(Z)-2-(2-Oxoindolin-3-yl-idene)-N-phenylhydrazinecarbothio-amide.

In the title compound, C(15)H(12)N(4)OS, the dihedral angle between the nine-membered indolin-2-one ring system and the phenyl ring is 2.72 (7)°. Intra-molecular cyclic N-H⋯O and C-H⋯S hydrogen-bonding inter-actions [graph set S(6)] are present, as are weak N-H⋯N inter-actions [graph set S(5)]. In the crystal, mol-ecules form centrosymmetric cyclic dimers through pairs of N-H⋯O hydrogen bonds [graph set R(2) (2)(8)] and these are extended by C-H⋯S inter-actions. The crystal structure also features weak C-H⋯π inter-actions.

Related literature

For related crystal structures, see: Ali et al. (2012 ▶); Qasem Ali et al. (2011a ▶,b ▶); 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 the 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

C15H12N4OS

M = 296.35

Monoclinic,

a = 6.3674 (1) Å

b = 15.4594 (3) Å

c = 14.2199 (3) Å

β = 93.383 (1)°

V = 1397.31 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 100 K

0.47 × 0.13 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.897, T max = 0.971

15557 measured reflections

4159 independent reflections

2985 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.113

S = 1.02

4159 reflections

202 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.49 e Å−3

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/S160053681200400X/wn2464sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681200400X/wn2464Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681200400X/wn2464Isup3.cml

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

C15H12N4OS	F(000) = 616
Mr = 296.35	Dx = 1.409 Mg m−3
Monoclinic, P21/c	Melting point = 510.2–511.6 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.3674 (1) Å	Cell parameters from 4743 reflections
b = 15.4594 (3) Å	θ = 3.0–30.1°
c = 14.2199 (3) Å	µ = 0.24 mm−1
β = 93.383 (1)°	T = 100 K
V = 1397.31 (5) Å3	Needle, yellow
Z = 4	0.47 × 0.13 × 0.13 mm

Bruker APEXII CCD diffractometer	4159 independent reflections
Radiation source: fine-focus sealed tube	2985 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 30.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→8
Tmin = 0.897, Tmax = 0.971	k = −21→18
15557 measured reflections	l = −17→20

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.038P)2 + 0.7736P] where P = (Fo2 + 2Fc2)/3
4159 reflections	(Δ/σ)max = 0.001
202 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.49 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	0.15701 (8)	0.72368 (4)	1.06040 (3)	0.03145 (15)
O1	0.73491 (19)	0.55698 (8)	1.00760 (8)	0.0228 (3)
N1	0.9075 (2)	0.50533 (10)	0.87950 (10)	0.0208 (3)
N2	0.4169 (2)	0.61290 (9)	0.85318 (10)	0.0177 (3)
N3	0.3689 (2)	0.63773 (9)	0.94027 (10)	0.0191 (3)
N4	0.0843 (2)	0.70518 (9)	0.87089 (10)	0.0181 (3)
C1	0.8690 (3)	0.50379 (11)	0.78102 (12)	0.0195 (4)
C2	0.9950 (3)	0.47108 (12)	0.71370 (13)	0.0241 (4)
H2A	1.1264	0.4445	0.7306	0.029*
C3	0.9210 (3)	0.47880 (12)	0.61995 (13)	0.0253 (4)
H3A	1.0027	0.4560	0.5719	0.030*
C4	0.7296 (3)	0.51916 (12)	0.59478 (13)	0.0231 (4)
H4A	0.6846	0.5243	0.5301	0.028*
C5	0.6042 (3)	0.55185 (11)	0.66319 (12)	0.0206 (4)
H5A	0.4741	0.5794	0.6462	0.025*
C6	0.6740 (3)	0.54324 (11)	0.75712 (12)	0.0184 (4)
C7	0.5904 (3)	0.57114 (11)	0.84497 (12)	0.0176 (3)
C8	0.7491 (3)	0.54476 (11)	0.92218 (12)	0.0188 (4)
C9	0.1964 (3)	0.68962 (11)	0.95214 (12)	0.0185 (4)
C10	−0.1096 (3)	0.74787 (11)	0.85012 (12)	0.0168 (3)
C11	−0.1753 (3)	0.74938 (11)	0.75467 (12)	0.0190 (4)
H11A	−0.0892	0.7245	0.7095	0.023*
C12	−0.3656 (3)	0.78705 (11)	0.72568 (13)	0.0237 (4)
H12A	−0.4098	0.7878	0.6607	0.028*
C13	−0.4917 (3)	0.82369 (11)	0.79112 (13)	0.0247 (4)
H13A	−0.6228	0.8492	0.7714	0.030*
C14	−0.4248 (3)	0.82279 (11)	0.88559 (13)	0.0229 (4)
H14A	−0.5106	0.8486	0.9303	0.027*
C15	−0.2349 (3)	0.78504 (11)	0.91642 (12)	0.0196 (4)
H15A	−0.1912	0.7846	0.9815	0.024*
H1N1	1.018 (3)	0.4836 (14)	0.9106 (15)	0.037 (6)*
H1N3	0.457 (4)	0.6258 (14)	0.9879 (16)	0.039 (6)*
H1N4	0.144 (3)	0.6806 (14)	0.8234 (15)	0.029 (6)*

