Synthesis, characterization, and single crystal X-ray structures of [CoIII(acacen)(thioacetamide)2]ClO4 and [CoIII((BA)2en)(thioacetamide)2]PF6 — Solvatochromic properties of [CoIII(acacen)(thioacetamide)2]ClO4

2005 ◽  
Vol 83 (12) ◽  
pp. 2073-2081 ◽  
Author(s):  
Mehdi Amirnasr ◽  
Vratislav Langer ◽  
Nahid Rasouli ◽  
Mehdi Salehi ◽  
Soraia Meghdadi
Keyword(s):  
Solid State ◽  
Molecular Structures ◽  
Axial Position ◽  
Monoclinic Space Group ◽  
Solid State Method ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Ligand Charge Transfer ◽  
Wavelength Absorption

The trans-[CoIII(acacen)(ta)2]ClO4 (1) and trans-[CoIII((BA)2en)(ta)2]PF6 (2) complexes, where H2acacen = bis(acetylacetone)ethylenediimine, H2(BA)2en = bis(benzoylacetone)ethylenediimine, and ta = thioacetamide, have been synthesized by a solid-state method, and characterized by elemental analyses, IR, UV–vis, and 1H NMR spectroscopy. The crystal and molecular structures of 1 and 2 were determined by X-ray crystallography. Both compounds crystallize in the monoclinic space group P2/n. The ClO4 and PF6 ions are both disordered, ClO4 on a twofold axis in 1 and PF6 on an inversion center in 2. Also bridging N-CH2-CH2-N is disordered in both compounds. The octahedral coordination of Co(III) is slightly distorted in both cases. The thioacetamide ligands are S-bonded and occupy the axial position. The IR, UV–vis, and 1H NMR spectra of the two complexes and their solvatochromic properties are also discussed. The longest wavelength absorption that appears at 517 nm for 1 and at 528 nm for 2 in chloroform is solvent dependent, and is assigned as a metal-mediated ligand-to-ligand charge transfer (LLCT).Key words: solid-state synthesis, thioactamide, Co(III) (Schiff base), crystal structure, solvatochromism, metal-mediated LLCT.

Synthesis and characterization of [MII(bqb)] (M = Co, Ni, Cu), [N(n-Bu)4][CoIII(bqb)(CN)2], and [N(n-Bu)4][CoIII(bqb)(N3)2] containing deprotonated N,N'-bis(2-quinolinecarboxamide)-1,2-benzene (bqb) – X-ray crystal structures of [NiII(bqb)] and [N(n-Bu)4][CoIII(bqb)(N3)2]

2006 ◽  
Vol 84 (7) ◽  
pp. 971-978 ◽  
Author(s):  
Soria Meghdadi ◽  
Mehdi Amirnasr ◽  
Vratislav Langer ◽  
Alison Zamanpoor
Keyword(s):  
Crystal Structures ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Square Planar ◽  
Distorted Octahedral ◽  
Elemental Analyses

Cobalt(II), nickel(II), copper(II), and two cobalt(III) complexes of a new dianionic ligand, bqb, [H2bqb = N,N'-bis(2-quinolinecarboxamide)-1,2-benzene] have been synthesized and characterized by elemental analyses, IR, and 1H NMR spectroscopy. The crystal and molecular structures of the [Ni(bqb)] (2) and [N(n-Bu)4][CoIII(bqb)(N3)2] (5) complexes were determined by X-ray crystallography. Complex 2 crystallizes in the monoclinic space group C2/c with a distorted square-planar structure including two short Ni–N (1.848 Å) and two long Ni–N (1.958 Å) bonds. The structure consists of sheets formed in the plane parallel to the b axis and diagonal to vectors a and c by intermolecular hydrogen bonds. Complex 5 crystallizes in the monoclinic space group C2 with a distorted octahedral structure. The [N(n-Bu)4]+ ion is disordered at the C3A and C4A atoms of one Bu. The IR and 1H NMR spectra of the complexes are also discussed.Key words: N4-dianionic amido ligand (bqb), (bqb) complexes of Co(II), Ni(II), Cu(II), and Co(III), azide, cyanide, X-ray crystal structures.

scholarly journals Strukturchemie ungesättigter Siliciumverbindungen: Kristall- und Molekülstrukturen des stabilen Silanimins ′Bu2Si=N—Si′Bu3 und von Silanimin-Donoraddukten (Donor = Tetrahydrofuran, Benzophenon) / Structural Chemistry of Unsaturated Silicon Compounds: Crystal and Molecular Structures of the Stable Silaneimine ′Bu2Si=N—Si′Bu3 and of Silaneimine Donor Adducts (Donor = Tetrahydrofuran, Benzophenone)

1989 ◽  
Vol 44 (7) ◽  
pp. 786-795 ◽  
Author(s):  
Gabriele Reber ◽  
Jürgen Riede ◽  
Nils Wiberg ◽  
Klaus Schurz ◽  
Gerhard Müller
Keyword(s):  
Solid State ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Double Bonds ◽  
Silicon Compounds ◽  
X Ray ◽  
X Ray Crystallography ◽  
Structure Factors ◽  
Nitrogen Double Bond ◽  
Distorted Tetrahedral Coordination

The structure of the first stable silaneimine ′Bu2Si=N—Si′Bu3 (1) (i.e. a compound containing a silicon nitrogen double bond) has been determined by X-ray crystallography (monoclinic, space group P21/n, a = 8.962(1), b = 18.361(1), c = 14.658(1) Å, β = 90.98(1)°, V = 2411.6 Å3.Z = 4, wR = 0.043, w = 1/σ2(Fo) for 208 refined parameters and 2610 observed structure factors. It is monomeric in the solid state and has a nearly linear Si=N—Si skeleton (Si—N—Si 177.8(2)°) with drastically different Si=N and Si—N bond lengths (1.568(3) and 1.695(3) A, respectively). The benzophenone adduct of ′Bu2Si=N—Si′Bu3 and the tetrahydrofuran (THF) adduct of the closely related silaneimine Me2Si=N—Si′Bu3 contain the donor molecules being coordinated exclusively to the unsaturated silicon atoms, which adopt a distorted tetrahedral coordination geometry upon coordination with characteristically elongated Si=N double bonds. The solid state structure of the benzophenone adduct strongly suggests that [2+2] cycloadditions of Si=N double bonds with aldehydes or ketones proceed in a non-concerted manner via prior formation of donor-Si bonds.((THF) • Me2Si=N—Si′Bu3 (2): P21/n, a = 18.480(4), b = 14.209(2), c = 18.683(5) Å, β = 115.11(2)°, V = 4442.2 Å3, Z = 8, wR = 0.094 for 397 parameters and 3432 observables; (Ph2C=O) · ′Bu2Si=N—Si′Bu3 (3): P21,/n, a = 13.247(2), b = 15.689(2), c = 17.073(2) Å. β = 110.53(1)°, V = 3323.0 Å3, Z = 4, wR = 0.039 for 379 refined parameters and 3789 observables.)

Supramoleküle aus Kronenethern und geminalen Sulfonen: Synthese von vier binären Komplexen und Kristallstruktur von (CH2CH2O)4·2H 2C(SO2C2H5)2/Supramolecules of Crown Ethers with Geminal Sulfones: Synthesis of Four Binary Complexes and Crystal Structure of (CH2CH2O )4·2H2C(SO2C2H5)2

1995 ◽  
Vol 50 (7) ◽  
pp. 1018-1024 ◽  
Author(s):  
Axel Michalides ◽  
Dagmar Henschel ◽  
Armand Blaschette ◽  
Peter G. Jones
Keyword(s):  
Monoclinic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Binary Complexes ◽  
Cyclic Polyethers ◽  
Adjacent Unit ◽  
Methylene Group

