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

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

doi:10.1107/S1600536810014078

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

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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810014078/pk2241sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810014078/pk2241Isup2.hkl Contains datablock I

CCDC reference: 778042

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R factor = 0.029
wR factor = 0.082
Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.13 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     --  C8      ..       5.36 su
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          7
PLAT745_ALERT_1_C D-H     Calc   0.865(14), Rep     0.87000 ......    Missing su
              N2   -H2N     1.555   1.555
PLAT746_ALERT_1_C H...A   Calc   2.622(14), Rep     2.62000 ......    Missing su
              H2N  -S1      1.555   3.666
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          3

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          5

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

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

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).