Acta Cryst.(2002). E58, o715±o716 DOI: 10.1107/S1600536802009807 Gainsford and Woolhouse C13H15NO3S
o715
organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
exo
-7-Phenyl-3-
n
-propyl-5-oxa-2-thia-6-azabicyclo[3.2.0
1,4]hept-6-ene 2,2-dioxide
Graeme J. Gainsford* and Anthony D. Woolhouse
Industrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 130 K
Mean(C±C) = 0.003 AÊ
Rfactor = 0.039
wRfactor = 0.092
Data-to-parameter ratio = 12.5
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, C13H15NO3, contains the novel exo
-thiabicyclo[3.2.01,4]hept-6-ene ring system, with pendant
phenyl and n-propyl substituents. Both fused rings in the bicyclic system are planar, their planes forming a dihedral angle of 65.6 (1).
Comment
The title compound, (I), was prepared as part of a study of the use of carnivore odours in mammal pest control; it is closely related to a previously reported structure of exo -7-aza-6-oxa-4-n-propyl-3-thiabicyclo[5.4.11,712,5]undecane 3,3-dioxide
(Woolhouse et al., 1993), which had been obtained from a thiete sulfone (Gainsford & Woolhouse, 1994).
The crystal structure of (I) is built of isolated molecules (Fig. 1) associated into in®nite chains along thebaxis of the crystal via weak intermolecular contacts C14ÐH14A O5i
[symmetry code: (i) 1/2ÿx, 1/2+y, 1/2ÿz], with H14A O5 and C14 O5 distances of 2.56 (2) and 3.343 (3) AÊ, respec-tively.
The fused four- and ®ve-membered rings are each planar, with average deviations of 0.015 (2) and 0.011 (2) AÊ, respec-tively; their least-squares planes form a dihedral angle of 65.6 (1). The pendant planar phenyl ring (C8±C13) is twisted
by 7.3 (1)from the ®ve-membered C
3NO ring.
Only two other compounds have been reported [Allen & Kennard (1993) and ConQuest (Cambridge Crystallographic Data Centre, 2002)] with an oxygen bound to the C3SO2ring.
Each of these (Beagley et al., 1992; Adiwidjala et al., 2000) have the oxygen bound to the carbon remote from the sulfur heteroatom, as is found when the fused ring system is constructed by cycloaddition.
Experimental
To an ethereal solution of 2-n-propyl-3-thiete sulfone (0.68 g,
4.7 mmol) and benzhydroxamoyl chloride (0.8 g, 5.1 mmol) at 273 K was added, dropwise, a solution of triethylamine (0.52 g, 5.1 mmol) in ether. The solution was stirred for 4 h at ambient temperature, then ®ltered and concentrated. The compound was obtained with the
endo-fused stereoisomer (0.62 g, 50%) by ¯ash chromatography over silica (0.42 g, 34% yield); crystals were grown from an ethylacetate/ hexane mixture.
Crystal data
C13H15NO3S
Mr= 265.32 Monoclinic,P21=n
a= 12.593 (5) AÊ b= 5.081 (2) AÊ c= 20.169 (8) AÊ = 104.028 (15)
V= 1252.0 (9) AÊ3
Z= 4
Dx= 1.408 Mg mÿ3 MoKradiation Cell parameters from 24
re¯ections = 5.6±14.2
= 0.26 mmÿ1
T= 130 (2) K Needle, colourless 0.440.190.04 mm
Data collection
Siemens/NicoletR3mfour-circle diffractometer
!scans
Absorption correction: none 2933 measured re¯ections 2794 independent re¯ections 1801 re¯ections withI> 2(I) Rint= 0.036
max= 27.9
h= 0!16 k= 0!6 l=ÿ26!25 3 standard re¯ections
every 97 re¯ections intensity decay: none
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.039
wR(F2) = 0.092
S= 0.85 2794 re¯ections 223 parameters
All H-atom parameters re®ned w= 1/[2(F
o2) + (0.0523P)2] whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.29 e AÊÿ3 min=ÿ0.69 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
S2ÐO21 1.4451 (17)
S2ÐO22 1.4413 (15)
S2ÐC1 1.834 (2)
S2ÐC3 1.835 (2)
O5ÐN6 1.411 (2)
O5ÐC4 1.453 (2)
N6ÐC7 1.298 (2)
C1ÐC7 1.502 (3)
C1ÐC4 1.545 (3)
C3ÐC4 1.557 (3)
O22ÐS2ÐO21 118.61 (9)
C1ÐS2ÐC3 80.68 (10)
N6ÐO5ÐC4 109.94 (14)
C7ÐN6ÐO5 110.41 (16)
C7ÐC1ÐC4 101.85 (16)
C7ÐC1ÐS2 112.64 (15)
C4ÐC1ÐS2 89.86 (13)
C4ÐC3ÐS2 89.46 (13)
O5ÐC4ÐC1 104.82 (17)
O5ÐC4ÐC3 113.08 (17)
C1ÐC4ÐC3 99.92 (16)
N6ÐC7ÐC1 112.90 (18)
C4ÐO5ÐN6ÐC7 ÿ2.9 (2)
S2ÐC1ÐC4ÐO5 ÿ114.97 (14)
C7ÐC1ÐC4ÐC3 115.42 (17)
O5ÐN6ÐC7ÐC8 177.53 (17)
S2ÐC1ÐC7ÐN6 95.10 (19)
S2ÐC1ÐC7ÐC8 ÿ80.6 (2)
All H atoms were re®ned with isotropic displacement parameters. The CÐH bonds are in the range 0.92 (3)±1.01 (3) AÊ.
Data collection:R3M Software (Siemens, 1983); cell re®nement:
R3M Software; data reduction: R3M Software; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:
ORTEP-3 in WinGX (Farrugia, 1997); software used to prepare material for publication:SHELXL97 andPLATON(Spek, 1990).
We thank Dr J. Wikaira and Professor Ward T Robinson of the University of Canterbury for their assistance.
References
Adiwidjala, G., Olbrich, F., Schulze, O. & Voss, J. (2000). Thesis, University of Hamburg, Germany.
Allen, F. H. & Kennard, O. (1993).Chem. Des. Autom. News,8, 1, 31±37. Beagley, B., James, M. R., Pritchard, R. G., Raynor, C. M., Smith, C. &
Stoodley, R. J. (1992).J. Chem. Soc. Perkin Trans1, pp. 2371±2382. Cambridge Crystallographic Data Centre (2002). ConQuest. Version 1.3.
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, England.
Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.
Gainsford, G. J. & Woolhouse, A. D. (1994).Acta Cryst.C50, 606±607. Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.
Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Siemens (1983). R3M Software. Version 4.11. Siemens Analytical X-ray
Instruments Inc., Madison, Wisconsin, USA. Spek, A. L. (1990).Acta Cryst.A46, C-34.
Woolhouse, A. D., Gainsford, G. J. & Crump, D. R. (1993).J. Heterocycl. Chem.30, 873±880.
Figure 1
supporting information
sup-1 Acta Cryst. (2002). E58, o715–o716
supporting information
Acta Cryst. (2002). E58, o715–o716 [https://doi.org/10.1107/S1600536802009807]
exo
-7-Phenyl-3-
n
-propyl-5-oxa-2-thia-6-azabicyclo[3.2.0
1,4]hept-6-ene
2,2-dioxide
Graeme J. Gainsford and Anthony D. Woolhouse
(I)
Crystal data
C13H15NO3S Mr = 265.32 Monoclinic, P21/n Hall symbol: -P 2yn
a = 12.593 (5) Å
b = 5.081 (2) Å
c = 20.169 (8) Å
β = 104.028 (15)°
V = 1252.0 (9) Å3 Z = 4
F(000) = 560
Dx = 1.408 Mg m−3
Mo Kα radiation, λ = 0.71069 Å Cell parameters from 24 reflections
θ = 5.6–14.2°
µ = 0.26 mm−1 T = 130 K Needle, colourless 0.44 × 0.19 × 0.04 mm
Data collection
Siemens/Nicolet R3m 4-circle diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω scans
2933 measured reflections 2794 independent reflections 1801 reflections with I > 2σ(I)
Rint = 0.036
θmax = 27.9°, θmin = 2.1° h = 0→16
k = 0→6
l = −26→25
3 standard reflections every 97 reflections intensity decay: none
Refinement
Refinement on F2 Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.039 wR(F2) = 0.092 S = 0.85 2794 reflections 223 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
All H-atom parameters refined
w = 1/[σ2(F
o2) + (0.0523P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001
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 (Å2)
x y z Uiso*/Ueq
S2 0.27233 (4) 0.10014 (11) 0.05798 (3) 0.01767 (13)
O21 0.27120 (13) 0.3840 (3) 0.06215 (7) 0.0225 (3)
O22 0.26540 (13) −0.0206 (3) −0.00760 (7) 0.0246 (4)
O5 0.31169 (12) −0.0020 (3) 0.22584 (7) 0.0204 (3)
N6 0.39738 (15) 0.1808 (3) 0.22982 (9) 0.0205 (4)
C1 0.38019 (17) −0.0420 (4) 0.12644 (10) 0.0179 (4)
C3 0.18686 (17) −0.0544 (4) 0.10890 (10) 0.0179 (4)
C4 0.29232 (18) −0.1451 (4) 0.16168 (11) 0.0190 (4)
C7 0.43769 (17) 0.1610 (4) 0.17658 (10) 0.0176 (4)
C8 0.52536 (18) 0.3374 (4) 0.16691 (11) 0.0198 (4)
C9 0.57268 (18) 0.5202 (5) 0.21756 (11) 0.0232 (5)
C10 0.65071 (19) 0.6975 (5) 0.20654 (12) 0.0255 (5)
C11 0.68237 (19) 0.6946 (5) 0.14469 (12) 0.0264 (5)
C12 0.63735 (19) 0.5108 (5) 0.09457 (12) 0.0273 (5)
C13 0.55871 (19) 0.3334 (4) 0.10537 (11) 0.0233 (5)
C14 0.10859 (17) 0.1300 (5) 0.13345 (10) 0.0208 (5)
C15 0.01075 (18) 0.2219 (5) 0.07661 (11) 0.0225 (5)
C16 −0.0624 (2) 0.4135 (6) 0.10292 (13) 0.0278 (5)
H1 0.425 (2) −0.161 (5) 0.1099 (13) 0.036 (7)*
H3 0.152 (2) −0.194 (5) 0.0836 (11) 0.024 (6)*
H4 0.292 (2) −0.329 (5) 0.1713 (12) 0.034 (7)*
H9 0.547 (2) 0.520 (5) 0.2585 (13) 0.037 (7)*
