3-(2-Ethyl-2-phenyl­hydrazin-1-yl­idene)indolin-2-one

Ashiq, U.; Jamal, R.A.; Ismail, H.; Khan, K.M.; Yousuf, S.

doi:10.1107/S1600536812047988

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3473

doi:10.1107/S1600536812047988

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3-(2-Ethyl-2-phenylhydrazin-1-ylidene)indolin-2-one

Uzma Ashiq,^a ^* Rifat Ara Jamal,^a Hina Ismail,^a Khalid Mohammed Khan ^b and Sammer Yousuf ^b ^*

^aDepartment of Chemistry, University of Karachi, Karachi 75270, Pakistan, and ^bH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
^*Correspondence e-mail: uzzmma@hotmail.com, dr.sammer.yousuf@gmail.com

(Received 20 November 2012; accepted 21 November 2012; online 28 November 2012)

In the title compound, C₁₆H₁₅N₃O, the dihedral angle between the indole ring system (r.m.s. deviation = 0.020 Å) and the phenyl ring is 14.49 (9)°. The molecular conformation is supported by an intramolecular C—H⋯O interaction, which closes an S(7) ring. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R₂²(8) loops.

Related literature

For a related structure, see: Jamal et al. (2011 ). For background to Schiff bases, see: Chaluvaraju & Zaranappa (2011 ); Khan et al. (2009 ).

Experimental

Crystal data

C₁₆H₁₅N₃O
M_r = 265.31
Monoclinic, P 2₁ /c
a = 9.463 (2) Å
b = 17.303 (4) Å
c = 8.5403 (18) Å
β = 104.427 (5)°
V = 1354.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 273 K
0.35 × 0.18 × 0.06 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.971, T_max = 0.995
7875 measured reflections
2448 independent reflections
1783 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.116
S = 1.08
2448 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15A⋯O1	0.97	2.21	2.916 (2)	128
N1—H1A⋯O1ⁱ	0.86	1.99	2.844 (2)	172
Symmetry code: (i) -x+1, -y, -z-1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812047988/hb6996sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047988/hb6996Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812047988/hb6996Isup3.cml

checkCIF report

Comment top

Isatin and its Schiff bases form an important class of organic compounds with a variety of biological activities. Many studies have reported regarding the biological activities of Schiff bases, including their antifungal, antibacterial, anticancer and antiglycation (Khan et al., 2009; Chaluvaraju & Zaranappa. 2011). In order to study the biological activity of title compound, we undertook the synthesis of title compound and report its crystal structure in this paper (Fig. 1). The title compound I was found a potent DPPH radical scavenger.

The title compound, C₁₆H₁₅N₃O is an structural analogue of our previously published compound 3-amino-N'-(2-oxoindolin-3-ylidene)- benzohydrazide (Jamal et al., 2011) with the difference that the keto amine phenyl moiety is replaced by phenyl ring (C9–C14) and N3 is substituted with ethyl group (C15–C16). The phenyl and indole rings are each planar with the dihedral angle of 14.49 (9)° between them. The geometry of molecule is stabilized by an intramolecular C15—H15A···O1 hydrogen bond. In the crystal molecules are consolidated by intermolecular N1—H1A···O1 hydrogen bond (Fig. 2. symmetry codes as in Table 2).

Related literature top

For a related structure, see: Jamal et al. (2011). For background to Schiff bases, see: Chaluvaraju et al. (2011); Khan et al. (2009).

Experimental top

To a solution of 2,3-Indolinedione (10 mmol, 1.47 g) in 15 ml of ethanol with few drops of glacial acetic acid and 1-ethyl-1-phenylhydrazine (10 mmol,1.36 g) in 15 ml e thanol were added. The mixture was refluxed for 24 h and a solid was obtained upon removal of the solvent by rotary evaporation.The resulting solid was washed with hexane to afford the title compound. Yellow plates were grown from a mixture of ethanol and methanol (1:1) solvents by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at 30% probability level.
	Fig. 2. The crystal packing of the title compound. Hydrogen atoms are omitted for clearity.

3-(2-Ethyl-2-phenylhydrazin-1-ylidene)indolin-2-one top

Crystal data top

C₁₆H₁₅N₃O	F(000) = 560
M_r = 265.31	D_x = 1.301 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.463 (2) Å	Cell parameters from 1614 reflections
b = 17.303 (4) Å	θ = 2.7–28.2°
c = 8.5403 (18) Å	µ = 0.08 mm⁻¹
β = 104.427 (5)°	T = 273 K
V = 1354.3 (5) Å³	Plate, yellow
Z = 4	0.35 × 0.18 × 0.06 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2448 independent reflections
Radiation source: fine-focus sealed tube	1783 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scan	θ_max = 25.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.971, T_max = 0.995	k = −20→20
7875 measured reflections	l = −10→10

Refinement top

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0444P)² + 0.2688P] where P = (F_o² + 2F_c²)/3
2448 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₆H₁₅N₃O	V = 1354.3 (5) Å³
M_r = 265.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.463 (2) Å	µ = 0.08 mm⁻¹
b = 17.303 (4) Å	T = 273 K
c = 8.5403 (18) Å	0.35 × 0.18 × 0.06 mm
β = 104.427 (5)°

Data collection top

Bruker SMART APEX CCD diffractometer	2448 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1783 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.995	R_int = 0.032
7875 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.08	Δρ_max = 0.18 e Å⁻³
2448 reflections	Δρ_min = −0.17 e Å⁻³
181 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.65674 (17)	0.05361 (9)	−0.36767 (16)	0.0663 (5)
N1	0.52529 (18)	−0.04875 (9)	−0.31253 (18)	0.0506 (5)
H1A	0.4712	−0.0548	−0.4088	0.061*
N2	0.79812 (16)	0.02839 (8)	0.01956 (17)	0.0389 (4)
N3	0.89404 (17)	0.08210 (9)	0.00675 (17)	0.0426 (4)
C1	0.5134 (2)	−0.09387 (10)	−0.1807 (2)	0.0419 (5)
C2	0.4213 (2)	−0.15483 (11)	−0.1754 (2)	0.0508 (5)
H2B	0.3551	−0.1723	−0.2682	0.061*
C3	0.4310 (2)	−0.18901 (12)	−0.0267 (3)	0.0547 (6)
H3A	0.3707	−0.2306	−0.0194	0.066*
C4	0.5286 (2)	−0.16256 (11)	0.1112 (2)	0.0515 (5)
H4A	0.5317	−0.1859	0.2101	0.062*
C5	0.6221 (2)	−0.10171 (11)	0.1042 (2)	0.0446 (5)
H5A	0.6884	−0.0844	0.1971	0.053*
C6	0.6148 (2)	−0.06736 (10)	−0.0437 (2)	0.0392 (4)
C7	0.6978 (2)	−0.00462 (10)	−0.0925 (2)	0.0397 (5)
C8	0.6314 (2)	0.00580 (11)	−0.2721 (2)	0.0473 (5)
C9	0.9830 (2)	0.10795 (10)	0.1577 (2)	0.0408 (5)
C10	1.0982 (2)	0.15798 (12)	0.1632 (2)	0.0526 (5)
H10A	1.1160	0.1764	0.0676	0.063*
C11	1.1871 (2)	0.18077 (13)	0.3106 (3)	0.0639 (6)
H11A	1.2647	0.2141	0.3128	0.077*
C12	1.1626 (3)	0.15511 (13)	0.4522 (3)	0.0685 (7)
H12A	1.2232	0.1703	0.5507	0.082*
C13	1.0470 (3)	0.10645 (13)	0.4474 (3)	0.0661 (7)
H13A	1.0295	0.0888	0.5437	0.079*
C14	0.9564 (2)	0.08325 (11)	0.3022 (2)	0.0524 (5)
H14A	0.8775	0.0510	0.3012	0.063*
C15	0.9259 (2)	0.10639 (11)	−0.1461 (2)	0.0485 (5)
H15A	0.8863	0.0684	−0.2289	0.058*
H15B	1.0308	0.1079	−0.1319	0.058*
C16	0.8632 (2)	0.18441 (12)	−0.2025 (3)	0.0636 (6)
H16A	0.8869	0.1974	−0.3022	0.095*
H16B	0.9037	0.2226	−0.1222	0.095*
H16C	0.7592	0.1831	−0.2190	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0818 (11)	0.0690 (10)	0.0388 (8)	−0.0259 (9)	−0.0025 (7)	0.0131 (7)
N1	0.0587 (11)	0.0518 (10)	0.0347 (8)	−0.0096 (9)	−0.0008 (7)	−0.0005 (7)
N2	0.0412 (9)	0.0364 (8)	0.0376 (8)	0.0002 (7)	0.0070 (7)	0.0019 (7)
N3	0.0475 (10)	0.0431 (9)	0.0362 (8)	−0.0058 (8)	0.0084 (7)	0.0035 (7)
C1	0.0452 (11)	0.0397 (10)	0.0392 (10)	0.0032 (9)	0.0075 (8)	−0.0009 (8)
C2	0.0502 (13)	0.0467 (12)	0.0536 (12)	−0.0066 (10)	0.0091 (10)	−0.0082 (10)
C3	0.0551 (13)	0.0460 (12)	0.0640 (14)	−0.0083 (10)	0.0167 (11)	0.0001 (10)
C4	0.0528 (13)	0.0500 (12)	0.0532 (12)	0.0005 (10)	0.0158 (10)	0.0110 (10)
C5	0.0427 (11)	0.0486 (11)	0.0405 (11)	0.0037 (9)	0.0068 (8)	0.0036 (9)
C6	0.0381 (10)	0.0375 (10)	0.0406 (10)	0.0039 (8)	0.0073 (8)	0.0005 (8)
C7	0.0434 (11)	0.0384 (10)	0.0354 (9)	0.0015 (9)	0.0063 (8)	0.0015 (8)
C8	0.0552 (13)	0.0466 (11)	0.0362 (10)	−0.0032 (10)	0.0040 (9)	0.0017 (9)
C9	0.0418 (11)	0.0359 (10)	0.0422 (10)	0.0025 (9)	0.0058 (8)	−0.0015 (8)
C10	0.0495 (12)	0.0522 (12)	0.0559 (13)	−0.0055 (10)	0.0124 (10)	−0.0013 (10)
C11	0.0513 (14)	0.0584 (14)	0.0742 (16)	−0.0082 (11)	0.0010 (11)	−0.0089 (12)
C12	0.0771 (17)	0.0580 (14)	0.0557 (14)	−0.0023 (13)	−0.0113 (12)	−0.0086 (11)
C13	0.0910 (18)	0.0603 (14)	0.0404 (12)	−0.0040 (14)	0.0042 (11)	−0.0006 (10)
C14	0.0635 (14)	0.0495 (12)	0.0422 (11)	−0.0071 (11)	0.0095 (10)	−0.0004 (9)
C15	0.0481 (12)	0.0550 (12)	0.0426 (11)	−0.0001 (10)	0.0119 (9)	0.0024 (9)
C16	0.0624 (15)	0.0605 (14)	0.0656 (14)	0.0000 (12)	0.0113 (11)	0.0163 (11)

Geometric parameters (Å, º) top

O1—C8	1.227 (2)	C7—C8	1.517 (2)
N1—C8	1.359 (2)	C9—C10	1.384 (3)
N1—C1	1.398 (2)	C9—C14	1.387 (3)
N1—H1A	0.8600	C10—C11	1.386 (3)
N2—C7	1.300 (2)	C10—H10A	0.9300
N2—N3	1.323 (2)	C11—C12	1.361 (3)
N3—C9	1.425 (2)	C11—H11A	0.9300
N3—C15	1.472 (2)	C12—C13	1.373 (3)
C1—C2	1.376 (3)	C12—H12A	0.9300
C1—C6	1.393 (2)	C13—C14	1.380 (3)
C2—C3	1.383 (3)	C13—H13A	0.9300
C2—H2B	0.9300	C14—H14A	0.9300
C3—C4	1.381 (3)	C15—C16	1.504 (3)
C3—H3A	0.9300	C15—H15A	0.9700
C4—C5	1.386 (3)	C15—H15B	0.9700
C4—H4A	0.9300	C16—H16A	0.9600
C5—C6	1.382 (2)	C16—H16B	0.9600
C5—H5A	0.9300	C16—H16C	0.9600
C6—C7	1.460 (3)

C8—N1—C1	112.74 (15)	C10—C9—C14	118.60 (18)
C8—N1—H1A	123.6	C10—C9—N3	120.67 (17)
C1—N1—H1A	123.6	C14—C9—N3	120.73 (17)
C7—N2—N3	129.64 (15)	C9—C10—C11	120.3 (2)
N2—N3—C9	114.13 (14)	C9—C10—H10A	119.9
N2—N3—C15	124.76 (15)	C11—C10—H10A	119.9
C9—N3—C15	120.49 (16)	C12—C11—C10	121.0 (2)
C2—C1—C6	122.30 (17)	C12—C11—H11A	119.5
C2—C1—N1	129.31 (17)	C10—C11—H11A	119.5
C6—C1—N1	108.40 (16)	C11—C12—C13	119.0 (2)
C1—C2—C3	117.40 (18)	C11—C12—H12A	120.5
C1—C2—H2B	121.3	C13—C12—H12A	120.5
C3—C2—H2B	121.3	C12—C13—C14	121.1 (2)
C4—C3—C2	121.2 (2)	C12—C13—H13A	119.4
C4—C3—H3A	119.4	C14—C13—H13A	119.4
C2—C3—H3A	119.4	C13—C14—C9	120.0 (2)
C3—C4—C5	120.91 (19)	C13—C14—H14A	120.0
C3—C4—H4A	119.5	C9—C14—H14A	120.0
C5—C4—H4A	119.5	N3—C15—C16	112.86 (17)
C6—C5—C4	118.62 (18)	N3—C15—H15A	109.0
C6—C5—H5A	120.7	C16—C15—H15A	109.0
C4—C5—H5A	120.7	N3—C15—H15B	109.0
C5—C6—C1	119.53 (18)	C16—C15—H15B	109.0
C5—C6—C7	132.28 (16)	H15A—C15—H15B	107.8
C1—C6—C7	108.18 (15)	C15—C16—H16A	109.5
N2—C7—C6	117.53 (15)	C15—C16—H16B	109.5
N2—C7—C8	137.30 (17)	H16A—C16—H16B	109.5
C6—C7—C8	105.09 (15)	C15—C16—H16C	109.5
O1—C8—N1	123.66 (17)	H16A—C16—H16C	109.5
O1—C8—C7	130.73 (18)	H16B—C16—H16C	109.5
N1—C8—C7	105.54 (16)

C7—N2—N3—C9	176.71 (17)	C1—N1—C8—O1	−177.0 (2)
C7—N2—N3—C15	−12.3 (3)	C1—N1—C8—C7	0.2 (2)
C8—N1—C1—C2	−178.8 (2)	N2—C7—C8—O1	−1.0 (4)
C8—N1—C1—C6	1.2 (2)	C6—C7—C8—O1	175.5 (2)
C6—C1—C2—C3	0.9 (3)	N2—C7—C8—N1	−178.0 (2)
N1—C1—C2—C3	−179.08 (19)	C6—C7—C8—N1	−1.4 (2)
C1—C2—C3—C4	0.5 (3)	N2—N3—C9—C10	173.23 (16)
C2—C3—C4—C5	−1.3 (3)	C15—N3—C9—C10	1.8 (3)
C3—C4—C5—C6	0.6 (3)	N2—N3—C9—C14	−6.5 (3)
C4—C5—C6—C1	0.7 (3)	C15—N3—C9—C14	−177.88 (17)
C4—C5—C6—C7	−178.50 (19)	C14—C9—C10—C11	1.9 (3)
C2—C1—C6—C5	−1.6 (3)	N3—C9—C10—C11	−177.84 (18)
N1—C1—C6—C5	178.46 (17)	C9—C10—C11—C12	−0.5 (3)
C2—C1—C6—C7	177.86 (17)	C10—C11—C12—C13	−0.5 (4)
N1—C1—C6—C7	−2.1 (2)	C11—C12—C13—C14	0.2 (4)
N3—N2—C7—C6	174.94 (17)	C12—C13—C14—C9	1.2 (3)
N3—N2—C7—C8	−8.8 (4)	C10—C9—C14—C13	−2.2 (3)
C5—C6—C7—N2	−1.2 (3)	N3—C9—C14—C13	177.49 (18)
C1—C6—C7—N2	179.53 (16)	N2—N3—C15—C16	106.2 (2)
C5—C6—C7—C8	−178.5 (2)	C9—N3—C15—C16	−83.3 (2)
C1—C6—C7—C8	2.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···O1	0.97	2.21	2.916 (2)	128
N1—H1A···O1ⁱ	0.86	1.99	2.844 (2)	172

Symmetry code: (i) −x+1, −y, −z−1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅N₃O
M_r	265.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	9.463 (2), 17.303 (4), 8.5403 (18)
β (°)	104.427 (5)
V (Å³)	1354.3 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.18 × 0.06

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.971, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	7875, 2448, 1783
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.116, 1.08
No. of reflections	2448
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···O1	0.97	2.21	2.916 (2)	128
N1—H1A···O1ⁱ	0.86	1.99	2.844 (2)	172

Symmetry code: (i) −x+1, −y, −z−1.

Acknowledgements

The authors are thankful to the Higher Education Commission (HEC) Pakistan for financial support under the National Research Grants Program for Universities (grant No. 20–1862/R&D/10).

References

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