2-(5-Chloro-2-oxoindolin-3-yl-idene)hydrazinecarbo-thio-amide.

The title mol-ecule, C9H7ClN4OS, is almost planar, with an r.m.s. deviation of 0.034 (2) Å for the mean plane through all the non-H atoms. Intra-molecular N-H⋯O and N-H⋯N hydrogen bonds form S(6) and S(5) ring motifs, respectively. In the crystal, mol-ecules are assembled into inversion dimers through pairs of co-operative N-H⋯Cl inter-actions. These dimers are connected along the b axis by N-H⋯O and N-H⋯S hydrogen bonds, generating layers parallel to (103). The layers are further connected along the a axis into a three-dimensional network, through weak π-π stacking inter-actions [centroid-centroid distance = 3.849 (2) Å].

Related literature

For the synthesis of the title compound, see: Qasem Ali et al. (2011 ▶). For similar hydrazinecarbo­thio­amide crystal structures, see: Bandeira et al. (2013 ▶); Ali et al. (2012 ▶); de Oliveira et al. (2012 ▶). For the biological activity of isatin and derivatives, see: Cerchiaro & Ferreira (2006 ▶).

Experimental

Crystal data

C9H7ClN4OS

M = 254.70

Monoclinic,

a = 5.260 (5) Å

b = 15.396 (10) Å

c = 13.215 (9) Å

β = 96.53 (2)°

V = 1063.4 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.54 mm−1

T = 173 K

1.27 × 0.38 × 0.35 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.639, T max = 0.746

6939 measured reflections

2540 independent reflections

2374 reflections with I > 2σ(I)

R int = 0.014

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.084

S = 0.81

2540 reflections

161 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.52 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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, New_Global_Publ_Block. DOI: 10.1107/S1600536813033369/lr2119sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813033369/lr2119Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536813033369/lr2119Isup3.cml

Additional supporting information: crystallographic information; 3D view; checkCIF report

C9H7ClN4OS	Z = 4
Mr = 254.70	F(000) = 520
Monoclinic, P21/n	Dx = 1.591 Mg m−3
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 5.260 (5) Å	θ = 2.0–28.3°
b = 15.396 (10) Å	µ = 0.54 mm−1
c = 13.215 (9) Å	T = 173 K
β = 96.53 (2)°	Block, yellow
V = 1063.4 (14) Å3	1.27 × 0.38 × 0.35 mm

Bruker APEXII CCD diffractometer	2540 independent reflections
Radiation source: fine-focus sealed tube	2374 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
φ and ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→7
Tmin = 0.639, Tmax = 0.746	k = −20→18
6939 measured reflections	l = −17→17

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 0.81	w = 1/[σ2(Fo2) + (0.0594P)2 + 1.1793P] where P = (Fo2 + 2Fc2)/3
2540 reflections	(Δ/σ)max = 0.001
161 parameters	Δρmax = 0.52 e Å−3
0 restraints	Δρmin = −0.30 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
Cl1	1.30216 (7)	0.60089 (2)	−0.07671 (3)	0.02850 (11)
S1	0.02044 (6)	0.54702 (2)	0.36977 (3)	0.01934 (10)
O1	0.35742 (18)	0.80256 (6)	0.24115 (7)	0.0187 (2)
N1	0.3377 (3)	0.47463 (8)	0.24996 (11)	0.0285 (3)
N2	0.3459 (2)	0.62260 (7)	0.25988 (8)	0.0162 (2)
N3	0.5262 (2)	0.62044 (7)	0.19443 (8)	0.0159 (2)
N4	0.6662 (2)	0.83859 (7)	0.13477 (8)	0.0166 (2)
C1	0.2444 (2)	0.54529 (8)	0.28857 (10)	0.0163 (2)
C2	0.6101 (2)	0.69327 (8)	0.16351 (9)	0.0148 (2)
C3	0.8029 (2)	0.70274 (8)	0.09346 (9)	0.0152 (2)
C4	0.9460 (2)	0.64250 (8)	0.04630 (10)	0.0173 (2)
H4	0.9271	0.5819	0.0565	0.021*
C5	1.1187 (2)	0.67488 (9)	−0.01663 (10)	0.0189 (3)
C6	1.1518 (2)	0.76349 (9)	−0.03214 (10)	0.0192 (3)
H6	1.2728	0.7829	−0.0753	0.023*
C8	0.8326 (2)	0.79228 (8)	0.07785 (9)	0.0152 (2)
C9	0.5256 (2)	0.78350 (8)	0.18693 (10)	0.0156 (2)
C7	1.0070 (3)	0.82389 (9)	0.01575 (10)	0.0180 (3)
H7	1.0274	0.8845	0.0061	0.022*
H21	0.291 (3)	0.6714 (12)	0.2814 (13)	0.017 (4)*
H41	0.637 (4)	0.8958 (15)	0.1304 (16)	0.035 (5)*
H11	0.276 (4)	0.4232 (15)	0.2616 (16)	0.033 (5)*
H12	0.459 (5)	0.4835 (18)	0.210 (2)	0.054 (7)*

