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.
Supporting information
CCDC reference: 287472
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.002 Å
- R factor = 0.042
- wR factor = 0.125
- Data-to-parameter ratio = 14.6
checkCIF/PLATON results
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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.
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 Uiso(H) set to 1.2Ueq(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.
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.
2-oxo-2,3-dihydro-1
H-indole-3-carbaldehyde benzoylhydrazone
top
Crystal data top
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) Å3 | 0.48 × 0.32 × 0.26 mm |
Z = 4 | |
Data collection top
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 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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0678P)2 + 0.1615P] where P = (Fo2 + 2Fc2)/3 |
2762 reflections | (Δ/σ)max = 0.001 |
189 parameters | Δρmax = 0.17 e Å−3 |
2 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C15H11N3O2 | V = 1266.0 (2) Å3 |
Mr = 265.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.9279 (6) Å | µ = 0.10 mm−1 |
b = 12.1099 (9) Å | T = 295 K |
c = 11.7567 (9) Å | 0.48 × 0.32 × 0.26 mm |
β = 95.117 (1)° | |
Data collection top
Bruker SMART area-detector diffractometer | 1878 reflections with I > 2σ(I) |
7680 measured reflections | Rint = 0.026 |
2762 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 2 restraints |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.17 e Å−3 |
2762 reflections | Δρmin = −0.18 e Å−3 |
189 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
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···O1i | 0.87 (1) | 2.15 (1) | 2.918 (2) | 148 (2) |
Symmetry code: (i) x, −y+3/2, z−1/2. |
Experimental details
Crystal data |
Chemical formula | C15H11N3O2 |
Mr | 265.27 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 8.9279 (6), 12.1099 (9), 11.7567 (9) |
β (°) | 95.117 (1) |
V (Å3) | 1266.0 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.48 × 0.32 × 0.26 |
|
Data collection |
Diffractometer | Bruker SMART area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7680, 2762, 1878 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.641 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.125, 1.01 |
No. of reflections | 2762 |
No. of parameters | 189 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.18 |
Hydrogen-bond geometry (Å, º) top
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···O1i | 0.87 (1) | 2.15 (1) | 2.918 (2) | 148 (2) |
Symmetry code: (i) x, −y+3/2, z−1/2. |
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.