2,4-Dihydroxy­benzaldehyde 4-methyl­thio­semicarbazone

Tan, K.W.; Ng, C.H.; Maah, M.J.; Ng, S.W.

doi:10.1107/S1600536808033308

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2224

doi:10.1107/S1600536808033308

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2,4-Dihydroxybenzaldehyde 4-methylthiosemicarbazone

Kong Wai Tan,^a Chew Hee Ng,^b Mohd. Jamil Maah ^a ^* and Seik Weng Ng ^a

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^bFaculty of Engineering and Science, Universiti Tunku Abdul Rahman, 53300 Kuala Lumpur, Malaysia
^*Correspondence e-mail: mjamil@um.edu.my

(Received 11 October 2008; accepted 14 October 2008; online 31 October 2008)

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, C c
a = 18.0046 (6) Å
b = 4.6436 (1) Å
c = 12.2842 (4) Å
β = 106.695 (2)°
V = 983.74 (5) Å³
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[F² > 2σ(F²)] = 0.038
wR(F²) = 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)

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) $[x+{\script{1\over 2}}, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y, z-{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808033308/tk2316sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808033308/tk2316Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

Fig. 1. Thermal ellipsoid (Barbour, 2001) plot of (I) drawn at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.

2,4-Dihydroxybenzaldehyde 4-methylthiosemicarbazone top

Crystal data top

C₉H₁₁N₃O₂S	F(000) = 472
M_r = 225.27	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0598P)²] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
2128 reflections	Δρ_max = 0.31 e Å⁻³
153 parameters	Δρ_min = −0.22 e Å⁻³
6 restraints	Absolute structure: Flack (1983), 814 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (1)

Crystal data top

C₉H₁₁N₃O₂S	V = 983.74 (5) Å³
M_r = 225.27	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 18.0046 (6) Å	µ = 0.31 mm⁻¹
b = 4.6436 (1) Å	T = 100 K
c = 12.2842 (4) Å	0.09 × 0.06 × 0.03 mm
β = 106.695 (2)°

Data collection top

Bruker SMART APEX diffractometer	2128 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1925 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.991	R_int = 0.034
4390 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.109	Δρ_max = 0.31 e Å⁻³
S = 1.11	Δρ_min = −0.22 e Å⁻³
2128 reflections	Absolute structure: Flack (1983), 814 Friedel pairs
153 parameters	Absolute structure parameter: 0.00 (1)
6 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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.

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O₂S
M_r	225.27
Crystal system, space group	Monoclinic, Cc
Temperature (K)	100
a, b, c (Å)	18.0046 (6), 4.6436 (1), 12.2842 (4)
β (°)	106.695 (2)
V (Å³)	983.74 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.09 × 0.06 × 0.03

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	4390, 2128, 1925
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.109, 1.11
No. of reflections	2128
No. of parameters	153
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.22
Absolute structure	Flack (1983), 814 Friedel pairs
Absolute structure parameter	0.00 (1)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

We thank the University of Malaya (PJP FS316/2008 C) for supporting this study. KWT thanks the Ministry of Higher Education for an SLAI scholarship.

References

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