(Z)-2-(5-Chloro-2-oxoindolin-3-yl-idene)-N-methyl-hydrazinecarbothio-amide.

In the title compound, C(10)H(9)ClN(4)OS, an intra-molecular N-H⋯O hydrogen-bonding inter-action and an N-H⋯N inter-action generate ring motifs [graph sets S(6) and S(5), respectively]. In the crystal, mol-ecules form a chain through N-H⋯O hydrogen bonds, and these are extended by N-H⋯S hydrogen-bonding inter-actions into an infinite three-dimensional network. The crystal structure also exhibits weak C-H⋯π inter-actions.

Related literature

For related structures, see: Qasem Ali et al. (2012 ▶, 2011a ▶,b ▶); Ali et al. (2012 ▶). For various biological activities of Schiff bases, see: Bhandari et al. (2008 ▶); Bhardwaj et al. (2010 ▶); Pandeya et al. (1999 ▶); Sridhar et al. (2002 ▶); Suryavanshi & Pai (2006 ▶). For cytotoxic and anti­cancer activities of isatin and its derivatives, see: Vine et al. (2009 ▶). For graph-set analysis, see Bernstein et al. (1995 ▶).

Experimental

Crystal data

C10H9ClN4OS

M = 268.72

Orthorhombic,

a = 6.2558 (1) Å

b = 10.1449 (1) Å

c = 18.5682 (2) Å

V = 1178.42 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.49 mm−1

T = 100 K

0.34 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.853, T max = 0.961

16807 measured reflections

4886 independent reflections

4072 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.078

S = 1.05

4886 reflections

167 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.32 e Å−3

Absolute structure: Flack (1983 ▶), 2074 Friedel pairs

Flack parameter: 0.01 (5)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812007386/zs2177sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007386/zs2177Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812007386/zs2177Isup3.cml

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

C10H9ClN4OS	Dx = 1.515 Mg m−3
Mr = 268.72	Melting point = 568.4–569.0 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5715 reflections
a = 6.2558 (1) Å	θ = 3.0–34.1°
b = 10.1449 (1) Å	µ = 0.49 mm−1
c = 18.5682 (2) Å	T = 100 K
V = 1178.42 (3) Å3	Needle, yellow
Z = 4	0.34 × 0.10 × 0.08 mm
F(000) = 552

Bruker APEXII CCD diffractometer	4886 independent reflections
Radiation source: fine-focus sealed tube	4072 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
φ and ω scans	θmax = 34.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→9
Tmin = 0.853, Tmax = 0.961	k = −16→16
16807 measured reflections	l = −29→29

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078	w = 1/[σ2(Fo2) + (0.0318P)2 + 0.1624P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
4886 reflections	Δρmax = 0.41 e Å−3
167 parameters	Δρmin = −0.32 e Å−3
0 restraints	Absolute structure: Flack (1983), 2074 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (5)

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	−0.30754 (7)	0.94253 (3)	0.877263 (19)	0.02071 (9)
S1	0.74171 (6)	0.27814 (3)	0.785567 (19)	0.01723 (8)
O1	0.15801 (18)	0.26544 (10)	0.93453 (5)	0.0176 (2)
N1	−0.1313 (2)	0.39745 (12)	0.96526 (6)	0.0154 (3)
N2	0.2697 (2)	0.50267 (11)	0.84352 (6)	0.0131 (2)
N3	0.4038 (2)	0.39983 (12)	0.83590 (6)	0.0144 (2)
N4	0.6135 (2)	0.52656 (12)	0.76196 (7)	0.0147 (2)
C1	−0.2019 (3)	0.52525 (13)	0.94808 (7)	0.0138 (3)
C2	−0.3841 (3)	0.58915 (15)	0.97154 (7)	0.0160 (3)
H2A	−0.4830	0.5474	1.0029	0.019*
C3	−0.4167 (2)	0.71814 (15)	0.94706 (7)	0.0163 (3)
H3A	−0.5411	0.7650	0.9613	0.020*
C4	−0.2680 (3)	0.77827 (13)	0.90194 (7)	0.0148 (3)
C5	−0.0871 (2)	0.71336 (14)	0.87730 (7)	0.0139 (3)
H5A	0.0114	0.7551	0.8458	0.017*
C6	−0.0562 (2)	0.58458 (14)	0.90075 (7)	0.0124 (3)
C7	0.1086 (2)	0.48782 (13)	0.88630 (7)	0.0127 (3)
C8	0.0532 (3)	0.36840 (14)	0.93058 (7)	0.0139 (3)
C9	0.5824 (2)	0.41081 (13)	0.79306 (7)	0.0127 (3)
C10	0.7903 (3)	0.55324 (15)	0.71346 (8)	0.0201 (3)
H10A	0.8041	0.6486	0.7065	0.030*
H10B	0.7634	0.5107	0.6670	0.030*
H10C	0.9228	0.5184	0.7342	0.030*
H1N4	0.516 (4)	0.588 (2)	0.7671 (10)	0.033 (6)*
H1N3	0.383 (3)	0.328 (2)	0.8590 (10)	0.032 (6)*
H1N1	−0.189 (4)	0.3462 (19)	0.9928 (11)	0.035 (6)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0223 (2)	0.01646 (14)	0.02338 (15)	0.00725 (15)	−0.00058 (16)	0.00258 (13)
S1	0.01584 (18)	0.01392 (14)	0.02193 (15)	0.00320 (15)	0.00197 (16)	−0.00174 (13)
O1	0.0214 (6)	0.0140 (4)	0.0174 (4)	0.0042 (5)	−0.0002 (4)	0.0032 (4)
N1	0.0183 (7)	0.0138 (5)	0.0141 (5)	−0.0012 (5)	0.0033 (5)	0.0017 (4)
N2	0.0134 (6)	0.0118 (4)	0.0140 (5)	0.0016 (5)	−0.0007 (5)	−0.0013 (4)
N3	0.0150 (7)	0.0122 (5)	0.0161 (5)	0.0026 (5)	0.0026 (5)	0.0008 (4)
N4	0.0129 (6)	0.0138 (5)	0.0175 (5)	0.0005 (5)	0.0018 (5)	0.0017 (4)
C1	0.0155 (7)	0.0135 (5)	0.0123 (5)	−0.0014 (5)	−0.0011 (6)	−0.0011 (4)
C2	0.0145 (7)	0.0189 (6)	0.0148 (6)	−0.0014 (6)	0.0018 (6)	−0.0014 (5)
C3	0.0130 (7)	0.0201 (6)	0.0159 (6)	0.0021 (6)	−0.0002 (6)	−0.0040 (5)
C4	0.0157 (7)	0.0142 (5)	0.0146 (5)	0.0022 (6)	−0.0034 (6)	−0.0002 (5)
C5	0.0144 (7)	0.0146 (5)	0.0128 (5)	0.0000 (6)	0.0003 (6)	0.0013 (5)
C6	0.0119 (7)	0.0145 (6)	0.0108 (5)	−0.0006 (5)	−0.0009 (5)	−0.0003 (4)
C7	0.0142 (7)	0.0109 (5)	0.0129 (6)	0.0000 (5)	−0.0013 (5)	0.0010 (4)
C8	0.0168 (7)	0.0135 (6)	0.0113 (5)	−0.0019 (6)	−0.0007 (6)	0.0010 (4)
C9	0.0115 (7)	0.0129 (5)	0.0136 (6)	0.0000 (5)	−0.0023 (5)	−0.0026 (5)
C10	0.0162 (8)	0.0229 (7)	0.0211 (6)	−0.0025 (6)	0.0021 (6)	0.0042 (6)

