(E)-1-(2-Hy­droxy-5-meth­oxy­benzyl­idene)thio­semicarbazide

Adabi Ardakani, A.; Kargar, H.; Kia, R.; Tahir, M.N.

doi:10.1107/S1600536811056182

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages o324-o325

doi:10.1107/S1600536811056182

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(E)-1-(2-Hydroxy-5-methoxybenzylidene)thiosemicarbazide

Amir Adabi Ardakani,^a ^* Hadi Kargar,^b Reza Kia ^c,^d and Muhammad Nawaz Tahir ^e ^*

^aArdakan Branch, Islamic Azad University, Ardakan, Iran, ^bDepartment of Chemistry, Payame Noor University, PO BOX 19395-3697 Tehran, I. R. of IRAN, ^cX-ray Crystallography Lab., Plasma Physics Research Center, Science and Research Branch, Islamic Azad University, Tehran, IRAN, ^dDepartment of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran, and ^eDepartment of Physics, University of Sargodha, Punjab, Pakistan
^*Correspondence e-mail: A.Adabi@iauardakan.ac.ir, dmntahir_uos@yahoo.com

(Received 28 December 2011; accepted 29 December 2011; online 11 January 2012)

In the title molecule, C₉H₁₁N₃O₂S, an intramolecular O—H⋯N hydrogen bond generates an S(6) ring motif. In the crystal, molecules are linked via pairs of N—H⋯S interactions, forming inversion dimers with R₂²(8) ring motifs. These dimers are further linked via N—H⋯S and N—H⋯O hydrogen bonds, forming a two-dimensional network lying parallel to (100). The crystal structure is further stabilized by intermolecular π–π interactions [centroid–centroid distance = 3.7972 (9) Å].

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For background to thiosemicarbazones in coordination chemistry, see: Casas et al. (2000 ). For their biological applications, see: Maccioni et al. (2003 ); Ferrari et al. (2000 ). For related structures, see: Kargar et al. (2010a ,b ); Adabi Ardakani et al. (2012 ).

Experimental

Crystal data

C₉H₁₁N₃O₂S
M_r = 225.27
Monoclinic, P 2₁ /c
a = 7.4878 (2) Å
b = 9.9880 (2) Å
c = 14.3754 (3) Å
β = 91.846 (1)°
V = 1074.55 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 291 K
0.24 × 0.14 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.800, T_max = 0.926
10176 measured reflections
2673 independent reflections
2365 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.110
S = 1.07
2673 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.97	2.6844 (15)	146
N2—H2⋯S1ⁱ	0.86	2.61	3.3706 (12)	148
N3—H3A⋯S1ⁱⁱ	0.86	2.66	3.2706 (12)	129
N3—H3B⋯O1ⁱⁱⁱ	0.86	2.11	2.9604 (17)	172
Symmetry codes: (i) -x, -y, -z+2; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{5\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811056182/su2361sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811056182/su2361Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811056182/su2361Isup3.cml

checkCIF report

Comment top

Thiosemicarbazones constitute an important class of N,S donor ligands due to their propensity to react with a wide range of metals (Casas et al., 2000). Thiosemicarbazones exhibit various biological activities and have therefore attracted considerable pharmaceutical interest (Maccioni et al., 2003; Ferrari et al., 2000). We report herein on the synthesis and crystal structure of the title a hydrazone Schiff base compound.

The asymmetric unit of the title compound, Fig. 1, comprises a hydrazone Schiff base ligand. The bond lengths and angles are within the normal ranges and are comparable to those reported for related structures (Kargar et al., 2010a,b; Adabi et al., 2012). An intramolecular O—H···N hydrogen bond (Table 1) generates an S(6) ring motif (Bernstein et al., 1995).

In the crystal, pairs of intermolecular N—H···S hydrogen bonds make inversion dimers with an R²₂(8) ring motif. Intermolecular N—H···S and N—H···O hydrogen bonds link neighbouring molecules into a two-dimensional extended network parallel to (1 0 0). For details of the hydrogen bonding see Table 1, and Fig. 2. The crystal structure is further stabilized by an intermolecular π···π interaction [Cg1···Cg1ⁱ = 3.7972 (9)Å; (i) -x+1, -y+1, -z+2; Cg1 is the centroid of ring (C1–C6)].

Related literature top

For hydrogen-bond motifs, see: Bernstein et al. (1995). For background to thiosemicarbazones in coordination chemistry, see: Casas et al. (2000). For their biological applications, see: Maccioni et al. (2003); Ferrari et al. (2000). For related structures, see: Kargar et al. (2010a,b); Adabi Ardakani et al. (2012).

Experimental top

A mixture of 5-methoxysalicylalehyde (0.01 mol) and hydrazinecarbothioamide (0.01 mol) in 20 ml of ethanol was refluxed for about 2 h. On cooling, the solid separated was filtered and recrystallized from ethanol. Colourless plate-like crystals of the title compound, suitable for X-ray diffraction, were obtained by slow evaporation of a solution in ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, showing 40% probability displacement ellipsoids and the atomic numbering. The intramolecular O-H···N hydrogen bond is drawn as a dashed line.
	Fig. 2. The crystal packing of the title compound, viewed along the a-axis, showing the two-dimensional extended network parallel to (1 0 0). The N—H···S and N—H···O, hydrogen bonds are shown as dashed lines [see Table 1 for details; only the H atoms involved in these interactions are shown].

(E)-1-(2-Hydroxy-5-methoxybenzylidene)thiosemicarbazide top

Crystal data top

C₉H₁₁N₃O₂S	F(000) = 472
M_r = 225.27	D_x = 1.392 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2750 reflections
a = 7.4878 (2) Å	θ = 2.4–27.5°
b = 9.9880 (2) Å	µ = 0.29 mm⁻¹
c = 14.3754 (3) Å	T = 291 K
β = 91.846 (1)°	Plate, colourless
V = 1074.55 (4) Å³	0.24 × 0.14 × 0.08 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2673 independent reflections
Radiation source: fine-focus sealed tube	2365 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 28.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
T_min = 0.800, T_max = 0.926	k = −13→13
10176 measured reflections	l = −17→19

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0594P)² + 0.2733P] where P = (F_o² + 2F_c²)/3
2673 reflections	(Δ/σ)_max = 0.001
138 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₉H₁₁N₃O₂S	V = 1074.55 (4) Å³
M_r = 225.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4878 (2) Å	µ = 0.29 mm⁻¹
b = 9.9880 (2) Å	T = 291 K
c = 14.3754 (3) Å	0.24 × 0.14 × 0.08 mm
β = 91.846 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2673 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2365 reflections with I > 2σ(I)
T_min = 0.800, T_max = 0.926	R_int = 0.016
10176 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.07	Δρ_max = 0.31 e Å⁻³
2673 reflections	Δρ_min = −0.24 e Å⁻³
138 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
C1	0.26170 (16)	0.48062 (13)	0.97372 (9)	0.0346 (3)
C2	0.24057 (17)	0.58273 (14)	1.03826 (10)	0.0386 (3)
C3	0.2907 (2)	0.71257 (15)	1.01635 (13)	0.0510 (4)
H3	0.2758	0.7812	1.0591	0.061*
C4	0.3626 (2)	0.73967 (16)	0.93147 (14)	0.0573 (4)
H4	0.3962	0.8268	0.9175	0.069*
C5	0.3857 (2)	0.63922 (17)	0.86653 (12)	0.0512 (4)
C6	0.33436 (19)	0.51057 (16)	0.88716 (10)	0.0438 (3)
H6	0.3478	0.4429	0.8435	0.053*
C7	0.4842 (3)	0.5753 (3)	0.71703 (14)	0.0797 (7)
H7A	0.5574	0.5054	0.7437	0.120*
H7B	0.5415	0.6124	0.6641	0.120*
H7C	0.3701	0.5392	0.6978	0.120*
C8	0.21137 (17)	0.34293 (13)	0.99115 (9)	0.0365 (3)
H8	0.2270	0.2798	0.9445	0.044*
C9	0.02639 (18)	0.11834 (12)	1.14708 (9)	0.0353 (3)
N1	0.14624 (14)	0.30443 (10)	1.06812 (8)	0.0349 (2)
N2	0.10299 (16)	0.17032 (11)	1.07211 (8)	0.0388 (3)
H2	0.1255	0.1192	1.0258	0.047*
N3	0.0098 (2)	0.19397 (12)	1.22149 (8)	0.0507 (3)
H3A	0.0478	0.2752	1.2214	0.061*
H3B	−0.0390	0.1620	1.2701	0.061*
O1	0.17090 (17)	0.56061 (11)	1.12351 (8)	0.0514 (3)
H1	0.1484	0.4807	1.1292	0.077*
O2	0.4601 (2)	0.67718 (16)	0.78420 (11)	0.0777 (4)
S1	−0.04238 (6)	−0.04281 (3)	1.14369 (3)	0.04739 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0324 (6)	0.0336 (6)	0.0378 (6)	−0.0011 (5)	0.0011 (5)	0.0040 (5)
C2	0.0356 (6)	0.0346 (6)	0.0455 (7)	0.0003 (5)	0.0019 (5)	0.0011 (5)
C3	0.0486 (8)	0.0323 (7)	0.0722 (10)	−0.0006 (6)	0.0028 (7)	−0.0008 (7)
C4	0.0489 (8)	0.0387 (7)	0.0844 (12)	−0.0041 (6)	0.0022 (8)	0.0213 (8)
C5	0.0422 (7)	0.0543 (9)	0.0573 (9)	−0.0021 (6)	0.0051 (6)	0.0232 (7)
C6	0.0430 (7)	0.0474 (8)	0.0411 (7)	−0.0017 (6)	0.0048 (5)	0.0072 (6)
C7	0.0654 (11)	0.123 (2)	0.0515 (10)	0.0004 (12)	0.0163 (9)	0.0260 (12)
C8	0.0411 (6)	0.0329 (6)	0.0356 (6)	−0.0024 (5)	0.0041 (5)	−0.0009 (5)
C9	0.0440 (6)	0.0293 (6)	0.0326 (6)	0.0004 (5)	0.0021 (5)	0.0016 (5)
N1	0.0401 (5)	0.0285 (5)	0.0362 (5)	−0.0025 (4)	0.0027 (4)	0.0010 (4)
N2	0.0540 (6)	0.0282 (5)	0.0346 (5)	−0.0040 (4)	0.0091 (5)	−0.0012 (4)
N3	0.0834 (9)	0.0347 (6)	0.0347 (6)	−0.0109 (6)	0.0138 (6)	−0.0034 (5)
O1	0.0678 (7)	0.0401 (5)	0.0473 (6)	−0.0046 (5)	0.0163 (5)	−0.0072 (4)
O2	0.0770 (9)	0.0822 (10)	0.0750 (9)	−0.0103 (7)	0.0193 (7)	0.0389 (8)
S1	0.0754 (3)	0.02908 (19)	0.0382 (2)	−0.00904 (14)	0.01049 (17)	0.00096 (12)

Geometric parameters (Å, º) top

C1—C2	1.3912 (19)	C7—H7A	0.9600
C1—C6	1.4063 (18)	C7—H7B	0.9600
C1—C8	1.4499 (17)	C7—H7C	0.9600
C2—O1	1.3653 (17)	C8—N1	1.2824 (16)
C2—C3	1.389 (2)	C8—H8	0.9300
C3—C4	1.376 (2)	C9—N3	1.3187 (17)
C3—H3	0.9300	C9—N2	1.3415 (16)
C4—C5	1.385 (3)	C9—S1	1.6901 (13)
C4—H4	0.9300	N1—N2	1.3797 (14)
C5—C6	1.376 (2)	N2—H2	0.8600
C5—O2	1.3774 (19)	N3—H3A	0.8600
C6—H6	0.9300	N3—H3B	0.8600
C7—O2	1.418 (3)	O1—H1	0.8200

C2—C1—C6	119.32 (13)	H7A—C7—H7B	109.5
C2—C1—C8	122.98 (12)	O2—C7—H7C	109.5
C6—C1—C8	117.70 (12)	H7A—C7—H7C	109.5
O1—C2—C3	117.94 (13)	H7B—C7—H7C	109.5
O1—C2—C1	122.33 (12)	N1—C8—C1	122.80 (12)
C3—C2—C1	119.72 (13)	N1—C8—H8	118.6
C4—C3—C2	120.06 (15)	C1—C8—H8	118.6
C4—C3—H3	120.0	N3—C9—N2	118.93 (12)
C2—C3—H3	120.0	N3—C9—S1	122.17 (10)
C3—C4—C5	121.07 (14)	N2—C9—S1	118.89 (10)
C3—C4—H4	119.5	C8—N1—N2	115.04 (11)
C5—C4—H4	119.5	C9—N2—N1	121.08 (11)
C6—C5—O2	124.45 (17)	C9—N2—H2	119.5
C6—C5—C4	119.29 (14)	N1—N2—H2	119.5
O2—C5—C4	116.26 (15)	C9—N3—H3A	120.0
C5—C6—C1	120.53 (15)	C9—N3—H3B	120.0
C5—C6—H6	119.7	H3A—N3—H3B	120.0
C1—C6—H6	119.7	C2—O1—H1	109.5
O2—C7—H7A	109.5	C5—O2—C7	116.83 (15)
O2—C7—H7B	109.5

C6—C1—C2—O1	179.97 (12)	C2—C1—C6—C5	0.6 (2)
C8—C1—C2—O1	0.2 (2)	C8—C1—C6—C5	−179.64 (13)
C6—C1—C2—C3	0.2 (2)	C2—C1—C8—N1	−1.2 (2)
C8—C1—C2—C3	−179.54 (13)	C6—C1—C8—N1	179.03 (12)
O1—C2—C3—C4	179.62 (14)	C1—C8—N1—N2	178.93 (11)
C1—C2—C3—C4	−0.6 (2)	N3—C9—N2—N1	−7.2 (2)
C2—C3—C4—C5	0.2 (2)	S1—C9—N2—N1	173.92 (10)
C3—C4—C5—C6	0.6 (2)	C8—N1—N2—C9	−177.01 (12)
C3—C4—C5—O2	−179.49 (14)	C6—C5—O2—C7	0.0 (2)
O2—C5—C6—C1	179.10 (14)	C4—C5—O2—C7	−179.90 (16)
C4—C5—C6—C1	−1.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.97	2.6844 (15)	146
N2—H2···S1ⁱ	0.86	2.61	3.3706 (12)	148
N3—H3A···S1ⁱⁱ	0.86	2.66	3.2706 (12)	129
N3—H3B···O1ⁱⁱⁱ	0.86	2.11	2.9604 (17)	172

Symmetry codes: (i) −x, −y, −z+2; (ii) −x, y+1/2, −z+5/2; (iii) −x, y−1/2, −z+5/2.

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O₂S
M_r	225.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	7.4878 (2), 9.9880 (2), 14.3754 (3)
β (°)	91.846 (1)
V (Å³)	1074.55 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.24 × 0.14 × 0.08

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.800, 0.926
No. of measured, independent and observed [I > 2σ(I)] reflections	10176, 2673, 2365
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.110, 1.07
No. of reflections	2673
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.24

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.97	2.6844 (15)	146
N2—H2···S1ⁱ	0.86	2.61	3.3706 (12)	148
N3—H3A···S1ⁱⁱ	0.86	2.66	3.2706 (12)	129
N3—H3B···O1ⁱⁱⁱ	0.86	2.11	2.9604 (17)	172

Symmetry codes: (i) −x, −y, −z+2; (ii) −x, y+1/2, −z+5/2; (iii) −x, y−1/2, −z+5/2.

Acknowledgements

AAA thanks the Islamic Azad University, Ardakan Branch (this paper was extracted from the research project). HK thanks PNU for financial support. MNT thanks Sargodha University for research facilities.

References

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