	U11	U22	U33	U12	U13	U23
Cl1	0.02824 (19)	0.0271 (2)	0.0332 (2)	0.00156 (13)	0.01668 (14)	−0.00782 (13)
S1	0.02276 (18)	0.01321 (17)	0.02450 (18)	−0.00194 (11)	0.01337 (13)	−0.00236 (11)
O1	0.0228 (5)	0.0133 (4)	0.0215 (5)	0.0022 (3)	0.0088 (4)	0.0002 (3)
N1	0.0363 (7)	0.0112 (5)	0.0437 (8)	−0.0024 (5)	0.0288 (6)	−0.0028 (5)
N2	0.0209 (5)	0.0099 (5)	0.0195 (5)	0.0005 (4)	0.0093 (4)	0.0002 (4)
N3	0.0180 (5)	0.0136 (5)	0.0171 (5)	0.0003 (4)	0.0067 (4)	0.0007 (4)
N4	0.0199 (5)	0.0094 (5)	0.0216 (5)	0.0005 (4)	0.0066 (4)	0.0016 (4)
C1	0.0183 (6)	0.0117 (6)	0.0196 (6)	−0.0004 (4)	0.0051 (5)	0.0006 (4)
C2	0.0169 (5)	0.0117 (5)	0.0163 (5)	0.0010 (4)	0.0040 (4)	0.0002 (4)
C3	0.0168 (5)	0.0127 (6)	0.0165 (5)	−0.0006 (4)	0.0044 (4)	0.0016 (4)
C4	0.0191 (6)	0.0132 (6)	0.0202 (6)	0.0003 (4)	0.0050 (5)	−0.0010 (4)
C5	0.0184 (6)	0.0194 (6)	0.0198 (6)	0.0011 (5)	0.0061 (5)	−0.0014 (5)
C6	0.0179 (6)	0.0216 (7)	0.0191 (6)	−0.0028 (5)	0.0059 (5)	0.0018 (5)
C8	0.0164 (6)	0.0132 (6)	0.0162 (6)	0.0006 (4)	0.0024 (4)	0.0007 (4)
C9	0.0190 (6)	0.0111 (5)	0.0170 (6)	0.0004 (4)	0.0035 (4)	0.0008 (4)
C7	0.0199 (6)	0.0157 (6)	0.0187 (6)	−0.0014 (5)	0.0037 (5)	0.0036 (4)

