Iron(II) and Nickel(II) Complexes of 2,6-Di(Thiazol-4-Yl)Pyridine and Related Ligands: Magnetic, Spectral and Structural Studies

1986 ◽  
Vol 39 (2) ◽  
pp. 209 ◽  
Author(s):  
AT Baker ◽  
HA Goodwin
Keyword(s):  
Solid State ◽  
Metal Complexes ◽  
Single Crystal ◽  
Coordination Sphere ◽  
Structural Parameters ◽  
Complex Cation ◽  
Magnetic Behaviour ◽  
Structural Studies ◽  
Thermally Induced ◽  
X Ray

2,6-Di(thiazol-4-yl)pyridine (1a), 2,6-di(2-methylthiazol-4-yl)pyridine (1b) and 2,6-di(2-phenylthiazol-4-yl)pyridine (1c) have been prepared by Hantzsch syntheses from 2,6-di(ω- bromoacetyl )pyridine and the appropriate thioamide. Bis ( ligand ) iron(II) and nickel(II) complexes of (1a) and (1b) have been prepared but no metal complexes of (1c) were isolated. The bis ( ligand ) iron(II) complexes of (1a) are low-spin whereas those of (1b) undergo thermally induced spin-transitions, both in the solid state and solution. The field strengths of the ligands , determined from the spectra of their nickel(II) complexes, correlate well with the observed magnetic behaviour of their iron(II) complexes. The structure of [FeL2][ClO4]2.H2O, L = (1a), was determined by single-crystal X-ray diffractometry . The complex cation has the meridional configuration with the ligand functioning as an approximately planar tridentate. The structural parameters relating to the Fe-N6 coordination sphere are remarkably similar to those found for bis (2,2′:6′, 2′- terpyridine )iron(II) bis ( perchlorate ) monohydrate.

Iron(II) and Nickel(II) Complexes of 4,4′-Bithiazole: Spectral, Magnetic and Structural Studies

1985 ◽  
Vol 38 (6) ◽  
pp. 851 ◽  
Author(s):  
AT Baker ◽  
HA Goodwin
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Bond Length ◽  
Least Squares ◽  
State Transitions ◽  
Structural Studies ◽  
Octahedral Structure ◽  
Thermally Induced ◽  
X Ray ◽  
Distorted Octahedral

Iron(II) and nickel(II) complexes of 4,4′-bithiazole (L) have been prepared. Salts of [FeL3]2+ undergo thermally induced spin-state transitions, in the solid state and in solution. The structures of both [FeL3] [ClO4]2 and [NiL3] [ClO4]2 have been determined by single-crystal X-ray diffractometry . The compounds are isomorphous : monoclinic with space group C2/c, with four molecules in a unit cell of dimensions (Fe, Ni): a 17.250(3), 17.379(3); b 9.8168(9), 9.685(1); c 16.867(3), 17.135(3) Ǻ; β 105.943(7), 104.860(7)°. The structures were refined by least-squares methods to residuals of 0.033 (Fe) and 0.033 (Ni) for 1917 (Fe) and 2017 (Ni) observed reflections. The cations have a distorted octahedral structure with the average Ni-N bond length being 0.11 Ǻ longer than the average Fe-N bond length.

scholarly journals Thermal Reactivity in Metal Organic Materials (MOMs): From Single-Crystal-to-Single-Crystal Reactions and Beyond

Materials ◽  
2019 ◽  
Vol 12 (24) ◽  
pp. 4088
Author(s):  
Javier Martí-Rujas
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Organic Materials ◽  
Structural Transformations ◽  
Atomic Motion ◽  
X Ray Diffraction ◽  
Thermally Induced ◽  
X Ray ◽  
Thermal Reactivity ◽  
Metal Organic

Thermal treatment is important in the solid-state chemistry of metal organic materials (MOMs) because it can create unexpected new structures with unique properties and applications that otherwise in the solution state are very difficult or impossible to achieve. Additionally, high-temperature solid-state reactivity provide insights to better understand chemical processes taking place in the solid-state. This review article describes relevant thermally induced solid-state reactions in metal organic materials, which include metal organic frameworks (MOFs)/coordination polymers (CPs), and second coordination sphere adducts (SSCs). High temperature solid-state reactivity can occur in a single-crystal-to-single crystal manner (SCSC) usually for cases where there is small atomic motion, allowing full structural characterization by single crystal X-ray diffraction (SC-XRD) analysis. However, for the cases in which the structural transformations are severe, often the crystallinity of the metal-organic material is damaged, and this happens in a crystal-to-polycrystalline manner. For such cases, in the absence of suitable single crystals, structural characterization has to be carried out using ab initio powder X-ray diffraction analysis or pair distribution function (PDF) analysis when the product is amorphous. In this article, relevant thermally induced SCSC reactions and crystal-to-polycrystalline reactions in MOMs that involve significant structural transformations as a result of the molecular/atomic motion are described. Thermal reactivity focusing on cleavage and formation of coordination and covalent bonds, crystalline-to-amorphous-to-crystalline transformations, host–guest behavior and dehydrochlorination reactions in MOFs and SSCs will be discussed.

Group 6 Metal Mixed Carbonyl Complexes with a Carboxyferrocenylphosphane

2000 ◽  
Vol 65 (12) ◽  
pp. 1897-1910 ◽  
Author(s):  
Lenka Lukešová ◽  
Jiří Ludvík ◽  
Ivana Císařová ◽  
Petr Štěpnička
Keyword(s):  
Carbon Monoxide ◽  
Cyclic Voltammetry ◽  
Solid State ◽  
Single Crystal ◽  
Carbonyl Complexes ◽  
State Structure ◽  
X Ray Diffraction ◽  
Thermally Induced ◽  
X Ray ◽  
Ferrocenecarboxylic Acid

A series of complexes [M(CO)5(Hdpf-κP)], where M = Cr (1), Mo (2) and W (3), and Hdpf is 1'-(diphenylphosphanyl)ferrocenecarboxylic acid, was obtained by thermally-induced (2) or photochemically-assisted (1, 3) displacement of carbon monoxide with Hdpf from the corresponding hexacarbonyl complexes. The complexes were characterized by NMR, UV-VIS and IR spectroscopies and further studied by cyclic voltammetry. The solid-state structure of complex 1 has been determined by single-crystal X-ray diffraction.

Physical and structural studies of N-substituted-3-hydroxy-2-methyl-4(1H)-pyridinones

1988 ◽  
Vol 66 (1) ◽  
pp. 123-131 ◽  
Author(s):  
William O. Nelson ◽  
Timothy B. Karpishin ◽  
Steven J. Rettig ◽  
Chris Orvig
Keyword(s):  
Mass Spectrometry ◽  
Hydrogen Bonding ◽  
Solid State ◽  
Single Crystal ◽  
Direct Methods ◽  
Structural Studies ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
Space Group ◽  
X Ray

A series of 3-hydroxy-2-methyl-4(1H)-pyridinones has been prepared with the substituents H, CH3, n-C6H11, and CH2CH2NH2 at the ring N. The dipyridinone 1,6-bis(3-hydroxy-2-methyl-4(1H)-pyridinon-1-yl)hexane has also been synthesized. The products with H and CH3 substituents have been studied by single crystal X-ray diffraction. Crystals of 3-hydroxy-2-methyl-4-pyridinone are monoclinic, a = 6.8351(4), b = 10.2249(4), c = 8.6525(4) Å, β = 105.215(4)°, Z = 4, space group P21/n and those of 3-hydroxy-1,2-dimethyl-4-pyridinone are orthorhombic, a = 7.3036(4), b = 13.0490(6), c = 13.7681(7) Å, Z = 8, space group Pbca. Both structures were solved by direct methods and were refined by full-matrix least-squares procedures to R = 0.037 and 0.044 for 914 and 857 reflections with I ≥ 3σ(I), respectively. Bond lengths and angles in the two compounds were normal. All the compounds have been studied by mass spectrometry, and by infrared and proton nmr spectroscopies. The importance of hydrogen bonding to both the solution and solid state properties of these compounds has been confirmed by these techniques.

Lewis-Base Adducts of Lead(II) Compounds. VII. Synthetic and Structural Studies of Some 1:1 Adducts of Linear Polyamines With Lead(II) Nitrate

1996 ◽  
Vol 49 (10) ◽  
pp. 1029 ◽  
Author(s):  
JM Harrowfield ◽  
H Miyamae ◽  
BW Skelton ◽  
AA Soudi ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Coordination Sphere ◽  
Room Temperature ◽  
Internal Symmetry ◽  
Lewis Base ◽  
Structural Studies ◽  
One Dimensional ◽  
X Ray ◽  
Structure Determinations

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 1 : 1 adducts of lead(II) nitrate with the linear multidentate polyamines ethane-1,2-diamine ('en'(= '2')), H2N(CH2)2NH(CH2)2NH2(' dien ' = '22') and H2N(CH2)xNH(CH2)yNH(CH2)zNH2 ( xyztet = '222tet' (= ' trien '), '232tet', '323tet'). Crystal/refinement data are as follows: [(en) Pb (NO3)2](∞|∞) is monoclinic, P 21/c, a 5.388(2), b 12.440(5), c 13.123(3) Ǻ, β 102.33(3)°, Z = 4 f.u .; R 0.037 for No 2698 'observed' (I > 3σ(I)) reflections. [( dien ) Pb (NO3)2](∞|∞) is orthorhombic, Ccma , a 9.800(2), b 10.840(2), c 20.521(5), Z = 8; R 0.045, No 991. [( trien ) Pb (NO3)2](∞|∞) is orthorhombic, P 212121, a 14.815(3), b 10.975(3), c 8.410(2) Ǻ, Z = 4; R 0.050, No 1360; [(232tet) Pb (NO3)2](∞|∞) is isomorphous, a 14.524(6), b 11.221(1), c 8.860(2) Ǻ, R 0.036, No 2371. [(323tet) Pb (NO3)2](∞|∞) is monoclinic, P21/c, a 8.195(4), b 14.407(7), c 13.312(4) Ǻ, β 91.05(3)°, Z = 4; R 0.049, No 1644. In general, the degree of complexity of the adduct diminishes as the ligand size increases: whereas the en adduct is a compact one-dimensional two stranded polymer with nearly all nitrate oxygens involved in tight bridging interactions, the extent of bridging diminishes in the adducts of the larger amines, until, for the 323tet species, a monomer is obtained involving a lead coordination sphere containing the ligand and a pair of bidentate nitrate groups. The 1 : 2 adduct with en is also recorded, and is a dimer with quasi-i internal symmetry. [(en)2Pb(NO3)2]2 is monoclinic, P21, a 6.661(2), b 14.226(8), C 13.618(4)Ǻ, β 96.51(2)°; R 0.072, No 1713.

Two Consecutive Magneto-Structural Gas-Solid Transformations with Single-Crystal Retention in Non-Porous Molecular Materials

2018 ◽  
Author(s):  
Julia Miguel-Donet ◽  
Javier López-Cabrelles ◽  
Nestor Calvo Galve ◽  
Eugenio Coronado ◽  
Guillermo Minguez Espallargas
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Structural Rearrangement ◽  
Magnetic Behaviour ◽  
Porous Solids ◽  
Potential Applications ◽  
Hcl Gas ◽  
Porous Coordination Polymer ◽  
Gas Molecules ◽  
Magnetostructural Transformation

<p>Modification of the magnetic properties in a solid-state material upon external stimulus has attracted much attention in the recent years for their potential applications as switches and sensors. Within the field of coordination polymers, gas sorption studies typically focus on porous solids, with the gas molecules accommodating in the channels. Here we present a 1D non-porous coordination polymer capable of incorporating HCl gas molecules, which not only causes a reordering of its atoms in the solid state but also provokes dramatic changes in the magnetic behaviour. Subsequently, a further solid-gas transformation can occur with the extrusion of HCl gas molecules causing a second structural rearrangement which is also accompanied by modification in the magnetic path between the metal centres. Unequivocal evidence of the two-step magnetostructural transformation is provided by X-ray single-crystal diffraction.</p>

Solid-state dynamics and single-crystal to single-crystal structural transformations in octakis(3-chloropropyl)octasilsesquioxane and octavinyloctasilsesquioxane

2017 ◽  
Vol 19 (40) ◽  
pp. 27516-27529 ◽  
Author(s):  
A. Kowalewska ◽  
M. Nowacka ◽  
M. Włodarska ◽  
B. Zgardzińska ◽  
R. Zaleski ◽  
...  
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Structural Transformations ◽  
Crystal Lattices ◽  
Thermally Induced ◽  
Crystal Structural

Thermally induced formation of symmetric crystal lattices in functional POSS proceeds via different mechanisms and results in unique reversible phenomena.

Synthesis and structural characterization of a magnesium phthalocyanine(3–) anion

2012 ◽  
Vol 16 (01) ◽  
pp. 154-162 ◽  
Author(s):  
Edwin W.Y. Wong ◽  
Daniel B. Leznoff
Keyword(s):  
Absorption Spectrum ◽  
Solid State ◽  
Single Crystal ◽  
Structural Characterization ◽  
Heterometallic Complex ◽  
State Structure ◽  
Solid State Structure ◽  
X Ray ◽  
X Ray Crystallography

The reduction of magnesium phthalocyanine (MgPc) with 2.2 equivalents of potassium graphite in 1,2-dimethoxyethane (DME) gives [K2(DME)4]PcMg(OH)(1) in 67% yield. Compound 1 was structurally characterized using single crystal X-ray crystallography and was found to be a monomeric, heterometallic complex consisting of a μ3-OH ligand that bridges a [MgIIPc3-]- anion to two potassium cations solvated by four DME molecules. An absorption spectrum of 1 confirms the Pc ligand is singly reduced and has a 3–charge. The solid-state structure of 1 does not indicate breaking of the aromaticity of the Pc ligand. Compound 1 is only the second Pc3- complex and the first reduced MgPc to be isolated and structurally characterized.

Sign in / Sign up

Export Citation Format

Share Document