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

Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 69| Part 8| August 2013| Pages o1251-o1252

1-(5-Bromo-2-oxoindolin-3-yl­­idene)thio­semicarbazone

aEscola de Química e Alimentos, Universidade Federal do Rio Grande, Av. Itália km 08, Campus Carreiros, 96203-903 Rio Grande-RS, Brazil, bInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth Strasse 2, D-24118 Kiel, Germany, and cDepartamento de Química, Universidade Federal de Sergipe, Av. Marechal Rondon s/n, Campus, 49100-000 São Cristóvão-SE, Brazil
*Correspondence e-mail: adriano@daad-alumni.de

(Received 18 June 2013; accepted 4 July 2013; online 13 July 2013)

The title mol­ecule, C9H7BrN4OS, is essentially planar [r.m.s. deviation = 0.066 (2) Å], the maximum deviation from the mean plane through the non-H atoms being 0.190 (3) Å for the terminal amine N atom. In the crystal, mol­ecules are linked through N—H⋯O and N—H⋯S inter­actions, generating infinite chains along the b-axis direction. In turn, the chains are stacked along the a axis via ππ inter­actions [centroid–centroid distance = 3.470 (2) Å] and further connected by N—H⋯Br inter­actions into a three-dimensional network. An intra­molecular N—H⋯O hydrogen bond is also observed.

Related literature

For the pharmacological properties of isatin-thio­semicarbazone derivatives against cruzain, falcipain-2 and rhodesain, see: Chiyanzu et al. (2003[Chiyanzu, I., Hansell, E., Gut, J., Rosenthal, P. J., McKerrow, J. H. & Chibale, K. (2003). Bioorg. Med. Chem. Lett. 13, 3527-3530.]). For the synthesis of 5-bromo­isatin-3-thio­semicarbazone, see: Campaigne & Archer (1952[Campaigne, E. & Archer, W. L. (1952). J. Am. Chem. Soc. 74, 5801.]). For the crystal structure of 1-(5-bromo-2-oxoindolin-3-yl­idene)thio­semicarbazide aceto­nitrile monosolvate, see: Pederzolli et al. (2011[Pederzolli, F. R. S., Bresolin, L., Carratu, V. S., Locatelli, A. & Oliveira, A. B. de (2011). Acta Cryst. E67, o1804.]).

[Scheme 1]

Experimental

Crystal data
  • C9H7BrN4OS

  • Mr = 299.16

  • Orthorhombic, P 21 21 21

  • a = 4.0185 (2) Å

  • b = 14.6418 (8) Å

  • c = 18.8276 (11) Å

  • V = 1107.78 (10) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 3.88 mm−1

  • T = 293 K

  • 0.10 × 0.06 × 0.04 mm

Data collection
  • Stoe IPDS-1 diffractometer

  • 7791 measured reflections

  • 2405 independent reflections

  • 2106 reflections with I > 2σ(I)

  • Rint = 0.051

Refinement
  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.091

  • S = 1.02

  • 2405 reflections

  • 148 parameters

  • H-atom parameters constrained

  • Δρmax = 0.73 e Å−3

  • Δρmin = −0.55 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 951 Friedel pairs

  • Absolute structure parameter: −0.015 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯S1i 0.86 2.82 3.507 (3) 139
N3—H3⋯O1 0.86 2.04 2.726 (4) 135
N4—H2N4⋯Br1ii 0.83 2.91 3.665 (4) 152
N4—H1N4⋯O1iii 0.87 1.99 2.851 (4) 167
Symmetry codes: (i) [-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]; (iii) [-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: X-AREA (Stoe & Cie, 2008[Stoe & Cie (2008). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2008[Stoe & Cie (2008). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.]); 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: DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Thiosemicarbazone derivatives have a wide range of biological properties. For example, isatin-based synthetic thiosemicarbazones show pharmacological activity against cruzain, falcipain-2 and rhodesain (Chiyanzu et al., 2003). As part of our study of thiosemicarbazone derivatives, we report herein the crystal structure of 5-bromoisatin-3-thiosemicarbazone (Campaigne & Archer, 1952). In the title compound, in which the molecular structure matches the asymmetric unit, the maximal deviation from the least squares plane through all non-hydrogen atoms amount to 0.1896 (32) Å for N4.The molecule shows an E conformation for the atoms about the N2—N3 bond (Fig. 1). The E conformation for the thiosemicarbazone fragment is also observed in the crystal structure of the 5-bromoisatin-3-thiosemicarbazone acetonitrile monosolvate (Pederzolli et al., 2011) and is related with the intramolecular N—H···O H-interaction (Table 1). The mean deviations from the least squares planes for the C1—C8/Br1/N1 and C9/N2—N4/S1 fragments amount to 0.0568 (26) Å for O1 and 0.0394 (27) Å for N3, respectively, and the dihedral angle between the two planes is 9.01 (12)°. The molecules are connected via centrosymmetric pairs of N—H···S and N—H···O interactions and additionally by N—H···Br interactions (Fig. 2 and Table 1) forming a three-dimensional hydrogen-bonded network, which stabilizes the crystal packing. Additionally, ππ-interactions are observed, with C···C distances = 3.396 (6) Å. The molecules are arranged in layers and are stacked into the crystallographic a-axis direction (Fig. 3).

