1-(5-Bromo-2-oxoindolin-3-yl-idene)thio-semicarbazone.

The title mol-ecule, 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, mol-ecules are linked through N-H⋯O and N-H⋯S inter-actions, generating infinite chains along the b-axis direction. In turn, the chains are stacked along the a axis via π-π inter-actions [centroid-centroid distance = 3.470 (2) Å] and further connected by N-H⋯Br inter-actions into a three-dimensional network. An intra-molecular 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 = 299.16

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 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 ▶), 951 Friedel pairs

Absolute structure parameter: −0.015 (13)

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 ▶).

Crystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S1600536813018564/lr2109sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C9H7BrN4OS	Z = 4
Mr = 299.16	F(000) = 592
Orthorhombic, P212121	Dx = 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

Stoe IPDS-1 diffractometer	2106 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, Stoe IPDS-1	Rint = 0.051
Graphite monochromator	θmax = 27.0°, θmin = 2.6°
φ scans	h = −4→5
7791 measured reflections	k = −18→17
2405 independent reflections	l = −24→24

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(Fo2) + (0.0516P)2 + 0.9296P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.091	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.73 e Å−3
2405 reflections	Δρmin = −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	Flack parameter: −0.015 (13)

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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

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) ; (ii) ; (iii) .