Polymorphism in metal complexes of thiazole-4-carboxylic acid

Five new molecular complexes of chemical formula [M(4-tza)₂(H₂O)₂] (M = Co, Ni, and Cu) and a complex of [Cu(4-tza)₂]∙4H₂O using thiazole-4-carboxylic acid (4-tza) as the ligand have been successfully synthesized and structurally characterized by single crystal X-ray diffraction. Two district polymorphs (α and β) are found for both [Co(4-tza)₂(H₂O)₂] and [Ni(4-tza)₂(H₂O)₂]. The effects of solvent composition and temperature on the formation of these polymorphs have been investigated and phase behaviour of the polymorphs was studied through X-ray powder diffraction. Unlike two complexes of Co and Ni, [Cu(4-tza)₂(H₂O)₂] does not display polymorphism but exhibits irreversible structural transformation from [Cu(4-tza)₂(H₂O)₂] to the dehydrated form, [Cu(4-tza)₂], upon heating

(1-Butyl-1,4-diazabicyclo[2.2.2]octon-1-ium-κN4)trichloridocobalt(II)

The title compound, [Co(C 10 H 21 N 2 )Cl3], was obtained as the by-product of the attempted synthesis of a cobalt sulfate framework using 1,4-diaza-bicyclo-[2.2.2] octane as an organic template. The asymmetric unit comprises two distinct mol-ecules, and in each, the cobalt(II) ions are tetra-hedrally coordinated by three chloride anions and one 1-butyl-diaza-bicyclo-[2.2.2]octan-1-ium cation. The organic ligands are generated in situ, and exhibit two forms differentiated by the eclipsed and staggered conformations of the butyl groups. These mol-ecules inter-act by way of C - H⋯Cl hydrogen bonds, forming a three-dimensional hydrogen-bonding array

Microwave-assisted hydrothermal synthesis of carbon monolith via a soft-template method using resorcinol and formaldehyde as carbon precursor and pluronic F127 as template

A new microwave-assisted hydrothermal synthesis of carbon monolith is reported in this work. The process uses microwave heating at 100 °C under acidic condition by employing a triblock copolymer F127 as the template, and resorcinol–formaldehyde as the carbon precursor. Scanning electron microscopy, Fourier transform infrared spectroscopy, nitrogen sorption measurements, transmission electron microscopy, X-ray studies and thermogravimetic analysis were used to characterize the synthesized material. The carbon monolith is crack-free, mesoporous and has a high surface area of 697 m²/g. The results demonstrate that the microwave-assisted hydrothermal synthesis is a fast and simple approach to obtain carbon monoliths, as it reduces effectively the synthesis time from hours to a few minutes which could be an advantage in the large scale production of the material

Crystal structure of 4-carbamoylpyridinium chloride

The hydro­chloride salt of isonicotinamide, C6H7N2O+·Cl-, has been synthesized from a dilute solution of hydro­chloric acid in aceto­nitrile. The compound displays monoclinic symmetry (space group C2/c) at 150 K, similar to the related hydro­chloride salt of nicotinamide. The asymmetric unit contains one protonated isonicotinamide mol­ecule and a chloride anion. An array of hydrogen-bonding inter­actions, including a peculiar bifurcated pyridinium-chloride inter­action, results in linear chains running almost perpendicularly in the [150] and [1-50] directions within the structure. A description of the hydrogen-bonding network and comparison with similar compounds are presented

Polymorphism and solid−gas/solid−solid reactions of isonicotinic acid, isonicotinamide, and nicotinamide copper chloride compounds

The crystal structures of eight new copper chloride coordination complexes with substituted pyridines have been determined through a combination of single crystal X-ray diffraction and ab initio structure solution from X-ray powder diffraction data. The polymeric compounds [CuCl₂(INAc)₂]n (1), [CuCl₂(INAm)₂]n (2), and [CuCl₂(NAm)₂]n (3) (INAc = isonicotinic acid; INAm = isonicotinamide; NAm = nicotinamide) consist of chains of CuCl4 edge-sharing rhombi decorated by the pyridine-based ligands. All three compounds display similar hydrogen bonding interactions but differ in the arrangement of the polymeric chains. 1, 2, and 3 react reversibly with hydrochloric acid in solution/vapor form to produce the corresponding tetrachlorocuprate salts [CuCl₄](H-INAc)₂(H₂O) (4a), [CuCl₄](H-INAc)₂ (4b), [CuCl₄](H-INAm)₂ (form I/form II 5a/5b), and [CuCl₄](H-NAm)₂ (form I/form II 6a/6b). 4a exhibits discrete square planar [CuCl4]₂– ions, whereas the Cu in 4b, 5a, and 5b is in a 4 + 2 coordination. All four compounds display hydrogen bonding arrangements similar to those found in 1 and 2. 6a and 6b differ substantially from these compounds in both the hydrogen bonding contacts and the coordination geometry of the cuprate ion (flattened tetrahedral), though they differ from each other only in the orientation of the amide groups and packing arrangements. The formation of 6a/6b depends on the configuration of nicotinamide in the starting material

Vanadium(V) tetra-phenolate complexes: synthesis, structural studies and ethylene homo-(co-)polymerization capability

Reaction of α,α,α′,α′-tetrakis(3,5-di-tert-butyl-2-hydroxyphenyl)-p-xylene (p-L¹H₄) with two equivalents of [VO(OR)₃] (R = nPr, tBu) in refluxing toluene afforded, after work-up, the complexes {[VO(OnPr)(THF)]₂ (μ-p-L¹)}·2(THF) (1·2(THF)) or {[VO(OtBu)]₂ (μ-p-L¹)}·2MeCN (2·2MeCN), respectively in moderate to good yield. A similar reaction using the meta pro-ligand, namely α,α,α′,α′-tetrakis(3,5-di-tert-butyl-2-hydroxyphenyl)-m-xylene (m-L²H₄) afforded the complex {[VO(OnPr)(THF)]₂ (μ-p-L²)} (3). Use of [V(Np-R¹C₆H₄)(tBuO)₃] (R¹ = Me, CF₃) with p-L¹H₄ led to the isolation of the oxo–imido complexes {[VO(tBuO)][V(Np-R¹C₆H₄) (tBuO)](μ-p-L¹)} (R¹ = Me, 4·CH2Cl₂; CF₃, 5·CH2Cl₂), whereas use of [V(Np-R¹C₆H₄)CL³] (R¹ = Me, CF₃) in combination with Et₃N/p-L¹H₄ or p-L¹Na₄ afforded the diimido complexes {[V(Np-MeC₆H₄)(THF)Cl]₂ (μ-p-L¹)}·4toluene (6·4toluene) or {[V(Np-CF₃C₆H₄)(THF)Cl]₂ (μ-p-L¹)} (7). For comparative studies, the complex [(VO)(μ-OnPr)L³]₂ (8) has also been prepared via the interaction of [VO(nPrO)₃] and 2-(α-(2-hydroxy-3,5-di-tert-butylphenyl)benzyl)-4,6-di-tert-butylphenol (L³H2). The crystal structures of 1·2THF, 2·2MeCN, 3, 4·CH2Cl₂, 5·CH2Cl₂, 6·4toluene·THF, 7 and 8 have been determined. Complexes 1–3 and 5–8 have been screened as pre-catalysts for the polymerization of ethylene in the presence of a variety of co-catalysts (with and without a re-activator), including DMAC (dimethylaluminium chloride), DEAC (diethylaluminium chloride), EADC (ethylaluminium dichloride) and EASC (ethylaluminium sesquichloride) at various temperatures and for the co-polymerization of ethylene with propylene; results are compared versus the benchmark catalyst [VO(OEt)Cl₂]. In some cases, activities as high as 243 400 g mmol⁻¹ V⁻¹ h⁻¹ (30.43 kgPE mmol V⁻¹ h⁻¹ bar⁻¹) were achievable, whilst it also proved possible to obtain higher molecular weight polymers (in comparable yields to the use of [VO(OEt)Cl₂]). In all cases with dimethylaluminium chloride (DMAC)/ethyltrichloroacetate (ETA) activation, the activities achieved surpassed those of the benchmark catalyst. In the case of the co-polymerization of ethylene with propylene, complexes 1–3 and 5–8 showed comparable or higher molecular weight than [VO(OEt)Cl₂] with comparable catalytic activities or higher in the case of the imido complexes 6 and 7

Multimetallic lithium complexes derived from the acids Ph₂C(X)CO₂H (X = OH, NH₂) : synthesis, structure and ring opening polymerization of lactides and lactones