H10 0.681 (2) 0.828 (5) 0.2420 (12) 0.027 (7)*
H11 0.737 (2) 0.821 (5) 0.1348 (13) 0.040 (8)*
H12 0.657 (2) 0.511 (5) 0.0520 (14) 0.042 (8)*
H13 0.527 (2) 0.217 (5) 0.0694 (12) 0.024 (6)*
H14A 0.148 (2) 0.286 (5) 0.1557 (11) 0.023 (6)*
H14B 0.082 (2) 0.031 (5) 0.1682 (13) 0.040 (7)*
H15A −0.033 (2) 0.066 (5) 0.0564 (12) 0.026 (6)*
H15B 0.038 (2) 0.301 (5) 0.0391 (12) 0.032 (7)*
H16A −0.027 (3) 0.571 (7) 0.1211 (15) 0.053 (9)*
H16B −0.119 (3) 0.473 (6) 0.0640 (15) 0.055 (9)*
supporting information
sup-3 Acta Cryst. (2002). E58, o715–o716
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
S2 0.0200 (3) 0.0167 (2) 0.0158 (2) 0.0002 (2) 0.00346 (18) −0.0003 (2)
O21 0.0272 (8) 0.0162 (7) 0.0228 (7) 0.0001 (8) 0.0038 (6) 0.0013 (7)
O22 0.0301 (9) 0.0278 (9) 0.0159 (7) −0.0037 (7) 0.0060 (6) −0.0059 (6)
O5 0.0240 (8) 0.0213 (7) 0.0152 (7) −0.0049 (7) 0.0037 (6) −0.0007 (6)
N6 0.0196 (9) 0.0192 (9) 0.0221 (9) −0.0018 (8) 0.0036 (7) 0.0009 (7)
C1 0.0197 (11) 0.0154 (11) 0.0179 (10) 0.0012 (9) 0.0034 (8) −0.0003 (8)
C3 0.0217 (10) 0.0137 (11) 0.0177 (10) −0.0015 (9) 0.0038 (8) −0.0003 (8)
C4 0.0227 (11) 0.0149 (11) 0.0186 (9) −0.0004 (9) 0.0033 (8) −0.0014 (8)
C7 0.0184 (10) 0.0161 (10) 0.0169 (9) 0.0033 (9) 0.0015 (8) 0.0004 (8)
C8 0.0184 (10) 0.0184 (11) 0.0224 (10) 0.0040 (9) 0.0046 (8) 0.0024 (8)
C9 0.0203 (11) 0.0260 (12) 0.0229 (11) 0.0006 (10) 0.0044 (9) −0.0017 (9)
C10 0.0218 (11) 0.0219 (12) 0.0308 (12) 0.0001 (10) 0.0026 (9) −0.0020 (10)
C11 0.0210 (11) 0.0229 (13) 0.0356 (13) −0.0017 (10) 0.0073 (10) 0.0055 (10)
C12 0.0270 (12) 0.0271 (12) 0.0311 (12) 0.0001 (11) 0.0133 (10) 0.0032 (10)
C13 0.0259 (12) 0.0217 (12) 0.0226 (11) 0.0002 (10) 0.0063 (9) −0.0022 (9)
C14 0.0205 (10) 0.0240 (12) 0.0178 (10) 0.0007 (10) 0.0041 (8) 0.0011 (9)
C15 0.0231 (11) 0.0221 (12) 0.0209 (10) 0.0027 (10) 0.0025 (9) 0.0000 (10)
C16 0.0251 (12) 0.0289 (13) 0.0284 (12) 0.0061 (12) 0.0043 (10) −0.0008 (11)
Geometric parameters (Å, º)
S2—O21 1.4451 (17) C9—H9 0.96 (2)
S2—O22 1.4413 (15) C10—C11 1.399 (3)
S2—C1 1.834 (2) C10—H10 0.98 (2)
S2—C3 1.835 (2) C11—C12 1.392 (3)
O5—N6 1.411 (2) C11—H11 0.99 (3)
O5—C4 1.453 (2) C12—C13 1.395 (3)
N6—C7 1.298 (2) C12—H12 0.95 (3)
C1—C7 1.502 (3) C13—H13 0.95 (2)
C1—C4 1.545 (3) C14—C15 1.538 (3)
C1—H1 0.94 (3) C14—H14A 0.98 (2)
C3—C14 1.527 (3) C14—H14B 0.99 (3)
C3—C4 1.557 (3) C15—C16 1.521 (3)
C3—H3 0.92 (2) C15—H15A 1.00 (3)
C4—H4 0.96 (3) C15—H15B 0.99 (2)
C7—C8 1.471 (3) C16—H16A 0.94 (3)
C8—C9 1.402 (3) C16—H16B 0.97 (3)
C8—C13 1.404 (3) C16—H16C 1.01 (3)
C9—C10 1.390 (3)
O22—S2—O21 118.61 (9) C10—C9—H9 122.4 (16)
O22—S2—C1 113.10 (10) C8—C9—H9 117.2 (16)
O21—S2—C1 111.41 (10) C9—C10—C11 120.1 (2)
O22—S2—C3 114.74 (10) C9—C10—H10 118.9 (14)
C1—S2—C3 80.68 (10) C12—C11—C10 120.0 (2)
N6—O5—C4 109.94 (14) C12—C11—H11 117.9 (15)
C7—N6—O5 110.41 (16) C10—C11—H11 122.1 (15)
C7—C1—C4 101.85 (16) C11—C12—C13 120.0 (2)
C7—C1—S2 112.64 (15) C11—C12—H12 120.4 (17)
C4—C1—S2 89.86 (13) C13—C12—H12 119.5 (17)
C7—C1—H1 116.6 (16) C12—C13—C8 120.3 (2)
C4—C1—H1 120.1 (16) C12—C13—H13 117.8 (14)
S2—C1—H1 112.6 (16) C8—C13—H13 121.9 (14)
C14—C3—C4 118.08 (17) C3—C14—C15 114.08 (17)
C14—C3—S2 115.56 (15) C3—C14—H14A 110.4 (14)
C4—C3—S2 89.46 (13) C15—C14—H14A 108.7 (14)
C14—C3—H3 112.8 (15) C3—C14—H14B 105.9 (16)
C4—C3—H3 111.5 (15) C15—C14—H14B 109.7 (16)
S2—C3—H3 106.8 (14) H14A—C14—H14B 107.9 (19)
O5—C4—C1 104.82 (17) C16—C15—C14 112.17 (18)
O5—C4—C3 113.08 (17) C16—C15—H15A 109.2 (14)
C1—C4—C3 99.92 (16) C14—C15—H15A 109.1 (14)
O5—C4—H4 108.5 (15) C16—C15—H15B 111.2 (15)
C1—C4—H4 117.4 (15) C14—C15—H15B 109.0 (15)
C3—C4—H4 112.8 (16) H15A—C15—H15B 105.9 (19)
N6—C7—C8 121.25 (19) C15—C16—H16A 114.3 (18)
N6—C7—C1 112.90 (18) C15—C16—H16B 107.5 (18)
C8—C7—C1 125.72 (17) H16A—C16—H16B 104 (3)
C9—C8—C13 119.2 (2) C15—C16—H16C 109.9 (16)
C9—C8—C7 120.46 (18) H16A—C16—H16C 111 (2)
C13—C8—C7 120.22 (19) H16B—C16—H16C 111 (2)
C10—C9—C8 120.3 (2)
C4—O5—N6—C7 −2.9 (2) S2—C3—C4—C1 −2.29 (15)
O22—S2—C1—C7 142.25 (14) O5—N6—C7—C8 177.53 (17)
O21—S2—C1—C7 5.65 (18) O5—N6—C7—C1 1.6 (2)
C3—S2—C1—C7 −104.73 (16) C4—C1—C7—N6 0.2 (2)
O22—S2—C1—C4 −114.96 (13) S2—C1—C7—N6 95.10 (19)
O21—S2—C1—C4 108.44 (13) C4—C1—C7—C8 −175.51 (19)
C3—S2—C1—C4 −1.94 (12) S2—C1—C7—C8 −80.6 (2)
O22—S2—C3—C14 −125.69 (16) N6—C7—C8—C9 4.4 (3)
O21—S2—C3—C14 13.66 (19) C1—C7—C8—C9 179.8 (2)
C1—S2—C3—C14 123.08 (17) N6—C7—C8—C13 −172.5 (2)
O22—S2—C3—C4 113.16 (14) C1—C7—C8—C13 3.0 (3)
O21—S2—C3—C4 −107.50 (13) C13—C8—C9—C10 0.8 (3)
C1—S2—C3—C4 1.93 (12) C7—C8—C9—C10 −176.0 (2)
N6—O5—C4—C1 2.9 (2) C8—C9—C10—C11 0.1 (4)
N6—O5—C4—C3 −105.00 (19) C9—C10—C11—C12 −1.3 (3)
C7—C1—C4—O5 −1.8 (2) C10—C11—C12—C13 1.5 (4)
S2—C1—C4—O5 −114.97 (14) C11—C12—C13—C8 −0.6 (4)
C7—C1—C4—C3 115.42 (17) C9—C8—C13—C12 −0.5 (3)
supporting information
sup-5 Acta Cryst. (2002). E58, o715–o716
C14—C3—C4—O5 −10.3 (3) C4—C3—C14—C15 176.37 (18)
S2—C3—C4—O5 108.62 (16) S2—C3—C14—C15 72.3 (2)