Crystal structure of 2-oxo-2H-chromen-7-yl 4-fluoro­benzoate

Abou, A.; Yoda, J.; Djandé, A.; Coussan, S.; Zoueu, T.J.

doi:10.1107/S205698901800614X

Crystal structure of 2-oxo-2H-chromen-7-yl 4-fluorobenzoate

A. Abou, J. Yoda, A. Djandé, S. Coussan and T. J. Zoueu

The structure of a coumarin ester stabilized by C—H

O hydrogen bonds and C=O

π and π–π stacking interactions has been studied by X-ray diffraction, Hirshfeld surface analysis and quantum chemical calculations.

Keywords: coumarin ester; C—H

O hydrogen bonds; π–π stacking interactions; Hirshfeld surface analysis; quantum chemical calculations; crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S205698901800614X/kq2021sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S205698901800614X/kq2021Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S205698901800614X/kq2021Isup3.cml Supplementary material

CCDC reference: 1834035

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.005 Å
R factor = 0.035
wR factor = 0.098
Data-to-parameter ratio = 11.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax < 18) ........       6.67 Note
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............      0.005 Ang.
PLAT934_ALERT_3_C Number of (Iobs-Icalc)/SigmaW > 10 Outliers ....          1 Check

Alert level G
PLAT909_ALERT_3_G Percentage of I>2sig(I) Data at Theta(Max) Still        90% Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 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
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015), publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).

2-Oxo-2H-chromen-7-yl 4-fluorobenzoate top

Crystal data top

C₁₆H₉FO₄	F(000) = 292
M_r = 284.23	D_x = 1.489 Mg m⁻³
Monoclinic, P2₁	Melting point = 467–468 K
Hall symbol: P2yb	Cu Kα radiation, λ = 1.54184 Å
a = 4.0181 (2) Å	Cell parameters from 4751 reflections
b = 5.7296 (3) Å	θ = 4.8–67.5°
c = 27.5566 (14) Å	µ = 1.00 mm⁻¹
β = 91.660 (4)°	T = 298 K
V = 634.14 (6) Å³	Prism, pale yellow
Z = 2	0.40 × 0.12 × 0.05 mm

Data collection top

Rigaku SuperNova, Dual, Cu at zero, Atlas S2 diffractometer	2228 independent reflections
Radiation source: micro-focus sealed X-ray tube	2149 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.026
Detector resolution: 5.3048 pixels mm^-1	θ_max = 67.9°, θ_min = 4.8°
ω scans	h = −4→4
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −6→6
T_min = 0.683, T_max = 1.000	l = −32→32
8239 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0396P)² + 0.1688P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
2228 reflections	Δρ_max = 0.13 e Å⁻³
190 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 875 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
36 constraints	Absolute structure parameter: −0.03 (8)
Primary atom site location: structure-invariant direct methods

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	0.6427 (6)	0.3343 (4)	0.88096 (8)	0.0524 (6)
O3	0.0412 (6)	0.4724 (4)	0.73539 (8)	0.0615 (6)
C7	0.1548 (8)	0.5614 (6)	0.78012 (11)	0.0497 (7)
C10	0.1085 (8)	0.5845 (6)	0.69372 (12)	0.0530 (8)
C5	0.4431 (7)	0.4840 (5)	0.85424 (11)	0.0441 (6)
O2	0.9356 (7)	0.2473 (5)	0.94698 (9)	0.0754 (8)
C6	0.3531 (8)	0.4146 (6)	0.80778 (11)	0.0478 (7)
H6	0.4246	0.2726	0.7955	0.057*
C9	0.1406 (8)	0.8388 (6)	0.84388 (12)	0.0521 (7)
H9	0.0667	0.9806	0.8560	0.062*
C4	0.3401 (8)	0.6973 (5)	0.87346 (11)	0.0460 (7)
C11	−0.0314 (8)	0.4585 (6)	0.65121 (11)	0.0503 (7)
C16	−0.1991 (9)	0.2483 (7)	0.65592 (12)	0.0573 (8)
H16	−0.2289	0.1853	0.6866	0.069*
F1	−0.3952 (7)	0.1157 (6)	0.53091 (9)	0.1069 (10)
O4	0.2703 (7)	0.7609 (5)	0.69274 (9)	0.0745 (8)
C3	0.4468 (8)	0.7532 (6)	0.92219 (11)	0.0535 (8)
H3	0.3784	0.8923	0.9361	0.064*
C12	0.0095 (8)	0.5513 (7)	0.60524 (13)	0.0613 (9)
H12	0.1210	0.6923	0.6018	0.074*
C1	0.7538 (8)	0.3880 (6)	0.92768 (12)	0.0536 (8)
C8	0.0489 (8)	0.7757 (6)	0.79730 (12)	0.0546 (8)
H8	−0.0810	0.8743	0.7778	0.066*
C14	−0.2763 (10)	0.2274 (9)	0.57115 (14)	0.0705 (11)
C2	0.6429 (9)	0.6080 (7)	0.94771 (12)	0.0570 (8)
H2	0.7103	0.6486	0.9792	0.068*
C15	−0.3218 (10)	0.1325 (7)	0.61538 (14)	0.0679 (10)
H15	−0.4339	−0.0085	0.6184	0.081*
C13	−0.1144 (10)	0.4358 (9)	0.56453 (13)	0.0735 (11)
H13	−0.0889	0.4972	0.5336	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0609 (13)	0.0430 (13)	0.0528 (12)	0.0028 (10)	−0.0050 (10)	−0.0037 (10)
O3	0.0801 (15)	0.0560 (15)	0.0479 (12)	−0.0166 (13)	−0.0091 (10)	0.0029 (11)
C7	0.0542 (16)	0.0476 (19)	0.0470 (16)	−0.0114 (15)	−0.0026 (13)	0.0003 (14)
C10	0.0528 (17)	0.052 (2)	0.0542 (18)	0.0026 (16)	−0.0010 (13)	0.0049 (15)
C5	0.0439 (14)	0.0383 (16)	0.0501 (15)	−0.0058 (12)	0.0007 (11)	0.0008 (12)
O2	0.0877 (19)	0.0643 (18)	0.0726 (16)	0.0051 (16)	−0.0235 (14)	0.0052 (14)
C6	0.0553 (16)	0.0396 (17)	0.0486 (16)	−0.0033 (13)	0.0039 (12)	−0.0033 (13)
C9	0.0527 (17)	0.0378 (17)	0.0660 (19)	0.0015 (13)	0.0063 (14)	−0.0016 (14)
C4	0.0484 (16)	0.0366 (17)	0.0532 (16)	−0.0052 (13)	0.0058 (12)	−0.0037 (12)
C11	0.0503 (16)	0.0493 (19)	0.0511 (16)	0.0079 (14)	−0.0034 (12)	0.0015 (14)
C16	0.0611 (19)	0.054 (2)	0.0567 (18)	0.0012 (17)	−0.0044 (14)	0.0021 (16)
F1	0.116 (2)	0.129 (3)	0.0749 (15)	−0.0067 (19)	−0.0203 (14)	−0.0386 (16)
O4	0.097 (2)	0.0636 (17)	0.0629 (15)	−0.0291 (16)	0.0016 (13)	0.0011 (13)
C3	0.0615 (19)	0.0438 (18)	0.0556 (18)	−0.0076 (16)	0.0066 (14)	−0.0096 (15)
C12	0.0592 (19)	0.064 (2)	0.060 (2)	−0.0040 (18)	−0.0001 (15)	0.0055 (17)
C1	0.0577 (18)	0.050 (2)	0.0527 (17)	−0.0078 (16)	−0.0050 (14)	0.0021 (15)
C8	0.0580 (19)	0.0442 (18)	0.0613 (19)	0.0014 (15)	−0.0029 (14)	0.0062 (14)
C14	0.067 (2)	0.081 (3)	0.063 (2)	0.004 (2)	−0.0124 (17)	−0.022 (2)
C2	0.065 (2)	0.056 (2)	0.0498 (17)	−0.0123 (16)	−0.0016 (14)	−0.0059 (15)
C15	0.070 (2)	0.061 (2)	0.072 (2)	−0.0016 (19)	−0.0067 (17)	−0.0090 (18)
C13	0.077 (2)	0.095 (3)	0.0480 (18)	0.011 (2)	−0.0041 (16)	0.002 (2)

