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

In the title compound, C(15)H(11)ClN(4)OS, the dihedral angle between the nine-membered 5-chloro-indolin-2-one ring system and the benzene ring is 10.00 (6)°. Intra-molecular cyclic N-H⋯O and C-H⋯S hydrogen-bonding inter-actions [graph set S(6)] are present in the N-N-C-N chain between the ring systems. In the crystal, mol-ecules form centrosymmetric cyclic dimers through inter-molecular N-H⋯O hydrogen bonds [graph-set R(2) (2)(8)] and are extended by C-H⋯Cl inter-actions into infinite chains which propagate along [100].

Related literature

For related structures, see: Ferrari et al. (2002 ▶); Pervez et al. (2010 ▶); Ramzan et al. (2010 ▶). 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 n class="Chemical">isatin and its derivatives, see: Vine et al. (2009 ▶). For bond-length data, see; Allen et al. (1987 ▶). For graph-set analysis, see Bernstein et al. (1995 ▶).

Experimental

Crystal data

C15H11ClN4OS

M = 330.79

Monoclinic,

a = 5.7117 (2) Å

b = 17.9510 (7) Å

c = 14.2455 (5) Å

β = 91.262 (2)°

V = 1460.25 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.41 mm−1

T = 100 K

0.53 × 0.16 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.812, T max = 0.950

15819 measured reflections

4183 independent reflections

3424 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.101

S = 1.04

4183 reflections

211 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAIn class="Chemical">NT; 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/S1600536811044199/zs2150sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044199/zs2150Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811044199/zs2150Isup3.cml

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

C15H11ClN4OS	F(000) = 680
Mr = 330.79	Dx = 1.505 Mg m−3
Monoclinic, P21/c	Melting point = 521.3–521.9 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 5.7117 (2) Å	Cell parameters from 6388 reflections
b = 17.9510 (7) Å	θ = 2.3–29.8°
c = 14.2455 (5) Å	µ = 0.41 mm−1
β = 91.262 (2)°	T = 100 K
V = 1460.25 (9) Å3	Block, orange
Z = 4	0.53 × 0.16 × 0.13 mm

Bruker APEXII CCD diffractometer	4183 independent reflections
Radiation source: fine-focus sealed tube	3424 reflections with I > 2σ(I)
graphite	Rint = 0.044
φ and ω scans	θmax = 29.9°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→7
Tmin = 0.812, Tmax = 0.950	k = −16→25
15819 measured reflections	l = −19→19

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0482P)2 + 0.4941P] where P = (Fo2 + 2Fc2)/3
4183 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.23 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
S1	0.08445 (7)	0.29509 (2)	0.51315 (3)	0.02175 (10)
Cl1	0.74643 (8)	0.58625 (3)	1.01336 (3)	0.03431 (13)
O1	0.71079 (18)	0.45044 (6)	0.51237 (8)	0.0202 (2)
N1	0.9178 (2)	0.52737 (7)	0.61568 (10)	0.0192 (3)
N2	0.3993 (2)	0.43359 (7)	0.68077 (9)	0.0169 (2)
N3	0.3263 (2)	0.39602 (7)	0.60374 (9)	0.0176 (2)
N4	0.0298 (2)	0.34863 (7)	0.69041 (9)	0.0162 (2)
C1	0.7024 (2)	0.51529 (8)	0.74926 (11)	0.0175 (3)
C2	0.6515 (3)	0.52627 (8)	0.84293 (11)	0.0202 (3)
H2A	0.5189	0.5055	0.8692	0.024*
C3	0.8066 (3)	0.56950 (9)	0.89592 (11)	0.0213 (3)
C4	1.0055 (3)	0.60157 (9)	0.85810 (12)	0.0226 (3)
H4A	1.1051	0.6301	0.8960	0.027*
C5	1.0559 (3)	0.59112 (9)	0.76381 (12)	0.0218 (3)
H5A	1.1876	0.6125	0.7376	0.026*
C6	0.9031 (2)	0.54775 (8)	0.71060 (11)	0.0177 (3)
C7	0.7407 (2)	0.48082 (8)	0.58967 (11)	0.0176 (3)
C8	0.5894 (2)	0.47276 (8)	0.67398 (10)	0.0164 (3)
C9	0.1396 (2)	0.34679 (8)	0.60775 (10)	0.0163 (3)
C10	−0.1615 (2)	0.30657 (8)	0.72387 (10)	0.0158 (3)
C11	−0.3209 (2)	0.26888 (8)	0.66549 (11)	0.0175 (3)
H11A	−0.3036	0.2690	0.6007	0.021*
C12	−0.5073 (3)	0.23099 (8)	0.70597 (12)	0.0205 (3)
H12A	−0.6127	0.2050	0.6675	0.025*
C13	−0.5381 (3)	0.23133 (9)	0.80179 (12)	0.0227 (3)
H13A	−0.6635	0.2061	0.8277	0.027*
C14	−0.3798 (3)	0.26976 (10)	0.85915 (12)	0.0248 (3)
H14A	−0.4001	0.2707	0.9237	0.030*
C15	−0.1915 (3)	0.30674 (9)	0.82049 (11)	0.0212 (3)
H15A	−0.0849	0.3318	0.8594	0.025*
H1N1	1.030 (4)	0.5395 (14)	0.5766 (17)	0.049 (7)*
H1N3	0.406 (4)	0.3978 (11)	0.5537 (15)	0.029 (5)*
H1N4	0.095 (3)	0.3761 (11)	0.7308 (14)	0.026 (5)*

	U11	U22	U33	U12	U13	U23
S1	0.02155 (19)	0.0258 (2)	0.01799 (19)	−0.00283 (14)	0.00246 (14)	−0.00359 (14)
Cl1	0.0431 (3)	0.0386 (3)	0.0214 (2)	−0.01947 (19)	0.00487 (17)	−0.00397 (16)
O1	0.0156 (5)	0.0242 (5)	0.0208 (5)	0.0009 (4)	0.0028 (4)	0.0007 (4)
N1	0.0136 (6)	0.0218 (6)	0.0225 (7)	−0.0018 (5)	0.0038 (5)	0.0018 (5)
N2	0.0141 (5)	0.0175 (6)	0.0192 (6)	0.0004 (4)	0.0003 (5)	0.0011 (5)
N3	0.0148 (6)	0.0202 (6)	0.0178 (6)	−0.0015 (4)	0.0032 (5)	0.0001 (5)
N4	0.0140 (5)	0.0193 (6)	0.0154 (6)	−0.0035 (4)	0.0003 (4)	−0.0013 (5)
C1	0.0140 (6)	0.0153 (6)	0.0233 (8)	−0.0001 (5)	0.0017 (5)	0.0022 (5)
C2	0.0174 (7)	0.0198 (7)	0.0235 (8)	−0.0035 (5)	0.0021 (6)	0.0023 (6)
C3	0.0231 (7)	0.0199 (7)	0.0209 (7)	−0.0022 (6)	0.0007 (6)	0.0009 (6)
C4	0.0200 (7)	0.0200 (7)	0.0277 (8)	−0.0032 (5)	−0.0023 (6)	0.0022 (6)
C5	0.0144 (6)	0.0222 (7)	0.0288 (8)	−0.0025 (5)	0.0025 (6)	0.0016 (6)
C6	0.0136 (6)	0.0166 (6)	0.0231 (7)	0.0017 (5)	0.0033 (5)	0.0026 (5)
C7	0.0126 (6)	0.0182 (7)	0.0221 (7)	0.0028 (5)	0.0027 (5)	0.0046 (5)
C8	0.0127 (6)	0.0179 (7)	0.0188 (7)	0.0010 (5)	0.0018 (5)	0.0026 (5)
C9	0.0132 (6)	0.0174 (6)	0.0183 (7)	0.0014 (5)	−0.0007 (5)	0.0023 (5)
C10	0.0118 (6)	0.0165 (6)	0.0192 (7)	0.0003 (5)	0.0002 (5)	0.0017 (5)
C11	0.0136 (6)	0.0188 (7)	0.0200 (7)	0.0008 (5)	−0.0017 (5)	−0.0002 (5)
C12	0.0136 (6)	0.0180 (7)	0.0298 (8)	−0.0002 (5)	−0.0025 (6)	0.0007 (6)
C13	0.0143 (6)	0.0245 (8)	0.0295 (9)	−0.0013 (5)	0.0026 (6)	0.0059 (6)
C14	0.0187 (7)	0.0364 (9)	0.0192 (8)	−0.0017 (6)	0.0023 (6)	0.0058 (7)
C15	0.0154 (7)	0.0301 (8)	0.0182 (7)	−0.0038 (6)	−0.0011 (5)	0.0005 (6)

