organic compounds
5-Phenyl-1,2,5-dithiazepane
aDepartment of Chemistry, The University of Texas at Austin, 105 E 24th Street, Stop A5300, Austin, Texas 78712, USA
*Correspondence e-mail: bholliday@cm.utexas.edu
In the title compound, C10H13NS2, the seven-membered ring adopts a chair conformation. The S—S bond length is 2.0406 (5) Å and the C—S—S—C torsion angle is −83.89 (7)°. The amine group is sp2-hybridized. In the crystal, molecules are linked into chains along [001] by weak intermolecular S⋯S contacts of 3.5246 (5) Å.
CCDC reference: 984235
Related literature
For properties of disulfide compounds, see: Pazderlová et al. (2012). For similar compounds, see: Roze et al. (2006); Bulavin (1971). For related structures, see: Pickardt et al. (2006); Capasso et al. (1977). For standard bond lengths, see: Allen et al. (1987). For previous reports of S⋯S interactions, see: Chen et al. (2009); Reinheimer et al. (2009). For the calculation of the functionality of the amine group in terms of see: Allen et al. (1995). For the synthesis, see: Elderfield et al. (1958).
Experimental
Crystal data
|
Data collection: COLLECT (Nonius, 1998); cell COLLECT; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999) within WinGX (Farrugia, 2012); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010).
Supporting information
CCDC reference: 984235
10.1107/S1600536814002207/lh5658sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814002207/lh5658Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814002207/lh5658Isup3.cml
The title compound was prepared from N,N-bis(2-chloroethyl)aniline which had been prepared following literature methods reported by Elderfield et al. (1958). NaSH·H2O (1.08 g, 14.78 mmol) was stirred in ethanol (20 ml) under an argon atmosphere for 1 hr. N,N-bis(2-chloroethyl)aniline (0.5124 g, 2.35 mmol) was dissolved in ethanol (10 ml) under argon and then transferred into the NaSH·H2O solution via cannula. The reaction mixture was then heated to reflux for 24 hrs. The solvent volume was reduced by half in vacuo before degassed CH2Cl2 and H2O were added to the reaction flask and the product was extracted under argon. The organic phase was then transferred via cannula into a flask containing MgSO4. The product was isolated by filtration and removal of the solvent under vacuum. The X-ray quality crystals were obtained from a saturated dichloromethane solution of the title compound upon standing at 263 K for several days. Yield = 83%. 1H NMR (300 MHz, CDCl3): δ 7.25 (m, 2H), 6.85 (m, 3H), 3.52 (m, 4H), 2.74 (m, 4H).
All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C).
Data collection: COLLECT (Nonius, 1998); cell
COLLECT (Nonius, 1998); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999) within WinGX (Farrugia, 2012); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).C10H13NS2 | F(000) = 448 |
Mr = 211.33 | Dx = 1.392 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2ybc | Cell parameters from 1974 reflections |
a = 9.5760 (2) Å | θ = 1.0–27.5° |
b = 12.2310 (3) Å | µ = 0.48 mm−1 |
c = 9.9811 (2) Å | T = 153 K |
β = 120.392 (2)° | Block, white |
V = 1008.38 (4) Å3 | 0.50 × 0.30 × 0.20 mm |
Z = 4 |
Nonius Kappa CCD diffractometer | 1763 independent reflections |
Radiation source: fine-focus sealed tube | 1675 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
ω scans | θmax = 25.0°, θmin = 4.1° |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) | h = −11→11 |
Tmin = 0.856, Tmax = 1 | k = −12→14 |
3055 measured reflections | l = −11→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0266P)2 + 0.5691P] where P = (Fo2 + 2Fc2)/3 |
1763 reflections | (Δ/σ)max = 0.002 |
118 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C10H13NS2 | V = 1008.38 (4) Å3 |
Mr = 211.33 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.5760 (2) Å | µ = 0.48 mm−1 |
b = 12.2310 (3) Å | T = 153 K |
c = 9.9811 (2) Å | 0.50 × 0.30 × 0.20 mm |
β = 120.392 (2)° |
Nonius Kappa CCD diffractometer | 1763 independent reflections |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) | 1675 reflections with I > 2σ(I) |
Tmin = 0.856, Tmax = 1 | Rint = 0.012 |
3055 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.25 e Å−3 |
1763 reflections | Δρmin = −0.21 e Å−3 |
118 parameters |
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 > 2Σ(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. |
x | y | z | Uiso*/Ueq | ||
S1 | 1.04272 (4) | 0.28440 (3) | 0.62971 (4) | 0.02268 (12) | |
S2 | 1.07376 (4) | 0.34787 (3) | 0.83210 (4) | 0.02409 (12) | |
N1 | 0.74239 (13) | 0.43703 (9) | 0.57782 (13) | 0.0190 (3) | |
C1 | 0.65295 (16) | 0.42454 (11) | 0.65031 (15) | 0.0187 (3) | |
C2 | 0.66903 (17) | 0.49796 (12) | 0.76593 (16) | 0.0218 (3) | |
H2 | 0.7434 | 0.5548 | 0.7965 | 0.026* | |
C3 | 0.57560 (17) | 0.48654 (13) | 0.83458 (16) | 0.0261 (3) | |
H3 | 0.5882 | 0.5360 | 0.9107 | 0.031* | |
C4 | 0.46349 (18) | 0.40283 (13) | 0.79229 (17) | 0.0282 (3) | |
H4 | 0.4006 | 0.3960 | 0.8386 | 0.034* | |
C5 | 0.44731 (17) | 0.32959 (13) | 0.67931 (17) | 0.0261 (3) | |
H5 | 0.3723 | 0.2732 | 0.6495 | 0.031* | |
C6 | 0.54029 (17) | 0.33875 (12) | 0.61020 (16) | 0.0223 (3) | |
H6 | 0.5285 | 0.2877 | 0.5362 | 0.027* | |
C7 | 0.72559 (17) | 0.36111 (11) | 0.45867 (16) | 0.0217 (3) | |
H7A | 0.7562 | 0.3982 | 0.3915 | 0.026* | |
H7B | 0.6125 | 0.3407 | 0.3958 | 0.026* | |
C8 | 0.82641 (17) | 0.25754 (11) | 0.52070 (17) | 0.0224 (3) | |
H8A | 0.8026 | 0.2096 | 0.4342 | 0.027* | |
H8B | 0.7956 | 0.2197 | 0.5873 | 0.027* | |
C9 | 0.87194 (17) | 0.51649 (11) | 0.63274 (17) | 0.0231 (3) | |
H9A | 0.8296 | 0.5868 | 0.6406 | 0.028* | |
H9B | 0.9037 | 0.5236 | 0.5550 | 0.028* | |
C10 | 1.02434 (18) | 0.49172 (12) | 0.78971 (17) | 0.0259 (3) | |
H10A | 1.0103 | 0.5229 | 0.8715 | 0.031* | |
H10B | 1.1157 | 0.5283 | 0.7926 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0207 (2) | 0.0222 (2) | 0.0268 (2) | 0.00209 (13) | 0.01317 (16) | 0.00058 (13) |
S2 | 0.0215 (2) | 0.0287 (2) | 0.0192 (2) | −0.00065 (14) | 0.00822 (15) | 0.00285 (13) |
N1 | 0.0195 (6) | 0.0174 (6) | 0.0198 (6) | −0.0004 (4) | 0.0097 (5) | −0.0012 (4) |
C1 | 0.0171 (7) | 0.0180 (7) | 0.0177 (6) | 0.0048 (5) | 0.0062 (5) | 0.0045 (5) |
C2 | 0.0202 (7) | 0.0199 (7) | 0.0222 (7) | 0.0019 (5) | 0.0085 (6) | 0.0003 (5) |
C3 | 0.0253 (7) | 0.0307 (8) | 0.0217 (7) | 0.0072 (6) | 0.0115 (6) | 0.0004 (6) |
C4 | 0.0225 (7) | 0.0376 (8) | 0.0274 (7) | 0.0064 (6) | 0.0148 (6) | 0.0083 (7) |
C5 | 0.0178 (7) | 0.0270 (8) | 0.0296 (8) | 0.0004 (6) | 0.0090 (6) | 0.0063 (6) |
C6 | 0.0196 (7) | 0.0209 (7) | 0.0219 (7) | 0.0010 (5) | 0.0072 (6) | 0.0000 (5) |
C7 | 0.0223 (7) | 0.0235 (7) | 0.0180 (7) | 0.0018 (6) | 0.0091 (6) | −0.0007 (5) |
C8 | 0.0215 (7) | 0.0206 (7) | 0.0242 (7) | −0.0005 (6) | 0.0109 (6) | −0.0044 (6) |
C9 | 0.0280 (7) | 0.0183 (7) | 0.0275 (7) | −0.0024 (6) | 0.0173 (6) | 0.0002 (6) |
C10 | 0.0241 (7) | 0.0238 (7) | 0.0291 (8) | −0.0048 (6) | 0.0130 (6) | −0.0069 (6) |
S1—C8 | 1.8171 (14) | C5—C6 | 1.379 (2) |
S1—S2 | 2.0406 (5) | C5—H5 | 0.9300 |
S2—C10 | 1.8155 (15) | C6—H6 | 0.9300 |
N1—C1 | 1.3811 (18) | C7—C8 | 1.5216 (19) |
N1—C7 | 1.4523 (18) | C7—H7A | 0.9700 |
N1—C9 | 1.4478 (18) | C7—H7B | 0.9700 |
C1—C2 | 1.408 (2) | C8—H8A | 0.9700 |
C1—C6 | 1.410 (2) | C8—H8B | 0.9700 |
C2—C3 | 1.382 (2) | C9—C10 | 1.537 (2) |
C2—H2 | 0.9300 | C9—H9A | 0.9700 |
C3—C4 | 1.386 (2) | C9—H9B | 0.9700 |
C3—H3 | 0.9300 | C10—H10A | 0.9700 |
C4—C5 | 1.386 (2) | C10—H10B | 0.9700 |
C4—H4 | 0.9300 | ||
C8—S1—S2 | 102.27 (5) | N1—C7—H7A | 108.6 |
C10—S2—S1 | 104.34 (5) | C8—C7—H7A | 108.6 |
C1—N1—C7 | 121.14 (11) | N1—C7—H7B | 108.6 |
C1—N1—C9 | 121.04 (11) | C8—C7—H7B | 108.6 |
C7—N1—C9 | 117.26 (11) | H7A—C7—H7B | 107.6 |
N1—C1—C2 | 121.28 (12) | C7—C8—S1 | 112.92 (10) |
N1—C1—C6 | 121.45 (12) | C7—C8—H8A | 109.0 |
C2—C1—C6 | 117.26 (13) | S1—C8—H8A | 109.0 |
C3—C2—C1 | 120.81 (14) | C7—C8—H8B | 109.0 |
C3—C2—H2 | 119.6 | S1—C8—H8B | 109.0 |
C1—C2—H2 | 119.6 | H8A—C8—H8B | 107.8 |
C2—C3—C4 | 121.32 (14) | N1—C9—C10 | 116.32 (11) |
C2—C3—H3 | 119.3 | N1—C9—H9A | 108.2 |
C4—C3—H3 | 119.3 | C10—C9—H9A | 108.2 |
C5—C4—C3 | 118.41 (14) | N1—C9—H9B | 108.2 |
C5—C4—H4 | 120.8 | C10—C9—H9B | 108.2 |
C3—C4—H4 | 120.8 | H9A—C9—H9B | 107.4 |
C6—C5—C4 | 121.30 (14) | C9—C10—S2 | 115.45 (10) |
C6—C5—H5 | 119.3 | C9—C10—H10A | 108.4 |
C4—C5—H5 | 119.3 | S2—C10—H10A | 108.4 |
C5—C6—C1 | 120.88 (14) | C9—C10—H10B | 108.4 |
C5—C6—H6 | 119.6 | S2—C10—H10B | 108.4 |
C1—C6—H6 | 119.6 | H10A—C10—H10B | 107.5 |
N1—C7—C8 | 114.49 (11) | ||
C8—S1—S2—C10 | −83.89 (7) | N1—C1—C6—C5 | −177.53 (12) |
C7—N1—C1—C2 | 179.96 (12) | C2—C1—C6—C5 | 1.6 (2) |
C9—N1—C1—C2 | 8.78 (19) | C1—N1—C7—C8 | −83.69 (15) |
C7—N1—C1—C6 | −0.92 (19) | C9—N1—C7—C8 | 87.82 (15) |
C9—N1—C1—C6 | −172.10 (12) | N1—C7—C8—S1 | −62.44 (14) |
N1—C1—C2—C3 | 178.13 (12) | S2—S1—C8—C7 | 73.74 (10) |
C6—C1—C2—C3 | −1.0 (2) | C1—N1—C9—C10 | 69.91 (16) |
C1—C2—C3—C4 | 0.0 (2) | C7—N1—C9—C10 | −101.60 (14) |
C2—C3—C4—C5 | 0.4 (2) | N1—C9—C10—S2 | 32.78 (16) |
C3—C4—C5—C6 | 0.2 (2) | S1—S2—C10—C9 | 44.11 (12) |
C4—C5—C6—C1 | −1.3 (2) |
Experimental details
Crystal data | |
Chemical formula | C10H13NS2 |
Mr | 211.33 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 153 |
a, b, c (Å) | 9.5760 (2), 12.2310 (3), 9.9811 (2) |
β (°) | 120.392 (2) |
V (Å3) | 1008.38 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.50 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Nonius Kappa CCD diffractometer |
Absorption correction | Multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.856, 1 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3055, 1763, 1675 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.064, 1.03 |
No. of reflections | 1763 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.21 |
Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999) within WinGX (Farrugia, 2012), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
Acknowledgements
The Welch Foundation (grant No. F-1631) and the National Science Foundation (grant No. CHE-0847763) are acknowledged for financial support of this research.
