1-Methyl-3-phenyl­sulfonyl-2-piperidone

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.

Key indicators

• Single-crystal X-ray study
• T = 98 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.119
• Data-to-parameter ratio = 17.7

checkCIF/PLATON results

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Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H11    ..  O3      ..       2.62 Ang.

Alert level G
PLAT793_ALERT_2_G Check the Absolute Configuration of C2     .....          S

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
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S1. Comment

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

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).

S2. Experimental

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%.

S3. Refinement

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

Computing details

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

	Fig. 1. Molecular structure of (I) showing atom labelling and displacement ellipsoids at the 50% probability level.
	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

Crystal data

C12H15NO3S	F(000) = 536
Mr = 253.32	Dx = 1.389 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2yn	Cell parameters from 4417 reflections
a = 9.0191 (16) Å	θ = 2.4–40.6°
b = 10.4920 (18) Å	µ = 0.26 mm^−1
c = 13.446 (3) Å	T = 98 K
β = 107.861 (3)°	Block, colourless
V = 1211.1 (4) Å^3	0.25 × 0.18 × 0.10 mm
Z = 4

Data collection

Rigaku AFC12κ/SATURN724 diffractometer	2729 independent reflections
Radiation source: fine-focus sealed tube	2549 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→11
Tmin = 0.945, Tmax = 0.974	k = −13→11
5193 measured reflections	l = −17→7

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0539P)^2 + 0.7818P] where P = (Fo^2 + 2Fc^2)/3
2729 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.76305 (5)	0.20597 (4)	0.49677 (3)	0.01768 (15)
O1	1.13033 (15)	0.14856 (13)	0.56636 (9)	0.0186 (3)
O2	0.79732 (18)	0.33520 (13)	0.53443 (11)	0.0265 (3)
O3	0.60745 (15)	0.17739 (15)	0.43018 (11)	0.0275 (3)
N1	1.11807 (17)	0.30781 (15)	0.45077 (11)	0.0170 (3)
C1	1.0585 (2)	0.20646 (17)	0.48622 (13)	0.0147 (3)
C2	0.8952 (2)	0.16205 (17)	0.42479 (13)	0.0153 (3)
H2	0.8969	0.0669	0.4210	0.018*
C3	0.8348 (2)	0.21313 (18)	0.31267 (14)	0.0196 (4)
H3A	0.8843	0.1657	0.2676	0.024*
H3B	0.7208	0.1998	0.2850	0.024*
C4	0.8711 (2)	0.35463 (19)	0.30992 (14)	0.0214 (4)
H4A	0.8313	0.3865	0.2372	0.026*
H4B	0.8188	0.4027	0.3530	0.026*
C5	1.0457 (2)	0.37553 (19)	0.35160 (14)	0.0208 (4)
H5A	1.0942	0.3460	0.2989	0.025*
H5B	1.0668	0.4679	0.3625	0.025*
C6	1.2777 (2)	0.3460 (2)	0.50751 (14)	0.0213 (4)
H6A	1.3156	0.2956	0.5717	0.032*
H6B	1.2794	0.4367	0.5254	0.032*
H6C	1.3448	0.3314	0.4635	0.032*
C7	0.8027 (2)	0.10460 (17)	0.60682 (13)	0.0166 (3)
C8	0.9117 (2)	0.14160 (19)	0.70016 (14)	0.0199 (4)
H8	0.9681	0.2189	0.7041	0.024*
C9	0.9368 (2)	0.0641 (2)	0.78751 (14)	0.0211 (4)
H9	1.0114	0.0879	0.8516	0.025*
C10	0.8528 (2)	−0.04843 (19)	0.78116 (14)	0.0215 (4)
H10	0.8704	−0.1013	0.8411	0.026*
C11	0.7431 (2)	−0.08410 (19)	0.68753 (15)	0.0209 (4)
H11	0.6856	−0.1607	0.6839	0.025*
C12	0.7177 (2)	−0.00801 (18)	0.59943 (14)	0.0185 (4)
H12	0.6437	−0.0322	0.5352	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0168 (2)	0.0151 (3)	0.0225 (2)	0.00200 (16)	0.00796 (18)	0.00263 (16)
O1	0.0179 (6)	0.0205 (7)	0.0155 (6)	0.0007 (5)	0.0026 (5)	0.0026 (5)
O2	0.0382 (8)	0.0134 (7)	0.0353 (8)	0.0021 (6)	0.0223 (7)	0.0004 (6)
O3	0.0144 (6)	0.0339 (8)	0.0324 (7)	0.0022 (6)	0.0044 (6)	0.0120 (6)
N1	0.0153 (7)	0.0180 (8)	0.0159 (7)	−0.0018 (6)	0.0023 (6)	0.0013 (6)
C1	0.0153 (8)	0.0149 (9)	0.0147 (7)	−0.0002 (6)	0.0056 (6)	−0.0023 (6)
C2	0.0153 (8)	0.0141 (8)	0.0163 (8)	0.0000 (6)	0.0046 (6)	−0.0010 (6)
C3	0.0181 (9)	0.0224 (10)	0.0154 (8)	0.0001 (7)	0.0008 (7)	−0.0005 (7)
C4	0.0218 (9)	0.0215 (9)	0.0178 (8)	0.0016 (7)	0.0015 (7)	0.0027 (7)
C5	0.0242 (9)	0.0193 (9)	0.0174 (8)	−0.0015 (7)	0.0043 (7)	0.0044 (7)
C6	0.0187 (9)	0.0233 (10)	0.0205 (8)	−0.0054 (7)	0.0039 (7)	0.0003 (7)
C7	0.0180 (8)	0.0145 (8)	0.0194 (8)	0.0015 (7)	0.0090 (7)	0.0004 (7)
C8	0.0192 (9)	0.0192 (9)	0.0232 (9)	−0.0026 (7)	0.0096 (7)	−0.0035 (7)
C9	0.0197 (9)	0.0254 (10)	0.0191 (8)	−0.0010 (7)	0.0072 (7)	−0.0037 (7)
C10	0.0230 (9)	0.0243 (10)	0.0205 (8)	0.0027 (8)	0.0113 (7)	0.0037 (7)
C11	0.0204 (9)	0.0180 (9)	0.0274 (9)	−0.0019 (7)	0.0120 (7)	0.0002 (7)
C12	0.0173 (8)	0.0170 (9)	0.0214 (8)	−0.0014 (7)	0.0061 (7)	−0.0018 (7)

Geometric parameters (Å, º)

S1—O3	1.4457 (15)	C5—H5A	0.9900
S1—O2	1.4472 (15)	C5—H5B	0.9900
S1—C7	1.7674 (18)	C6—H6A	0.9800
S1—C2	1.8101 (18)	C6—H6B	0.9800
O1—C1	1.233 (2)	C6—H6C	0.9800
N1—C1	1.343 (2)	C7—C8	1.391 (3)
N1—C6	1.463 (2)	C7—C12	1.395 (3)
N1—C5	1.475 (2)	C8—C9	1.389 (3)
C1—C2	1.524 (2)	C8—H8	0.9500
C2—C3	1.534 (2)	C9—C10	1.391 (3)
C2—H2	1.0000	C9—H9	0.9500
C3—C4	1.523 (3)	C10—C11	1.393 (3)
C3—H3A	0.9900	C10—H10	0.9500
C3—H3B	0.9900	C11—C12	1.388 (3)
C4—C5	1.517 (3)	C11—H11	0.9500
C4—H4A	0.9900	C12—H12	0.9500
C4—H4B	0.9900
O3—S1—O2	118.26 (9)	N1—C5—C4	112.68 (15)
O3—S1—C7	107.61 (9)	N1—C5—H5A	109.1
O2—S1—C7	107.71 (9)	C4—C5—H5A	109.1
O3—S1—C2	106.81 (9)	N1—C5—H5B	109.1
O2—S1—C2	108.70 (8)	C4—C5—H5B	109.1
C7—S1—C2	107.28 (8)	H5A—C5—H5B	107.8
C1—N1—C6	117.93 (15)	N1—C6—H6A	109.5
C1—N1—C5	126.04 (15)	N1—C6—H6B	109.5
C6—N1—C5	115.53 (15)	H6A—C6—H6B	109.5
O1—C1—N1	122.70 (16)	N1—C6—H6C	109.5
O1—C1—C2	118.95 (16)	H6A—C6—H6C	109.5
N1—C1—C2	118.35 (15)	H6B—C6—H6C	109.5
C1—C2—C3	114.75 (15)	C8—C7—C12	121.42 (17)
C1—C2—S1	108.53 (11)	C8—C7—S1	119.54 (14)
C3—C2—S1	110.06 (12)	C12—C7—S1	118.96 (14)
C1—C2—H2	107.8	C9—C8—C7	119.10 (18)
C3—C2—H2	107.8	C9—C8—H8	120.4
S1—C2—H2	107.8	C7—C8—H8	120.4
C4—C3—C2	110.50 (15)	C8—C9—C10	120.03 (17)
C4—C3—H3A	109.6	C8—C9—H9	120.0
C2—C3—H3A	109.6	C10—C9—H9	120.0
C4—C3—H3B	109.6	C9—C10—C11	120.40 (17)
C2—C3—H3B	109.6	C9—C10—H10	119.8
H3A—C3—H3B	108.1	C11—C10—H10	119.8
C5—C4—C3	109.79 (16)	C12—C11—C10	120.17 (18)
C5—C4—H4A	109.7	C12—C11—H11	119.9
C3—C4—H4A	109.7	C10—C11—H11	119.9
C5—C4—H4B	109.7	C11—C12—C7	118.87 (17)
C3—C4—H4B	109.7	C11—C12—H12	120.6
H4A—C4—H4B	108.2	C7—C12—H12	120.6
C6—N1—C1—O1	3.1 (3)	C1—N1—C5—C4	21.7 (3)
C5—N1—C1—O1	174.61 (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—C3	17.0 (2)	C2—S1—C7—C8	90.58 (15)
O1—C1—C2—S1	73.16 (18)	O3—S1—C7—C12	21.86 (17)
N1—C1—C2—S1	−106.55 (15)	O2—S1—C7—C12	150.39 (14)
O3—S1—C2—C1	172.73 (12)	C2—S1—C7—C12	−92.76 (15)
O2—S1—C2—C1	44.09 (14)	C12—C7—C8—C9	0.5 (3)
C7—S1—C2—C1	−72.12 (14)	S1—C7—C8—C9	177.05 (14)
O3—S1—C2—C3	46.40 (15)	C7—C8—C9—C10	−0.5 (3)
O2—S1—C2—C3	−82.24 (14)	C8—C9—C10—C11	0.0 (3)
C7—S1—C2—C3	161.55 (12)	C9—C10—C11—C12	0.5 (3)
C1—C2—C3—C4	−44.1 (2)	C10—C11—C12—C7	−0.5 (3)
S1—C2—C3—C4	78.63 (17)	C8—C7—C12—C11	0.0 (3)
C2—C3—C4—C5	59.6 (2)	S1—C7—C12—C11	−176.58 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1^i	1.00	2.29	3.272 (2)	168
C6—H6B···O2^ii	0.98	2.55	3.424 (3)	148
C11—H11···O3^iii	0.95	2.62	3.224 (3)	122
C4—H4A···O1^iv	0.99	2.48	3.328 (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.