1-(2,3,4-Trihydroxy­benzyl­idene)-4-ethyl­thio­semicarbazide

Shawish, H.B.; Maah, M.J.; Ng, S.W.

doi:10.1107/S1600536810014078

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1151

https://doi.org/10.1107/S1600536810014078

Open

access

1-(2,3,4-Trihydroxybenzylidene)-4-ethylthiosemicarbazide

Hana Bashir Shawish,^a M. Jamil Maah ^a ^* and Seik Weng Ng ^a

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: mjamil@um.edu.my

(Received 8 April 2010; accepted 16 April 2010; online 24 April 2010)

In the title molecule, C₁₀H₁₃N₃O₃S, the thiosemicarbazide =N—NH—C(=S)—NH– fragment is twisted with respect to the aromatic ring [dihedral angle = 20.5 (1)°]. A weak N—H⋯S hydrogen bond [3.480 (1) Å] links two molecules about a center of inversion to generate a ring. The hydroxy groups are engaged in intermolecular hydrogen bonding; the O—H⋯O and O—H⋯S hydrogen bonds generate a layer motif.

Related literature

For the crystal structures of 3,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazone and 2,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazone, see: Kayed et al. (2008 ); Tan et al. (2008 ).

Experimental

Crystal data

C₁₀H₁₃N₃O₃S
M_r = 255.29
Monoclinic, P 2₁ /c
a = 7.5668 (5) Å
b = 14.6754 (10) Å
c = 10.8700 (7) Å
β = 104.711 (1)°
V = 1167.50 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.921, T_max = 0.973
10870 measured reflections
2660 independent reflections
2364 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.082
S = 1.04
2660 reflections
174 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O2	0.83 (1)	2.26 (2)	2.717 (1)	115 (2)
O1—H1O⋯S1ⁱ	0.83 (1)	2.55 (1)	3.291 (1)	150 (2)
O2—H2O⋯O3	0.84 (1)	2.31 (2)	2.745 (1)	112 (2)
O2—H2O⋯O1ⁱⁱ	0.84 (1)	2.07 (1)	2.832 (1)	151 (2)
O3—H3O⋯S1ⁱⁱⁱ	0.84 (1)	2.36 (1)	3.189 (1)	170 (2)
N2—H2N⋯S1^iv	0.87	2.62	3.480 (1)	171
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x, y, z-1; (iv) -x+1, -y+1, -z+1.

Data collection: APEX2 software (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); 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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810014078/pk2241sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810014078/pk2241Isup2.hkl

checkCIF report

Related literature top

For the crystal structures of 3,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazone and 2,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazone, see: Kayed et al. (2008); Tan et al. (2008).

Experimental top

2,3,4-Trihydroxybenzaldehyde (1.54 g, 10 mmol) and 4-ethylthiosemicarbazide (1.19 g, 1 mmol) were heated in ethanol (20 ml) for 2 hours; acetic acid (0.5 ml) was also added. A brown solid separated from the cool solution; this was recrystallized from methanol.

Structure description top

For the crystal structures of 3,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazone and 2,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazone, see: Kayed et al. (2008); Tan et al. (2008).

Computing details top

Data collection: APEX2 software [SMART?] (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₀H₁₃N₃O₃S at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

1-(2,3,4-Trihydroxybenzylidene)-4-ethylthiosemicarbazide top

Crystal data top

C₁₀H₁₃N₃O₃S	F(000) = 536
M_r = 255.29	D_x = 1.452 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5730 reflections
a = 7.5668 (5) Å	θ = 2.4–28.3°
b = 14.6754 (10) Å	µ = 0.28 mm⁻¹
c = 10.8700 (7) Å	T = 100 K
β = 104.711 (1)°	Prism, colorless
V = 1167.50 (13) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2660 independent reflections
Radiation source: fine-focus sealed tube	2364 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.921, T_max = 0.973	k = −19→19
10870 measured reflections	l = −14→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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0437P)² + 0.4981P] where P = (F_o² + 2F_c²)/3
2660 reflections	(Δ/σ)_max = 0.001
174 parameters	Δρ_max = 0.34 e Å⁻³
5 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₀H₁₃N₃O₃S	V = 1167.50 (13) Å³
M_r = 255.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5668 (5) Å	µ = 0.28 mm⁻¹
b = 14.6754 (10) Å	T = 100 K
c = 10.8700 (7) Å	0.30 × 0.20 × 0.10 mm
β = 104.711 (1)°

Data collection top

Bruker SMART APEX diffractometer	2660 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2364 reflections with I > 2σ(I)
T_min = 0.921, T_max = 0.973	R_int = 0.026
10870 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	5 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.34 e Å⁻³
2660 reflections	Δρ_min = −0.22 e Å⁻³
174 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.70929 (4)	0.59538 (2)	0.58991 (3)	0.01292 (10)
O1	0.50792 (13)	0.28115 (6)	0.03429 (8)	0.0153 (2)
O2	0.54351 (14)	0.26317 (6)	−0.20701 (9)	0.0176 (2)
O3	0.73079 (14)	0.39064 (6)	−0.30899 (9)	0.0167 (2)
N1	0.73526 (15)	0.49383 (7)	0.26113 (10)	0.0133 (2)
N2	0.69204 (15)	0.50533 (7)	0.37631 (10)	0.0132 (2)
N3	0.91494 (16)	0.61386 (8)	0.42338 (11)	0.0150 (2)
C1	0.66760 (17)	0.42305 (8)	0.05845 (12)	0.0114 (2)
C2	0.59670 (17)	0.34728 (8)	−0.01603 (12)	0.0114 (2)
C3	0.61719 (17)	0.33861 (8)	−0.13940 (12)	0.0122 (2)
C4	0.71179 (18)	0.40505 (8)	−0.18813 (12)	0.0123 (2)
C5	0.78291 (17)	0.48082 (9)	−0.11516 (12)	0.0134 (3)
H5	0.8474	0.5261	−0.1486	0.016*
C6	0.75918 (17)	0.48975 (8)	0.00612 (12)	0.0127 (2)
H6	0.8059	0.5421	0.0550	0.015*
C7	0.64158 (17)	0.43394 (8)	0.18633 (12)	0.0124 (2)
H7	0.5559	0.3969	0.2138	0.015*
C8	0.77826 (17)	0.57177 (8)	0.45530 (12)	0.0118 (2)
C9	1.01416 (19)	0.69298 (9)	0.48851 (13)	0.0168 (3)
H9A	1.1456	0.6869	0.4917	0.020*
H9B	1.0020	0.6951	0.5770	0.020*
C10	0.9416 (2)	0.78045 (10)	0.42107 (17)	0.0283 (4)
H10A	1.0080	0.8323	0.4678	0.042*
H10B	0.8112	0.7863	0.4171	0.042*
H10C	0.9584	0.7795	0.3346	0.042*
H1O	0.472 (3)	0.2409 (11)	−0.0195 (16)	0.039 (6)*
H2O	0.554 (3)	0.2673 (15)	−0.2817 (11)	0.045 (6)*
H3O	0.731 (3)	0.4420 (9)	−0.343 (2)	0.047 (6)*
H2N	0.5992 (17)	0.4785 (11)	0.3933 (15)	0.021 (4)*
H3N	0.936 (2)	0.5975 (11)	0.3531 (11)	0.023 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01775 (18)	0.01251 (16)	0.00958 (16)	−0.00113 (11)	0.00547 (12)	−0.00111 (10)
O1	0.0228 (5)	0.0130 (4)	0.0113 (4)	−0.0065 (4)	0.0064 (4)	−0.0022 (3)
O2	0.0281 (5)	0.0147 (5)	0.0114 (5)	−0.0064 (4)	0.0078 (4)	−0.0041 (4)
O3	0.0259 (5)	0.0153 (5)	0.0110 (5)	0.0000 (4)	0.0089 (4)	0.0007 (3)
N1	0.0157 (5)	0.0150 (5)	0.0104 (5)	−0.0001 (4)	0.0056 (4)	−0.0018 (4)
N2	0.0155 (5)	0.0149 (5)	0.0109 (5)	−0.0040 (4)	0.0063 (4)	−0.0028 (4)
N3	0.0185 (6)	0.0158 (5)	0.0126 (5)	−0.0046 (4)	0.0075 (4)	−0.0047 (4)
C1	0.0116 (6)	0.0122 (5)	0.0103 (6)	0.0016 (4)	0.0024 (4)	0.0003 (4)
C2	0.0118 (6)	0.0105 (5)	0.0124 (6)	0.0007 (4)	0.0038 (5)	0.0015 (4)
C3	0.0144 (6)	0.0109 (6)	0.0109 (6)	0.0011 (5)	0.0023 (5)	−0.0012 (4)
C4	0.0137 (6)	0.0144 (6)	0.0096 (6)	0.0034 (5)	0.0042 (5)	0.0009 (4)
C5	0.0132 (6)	0.0129 (6)	0.0144 (6)	−0.0004 (5)	0.0040 (5)	0.0027 (5)
C6	0.0127 (6)	0.0118 (6)	0.0126 (6)	−0.0003 (5)	0.0016 (5)	−0.0010 (5)
C7	0.0138 (6)	0.0111 (6)	0.0128 (6)	0.0005 (5)	0.0042 (5)	0.0002 (4)
C8	0.0140 (6)	0.0104 (5)	0.0110 (6)	0.0015 (5)	0.0028 (5)	0.0011 (4)
C9	0.0182 (7)	0.0164 (6)	0.0167 (6)	−0.0067 (5)	0.0060 (5)	−0.0043 (5)
C10	0.0201 (8)	0.0167 (7)	0.0444 (10)	−0.0032 (6)	0.0012 (7)	0.0005 (6)

