(2Z)-N-(2-Chloro-benz-yl)-2-(2-oxo-2,3-dihydro-1H-indol-3-yl-idene)hydrazinecarbothio-amide.

In the title compound, C(16)H(13)ClN(4)OS, the isatin ring system is oriented at dihedral angles of 10.60 (7) and 72.60 (3)° with respect to the thio-semicarbazide and 2-chloro-benzyl groups, respectively. The near planarity of the isatin and thio-semicarbazide groups [r.m.s. deviations of 0.0420 and 0.0163 Å, respectively] is reinforced by intra-molecular N-H⋯O and N-H⋯N hydrogen bonds, which generate S(6) and S(5) rings, respectively. In the crystal, inversion dimers linked by pairs of N-H⋯O hydrogen bonds generate R(2) (2)(8) loops. Aromatic π-π stacking inter-actions between the centroids of heterocyclic five-membered and benzene rings [distance = 3.6866 (11) Å] are also observed.

Related literature

For biochemical background to isatins, see: Pervez et al. (2012 ▶). For a related structure, see: Ramzan et al. (2010 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C16H13ClN4OS

M = 344.81

Monoclinic,

a = 13.7017 (10) Å

b = 14.1585 (10) Å

c = 8.2698 (5) Å

β = 93.151 (3)°

V = 1601.88 (19) Å3

Z = 4

Mo Kα radiation

μ = 0.38 mm−1

T = 296 K

0.32 × 0.23 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.888, T max = 0.929

14957 measured reflections

3935 independent reflections

2541 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.105

S = 1.02

3935 reflections

208 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.29 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: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812035076/hb6928sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035076/hb6928Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812035076/hb6928Isup3.cml

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

C16H13ClN4OS	F(000) = 712
Mr = 344.81	Dx = 1.430 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2075 reflections
a = 13.7017 (10) Å	θ = 1.5–28.4°
b = 14.1585 (10) Å	µ = 0.38 mm−1
c = 8.2698 (5) Å	T = 296 K
β = 93.151 (3)°	Prism, orange
V = 1601.88 (19) Å3	0.32 × 0.23 × 0.20 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	3935 independent reflections
Radiation source: fine-focus sealed tube	2541 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 7.50 pixels mm-1	θmax = 28.4°, θmin = 1.5°
ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −13→18
Tmin = 0.888, Tmax = 0.929	l = −8→11
14957 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0415P)2 + 0.3273P] where P = (Fo2 + 2Fc2)/3
3935 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.34601 (5)	−0.04349 (4)	0.12764 (8)	0.0798 (3)
S1	0.30114 (4)	0.37338 (4)	−0.01319 (6)	0.0502 (2)
O1	0.07991 (10)	0.44729 (9)	0.35390 (16)	0.0505 (5)
N1	−0.05032 (11)	0.37716 (11)	0.47406 (17)	0.0434 (5)
N2	0.11200 (10)	0.24682 (10)	0.24169 (15)	0.0336 (4)
N3	0.17023 (10)	0.31195 (10)	0.17804 (16)	0.0363 (5)
N4	0.26056 (11)	0.19523 (11)	0.06682 (17)	0.0402 (5)
C1	−0.02814 (12)	0.22197 (12)	0.40963 (19)	0.0352 (5)
C2	−0.04817 (15)	0.12656 (14)	0.4110 (2)	0.0488 (7)
C3	−0.12841 (17)	0.09610 (16)	0.4929 (3)	0.0615 (8)
C4	−0.18653 (16)	0.16013 (18)	0.5692 (3)	0.0628 (8)
C5	−0.16717 (15)	0.25630 (16)	0.5693 (2)	0.0517 (7)
C6	−0.08666 (13)	0.28509 (13)	0.48984 (19)	0.0382 (6)
C7	0.02986 (13)	0.37795 (13)	0.3854 (2)	0.0380 (6)
C8	0.04609 (12)	0.27811 (12)	0.33533 (18)	0.0329 (5)
C9	0.24367 (12)	0.28702 (12)	0.07912 (19)	0.0351 (5)
C10	0.34135 (14)	0.15508 (15)	−0.0198 (2)	0.0469 (7)
C11	0.42635 (14)	0.12971 (14)	0.0949 (2)	0.0424 (6)
C12	0.43573 (15)	0.04174 (14)	0.1681 (2)	0.0493 (7)
C13	0.51332 (19)	0.01890 (19)	0.2740 (3)	0.0655 (9)
C14	0.5822 (2)	0.0854 (2)	0.3117 (3)	0.0775 (10)
C15	0.57512 (18)	0.1745 (2)	0.2452 (3)	0.0716 (10)
C16	0.49822 (16)	0.19569 (16)	0.1363 (3)	0.0563 (8)
H1	−0.07566	0.42658	0.51532	0.0520*
H2	−0.00915	0.08379	0.35873	0.0585*
H3	−0.14309	0.03203	0.49624	0.0737*
H3A	0.16137	0.37063	0.19967	0.0436*
H4	−0.24022	0.13810	0.62202	0.0754*
H4A	0.22182	0.15693	0.11237	0.0482*
H5	−0.20661	0.29916	0.62051	0.0620*
H10A	0.36248	0.20052	−0.09843	0.0563*
H10B	0.31882	0.09901	−0.07802	0.0563*
H13	0.51841	−0.04121	0.31903	0.0786*
H14	0.63470	0.07069	0.38322	0.0930*
H15	0.62188	0.22004	0.27339	0.0861*
H16	0.49455	0.25549	0.08983	0.0676*

