3-(4-Fluoro­benz­yl)-1H-isochromene-1-thione

Babar, T.M.; Qadeer, G.; Rama, N.H.; Khawar Rauf, M.; Wong, W.-Y.

doi:10.1107/S1600536809004152

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o500

doi:10.1107/S1600536809004152

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3-(4-Fluorobenzyl)-1H-isochromene-1-thione

Tariq Mahmood Babar,^a Ghulam Qadeer,^a ^* Nasim Hasan Rama,^a ‡ Muhammad Khawar Rauf ^a and Wai-Yeung Wong ^b §

^aDepartment of Chemistry, Quaid-i-azam University, Islamabad 45320, Pakistan, and ^bDepartment of Chemistry, Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong, People's Republic of China
^*Correspondence e-mail: qadeerqau@yahoo.com

(Received 23 January 2009; accepted 4 February 2009; online 11 February 2009)

In the molecule of the title compound, C₁₆H₁₁FOS, the benzene ring is oriented at a dihedral angle of 89.68 (3)° with respect to the planar [maximum deviation 0.009 (2) Å] isocoumarin ring system. An intramolecular C—H⋯S interaction results in the formation of a planar five-membered ring. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules into chains parallel to the c axis. A π–π contact between the isocoumarin rings [centroid–centroid distance = 3.818 (3) Å] may further stabilize the structure.

Related literature

For general background, see: Barry (1964 ); Sturtz et al. (2002 ); Rossi et al. (2003 ); Powers et al. (2002 ); Thomas & Jens (1999 ). For a related structure, see: Abid et al. (2006 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₁FOS
M_r = 270.31
Monoclinic, P 2₁ /c
a = 8.7346 (6) Å
b = 17.9516 (11) Å
c = 8.4481 (5) Å
β = 95.026 (1)°
V = 1319.57 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 294 (2) K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.805, T_max = 0.952
7856 measured reflections
3188 independent reflections
2655 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.150
S = 1.03
3188 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯S1	0.93	2.78	3.142 (2)	105
C3—H3A⋯O1ⁱ	0.93	2.60	3.529 (2)	178
Symmetry code: (i) x, y, z-1.

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: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809004152/hk2617sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809004152/hk2617Isup2.hkl

checkCIF report

Comment top

The isocoumarin nucleus is an abundant structural motif in natural products (Barry, 1964). Many constituents of the steadily growing class of known isocoumarins exhibit valuable biological properties such as antifungal (Sturtz et al., 2002), antitumor or cytotoxic, anti-inflammatory, anti-allergic (Rossi et al., 2003) and enzyme inhibitory (Powers et al., 2002) activities. Naturally occurring halo-isocoumarins and their halogeno-3,4-dihydroiscoumarin derivatives are very rare. However, a few examples of naturally occurring chlorine containing isocoumarins are known (Thomas & Jens, 1999). In view of the importance of this class of compounds, the title compound, an isocoumarine derivative containing 4-fluorobenzyl substituent has been synthesized, and we report herein its crystal structure.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges, and comparable with the corresponding values in 3-(2-chlorobenzyl)isocoumarin (Abid et al., 2006). Rings A (C1-C6), B (O1/C5-C9) and C (C11-C16) are, of course, planar and the dihedral angles between them are A/B = 0.29 (3)°, A/C = 89.77 (4)° and B/C = 89.53 (3)°. The intramolecular C-H···S interaction (Table 1) results in the formation of a planar five-membered ring D (S1/C1/C6/C7/H1A).

In the crystal structure, intermolecular C-H···O hydrogen bonds (Table 1) link the molecules into chains parallel to the c-axis (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contact between the isocoumarine rings, Cg1—Cg2ⁱ [symmetry code: (i) -x, -y, 1 - z, where Cg1 and Cg2 are centroids of the rings A (C1-C6) and B (O1/C5-C9), respectively] may further stabilize the structure, with centroid-centroid distance of 3.818 (3) Å.

Related literature top

For general background, see: Barry (1964); Sturtz et al. (2002); Rossi et al. (2003); Powers et al. (2002); Thomas & Jens (1999). For a related structure, see: Abid et al. (2006). For bond-length data, see: Allen et al. (1987).

Experimental top

As shown in Scheme 2, the title compound was synthesized by refluxing 3-(4-fluorobenzyl)-1H-isochromen-1-one (0.5 g, 1.8 mmol) with Lawesson's reagent (0.89 g, 2.2 mmol) in dry toluene for 4 h. Pure thioisocoumarin was obtained by recrystalization in methanol (yield; 90%, m.p. 665-667 K).

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: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
	Fig. 3. The formation of the title compound.

3-(4-Fluorobenzyl)-1H-isochromene-1-thione top

Crystal data top

C₁₆H₁₁FOS	F(000) = 560
M_r = 270.31	D_x = 1.361 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 392(2) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.7346 (6) Å	Cell parameters from 1423 reflections
b = 17.9516 (11) Å	θ = 4.2–25.4°
c = 8.4481 (5) Å	µ = 0.25 mm⁻¹
β = 95.026 (1)°	T = 294 K
V = 1319.57 (14) Å³	Block, yellow
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3188 independent reflections
Radiation source: fine-focus sealed tube	2655 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
T_min = 0.805, T_max = 0.952	k = −23→22
7856 measured reflections	l = −8→11

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0856P)² + 0.2983P] where P = (F_o² + 2F_c²)/3
3188 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₆H₁₁FOS	V = 1319.57 (14) Å³
M_r = 270.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.7346 (6) Å	µ = 0.25 mm⁻¹
b = 17.9516 (11) Å	T = 294 K
c = 8.4481 (5) Å	0.30 × 0.25 × 0.20 mm
β = 95.026 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3188 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2655 reflections with I > 2σ(I)
T_min = 0.805, T_max = 0.952	R_int = 0.016
7856 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.03	Δρ_max = 0.34 e Å⁻³
3188 reflections	Δρ_min = −0.30 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
S1	0.07012 (6)	0.65948 (3)	0.36335 (6)	0.0646 (2)
O1	0.20272 (15)	0.53300 (6)	0.37410 (13)	0.0506 (3)
F1	0.51024 (16)	0.13358 (7)	0.29180 (19)	0.0845 (4)
C1	0.0938 (2)	0.63191 (10)	−0.0010 (2)	0.0563 (4)
H1A	0.0472	0.6745	0.0350	0.068*
C2	0.1045 (3)	0.62201 (12)	−0.1609 (2)	0.0665 (5)
H2A	0.0656	0.6581	−0.2326	0.080*
C3	0.1727 (3)	0.55866 (12)	−0.2156 (2)	0.0706 (6)
H3A	0.1785	0.5521	−0.3241	0.085*
C4	0.2320 (3)	0.50543 (11)	−0.1113 (2)	0.0656 (5)
H4A	0.2784	0.4633	−0.1496	0.079*
C5	0.2234 (2)	0.51390 (9)	0.05279 (18)	0.0483 (4)
C6	0.15271 (18)	0.57814 (8)	0.10781 (17)	0.0439 (3)
C7	0.14344 (18)	0.58791 (9)	0.27669 (18)	0.0446 (3)
C8	0.2707 (2)	0.46929 (8)	0.32005 (19)	0.0482 (4)
C9	0.2829 (2)	0.45929 (9)	0.1661 (2)	0.0523 (4)
H9A	0.3304	0.4166	0.1313	0.063*
C10	0.3182 (3)	0.41971 (10)	0.4583 (2)	0.0615 (5)
H10A	0.2320	0.4141	0.5222	0.074*
H10B	0.4006	0.4438	0.5237	0.074*
C11	0.3716 (2)	0.34333 (9)	0.4123 (2)	0.0515 (4)
C12	0.5239 (3)	0.32831 (12)	0.3957 (3)	0.0741 (6)
H12A	0.5961	0.3662	0.4129	0.089*
C13	0.5718 (2)	0.25794 (14)	0.3540 (3)	0.0799 (7)
H13A	0.6748	0.2483	0.3421	0.096*
C14	0.4648 (2)	0.20356 (10)	0.3309 (2)	0.0585 (4)
C15	0.3136 (2)	0.21543 (11)	0.3461 (3)	0.0671 (5)
H15A	0.2425	0.1771	0.3292	0.081*
C16	0.2677 (2)	0.28622 (11)	0.3875 (3)	0.0644 (5)
H16A	0.1644	0.2952	0.3987	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0761 (4)	0.0604 (3)	0.0583 (3)	0.0200 (2)	0.0112 (2)	−0.0054 (2)
O1	0.0702 (8)	0.0431 (6)	0.0390 (5)	0.0077 (5)	0.0071 (5)	−0.0006 (4)
F1	0.0826 (9)	0.0557 (7)	0.1132 (11)	0.0188 (6)	−0.0030 (8)	−0.0146 (7)
C1	0.0629 (11)	0.0529 (9)	0.0526 (9)	0.0022 (8)	0.0028 (7)	0.0071 (7)
C2	0.0840 (14)	0.0661 (11)	0.0485 (9)	−0.0040 (10)	−0.0003 (9)	0.0157 (9)
C3	0.1044 (17)	0.0684 (12)	0.0396 (8)	−0.0116 (11)	0.0106 (9)	0.0040 (8)
C4	0.1026 (16)	0.0520 (9)	0.0441 (9)	−0.0023 (10)	0.0173 (9)	−0.0040 (7)
C5	0.0635 (10)	0.0415 (7)	0.0408 (7)	−0.0063 (7)	0.0093 (7)	−0.0009 (6)
C6	0.0473 (8)	0.0431 (7)	0.0412 (7)	−0.0052 (6)	0.0042 (6)	0.0012 (6)
C7	0.0462 (8)	0.0438 (7)	0.0437 (7)	−0.0001 (6)	0.0043 (6)	0.0000 (6)
C8	0.0623 (10)	0.0364 (7)	0.0460 (8)	0.0016 (6)	0.0053 (7)	−0.0004 (6)
C9	0.0713 (11)	0.0383 (7)	0.0484 (8)	0.0032 (7)	0.0110 (7)	−0.0020 (6)
C10	0.0910 (14)	0.0465 (9)	0.0466 (9)	0.0090 (9)	0.0037 (8)	0.0035 (7)
C11	0.0653 (10)	0.0424 (8)	0.0464 (8)	0.0041 (7)	0.0019 (7)	0.0069 (6)
C12	0.0598 (12)	0.0560 (11)	0.1061 (18)	−0.0107 (9)	0.0047 (11)	−0.0067 (11)
C13	0.0506 (11)	0.0685 (13)	0.121 (2)	0.0047 (9)	0.0111 (12)	−0.0073 (13)
C14	0.0621 (11)	0.0453 (8)	0.0666 (11)	0.0093 (7)	−0.0027 (8)	−0.0016 (8)
C15	0.0561 (11)	0.0462 (9)	0.0976 (15)	−0.0034 (8)	−0.0018 (10)	−0.0022 (9)
C16	0.0508 (10)	0.0538 (10)	0.0891 (14)	0.0065 (8)	0.0080 (9)	0.0029 (9)

Geometric parameters (Å, º) top

C1—C2	1.373 (3)	C8—C10	1.498 (2)
C1—C6	1.400 (2)	C9—H9A	0.9300
C1—H1A	0.9300	C10—C11	1.510 (2)
C2—C3	1.382 (3)	C10—H10A	0.9700
C2—H2A	0.9300	C10—H10B	0.9700
C3—C4	1.370 (3)	C11—C16	1.373 (3)
C3—H3A	0.9300	C11—C12	1.376 (3)
C4—C5	1.403 (2)	C12—C13	1.386 (3)
C4—H4A	0.9300	C12—H12A	0.9300
C5—C6	1.406 (2)	C13—C14	1.353 (3)
C5—C9	1.435 (2)	C13—H13A	0.9300
C6—C7	1.447 (2)	C14—C15	1.355 (3)
C7—O1	1.3573 (19)	C14—F1	1.367 (2)
C7—S1	1.6367 (16)	C15—C16	1.387 (3)
C8—C9	1.327 (2)	C15—H15A	0.9300
C8—O1	1.3843 (18)	C16—H16A	0.9300

C2—C1—C6	120.26 (18)	C5—C9—H9A	119.8
C2—C1—H1A	119.9	C8—C10—C11	114.22 (15)
C6—C1—H1A	119.9	C8—C10—H10A	108.7
C1—C2—C3	120.26 (18)	C11—C10—H10A	108.7
C1—C2—H2A	119.9	C8—C10—H10B	108.7
C3—C2—H2A	119.9	C11—C10—H10B	108.7
C4—C3—C2	120.55 (17)	H10A—C10—H10B	107.6
C4—C3—H3A	119.7	C16—C11—C12	118.03 (17)
C2—C3—H3A	119.7	C16—C11—C10	120.16 (18)
C3—C4—C5	120.66 (18)	C12—C11—C10	121.81 (18)
C3—C4—H4A	119.7	C11—C12—C13	121.35 (19)
C5—C4—H4A	119.7	C11—C12—H12A	119.3
C4—C5—C6	118.58 (15)	C13—C12—H12A	119.3
C4—C5—C9	122.49 (16)	C14—C13—C12	118.3 (2)
C6—C5—C9	118.92 (14)	C14—C13—H13A	120.8
C1—C6—C5	119.68 (15)	C12—C13—H13A	120.8
C1—C6—C7	121.00 (15)	C13—C14—C15	122.61 (18)
C5—C6—C7	119.31 (14)	C13—C14—F1	119.12 (18)
O1—C7—C6	117.29 (13)	C15—C14—F1	118.27 (18)
O1—C7—S1	116.25 (11)	C14—C15—C16	118.29 (18)
C6—C7—S1	126.45 (12)	C14—C15—H15A	120.9
C9—C8—O1	120.60 (14)	C16—C15—H15A	120.9
C9—C8—C10	130.03 (16)	C11—C16—C15	121.39 (18)
O1—C8—C10	109.36 (13)	C11—C16—H16A	119.3
C8—C9—C5	120.38 (15)	C15—C16—H16A	119.3
C8—C9—H9A	119.8	C7—O1—C8	123.49 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···S1	0.93	2.78	3.142 (2)	105
C3—H3A···O1ⁱ	0.93	2.60	3.529 (2)	178

Symmetry code: (i) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₁FOS
M_r	270.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	8.7346 (6), 17.9516 (11), 8.4481 (5)
β (°)	95.026 (1)
V (Å³)	1319.57 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.805, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	7856, 3188, 2655
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.150, 1.03
No. of reflections	3188
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.30

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···S1	0.93	2.78	3.142 (2)	105
C3—H3A···O1ⁱ	0.93	2.60	3.529 (2)	178

Symmetry code: (i) x, y, z−1.

Footnotes

‡Additional correspondence author, e-mail nasimhrama@yahoo.com.

§Additional correspondence author, e-mail rwywong@hkbu.edu.hk.

Acknowledgements

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

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