Structural, spectral and thermal studies of N-2-(4,6-lutidyl)-N′-chlorophenylthioureas (original) (raw)
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Journal of Molecular Structure, 2002
N-2-(4-picolyl)-N′-4-chlorophenylthiourea, 4PicTu4ClPh, triclinic, P-1, a=7.5235(3), b=9.1585(5), c=10.5158(7)Å,α=76.015(3), β=70.015(4), γ=82.010(4)°, V=1309.8(2)Å3 and Z=2; N-2-(5-picolyl)-N′-4-chlorophenylthiourea, 5PicTu4ClPh, monoclinic, P21/c, a=15.139(2), b=4.8386(3), c=17.338(2)Å,β=90.661(4)°, V=1270.0(2)Å3 and Z=4 and N-2-(6-picolyl)-N′-4-chlorophenylthiourea, 6PicTu4ClPh, monoclinic, C2/c, a=33.520(6), b=4.0750(3), c=18.658(4)Å,β=97.500(6)°, V=2526.8(7)Å3 and Z=8. The most striking difference between the structures of the three thioureas is the difference in planarity, and among the four N-2-(picolyl)-N′-4-chlorophenylthioureas, their values for ΔHfus.
Journal of Molecular Structure, 2002
The following molecules were found to have intramolecular hydrogen bonding between the N 0 H and the pyridine nitrogen and intermolecular hydrogen bonding between the NH and a thione sulfur of a second molecule to form dimers: N-(2-pyridyl)-N 0 -(4-methoxyphenyl)thiourea, PyTu4OMe, triclinic, P-1, a 7:1584; b 8:7423; c 10:8334 A; a 70:533; b 74:383; g 73:9748; V 635:55 A 3 and Z 2; N-(2-pyridyl)-N 0 -(4-nitrophenyl)thiourea, PyTu4NO 2 , monoclinic, P2 1 / c, a 11:6701; b 5:92259; c 18:7924 A; b 107:9918; V 1244:87 A 3 and Z 4; N-(2-pyridyl)-N 0 -(4chlorophenyl)thiourea, PyTu4Cl, triclinic, P-1, a 9:9393; b 11:3994; c 12:2645 A; a 65:504; b 87:463; g 76:6338; V 1228:17 A 3 and Z 4 and N-(2-pyridyl)-N 0 -(4-bromophenyl)thiourea, PyTu4Br, triclinic, P-1, a 10:0202; b 11:4442; c 12:3535 A; a 64:762; b 87:613; g 77:8828; V 1250:87 A 3 and Z 4:
Structural, spectral and thermal studies of substituted N-(2-pyridyl)-N′-phenylthioureas
Journal of Molecular Structure, 2002
N-2-(3-picolyl)-N′-phenylthiourea, 3PicTuPh, monoclinic, P2 1 /n, a=7.617(2) b=7.197(5), c=22.889(5) Å, β=94.63(4)°, V=1250.7(1) Å 3 and Z=4; N-2-(4-picolyl)-N′-phenylthiourea, 4PicTuPh, triclinic, P-1, a=7.3960(5), b=7.9660(12), c=21.600(3) Å, α=86.401(4), ...
Two novel 1-(1-naphthoyl)-3-(halo-phenyl) substituted thioureas, namely 1-(1-naph thoyl)-3-(2,4-di-fluoro-phenyl)-thiourea (1) and 1-(1-naphthoyl)-3-(3-chloro-4-fluoro-phenyl)-thiourea (2), were synthesized and fully characterized. The X-ray crystal and molecular structures have been determined resulting in a planar acylthiourea group, with the C@O and C@S adopting a pseudo-antiperiplanar conformation. An intramolecular NAH O@C hydrogen bond occurs between the thioamide and carbonyl groups. The crystal packing of both compounds is characterized by extended intermolecular NAH S@C and NAH O@C hydrogen-bonding interactions involving the acylthiourea moiety. Compound 2 is further stabilized by p-stacking between adjacent naphthalene and phenyl rings. The thermal behavior, as well as the vibrational properties, studied by infrared and Raman spectroscopy data complemented by quantum chemical calculations at the B3PW91/6-311++G(d,p) support the formation of these intra- and intermolecular hydrogen bonds. Furthermore, the UV–Vis spectrum is interpreted in terms of TD-DFT quantum chemical calculations with the shapes of the simulated absorption spectra in good accordance with the experimental data.
Structural studies of N-2-(6-aminopyridine)-N′-arylthioureas
Journal of Molecular Structure, 2003
N-2-(6-aminopyridine)-N′-2-methoxyphenylthiourea, 6AmTu2OMe, monoclinic, C2/c, a=16.3150(17), b=11.3000(13), c=14.8970(9)Å, β=101.219(7)°, V=2693.9(4)Å3 and Z=8; N-2-(6-aminopyridine)-N′-4-chlorophenylthiourea, 6AmTu4Cl, monoclinic, P21/n, a=14.2080(9), b=9.8060(7), c=19.041(1)Å, β=104.616(4)°, V=2567.0(3)Å3 and Z=8 and N-2-(6-aminopyridine)-N′-4-nitrophenylthiourea, 6AmTu4NO2, monoclinic, P21/n, a=10.809(8), b=10.427(8), c=12.303(7)Å, β=110.47(7)°, V=1299.1(16)Å3 and Z=4. The intramolecular hydrogen bonding common to 2-pyridylthioureas between N′H and the pyridine nitrogen is present as well as the intermolecular hydrogen bonding involving the thione sulfur
Comprehensive Thermochemical Study of Cyclic Five- and Six-Membered N,N′-Thioureas
Journal of Chemical & Engineering Data, 2017
An experimental and computational study of the thermochemical and structural properties of ethylenethiourea (ETU) has been carried out. The enthalpies of combustion and sublimation, measured respectively by rotating-bomb combustion calorimetry and Calvet microcalorimetry, yielded the gas-phase enthalpy of formation of ETU at T = 298.15 K. This latter parameter was also derived from high-level molecular orbital calculations at the G3(MP2)//B3LYP level of theory, leading to a value in excellent agreement with the one obtained from experimental data. With the purpose of evaluating the influence of the ring size in the enthalpy of formation of cyclic N,N′thiourea derivatives, the calculation of the enthalpy of formation of N,N′-trimethylenethiourea (MTU) was performed using the G3-(MP2)//B3LYP approach. The effects of substituents (carbonyl and thiocarbonyl) on the molecular stability of several N-alkyl (cyclic) ureas/thioureas were also studied.
Growth, characterization, crystal and molecular structure studies of
Journal of Crystal Growth, 2011
1-ð2 0-ThiophenÞ-3-ð2,3,5-trichlorophenylÞ-2-propen-1-one (TTCP) was synthesized by Claisen-Schmidt condensation reaction. FT-IR spectra were recorded to identify the functional groups present in the compound. The NLO test carried out on the sample using Z-scan technique confirms the existence of nonlinearity in the third harmonic generation. Further, the compound is characterized by UV-visible spectral studies for the optical transmission. Finally, the structure of the product obtained was confirmed by the X-ray diffraction studies. The compound crystallizes in the monoclinic space group P2 1 =c with a ¼ 16:6170ð6ÞÅ, b ¼ 7:6180ð5ÞÅ, c ¼ 10:9280ð11ÞÅ and b ¼ 104:635ð3Þ1. The thiophene ring shows planar conformation and is affected by p conjugation. The unsaturated keto group is in þ syn-periplanar conformation. The molecule exhibits both inter and intramolecular hydrogen bonds of the type C-H Á Á Á O and C-H Á Á Á Cl which can account for the stability of the molecule.
Journal of Molecular Structure, 2010
The 1-(2-chlorobenzoyl)-3-(isomeric fluorophenyl)thiourea derivatives (1-3) were prepared by the reaction of 2-chlorobenzoyl isothiocyanate produced in situ with isomeric fluoroanilines in excellent yields. The novel compounds are characterized by multinuclear (1 H and 13 C) NMR, GC-MS, elemental analyses and FTIR spectroscopy techniques. Structural and conformational properties of compounds 1-3 are analyzed using a combined approach including X-ray diffraction, vibrational spectra (solid FTIR and FT-Raman) and theoretical calculation methods. The crystal structures have been determined by X-ray diffraction methods. The three species crystallize in the monoclinic C2/c space group with and Z = 8 molecules per unit cell. The carbonyl and thiourea groups are almost planar and the conformation adopted by the C@S and the C@O double bonds is antiperiplanar. The crystal lattices show the presence of centrosymmetric dimeric units held by NÀHÁÁÁS hydrogen bonds stacked along the [0 1 0] plane. The effect of fluorine substitution on the vibrational properties and on the conformational space has been determined by quantum chemical calculations (B3LYP functional in connection with the 6-311+G Ã basis sets) and vibrational spectroscopy.
N -(4-Chlorobutanoyl)- N ′-phenylthiourea
Acta Crystallographica Section E Structure Reports Online, 2011
Key indicators: single-crystal X-ray study; T = 298 K; mean (C-C) = 0.005 Å; R factor = 0.048; wR factor = 0.131; data-to-parameter ratio = 16.3.
2004
Basic concepts and background of some computational methods and infrared spectroscopy 2.1 Introduction 2.2 The quantum mechanical "ab initio" method 2.2.1 The Hartree-Fock (HF) method 2.3 Basis Sets 2.3.1 Slater and Gaussian type orbitals 2.3.3 Types of basis sets 2.3.3.1 Contracted basis sets 2.3.3.2 Effective core potential basis sets 2.4 Electron correlation methods 2.4.1 Configuration Interaction 2.4.2 Moller-Plesset Perturbation Theory 2.4.3 The Coupled Cluster Method 2.5 Semi-empirical methods 2.6 Molecular Mechanics Method 2.7 Electronic Structure Analysis methods 2.7.1 Theory of atoms in molecules (AIM) 2.7.1.1 Electron density p (r) 2.7.1.2 Laplacian of the electron density V 2 p (r) 2.7.2 Natural Bond Orbital Analysis (NBO) 2.7.3 The natural resonance theory analysis (NRT)