2,4-Dihydroxy­benzaldehyde 4-ethyl­thio­semicarbazone

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

doi:10.1107/S160053680803300X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2123

doi:10.1107/S160053680803300X

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2,4-Dihydroxybenzaldehyde 4-ethylthiosemicarbazone

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 6 October 2008; accepted 12 October 2008; online 18 October 2008)

The molecular conformation of the title compound, C₁₀H₁₃N₃O₂S, is stabilized by an intramolecular O—H⋯N hydrogen bond. Adjacent molecules are linked by O—H⋯O hydrogen bonds to furnish a zigzag chain.

Related literature

For the structure of 3,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazone, see: Kayed et al. (2008 ).

Experimental

Crystal data

C₁₀H₁₃N₃O₂S
M_r = 239.29
Monoclinic, P 2₁ /n
a = 4.6592 (6) Å
b = 24.067 (3) Å
c = 10.047 (1) Å
β = 99.060 (2)°
V = 1112.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 100 (2) K
0.40 × 0.12 × 0.06 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.896, T_max = 0.983
6303 measured reflections
2517 independent reflections
1972 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.109
S = 1.08
2517 reflections
148 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N3	0.84	1.84	2.583 (2)	147
O2—H2⋯O1ⁱ	0.84	1.92	2.714 (2)	158
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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/S160053680803300X/bt2806sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803300X/bt2806Isup2.hkl

checkCIF report

Related literature top

For the structure of 3,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazone, see: Kayed et al. (2008). [Figure caption mentions three molecules, but only one is shown and no mention is made of them in the Abstract. Please clarify]

Experimental top

4-Ethylthiosemicarbazide (1.19 g, 10 mmol) and 2,4-dihydroxybenzaldehyde (1.38 g, 10 mmol) were refluxed in ethanol (40 ml) for 6 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. Displacement ellipsoid (Barbour, 2001) plot of the title compound at the 70% probability level. H atoms are drawn as spheres of arbitrary radius.

2,4-Dihydroxybenzaldehyde 4-ethylthiosemicarbazone top

Crystal data top

C₁₀H₁₃N₃O₂S	F(000) = 504
M_r = 239.29	D_x = 1.429 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1634 reflections
a = 4.6592 (6) Å	θ = 2.6–28.1°
b = 24.067 (3) Å	µ = 0.28 mm⁻¹
c = 10.047 (1) Å	T = 100 K
β = 99.060 (2)°	Plate, yellow
V = 1112.5 (2) Å³	0.40 × 0.12 × 0.06 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2517 independent reflections
Radiation source: fine-focus sealed tube	1972 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→4
T_min = 0.896, T_max = 0.983	k = −30→31
6303 measured reflections	l = −13→12

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0512P)² + 0.3651P] where P = (F_o² + 2F_c²)/3
2517 reflections	(Δ/σ)_max = 0.001
148 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₀H₁₃N₃O₂S	V = 1112.5 (2) Å³
M_r = 239.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.6592 (6) Å	µ = 0.28 mm⁻¹
b = 24.067 (3) Å	T = 100 K
c = 10.047 (1) Å	0.40 × 0.12 × 0.06 mm
β = 99.060 (2)°

Data collection top

Bruker SMART APEX diffractometer	2517 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1972 reflections with I > 2σ(I)
T_min = 0.896, T_max = 0.983	R_int = 0.028
6303 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.08	Δρ_max = 0.38 e Å⁻³
2517 reflections	Δρ_min = −0.25 e Å⁻³
148 parameters

