2,4-Dihydroxy­benzaldehyde 4-ethyl­thio­semicarbazone

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

doi:10.1107/S160053680803300X

2,4-Dihydroxybenzaldehyde 4-ethylthiosemicarbazone

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

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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680803300X/bt2806sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680803300X/bt2806Isup2.hkl Contains datablock I

CCDC reference: 709361

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
R factor = 0.039
wR factor = 0.109
Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   100.000
            Value of melting point given =     0.000
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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).