Prop-2-ynyl 2-oxo-1-(prop-2-yn­yl)-1,2-di­hydro­quinoline-4-carboxyl­ate

Filali Baba, Y.; Kandri Rodi, Y.; Jasinski, J.P.; Kaur, M.; Ouzidan, Y.; Essassi, E.M.

doi:10.1107/S2414314617010720

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x171072

https://doi.org/10.1107/S2414314617010720

Open

access

Prop-2-ynyl 2-oxo-1-(prop-2-ynyl)-1,2-dihydroquinoline-4-carboxylate

Yassir Filali Baba,^a ^* Youssef Kandri Rodi,^a Jerry P. Jasinski,^b Manpreet Kaur,^b Younes Ouzidan ^a ‡ and El Mokhtar Essassi ^c

^aLaboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, Université Sidi Mohammed Ben Abdellah, Fès, Morocco, ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, and ^cLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Mohammed V University in Rabat, BP 1014, Avenue Ibn Batouta, Rabat, Morocco
^*Correspondence e-mail: yassir.filali.baba@gmail.com

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 19 July 2017; accepted 20 July 2017; online 25 July 2017)

In the title compound, C₁₆H₁₁NO₃, the dihedral angles between the mean planes of the quinolone ring system and the prop-2-ynyl and carboxyprop-2-ynyl groups are 87.9 (8) and 41.6 (8)°, respectively. In the crystal, a weak C—H⋯O interaction links the molecules into chains along the c-axis direction and weak π–π stacking interactions further stabilize the crystal packing.

Keywords: crystal structure; quinolone.

Structure description

Quinolone derivatives are a classical division of organic chemistry and many of these molecules have shown remarkable biological properties, including exceptional antibacterial activity (Chai et al., 2011 ; Hoshino et al., 2008 ). Quinolone derivatives are also frequently associated with medicinal applications, such as anti-fungal (Musiol et al., 2010 ), anti-tumoral (Bergh et al., 1997 ) and anti-cancer drugs (Elderfield & LeVon, 1960 ). As a continuation of our research work devoted to the development of substituted quinoline derivatives (Filali Baba et al., 2017 ), we report here the synthesis of prop-2-ynyl 2-oxo-1-(prop-2-ynyl)-1,2-dihydroquinoline-4-carboxylate, by reacting 2-oxo-1,2-dihydroquinoline-4-carboxylic acid with 3-bromoprop-1-yne, under phase-transfer catalysis conditions using tetra-n-butyl ammonium bromide (TBAB) as a catalyst and potassium carbonate as a base.

The title compound crystallizes with one independent molecule in the asymmetric unit (Fig. 1). The CH₂ group attached to N1 occupies an equatorial position with respect to the mean plane of the quinolone ring. The mean plane through the prop-2-ynyl substituent (N1/C14/C15/C16) makes a dihedral angle of 87.9 (8)° with the mean plane of the quinolone ring system. The dihedral angle between the mean planes of the quinolone ring and the carboxy-prop-2-ynyl unit is 41.6 (8)°.

Figure 1
Structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level.

In the crystal, a single weak C16—H16⋯O2 intermolecular interaction links the molecules forming one-dimensional chains along the c axis (Fig. 2, Table 1). In addition, weak π–π stacking interactions involving the quinolone rings form wave-like layers [intercentroid distances Cg1⋯Cg2ⁱⁱ = 3.6169 (5) Å, Cg2⋯Cg1ⁱⁱⁱ = 3.8112 (6) Å; symmetry codes: (ii) −x, 1 − y, 1 − z; (iii) 1 − x, 1 − y, 1 − z; Cg1 and Cg2 are the centroids of the N1/C1/C2/C3/C4/C9 and C4–C9 rings, respectively].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯O2ⁱ	0.93	2.34	3.214 (3)	157
Symmetry code: (i) x, y, z-1.

Figure 2
Molecular packing for the title compound, viewed along the b axis. Hydrogen bonds are drawn as dashed lines and H atoms not involved in the packing have been omitted for clarity.