Geometric parameters (Å, º) top

S1—C8	1.7092 (13)	C1—C6	1.4007 (17)
O1—C2	1.3707 (15)	C1—C7	1.4613 (17)
O1—H1O	0.827 (9)	C2—C3	1.3944 (17)
O2—C3	1.3669 (15)	C3—C4	1.3914 (17)
O2—H2O	0.838 (9)	C4—C5	1.3923 (17)
O3—C4	1.3738 (15)	C5—C6	1.3811 (17)
O3—H3O	0.841 (9)	C5—H5	0.9500
N1—C7	1.2819 (16)	C6—H6	0.9500
N1—N2	1.3824 (14)	C7—H7	0.9500
N2—C8	1.3523 (16)	C9—C10	1.511 (2)
N2—H2N	0.866 (9)	C9—H9A	0.9900
N3—C8	1.3244 (17)	C9—H9B	0.9900
N3—C9	1.4639 (16)	C10—H10A	0.9800
N3—H3N	0.853 (9)	C10—H10B	0.9800
C1—C2	1.3996 (17)	C10—H10C	0.9800

C2—O1—H1O	109.3 (15)	C6—C5—H5	120.2
C3—O2—H2O	109.6 (15)	C4—C5—H5	120.2
C4—O3—H3O	107.5 (15)	C5—C6—C1	121.26 (11)
C7—N1—N2	115.99 (11)	C5—C6—H6	119.4
C8—N2—N1	118.43 (11)	C1—C6—H6	119.4
C8—N2—H2N	118.7 (11)	N1—C7—C1	119.47 (11)
N1—N2—H2N	122.0 (11)	N1—C7—H7	120.3
C8—N3—C9	125.59 (11)	C1—C7—H7	120.3
C8—N3—H3N	116.0 (12)	N3—C8—N2	116.93 (11)
C9—N3—H3N	117.8 (12)	N3—C8—S1	123.94 (10)
C2—C1—C6	118.47 (11)	N2—C8—S1	119.13 (10)
C2—C1—C7	120.84 (11)	N3—C9—C10	111.14 (11)
C6—C1—C7	120.66 (11)	N3—C9—H9A	109.4
O1—C2—C3	120.30 (11)	C10—C9—H9A	109.4
O1—C2—C1	119.11 (11)	N3—C9—H9B	109.4
C3—C2—C1	120.59 (11)	C10—C9—H9B	109.4
O2—C3—C4	122.81 (11)	H9A—C9—H9B	108.0
O2—C3—C2	117.46 (11)	C9—C10—H10A	109.5
C4—C3—C2	119.72 (11)	C9—C10—H10B	109.5
O3—C4—C3	116.43 (11)	H10A—C10—H10B	109.5
O3—C4—C5	123.27 (11)	C9—C10—H10C	109.5
C3—C4—C5	120.30 (12)	H10A—C10—H10C	109.5
C6—C5—C4	119.63 (12)	H10B—C10—H10C	109.5

C7—N1—N2—C8	−175.71 (11)	O3—C4—C5—C6	−179.39 (12)
C6—C1—C2—O1	179.53 (11)	C3—C4—C5—C6	0.03 (19)
C7—C1—C2—O1	−2.47 (18)	C4—C5—C6—C1	1.21 (19)
C6—C1—C2—C3	0.05 (18)	C2—C1—C6—C5	−1.25 (19)
C7—C1—C2—C3	178.06 (11)	C7—C1—C6—C5	−179.26 (12)
O1—C2—C3—O2	0.95 (18)	N2—N1—C7—C1	174.75 (11)
C1—C2—C3—O2	−179.58 (11)	C2—C1—C7—N1	167.00 (12)
O1—C2—C3—C4	−178.31 (11)	C6—C1—C7—N1	−15.04 (18)
C1—C2—C3—C4	1.16 (19)	C9—N3—C8—N2	173.77 (12)
O2—C3—C4—O3	−0.96 (18)	C9—N3—C8—S1	−7.36 (19)
C2—C3—C4—O3	178.26 (11)	N1—N2—C8—N3	−8.18 (17)
O2—C3—C4—C5	179.58 (12)	N1—N2—C8—S1	172.89 (9)
C2—C3—C4—C5	−1.20 (19)	C8—N3—C9—C10	−97.70 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O2	0.83 (1)	2.26 (2)	2.717 (1)	115 (2)
O1—H1o···S1ⁱ	0.83 (1)	2.55 (1)	3.291 (1)	150 (2)
O2—H2o···O3	0.84 (1)	2.31 (2)	2.745 (1)	112 (2)
O2—H2o···O1ⁱⁱ	0.84 (1)	2.07 (1)	2.832 (1)	151 (2)
O3—H3o···S1ⁱⁱⁱ	0.84 (1)	2.36 (1)	3.189 (1)	170 (2)
N2—H2N···S1^iv	0.87	2.62	3.480 (1)	171

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃O₃S
M_r	255.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.5668 (5), 14.6754 (10), 10.8700 (7)
β (°)	104.711 (1)
V (Å³)	1167.50 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.921, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	10870, 2660, 2364
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.082, 1.04
No. of reflections	2660
No. of parameters	174
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.22

Computer programs: APEX2 software [SMART?] (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O2	0.83 (1)	2.26 (2)	2.717 (1)	115 (2)
O1—H1o···S1ⁱ	0.83 (1)	2.55 (1)	3.291 (1)	150 (2)
O2—H2o···O3	0.84 (1)	2.31 (2)	2.745 (1)	112 (2)
O2—H2o···O1ⁱⁱ	0.84 (1)	2.07 (1)	2.832 (1)	151 (2)
O3—H3o···S1ⁱⁱⁱ	0.84 (1)	2.36 (1)	3.189 (1)	170 (2)
N2—H2N···S1^iv	0.87	2.62	3.480 (1)	171.4

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

Acknowledgements

The authors thank the University of Malaya (grant No. PS354/2009) and MOHE (grant No. FRGS-FP001/2009) for supporting this study. HBS thanks the Libyan People's Bureau in Malaysia for a scholarship.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). 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
Tan, K. W., Ng, C. H., Maah, M. J. & Ng, S. W. (2008). Acta Cryst. E64, o2123. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar