
Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053111/cv2320sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053111/cv2320Isup2.hkl |
CCDC reference: 667480
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%.
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 Uiso(H) = 1.2Ueq(C).
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.
For a related crystal structure, see Thiruvalluvar et al. (2007). For applications of sulfoxides, see: Pandiarajan et al. (1993) and Yavari et al. (2006).
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).
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) Å3 | 0.47 × 0.42 × 0.22 mm |
Z = 4 |
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 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)] = 0.085 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.170 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.23 | w = 1/[σ2(Fo2) + 6.1662P] where P = (Fo2 + 2Fc2)/3 |
1297 reflections | (Δ/σ)max < 0.004 |
108 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
C17H14FO2S | V = 1455.32 (12) Å3 |
Mr = 301.35 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.3887 (5) Å | µ = 0.23 mm−1 |
b = 24.6558 (14) Å | T = 200 K |
c = 5.1828 (2) Å | 0.47 × 0.42 × 0.22 mm |
CrysAlis CCD diffractometer | 1297 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | 1218 reflections with I > 2σ(I) |
Tmin = 0.915, Tmax = 1.000 | Rint = 0.064 |
12255 measured reflections |
R[F2 > 2σ(F2)] = 0.085 | 0 restraints |
wR(F2) = 0.170 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.23 | Δρmax = 0.41 e Å−3 |
1297 reflections | Δρmin = −0.61 e Å−3 |
108 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
S1—O1 | 1.5065 (18) | C13B—C14B | 1.391 (12) |
S1—C2 | 1.831 (2) | C14A—C15A | 1.390 (4) |
S1—C2i | 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—C2i | 105.88 (8) | S1—C2—H2 | 105.7 (10) |
C2—S1—C2i | 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—C3i | 121.82 (11) | C11A—C12A—H12A | 120.00 |
C3—C4—C3i | 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—C3i | −50.3 (3) |
C2i—S1—C2—C3 | −59.94 (16) | C2—C11A—C12A—C13A | −179.0 (2) |
C2i—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1ii | 0.965 (16) | 2.430 (16) | 3.206 (3) | 137.2 (13) |
Symmetry code: (ii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C17H14FO2S |
Mr | 301.35 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 200 |
a, b, c (Å) | 11.3887 (5), 24.6558 (14), 5.1828 (2) |
V (Å3) | 1455.32 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.47 × 0.42 × 0.22 |
Data collection | |
Diffractometer | CrysAlis CCD |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2007) |
Tmin, Tmax | 0.915, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12255, 1297, 1218 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.085, 0.170, 1.23 |
No. of reflections | 1297 |
No. of parameters | 108 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.41, −0.61 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).
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.