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

Abstract

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,

• a = 7.057 (3) Å

• b = 14.673 (5) Å

• c = 10.738 (4) Å

• β = 108.412 (7)°

• V = 1055.0 (7) ų

• 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[F ² > 2σ(F ²)] = 0.059

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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⋯O1iv	0.86	2.28	2.943 (4)	134

Symmetry codes: (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

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).

Experimental

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%.

Refinement

The H-atoms were geometrically positioned (C-H 0.93-0.96 Å, N-H 0.86 Å, O-H 0.82 Å), and refined as riding on their parent atoms, with U_iso(H) = 1.2U_eq(C-aromatic and N) and U_iso(H) = 1.5U_eq(C-methyl and O).

Figures

Fig. 1.

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

Crystal data

C9H11N3O2S	F(000) = 472
Mr = 225.27	Dx = 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

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

Refinement

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(Fo2) + (0.0641P)2 + 0.0089P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
1872 reflections	Δρmax = 0.19 e Å−3
138 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+2, −y+1, −z.

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···O1iv	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.