2,5-Dihydroxy­benzaldehyde 4-methyl­thio­semicarbazone

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

doi:10.1107/S1600536808018801

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1344

doi:10.1107/S1600536808018801

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2,5-Dihydroxybenzaldehyde 4-methylthiosemicarbazone

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

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

(Received 20 June 2008; accepted 21 June 2008; online 28 June 2008)

The planar molecules of the title compound, C₉H₁₁N₃O₂S, are linked into a supramolecualr chain via O—H⋯S hydrogen bonds. These chains are connected into a two-dimensional array via N—H⋯O hydrogen bonds; an intramolecular O—H⋯N hydrogen bond is also present.

Related literature

For the medicinal activity of 2,5-dihydroxybenzaldehyde thiosemicarbazone, see: Libermann et al. (1953 ); Taniyama & Tanaka (1965 ); Xue et al. (2007 ). For the structure of 2-hydroxybenzaldehyde 4-methylthiosemicarbazone, see: Vrdoljak et al. (2005 ). For the structure of 3,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazone, see: Kayed et al. (2008 ).

Experimental

Crystal data

C₉H₁₁N₃O₂S
M_r = 225.27
Triclinic, $[P \overline 1]$
a = 5.9932 (4) Å
b = 8.5207 (6) Å
c = 10.3272 (6) Å
α = 78.552 (4)°
β = 74.181 (4)°
γ = 81.743 (4)°
V = 495.06 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 100 (2) K
0.24 × 0.16 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.929, T_max = 0.994
4189 measured reflections
2258 independent reflections
1580 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.123
S = 1.03
2258 reflections
153 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯N3	0.84 (3)	1.97 (2)	2.698 (3)	144 (3)
O2—H2o⋯S1ⁱ	0.84 (3)	2.46 (2)	3.182 (2)	144 (3)
N2—H2n⋯O1ⁱⁱ	0.84 (3)	2.47 (3)	3.111 (3)	134 (3)
Symmetry codes: (i) x+1, y+1, z-1; (ii) x-1, y, z.

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/S1600536808018801/tk2278sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018801/tk2278Isup2.hkl

checkCIF report

Comment top

The title compound (I, Fig. 1) possesses useful medicinal properties (Libermann et al., 1953; Taniyama & Tanaka, 1965; Xue et al., 2007). The molecules are linked into supramolecular chains by O-H···S hydrogen bonds involving the O2-hydroxy group, Table 1. The hydrogen-bonded chains are consolidated into a layer motif via N-NH···O hydrogen bond, involving the O1-hydroxy group. An intramolecular N-H···O hydrogen bond, also involving the O1-hydroxy group is also noted. In contrast, 2-hydroxybenzaldehyde 4-methylthiosemicarbazone, which features an intramolecular O–H···N hydrogen bond, adopts a chain structure (Vrdoljak et al., 2005) as it lacks a second hydroxy substituent for layer formation.

Related literature top

For the medicinal activity of 2,5-dihydroxybenzaldehyde thiosemicarbazone, see: Libermann et al. (1953); Taniyama & Tanaka (1965); Xue et al. (2007). For the structure of 2-hydroxybenzaldehyde 4-methylthiosemicarbazone, see: Vrdoljak et al. (2005). For the structur of 3,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazone, see: Kayed et al. (2008).

Experimental top

4-Methylthiosemicarbazide (0.11 g, 1 mmol) and 2,5-dihydroxybenzaldehyde (0.14 g, 1 mmol) were heated in ethanol (10 ml) for 1 h. Slow evaporation of the solvent yielded yellow crystals of (I).

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 plot of (I) at the 70% probability level showing atom labeling. Hydrogen atoms are drawn as spheres of arbitrary radii.

2,5-Dihydroxybenzaldehyde 4-methylthiosemicarbazone top

Crystal data top

C₉H₁₁N₃O₂S	Z = 2
M_r = 225.27	F(000) = 236
Triclinic, P1	D_x = 1.511 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.9932 (4) Å	Cell parameters from 558 reflections
b = 8.5207 (6) Å	θ = 2.9–23.0°
c = 10.3272 (6) Å	µ = 0.31 mm⁻¹
α = 78.552 (4)°	T = 100 K
β = 74.181 (4)°	Plate, yellow
γ = 81.743 (4)°	0.24 × 0.16 × 0.02 mm
V = 495.06 (6) Å³

Data collection top

Bruker SMART APEX diffractometer	2258 independent reflections
Radiation source: fine-focus sealed tube	1580 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.929, T_max = 0.994	k = −11→8
4189 measured reflections	l = −13→13

Refinement top

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0471P)²] where P = (F_o² + 2F_c²)/3
2258 reflections	(Δ/σ)_max = 0.001
153 parameters	Δρ_max = 0.32 e Å⁻³
4 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

C₉H₁₁N₃O₂S	γ = 81.743 (4)°
M_r = 225.27	V = 495.06 (6) Å³
Triclinic, P1	Z = 2
a = 5.9932 (4) Å	Mo Kα radiation
b = 8.5207 (6) Å	µ = 0.31 mm⁻¹
c = 10.3272 (6) Å	T = 100 K
α = 78.552 (4)°	0.24 × 0.16 × 0.02 mm
β = 74.181 (4)°

Data collection top

Bruker SMART APEX diffractometer	2258 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1580 reflections with I > 2σ(I)
T_min = 0.929, T_max = 0.994	R_int = 0.050
4189 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	4 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.32 e Å⁻³
2258 reflections	Δρ_min = −0.47 e Å⁻³
153 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.44298 (12)	0.47335 (9)	0.72966 (7)	0.0189 (2)
O1	1.3132 (3)	0.8655 (2)	0.47568 (18)	0.0188 (4)
O2	1.2446 (3)	1.1893 (2)	−0.03406 (18)	0.0200 (5)
N1	0.8637 (4)	0.5405 (3)	0.7312 (2)	0.0147 (5)
N2	0.7415 (4)	0.6387 (3)	0.5359 (2)	0.0159 (5)
N3	0.9289 (4)	0.7298 (3)	0.4833 (2)	0.0145 (5)
C1	0.8391 (5)	0.4576 (3)	0.8709 (2)	0.0188 (6)
H1A	0.9802	0.4633	0.8996	0.028*
H1B	0.8160	0.3447	0.8763	0.028*
H1C	0.7044	0.5088	0.9310	0.028*
C2	0.7001 (4)	0.5552 (3)	0.6642 (2)	0.0134 (6)
C3	0.9368 (4)	0.8121 (3)	0.3637 (2)	0.0136 (6)
H3	0.8213	0.8018	0.3194	0.016*
C4	1.1147 (4)	0.9200 (3)	0.2937 (2)	0.0133 (6)
C5	1.2915 (4)	0.9450 (3)	0.3503 (2)	0.0140 (6)
C6	1.4505 (5)	1.0551 (3)	0.2796 (2)	0.0157 (6)
H6	1.5673	1.0745	0.3193	0.019*
C7	1.4389 (5)	1.1372 (3)	0.1504 (3)	0.0153 (6)
H7	1.5496	1.2111	0.1016	0.018*
C8	1.2669 (4)	1.1117 (3)	0.0929 (2)	0.0149 (6)
C9	1.1055 (4)	1.0049 (3)	0.1638 (2)	0.0146 (6)
H9	0.9866	0.9887	0.1243	0.018*
H1o	1.206 (4)	0.805 (3)	0.511 (3)	0.048 (12)*
H2o	1.352 (5)	1.245 (4)	−0.082 (3)	0.059 (13)*
H1n	0.988 (3)	0.581 (4)	0.689 (3)	0.032 (9)*
H2n	0.640 (4)	0.656 (4)	0.491 (3)	0.042 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0149 (4)	0.0241 (4)	0.0175 (3)	−0.0083 (3)	−0.0051 (3)	0.0033 (3)
O1	0.0222 (11)	0.0221 (12)	0.0140 (9)	−0.0081 (9)	−0.0089 (8)	0.0025 (8)
O2	0.0244 (11)	0.0202 (12)	0.0149 (9)	−0.0088 (9)	−0.0059 (8)	0.0047 (8)
N1	0.0114 (12)	0.0181 (13)	0.0148 (11)	−0.0035 (10)	−0.0038 (9)	−0.0007 (9)
N2	0.0153 (12)	0.0168 (13)	0.0158 (11)	−0.0060 (10)	−0.0056 (9)	0.0024 (9)
N3	0.0121 (11)	0.0136 (12)	0.0175 (11)	−0.0050 (9)	−0.0013 (9)	−0.0023 (9)
C1	0.0198 (15)	0.0231 (16)	0.0128 (12)	−0.0048 (12)	−0.0051 (11)	0.0015 (11)
C2	0.0137 (13)	0.0106 (14)	0.0155 (12)	−0.0011 (11)	−0.0032 (10)	−0.0022 (11)
C3	0.0136 (13)	0.0138 (14)	0.0147 (12)	−0.0019 (11)	−0.0053 (10)	−0.0025 (11)
C4	0.0134 (13)	0.0118 (14)	0.0153 (12)	−0.0008 (10)	−0.0034 (10)	−0.0038 (11)
C5	0.0137 (13)	0.0154 (15)	0.0133 (12)	0.0001 (11)	−0.0041 (10)	−0.0034 (11)
C6	0.0139 (13)	0.0162 (15)	0.0193 (13)	−0.0029 (11)	−0.0070 (10)	−0.0039 (11)
C7	0.0163 (14)	0.0102 (14)	0.0178 (13)	−0.0021 (11)	−0.0024 (10)	−0.0006 (11)
C8	0.0160 (14)	0.0144 (15)	0.0143 (12)	0.0006 (11)	−0.0050 (10)	−0.0023 (11)
C9	0.0158 (14)	0.0156 (15)	0.0140 (12)	−0.0021 (11)	−0.0059 (10)	−0.0031 (11)

Geometric parameters (Å, º) top

S1—C2	1.695 (3)	C1—H1B	0.9800
O1—C5	1.367 (3)	C1—H1C	0.9800
O1—H1o	0.84 (3)	C3—C4	1.450 (4)
O2—C8	1.379 (3)	C3—H3	0.9500
O2—H2o	0.84 (3)	C4—C5	1.401 (4)
N1—C2	1.325 (3)	C4—C9	1.403 (3)
N1—C1	1.453 (3)	C5—C6	1.388 (4)
N1—H1n	0.84 (3)	C6—C7	1.393 (3)
N2—C2	1.349 (3)	C6—H6	0.9500
N2—N3	1.382 (3)	C7—C8	1.383 (4)
N2—H2n	0.84 (3)	C7—H7	0.9500
N3—C3	1.286 (3)	C8—C9	1.379 (4)
C1—H1A	0.9800	C9—H9	0.9500

C5—O1—H1O	110 (2)	C4—C3—H3	118.6
C8—O2—H2O	117 (3)	C5—C4—C9	118.9 (2)
C2—N1—C1	123.8 (2)	C5—C4—C3	123.2 (2)
C2—N1—H1N	117 (2)	C9—C4—C3	117.9 (2)
C1—N1—H1N	119 (2)	O1—C5—C6	117.7 (2)
C2—N2—N3	121.3 (2)	O1—C5—C4	122.3 (2)
C2—N2—H2N	122 (2)	C6—C5—C4	120.0 (2)
N3—N2—H2N	116 (2)	C5—C6—C7	120.1 (3)
C3—N3—N2	114.5 (2)	C5—C6—H6	120.0
N1—C1—H1A	109.5	C7—C6—H6	120.0
N1—C1—H1B	109.5	C8—C7—C6	120.3 (2)
H1A—C1—H1B	109.5	C8—C7—H7	119.9
N1—C1—H1C	109.5	C6—C7—H7	119.9
H1A—C1—H1C	109.5	O2—C8—C9	116.7 (2)
H1B—C1—H1C	109.5	O2—C8—C7	123.3 (2)
N1—C2—N2	118.2 (2)	C9—C8—C7	119.9 (2)
N1—C2—S1	123.80 (19)	C8—C9—C4	120.8 (2)
N2—C2—S1	118.0 (2)	C8—C9—H9	119.6
N3—C3—C4	122.7 (2)	C4—C9—H9	119.6
N3—C3—H3	118.6

C2—N2—N3—C3	−175.1 (2)	C3—C4—C5—C6	−177.4 (2)
C1—N1—C2—N2	178.3 (2)	O1—C5—C6—C7	178.8 (2)
C1—N1—C2—S1	−2.5 (4)	C4—C5—C6—C7	−2.0 (4)
N3—N2—C2—N1	−11.0 (4)	C5—C6—C7—C8	1.1 (4)
N3—N2—C2—S1	169.69 (19)	C6—C7—C8—O2	179.7 (2)
N2—N3—C3—C4	177.5 (2)	C6—C7—C8—C9	0.2 (4)
N3—C3—C4—C5	−0.6 (4)	O2—C8—C9—C4	179.8 (2)
N3—C3—C4—C9	−179.5 (2)	C7—C8—C9—C4	−0.7 (4)
C9—C4—C5—O1	−179.3 (2)	C5—C4—C9—C8	−0.2 (4)
C3—C4—C5—O1	1.8 (4)	C3—C4—C9—C8	178.8 (2)
C9—C4—C5—C6	1.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N3	0.84 (3)	1.97 (2)	2.698 (3)	144 (3)
O2—H2o···S1ⁱ	0.84 (3)	2.46 (2)	3.182 (2)	144 (3)
N2—H2n···O1ⁱⁱ	0.84 (3)	2.47 (3)	3.111 (3)	134 (3)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O₂S
M_r	225.27
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	5.9932 (4), 8.5207 (6), 10.3272 (6)
α, β, γ (°)	78.552 (4), 74.181 (4), 81.743 (4)
V (Å³)	495.06 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.24 × 0.16 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.929, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	4189, 2258, 1580
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.123, 1.03
No. of reflections	2258
No. of parameters	153
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.47

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···N3	0.84 (3)	1.97 (2)	2.698 (3)	144 (3)
O2—H2o···S1ⁱ	0.84 (3)	2.46 (2)	3.182 (2)	144 (3)
N2—H2n···O1ⁱⁱ	0.84 (3)	2.47 (3)	3.111 (3)	134 (3)

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

Acknowledgements

We thank the University of Malaya (P0265/2007 A) for supporting this study. KWT thanks the Ministry of Higher Education for a SLAI scholarship.

References

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