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A single addition product has been confirmed in the radical cyclization of a 1,6-diene by a sulfonyl radical. The product, (3R,4S,5R,6R)-5-[(1R)-1-chloro­(phenyl­methyl)]-3-[(4-methyl­phenyl)­sulfonyl]-4-phenyl-1-aza-8-oxabi­cyclo­[4.3.0]­nonan-9-one, C27H26ClNO4S, results in a highly substituted piperidine.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801019055/ci6075sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801019055/ci6075Isup2.hkl
Contains datablock I

CCDC reference: 177209

Key indicators

  • Single-crystal X-ray study
  • T = 89 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.030
  • wR factor = 0.071
  • Data-to-parameter ratio = 21.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

REFLT_03 From the CIF: _diffrn_reflns_theta_max 30.00 From the CIF: _reflns_number_total 6690 Count of symmetry unique reflns 3697 Completeness (_total/calc) 180.96% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2993 Fraction of Friedel pairs measured 0.810 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.

(3R,4S,5R,6R)-5-[(1R)-1-Chloro(phenylmethyl)]-3-[(4-methylphenyl) sulfonyl]-4-phenyl-1-aza-8-oxabicyclo[4.3.0]nonan-9-one top
Crystal data top
C27H26ClNO4SF(000) = 520
Mr = 496.00Dx = 1.376 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 9.5207 (10) ÅCell parameters from 880 reflections
b = 9.1141 (10) Åθ = 2.2–31.2°
c = 14.1033 (14) ŵ = 0.28 mm1
β = 101.957 (8)°T = 89 K
V = 1197.2 (2) Å3Plate, colorless
Z = 20.30 × 0.24 × 0.06 mm
Data collection top
Bruker SMART 1000
diffractometer
6690 independent reflections
Radiation source: normal-focus sealed tube5850 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
Detector resolution: 8.3 pixels mm-1θmax = 30.0°, θmin = 1.5°
ω scansh = 1313
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)
k = 1212
Tmin = 0.920, Tmax = 0.983l = 1919
16388 measured reflections
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)] = 0.030H-atom parameters constrained
wR(F2) = 0.071 w = 1/[σ2(Fo2) + (0.0384P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max = 0.004
6690 reflectionsΔρmax = 0.28 e Å3
308 parametersΔρmin = 0.21 e Å3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.03 (4)
Special details top

Experimental. 1H NMR δ 2.20 (br t, 1H, J = 8.1 Hz), 2.34 (s, 3H), 2.66 (t, 1H, J = 8.3 Hz), 3.20 (m, 1H), 3.66 (m, 2H), 3.72 (t, 1H, J = 8.7 Hz), 4.07 (app q, 1H, splitting 8.4 Hz), 4.35 (br d, 1H, J = 14.8 Hz), 4.59 (s, 1H), 7.04–7.10 (m, 4H), 7.20–7.27 (m, 10H); 13C NMR: δ 21.5, 40.1, 45.6, 52.7, 55.7, 61.1, 63.7, 67.0, 126.1, 127.7, 128.0, 128.6, 128.7, 129.0, 129.5, 135.9, 137.0, 138.0, 144.1, 156.0; IR 760(s), 1043(m), 1139(s), 1302(m), 1448(m), 1732(versus) cm-1; HRMS: calcd for C27H27ClNO4S (MH)+ 496.1349, found 496.1342.