Cl1—C5	1.7417 (16)	N4—H41	0.90 (2)
S1—C1	1.6816 (17)	C2—C3	1.4561 (19)
O1—C9	1.2354 (18)	C2—C9	1.5015 (19)
N1—C1	1.3196 (18)	C3—C4	1.3863 (18)
N1—H11	0.88 (2)	C3—C8	1.4052 (19)
N1—H12	0.88 (3)	C4—C5	1.3919 (19)
N2—N3	1.3548 (17)	C4—H4	0.9500
N2—C1	1.3753 (17)	C5—C6	1.393 (2)
N2—H21	0.865 (18)	C6—C7	1.398 (2)
N3—C2	1.2886 (18)	C6—H6	0.9500
N4—C9	1.3629 (17)	C8—C7	1.3869 (19)
N4—C8	1.4108 (17)	C7—H7	0.9500
C1—N1—H11	121.0 (14)	C3—C4—C5	116.98 (13)
C1—N1—H12	115.4 (18)	C3—C4—H4	121.5
H11—N1—H12	124 (2)	C5—C4—H4	121.5
N3—N2—C1	118.47 (11)	C4—C5—C6	122.65 (12)
N3—N2—H21	121.0 (12)	C4—C5—Cl1	118.11 (11)
C1—N2—H21	120.5 (12)	C6—C5—Cl1	119.23 (11)
C2—N3—N2	118.11 (11)	C5—C6—C7	120.06 (12)
C9—N4—C8	111.12 (11)	C5—C6—H6	120.0
C9—N4—H41	123.0 (14)	C7—C6—H6	120.0
C8—N4—H41	125.2 (14)	C7—C8—C3	121.54 (12)
N1—C1—N2	115.72 (13)	C7—C8—N4	129.09 (12)
N1—C1—S1	125.31 (10)	C3—C8—N4	109.36 (11)
N2—C1—S1	118.97 (10)	O1—C9—N4	127.66 (12)
N3—C2—C3	125.26 (11)	O1—C9—C2	126.00 (11)
N3—C2—C9	128.28 (12)	N4—C9—C2	106.33 (11)
C3—C2—C9	106.41 (10)	C8—C7—C6	117.75 (13)
C4—C3—C8	121.02 (12)	C8—C7—H7	121.1
C4—C3—C2	132.21 (12)	C6—C7—H7	121.1
C8—C3—C2	106.77 (11)
C1—N2—N3—C2	176.25 (12)	C4—C3—C8—C7	−0.62 (19)
N3—N2—C1—N1	1.08 (19)	C2—C3—C8—C7	178.86 (11)
N3—N2—C1—S1	180.00 (9)	C4—C3—C8—N4	−179.71 (11)
N2—N3—C2—C3	−179.99 (11)	C2—C3—C8—N4	−0.23 (14)
N2—N3—C2—C9	−3.0 (2)	C9—N4—C8—C7	−179.50 (12)
N3—C2—C3—C4	−2.3 (2)	C9—N4—C8—C3	−0.49 (15)
C9—C2—C3—C4	−179.81 (13)	C8—N4—C9—O1	−177.55 (12)
N3—C2—C3—C8	178.32 (12)	C8—N4—C9—C2	0.97 (14)
C9—C2—C3—C8	0.79 (14)	N3—C2—C9—O1	0.0 (2)
C8—C3—C4—C5	−0.01 (19)	C3—C2—C9—O1	177.47 (12)
C2—C3—C4—C5	−179.33 (13)	N3—C2—C9—N4	−178.51 (13)
C3—C4—C5—C6	0.6 (2)	C3—C2—C9—N4	−1.08 (13)
C3—C4—C5—Cl1	179.81 (9)	C3—C8—C7—C6	0.66 (19)
C4—C5—C6—C7	−0.5 (2)	N4—C8—C7—C6	179.56 (12)
Cl1—C5—C6—C7	−179.75 (10)	C5—C6—C7—C8	−0.11 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1	0.865 (18)	2.127 (18)	2.783 (2)	132.2 (15)
N4—H41···S1i	0.90 (2)	2.47 (2)	3.354 (2)	169.5 (19)
N1—H11···O1ii	0.88 (2)	1.98 (2)	2.848 (2)	169 (2)
N1—H12···N3	0.88 (3)	2.15 (3)	2.594 (2)	110 (2)
N1—H12···Cl1iii	0.88 (3)	2.62 (3)	3.342 (2)	139 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1	0.865 (18)	2.127 (18)	2.783 (2)	132.2 (15)
N4—H41⋯S1i	0.90 (2)	2.47 (2)	3.354 (2)	169.5 (19)
N1—H11⋯O1ii	0.88 (2)	1.98 (2)	2.848 (2)	169 (2)
N1—H12⋯N3	0.88 (3)	2.15 (3)	2.594 (2)	110 (2)
N1—H12⋯Cl1iii	0.88 (3)	2.62 (3)	3.342 (2)	139 (2)

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