Reaction of LiOR (R=t-Bu, Ph) with the acids 2,2/-Ph₂C(X)(CO₂H), X=OH (benzH), NH₂ (dpgH) was investigated. For benzH, one equivalent LiOt-Bu in THF afforded [Li(benz)]2⋅2THF (1⋅2THF), which adopts a 1D chain structure. If acetonitrile is used (mild conditions), another polymorph of 1 is isolated; LiOPh also led to 1. Robust work-up afforded [Li₇(benz)₇(MeCN)] 2MeCN THF (2⋅2MeCN⋅THF). Use of LiOt-Bu (2 equivalents) led to {Li₈(Ot-Bu)₂[(benz)](OCPh₂CO₂CPh₂CO2t-Bu)₂(THF)₄} (3), the core of which comprises two open cubes linked by benz ligands. For dpgH, two equivalents of LiOt-Bu in THF afforded [Li6(Ot-Bu)₂(dpg)₂(THF)₂] (4), which contains an Li₂Ov 6-step ladder. Similar reaction of LiOPh afforded [Li₈(PhO)₄(dpg)₄(MeCN)₄] (5). Complexes 1–5 were screened for their potential as catalysts for ring opening polymerization (ROP) of ϵ-caprolactone (ϵ-CL), rac-lactide (rac-LA) and δ-valerolactone (δ-VL). For ROP of ϵ-CL, conversions > 70 % were achievable at 110 °C with good control. For rac-LA and δ-VL, temperatures of at least 110 °C over 12 h were necessary for activity (conversions > 60 %). Systems employing 2 were inactiv

Turning on ROP activity in a bimetallic Co/Zn complex supported by a [2+2] Schiff-base macrocycle

Homo-dinuclear Co and Zn complexes derived from the macrocycle LH2, {[2-(OH)-5-(R)-C6H2-1,3-(CH)2][CH2CH2(2-C6H4N)2]}2 (R = Me, tBu), revealed near inactivity for the ring opening polymerization (ROP) of the cyclic esters δ-valerolactone (δ-VL) and ϵ-caprolactone (ϵ-CL). By contrast, the hetero-bimetallic complexes [LCo(NCMe)(μ-Br)ZnBr]·nMeCN (n = 3 or 3.25) were found to be efficient catalysts for the ROP of ϵ-CL and δ-VL

Copper coordination polymers constructed from thiazole-5-carboxylic acid: Synthesis, crystal structures, and structural transformation

© 2016 Elsevier Inc. We have successfully prepared crystals of thiazole-5-carboxylic acid (5-Htza) (L) and three new thiazole-5-carboxylate-based Cu 2+ coordination polymers with different dimensionality, namely, 1D [Cu 2 (5-tza) 2 (1,10-phenanthroline) 2 (NO 3 ) 2 ] (1), 2D [Cu(5-tza) 2 (MeOH) 2 ] (2), and 3D [Cu(5-tza) 2 ]·H 2 O (3). These have been characterized by single crystal X-ray diffraction and thermogravimetry. Interestingly, the 2D network structure of 2 can directly transform into the 3D framework of 3 upon removal of methanol molecules at room temperature. 2 can also undergo structural transformation to produce the same 2D network present in the known [Cu(5-tza) 2 ]·1.5H 2 O upon heat treatment for 2 h. This 2D network can adsorb water and convert to 3 upon exposure to air

Crystal structure of (1,3-thiazole-2-carboxylato-κ N)(1,3-thiazole-2-carboxylic acid-κ N)silver(I)

© Meundaeng et al. 2019. The linear two-coordinate silver (I) complex [Ag(C 4 H 2 NO 2 S)(C 4 H 3 NO 2 S)] or [Ag(2-Htza)(2-tza)] is reported (2-Htza = 1,3-thiazole-2-carboxylic acid). The Ag I ion is coordinated by two heterocyclic N atoms from two ligands in a linear configuration, forming a discrete coordination complex. There is an O - H⋯O hydrogen bond between 2-tza - and 2tzaH of adjacent complexes. The hydrogen atom is shared between the two oxygen atoms. This interaction produces a hydrogen-bonded tape parallel to the [110] direction, which is augmented through intermolecular C - H⋯O hydrogen-bonding interactions between the bound thiazole groups. There is a further rather long Ag⋯O interaction [2.8401 (13) Å, compared with a mean of 2.54 (11) Å for 23 structures in the CSD] that assembles these tapes into columns, between which there are C - H⋯π interactions, leading to the formation of a three-dimensional supramolecular architecture