Crystal structure of 2-chloro-1-(6-fluoro-3,4-di­hydro-2H-chromen-2-yl)ethanone

Abstract

In the title mol­ecule, C₁₁H₁₀ClFO₂, the benzene ring, the F atom and the O atom of the di­hydro­pyran ring are essentially coplanar, with an r.m.s. deviation of 0.007 Å. The di­hydro­pyran ring is in a half-chair conformation. In the crystal, mol­ecules are linked by pairs of weak C—H⋯π hydrogen bonds, forming inversion dimers.

Related literature  

For the application of the title compound as a key inter­mediate in the preparation of nebivolol, which is useful in treating essential hypertension, see: Raffaella et al. (2011 ▶).

Experimental  

Crystal data  

• C₁₁H₁₀ClFO₂

• M _r = 228.64

• Monoclinic,

• a = 9.704 (3) Å

• b = 9.720 (3) Å

• c = 10.804 (4) Å

• β = 101.637 (7)°

• V = 998.2 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 0.37 mm⁻¹

• T = 296 K

• 0.20 × 0.20 × 0.20 mm

Data collection  

• Rigaku SCXmini diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.983, T _max = 0.983

• 5810 measured reflections

• 1940 independent reflections

• 1701 reflections with I > 2σ(I)

• R _int = 0.037

Refinement  

• R[F ² > 2σ(F ²)] = 0.058

• wR(F ²) = 0.169

• S = 1.06

• 1940 reflections

• 136 parameters

• H-atom parameters constrained

• Δρ_max = 0.87 e Å⁻³

• Δρ_min = −0.61 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

CCDC reference: 992910

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11B⋯Cg i	0.97	2.76	3.457 (3)	129

Symmetry code: (i) .

supplementary crystallographic information

S1. Comment

The title compound is a key intermediate in preparating nebivolol, which is useful in treating essential hypertension (Raffaella, et al., 2011). As part of our interest in these types of materials, we report herein the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig.1. Atoms F1 and O2 atoms are approximately coplanar with the benzene ring, with an r.m.s deviation of 0.007Å. The dihydropyran ring is in a half-chair conformation. In the crystal, molecules are linked by pairs of weak C—H···π hydrogen bonds forming inversion dimers (Fig. 2).

S2. Experimental

The title compound was provided by Changzhou Siyao Pham, Ltd (Changzhou, Jiangsu). Crystals of it suitable for X-ray diffraction were obstained by slow evaporation of a methanol solution.

S3. Refinement

All H atoms were positioned geometrically and treated as riding with C—H = 0.93 Å (aryl), C—H = 0.97 Å (methylene) and C—H = 0.98 Å (methine) with U_iso(H) = 1.2U_eq.

Figures

Fig. 1.

The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.

Fig. 2.

Part of the crystal structure viewed along the a axis.

Crystal data

C11H10ClFO2	F(000) = 472
Mr = 228.64	Dx = 1.521 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1940 reflections
a = 9.704 (3) Å	θ = 2.1–26.0°
b = 9.720 (3) Å	µ = 0.37 mm−1
c = 10.804 (4) Å	T = 296 K
β = 101.637 (7)°	Prism, colourless
V = 998.2 (6) Å3	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer	1940 independent reflections
Radiation source: fine-focus sealed tube	1701 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 13.6612 pixels mm-1	θmax = 26.0°, θmin = 2.1°
CCD_Profile_fitting scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
Tmin = 0.983, Tmax = 0.983	l = −12→13
5810 measured reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.087P)2 + 0.9962P] where P = (Fo2 + 2Fc2)/3
1940 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.87 e Å−3
0 restraints	Δρmin = −0.61 e Å−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.29999 (8)	0.06003 (8)	0.46282 (7)	0.0520 (3)
O2	0.6337 (2)	0.3728 (2)	0.50089 (17)	0.0446 (5)
F1	1.0157 (2)	0.7779 (2)	0.4805 (2)	0.0693 (6)
C5	0.7331 (3)	0.4738 (3)	0.5024 (2)	0.0370 (6)
C1	0.9201 (3)	0.6183 (3)	0.6021 (3)	0.0465 (7)
H1	0.9827	0.6483	0.6738	0.056*
C6	0.8247 (3)	0.5141 (3)	0.6117 (3)	0.0399 (6)
C4	0.7381 (3)	0.5330 (3)	0.3864 (3)	0.0415 (6)
H4	0.6773	0.5026	0.3137	0.050*
C3	0.8324 (3)	0.6361 (3)	0.3789 (3)	0.0476 (7)
H3	0.8355	0.6776	0.3019	0.057*
C7	0.8214 (3)	0.4463 (3)	0.7360 (3)	0.0504 (7)
H7A	0.9162	0.4203	0.7767	0.060*
H7B	0.7865	0.5112	0.7906	0.060*
C11	0.4282 (3)	0.1895 (3)	0.4699 (3)	0.0433 (6)
H11A	0.4958	0.1617	0.4197	0.052*
H11B	0.3834	0.2735	0.4335	0.052*
C10	0.5040 (3)	0.2175 (3)	0.6024 (3)	0.0458 (7)
C2	0.9219 (3)	0.6765 (3)	0.4875 (3)	0.0483 (7)
O1	0.4794 (3)	0.1587 (3)	0.6926 (2)	0.0607 (6)
C9	0.6086 (4)	0.3338 (5)	0.6206 (3)	0.0700 (11)
H9	0.5568	0.4116	0.6465	0.084*
C8	0.7298 (5)	0.3218 (5)	0.7187 (4)	0.0829 (14)
H8A	0.7849	0.2438	0.7006	0.099*
H8B	0.6999	0.3028	0.7974	0.099*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0554 (5)	0.0483 (5)	0.0536 (5)	−0.0019 (3)	0.0140 (3)	−0.0035 (3)
O2	0.0478 (11)	0.0536 (12)	0.0315 (9)	−0.0070 (9)	0.0054 (8)	0.0040 (8)
F1	0.0627 (12)	0.0574 (12)	0.0896 (15)	−0.0171 (10)	0.0197 (11)	−0.0058 (11)
C5	0.0363 (13)	0.0358 (13)	0.0388 (14)	0.0062 (10)	0.0070 (11)	−0.0012 (10)
C1	0.0396 (14)	0.0454 (16)	0.0528 (16)	0.0045 (12)	0.0052 (12)	−0.0122 (13)
C6	0.0376 (13)	0.0417 (14)	0.0398 (14)	0.0112 (11)	0.0062 (11)	−0.0056 (11)
C4	0.0409 (14)	0.0452 (15)	0.0380 (14)	0.0029 (11)	0.0073 (11)	−0.0007 (11)
C3	0.0486 (16)	0.0464 (16)	0.0505 (16)	0.0062 (13)	0.0159 (13)	0.0041 (13)
C7	0.0517 (17)	0.0602 (19)	0.0357 (14)	0.0038 (14)	0.0007 (12)	−0.0048 (13)
C11	0.0477 (15)	0.0429 (14)	0.0399 (14)	0.0034 (12)	0.0100 (12)	0.0038 (11)
C10	0.0455 (15)	0.0534 (17)	0.0388 (14)	0.0048 (13)	0.0091 (12)	0.0093 (12)
C2	0.0417 (15)	0.0381 (14)	0.067 (2)	−0.0003 (11)	0.0159 (14)	−0.0067 (13)
O1	0.0602 (13)	0.0790 (16)	0.0427 (12)	−0.0096 (12)	0.0101 (10)	0.0160 (11)
C9	0.078 (2)	0.092 (3)	0.0366 (16)	−0.028 (2)	0.0032 (15)	0.0125 (17)
C8	0.088 (3)	0.108 (3)	0.0448 (19)	−0.035 (3)	−0.0046 (18)	0.022 (2)

Geometric parameters (Å, º)

Cl1—C11	1.761 (3)	C3—H3	0.9300
O2—C5	1.374 (3)	C7—C8	1.492 (5)
O2—C9	1.416 (4)	C7—H7A	0.9700
F1—C2	1.354 (3)	C7—H7B	0.9700
C5—C6	1.383 (4)	C11—C10	1.497 (4)
C5—C4	1.389 (4)	C11—H11A	0.9700
C1—C2	1.364 (5)	C11—H11B	0.9700
C1—C6	1.391 (4)	C10—O1	1.194 (4)
C1—H1	0.9300	C10—C9	1.506 (5)
C6—C7	1.501 (4)	C9—C8	1.420 (5)
C4—C3	1.370 (4)	C9—H9	0.9800
C4—H4	0.9300	C8—H8A	0.9700
C3—C2	1.370 (5)	C8—H8B	0.9700
C5—O2—C9	115.5 (2)	C10—C11—H11A	109.2
O2—C5—C6	122.7 (2)	Cl1—C11—H11A	109.2
O2—C5—C4	115.9 (2)	C10—C11—H11B	109.2
C6—C5—C4	121.3 (3)	Cl1—C11—H11B	109.2
C2—C1—C6	120.1 (3)	H11A—C11—H11B	107.9
C2—C1—H1	120.0	O1—C10—C11	123.6 (3)
C6—C1—H1	120.0	O1—C10—C9	119.5 (3)
C5—C6—C1	117.7 (3)	C11—C10—C9	116.7 (2)
C5—C6—C7	120.9 (3)	F1—C2—C1	119.0 (3)
C1—C6—C7	121.4 (3)	F1—C2—C3	118.6 (3)
C3—C4—C5	120.1 (3)	C1—C2—C3	122.4 (3)
C3—C4—H4	119.9	O2—C9—C8	115.8 (3)
C5—C4—H4	119.9	O2—C9—C10	108.5 (3)
C2—C3—C4	118.3 (3)	C8—C9—C10	118.1 (3)
C2—C3—H3	120.8	O2—C9—H9	104.2
C4—C3—H3	120.8	C8—C9—H9	104.2
C8—C7—C6	111.3 (2)	C10—C9—H9	104.2
C8—C7—H7A	109.4	C9—C8—C7	114.2 (3)
C6—C7—H7A	109.4	C9—C8—H8A	108.7
C8—C7—H7B	109.4	C7—C8—H8A	108.7
C6—C7—H7B	109.4	C9—C8—H8B	108.7
H7A—C7—H7B	108.0	C7—C8—H8B	108.7
C10—C11—Cl1	112.2 (2)	H8A—C8—H8B	107.6

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···Cgi	0.97	2.76	3.457 (3)	129

Symmetry code: (i) −x+1, −y+1, −z+1.