Isatin 3-benzoyl­hydrazone: a monoclinic form

The amine N atom of the isatin portion of the title compound (systematic name: 2-oxo-2,3-dihydro-1H-indole-3-carbaldehyde benzoylhydrazone), C₁₅H₁₁N₃O₂, forms a hydrogen bond with the amide O atom of the benzoyl­hydrazone portion of a symmetry-related mol­ecule, giving rise to a hydrogen-bonded chain structure that propagates by a glide plane along the c axis of the monoclinic unit cell.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.042
• wR factor = 0.125
• Data-to-parameter ratio = 14.6

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S1. Comment

There are a large number of structurally authenticated Schiff bases that are the condensation products of an aroylhydrazine and a carbonyl compound, as noted from the Cambridge Structural Database (Version 5.26; Allen, 2002). Among this number is a sole example of an isatin derivative, the 3-picolinoylhydrazone. Isatin aroylhydrazones are expected to function as a terdentate chelate to metals; however, in nickel bis(1-methylisatin 3-picolinoylhydrazonate), the pyridyl N atom coordinates in place of the amido oxygen atom (Rodrìguez-Argüelles et al., 2004). Isatin 3-benzoylhydrazone, (I) (Fig. 1), is a nearly planar molecule. The 3-picolinoylhydrazone mentioned above is also planar, and the planarity of the two compounds can be attributed to delocalization of the π electrons over the entire molecule through the –N—NH—C(O)– portion. Other Schiff-base derivatives of isatin that have been crystallographically verified include (4-hexylphenyl)imino-1H-indol-2(3H-3 one) (Öztürk et al., 2003), indole-2,3-dione 3-(trimethylammonioacetyl)hydrazone chloride (Sun et al., 2001), indole-2,3-dione 3-(hexamethyleneiminyl)thiosemicarbazone (Bain et al., 1997), 2,3-bis(thiosemicarbazone) (Casas et al., 2000) and indole-2,3-dione β-4-(4-tolyl)thiocarbazone (Revenko et al., 1994). Useful biological properties (Öztürk et al., 2003) are expected of the title and the other Schiff bases. The title compound features an intramolecular hydrogen bond; adjacent molecules are linked by another hydrogen bond to form a chain. The following paper (Ali et al., 2005) describes an orthorhombic polymorph of the title compound.

S2. Experimental

Benzhydrazide (0.50 g, 3.7 mmol) and isatin (0.54 g, 3.7 mol) were refluxed in ethanol (50 ml) for 2 h. The solid that was formed was filtered off and recrystallized from pyridine to give well defined orange-colored blocks.

S3. Refinement

The C-bound H atoms were placed at calculated positions (C—H = 0.93 Å), and they were included in the refinement in the riding-model approximation with U_iso(H) set to 1.2U_eq(C). The N-bound H atoms were located in a difference Fourier map and refined with a distance restraint of N—H = 0.86 (1) Å.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. ORTEPII (Johnson, 1976) plot of C15H11N3O2. Displacement ellipsoids are drawn at the 50% probability level, and H atoms are shown as spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.

2-oxo-2,3-dihydro-1H-indole-3-carbaldehyde benzoylhydrazone

Crystal data

C15H11N3O2	F(000) = 552
Mr = 265.27	Dx = 1.392 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2811 reflections
a = 8.9279 (6) Å	θ = 2.4–26.3°
b = 12.1099 (9) Å	µ = 0.10 mm^−1
c = 11.7567 (9) Å	T = 295 K
β = 95.117 (1)°	Block, orange
V = 1266.0 (2) Å^3	0.48 × 0.32 × 0.26 mm
Z = 4

Data collection

Bruker SMART area-detector diffractometer	1878 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 27.1°, θmin = 2.3°
ϕ and ω scans	h = −11→10
7680 measured reflections	k = −15→15
2762 independent reflections	l = −15→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0678P)^2 + 0.1615P] where P = (Fo^2 + 2Fc^2)/3
2762 reflections	(Δ/σ)max = 0.001
189 parameters	Δρmax = 0.17 e Å^−3
2 restraints	Δρmin = −0.18 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.3608 (1)	0.4827 (1)	0.6519 (1)	0.0507 (3)
O2	0.3141 (1)	0.7066 (1)	0.2965 (1)	0.0604 (4)
N1	0.3453 (2)	0.5853 (1)	0.4910 (1)	0.0416 (3)
N2	0.4491 (1)	0.6590 (1)	0.5365 (1)	0.0384 (3)
N3	0.4830 (2)	0.8517 (1)	0.3151 (1)	0.0510 (4)
C1	0.1868 (2)	0.4251 (1)	0.4983 (1)	0.0402 (4)
C2	0.1148 (2)	0.3534 (1)	0.5662 (2)	0.0515 (4)
C3	0.0004 (2)	0.2862 (2)	0.5196 (2)	0.0631 (5)
C4	−0.0423 (2)	0.2895 (2)	0.4056 (2)	0.0633 (5)
C5	0.0287 (2)	0.3593 (2)	0.3370 (2)	0.0681 (6)
C6	0.1437 (2)	0.4272 (2)	0.3823 (2)	0.0580 (5)
C7	0.3052 (2)	0.4984 (1)	0.5548 (1)	0.0385 (4)
C8	0.4794 (2)	0.7397 (1)	0.4706 (1)	0.0370 (3)
C9	0.4131 (2)	0.7611 (1)	0.3502 (1)	0.0443 (4)
C10	0.5862 (2)	0.8944 (1)	0.4013 (1)	0.0426 (4)
C11	0.6755 (2)	0.9861 (1)	0.3993 (2)	0.0554 (5)
C12	0.7688 (2)	1.0091 (2)	0.4960 (2)	0.0631 (5)
C13	0.7704 (2)	0.9445 (2)	0.5928 (2)	0.0616 (5)
C14	0.6787 (2)	0.8532 (1)	0.5949 (1)	0.0488 (4)
C15	0.5871 (2)	0.8272 (1)	0.4982 (1)	0.0382 (4)
H1n	0.302 (2)	0.5983 (14)	0.424 (1)	0.056 (5)*
H3n	0.458 (2)	0.8803 (16)	0.249 (1)	0.078 (7)*
H2	0.1436	0.3501	0.6441	0.062*
H3	−0.0478	0.2384	0.5664	0.076*
H4	−0.1196	0.2443	0.3745	0.076*
H5	−0.0005	0.3614	0.2591	0.082*
H6	0.1920	0.4742	0.3348	0.070*
H11	0.6733	1.0312	0.3352	0.066*
H12	0.8326	1.0698	0.4961	0.076*
H13	0.8338	0.9627	0.6571	0.074*
H14	0.6788	0.8099	0.6602	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0677 (8)	0.0500 (7)	0.0325 (6)	−0.0146 (6)	−0.0055 (5)	0.0012 (5)
O2	0.0674 (8)	0.0662 (8)	0.0435 (7)	−0.0109 (7)	−0.0187 (6)	0.0071 (6)
N1	0.0452 (8)	0.0440 (7)	0.0336 (7)	−0.0064 (6)	−0.0071 (6)	0.0019 (6)
N2	0.0428 (7)	0.0375 (7)	0.0340 (7)	−0.0021 (5)	−0.0009 (5)	−0.0009 (5)
N3	0.0665 (9)	0.0520 (9)	0.0331 (8)	−0.0011 (7)	−0.0041 (7)	0.0098 (6)
C1	0.044 (1)	0.038 (1)	0.037 (1)	0.001 (1)	−0.002 (1)	−0.004 (1)
C2	0.058 (1)	0.051 (1)	0.045 (1)	−0.011 (1)	0.000 (1)	−0.001 (1)
C3	0.063 (1)	0.058 (1)	0.068 (1)	−0.020 (1)	0.002 (1)	−0.004 (1)
C4	0.059 (1)	0.052 (1)	0.075 (1)	−0.010 (1)	−0.016 (1)	−0.010 (1)
C5	0.087 (2)	0.061 (1)	0.052 (1)	−0.007 (1)	−0.025 (1)	−0.007 (1)
C6	0.077 (1)	0.053 (1)	0.043 (1)	−0.013 (1)	−0.008 (1)	−0.001 (1)
C7	0.044 (1)	0.039 (1)	0.032 (1)	−0.001 (1)	0.002 (1)	−0.002 (1)
C8	0.041 (1)	0.038 (1)	0.031 (1)	0.003 (1)	−0.001 (1)	0.002 (1)
C9	0.051 (1)	0.047 (1)	0.034 (1)	0.003 (1)	−0.004 (1)	0.003 (1)
C10	0.054 (1)	0.039 (1)	0.035 (1)	0.003 (1)	0.005 (1)	0.001 (1)
C11	0.077 (1)	0.042 (1)	0.049 (1)	−0.005 (1)	0.014 (1)	0.006 (1)
C12	0.080 (1)	0.047 (1)	0.064 (1)	−0.021 (1)	0.012 (1)	−0.005 (1)
C13	0.072 (1)	0.058 (1)	0.053 (1)	−0.018 (1)	−0.003 (1)	−0.007 (1)
C14	0.061 (1)	0.045 (1)	0.039 (1)	−0.008 (1)	−0.004 (1)	0.000 (1)
C15	0.046 (1)	0.035 (1)	0.034 (1)	0.002 (1)	0.004 (1)	−0.001 (1)

Geometric parameters (Å, º)

O1—C7	1.218 (2)	C10—C15	1.399 (2)
O2—C9	1.232 (2)	C11—C12	1.376 (3)
N1—C7	1.358 (2)	C12—C13	1.380 (3)
N1—N2	1.361 (2)	C13—C14	1.377 (2)
N2—C8	1.290 (2)	C14—C15	1.376 (2)
N3—C9	1.345 (2)	N1—H1n	0.86 (1)
N3—C10	1.406 (2)	N3—H3n	0.87 (1)
C1—C2	1.377 (2)	C2—H2	0.93
C1—C6	1.383 (2)	C3—H3	0.93
C1—C7	1.491 (2)	C4—H4	0.93
C2—C3	1.381 (2)	C5—H5	0.93
C3—C4	1.361 (3)	C6—H6	0.93
C4—C5	1.362 (3)	C11—H11	0.93
C5—C6	1.385 (3)	C12—H12	0.93
C8—C15	1.449 (2)	C13—H13	0.93
C8—C9	1.507 (2)	C14—H14	0.93
C10—C11	1.370 (2)
C7—N1—N2	119.7 (1)	C13—C14—C15	118.6 (2)
C8—N2—N1	115.6 (1)	C14—C15—C10	120.0 (1)
C9—N3—C10	111.7 (1)	C14—C15—C8	133.3 (1)
C2—C1—C6	118.7 (2)	C10—C15—C8	106.7 (1)
C2—C1—C7	117.8 (1)	C7—N1—H1n	122 (1)
C6—C1—C7	123.5 (2)	N2—N1—H1n	118 (1)
C1—C2—C3	120.6 (2)	C9—N3—H3n	121 (1)
C4—C3—C2	120.4 (2)	C10—N3—H3n	127 (1)
C5—C4—C3	119.8 (2)	C1—C2—H2	119.7
C4—C5—C6	120.6 (2)	C3—C2—H2	119.7
C5—C6—C1	120.0 (2)	C4—C3—H3	119.8
O1—C7—N1	122.2 (1)	C2—C3—H3	119.8
O1—C7—C1	122.6 (1)	C5—C4—H4	120.1
N1—C7—C1	115.2 (1)	C3—C4—H4	120.1
N2—C8—C15	126.2 (1)	C4—C5—H5	119.7
N2—C8—C9	127.5 (1)	C6—C5—H5	119.7
C15—C8—C9	106.4 (1)	C5—C6—H6	120.0
O2—C9—N3	127.7 (1)	C1—C6—H6	120.0
O2—C9—C8	126.4 (2)	C10—C11—H11	121.3
N3—C9—C8	106.0 (1)	C12—C11—H11	121.3
C11—C10—C15	121.6 (2)	C11—C12—H12	119.1
C11—C10—N3	129.1 (2)	C13—C12—H12	119.1
C15—C10—N3	109.2 (1)	C14—C13—H13	119.7
C10—C11—C12	117.4 (2)	C12—C13—H13	119.7
C11—C12—C13	121.8 (2)	C13—C14—H14	120.7
C14—C13—C12	120.5 (2)	C15—C14—H14	120.7
C7—N1—N2—C8	−179.2 (1)	C15—C8—C9—O2	−177.9 (2)
C6—C1—C2—C3	−1.0 (3)	N2—C8—C9—N3	−177.6 (2)
C7—C1—C2—C3	177.6 (2)	C15—C8—C9—N3	1.5 (2)
C1—C2—C3—C4	0.4 (3)	C9—N3—C10—C11	−178.4 (2)
C2—C3—C4—C5	0.2 (3)	C9—N3—C10—C15	1.3 (2)
C3—C4—C5—C6	−0.1 (3)	C15—C10—C11—C12	1.1 (3)
C4—C5—C6—C1	−0.5 (3)	N3—C10—C11—C12	−179.3 (2)
C2—C1—C6—C5	1.1 (3)	C10—C11—C12—C13	−1.7 (3)
C7—C1—C6—C5	−177.5 (2)	C11—C12—C13—C14	0.8 (3)
N2—N1—C7—O1	−1.1 (2)	C12—C13—C14—C15	0.7 (3)
N2—N1—C7—C1	177.9 (1)	C13—C14—C15—C10	−1.2 (2)
C2—C1—C7—O1	14.9 (2)	C13—C14—C15—C8	179.9 (2)
C6—C1—C7—O1	−166.5 (2)	C11—C10—C15—C14	0.3 (2)
C2—C1—C7—N1	−164.1 (1)	N3—C10—C15—C14	−179.4 (2)
C6—C1—C7—N1	14.5 (2)	C11—C10—C15—C8	179.4 (2)
N1—N2—C8—C15	−178.9 (1)	N3—C10—C15—C8	−0.2 (2)
N1—N2—C8—C9	0.0 (2)	N2—C8—C15—C14	−2.7 (3)
C10—N3—C9—O2	177.7 (2)	C9—C8—C15—C14	178.2 (2)
C10—N3—C9—C8	−1.7 (2)	N2—C8—C15—C10	178.3 (2)
N2—C8—C9—O2	3.1 (3)	C9—C8—C15—C10	−0.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O2	0.86 (1)	2.00 (1)	2.712 (2)	139 (2)
N3—H3n···O1^i	0.87 (1)	2.15 (1)	2.918 (2)	148 (2)

Symmetry code: (i) x, −y+3/2, z−1/2.