(E)-2-Hydr-oxy-3-methoxy-benzaldehyde thio-semicarbazone.

In the title compound, C(9)H(11)N(3)O(2)S, intra-molecular O-H⋯O and N-H⋯N hydrogen bonds contribute to the planarity of the mol-ecular skeleton. Inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into zigzag chains along the b axis; these mol-ecules are futher paired by π-π inter-actions [centroid-centroid distance 4.495 (5) Å]. The crystal structure also exhibits weak inter-molecular 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 = 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) 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[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.163

S = 1.10

1872 reflections

138 parameters

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −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.

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

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

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

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

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 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)

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.

	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*

	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)

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)

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.

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) .