The structure of [Fe(CO)3(η4-6-exo-(4-biphenylamino)cyclohepta-2,4-dien-1-one] [monoclinic, a = 20.368 (1), b = 6.2757(4), c = 29.5214(14), β = 101.024(5), space group C2/c] has been determined. There is a moderate hydrogen-bond between the amine proton and the oxygen atom of the ketone in another molecule. There is no significant π-stacking of the phenyl rings, but the nitrogen atom is fairly planar likely due to interaction with the π-system of the 4-biphenyl group and the hydrogen-bonding.
Addition of two equivalents of 4-biphenylamine to [Fe(CO)3(η5-cyclohepta-2,4-dien-5-yl-1-one)][BF4] results in exo- attack at the coordinated ring forming the [Fe(CO)3(η4-6-exo-(NH(4-biphenyl)))cyclohepta-2,4-dien-1-one], which was structurally characterized
Lithiated N-(2,6-diisopropylphenyl)-[6-(2,4,6-triisopropylphenyl)-pyridine-2-yl]-amine (ApH) undergoes a salt metathesis reaction with MnBr2 in tetrahydrofuran (THF) at 50 °C in the presence of two equivalents of 4-tert-butylpyridine (tBuPy) to yield only the second example of mononuclear manganese aminopyridinates, [Mn(Ap)2(tBuPy)]. The compound [C59H71MnN5], crystallized in the monoclinic space group, P21/c with unit cell parameters: a = 11.9650(5) b = 17.9530(7) c = 24.3110(10) Å, β = 95.081(3)°, V = 5201.7(4) A3, Z = 4. Hirshfeld analyses show that H⋯H (89.1%) and H⋯C/C⋯H (10.9%) interactions are the two main contributors that lead to intermolecular stabilization in the solid-state structure.
The crystal structures of four 2-pyridineformamide thiosemicarbazone derivatives viz, (Z, Z’)-4-methyl-N’-(morpholine-4-carbonothioyl)picolinohydrazonamide (1), (Z, Z’)-4-methyl-N’-(thiomorpholine-4-carbonothioyl) picolinohydrazonamide (2), (Z, Z’)-6-methyl-N’-(thiomorpholine-4-carbonothioyl)picolinohydrazonamide (3) and (Z, Z’)-N’-(azepane-1-carbonothioyl)-4-methylpicolinohydrazonamide (4) has been determined by single crystal X-ray diffraction analysis. Combined quantum mechanical methods (ORCA) and computation of non-spherical scattering form factors (NoSpherA2) were used for the refinement with anisotropic hydrogen atoms. The results of using independent atom model (IAM) and Hirshfield atom refinement (HAR) method based R2SCAN/ def2-TZVP functional were compared. All compounds show an improvement in the model after HAR refinement compared to independent atom model (IAM). There is a significant decrease in the residual factors with the use of anisotropic hydrogen refinement. HAR refinement provides a clearer understanding of electron delocalization, lone pairs, and the accumulation and depletion of electron density. The information obtained came from standard resolution single crystal X-ray diffraction data, indicating that high-quality structural analysis can now be performed without the need for neutron or synchrotron facilities.
Structural studies of four 2-pyridineformamide thiosemicarbazone derivatives using non-spherical atomic form factors
Reaction of N-benzyl-1-chloromethanesulfonamide with phenyl isothiocyanate formed N-benzyl-3-phenylimino-1,4,2-dithiazolidine 1,1-dioxide. Crystals of this compound occurred in the monoclinic system, space group P 2(1), a = 26.7099(16) Å, b = 13.2518(5) Å, c = 8.2769(4) Å, β = 97.099(5)o, Z = 8, with four molecules in the asymmetric unit. The structure confirms a prior assignment that the C = S bond of the isothiocyanate was the reactive moiety. Using the same reaction conditions, 3,5-dimethylphenyl isocyanate was reacted N-benzyl-1-chloromethanesulfonamide to produce a product in 81% yield, which was determined to be 2-benzyl-4-(3’,5’-dimethylphenyl)-1,2,4-thiadiazolidin-3-one 1,1-dioxide. Crystals of this compound are monoclinic, space group P 2(1)/n, a = 5.2243(11) Å, b = 15.844(5) Å, c = 18.628(3) Å, β = 96.72(2)o, and Z = 4. This product demonstrated that the C = N bond of the aryl isocyanate reacted to form the 1,2,4-thiadiazolidin-3-one 1,1-dioxide ring system.
Heterocyclic rings formed from N-benzyl-1-chloromethanesulfonamide and phenyl isothiocyanate via the C = S bond (structure on the left) or 3,5-dimethylphenyl isocyanate via the C = N bond (structure on the right)
8-Nitrobenzo-1,3-thiazin-4-ones (BTZs) are a promising class of antitubercular agents with a novel mechanism of action, viz. suicide inhibition of decaprenylphosphoryl-β-D-ribose 2’-epimerase 1 (DprE1), an enzyme crucial for cell wall synthesis in the pathogen Mycobacterium tuberculosis. 8-Nitro-2-(piperidin-1-yl)-6-(trifluoromethyl)-4H-benzo-1,3-thiazin-4-one (1) is a chemically simplified analogue of the anti-tuberculosis phase 2 clinical drug candidate BTZ-043. Structural elucidation of 1 in the solid-state has been carried out by X-ray crystallography and two polymorphic forms of 1 have been revealed. 1-I crystallizes in the triclinic system (space group P-1, Z = 6) with one molecule exhibiting whole-molecule disorder with a preferred orientation. The crystal structure of 1-II belongs to the tetragonal system (space group P43, Z = 4) and exhibits positional disorder in several parts of the molecule.
X-ray crystallography revealed a triclinic (space group P-1, Z = 6) and a tetragonal (space group P43, Z = 4) polymorph of the antimycobacterial agent 8-nitro-2-(piperidin-1-yl)-6-(trifluoromethyl)-4H-benzo-1,3-thiazin-4-one
The study about the supramolecular interactions in the organic–inorganic hybrids will be significant for the design of new photo/electrical functional materials. In this work, 1,ω-bis(isoquinoline)alkane cations with different spacer lengths (n = 3, 5, 6) have been incorporated with iodobismuthates to construct three new hybrids, which have been formula as [BIQPP]2[Bi4I16] (1), [BIQPT]2[Bi4I16] (2) and [BIQHX]2[Bi4I16] (3) through X-ray single crystal diffraction method (BIQPP2+ = 1,3-bis(isoquinoline)propane, BIQPT2+ = 1,5-bis(isoquinoline) pentane, BIQHX2+ = 1,6-bis(isoquinoline)hexane). The centrosymmetric [Bi4I16]4− anions are constructed from four edge-sharing BiI6 octahedra. Interestingly, with the elongation of spacer length on isoquinoline from 3, 5 to 6, the iodobismuthate anions exhibit 0-D [Bi4I16]4− tetramers (n = 3, 6 for 1 and 3) and pseudo 3-D [Bi4I16]n4n− network (n = 5, for 2) based on I···I interactions. Supramolecular interactions including π–π stacking interactions and C–H···I hydrogen bonds contribute to their structural extensions. Consequently, the enhanced red emission intensity and the lower thermochromic temperature can be observed in 2. The clarification on the spacer effect on the supramolecular interactions and functional properties of this work will be beneficial for the design of new functional materials.
Different iodobismuthate anions and photo-physical properties including red emission intensity and thermochromism can be achieved by elongating the spacer lengths in 1,ω-Bis(isoquinoline)alkane cations
The structures of [Fe(CO)3(η4-6-exo-(tri-m-tolylphosphine)cyclohepta-2,4-dien-1-one][BF4] [tetragonal, a = 35.6005(7), b = 35.6005(7), c = 10.5456(3), space group I41/a] and [Fe(CO)3(η4-6-exo-(tri-p-fluorophenylphosphine)cyclohepta-2,4-dien-1-one][BF4] [triclinic, a = 9.8852(3), b = 10.0996(4), c = 16.0526(4), α = 99.813(3), β = 94.164(2), g = 102.911(3) space group P-1] have been determined. Both structures contain a disordered CH2Cl2 molecule. The tetrafluoroborate ion in [Fe(CO)3(η4-6-exo-(tri-m-tolylphosphine)cyclohepta-2,4-dien-1-one][BF4] is also disordered. There are no close contacts indicative of hydrogen bonding within either structure, but there is π-π stacking observed for [Fe(CO)3(η4-6-exo-(tri-m-tolylphosphine)cyclohepta-2,4-dien-1-one][BF4].
Addition of PAr3 (Ar = m-C6H4CH3 or p-C6H4F) to [Fe(CO)3(η5-cyclohepta-2,4-dien-5-yl-1-one)][BF4] results in attack at the coordinated ring in a position exo- to the iron atom forming the corresponding [Fe(CO)3(η4-6-exo-(PAr3)cyclohepta-2,4-dien-1-one][BF4] compounds, which were structurally characterized
The structures of [Fe(CO)3(η4-6-exo-(methyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF4] [orthorhombic, a = 12.3269(4), b = 13.5243(5), c = 13.7127(4), space group Pna21] and [Fe(CO)3(η4-6-exo-(tert-butyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF4] [monoclinic, a = 9.7947(3), b = 12.8766(3), c = 20.2168(5), β = 91.089(3), space group P21/c] have been determined. The disordered tetrafluoroborate ion in [Fe(CO)3(η4-6-exo-(methyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF4] sits between two of the cations and displays interactions with hydrogen atoms in the ortho- position of the phenyl rings, the methyl group and the 6-position of the seven-membered ring. There is also close contact between the ketone oxygen atom and two protons in another cation, a proton of the methyl group and the proton in the 5-position of the seven-membered ring. The tetrafluoroborate anion in [Fe(CO)3(η4-6-exo-(tert-butyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF4] is not disordered and shows close contacts with protons in three cation units. In one cation the interaction is with two protons from separate methyl groups of the tert-butyl substituent. The remaining interactions are with a proton in the ortho- position of a phenyl ring in one cation and the proton in the 2-position of the seven-membered ring. There is also an interaction between the ketone oxygen and a proton from the tert-butyl group in another cationic unit.
Addition of PPh2R (R = Me or tBu) to [Fe(CO)3(η5-cyclohepta-2,4-dien-5-yl-1-one)][BF4] results in exo- attack at the coordinated ring forming the [Fe(CO)3(η4-6-exo-(PPh2R)cyclohepta-2,4-dien-1-one][BF4] compounds, both of which were structurally characterized.
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