Acetone Solvent Mol-ecule Research Articles

Chiral spin-crossover complexes based on an enantiopure Schiff base ligand with three chiral carbon centers.

The preparation of Fe(II) complexes combining monodentate NCX- (X = S or Se) and the tetradentate Schiff base chiral ligands RR-L1 and SS-L1 = (RR- or SS-L1 = 1R,2R or 1S,2S)-N1,N2-bis(pyridin-2-ylmethylen)cyclohexane-1,2-diamine in acetone results in an unexpected reaction. Thus, four enantiomerically pure compounds of formulas [Fe(RR-S-L2)(NCX)2] and [Fe(SS-R-L2)(NCX)2] (X = S or Se) are formed by the new asymmetrical ligand L2. In L2, one acetone solvent molecule is incorporated into the ligand forming a bond with the C atom of one of the two CN imine groups of L1, which is transformed into an amine (Mannich reaction). This reaction is diastereoselective as the incorporation of acetone leads to an asymmetric C adjacent to the NH group with opposite chirality S- or R- to that of the cyclohexane carbons (RR- or SS-, respectively). Therefore, L2 contains three C chiral centers. Structural and magnetic characterization of these compounds demonstrates that they show in the bulk a gradual spin-crossover behavior and LIESST effect. Interestingly, the presence of an intramolecular hydrogen bond between the integrated acetone molecule and the NH group can trigger a secondary stimuli-responsive behavior in the system. Therefore, by changing the solvent polarity, the color of the complex in solution can be easily tuned.

How the nature and charge of metal cations affect vibrations in acetone solvent molecules.

Vibrational spectra of a series of gas-phase metal 1+ and 2+ ions solvated by acetone molecules are collected to investigate how the metal charge, number of solvent molecules and nature of the metal affect the acetone. The spectra of Cu+(Ace)(N2)2, Cu+(Ace)4, and M2+(Ace)4, where M = Co, Ni, Cu, and Zn are measured via photodissociation by monitoring fragment ion signal as a function of IR wavenumber. The spectra show a red shift of the CO stretch and a blue shift of the C-C antisymmetric stretch. DFT calculations are carried out to provide the simulated spectra of possible isomers to be compared with the observed vibrational spectra, and specific structures are proposed. The red shift of the CO stretch increases as the number of acetone molecules decreases. Higher charge on the metal leads to a larger red shift in the CO stretch. Although all of the M2+ complexes have very similar red shifts, they are predicted to have different geometries due to their different electron configurations. Unexpectedly, we find that the calculated red shift in the CO stretch in M+/2+(Ace) is highly linearly correlated with the ionization energy of the metal for a wide range of metal cations and dications.

Syntheses, crystal structures and Hirshfeld surface analyses of bis-(2-mercaptobenzimidazole)-bromo- and iodo-copper(I) complexes.

The title complexes, bromidobis(2,3-dihydro-1H-1,3-benzodiazole-2-thi-one)copper(I), [CuBr(C7H6N2S)2] (1), and bis(2,3-dihydro-1H-1,3-benzodiazole-2-thione)iodidocopper(I) acetone monosolvate, [CuI(C7H6N2S)2]·CH3COCH3 (2), were prepared by the reaction of copper(I) bromide/iodide with 2-mercaptobenzimidazole. Both complexes have mononuclear structures with the copper atom coordinated by two 2-mercaptobenzimidazole mol-ecules via their S atoms and one halide atom in an approximate trigonal-planar arrangement. In their extended structures, N-H⋯S hydrogen bonds and π-π contacts are found in both complexes; as a result of the acetone solvent mol-ecule in (2), N-H⋯O contacts are also observed. Hirshfeld surface analyses were carried out to aid in the visualization of these inter-actions, which showed that H⋯H contacts contribute 34.6% for (1) and 34.1% for (2) to the overall surface, followed by contributions from H⋯S/S⋯H, H⋯C/C⋯H and C⋯C contacts, respectively. As expected, H⋯O/O⋯H contacts are observed only in (2). The IR and 1H and 13C NMR spectra of (1) and (2) are described.