S1—C9	1.6606 (15)	C3—C4	1.392 (2)
Cl1—C3	1.7416 (17)	C4—C5	1.393 (2)
O1—C7	1.2374 (18)	C4—H4A	0.9300
N1—C7	1.3573 (19)	C5—C6	1.383 (2)
N1—C6	1.405 (2)	C5—H5A	0.9300
N1—H1N1	0.88 (3)	C7—C8	1.502 (2)
N2—C8	1.2992 (18)	C10—C15	1.391 (2)
N2—N3	1.3462 (18)	C10—C11	1.395 (2)
N3—C9	1.3872 (18)	C11—C12	1.398 (2)
N3—H1N3	0.85 (2)	C11—H11A	0.9300
N4—C9	1.3467 (19)	C12—C13	1.380 (2)
N4—C10	1.4190 (18)	C12—H12A	0.9300
N4—H1N4	0.84 (2)	C13—C14	1.389 (2)
C1—C2	1.386 (2)	C13—H13A	0.9300
C1—C6	1.409 (2)	C14—C15	1.388 (2)
C1—C8	1.456 (2)	C14—H14A	0.9300
C2—C3	1.389 (2)	C15—H15A	0.9300
C2—H2A	0.9300
C7—N1—C6	111.28 (13)	O1—C7—N1	126.99 (14)
C7—N1—H1N1	121.6 (16)	O1—C7—C8	126.77 (13)
C6—N1—H1N1	127.0 (16)	N1—C7—C8	106.23 (13)
C8—N2—N3	117.04 (13)	N2—C8—C1	125.93 (14)
N2—N3—C9	120.67 (13)	N2—C8—C7	127.47 (14)
N2—N3—H1N3	120.1 (14)	C1—C8—C7	106.56 (12)
C9—N3—H1N3	118.8 (14)	N4—C9—N3	113.18 (13)
C9—N4—C10	131.11 (13)	N4—C9—S1	129.76 (11)
C9—N4—H1N4	113.9 (14)	N3—C9—S1	117.06 (11)
C10—N4—H1N4	114.6 (14)	C15—C10—C11	119.87 (13)
C2—C1—C6	120.49 (14)	C15—C10—N4	116.35 (13)
C2—C1—C8	133.22 (13)	C11—C10—N4	123.73 (13)
C6—C1—C8	106.28 (13)	C10—C11—C12	118.89 (14)
C1—C2—C3	117.25 (14)	C10—C11—H11A	120.6
C1—C2—H2A	121.4	C12—C11—H11A	120.6
C3—C2—H2A	121.4	C13—C12—C11	121.37 (14)
C2—C3—C4	122.48 (15)	C13—C12—H12A	119.3
C2—C3—Cl1	118.78 (12)	C11—C12—H12A	119.3
C4—C3—Cl1	118.71 (12)	C12—C13—C14	119.25 (14)
C3—C4—C5	120.36 (15)	C12—C13—H13A	120.4
C3—C4—H4A	119.8	C14—C13—H13A	120.4
C5—C4—H4A	119.8	C15—C14—C13	120.28 (15)
C6—C5—C4	117.56 (14)	C15—C14—H14A	119.9
C6—C5—H5A	121.2	C13—C14—H14A	119.9
C4—C5—H5A	121.2	C14—C15—C10	120.34 (14)
C5—C6—N1	128.57 (14)	C14—C15—H15A	119.8
C5—C6—C1	121.85 (15)	C10—C15—H15A	119.8
N1—C6—C1	109.57 (13)
C8—N2—N3—C9	173.15 (13)	C6—C1—C8—N2	179.26 (14)
C6—C1—C2—C3	−0.6 (2)	C2—C1—C8—C7	−177.07 (15)
C8—C1—C2—C3	177.83 (15)	C6—C1—C8—C7	1.51 (15)
C1—C2—C3—C4	0.5 (2)	O1—C7—C8—N2	−1.1 (2)
C1—C2—C3—Cl1	178.76 (11)	N1—C7—C8—N2	179.62 (14)
C2—C3—C4—C5	0.1 (2)	O1—C7—C8—C1	176.64 (14)
Cl1—C3—C4—C5	−178.24 (12)	N1—C7—C8—C1	−2.68 (15)
C3—C4—C5—C6	−0.4 (2)	C10—N4—C9—N3	−178.02 (13)
C4—C5—C6—N1	−178.16 (14)	C10—N4—C9—S1	1.7 (2)
C4—C5—C6—C1	0.3 (2)	N2—N3—C9—N4	7.47 (19)
C7—N1—C6—C5	176.63 (15)	N2—N3—C9—S1	−172.31 (10)
C7—N1—C6—C1	−1.99 (16)	C9—N4—C10—C15	162.39 (15)
C2—C1—C6—C5	0.2 (2)	C9—N4—C10—C11	−20.3 (2)
C8—C1—C6—C5	−178.57 (13)	C15—C10—C11—C12	−0.8 (2)
C2—C1—C6—N1	178.95 (13)	N4—C10—C11—C12	−178.04 (13)
C8—C1—C6—N1	0.15 (15)	C10—C11—C12—C13	1.1 (2)
C6—N1—C7—O1	−176.46 (14)	C11—C12—C13—C14	−0.4 (2)
C6—N1—C7—C8	2.86 (16)	C12—C13—C14—C15	−0.6 (2)
N3—N2—C8—C1	−177.80 (13)	C13—C14—C15—C10	0.9 (2)
N3—N2—C8—C7	−0.5 (2)	C11—C10—C15—C14	−0.2 (2)
C2—C1—C8—N2	0.7 (3)	N4—C10—C15—C14	177.23 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1i	0.89 (2)	1.98 (2)	2.8560 (17)	171 (2)
N3—H1N3···O1	0.86 (2)	2.08 (2)	2.7563 (16)	135.9 (19)
N4—H1N4···N2	0.84 (2)	2.156 (18)	2.6099 (17)	113.8 (16)
C2—H2A···Cl1ii	0.93	2.81	3.6935 (17)	158
C11—H11A···S1	0.93	2.61	3.2423 (14)	126

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1i	0.89 (2)	1.98 (2)	2.8560 (17)	171 (2)
N3—H1N3⋯O1	0.86 (2)	2.08 (2)	2.7563 (16)	135.9 (19)
C2—H2A⋯Cl1ii	0.93	2.81	3.6935 (17)	158
C11—H11A⋯S1	0.93	2.61	3.2423 (14)	126

Symmetry codes: (i) ; (ii) .