Ethyl 2-[(Z)-2-(2-nitro­phen­yl)hydrazinyl­idene]propano­ate

Errossafi, A.; El Kihel, A.; Guesmi, S.; Saadi, M.; El Ammari, L.

doi:10.1107/S2414314616010154

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 6| June 2016| x161015

doi:10.1107/S2414314616010154

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Ethyl 2-[(Z)-2-(2-nitrophenyl)hydrazinylidene]propanoate

Amal Errossafi,^a ^* Abdellatif El Kihel,^a Salaheddine Guesmi,^b Mohamed Saadi ^c and Lahcen El Ammari ^c

^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

Edited by M. Bolte, Goethe-Universität Frankfurt Germany (Received 8 June 2016; accepted 21 June 2016; online 24 June 2016)

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 carbonyl compounds 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).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O1	0.88	1.94	2.6085 (17)	132

Figure 1
The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.

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).

Figure 2
Molecules linked by π–π interactions, forming a three-dimensional network.

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 refinement details are summarized in Table 2. The reflection (100) affected by the beam-stop was removed during refinement.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₃N₃O₄
M_r	251.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.8614 (4), 15.8834 (6), 6.7495 (2)
β (°)	102.411 (2)
V (Å³)	1241.89 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.42 × 0.33 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2015)
T_min, T_max	0.452, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	37344, 3487, 1892
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.694

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.146, 1.02
No. of reflections	3487
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22
Computer programs: APEX2 and SAINT-Plus (Bruker, 2009 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1486941

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616010154/bt4015sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616010154/bt4015Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616010154/bt4015Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Ethyl 2-[(Z)-2-(2-nitrophenyl)hydrazinylidene]propanoate top

Crystal data top

C₁₁H₁₃N₃O₄	F(000) = 528
M_r = 251.24	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	1892 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.058
φ and ω scans	θ_max = 29.6°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2015)	h = −16→16
T_min = 0.452, T_max = 0.746	k = −22→22
37344 measured reflections	l = −9→6
3487 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.049	w = 1/[σ²(F_o²) + (0.0566P)² + 0.2115P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.146	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.22 e Å⁻³
3487 reflections	Δρ_min = −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)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1	0.88	1.94	2.6085 (17)	132

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.

References

Bruker (2009). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
El Kihel, A., Ahbala, M., Harjane, T., Essassi, E. M. & Bauchat, P. (2007). Phys. Chem. News, 34, 85–88. CAS Google Scholar
El Kihel, A., Lagnaoui, A., Harjane, T., Kattir, Y., Guesmi, S. & Bauchat, P. (2013). Arabian J. Chem. 6, 173–176. Web of Science CrossRef CAS Google Scholar
El Ouar, M., Knouzi, N., El Kihel, A., Essassi, E. M., Benchidmi, M., Hamelin, J., Carrié, R. & Danion-Bougot, R. (1995). Synth. Commun. 25, 1601–1604. CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kuethe, J. T., Wong, A., Qu, C., Smitrovich, J., Davies, I. W. & Hughes, D. L. (2005). J. Org. Chem. 70, 2555–2567. Web of Science CrossRef PubMed CAS Google Scholar
Lipińska, T., Guibé-jampel, E., Petit, A. & Loupy, A. (1999). Synth. Commun. 29, 1349–1354. Google Scholar
Murakami, Y., Watanabe, T., Yokoyama, Y., Naomachi, J., Iwase, H., Watanabe, N., Morihata, M., Okuyama, N., Kamakura, H., Takahashi, T., Atoda, H., Tojo, T., Morita, K. & Ishii, H. (1993). Chem. Pharm. Bull. 41, 1910–1919. CrossRef CAS Google Scholar
Murakami, Y., Yokoo, H., Yokoyama, Y. & Watanabe, T. (1999). Chem. Pharm. Bull. 47, 791–797. CrossRef CAS Google Scholar
Narayana, B., Ashalatha, B. V., Vijaya Raj, K. K., Fernandes, J. & Sarojini, B. K. (2005). Bioorg. Med. Chem. 13, 4638–4644. Web of Science CrossRef PubMed CAS Google Scholar
Parmerter, S. M., Cook, A. G. & Dixon, W. B. (1958). J. Am. Chem. Soc. 80, 4621–4622. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wagaw, S., Yang, B. H. & Buchwald, S. L. (1999). J. Am. Chem. Soc. 121, 10251–10263. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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