Synthesis and crystal structure of [Zn6Br4(C9H18NO)4(OH)4]·2C3H6O2.

The complete mol-ecule of the hexa-metallic title complex, namely, tetra-bromido-tetra-μ-hydroxido-hexa-kis-[μ-2-methyl-3-(pyrrolidin-1-yl)propan-2-olato]hexa-zinc(II) acetone disolvate, [Zn6Br4(C9H18NO)4(OH)4]·2C3H6O2, is generated by a crystallographic centre of symmetry. Two of the unique zinc atoms adopt distorted ZnO2NBr tetra-hedral coordination geometries and the other adopts a ZnO3N tetra-hedral arrangement. Both unique alkoxide ligands are N,O-chelating and both hydroxide ions are μ2 bridging. The crystal structure displays an O-H⋯O hydrogen bond between a μ2-OH group and an acetone solvent mol-ecule. The Hirshfeld surface has been calculated and is described.

Crystal structure of fac-{5-[(hexyl-aza-nium-yl)meth-yl]-2-(pyridin-2-yl)phenyl-κ2 N,C 1}bis-[2-(pyridin-2-yl)phenyl-κ2 N,C 1]iridium(III) chloride.

The asymmetric unit of the title compound, fac-[Ir(C11H8N)2(C18H24N2)]Cl or fac-[Ir(ppy)2(Hppy-NC6)]Cl, contains two [Ir(ppy)2(ppy-NC6)](H+) cations, two Cl- anions and disordered solvent. In each complex mol-ecule, the IrIII ion is coordinated by two C,N-bidentate 2-(pyridin-2-yl)phenyl ligands and one C,N-bidentate N-[4-(pyridin-2-yl)benz-yl]hexan-1-aminium ligand, leading to a distorted fac-octa-hedral coordination environment. In the crystal, the mol-ecules are linked by N-H⋯Cl, C-H⋯π and π-π inter-actions, forming a three-dimensional supra-molecular structure. The hexyl group of one mol-ecule is disordered over two orientations with a refined occupancy ratio of 0.412 (13):0.588 (13). The acetone and hexane solvent mol-ecules were found to be highly disordered and their contribution to the scattering was masked using the solvent-masking routine smtbx.mask in OLEX2 [Rees et al. (2005 ▸). Acta Cryst. D61, 1299-1301]. These solvent mol-ecules are not considered in the given chemical formula and other crystal data.

N,N,N′,N′-Tetramethyl-N′′-[2-(trimethylazaniumyl)ethyl]guanidinium bis(tetraphenylborate) acetone disolvate

The asymmetric unit of the title solvated salt, C10H26N42+·2C24H20B−·2C3H6O, comprises one cation, two tetraphenylborate ions and two acetone solvent molecules. The N and methyl C atoms of the terminal trimethylammonium group are disordered over two sets of sites, with a refined occupancy ratio of 0.846 (3):0.154 (3). The C—N bond lengths in the central C3N unit of the guanidinium ion range between 1.3308 (16) and 1.3508 (16) Å, indicating a degree of double-bond character. The central C atom is bonded to the three N atoms in a nearly ideal trigonal–planar geometry and the positive charge is delocalized in the CN3plane. The C—N bond lengths in the terminal trimethylammonium group have values close to that of a typical single bond, and the second positive charge is localized there. In the crystal, the guanidinium ion is connected by N—H...O and C—H...O hydrogen bonds with the acetone molecules. C—H...π interactions are present between the guanidinium H atoms and the phenyl rings of the tetraphenylborate ions, leading to the formation of a two-dimensional supramolecular pattern along thebcplane.

Crystal structure of bis-(tetra-phenyl-phospho-nium) bis-(cyanido-κC)(29H,31H-tetra-benzo[b,g,l,q]porphinato-κ(4) N (29),N (30),N (31),N (32))ferrate(II) acetone disolvate.

The crystal structure of the title compound, (C24H20P)2[Fe(C36H20N4)(CN)2]·2C3H6O, is constructed from a tetra­hedral Ph4P+ (tetra­phenyl­phospho­nium) cation, one [Fe(tbp)(CN)2]2− anion (tbp = tetra­benzoporphyrin in its doubly deprotonated form), located on a centre of inversion, and an acetone mol­ecule as crystallization solvent. Since the mol­ecular structure of the M(tbp) moiety is insensitive to the kind of metal ion and its oxidation state, bond lengths and angles in the [Fe(tbp)(CN)2]2− anion are similar to those in other M(tbp) compounds. The Fe2+ ion, located on a centre of inversion, is coordinated by four N atoms of tpb in the equatorial plane and by two C atoms of the cyanide anion at axial positions in a slightly distorted octa­hedral configuration. The packing is stabilized by C—H⋯N inter­actions between the Ph4P+ cation and the CN− ligand of the [Fe(tbp)(CN)2]2− anion, and by C—H⋯π inter­actions between the Ph4P+ cation, acetone solvent mol­ecules and the [Fe(tbp)(CN)2]2− anion.

Bromido({2-[2-(diphenylphosphanyl)benzylidene]hydrazin-1-ylidene}(4-methoxyanilino)methanethiolato)palladium(II) acetone monosolvate

In the title compound, [PdBr(C27H23N3OPS)]·C3H6O, the coordination geometry about the PdII atom is distorted square-planar, arising from the attached Br, S, P and N atoms (N and Br are trans), the maximum deviation from the plane being 0.2053 (4) Å for the N atom. The three benzene rings attached to the P atom make dihedral angles of 69.78 (7), 87.05 (7) and 77.50 (7)° with each other. An intra­molecular C—H⋯N hydrogen bond forms an S(6) ring motif. In the crystal, the complex mol­ecules form infinite chains along the a-axis direction through C—H⋯Br inter­actions, and a C—H⋯O inter­action links the main mol­ecule with the acetone solvent mol­ecule.

1,1,2,2-Tetrakis(dimethylamino)ethane-1,2-diium bis(tetraphenylborate) acetone disolvate

The title compound, C10H24N4 2+·2C24H20B−·2C3H6O, crystallizes with two acetone solvent mol­ecules per asymmetric unit. In the dication, both amidinium units are twisted about the central C—C single bond by 63.8 (3)° and the positive charges are delocalized over both N—C—N planes.

(Acetylacetonato-κ2O,O′)carbonyl[tris(naphthalen-1-yl)phosphane-κP]rhodium(I) acetone hemisolvate

The title compound, [Rh(C5H7O2)(C30H21P)(CO)]·0.5C3H6O, has two different complex molecules in the asymmetric unit, with the RhI atoms in slightly distorted square-planar coordination environments. The molecules are packed as two monomeric mol­ecules with one acetone solvent mol­ecule sitting at the centre.

Rubrene endoperoxide acetone monosolvate

The title acetone solvate, C42H28O2·C3H6O [systematic name: 1,3,10,12-tetra­phenyl-19,20-dioxapenta­cyclo­[10.6.2.02,11.04,9.013,18]icosa-2(11),3,5,7,9,13,15,17-octa­ene acetone monosolvate], is a photooxygenation product of rubrene (systematic name: 5,6,11,12-tetra­phenyl­tetra­cene). The mol­ecule bends at the bridgehead atoms, which are linked by the O—O transannular bond, with a dihedral angle of 49.21 (6)° between the benzene ring and the naphthalene ring system of the tetra­cene unit. In the crystal, the rubrene mol­ecules are linked by C—H⋯O hydrogen bonds into a column along the c axis. The acetone solvent mol­ecules form a dimer around a crystallographic inversion centre through a carbon­yl–carbonyl dipolar inter­action. A C—H⋯O hydrogen bond between the rubrene and acetone mol­ecules is also observed.

