 7.831(1), c = 8.414(2) Å, β = 94.42(2)°, and Z = 2. The structures were solved by direct methods and refined to final agreement factors of R = 0.041 and R = 0.034 for 3 and 4 respectively. Compound 3 exists in a chair–chair conformation and there is no significant flattening of the chair rings. However, in 4, the non-ketone ring is forced into a boat conformation. These results are significant in interpreting what conformations may be present in the related sp2-hybridized carbocations.

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