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Acta Cryst. (2008). E64, o835-o836    [ doi:10.1107/S1600536808009288 ]

1-Methyl-3-phenylsulfonyl-2-piperidone

J. Zukerman-Schpector, P. R. Olivato, C. R. Cerqueira Jr, E. Vinhato and E. R. T. Tiekink

Abstract top

The piperidone ring in the title compound, C12H15NO3S, has a slightly distorted half-chair conformation with the methyl, carbonyl and phenylsulfonyl ring substituents occupying equatorial, equatorial and axial positions, respectively. Molecules are connected into centrosymmetric dimers via C-H...O interactions and these associate into layers via C-H...O-S contacts. Further C-H...O interactions involving both the carbonyl and sulfonyl O atoms consolidate the crystal packing by providing connections between the layers.

Comment top

The title compound (I), Fig. 1, was studied as a part of an on-going investigation of conformational and electronic aspects of different classes of β-keto-sulfones, i.e. α-phenylsulfonyl -acetones, -acetophenones and -cyclohexanones, utilizing spectroscopic, theoretical and X-ray diffraction methods (Dal Colle et al., 1995; Zukerman-Schpector et al., 1999; 2006).

The piperidone ring has a slightly distorted half-chair conformation with a tendency towards a half-boat conformation: the ring-puckering parameters are q2 = 0.340 (2) Å, q3 = 0.332 (2) Å, QT = 0.476 (2) °, φ2 = -145.0 (3)° (Cremer & Pople, 1975). The ring substituents, i.e. N-methyl, C-carbonyl and C-phenylsulfonyl, occupy equatorial, equatorial and axial positions, respectively.

The crystal packing is dominated by C—H···O interactions, Table 1. Centrosymmetrically related molecules of (I) are connected into dimeric aggregates via C2—H···O1 contacts and these are linked into layers stacked along (1 0 1) via C6—H···O2 contacts. Connections betweem layers are also of the type C—H···O and serve to consolidate the crystal packing.

Related literature top

For related structures, see: Zukerman-Schpector et al. (1999, 2006). For related literature, see: Distefano et al. (1991); Olivato et al. (1992, 1997, 2003, 2004); Dal Colle et al. (1995). For ring conformational analysis, see: Cremer & Pople (1975). For the synthesis, see: Drabowicz et al. (1983); Zoretic & Soja (1976).

Experimental top

Initially, the 3-phenylsulfanyl-1-methyl-2-piperidone was obtained from the reaction of 1-methyl-2-piperidinone and diphenyl disulfide with LDA in THF as described in the literature (Zoretic and Soja, 1976). The product was oxidized with H2O2 and SeO2 (as catalyst) in methanol (Drabowicz et al. 1983) to give compound (I). After extraction with chloroform and subsequent evaporation, a crude solid was obtained. This product was subjected to flash chromatography with a solution of ethyl acetate and acetone in a 7:3 ratio. Suitable crystals were obtained by vapor diffusion from chloroform/n-hexane at 283 K.; m.p. 414–415 K. IR (cm-1): ν(C=O) 1652, ν(SO2)(as) 1307, ν(SO2)(s) 1148. NMR (CDCl3, p.p.m.): δ 1.79–2.74 (4H, m), 2.95 (3H, s), 3.30–3.48 (2H, m), 3.97 (1H, triplet, J = 6.1 Hz), 7.53–7.57 (2H, m, aryl-H), 7.62–7.67 (1H, m, aryl-H), 7.92–7.94 (2H, m, aryl-H). Analysis found: C 56.86, H 6.04, N 5.58; C12H15O3NS requires: C 56.89, H 5.97, N 5.53%.

Refinement top

All H atoms were included in the riding-model approximation with C—H = 0.95 - 1.00 Å, and with Uiso(H) = 1.5Ueq(methyl-C) or 1.2Ueq(remaining-C).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing atom labelling and displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. Crystal packing in (I) highlighting the C—H···O hydrogen bonding contacts (orange dashed lines) leading to the formation of dimeric aggregates and the overall layer arrangement.
1-Methyl-3-phenylsulfonyl-2-piperidone top
Crystal data top
C12H15NO3SF000 = 536
Mr = 253.32Dx = 1.389 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71070 Å
Hall symbol: -P 2ynCell parameters from 4417 reflections
a = 9.0191 (16) Åθ = 2.4–40.6º
b = 10.4920 (18) ŵ = 0.26 mm−1
c = 13.446 (3) ÅT = 98 (2) K
β = 107.861 (3)ºBlock, colourless
V = 1211.1 (4) Å30.25 × 0.18 × 0.10 mm
Z = 4
Data collection top
Rigaku AFC12κ/SATURN724
diffractometer		2729 independent reflections
Radiation source: fine-focus sealed tube2549 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.025
T = 98(2) Kθmax = 27.5º
ω scansθmin = 2.5º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −10→11
Tmin = 0.945, Tmax = 0.974k = −13→11
5193 measured reflectionsl = −17→7
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.118  w = 1/[σ2(Fo2) + (0.0539P)2 + 0.7818P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
2729 reflectionsΔρmax = 0.39 e Å−3
154 parametersΔρmin = −0.45 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C12H15NO3SV = 1211.1 (4) Å3
Mr = 253.32Z = 4
Monoclinic, P21/nMo Kα
a = 9.0191 (16) ŵ = 0.26 mm−1
b = 10.4920 (18) ÅT = 98 (2) K
c = 13.446 (3) Å0.25 × 0.18 × 0.10 mm
β = 107.861 (3)º
Data collection top
Rigaku AFC12κ/SATURN724
diffractometer		2729 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2549 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.974Rint = 0.025
5193 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047154 parameters
wR(F2) = 0.118H-atom parameters constrained
S = 1.12Δρmax = 0.39 e Å−3
2729 reflectionsΔρmin = −0.45 e Å−3
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
xyzUiso*/Ueq
S10.76305 (5)0.20597 (4)0.49677 (3)0.01768 (15)
O11.13033 (15)0.14856 (13)0.56636 (9)0.0186 (3)
O20.79732 (18)0.33520 (13)0.53443 (11)0.0265 (3)
O30.60745 (15)0.17739 (15)0.43018 (11)0.0275 (3)
N11.11807 (17)0.30781 (15)0.45077 (11)0.0170 (3)
C11.0585 (2)0.20646 (17)0.48622 (13)0.0147 (3)
C20.8952 (2)0.16205 (17)0.42479 (13)0.0153 (3)
H20.89690.06690.42100.018*
C30.8348 (2)0.21313 (18)0.31267 (14)0.0196 (4)
H3A0.88430.16570.26760.024*
H3B0.72080.19980.28500.024*
C40.8711 (2)0.35463 (19)0.30992 (14)0.0214 (4)
H4A0.83130.38650.23720.026*
H4B0.81880.40270.35300.026*
C51.0457 (2)0.37553 (19)0.35160 (14)0.0208 (4)
H5A1.09420.34600.29890.025*
H5B1.06680.46790.36250.025*
C61.2777 (2)0.3460 (2)0.50751 (14)0.0213 (4)
H6A1.31560.29560.57170.032*
H6B1.27940.43670.52540.032*
H6C1.34480.33140.46350.032*
C70.8027 (2)0.10460 (17)0.60682 (13)0.0166 (3)
C80.9117 (2)0.14160 (19)0.70016 (14)0.0199 (4)
H80.96810.21890.70410.024*
C90.9368 (2)0.0641 (2)0.78751 (14)0.0211 (4)
H91.01140.08790.85160.025*
C100.8528 (2)−0.04843 (19)0.78116 (14)0.0215 (4)
H100.8704−0.10130.84110.026*
C110.7431 (2)−0.08410 (19)0.68753 (15)0.0209 (4)
H110.6856−0.16070.68390.025*
C120.7177 (2)−0.00801 (18)0.59943 (14)0.0185 (4)
H120.6437−0.03220.53520.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0168 (2)0.0151 (3)0.0225 (2)0.00200 (16)0.00796 (18)0.00263 (16)
O10.0179 (6)0.0205 (7)0.0155 (6)0.0007 (5)0.0026 (5)0.0026 (5)
O20.0382 (8)0.0134 (7)0.0353 (8)0.0021 (6)0.0223 (7)0.0004 (6)
O30.0144 (6)0.0339 (8)0.0324 (7)0.0022 (6)0.0044 (6)0.0120 (6)
N10.0153 (7)0.0180 (8)0.0159 (7)−0.0018 (6)0.0023 (6)0.0013 (6)
C10.0153 (8)0.0149 (9)0.0147 (7)−0.0002 (6)0.0056 (6)−0.0023 (6)
C20.0153 (8)0.0141 (8)0.0163 (8)0.0000 (6)0.0046 (6)−0.0010 (6)
C30.0181 (9)0.0224 (10)0.0154 (8)0.0001 (7)0.0008 (7)−0.0005 (7)
C40.0218 (9)0.0215 (9)0.0178 (8)0.0016 (7)0.0015 (7)0.0027 (7)
C50.0242 (9)0.0193 (9)0.0174 (8)−0.0015 (7)0.0043 (7)0.0044 (7)
C60.0187 (9)0.0233 (10)0.0205 (8)−0.0054 (7)0.0039 (7)0.0003 (7)
C70.0180 (8)0.0145 (8)0.0194 (8)0.0015 (7)0.0090 (7)0.0004 (7)
C80.0192 (9)0.0192 (9)0.0232 (9)−0.0026 (7)0.0096 (7)−0.0035 (7)
C90.0197 (9)0.0254 (10)0.0191 (8)−0.0010 (7)0.0072 (7)−0.0037 (7)
C100.0230 (9)0.0243 (10)0.0205 (8)0.0027 (8)0.0113 (7)0.0037 (7)
C110.0204 (9)0.0180 (9)0.0274 (9)−0.0019 (7)0.0120 (7)0.0002 (7)
C120.0173 (8)0.0170 (9)0.0214 (8)−0.0014 (7)0.0061 (7)−0.0018 (7)
Geometric parameters (Å, °) top
S1—O31.4457 (15)C5—H5A0.9900
S1—O21.4472 (15)C5—H5B0.9900
S1—C71.7674 (18)C6—H6A0.9800
S1—C21.8101 (18)C6—H6B0.9800
O1—C11.233 (2)C6—H6C0.9800
N1—C11.343 (2)C7—C81.391 (3)
N1—C61.463 (2)C7—C121.395 (3)
N1—C51.475 (2)C8—C91.389 (3)
C1—C21.524 (2)C8—H80.9500
C2—C31.534 (2)C9—C101.391 (3)
C2—H21.0000C9—H90.9500
C3—C41.523 (3)C10—C111.393 (3)
C3—H3A0.9900C10—H100.9500
C3—H3B0.9900C11—C121.388 (3)
C4—C51.517 (3)C11—H110.9500
C4—H4A0.9900C12—H120.9500
C4—H4B0.9900
O3—S1—O2118.26 (9)N1—C5—C4112.68 (15)
O3—S1—C7107.61 (9)N1—C5—H5A109.1
O2—S1—C7107.71 (9)C4—C5—H5A109.1
O3—S1—C2106.81 (9)N1—C5—H5B109.1
O2—S1—C2108.70 (8)C4—C5—H5B109.1
C7—S1—C2107.28 (8)H5A—C5—H5B107.8
C1—N1—C6117.93 (15)N1—C6—H6A109.5
C1—N1—C5126.04 (15)N1—C6—H6B109.5
C6—N1—C5115.53 (15)H6A—C6—H6B109.5
O1—C1—N1122.70 (16)N1—C6—H6C109.5
O1—C1—C2118.95 (16)H6A—C6—H6C109.5
N1—C1—C2118.35 (15)H6B—C6—H6C109.5
C1—C2—C3114.75 (15)C8—C7—C12121.42 (17)
C1—C2—S1108.53 (11)C8—C7—S1119.54 (14)
C3—C2—S1110.06 (12)C12—C7—S1118.96 (14)
C1—C2—H2107.8C9—C8—C7119.10 (18)
C3—C2—H2107.8C9—C8—H8120.4
S1—C2—H2107.8C7—C8—H8120.4
C4—C3—C2110.50 (15)C8—C9—C10120.03 (17)
C4—C3—H3A109.6C8—C9—H9120.0
C2—C3—H3A109.6C10—C9—H9120.0
C4—C3—H3B109.6C9—C10—C11120.40 (17)
C2—C3—H3B109.6C9—C10—H10119.8
H3A—C3—H3B108.1C11—C10—H10119.8
C5—C4—C3109.79 (16)C12—C11—C10120.17 (18)
C5—C4—H4A109.7C12—C11—H11119.9
C3—C4—H4A109.7C10—C11—H11119.9
C5—C4—H4B109.7C11—C12—C7118.87 (17)
C3—C4—H4B109.7C11—C12—H12120.6
H4A—C4—H4B108.2C7—C12—H12120.6
C6—N1—C1—O13.1 (3)C1—N1—C5—C421.7 (3)
C5—N1—C1—O1174.61 (17)C6—N1—C5—C4−166.58 (16)
C6—N1—C1—C2−177.19 (15)C3—C4—C5—N1−47.8 (2)
C5—N1—C1—C2−5.7 (3)O3—S1—C7—C8−154.80 (15)
O1—C1—C2—C3−163.27 (15)O2—S1—C7—C8−26.27 (17)
N1—C1—C2—C317.0 (2)C2—S1—C7—C890.58 (15)
O1—C1—C2—S173.16 (18)O3—S1—C7—C1221.86 (17)
N1—C1—C2—S1−106.55 (15)O2—S1—C7—C12150.39 (14)
O3—S1—C2—C1172.73 (12)C2—S1—C7—C12−92.76 (15)
O2—S1—C2—C144.09 (14)C12—C7—C8—C90.5 (3)
C7—S1—C2—C1−72.12 (14)S1—C7—C8—C9177.05 (14)
O3—S1—C2—C346.40 (15)C7—C8—C9—C10−0.5 (3)
O2—S1—C2—C3−82.24 (14)C8—C9—C10—C110.0 (3)
C7—S1—C2—C3161.55 (12)C9—C10—C11—C120.5 (3)
C1—C2—C3—C4−44.1 (2)C10—C11—C12—C7−0.5 (3)
S1—C2—C3—C478.63 (17)C8—C7—C12—C110.0 (3)
C2—C3—C4—C559.6 (2)S1—C7—C12—C11−176.58 (14)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O1i1.002.293.272 (2)168
C6—H6B···O2ii0.982.553.424 (3)148
C11—H11···O3iii0.952.623.224 (3)122
C4—H4A···O1iv0.992.483.328 (2)144
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y, −z+1; (iv) x−1/2, −y+1/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O1i1.002.293.272 (2)168
C6—H6B···O2ii0.982.553.424 (3)148
C11—H11···O3iii0.952.623.224 (3)122
C4—H4A···O1iv0.992.483.328 (2)144
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y, −z+1; (iv) x−1/2, −y+1/2, z−1/2.
Acknowledgements top

We thank FAPESP and CNPq for financial support. CRC and EV thank CNPq for doctoral fellowships; PRO and JZ–S thank CNPq for fellowships (Brazil). Support from UTSA, CNPq and FAPESP to allow JZ–S to spend a sabbatical at UTSA is gratefully ackowledged.

references
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