Cl1—C4	1.7458 (14)	C1—C6	1.402 (2)
S1—C9	1.6806 (14)	C2—C3	1.400 (2)
O1—C8	1.2354 (18)	C2—H2A	0.9500
N1—C8	1.355 (2)	C3—C4	1.392 (2)
N1—C1	1.4062 (18)	C3—H3A	0.9500
N1—H1N1	0.81 (2)	C4—C5	1.387 (2)
N2—C7	1.292 (2)	C5—C6	1.3906 (19)
N2—N3	1.3463 (17)	C5—H5A	0.9500
N3—C9	1.376 (2)	C6—C7	1.449 (2)
N3—H1N3	0.86 (2)	C7—C8	1.5044 (19)
N4—C9	1.3229 (18)	C10—H10A	0.9800
N4—C10	1.4520 (19)	C10—H10B	0.9800
N4—H1N4	0.88 (2)	C10—H10C	0.9800
C1—C2	1.382 (2)
C8—N1—C1	111.11 (12)	C4—C5—C6	117.14 (13)
C8—N1—H1N1	122.4 (16)	C4—C5—H5A	121.4
C1—N1—H1N1	126.4 (16)	C6—C5—H5A	121.4
C7—N2—N3	117.41 (11)	C5—C6—C1	120.62 (14)
N2—N3—C9	120.27 (12)	C5—C6—C7	132.66 (13)
N2—N3—H1N3	121.0 (14)	C1—C6—C7	106.73 (12)
C9—N3—H1N3	118.7 (14)	N2—C7—C6	126.15 (12)
C9—N4—C10	123.25 (13)	N2—C7—C8	127.55 (13)
C9—N4—H1N4	119.0 (14)	C6—C7—C8	106.30 (12)
C10—N4—H1N4	117.5 (14)	O1—C8—N1	127.44 (13)
C2—C1—C6	122.18 (13)	O1—C8—C7	126.25 (14)
C2—C1—N1	128.31 (14)	N1—C8—C7	106.31 (12)
C6—C1—N1	109.52 (13)	N4—C9—N3	116.33 (13)
C1—C2—C3	117.14 (14)	N4—C9—S1	125.98 (12)
C1—C2—H2A	121.4	N3—C9—S1	117.69 (10)
C3—C2—H2A	121.4	N4—C10—H10A	109.5
C4—C3—C2	120.50 (14)	N4—C10—H10B	109.5
C4—C3—H3A	119.7	H10A—C10—H10B	109.5
C2—C3—H3A	119.7	N4—C10—H10C	109.5
C5—C4—C3	122.37 (13)	H10A—C10—H10C	109.5
C5—C4—Cl1	118.82 (11)	H10B—C10—H10C	109.5
C3—C4—Cl1	118.79 (12)
C7—N2—N3—C9	−177.77 (13)	N3—N2—C7—C6	−178.53 (13)
C8—N1—C1—C2	178.80 (14)	N3—N2—C7—C8	1.2 (2)
C8—N1—C1—C6	−0.92 (16)	C5—C6—C7—N2	−2.2 (3)
C6—C1—C2—C3	−1.2 (2)	C1—C6—C7—N2	177.97 (14)
N1—C1—C2—C3	179.15 (13)	C5—C6—C7—C8	177.99 (15)
C1—C2—C3—C4	−1.0 (2)	C1—C6—C7—C8	−1.83 (15)
C2—C3—C4—C5	2.3 (2)	C1—N1—C8—O1	179.09 (15)
C2—C3—C4—Cl1	−176.16 (11)	C1—N1—C8—C7	−0.27 (16)
C3—C4—C5—C6	−1.3 (2)	N2—C7—C8—O1	2.1 (3)
Cl1—C4—C5—C6	177.14 (11)	C6—C7—C8—O1	−178.07 (14)
C4—C5—C6—C1	−0.9 (2)	N2—C7—C8—N1	−178.50 (14)
C4—C5—C6—C7	179.33 (14)	C6—C7—C8—N1	1.30 (15)
C2—C1—C6—C5	2.1 (2)	C10—N4—C9—N3	−178.06 (13)
N1—C1—C6—C5	−178.12 (13)	C10—N4—C9—S1	2.7 (2)
C2—C1—C6—C7	−178.02 (13)	N2—N3—C9—N4	1.08 (19)
N1—C1—C6—C7	1.72 (15)	N2—N3—C9—S1	−179.58 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···N2	0.88 (2)	2.27 (2)	2.6416 (18)	105.6 (15)
N4—H1N4···S1i	0.88 (2)	2.70 (2)	3.4972 (13)	152.2 (16)
N3—H1N3···O1	0.86 (2)	2.086 (19)	2.7526 (16)	134.3 (17)
N1—H1N1···O1ii	0.81 (2)	2.01 (2)	2.8161 (16)	175 (2)
C3—H3A···Cg2iii	0.95	2.59	3.38	141

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯N2	0.88 (2)	2.27 (2)	2.6416 (18)	105.6 (15)
N4—H1N4⋯S1i	0.88 (2)	2.70 (2)	3.4972 (13)	152.2 (16)
N3—H1N3⋯O1	0.86 (2)	2.086 (19)	2.7526 (16)	134.3 (17)
N1—H1N1⋯O1ii	0.81 (2)	2.01 (2)	2.8161 (16)	175 (2)
C3—H3A⋯Cg2iii	0.95	2.59	3.38	141

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