References
Allen, F. H., Bird, C. M., Rowland, R. S., Harris, S. E. & Schwalbe, C. H. (1995). Acta Cryst. B51, 1068–1081. CrossRef CAS Web of Science IUCr Journals Google Scholar
Allen, F. H., Kennard, O. & Watson, D. G. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bulavin, L. G. (1971). Zh. Org. Khim. 7, 2604–2610. CAS Google Scholar
Capasso, S., Mattia, C., Mazzarella, L. & Puliti, R. (1977). Acta Cryst. B33, 2080–2083. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Chen, H.-F., Fang, Q., Yu, W.-T., Batsanov, A. S. & Howard, J. A. K. (2009). Acta Cryst. C65, o198–o201. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Elderfield, R. C., Covey, I. S., Geiduschek, J. B., Meyer, W. L., Ross, A. B. & Ross, J. H. (1958). J. Org. Chem. 23, 1749–1753. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Nonius (1998). KappaCCD Software. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Pazderlová, M., Bednárová, L., Dlouhá, H., Flegel, M., Lebl, M., Hlaváček, J., Setnička, V., Urbanová, M., Hynie, S., Klenerová, V., Baumruk, V. & Maloň, P. (2012). Biopolymers, 97, 923–932. Web of Science PubMed Google Scholar
Pickardt, J., von Chrzanowski, L. & Borowski, M. (2006). Acta Cryst. E62, o3401–o3402. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Reinheimer, E. W., Fourmigué, M. & Dunbar, K. R. (2009). J. Chem. Crystallogr. 39, 723–729. Web of Science CSD CrossRef CAS Google Scholar
Roze, M., Kirichenko, N. & Neilands, O. (2006). Latv. Kim. Z. 4, 351–355. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Cyclic disulfides are of special interest because they are often a key component in many biologically relevant peptides (Pazderlová et al., 2012). Because of this disulfide compounds are regularly found to have pharmacological activities. Herein is described the crystallographic properties of a 7-membered cyclic disulfide compound. The molecular structure of the title compound can be seen in Fig. 1.
The S—S bond distance is 2.0406 (5) Å. This value is comparable to other disulfide compounds. The mean average bond length for C—S—S—C bonds from 99 samples, reported by (Allen et al., 1987) is 2.048 Å. The torsion in the C—S—S—C bonds is -83.89 (7)°, this compares similarly to the C—S—S—C torsion in the 7-membered ring disulfide 1,2,4,6-tetrathiacycloheptane reported in (Pickardt et al., 2006), which has a C—S—S—C torsion of -89.4 (2)°.
The seven-membered ring adopts a chair conformation, as it does in the cyclic disulfide compound reported by Pickardt et al. (2006). The dominant intermolecular interactions are between S1···S2 of symmetry-related molecules. The contacts have a distance of 3.5246 (5) Å, this compares similarly to S···S interactions observed perviously by Chen et al. (2009) and Reinheimer et al. (2009) which are 3.396 (1) - 3.470 (1) Å and 3.580 (4) Å respectively.
The pyramidality of the amine functionality, measured by χn, the angle between the C1—N1 vector and the N1/C7/C9 plane, described by Allen et al. (1995), is 7.26 (15)°, indicating that the hybridization of the nitrogen atoms is mainly sp2 (sp2 χn ≈ 0°, sp3 χn ≈ 60°).