Crystal structure of 4-hy­droxy-3-meth­oxy­benzaldehyde 4-methyl­thio­semi­carbazone methanol monosolvate

Adriano Bof de Oliveira; Johannes Beck; Christian Landvogt; Bárbara Regina Santos Feitosa

doi:10.1107/S2056989015007227

. 2015 Apr 18;71(Pt 5):o313–o314. doi: 10.1107/S2056989015007227

Crystal structure of 4-hydroxy-3-methoxybenzaldehyde 4-methylthiosemicarbazone methanol monosolvate

Adriano Bof de Oliveira ^a,^*, Johannes Beck ^b, Christian Landvogt ^b, Bárbara Regina Santos Feitosa ^a

PMCID: PMC4420048 PMID: 25995922

Abstract

In the title solvate, C₁₅H₁₅N₃O₂S·CH₃OH, the thiosemicarbazone molecule is approximately planar; the maximum deviation from the mean plane is 0.4659 (14) Å and the dihedral angle between the aromatic rings is 9.83 (8)°. This conformation is supported by an intramolecular N—H⋯N hydrogen bond. In the crystal, the thiosemicarbazone molecules are linked into dimers by pairs of N—H⋯S hydrogen bonds, thereby generating R ₂ ²(8) loops. The methanol solvent molecule bonds to the thiosemicarbazone molecule through a bifurcated O—H⋯(O,O) hydrogen bond and also accepts an O—H⋯O link from the thiosemicarbazone molecule. Together, these links generate a three-dimensional network.

Keywords: crystal structure, bifurcated hydrogen bond, thiosemicarbazone derivative from natural product (vanillin)

Related literature

For one of the first reports of thiosemicarbazone derivatives synthesis, see: Freund & Schander (1902 ▸). For the report concerning the synthesis and crystal structure of 4-hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazone, see: Oliveira et al. (2014 ▸). graphic file with name e-71-0o313-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₅N₃O₂S·CH₄O
M _r = 333.40
Monoclinic,
a = 11.1833 (2) Å
b = 8.4207 (2) Å
c = 17.2521 (4) Å
β = 95.752 (1)°
V = 1616.47 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 123 K
0.29 × 0.15 × 0.09 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▸) T _min = 0.924, T _max = 0.983
46461 measured reflections
3692 independent reflections
2926 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.091
S = 1.05
3692 reflections
284 parameters
All H-atom parameters refined
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▸); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▸); data reduction: DENZO (Otwinowski & Minor, 1997 ▸) and SCALEPACK; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: DIAMOND (Brandenburg, 2010 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸) and WinGX (Farrugia, 2012 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S2056989015007227/hb7402sup1.cif

e-71-0o313-sup1.cif^{(26.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015007227/hb7402Isup2.hkl

e-71-0o313-Isup2.hkl^{(181KB, hkl)}

Click here for additional data file.^{(5.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015007227/hb7402Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015007227/hb7402fig1.tif

The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn isotropically. The bifurcated hydrogen bonds are shown as dashed lines.

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015007227/hb7402fig2.tif

View of the hydrogen bonding in the structure of the title compound showing the three dimensional H-bonded network. Hydrogen bonding is shown as dashed lines.

CCDC reference: 1059141

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N3H13N2	0.866(18)	2.082(17)	2.5865(16)	116.4(14)
N1H14S1ⁱ	0.896(19)	2.530(19)	3.4033(13)	165.2(15)
O1H15O3ⁱⁱ	0.86(2)	1.81(2)	2.6562(14)	167.7(19)
O3H19O2	0.83(2)	2.26(2)	2.8853(14)	132.1(18)
O3H19O1	0.83(2)	2.46(2)	3.1645(15)	144.2(18)

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

BRSF thanks CNPq/UFS for the award of a PIBIC scholarship.

supplementary crystallographic information

S1. Structural commentary

Concerning our on-going research on the supramolecular chemistry of thiosemicarbazone derivatives from natural products, we report herein the synthesis and structure of the 4-hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazone methanol monosolvate, a thiosemicarbazone derivative from vanillin. The thiosemicarbazone group of the title compound doesn't match the ideal planarity and the maximum deviation from the mean plane of the non-H atoms concerning the thiosemicarbazone group amounts to 0.4659 (14) Å for C15 and the dihedral angle between the two aromatic rings amounts to 9.83 (8)° (Fig. 1). In the crystal, molecules are linked into dimers via pairs of N1—H14···S1 hydrogen bonds. The dimers are linked into a three dimensional hydrogen bonded network through the methanol molecules by the O1—H15···O3, O3—H19···O2 and O3—H19···O1 hydrogen interactions (Fig. 2). In addition, one intermolecular N3—H13···N2 hydrogen interaction is also observed (Table 1).

The crystal structure of the solvate free 4-hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazone is already published (Oliveira et al., 2014) and the molecules are linked by N—H···S hydrogen interactions into dimers. Additionally, the dimers are linked by N—H···O and O—H···S hydrogen interactions building a three-dimensional hydrogen-bonded network.

In the actual structure, the presence of the methanol solvate molecules maintains the dimensionality of the network. As the outstanding feature, a bifurcated hydrogen bond is observed. The atom H19 of the hydroxy group of the methanol solvate builds a bifurcated hydrogen bond with the O1 and O2 atoms of the ortho-hydroxy-methoxy entity of the thiosemicarbazone derivative. The H19···O2 and H19···O1 distances amount to 2.26 (2) Å and 2.46 (2) Å (Fig. 1). As the difference between the lengths of the two hydrogen interactions is about 0.2 Å, the bifurcation is considered symmetric. Due to the hydrogen-bond interactions promoted by the solvate molecule, the supramolecularity of the structure modifies the arrangement molecules but the three-dimensional H-bonded network is preserved (Fig. 2).

S2. Synthesis and crystallization

Starting materials were commercially available and were used without further purification. The synthesis of the title compound, 4-hydroxy-3-methoxybenzaldehyde-4-methylthiosemicarbazone, was adapted from a previously procedure (Freund & Schander, 1902 and Oliveira et al., 2014). Colourless blocks were obtained unexpectedly from a mixture containing uranyl acetate dihydrate and the title compound in methanol by the slow evaporation of the solvent.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in the Experimental part. All hydrogen atoms were localized in a difference density Fourier map. Their positions and isotropic displacement parameters were refined.