(E)-1-(4-Hy­droxy­benzyl­idene)-4-methyl­thio­semi­carbazide

Kassim, K.; Hashim, N.Z.N.; M.Yamin, B.; Zaki, H.M.

doi:10.1107/S2414314616010488

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161048

https://doi.org/10.1107/S2414314616010488

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(E)-1-(4-Hydroxybenzylidene)-4-methylthiosemicarbazide

Karimah Kassim,^a Nor Zakiah Nor Hashim,^b Bohari M.Yamin ^c and Hamizah Mohd Zaki ^d,^e ^*

^aInstitute of Science, Applied Sciences Faculty, Universiti Teknologi MARA, Shah Alam, 45400 Shah Alam, Selangor, Malaysia, ^bApplied Sciences Faculty, Universiti Teknologi MARA Cawangan Perak, Kampus Tapah, 35400 Tapah Road, Perak, Malaysia, ^cSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor D.E. , Malaysia, ^dAtta-ur-Rahman Institute for Natural Product Discovery, Universiti Teknologi MARA (UiTM) Puncak Alam Campus, 42300 Bandar Puncak Alam, Selangor D. E. , Malaysia, and ^eFaculty of Applied Sciences, Universiti Tecknologi MARA, Shah Alam, 40000 Selangor, Malaysia
^*Correspondence e-mail: hamiz410@salam.uitm.edu.my

Edited by P. C. Healy, Griffith University, Australia (Received 27 May 2016; accepted 28 June 2016; online 15 July 2016)

The title compound, C₉H₁₁N₃OS, is derived from methylthiosemicarbazide and hydroxybenzylidene fragments with a trans configuration at the C=N bond. The structure is stabilized by intermolecular N—H⋯S, N—H⋯O and O—H⋯S hydrogen bonds that form a two-dimensional network parallel to (102).

Keywords: crystal structure; thiosemicarbazide; hydrogen bonding.

CCDC reference: 1488061

Structure description

Thiosemicarbazones are known for their diverse biological activity and are also useful as chelating ligands for transition metal ions. (Fang et al., 2007 ). The compounds 1-(2,3,4-trihydroxybenzylidene) thiosemicarbazide (Shawish et al., 2010a ) and 1-(2,3,4-trihydroxybenzylidene)-4-ethylthiosemicarbazide (Shawish et al., 2010b ) are analogous except for the presence of the ethyl group in the later compound. The present compound (Fig. 1) is similar to these compounds but has only one hydroxy substituent of the benzylidene group and a methyl substituent of the thiocarbazide fragment. The thiourea fragment, S1/N1/N2/C8/C9, is planar with maximum deviation from the least-squares plane of 0.021 (2) Å for the N1 atom. It makes a dihedral angle of 12.01 (9)° with the benzene ring (C1–C6), considerably smaller than that in 1-(2,3,4-trihydroxybenzylidene)-4-ethylthiosemicarbazide [20.5 (1)°]. No intramolecular hydrogen bonds are observed in the molecule.

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

In the crystal, the molecules are linked by N1—H1B⋯S1, N1—H1B⋯O1 and O1—H1A⋯S1 hydrogen bonds (Table 1), to forming two-dimensional network parallel to (102) (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯S1ⁱ	0.82 (2)	2.41 (2)	3.220 (2)	171 (3)
N1—H1B⋯O1ⁱⁱ	0.86 (2)	2.47 (2)	3.018 (3)	123 (2)
N2—H2A⋯S1ⁱⁱⁱ	0.87 (2)	2.62 (1)	3.4177 (19)	154 (2)
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x-1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x, -y+2, -z+1.

Figure 2
The crystal packing of the title compound, viewed along the a axis. The dashed lines indicate hydrogen bonds.

Synthesis and crystallization

4-Methyl-3-thiosemicarbazide (0.5258 g, 0.005 mol) in an ethanol solution (15 ml) was slowly added to an ethanolic solution (15 ml) containing 4-hydroxybenzaldehyde (0.6106 g, 0.005 mol). The mixture was refluxed for 3 h and then cooled down to room temperature. Colorless crystals were collected by slow evaporation from the ethanolic mixture solution.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃OS
M_r	209.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	302
a, b, c (Å)	5.2320 (4), 9.9727 (9), 19.9900 (18)
β (°)	97.5196 (18)
V (Å³)	1034.05 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.28
Crystal size (mm)	0.50 × 0.30 × 0.24

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.903, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	19497, 2572, 1977
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.130, 1.06
No. of reflections	2572
No. of parameters	140
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.32
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1488061

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616010488/hg4008sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616010488/hg4008Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616010488/hg4008Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

(E)-1-(4-Hydroxybenzylidene)-4-methylthiosemicarbazide top

Crystal data top

C₉H₁₁N₃OS	F(000) = 440
M_r = 209.27	D_x = 1.344 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.2320 (4) Å	Cell parameters from 8733 reflections
b = 9.9727 (9) Å	θ = 2.9–28.3°
c = 19.9900 (18) Å	µ = 0.28 mm⁻¹
β = 97.5196 (18)°	T = 302 K
V = 1034.05 (15) Å³	Block, colorless
Z = 4	0.50 × 0.30 × 0.24 mm

Data collection top

Bruker APEXII CCD diffractometer	2572 independent reflections
Radiation source: 'fire-focus sealed tube'	1977 reflections with I > 2σ(I)
Detector resolution: 83.66 pixels mm^-1	R_int = 0.062
φ and ω scans	θ_max = 28.4°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −7→6
T_min = 0.903, T_max = 0.934	k = −13→13
19497 measured reflections	l = −26→26

Refinement top

Refinement on F²	Secondary atom site location: inferred from neighbouring sites
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.130	w = 1/[σ²(F_o²) + (0.0508P)² + 0.5068P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2572 reflections	Δρ_max = 0.26 e Å⁻³
140 parameters	Δρ_min = −0.32 e Å⁻³
3 restraints	Extinction correction: SHELXL2013 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (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.

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
S1	0.18138 (12)	0.81497 (6)	0.46654 (3)	0.0587 (2)
N1	0.0989 (3)	0.65738 (17)	0.56994 (9)	0.0485 (4)
N2	−0.1481 (3)	0.84494 (18)	0.55381 (8)	0.0484 (4)
N3	−0.2569 (3)	0.81887 (16)	0.61222 (8)	0.0444 (4)
O1	−0.9364 (4)	0.91660 (19)	0.85451 (9)	0.0705 (5)
C1	−0.5004 (5)	0.8075 (2)	0.73541 (11)	0.0553 (6)
H1C	−0.3699	0.7426	0.7319	0.066*
C2	−0.6242 (4)	0.8105 (2)	0.79267 (11)	0.0578 (6)
H2B	−0.5789	0.7476	0.8280	0.069*
C3	−0.8139 (4)	0.9049 (2)	0.79833 (10)	0.0485 (5)
C4	−0.8827 (4)	0.9941 (2)	0.74681 (10)	0.0499 (5)
H4A	−1.0152	1.0579	0.7503	0.060*
C5	−0.7585 (4)	0.9908 (2)	0.68979 (10)	0.0459 (5)
H5A	−0.8066	1.0531	0.6544	0.055*
C6	−0.5644 (3)	0.89803 (19)	0.68337 (9)	0.0412 (4)
C7	−0.4324 (4)	0.9023 (2)	0.62330 (9)	0.0436 (4)
H7A	−0.4793	0.9705	0.5908	0.052*
C8	0.0386 (4)	0.7664 (2)	0.53477 (9)	0.0425 (4)
C9	0.3028 (4)	0.5649 (2)	0.55772 (13)	0.0623 (6)
H9A	0.3113	0.4913	0.5904	0.094*
H9B	0.4681	0.6125	0.5626	0.094*
H9C	0.2663	0.5287	0.5119	0.094*
H1B	0.012 (4)	0.643 (2)	0.6027 (8)	0.059 (7)*
H2A	−0.175 (5)	0.9226 (14)	0.5346 (11)	0.069 (8)*
H1A	−0.894 (6)	0.854 (2)	0.8803 (14)	0.100 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0796 (4)	0.0591 (4)	0.0444 (3)	−0.0017 (3)	0.0344 (3)	0.0018 (2)
N1	0.0535 (10)	0.0480 (9)	0.0491 (9)	−0.0002 (7)	0.0259 (8)	0.0027 (8)
N2	0.0575 (10)	0.0522 (10)	0.0394 (9)	0.0035 (8)	0.0218 (7)	0.0046 (8)
N3	0.0480 (9)	0.0508 (9)	0.0373 (8)	−0.0035 (7)	0.0167 (7)	−0.0012 (7)
O1	0.0869 (12)	0.0776 (12)	0.0552 (10)	0.0215 (10)	0.0402 (9)	0.0038 (9)
C1	0.0646 (13)	0.0535 (12)	0.0530 (12)	0.0185 (10)	0.0270 (10)	0.0079 (9)
C2	0.0710 (14)	0.0584 (13)	0.0486 (12)	0.0185 (11)	0.0254 (10)	0.0125 (10)
C3	0.0524 (11)	0.0528 (11)	0.0439 (10)	0.0000 (9)	0.0195 (8)	−0.0058 (9)
C4	0.0473 (11)	0.0513 (11)	0.0537 (11)	0.0088 (9)	0.0159 (9)	−0.0035 (9)
C5	0.0455 (10)	0.0479 (11)	0.0452 (10)	0.0027 (8)	0.0091 (8)	0.0017 (8)
C6	0.0418 (10)	0.0430 (10)	0.0407 (9)	−0.0037 (8)	0.0124 (7)	−0.0043 (8)
C7	0.0468 (10)	0.0472 (11)	0.0388 (9)	−0.0028 (8)	0.0126 (8)	0.0000 (8)
C8	0.0478 (10)	0.0463 (10)	0.0356 (9)	−0.0078 (8)	0.0140 (7)	−0.0048 (8)
C9	0.0595 (13)	0.0524 (12)	0.0811 (16)	0.0042 (10)	0.0317 (12)	0.0035 (12)

Geometric parameters (Å, º) top

S1—C8	1.7087 (18)	C2—C3	1.383 (3)
N1—C8	1.311 (3)	C2—H2B	0.9500
N1—C9	1.454 (3)	C3—C4	1.373 (3)
N1—H1B	0.858 (10)	C4—C5	1.384 (3)
N2—C8	1.345 (3)	C4—H4A	0.9500
N2—N3	1.389 (2)	C5—C6	1.392 (3)
N2—H2A	0.868 (10)	C5—H5A	0.9500
N3—C7	1.279 (2)	C6—C7	1.462 (2)
O1—C3	1.369 (2)	C7—H7A	0.9500
O1—H1A	0.823 (10)	C9—H9A	0.9800
C1—C6	1.385 (3)	C9—H9B	0.9800
C1—C2	1.388 (3)	C9—H9C	0.9800
C1—H1C	0.9500

C8—N1—C9	124.47 (17)	C5—C4—H4A	120.1
C8—N1—H1B	115.4 (16)	C4—C5—C6	121.23 (18)
C9—N1—H1B	120.1 (16)	C4—C5—H5A	119.4
C8—N2—N3	121.45 (17)	C6—C5—H5A	119.4
C8—N2—H2A	118.6 (17)	C1—C6—C5	118.15 (17)
N3—N2—H2A	118.5 (16)	C1—C6—C7	122.80 (17)
C7—N3—N2	113.97 (16)	C5—C6—C7	119.03 (17)
C3—O1—H1A	109 (2)	N3—C7—C6	123.38 (18)
C6—C1—C2	120.85 (19)	N3—C7—H7A	118.3
C6—C1—H1C	119.6	C6—C7—H7A	118.3
C2—C1—H1C	119.6	N1—C8—N2	117.64 (17)
C3—C2—C1	119.95 (19)	N1—C8—S1	124.30 (15)
C3—C2—H2B	120.0	N2—C8—S1	118.06 (15)
C1—C2—H2B	120.0	N1—C9—H9A	109.5
O1—C3—C4	117.05 (18)	N1—C9—H9B	109.5
O1—C3—C2	122.90 (19)	H9A—C9—H9B	109.5
C4—C3—C2	120.04 (18)	N1—C9—H9C	109.5
C3—C4—C5	119.78 (18)	H9A—C9—H9C	109.5
C3—C4—H4A	120.1	H9B—C9—H9C	109.5

C8—N2—N3—C7	−179.80 (18)	C4—C5—C6—C1	0.7 (3)
C6—C1—C2—C3	−0.2 (4)	C4—C5—C6—C7	−177.60 (18)
C1—C2—C3—O1	−177.4 (2)	N2—N3—C7—C6	−177.01 (17)
C1—C2—C3—C4	1.2 (4)	C1—C6—C7—N3	3.7 (3)
O1—C3—C4—C5	177.5 (2)	C5—C6—C7—N3	−178.03 (18)
C2—C3—C4—C5	−1.2 (3)	C9—N1—C8—N2	−177.4 (2)
C3—C4—C5—C6	0.2 (3)	C9—N1—C8—S1	2.6 (3)
C2—C1—C6—C5	−0.7 (3)	N3—N2—C8—N1	5.9 (3)
C2—C1—C6—C7	177.5 (2)	N3—N2—C8—S1	−174.09 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···S1ⁱ	0.82 (2)	2.41 (2)	3.220 (2)	171 (3)
N1—H1B···N3	0.86 (2)	2.27 (2)	2.681 (2)	109 (2)
N1—H1B···O1ⁱⁱ	0.86 (2)	2.47 (2)	3.018 (3)	123 (2)
N2—H2A···S1ⁱⁱⁱ	0.87 (2)	2.62 (1)	3.4177 (19)	154 (2)

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

Acknowledgements

The authors thank the Ministry of Higher Education of Malaysia and Universiti Teknologi MARA for the research grant FRGS 1/2013/ST01/UiTM/01/6, RAGS/1/2015/sg0/uitm03/12 and the Atta Ur Rahman Institute for Natural Product Discovery (AURINs UiTM Puncak Alam) for the X-ray facility.

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