	U11	U22	U33	U12	U13	U23
S1	0.0267 (2)	0.0507 (3)	0.0168 (2)	0.0076 (2)	0.00014 (18)	−0.0045 (2)
O1	0.0242 (6)	0.0248 (7)	0.0189 (6)	0.0016 (5)	−0.0032 (5)	0.0026 (5)
N1	0.0191 (7)	0.0199 (8)	0.0228 (8)	0.0043 (6)	−0.0032 (6)	0.0020 (6)
N2	0.0189 (7)	0.0153 (7)	0.0187 (7)	−0.0008 (6)	0.0001 (5)	0.0008 (6)
N3	0.0184 (7)	0.0216 (8)	0.0171 (7)	0.0022 (6)	−0.0011 (6)	0.0020 (6)
N4	0.0184 (7)	0.0193 (8)	0.0166 (7)	0.0032 (6)	0.0014 (6)	0.0000 (6)
C1	0.0195 (8)	0.0131 (8)	0.0254 (9)	0.0000 (7)	−0.0025 (7)	0.0014 (7)
C2	0.0211 (9)	0.0197 (9)	0.0315 (10)	0.0045 (7)	0.0006 (8)	0.0030 (8)
C3	0.0265 (9)	0.0231 (9)	0.0268 (9)	0.0049 (8)	0.0064 (8)	0.0016 (8)
C4	0.0248 (9)	0.0220 (9)	0.0225 (9)	0.0017 (7)	0.0004 (7)	0.0018 (7)
C5	0.0187 (8)	0.0181 (9)	0.0248 (9)	0.0010 (7)	−0.0016 (7)	0.0016 (7)
C6	0.0190 (8)	0.0140 (8)	0.0220 (8)	0.0005 (7)	−0.0007 (7)	0.0009 (7)
C7	0.0183 (8)	0.0127 (8)	0.0213 (8)	−0.0015 (6)	−0.0020 (7)	0.0023 (6)
C8	0.0187 (8)	0.0120 (8)	0.0254 (9)	−0.0013 (7)	−0.0021 (7)	0.0031 (7)
C9	0.0173 (8)	0.0186 (8)	0.0195 (8)	−0.0036 (7)	0.0016 (6)	0.0035 (7)
C10	0.0164 (8)	0.0136 (8)	0.0205 (8)	−0.0016 (6)	0.0017 (6)	0.0014 (6)
C11	0.0198 (8)	0.0179 (8)	0.0194 (8)	0.0002 (7)	0.0023 (7)	0.0013 (7)
C12	0.0243 (9)	0.0204 (9)	0.0257 (9)	−0.0013 (7)	−0.0043 (7)	0.0044 (7)
C13	0.0187 (8)	0.0167 (9)	0.0383 (11)	0.0006 (7)	−0.0014 (8)	0.0044 (8)
C14	0.0201 (8)	0.0153 (8)	0.0339 (10)	0.0008 (7)	0.0066 (7)	−0.0026 (8)
C15	0.0214 (8)	0.0165 (8)	0.0211 (8)	−0.0007 (7)	0.0024 (7)	−0.0021 (7)

S1—C9	1.6600 (18)	C4—C5	1.389 (3)
O1—C8	1.238 (2)	C4—H4A	0.9500
N1—C8	1.352 (2)	C5—C6	1.389 (2)
N1—C1	1.408 (2)	C5—H5A	0.9500
N1—H1N1	0.88 (2)	C6—C7	1.452 (2)
N2—C7	1.291 (2)	C7—C8	1.504 (2)
N2—N3	1.349 (2)	C10—C15	1.394 (2)
N3—C9	1.378 (2)	C10—C11	1.397 (2)
N3—H1N3	0.87 (2)	C11—C12	1.385 (2)
N4—C9	1.343 (2)	C11—H11A	0.9500
N4—C10	1.416 (2)	C12—C13	1.386 (3)
N4—H1N4	0.88 (2)	C12—H12A	0.9500
C1—C2	1.381 (3)	C13—C14	1.385 (3)
C1—C6	1.407 (2)	C13—H13A	0.9500
C2—C3	1.393 (3)	C14—C15	1.390 (2)
C2—H2A	0.9500	C14—H14A	0.9500
C3—C4	1.397 (2)	C15—H15A	0.9500
C3—H3A	0.9500
C8—N1—C1	111.31 (14)	N2—C7—C6	125.83 (15)
C8—N1—H1N1	123.0 (14)	N2—C7—C8	127.70 (16)
C1—N1—H1N1	125.7 (14)	C6—C7—C8	106.43 (14)
C7—N2—N3	117.83 (14)	O1—C8—N1	127.51 (15)
N2—N3—C9	120.23 (14)	O1—C8—C7	126.16 (16)
N2—N3—H1N3	118.7 (15)	N1—C8—C7	106.34 (15)
C9—N3—H1N3	120.6 (15)	N4—C9—N3	112.68 (15)
C9—N4—C10	132.49 (16)	N4—C9—S1	129.71 (14)
C9—N4—H1N4	110.5 (13)	N3—C9—S1	117.61 (12)
C10—N4—H1N4	116.9 (13)	C15—C10—C11	119.98 (15)
C2—C1—C6	122.14 (16)	C15—C10—N4	125.29 (15)
C2—C1—N1	128.43 (15)	C11—C10—N4	114.71 (15)
C6—C1—N1	109.42 (15)	C12—C11—C10	120.19 (17)
C1—C2—C3	117.03 (16)	C12—C11—H11A	119.9
C1—C2—H2A	121.5	C10—C11—H11A	119.9
C3—C2—H2A	121.5	C11—C12—C13	120.24 (16)
C2—C3—C4	121.63 (18)	C11—C12—H12A	119.9
C2—C3—H3A	119.2	C13—C12—H12A	119.9
C4—C3—H3A	119.2	C14—C13—C12	119.32 (16)
C5—C4—C3	120.78 (16)	C14—C13—H13A	120.3
C5—C4—H4A	119.6	C12—C13—H13A	120.3
C3—C4—H4A	119.6	C13—C14—C15	121.48 (17)
C6—C5—C4	118.29 (16)	C13—C14—H14A	119.3
C6—C5—H5A	120.9	C15—C14—H14A	119.3
C4—C5—H5A	120.9	C14—C15—C10	118.79 (16)
C5—C6—C1	120.11 (17)	C14—C15—H15A	120.6
C5—C6—C7	133.33 (16)	C10—C15—H15A	120.6
C1—C6—C7	106.50 (14)
C7—N2—N3—C9	173.69 (15)	C1—N1—C8—O1	−179.73 (17)
C8—N1—C1—C2	178.50 (18)	C1—N1—C8—C7	0.46 (18)
C8—N1—C1—C6	−0.7 (2)	N2—C7—C8—O1	2.3 (3)
C6—C1—C2—C3	0.1 (3)	C6—C7—C8—O1	−179.84 (16)
N1—C1—C2—C3	−179.09 (17)	N2—C7—C8—N1	−177.88 (17)
C1—C2—C3—C4	1.1 (3)	C6—C7—C8—N1	−0.03 (18)
C2—C3—C4—C5	−1.1 (3)	C10—N4—C9—N3	174.00 (16)
C3—C4—C5—C6	−0.1 (3)	C10—N4—C9—S1	−6.4 (3)
C4—C5—C6—C1	1.2 (3)	N2—N3—C9—N4	4.1 (2)
C4—C5—C6—C7	177.76 (18)	N2—N3—C9—S1	−175.54 (12)
C2—C1—C6—C5	−1.3 (3)	C9—N4—C10—C15	−0.6 (3)
N1—C1—C6—C5	178.05 (15)	C9—N4—C10—C11	−179.21 (17)
C2—C1—C6—C7	−178.61 (16)	C15—C10—C11—C12	−0.6 (3)
N1—C1—C6—C7	0.69 (19)	N4—C10—C11—C12	178.11 (15)
N3—N2—C7—C6	−176.52 (15)	C10—C11—C12—C13	0.2 (3)
N3—N2—C7—C8	0.9 (3)	C11—C12—C13—C14	0.5 (3)
C5—C6—C7—N2	0.6 (3)	C12—C13—C14—C15	−0.8 (3)
C1—C6—C7—N2	177.50 (16)	C13—C14—C15—C10	0.4 (3)
C5—C6—C7—C8	−177.26 (19)	C11—C10—C15—C14	0.3 (2)
C1—C6—C7—C8	−0.40 (18)	N4—C10—C15—C14	−178.24 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1i	0.88 (2)	2.00 (2)	2.8737 (18)	173.9 (18)
N3—H1N3···O1	0.87 (2)	2.07 (2)	2.7646 (18)	136 (2)
N4—H1N4···N2	0.88 (2)	2.05 (2)	2.5781 (19)	117.4 (17)
C11—H11A···S1ii	0.95	2.83	3.6017 (19)	139
C15—H15A···S1	0.95	2.60	3.2735 (19)	128
C2—H2A···Cg3iii	0.95	2.80	3.510 (2)	132
C13—H13A···Cg2iv	0.95	2.82	3.5201 (19)	131

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 ring and Cg3 is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1i	0.88 (2)	2.00 (2)	2.8737 (18)	173.9 (18)
N3—H1N3⋯O1	0.87 (2)	2.07 (2)	2.7646 (18)	136 (2)
N4—H1N4⋯N2	0.88 (2)	2.05 (2)	2.5781 (19)	117.4 (17)
C11—H11A⋯S1ii	0.95	2.83	3.6017 (19)	139
C15—H15A⋯S1	0.95	2.60	3.2735 (19)	128
C2—H2A⋯Cg3iii	0.95	2.80	3.510 (2)	132
C13—H13A⋯Cg2iv	0.95	2.82	3.5201 (19)	131

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