2-Hy-droxy-4-meth-oxy-benzaldehyde thio-semicarbazone.

The title Schiff base compound, C(9)H(11)N(3)O(2)S, was prepared by the reaction of equimolar quanti-ties of 2-hy-droxy-4-meth-oxy-benzaldehyde with thio-semicarbazide in methanol. The mol-ecule adopts a trans configuration with respect to the azo-methine group and an intra-molecular O-H⋯N hydrogen bond generates an S(6) ring. In the crystal structure, mol-ecules are linked through inter-molecular 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 = 225.27

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.101

S = 1.04

2247 reflections

147 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.23 e Å−3

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.

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029594/hb5575Isup2.hkl

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

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

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

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(Fo2) + (0.0453P)2 + 0.1092P] where P = (Fo2 + 2Fc2)/3
2247 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 0.18 e Å−3
4 restraints	Δρmin = −0.23 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) ; (ii) ; (iii) .