Crystal structure, Hirshfeld surface analysis, inter­action energy and energy framework calculations, as well as density functional theory (DFT) com­putation, of methyl 2-oxo-1-(prop-2-yn­yl)-1,2-di­hydro­quinoline-4-carboxyl­ate

El-Mrabet, A.; Haoudi, A.; Dalbouha, S.; Skalli, M.K.; Hökelek, T.; Capet, F.; Kandri Rodi, Y.; Mazzah, A.; Sebbar, N.K.

doi:10.1107/S2056989023007557

Crystal structure, Hirshfeld surface analysis, interaction energy and energy framework calculations, as well as density functional theory (DFT) computation, of methyl 2-oxo-1-(prop-2-ynyl)-1,2-dihydroquinoline-4-carboxylate

A. El-Mrabet, A. Haoudi, S. Dalbouha, M. K. Skalli, T. Hökelek, F. Capet, Y. Kandri Rodi, A. Mazzah and N. K. Sebbar

In the crystal of the title compound, C—H

O hydrogen bonds link the molecules, enclosing $R_{2}^{2}$ (10) and $R_{2}^{2}$ (16) ring motifs, into layers almost parallel to the bc plane. The layers are further connected by π–π stacking interactions.

Keywords: crystal structure; π-stacking; C—H

O hydrogen bonds; dihydroquinoline.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989023007557/wm5688sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989023007557/wm5688Isup2.hkl Contains datablock I
	Chemdraw file https://doi.org/10.1107/S2056989023007557/wm5688Isup3.cdx Supplementary material
	Chemdraw file https://doi.org/10.1107/S2056989023007557/wm5688Isup4.cdx Supplementary material

CCDC reference: 2291603

checkCIF report

Key indicators

Structure: I

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.002 Å
R factor = 0.047
wR factor = 0.148
Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of        C13 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.667 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          3 Report

Alert level G
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.002 Degree
PLAT230_ALERT_2_G Hirshfeld Test Diff for    C10      --C11      .        5.4 s.u.
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note
PLAT933_ALERT_2_G Number of HKL-OMIT Records in Embedded .res File          3 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         14 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Computing details top

Data collection: APEX3 (Bruker, 2019); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

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

Crystal data top

C₁₄H₁₁NO₃	Z = 2
M_r = 241.24	F(000) = 252
Triclinic, P1	D_x = 1.372 Mg m⁻³
a = 4.7033 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.1113 (6) Å	Cell parameters from 9957 reflections
c = 11.3876 (5) Å	θ = 2.4–30.2°
α = 81.759 (2)°	µ = 0.10 mm⁻¹
β = 83.356 (2)°	T = 296 K
γ = 85.564 (2)°	Block, colourless
V = 583.89 (5) Å³	0.24 × 0.14 × 0.11 mm

Data collection top

Bruker DUO PHOTON III diffractometer	R_int = 0.045
Radiation source: microfocus sealed X-ray tube	θ_max = 30.5°, θ_min = 1.8°
φ and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −15→15
T_min = 0.708, T_max = 0.746	l = −16→16
45341 measured reflections	3 standard reflections every 1000 reflections
3559 independent reflections	intensity decay: 1%
2489 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: difference Fourier map
wR(F²) = 0.148	All H-atom parameters refined
S = 1.11	w = 1/[σ²(F_o²) + (0.0712P)² + 0.064P] where P = (F_o² + 2F_c²)/3
3559 reflections	(Δ/σ)_max < 0.001
207 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

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
O1	0.3589 (2)	0.16022 (9)	0.53718 (9)	0.0571 (3)
N1	0.6716 (2)	0.14916 (9)	0.67741 (9)	0.0381 (2)
O2	0.2219 (3)	0.56421 (9)	0.64710 (10)	0.0655 (3)
O3	0.3962 (3)	0.56270 (10)	0.81846 (12)	0.0812 (4)
C5	0.7779 (2)	0.19819 (10)	0.76892 (10)	0.0359 (2)
C4	0.6875 (2)	0.31800 (10)	0.79156 (10)	0.0357 (2)
C3	0.4848 (3)	0.38599 (10)	0.71625 (10)	0.0372 (3)
C10	0.7636 (3)	0.02397 (11)	0.65470 (13)	0.0441 (3)
C13	0.3695 (3)	0.51328 (11)	0.73414 (12)	0.0434 (3)
C11	0.6261 (3)	−0.06721 (11)	0.74351 (13)	0.0463 (3)
C6	0.9724 (3)	0.12821 (12)	0.83921 (12)	0.0439 (3)
C1	0.4663 (3)	0.20952 (11)	0.60989 (11)	0.0411 (3)
C2	0.3857 (3)	0.33419 (11)	0.63055 (11)	0.0422 (3)
C9	0.8005 (3)	0.36311 (12)	0.88452 (12)	0.0438 (3)
C8	0.9935 (3)	0.29352 (14)	0.95173 (12)	0.0500 (3)
C7	1.0789 (3)	0.17610 (14)	0.92919 (13)	0.0497 (3)
C12	0.5140 (4)	−0.14126 (14)	0.81495 (17)	0.0605 (4)
C14	0.0863 (5)	0.68407 (15)	0.6591 (2)	0.0686 (5)
H10A	0.720 (4)	0.0174 (14)	0.5791 (15)	0.053 (4)*
H9	0.736 (3)	0.4439 (15)	0.9029 (14)	0.054 (4)*
H10B	0.974 (3)	0.0129 (13)	0.6502 (12)	0.044 (4)*
H6	1.030 (3)	0.0475 (15)	0.8245 (14)	0.052 (4)*
H2	0.247 (4)	0.3772 (15)	0.5795 (15)	0.056 (4)*
H8	1.067 (4)	0.3254 (16)	1.0161 (17)	0.070 (5)*
H7	1.214 (4)	0.1274 (17)	0.9743 (16)	0.066 (5)*
H14A	0.232 (6)	0.741 (2)	0.657 (2)	0.111 (8)*
H14B	−0.011 (5)	0.7061 (19)	0.590 (2)	0.083 (6)*
H14C	−0.036 (6)	0.684 (2)	0.729 (2)	0.100 (8)*
H12	0.435 (5)	−0.201 (2)	0.874 (2)	0.091 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0699 (7)	0.0505 (6)	0.0589 (6)	0.0021 (5)	−0.0237 (5)	−0.0248 (5)
N1	0.0416 (5)	0.0328 (5)	0.0416 (5)	0.0006 (4)	−0.0036 (4)	−0.0131 (4)
O2	0.0899 (8)	0.0451 (6)	0.0658 (7)	0.0234 (5)	−0.0303 (6)	−0.0185 (5)
O3	0.1245 (11)	0.0485 (6)	0.0815 (8)	0.0261 (6)	−0.0469 (8)	−0.0339 (6)
C5	0.0346 (5)	0.0359 (6)	0.0379 (6)	−0.0031 (4)	−0.0010 (4)	−0.0092 (4)
C4	0.0357 (5)	0.0355 (6)	0.0367 (5)	−0.0027 (4)	−0.0009 (4)	−0.0097 (4)
C3	0.0401 (6)	0.0323 (5)	0.0395 (6)	−0.0015 (4)	−0.0015 (4)	−0.0083 (4)
C10	0.0468 (7)	0.0369 (6)	0.0508 (7)	0.0033 (5)	−0.0026 (5)	−0.0189 (5)
C13	0.0488 (7)	0.0337 (6)	0.0488 (7)	−0.0004 (5)	−0.0053 (5)	−0.0097 (5)
C11	0.0466 (7)	0.0352 (6)	0.0607 (8)	0.0035 (5)	−0.0097 (6)	−0.0185 (6)
C6	0.0423 (6)	0.0402 (6)	0.0491 (7)	0.0027 (5)	−0.0061 (5)	−0.0075 (5)
C1	0.0461 (6)	0.0387 (6)	0.0407 (6)	−0.0015 (5)	−0.0056 (5)	−0.0125 (5)
C2	0.0485 (7)	0.0368 (6)	0.0425 (6)	0.0022 (5)	−0.0101 (5)	−0.0085 (5)
C9	0.0460 (6)	0.0440 (7)	0.0447 (6)	−0.0034 (5)	−0.0051 (5)	−0.0161 (5)
C8	0.0501 (7)	0.0602 (8)	0.0438 (7)	−0.0047 (6)	−0.0105 (6)	−0.0154 (6)
C7	0.0454 (7)	0.0572 (8)	0.0472 (7)	0.0010 (6)	−0.0119 (6)	−0.0055 (6)
C12	0.0642 (9)	0.0447 (8)	0.0737 (10)	−0.0063 (7)	−0.0086 (8)	−0.0093 (7)
C14	0.0861 (13)	0.0412 (8)	0.0810 (12)	0.0209 (8)	−0.0280 (11)	−0.0148 (8)

Geometric parameters (Å, º) top

O1—C1	1.2288 (14)	C10—H10B	0.983 (15)
N1—C5	1.3993 (14)	C11—C12	1.180 (2)
N1—C10	1.4742 (14)	C6—C7	1.3785 (19)
N1—C1	1.3774 (16)	C6—H6	0.949 (17)
O2—C13	1.3123 (17)	C1—C2	1.4524 (17)
O2—C14	1.4491 (17)	C2—H2	0.977 (18)
O3—C13	1.1955 (16)	C9—C8	1.3750 (19)
C5—C4	1.4159 (16)	C9—H9	0.969 (17)
C5—C6	1.4011 (17)	C8—C7	1.386 (2)
C4—C3	1.4516 (16)	C8—H8	0.966 (19)
C4—C9	1.4064 (16)	C7—H7	0.950 (19)
C3—C13	1.5081 (16)	C12—H12	0.94 (2)
C3—C2	1.3449 (17)	C14—H14A	0.97 (3)
C10—C11	1.457 (2)	C14—H14B	0.95 (2)
C10—H10A	0.922 (16)	C14—H14C	0.93 (3)

C5—N1—C10	120.18 (10)	C7—C6—C5	120.28 (12)
C1—N1—C5	123.16 (9)	C7—C6—H6	120.2 (9)
C1—N1—C10	116.52 (10)	O1—C1—N1	121.71 (11)
C13—O2—C14	116.39 (12)	O1—C1—C2	122.56 (12)
N1—C5—C4	120.23 (10)	N1—C1—C2	115.73 (10)
N1—C5—C6	119.97 (10)	C3—C2—C1	123.09 (11)
C6—C5—C4	119.80 (10)	C3—C2—H2	121.9 (10)
C5—C4—C3	117.38 (10)	C1—C2—H2	114.9 (10)
C9—C4—C5	118.06 (11)	C4—C9—H9	119.0 (10)
C9—C4—C3	124.56 (11)	C8—C9—C4	121.30 (12)
C4—C3—C13	121.83 (10)	C8—C9—H9	119.6 (10)
C2—C3—C4	120.15 (10)	C9—C8—C7	120.08 (12)
C2—C3—C13	117.97 (11)	C9—C8—H8	120.2 (11)
N1—C10—H10A	106.8 (10)	C7—C8—H8	119.7 (11)
N1—C10—H10B	109.5 (8)	C6—C7—C8	120.47 (13)
C11—C10—N1	112.13 (10)	C6—C7—H7	118.6 (11)
C11—C10—H10A	111.3 (10)	C8—C7—H7	120.9 (11)
C11—C10—H10B	111.7 (8)	C11—C12—H12	176.4 (14)
H10A—C10—H10B	105.1 (13)	O2—C14—H14A	109.5 (16)
O2—C13—C3	111.85 (10)	O2—C14—H14B	105.1 (13)
O3—C13—O2	122.55 (12)	O2—C14—H14C	111.5 (16)
O3—C13—C3	125.54 (12)	H14A—C14—H14B	107.6 (19)
C12—C11—C10	179.65 (16)	H14A—C14—H14C	110 (2)
C5—C6—H6	119.5 (9)	H14B—C14—H14C	113 (2)

O1—C1—C2—C3	174.62 (13)	C10—N1—C5—C4	−179.38 (10)
N1—C5—C4—C3	−0.33 (16)	C10—N1—C5—C6	0.02 (17)
N1—C5—C4—C9	179.99 (10)	C10—N1—C1—O1	2.22 (18)
N1—C5—C6—C7	179.74 (11)	C10—N1—C1—C2	−177.92 (10)
N1—C1—C2—C3	−5.23 (19)	C13—C3—C2—C1	−175.93 (11)
C5—N1—C10—C11	75.59 (14)	C6—C5—C4—C3	−179.73 (10)
C5—N1—C1—O1	−173.59 (11)	C6—C5—C4—C9	0.59 (17)
C5—N1—C1—C2	6.27 (18)	C1—N1—C5—C4	−3.71 (17)
C5—C4—C3—C13	178.69 (10)	C1—N1—C5—C6	175.68 (11)
C5—C4—C3—C2	1.31 (17)	C1—N1—C10—C11	−100.36 (13)
C5—C4—C9—C8	0.10 (19)	C2—C3—C13—O2	−11.40 (17)
C5—C6—C7—C8	0.4 (2)	C2—C3—C13—O3	165.96 (15)
C4—C5—C6—C7	−0.86 (19)	C9—C4—C3—C13	−1.66 (18)
C4—C3—C13—O2	171.16 (11)	C9—C4—C3—C2	−179.04 (12)
C4—C3—C13—O3	−11.5 (2)	C9—C8—C7—C6	0.3 (2)
C4—C3—C2—C1	1.54 (19)	C14—O2—C13—O3	−1.1 (2)
C4—C9—C8—C7	−0.5 (2)	C14—O2—C13—C3	176.33 (15)
C3—C4—C9—C8	−179.56 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O3	0.969 (17)	2.210 (15)	2.8807 (19)	125.3 (12)
C10—H10A···O1	0.922 (16)	2.277 (17)	2.6961 (17)	107.1 (12)
C14—H14B···O1ⁱ	0.95 (2)	2.56 (2)	3.433 (2)	153.8 (18)

Symmetry code: (i) −x, −y+1, −z+1.

Comparison (X-ray and DFT) of selected bond lengths and angles (Å, °) top

Bonds/angles	X-ray	B3LYP/6-311G(d,p)
O1—C1	1.2288 (14)	1.2231
N1—C5	1.3993 (14)	1.3955
N1—C10	1.4742 (14)	1.4727
N1—C1	1.3774 (16)	1.4035
O2—C13	1.3123 (17)	1.3460
O2—C14	1.4491 (17)	1.4399
O3—C13	1.1955 (16)	1.2081
C5—C4	1.4159 (16)	1.4234
C5—C6	1.4011 (17)	1.4062
C4—C3	1.4516 (16)	1.4539
C4—C9	1.4064 (16)	1.4096

C5—N1—C10	120.18 (10)	120.925
C1—N1—C5	123.16 (9)	123.436
C1—N1—C10	116.52 (10)	115.623
C13—O2—C14	116.39 (12)	115.680
N1—C5—C4	120.23 (10)	120.142
N1—C5—C6	119.97 (10)	120.504
C6—C5—C4	119.80 (10)	119.355
C5—C4—C3	117.38 (10)	117.701
C9—C4—C5	118.06 (11)	118.477

Calculated energies for compound (I) top

Total energy, TE (eV)	-22331.1678
E_HOMO (eV)	–6,35
E_LUMO (eV)	–2.35
Gap ΔE (eV)	–4.0
Dipole moment, µ (Debye)	2.1062
Ionization potential, I (eV)	6.35
Electron affinity, A	2.35
Electronegativity, χ	4.35
Hardness, η	2
Electrophilicity index, ω	4.73
Softness, σ	0.5
Fraction of electron transferred ΔN	0.66

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Crystal structure, Hirshfeld surface analysis, inter­action energy and energy framework calculations, as well as density functional theory (DFT) com­putation, of methyl 2-oxo-1-(prop-2-yn­yl)-1,2-di­hydro­quinoline-4-carboxyl­ate

Supporting information

Key indicators

checkCIF/PLATON results

Crystal structure, Hirshfeld surface analysis, interaction energy and energy framework calculations, as well as density functional theory (DFT) computation, of methyl 2-oxo-1-(prop-2-ynyl)-1,2-dihydroquinoline-4-carboxylate