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access10-(Prop-1-yn-1-yl)-10H-phenothiazine
aDepartment of Material Science and Chemistry, Wakayama University, Sakaedani, Wakayama 640-8510, Japan
*Correspondence e-mail: okuno@center.wakayama-u.ac.jp
In the title compound, C15H11NS, the comprises one half-molecule; a mirror plane passes through the S atom, the ynamine fragment, the methyl C atom and one methyl H atom. The phenothiazine moiety has a butterfly conformation and the central six-membered ring has a boat conformation. The dihedral angle between the benzene rings is 149.40 (4)°. The is stabilized by van der Waals interactions.
Related literature
For related structures of phenothiazine compounds, see: Okuno et al. (2006![[Okuno, T., Ikeda, S., Kubo, N. & Sandman, D. J. (2006). Mol. Cryst. Liq. Cryst. 456, 35-44.]](../../../../../../logos/arrows/e_arr.gif "Okuno, T., Ikeda, S., Kubo, N. & Sandman, D. J. (2006). Mol. Cryst. Liq. Cryst. 456, 35-44.")
); Tabata & Okuno (2012). For the preparation of the title compound, see: Zaugg et al. (1958).
![[Scheme 1]](bx2425scheme1.gif)
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku, 2008); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536812036537/bx2425sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536812036537/bx2425Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812036537/bx2425Isup3.cml
The title compound was prepared according to a published procedure (Zaugg et al., 1958). The single crystals with sufficient quality for X-ray analysis were obtained by slow concentration of a methanol solution.
The C-bound H atoms were placed at ideal positions and were refined as riding on their parent C atoms. Uiso(H) values of H2—H5 atoms were set at 1.2Ueq(parent atom).
Data collection: CrystalClear (Rigaku, 2008); cell CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
| ORTEP view of the title compound with atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres. [Symmetry code: (i) -x, y, z.] |
| C15H11NS | F(000) = 496 |
| Mr = 237.31 | Dx = 1.366 Mg m−3 |
| Orthorhombic, Cmc21 | Mo Kα radiation, λ = 0.71075 Å |
| Hall symbol: C 2c -2 | Cell parameters from 2342 reflections |
| a = 14.717 (6) Å | θ = 2.4–31.2° |
| b = 10.631 (4) Å | µ = 0.25 mm−1 |
| c = 7.375 (3) Å | T = 93 K |
| V = 1153.9 (8) Å3 | Block, colorless |
| Z = 4 | 0.12 × 0.10 × 0.08 mm |
| Rigaku Saturn724+ diffractometer | 1441 reflections with I > 2σ(I) |
| Detector resolution: 28.445 pixels mm-1 | Rint = 0.019 |
| ω scans | θmax = 28.5°, θmin = 2.4° |
| Absorption correction: numerical (NUMABS; Rigaku, 1999) | h = −19→16 |
| Tmin = 0.959, Tmax = 0.980 | k = −14→12 |
| 4889 measured reflections | l = −9→9 |
| 1486 independent reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
| wR(F2) = 0.065 | w = 1/[σ2(Fo2) + (0.0354P)2 + 0.514P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.08 | (Δ/σ)max < 0.001 |
| 1486 reflections | Δρmax = 0.20 e Å−3 |
| 87 parameters | Δρmin = −0.16 e Å−3 |
| 1 restraint | Absolute structure: Flack (1983), 670 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (6) |
| C15H11NS | V = 1153.9 (8) Å3 |
| Mr = 237.31 | Z = 4 |
| Orthorhombic, Cmc21 | Mo Kα radiation |
| a = 14.717 (6) Å | µ = 0.25 mm−1 |
| b = 10.631 (4) Å | T = 93 K |
| c = 7.375 (3) Å | 0.12 × 0.10 × 0.08 mm |
| Rigaku Saturn724+ diffractometer | 1486 independent reflections |
| Absorption correction: numerical (NUMABS; Rigaku, 1999) | 1441 reflections with I > 2σ(I) |
| Tmin = 0.959, Tmax = 0.980 | Rint = 0.019 |
| 4889 measured reflections |
| R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
| wR(F2) = 0.065 | Δρmax = 0.20 e Å−3 |
| S = 1.08 | Δρmin = −0.16 e Å−3 |
| 1486 reflections | Absolute structure: Flack (1983), 670 Friedel pairs |
| 87 parameters | Absolute structure parameter: −0.01 (6) |
| 1 restraint |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.0000 | 0.03514 (4) | −0.00174 (4) | 0.01839 (11) | |
| N1 | 0.0000 | 0.28986 (13) | 0.1771 (2) | 0.0165 (3) | |
| C1 | 0.08381 (8) | 0.22366 (10) | 0.19225 (16) | 0.0153 (2) | |
| C2 | 0.15834 (8) | 0.27842 (11) | 0.27878 (17) | 0.0176 (2) | |
| H2 | 0.1524 | 0.3585 | 0.3346 | 0.021* | |
| C3 | 0.24154 (8) | 0.21576 (12) | 0.28336 (18) | 0.0201 (3) | |
| H3 | 0.2926 | 0.2542 | 0.3393 | 0.024* | |
| C4 | 0.24978 (8) | 0.09669 (12) | 0.20594 (18) | 0.0212 (3) | |
| H4 | 0.3067 | 0.0545 | 0.2075 | 0.025* | |
| C5 | 0.17460 (9) | 0.03964 (11) | 0.12637 (17) | 0.0189 (3) | |
| H5 | 0.1797 | −0.0430 | 0.0783 | 0.023* | |
| C6 | 0.09172 (8) | 0.10329 (11) | 0.11690 (15) | 0.0163 (2) | |
| C7 | 0.0000 | 0.41727 (16) | 0.1900 (2) | 0.0164 (3) | |
| C8 | 0.0000 | 0.52987 (15) | 0.1916 (3) | 0.0171 (3) | |
| C9 | 0.0000 | 0.66718 (16) | 0.1911 (3) | 0.0218 (4) | |
| H9A | 0.0000 | 0.7026 | 0.3042 | 0.045 (8)* | |
| H9B | −0.0435 | 0.7017 | 0.1183 | 0.050 (6)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0226 (2) | 0.01654 (18) | 0.01607 (19) | 0.000 | 0.000 | −0.00403 (15) |
| N1 | 0.0160 (7) | 0.0124 (6) | 0.0212 (7) | 0.000 | 0.000 | −0.0023 (5) |
| C1 | 0.0150 (5) | 0.0154 (5) | 0.0155 (5) | 0.0004 (4) | 0.0028 (4) | 0.0021 (4) |
| C2 | 0.0188 (6) | 0.0159 (5) | 0.0180 (5) | −0.0016 (5) | 0.0009 (5) | 0.0001 (4) |
| C3 | 0.0165 (6) | 0.0225 (6) | 0.0212 (6) | −0.0021 (5) | 0.0001 (5) | 0.0039 (4) |
| C4 | 0.0178 (5) | 0.0209 (6) | 0.0249 (6) | 0.0043 (5) | 0.0040 (5) | 0.0060 (5) |
| C5 | 0.0218 (6) | 0.0159 (5) | 0.0189 (6) | 0.0030 (4) | 0.0061 (5) | 0.0021 (4) |
| C6 | 0.0183 (5) | 0.0160 (5) | 0.0144 (5) | −0.0007 (4) | 0.0027 (4) | 0.0011 (4) |
| C7 | 0.0146 (7) | 0.0172 (8) | 0.0175 (7) | 0.000 | 0.000 | −0.0018 (6) |
| C8 | 0.0143 (7) | 0.0165 (8) | 0.0206 (8) | 0.000 | 0.000 | −0.0014 (6) |
| C9 | 0.0232 (9) | 0.0142 (7) | 0.0278 (9) | 0.000 | 0.000 | −0.0011 (7) |
| S1—C6i | 1.7642 (13) | C3—H3 | 0.9500 |
| S1—C6 | 1.7643 (13) | C4—C5 | 1.3914 (19) |
| N1—C7 | 1.358 (2) | C4—H4 | 0.9500 |
| N1—C1 | 1.4246 (14) | C5—C6 | 1.3966 (17) |
| N1—C1i | 1.4246 (14) | C5—H5 | 0.9500 |
| C1—C2 | 1.3961 (17) | C7—C8 | 1.197 (3) |
| C1—C6 | 1.3999 (17) | C8—C9 | 1.460 (2) |
| C2—C3 | 1.3944 (17) | C9—H9A | 0.9152 |
| C2—H2 | 0.9500 | C9—H9B | 0.9126 |
| C3—C4 | 1.3940 (18) | ||
| C6i—S1—C6 | 99.84 (8) | C5—C4—H4 | 120.0 |
| C7—N1—C1 | 119.16 (7) | C3—C4—H4 | 120.0 |
| C7—N1—C1i | 119.16 (7) | C4—C5—C6 | 120.29 (11) |
| C1—N1—C1i | 119.97 (14) | C4—C5—H5 | 119.9 |
| C2—C1—C6 | 119.82 (11) | C6—C5—H5 | 119.9 |
| C2—C1—N1 | 120.67 (11) | C5—C6—C1 | 119.71 (11) |
| C6—C1—N1 | 119.50 (11) | C5—C6—S1 | 119.61 (9) |
| C3—C2—C1 | 120.12 (11) | C1—C6—S1 | 120.57 (9) |
| C3—C2—H2 | 119.9 | C8—C7—N1 | 176.53 (19) |
| C1—C2—H2 | 119.9 | C7—C8—C9 | 179.3 (2) |
| C4—C3—C2 | 120.02 (11) | C8—C9—H9A | 114.2 |
| C4—C3—H3 | 120.0 | C8—C9—H9B | 113.8 |
| C2—C3—H3 | 120.0 | H9A—C9—H9B | 111.8 |
| C5—C4—C3 | 119.96 (11) | ||
| C7—N1—C1—C2 | 21.9 (2) | C4—C5—C6—S1 | 174.51 (9) |
| C1i—N1—C1—C2 | −143.06 (11) | C2—C1—C6—C5 | −1.00 (17) |
| C7—N1—C1—C6 | −157.02 (14) | N1—C1—C6—C5 | 177.97 (12) |
| C1i—N1—C1—C6 | 38.0 (2) | C2—C1—C6—S1 | −177.19 (9) |
| C6—C1—C2—C3 | 2.76 (17) | N1—C1—C6—S1 | 1.78 (15) |
| N1—C1—C2—C3 | −176.20 (12) | C6i—S1—C6—C5 | 152.23 (7) |
| C1—C2—C3—C4 | −1.81 (18) | C6i—S1—C6—C1 | −31.58 (13) |
| C2—C3—C4—C5 | −0.91 (18) | C1—N1—C7—C8 | 97.44 (13) |
| C3—C4—C5—C6 | 2.68 (18) | C1i—N1—C7—C8 | −97.44 (13) |
| C4—C5—C6—C1 | −1.72 (18) | N1—C7—C8—C9 | 0.00 (5) |
| Symmetry code: (i) −x, y, z. |
Experimental details
| Crystal data | |
| Chemical formula | C15H11NS |
| Mr | 237.31 |
| Crystal system, space group | Orthorhombic, Cmc21 |
| Temperature (K) | 93 |
| a, b, c (Å) | 14.717 (6), 10.631 (4), 7.375 (3) |
| V (Å3) | 1153.9 (8) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.25 |
| Crystal size (mm) | 0.12 × 0.10 × 0.08 |
| Data collection | |
| Diffractometer | Rigaku Saturn724+ diffractometer |
| Absorption correction | Numerical (NUMABS; Rigaku, 1999) |
| Tmin, Tmax | 0.959, 0.980 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 4889, 1486, 1441 |
| Rint | 0.019 |
| (sin θ/λ)max (Å−1) | 0.671 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.065, 1.08 |
| No. of reflections | 1486 |
| No. of parameters | 87 |
| No. of restraints | 1 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.20, −0.16 |
| Absolute structure | Flack (1983), 670 Friedel pairs |
| Absolute structure parameter | −0.01 (6) |
Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).
Acknowledgements
This work was supported by Research for Promoting Technological Seeds from the Japan Science and Technology Agency (JST).
References
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Okuno, T., Ikeda, S., Kubo, N. & Sandman, D. J. (2006). Mol. Cryst. Liq. Cryst. 456, 35–44. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tabata, H. & Okuno, T. (2012). Acta Cryst. E68, o2214. CSD CrossRef IUCr Journals Google Scholar
Zaugg, H. E., Swett, L. R. & Stone, G. R. (1958). J. Org. Chem. 23, 1389–1390. CrossRef CAS Web of Science Google Scholar
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Ynamines, where amino groups connect to acetylene groups, are known to be unstable because of their high reactivity. The title compound, C15H11NS, is the first ynamine compound which was prepared accidentally (Zaugg et al., 1958). The asymmetric unit comprises one half-molecule; a mirror plane passes through the S, ynamine fragment, one C atom of methyl group and one H atom of methyl group. The bond distances and angles are comparable with others reported ynamines (Okuno et al., 2006; Tabata et al., 2012). The crystal structure is stabilized by van der Waals interactions. The phenothiazine moiety has a butterfly conformation, and the central six-membered ring has a boat conformation. The dihedral angle between two benzene rings is 149.40 (4)°.