In a systematic search for supramolecular complexes involving all combinations of the cyclic polyethers 12-crown-4 (12C4), 15-crown-5 (15C 5), 18-crown-6 (18C 6) and dibenzo- 18-crown-6 (DB -18C6), and the geminal di- or trisulfones H2C(SO 2Me)2, H2C (SO2Et)2 and HC (SO2Me)3-n (SO2Et)n (n = 0 -3 ) , only the following four complexes could be isolated and unequivocally characterized by elemental analysis and 1H NMR spectroscopy: [(12C4){H2C (SO2Et)2}2] (3), [(18C6){H2C (S O2Me)2}] (4), [(DB -18C 6){H2C (SO2Et)2}] (5) and [(D B -18C 6)2{HC (SO2Me )(SO2Et)2}3] (6). The structure of 3 (triclinic, space group P1̄) consists of crystallographically centrosymmetric formula units, in which the disulfone molecules are bonded on each side of the ring by two C -H ··· O(crown) interactions originating from the central methylene group (H···O 213 pm) and from the methylene group of one EtSO2 moiety ( H ··· O 237 pm). Formula units related by translation are connected into parallel strands by a third type of reciprocal C -H ···O bond (H ···O 232 pm) between the second H atom of the central methylene group and a sulfonyl oxygen atom of the adjacent unit. The structure of 4 (monoclinic, space group C2/c) showed severe disorder of the crown ether and could not be refined satisfactorily. Compounds 5 and 6 crystallized as long and extremely thin fibres, indicative of linear-polymeric supramolecular structures; single crystals for X-ray crystallography were not available.

scholarly journals A ferrocene redox-active triazolium macrocycle that binds and senses chloride

2012 ◽  
Vol 8 ◽  
pp. 246-252 ◽  
Author(s):  
Nicholas G White ◽  
Paul D Beer
Keyword(s):  
Solid State ◽  
Good Yield ◽  
Electrochemical Studies ◽  
Nmr Titration ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Redox Active

A ferrocene bis(triazole) macrocycle was synthesised in good yield by the Eglinton coupling of an acyclic bis(alkyne) precursor and characterised in the solid state by X-ray crystallography. Alkylation gives the corresponding triazolium macrocycle, which binds chloride and benzoate strongly in CD3CN solution through favourable charge-assisted C–H···anion interactions, as evidenced by 1H NMR titration experiments. Preliminary electrochemical studies reveal that the redox-active macrocycle is capable of sensing chloride in CH3CN solution.

scholarly journals Cavity-Containing [Fe2L3]4+ Helicates: An Examination of Host-Guest Chemistry and Cytotoxicity

2021 ◽  
Vol 9 ◽  
Author(s):  
Lynn S. Lisboa ◽  
Mie Riisom ◽  
Roan A. S. Vasdev ◽  
Stephen M. F. Jamieson ◽  
L. James Wright ◽  
...  
Keyword(s):  
Cell Lines ◽  
Molecular Structures ◽  
Ionization Mass ◽  
Antiproliferative Effects ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Drug Molecules ◽  
Guest Chemistry

Two new di(2,2′-bipyridine) ligands, 2,6-bis([2,2′-bipyridin]-5-ylethynyl)pyridine (L1) and bis(4-([2,2′-bipyridin]-5-ylethynyl)phenyl)methane (L2) were synthesized and used to generate two metallosupramolecular [Fe2(L)3](BF4)4 cylinders. The ligands and cylinders were characterized using elemental analysis, electrospray ionization mass spectrometry, UV-vis, 1H-, 13C and DOSY nuclear magnetic resonance (NMR) spectroscopies. The molecular structures of the [Fe2(L)3](BF4)4 cylinders were confirmed using X-ray crystallography. Both the [Fe2(L1)3](BF4)4 and [Fe2(L2)3](BF4)4 complexes crystallized as racemic (rac) mixtures of the ΔΔ (P) and ΛΛ (M) helicates. However, 1H NMR spectra showed that in solution the larger [Fe2(L2)3](BF4)4 was a mixture of the rac-ΔΔ/ΛΛ and meso-ΔΛ isomers. The host-guest chemistry of the helicates, which both feature a central cavity, was examined with several small drug molecules. However, none of the potential guests were found to bind within the helicates. In vitro cytotoxicity assays demonstrated that both helicates were active against four cancer cell lines. The smaller [Fe2(L1)3](BF4)4 system displayed low μM activity against the HCT116 (IC50 = 7.1 ± 0.5 μM) and NCI-H460 (IC50 = 4.9 ± 0.4 μM) cancer cells. While the antiproliferative effects against all the cell lines examined were less than the well-known anticancer drug cisplatin, their modes of action would be expected to be very different.

