(3Z)-3-Hydrazinylideneindolin-2-one

Abstract

The title mol­ecule, C₈H₇N₃O, is almost planar, with a maximum deviation of 0.0232 (2) Å from the least-squares plane. The Z conformation of the C=N double bond is stabilized by an intra­molecular N—H⋯O hydrogen bond. In the crystal, adjacent mol­ecules are linked by inter­molecular N—H⋯N and N—H⋯O hydrogen bonds, forming zigzag sheets parallel to the c axis; the sheets are further stabilized by π–π inter­actions [centroid–centroid distance = 3.7390 (10) Å].

Related literature

For the biological activity of related compounds, see: Sarangapani et al. (1994 ▶). For related structures, see: Ali et al. (2005a ▶,b ▶); Pelosi et al. (2005 ▶).

Experimental

Crystal data

• C₈H₇N₃O

• M _r = 161.17

• Orthorhombic,

• a = 4.7211 (5) Å

• b = 11.4263 (13) Å

• c = 13.3693 (15) Å

• V = 721.20 (14) ų

• Z = 4

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 273 K

• 0.50 × 0.10 × 0.09 mm

Data collection

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.950, T _max = 0.991

• 4234 measured reflections

• 811 independent reflections

• 776 reflections with I > 2σ(I)

• R _int = 0.021

Refinement

• R[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 0.079

• S = 1.08

• 811 reflections

• 121 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.12 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

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: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811035367/ng5222Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H2N3⋯O1	0.88 (2)	2.09 (2)	2.784 (2)	135 (2)
N3—H1N3⋯N2i	0.91 (2)	2.20 (3)	3.098 (2)	169 (2)
N1—H1N1⋯O1ii	0.90 (2)	1.98 (2)	2.866 (2)	168 (3)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Isatins are very important compounds due to their antifungal properties (Sarangapani & Reddy, 1994). In view of this biological significance, the crystal structure of the title compound has been determined (Fig. 1). The title compound I was found to be antifungal and phytotoxic (U. Ashiq & R.A. Jamal, unpublished results).

The title structure consists of a hydrazine group and indole ring linked by C=N bond exist in Z conformation. The molecule is essentially planar with a maximum deviation of 0.0232 (2) Å from the least-square plane. The Z conformation of the olefinic bond is get stablized by N3—H2N3···O1 intramolecular hydrogen bond (Fig. 1). The bond lengths and angles all are in normal range as in other structurally related compounds (Ali et al., 2005a,2005b; Pelosi et al., 2005)]. In the crystal structure, the molecules are linked by N3—H1N3···N2 and N1—H1N1···O1 intermolecular hydrogen bonds to form zig zag sheets running parallel to c axis. (symmetry codes as in Table 1, Fig. 2). The intermolecular interactions network is further strengthened by significant π–π interactions between pyrrole (Cg(1)= N1/C5–C8) and phenyl (Cg(2)= C1–C5/C8) rings; (Cg(1)to Cg(2) distance = 3.7390 (10) Å; -1+X,Y,Z).

Experimental

To a solution of 2,3-Indolinedione (25 mmol, 3.67 g) in 30 ml of ethanol with few drops of glacial acetic acid, hydrazine hydrate (12.5 ml, 250 mmol), was added. The mixture was refluxed for 2 h and a solid was obtained upon removal of the solvent by rotary evaporation. Crystal of the title compound suitable for X-ray crystallographic study were grown from a solution of ethanol by slow evaporation at room temperature.

Refinement

H atoms on the C of methine were positioned geomatrically with C–H= 0.93 Å, and constrained to ride on their parent atoms with U_iso(H)= 1.2U_eq(CH). The H atoms on the N atoms (N–H= 0.91 (2)–0.886 (19) Å) atoms were located in difference Fourier maps and refined isotropically. During refinement 521 Friedel pairs were merged.

Figures

Fig. 1.

The molecular structure of (I) with displacement ellipsoids drawn at 50% probability level. The dashed lines indicates the intramolecular hydrogen bonds.

Fig. 2.

The crystal packing of the title compound I. Only hydrogen atoms involved in hydrogen bonding are shown.

Crystal data

C8H7N3O	Dx = 1.484 Mg m−3
Mr = 161.17	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 2104 reflections
a = 4.7211 (5) Å	θ = 3.1–27.5°
b = 11.4263 (13) Å	µ = 0.10 mm−1
c = 13.3693 (15) Å	T = 273 K
V = 721.20 (14) Å3	Plate, colorles
Z = 4	0.50 × 0.10 × 0.09 mm
F(000) = 336

Data collection

Bruker SMART APEX CCD area-detector diffractometer	811 independent reflections
Radiation source: fine-focus sealed tube	776 reflections with I > 2σ(I)
graphite	Rint = 0.021
ω scans	θmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −5→5
Tmin = 0.950, Tmax = 0.991	k = −13→13
4234 measured reflections	l = −16→15

Refinement

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0512P)2 + 0.0832P] where P = (Fo2 + 2Fc2)/3
811 reflections	(Δ/σ)max < 0.001
121 parameters	Δρmax = 0.12 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.1159 (3)	0.11147 (11)	0.46693 (10)	0.0443 (4)
N2	0.2067 (3)	−0.13322 (13)	0.54465 (10)	0.0345 (4)
N3	0.0172 (4)	−0.12868 (16)	0.47156 (13)	0.0429 (4)
C8	0.5392 (4)	−0.02667 (15)	0.65275 (13)	0.0331 (4)
C6	0.2809 (4)	0.08289 (15)	0.53444 (14)	0.0343 (4)
C7	0.3271 (4)	−0.03705 (14)	0.57432 (13)	0.0317 (4)
N1	0.4577 (4)	0.15444 (13)	0.58597 (13)	0.0405 (4)
C1	0.6635 (5)	−0.10479 (17)	0.71866 (14)	0.0408 (5)
H1A	0.6159	−0.1837	0.7167	0.049*
C4	0.8090 (5)	0.13277 (19)	0.72546 (15)	0.0460 (5)
H4A	0.8570	0.2117	0.7277	0.055*
C2	0.8591 (5)	−0.06419 (19)	0.78751 (15)	0.0469 (5)
H2B	0.9425	−0.1160	0.8323	0.056*
C5	0.6139 (4)	0.09186 (16)	0.65757 (14)	0.0357 (5)
C3	0.9315 (5)	0.0535 (2)	0.79003 (16)	0.0491 (6)
H3A	1.0651	0.0794	0.8361	0.059*
H2N3	−0.028 (5)	−0.060 (2)	0.4466 (16)	0.048 (6)*
H1N3	−0.064 (6)	−0.199 (2)	0.4587 (17)	0.066 (8)*
H1N1	0.481 (6)	0.231 (2)	0.5712 (16)	0.060 (7)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0552 (9)	0.0305 (7)	0.0471 (7)	0.0065 (6)	−0.0067 (7)	0.0062 (6)
N2	0.0372 (8)	0.0285 (8)	0.0379 (8)	−0.0002 (7)	0.0034 (7)	0.0003 (6)
N3	0.0488 (10)	0.0313 (9)	0.0485 (9)	−0.0036 (8)	−0.0060 (9)	0.0006 (8)
C8	0.0338 (10)	0.0300 (9)	0.0356 (9)	0.0003 (9)	0.0061 (8)	0.0005 (7)
C6	0.0382 (10)	0.0273 (9)	0.0374 (9)	0.0020 (8)	0.0044 (9)	0.0014 (7)
C7	0.0342 (9)	0.0237 (8)	0.0371 (8)	0.0007 (8)	0.0047 (8)	0.0004 (7)
N1	0.0488 (10)	0.0234 (8)	0.0494 (9)	−0.0043 (7)	0.0025 (9)	0.0039 (7)
C1	0.0448 (11)	0.0346 (10)	0.0430 (10)	0.0047 (10)	0.0000 (10)	0.0022 (8)
C4	0.0437 (12)	0.0425 (11)	0.0517 (11)	−0.0096 (11)	0.0048 (10)	−0.0088 (9)
C2	0.0454 (12)	0.0545 (12)	0.0407 (10)	0.0126 (11)	−0.0036 (10)	−0.0016 (9)
C5	0.0365 (11)	0.0313 (9)	0.0393 (9)	−0.0031 (8)	0.0062 (8)	−0.0005 (7)
C3	0.0402 (12)	0.0627 (14)	0.0443 (10)	0.0001 (11)	−0.0030 (10)	−0.0113 (10)

Geometric parameters (Å, °)

O1—C6	1.236 (2)	N1—C5	1.404 (3)
N2—C7	1.299 (2)	N1—H1N1	0.90 (2)
N2—N3	1.326 (2)	C1—C2	1.384 (3)
N3—H2N3	0.88 (2)	C1—H1A	0.9300
N3—H1N3	0.91 (3)	C4—C5	1.375 (3)
C8—C1	1.385 (3)	C4—C3	1.378 (3)
C8—C5	1.401 (3)	C4—H4A	0.9300
C8—C7	1.455 (3)	C2—C3	1.388 (3)
C6—N1	1.356 (3)	C2—H2B	0.9300
C6—C7	1.487 (2)	C3—H3A	0.9300
C7—N2—N3	119.15 (15)	C2—C1—C8	119.33 (19)
N2—N3—H2N3	118.5 (15)	C2—C1—H1A	120.3
N2—N3—H1N3	112.9 (15)	C8—C1—H1A	120.3
H2N3—N3—H1N3	128 (2)	C5—C4—C3	118.1 (2)
C1—C8—C5	119.17 (19)	C5—C4—H4A	120.9
C1—C8—C7	134.24 (18)	C3—C4—H4A	120.9
C5—C8—C7	106.57 (15)	C1—C2—C3	120.3 (2)
O1—C6—N1	126.82 (17)	C1—C2—H2B	119.8
O1—C6—C7	126.73 (17)	C3—C2—H2B	119.8
N1—C6—C7	106.45 (16)	C4—C5—C8	121.84 (18)
N2—C7—C8	126.17 (16)	C4—C5—N1	128.95 (18)
N2—C7—C6	127.29 (17)	C8—C5—N1	109.21 (17)
C8—C7—C6	106.52 (15)	C4—C3—C2	121.2 (2)
C6—N1—C5	111.25 (15)	C4—C3—H3A	119.4
C6—N1—H1N1	123.2 (16)	C2—C3—H3A	119.4
C5—N1—H1N1	125.3 (17)
N3—N2—C7—C8	−179.67 (18)	C7—C8—C1—C2	−178.4 (2)
N3—N2—C7—C6	−0.8 (3)	C8—C1—C2—C3	−0.4 (3)
C1—C8—C7—N2	−3.2 (4)	C3—C4—C5—C8	−0.2 (3)
C5—C8—C7—N2	178.52 (18)	C3—C4—C5—N1	178.8 (2)
C1—C8—C7—C6	177.8 (2)	C1—C8—C5—C4	0.6 (3)
C5—C8—C7—C6	−0.5 (2)	C7—C8—C5—C4	179.15 (17)
O1—C6—C7—N2	1.1 (3)	C1—C8—C5—N1	−178.57 (17)
N1—C6—C7—N2	−178.18 (18)	C7—C8—C5—N1	0.0 (2)
O1—C6—C7—C8	−179.83 (17)	C6—N1—C5—C4	−178.5 (2)
N1—C6—C7—C8	0.8 (2)	C6—N1—C5—C8	0.6 (2)
O1—C6—N1—C5	179.82 (17)	C5—C4—C3—C2	−0.5 (3)
C7—C6—N1—C5	−0.9 (2)	C1—C2—C3—C4	0.8 (3)
C5—C8—C1—C2	−0.2 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2N3···O1	0.88 (2)	2.09 (2)	2.784 (2)	135 (2)
N3—H1N3···N2i	0.91 (2)	2.20 (3)	3.098 (2)	169 (2)
N1—H1N1···O1ii	0.90 (2)	1.98 (2)	2.866 (2)	168 (3)

Symmetry codes: (i) x−1/2, −y−1/2, −z+1; (ii) x+1/2, −y+1/2, −z+1.