organic compounds
Ethyl 2-[(Z)-2-(2-nitrophenyl)hydrazinylidene]propanoate
aLaboratoire de Chimie Bioorganique, Faculté des Sciences, Université Chouaib Doukkali, BP 20, M-24000 El Jadida, Morocco, bLaboratoire de Chimie de Coordination et d'Analytique (LCCA), Faculté des Sciences, Université Chouaib Doukkali, BP 20, M-24000 El Jadida, Morocco, and cLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
*Correspondence e-mail: amal_errossafi@yahoo.fr
In the molecule of the title compound, C11H13N3O4, all non-H atoms are nearly coplanar with the largest deviation from the mean plane being 0.152 (2) Å. A strong intramolecular N—H⋯O hydrogen bond closes a six-membered ring. In the crystal, molecules are linked by π–π interactions [intercentroid distance = 3.724 (2) Å], forming stacks parallel to the c axis.
Keywords: crystal structure; nitrophenyl; π–π interaction.
CCDC reference: 1486941
Structure description
The indole ring is an important pharmocophore in modern drug discovery (Kuethe et al., 2005). Phenylhydrazones represent the principal starting material in the synthesis of indole derivatives. Some works have reported the synthesis of indole derivatives from the mixture of the two tautomers of phenylhydrazone without separation (Parmerter et al., 1958; Murakami et al., 1999; Narayana et al., 2005; El Kihel et al., 2013). Among these, Murakami et al. (1999) reported the separation of the mixture of indole normal and indole abnormal. However, the synthesis of phenylhydrazone by the condensation of phenylhydrazine with or by condensation of o-nitroaniline diazonium with ethyl α-methylacetoacetate in basic medium (Japp–Klingemann reaction) lead to two tautomeric products (Murakami et al., 1993; Wagaw et al., 1999; Lipinska et al., 1999). Based on our indole synthesis program (El Kihel et al., 2013, 2007; El Ouar et al., 1995), we report in this work the isolation of the majority product of the mixture of the two tautomers.
The title compound is built up from a 2-nitrophenyl ring linked to an ethyl hydrazono propanoate group, as shown in Fig. 1. Apart from the methyl H atoms, all atoms of the molecule are almost coplanar with a maximum deviation of 0.152 (2) Å for C11. The conformation of the molecule is stabilized by a strong intramolecular N—H⋯O hydrogen bond (Table 1).
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In the crystal, molecules are linked by π–π interactions [inter-centroid distance = 3.724 (2) Å], forming stacks parallel to the c axis (Fig. 2).
Synthesis and crystallization
The title compound was synthesized by mixing 2-nitrophenyhydrazine and ethyl pyruvate in stoichiometric quantity, in ethanol and heated over a steam bath. The crude product was filtered and crystallized from ethanol. Yellow single crystals appeared after two weeks. The crystals were washed with cold ethanol and dried in air at room temperature.
Refinement
Crystal data, data collection and structure . The reflection (100) affected by the beam-stop was removed during refinement.
details are summarized in Table 2Structural data
CCDC reference: 1486941
10.1107/S2414314616010154/bt4015sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616010154/bt4015Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616010154/bt4015Isup3.cml
Data collection: APEX2 (Bruker, 2009); cell
SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).C11H13N3O4 | F(000) = 528 |
Mr = 251.24 | Dx = 1.344 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.8614 (4) Å | Cell parameters from 3487 reflections |
b = 15.8834 (6) Å | θ = 2.2–29.6° |
c = 6.7495 (2) Å | µ = 0.10 mm−1 |
β = 102.411 (2)° | T = 296 K |
V = 1241.89 (7) Å3 | Plate, yellow |
Z = 4 | 0.42 × 0.33 × 0.19 mm |
Bruker APEXII CCD diffractometer | 1892 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.058 |
φ and ω scans | θmax = 29.6°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2015) | h = −16→16 |
Tmin = 0.452, Tmax = 0.746 | k = −22→22 |
37344 measured reflections | l = −9→6 |
3487 independent reflections |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.049 | w = 1/[σ2(Fo2) + (0.0566P)2 + 0.2115P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.146 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.22 e Å−3 |
3487 reflections | Δρmin = −0.22 e Å−3 |
164 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0117 (17) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.65861 (13) | 0.28676 (10) | 0.4729 (2) | 0.0471 (4) | |
C2 | 0.75897 (14) | 0.23883 (12) | 0.5128 (3) | 0.0589 (4) | |
H2 | 0.8304 | 0.2655 | 0.5410 | 0.071* | |
C3 | 0.75360 (16) | 0.15360 (12) | 0.5110 (3) | 0.0653 (5) | |
H3 | 0.8209 | 0.1217 | 0.5383 | 0.078* | |
C4 | 0.64643 (16) | 0.11452 (11) | 0.4679 (3) | 0.0637 (5) | |
H4 | 0.6425 | 0.0560 | 0.4661 | 0.076* | |
C5 | 0.54619 (14) | 0.16054 (10) | 0.4280 (3) | 0.0534 (4) | |
H5 | 0.4755 | 0.1328 | 0.3993 | 0.064* | |
C6 | 0.54875 (12) | 0.24845 (9) | 0.4298 (2) | 0.0438 (3) | |
C7 | 0.25524 (13) | 0.30082 (10) | 0.3148 (2) | 0.0480 (4) | |
C8 | 0.25598 (16) | 0.39424 (11) | 0.3224 (4) | 0.0789 (6) | |
H8A | 0.1780 | 0.4147 | 0.2918 | 0.118* | |
H8B | 0.2938 | 0.4126 | 0.4557 | 0.118* | |
H8C | 0.2966 | 0.4158 | 0.2246 | 0.118* | |
C9 | 0.14199 (13) | 0.25757 (11) | 0.2633 (2) | 0.0516 (4) | |
C10 | 0.04194 (14) | 0.12833 (12) | 0.2233 (3) | 0.0683 (5) | |
H10A | 0.0062 | 0.1356 | 0.0809 | 0.082* | |
H10B | −0.0109 | 0.1488 | 0.3039 | 0.082* | |
C11 | 0.06936 (18) | 0.03794 (13) | 0.2684 (4) | 0.0847 (6) | |
H11A | −0.0005 | 0.0054 | 0.2371 | 0.127* | |
H11B | 0.1216 | 0.0185 | 0.1876 | 0.127* | |
H11C | 0.1046 | 0.0316 | 0.4095 | 0.127* | |
N1 | 0.67284 (12) | 0.37725 (9) | 0.4780 (2) | 0.0566 (4) | |
N2 | 0.44815 (10) | 0.29405 (8) | 0.3914 (2) | 0.0483 (3) | |
H2N | 0.4542 | 0.3492 | 0.3880 | 0.058* | |
N3 | 0.34528 (10) | 0.25358 (8) | 0.34835 (19) | 0.0453 (3) | |
O1 | 0.58726 (11) | 0.42318 (7) | 0.4422 (2) | 0.0711 (4) | |
O2 | 0.77058 (11) | 0.40635 (9) | 0.5191 (2) | 0.0821 (4) | |
O3 | 0.05164 (10) | 0.29500 (8) | 0.2177 (2) | 0.0730 (4) | |
O4 | 0.15006 (9) | 0.17423 (7) | 0.27317 (19) | 0.0618 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0443 (8) | 0.0505 (9) | 0.0472 (9) | −0.0012 (7) | 0.0111 (7) | −0.0009 (7) |
C2 | 0.0433 (8) | 0.0718 (12) | 0.0616 (11) | 0.0028 (8) | 0.0112 (7) | 0.0023 (9) |
C3 | 0.0551 (10) | 0.0688 (12) | 0.0737 (12) | 0.0187 (9) | 0.0177 (9) | 0.0083 (9) |
C4 | 0.0738 (12) | 0.0490 (9) | 0.0716 (12) | 0.0105 (9) | 0.0229 (9) | 0.0052 (9) |
C5 | 0.0533 (9) | 0.0480 (9) | 0.0602 (10) | −0.0013 (7) | 0.0153 (8) | −0.0002 (8) |
C6 | 0.0433 (8) | 0.0473 (8) | 0.0415 (8) | 0.0013 (6) | 0.0106 (6) | 0.0004 (6) |
C7 | 0.0435 (8) | 0.0507 (9) | 0.0489 (9) | 0.0016 (6) | 0.0081 (7) | −0.0014 (7) |
C8 | 0.0584 (11) | 0.0524 (10) | 0.1209 (18) | 0.0058 (9) | 0.0080 (11) | −0.0006 (11) |
C9 | 0.0435 (8) | 0.0579 (10) | 0.0530 (10) | 0.0030 (7) | 0.0095 (7) | −0.0016 (8) |
C10 | 0.0437 (9) | 0.0739 (12) | 0.0857 (14) | −0.0127 (8) | 0.0106 (9) | −0.0092 (10) |
C11 | 0.0770 (13) | 0.0692 (13) | 0.1053 (18) | −0.0216 (11) | 0.0139 (12) | −0.0040 (12) |
N1 | 0.0490 (8) | 0.0564 (8) | 0.0653 (9) | −0.0086 (6) | 0.0142 (7) | −0.0056 (7) |
N2 | 0.0406 (7) | 0.0434 (7) | 0.0601 (8) | −0.0015 (5) | 0.0089 (6) | −0.0003 (6) |
N3 | 0.0397 (6) | 0.0499 (7) | 0.0461 (7) | −0.0037 (5) | 0.0089 (5) | −0.0017 (6) |
O1 | 0.0567 (7) | 0.0492 (7) | 0.1059 (10) | −0.0022 (6) | 0.0143 (7) | −0.0023 (7) |
O2 | 0.0521 (7) | 0.0716 (9) | 0.1210 (12) | −0.0189 (6) | 0.0154 (7) | −0.0065 (8) |
O3 | 0.0443 (7) | 0.0746 (9) | 0.0952 (10) | 0.0100 (6) | 0.0041 (6) | 0.0009 (7) |
O4 | 0.0386 (6) | 0.0560 (7) | 0.0885 (9) | −0.0046 (5) | 0.0084 (5) | −0.0047 (6) |
C1—C2 | 1.390 (2) | C8—H8B | 0.9600 |
C1—C6 | 1.411 (2) | C8—H8C | 0.9600 |
C1—N1 | 1.447 (2) | C9—O3 | 1.2062 (18) |
C2—C3 | 1.355 (3) | C9—O4 | 1.328 (2) |
C2—H2 | 0.9300 | C10—O4 | 1.4505 (19) |
C3—C4 | 1.388 (3) | C10—C11 | 1.489 (3) |
C3—H3 | 0.9300 | C10—H10A | 0.9700 |
C4—C5 | 1.372 (2) | C10—H10B | 0.9700 |
C4—H4 | 0.9300 | C11—H11A | 0.9600 |
C5—C6 | 1.397 (2) | C11—H11B | 0.9600 |
C5—H5 | 0.9300 | C11—H11C | 0.9600 |
C6—N2 | 1.3722 (18) | N1—O2 | 1.2233 (17) |
C7—N3 | 1.2849 (18) | N1—O1 | 1.2311 (17) |
C7—C9 | 1.482 (2) | N2—N3 | 1.3542 (16) |
C7—C8 | 1.485 (2) | N2—H2N | 0.8796 |
C8—H8A | 0.9600 | ||
C2—C1—C6 | 121.23 (15) | H8A—C8—H8C | 109.5 |
C2—C1—N1 | 116.67 (14) | H8B—C8—H8C | 109.5 |
C6—C1—N1 | 122.10 (13) | O3—C9—O4 | 123.69 (15) |
C3—C2—C1 | 120.59 (16) | O3—C9—C7 | 122.84 (16) |
C3—C2—H2 | 119.7 | O4—C9—C7 | 113.48 (13) |
C1—C2—H2 | 119.7 | O4—C10—C11 | 107.09 (15) |
C2—C3—C4 | 119.19 (16) | O4—C10—H10A | 110.3 |
C2—C3—H3 | 120.4 | C11—C10—H10A | 110.3 |
C4—C3—H3 | 120.4 | O4—C10—H10B | 110.3 |
C5—C4—C3 | 121.25 (16) | C11—C10—H10B | 110.3 |
C5—C4—H4 | 119.4 | H10A—C10—H10B | 108.6 |
C3—C4—H4 | 119.4 | C10—C11—H11A | 109.5 |
C4—C5—C6 | 120.96 (16) | C10—C11—H11B | 109.5 |
C4—C5—H5 | 119.5 | H11A—C11—H11B | 109.5 |
C6—C5—H5 | 119.5 | C10—C11—H11C | 109.5 |
N2—C6—C5 | 120.64 (14) | H11A—C11—H11C | 109.5 |
N2—C6—C1 | 122.58 (14) | H11B—C11—H11C | 109.5 |
C5—C6—C1 | 116.78 (14) | O2—N1—O1 | 121.46 (15) |
N3—C7—C9 | 116.60 (14) | O2—N1—C1 | 118.74 (14) |
N3—C7—C8 | 125.38 (15) | O1—N1—C1 | 119.80 (13) |
C9—C7—C8 | 118.01 (14) | N3—N2—C6 | 119.79 (13) |
C7—C8—H8A | 109.5 | N3—N2—H2N | 122.8 |
C7—C8—H8B | 109.5 | C6—N2—H2N | 117.2 |
H8A—C8—H8B | 109.5 | C7—N3—N2 | 115.92 (13) |
C7—C8—H8C | 109.5 | C9—O4—C10 | 116.03 (13) |
Acknowledgements
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements and Chouaib Doukkali University, El Jadida, Morocco, for financial support.
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