organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

2-(Pyridin-2-yl)-1,3-oxa­thiane

aThermal Sciences and Materials Branch, Material and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, OH 45433, USA, bUniversal Technology Corporation, 1270 N. Fairfield Road, Beavercreek, OH 45432, USA, cChemistry Department, University of Dayton, 300 College Park, Dayton, OH 45469-2357, USA, and dChemistry Department, The Ohio State University, 154 W. 12th Avenue, Columbus, OH 43210, USA
*Correspondence e-mail: david.turner.ctr@wpafb.af.mil

(Received 22 March 2012; accepted 25 April 2012; online 12 May 2012)

The title compound, C9H11NOS, exhibits a unique structural motif, with free rotation of the aliphatic oxathiane ring about the C—C bond connecting this moiety to the aromatic pyridine ring. The structure elucidation was undertaken due to its potential as a bidentate ligand for organometallic complexes. The oxathiane ring adopts the expected chair conformation, with the S atom in proximity to the N atom on the pyridine ring. The corresponding S—C—C—N torsion angle is 69.07 (14)°. In the crystal, mol­ecules aggregate as centrosymmetric pairs connected by pairs of C—H⋯N hydrogen bonds.

Related literature

The corresponding organic compound, 2-(2-pyridyl)-1,3-oxathiane, forms dimers via weak inter­molecular C—H⋯N hydrogen bonds, exhibiting similar photophysical properties as previously observed (Rachford et al., 2005[Rachford, A., Petersen, J. & Rack, J. (2005). Inorg. Chem. 44, 8065-8075.]; Rachford & Rack, 2006[Rachford, A. & Rack, J. (2006). J. Am. Chem. Soc. 128, 14318-14324.]).

[Scheme 1]

Experimental

Crystal data
  • C9H11NOS

  • Mr = 181.26

  • Monoclinic, P 21 /n

  • a = 7.5329 (3) Å

  • b = 11.8099 (5) Å

  • c = 9.7632 (4) Å

  • β = 92.940 (3)°

  • V = 867.42 (6) Å3

  • Z = 4

  • Cu Kα radiation

  • μ = 2.89 mm−1

  • T = 110 K

  • 0.48 × 0.46 × 0.36 mm

Data collection
  • Oxford Diffraction Xcalibur Sapphire3 diffractometer

  • Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]), based on expressions derived by Clark & Reid (1995[Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897.])] Tmin = 0.344, Tmax = 0.519

  • 3675 measured reflections

  • 1708 independent reflections

  • 1656 reflections with I > 2σ(I)

  • Rint = 0.020

Refinement
  • R[F2 > 2σ(F2)] = 0.032

  • wR(F2) = 0.085

  • S = 1.07

  • 1708 reflections

  • 154 parameters

  • All H-atom parameters refined

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.30 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C1—H1⋯N1i 0.979 (19) 2.586 (19) 3.5399 (19) 164.8 (14)
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008)[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Supporting information


Comment top

Photo-induced or photo-triggered molecular isomerizations employ the stored energy in an electronic excited state for rapid bond-breaking and bond-making reactions. One of the most well studied examples of this type of reaction is photo-isomerization of stilbene and its derivatives, where phenyl group rotation occurs following ππ* excitation on an ultrafast time scale. Photo-induced or photo-triggered linkage isomerizations have also been observed in certain late transition metal complexes containing NO+, NO2-, N2, SO2, and DMSO (dimethylsulfoxide). Rack et al. has worked on ruthenium complexes with DMSO ligands and has observed photo- isomerization between the S-bound to the O-bound state upon uv/visible irradiation. However, this conversion can only be demonstrated in a solvent of DMSO (Rachford et al., 2005; Rachford & Rack, 2006). The development of photo-switchable molecules is of interest due to potential use in applications such as optical molecular information storage, optical limiting devices, and molecular sensing. For photonic devices, the design of such molecules requires the efficient conversion of light energy to potential energy. Thus, bistable molecules are also of a fundamental interest in that the design of such molecules requires specific electronic structures in order to exhibit two stable interconvertible states. Rack et al. has worked on ruthenium complexes with DMSO ligands and has observed photo-isomerization between the S-bound to the O-bound state upon uv/visible irradiation. However, this conversion can only be demonstrated in a solvent of DMSO (Rachford et al., 2005; Rachford & Rack, 2006). The synthesis and bonding of 2-(2-pyridyl)-1,3-oxathiane to a ruthenium metal center would still allow for the photo-isomerization between a S-bound to an O-bound state upon uv/visible irradiation due to the ability of the bidentate ligand to rotate about the C—C bond between the aliphatic, oxathiane moiety and the aromatic, pyridyl moiety. The major benefit of using this bidentate ligand would be that the photo-isomerization could be performed in a wide variety of solvents.

Related literature top

The corresponding organic compound forms dimers via weak intermolecular C—H···N hydrogen bonds, exhibiting similar photophysical properties as previously observed (Rachford et al., 2005; Rachford & Rack, 2006).

Experimental top

The title compound was synthesized as follows: A solution of 3.34 g (31.2 mmol) of 2-pyridinecarbaldehyde, 10.0 g (109 mmol) of 3-mercapto-1-propanol, and 0.475 g (2.50 mmol) of p-toluenesulfonic acid monohydrate in 400 ml of 1,2-dichloroethane were refluxed for 24 h with a Dean-Stark trap to collect the azeotroped water. After cooling, the azeotroped water was disposed of. The reacted mixture was washed with 70 ml of 7 M KOH and water. The aqueous and organic layers were separated in a separatory funnel. The organic layer was then dried over anhydrous sodium sulfate and filtered to remove the Na2SO4. The resulting solution was evaporated under reduced pressure to yield a brown oil. The brown oil was then passed through a silica column with diethyl ether. The 2-(2-pyridyl)-1,3-oxathiane was collected from the column and dried in air with a yield of 4.29 g (76%): 1H-NMR (400 MHz Bruker, CDCl3) δ(p.p.m.) 1.58 (d, 1 H), 1.92 (dd, 1 H), 2.68 (d, 1 H), 3.05 (dd, 1 H), 3.64 (dd, 1 H), 4.17 (d, 1 H), 5.80 (s, 1 H), 7.04 (t, 1 H), 7.41 (d, 1 H), 7.54 (t, 1 H), 8.41 (d, 1 H). 13C-NMR (400 MHz Bruker, CDCl3) δ(p.p.m.) 24.8 (CH2), 27.9 (CH2), 69.6 (CH2), 84.3 (CH), 120.1 (CH), 122.4 (CH), 136.0 (CH), 148.0 (CH), 157.2 (C). The experimental protocol for recrystallizing the title compound was as follows: 100 mg of 2-(2-pyridyl)-1,3-oxathiane was dissolved in 0.5 ml of methylene chloride, followed by the addition of 2.0 ml of hexane to the solution. The solution was filtered and then placed in a vial, covered with parafilm, and allowed to evaporate at room temperature over the course of days, after which time large crystals were obtained.

Refinement top

All non-hydrogen atoms were refined anistropically. All H-atoms were located in difference maps and refined free with isotropic displacement parameters.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Thermal ellipsoids are drawn at 50% probability for non-H atoms.
[Figure 2] Fig. 2. The crystal packing plot of the title compound viewed down the c-axis. C1—H1···N1 hydrogen bonds are drawn as dashed lines.
2-(Pyridin-2-yl)-1,3-oxathiane top
Crystal data top
C9H11NOSF(000) = 384
Mr = 181.26Dx = 1.388 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ynCell parameters from 3102 reflections
a = 7.5329 (3) Åθ = 0.5–72.0°
b = 11.8099 (5) ŵ = 2.89 mm1
c = 9.7632 (4) ÅT = 110 K
β = 92.940 (3)°Block, colourless
V = 867.42 (6) Å30.48 × 0.46 × 0.36 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur Sapphire3
diffractometer
1708 independent reflections
Radiation source: Enhance (Cu) xray source1656 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
Detector resolution: 16.3384 pixels mm-1θmax = 72.1°, θmin = 5.9°
ω scansh = 69
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2010), based on expressions derived by Clark & Reid (1995)]
k = 1214
Tmin = 0.344, Tmax = 0.519l = 1212
3675 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)] = 0.032All H-atom parameters refined
wR(F2) = 0.085 w = 1/[σ2(Fo2) + (0.0498P)2 + 0.3816P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1708 reflectionsΔρmax = 0.32 e Å3
154 parametersΔρmin = 0.30 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0187 (14)
Crystal data top
C9H11NOSV = 867.42 (6) Å3
Mr = 181.26Z = 4
Monoclinic, P21/nCu Kα radiation
a = 7.5329 (3) ŵ = 2.89 mm1
b = 11.8099 (5) ÅT = 110 K
c = 9.7632 (4) Å0.48 × 0.46 × 0.36 mm
β = 92.940 (3)°
Data collection top
Oxford Diffraction Xcalibur Sapphire3
diffractometer
1708 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2010), based on expressions derived by Clark & Reid (1995)]
1656 reflections with I > 2σ(I)
Tmin = 0.344, Tmax = 0.519Rint = 0.020
3675 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.085All H-atom parameters refined
S = 1.07Δρmax = 0.32 e Å3
1708 reflectionsΔρmin = 0.30 e Å3
154 parameters
Special details top

Experimental. CrysAlis PRO (Oxford Diffraction, 2010). Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R. C. Clark & J. S. Reid (Clark & Reid, 1995).

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
S10.20151 (4)0.36641 (3)0.12188 (3)0.01796 (16)
O10.39908 (13)0.45308 (9)0.33518 (10)0.0168 (2)
N10.59533 (16)0.33730 (11)0.03808 (12)0.0174 (3)
C10.40671 (19)0.43156 (12)0.19284 (14)0.0153 (3)
H10.421 (2)0.5024 (17)0.1426 (18)0.020 (4)*
C20.05140 (19)0.47642 (13)0.17565 (15)0.0190 (3)
H2A0.070 (3)0.5468 (17)0.1214 (19)0.025 (5)*
H2B0.069 (3)0.4511 (17)0.1510 (19)0.023 (5)*
C30.0792 (2)0.49944 (14)0.32842 (15)0.0202 (3)
H3B0.002 (3)0.5605 (18)0.354 (2)0.032 (5)*
H3A0.049 (3)0.4302 (18)0.381 (2)0.029 (5)*
C40.2682 (2)0.53679 (13)0.36591 (16)0.0209 (3)
H4A0.295 (3)0.6069 (18)0.316 (2)0.028 (5)*
H4B0.283 (2)0.5485 (16)0.465 (2)0.022 (5)*
C50.55562 (19)0.35019 (12)0.16969 (14)0.0150 (3)
C60.64241 (19)0.29098 (12)0.27685 (15)0.0173 (3)
H60.607 (3)0.3005 (17)0.368 (2)0.025 (5)*
C70.7761 (2)0.21501 (13)0.24709 (16)0.0196 (3)
H70.839 (3)0.1741 (17)0.322 (2)0.024 (5)*
C80.81619 (19)0.19959 (13)0.11104 (16)0.0192 (3)
H80.903 (3)0.1456 (16)0.089 (2)0.023 (5)*
C90.72283 (19)0.26255 (13)0.01104 (15)0.0182 (3)
H90.751 (2)0.2565 (16)0.082 (2)0.018 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0163 (2)0.0193 (2)0.0182 (2)0.00117 (12)0.00020 (14)0.00488 (12)
O10.0182 (5)0.0197 (5)0.0127 (5)0.0034 (4)0.0013 (4)0.0034 (4)
N10.0188 (6)0.0182 (6)0.0155 (6)0.0010 (5)0.0038 (5)0.0002 (5)
C10.0175 (7)0.0164 (7)0.0120 (6)0.0013 (5)0.0021 (5)0.0006 (5)
C20.0171 (7)0.0217 (7)0.0183 (7)0.0028 (6)0.0006 (5)0.0000 (6)
C30.0200 (7)0.0224 (8)0.0188 (7)0.0057 (6)0.0047 (5)0.0012 (6)
C40.0231 (7)0.0193 (7)0.0202 (7)0.0046 (6)0.0008 (6)0.0069 (6)
C50.0147 (7)0.0149 (6)0.0156 (7)0.0033 (5)0.0033 (5)0.0009 (5)
C60.0167 (7)0.0198 (7)0.0154 (7)0.0004 (5)0.0015 (5)0.0002 (5)
C70.0184 (7)0.0200 (7)0.0202 (7)0.0006 (6)0.0003 (6)0.0011 (6)
C80.0151 (7)0.0193 (7)0.0234 (8)0.0001 (6)0.0036 (6)0.0029 (6)
C90.0187 (7)0.0201 (7)0.0163 (7)0.0020 (6)0.0050 (5)0.0020 (6)
Geometric parameters (Å, º) top
S1—C21.8174 (15)C3—H3B0.97 (2)
S1—C11.8307 (14)C3—H3A1.00 (2)
O1—C11.4168 (16)C4—H4A0.99 (2)
O1—C41.4386 (17)C4—H4B0.973 (19)
N1—C91.3407 (19)C5—C61.393 (2)
N1—C51.3428 (18)C6—C71.390 (2)
C1—C51.5030 (19)C6—H60.95 (2)
C1—H10.979 (19)C7—C81.389 (2)
C2—C31.520 (2)C7—H70.98 (2)
C2—H2A1.00 (2)C8—C91.389 (2)
C2—H2B0.97 (2)C8—H80.95 (2)
C3—C41.517 (2)C9—H90.951 (19)
C2—S1—C196.66 (7)O1—C4—C3113.23 (12)
C1—O1—C4112.99 (11)O1—C4—H4A108.2 (12)
C9—N1—C5117.39 (13)C3—C4—H4A109.6 (12)
O1—C1—C5109.29 (11)O1—C4—H4B105.1 (11)
O1—C1—S1111.76 (9)C3—C4—H4B109.6 (11)
C5—C1—S1107.25 (10)H4A—C4—H4B111.0 (16)
O1—C1—H1110.5 (11)N1—C5—C6122.87 (13)
C5—C1—H1111.6 (11)N1—C5—C1114.90 (12)
S1—C1—H1106.5 (11)C6—C5—C1122.22 (13)
C3—C2—S1110.78 (10)C7—C6—C5118.94 (14)
C3—C2—H2A110.8 (11)C7—C6—H6120.8 (12)
S1—C2—H2A109.6 (11)C5—C6—H6120.2 (12)
C3—C2—H2B112.2 (11)C8—C7—C6118.67 (14)
