4-Hy-droxy-3-meth-oxy-benzaldehyde thio-semicarbazone.

In the title compound, C9H11N3S, there is an intra-molecular O-H⋯O hydrogen bond involving the OH group and the adjacent methoxy O atom. The mol-ecule is essentially planar, with the maximum deviation from the mean plane of the non-H atoms being 0.1127 (14) Å for the methyl C atom. In the crystal, mol-ecules are connected via centrosymmetric pairs of N-H⋯S and O-H⋯O hydrogen bonds into a two-dimensional network parallel to (10-3).

Related literature

For the in vitro anti­malarial and anti­tubercular activity of hy­droxy-meth­oxy­benzaldehyde thio­semicarbazone derivatives, see: Khanye et al. (2011 ▶). For the first report of the synthesis, see: Freund & Schander (1902 ▶). For the synthesis and crystal structure of an isomer of the title compound, see: Hao (2010 ▶).

Experimental

Crystal data

C9H11N3O2S

M = 225.27

Triclinic,

a = 4.5886 (5) Å

b = 8.5213 (11) Å

c = 13.9621 (15) Å

α = 75.898 (13)°

β = 87.669 (13)°

γ = 77.580 (14)°

V = 517.05 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.30 mm−1

T = 200 K

0.4 × 0.3 × 0.2 mm

Data collection

Stoe IPDS-1 diffractometer

Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T min = 0.865, T max = 0.982

5179 measured reflections

2211 independent reflections

1829 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.100

S = 1.03

2211 reflections

139 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.27 e Å−3

Data collection: X-AREA (Stoe & Cie, 2008 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813032303/fy2108sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813032303/fy2108Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813032303/fy2108Isup3.cml

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

C9H11N3O2S	Z = 2
Mr = 225.27	F(000) = 236
Triclinic, P1	Dx = 1.447 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.5886 (5) Å	Cell parameters from 5179 reflections
b = 8.5213 (11) Å	θ = 2.5–27.0°
c = 13.9621 (15) Å	µ = 0.30 mm−1
α = 75.898 (13)°	T = 200 K
β = 87.669 (13)°	Block, yellow
γ = 77.580 (14)°	0.4 × 0.3 × 0.2 mm
V = 517.05 (10) Å3

Stoe IPDS-1 diffractometer	2211 independent reflections
Radiation source: fine-focus sealed tube, Stoe IPDS-1	1829 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ scans	θmax = 27.0°, θmin = 2.5°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −5→5
Tmin = 0.865, Tmax = 0.982	k = −10→10
5179 measured reflections	l = −17→17

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)] = 0.036	H-atom parameters constrained
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.0666P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
2211 reflections	Δρmax = 0.32 e Å−3
139 parameters	Δρmin = −0.27 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: 0.055 (15)

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
C1	0.1779 (3)	0.65909 (18)	0.22576 (11)	0.0210 (3)
C2	0.0643 (3)	0.81737 (19)	0.16881 (12)	0.0252 (3)
H2	0.1261	0.9096	0.1820	0.030*
C3	−0.1384 (4)	0.84153 (19)	0.09296 (12)	0.0255 (3)
H3	−0.2163	0.9501	0.0546	0.031*
C4	−0.2278 (3)	0.70678 (19)	0.07295 (11)	0.0223 (3)
C5	−0.1165 (3)	0.54775 (17)	0.12986 (11)	0.0203 (3)
C6	0.0858 (3)	0.52373 (18)	0.20585 (11)	0.0207 (3)
H6	0.1622	0.4152	0.2445	0.025*
O1	−0.4253 (3)	0.73483 (14)	−0.00291 (9)	0.0306 (3)
H1	−0.4773	0.6463	−0.0034	0.046*
O2	−0.2264 (3)	0.42408 (13)	0.10546 (8)	0.0268 (3)
C7	−0.1404 (4)	0.2626 (2)	0.16928 (14)	0.0354 (4)
H7A	0.0761	0.2238	0.1664	0.053*
H7B	−0.2414	0.1863	0.1481	0.053*
H7C	−0.1969	0.2671	0.2372	0.053*
C8	0.3893 (3)	0.62554 (19)	0.30740 (11)	0.0218 (3)
H8	0.4565	0.5145	0.3439	0.026*
N1	0.4870 (3)	0.74084 (16)	0.33129 (9)	0.0222 (3)
N2	0.6853 (3)	0.68715 (15)	0.40998 (10)	0.0222 (3)
H2A	0.7455	0.5805	0.4362	0.027*
C9	0.7865 (3)	0.79732 (18)	0.44648 (11)	0.0218 (3)
N3	0.6948 (4)	0.95590 (17)	0.40253 (11)	0.0344 (4)
H3A	0.5720	0.9854	0.3514	0.041*
H3B	0.7565	1.0318	0.4244	0.041*
S1	1.01872 (9)	0.72984 (5)	0.54636 (3)	0.02745 (16)

