organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

5-Bromo-2-hy­dr­oxy­benzaldehyde 4-ethyl­thio­semicarbazone

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[Lo, K. M. & Ng, S. W. (2011). Acta Cryst. E67, o1453.])

[Scheme 1]

Experimental

Crystal data
  • C10H12BrN3OS

  • Mr = 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[Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.661, Tmax = 0.838

  • 4201 measured reflections

  • 2331 independent reflections

  • 1760 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.70 e Å−3

  • Δρmin = −1.01 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95, 0.98 and 0.99 Å) and were included in the refinement in the riding model approximation, with Uiso(H) =1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for the others. The hydroxy and amino H atoms were located in a difference Fourier map, and were refined with distance restraints of O—H 0.85±0.01 and N—H 0.88±0.01 Å; with Uiso(H) =1.2Ueq(N and O).

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
[Figure 1] 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.
[Figure 2] 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
C10H12BrN3OSF(000) = 1216
Mr = 302.20Dx = 1.651 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.710747 Å
Hall symbol: -C 2ycCell parameters from 3650 reflections
a = 22.040 (4) Åθ = 3.1–27.5°
b = 11.844 (2) ŵ = 3.54 mm1
c = 9.5102 (19) ÅT = 123 K
β = 101.69 (3)°Block, colourless
V = 2431.1 (8) Å30.20 × 0.10 × 0.05 mm
Z = 8
Data collection top
Rigaku Saturn70
diffractometer
2331 independent reflections
Radiation source: Rotating Anode1760 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.032
Detector resolution: 28.5714 pixels mm-1θmax = 26.0°, θmin = 3.1°
dtprofit.ref scansh = 2720
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2008)
k = 914
Tmin = 0.661, Tmax = 0.838l = 1110
4201 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 0.95 w = 1/[σ2(Fo2) + (0.0752P)2]
where P = (Fo2 + 2Fc2)/3
2331 reflections(Δ/σ)max = 0.001
155 parametersΔρmax = 0.70 e Å3
3 restraintsΔρmin = 1.01 e Å3
Crystal data top
C10H12BrN3OSV = 2431.1 (8) Å3
Mr = 302.20Z = 8
Monoclinic, C2/cMo Kα radiation
a = 22.040 (4) ŵ = 3.54 mm1
b = 11.844 (2) ÅT = 123 K
c = 9.5102 (19) Å0.20 × 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)
Tmin = 0.661, Tmax = 0.838Rint = 0.032
4201 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0423 restraints
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 0.95Δρmax = 0.70 e Å3
2331 reflectionsΔρmin = 1.01 e Å3
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
xyzUiso*/Ueq
Br10.484097 (17)0.67444 (4)1.01744 (4)0.04059 (19)
C10.69767 (15)0.6276 (2)1.0597 (3)0.0180 (7)
C20.67216 (16)0.6364 (3)1.1818 (3)0.0197 (7)
H20.69850.63521.27420.024*
C30.60893 (17)0.6470 (3)1.1699 (4)0.0227 (7)
H30.59190.65371.25360.027*
C40.57021 (16)0.6476 (3)1.0343 (4)0.0222 (7)
C50.59471 (16)0.6361 (3)0.9125 (3)0.0198 (7)
H50.56780.63430.82080.024*
C60.65841 (15)0.6271 (3)0.9228 (3)0.0164 (7)
C70.68243 (15)0.6269 (3)0.7906 (3)0.0179 (7)
H70.65420.63400.70120.021*
C80.81461 (14)0.6124 (2)0.6421 (3)0.0150 (6)
C90.91521 (15)0.5238 (3)0.7381 (3)0.0216 (7)
H9A0.94080.51820.83630.026*
H9B0.93390.58210.68550.026*
C100.91576 (17)0.4111 (3)0.6625 (4)0.0270 (8)
H10A0.90080.35190.71900.040*
H10B0.95810.39350.65240.040*
H10C0.88870.41520.56720.040*
H1A0.7730 (17)0.634 (3)1.002 (2)0.032*
H2A0.7325 (16)0.680 (2)0.600 (3)0.032*
H3A0.8346 (17)0.525 (3)0.810 (3)0.032*
N10.74029 (12)0.6174 (2)0.7914 (3)0.0169 (6)
