2-Hy­droxy-4-meth­oxy­benzaldehyde thio­semicarbazone

Hao, Y.-M.

doi:10.1107/S1600536810029594

organic compounds

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https://doi.org/10.1107/S1600536810029594

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2-Hydroxy-4-methoxybenzaldehyde thiosemicarbazone

Yu-Mei Hao ^a ^*

^aDepartment of Chemistry, Baicheng Normal University, Baicheng 137000, People's Republic of China
^*Correspondence e-mail: jyxygzb@163.com

(Received 24 July 2010; accepted 25 July 2010; online 4 August 2010)

The title Schiff base compound, C₉H₁₁N₃O₂S, was prepared by the reaction of equimolar quantities of 2-hydroxy-4-methoxybenzaldehyde with thiosemicarbazide in methanol. The molecule adopts a trans configuration with respect to the azomethine group and an intramolecular O—H⋯N hydrogen bond generates an S(6) ring. In the crystal structure, molecules are linked through intermolecular N—H⋯O and N—H⋯S hydrogen bonds, forming a three-dimensional network.

Related literature

For a related structure and background references, see: Hao (2010 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₁₁N₃O₂S
M_r = 225.27
Monoclinic, P 2₁ /n
a = 4.929 (1) Å
b = 10.519 (2) Å
c = 20.357 (3) Å
β = 92.838 (2)°
V = 1054.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 298 K
0.17 × 0.13 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.952, T_max = 0.966
5879 measured reflections
2247 independent reflections
1650 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.101
S = 1.04
2247 reflections
147 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O2ⁱ	0.89 (1)	2.26 (2)	2.998 (3)	141 (2)
N3—H3A⋯O1ⁱⁱ	0.88 (1)	2.23 (1)	3.076 (3)	162 (2)
N2—H2⋯S1ⁱⁱⁱ	0.90 (1)	2.48 (1)	3.366 (3)	168 (2)
O1—H1⋯N1	0.82	1.99	2.700 (2)	145
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+2, -y, -z.

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810029594/hb5575sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029594/hb5575Isup2.hkl

checkCIF report

Comment top

As a continuation of our structural studies of Schiff bases (Hao, 2010), in this paper, the title new Schiff base compound, (I), Fig. 1, is reported.

The molecule of the title compound adopts a trans configuration with respect to the azomethine group. All the bond lengths are within normal values (Allen et al., 1987). There is an intramolecular O—H···N hydrogen bond (Table 1) in the molecule. In the crystal structure, molecules are linked through intermolecular N—H···O and N—H···S hydrogen bonds (Table 1), forming a 3D network (Fig. 2).

Related literature top

For a related structure and background references, see: Hao (2010). For reference structural data, see: Allen et al. (1987).

Experimental top

2-Hydroxy-4-methoxybenzaldehyde (0.1 mmol, 15.2 mg) and thiosemicarbazide (0.1 mmol, 9.1 mg) were refluxed in a 30 ml methanol solution for 30 min to give a clear colorless solution. Colorless blocks of (I) were formed by slow evaporation of the solvent over several days at room temperature.

Structure description top

As a continuation of our structural studies of Schiff bases (Hao, 2010), in this paper, the title new Schiff base compound, (I), Fig. 1, is reported.

For a related structure and background references, see: Hao (2010). For reference structural data, see: Allen et al. (1987).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with 30% probability ellipsoids. Intramolecular hydrogen bond is drawn as a dashed line.
	Fig. 2. Molecular packing of the title compound with hydrogen bonds drawn as dashed lines.

2-Hydroxy-4-methoxybenzaldehyde thiosemicarbazone top

Crystal data top

C₉H₁₁N₃O₂S	F(000) = 472
M_r = 225.27	D_x = 1.420 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1566 reflections
a = 4.929 (1) Å	θ = 2.8–26.2°
b = 10.519 (2) Å	µ = 0.29 mm⁻¹
c = 20.357 (3) Å	T = 298 K
β = 92.838 (2)°	Block, colorless
V = 1054.2 (3) Å³	0.17 × 0.13 × 0.12 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2247 independent reflections
Radiation source: fine-focus sealed tube	1650 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 26.9°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
T_min = 0.952, T_max = 0.966	k = −13→11
5879 measured reflections	l = −20→25

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0453P)² + 0.1092P] where P = (F_o² + 2F_c²)/3
2247 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.18 e Å⁻³
4 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₁₁N₃O₂S	V = 1054.2 (3) Å³
M_r = 225.27	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.929 (1) Å	µ = 0.29 mm⁻¹
b = 10.519 (2) Å	T = 298 K
c = 20.357 (3) Å	0.17 × 0.13 × 0.12 mm
β = 92.838 (2)°

Data collection top

Bruker SMART CCD diffractometer	2247 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1650 reflections with I > 2σ(I)
T_min = 0.952, T_max = 0.966	R_int = 0.030
5879 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	4 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.18 e Å⁻³
2247 reflections	Δρ_min = −0.23 e Å⁻³
147 parameters

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 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 > 2sigma(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
N1	0.6185 (3)	0.11719 (14)	0.11874 (8)	0.0391 (4)
N2	0.7882 (3)	0.04027 (15)	0.08411 (7)	0.0420 (4)
N3	0.9140 (4)	−0.06702 (18)	0.17762 (8)	0.0528 (5)
O1	0.4001 (3)	0.22381 (13)	0.22458 (6)	0.0520 (4)
H1	0.4909	0.1714	0.2055	0.078*
O2	−0.2624 (3)	0.53431 (13)	0.19151 (6)	0.0483 (4)
S1	1.12828 (11)	−0.14847 (5)	0.06920 (2)	0.0530 (2)
C1	0.2729 (4)	0.27756 (17)	0.11180 (9)	0.0370 (4)
C2	0.2464 (4)	0.29172 (18)	0.17967 (9)	0.0371 (4)
C3	0.0662 (4)	0.37755 (18)	0.20376 (9)	0.0419 (5)
H3	0.0521	0.3855	0.2490	0.050*
C4	−0.0943 (4)	0.45216 (17)	0.16165 (9)	0.0381 (4)
C5	−0.0757 (4)	0.43980 (18)	0.09409 (9)	0.0425 (5)
H5	−0.1835	0.4891	0.0652	0.051*
C6	0.1059 (4)	0.35287 (19)	0.07061 (9)	0.0445 (5)
H6	0.1171	0.3443	0.0254	0.053*
C7	−0.4289 (4)	0.61772 (19)	0.15119 (11)	0.0536 (6)
H7A	−0.3154	0.6726	0.1267	0.080*
H7B	−0.5402	0.6681	0.1785	0.080*
H7C	−0.5429	0.5684	0.1213	0.080*
C8	0.4607 (4)	0.18930 (18)	0.08365 (9)	0.0420 (5)
H8	0.4667	0.1849	0.0381	0.050*
C9	0.9333 (4)	−0.05273 (18)	0.11353 (9)	0.0382 (4)
H2	0.799 (5)	0.058 (2)	0.0411 (5)	0.080*
H3A	0.998 (4)	−0.1287 (16)	0.1999 (10)	0.080*
H3B	0.830 (4)	−0.0115 (18)	0.2022 (10)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0443 (9)	0.0365 (9)	0.0377 (9)	−0.0007 (7)	0.0136 (7)	−0.0049 (7)
N2	0.0523 (10)	0.0419 (9)	0.0331 (9)	0.0090 (7)	0.0157 (8)	−0.0006 (7)
N3	0.0661 (12)	0.0616 (12)	0.0315 (9)	0.0130 (9)	0.0107 (8)	0.0032 (8)
O1	0.0617 (9)	0.0581 (9)	0.0365 (8)	0.0216 (7)	0.0051 (6)	−0.0001 (6)
O2	0.0500 (8)	0.0493 (8)	0.0463 (8)	0.0142 (6)	0.0110 (7)	−0.0011 (6)
S1	0.0681 (4)	0.0523 (3)	0.0400 (3)	0.0193 (3)	0.0167 (3)	0.0030 (2)
C1	0.0411 (10)	0.0370 (10)	0.0336 (10)	−0.0025 (8)	0.0084 (8)	−0.0039 (8)
C2	0.0380 (10)	0.0402 (10)	0.0333 (10)	−0.0004 (8)	0.0049 (8)	−0.0005 (8)
C3	0.0472 (11)	0.0478 (12)	0.0314 (10)	0.0040 (9)	0.0085 (9)	−0.0041 (8)
C4	0.0367 (10)	0.0380 (10)	0.0404 (11)	−0.0010 (8)	0.0085 (8)	−0.0007 (8)
C5	0.0460 (11)	0.0430 (11)	0.0386 (11)	0.0049 (9)	0.0025 (9)	0.0045 (9)
C6	0.0545 (12)	0.0485 (12)	0.0311 (10)	0.0008 (10)	0.0072 (9)	−0.0017 (8)
C7	0.0537 (13)	0.0443 (12)	0.0631 (14)	0.0107 (10)	0.0073 (11)	0.0033 (10)
C8	0.0510 (12)	0.0427 (11)	0.0332 (10)	−0.0005 (9)	0.0114 (9)	−0.0039 (8)
C9	0.0416 (11)	0.0401 (11)	0.0333 (10)	−0.0046 (8)	0.0077 (8)	−0.0021 (8)

Geometric parameters (Å, º) top

N1—C8	1.279 (2)	C1—C2	1.402 (3)
N1—N2	1.382 (2)	C1—C8	1.449 (3)
N2—C9	1.336 (2)	C2—C3	1.374 (3)
N2—H2	0.899 (10)	C3—C4	1.382 (3)
N3—C9	1.321 (2)	C3—H3	0.9300
N3—H3A	0.882 (9)	C4—C5	1.389 (3)
N3—H3B	0.886 (9)	C5—C6	1.381 (3)
O1—C2	1.361 (2)	C5—H5	0.9300
O1—H1	0.8200	C6—H6	0.9300
O2—C4	1.361 (2)	C7—H7A	0.9600
O2—C7	1.432 (2)	C7—H7B	0.9600
S1—C9	1.685 (2)	C7—H7C	0.9600
C1—C6	1.393 (3)	C8—H8	0.9300

C8—N1—N2	115.42 (16)	C3—C4—C5	119.83 (17)
C9—N2—N1	121.62 (16)	C6—C5—C4	118.70 (17)
C9—N2—H2	122.0 (15)	C6—C5—H5	120.7
N1—N2—H2	116.4 (15)	C4—C5—H5	120.7
C9—N3—H3A	122.4 (15)	C5—C6—C1	122.82 (18)
C9—N3—H3B	122.7 (15)	C5—C6—H6	118.6
H3A—N3—H3B	114.6 (18)	C1—C6—H6	118.6
C2—O1—H1	109.5	O2—C7—H7A	109.5
C4—O2—C7	118.50 (16)	O2—C7—H7B	109.5
C6—C1—C2	116.84 (17)	H7A—C7—H7B	109.5
C6—C1—C8	119.77 (17)	O2—C7—H7C	109.5
C2—C1—C8	123.39 (17)	H7A—C7—H7C	109.5
O1—C2—C3	116.95 (16)	H7B—C7—H7C	109.5
O1—C2—C1	122.03 (16)	N1—C8—C1	122.81 (18)
C3—C2—C1	121.00 (17)	N1—C8—H8	118.6
C2—C3—C4	120.80 (17)	C1—C8—H8	118.6
C2—C3—H3	119.6	N3—C9—N2	117.57 (17)
C4—C3—H3	119.6	N3—C9—S1	122.11 (15)
O2—C4—C3	115.21 (17)	N2—C9—S1	120.31 (14)
O2—C4—C5	124.97 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O2ⁱ	0.89 (1)	2.26 (2)	2.998 (3)	141 (2)
N3—H3A···O1ⁱⁱ	0.88 (1)	2.23 (1)	3.076 (3)	162 (2)
N2—H2···S1ⁱⁱⁱ	0.90 (1)	2.48 (1)	3.366 (3)	168 (2)
O1—H1···N1	0.82	1.99	2.700 (2)	145

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O₂S
M_r	225.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	4.929 (1), 10.519 (2), 20.357 (3)
β (°)	92.838 (2)
V (Å³)	1054.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.17 × 0.13 × 0.12

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.952, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	5879, 2247, 1650
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.636

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.101, 1.04
No. of reflections	2247
No. of parameters	147
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.23

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O2ⁱ	0.886 (9)	2.258 (17)	2.998 (3)	141.0 (19)
N3—H3A···O1ⁱⁱ	0.882 (9)	2.225 (12)	3.076 (3)	162 (2)
N2—H2···S1ⁱⁱⁱ	0.899 (10)	2.482 (11)	3.366 (3)	168 (2)
O1—H1···N1	0.82	1.99	2.700 (2)	145

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bruker (2002). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hao, Y.-M. (2010). Acta Cryst. E66, o1177. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2211

https://doi.org/10.1107/S1600536810029594

Open

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