Related literature top

For the pharmacological properties of isatin-thiosemicarbazone derivatives against cruzain, falcipain-2 and rhodesain, see: Chiyanzu et al. (2003). For the synthesis of 5-bromoisatin-3-thiosemicarbazone, see: Campaigne & Archer (1952). For the crystal structure of 1-(5-bromo-2-oxoindolin-3-ylidene)thiosemicarbazide acetonitrile monosolvate, see: Pederzolli et al. (2011).

Experimental top

Starting materials were commercially available and were used without further purification. The 5-bromoisatine-3-thiosemicarbazone synthesis was adapted from a procedure reported previously (Campaigne & Archer, 1952). A mixture of of 5-bromoisatin (8,83 mmol) and thiosemicarbazide (8,83 mmol) in ethanol (50 ml) in the presence of a catalytic amount of hydrochloric acid was refluxed for 6 h. After cooling and filtering, the title compound was obtained. Crystals suitable for X-ray diffraction of 5-bromoisatine-3-thiosemicarbazone were obtained unexpectedly from an unsuccessful reaction of SnCl2 dihydrate with the title compound in methanol and dichloromethane by the slow evaporation of the solvents. Elemental analysis(%): Calc. 36.01 C, 2.69 H, 18.67 N, 10.68 S; found 35.95 C, 2.25 H, 18.67 N, 10.60 S.

Refinement top

All non-hydrogen atoms were refined anisotropically. All C—H and N—H atoms were located in difference map but were positioned with idealized geometry and refined isotropically with Uiso(H) = 1.2 Ueq(C) using a riding model with C—H = 0.93 Å for aromatic and N—H = 0.86 Å for methyl H atoms. The terminal N—H atoms were located in difference map, their bond lengths were set to 0.86 Å and afterwards they were refined isotropically with Uiso(H) = 1.5 Ueq(N) using a riding model.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-RED32 (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 40% probability level.
[Figure 2] Fig. 2. Molecules of the title compound connected via N—H···S, N—H···O and N—H···Br interactions. H-interactions are indicated as dashed lines and the Figure is simplified for clarity.
[Figure 3] Fig. 3. A view of the stacking along the crystallographic a-axis. The ππ-interactions are drawn as dashed lines.Symmetry codes are: (iv) x - 1,y,z; (v) x + 1,y,z.
1-(5-Bromo-2-oxoindolin-3-ylidene)thiosemicarbazone top
Crystal data top
C9H7BrN4OSZ = 4
Mr = 299.16F(000) = 592
Orthorhombic, P212121Dx = 1.794 Mg m3
Hall symbol: P 2ac 2abMo Kα radiation, λ = 0.71073 Å
a = 4.0185 (2) ŵ = 3.88 mm1
b = 14.6418 (8) ÅT = 293 K
c = 18.8276 (11) ÅPrism, yellow
V = 1107.78 (10) Å30.10 × 0.06 × 0.04 mm
Data collection top
Stoe IPDS-1
diffractometer
2106 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, Stoe IPDS-1Rint = 0.051
Graphite monochromatorθmax = 27.0°, θmin = 2.6°
ϕ scansh = 45
7791 measured reflectionsk = 1817
2405 independent reflectionsl = 2424
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.039 w = 1/[σ2(Fo2) + (0.0516P)2 + 0.9296P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.091(Δ/σ)max < 0.001
S = 1.02Δρmax = 0.73 e Å3
2405 reflectionsΔρmin = 0.55 e Å3
148 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0123 (16)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 951 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.015 (13)
Crystal data top
C9H7BrN4OSV = 1107.78 (10) Å3
Mr = 299.16Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 4.0185 (2) ŵ = 3.88 mm1
b = 14.6418 (8) ÅT = 293 K
c = 18.8276 (11) Å0.10 × 0.06 × 0.04 mm
Data collection top
Stoe IPDS-1
diffractometer
2106 reflections with I > 2σ(I)
7791 measured reflectionsRint = 0.051
2405 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.091Δρmax = 0.73 e Å3
S = 1.02Δρmin = 0.55 e Å3
2405 reflectionsAbsolute structure: Flack (1983), 951 Friedel pairs
148 parametersAbsolute structure parameter: 0.015 (13)
0 restraints
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Br11.14379 (13)0.36317 (4)0.59001 (2)0.04209 (17)
S10.1204 (3)0.31338 (7)0.15460 (5)0.0298 (2)
O10.2574 (8)0.5699 (2)0.26587 (16)0.0352 (8)
N10.5769 (10)0.6107 (2)0.36442 (17)0.0271 (8)
H10.57880.66900.35900.033*
N20.3785 (9)0.3806 (2)0.32307 (15)0.0223 (6)
N30.2026 (9)0.3844 (2)0.26195 (17)0.0248 (7)
H30.17640.43590.24060.030*
N40.0979 (10)0.2311 (2)0.27236 (17)0.0285 (7)
H1N40.01540.17990.25620.029 (13)*
H2N40.17930.22420.31240.038 (15)*
C10.4265 (11)0.5512 (3)0.31935 (19)0.0254 (9)
C20.4870 (10)0.4577 (2)0.3483 (2)0.0209 (7)
C30.6801 (9)0.4700 (2)0.4126 (2)0.0213 (7)
C40.8021 (10)0.4087 (3)0.4623 (2)0.0253 (8)
H40.77010.34610.45740.030*
C50.9739 (11)0.4448 (3)0.5197 (2)0.0299 (9)
C61.0274 (11)0.5383 (3)0.5283 (2)0.0335 (10)
H61.14550.55970.56740.040*
C70.9031 (13)0.5993 (3)0.4782 (2)0.0344 (10)
H70.93630.66180.48320.041*
C80.7292 (10)0.5647 (3)0.4210 (2)0.0269 (9)
C90.0663 (9)0.3069 (3)0.2340 (2)0.0227 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0320 (2)0.0652 (3)0.0290 (2)0.0030 (3)0.0044 (2)0.0148 (2)
S10.0302 (5)0.0322 (5)0.0270 (4)0.0033 (5)0.0081 (5)0.0052 (4)
O10.052 (2)0.0260 (14)0.0281 (14)0.0089 (13)0.0046 (13)0.0020 (12)
N10.038 (2)0.0155 (15)0.0274 (16)0.0004 (13)0.0009 (15)0.0012 (11)
N20.0221 (15)0.0232 (15)0.0218 (13)0.0011 (14)0.0005 (14)0.0003 (11)
N30.030 (2)0.0213 (16)0.0228 (14)0.0008 (13)0.0016 (13)0.0024 (12)
N40.035 (2)0.0228 (16)0.0272 (16)0.0010 (15)0.0076 (16)0.0050 (12)
C10.030 (2)0.0227 (18)0.0233 (18)0.0025 (16)0.0038 (16)0.0031 (14)
C20.0209 (18)0.0195 (17)0.0223 (17)0.0033 (14)0.0046 (14)0.0013 (14)
C30.0202 (19)0.0214 (16)0.0224 (16)0.0034 (14)0.0063 (17)0.0001 (14)
C40.020 (2)0.0313 (19)0.0241 (17)0.0021 (15)0.0031 (15)0.0055 (15)
C50.021 (2)0.046 (2)0.0223 (18)0.0016 (17)0.0043 (15)0.0033 (17)
C60.029 (2)0.045 (3)0.027 (2)0.0087 (19)0.0034 (17)0.0087 (18)
C70.036 (3)0.036 (2)0.0306 (19)0.010 (2)0.010 (2)0.0104 (16)
C80.030 (2)0.0275 (19)0.0236 (19)0.0019 (15)0.0086 (15)0.0031 (15)
C90.018 (2)0.0256 (18)0.0248 (17)0.0018 (14)0.0051 (14)0.0014 (15)
Geometric parameters (Å, º) top
Br1—C51.910 (4)N4—H2N40.8285
S1—C91.675 (4)C1—C21.494 (5)
O1—C11.245 (5)C2—C31.449 (6)
N1—C11.358 (5)C3—C41.387 (5)
N1—C81.400 (5)C3—C81.409 (5)
N1—H10.8598C4—C51.386 (6)
N2—C21.299 (5)C4—H40.9300
N2—N31.352 (4)C5—C61.396 (6)
N3—C91.367 (5)C6—C71.392 (7)
N3—H30.8600C6—H60.9300
N4—C91.330 (5)C7—C81.381 (6)
N4—H1N40.8746C7—H70.9300
C1—N1—C8111.2 (3)C5—C4—C3117.1 (4)
C1—N1—H1124.5C5—C4—H4121.4
C8—N1—H1124.3C3—C4—H4121.4
C2—N2—N3116.8 (3)C4—C5—C6122.8 (4)
N2—N3—C9120.2 (3)C4—C5—Br1118.7 (3)
N2—N3—H3119.9C6—C5—Br1118.5 (3)
C9—N3—H3119.9C7—C6—C5119.7 (4)
C9—N4—H1N4119.3C7—C6—H6120.2
C9—N4—H2N4129.3C5—C6—H6120.2
H1N4—N4—H2N4111.2C8—C7—C6118.4 (4)
O1—C1—N1127.3 (4)C8—C7—H7120.8
O1—C1—C2125.9 (4)C6—C7—H7120.8
N1—C1—C2106.7 (3)C7—C8—N1129.6 (4)
N2—C2—C3126.4 (3)C7—C8—C3121.3 (4)
N2—C2—C1127.4 (4)N1—C8—C3109.1 (3)
C3—C2—C1106.1 (3)N4—C9—N3116.4 (3)
C4—C3—C8120.7 (4)N4—C9—S1125.1 (3)
C4—C3—C2132.3 (3)N3—C9—S1118.4 (3)
C8—C3—C2106.9 (3)
C2—N2—N3—C9176.8 (4)C3—C4—C5—C60.3 (6)
C8—N1—C1—O1176.5 (4)C3—C4—C5—Br1179.5 (3)
C8—N1—C1—C20.5 (5)C4—C5—C6—C70.5 (7)
N3—N2—C2—C3179.9 (4)Br1—C5—C6—C7179.3 (3)
N3—N2—C2—C13.1 (6)C5—C6—C7—C80.0 (7)
O1—C1—C2—N20.6 (7)C6—C7—C8—N1179.1 (4)
N1—C1—C2—N2177.7 (4)C6—C7—C8—C30.6 (6)
O1—C1—C2—C3176.9 (4)C1—N1—C8—C7179.1 (4)
N1—C1—C2—C30.2 (4)C1—N1—C8—C30.6 (5)
N2—C2—C3—C40.9 (7)C4—C3—C8—C70.8 (6)
C1—C2—C3—C4178.4 (4)C2—C3—C8—C7179.3 (4)
N2—C2—C3—C8177.4 (4)C4—C3—C8—N1178.9 (3)
C1—C2—C3—C80.1 (4)C2—C3—C8—N10.4 (4)
C8—C3—C4—C50.3 (6)N2—N3—C9—N44.4 (6)
C2—C3—C4—C5178.4 (4)N2—N3—C9—S1174.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.862.823.507 (3)139
N3—H3···O10.862.042.726 (4)135
N4—H2N4···Br1ii0.832.913.665 (4)152
N4—H1N4···O1iii0.871.992.851 (4)167
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x1/2, y+1/2, z+1; (iii) x, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.862.823.507 (3)139
N3—H3···O10.862.042.726 (4)135
N4—H2N4···Br1ii0.832.913.665 (4)152
N4—H1N4···O1iii0.871.992.851 (4)167
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x1/2, y+1/2, z+1; (iii) x, y1/2, z+1/2.
 

Acknowledgements

We gratefully acknowledge financial support by the State of Schleswig–Holstein, Germany. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities. We gratefully acknowledge financial support through the DECIT/SCTIE-MS-CNPq-FAPERGS-Pronem-# 11/2029–1 and PRONEX-CNPq-FAPERGS projects. KCTB thanks FAPEAM for the award of a scholarship and ABO acknowledges financial support through the FAPITEC/SE/FUNTEC/CNPq PPP 04/2011 program.

References

First citationBrandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationCampaigne, E. & Archer, W. L. (1952). J. Am. Chem. Soc. 74, 5801.  CrossRef
First citationChiyanzu, I., Hansell, E., Gut, J., Rosenthal, P. J., McKerrow, J. H. & Chibale, K. (2003). Bioorg. Med. Chem. Lett. 13, 3527–3530.  Web of Science CrossRef PubMed CAS
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals
First citationPederzolli, F. R. S., Bresolin, L., Carratu, V. S., Locatelli, A. & Oliveira, A. B. de (2011). Acta Cryst. E67, o1804.  Web of Science CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationStoe & Cie (2008). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals

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ISSN: 2056-9890
Volume 69| Part 8| August 2013| Pages o1251-o1252
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