Geometric parameters (Å, º) top

O1—C5	1.374 (3)	C11—C16	1.388 (5)
O1—C1	1.385 (4)	C11—C12	1.388 (5)
O3—C10	1.350 (4)	C16—C15	1.378 (5)
O3—C7	1.398 (4)	C16—H16	0.9300
C7—C6	1.374 (4)	F1—C14	1.355 (4)
C7—C8	1.387 (5)	C3—C2	1.332 (5)
C10—O4	1.202 (4)	C3—H3	0.9300
C10—C11	1.473 (4)	C12—C13	1.383 (5)
C5—C6	1.379 (4)	C12—H12	0.9300
C5—C4	1.399 (4)	C1—C2	1.451 (5)
O2—C1	1.202 (4)	C8—H8	0.9300
C6—H6	0.9300	C14—C15	1.352 (6)
C9—C8	1.373 (5)	C14—C13	1.374 (7)
C9—C4	1.388 (4)	C2—H2	0.9300
C9—H9	0.9300	C15—H15	0.9300
C4—C3	1.434 (4)	C13—H13	0.9300

C5—O1—C1	121.8 (2)	C11—C16—H16	119.8
C10—O3—C7	120.5 (3)	C2—C3—C4	120.7 (3)
C6—C7—C8	122.1 (3)	C2—C3—H3	119.6
C6—C7—O3	115.8 (3)	C4—C3—H3	119.6
C8—C7—O3	121.9 (3)	C13—C12—C11	120.5 (4)
O4—C10—O3	122.7 (3)	C13—C12—H12	119.7
O4—C10—C11	126.0 (3)	C11—C12—H12	119.7
O3—C10—C11	111.2 (3)	O2—C1—O1	116.0 (3)
O1—C5—C6	116.8 (3)	O2—C1—C2	127.1 (3)
O1—C5—C4	121.1 (3)	O1—C1—C2	116.9 (3)
C6—C5—C4	122.1 (3)	C9—C8—C7	118.4 (3)
C7—C6—C5	118.1 (3)	C9—C8—H8	120.8
C7—C6—H6	121.0	C7—C8—H8	120.8
C5—C6—H6	121.0	C15—C14—F1	119.6 (4)
C8—C9—C4	122.0 (3)	C15—C14—C13	123.1 (4)
C8—C9—H9	119.0	F1—C14—C13	117.3 (4)
C4—C9—H9	119.0	C3—C2—C1	121.7 (3)
C9—C4—C5	117.4 (3)	C3—C2—H2	119.2
C9—C4—C3	124.9 (3)	C1—C2—H2	119.2
C5—C4—C3	117.8 (3)	C14—C15—C16	118.9 (4)
C16—C11—C12	119.2 (3)	C14—C15—H15	120.6
C16—C11—C10	121.7 (3)	C16—C15—H15	120.6
C12—C11—C10	119.0 (3)	C14—C13—C12	118.0 (4)
C15—C16—C11	120.4 (3)	C14—C13—H13	121.0
C15—C16—H16	119.8	C12—C13—H13	121.0

C10—O3—C7—C6	−122.3 (3)	C12—C11—C16—C15	0.4 (5)
C10—O3—C7—C8	63.4 (4)	C10—C11—C16—C15	−178.8 (3)
C7—O3—C10—O4	1.1 (5)	C9—C4—C3—C2	−179.0 (3)
C7—O3—C10—C11	179.3 (3)	C5—C4—C3—C2	1.3 (5)
C1—O1—C5—C6	178.7 (3)	C16—C11—C12—C13	−0.2 (5)
C1—O1—C5—C4	−0.7 (4)	C10—C11—C12—C13	179.0 (3)
C8—C7—C6—C5	1.0 (4)	C5—O1—C1—O2	−177.7 (3)
O3—C7—C6—C5	−173.3 (3)	C5—O1—C1—C2	1.5 (4)
O1—C5—C6—C7	−179.7 (3)	C4—C9—C8—C7	1.4 (5)
C4—C5—C6—C7	−0.3 (4)	C6—C7—C8—C9	−1.5 (5)
C8—C9—C4—C5	−0.8 (5)	O3—C7—C8—C9	172.5 (3)
C8—C9—C4—C3	179.5 (3)	C4—C3—C2—C1	−0.5 (5)
O1—C5—C4—C9	179.6 (3)	O2—C1—C2—C3	178.2 (4)
C6—C5—C4—C9	0.2 (4)	O1—C1—C2—C3	−0.9 (5)
O1—C5—C4—C3	−0.7 (4)	F1—C14—C15—C16	180.0 (3)
C6—C5—C4—C3	179.9 (3)	C13—C14—C15—C16	−0.4 (6)
O4—C10—C11—C16	176.2 (3)	C11—C16—C15—C14	−0.1 (5)
O3—C10—C11—C16	−1.9 (4)	C15—C14—C13—C12	0.6 (6)
O4—C10—C11—C12	−3.0 (5)	F1—C14—C13—C12	−179.7 (3)
O3—C10—C11—C12	178.9 (3)	C11—C12—C13—C14	−0.3 (6)

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg4 are the centroids of the C4–C9 benzene ring and the coumarin ring system, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O3	0.93	2.37	2.693 (4)	100
C2—H2···O2ⁱ	0.93	2.51	3.412 (4)	163
C1—O2···Cg2ⁱⁱ	1.20 (1)	3.27 (1)	3.403 (3)	86 (1)
C1—O2···Cg4ⁱⁱ	1.20 (1)	3.57 (1)	3.368 (3)	71 (1)

Symmetry codes: (i) −x+2, y+1/2, −z+2; (ii) x−1, y, z.

Analysis of short ring interactions (Å) top

Cg(I)	Cg(J)	Symmetry Cg(J)	Cg(I)···Cg(J)	CgI_Perp	CgJ_Perp	Slippage
Cg1	Cg2	-1 + x, y, z	3.5758 (18)	3.3139 (13)	-3.3124 (13)	1.347
Cg1	Cg4	-1 + x, y, z	3.6116 (16)	3.3133 (13)	-3.3044 (10)	1.458
Cg2	Cg1	1 + x, y, z	3.5758 (18)	-3.3123 (13)	3.3140 (13)	1.343
Cg2	Cg4	1 + x, y, z	3.6047 (16)	-3.3109 (13)	3.3195 (10)	1.405
Cg4	Cg1	1 + x, y, z	3.6115 (16)	-3.3043 (10)	3.3134(13	1.437
Cg4	Cg2	-1 + x, y, z	3.6049 (16)	3.3196 (10)	-3.3110 (13)	1.426

Cg(I) and Cg(J) are centroids of rings I and J; CgI_Perp is the perpendicular distance of Cg(I) on ring J and slippage is distance between Cg(I) and the perpendicular projection of Cg(J) on ring I.

Table S1 top

Experimental and calculated bond lengths (Å)

Bond	X-ray	6-311⁺⁺G(d,p)
O1—C5	1.374 (3)	1.348
O1—C1	1.385 (4)	1.354
O3—C10	1.350 (4)	1.342
O3—C7	1.398 (4)	1.375
C7—C6	1.374 (4)	1.373
C7—C8	1.387 (5)	1.3889
C10—O4	1.202 (4)	1.180
C10—C11	1.473 (4)	1.486
C5—C6	1.379 (4)	1.385
C5—C4	1.399 (4)	1.385
O2—C1	1.202 (4)	1.178
C9—C8	1.373 (5)	1.374
C9—C4	1.388 (4)	1.395
C4—C3	1.434 (4)	1.452
C11—C16	1.388 (5)	1.390
C11—C12	1.388 (5)	1.391
C16—C15	1.378 (5)	1.383
F1—C14	1.355 (4)	1.321
C3—C2	1.332 (5)	1.329
C12—C13	1.383 (5)	1.380
C1—C2	1.451 (5)	1.468
C14—C15	1.352 (6)	1.378
C14—C13	1.374 (7)	1.379

Table S2 top

Experimental and calculated bond angles (°)

Bond angle	X-ray	6-311⁺⁺G(d,p)
C5—O1—C1	121.8 (2)	123.7
C10—O3—C7	120.5 (3)	119.9
C6—C7—C8	122.1 (3)	122.0
C6—C7—O3	115.8 (3)	117.7
C8—C7—O3	121.9 (3)	120.1
O4—C10—O3	122.7 (3)	123.1
O4—C10—C11	126.0 (3)	124.8
O3—C10—C11	111.2 (3)	112.1
O1—C5—C6	116.8 (3)	117.1
O1—C5—C4	121.1 (3)	121.4
C6—C5—C4	122.1 (3)	121.5
C7—C6—C5	118.1 (3)	118.2
C8—C9—C4	122.0 (3)	121.0
C9—C4—C5	117.4 (3)	118.6
C9—C4—C3	124.9 (3)	124.2
C5—C4—C3	117.8 (3)	117.2
C16—C11—C12	119.2 (3)	119.7
C16—C11—C10	121.7 (3)	122.4
C12—C11—C10	119.0 (3)	117.8
C15—C16—C11	120.4 (3)	120.3
C2—C3—C4	120.7 (3)	120.5
C13—C12—C11	120.5 (4)	120.5
O2—C1—O1	116.0 (3)	118.7
O2—C1—C2	127.1 (3)	124.9
O1—C1—C2	116.9 (3)	116.3
C9—C8—C7	118.4 (3)	118.7
C15—C14—F1	119.6 (4)	118.7
C15—C14—C13	123.1 (4)	122.6
F1—C14—C13	117.3 (4)	118.7
C3—C2—C1	121.7 (3)	121.0
C14—C15—C16	118.9 (4)	118.5
C14—C13—C12	118.0 (4)	118.3

Table S3 top

Experimental and calculated torsion angles (°)

Torsion angle	X-ray	6-311⁺⁺G(d,p)
C10—O3—C7—C6	-122.3 (3)	-109.7
C10—O3—C7—C8	63.4 (4)	73.7
C7—O3—C10—O4	1.1 (5)	-0.1
C7—O3—C10—C11	179.3 (3)	179.9
C1—O1—C5—C6	178.7 (3)	-180.0
C1—O1—C5—C4	-0.7 (4)	-0.1
C8—C7—C6—C5	1.0 (4)	-0.2
O3—C7—C6—C5	-173.3 (3)	-176.7
O1—C5—C6—C7	-179.7 (3)	179.9
C4—C5—C6—C7	-0.3 (4)	-0.0
C8—C9—C4—C5	-0.8 (5)	0.0
C8—C9—C4—C3	179.5 (3)	-179.9
O1—C5—C4—C9	179.6 (3)	-179.7
C6—C5—C4—C9	0.2 (4)	0.1
O1—C5—C4—C3	-0.7 (4)	0.2
C6—C5—C4—C3	179.9 (3)	-179.9
O4—C10—C11—C16	176.2 (3)	-179.7
O3—C10—C11—C16	-1.9 (4)	0.3
O4—C10—C11—C12	-3.0 (5)	0.4
O3—C10—C11—C12	178.9 (3)	-179.6
C12—C11—C16—C15	0.4 (5)	-0.1
C10—C11—C16—C15	-178.8 (3)	179.9
C9—C4—C3—C2	-179.0 (3)	179.8
C5—C4—C3—C2	1.3 (5)	-0.2
C16—C11—C12—C13	-0.2 (5)	0.0
C10—C11—C12—C13	179.0 (3)	-180.0
C5—O1—C1—O2	-177.7 (3)	180.0
C5—O1—C1—C2	1.5 (4)	-0.1
C4—C9—C8—C7	1.4 (5)	-0.3
C6—C7—C8—C9	-1.5 (5)	0.4
O3—C7—C8—C9	172.5 (3)	176.8
C4—C3—C2—C1	-0.5 (5)	-0.0
O2—C1—C2—C3	178.2 (4)	-179.8
O1—C1—C2—C3	-0.9 (5)	0.1
F1—C14—C15—C16	180.0 (3)	180.0
C13—C14—C15—C16	-0.4 (6)	-0.0
C11—C16—C15—C14	-0.1 (5)	0.1
C15—C14—C13—C12	0.6 (6)	-0.0
F1—C14—C13—C12	-179.7 (3)	180.0
C11—C12—C13—C14	-0.3 (6)	0.0

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Crystal structure of 2-oxo-2H-chromen-7-yl 4-fluoro­benzoate

Supporting information

Key indicators

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Crystal structure of 2-oxo-2H-chromen-7-yl 4-fluorobenzoate