Synthesis and crystallization

A solution of 0.5 g (2.64 mmol) 2-oxo-1,2-dihydroquinoline-4-carboxylic acid in 10 ml of DMF was mixed with 0.55 ml (6.34 mmol) 3-bromoprop-1-yne, and 1.09 g (7.92 mmol) K₂CO₃ and 0.17 g (0.52 mmol) TBAB. The reaction mixture was stirred at room temperature in DMF for 6 h. After removal of salts by filtration, the DMF was evaporated under reduced pressure and the residue obtained was dissolved in dichloromethane. The organic phase was dried over Na₂SO₄ then concentrated in vacuo. The resulting mixture was chromatographed on a silica gel column [eluent: ethyl acetate / hexane (1/2)]. Crystals were obtained when the solvent was allowed to evaporate (yield = 87%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₁NO₃
M_r	265.26
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	7.3070 (11), 8.7763 (13), 11.2927 (13)
α, β, γ (°)	91.059 (11), 107.867 (12), 109.814 (14)
V (Å³)	642.36 (17)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	0.79
Crystal size (mm)	0.4 × 0.12 × 0.06

Data collection
Diffractometer	Rigaku Oxford Diffraction
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku, 2015 )
T_min, T_max	0.833, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3962, 2418, 1624
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.613

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.142, 1.02
No. of reflections	2418
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.20
Computer programs: CrysAlis PRO (Rigaku, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010720/vm4026sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010720/vm4026Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617010720/vm4026Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617010720/vm4026Isup4.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku, 2015); cell refinement: CrysAlis PRO (Rigaku, 2015); data reduction: CrysAlis PRO (Rigaku, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Prop-2-ynyl 2-oxo-1-(prop-2-ynyl)-1,2-dihydroquinoline-4-carboxylate top

Crystal data top

C₁₆H₁₁NO₃	Z = 2
M_r = 265.26	F(000) = 276
Triclinic, P1	D_x = 1.371 Mg m⁻³
a = 7.3070 (11) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.7763 (13) Å	Cell parameters from 943 reflections
c = 11.2927 (13) Å	θ = 4.1–70.2°
α = 91.059 (11)°	µ = 0.79 mm⁻¹
β = 107.867 (12)°	T = 293 K
γ = 109.814 (14)°	Plate, colourless
V = 642.36 (17) Å³	0.4 × 0.12 × 0.06 mm

Data collection top

Rigaku Oxford Diffraction diffractometer	2418 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	1624 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 16.0416 pixels mm^-1	θ_max = 71.0°, θ_min = 4.2°
ω scans	h = −8→6
Absorption correction: multi-scan (CrysAlis PRO; Rigaku, 2015)	k = −10→10
T_min = 0.833, T_max = 1.000	l = −13→13
3962 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0621P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2418 reflections	Δρ_max = 0.14 e Å⁻³
181 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints

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.

Refinement. All H atoms were placed in calculated positions and refined using the riding model with C—H bond lengths of 0.93 Å (CH) or 0.97 Å (CH₂). Isotropic displacement parameters for these atoms were set to 1.2 times U_eq of the parent atom. In the final cycles of refinement, 4 outliers were omitted.

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

	x	y	z	U_iso*/U_eq
O1	0.0174 (3)	0.0643 (2)	0.29315 (16)	0.0698 (5)
O2	0.3186 (3)	0.4028 (2)	0.79834 (14)	0.0621 (5)
O3	0.4300 (2)	0.2141 (2)	0.74109 (13)	0.0568 (4)
N1	0.0822 (3)	0.3367 (2)	0.32712 (15)	0.0455 (4)
C1	0.0936 (3)	0.1917 (3)	0.3668 (2)	0.0499 (5)
C2	0.1935 (3)	0.1990 (3)	0.5004 (2)	0.0497 (5)
H2	0.2045	0.1041	0.5317	0.060*
C3	0.2707 (3)	0.3380 (3)	0.58080 (18)	0.0433 (5)
C4	0.2700 (3)	0.4906 (3)	0.53617 (18)	0.0418 (5)
C5	0.3604 (3)	0.6417 (3)	0.6127 (2)	0.0513 (5)
H5	0.4252	0.6466	0.6984	0.062*
C6	0.3554 (4)	0.7834 (3)	0.5639 (2)	0.0585 (6)
H6	0.4145	0.8827	0.6163	0.070*
C7	0.2618 (4)	0.7773 (3)	0.4359 (2)	0.0571 (6)
H7	0.2576	0.8728	0.4029	0.068*
C8	0.1753 (3)	0.6319 (3)	0.3576 (2)	0.0507 (5)
H8	0.1163	0.6300	0.2717	0.061*
C9	0.1753 (3)	0.4868 (3)	0.40563 (19)	0.0424 (5)
C10	0.3424 (3)	0.3264 (3)	0.71837 (19)	0.0477 (5)
C11	0.4825 (4)	0.1777 (3)	0.8687 (2)	0.0624 (6)
H11A	0.3585	0.1216	0.8886	0.075*
H11B	0.5623	0.2777	0.9271	0.075*
C12	0.6031 (4)	0.0739 (3)	0.8771 (2)	0.0645 (7)
C13	0.7044 (5)	−0.0037 (4)	0.8812 (3)	0.0873 (10)
H13	0.7860	−0.0661	0.8845	0.105*
C14	−0.0384 (3)	0.3270 (3)	0.19428 (19)	0.0534 (6)
H14A	−0.1455	0.2193	0.1664	0.064*
H14B	−0.1052	0.4066	0.1867	0.064*
C15	0.0878 (4)	0.3570 (3)	0.1123 (2)	0.0546 (6)
C16	0.1826 (5)	0.3752 (4)	0.0445 (2)	0.0720 (7)
H16	0.2586	0.3898	−0.0098	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0967 (13)	0.0552 (10)	0.0540 (10)	0.0319 (10)	0.0157 (9)	0.0002 (8)
O2	0.0823 (11)	0.0796 (12)	0.0427 (9)	0.0450 (10)	0.0278 (8)	0.0133 (8)
O3	0.0763 (10)	0.0698 (11)	0.0410 (8)	0.0430 (9)	0.0235 (7)	0.0188 (7)
N1	0.0536 (10)	0.0534 (11)	0.0363 (9)	0.0261 (9)	0.0166 (7)	0.0099 (8)
C1	0.0610 (13)	0.0505 (13)	0.0457 (12)	0.0254 (11)	0.0217 (10)	0.0091 (10)
C2	0.0652 (13)	0.0503 (12)	0.0453 (12)	0.0298 (11)	0.0241 (10)	0.0160 (9)
C3	0.0476 (11)	0.0541 (12)	0.0395 (11)	0.0259 (10)	0.0212 (9)	0.0114 (9)
C4	0.0429 (10)	0.0502 (12)	0.0413 (11)	0.0217 (9)	0.0208 (8)	0.0086 (9)
C5	0.0569 (12)	0.0546 (13)	0.0465 (12)	0.0216 (11)	0.0211 (10)	0.0054 (10)
C6	0.0689 (14)	0.0478 (13)	0.0650 (15)	0.0197 (12)	0.0323 (12)	0.0053 (11)
C7	0.0688 (14)	0.0494 (13)	0.0683 (15)	0.0288 (12)	0.0347 (12)	0.0190 (11)
C8	0.0560 (12)	0.0581 (14)	0.0479 (12)	0.0286 (11)	0.0216 (10)	0.0166 (10)
C9	0.0449 (10)	0.0494 (12)	0.0428 (11)	0.0232 (9)	0.0211 (8)	0.0107 (9)
C10	0.0551 (12)	0.0552 (13)	0.0405 (11)	0.0254 (11)	0.0199 (9)	0.0131 (9)
C11	0.0902 (17)	0.0701 (16)	0.0387 (12)	0.0441 (14)	0.0198 (12)	0.0188 (11)
C12	0.0861 (17)	0.0691 (16)	0.0412 (12)	0.0391 (15)	0.0124 (12)	0.0127 (11)
C13	0.114 (2)	0.101 (2)	0.0633 (18)	0.073 (2)	0.0142 (16)	0.0096 (16)
C14	0.0577 (13)	0.0604 (14)	0.0403 (11)	0.0254 (11)	0.0095 (10)	0.0063 (10)
C15	0.0749 (14)	0.0583 (14)	0.0374 (11)	0.0346 (12)	0.0161 (10)	0.0088 (10)
C16	0.105 (2)	0.0784 (19)	0.0522 (15)	0.0481 (17)	0.0356 (15)	0.0166 (13)

Geometric parameters (Å, º) top

O1—C1	1.229 (3)	C6—H6	0.9300
O2—C10	1.203 (2)	C6—C7	1.387 (3)
O3—C10	1.336 (3)	C7—H7	0.9300
O3—C11	1.444 (2)	C7—C8	1.371 (3)
N1—C1	1.378 (3)	C8—H8	0.9300
N1—C9	1.401 (3)	C8—C9	1.393 (3)
N1—C14	1.472 (3)	C11—H11A	0.9700
C1—C2	1.450 (3)	C11—H11B	0.9700
C2—H2	0.9300	C11—C12	1.454 (3)
C2—C3	1.345 (3)	C12—C13	1.155 (4)
C3—C4	1.441 (3)	C13—H13	0.9300
C3—C10	1.497 (3)	C14—H14A	0.9700
C4—C5	1.399 (3)	C14—H14B	0.9700
C4—C9	1.418 (3)	C14—C15	1.464 (3)
C5—H5	0.9300	C15—C16	1.161 (3)
C5—C6	1.377 (3)	C16—H16	0.9300

C10—O3—C11	115.86 (16)	C7—C8—H8	119.8
C1—N1—C9	123.77 (18)	C7—C8—C9	120.5 (2)
C1—N1—C14	116.01 (19)	C9—C8—H8	119.8
C9—N1—C14	120.21 (18)	N1—C9—C4	119.30 (19)
O1—C1—N1	121.4 (2)	C8—C9—N1	121.09 (19)
O1—C1—C2	122.9 (2)	C8—C9—C4	119.6 (2)
N1—C1—C2	115.6 (2)	O2—C10—O3	123.80 (19)
C1—C2—H2	118.8	O2—C10—C3	125.2 (2)
C3—C2—C1	122.5 (2)	O3—C10—C3	110.91 (17)
C3—C2—H2	118.8	O3—C11—H11A	110.4
C2—C3—C4	120.96 (19)	O3—C11—H11B	110.4
C2—C3—C10	117.7 (2)	O3—C11—C12	106.68 (18)
C4—C3—C10	121.16 (19)	H11A—C11—H11B	108.6
C5—C4—C3	124.25 (19)	C12—C11—H11A	110.4
C5—C4—C9	118.2 (2)	C12—C11—H11B	110.4
C9—C4—C3	117.50 (19)	C13—C12—C11	176.9 (3)
C4—C5—H5	119.3	C12—C13—H13	180.0
C6—C5—C4	121.3 (2)	N1—C14—H14A	109.0
C6—C5—H5	119.3	N1—C14—H14B	109.0
C5—C6—H6	120.2	H14A—C14—H14B	107.8
C5—C6—C7	119.6 (2)	C15—C14—N1	112.87 (18)
C7—C6—H6	120.2	C15—C14—H14A	109.0
C6—C7—H7	119.6	C15—C14—H14B	109.0
C8—C7—C6	120.7 (2)	C16—C15—C14	177.4 (3)
C8—C7—H7	119.6	C15—C16—H16	180.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O2ⁱ	0.93	2.34	3.214 (3)	157

Symmetry code: (i) x, y, z−1.

Footnotes

‡Additional correspondence author, e-mail: younes.ouzidan@usmba.ac.ma.

Acknowledgements

JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

References

Bergh, J. C. S., Tötterman, T. H., Termander, B. C., Strandgarden, K. A.-M. P., Gunnarsson, P. O. G. & Nilsson, B. I. (1997). Cancer Invest. 15, 204–211. CrossRef CAS PubMed Web of Science Google Scholar
Chai, Y., Liu, M.-L., Lv, K., Feng, L.-S., Li, S.-J., Sun, L.-Y., Wang, S. & Guo, H.-Y. (2011). Eur. J. Med. Chem. 46, 4267–4273. Web of Science CrossRef CAS PubMed Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Elderfield, R. C. & LeVon, E. F. (1960). J. Org. Chem. 25, 1576–1583. CrossRef CAS Web of Science Google Scholar
Filali Baba, Y., Kandri Rodi, Y., Hayani, S., Jasinski, J. P., Kaur, M. & Essassi, E. M. (2017). IUCrData, 2, x170917. Google Scholar
Hoshino, K., Inoue, K., Murakami, Y., Kurosaka, Y., Namba, K., Kashimoto, Y., Uoyama, S., Okumura, R., Higuchi, S. & Otani, T. (2008). Antimicrob. Agents Chemother. 52, 65–76. Web of Science CrossRef PubMed CAS Google Scholar
Musiol, R., Serda, M., Hensel-Bielowka, S. & Polanski, J. (2010). Curr. Med. Chem. 17, 1960–1973. CrossRef CAS PubMed Google Scholar
Rigaku (2015). CrysAlis PRO, Rigaku Americas, The Woodlands, Texas, USA. 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