N20.75628 (13)0.6333 (2)0.6594 (3)0.0177 (6)
N30.85244 (13)0.5580 (2)0.7468 (3)0.0172 (6)
O10.75977 (11)0.62315 (19)1.0781 (2)0.0207 (5)
S10.83506 (4)0.65794 (7)0.48834 (9)0.0201 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0165 (2)0.0815 (4)0.0261 (2)0.00156 (19)0.00976 (16)0.00158 (19)
C10.0186 (18)0.0130 (14)0.0228 (17)0.0006 (13)0.0052 (14)0.0009 (13)
C20.0227 (19)0.0187 (15)0.0172 (16)0.0008 (13)0.0031 (14)0.0002 (13)
C30.026 (2)0.0234 (16)0.0223 (16)0.0019 (14)0.0134 (15)0.0023 (14)
C40.0145 (18)0.0314 (18)0.0221 (17)0.0023 (14)0.0066 (14)0.0001 (14)
C50.0163 (17)0.0239 (16)0.0180 (16)0.0019 (13)0.0010 (13)0.0013 (13)
C60.0173 (17)0.0151 (14)0.0180 (16)0.0018 (13)0.0065 (13)0.0018 (13)
C70.0176 (17)0.0187 (15)0.0172 (15)0.0003 (13)0.0032 (13)0.0011 (13)
C80.0166 (17)0.0131 (14)0.0162 (15)0.0007 (12)0.0056 (13)0.0023 (13)
C90.0152 (17)0.0291 (17)0.0198 (16)0.0029 (14)0.0017 (13)0.0026 (14)
C100.021 (2)0.033 (2)0.0274 (18)0.0060 (15)0.0064 (15)0.0024 (15)
N10.0195 (15)0.0169 (12)0.0158 (13)0.0005 (11)0.0073 (11)0.0006 (11)
N20.0166 (15)0.0213 (13)0.0164 (13)0.0046 (11)0.0060 (11)0.0034 (11)
N30.0145 (14)0.0227 (14)0.0145 (13)0.0024 (11)0.0036 (11)0.0030 (11)
O10.0153 (13)0.0259 (12)0.0205 (12)0.0017 (10)0.0031 (10)0.0040 (10)
S10.0192 (5)0.0253 (4)0.0175 (4)0.0038 (3)0.0079 (3)0.0032 (3)
Geometric parameters (Å, º) top
Br1—C41.899 (4)C8—N31.329 (4)
C1—O11.345 (4)C8—N21.351 (4)
C1—C21.393 (5)C8—S11.703 (3)
C1—C61.410 (5)C9—N31.460 (4)
C2—C31.381 (5)C9—C101.517 (5)
C2—H20.9500C9—H9A0.9900
C3—C41.395 (5)C9—H9B0.9900
C3—H30.9500C10—H10A0.9800
C4—C51.380 (5)C10—H10B0.9800
C5—C61.391 (4)C10—H10C0.9800
C5—H50.9500N1—N21.384 (3)
C6—C71.460 (4)N2—H2A0.879 (10)
C7—N11.278 (4)N3—H3A0.876 (10)
C7—H70.9500O1—H1A0.846 (10)
O1—C1—C2117.8 (3)N3—C8—S1124.2 (2)
O1—C1—C6122.5 (3)N2—C8—S1118.0 (2)
C2—C1—C6119.6 (3)N3—C9—C10111.7 (3)
C3—C2—C1120.6 (3)N3—C9—H9A109.3
C3—C2—H2119.7C10—C9—H9A109.3
C1—C2—H2119.7N3—C9—H9B109.3
C2—C3—C4119.7 (3)C10—C9—H9B109.3
C2—C3—H3120.2H9A—C9—H9B107.9
C4—C3—H3120.2C9—C10—H10A109.5
C5—C4—C3120.4 (3)C9—C10—H10B109.5
C5—C4—Br1120.0 (3)H10A—C10—H10B109.5
C3—C4—Br1119.5 (3)C9—C10—H10C109.5
C4—C5—C6120.6 (3)H10A—C10—H10C109.5
C4—C5—H5119.7H10B—C10—H10C109.5
C6—C5—H5119.7C7—N1—N2114.8 (3)
C5—C6—C1119.1 (3)C8—N2—N1120.6 (3)
C5—C6—C7118.4 (3)C8—N2—H2A120 (3)
C1—C6—C7122.2 (3)N1—N2—H2A116 (3)
N1—C7—C6122.0 (3)C8—N3—C9123.4 (3)
N1—C7—H7119.0C8—N3—H3A115 (3)
C6—C7—H7119.0C9—N3—H3A119 (3)
N3—C8—N2117.8 (3)C1—O1—H1A114 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N10.84 (3)2.00 (2)2.674 (3)137 (3)
N2—H2A···S1i0.88 (3)2.47 (3)3.316 (3)161 (2)
N3—H3A···S1ii0.87 (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 formulaC10H12BrN3OS
Mr302.20
Crystal system, space groupMonoclinic, C2/c
Temperature (K)123
a, b, c (Å)22.040 (4), 11.844 (2), 9.5102 (19)
β (°) 101.69 (3)
V3)2431.1 (8)
Z8
Radiation typeMo Kα
µ (mm1)3.54
Crystal size (mm)0.20 × 0.10 × 0.05
Data collection
DiffractometerRigaku Saturn70
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2008)
Tmin, Tmax0.661, 0.838
No. of measured, independent and
observed [I > 2σ(I)] reflections
4201, 2331, 1760
Rint0.032
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.114, 0.95
No. of reflections2331
No. of parameters155
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O1—H1A···N10.84 (3)2.00 (2)2.674 (3)137 (3)
N2—H2A···S1i0.88 (3)2.47 (3)3.316 (3)161 (2)
N3—H3A···S1ii0.87 (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

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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds