5-Bromo-2-hy­droxy­benzaldehyde 4-ethyl­thio­semicarbazone

Li, Z.; Sato, O.

doi:10.1107/S1600536813008787

organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Page o762

https://doi.org/10.1107/S1600536813008787

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5-Bromo-2-hydroxybenzaldehyde 4-ethylthiosemicarbazone

Zhaoyang Li ^a and Osamu Sato ^a ^*

^aInstitute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan
^*Correspondence e-mail: sato@cm.kyushu-u.ac.jp

(Received 31 March 2013; accepted 1 April 2013; online 20 April 2013)

In the title Schiff base compound, C₁₀H₁₂BrN₃OS, the C—N—N—C torsion angle is 172.07 (11)°. An intramolecular hydrogen bond exists between the hydroxy H atom and the azomethine N atom. In the crystal, pairs of hydrogen bonds involving the imino H atom and the S atom give rise to supramolecular dimers.

Related literature

For the isostructural compound 5-chloro-2-hydroxybenzaldehyde 4-ethylthiosemicarbazone, see: Lo et al. (2011 )

Experimental

Crystal data

C₁₀H₁₂BrN₃OS
M_r = 302.20
Monoclinic, C 2/c
a = 22.040 (4) Å
b = 11.844 (2) Å
c = 9.5102 (19) Å
β = 101.69 (3)°
V = 2431.1 (8) Å³
Z = 8
Mo Kα radiation
μ = 3.54 mm⁻¹
T = 123 K
0.20 × 0.10 × 0.05 mm

Data collection

Rigaku Saturn70 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.661, T_max = 0.838
4201 measured reflections
2331 independent reflections
1760 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.114
S = 0.95
2331 reflections
155 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −1.01 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1	0.84 (3)	2.00 (2)	2.674 (3)	137 (3)
N2—H2A⋯S1ⁱ	0.88 (3)	2.47 (3)	3.316 (3)	161 (2)
N3—H3A⋯S1ⁱⁱ	0.87 (3)	2.75 (3)	3.510 (3)	146 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813008787/ng5322sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813008787/ng5322Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813008787/ng5322Isup3.cml

checkCIF report

Comment top

A Schiff ligand was synthesized through one-pot reaction with high yield using 5-bromo-2-hydroxybenzaldehyde and 4-ethyl-3-thiosemicarbazide (Fig. 1). The title compound can be used as tridentate chelating ligand to construct spin-crossover complexes. Isostructural 5-chloro-2-hydroxybenzaldehyde-4-ethylthiosemicarbazone was reported previously (Lo et al., 2011).

In the title compound, a strong intramolecular hydrogen bond O—H···N is observed. An intermolecular N—H···S hydrogen bond connects two molecules into a supramolecular dimer as shown in Figure 2.

Related literature top

For the isostructural compound 5-chloro-2-hydroxybenzaldehyde 4-ethylthiosemicarbazone, see: Lo et al. (2011)

Experimental top

5-Bromo-2-hydroxybenzaldehyde (4.02 g, 20 mmol) in 50 ml ethanol and 4-ethyl-3-thiosemicarbazide (2.38 g, 20 mmol) were reacted for 6 h at 350 K. Slow evaporation of the yellow solution gave large colorless crystals.

Structure description top

For the isostructural compound 5-chloro-2-hydroxybenzaldehyde 4-ethylthiosemicarbazone, see: Lo et al. (2011)

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Displacement ellipsoid plot (50% probability level) of the title compound, with atom numbering of structurally unique non-H atoms and the H atoms.
	Fig. 2. The packing diagram of the title compound, with H atoms omitted for clarity. Hydrogen bonds are shown as dashed lines.

5-Bromo-2-hydroxybenzaldehyde 4-ethylthiosemicarbazone top

Crystal data top

C₁₀H₁₂BrN₃OS	F(000) = 1216
M_r = 302.20	D_x = 1.651 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.710747 Å
Hall symbol: -C 2yc	Cell parameters from 3650 reflections
a = 22.040 (4) Å	θ = 3.1–27.5°
b = 11.844 (2) Å	µ = 3.54 mm⁻¹
c = 9.5102 (19) Å	T = 123 K
β = 101.69 (3)°	Block, colourless
V = 2431.1 (8) Å³	0.20 × 0.10 × 0.05 mm
Z = 8

Data collection top

Rigaku Saturn70 diffractometer	2331 independent reflections
Radiation source: Rotating Anode	1760 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.032
Detector resolution: 28.5714 pixels mm^-1	θ_max = 26.0°, θ_min = 3.1°
dtprofit.ref scans	h = −27→20
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	k = −9→14
T_min = 0.661, T_max = 0.838	l = −11→10
4201 measured reflections

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ²(F_o²) + (0.0752P)²] where P = (F_o² + 2F_c²)/3
2331 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 0.70 e Å⁻³
3 restraints	Δρ_min = −1.01 e Å⁻³

Crystal data top

C₁₀H₁₂BrN₃OS	V = 2431.1 (8) Å³
M_r = 302.20	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 22.040 (4) Å	µ = 3.54 mm⁻¹
b = 11.844 (2) Å	T = 123 K
c = 9.5102 (19) Å	0.20 × 0.10 × 0.05 mm
β = 101.69 (3)°

Data collection top

Rigaku Saturn70 diffractometer	2331 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	1760 reflections with I > 2σ(I)
T_min = 0.661, T_max = 0.838	R_int = 0.032
4201 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	3 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.70 e Å⁻³
2331 reflections	Δρ_min = −1.01 e Å⁻³
155 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Br1	0.484097 (17)	0.67444 (4)	1.01744 (4)	0.04059 (19)
C1	0.69767 (15)	0.6276 (2)	1.0597 (3)	0.0180 (7)
C2	0.67216 (16)	0.6364 (3)	1.1818 (3)	0.0197 (7)
H2	0.6985	0.6352	1.2742	0.024*
C3	0.60893 (17)	0.6470 (3)	1.1699 (4)	0.0227 (7)
H3	0.5919	0.6537	1.2536	0.027*
C4	0.57021 (16)	0.6476 (3)	1.0343 (4)	0.0222 (7)
C5	0.59471 (16)	0.6361 (3)	0.9125 (3)	0.0198 (7)
H5	0.5678	0.6343	0.8208	0.024*
C6	0.65841 (15)	0.6271 (3)	0.9228 (3)	0.0164 (7)
C7	0.68243 (15)	0.6269 (3)	0.7906 (3)	0.0179 (7)
H7	0.6542	0.6340	0.7012	0.021*
C8	0.81461 (14)	0.6124 (2)	0.6421 (3)	0.0150 (6)
C9	0.91521 (15)	0.5238 (3)	0.7381 (3)	0.0216 (7)
H9A	0.9408	0.5182	0.8363	0.026*
H9B	0.9339	0.5821	0.6855	0.026*
C10	0.91576 (17)	0.4111 (3)	0.6625 (4)	0.0270 (8)
H10A	0.9008	0.3519	0.7190	0.040*
H10B	0.9581	0.3935	0.6524	0.040*
H10C	0.8887	0.4152	0.5672	0.040*
H1A	0.7730 (17)	0.634 (3)	1.002 (2)	0.032*
H2A	0.7325 (16)	0.680 (2)	0.600 (3)	0.032*
H3A	0.8346 (17)	0.525 (3)	0.810 (3)	0.032*
N1	0.74029 (12)	0.6174 (2)	0.7914 (3)	0.0169 (6)
N2	0.75628 (13)	0.6333 (2)	0.6594 (3)	0.0177 (6)
N3	0.85244 (13)	0.5580 (2)	0.7468 (3)	0.0172 (6)
O1	0.75977 (11)	0.62315 (19)	1.0781 (2)	0.0207 (5)
S1	0.83506 (4)	0.65794 (7)	0.48834 (9)	0.0201 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0165 (2)	0.0815 (4)	0.0261 (2)	0.00156 (19)	0.00976 (16)	0.00158 (19)
C1	0.0186 (18)	0.0130 (14)	0.0228 (17)	0.0006 (13)	0.0052 (14)	−0.0009 (13)
C2	0.0227 (19)	0.0187 (15)	0.0172 (16)	0.0008 (13)	0.0031 (14)	0.0002 (13)
C3	0.026 (2)	0.0234 (16)	0.0223 (16)	−0.0019 (14)	0.0134 (15)	0.0023 (14)
C4	0.0145 (18)	0.0314 (18)	0.0221 (17)	−0.0023 (14)	0.0066 (14)	−0.0001 (14)
C5	0.0163 (17)	0.0239 (16)	0.0180 (16)	−0.0019 (13)	0.0010 (13)	0.0013 (13)
C6	0.0173 (17)	0.0151 (14)	0.0180 (16)	0.0018 (13)	0.0065 (13)	0.0018 (13)
C7	0.0176 (17)	0.0187 (15)	0.0172 (15)	0.0003 (13)	0.0032 (13)	0.0011 (13)
C8	0.0166 (17)	0.0131 (14)	0.0162 (15)	0.0007 (12)	0.0056 (13)	−0.0023 (13)
C9	0.0152 (17)	0.0291 (17)	0.0198 (16)	0.0029 (14)	0.0017 (13)	0.0026 (14)
C10	0.021 (2)	0.033 (2)	0.0274 (18)	0.0060 (15)	0.0064 (15)	−0.0024 (15)
N1	0.0195 (15)	0.0169 (12)	0.0158 (13)	−0.0005 (11)	0.0073 (11)	0.0006 (11)
N2	0.0166 (15)	0.0213 (13)	0.0164 (13)	0.0046 (11)	0.0060 (11)	0.0034 (11)
N3	0.0145 (14)	0.0227 (14)	0.0145 (13)	0.0024 (11)	0.0036 (11)	0.0030 (11)
O1	0.0153 (13)	0.0259 (12)	0.0205 (12)	0.0017 (10)	0.0031 (10)	0.0040 (10)
S1	0.0192 (5)	0.0253 (4)	0.0175 (4)	0.0038 (3)	0.0079 (3)	0.0032 (3)

Geometric parameters (Å, º) top

Br1—C4	1.899 (4)	C8—N3	1.329 (4)
C1—O1	1.345 (4)	C8—N2	1.351 (4)
C1—C2	1.393 (5)	C8—S1	1.703 (3)
C1—C6	1.410 (5)	C9—N3	1.460 (4)
C2—C3	1.381 (5)	C9—C10	1.517 (5)
C2—H2	0.9500	C9—H9A	0.9900
C3—C4	1.395 (5)	C9—H9B	0.9900
C3—H3	0.9500	C10—H10A	0.9800
C4—C5	1.380 (5)	C10—H10B	0.9800
C5—C6	1.391 (4)	C10—H10C	0.9800
C5—H5	0.9500	N1—N2	1.384 (3)
C6—C7	1.460 (4)	N2—H2A	0.879 (10)
C7—N1	1.278 (4)	N3—H3A	0.876 (10)
C7—H7	0.9500	O1—H1A	0.846 (10)

O1—C1—C2	117.8 (3)	N3—C8—S1	124.2 (2)
O1—C1—C6	122.5 (3)	N2—C8—S1	118.0 (2)
C2—C1—C6	119.6 (3)	N3—C9—C10	111.7 (3)
C3—C2—C1	120.6 (3)	N3—C9—H9A	109.3
C3—C2—H2	119.7	C10—C9—H9A	109.3
C1—C2—H2	119.7	N3—C9—H9B	109.3
C2—C3—C4	119.7 (3)	C10—C9—H9B	109.3
C2—C3—H3	120.2	H9A—C9—H9B	107.9
C4—C3—H3	120.2	C9—C10—H10A	109.5
C5—C4—C3	120.4 (3)	C9—C10—H10B	109.5
C5—C4—Br1	120.0 (3)	H10A—C10—H10B	109.5
C3—C4—Br1	119.5 (3)	C9—C10—H10C	109.5
C4—C5—C6	120.6 (3)	H10A—C10—H10C	109.5
C4—C5—H5	119.7	H10B—C10—H10C	109.5
C6—C5—H5	119.7	C7—N1—N2	114.8 (3)
C5—C6—C1	119.1 (3)	C8—N2—N1	120.6 (3)
C5—C6—C7	118.4 (3)	C8—N2—H2A	120 (3)
C1—C6—C7	122.2 (3)	N1—N2—H2A	116 (3)
N1—C7—C6	122.0 (3)	C8—N3—C9	123.4 (3)
N1—C7—H7	119.0	C8—N3—H3A	115 (3)
C6—C7—H7	119.0	C9—N3—H3A	119 (3)
N3—C8—N2	117.8 (3)	C1—O1—H1A	114 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.84 (3)	2.00 (2)	2.674 (3)	137 (3)
N2—H2A···S1ⁱ	0.88 (3)	2.47 (3)	3.316 (3)	161 (2)
N3—H3A···S1ⁱⁱ	0.87 (3)	2.75 (3)	3.510 (3)	146 (3)

Symmetry codes: (i) −x+3/2, −y+3/2, −z+1; (ii) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂BrN₃OS
M_r	302.20
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	123
a, b, c (Å)	22.040 (4), 11.844 (2), 9.5102 (19)
β (°)	101.69 (3)
V (Å³)	2431.1 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.54
Crystal size (mm)	0.20 × 0.10 × 0.05

Data collection
Diffractometer	Rigaku Saturn70
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.661, 0.838
No. of measured, independent and observed [I > 2σ(I)] reflections	4201, 2331, 1760
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.114, 0.95
No. of reflections	2331
No. of parameters	155
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.70, −1.01

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.84 (3)	2.00 (2)	2.674 (3)	137 (3)
N2—H2A···S1ⁱ	0.88 (3)	2.47 (3)	3.316 (3)	161 (2)
N3—H3A···S1ⁱⁱ	0.87 (3)	2.75 (3)	3.510 (3)	146 (3)

Symmetry codes: (i) −x+3/2, −y+3/2, −z+1; (ii) x, −y+1, z+1/2.

Acknowledgements

The authors would like to thank the China Scholarship Council (CSC).

References

Lo, K. M. & Ng, S. W. (2011). Acta Cryst. E67, o1453. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar