3-(3-Fluoro­benz­yl)isochroman-1-one

Babar, T.M.; Qadeer, G.; Rama, N.H.; Akhtar, J.; Helliwell, M.

doi:10.1107/S1600536809003304

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o418

doi:10.1107/S1600536809003304

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3-(3-Fluorobenzyl)isochroman-1-one

Tariq Mahmood Babar,^a Ghulam Qadeer,^a ^* Nasim Hasan Rama,^a Javeed Akhtar ^b and Madeleine Helliwell ^b

^aDepartment of Chemistry, Quaid-i-Azam Univeristy, Islamabad 45320, Pakistan, and ^bManchester Materials Science Centre and Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, England
^*Correspondence e-mail: qadeerqau@yahoo.com

(Received 22 January 2009; accepted 27 January 2009; online 31 January 2009)

In the molecule of the title compound, C₁₆H₁₃FO₂, the aromatic rings are oriented at a dihedral angle of 74.46 (4)°. The heterocyclic ring adopts a twisted conformation. In the crystal structure, there is a weak C—H⋯π interaction.

Related literature

For related structures, see: Schmalle et al. (1982 ); Schnebel et al. (2003 ). For bond-length data, see: Allen et al. (1987 ). For ring-puckering parameters, see: Cremer & Pople (1975 ). For details of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₁₆H₁₃FO₂
M_r = 256.26
Monoclinic, P 2₁ /c
a = 12.6154 (16) Å
b = 7.6918 (10) Å
c = 13.0532 (17) Å
β = 103.705 (2)°
V = 1230.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 (2) K
0.50 × 0.40 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
6739 measured reflections
2501 independent reflections
1805 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.096
S = 0.93
2501 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C3–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯Cg1ⁱ	0.95	2.95	3.806 (3)	151
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003304/hk2616sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003304/hk2616Isup2.hkl

checkCIF report

Comment top

The title compound was prepared in order to evalute its potential as antibacterial and antifungal agents. The CCDC search (Allen, 2002) showed that the crystal structures of rac-exo-tricarbonyl-(h6-3-phenyl isochromanone)chromium (Schnebel et al., 2003) and 3,4-dihydro-8-hydroxy-3-(4-hydroxyphenyl)isocoumarin (Schmalle et al., 1982) have been reported, which have close resemblance as far as isochromane and attached phenyl ring is considered. We report herein the synthesis and crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C3–C8) and C (C11–C16) are, of course, planar, and they are oriented at a dihedral angle of 74.46 (4)°. Ring B (O1/C1–C3/C8/C9) is not planar, having total puckering amplitude, Q_T, of 0.467 (3) Å and twisted conformation [ϕ = -105.12 (3)° and θ = 118.02 (3)°] (Cremer & Pople, 1975).

In the crystal structure, there is a C—H···π interaction (Table 1).

Related literature top

For related structures, see: Schmalle et al. (1982); Schnebel et al. (2003). For bond-length data, see: Allen et al. (1987). For ring-puckering parameters, see: Cremer & Pople (1975). For details of the Cambridge Structural Database, see: Allen (2002).

Experimental top

As shown in Scheme 2, a mixture of homophthalic acid (1.98 g, 11.0 mmol) and 2-(3-fluorophenyl) acetyl chloride (7.91 g, 46 mmol) was heated under reflux at 473 K. After concentration, the residue was chromatographed on silica gel column using petroleum ether (333–353 K) to give 3-(3-fluorobenzyl)-1H-isochromen-1-one. 2-(3-(3-fluorophenyl)-2-oxopropyl)benzoic acid was obtained by refluxing a solution of 3-(3-fluorobenzyl)-1H-isochromen-1-one (3.6 g, 15.9 mmol) in ethanol (200 ml) and potassium hydroxide (5%,200 ml) for 6 h. NaBH4 (1.6 g) was added to a solution of 2-(3-(3-fluorophenyl)-2-oxopropyl)benzoic acid (4.23 g, 17.8 mmol) in sodium hydroxide (1%, 180 ml), and the resulting solution was stirred overnight at room temperature. After being acidified with HCl, the whole mixture was extracted with dichloromethane (2 × 15 ml). Usual work-up gave crude racemic hydroxy-acid, 2-(3-(3-fluorophenyl)-2-hydroxy propyl)benzoic acid, which was dissolved in acetic anhydride (5 ml) and heated under reflux for 2 h to get the title compound (yield; 81%, m.p, 374–375 °). The crude compound was purified by column chromatography on silica gel with petroleum ether and recrystallized in ethanol.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The formation of the title compound.

3-(3-Fluorobenzyl)isochroman-1-one top

Crystal data top

C₁₆H₁₃FO₂	F(000) = 536
M_r = 256.26	D_x = 1.383 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 374(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.6154 (16) Å	Cell parameters from 1804 reflections
b = 7.6918 (10) Å	θ = 3.2–26.2°
c = 13.0532 (17) Å	µ = 0.10 mm⁻¹
β = 103.705 (2)°	T = 100 K
V = 1230.6 (3) Å³	Plate, colourless
Z = 4	0.50 × 0.40 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1805 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.055
Graphite monochromator	θ_max = 26.4°, θ_min = 1.7°
ϕ and ω scans	h = −15→15
6739 measured reflections	k = −8→9
2501 independent reflections	l = −16→9

Refinement top

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0463P)²] where P = (F_o² + 2F_c²)/3
2501 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₆H₁₃FO₂	V = 1230.6 (3) Å³
M_r = 256.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.6154 (16) Å	µ = 0.10 mm⁻¹
b = 7.6918 (10) Å	T = 100 K
c = 13.0532 (17) Å	0.50 × 0.40 × 0.10 mm
β = 103.705 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1805 reflections with I > 2σ(I)
6739 measured reflections	R_int = 0.055
2501 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 0.93	Δρ_max = 0.24 e Å⁻³
2501 reflections	Δρ_min = −0.19 e Å⁻³
172 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
F1	0.04488 (8)	0.11657 (13)	0.39583 (8)	0.0386 (3)
O1	0.45079 (8)	0.20180 (13)	0.44056 (8)	0.0218 (3)
O2	0.50042 (9)	0.34257 (14)	0.59049 (9)	0.0268 (3)
C1	0.47167 (12)	0.1662 (2)	0.33687 (12)	0.0196 (4)
H1	0.4666	0.2776	0.2964	0.024*
C2	0.58453 (12)	0.0910 (2)	0.34910 (13)	0.0212 (4)
H2A	0.5877	−0.0258	0.3815	0.025*
H2B	0.6005	0.0783	0.2788	0.025*
C3	0.66870 (12)	0.20666 (19)	0.41701 (12)	0.0200 (4)
C4	0.77528 (12)	0.2189 (2)	0.40595 (13)	0.0241 (4)
H4	0.7972	0.1532	0.3529	0.029*
C5	0.84964 (13)	0.3259 (2)	0.47153 (14)	0.0288 (4)
H5	0.9225	0.3325	0.4636	0.035*
C6	0.81851 (13)	0.4239 (2)	0.54894 (14)	0.0295 (4)
H6	0.8699	0.4974	0.5938	0.035*
C7	0.71298 (13)	0.4138 (2)	0.56045 (14)	0.0259 (4)
H7	0.6915	0.4811	0.6131	0.031*
C8	0.63765 (12)	0.30552 (19)	0.49515 (13)	0.0206 (4)
C9	0.52632 (13)	0.28886 (19)	0.51240 (13)	0.0214 (4)
C10	0.38215 (12)	0.0446 (2)	0.28054 (13)	0.0219 (4)
H10A	0.3948	0.0162	0.2104	0.026*
H10B	0.3872	−0.0651	0.3211	0.026*
C11	0.26821 (12)	0.1165 (2)	0.26575 (13)	0.0209 (4)
C12	0.20723 (12)	0.0833 (2)	0.33946 (13)	0.0230 (4)
H12	0.2368	0.0155	0.4003	0.028*
C13	0.10394 (13)	0.1499 (2)	0.32292 (14)	0.0256 (4)
C14	0.05618 (14)	0.2488 (2)	0.23648 (15)	0.0301 (4)
H14	−0.0159	0.2923	0.2272	0.036*
C15	0.11730 (13)	0.2824 (2)	0.16351 (15)	0.0310 (4)
H15	0.0871	0.3507	0.1030	0.037*
C16	0.22210 (13)	0.2173 (2)	0.17798 (14)	0.0263 (4)
H16	0.2631	0.2417	0.1273	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0329 (6)	0.0451 (7)	0.0432 (7)	−0.0007 (5)	0.0195 (5)	−0.0039 (5)
O1	0.0239 (6)	0.0238 (6)	0.0181 (6)	0.0009 (5)	0.0059 (5)	−0.0008 (5)
O2	0.0334 (7)	0.0281 (6)	0.0203 (7)	0.0060 (5)	0.0091 (6)	−0.0012 (5)
C1	0.0257 (8)	0.0187 (8)	0.0150 (8)	0.0008 (6)	0.0058 (7)	0.0018 (7)
C2	0.0258 (9)	0.0201 (8)	0.0189 (9)	0.0005 (7)	0.0079 (7)	−0.0004 (7)
C3	0.0242 (8)	0.0161 (8)	0.0189 (9)	0.0045 (6)	0.0038 (7)	0.0046 (7)
C4	0.0251 (9)	0.0212 (8)	0.0262 (10)	0.0028 (7)	0.0065 (8)	0.0008 (7)
C5	0.0221 (9)	0.0258 (9)	0.0380 (11)	0.0020 (7)	0.0063 (8)	0.0015 (8)
C6	0.0271 (9)	0.0229 (9)	0.0341 (11)	−0.0002 (7)	−0.0016 (8)	−0.0044 (8)
C7	0.0311 (9)	0.0210 (9)	0.0236 (10)	0.0053 (7)	0.0028 (8)	−0.0020 (7)
C8	0.0241 (8)	0.0175 (8)	0.0191 (9)	0.0043 (6)	0.0028 (7)	0.0029 (7)
C9	0.0286 (9)	0.0163 (8)	0.0190 (9)	0.0046 (7)	0.0052 (8)	0.0041 (7)
C10	0.0263 (9)	0.0183 (8)	0.0218 (9)	−0.0005 (6)	0.0070 (8)	0.0004 (7)
C11	0.0238 (9)	0.0157 (8)	0.0220 (9)	−0.0038 (6)	0.0031 (7)	−0.0029 (7)
C12	0.0255 (9)	0.0198 (8)	0.0221 (9)	−0.0009 (7)	0.0028 (8)	−0.0002 (7)
C13	0.0248 (9)	0.0247 (9)	0.0293 (10)	−0.0048 (7)	0.0100 (8)	−0.0063 (8)
C14	0.0219 (9)	0.0236 (9)	0.0409 (12)	0.0016 (7)	−0.0002 (8)	−0.0077 (8)
C15	0.0314 (10)	0.0248 (9)	0.0312 (11)	−0.0001 (7)	−0.0039 (9)	0.0033 (8)
C16	0.0290 (9)	0.0249 (9)	0.0232 (10)	−0.0051 (7)	0.0030 (8)	0.0013 (8)

Geometric parameters (Å, º) top

F1—C13	1.3648 (19)	C6—H6	0.9500
O1—C1	1.4646 (18)	C7—C8	1.393 (2)
O1—C9	1.3461 (19)	C7—H7	0.9500
O2—C9	1.2141 (19)	C8—C9	1.480 (2)
C1—C2	1.510 (2)	C10—C11	1.509 (2)
C1—C10	1.516 (2)	C10—H10A	0.9900
C1—H1	1.0000	C10—H10B	0.9900
C2—C3	1.503 (2)	C11—C12	1.391 (2)
C2—H2A	0.9900	C11—C16	1.391 (2)
C2—H2B	0.9900	C12—C13	1.369 (2)
C3—C4	1.389 (2)	C12—H12	0.9500
C3—C8	1.400 (2)	C13—C14	1.376 (3)
C4—C5	1.382 (2)	C14—C15	1.384 (2)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.390 (2)	C15—C16	1.384 (2)
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.377 (2)	C16—H16	0.9500

C9—O1—C1	118.95 (12)	C7—C8—C9	119.56 (14)
O1—C1—C2	110.20 (13)	C3—C8—C9	120.21 (14)
O1—C1—C10	106.69 (12)	O2—C9—O1	117.85 (14)
C2—C1—C10	112.96 (13)	O2—C9—C8	123.52 (15)
O1—C1—H1	109.0	O1—C9—C8	118.54 (14)
C2—C1—H1	109.0	C11—C10—C1	114.41 (13)
C10—C1—H1	109.0	C11—C10—H10A	108.7
C3—C2—C1	110.62 (12)	C1—C10—H10A	108.7
C3—C2—H2A	109.5	C11—C10—H10B	108.7
C1—C2—H2A	109.5	C1—C10—H10B	108.7
C3—C2—H2B	109.5	H10A—C10—H10B	107.6
C1—C2—H2B	109.5	C12—C11—C16	118.69 (15)
H2A—C2—H2B	108.1	C12—C11—C10	120.69 (15)
C4—C3—C8	118.91 (15)	C16—C11—C10	120.61 (15)
C4—C3—C2	123.01 (14)	C13—C12—C11	118.96 (16)
C8—C3—C2	118.07 (14)	C13—C12—H12	120.5
C5—C4—C3	120.51 (15)	C11—C12—H12	120.5
C5—C4—H4	119.7	F1—C13—C12	118.44 (16)
C3—C4—H4	119.7	F1—C13—C14	118.07 (15)
C4—C5—C6	120.40 (15)	C12—C13—C14	123.49 (17)
C4—C5—H5	119.8	C13—C14—C15	117.42 (15)
C6—C5—H5	119.8	C13—C14—H14	121.3
C7—C6—C5	119.75 (16)	C15—C14—H14	121.3
C7—C6—H6	120.1	C14—C15—C16	120.54 (17)
C5—C6—H6	120.1	C14—C15—H15	119.7
C6—C7—C8	120.26 (16)	C16—C15—H15	119.7
C6—C7—H7	119.9	C15—C16—C11	120.89 (16)
C8—C7—H7	119.9	C15—C16—H16	119.6
C7—C8—C3	120.17 (15)	C11—C16—H16	119.6

C9—O1—C1—C2	48.49 (17)	C7—C8—C9—O2	−12.0 (2)
C9—O1—C1—C10	171.47 (12)	C3—C8—C9—O2	164.92 (15)
O1—C1—C2—C3	−53.65 (16)	C7—C8—C9—O1	171.54 (14)
C10—C1—C2—C3	−172.87 (13)	C3—C8—C9—O1	−11.5 (2)
C1—C2—C3—C4	−150.46 (15)	O1—C1—C10—C11	59.46 (17)
C1—C2—C3—C8	29.9 (2)	C2—C1—C10—C11	−179.30 (14)
C8—C3—C4—C5	0.5 (2)	C1—C10—C11—C12	−92.74 (17)
C2—C3—C4—C5	−179.19 (15)	C1—C10—C11—C16	87.32 (19)
C3—C4—C5—C6	−0.5 (2)	C16—C11—C12—C13	0.4 (2)
C4—C5—C6—C7	0.1 (3)	C10—C11—C12—C13	−179.59 (14)
C5—C6—C7—C8	0.3 (3)	C11—C12—C13—F1	−179.96 (13)
C6—C7—C8—C3	−0.3 (2)	C11—C12—C13—C14	0.1 (2)
C6—C7—C8—C9	176.63 (14)	F1—C13—C14—C15	179.63 (14)
C4—C3—C8—C7	−0.1 (2)	C12—C13—C14—C15	−0.5 (3)
C2—C3—C8—C7	179.61 (14)	C13—C14—C15—C16	0.3 (2)
C4—C3—C8—C9	−176.99 (14)	C14—C15—C16—C11	0.1 (2)
C2—C3—C8—C9	2.7 (2)	C12—C11—C16—C15	−0.5 (2)
C1—O1—C9—O2	167.83 (13)	C10—C11—C16—C15	179.45 (14)
C1—O1—C9—C8	−15.51 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cg1ⁱ	0.95	2.95	3.806 (3)	151

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃FO₂
M_r	256.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.6154 (16), 7.6918 (10), 13.0532 (17)
β (°)	103.705 (2)
V (Å³)	1230.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.50 × 0.40 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6739, 2501, 1805
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.096, 0.93
No. of reflections	2501
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cg1ⁱ	0.95	2.95	3.806 (3)	151

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Acknowledgements

The authors gratefully acknowledge the financial support of the Higher Education Commission, Islamabad, Pakistan.

References

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