3,5-Bis(2,4-dinitrophenyl)-4-nitro-1H-pyrazole acetone monosolvate

The title structure, C15H7N7O10·C3H6O, was prepared by penta­nitration of 3,5-diphenyl-1H-pyrazole. The proton attached to a pyrazole N atom forms a hydrogen bond with the O atom of the acetone solvent mol­ecule, owing to the NO2 enhanced acidity of the proton. The NO2 group on the phenyl C atom is twisted by 33.9 (2)° from coplanarity with the ring in order to avoid a short intra­molecular O⋯O contact with an O atom of an adjacent pyrazole-bonded NO2 group.

Synthesis, characterization, spectroscopic and crystallographic investigation of Cobalt(III) schiff base complex with two perpendicular diamine coumarin ligands

New transition metal complex of Cobalt(III) of the ligand (E)-3-(1-(2-aminoethylimino)ethyl)-4-hydroxy-2H-chromen-2-one, derived from condensation of ethylene diamine with 3-acetyl-4-hydroxy-chromene-2-one have been synthesized by reaction of cobalt(III) salt and the ligand, in amounts equal to metal-ligand molar ratio of 1:2. Both the Schiff base and the complex of Co(III) were characterized by IR, UV-Vis, 1H NMR- and 13C NMR-spectroscopy techniques. Single crystal X-ray diffraction investigation, at low temperature T = 120 K, shows that the cobalt complex is triclinic P-1, a = 10.426(5) A, b = 11.3234(2) A, c = 15.729(5) A, α(°) = 70.102(4), β(°) = 86.049(4), γ(°) = 82.497(4), Z = 2, and its structure consists of isolated [Co(III)(C13H13N2O3)2]+ complex cations with distorted octahedral geometry, ClO-4 counter anions, acetone solvent and water molecules. The crystal cohesion is stabilized by hydrogen bonds between ligands and water molecules, and ionic interactions between complex cations and counter anions.

Synthesis, crystal structure, DNA interaction and cytotoxicity of a dinuclear nickel(II) complex with 5,7-dichloro-8-hydroxylquinoline

A new nickel(II) complex with 5,7-dichloro-8-hydroxylquinoline (H–ClQ), [NiCl(ClQ)(H–ClQ)(μ-Cl)Ni(ClQ)(CH3CH2OH)(H–ClQ)]·CH3COCH3 (1), was synthesized and characterized. In solid state, 1 is consisted of a dinuclear nickel(II) complex and one acetone solvent molecule. Two Ni(II) atoms are chelated by two bidentate 5,7-dichloro-8-hydroxylquinolines and coordinated by one terminal Cl atom or ethanol ligand and one μ-Cl in a distorted octahedral coordination environment. The ESI-MS result shows that the μ-Cl bridge is easily broken in solution to give mononuclear species (omitted as ClQ–Ni complex). The IC50 values of 1 for the inhibition of the proliferation of BEL7404, SGC7901 and MCF-7 tumor cells are 13.0±2.1, 15.9±5.3, and 29.8±9.5μM, respectively, which exhibit significantly enhanced cytotoxicity comparing with free H–ClQ and NiCl2. The binding properties of ClQ–Ni complex to DNA were investigated by UV–Vis, fluorescence, CD spectroscopy, viscosity and agarose gel electrophoresis. The results indicate that intercalation is the most probable binding mode for ClQ–Ni complex to DNA. The ClQ–Ni complex exhibits potent TOPO I inhibition activity at 50μM.

(η6-IsopropylN-phenylcarbamate)(η5-pentamethylcyclopentadienyl)ruthenium(II) tetraphenylborate acetone monosolvate

The title complex, [Ru(C10H15)(C10H13NO2)](C24H20B)·C3H6O, is related to the analogous O-methyl complex. The average Ru—C distance to the penta­methyl­cyclo­penta­dienyl (Cp*) group is 2.19 (3) Å, and 2.21 (1) Å to the ortho, meta and para C atoms of the arene ring. The Ru—Cipso bond length of 2.272 (3) Å is significantly longer, reflecting movement of the Ru atom away from the C atoms with electronegative substituents attached. The amide H atom in the cation forms an inter­molecular N—H⋯O hydrogen bond with the carbonyl O atom of the acetone solvent mol­ecule. A C—H⋯O inter­action also occurs.

