Crystal structure, Hirshfeld surface analysis and inter­action energy and DFT studies of 2-chloro­ethyl 2-oxo-1-(prop-2-yn-1-yl)-1,2-di­hydro­quinoline-4-carboxyl­ate

The title compound consists of a 1,2-di­hydro­quinoline-4-carboxyl­ate unit with 2-chloro­ethyl and propynyl substituents, where the quinoline moiety is almost planar and the propynyl substituent is nearly perpendicular to its mean plane. In the crystal, the mol­ecules form zigzag stacks along the a-axis direction through slightly offset π-stacking inter­actions between inversion-related quinoline moieties, which are tied together by inter­molecular C—H_Prpn­yl...O_Carbx and C—H_Chlethy...O_Carbx (Prpnyl = propynyl, Carbx = carboxyl­ate and Chlethy = chloro­eth­yl) hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.078
• wR factor = 0.178
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.09 Report
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00546 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      8.154 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.234 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         31 Report
PLAT975_ALERT_2_C Check Calcd Resid. Dens.  0.84A   From O3              0.52 eA-3

Alert level G
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         13 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

2-Chloroethyl 2-oxo-1-(prop-2-yn-1-yl)-1,2-dihydroquinoline-4-carboxylate

Crystal data

C15H12ClNO3	F(000) = 600
Mr = 289.71	Dx = 1.403 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 7.1809 (2) Å	Cell parameters from 6719 reflections
b = 21.4466 (5) Å	θ = 4.1–69.9°
c = 8.9173 (2) Å	µ = 2.53 mm^−1
β = 92.784 (2)°	T = 150 K
V = 1371.70 (6) Å^3	Plate, colourless
Z = 4	0.19 × 0.14 × 0.01 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2555 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2170 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.047
Detector resolution: 10.4167 pixels mm^-1	θmax = 70.1°, θmin = 4.1°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −26→25
Tmin = 0.64, Tmax = 0.97	l = −10→10
10119 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual space
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.178	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0332P)^2 + 4.0657P] where P = (Fo^2 + 2Fc^2)/3
2555 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.73 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

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. 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 > 2sigma(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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. The largest peaks and holes in the final difference map are < +/-1 e^--/%A^-3 and are associated with the 2-chloroethylcarboxy group and may indicate a slight degree of disorder here but it was not considered serious enough to model.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.7800 (2)	0.24965 (6)	0.45136 (18)	0.0683 (4)
O1	0.1693 (4)	0.43876 (13)	0.9233 (3)	0.0390 (7)
O2	0.1917 (5)	0.33835 (15)	0.3272 (4)	0.0569 (9)
O3	0.3893 (5)	0.30409 (14)	0.5116 (4)	0.0505 (8)
N1	0.1864 (4)	0.50421 (13)	0.7226 (3)	0.0269 (6)
C1	0.2615 (5)	0.46384 (17)	0.4782 (4)	0.0282 (8)
C2	0.2997 (5)	0.47567 (19)	0.3269 (4)	0.0345 (9)
H2	0.324683	0.441692	0.262595	0.041*
C3	0.3014 (5)	0.5349 (2)	0.2715 (4)	0.0372 (9)
H3	0.326460	0.541915	0.169253	0.045*
C4	0.2661 (5)	0.58513 (19)	0.3654 (4)	0.0363 (9)
H4	0.267501	0.626395	0.326807	0.044*
C5	0.2290 (5)	0.57527 (18)	0.5145 (4)	0.0312 (8)
H5	0.205814	0.609762	0.577824	0.037*
C6	0.2256 (5)	0.51487 (17)	0.5719 (4)	0.0266 (7)
C7	0.1967 (5)	0.44600 (17)	0.7888 (4)	0.0296 (8)
C8	0.2365 (5)	0.39456 (17)	0.6907 (4)	0.0326 (8)
H8	0.244434	0.353690	0.731581	0.039*
C9	0.2627 (5)	0.40246 (17)	0.5429 (4)	0.0308 (8)
C10	0.1343 (5)	0.55651 (17)	0.8183 (4)	0.0295 (8)
H10A	0.047696	0.584337	0.760268	0.035*
H10B	0.067963	0.540162	0.904796	0.035*
C11	0.2966 (6)	0.59261 (18)	0.8741 (4)	0.0346 (9)
C12	0.4275 (7)	0.6208 (2)	0.9178 (5)	0.0485 (11)
H12	0.533984	0.643689	0.953389	0.058*
C13	0.2778 (6)	0.34610 (18)	0.4461 (5)	0.0385 (9)
C14	0.4018 (8)	0.2450 (2)	0.4316 (6)	0.0595 (14)
H14A	0.286502	0.220384	0.441323	0.071*
H14B	0.419443	0.252540	0.323617	0.071*
C15	0.5603 (9)	0.2122 (2)	0.4990 (6)	0.0629 (14)
H15A	0.559154	0.168527	0.463120	0.076*
H15B	0.551442	0.211642	0.609416	0.076*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0708 (9)	0.0393 (6)	0.0940 (11)	0.0187 (6)	−0.0052 (7)	−0.0096 (6)
O1	0.0464 (16)	0.0416 (15)	0.0301 (15)	0.0056 (13)	0.0132 (12)	0.0061 (12)
O2	0.074 (2)	0.0488 (19)	0.0469 (19)	0.0006 (17)	−0.0037 (17)	−0.0143 (15)
O3	0.057 (2)	0.0357 (16)	0.060 (2)	0.0087 (14)	0.0107 (16)	−0.0126 (14)
N1	0.0262 (15)	0.0270 (15)	0.0282 (16)	0.0024 (12)	0.0081 (12)	−0.0009 (12)
C1	0.0206 (16)	0.0332 (19)	0.0314 (19)	−0.0018 (14)	0.0064 (14)	−0.0014 (15)
C2	0.0276 (19)	0.047 (2)	0.030 (2)	−0.0039 (17)	0.0062 (15)	−0.0071 (17)
C3	0.033 (2)	0.051 (2)	0.028 (2)	−0.0076 (18)	0.0037 (16)	0.0055 (17)
C4	0.033 (2)	0.041 (2)	0.035 (2)	−0.0045 (17)	−0.0001 (16)	0.0091 (17)
C5	0.0264 (18)	0.0325 (19)	0.035 (2)	−0.0008 (15)	0.0035 (15)	0.0018 (16)
C6	0.0194 (16)	0.0335 (19)	0.0273 (18)	0.0005 (14)	0.0058 (13)	0.0004 (15)
C7	0.0252 (18)	0.0302 (19)	0.034 (2)	0.0011 (14)	0.0082 (15)	0.0029 (15)
C8	0.0317 (19)	0.0285 (19)	0.038 (2)	0.0020 (15)	0.0080 (16)	0.0044 (16)
C9	0.0249 (18)	0.0323 (19)	0.036 (2)	0.0006 (14)	0.0088 (15)	−0.0020 (16)
C10	0.0287 (18)	0.0307 (19)	0.0297 (19)	0.0034 (15)	0.0076 (15)	−0.0025 (15)
C11	0.043 (2)	0.034 (2)	0.028 (2)	0.0003 (17)	0.0101 (17)	−0.0039 (16)
C12	0.047 (3)	0.056 (3)	0.043 (3)	−0.009 (2)	0.006 (2)	−0.010 (2)
C13	0.038 (2)	0.030 (2)	0.049 (3)	0.0004 (17)	0.0092 (19)	−0.0001 (18)
C14	0.086 (4)	0.029 (2)	0.065 (3)	0.012 (2)	0.021 (3)	−0.005 (2)
C15	0.091 (4)	0.046 (3)	0.051 (3)	0.013 (3)	0.007 (3)	0.002 (2)

Geometric parameters (Å, º)

Cl1—C15	1.838 (6)	C5—C6	1.393 (5)
O1—C7	1.235 (5)	C5—H5	0.9500
O2—C13	1.213 (5)	C7—C8	1.445 (5)
O3—C13	1.322 (5)	C8—C9	1.351 (5)
O3—C14	1.459 (5)	C8—H8	0.9500
N1—C7	1.381 (5)	C9—C13	1.492 (5)
N1—C6	1.405 (4)	C10—C11	1.465 (5)
N1—C10	1.469 (4)	C10—H10A	0.9900
C1—C6	1.409 (5)	C10—H10B	0.9900
C1—C2	1.412 (5)	C11—C12	1.169 (6)
C1—C9	1.437 (5)	C12—H12	0.9500
C2—C3	1.363 (6)	C14—C15	1.444 (8)
C2—H2	0.9500	C14—H14A	0.9900
C3—C4	1.396 (6)	C14—H14B	0.9900
C3—H3	0.9500	C15—H15A	0.9900
C4—C5	1.385 (5)	C15—H15B	0.9900
C4—H4	0.9500
Cl1···O3	3.110 (3)	C1···C6^viii	3.534 (5)
Cl1···C12^i	3.629 (5)	C2···C6^ii	3.489 (5)
Cl1···H12^i	2.75	C2···C10^viii	3.388 (5)
Cl1···H5^ii	3.03	C4···C7^viii	3.597 (5)
Cl1···H8^iii	2.96	C4···C9^ii	3.452 (5)
O1···C10^iv	3.250 (5)	C5···C11	3.241 (5)
O1···C12^v	3.409 (6)	C5···C9^viii	3.575 (5)
O1···C15^vi	3.406 (5)	C6···C6^viii	3.485 (4)
O2···C2	3.045 (5)	C2···H10A^viii	2.88
O2···C15^vii	3.219 (6)	C5···H10A	2.61
O3···Cl1	3.110 (3)	C10···H5	2.50
O1···H10B	2.30	C11···H3^ix	2.85
O1···H10B^iv	2.39	C11···H5	2.72
O1···H15A^vi	2.46	C12···H14A^x	2.95
O2···H14B	2.46	C12···H2^ii	2.80
O2···H2	2.49	C12···H3^ix	2.93
O2···H14A	2.80	C13···H2	2.65
O2···H15B^vii	2.40	H5···H10A	2.10
O2···H10A^viii	2.49	H8···H15A^vi	2.55
O3···H8	2.50
C13—O3—C14	115.2 (4)	C7—C8—H8	118.8
C7—N1—C6	123.1 (3)	C8—C9—C1	120.5 (3)
C7—N1—C10	116.9 (3)	C8—C9—C13	118.7 (3)
C6—N1—C10	120.0 (3)	C1—C9—C13	120.6 (3)
C6—C1—C2	118.5 (3)	C11—C10—N1	112.3 (3)
C6—C1—C9	118.1 (3)	C11—C10—H10A	109.1
C2—C1—C9	123.4 (3)	N1—C10—H10A	109.1
C3—C2—C1	121.3 (4)	C11—C10—H10B	109.1
C3—C2—H2	119.4	N1—C10—H10B	109.1
C1—C2—H2	119.4	H10A—C10—H10B	107.9
C2—C3—C4	119.8 (4)	C12—C11—C10	179.1 (5)
C2—C3—H3	120.1	C11—C12—H12	180.0
C4—C3—H3	120.1	O2—C13—O3	124.4 (4)
C5—C4—C3	120.5 (4)	O2—C13—C9	124.6 (4)
C5—C4—H4	119.8	O3—C13—C9	110.8 (4)
C3—C4—H4	119.8	C15—C14—O3	106.6 (5)
C4—C5—C6	120.1 (4)	C15—C14—H14A	110.4
C4—C5—H5	119.9	O3—C14—H14A	110.4
C6—C5—H5	119.9	C15—C14—H14B	110.4
C5—C6—N1	120.7 (3)	O3—C14—H14B	110.4
C5—C6—C1	119.8 (3)	H14A—C14—H14B	108.6
N1—C6—C1	119.5 (3)	C14—C15—Cl1	111.0 (4)
O1—C7—N1	121.4 (3)	C14—C15—H15A	109.4
O1—C7—C8	122.5 (3)	Cl1—C15—H15A	109.4
N1—C7—C8	116.1 (3)	C14—C15—H15B	109.4
C9—C8—C7	122.4 (3)	Cl1—C15—H15B	109.4
C9—C8—H8	118.8	H15A—C15—H15B	108.0
C6—C1—C2—C3	−0.3 (5)	O1—C7—C8—C9	178.7 (4)
C9—C1—C2—C3	−178.4 (4)	N1—C7—C8—C9	0.1 (5)
C1—C2—C3—C4	0.4 (6)	C7—C8—C9—C1	3.3 (6)
C2—C3—C4—C5	−0.1 (6)	C7—C8—C9—C13	−171.9 (3)
C3—C4—C5—C6	−0.4 (6)	C6—C1—C9—C8	−2.3 (5)
C4—C5—C6—N1	−179.4 (3)	C2—C1—C9—C8	175.9 (4)
C4—C5—C6—C1	0.5 (5)	C6—C1—C9—C13	172.9 (3)
C7—N1—C6—C5	−174.3 (3)	C2—C1—C9—C13	−9.0 (5)
C10—N1—C6—C5	4.7 (5)	C7—N1—C10—C11	99.5 (4)
C7—N1—C6—C1	5.7 (5)	C6—N1—C10—C11	−79.6 (4)
C10—N1—C6—C1	−175.2 (3)	C14—O3—C13—O2	−0.9 (6)
C2—C1—C6—C5	−0.2 (5)	C14—O3—C13—C9	175.3 (4)
C9—C1—C6—C5	178.0 (3)	C8—C9—C13—O2	131.0 (5)
C2—C1—C6—N1	179.7 (3)	C1—C9—C13—O2	−44.2 (6)
C9—C1—C6—N1	−2.1 (5)	C8—C9—C13—O3	−45.2 (5)
C6—N1—C7—O1	176.8 (3)	C1—C9—C13—O3	139.6 (4)
C10—N1—C7—O1	−2.3 (5)	C13—O3—C14—C15	166.2 (4)
C6—N1—C7—C8	−4.7 (5)	O3—C14—C15—Cl1	−70.8 (5)
C10—N1—C7—C8	176.2 (3)

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+1, −y+1, −z+1; (iii) x+1/2, −y+1/2, z−1/2; (iv) −x, −y+1, −z+2; (v) −x+1, −y+1, −z+2; (vi) x−1/2, −y+1/2, z+1/2; (vii) x−1/2, −y+1/2, z−1/2; (viii) −x, −y+1, −z+1; (ix) x, y, z+1; (x) −x+1/2, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O2^viii	0.99	2.49	3.458 (5)	167
C10—H10B···O1^iv	0.99	2.39	3.250 (4)	145
C15—H15A···O1^iii	0.99	2.46	3.406 (6)	159
C15—H15B···O2^xi	0.99	2.40	3.219 (6)	140

Symmetry codes: (iii) x+1/2, −y+1/2, z−1/2; (iv) −x, −y+1, −z+2; (viii) −x, −y+1, −z+1; (xi) x+1/2, −y+1/2, z+1/2.