supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

fb2081 scheme

Acta Cryst. (2008). E64, o640    [ doi:10.1107/S1600536808005370 ]

4-(3-Nitrophenyl)-3-(phenylsulfonyl)but-3-en-2-one

Y. Wang and W. Pei

Abstract top

The C=C double bond in the title molecule, C16H13NO5S, has an E configuration. The crystal structure is stabilized by C-H...O hydrogen bonds. There is also a weak C-H...[pi]-ring interaction in the structure.

Comment top

Phenylsulfonyl-3-alken-2-ones have been used as asymmetric synthetic reagents (Wada et al., 1996) as well as electron-deficient dienophiles. They have been applied in asymmetric Diels–Alder chemistry (Pei, 1998). The title compound has been prepared and studied in order to get a better understanding about the synthesis of phenylsulfonyl-3-alken-2-ones. The molecular structure, Fig. 1, shows that an E-configuration is present on the C=C double bond between the atoms C1 and C4. There is also present a C—H···π-electron ring interaction in the structure. It involves the phenyl ring C11–C16 with centroid Cg1 (Table 1).

Related literature top

For related literature, see: Pei (1998). For chemical preparation, see:Wada et al. (1996).

Experimental top

The title compound was prepared according to the procedure of Wada et al. (1996). Diffraction quality crystals were obtained by recrystallization from ethanol solution by slow evaporation at room temperature. The average dimension of the block crystals was about 0.2 mm.

Refinement top

All the H atoms were discerned in the difference Fourier map. Nevertheless, the H atoms were positioned into the idealized positions and their parameters were constrained in riding-mode approximation. The constraints: C—Haryl,alkenyl)=0.93 and C—Hmethyl=0.96 Å. Uiso(Haryl,Halkenyl)= 1.2Ueq(Caryl,Calkenyl) and Uiso(Hmetyl)=1.5Ueq(Cmethyl).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).

Figures top
[Figure 1] Fig. 1. View of the title molecule showing the atom labelling scheme. The displacement ellipsoids are drawn at the 40% probability level.
4-(3-Nitrophenyl)-3-(phenylsulfonyl)but-3-en-2-one top
Crystal data top
C16H13NO5SF000 = 688.00
Mr = 331.34Dx = 1.439 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71075 Å
Hall symbol: -P 2ynCell parameters from 12472 reflections
a = 7.957 (2) Åθ = 3.2–27.5º
b = 10.580 (3) ŵ = 0.24 mm−1
c = 18.271 (6) ÅT = 298 (1) K
β = 95.976 (14)ºBlock, colourless
V = 1529.7 (8) Å30.25 × 0.20 × 0.20 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3507 independent reflections
Monochromator: graphite2890 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1Rint = 0.027
T = 285 Kθmax = 27.5º
ω scansθmin = 3.2º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −8→10
Tmin = 0.923, Tmax = 0.954k = −13→13
14836 measured reflectionsl = −23→23
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.106  w = 1/[σ2(Fo2) + (0.0516P)2 + 0.4387P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3507 reflectionsΔρmax = 0.34 e Å−3
210 parametersΔρmin = −0.40 e Å−3
42 constraintsExtinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0097 (17)
Crystal data top
C16H13NO5SV = 1529.7 (8) Å3
Mr = 331.34Z = 4
Monoclinic, P21/nMo Kα
a = 7.957 (2) ŵ = 0.24 mm−1
b = 10.580 (3) ÅT = 298 (1) K
c = 18.271 (6) Å0.25 × 0.20 × 0.20 mm
β = 95.976 (14)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3507 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2890 reflections with I > 2σ(I)
Tmin = 0.923, Tmax = 0.954Rint = 0.027
14836 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038210 parameters
wR(F2) = 0.106H-atom parameters constrained
S = 1.05Δρmax = 0.34 e Å−3
3507 reflectionsΔρmin = −0.40 e Å−3
Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.84122 (5)0.43647 (4)0.25330 (2)0.03894 (14)
O10.99494 (16)0.40871 (14)0.10399 (8)0.0607 (4)
O20.02708 (17)0.12269 (16)0.11304 (9)0.0674 (4)
O3−0.02286 (17)0.14516 (19)−0.00423 (9)0.0806 (5)
O40.89564 (17)0.56378 (11)0.24210 (8)0.0568 (4)
O50.72060 (15)0.41361 (14)0.30472 (7)0.0566 (4)
N10.07214 (18)0.14380 (15)0.05295 (9)0.0508 (4)
C10.75310 (18)0.37984 (14)0.16622 (8)0.0349 (3)
C20.8455 (2)0.42725 (15)0.10363 (9)0.0418 (4)
C30.7499 (3)0.5076 (2)0.04658 (14)0.0770 (7)
H310.81050.51210.00390.116*
H320.73710.59100.06590.116*
H330.64040.47130.03320.116*
C40.61399 (18)0.30895 (15)0.16516 (8)0.0370 (3)
H40.57390.29560.21060.044*
C50.51608 (18)0.24949 (14)0.10202 (8)0.0357 (3)
C60.34611 (19)0.22278 (15)0.10721 (9)0.0376 (3)
H60.29740.24060.15020.045*
C70.25178 (19)0.16961 (15)0.04761 (9)0.0385 (3)
C80.3182 (2)0.13919 (17)−0.01672 (9)0.0473 (4)
H80.25070.1052−0.05650.057*
C90.4884 (2)0.16088 (19)−0.02025 (10)0.0526 (4)
H90.53740.1386−0.06250.063*
C100.5862 (2)0.21504 (17)0.03795 (10)0.0462 (4)
H100.70050.22890.03460.055*
C111.02028 (18)0.34291 (15)0.28003 (8)0.0369 (3)
C121.1754 (2)0.40079 (18)0.29545 (9)0.0453 (4)
H121.18830.48670.28680.054*
C131.3113 (2)0.3282 (2)0.32406 (11)0.0590 (5)
H131.41680.36540.33500.071*
C141.2909 (3)0.2017 (2)0.33632 (12)0.0655 (6)
H141.38240.15380.35630.079*
C151.1369 (3)0.1452 (2)0.31942 (13)0.0658 (6)
H151.12520.05890.32710.079*
C160.9995 (2)0.21509 (17)0.29120 (11)0.0524 (4)
H160.89470.17700.27990.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0325 (2)0.0432 (2)0.0403 (2)0.00241 (15)−0.00025 (15)−0.00634 (16)
O10.0424 (7)0.0742 (9)0.0676 (9)−0.0004 (6)0.0163 (6)0.0104 (7)
O20.0468 (7)0.0850 (11)0.0725 (10)−0.0159 (7)0.0157 (7)−0.0016 (8)
O30.0393 (7)0.1266 (15)0.0713 (10)0.0022 (8)−0.0154 (7)−0.0245 (10)
O40.0583 (8)0.0375 (6)0.0717 (9)0.0017 (5)−0.0075 (7)−0.0083 (6)
O50.0395 (6)0.0887 (10)0.0420 (7)0.0056 (6)0.0062 (5)−0.0108 (6)
N10.0348 (7)0.0560 (9)0.0606 (10)−0.0022 (6)0.0003 (7)−0.0121 (7)
C10.0321 (7)0.0371 (7)0.0346 (7)0.0026 (6)−0.0009 (6)0.0016 (6)
C20.0411 (8)0.0418 (8)0.0423 (9)−0.0043 (7)0.0038 (7)0.0017 (6)
C30.0709 (14)0.0856 (16)0.0746 (15)0.0032 (12)0.0080 (12)0.0424 (13)
C40.0335 (7)0.0425 (8)0.0344 (7)0.0013 (6)0.0012 (6)0.0035 (6)
C50.0325 (7)0.0384 (7)0.0355 (7)0.0008 (6)0.0004 (6)0.0036 (6)
C60.0345 (7)0.0437 (8)0.0348 (8)−0.0007 (6)0.0047 (6)0.0001 (6)
C70.0319 (7)0.0412 (8)0.0413 (8)0.0020 (6)−0.0006 (6)0.0001 (6)
C80.0476 (9)0.0549 (10)0.0377 (8)0.0027 (8)−0.0039 (7)−0.0071 (7)
C90.0516 (10)0.0671 (12)0.0406 (9)0.0026 (9)0.0128 (8)−0.0096 (8)
C100.0356 (8)0.0568 (10)0.0472 (9)0.0010 (7)0.0086 (7)−0.0031 (8)
C110.0317 (7)0.0447 (8)0.0336 (7)0.0004 (6)0.0004 (6)−0.0030 (6)
C120.0347 (8)0.0575 (10)0.0435 (9)−0.0072 (7)0.0031 (7)−0.0021 (7)
C130.0308 (8)0.0930 (16)0.0526 (11)0.0023 (9)0.0016 (7)−0.0053 (10)
C140.0525 (11)0.0838 (15)0.0587 (12)0.0304 (11)−0.0011 (9)−0.0044 (11)
C150.0724 (14)0.0492 (11)0.0744 (14)0.0161 (10)0.0006 (11)−0.0012 (9)
C160.0471 (10)0.0451 (9)0.0633 (11)−0.0017 (7)−0.0020 (8)−0.0047 (8)
Geometric parameters (Å, °) top
S1—O51.4317 (13)C6—H60.9300
S1—O41.4360 (13)C7—C81.376 (2)
S1—C111.7617 (16)C8—C91.382 (3)
S1—C11.7747 (16)C8—H80.9300
O1—C21.204 (2)C9—C101.375 (2)
O2—N11.211 (2)C9—H90.9300
O3—N11.224 (2)C10—H100.9300
N1—C71.468 (2)C11—C161.380 (2)
C1—C41.335 (2)C11—C121.381 (2)
C1—C21.508 (2)C12—C131.384 (3)
C2—C31.491 (3)C12—H120.9300
C3—H310.9600C13—C141.369 (3)
C3—H320.9600C13—H130.9300
C3—H330.9600C14—C151.369 (3)
C4—C51.465 (2)C14—H140.9300
C4—H40.9300C15—C161.375 (3)
C5—C61.394 (2)C15—H150.9300
C5—C101.396 (2)C16—H160.9300
C6—C71.377 (2)
O5—S1—O4118.99 (9)C8—C7—C6123.02 (15)
O5—S1—C11107.53 (8)C8—C7—N1118.44 (14)
O4—S1—C11108.63 (8)C6—C7—N1118.54 (14)
O5—S1—C1107.57 (8)C7—C8—C9117.81 (15)
O4—S1—C1106.61 (8)C7—C8—H8121.1
C11—S1—C1106.95 (7)C9—C8—H8121.1
O2—N1—O3124.14 (16)C10—C9—C8120.74 (16)
O2—N1—C7118.48 (15)C10—C9—H9119.6
O3—N1—C7117.38 (16)C8—C9—H9119.6
C4—C1—C2130.13 (14)C9—C10—C5120.92 (15)
C4—C1—S1116.88 (12)C9—C10—H10119.5
C2—C1—S1112.89 (11)C5—C10—H10119.5
O1—C2—C3121.90 (17)C16—C11—C12121.53 (15)
O1—C2—C1120.05 (15)C16—C11—S1119.05 (12)
C3—C2—C1117.76 (16)C12—C11—S1119.18 (13)
C2—C3—H31109.5C11—C12—C13118.54 (18)
C2—C3—H32109.5C11—C12—H12120.7
H31—C3—H32109.5C13—C12—H12120.7
C2—C3—H33109.5C14—C13—C12120.20 (18)
H31—C3—H33109.5C14—C13—H13119.9
H32—C3—H33109.5C12—C13—H13119.9
C1—C4—C5128.65 (14)C15—C14—C13120.55 (18)
C1—C4—H4115.7C15—C14—H14119.7
C5—C4—H4115.7C13—C14—H14119.7
C6—C5—C10118.61 (14)C14—C15—C16120.5 (2)
C6—C5—C4118.26 (14)C14—C15—H15119.7
C10—C5—C4123.10 (14)C16—C15—H15119.7
C7—C6—C5118.80 (14)C15—C16—C11118.64 (18)
C7—C6—H6120.6C15—C16—H16120.7
C5—C6—H6120.6C11—C16—H16120.7
O4—S1—C1—C236.47 (12)C4—C1—C2—C358.5 (2)
O4—S1—C1—C4−140.16 (11)C1—C4—C5—C6−155.46 (15)
O4—S1—C11—C128.06 (15)C1—C4—C5—C1026.5 (2)
O4—S1—C11—C16−177.55 (14)C4—C5—C6—C7178.54 (13)
O5—S1—C1—C2165.12 (10)C4—C5—C10—C9−179.12 (15)
O5—S1—C1—C4−11.50 (13)C6—C5—C10—C92.9 (2)
O5—S1—C11—C12−121.99 (13)C10—C5—C6—C7−3.4 (2)
O5—S1—C11—C1652.59 (15)C5—C6—C7—N1−178.84 (13)
C1—S1—C11—C12122.77 (13)C5—C6—C7—C81.3 (2)
C1—S1—C11—C16−62.81 (15)N1—C7—C8—C9−178.34 (14)
C11—S1—C1—C2−79.59 (11)C6—C7—C8—C91.6 (2)
C11—S1—C1—C4103.79 (12)C7—C8—C9—C10−2.2 (2)
O2—N1—C7—C6−28.2 (2)C8—C9—C10—C5−0.0 (2)
O2—N1—C7—C8151.86 (15)S1—C11—C12—C13173.00 (13)
O3—N1—C7—C6151.83 (16)S1—C11—C16—C15−173.37 (15)
O3—N1—C7—C8−28.2 (2)C12—C11—C16—C151.0 (2)
S1—C1—C2—O156.37 (18)C16—C11—C12—C13−1.3 (2)
S1—C1—C2—C3−117.54 (15)C11—C12—C13—C140.2 (2)
S1—C1—C4—C5−179.53 (12)C12—C13—C14—C151.0 (3)
C2—C1—C4—C54.5 (2)C13—C14—C15—C16−1.3 (3)
C4—C1—C2—O1−127.56 (18)C14—C15—C16—C110.3 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O4i0.932.603.104 (2)114
C8—H8···O5ii0.932.533.321 (2)143
C10—H10···O3iii0.932.543.364 (2)148
C13—H13···O5iii0.932.593.433 (2)152
C12—H12···O40.932.522.903 (2)105
C16—H16···O4i0.932.603.524 (2)176
C9—H9···Cg1ii0.932.803.608 (2)145
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O4i0.932.603.104 (2)114
C8—H8···O5ii0.932.533.321 (2)143
C10—H10···O3iii0.932.543.364 (2)148
C13—H13···O5iii0.932.593.433 (2)152
C12—H12···O40.932.522.903 (2)105
C16—H16···O4i0.932.603.524 (2)176
C9—H9···Cg1ii0.932.803.608 (2)145
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1, y, z.
Acknowledgements top

This work was supported by the Open Foundation of Key Discipline of Industrial Catalysis.

references
References top

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Pei, W. (1998). Chem. J. Chin. Univ. 19, 402–404.

Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wada, E., Pei, W., Yasuoka, H., Chin, U. & Kanemasa, S. (1996). Tetrahedron, 52, 1205–1220.