N,N′-Diphenylthiourea acetone monosolvate

In the title compound, C13H12N2S·C3H6O, the phenyl rings of the thio­urea mol­ecule are in syn and anti positions in relation to the C=S bond. Two mol­ecules are connected by N—H⋯S=C hydrogen bonds into a centrosymmetric dimer. An additional N—H⋯O=C hydrogen bond to the acetone solvent mol­ecule and some weak C—H⋯π inter­actions reinforce the crystal structure.

Trans-Carbonylchloridobis[tris(4-chlorophenyl)phosphane]rhodium(I) acetone monosolvate

The title compound, trans-[RhCl(C18H12Cl3P)2(CO)]·C3H6O, contains an Rh(I) atom in a distorted square-planar coordination with a P—Rh—P angle of 175.27 (2)° and Rh—P bond lengths of 2.3127 (4) and 2.3219 (4) Å. The rhodium complexes link each other through weak inter­molecular contacts between the acetone methyl groups and the carbonyl O atom. Inter­actions between the acetone solvent mol­ecule and the Cl—Rh unit results in a reduced P—Rh—Cl angle of 86.675 (15)°.

Poly[[aquadi-μ3-malonato-hexaphenylditin(IV)] acetone solvate

The asymmetric unit of the title polymeric complex, {[Sn2=(C6H5)6(C3H2O4)(H2O)]·C3H6O}n, comprises of two Sn cations, one malonate anion and a non-coordinating acetone solvent mol­ecule. Both crystallographically independent Sn cations are five-coordinated by two O and three C atoms in a distorted trigonal-bipyrimidal geometry. One of the Sn cations is bridged by the malonate units, affording polymeric chains which run along [001]. Weak intra­molecular C—H⋯π inter­actions stabilize the mol­ecular structure. In the crystal structure, adjacent chains are inter­connected by inter­molecular O—H⋯O and C—H⋯O hydrogen bonds into a three-dimensional supra­molecular structure. A weak inter­molecular C—H⋯π inter­action is also observed.

4,5,7-Trimethoxy-2-methyl-3-(2,4,5-trimethoxyphenyl)-1-[3-(2,4,5-trimethoxyphenyl)pentan-2-yl]indane acetone 0.858-solvate

In the title compound, C36H48O9.0.858C3H6O, the five-membered ring adopts an envelope conformation. The acetone solvent mol­ecule was disordered and was refined over two positions with equal occupancies, giving an overall occupancy of 0.858 (4). There are weak intra­molecular C—H⋯O hydrogen bonds and intermolecular C—H⋯π inter­actions in the structure.

A neutral cubane with a ZnII4O4core: tetrabenzoatotetrakis(μ3-hydroxydi-2-pyridylmethanolato)tetrazinc(II)–acetone–methanol (1/2/1)

In the title compound, [Zn4(C11H9N2O2)4(C7H5O2)4]·2(CH3)2CO·CH3OH, the tetra­nuclear mol­ecule lies on a fourfold inversion axis. ZnII ions and μ3-O atoms in the cubane core occupy alternating vertices, forming two inter­penetrating tetra­hedra. Each ZnII ion is further coordinated by two N atoms from two different (py)2C(OH)O ligands (py is pyrid­yl) and one O atom from a monodentate benzoate ligand, forming a distorted octa­hedral environment. The (py)2C(OH)O ligand acts in an η1:η3:η1:μ3 manner, forming two five-membered ZnNCCO chelating rings with two different ZnII atoms sharing a common C—O bond, and an alkoxide-type bond to a third ZnII ion. There are four symmetry-related intra­molecular O—H⋯O hydrogen bonds between the two types of ligands. In the asymmetric unit, there is a half-occupancy acetone solvent mol­ecule and a half-occupancy methanol solvent molecule that lies on a twofold rotation axis.