	U11	U22	U33	U12	U13	U23
Cl1	0.0945 (5)	0.0626 (4)	0.0842 (4)	−0.0105 (3)	0.0230 (4)	0.0024 (3)
S1	0.0545 (3)	0.0484 (3)	0.0491 (3)	−0.0073 (3)	0.0144 (2)	0.0011 (2)
O1	0.0604 (9)	0.0332 (7)	0.0602 (8)	−0.0045 (7)	0.0230 (7)	−0.0027 (6)
N1	0.0451 (10)	0.0386 (9)	0.0477 (9)	0.0048 (7)	0.0148 (7)	−0.0051 (7)
N2	0.0338 (8)	0.0342 (8)	0.0326 (7)	0.0000 (7)	−0.0002 (6)	−0.0001 (6)
N3	0.0378 (9)	0.0321 (8)	0.0396 (8)	0.0006 (7)	0.0073 (7)	−0.0032 (6)
N4	0.0364 (9)	0.0423 (9)	0.0424 (8)	0.0042 (7)	0.0080 (7)	0.0018 (7)
C1	0.0363 (10)	0.0384 (10)	0.0304 (8)	−0.0040 (8)	−0.0014 (7)	−0.0002 (7)
C2	0.0574 (13)	0.0422 (11)	0.0466 (11)	−0.0061 (10)	0.0023 (9)	−0.0018 (9)
C3	0.0712 (16)	0.0534 (13)	0.0598 (13)	−0.0266 (12)	0.0038 (12)	0.0019 (11)
C4	0.0571 (14)	0.0799 (17)	0.0526 (12)	−0.0262 (13)	0.0135 (11)	0.0042 (12)
C5	0.0434 (12)	0.0663 (14)	0.0460 (11)	−0.0069 (11)	0.0091 (9)	−0.0059 (10)
C6	0.0381 (11)	0.0440 (10)	0.0323 (9)	−0.0036 (9)	0.0007 (8)	−0.0011 (8)
C7	0.0415 (11)	0.0363 (10)	0.0366 (9)	0.0018 (9)	0.0057 (8)	−0.0005 (7)
C8	0.0350 (10)	0.0340 (9)	0.0295 (8)	0.0011 (8)	−0.0010 (7)	−0.0008 (7)
C9	0.0343 (10)	0.0420 (10)	0.0287 (8)	0.0015 (8)	−0.0015 (7)	−0.0040 (7)
C10	0.0504 (12)	0.0531 (12)	0.0376 (10)	0.0165 (10)	0.0065 (9)	−0.0019 (9)
C11	0.0421 (12)	0.0499 (11)	0.0364 (9)	0.0132 (10)	0.0121 (8)	−0.0004 (8)
C12	0.0519 (13)	0.0535 (12)	0.0439 (11)	0.0106 (10)	0.0159 (10)	−0.0010 (9)
C13	0.0745 (17)	0.0705 (16)	0.0519 (13)	0.0304 (15)	0.0065 (12)	0.0110 (11)
C14	0.0614 (17)	0.103 (2)	0.0668 (16)	0.0278 (17)	−0.0094 (13)	−0.0021 (15)
C15	0.0481 (14)	0.090 (2)	0.0766 (16)	0.0000 (14)	0.0015 (12)	−0.0178 (15)
C16	0.0509 (14)	0.0575 (14)	0.0615 (13)	0.0094 (12)	0.0111 (11)	0.0021 (10)

Cl1—C12	1.742 (2)	C5—C6	1.376 (3)
S1—C9	1.6625 (18)	C7—C8	1.493 (2)
O1—C7	1.234 (2)	C10—C11	1.505 (3)
N1—C6	1.404 (2)	C11—C16	1.387 (3)
N1—C7	1.354 (2)	C11—C12	1.388 (3)
N2—N3	1.345 (2)	C12—C13	1.378 (3)
N2—C8	1.299 (2)	C13—C14	1.357 (4)
N3—C9	1.377 (2)	C14—C15	1.378 (4)
N4—C9	1.325 (2)	C15—C16	1.381 (3)
N4—C10	1.466 (2)	C2—H2	0.9300
N1—H1	0.8600	C3—H3	0.9300
N3—H3A	0.8600	C4—H4	0.9300
N4—H4A	0.8600	C5—H5	0.9300
C1—C8	1.453 (2)	C10—H10A	0.9700
C1—C2	1.379 (3)	C10—H10B	0.9700
C1—C6	1.393 (2)	C13—H13	0.9300
C2—C3	1.391 (3)	C14—H14	0.9300
C3—C4	1.382 (3)	C15—H15	0.9300
C4—C5	1.387 (3)	C16—H16	0.9300
C6—N1—C7	111.13 (15)	C10—C11—C16	120.63 (18)
N3—N2—C8	116.49 (14)	C10—C11—C12	122.63 (18)
N2—N3—C9	121.67 (14)	C11—C12—C13	122.5 (2)
C9—N4—C10	123.90 (15)	Cl1—C12—C11	119.38 (15)
C7—N1—H1	124.00	Cl1—C12—C13	118.11 (17)
C6—N1—H1	124.00	C12—C13—C14	119.1 (2)
C9—N3—H3A	119.00	C13—C14—C15	120.7 (2)
N2—N3—H3A	119.00	C14—C15—C16	119.6 (2)
C9—N4—H4A	118.00	C11—C16—C15	121.4 (2)
C10—N4—H4A	118.00	C1—C2—H2	121.00
C2—C1—C6	120.31 (16)	C3—C2—H2	121.00
C2—C1—C8	133.12 (16)	C2—C3—H3	120.00
C6—C1—C8	106.56 (15)	C4—C3—H3	120.00
C1—C2—C3	118.08 (18)	C3—C4—H4	119.00
C2—C3—C4	120.6 (2)	C5—C4—H4	119.00
C3—C4—C5	122.0 (2)	C4—C5—H5	122.00
C4—C5—C6	116.66 (19)	C6—C5—H5	122.00
N1—C6—C1	109.58 (15)	N4—C10—H10A	109.00
N1—C6—C5	128.09 (17)	N4—C10—H10B	109.00
C1—C6—C5	122.33 (18)	C11—C10—H10A	109.00
O1—C7—N1	126.73 (17)	C11—C10—H10B	109.00
O1—C7—C8	127.01 (16)	H10A—C10—H10B	108.00
N1—C7—C8	106.26 (15)	C12—C13—H13	120.00
N2—C8—C7	127.38 (15)	C14—C13—H13	120.00
N2—C8—C1	126.22 (16)	C13—C14—H14	120.00
C1—C8—C7	106.39 (14)	C15—C14—H14	120.00
S1—C9—N3	117.66 (13)	C14—C15—H15	120.00
S1—C9—N4	126.66 (13)	C16—C15—H15	120.00
N3—C9—N4	115.68 (15)	C11—C16—H16	119.00
N4—C10—C11	111.33 (14)	C15—C16—H16	119.00
C12—C11—C16	116.71 (18)
C7—N1—C6—C1	0.42 (19)	C1—C2—C3—C4	0.6 (3)
C7—N1—C6—C5	−179.26 (17)	C2—C3—C4—C5	−0.8 (4)
C6—N1—C7—O1	−177.87 (17)	C3—C4—C5—C6	−0.2 (3)
C6—N1—C7—C8	1.46 (18)	C4—C5—C6—N1	−178.93 (18)
C8—N2—N3—C9	178.97 (14)	C4—C5—C6—C1	1.4 (3)
N3—N2—C8—C1	176.21 (14)	O1—C7—C8—N2	−4.5 (3)
N3—N2—C8—C7	−2.4 (2)	O1—C7—C8—C1	176.61 (17)
N2—N3—C9—S1	171.76 (11)	N1—C7—C8—N2	176.14 (16)
N2—N3—C9—N4	−7.8 (2)	N1—C7—C8—C1	−2.73 (18)
C10—N4—C9—S1	6.5 (2)	N4—C10—C11—C12	89.5 (2)
C10—N4—C9—N3	−174.00 (14)	N4—C10—C11—C16	−88.4 (2)
C9—N4—C10—C11	98.6 (2)	C10—C11—C12—Cl1	−0.3 (2)
C6—C1—C2—C3	0.6 (3)	C10—C11—C12—C13	−179.54 (19)
C8—C1—C2—C3	−178.34 (19)	C16—C11—C12—Cl1	177.75 (15)
C2—C1—C6—N1	178.63 (15)	C16—C11—C12—C13	−1.5 (3)
C2—C1—C6—C5	−1.7 (3)	C10—C11—C16—C15	178.0 (2)
C8—C1—C6—N1	−2.16 (18)	C12—C11—C16—C15	−0.1 (3)
C8—C1—C6—C5	177.54 (16)	Cl1—C12—C13—C14	−177.65 (19)
C2—C1—C8—N2	3.1 (3)	C11—C12—C13—C14	1.7 (3)
C2—C1—C8—C7	−177.98 (18)	C12—C13—C14—C15	−0.1 (4)
C6—C1—C8—N2	−175.93 (15)	C13—C14—C15—C16	−1.4 (4)
C6—C1—C8—C7	2.96 (17)	C14—C15—C16—C11	1.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.86	2.05	2.7416 (19)	137
N4—H4A···N2	0.86	2.28	2.663 (2)	107
N1—H1···O1i	0.86	2.09	2.903 (2)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1	0.86	2.05	2.7416 (19)	137
N4—H4A⋯N2	0.86	2.28	2.663 (2)	107
N1—H1⋯O1i	0.86	2.09	2.903 (2)	157

Symmetry code: (i) .