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

	x	y	z	U_iso*/U_eq
S1	1.01421 (11)	0.514276 (19)	0.28484 (5)	0.02112 (15)
O1	0.1480 (3)	0.32859 (6)	0.28304 (13)	0.0240 (3)
H1	0.2707	0.3544	0.2908	0.036*
O2	−0.4004 (3)	0.21979 (5)	0.53651 (13)	0.0238 (3)
H2	−0.4152	0.2117	0.6165	0.036*
N1	0.6825 (4)	0.43087 (7)	0.17727 (16)	0.0225 (4)
H1N	0.5495	0.4056	0.1845	0.027*
N2	0.6791 (3)	0.44770 (6)	0.40159 (15)	0.0175 (3)
H2N	0.7378	0.4666	0.4760	0.021*
N3	0.4854 (3)	0.40468 (6)	0.40248 (15)	0.0169 (3)
C1	0.6265 (5)	0.39432 (9)	−0.0504 (2)	0.0270 (5)
H1A	0.6985	0.3971	−0.1367	0.040*
H1B	0.4169	0.4015	−0.0644	0.040*
H1C	0.6644	0.3569	−0.0132	0.040*
C2	0.7804 (5)	0.43673 (9)	0.0471 (2)	0.0276 (5)
H2A	0.9932	0.4309	0.0578	0.033*
H2B	0.7371	0.4747	0.0115	0.033*
C3	0.7800 (4)	0.46113 (7)	0.28620 (18)	0.0174 (4)
C4	0.3905 (4)	0.39384 (7)	0.51361 (17)	0.0162 (4)
H4	0.4568	0.4152	0.5920	0.019*
C5	0.1834 (4)	0.34936 (7)	0.51966 (18)	0.0154 (4)
C6	0.0690 (4)	0.31772 (7)	0.40586 (18)	0.0174 (4)
C7	−0.1245 (4)	0.27525 (8)	0.41357 (19)	0.0195 (4)
H7	−0.1983	0.2545	0.3352	0.023*
C8	−0.2121 (4)	0.26265 (7)	0.53563 (18)	0.0179 (4)
C9	−0.1092 (4)	0.29412 (7)	0.65039 (18)	0.0181 (4)
H9	−0.1729	0.2864	0.7338	0.022*
C10	0.0857 (4)	0.33653 (7)	0.64102 (18)	0.0171 (4)
H10	0.1560	0.3577	0.7192	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0235 (3)	0.0188 (2)	0.0214 (2)	−0.0054 (2)	0.00430 (19)	0.00073 (18)
O1	0.0316 (9)	0.0240 (7)	0.0169 (6)	−0.0099 (6)	0.0059 (6)	−0.0026 (5)
O2	0.0275 (8)	0.0207 (7)	0.0225 (7)	−0.0089 (6)	0.0019 (6)	0.0036 (5)
N1	0.0235 (9)	0.0242 (8)	0.0207 (8)	−0.0087 (7)	0.0063 (7)	−0.0028 (7)
N2	0.0181 (8)	0.0176 (8)	0.0167 (7)	−0.0047 (6)	0.0022 (6)	−0.0009 (6)
N3	0.0154 (8)	0.0139 (7)	0.0211 (8)	−0.0016 (6)	0.0019 (6)	0.0017 (6)
C1	0.0302 (12)	0.0283 (11)	0.0228 (10)	−0.0037 (9)	0.0056 (9)	−0.0022 (8)
C2	0.0301 (12)	0.0332 (11)	0.0209 (10)	−0.0089 (10)	0.0081 (9)	−0.0025 (8)
C3	0.0141 (10)	0.0168 (9)	0.0209 (9)	0.0029 (7)	0.0017 (7)	0.0019 (7)
C4	0.0151 (10)	0.0162 (8)	0.0165 (9)	0.0004 (7)	0.0004 (7)	−0.0011 (7)
C5	0.0138 (9)	0.0133 (8)	0.0185 (9)	0.0021 (7)	0.0006 (7)	0.0002 (7)
C6	0.0176 (10)	0.0179 (9)	0.0166 (9)	0.0025 (7)	0.0027 (7)	0.0007 (7)
C7	0.0208 (10)	0.0169 (9)	0.0195 (9)	−0.0012 (8)	−0.0010 (8)	−0.0014 (7)
C8	0.0154 (10)	0.0139 (8)	0.0232 (9)	−0.0007 (7)	−0.0005 (8)	0.0031 (7)
C9	0.0184 (10)	0.0190 (9)	0.0168 (9)	0.0012 (7)	0.0021 (7)	0.0033 (7)
C10	0.0180 (10)	0.0170 (9)	0.0155 (8)	0.0015 (8)	−0.0003 (7)	−0.0017 (7)

Geometric parameters (Å, º) top

S1—C3	1.6826 (19)	C1—H1C	0.9800
O1—C6	1.367 (2)	C2—H2A	0.9900
O1—H1	0.8400	C2—H2B	0.9900
O2—C8	1.355 (2)	C4—C5	1.449 (2)
O2—H2	0.8400	C4—H4	0.9500
N1—C3	1.333 (2)	C5—C10	1.401 (2)
N1—C2	1.458 (2)	C5—C6	1.407 (2)
N1—H1N	0.8800	C6—C7	1.373 (3)
N2—C3	1.357 (2)	C7—C8	1.386 (3)
N2—N3	1.374 (2)	C7—H7	0.9500
N2—H2N	0.8800	C8—C9	1.400 (3)
N3—C4	1.291 (2)	C9—C10	1.379 (3)
C1—C2	1.515 (3)	C9—H9	0.9500
C1—H1A	0.9800	C10—H10	0.9500
C1—H1B	0.9800

C6—O1—H1	109.5	N2—C3—S1	120.03 (14)
C8—O2—H2	109.5	N3—C4—C5	120.45 (16)
C3—N1—C2	124.66 (16)	N3—C4—H4	119.8
C3—N1—H1N	117.7	C5—C4—H4	119.8
C2—N1—H1N	117.7	C10—C5—C6	117.04 (17)
C3—N2—N3	120.08 (15)	C10—C5—C4	120.59 (16)
C3—N2—H2N	120.0	C6—C5—C4	122.37 (16)
N3—N2—H2N	120.0	O1—C6—C7	117.76 (17)
C4—N3—N2	118.21 (15)	O1—C6—C5	120.57 (17)
C2—C1—H1A	109.5	C7—C6—C5	121.67 (17)
C2—C1—H1B	109.5	C6—C7—C8	120.03 (17)
H1A—C1—H1B	109.5	C6—C7—H7	120.0
C2—C1—H1C	109.5	C8—C7—H7	120.0
H1A—C1—H1C	109.5	O2—C8—C7	116.98 (17)
H1B—C1—H1C	109.5	O2—C8—C9	123.01 (17)
N1—C2—C1	109.36 (17)	C7—C8—C9	120.00 (17)
N1—C2—H2A	109.8	C10—C9—C8	119.21 (17)
C1—C2—H2A	109.8	C10—C9—H9	120.4
N1—C2—H2B	109.8	C8—C9—H9	120.4
C1—C2—H2B	109.8	C9—C10—C5	122.00 (17)
H2A—C2—H2B	108.3	C9—C10—H10	119.0
N1—C3—N2	116.86 (17)	C5—C10—H10	119.0
N1—C3—S1	123.11 (14)

C3—N2—N3—C4	−178.76 (17)	C10—C5—C6—C7	−1.5 (3)
C3—N1—C2—C1	178.52 (18)	C4—C5—C6—C7	179.20 (17)
C2—N1—C3—N2	−175.78 (18)	O1—C6—C7—C8	−179.83 (17)
C2—N1—C3—S1	4.9 (3)	C5—C6—C7—C8	0.1 (3)
N3—N2—C3—N1	0.0 (2)	C6—C7—C8—O2	−179.15 (16)
N3—N2—C3—S1	179.30 (13)	C6—C7—C8—C9	1.6 (3)
N2—N3—C4—C5	179.27 (15)	O2—C8—C9—C10	179.01 (17)
N3—C4—C5—C10	178.30 (17)	C7—C8—C9—C10	−1.8 (3)
N3—C4—C5—C6	−2.4 (3)	C8—C9—C10—C5	0.3 (3)
C10—C5—C6—O1	178.39 (16)	C6—C5—C10—C9	1.3 (3)
C4—C5—C6—O1	−0.9 (3)	C4—C5—C10—C9	−179.39 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N3	0.84	1.84	2.583 (2)	147
O2—H2···O1ⁱ	0.84	1.92	2.714 (2)	158

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃O₂S
M_r	239.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	4.6592 (6), 24.067 (3), 10.047 (1)
β (°)	99.060 (2)
V (Å³)	1112.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.40 × 0.12 × 0.06

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.896, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	6303, 2517, 1972
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.109, 1.08
No. of reflections	2517
No. of parameters	148
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.25

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—H1···N3	0.84	1.84	2.583 (2)	147
O2—H2···O1ⁱ	0.84	1.92	2.714 (2)	158

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

Acknowledgements

We thank the University of Malaya (grant No. PJP F316/2008C) for supporting this study. KWT thanks the Ministry of Higher Education for an SLAI scholarship in this research.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kayed, S. F., Farina, Y., Baba, I. & Simpson, J. (2008). Acta Cryst. E64, o824–o825. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar