4-Hy­droxy-3-meth­oxy­benzaldehyde thio­semicarbazone

Oliveira, A.B. de; Feitosa, B.R.S.; Näther, C.; Jess, I.

doi:10.1107/S1600536813032303

organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Page o1861

doi:10.1107/S1600536813032303

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4-Hydroxy-3-methoxybenzaldehyde thiosemicarbazone

Adriano Bof de Oliveira,^a ^* Bárbara Regina Santos Feitosa,^a Christian Näther ^b and Inke Jess ^b

^aDepartamento de Química, Universidade Federal de Sergipe, Av. Marechal Rondon s/n, Campus, 49100-000 São Cristóvão–SE, Brazil, and ^bInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth Strasse 2, D-24118 Kiel, Germany
^*Correspondence e-mail: adriano@daad-alumni.de

(Received 21 October 2013; accepted 27 November 2013; online 30 November 2013)

In the title compound, C₉H₁₁N₃S, there is an intramolecular O—H⋯O hydrogen bond involving the OH group and the adjacent methoxy O atom. The molecule is essentially planar, with the maximum deviation from the mean plane of the non-H atoms being 0.1127 (14) Å for the methyl C atom. In the crystal, molecules are connected via centrosymmetric pairs of N—H⋯S and O—H⋯O hydrogen bonds into a two-dimensional network parallel to (10-3).

CCDC reference: 973962

Related literature

For the in vitro antimalarial and antitubercular activity of hydroxy-methoxybenzaldehyde thiosemicarbazone derivatives, see: Khanye et al. (2011 ). For the first report of the synthesis, see: Freund & Schander (1902 ). For the synthesis and crystal structure of an isomer of the title compound, see: Hao (2010 ).

Experimental

Crystal data

C₉H₁₁N₃O₂S
M_r = 225.27
Triclinic, $[P \overline 1]$
a = 4.5886 (5) Å
b = 8.5213 (11) Å
c = 13.9621 (15) Å
α = 75.898 (13)°
β = 87.669 (13)°
γ = 77.580 (14)°
V = 517.05 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 200 K
0.4 × 0.3 × 0.2 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.865, T_max = 0.982
5179 measured reflections
2211 independent reflections
1829 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.100
S = 1.03
2211 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.84	2.24	2.6934 (16)	114
O1—H1⋯O2ⁱ	0.84	2.27	2.9153 (15)	134
N2—H2A⋯S1ⁱⁱ	0.88	2.59	3.4319 (14)	161
N3—H3B⋯S1ⁱⁱⁱ	0.88	2.59	3.4540 (15)	169
Symmetry codes: (i) -x-1, -y+1, -z; (ii) -x+2, -y+1, -z+1; (iii) -x+2, -y+2, -z+1.

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 973962

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813032303/fy2108sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813032303/fy2108Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813032303/fy2108Isup3.cml

checkCIF report

Comment top

Thiosemicarbazone derivatives have a wide range of pharmacological properties. For example, benzaldehyde-thiosemicarbazone derivatives show in vitro antimalarial and antitubercular activity (Khanye et al., 2011). As part of our study on the synthesis of thiosemicarbazone derivatives, we report herein the crystal structure of 4-hydroxy-3-methoxybenzaldehyde thiosemicarbazone. In the title compound (Fig. 1), in which the molecular structure matches the asymmetric unit, the maximal deviation from the least squares plane through all non-hydrogen atoms amount to 0.1127 (14) Å for C7. The molecule shows a trans conformation for the atoms about the C8—N1/N1—N2/N2—C9/ bonds. This conformation is also observed in the literature for an isomer of the title compound (Hao, 2010). The mean deviations from the least squares planes for the C1—C8/O1—O2 and C9/N1—N3/S1 fragments amount to 0.0733 (12) Å for C7 and 0.0188 (10) Å for N2, respectively, and the dihedral angle between the two planes is 5.08 (6)°.

The molecules are connected via centrosymmetric pairs of N—H···S and O—H···O hydrogen interactions, forming a two-dimensional H-bonded polymer. An O—H···O intramolecular H-interaction is also observed (Fig. 2 and Table 1). The molecules are arranged in layers, stacked along the a-axis direction through π–π-interactions, with the shortest C···C distance being 3.380 (23) Å [C8···C5^iv, (iv): 1+x, y, z].

Related literature top

For the in vitro antimalarial and antitubercular activity of hydroxy-methoxybenzaldehyde thiosemicarbazone derivatives, see: Khanye et al. (2011). For the first report of the synthesis, see: Freund & Schander (1902). For the synthesis and crystal structure of an isomer of 4-hydroxy-3-methoxybenzaldehyde thiosemicarbazone, see: Hao (2010).

Experimental top

The starting materials were commercially available and were used without further purification. The 4-hydroxy-3-methoxybenzaldehyde thiosemicarbazone synthesis was adapted from a procedure reported previously (Freund & Schander, 1902). The hydrochloric acid catalyzed reaction of vanillin (8.83 mmol) and thiosemicarbazide (8.83 mmol) in ethanol (50 ml) was refluxed for 6 h. After cooling and filtering, the title compound was obtained. Crystals suitable for X-ray diffraction were obtained from the reaction mixture by the slow evaporation of solvent.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-RED32 (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 70% probability level.
	Fig. 2. Crystal structure of the title compound with hydrogen bonds shown as dashed lines.

4-Hydroxy-3-methoxybenzaldehyde thiosemicarbazone top

Crystal data top

C₉H₁₁N₃O₂S	Z = 2
M_r = 225.27	F(000) = 236
Triclinic, P1	D_x = 1.447 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.5886 (5) Å	Cell parameters from 5179 reflections
b = 8.5213 (11) Å	θ = 2.5–27.0°
c = 13.9621 (15) Å	µ = 0.30 mm⁻¹
α = 75.898 (13)°	T = 200 K
β = 87.669 (13)°	Block, yellow
γ = 77.580 (14)°	0.4 × 0.3 × 0.2 mm
V = 517.05 (10) Å³

Data collection top

Stoe IPDS-1 diffractometer	2211 independent reflections
Radiation source: fine-focus sealed tube, Stoe IPDS-1	1829 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ scans	θ_max = 27.0°, θ_min = 2.5°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −5→5
T_min = 0.865, T_max = 0.982	k = −10→10
5179 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0666P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2211 reflections	Δρ_max = 0.32 e Å⁻³
139 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.055 (15)

Crystal data top

C₉H₁₁N₃O₂S	γ = 77.580 (14)°
M_r = 225.27	V = 517.05 (10) Å³
Triclinic, P1	Z = 2
a = 4.5886 (5) Å	Mo Kα radiation
b = 8.5213 (11) Å	µ = 0.30 mm⁻¹
c = 13.9621 (15) Å	T = 200 K
α = 75.898 (13)°	0.4 × 0.3 × 0.2 mm
β = 87.669 (13)°

Data collection top

Stoe IPDS-1 diffractometer	2211 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	1829 reflections with I > 2σ(I)
T_min = 0.865, T_max = 0.982	R_int = 0.040
5179 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.03	Δρ_max = 0.32 e Å⁻³
2211 reflections	Δρ_min = −0.27 e Å⁻³
139 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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
C1	0.1779 (3)	0.65909 (18)	0.22576 (11)	0.0210 (3)
C2	0.0643 (3)	0.81737 (19)	0.16881 (12)	0.0252 (3)
H2	0.1261	0.9096	0.1820	0.030*
C3	−0.1384 (4)	0.84153 (19)	0.09296 (12)	0.0255 (3)
H3	−0.2163	0.9501	0.0546	0.031*
C4	−0.2278 (3)	0.70678 (19)	0.07295 (11)	0.0223 (3)
C5	−0.1165 (3)	0.54775 (17)	0.12986 (11)	0.0203 (3)
C6	0.0858 (3)	0.52373 (18)	0.20585 (11)	0.0207 (3)
H6	0.1622	0.4152	0.2445	0.025*
O1	−0.4253 (3)	0.73483 (14)	−0.00291 (9)	0.0306 (3)
H1	−0.4773	0.6463	−0.0034	0.046*
O2	−0.2264 (3)	0.42408 (13)	0.10546 (8)	0.0268 (3)
C7	−0.1404 (4)	0.2626 (2)	0.16928 (14)	0.0354 (4)
H7A	0.0761	0.2238	0.1664	0.053*
H7B	−0.2414	0.1863	0.1481	0.053*
H7C	−0.1969	0.2671	0.2372	0.053*
C8	0.3893 (3)	0.62554 (19)	0.30740 (11)	0.0218 (3)
H8	0.4565	0.5145	0.3439	0.026*
N1	0.4870 (3)	0.74084 (16)	0.33129 (9)	0.0222 (3)
N2	0.6853 (3)	0.68715 (15)	0.40998 (10)	0.0222 (3)
H2A	0.7455	0.5805	0.4362	0.027*
C9	0.7865 (3)	0.79732 (18)	0.44648 (11)	0.0218 (3)
N3	0.6948 (4)	0.95590 (17)	0.40253 (11)	0.0344 (4)
H3A	0.5720	0.9854	0.3514	0.041*
H3B	0.7565	1.0318	0.4244	0.041*
S1	1.01872 (9)	0.72984 (5)	0.54636 (3)	0.02745 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0178 (7)	0.0265 (7)	0.0203 (7)	−0.0054 (6)	−0.0038 (5)	−0.0074 (6)
C2	0.0253 (8)	0.0239 (7)	0.0286 (8)	−0.0074 (6)	−0.0071 (6)	−0.0074 (6)
C3	0.0270 (8)	0.0216 (7)	0.0265 (8)	−0.0051 (6)	−0.0080 (6)	−0.0015 (6)
C4	0.0207 (7)	0.0270 (7)	0.0193 (7)	−0.0040 (6)	−0.0073 (6)	−0.0054 (6)
C5	0.0203 (7)	0.0223 (7)	0.0208 (7)	−0.0055 (6)	−0.0027 (5)	−0.0085 (6)
C6	0.0203 (7)	0.0229 (7)	0.0193 (7)	−0.0041 (6)	−0.0040 (6)	−0.0054 (6)
O1	0.0350 (6)	0.0285 (6)	0.0283 (6)	−0.0066 (5)	−0.0196 (5)	−0.0035 (5)
O2	0.0334 (6)	0.0224 (5)	0.0266 (6)	−0.0065 (4)	−0.0144 (5)	−0.0064 (4)
C7	0.0458 (10)	0.0233 (8)	0.0377 (10)	−0.0093 (7)	−0.0219 (8)	−0.0031 (7)
C8	0.0192 (7)	0.0261 (7)	0.0212 (7)	−0.0049 (5)	−0.0050 (6)	−0.0070 (6)
N1	0.0197 (6)	0.0278 (6)	0.0204 (6)	−0.0038 (5)	−0.0070 (5)	−0.0078 (5)
N2	0.0232 (6)	0.0224 (6)	0.0224 (7)	−0.0045 (5)	−0.0095 (5)	−0.0068 (5)
C9	0.0210 (7)	0.0247 (7)	0.0217 (7)	−0.0060 (6)	−0.0020 (6)	−0.0080 (6)
N3	0.0470 (9)	0.0227 (7)	0.0346 (8)	−0.0065 (6)	−0.0228 (7)	−0.0059 (6)
S1	0.0345 (3)	0.0250 (2)	0.0248 (2)	−0.00760 (16)	−0.01444 (16)	−0.00630 (15)

Geometric parameters (Å, º) top

C1—C2	1.390 (2)	O2—C7	1.428 (2)
C1—C6	1.401 (2)	C7—H7A	0.9800
C1—C8	1.4608 (19)	C7—H7B	0.9800
C2—C3	1.386 (2)	C7—H7C	0.9800
C2—H2	0.9500	C8—N1	1.2801 (19)
C3—C4	1.390 (2)	C8—H8	0.9500
C3—H3	0.9500	N1—N2	1.3792 (17)
C4—O1	1.3643 (17)	N2—C9	1.3404 (19)
C4—C5	1.393 (2)	N2—H2A	0.8800
C5—O2	1.3779 (17)	C9—N3	1.324 (2)
C5—C6	1.386 (2)	C9—S1	1.6962 (15)
C6—H6	0.9500	N3—H3A	0.8800
O1—H1	0.8400	N3—H3B	0.8800

C2—C1—C6	119.42 (13)	O2—C7—H7A	109.5
C2—C1—C8	123.13 (13)	O2—C7—H7B	109.5
C6—C1—C8	117.45 (13)	H7A—C7—H7B	109.5
C3—C2—C1	120.45 (13)	O2—C7—H7C	109.5
C3—C2—H2	119.8	H7A—C7—H7C	109.5
C1—C2—H2	119.8	H7B—C7—H7C	109.5
C2—C3—C4	119.99 (14)	N1—C8—C1	122.15 (14)
C2—C3—H3	120.0	N1—C8—H8	118.9
C4—C3—H3	120.0	C1—C8—H8	118.9
O1—C4—C3	118.45 (13)	C8—N1—N2	114.48 (12)
O1—C4—C5	121.52 (13)	C9—N2—N1	120.04 (12)
C3—C4—C5	120.02 (13)	C9—N2—H2A	120.0
O2—C5—C6	124.88 (13)	N1—N2—H2A	120.0
O2—C5—C4	115.17 (13)	N3—C9—N2	117.44 (14)
C6—C5—C4	119.95 (13)	N3—C9—S1	123.06 (11)
C5—C6—C1	120.17 (14)	N2—C9—S1	119.49 (11)
C5—C6—H6	119.9	C9—N3—H3A	120.0
C1—C6—H6	119.9	C9—N3—H3B	120.0
C4—O1—H1	109.5	H3A—N3—H3B	120.0
C5—O2—C7	116.19 (11)

C6—C1—C2—C3	0.1 (2)	C2—C1—C6—C5	0.1 (2)
C8—C1—C2—C3	−179.27 (15)	C8—C1—C6—C5	179.45 (13)
C1—C2—C3—C4	−0.5 (3)	C6—C5—O2—C7	5.2 (2)
C2—C3—C4—O1	−179.32 (15)	C4—C5—O2—C7	−173.55 (15)
C2—C3—C4—C5	0.8 (3)	C2—C1—C8—N1	−0.7 (2)
O1—C4—C5—O2	−1.7 (2)	C6—C1—C8—N1	179.91 (14)
C3—C4—C5—O2	178.21 (14)	C1—C8—N1—N2	−179.89 (13)
O1—C4—C5—C6	179.46 (14)	C8—N1—N2—C9	−175.18 (14)
C3—C4—C5—C6	−0.6 (2)	N1—N2—C9—N3	−1.7 (2)
O2—C5—C6—C1	−178.53 (14)	N1—N2—C9—S1	177.37 (11)
C4—C5—C6—C1	0.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84	2.24	2.6934 (16)	114
O1—H1···O2ⁱ	0.84	2.27	2.9153 (15)	134
N2—H2A···S1ⁱⁱ	0.88	2.59	3.4319 (14)	161
N3—H3B···S1ⁱⁱⁱ	0.88	2.59	3.4540 (15)	169

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84	2.24	2.6934 (16)	113.9
O1—H1···O2ⁱ	0.84	2.27	2.9153 (15)	133.5
N2—H2A···S1ⁱⁱ	0.88	2.59	3.4319 (14)	160.8
N3—H3B···S1ⁱⁱⁱ	0.88	2.59	3.4540 (15)	168.5

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

Acknowledgements

We gratefully acknowledge financial support by the State of Schleswig–Holstein, Germany. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities. BRSF thanks CNPq/UFS for the award of a PIBIC scholarship and ABO acknowledges financial support through the FAPITEC/SE/FUNTEC/CNPq PPP 04/2011 program.

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