The cis form of N-methylthiourea in the solid state: Raman spectroscopy, X-ray diffraction and ab initio molecular orbital calculations

Mido, Yoshiyuki; Okada, Hiroko; Fujita, Naokatsu; Kitagawa, Isao; Kitahata, T.; Hashimoto, Masao; Yoshida, Hiroshi

doi:10.1016/s0022-2860(97)00100-2

Cited by 9 publications

(12 citation statements)

References 20 publications

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“…Continuing our studies of alternative crystalline forms of methylureas and methylthioureas, we have now isolated crystalline adducts of methylthiourea (MTU) with morpholine (1:1), 1,1-dimethylthiourea (1,1-DMTU) with 1,4-dioxane (2:1) and 1,3-DMTU with 1,4-dioxane (2:1); we deliberately avoid the term 'pseudopolymorph', which has generated much controversy (Nangia & Desiraju, 1999;Desiraju, 2003Desiraju, , 2004Seddon, 2004;Bernstein, 2005;Nangia, 2006) for solvates or adducts. We have also confirmed and redetermined the known structures of MTU (Mido et al, 1997) and 1,1-DMTU (Pathirana et al, 1994), and investigated the structure of 1,3-DMTU, which was however found to be severely disordered (see below). Finally, we have determined the structure of tetramethylthiourea (TetMTU).…”

Section: Introductionsupporting

confidence: 65%

“…The room-temperature structure of MTU was reported by Mido et al (1997) in P1 with a = 7.823 (2), b = 12.051 7, c = 7.754 (8) Å , = 124.13 (5), = 80.49 (5), = 128.33 (2) . This cell can be transformed to the conventional reduced cell (Table 1) by the matrix (0 0 1 / 1 0 0 / 1 1 1).…”

Section: Methylthioureamentioning

confidence: 95%

“…1) confirms the earlier determination but is somewhat more precise. Mido et al (1997) were primarily interested in establishing the conformation of the methyl group, which proved to be trans to the C S group across the C-N bond (we use this definition of cis and trans throughout). As discussed in our earlier paper (Nä ther et al, 2013), this would be highly unusual for an RNH group in a The two independent molecules of MTU in the crystal.…”

Section: Methylthioureamentioning

confidence: 99%

“…We were interested in the molecular packing of MTU, which was not discussed by Mido et al (1997). The most obvious feature is that the two independent molecules are connected to form a dimer by mutual N1-H01Á Á ÁS1 C2 interactions Details of hydrogen bonding (Å , ).…”

Section: Methylthioureamentioning

confidence: 99%

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Methylthioureas and their morpholine and dioxane adducts; hydrogen-bonding patterns

Jones

Taouss

Teschmit

et al. 2013

Acta Crystallogr Sect B

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We have redetermined the known structures of (i) methylthiourea (MTU) and (ii) 1,1-dimethylthiourea (1,1-DMTU), and investigated the structure of 1,3-dimethylthiourea (1,3-DMTU), which was however severely disordered. We report the structures of crystalline adducts of (iii) MTU with morpholine (1:1), (iv) 1,1-DMTU with 1,4-dioxane (2:1) and (v) 1,3-DMTU with 1,4-dioxane (2:1). Finally, (vi) we determined the structure of tetramethylthiourea (TetMTU). (i) In both independent molecules of MTU, the methyl group is trans to the C=S group across the C-N bond. The two molecules are connected to form an R2(2)(8) dimer by mutual N-H...S=C interactions. The packing involves six N-H...S=C interactions and is three-dimensional. (ii) The packing of the MTU-morpholine adduct is a layer structure, within which both molecules form linear aggregates parallel to the b axis. (iii) The packing of 1,1-DMTU involves N-H...S=C hydrogen bonds forming a corrugated layer structure. (iv) In the 2:1 adduct between 1,1-DMTU and 1,4-dioxane, the DMTU molecule occupies a general position whereas the dioxane molecule lies across an inversion centre. The crystal packing involves chains of alternating 1,1-DMTU R2(2)(8) dimers and dioxanes, both across inversion centres. (v) In the 2:1 adduct between 1,3-DMTU and dioxane, the 1,3-DMTU molecule occupies a general position, while the dioxane molecule lies across an inversion centre. One methyl group of the DMTU is trans and one cis to the sulfur across the corresponding C-N bond. The molecules form chains of alternating 1,3-DMTU R2(2)(8) dimers and dioxanes, both across inversion centres. Crystals of the 2:1 adduct between 1,3-DMTU and morpholine were also obtained, and were isotypic with the dioxane adduct. The morpholine molecule is disordered across the inversion centre. (vi) The molecule of TetMTU displays crystallographic twofold symmetry. Significant distortions reflect the steric pressure between methyl groups trans to sulfur. The packing of TetMTU involves only a weak hydrogen bond, C-Hmethyl...S, which connects the molecules to form layers.