	U11	U22	U33	U12	U13	U23
C1	0.0178 (7)	0.0265 (7)	0.0203 (7)	−0.0054 (6)	−0.0038 (5)	−0.0074 (6)
C2	0.0253 (8)	0.0239 (7)	0.0286 (8)	−0.0074 (6)	−0.0071 (6)	−0.0074 (6)
C3	0.0270 (8)	0.0216 (7)	0.0265 (8)	−0.0051 (6)	−0.0080 (6)	−0.0015 (6)
C4	0.0207 (7)	0.0270 (7)	0.0193 (7)	−0.0040 (6)	−0.0073 (6)	−0.0054 (6)
C5	0.0203 (7)	0.0223 (7)	0.0208 (7)	−0.0055 (6)	−0.0027 (5)	−0.0085 (6)
C6	0.0203 (7)	0.0229 (7)	0.0193 (7)	−0.0041 (6)	−0.0040 (6)	−0.0054 (6)
O1	0.0350 (6)	0.0285 (6)	0.0283 (6)	−0.0066 (5)	−0.0196 (5)	−0.0035 (5)
O2	0.0334 (6)	0.0224 (5)	0.0266 (6)	−0.0065 (4)	−0.0144 (5)	−0.0064 (4)
C7	0.0458 (10)	0.0233 (8)	0.0377 (10)	−0.0093 (7)	−0.0219 (8)	−0.0031 (7)
C8	0.0192 (7)	0.0261 (7)	0.0212 (7)	−0.0049 (5)	−0.0050 (6)	−0.0070 (6)
N1	0.0197 (6)	0.0278 (6)	0.0204 (6)	−0.0038 (5)	−0.0070 (5)	−0.0078 (5)
N2	0.0232 (6)	0.0224 (6)	0.0224 (7)	−0.0045 (5)	−0.0095 (5)	−0.0068 (5)
C9	0.0210 (7)	0.0247 (7)	0.0217 (7)	−0.0060 (6)	−0.0020 (6)	−0.0080 (6)
N3	0.0470 (9)	0.0227 (7)	0.0346 (8)	−0.0065 (6)	−0.0228 (7)	−0.0059 (6)
S1	0.0345 (3)	0.0250 (2)	0.0248 (2)	−0.00760 (16)	−0.01444 (16)	−0.00630 (15)

C1—C2	1.390 (2)	O2—C7	1.428 (2)
C1—C6	1.401 (2)	C7—H7A	0.9800
C1—C8	1.4608 (19)	C7—H7B	0.9800
C2—C3	1.386 (2)	C7—H7C	0.9800
C2—H2	0.9500	C8—N1	1.2801 (19)
C3—C4	1.390 (2)	C8—H8	0.9500
C3—H3	0.9500	N1—N2	1.3792 (17)
C4—O1	1.3643 (17)	N2—C9	1.3404 (19)
C4—C5	1.393 (2)	N2—H2A	0.8800
C5—O2	1.3779 (17)	C9—N3	1.324 (2)
C5—C6	1.386 (2)	C9—S1	1.6962 (15)
C6—H6	0.9500	N3—H3A	0.8800
O1—H1	0.8400	N3—H3B	0.8800
C2—C1—C6	119.42 (13)	O2—C7—H7A	109.5
C2—C1—C8	123.13 (13)	O2—C7—H7B	109.5
C6—C1—C8	117.45 (13)	H7A—C7—H7B	109.5
C3—C2—C1	120.45 (13)	O2—C7—H7C	109.5
C3—C2—H2	119.8	H7A—C7—H7C	109.5
C1—C2—H2	119.8	H7B—C7—H7C	109.5
C2—C3—C4	119.99 (14)	N1—C8—C1	122.15 (14)
C2—C3—H3	120.0	N1—C8—H8	118.9
C4—C3—H3	120.0	C1—C8—H8	118.9
O1—C4—C3	118.45 (13)	C8—N1—N2	114.48 (12)
O1—C4—C5	121.52 (13)	C9—N2—N1	120.04 (12)
C3—C4—C5	120.02 (13)	C9—N2—H2A	120.0
O2—C5—C6	124.88 (13)	N1—N2—H2A	120.0
O2—C5—C4	115.17 (13)	N3—C9—N2	117.44 (14)
C6—C5—C4	119.95 (13)	N3—C9—S1	123.06 (11)
C5—C6—C1	120.17 (14)	N2—C9—S1	119.49 (11)
C5—C6—H6	119.9	C9—N3—H3A	120.0
C1—C6—H6	119.9	C9—N3—H3B	120.0
C4—O1—H1	109.5	H3A—N3—H3B	120.0
C5—O2—C7	116.19 (11)
C6—C1—C2—C3	0.1 (2)	C2—C1—C6—C5	0.1 (2)
C8—C1—C2—C3	−179.27 (15)	C8—C1—C6—C5	179.45 (13)
C1—C2—C3—C4	−0.5 (3)	C6—C5—O2—C7	5.2 (2)
C2—C3—C4—O1	−179.32 (15)	C4—C5—O2—C7	−173.55 (15)
C2—C3—C4—C5	0.8 (3)	C2—C1—C8—N1	−0.7 (2)
O1—C4—C5—O2	−1.7 (2)	C6—C1—C8—N1	179.91 (14)
C3—C4—C5—O2	178.21 (14)	C1—C8—N1—N2	−179.89 (13)
O1—C4—C5—C6	179.46 (14)	C8—N1—N2—C9	−175.18 (14)
C3—C4—C5—C6	−0.6 (2)	N1—N2—C9—N3	−1.7 (2)
O2—C5—C6—C1	−178.53 (14)	N1—N2—C9—S1	177.37 (11)
C4—C5—C6—C1	0.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84	2.24	2.6934 (16)	114
O1—H1···O2i	0.84	2.27	2.9153 (15)	134
N2—H2A···S1ii	0.88	2.59	3.4319 (14)	161
N3—H3B···S1iii	0.88	2.59	3.4540 (15)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.84	2.24	2.6934 (16)	114
O1—H1⋯O2i	0.84	2.27	2.9153 (15)	134
N2—H2A⋯S1ii	0.88	2.59	3.4319 (14)	161
N3—H3B⋯S1iii	0.88	2.59	3.4540 (15)	169

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