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

Bandeira, K.C.T.; Bresolin, L.; Näther, C.; Jess, I.; Oliveira, A.B.

doi:10.1107/S1600536813018564

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages o1251-o1252

doi:10.1107/S1600536813018564

Open

access

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

Katlen C. T. Bandeira,^a Leandro Bresolin,^a Christian Näther,^b Inke Jess ^b and Adriano B. Oliveira ^c ^*

^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 π–π 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 ). 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

Crystal data

C₉H₇BrN₄OS
M_r = 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)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.091
S = 1.02
2405 reflections
148 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.55 e Å⁻³
Absolute structure: Flack (1983 ), 951 Friedel pairs
Absolute structure parameter: −0.015 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: X-AREA; 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 ).

Supporting information

Crystal structure: contains datablocks I, publication_text. DOI: 10.1107/S1600536813018564/lr2109sup1.cif

Structure factors: contains datablock platon_shelxl. DOI: 10.1107/S1600536813018564/lr2109Isup2.hkl

checkCIF report

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, π–π-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.

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

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 40% probability level.
	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.
	Fig. 3. A view of the stacking along the crystallographic a-axis. The π–π-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

C₉H₇BrN₄OS	Z = 4
M_r = 299.16	F(000) = 592
Orthorhombic, P2₁2₁2₁	D_x = 1.794 Mg m⁻³
Hall symbol: P 2ac 2ab	Mo Kα radiation, λ = 0.71073 Å
a = 4.0185 (2) Å	µ = 3.88 mm⁻¹
b = 14.6418 (8) Å	T = 293 K
c = 18.8276 (11) Å	Prism, yellow
V = 1107.78 (10) Å³	0.10 × 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-1	R_int = 0.051
Graphite monochromator	θ_max = 27.0°, θ_min = 2.6°
ϕ scans	h = −4→5
7791 measured reflections	k = −18→17
2405 independent reflections	l = −24→24

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.039	w = 1/[σ²(F_o²) + (0.0516P)² + 0.9296P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.091	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.73 e Å⁻³
2405 reflections	Δρ_min = −0.55 e Å⁻³
148 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0123 (16)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 951 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.015 (13)

Crystal data top

C₉H₇BrN₄OS	V = 1107.78 (10) Å³
M_r = 299.16	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.0185 (2) Å	µ = 3.88 mm⁻¹
b = 14.6418 (8) Å	T = 293 K
c = 18.8276 (11) Å	0.10 × 0.06 × 0.04 mm

Data collection top

Stoe IPDS-1 diffractometer	2106 reflections with I > 2σ(I)
7791 measured reflections	R_int = 0.051
2405 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.091	Δρ_max = 0.73 e Å⁻³
S = 1.02	Δρ_min = −0.55 e Å⁻³
2405 reflections	Absolute structure: Flack (1983), 951 Friedel pairs
148 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
Br1	1.14379 (13)	0.36317 (4)	0.59001 (2)	0.04209 (17)
S1	−0.1204 (3)	0.31338 (7)	0.15460 (5)	0.0298 (2)
O1	0.2574 (8)	0.5699 (2)	0.26587 (16)	0.0352 (8)
N1	0.5769 (10)	0.6107 (2)	0.36442 (17)	0.0271 (8)
H1	0.5788	0.6690	0.3590	0.033*
N2	0.3785 (9)	0.3806 (2)	0.32307 (15)	0.0223 (6)
N3	0.2026 (9)	0.3844 (2)	0.26195 (17)	0.0248 (7)
H3	0.1764	0.4359	0.2406	0.030*
N4	0.0979 (10)	0.2311 (2)	0.27236 (17)	0.0285 (7)
H1N4	0.0154	0.1799	0.2562	0.029 (13)*
H2N4	0.1793	0.2242	0.3124	0.038 (15)*
C1	0.4265 (11)	0.5512 (3)	0.31935 (19)	0.0254 (9)
C2	0.4870 (10)	0.4577 (2)	0.3483 (2)	0.0209 (7)
C3	0.6801 (9)	0.4700 (2)	0.4126 (2)	0.0213 (7)
C4	0.8021 (10)	0.4087 (3)	0.4623 (2)	0.0253 (8)
H4	0.7701	0.3461	0.4574	0.030*
C5	0.9739 (11)	0.4448 (3)	0.5197 (2)	0.0299 (9)
C6	1.0274 (11)	0.5383 (3)	0.5283 (2)	0.0335 (10)
H6	1.1455	0.5597	0.5674	0.040*
C7	0.9031 (13)	0.5993 (3)	0.4782 (2)	0.0344 (10)
H7	0.9363	0.6618	0.4832	0.041*
C8	0.7292 (10)	0.5647 (3)	0.4210 (2)	0.0269 (9)
C9	0.0663 (9)	0.3069 (3)	0.2340 (2)	0.0227 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0320 (2)	0.0652 (3)	0.0290 (2)	−0.0030 (3)	−0.0044 (2)	0.0148 (2)
S1	0.0302 (5)	0.0322 (5)	0.0270 (4)	−0.0033 (5)	−0.0081 (5)	0.0052 (4)
O1	0.052 (2)	0.0260 (14)	0.0281 (14)	0.0089 (13)	−0.0046 (13)	0.0020 (12)
N1	0.038 (2)	0.0155 (15)	0.0274 (16)	0.0004 (13)	0.0009 (15)	−0.0012 (11)
N2	0.0221 (15)	0.0232 (15)	0.0218 (13)	0.0011 (14)	−0.0005 (14)	−0.0003 (11)
N3	0.030 (2)	0.0213 (16)	0.0228 (14)	0.0008 (13)	−0.0016 (13)	0.0024 (12)
N4	0.035 (2)	0.0228 (16)	0.0272 (16)	−0.0010 (15)	−0.0076 (16)	0.0050 (12)
C1	0.030 (2)	0.0227 (18)	0.0233 (18)	0.0025 (16)	0.0038 (16)	0.0031 (14)
C2	0.0209 (18)	0.0195 (17)	0.0223 (17)	0.0033 (14)	0.0046 (14)	0.0013 (14)
C3	0.0202 (19)	0.0214 (16)	0.0224 (16)	−0.0034 (14)	0.0063 (17)	−0.0001 (14)
C4	0.020 (2)	0.0313 (19)	0.0241 (17)	−0.0021 (15)	0.0031 (15)	0.0055 (15)
C5	0.021 (2)	0.046 (2)	0.0223 (18)	−0.0016 (17)	0.0043 (15)	0.0033 (17)
C6	0.029 (2)	0.045 (3)	0.027 (2)	−0.0087 (19)	0.0034 (17)	−0.0087 (18)
C7	0.036 (3)	0.036 (2)	0.0306 (19)	−0.010 (2)	0.010 (2)	−0.0104 (16)
C8	0.030 (2)	0.0275 (19)	0.0236 (19)	−0.0019 (15)	0.0086 (15)	−0.0031 (15)
C9	0.018 (2)	0.0256 (18)	0.0248 (17)	−0.0018 (14)	0.0051 (14)	0.0014 (15)

Geometric parameters (Å, º) top

Br1—C5	1.910 (4)	N4—H2N4	0.8285
S1—C9	1.675 (4)	C1—C2	1.494 (5)
O1—C1	1.245 (5)	C2—C3	1.449 (6)
N1—C1	1.358 (5)	C3—C4	1.387 (5)
N1—C8	1.400 (5)	C3—C8	1.409 (5)
N1—H1	0.8598	C4—C5	1.386 (6)
N2—C2	1.299 (5)	C4—H4	0.9300
N2—N3	1.352 (4)	C5—C6	1.396 (6)
N3—C9	1.367 (5)	C6—C7	1.392 (7)
N3—H3	0.8600	C6—H6	0.9300
N4—C9	1.330 (5)	C7—C8	1.381 (6)
N4—H1N4	0.8746	C7—H7	0.9300

C1—N1—C8	111.2 (3)	C5—C4—C3	117.1 (4)
C1—N1—H1	124.5	C5—C4—H4	121.4
C8—N1—H1	124.3	C3—C4—H4	121.4
C2—N2—N3	116.8 (3)	C4—C5—C6	122.8 (4)
N2—N3—C9	120.2 (3)	C4—C5—Br1	118.7 (3)
N2—N3—H3	119.9	C6—C5—Br1	118.5 (3)
C9—N3—H3	119.9	C7—C6—C5	119.7 (4)
C9—N4—H1N4	119.3	C7—C6—H6	120.2
C9—N4—H2N4	129.3	C5—C6—H6	120.2
H1N4—N4—H2N4	111.2	C8—C7—C6	118.4 (4)
O1—C1—N1	127.3 (4)	C8—C7—H7	120.8
O1—C1—C2	125.9 (4)	C6—C7—H7	120.8
N1—C1—C2	106.7 (3)	C7—C8—N1	129.6 (4)
N2—C2—C3	126.4 (3)	C7—C8—C3	121.3 (4)
N2—C2—C1	127.4 (4)	N1—C8—C3	109.1 (3)
C3—C2—C1	106.1 (3)	N4—C9—N3	116.4 (3)
C4—C3—C8	120.7 (4)	N4—C9—S1	125.1 (3)
C4—C3—C2	132.3 (3)	N3—C9—S1	118.4 (3)
C8—C3—C2	106.9 (3)

C2—N2—N3—C9	−176.8 (4)	C3—C4—C5—C6	−0.3 (6)
C8—N1—C1—O1	176.5 (4)	C3—C4—C5—Br1	179.5 (3)
C8—N1—C1—C2	−0.5 (5)	C4—C5—C6—C7	0.5 (7)
N3—N2—C2—C3	−179.9 (4)	Br1—C5—C6—C7	−179.3 (3)
N3—N2—C2—C1	3.1 (6)	C5—C6—C7—C8	0.0 (7)
O1—C1—C2—N2	0.6 (7)	C6—C7—C8—N1	179.1 (4)
N1—C1—C2—N2	177.7 (4)	C6—C7—C8—C3	−0.6 (6)
O1—C1—C2—C3	−176.9 (4)	C1—N1—C8—C7	−179.1 (4)
N1—C1—C2—C3	0.2 (4)	C1—N1—C8—C3	0.6 (5)
N2—C2—C3—C4	0.9 (7)	C4—C3—C8—C7	0.8 (6)
C1—C2—C3—C4	178.4 (4)	C2—C3—C8—C7	179.3 (4)
N2—C2—C3—C8	−177.4 (4)	C4—C3—C8—N1	−178.9 (3)
C1—C2—C3—C8	0.1 (4)	C2—C3—C8—N1	−0.4 (4)
C8—C3—C4—C5	−0.3 (6)	N2—N3—C9—N4	4.4 (6)
C2—C3—C4—C5	−178.4 (4)	N2—N3—C9—S1	−174.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1; (iii) −x, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1; (iii) −x, y−1/2, −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

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Campaigne, E. & Archer, W. L. (1952). J. Am. Chem. Soc. 74, 5801. CrossRef Google Scholar
Chiyanzu, 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 Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Pederzolli, 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 Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2008). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar