organic compounds
2-(1H-Indol-3-yl)acetohydrazide
aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan, bInterdisciplinary Research Center in Biomedical Materials, COMSATS Institute of Information Technology, Lahore 54000, Pakistan, and cDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
*Correspondence e-mail: iuklodhi@yahoo.com
In the title compound C10H11N3O, the mean plane of the indole ring system (r.m.s. deviation 0.0131 Å) subtends a dihedral angle of 87.27 (5)° to the almost planar acetohydrazide substituent (r.m.s. deviation 0.0291 Å). In the crystal, bifurcated N—H⋯(O,N) and N—H⋯N hydrogen bonds involving the pyrrole N–H grouping combine to form zigzag chains along a. Additional N—H⋯O contacts from the hydrazide N–H group augmented by C—H⋯π interactions link the molecules into chains along the a axis. The overall effect of these contacts is a three-dimensional network structure with molecules stacked along the b-axis direction.
Related literature
For the use of et al. (2005a,b) and in the production of pharmaceuticals, see: Liu et al. (2006). For related structures, see: Butcher et al. (2007); Hou (2009); Li & Ban (2009); Sarojini et al. (2007a,b,c,d).
in the synthesis of see: NarayanaExperimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker 2005); cell APEX2 and 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: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004), PLATON (Spek, 2009), publCIF (Westrip 2010).
Supporting information
10.1107/S1600536812041694/hg5253sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812041694/hg5253Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812041694/hg5253Isup3.cml
Indole 3-methyl ester (500 mg, 2.6 mmole, 1eq) was added to hydrazine hydrate (80%, 4eq) in ethanol. The reaction mixture was refluxed for 2–3 h, allowed to cool and poured into 100 ml of chilled water. The resulting solid was filtered, dried and re-crystallized from ethanol to obtain the product (300 mg, 60%), mp: 143°C. The purity of the compound was confirmed using thin layer
Rf: 0.18, (n-hexane: ethyl acetate). Crystals of the title compound suitable for X-ray analysis were grown from a solution in ethanol at room temperature.N bound H atoms were located in difference Fourier maps and their coordinates were refined with Uiso=1.2Ueq (N). All H-atoms bound to carbon were refined using a riding model with d(C—H) = 0.93 Å, for aromatic and 0.97 Å for CH2 H atoms with Uiso = 1.2Ueq (C).
Data collection: APEX2 (Bruker 2005); cell
APEX2 and SAINT (Bruker 2005); data reduction: SAINT (Bruker 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004), PLATON (Spek, 2009), publCIF (Westrip 2010).Fig. 1. The structure of the title compound showing the atom numbering scheme with displacement ellipsoids drawn at the 50% probability level | |
Fig. 2. Zigzag chains along a with hydrogen bonds drawn as dashed lines. | |
Fig. 3. Molecules linked into rows along the b by N–H···O hydrogen bonds (dashed lines) and C–H···π contacts (dotted lines). | |
Fig. 4. A three dimensional network structure of molecules stacked along the b axis with hydrogen bonds drawn as dashed lines. |
C10H11N3O | F(000) = 800 |
Mr = 189.22 | Dx = 1.324 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 1251 reflections |
a = 12.1599 (7) Å | θ = 3.0–22.1° |
b = 9.6153 (4) Å | µ = 0.09 mm−1 |
c = 16.2345 (8) Å | T = 296 K |
V = 1898.16 (16) Å3 | Prism, colorless |
Z = 8 | 0.17 × 0.14 × 0.11 mm |
Bruker APEXII CCD area detector diffractometer | 1294 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.039 |
Graphite monochromator | θmax = 28.3°, θmin = 3.0° |
ϕ and ω scans | h = −16→14 |
8600 measured reflections | k = −12→12 |
2329 independent reflections | l = −20→21 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0512P)2 + 0.1536P] where P = (Fo2 + 2Fc2)/3 |
2329 reflections | (Δ/σ)max < 0.001 |
139 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C10H11N3O | V = 1898.16 (16) Å3 |
Mr = 189.22 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 12.1599 (7) Å | µ = 0.09 mm−1 |
b = 9.6153 (4) Å | T = 296 K |
c = 16.2345 (8) Å | 0.17 × 0.14 × 0.11 mm |
Bruker APEXII CCD area detector diffractometer | 1294 reflections with I > 2σ(I) |
8600 measured reflections | Rint = 0.039 |
2329 independent reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.16 e Å−3 |
2329 reflections | Δρmin = −0.16 e Å−3 |
139 parameters |
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 | ||
N1 | 0.51122 (13) | 0.27482 (16) | 0.60889 (11) | 0.0549 (5) | |
H1N | 0.5591 (17) | 0.321 (2) | 0.5893 (12) | 0.066* | |
C1 | 0.45025 (15) | 0.30809 (17) | 0.67668 (12) | 0.0463 (5) | |
C2 | 0.46525 (18) | 0.4106 (2) | 0.73576 (14) | 0.0615 (6) | |
H2 | 0.5251 | 0.4707 | 0.7335 | 0.074* | |
C3 | 0.3892 (2) | 0.4202 (2) | 0.79725 (14) | 0.0683 (6) | |
H3 | 0.3980 | 0.4878 | 0.8377 | 0.082* | |
C4 | 0.29916 (19) | 0.3318 (2) | 0.80094 (13) | 0.0664 (6) | |
H4 | 0.2479 | 0.3428 | 0.8430 | 0.080* | |
C5 | 0.28434 (16) | 0.22822 (19) | 0.74347 (12) | 0.0542 (5) | |
H5 | 0.2242 | 0.1687 | 0.7466 | 0.065* | |
C6 | 0.36154 (14) | 0.21440 (16) | 0.68030 (11) | 0.0418 (4) | |
C7 | 0.37296 (14) | 0.12255 (16) | 0.61199 (11) | 0.0437 (4) | |
C8 | 0.46342 (15) | 0.16439 (18) | 0.57039 (12) | 0.0512 (5) | |
H8 | 0.4894 | 0.1235 | 0.5222 | 0.061* | |
C9 | 0.29943 (16) | 0.00197 (17) | 0.59225 (12) | 0.0526 (5) | |
H9A | 0.2600 | −0.0243 | 0.6418 | 0.063* | |
H9B | 0.3448 | −0.0764 | 0.5762 | 0.063* | |
C10 | 0.21718 (14) | 0.02925 (16) | 0.52500 (11) | 0.0404 (4) | |
O10 | 0.18296 (11) | 0.14649 (11) | 0.50855 (8) | 0.0575 (4) | |
N2 | 0.18364 (13) | −0.08386 (15) | 0.48613 (10) | 0.0505 (4) | |
H2N | 0.2143 (16) | −0.165 (2) | 0.4996 (11) | 0.061* | |
N3 | 0.09921 (17) | −0.07433 (16) | 0.42677 (12) | 0.0631 (5) | |
H3N1 | 0.1226 (17) | −0.128 (2) | 0.3824 (13) | 0.076* | |
H3N2 | 0.0381 (19) | −0.125 (2) | 0.4406 (14) | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0422 (9) | 0.0513 (10) | 0.0711 (12) | −0.0088 (7) | 0.0042 (9) | 0.0060 (9) |
C1 | 0.0431 (10) | 0.0411 (9) | 0.0548 (11) | −0.0031 (7) | −0.0091 (9) | 0.0057 (9) |
C2 | 0.0620 (14) | 0.0526 (11) | 0.0699 (15) | −0.0112 (10) | −0.0161 (12) | −0.0005 (10) |
C3 | 0.0867 (17) | 0.0570 (13) | 0.0612 (14) | 0.0031 (12) | −0.0161 (13) | −0.0101 (11) |
C4 | 0.0741 (15) | 0.0708 (14) | 0.0542 (13) | 0.0138 (12) | 0.0036 (11) | 0.0026 (11) |
C5 | 0.0498 (11) | 0.0527 (11) | 0.0600 (12) | −0.0022 (9) | 0.0011 (10) | 0.0136 (10) |
C6 | 0.0415 (9) | 0.0341 (8) | 0.0497 (10) | 0.0006 (7) | −0.0065 (8) | 0.0085 (8) |
C7 | 0.0442 (10) | 0.0335 (8) | 0.0534 (11) | 0.0010 (7) | −0.0056 (9) | 0.0087 (8) |
C8 | 0.0537 (11) | 0.0422 (10) | 0.0577 (12) | 0.0064 (8) | 0.0021 (10) | 0.0009 (9) |
C9 | 0.0625 (12) | 0.0328 (9) | 0.0624 (12) | −0.0039 (8) | −0.0095 (10) | 0.0070 (8) |
C10 | 0.0444 (10) | 0.0282 (8) | 0.0485 (10) | −0.0012 (7) | 0.0029 (8) | 0.0015 (7) |
O10 | 0.0671 (9) | 0.0300 (6) | 0.0752 (9) | 0.0049 (6) | −0.0198 (7) | −0.0020 (6) |
N2 | 0.0627 (10) | 0.0292 (8) | 0.0594 (10) | 0.0020 (7) | −0.0114 (9) | −0.0020 (7) |
N3 | 0.0782 (13) | 0.0455 (10) | 0.0656 (12) | −0.0004 (8) | −0.0177 (11) | −0.0082 (8) |
N1—C8 | 1.362 (2) | C6—C7 | 1.425 (2) |
N1—C1 | 1.365 (3) | C7—C8 | 1.352 (2) |
N1—H1N | 0.80 (2) | C7—C9 | 1.499 (2) |
C1—C2 | 1.387 (3) | C8—H8 | 0.9300 |
C1—C6 | 1.407 (2) | C9—C10 | 1.504 (2) |
C2—C3 | 1.364 (3) | C9—H9A | 0.9700 |
C2—H2 | 0.9300 | C9—H9B | 0.9700 |
C3—C4 | 1.388 (3) | C10—O10 | 1.2310 (18) |
C3—H3 | 0.9300 | C10—N2 | 1.322 (2) |
C4—C5 | 1.377 (3) | N2—N3 | 1.411 (2) |
C4—H4 | 0.9300 | N2—H2N | 0.89 (2) |
C5—C6 | 1.397 (2) | N3—H3N1 | 0.93 (2) |
C5—H5 | 0.9300 | N3—H3N2 | 0.92 (2) |
C8—N1—C1 | 108.72 (15) | C8—C7—C6 | 106.48 (15) |
C8—N1—H1N | 124.2 (15) | C8—C7—C9 | 127.50 (18) |
C1—N1—H1N | 125.9 (15) | C6—C7—C9 | 126.01 (16) |
N1—C1—C2 | 130.74 (18) | C7—C8—N1 | 110.48 (17) |
N1—C1—C6 | 107.46 (16) | C7—C8—H8 | 124.8 |
C2—C1—C6 | 121.79 (18) | N1—C8—H8 | 124.8 |
C3—C2—C1 | 117.75 (19) | C7—C9—C10 | 114.65 (14) |
C3—C2—H2 | 121.1 | C7—C9—H9A | 108.6 |
C1—C2—H2 | 121.1 | C10—C9—H9A | 108.6 |
C2—C3—C4 | 121.66 (19) | C7—C9—H9B | 108.6 |
C2—C3—H3 | 119.2 | C10—C9—H9B | 108.6 |
C4—C3—H3 | 119.2 | H9A—C9—H9B | 107.6 |
C5—C4—C3 | 121.2 (2) | O10—C10—N2 | 123.07 (16) |
C5—C4—H4 | 119.4 | O10—C10—C9 | 122.82 (15) |
C3—C4—H4 | 119.4 | N2—C10—C9 | 114.10 (14) |
C4—C5—C6 | 118.58 (18) | C10—N2—N3 | 119.81 (15) |
C4—C5—H5 | 120.7 | C10—N2—H2N | 118.4 (12) |
C6—C5—H5 | 120.7 | N3—N2—H2N | 121.8 (12) |
C5—C6—C1 | 119.03 (17) | N2—N3—H3N1 | 105.6 (13) |
C5—C6—C7 | 134.12 (16) | N2—N3—H3N2 | 112.8 (15) |
C1—C6—C7 | 106.84 (16) | H3N1—N3—H3N2 | 97.9 (18) |
C8—N1—C1—C2 | 179.29 (19) | C5—C6—C7—C8 | 177.68 (18) |
C8—N1—C1—C6 | 0.1 (2) | C1—C6—C7—C8 | −1.15 (18) |
N1—C1—C2—C3 | 179.47 (19) | C5—C6—C7—C9 | −3.4 (3) |
C6—C1—C2—C3 | −1.5 (3) | C1—C6—C7—C9 | 177.72 (16) |
C1—C2—C3—C4 | −0.5 (3) | C6—C7—C8—N1 | 1.3 (2) |
C2—C3—C4—C5 | 1.6 (3) | C9—C7—C8—N1 | −177.58 (16) |
C3—C4—C5—C6 | −0.7 (3) | C1—N1—C8—C7 | −0.9 (2) |
C4—C5—C6—C1 | −1.2 (2) | C8—C7—C9—C10 | −79.8 (2) |
C4—C5—C6—C7 | −179.92 (18) | C6—C7—C9—C10 | 101.5 (2) |
N1—C1—C6—C5 | −178.42 (15) | C7—C9—C10—O10 | −26.0 (3) |
C2—C1—C6—C5 | 2.3 (3) | C7—C9—C10—N2 | 155.06 (17) |
N1—C1—C6—C7 | 0.62 (18) | O10—C10—N2—N3 | −4.6 (3) |
C2—C1—C6—C7 | −178.61 (16) | C9—C10—N2—N3 | 174.30 (17) |
Cg2 is the centroid of the C1–C6 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O10i | 0.80 (2) | 2.21 (2) | 2.927 (2) | 149.4 (19) |
N1—H1N···N3i | 0.80 (2) | 2.50 (2) | 3.126 (2) | 136.6 (19) |
N2—H2N···O10ii | 0.89 (2) | 2.20 (2) | 3.0799 (19) | 166.3 (17) |
C9—H9A···Cg2iii | 0.97 | 2.73 | 3.644 (2) | 157 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x+1/2, y−1/2, z; (iii) x, −y−3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C10H11N3O |
Mr | 189.22 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 296 |
a, b, c (Å) | 12.1599 (7), 9.6153 (4), 16.2345 (8) |
V (Å3) | 1898.16 (16) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.17 × 0.14 × 0.11 |
Data collection | |
Diffractometer | Bruker APEXII CCD area detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8600, 2329, 1294 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.122, 1.00 |
No. of reflections | 2329 |
No. of parameters | 139 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.16 |
Computer programs: APEX2 (Bruker 2005), APEX2 and SAINT (Bruker 2005), SAINT (Bruker 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97, enCIFer (Allen et al., 2004), PLATON (Spek, 2009), publCIF (Westrip 2010).
Cg2 is the centroid of the C1–C6 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O10i | 0.80 (2) | 2.21 (2) | 2.927 (2) | 149.4 (19) |
N1—H1N···N3i | 0.80 (2) | 2.50 (2) | 3.126 (2) | 136.6 (19) |
N2—H2N···O10ii | 0.89 (2) | 2.20 (2) | 3.0799 (19) | 166.3 (17) |
C9—H9A···Cg2iii | 0.97 | 2.73 | 3.644 (2) | 157 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x+1/2, y−1/2, z; (iii) x, −y−3/2, z−1/2. |
Acknowledgements
The authors acknowledge the Higher Education Commission of Pakistan for the purchase of the diffractometer.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Hydrazides are useful precursors in the synthesis of several heterocyclic compounds. (Narayana et al., 2005a,b). They are also intermediates in the production of many pharmaceutically important compounds (Liu et al., 2006). The structures of a number of hydrazides and their derivatives have also been reported (Butcher et al., 2007; Hou, 2009; Li & Ban, 2009; Sarojini et al., 2007a,b,c,d).
In the title hydrazide compound, the indole ring system is planar (r.m.s. deviation 0.0131 Å) and subtends an angle of 87.27 (5)° to the C9, C10, O10, N2, N3 acetohydrazide substituent which is also planar (r.m.s. deviation 0.0291 Å). In the crystal structure, bifurcated N1–H1N···O10 and N1–H1N···N6 hydrogen bonds together form zigzag chains along a, Table 1, Fig 2. Additional N2–H2N···O10 contacts augmented by C9–H9A···π interactions link the molecules into rows along b, Fig 3. The overall effect of these contacts is a three dimensional network structure with molecules stacked along the b axis, Fig 4.