1-(5-Nitro-2-oxoindolin-3-yl-idene)thio-semicarbazide.

In the title molecule, C(9)H(7)N(5)O(3)S, there is an intramolecular N-H⋯O. The molecule is essentially planar, with the maximum deviation from the mean plane of the 18 non-H atoms being 0.135 (2) Å for the amine N atom. In the crystal, the molecules are connected via intermolecular N-H⋯O and N-H⋯S hydrogen bonds, forming two-dimensional networks lying parallel to (10[Formula: see text]). They are separated by an interplanar distance of 3.3214 (9) Å, leading to π-π interactions which stabilize the crystal structure.

Related literature

For the pharmacological properties of isatine-thio­semi­carb­azone derivatives, including the title compound, against cruzain, falcipain-2 and rhodesain, see: Chiyanzu et al. (2003 ▶). For the synthesis of 5-nitro­isatine-3-thio­semi­carbazone, see: Campaigne & Archer (1952 ▶). For an example of a similar structure, 5-bromo­isatin-thio­semicarbazone, see: Pederzolli et al. (2011 ▶).

Experimental

Crystal data

C9H7N5O3S

M = 265.26

Monoclinic,

a = 5.2112 (2) Å

b = 15.5354 (5) Å

c = 13.8711 (5) Å

β = 105.855 (2)°

V = 1080.25 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 293 K

0.08 × 0.07 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: analytical (Alcock, 1970 ▶) T min = 0.966, T max = 0.983

15688 measured reflections

2469 independent reflections

1646 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.108

S = 1.02

2469 reflections

191 parameters

All H-atom parameters refined

Δρmax = 0.18 e Å−3

Δρmin = −0.27 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811040293/vm2117sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040293/vm2117Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811040293/vm2117Isup3.cml

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

C9H7N5O3S	F(000) = 544
Mr = 265.26	Dx = 1.631 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 26694 reflections
a = 5.2112 (2) Å	θ = 2.9–27.5°
b = 15.5354 (5) Å	µ = 0.31 mm−1
c = 13.8711 (5) Å	T = 293 K
β = 105.855 (2)°	Prism, colourless
V = 1080.25 (7) Å3	0.08 × 0.07 × 0.03 mm
Z = 4

Nonius KappaCCD diffractometer	2469 independent reflections
Radiation source: fine-focus sealed tube	1646 reflections with I > 2σ(I)
graphite	Rint = 0.055
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 3.0°
CCD rotation images, thick slices scans	h = −6→6
Absorption correction: analytical (Alcock, 1970)	k = −19→20
Tmin = 0.966, Tmax = 0.983	l = −18→17
15688 measured reflections

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)] = 0.041	Hydrogen site location: difference Fourier map
wR(F2) = 0.108	All H-atom parameters refined
S = 1.02	w = 1/[σ2(Fo2) + (0.0502P)2 + 0.2777P] where P = (Fo2 + 2Fc2)/3
2469 reflections	(Δ/σ)max < 0.001
191 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
S	−0.82185 (11)	0.04442 (3)	0.13953 (5)	0.0550 (2)
O1	−0.3758 (3)	0.30256 (9)	0.25265 (11)	0.0497 (4)
O2	0.8282 (4)	0.06044 (11)	0.57143 (16)	0.0833 (6)
O3	1.0641 (3)	0.17173 (11)	0.62922 (13)	0.0689 (5)
N1	0.0324 (3)	0.34347 (11)	0.35807 (13)	0.0456 (4)
H4	−0.001 (5)	0.3986 (19)	0.3598 (18)	0.068 (8)*
N2	0.8602 (4)	0.13826 (13)	0.57750 (14)	0.0534 (5)
N3	−0.1521 (3)	0.12472 (10)	0.31461 (13)	0.0416 (4)
N4	−0.3969 (3)	0.12302 (10)	0.24907 (13)	0.0438 (4)
H5	−0.481 (5)	0.1742 (16)	0.2237 (17)	0.059 (7)*
N5	−0.3935 (4)	−0.02231 (12)	0.26970 (16)	0.0564 (5)
H6	−0.469 (5)	−0.0697 (16)	0.2592 (18)	0.059 (7)*
H7	−0.234 (6)	−0.0184 (18)	0.315 (2)	0.072 (8)*
C1	0.2206 (4)	0.21247 (12)	0.40888 (14)	0.0382 (4)
C2	0.2575 (4)	0.30160 (12)	0.41775 (15)	0.0407 (5)
C3	0.4895 (4)	0.33798 (14)	0.47706 (16)	0.0473 (5)
H1	0.519 (5)	0.3964 (16)	0.4829 (16)	0.055 (6)*
C4	0.6870 (4)	0.28252 (14)	0.52923 (16)	0.0470 (5)
H2	0.847 (5)	0.3009 (15)	0.5747 (17)	0.058 (6)*
C5	0.6461 (4)	0.19440 (13)	0.52072 (15)	0.0423 (5)
C6	0.4156 (4)	0.15681 (13)	0.46118 (16)	0.0430 (5)
H3	0.394 (4)	0.0988 (15)	0.4573 (16)	0.050 (6)*
C7	−0.0416 (4)	0.19895 (12)	0.33974 (14)	0.0398 (5)
C8	−0.1545 (4)	0.28607 (12)	0.30925 (15)	0.0416 (5)
C9	−0.5237 (4)	0.04538 (12)	0.22445 (15)	0.0420 (5)