Synthesis, Characterization and Crystal Structures of 1,2-Disubstituted Ferrocenyl Stibines

2012 ◽  
Vol 67 (1) ◽  
pp. 36-40
Author(s):  
Diego Pérez ◽  
Pankaj Sharma ◽  
Ana M. Ortiz ◽  
Armando Cabrera ◽  
Simon Hernández ◽  
...  
Keyword(s):  
Solid State ◽  
Acetic Anhydride ◽  
Nucleophilic Substitution ◽  
Sodium Hydroxide ◽  
Crystal Structures ◽  
Analytical Methods ◽  
Molecular Structures ◽  
X Ray ◽  
X Ray Crystallography ◽  
Pendant Arm

New 1,2-disubstituted ferrocenyl stibines containing a -CH2OR pendant arm were synthesized and characterized by various spectral and analytical methods. Nucleophilic substitution of rac-diphenyl[( 2-trimethylammoniomethylferrocen-1-yl)]stibine iodide by methanol produces compound Fc(CH2OMe)SbPh2 (1). The acetylation of diphenyl(2-dimethylaminomethylferrocen-1-yl)stibine by acetic anhydride affords compound Fc(CH2OCOCH3)SbPh2 (2), which on further reaction with sodium hydroxide affords the alcohol Fc(CH2OH)SbPh2 (3). The molecular structures of the stibines 1, 2 and 3 were determined by X-ray crystallography. None of the heterobimetallic compounds containing a -CH2OR arm shows hypervalent interactions in the solid state. By contrast, hypervalent interactions were found in ferrocenyl stibines with a -CH2NR2 pendant arm.

Synthesis and molecular structures of N,N-dialkyl-4-nitrosoaniline adducts of formally d6 metalloporphyrins of ruthenium and cobalt

2001 ◽  
Vol 05 (09) ◽  
pp. 702-707 ◽  
Author(s):  
LI CHEN ◽  
JESSE B. FOX ◽  
GEUN-BAE YI ◽  
MASOOD A. KHAN ◽  
GEORGE B. RICHTER-ADDO
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Molecular Structures ◽  
Spectroscopic Methods ◽  
X Ray ◽  
X Ray Crystallography ◽  
High Yields ◽  
Solid State Structures

Para-aminosubstituted nitrosoarenes react with Ru ( CO )( OEP ) or [ Co ( TPP )( THF )2] SbF 6 (OEP2- = 2,3,7,8,12,13,17,18-octaethylporphyrinato dianion, TPP2- = 5,10,15,20-tetraphenylporphyrinato dianion) to generate Ru ( OEP )( ONC 6 H 4 NMe 2)2 and [ Co ( TPP )( ONC 6 H 4 NR 2)2] SbF 6 ( R = Me , Et ), respectively, in fair to high yields. These N -bound nitrosoarene complexes have been characterized by spectroscopic methods. The complexes Ru ( OEP )( ONC 6 H 4 NMe 2)2 and [ Co ( TPP )( ONC 6 H 4 NMe 2)2] ClO 4 have also been characterized by single-crystal X-ray crystallography. Their structures represent the first reported solid-state structures of Ru and Co porphyrins containing C-nitroso ligands.

Tris-triphenylsiloxy compounds of aluminium

1992 ◽  
Vol 70 (3) ◽  
pp. 771-778 ◽  
Author(s):  
Allen W. Apblett ◽  
Alison C. Warren ◽  
Andrew R. Barron
Keyword(s):  
Variable Temperature ◽  
Molecular Structures ◽  
Water Ligand ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Phenyl Rings ◽  
Coordinated Water ◽  
Hydrolysis Of ◽  
Solvent Complex

The reaction of AlMe3 with three equivalents of HOSiPh3 in THF results in the formation of the solvent complex Al(OSiPh3)3(THF) (1). Hydrolysis of 1 yields the stable water complex Al(OSiPh3)3(H2O)(THF)2 (2) in which the THF molecules are hydrogen bonded to the coordinated water ligand. Compounds 1 and 2 have been fully characterized by 1H, 13C, 17O, 27Al, and 29Si NMR and IR spectroscopy. In addition, variable temperature 1H NMR of 2 has been employed to investigate the steric interactions between the phenyl rings of adjacent siloxide ligands. The molecular structures of the solvates 1•(THF) and 2•(THF)1.25 have been determined by X-ray crystallography. 1•(THF): monoclinic P21/c, a = 10.03 (1), b = 23.758 (6), c = 23.294 (7) Å, β = 101.13 (6)°, Z = 4, R = 0.084, Rw = 0.094. 2•(THF)1.25: cubic [Formula: see text], a = 23.034 (3) Å, Z = 4, R = 0.093, Rw = 0.099. Keywords: aluminium, siloxide, hydrolysis, complex, NMR spectroscopy.

Tris(N,N-dialkyldithiocarbamato-S,S')thiotungsten(VI) Complexes and the X-Ray Crystal Structure of [WS(S2CNEt2)3]BF4

1994 ◽  
Vol 47 (11) ◽  
pp. 2075 ◽  
Author(s):  
CG Young ◽  
TO Kocaba ◽  
M Sadek ◽  
RTC Brownlee ◽  
ERT Tiekink
Keyword(s):  
Variable Temperature ◽  
The Other ◽  
Axial Position ◽  
Monoclinic Space Group ◽  
Equatorial Position ◽  
Full Matrix ◽  
X Ray ◽  
X Ray Crystallography ◽  
Dithiocarbamate Ligand ◽  
R Value

The orange, diamagnetic compounds [WS(S2CNR2)3]X(R = Me, X- = BF4-, BPh4-;R = Et, X- =BF4-) were prepared by reacting WSCl4 and Me3SiS2CNR2 in dichloromethane, followed by metathesis with NaX in methanol. The compounds were characterized by elemental analysis, infrared and variable-temperature 1H n.m.r. spectroscopy and X-ray crystallography. Crystals of [WS(S2CNEt2)3] BF4 were monoclinic, space group P21/a with a 12.293(1), b 17.229(5), c 14.257(2) Ǻ,β 113.69(1)°, V 2765(2) Ǻ3 and Dc = 1.796 g cm-3 for Z = 4. The structure was solved by the Patterson method and refined by a full-matrix least-squares procedure, 3961data being used, to a conventional R value of 0.039 ( Rw = 0.040). The seven-coordinate cation possesses a pentagonal-bipyramidal geometry; the terminal thio ligand [W=S 2.127(2)Ǻ] occupies an axial position, a unique dithiocarbamate ligand spans the other axial position and an equatorial position while the two other dithiocarbamate ligands occupy the four remaining equatorial sites.

scholarly journals Synthesis and molecular structures of monooxo aryl complexes of osmium(VI)

2001 ◽  
Vol 79 (5-6) ◽  
pp. 607-612 ◽  
Author(s):  
Man-Kit Lau ◽  
Joyce LC Chim ◽  
Wing-Tak Wong ◽  
Ian D Williams ◽  
Wa-Hung Leung
Keyword(s):  
Solid State ◽  
Molecular Structures ◽  
Cyclic Voltammograms ◽  
Apical Position ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Aryl Complexes ◽  
Oxo Ligand ◽  
Solid State Structures

Reaction of [OsO4] with C7H7MgBr (C7H7 = 2-methylphenyl) followed by column chromatography afforded the reported osmium tetraaryl [Os(C7H7)4] along with the oxo-osmium(VI) ([OsO(C7H7)4]) (1) (13%) and the dioxo-osmium(VI) ([OsO2(C7H7)2]) (2) (25%) complexes. Treatment of [OsO4] with C8H9MgBr (C8H9 = 2,5-dimethylphenyl) gave a mixture of [Os(C8H9)4] (3) (34%) and [OsO(C8H9)4] (4) (4%) while that with C8H9OMgBr (C8H9O = 4-methoxy-2-methylphenyl) afforded [OsO(C8H9O)4] (5) in 20% yield. Oxidation of 3 with 3-chloroperoxybenzoic acid afforded 4 in good yield. The solid-state structures of 1 and 4 have been established by X-ray crystallography. Crystals of 1 are tetragonal with a = 13.080(1) and c = 6.6506(5) Å, V = 1137.9(1) Å3, Z = 2, and space group of P4/n; while those of 4 are tetragonal with a = 13.593(2) and c = 7.377(2) Å, V = 1363.0(5) Å3, Z = 4, and space group of P4/n. The geometry around osmium in both complexes is square pyramidal with the oxo ligand occupying apical position. The Os—O and Os—C distances in 1 are 1.652(2) and 2.084(1) Å, respectively, while those in 4 are 1.688(7) and 2.088(4) Å, respectively. The cyclic voltammograms of the monooxo aryl osmium(VI) compounds show reversible Os(VI/V) couple at around –1.4 V vs. ferrocene/ferrocenium couple.Key words: osmium(VI), oxo aryl complexes.

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