2,4-Dihydroxy­benzaldehyde 4-methyl­thio­semicarbazone

Abstract

The approximately planar mol­ecule of the title compound, C₉H₁₁N₃O₂S, is linked to adjacent mol­ecules by O—H⋯S hydrogen bonds to form a zigzag chain. Adjacent chains are consolidated by N—H⋯O hydrogen bonds into a two-dimensional array. An intramolecular O—H⋯N link is also present.

Related literature

For the structure of isomeric 2,5-dihydroxy­benzaldehyde 4-methyl­thio­semicarbazone, see: Tan et al. (2008 ▶).

Experimental

Crystal data

• C₉H₁₁N₃O₂S

• M _r = 225.27

• Monoclinic,

• a = 18.0046 (6) Å

• b = 4.6436 (1) Å

• c = 12.2842 (4) Å

• β = 106.695 (2)°

• V = 983.74 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 0.31 mm⁻¹

• T = 100 (2) K

• 0.09 × 0.06 × 0.03 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.973, T _max = 0.991

• 4390 measured reflections

• 2128 independent reflections

• 1925 reflections with I > 2σ(I)

• R _int = 0.034

Refinement

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.109

• S = 1.11

• 2128 reflections

• 153 parameters

• 6 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.22 e Å⁻³

• Absolute structure: Flack (1983 ▶), with 814 Friedel pairs

• Flack parameter: 0.00 (1)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

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—H1O⋯N1	0.84 (1)	1.93 (3)	2.694 (3)	151 (6)
O2—H2O⋯S1i	0.84 (1)	2.54 (1)	3.365 (2)	170 (4)
N2—H2N⋯O1ii	0.87 (1)	2.11 (1)	2.950 (4)	162 (3)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

In continuation of on-going studies into the structural chemistry of thiosemicarbazones (Tan et al., 2008), the title compound (I) was investigated. Molecule (I), Fig. 1, is essentially planar and is consolidated into a 2-D array by a combination of N-H···O and O-H···S hydrogen bonding contacts, Table 1.

Experimental

4-Methylthiosemicarbazide (0.11 g, 1 mmol) and 2,4-dihydroxybenzaldehyde (0.14 g, 1 mmol) were heated in ethanol (10 ml) for 1 h. Slow evaporation of the solvent yielded yellow crystals.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U_iso>(H) set to 1.2-1.5 U_eq(C). The hydroxy and amino H-atoms were located in a difference Fourier map, and were refined with distance retraints of O–H = 0.84±0.01 and N–H = 0.88±0.01 Å; their temperature factors were freely refined.

Figures

Fig. 1.

Thermal ellipsoid (Barbour, 2001) plot of (I) drawn at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.

Crystal data

C9H11N3O2S	F(000) = 472
Mr = 225.27	Dx = 1.521 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1090 reflections
a = 18.0046 (6) Å	θ = 2.4–24.9°
b = 4.6436 (1) Å	µ = 0.31 mm−1
c = 12.2842 (4) Å	T = 100 K
β = 106.695 (2)°	Prims, yellow
V = 983.74 (5) Å3	0.09 × 0.06 × 0.03 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	2128 independent reflections
Radiation source: fine-focus sealed tube	1925 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→22
Tmin = 0.973, Tmax = 0.991	k = −6→6
4390 measured reflections	l = −15→15