S1—C2—H2B107.1 (12)C8—C7—H7122.0 (12)
H2A—C2—H2B106.2 (16)C6—C7—H7119.3 (12)
C4—C3—C2111.67 (12)C7—C8—C9118.34 (14)
C4—C3—H3B106.9 (12)C7—C8—H8119.3 (12)
C2—C3—H3B109.6 (12)C9—C8—H8122.4 (12)
C4—C3—H3A110.4 (12)N1—C9—C8123.77 (13)
C2—C3—H3A109.6 (12)N1—C9—H9115.9 (11)
H3B—C3—H3A108.6 (16)C8—C9—H9120.3 (11)
C4—O1—C1—C5175.71 (11)O1—C1—C5—N1169.60 (11)
C4—O1—C1—S165.74 (13)S1—C1—C5—N169.07 (14)
C2—S1—C1—O156.31 (11)O1—C1—C5—C611.82 (18)
C2—S1—C1—C5176.07 (9)S1—C1—C5—C6109.50 (13)
C1—S1—C2—C352.99 (12)N1—C5—C6—C70.0 (2)
S1—C2—C3—C459.31 (15)C1—C5—C6—C7178.42 (13)
C1—O1—C4—C364.95 (16)C5—C6—C7—C81.0 (2)
C2—C3—C4—O161.17 (17)C6—C7—C8—C91.2 (2)
C9—N1—C5—C60.9 (2)C5—N1—C9—C80.8 (2)
C9—N1—C5—C1177.62 (12)C7—C8—C9—N10.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N1i0.979 (19)2.586 (19)3.5399 (19)164.8 (14)
Symmetry code: (i) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC9H11NOS
Mr181.26
Crystal system, space groupMonoclinic, P21/n
Temperature (K)110
a, b, c (Å)7.5329 (3), 11.8099 (5), 9.7632 (4)
β (°) 92.940 (3)
V3)867.42 (6)
Z4
Radiation typeCu Kα
µ (mm1)2.89
Crystal size (mm)0.48 × 0.46 × 0.36
Data collection
DiffractometerOxford Diffraction Xcalibur Sapphire3
diffractometer
Absorption correctionAnalytical
[CrysAlis PRO (Oxford Diffraction, 2010), based on expressions derived by Clark & Reid (1995)]
Tmin, Tmax0.344, 0.519
No. of measured, independent and
observed [I > 2σ(I)] reflections
3675, 1708, 1656
Rint0.020
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.085, 1.07
No. of reflections1708
No. of parameters154
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.32, 0.30

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Selected torsion angles (º) top
C4—O1—C1—C5175.71 (11)C2—S1—C1—C5176.07 (9)
C4—O1—C1—S165.74 (13)O1—C1—C5—N1169.60 (11)
C2—S1—C1—O156.31 (11)S1—C1—C5—N169.07 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N1i0.979 (19)2.586 (19)3.5399 (19)164.8 (14)
Symmetry code: (i) x+1, y+1, z.
 

Acknowledgements

Funding from the US Air Force Office of Scientific Research, Thermal Sciences (Program Manager: Dr Joan Fuller) is gratefully acknowledged. In addition, the authors would like to acknowledge Dr Andrey Voevodin at the Air Force Research Laboratory, Thermal Sciences and Materials Branch, for helpful advice and guidance.

References

First citationClark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationOxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.  Google Scholar
First citationRachford, A., Petersen, J. & Rack, J. (2005). Inorg. Chem. 44, 8065–8075.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationRachford, A. & Rack, J. (2006). J. Am. Chem. Soc. 128, 14318–14324.  Web of Science CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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