	U11	U22	U33	U12	U13	U23
S	0.0442 (3)	0.0362 (3)	0.0713 (4)	−0.0030 (2)	−0.0065 (3)	0.0049 (2)
O1	0.0429 (8)	0.0369 (7)	0.0590 (9)	0.0058 (6)	−0.0035 (7)	−0.0004 (6)
O2	0.0670 (12)	0.0471 (10)	0.1111 (15)	0.0072 (8)	−0.0173 (10)	0.0094 (10)
O3	0.0427 (9)	0.0704 (11)	0.0784 (12)	−0.0001 (8)	−0.0093 (8)	0.0074 (9)
N1	0.0454 (10)	0.0282 (8)	0.0561 (11)	0.0011 (7)	0.0019 (8)	−0.0007 (7)
N2	0.0430 (10)	0.0537 (12)	0.0571 (11)	0.0054 (8)	0.0030 (9)	0.0054 (9)
N3	0.0381 (9)	0.0343 (8)	0.0480 (9)	−0.0002 (7)	0.0045 (7)	−0.0019 (7)
N4	0.0398 (9)	0.0309 (8)	0.0532 (10)	0.0015 (7)	0.0002 (8)	−0.0010 (7)
N5	0.0464 (11)	0.0318 (9)	0.0769 (14)	−0.0018 (8)	−0.0072 (10)	0.0044 (9)
C1	0.0392 (10)	0.0314 (9)	0.0416 (10)	−0.0009 (8)	0.0070 (8)	−0.0015 (8)
C2	0.0405 (11)	0.0342 (10)	0.0451 (11)	0.0008 (8)	0.0080 (9)	−0.0011 (8)
C3	0.0484 (12)	0.0355 (11)	0.0541 (13)	−0.0056 (9)	0.0076 (10)	−0.0060 (9)
C4	0.0415 (11)	0.0466 (12)	0.0483 (12)	−0.0038 (9)	0.0047 (10)	−0.0050 (9)
C5	0.0378 (10)	0.0432 (11)	0.0427 (11)	0.0043 (8)	0.0055 (9)	0.0028 (8)
C6	0.0420 (11)	0.0354 (10)	0.0485 (12)	0.0011 (8)	0.0073 (9)	−0.0002 (9)
C7	0.0412 (11)	0.0304 (9)	0.0446 (11)	0.0024 (8)	0.0063 (9)	−0.0011 (8)
C8	0.0406 (11)	0.0344 (10)	0.0463 (11)	0.0014 (8)	0.0058 (9)	−0.0013 (8)
C9	0.0404 (10)	0.0317 (9)	0.0506 (12)	0.0006 (8)	0.0069 (9)	−0.0014 (8)

S—C9	1.674 (2)	N5—H6	0.83 (2)
O1—C8	1.231 (2)	N5—H7	0.90 (3)
O2—N2	1.220 (2)	C1—C6	1.380 (3)
O3—N2	1.224 (2)	C1—C2	1.399 (3)
N1—C8	1.357 (3)	C1—C7	1.454 (3)
N1—C2	1.398 (2)	C2—C3	1.384 (3)
N1—H4	0.88 (3)	C3—C4	1.385 (3)
N2—C5	1.464 (3)	C3—H1	0.92 (2)
N3—C7	1.294 (2)	C4—C5	1.386 (3)
N3—N4	1.350 (2)	C4—H2	0.94 (2)
N4—C9	1.373 (2)	C5—C6	1.387 (3)
N4—H5	0.93 (2)	C6—H3	0.91 (2)
N5—C9	1.314 (3)	C7—C8	1.490 (3)
C8—N1—C2	111.20 (17)	C2—C3—H1	123.6 (15)
C8—N1—H4	122.3 (17)	C4—C3—H1	118.9 (15)
C2—N1—H4	125.5 (17)	C3—C4—C5	119.68 (19)
O2—N2—O3	122.80 (18)	C3—C4—H2	123.9 (14)
O2—N2—C5	118.90 (18)	C5—C4—H2	116.3 (14)
O3—N2—C5	118.30 (19)	C4—C5—C6	123.69 (19)
C7—N3—N4	117.92 (16)	C4—C5—N2	117.76 (18)
N3—N4—C9	119.14 (16)	C6—C5—N2	118.55 (18)
N3—N4—H5	119.9 (15)	C1—C6—C5	116.30 (19)
C9—N4—H5	120.9 (15)	C1—C6—H3	122.0 (14)
C9—N5—H6	117.8 (17)	C5—C6—H3	121.7 (14)
C9—N5—H7	122.6 (18)	N3—C7—C1	125.12 (17)
H6—N5—H7	119 (2)	N3—C7—C8	128.38 (17)
C6—C1—C2	120.68 (17)	C1—C7—C8	106.45 (15)
C6—C1—C7	132.90 (17)	O1—C8—N1	126.92 (18)
C2—C1—C7	106.43 (16)	O1—C8—C7	126.75 (17)
C3—C2—N1	128.15 (18)	N1—C8—C7	106.32 (16)
C3—C2—C1	122.23 (18)	N5—C9—N4	115.68 (18)
N1—C2—C1	109.61 (16)	N5—C9—S	126.01 (16)
C2—C3—C4	117.42 (19)	N4—C9—S	118.29 (14)
C7—N3—N4—C9	−177.19 (19)	C7—C1—C6—C5	179.5 (2)
C8—N1—C2—C3	179.0 (2)	C4—C5—C6—C1	−0.2 (3)
C8—N1—C2—C1	−0.1 (2)	N2—C5—C6—C1	−179.71 (19)
C6—C1—C2—C3	1.1 (3)	N4—N3—C7—C1	−179.81 (19)
C7—C1—C2—C3	−178.98 (19)	N4—N3—C7—C8	3.1 (3)
C6—C1—C2—N1	−179.75 (19)	C6—C1—C7—N3	2.1 (4)
C7—C1—C2—N1	0.1 (2)	C2—C1—C7—N3	−177.7 (2)
N1—C2—C3—C4	−179.6 (2)	C6—C1—C7—C8	179.7 (2)
C1—C2—C3—C4	−0.7 (3)	C2—C1—C7—C8	−0.1 (2)
C2—C3—C4—C5	−0.2 (3)	C2—N1—C8—O1	178.6 (2)
C3—C4—C5—C6	0.6 (3)	C2—N1—C8—C7	0.0 (2)
C3—C4—C5—N2	−179.8 (2)	N3—C7—C8—O1	−1.1 (4)
O2—N2—C5—C4	179.7 (2)	C1—C7—C8—O1	−178.6 (2)
O3—N2—C5—C4	−0.2 (3)	N3—C7—C8—N1	177.6 (2)
O2—N2—C5—C6	−0.7 (3)	C1—C7—C8—N1	0.1 (2)
O3—N2—C5—C6	179.4 (2)	N3—N4—C9—N5	1.3 (3)
C2—C1—C6—C5	−0.7 (3)	N3—N4—C9—S	−177.56 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H5···O1	0.93 (2)	2.08 (2)	2.791 (2)	132.6 (19)
N5—H6···O1i	0.83 (2)	2.13 (3)	2.957 (2)	173 (2)
N5—H7···O2ii	0.90 (3)	2.36 (3)	3.215 (3)	160 (2)
N1—H4···Siii	0.88 (3)	2.45 (3)	3.3123 (18)	170 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H5⋯O1	0.93 (2)	2.08 (2)	2.791 (2)	132.6 (19)
N5—H6⋯O1i	0.83 (2)	2.13 (3)	2.957 (2)	173 (2)
N5—H7⋯O2ii	0.90 (3)	2.36 (3)	3.215 (3)	160 (2)
N1—H4⋯Siii	0.88 (3)	2.45 (3)	3.3123 (18)	170 (2)

Symmetry codes: (i) ; (ii) ; (iii) .