(E)-2-Hydr­oxy-3-methoxy­benzaldehyde thio­semicarbazone

Zhao, R.-G.; Zhang, W.; Li, J.-K.; Zhang, L.-Y.

doi:10.1107/S1600536808014475

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1113

doi:10.1107/S1600536808014475

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(E)-2-Hydroxy-3-methoxybenzaldehyde thiosemicarbazone

Ren-Gao Zhao,^a ^* Wei Zhang,^b Ji-Kun Li ^a and Li-Ya Zhang ^a

^aDepartment of Materials Science and Chemical Engineering, Taishan University, 271021 Taian, Shandong, People's Republic of China, and ^bFeng Cheng Senior High School, 271100 Laiwu, Shandong, People's Republic of China
^*Correspondence e-mail: imlijikun@163.com

(Received 6 May 2008; accepted 14 May 2008; online 17 May 2008)

In the title compound, C₉H₁₁N₃O₂S, intramolecular O—H⋯O and N—H⋯N hydrogen bonds contribute to the planarity of the molecular skeleton. Intermolecular N—H⋯O hydrogen bonds link the molecules into zigzag chains along the b axis; these molecules are futher paired by π–π interactions [centroid–centroid distance 4.495 (5) Å]. The crystal structure also exhibits weak intermolecular N—H⋯S and O—H⋯S hydrogen bonds.

Related literature

For related crystal structures, see: Joseph et al. (2006 ). For biological activities of thiosemicarbazone Schiff bases, see: Kasuga et al. (2001 ); Fonari et al. (2003 ).

Experimental

Crystal data

C₉H₁₁N₃O₂S
M_r = 225.27
Monoclinic, P 2₁ /c
a = 7.057 (3) Å
b = 14.673 (5) Å
c = 10.738 (4) Å
β = 108.412 (7)°
V = 1055.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 273 (2) K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.958, T_max = 0.972
5510 measured reflections
1872 independent reflections
1023 reflections with I > 2σ(I)
R_int = 0.071

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.163
S = 1.10
1872 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.82	2.14	2.610 (4)	116
N3—H3A⋯N1	0.86	2.23	2.592 (5)	105
O1—H1⋯S1ⁱⁱ	0.82	2.69	3.290 (3)	131
N2—H2⋯S1ⁱⁱⁱ	0.86	2.62	3.470 (4)	172
N3—H3B⋯O1^iv	0.86	2.28	2.943 (4)	134
Symmetry codes: (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+2, -y+1, -z+1; (iv) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014475/cv2411sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014475/cv2411Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazone Schiff-bases have been investigated in terms of their chemistry and potentially beneficial biological activities, such as antitumor, antibacterial, antiviral and antimalarial activities (Kasuga et al., 2001; Fonari et al., 2003). In continuation of our studies on thiosemicarbazone Schiff-bases, we report the synthesis and crystal structure of the title compound, (I).

In (I) (Fig. 1), all bond lengths and angles are normal and in a good agreement with those found in the literature (Joseph et al., 2006). The intramolecular O—H···O and N—H···N hydrogen bonds (Table 2) contribute to the planarity of molecular skeleton. The intermolecular N—H···O hydrogen bonds (Table 2) link the molecules into zigzag chains along b axis, which are futher paired by π···π interactions proved by short intermolecular C···C distances (Table 1). The crystal packing exhibits also weak intermolecular N—H···S and O—H···S hydrogen bonds (Table 2).

Related literature top

For related crystal structures, see: Joseph et al. (2006). For biological activities of thiosemicarbazone Schiff bases, see: Kasuga et al. (2001); Fonari et al. (2003).

Experimental top

The title compound was synthesized by the reaction of 2-hydroxy-3-methoxybenzaldehyde (0.152 g, 1 mmol) and hydrazinecarbothioamide (0.091 g, 1 mmol) in ethanol solution and stirred under reflux conditions (353 K) for 6 h. When cooled to the room temperature, the solution was filtered off and after a week orange crystals suitable for X-ray diffraction study were obtained. Yield, 0.199 g, 82%. m.p. 358–360 K.

Analysis found: C 47.94, H 4.95, N 18.62%; C₉H₁₁N₃O₂S requires: C 47.99, H 4.92, N 18.65%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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).

Figures top

Fig. 1. The molecular structure of (I) showing the atomic numbering and 30% probability displacement ellipsoids.

(E)-2-Hydroxy-3-methoxybenzaldehyde thiosemicarbazone top

Crystal data top

C₉H₁₁N₃O₂S	F(000) = 472
M_r = 225.27	D_x = 1.418 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 511 reflections
a = 7.057 (3) Å	θ = 2.4–19.8°
b = 14.673 (5) Å	µ = 0.29 mm⁻¹
c = 10.738 (4) Å	T = 273 K
β = 108.412 (7)°	Block, orange
V = 1055.0 (7) Å³	0.15 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1872 independent reflections
Radiation source: fine-focus sealed tube	1023 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→6
T_min = 0.958, T_max = 0.972	k = −17→17
5510 measured reflections	l = −9→12

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)] = 0.060	H-atom parameters constrained
wR(F²) = 0.163	w = 1/[σ²(F_o²) + (0.0641P)² + 0.0089P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1872 reflections	Δρ_max = 0.19 e Å⁻³
138 parameters	Δρ_min = −0.28 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: 0.005 (2)

Crystal data top

C₉H₁₁N₃O₂S	V = 1055.0 (7) Å³
M_r = 225.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.057 (3) Å	µ = 0.29 mm⁻¹
b = 14.673 (5) Å	T = 273 K
c = 10.738 (4) Å	0.15 × 0.12 × 0.10 mm
β = 108.412 (7)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1872 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1023 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.972	R_int = 0.071
5510 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.10	Δρ_max = 0.19 e Å⁻³
1872 reflections	Δρ_min = −0.28 e Å⁻³
138 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
S1	1.0171 (2)	0.35387 (8)	0.55909 (10)	0.0534 (5)
O1	0.8111 (5)	0.65121 (18)	−0.0190 (3)	0.0600 (10)
H1	0.7915	0.6940	−0.0706	0.090*
O2	0.6495 (5)	0.6610 (2)	−0.2733 (3)	0.0637 (10)
N1	0.8421 (5)	0.4185 (2)	0.1879 (3)	0.0423 (10)
N2	0.9111 (5)	0.4247 (2)	0.3218 (3)	0.0464 (10)
H2	0.9351	0.4771	0.3595	0.056*
N3	0.9079 (6)	0.2710 (2)	0.3278 (3)	0.0583 (12)
H3A	0.8692	0.2716	0.2434	0.070*
H3B	0.9248	0.2199	0.3692	0.070*
C1	0.9411 (7)	0.3481 (3)	0.3936 (4)	0.0425 (11)
C2	0.8215 (7)	0.4935 (3)	0.1257 (4)	0.0442 (12)
H2A	0.8580	0.5480	0.1712	0.053*
C3	0.7403 (6)	0.4938 (3)	−0.0173 (4)	0.0383 (11)
C4	0.7340 (7)	0.5738 (3)	−0.0851 (4)	0.0410 (11)
C5	0.6465 (7)	0.5770 (3)	−0.2212 (4)	0.0443 (12)
C6	0.5703 (8)	0.4995 (3)	−0.2877 (4)	0.0556 (14)
H6	0.5123	0.5011	−0.3784	0.067*
C7	0.5789 (8)	0.4183 (3)	−0.2207 (4)	0.0625 (15)
H7	0.5275	0.3655	−0.2669	0.075*
C8	0.6621 (7)	0.4148 (3)	−0.0874 (4)	0.0552 (14)
H8	0.6667	0.3599	−0.0434	0.066*
C9	0.5673 (8)	0.6720 (3)	−0.4120 (4)	0.0628 (15)
H9A	0.6335	0.6316	−0.4551	0.094*
H9B	0.5859	0.7339	−0.4351	0.094*
H9C	0.4272	0.6582	−0.4392	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0790 (10)	0.0454 (7)	0.0340 (6)	0.0035 (7)	0.0154 (6)	0.0006 (5)
O1	0.100 (3)	0.0310 (16)	0.0406 (17)	−0.0114 (18)	0.0107 (17)	−0.0004 (14)
O2	0.092 (3)	0.054 (2)	0.0415 (19)	−0.0039 (19)	0.0147 (17)	0.0101 (15)
N1	0.055 (3)	0.041 (2)	0.0303 (19)	0.0000 (18)	0.0133 (17)	−0.0019 (16)
N2	0.068 (3)	0.038 (2)	0.032 (2)	0.000 (2)	0.0133 (18)	−0.0004 (16)
N3	0.098 (4)	0.039 (2)	0.032 (2)	−0.001 (2)	0.012 (2)	0.0005 (16)
C1	0.053 (3)	0.037 (2)	0.036 (2)	0.003 (2)	0.012 (2)	0.005 (2)
C2	0.056 (4)	0.035 (2)	0.042 (2)	0.000 (2)	0.016 (2)	0.0029 (19)
C3	0.046 (3)	0.036 (3)	0.032 (2)	0.004 (2)	0.011 (2)	0.0028 (18)
C4	0.043 (3)	0.038 (3)	0.040 (2)	0.003 (2)	0.012 (2)	−0.001 (2)
C5	0.056 (3)	0.042 (3)	0.035 (2)	0.001 (2)	0.014 (2)	0.008 (2)
C6	0.069 (4)	0.061 (3)	0.033 (3)	−0.004 (3)	0.010 (2)	−0.006 (2)
C7	0.087 (4)	0.045 (3)	0.049 (3)	−0.006 (3)	0.013 (3)	−0.011 (2)
C8	0.074 (4)	0.043 (3)	0.045 (3)	−0.003 (3)	0.013 (2)	−0.001 (2)
C9	0.063 (4)	0.074 (3)	0.047 (3)	0.004 (3)	0.011 (2)	0.017 (2)

Geometric parameters (Å, º) top

S1—C1	1.688 (4)	C2—H2A	0.9300
O1—C4	1.358 (4)	C3—C4	1.375 (5)
O1—H1	0.8200	C3—C8	1.396 (5)
O2—C5	1.357 (5)	C4—C5	1.397 (5)
O2—C9	1.426 (5)	C5—C6	1.360 (6)
N1—C2	1.271 (5)	C6—C7	1.382 (6)
N1—N2	1.367 (4)	C6—H6	0.9300
N2—C1	1.342 (5)	C7—C8	1.365 (6)
N2—H2	0.8600	C7—H7	0.9300
N3—C1	1.315 (5)	C8—H8	0.9300
N3—H3A	0.8600	C9—H9A	0.9600
N3—H3B	0.8600	C9—H9B	0.9600
C2—C3	1.460 (5)	C9—H9C	0.9600

C1···C9ⁱ	3.425 (7)	C2···C4ⁱ	3.445 (7)

C4—O1—H1	109.5	C3—C4—C5	120.8 (4)
C5—O2—C9	118.7 (3)	O2—C5—C6	126.7 (4)
C2—N1—N2	116.0 (3)	O2—C5—C4	113.7 (4)
C1—N2—N1	119.2 (3)	C6—C5—C4	119.5 (4)
C1—N2—H2	120.4	C5—C6—C7	120.1 (4)
N1—N2—H2	120.4	C5—C6—H6	119.9
C1—N3—H3A	120.0	C7—C6—H6	119.9
C1—N3—H3B	120.0	C8—C7—C6	120.8 (4)
H3A—N3—H3B	120.0	C8—C7—H7	119.6
N3—C1—N2	116.3 (4)	C6—C7—H7	119.6
N3—C1—S1	123.5 (3)	C7—C8—C3	120.0 (4)
N2—C1—S1	120.2 (3)	C7—C8—H8	120.0
N1—C2—C3	119.8 (4)	C3—C8—H8	120.0
N1—C2—H2A	120.1	O2—C9—H9A	109.5
C3—C2—H2A	120.1	O2—C9—H9B	109.5
C4—C3—C8	118.8 (4)	H9A—C9—H9B	109.5
C4—C3—C2	119.7 (4)	O2—C9—H9C	109.5
C8—C3—C2	121.4 (4)	H9A—C9—H9C	109.5
O1—C4—C3	119.8 (4)	H9B—C9—H9C	109.5
O1—C4—C5	119.4 (4)

C2—N1—N2—C1	−178.4 (4)	C9—O2—C5—C4	178.9 (4)
N1—N2—C1—N3	2.5 (6)	O1—C4—C5—O2	0.0 (7)
N1—N2—C1—S1	−177.5 (3)	C3—C4—C5—O2	179.1 (4)
N2—N1—C2—C3	−177.3 (4)	O1—C4—C5—C6	179.6 (4)
N1—C2—C3—C4	−174.4 (4)	C3—C4—C5—C6	−1.3 (7)
N1—C2—C3—C8	7.7 (7)	O2—C5—C6—C7	179.7 (5)
C8—C3—C4—O1	−179.3 (4)	C4—C5—C6—C7	0.2 (8)
C2—C3—C4—O1	2.8 (7)	C5—C6—C7—C8	0.5 (9)
C8—C3—C4—C5	1.7 (7)	C6—C7—C8—C3	−0.2 (8)
C2—C3—C4—C5	−176.3 (4)	C4—C3—C8—C7	−0.9 (7)
C9—O2—C5—C6	−0.6 (7)	C2—C3—C8—C7	177.0 (5)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	2.14	2.610 (4)	116
N3—H3A···N1	0.86	2.23	2.592 (5)	105
O1—H1···S1ⁱⁱ	0.82	2.69	3.290 (3)	131
N2—H2···S1ⁱⁱⁱ	0.86	2.62	3.470 (4)	172
N3—H3B···O1^iv	0.86	2.28	2.943 (4)	134

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O₂S
M_r	225.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	7.057 (3), 14.673 (5), 10.738 (4)
β (°)	108.412 (7)
V (Å³)	1055.0 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.958, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	5510, 1872, 1023
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.163, 1.10
No. of reflections	1872
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.28

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected interatomic distances (Å) top

C1···C9ⁱ

3.425 (7)

C2···C4ⁱ

3.445 (7)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	2.14	2.610 (4)	116.0
N3—H3A···N1	0.86	2.23	2.592 (5)	105.3
O1—H1···S1ⁱⁱ	0.82	2.69	3.290 (3)	131.4
N2—H2···S1ⁱⁱⁱ	0.86	2.62	3.470 (4)	171.8
N3—H3B···O1^iv	0.86	2.28	2.943 (4)	134.4

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

Acknowledgements

The authors thank the Postgraduate Foundation of Taishan University for financial support (grant No. Y06–2-12).

References

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