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Section: Introductionsupporting

confidence: 65%

Section: Methylthioureamentioning

confidence: 95%

Section: Methylthioureamentioning

confidence: 99%

Section: Methylthioureamentioning

confidence: 99%

See 2 more Smart Citations

Methylthioureas and their morpholine and dioxane adducts; hydrogen-bonding patterns

Jones

Taouss

Teschmit

et al. 2013

Acta Crystallogr Sect B

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“…The energies, dipole moments and thermodynamic functions of the thiourea ligands are shown in Table-1. It was reported that, N-methylthiourea and N,N'-dimethylthiourea exist in the cis-trans and trans-trans configuration, respectively 2,11 . The DFT gas phase calculations predicted the cisconformer of N-methylthiourea is more stable than the trans one while for N,N'-dimethylthiourea, the cis-trans conformer is more stable than the others.…”

Section: Stabilities Dipole Moments (µ) and Thermodynamic Functionsmentioning

confidence: 99%

DFT Studies on the Molecular Structure, Electronic and Spectroscopic Properties of Free and Zinc(II) Coordinated N-Alkyl Thiourea Ligands

Soliman¹,

Badr²

2014

Asian J. Chem.

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The study of thiourea and its N-substituted derivatives have great interest 1 in view of the potential use of these compounds as highly selective reagents for the separation of metal cations 1 and in biological applications such as their use as antibacterial, antiviral or antifungal agents 2,3 . Also the importance of these thioamides is due to the relevance of their binding sites to those in living systems 2 . Their transition metal complexes are also subject of interest due to the special roles played by these compounds in biological processes 1,4,5 .The coordination occurs between the metal with sulphur rather than between the metal and nitrogen 6 . It is also found that thiourea ligands can exist in the highly polar structure (Fig. 1). The molecular structure of these compounds is considered to be a resonance hybrid with this highly polar structure. In this work, the molecular structure and vibrational spectra of thiourea (TU), N-methylthiourea (MTU), N,N'dimethylthiourea (DMTU), tetramethylthiourea (TMTU), diazinane-2-thione (DAT); (Fig. 1) and their zinc chloride complexes [ZnL2Cl2] are calculated using DFT/B3LYP/6-311+G(d,p) method. The aim of this work is to explain the effect of N-alkyl substitution and metal ion coordination on the molecular structure, reactivity, electronic and spectroscopic properties of these compounds using DFT/B3LYP method.

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Synthesis, characterization and biological evaluation of novel antimony(III) iodide complexes with tetramethylthiourea and N-ethylthiourea

Öztürk

Yarar

Gürgan

et al. 2019

Inorganica Chimica Acta

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The cis form of N-methylthiourea in the solid state: Raman spectroscopy, X-ray diffraction and ab initio molecular orbital calculations

Cited by 9 publications

References 20 publications

Methylthioureas and their morpholine and dioxane adducts; hydrogen-bonding patterns

Methylthioureas and their morpholine and dioxane adducts; hydrogen-bonding patterns

DFT Studies on the Molecular Structure, Electronic and Spectroscopic Properties of Free and Zinc(II) Coordinated N-Alkyl Thiourea Ligands

Synthesis, characterization and biological evaluation of novel antimony(III) iodide complexes with tetramethylthiourea and N-ethylthiourea

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