2-(4-Fluoro­phen­yl)-6-phenyl­tetra­hydro-2H-thio­pyran-4-one 1-oxide

In the title compound, C₁₇H₁₅FO₂S, a crystallographic mirror plane bis­ects the mol­ecule, passing through O=S and C=O of the central ring, with statistical disorder of the F atom. Orientational disorder of the aromatic ring is also observed; the site occupancy factors are ca. 0.75 and 0.25. In the mol­ecule, the thio­pyran unit has a chair conformation; the geometries around the S and carbonyl C atoms are tetra­hedral and planar, respectively.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.085
• wR factor = 0.170
• Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.28 Ratio
PLAT301_ALERT_3_B Main Residue  Disorder .........................      36.00 Perc.
PLAT432_ALERT_2_B Short Inter X...Y Contact  O1     ..  C4      ..       2.87 Ang.
PLAT432_ALERT_2_B Short Inter X...Y Contact  C13B   ..  C16B    ..       3.04 Ang.

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.95
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for       C13A
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for       C13B
PLAT245_ALERT_2_C U(iso) H2      Smaller than U(eq) C2      by ...       0.01 AngSq

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.950
            Tmax scaled      0.950 Tmin scaled      0.869
PLAT793_ALERT_1_G Check the Absolute Configuration of C2     = ...          R

   0 ALERT level A = In general: serious problem
   4 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

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

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S1. Comment

The chemistry of organic cyclic sulfoxides continues to attract considerable attention due to their synthetic potential. The main advantage of sulfoxides over other sulfur function groups such as sulfides and sulfones is in their chirality. Sulfoxides are chiral groups which are easy to introduce and easy to remove and which give high asymmetric induction in many reactions. A large number of sulfoxides find applications in medicine and industry (Pandiarajan et al., 1993; Yavari et al., 2006). Thiruvalluvar et al. (2007) have reported a crystal structure of 2-[2,6-bis(4-methoxyphenyl)tetrahydrothiopyran- 4-ylidene]malononitrile, wherein the thiopyran unit is in chair form.

The molecular structure of the title compound, (I), is shown in Fig. 1. The thiopyran unit is in the chair form. The dihedral angle between the two orientations of disordered benzene ring is 16.5 (3)°. The geometry around S1 atom is tetrahedral and around C4 - planar. A crystallographic mirror plane bisects the molecule, passing through the O=S and opposite the C=O atoms of the central ring. The (p-fluoro)phenyl at the 2 position and the phenyl ring at the 6 position have equatorial orientations.

Related literature

For a related crystal structure, see Thiruvalluvar et al. (2007). For applications of sulfoxides, see: Pandiarajan et al. (1993) and Yavari et al. (2006).

S2. Experimental

A mixture of cis-2-(p-fluro)phenyl-6-phenyldithian-4-one (2.82 g, 0.01 mol), diethyl ether (60 ml), bromine (3.0 g) in water (30 ml) was shaken for few minutes. The solid that separated was filtered, washed with ether and recrystallized from chloroform-carbon tetrachloride mixture (1:1 v/v). The yield: 2.1 g, 70%.

S3. Refinement

The structure was solved in the space group Pnma with a half of molecule in the asymmetric unit. The sum of s.o.f. of F1A and F1B is 0.5. The (p-fluoro)phenyl group is disordered over two positions in a 0.751 (2):0.249 (2) ratio. All H atoms were positioned geometrically (C—H = 0.95–1.00 Å). Atom H2 was refined isotropically, while the rest H atoms were refined as riding, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis CCD (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

Fig. 1. The molecular structure of the title compound with the atomic numbering and 50% probability displacement ellipsoids. Only major component of the disordered (p-fluoro)phenyl group is shown (the occupancies of C11A—C16A and F1A atoms are 0.751 (2) and 0.376 (1), respectively). The unlabelled and labelled atoms are related by mirror plane [symmetry code: x, y, 1/2 - z].

2-(4-Fluorophenyl)-6-phenyltetrahydro-2H-thiopyran-4-one 1-oxide

Crystal data

C17H14FO2S	F(000) = 628
Mr = 301.35	Dx = 1.375 Mg m^−3
Orthorhombic, Pnma	Melting point: 429 K
Hall symbol: -P 2ac 2n	Mo Kα radiation, λ = 0.71073 Å
a = 11.3887 (5) Å	µ = 0.23 mm^−1
b = 24.6558 (14) Å	T = 200 K
c = 5.1828 (2) Å	Prism, colourless
V = 1455.32 (12) Å^3	0.47 × 0.42 × 0.22 mm
Z = 4

Data collection

CrysAlis CCD diffractometer	1297 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1218 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
Detector resolution: 10.5081 pixels mm^-1	θmax = 25.0°, θmin = 4.6°
φ and ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −29→29
Tmin = 0.915, Tmax = 1.000	l = −6→6
12255 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.085	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H atoms treated by a mixture of independent and constrained refinement
S = 1.23	w = 1/[σ^2(Fo^2) + 6.1662P] where P = (Fo^2 + 2Fc^2)/3
1297 reflections	(Δ/σ)max < 0.004
108 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.61 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	Occ. (<1)
S1	0.22216 (6)	0.25000	0.26615 (12)	0.0292 (2)
O1	0.29629 (18)	0.25000	0.0254 (3)	0.0430 (6)
O4	0.53648 (19)	0.25000	0.7603 (5)	0.0628 (8)
C2	0.27869 (17)	0.19474 (9)	0.4669 (4)	0.0363 (6)
C3	0.41209 (17)	0.19809 (10)	0.4870 (4)	0.0435 (7)
C4	0.4589 (2)	0.25000	0.6018 (5)	0.0407 (9)
C11A	0.23702 (14)	0.14190 (6)	0.3389 (3)	0.0389 (7)	0.751 (2)
C12A	0.29790 (18)	0.11851 (8)	0.1348 (4)	0.0640 (11)	0.751 (2)
C13A	0.2563 (3)	0.07115 (9)	0.0215 (5)	0.0893 (16)	0.751 (2)
C14A	0.1539 (3)	0.04718 (8)	0.1123 (6)	0.0757 (13)	0.751 (2)
C15A	0.09301 (19)	0.07057 (9)	0.3164 (6)	0.0666 (13)	0.751 (2)
C16A	0.13457 (15)	0.11792 (8)	0.4297 (4)	0.0510 (10)	0.751 (2)
F1A	0.1134 (4)	0.00221 (17)	0.0294 (12)	0.102 (2)	0.376 (1)
F1B	0.0819 (14)	0.0004 (5)	0.184 (4)	0.102 (2)	0.124 (1)
C11B	0.2246 (4)	0.14362 (19)	0.3974 (10)	0.0389 (7)	0.249 (2)
C12B	0.2571 (6)	0.1214 (3)	0.1615 (11)	0.0640 (11)	0.249 (2)
C13B	0.2080 (8)	0.0727 (3)	0.0801 (15)	0.0893 (16)	0.249 (2)
C14B	0.1264 (8)	0.0462 (3)	0.235 (2)	0.0757 (13)	0.249 (2)
C15B	0.0938 (6)	0.0685 (3)	0.4705 (19)	0.0666 (13)	0.249 (2)
C16B	0.1430 (5)	0.1171 (3)	0.5519 (12)	0.0510 (10)	0.249 (2)
H3A	0.44573	0.19371	0.31205	0.0522*
H3B	0.44008	0.16732	0.59314	0.0522*
H12A	0.36791	0.13490	0.07269	0.0769*	0.751 (2)
H13A	0.29794	0.05517	−0.11800	0.1071*	0.751 (2)
H15A	0.02300	0.05418	0.37848	0.0796*	0.751 (2)
H16A	0.09297	0.13391	0.56917	0.0610*	0.751 (2)
H2	0.2454 (15)	0.2004 (7)	0.636 (3)	0.025 (5)*
H12B	0.31295	0.13951	0.05590	0.0769*	0.249 (2)
H13B	0.23027	0.05754	−0.08116	0.1071*	0.249 (2)
H15B	0.03804	0.05035	0.57606	0.0796*	0.249 (2)
H16B	0.12072	0.13232	0.71313	0.0610*	0.249 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0222 (3)	0.0475 (4)	0.0180 (3)	0.0000	−0.0027 (3)	0.0000
O1	0.0384 (10)	0.0743 (14)	0.0162 (9)	0.0000	0.0048 (9)	0.0000
O4	0.0290 (10)	0.124 (2)	0.0355 (11)	0.0000	−0.0096 (10)	0.0000
C2	0.0271 (9)	0.0576 (12)	0.0242 (9)	0.0057 (9)	−0.0001 (9)	0.0059 (9)
C3	0.0257 (9)	0.0688 (14)	0.0360 (11)	0.0067 (10)	−0.0032 (10)	0.0015 (11)
C4	0.0204 (12)	0.077 (2)	0.0247 (14)	0.0000	0.0015 (12)	0.0000
C11A	0.0380 (11)	0.0472 (12)	0.0316 (12)	0.0079 (10)	−0.0068 (11)	0.0057 (10)
C12A	0.051 (2)	0.0641 (16)	0.0770 (19)	−0.0027 (16)	0.0194 (19)	−0.0227 (16)
C13A	0.080 (3)	0.079 (2)	0.109 (3)	0.013 (2)	−0.007 (3)	−0.042 (2)
C14A	0.0651 (19)	0.0520 (16)	0.110 (3)	0.0069 (16)	−0.024 (2)	−0.005 (2)
C15A	0.0582 (16)	0.0645 (17)	0.077 (3)	−0.0136 (15)	−0.015 (2)	0.018 (2)
C16A	0.0455 (13)	0.0615 (16)	0.046 (2)	−0.0030 (13)	−0.0031 (16)	−0.0034 (18)
F1A	0.099 (3)	0.0493 (17)	0.159 (5)	−0.007 (2)	−0.035 (3)	−0.039 (3)
F1B	0.099 (3)	0.0493 (17)	0.159 (5)	−0.007 (2)	−0.035 (3)	−0.039 (3)
C11B	0.0380 (11)	0.0472 (12)	0.0316 (12)	0.0079 (10)	−0.0068 (11)	0.0057 (10)
C12B	0.051 (2)	0.0641 (16)	0.0770 (19)	−0.0027 (16)	0.0194 (19)	−0.0227 (16)
C13B	0.080 (3)	0.079 (2)	0.109 (3)	0.013 (2)	−0.007 (3)	−0.042 (2)
C14B	0.0651 (19)	0.0520 (16)	0.110 (3)	0.0069 (16)	−0.024 (2)	−0.005 (2)
C15B	0.0582 (16)	0.0645 (17)	0.077 (3)	−0.0136 (15)	−0.015 (2)	0.018 (2)
C16B	0.0455 (13)	0.0615 (16)	0.046 (2)	−0.0030 (13)	−0.0031 (16)	−0.0034 (18)

Geometric parameters (Å, º)

S1—O1	1.5065 (18)	C13B—C14B	1.391 (12)
S1—C2	1.831 (2)	C14A—C15A	1.390 (4)
S1—C2^i	1.831 (2)	C14B—C15B	1.389 (14)
F1A—C14A	1.275 (5)	C15A—C16A	1.390 (3)
F1B—C14B	1.266 (15)	C15B—C16B	1.389 (10)
O4—C4	1.206 (3)	C2—H2	0.965 (16)
C2—C11B	1.448 (5)	C3—H3A	0.9900
C2—C3	1.525 (3)	C3—H3B	0.9900
C2—C11A	1.537 (3)	C12A—H12A	0.9500
C3—C4	1.509 (3)	C12B—H12B	0.9500
C11A—C16A	1.390 (2)	C13A—H13A	0.9500
C11A—C12A	1.390 (3)	C13B—H13B	0.9500
C11B—C16B	1.390 (8)	C15A—H15A	0.9500
C11B—C12B	1.390 (8)	C15B—H15B	0.9500
C12A—C13A	1.390 (3)	C16A—H16A	0.9500
C12B—C13B	1.390 (11)	C16B—H16B	0.9500
C13A—C14A	1.390 (4)
O1—S1—C2	105.88 (8)	C11B—C16B—C15B	120.1 (6)
O1—S1—C2^i	105.88 (8)	S1—C2—H2	105.7 (10)
C2—S1—C2^i	96.15 (10)	C3—C2—H2	108.8 (10)
S1—C2—C3	110.41 (15)	C11A—C2—H2	113.2 (10)
S1—C2—C11A	106.07 (13)	C11B—C2—H2	100.6 (11)
S1—C2—C11B	110.9 (2)	C2—C3—H3A	108.00
C3—C2—C11A	112.52 (17)	C2—C3—H3B	108.00
C3—C2—C11B	119.2 (2)	C4—C3—H3A	108.00
C2—C3—C4	115.14 (18)	C4—C3—H3B	108.00
O4—C4—C3	121.82 (11)	H3A—C3—H3B	107.00
O4—C4—C3^i	121.82 (11)	C11A—C12A—H12A	120.00
C3—C4—C3^i	116.1 (2)	C13A—C12A—H12A	120.00
C2—C11A—C12A	121.74 (15)	C13B—C12B—H12B	120.00
C2—C11A—C16A	118.26 (15)	C11B—C12B—H12B	120.00
C12A—C11A—C16A	119.99 (16)	C14A—C13A—H13A	120.00
C12B—C11B—C16B	120.0 (5)	C12A—C13A—H13A	120.00
C2—C11B—C12B	116.7 (5)	C14B—C13B—H13B	120.00
C2—C11B—C16B	123.4 (5)	C12B—C13B—H13B	120.00
C11A—C12A—C13A	120.0 (2)	C16A—C15A—H15A	120.00
C11B—C12B—C13B	120.0 (6)	C14A—C15A—H15A	120.00
C12A—C13A—C14A	120.0 (2)	C16B—C15B—H15B	120.00
C12B—C13B—C14B	120.0 (7)	C14B—C15B—H15B	120.00
C13A—C14A—C15A	120.0 (2)	C15A—C16A—H16A	120.00
C13B—C14B—C15B	120.0 (7)	C11A—C16A—H16A	120.00
C14A—C15A—C16A	120.0 (2)	C11B—C16B—H16B	120.00
C14B—C15B—C16B	120.1 (7)	C15B—C16B—H16B	120.00
C11A—C16A—C15A	120.00 (19)
O1—S1—C2—C3	48.52 (17)	C2—C3—C4—O4	135.9 (2)
O1—S1—C2—C11A	−73.65 (13)	C2—C3—C4—C3^i	−50.3 (3)
C2^i—S1—C2—C3	−59.94 (16)	C2—C11A—C12A—C13A	−179.0 (2)
C2^i—S1—C2—C11A	177.89 (13)	C16A—C11A—C12A—C13A	0.0 (3)
S1—C2—C3—C4	59.5 (2)	C2—C11A—C16A—C15A	179.01 (19)
C11A—C2—C3—C4	177.76 (17)	C12A—C11A—C16A—C15A	0.0 (3)
S1—C2—C11A—C12A	83.40 (18)	C11A—C12A—C13A—C14A	0.0 (4)
S1—C2—C11A—C16A	−95.60 (17)	C12A—C13A—C14A—C15A	0.0 (4)
C3—C2—C11A—C12A	−37.4 (2)	C13A—C14A—C15A—C16A	0.0 (4)
C3—C2—C11A—C16A	143.58 (18)	C14A—C15A—C16A—C11A	0.0 (4)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1^ii	0.965 (16)	2.430 (16)	3.206 (3)	137.2 (13)

Symmetry code: (ii) x, y, z+1.