1-[(E)-(3-Hy­droxy-4-meth­oxy­benzyl­idene)amino]-3-methyl­thio­urea

Arafath, M.A.; Adam, F.; Razali, M.R.

doi:10.1107/S2414314616015996

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 10| October 2016| x161599

https://doi.org/10.1107/S2414314616015996

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1-[(E)-(3-Hydroxy-4-methoxybenzylidene)amino]-3-methylthiourea

Md. Azharul Arafath,^a Farook Adam ^a ^* and Mohd. R. Razali ^a

^aThe School of Chemical Sciences, Universiti Sains Malaysia (USM), Minden 1800, Penang, Malaysia
^*Correspondence e-mail: farookdr@gmail.com

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 3 October 2016; accepted 10 October 2016; online 15 October 2016)

In the title thiosemicarbazone Schiff base compound, C₁₀H₁₃N₃O₂S, the dihedral angle between the benzene ring and methyl carbothioamide side arm was found to be 17.4 (4)°. The presence of two intramolecular hydrogen bonds is noted, namely hydroxy-O—H⋯O(methoxy) and amine-N—H⋯N(imine). In the crystal, pairwise amine-N—H⋯S hydrogen bonds give rise to centrosymmetric {⋯HNCS}₂ synthons, which lead to dimeric aggregates.

Keywords: crystal structure; carbothioamide; Schiff base; hydrogen bonding.

CCDC reference: 1411362

Structure description

The molecule of the title compound (Fig. 1) is not completely planar, as indicated by the dihedral angle of 17.4 (4)° between the benzene ring and carbothioamide side chain. The crystal packing is reinforced by pairwise N—H⋯S hydrogen bonds, which connect molecules into dimeric aggregates, Fig. 2 and Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯O1	0.85 (3)	2.18 (3)	2.6564 (19)	115 (2)
N3—H1N3⋯N1	0.847 (19)	2.32 (2)	2.682 (2)	106.1 (16)
N2—H1N2⋯S1ⁱ	0.86 (2)	2.63 (2)	3.4753 (16)	167.8 (16)
N3—H1N3⋯S1ⁱⁱ	0.847 (19)	2.85 (2)	3.4839 (16)	133.5 (17)
Symmetry codes: (i) -x, -y+1, -z-1; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. The intramolecular O—H⋯O hydrogen bond should be shown

Figure 2
The packing of the title compound viewed along the b axis. Hydrogen bonds are shown as dashed lines.

Similar structures of carbothioamide Schiff base compounds have been reported (Qasem Ali et al., 2012 ; Tayamon et al., 2012 ; Li, 2010 ; Shankara et al., 2013 ; Adam et al., 2015 ; de Oliveira et al., 2015 ). These molecules can coordinate metals in neutral and deprotonated forms, leading to biologically active species (Zhang et al., 2011 ).

Synthesis and crystallization

3-Hydroxy-4-methoxybenzaldehyde (0.761 g, 5 mmol) was dissolved in methanol (20 ml). Then, glacial acetic acid (0.2 ml) was added, followed by refluxing for 30 min. Separately, N-methylhydrazinecarbothioamide (0.526 g, 5 mmol) was dissolved in methanol (15 ml) and the solution was added dropwise with stirring to the aldehyde solution. The resulting colourless solution was refluxed for 4 h. The product was filtered and dried under reduced pressure overnight and washed with a mixture of methanol and n-hexane (1:3). The recovered product was recrystallized from methanol solution to yield colourless crystals suitable for X-ray diffraction. Yield: 95%; M.p: 512–513 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃O₂S
M_r	239.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.4893 (13), 13.5903 (19), 9.0554 (12)
β (°)	94.896 (2)
V (Å³)	1163.5 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.27
Crystal size (mm)	0.41 × 0.27 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	25305, 3429, 2573
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.707

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.121, 1.06
No. of reflections	3429
No. of parameters	159
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.25
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXS97 and SHELXTL (Sheldrick 2008 ) and SHELXL2014 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1411362

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314616015996/tk4022sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616015996/tk4022Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616015996/tk4022sup3.docx

Supporting information file. DOI: https://doi.org/10.1107/S2414314616015996/tk4022Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick 2008); software used to prepare material for publication: SHELXTL (Sheldrick 2008).

1-[(E)-(3-Hydroxy-4-methoxybenzylidene)amino]-3-methylthiourea top

Crystal data top

C₁₀H₁₃N₃O₂S	F(000) = 504
M_r = 239.29	D_x = 1.366 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.4893 (13) Å	Cell parameters from 5445 reflections
b = 13.5903 (19) Å	θ = 2.6–27.0°
c = 9.0554 (12) Å	µ = 0.27 mm⁻¹
β = 94.896 (2)°	T = 100 K
V = 1163.5 (3) Å³	Block, colourless
Z = 4	0.41 × 0.27 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.045
φ and ω scans	θ_max = 30.2°, θ_min = 2.2°
25305 measured reflections	h = −13→13
3429 independent reflections	k = −19→19
2573 reflections with I > 2σ(I)	l = −12→12

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0492P)² + 0.4456P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3429 reflections	Δρ_max = 0.33 e Å⁻³
159 parameters	Δρ_min = −0.25 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	−0.17921 (5)	0.60009 (3)	−0.56327 (4)	0.04224 (14)
O1	0.39288 (13)	0.61470 (9)	0.46152 (13)	0.0438 (3)
O2	0.51572 (14)	0.51474 (12)	0.25548 (15)	0.0540 (4)
N1	0.01610 (15)	0.61303 (10)	−0.16455 (14)	0.0362 (3)
N2	−0.02765 (16)	0.58746 (11)	−0.30889 (16)	0.0392 (3)
N3	−0.19422 (16)	0.70885 (11)	−0.32064 (17)	0.0419 (3)
C1	0.11997 (17)	0.63490 (12)	0.14732 (18)	0.0375 (3)
H1A	0.0295	0.6629	0.1217	0.045*
C2	0.18498 (18)	0.64841 (12)	0.28869 (18)	0.0380 (4)
H2A	0.1391	0.6854	0.3596	0.046*
C3	0.31735 (17)	0.60775 (11)	0.32641 (16)	0.0334 (3)
C4	0.38462 (17)	0.55389 (12)	0.22168 (17)	0.0352 (3)
C5	0.31840 (17)	0.53995 (12)	0.08188 (17)	0.0359 (3)
H5A	0.3636	0.5021	0.0114	0.043*
C6	0.18565 (16)	0.58084 (11)	0.04272 (17)	0.0328 (3)
C7	0.12370 (18)	0.56569 (12)	−0.10845 (18)	0.0369 (3)
H7A	0.1655	0.5182	−0.1681	0.044*
C8	−0.13334 (16)	0.63533 (11)	−0.38644 (17)	0.0334 (3)
C9	−0.3040 (2)	0.77017 (18)	−0.3935 (3)	0.0679 (7)
H9A	−0.3534	0.8053	−0.3187	0.102*
H9B	−0.3715	0.7289	−0.4534	0.102*
H9C	−0.2615	0.8179	−0.4576	0.102*
C10	0.3315 (2)	0.66986 (15)	0.57408 (19)	0.0497 (5)
H10A	0.3935	0.6667	0.6662	0.075*
H10B	0.2389	0.6421	0.5907	0.075*
H10C	0.3201	0.7386	0.5425	0.075*
H1N2	0.013 (2)	0.5400 (15)	−0.352 (2)	0.046 (5)*
H1N3	−0.162 (2)	0.7251 (16)	−0.234 (2)	0.051 (6)*
H1O2	0.542 (3)	0.5280 (18)	0.345 (3)	0.069 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0469 (3)	0.0460 (2)	0.0318 (2)	0.00772 (18)	−0.00814 (17)	−0.00491 (16)
O1	0.0449 (7)	0.0545 (7)	0.0308 (6)	0.0104 (6)	−0.0032 (5)	−0.0084 (5)
O2	0.0429 (7)	0.0768 (10)	0.0400 (7)	0.0263 (7)	−0.0101 (6)	−0.0146 (6)
N1	0.0384 (7)	0.0378 (7)	0.0310 (6)	−0.0014 (5)	−0.0052 (5)	−0.0004 (5)
N2	0.0431 (8)	0.0402 (7)	0.0325 (7)	0.0075 (6)	−0.0081 (6)	−0.0037 (6)
N3	0.0404 (8)	0.0465 (8)	0.0370 (7)	0.0071 (6)	−0.0071 (6)	−0.0097 (6)
C1	0.0308 (8)	0.0407 (8)	0.0408 (8)	0.0046 (6)	0.0014 (6)	0.0026 (7)
C2	0.0373 (8)	0.0417 (8)	0.0357 (8)	0.0057 (7)	0.0064 (6)	−0.0027 (6)
C3	0.0350 (8)	0.0360 (8)	0.0289 (7)	0.0010 (6)	0.0004 (6)	−0.0009 (6)
C4	0.0314 (8)	0.0395 (8)	0.0340 (8)	0.0063 (6)	−0.0008 (6)	−0.0013 (6)
C5	0.0373 (8)	0.0381 (8)	0.0319 (7)	0.0047 (6)	0.0005 (6)	−0.0040 (6)
C6	0.0328 (8)	0.0324 (7)	0.0324 (7)	−0.0019 (6)	−0.0021 (6)	0.0023 (6)
C7	0.0388 (8)	0.0358 (8)	0.0349 (8)	0.0014 (6)	−0.0032 (6)	−0.0012 (6)
C8	0.0323 (8)	0.0337 (7)	0.0333 (7)	−0.0029 (6)	−0.0024 (6)	0.0011 (6)
C9	0.0590 (13)	0.0712 (14)	0.0689 (14)	0.0316 (11)	−0.0215 (11)	−0.0248 (11)
C10	0.0649 (12)	0.0499 (10)	0.0345 (8)	0.0086 (9)	0.0041 (8)	−0.0075 (7)

Geometric parameters (Å, º) top

S1—C8	1.6923 (16)	C2—C3	1.388 (2)
O1—C3	1.3675 (18)	C2—H2A	0.9500
O1—C10	1.429 (2)	C3—C4	1.395 (2)
O2—C4	1.3636 (19)	C4—C5	1.377 (2)
O2—H1O2	0.85 (2)	C5—C6	1.395 (2)
N1—C7	1.275 (2)	C5—H5A	0.9500
N1—N2	1.3816 (18)	C6—C7	1.458 (2)
N2—C8	1.342 (2)	C7—H7A	0.9500
N2—H1N2	0.86 (2)	C9—H9A	0.9800
N3—C8	1.321 (2)	C9—H9B	0.9800
N3—C9	1.448 (2)	C9—H9C	0.9800
N3—H1N3	0.85 (2)	C10—H10A	0.9800
C1—C2	1.385 (2)	C10—H10B	0.9800
C1—C6	1.388 (2)	C10—H10C	0.9800
C1—H1A	0.9500

C3—O1—C10	117.40 (13)	C6—C5—H5A	119.7
C4—O2—H1O2	108.9 (17)	C1—C6—C5	119.07 (14)
C7—N1—N2	114.56 (14)	C1—C6—C7	123.17 (14)
C8—N2—N1	121.58 (14)	C5—C6—C7	117.75 (14)
C8—N2—H1N2	118.1 (13)	N1—C7—C6	123.22 (15)
N1—N2—H1N2	120.3 (13)	N1—C7—H7A	118.4
C8—N3—C9	123.71 (15)	C6—C7—H7A	118.4
C8—N3—H1N3	118.7 (14)	N3—C8—N2	117.80 (14)
C9—N3—H1N3	117.3 (14)	N3—C8—S1	123.62 (12)
C2—C1—C6	120.69 (15)	N2—C8—S1	118.57 (13)
C2—C1—H1A	119.7	N3—C9—H9A	109.5
C6—C1—H1A	119.7	N3—C9—H9B	109.5
C1—C2—C3	119.80 (15)	H9A—C9—H9B	109.5
C1—C2—H2A	120.1	N3—C9—H9C	109.5
C3—C2—H2A	120.1	H9A—C9—H9C	109.5
O1—C3—C2	125.93 (14)	H9B—C9—H9C	109.5
O1—C3—C4	114.16 (14)	O1—C10—H10A	109.5
C2—C3—C4	119.91 (14)	O1—C10—H10B	109.5
O2—C4—C5	119.24 (14)	H10A—C10—H10B	109.5
O2—C4—C3	120.91 (14)	O1—C10—H10C	109.5
C5—C4—C3	119.85 (14)	H10A—C10—H10C	109.5
C4—C5—C6	120.67 (14)	H10B—C10—H10C	109.5
C4—C5—H5A	119.7

C7—N1—N2—C8	−175.40 (16)	C2—C1—C6—C5	0.1 (2)
C6—C1—C2—C3	0.1 (3)	C2—C1—C6—C7	−178.82 (15)
C10—O1—C3—C2	−0.9 (2)	C4—C5—C6—C1	−0.8 (2)
C10—O1—C3—C4	179.23 (15)	C4—C5—C6—C7	178.14 (15)
C1—C2—C3—O1	−179.53 (15)	N2—N1—C7—C6	−179.36 (15)
C1—C2—C3—C4	0.3 (3)	C1—C6—C7—N1	11.6 (3)
O1—C3—C4—O2	−1.3 (2)	C5—C6—C7—N1	−167.35 (16)
C2—C3—C4—O2	178.84 (16)	C9—N3—C8—N2	176.56 (19)
O1—C3—C4—C5	178.83 (15)	C9—N3—C8—S1	−2.2 (3)
C2—C3—C4—C5	−1.0 (2)	N1—N2—C8—N3	0.5 (2)
O2—C4—C5—C6	−178.58 (15)	N1—N2—C8—S1	179.36 (12)
C3—C4—C5—C6	1.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O1	0.85 (3)	2.18 (3)	2.6564 (19)	115 (2)
N3—H1N3···N1	0.847 (19)	2.32 (2)	2.682 (2)	106.1 (16)
N2—H1N2···S1ⁱ	0.86 (2)	2.63 (2)	3.4753 (16)	167.8 (16)
N3—H1N3···S1ⁱⁱ	0.847 (19)	2.85 (2)	3.4839 (16)	133.5 (17)

Symmetry codes: (i) −x, −y+1, −z−1; (ii) x, −y+3/2, z+1/2.

Acknowledgements

The research was supported financially by RU grant 1001/PKIMIA/811269 from Universiti Sains Malaysia (USM). The authors wish to thank USM and The World Academy of Science for a TWAS–USM fellowship to MdAA. MdAA also wishes to acknowledge Shahjalal University of Science and Technology, Sylhet, Bangladesh, for study leave.

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