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109	w = 1/[σ2(Fo2) + (0.0598P)2] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max = 0.001
2128 reflections	Δρmax = 0.31 e Å−3
153 parameters	Δρmin = −0.22 e Å−3
6 restraints	Absolute structure: Flack (1983), 814 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.00 (1)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.50003 (5)	0.63599 (16)	0.50001 (6)	0.01776 (19)
O1	0.65168 (12)	−0.1181 (5)	0.93136 (19)	0.0174 (5)
O2	0.84529 (13)	−0.8242 (5)	1.05294 (19)	0.0198 (5)
N1	0.63927 (15)	0.1424 (5)	0.7309 (2)	0.0144 (5)
N2	0.60440 (15)	0.2962 (6)	0.6322 (2)	0.0147 (5)
N3	0.53164 (15)	0.5567 (6)	0.7241 (2)	0.0166 (6)
C1	0.73692 (17)	−0.2114 (7)	0.8141 (2)	0.0128 (6)
C2	0.71210 (17)	−0.2660 (7)	0.9113 (2)	0.0122 (6)
C3	0.74812 (18)	−0.4725 (7)	0.9891 (3)	0.0141 (6)
H3	0.7300	−0.5117	1.0530	0.017*
C4	0.81112 (16)	−0.6232 (6)	0.9739 (2)	0.0142 (6)
C5	0.83798 (18)	−0.5674 (7)	0.8800 (3)	0.0174 (7)
H5	0.8815	−0.6688	0.8704	0.021*
C6	0.80096 (17)	−0.3645 (7)	0.8017 (3)	0.0159 (7)
H6	0.8192	−0.3274	0.7378	0.019*
C7	0.69685 (17)	−0.0131 (7)	0.7250 (2)	0.0142 (6)
H7	0.7142	0.0020	0.6590	0.017*
C8	0.54711 (17)	0.4887 (7)	0.6279 (3)	0.0149 (6)
C9	0.47552 (19)	0.7743 (8)	0.7317 (3)	0.0206 (7)
H9A	0.4879	0.8460	0.8099	0.031*
H9B	0.4234	0.6899	0.7100	0.031*
H9C	0.4773	0.9340	0.6804	0.031*
H1O	0.633 (3)	−0.017 (11)	0.874 (3)	0.08 (2)*
H2O	0.8796 (19)	−0.909 (8)	1.032 (4)	0.038 (13)*
H2N	0.6097 (19)	0.218 (7)	0.5703 (17)	0.011 (8)*
H3N	0.5552 (19)	0.476 (7)	0.7898 (17)	0.018 (9)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0196 (4)	0.0180 (4)	0.0138 (3)	0.0027 (4)	0.0018 (3)	0.0021 (4)
O1	0.0193 (13)	0.0174 (12)	0.0159 (11)	0.0038 (9)	0.0059 (9)	0.0029 (10)
O2	0.0216 (12)	0.0196 (13)	0.0171 (12)	0.0069 (10)	0.0037 (9)	0.0040 (9)
N1	0.0159 (13)	0.0126 (13)	0.0125 (12)	−0.0018 (11)	0.0008 (10)	0.0013 (10)
N2	0.0176 (13)	0.0163 (13)	0.0097 (13)	0.0024 (11)	0.0030 (10)	−0.0001 (11)
N3	0.0195 (14)	0.0144 (13)	0.0152 (13)	0.0023 (11)	0.0037 (10)	0.0014 (10)
C1	0.0153 (14)	0.0135 (15)	0.0103 (14)	−0.0029 (12)	0.0048 (11)	−0.0005 (12)
C2	0.0105 (14)	0.0147 (15)	0.0129 (15)	−0.0017 (12)	0.0056 (11)	−0.0034 (12)
C3	0.0162 (15)	0.0159 (16)	0.0120 (15)	−0.0032 (12)	0.0069 (12)	−0.0012 (11)
C4	0.0148 (16)	0.0139 (14)	0.0113 (14)	−0.0007 (12)	−0.0006 (12)	0.0000 (12)
C5	0.0155 (16)	0.0163 (16)	0.0180 (17)	0.0012 (12)	0.0010 (12)	−0.0031 (12)
C6	0.0121 (15)	0.0214 (18)	0.0134 (15)	−0.0031 (14)	0.0023 (12)	−0.0033 (13)
C7	0.0157 (16)	0.0164 (16)	0.0117 (15)	−0.0035 (13)	0.0058 (12)	−0.0016 (12)
C8	0.0154 (15)	0.0127 (15)	0.0175 (16)	−0.0031 (12)	0.0064 (12)	0.0002 (12)
C9	0.0169 (16)	0.0266 (19)	0.0201 (17)	0.0003 (13)	0.0079 (13)	−0.0038 (13)

Geometric parameters (Å, °)

S1—C8	1.699 (3)	C1—C2	1.413 (4)
O1—C2	1.367 (4)	C1—C7	1.454 (4)
O1—H1O	0.838 (10)	C2—C3	1.378 (4)
O2—C4	1.360 (4)	C3—C4	1.391 (4)
O2—H2O	0.836 (10)	C3—H3	0.9500
N1—C7	1.283 (4)	C4—C5	1.397 (4)
N1—N2	1.392 (3)	C5—C6	1.374 (4)
N2—C8	1.354 (4)	C5—H5	0.9500
N2—H2N	0.871 (10)	C6—H6	0.9500
N3—C8	1.328 (4)	C7—H7	0.9500
N3—C9	1.451 (4)	C9—H9A	0.9800
N3—H3N	0.880 (10)	C9—H9B	0.9800
C1—C6	1.400 (4)	C9—H9C	0.9800
C2—O1—H1O	106 (4)	C3—C4—C5	120.5 (3)
C4—O2—H2O	109 (3)	C6—C5—C4	119.5 (3)
C7—N1—N2	114.1 (3)	C6—C5—H5	120.3
C8—N2—N1	121.4 (3)	C4—C5—H5	120.3
C8—N2—H2N	121 (2)	C5—C6—C1	121.4 (3)
N1—N2—H2N	114 (2)	C5—C6—H6	119.3
C8—N3—C9	123.4 (3)	C1—C6—H6	119.3
C8—N3—H3N	123 (3)	N1—C7—C1	123.2 (3)
C9—N3—H3N	114 (3)	N1—C7—H7	118.4
C6—C1—C2	118.1 (3)	C1—C7—H7	118.4
C6—C1—C7	119.1 (3)	N3—C8—N2	118.3 (3)
C2—C1—C7	122.8 (3)	N3—C8—S1	123.4 (2)
O1—C2—C3	117.7 (3)	N2—C8—S1	118.3 (2)
O1—C2—C1	121.6 (3)	N3—C9—H9A	109.5
C3—C2—C1	120.8 (3)	N3—C9—H9B	109.5
C2—C3—C4	119.8 (3)	H9A—C9—H9B	109.5
C2—C3—H3	120.1	N3—C9—H9C	109.5
C4—C3—H3	120.1	H9A—C9—H9C	109.5
O2—C4—C3	117.9 (3)	H9B—C9—H9C	109.5
O2—C4—C5	121.6 (3)
C7—N1—N2—C8	−174.4 (3)	C4—C5—C6—C1	0.2 (5)
C6—C1—C2—O1	177.7 (3)	C2—C1—C6—C5	1.4 (4)
C7—C1—C2—O1	−4.9 (4)	C7—C1—C6—C5	−176.0 (3)
C6—C1—C2—C3	−2.5 (4)	N2—N1—C7—C1	−174.0 (3)
C7—C1—C2—C3	174.8 (3)	C6—C1—C7—N1	−177.7 (3)
O1—C2—C3—C4	−178.3 (3)	C2—C1—C7—N1	5.0 (5)
C1—C2—C3—C4	1.9 (5)	C9—N3—C8—N2	175.6 (3)
C2—C3—C4—O2	179.7 (3)	C9—N3—C8—S1	−3.1 (4)
C2—C3—C4—C5	−0.2 (5)	N1—N2—C8—N3	8.8 (4)
O2—C4—C5—C6	179.3 (3)	N1—N2—C8—S1	−172.5 (2)
C3—C4—C5—C6	−0.9 (5)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.84 (1)	1.93 (3)	2.694 (3)	151 (6)
O2—H2O···S1i	0.84 (1)	2.54 (1)	3.365 (2)	170 (4)
N2—H2N···O1ii	0.87 (1)	2.11 (1)	2.950 (4)	162 (3)

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