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
Cl10.03246 (4)0.54506 (5)0.66211 (3)0.02364 (8)
S10.59988 (4)0.69668 (4)0.84106 (3)0.02191 (9)
O10.47149 (12)1.04176 (15)0.52740 (8)0.0295 (3)
O20.29488 (12)0.90714 (13)0.43707 (8)0.0237 (2)
O30.70540 (13)0.81015 (14)0.83908 (9)0.0304 (3)
O40.49724 (12)0.71662 (14)0.90223 (8)0.0280 (3)
N10.38012 (14)0.83525 (14)0.58723 (9)0.0202 (3)
C10.39121 (17)0.93761 (18)0.52011 (11)0.0221 (3)
C20.22978 (17)0.76500 (18)0.44840 (11)0.0221 (3)
H2A0.27710.68620.41820.027*
H2B0.12610.76570.41840.027*
C30.25317 (16)0.74276 (16)0.55887 (10)0.0184 (3)
H30.17100.78540.58370.022*
C40.28432 (15)0.58646 (16)0.59785 (10)0.0169 (3)
H40.35200.54050.56100.020*
C50.36094 (16)0.58965 (16)0.70678 (10)0.0174 (3)
H50.29630.64220.74300.021*
C60.50017 (15)0.68021 (17)0.71764 (10)0.0183 (3)
H60.56310.63580.67670.022*
C70.46377 (18)0.83870 (18)0.68489 (11)0.0224 (3)
H7A0.40830.88640.72850.027*
H7B0.55310.89540.68710.027*
C80.14778 (16)0.49122 (18)0.58137 (10)0.0191 (3)
H80.17870.38780.59780.023*
C90.06637 (16)0.49224 (17)0.47622 (10)0.0199 (3)
C100.06080 (16)0.56956 (17)0.44472 (11)0.0217 (3)
H100.10360.62020.49040.026*
C110.12578 (17)0.57327 (18)0.34657 (11)0.0250 (3)
H110.21280.62580.32560.030*
C120.06311 (19)0.5001 (2)0.27962 (12)0.0287 (4)
H120.10700.50320.21270.034*
C130.06368 (19)0.4222 (2)0.31027 (12)0.0290 (4)
H130.10640.37210.26440.035*
C140.12785 (17)0.41790 (19)0.40822 (11)0.0239 (3)
H140.21410.36400.42910.029*
C150.38572 (16)0.43633 (17)0.74933 (10)0.0186 (3)
C160.47879 (17)0.33880 (18)0.71741 (10)0.0199 (3)
H160.52190.36540.66490.024*
C170.50902 (17)0.20299 (19)0.76179 (11)0.0228 (3)
H170.57460.13840.74060.027*
C180.44356 (18)0.16149 (19)0.83710 (11)0.0254 (4)
H180.46440.06880.86760.030*
C190.34777 (18)0.25610 (19)0.86752 (11)0.0255 (3)
H190.30130.22740.91800.031*
C200.31967 (17)0.39255 (18)0.82433 (10)0.0210 (3)
H200.25460.45710.84600.025*
C210.69416 (15)0.53191 (19)0.87330 (10)0.0214 (3)
C220.80275 (17)0.4915 (2)0.82548 (11)0.0249 (3)
H220.82320.55060.77450.030*
C230.88011 (18)0.3651 (2)0.85277 (12)0.0277 (4)
H230.95320.33680.81970.033*
C240.85245 (18)0.2775 (2)0.92880 (12)0.0275 (4)
C250.74450 (18)0.3214 (2)0.97563 (11)0.0265 (4)
H250.72530.26401.02780.032*
C260.66442 (17)0.44655 (19)0.94810 (11)0.0232 (3)
H260.58980.47380.98010.028*
C270.9350 (2)0.1373 (2)0.95732 (15)0.0414 (5)
H27A0.93760.11621.02580.062*
H27B1.03330.14840.94720.062*
H27C0.88780.05620.91740.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.01822 (16)0.0319 (2)0.02152 (16)0.00255 (16)0.00573 (13)0.00138 (15)
S10.02000 (18)0.0241 (2)0.02078 (17)0.00203 (16)0.00239 (14)0.00539 (16)
O10.0294 (6)0.0258 (6)0.0358 (6)0.0070 (6)0.0122 (5)0.0023 (5)
O20.0224 (6)0.0247 (6)0.0252 (5)0.0010 (5)0.0073 (4)0.0052 (5)
O30.0273 (6)0.0272 (7)0.0337 (6)0.0075 (5)0.0010 (5)0.0053 (5)
O40.0260 (6)0.0358 (7)0.0223 (5)0.0030 (5)0.0050 (4)0.0073 (5)
N10.0209 (6)0.0161 (6)0.0240 (6)0.0026 (5)0.0053 (5)0.0004 (5)
C10.0194 (7)0.0216 (8)0.0276 (8)0.0024 (6)0.0105 (6)0.0011 (6)
C20.0229 (7)0.0200 (8)0.0235 (7)0.0016 (6)0.0048 (6)0.0044 (6)
C30.0167 (7)0.0171 (7)0.0217 (7)0.0001 (5)0.0046 (6)0.0009 (5)
C40.0168 (7)0.0164 (7)0.0176 (6)0.0009 (5)0.0035 (5)0.0001 (5)
C50.0156 (6)0.0181 (7)0.0188 (7)0.0004 (5)0.0042 (5)0.0015 (5)
C60.0175 (7)0.0193 (8)0.0181 (6)0.0002 (6)0.0035 (5)0.0009 (6)
C70.0235 (8)0.0188 (8)0.0246 (7)0.0019 (6)0.0046 (6)0.0039 (6)
C80.0187 (7)0.0193 (7)0.0194 (7)0.0006 (6)0.0043 (5)0.0001 (6)
C90.0215 (7)0.0172 (7)0.0200 (7)0.0046 (6)0.0019 (6)0.0007 (6)
C100.0210 (7)0.0194 (8)0.0239 (7)0.0030 (6)0.0029 (6)0.0016 (6)
C110.0227 (8)0.0232 (9)0.0265 (8)0.0029 (6)0.0011 (6)0.0036 (6)
C120.0335 (9)0.0284 (9)0.0214 (7)0.0053 (7)0.0005 (7)0.0038 (6)
C130.0333 (9)0.0287 (9)0.0253 (8)0.0036 (8)0.0067 (7)0.0039 (7)
C140.0229 (8)0.0224 (8)0.0262 (8)0.0016 (7)0.0044 (6)0.0009 (6)
C150.0180 (7)0.0205 (7)0.0154 (6)0.0039 (6)0.0007 (5)0.0010 (5)
C160.0208 (7)0.0199 (8)0.0186 (7)0.0037 (6)0.0032 (6)0.0016 (6)
C170.0250 (7)0.0192 (7)0.0221 (7)0.0006 (7)0.0002 (6)0.0022 (6)
C180.0295 (9)0.0230 (9)0.0194 (7)0.0047 (7)0.0046 (6)0.0025 (6)
C190.0264 (8)0.0317 (9)0.0164 (7)0.0075 (7)0.0000 (6)0.0049 (6)
C200.0185 (7)0.0268 (9)0.0167 (7)0.0020 (6)0.0015 (6)0.0010 (6)
C210.0167 (6)0.0259 (8)0.0201 (6)0.0018 (6)0.0006 (5)0.0042 (6)
C220.0202 (7)0.0306 (9)0.0244 (7)0.0028 (7)0.0062 (6)0.0018 (7)
C230.0197 (8)0.0363 (10)0.0279 (8)0.0029 (7)0.0067 (6)0.0011 (7)
C240.0209 (8)0.0328 (10)0.0271 (8)0.0005 (7)0.0010 (6)0.0006 (7)
C250.0245 (8)0.0337 (10)0.0201 (7)0.0041 (7)0.0018 (6)0.0028 (7)
C260.0184 (7)0.0330 (9)0.0178 (7)0.0029 (7)0.0030 (6)0.0050 (6)
C270.0367 (11)0.0454 (12)0.0427 (11)0.0121 (9)0.0098 (8)0.0120 (9)
Geometric parameters (Å, º) top
Cl1—C81.8058 (15)C11—C121.388 (2)
S1—O41.4427 (12)C11—H110.95
S1—O31.4461 (13)C12—C131.390 (3)
S1—C211.7603 (17)C12—H120.95
S1—C61.8080 (14)C13—C141.391 (2)
O1—C11.210 (2)C13—H130.95
O2—C11.358 (2)C14—H140.95
O2—C21.4592 (19)C15—C161.394 (2)
N1—C11.349 (2)C15—C201.396 (2)
N1—C71.441 (2)C16—C171.390 (2)
N1—C31.4598 (19)C16—H160.95
C2—C31.541 (2)C17—C181.391 (2)
C2—H2A0.99C17—H170.95
C2—H2B0.99C18—C191.386 (2)
C3—C41.534 (2)C18—H180.95
C3—H31.00C19—C201.386 (2)
C4—C81.540 (2)C19—H190.95
C4—C51.559 (2)C20—H200.95
C4—H41.00C21—C261.386 (2)
C5—C151.520 (2)C21—C221.396 (2)
C5—C61.542 (2)C22—C231.379 (2)
C5—H51.00C22—H220.95
C6—C71.534 (2)C23—C241.405 (2)
C6—H61.00C23—H230.95
C7—H7A0.99C24—C251.391 (2)
C7—H7B0.99C24—C271.511 (3)
C8—C91.524 (2)C25—C261.382 (2)
C8—H81.00C25—H250.95
C9—C101.392 (2)C26—H260.95
C9—C141.398 (2)C27—H27A0.98
C10—C111.395 (2)C27—H27B0.98
C10—H100.95C27—H27C0.98
O4—S1—O3118.74 (8)C9—C10—C11120.45 (14)
O4—S1—C21108.98 (7)C9—C10—H10119.8
O3—S1—C21107.22 (7)C11—C10—H10119.8
O4—S1—C6107.49 (7)C12—C11—C10119.92 (15)
O3—S1—C6105.61 (7)C12—C11—H11120.0
C21—S1—C6108.41 (7)C10—C11—H11120.0
C1—O2—C2108.27 (12)C11—C12—C13120.13 (15)
C1—N1—C7123.19 (13)C11—C12—H12119.9
C1—N1—C3112.82 (12)C13—C12—H12119.9
C7—N1—C3122.46 (12)C12—C13—C14119.87 (16)
O1—C1—N1128.54 (15)C12—C13—H13120.1
O1—C1—O2122.39 (15)C14—C13—H13120.1
N1—C1—O2109.07 (14)C13—C14—C9120.50 (16)
O2—C2—C3104.58 (12)C13—C14—H14119.7
O2—C2—H2A110.8C9—C14—H14119.7
C3—C2—H2A110.8C16—C15—C20118.59 (15)
O2—C2—H2B110.8C16—C15—C5121.06 (13)
C3—C2—H2B110.8C20—C15—C5120.30 (14)
H2A—C2—H2B108.9C17—C16—C15120.57 (14)
N1—C3—C4110.51 (12)C17—C16—H16119.7
N1—C3—C298.00 (11)C15—C16—H16119.7
C4—C3—C2117.47 (13)C16—C17—C18120.16 (16)
N1—C3—H3110.1C16—C17—H17119.9
C4—C3—H3110.1C18—C17—H17119.9
C2—C3—H3110.1C19—C18—C17119.66 (15)
C3—C4—C8112.01 (12)C19—C18—H18120.2
C3—C4—C5110.63 (12)C17—C18—H18120.2
C8—C4—C5111.55 (11)C18—C19—C20120.10 (15)
C3—C4—H4107.5C18—C19—H19120.0
C8—C4—H4107.5C20—C19—H19120.0
C5—C4—H4107.5C19—C20—C15120.87 (15)
C15—C5—C6113.14 (12)C19—C20—H20119.6
C15—C5—C4112.01 (12)C15—C20—H20119.6
C6—C5—C4108.97 (11)C26—C21—C22120.52 (15)
C15—C5—H5107.5C26—C21—S1120.11 (12)
C6—C5—H5107.5C22—C21—S1119.31 (13)
C4—C5—H5107.5C23—C22—C21119.48 (15)
C7—C6—C5109.76 (12)C23—C22—H22120.3
C7—C6—S1104.62 (10)C21—C22—H22120.3
C5—C6—S1114.15 (10)C22—C23—C24120.93 (15)
C7—C6—H6109.4C22—C23—H23119.5
C5—C6—H6109.4C24—C23—H23119.5
S1—C6—H6109.4C25—C24—C23118.23 (16)
N1—C7—C6108.22 (12)C25—C24—C27120.80 (16)
N1—C7—H7A110.1C23—C24—C27120.95 (16)
C6—C7—H7A110.1C26—C25—C24121.53 (16)
N1—C7—H7B110.1C26—C25—H25119.2
C6—C7—H7B110.1C24—C25—H25119.2
H7A—C7—H7B108.4C25—C26—C21119.29 (15)
C9—C8—C4112.74 (12)C25—C26—H26120.4
C9—C8—Cl1111.03 (11)C21—C26—H26120.4
C4—C8—Cl1110.86 (10)C24—C27—H27A109.5
C9—C8—H8107.3C24—C27—H27B109.5
C4—C8—H8107.3H27A—C27—H27B109.5
Cl1—C8—H8107.3C24—C27—H27C109.5
C10—C9—C14119.13 (14)H27A—C27—H27C109.5
C10—C9—C8123.16 (14)H27B—C27—H27C109.5
C14—C9—C8117.62 (14)
C7—N1—C1—O12.7 (3)Cl1—C8—C9—C1019.86 (19)
C3—N1—C1—O1168.90 (16)C4—C8—C9—C1471.24 (18)
C7—N1—C1—O2177.59 (13)Cl1—C8—C9—C14163.68 (12)
C3—N1—C1—O211.43 (17)C14—C9—C10—C110.2 (2)
C2—O2—C1—O1172.37 (15)C8—C9—C10—C11176.18 (14)
C2—O2—C1—N17.33 (16)C9—C10—C11—C120.3 (2)
C1—O2—C2—C321.65 (15)C10—C11—C12—C130.5 (3)
C1—N1—C3—C4146.60 (13)C11—C12—C13—C140.1 (3)
C7—N1—C3—C447.11 (19)C12—C13—C14—C90.5 (3)
C1—N1—C3—C223.24 (16)C10—C9—C14—C130.6 (2)
C7—N1—C3—C2170.48 (14)C8—C9—C14—C13175.97 (15)
O2—C2—C3—N125.63 (14)C6—C5—C15—C1657.76 (17)
O2—C2—C3—C4143.79 (13)C4—C5—C15—C1665.88 (17)
N1—C3—C4—C8172.28 (11)C6—C5—C15—C20119.62 (15)
C2—C3—C4—C876.50 (16)C4—C5—C15—C20116.74 (15)
N1—C3—C4—C547.14 (16)C20—C15—C16—C172.3 (2)
C2—C3—C4—C5158.36 (12)C5—C15—C16—C17175.12 (13)
C3—C4—C5—C15176.71 (12)C15—C16—C17—C181.7 (2)
C8—C4—C5—C1551.31 (16)C16—C17—C18—C190.2 (2)
C3—C4—C5—C657.34 (16)C17—C18—C19—C201.3 (2)
C8—C4—C5—C6177.26 (12)C18—C19—C20—C150.6 (2)
C15—C5—C6—C7172.83 (12)C16—C15—C20—C191.2 (2)
C4—C5—C6—C761.88 (15)C5—C15—C20—C19176.29 (13)
C15—C5—C6—S155.76 (15)O4—S1—C21—C260.73 (14)
C4—C5—C6—S1178.95 (10)O3—S1—C21—C26128.97 (13)
O4—S1—C6—C780.44 (11)C6—S1—C21—C26117.45 (13)
O3—S1—C6—C747.25 (12)O4—S1—C21—C22178.16 (12)
C21—S1—C6—C7161.89 (10)O3—S1—C21—C2248.45 (14)
O4—S1—C6—C539.55 (13)C6—S1—C21—C2265.13 (14)
O3—S1—C6—C5167.25 (11)C26—C21—C22—C230.4 (2)
C21—S1—C6—C578.11 (12)S1—C21—C22—C23177.81 (12)
C1—N1—C7—C6144.33 (14)C21—C22—C23—C240.8 (2)
C3—N1—C7—C650.81 (18)C22—C23—C24—C250.3 (3)
C5—C6—C7—N155.54 (15)C22—C23—C24—C27178.67 (17)
S1—C6—C7—N1178.43 (10)C23—C24—C25—C260.8 (2)
C3—C4—C8—C952.47 (17)C27—C24—C25—C26177.61 (16)
C5—C4—C8—C9177.10 (12)C24—C25—C26—C211.3 (2)
C3—C4—C8—Cl172.70 (13)C22—C21—C26—C250.6 (2)
C5—C4—C8—Cl151.92 (14)S1—C21—C26—C25176.75 (12)
C4—C8—C9—C10105.22 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O1i1.002.293.2237 (19)155
Symmetry code: (i) x+1, y1/2, z+1.
 

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