organic compounds
10-Acetyl-10H-phenothiazine 5-oxide
aDepartment of Physics and Chemistry, Henan Polytechnic University, Jiao Zuo 454000, People's Republic of China, and bDepartment of Medicine, Hebi College of Vocation and Technology, He Bi 458030, People's Republic of China
*Correspondence e-mail: wangqiang@hpu.edu.cn
In the title compound, C14H11NO2S, the sulfoxide O atom is disordered over two sites with occupancies of 0.886 (4) and 0.114 (4), reflecting a partial inversion of the lone pair at the tetrahedral S-atom site. In the crystal, a supramolecular arrangement arises from weak intermolecular C—H⋯O hydrogen bonds. π–π contacts between the aromatic rings of symmetry-related molecules [centroid–centroid distances = 3.7547 (15) and 3.9577 (15) Å] in parallel accumulation further stabilize the crystal structure.
Related literature
For synthetic details, see: Gilman & Nelson (1953); Chan et al. (1998). For a general background to phenothiazine-based molecules, see: Miller et al. (1999); Lam et al. (2001); Wermuth (2003); Wang et al. (2008).
Experimental
Crystal data
|
Refinement
|
Data collection: APEX2 (Bruker, 2003); cell SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536809028487/bh2235sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809028487/bh2235Isup2.hkl
All reagents were of analytical grade. The title sample was prepared according to a literature method (Gilman & Nelson, 1953; Chan et al., 1998) from the N-benzylphenothiazine. The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared spectra and elemental analyses. Single crystals of the title compound were obtained by slow evaporation of an ethanol solution. The X-ray diffraction studies were made at room temperature.
H atoms bonded to C atoms were positioned geometrically (C—H = 0.93 and 0.96Å for benzene and methyl H atoms, respectively) and included in the
in the riding-model approximation, with Uiso(H) = 1.2 or 1.5 Ueq(C). The sulfoxide O atom is disordered over two positions with partial site-occupancies of 0.88 and 0.12, respectively, which were fixed in the last least-squares cycles.Data collection: APEX2 (Bruker, 2003); cell
SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C14H11NO2S | F(000) = 536 |
Mr = 257.30 | Dx = 1.405 Mg m−3 |
Monoclinic, P21/n | Melting point: 443 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 8.1244 (1) Å | Cell parameters from 4917 reflections |
b = 14.1787 (2) Å | θ = 2.4–27.7° |
c = 10.7576 (1) Å | µ = 0.26 mm−1 |
β = 100.963 (1)° | T = 296 K |
V = 1216.59 (3) Å3 | Block, orange |
Z = 4 | 0.20 × 0.14 × 0.13 mm |
Bruker APEXII CCD area-detector diffractometer | 3067 independent reflections |
Radiation source: fine-focus sealed tube | 2404 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ϕ and ω scans | θmax = 28.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→10 |
Tmin = 0.950, Tmax = 0.967 | k = −18→18 |
11538 measured reflections | l = −14→14 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0506P)2 + 0.5122P] where P = (Fo2 + 2Fc2)/3 |
3067 reflections | (Δ/σ)max = 0.001 |
174 parameters | Δρmax = 0.34 e Å−3 |
2 restraints | Δρmin = −0.24 e Å−3 |
0 constraints |
C14H11NO2S | V = 1216.59 (3) Å3 |
Mr = 257.30 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.1244 (1) Å | µ = 0.26 mm−1 |
b = 14.1787 (2) Å | T = 296 K |
c = 10.7576 (1) Å | 0.20 × 0.14 × 0.13 mm |
β = 100.963 (1)° |
Bruker APEXII CCD area-detector diffractometer | 3067 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2404 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.967 | Rint = 0.019 |
11538 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 2 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.34 e Å−3 |
3067 reflections | Δρmin = −0.24 e Å−3 |
174 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.2768 (2) | 1.03984 (14) | 0.34599 (17) | 0.0419 (4) | |
C2 | 0.4325 (3) | 1.08344 (17) | 0.3653 (2) | 0.0552 (6) | |
H2A | 0.4440 | 1.1461 | 0.3911 | 0.066* | |
C3 | 0.5687 (3) | 1.0329 (2) | 0.3456 (2) | 0.0679 (7) | |
H3A | 0.6736 | 1.0614 | 0.3585 | 0.081* | |
C4 | 0.5520 (3) | 0.9400 (2) | 0.3069 (2) | 0.0603 (6) | |
H4A | 0.6461 | 0.9059 | 0.2960 | 0.072* | |
C5 | 0.3958 (2) | 0.89724 (16) | 0.28427 (19) | 0.0482 (5) | |
H5A | 0.3845 | 0.8353 | 0.2554 | 0.058* | |
C6 | 0.2563 (2) | 0.94696 (13) | 0.30478 (16) | 0.0372 (4) | |
C7 | −0.0305 (2) | 0.97033 (13) | 0.19798 (17) | 0.0383 (4) | |
C8 | −0.0329 (2) | 1.06443 (13) | 0.23222 (18) | 0.0415 (4) | |
C9 | −0.1414 (3) | 1.12817 (16) | 0.1596 (2) | 0.0552 (5) | |
H9A | −0.1414 | 1.1914 | 0.1824 | 0.066* | |
C10 | −0.2486 (3) | 1.09580 (18) | 0.0533 (2) | 0.0600 (6) | |
H10A | −0.3219 | 1.1375 | 0.0040 | 0.072* | |
C11 | −0.2480 (3) | 1.00256 (18) | 0.0197 (2) | 0.0580 (6) | |
H11A | −0.3223 | 0.9815 | −0.0515 | 0.070* | |
C12 | −0.1381 (2) | 0.93909 (15) | 0.09038 (19) | 0.0467 (5) | |
H12A | −0.1369 | 0.8763 | 0.0657 | 0.056* | |
C13 | 0.0405 (3) | 0.82363 (14) | 0.3156 (2) | 0.0479 (5) | |
C14 | 0.1638 (3) | 0.76880 (16) | 0.4099 (2) | 0.0602 (6) | |
H14A | 0.1048 | 0.7321 | 0.4622 | 0.090* | |
H14B | 0.2386 | 0.8116 | 0.4619 | 0.090* | |
H14C | 0.2271 | 0.7276 | 0.3659 | 0.090* | |
N1 | 0.09014 (18) | 0.90973 (10) | 0.27386 (15) | 0.0388 (3) | |
O2 | −0.1007 (2) | 0.79521 (12) | 0.2791 (2) | 0.0756 (6) | |
S1 | 0.09806 (7) | 1.10145 (4) | 0.37655 (5) | 0.05019 (17) | |
O1A | 0.1306 (3) | 1.20324 (11) | 0.37154 (19) | 0.0716 (7) | 0.886 (4) |
O1B | 0.0214 (17) | 1.0640 (10) | 0.4755 (10) | 0.068 (5) | 0.114 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0440 (10) | 0.0426 (10) | 0.0387 (9) | −0.0069 (8) | 0.0070 (7) | 0.0010 (8) |
C2 | 0.0588 (13) | 0.0576 (13) | 0.0471 (11) | −0.0228 (11) | 0.0047 (9) | 0.0040 (9) |
C3 | 0.0425 (11) | 0.100 (2) | 0.0595 (14) | −0.0217 (13) | 0.0069 (10) | 0.0140 (14) |
C4 | 0.0384 (10) | 0.0930 (19) | 0.0505 (12) | 0.0062 (11) | 0.0108 (9) | 0.0122 (12) |
C5 | 0.0444 (10) | 0.0558 (12) | 0.0440 (10) | 0.0094 (9) | 0.0074 (8) | 0.0036 (9) |
C6 | 0.0354 (9) | 0.0394 (10) | 0.0362 (9) | −0.0009 (7) | 0.0050 (7) | 0.0030 (7) |
C7 | 0.0326 (8) | 0.0359 (9) | 0.0469 (10) | 0.0023 (7) | 0.0090 (7) | 0.0043 (7) |
C8 | 0.0413 (10) | 0.0369 (9) | 0.0491 (10) | 0.0044 (8) | 0.0153 (8) | 0.0038 (8) |
C9 | 0.0607 (13) | 0.0416 (11) | 0.0674 (14) | 0.0151 (10) | 0.0230 (11) | 0.0118 (10) |
C10 | 0.0512 (12) | 0.0671 (15) | 0.0618 (13) | 0.0193 (11) | 0.0109 (10) | 0.0222 (11) |
C11 | 0.0445 (11) | 0.0760 (16) | 0.0510 (12) | 0.0027 (11) | 0.0028 (9) | 0.0102 (11) |
C12 | 0.0416 (10) | 0.0466 (11) | 0.0512 (11) | −0.0019 (9) | 0.0072 (8) | 0.0018 (9) |
C13 | 0.0452 (11) | 0.0334 (10) | 0.0637 (13) | 0.0001 (8) | 0.0065 (9) | 0.0048 (9) |
C14 | 0.0633 (14) | 0.0438 (12) | 0.0713 (14) | 0.0045 (10) | 0.0071 (11) | 0.0160 (10) |
N1 | 0.0348 (7) | 0.0305 (7) | 0.0496 (9) | 0.0005 (6) | 0.0040 (6) | 0.0027 (6) |
O2 | 0.0546 (10) | 0.0521 (10) | 0.1130 (15) | −0.0162 (8) | −0.0019 (9) | 0.0240 (9) |
S1 | 0.0644 (3) | 0.0362 (3) | 0.0524 (3) | −0.0005 (2) | 0.0175 (2) | −0.0066 (2) |
O1A | 0.1022 (16) | 0.0319 (9) | 0.0786 (14) | −0.0026 (9) | 0.0119 (11) | −0.0088 (8) |
O1B | 0.084 (11) | 0.080 (11) | 0.045 (8) | 0.017 (8) | 0.020 (7) | −0.003 (7) |
C1—C2 | 1.387 (3) | C8—S1 | 1.786 (2) |
C1—C6 | 1.389 (3) | C9—C10 | 1.377 (3) |
C1—S1 | 1.778 (2) | C9—H9A | 0.9300 |
C2—C3 | 1.369 (4) | C10—C11 | 1.371 (3) |
C2—H2A | 0.9300 | C10—H10A | 0.9300 |
C3—C4 | 1.380 (4) | C11—C12 | 1.388 (3) |
C3—H3A | 0.9300 | C11—H11A | 0.9300 |
C4—C5 | 1.385 (3) | C12—H12A | 0.9300 |
C4—H4A | 0.9300 | C13—O2 | 1.209 (2) |
C5—C6 | 1.388 (3) | C13—N1 | 1.387 (2) |
C5—H5A | 0.9300 | C13—C14 | 1.500 (3) |
C6—N1 | 1.428 (2) | C14—H14A | 0.9600 |
C7—C12 | 1.384 (3) | C14—H14B | 0.9600 |
C7—C8 | 1.385 (3) | C14—H14C | 0.9600 |
C7—N1 | 1.436 (2) | S1—O1B | 1.433 (5) |
C8—C9 | 1.394 (3) | S1—O1A | 1.4700 (17) |
C2—C1—C6 | 121.40 (19) | C11—C10—C9 | 120.4 (2) |
C2—C1—S1 | 120.45 (17) | C11—C10—H10A | 119.8 |
C6—C1—S1 | 118.14 (14) | C9—C10—H10A | 119.8 |
C3—C2—C1 | 119.0 (2) | C10—C11—C12 | 121.0 (2) |
C3—C2—H2A | 120.5 | C10—C11—H11A | 119.5 |
C1—C2—H2A | 120.5 | C12—C11—H11A | 119.5 |
C2—C3—C4 | 120.7 (2) | C7—C12—C11 | 119.3 (2) |
C2—C3—H3A | 119.6 | C7—C12—H12A | 120.4 |
C4—C3—H3A | 119.6 | C11—C12—H12A | 120.4 |
C3—C4—C5 | 120.3 (2) | O2—C13—N1 | 120.32 (18) |
C3—C4—H4A | 119.9 | O2—C13—C14 | 121.16 (19) |
C5—C4—H4A | 119.9 | N1—C13—C14 | 118.48 (18) |
C4—C5—C6 | 119.9 (2) | C13—C14—H14A | 109.5 |
C4—C5—H5A | 120.0 | C13—C14—H14B | 109.5 |
C6—C5—H5A | 120.0 | H14A—C14—H14B | 109.5 |
C5—C6—C1 | 118.67 (17) | C13—C14—H14C | 109.5 |
C5—C6—N1 | 122.65 (17) | H14A—C14—H14C | 109.5 |
C1—C6—N1 | 118.40 (16) | H14B—C14—H14C | 109.5 |
C12—C7—C8 | 119.46 (17) | C13—N1—C6 | 124.75 (15) |
C12—C7—N1 | 122.58 (17) | C13—N1—C7 | 120.12 (15) |
C8—C7—N1 | 117.90 (16) | C6—N1—C7 | 115.08 (14) |
C7—C8—C9 | 121.0 (2) | O1B—S1—O1A | 119.8 (6) |
C7—C8—S1 | 118.55 (14) | O1B—S1—C1 | 116.2 (6) |
C9—C8—S1 | 120.37 (16) | O1A—S1—C1 | 108.47 (11) |
C10—C9—C8 | 118.8 (2) | O1B—S1—C8 | 105.4 (6) |
C10—C9—H9A | 120.6 | O1A—S1—C8 | 109.77 (10) |
C8—C9—H9A | 120.6 | C1—S1—C8 | 93.87 (9) |
C6—C1—C2—C3 | −1.4 (3) | C14—C13—N1—C6 | 6.2 (3) |
S1—C1—C2—C3 | 177.45 (17) | O2—C13—N1—C7 | 6.8 (3) |
C1—C2—C3—C4 | 0.2 (3) | C14—C13—N1—C7 | −171.17 (19) |
C2—C3—C4—C5 | 1.7 (3) | C5—C6—N1—C13 | 54.0 (3) |
C3—C4—C5—C6 | −2.3 (3) | C1—C6—N1—C13 | −132.1 (2) |
C4—C5—C6—C1 | 1.1 (3) | C5—C6—N1—C7 | −128.52 (19) |
C4—C5—C6—N1 | 174.92 (18) | C1—C6—N1—C7 | 45.4 (2) |
C2—C1—C6—C5 | 0.8 (3) | C12—C7—N1—C13 | −51.1 (3) |
S1—C1—C6—C5 | −178.09 (14) | C8—C7—N1—C13 | 131.6 (2) |
C2—C1—C6—N1 | −173.37 (17) | C12—C7—N1—C6 | 131.29 (19) |
S1—C1—C6—N1 | 7.8 (2) | C8—C7—N1—C6 | −46.0 (2) |
C12—C7—C8—C9 | −0.4 (3) | C2—C1—S1—O1B | −116.3 (7) |
N1—C7—C8—C9 | 177.03 (17) | C6—C1—S1—O1B | 62.6 (7) |
C12—C7—C8—S1 | 176.25 (15) | C2—C1—S1—O1A | 22.1 (2) |
N1—C7—C8—S1 | −6.3 (2) | C6—C1—S1—O1A | −159.03 (15) |
C7—C8—C9—C10 | 0.9 (3) | C2—C1—S1—C8 | 134.44 (17) |
S1—C8—C9—C10 | −175.71 (16) | C6—C1—S1—C8 | −46.70 (16) |
C8—C9—C10—C11 | −0.2 (3) | C7—C8—S1—O1B | −72.4 (6) |
C9—C10—C11—C12 | −1.0 (3) | C9—C8—S1—O1B | 104.2 (6) |
C8—C7—C12—C11 | −0.8 (3) | C7—C8—S1—O1A | 157.27 (16) |
N1—C7—C12—C11 | −178.08 (18) | C9—C8—S1—O1A | −26.1 (2) |
C10—C11—C12—C7 | 1.5 (3) | C7—C8—S1—C1 | 46.07 (16) |
O2—C13—N1—C6 | −175.9 (2) | C9—C8—S1—C1 | −137.28 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O1Ai | 0.93 | 2.31 | 3.207 (3) | 163 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H11NO2S |
Mr | 257.30 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 8.1244 (1), 14.1787 (2), 10.7576 (1) |
β (°) | 100.963 (1) |
V (Å3) | 1216.59 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.20 × 0.14 × 0.13 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.950, 0.967 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11538, 3067, 2404 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.670 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.127, 1.09 |
No. of reflections | 3067 |
No. of parameters | 174 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.24 |
Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O1Ai | 0.93 | 2.31 | 3.207 (3) | 163 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
Acknowledgements
This work was supported by the Foundation of Hean Polytechnic University for Doctor Teachers. The authors thank Ms Q. F. Wang and Dr Z. Z. Zhang for their assistance with the data collection and analysis, respectively.
References
Bruker (2003). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chan, C., Yin, H., Garforth, J., McKie, J. H., Jaouhari, R., Speers, P., Douglas, K. T., Rock, P. J., Yardley, V., Croft, S. L. & Fairlamb, A. H. (1998). J. Med. Chem. 41, 148–156. Web of Science CrossRef CAS PubMed Google Scholar
Gilman, H. & Nelson, R. D. (1953). J. Am. Chem. Soc. 75, 5422–5425. CrossRef CAS Web of Science Google Scholar
Lam, M., Oleinick, N. L. & Nieminen, A. L. (2001). J. Biol. Chem. 276, 47379–47386. Web of Science CrossRef PubMed CAS Google Scholar
Miller, M. T., Gantzel, P. K. & Karpishin, T. B. (1999). J. Am. Chem. Soc. 121, 4292–4293. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, J., Dong, M., Liang, J., Chang, Z., Feng, S., Wang, H. & Ding, N. (2008). Chin. J. Lab. Diagn. 12, 381–382. Google Scholar
Wermuth, C. G. (2003). The Practice of Medicinal Chemistry, 2nd ed. London: Acdemic Press. Google Scholar
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Phenothiazine is a well known heterocycle. The phenothiazine structure occurs in many synthetic dyes, electroluminescent materials (Miller et al., 1999) and drugs, especially various antipsychotic drugs, e.g. Chlorpromazine and antihistaminic drugs, e.g. Promethazine (Wermuth, 2003). Recently, researchers find some new applications for phenothiazine derivatives in medicine, such as antitubercular (Wang et al., 2008) and antitumor (Lam et al., 2001). As a part of our program devoted to the new applications of phenothiazine derivatives in medicine, we report herein the crystal structure of the title compound, (I).
The molecular structure is shown in fig. 1, with the labeling scheme. The sulfoxide O atom is disordered over two sites (O1A and O1B) with occupancies of 0.88 and 0.12, respectively, corresponding to an inversion of the lone pair at tetrahedral S1 site.
The crystal structure of (I) consists of the self-assembly of the molecules through weak hydrogen bonding interactions of the kind C—H···O. The crystal packing (Fig. 2) consists of a wavy-like arrangement in the ab plane generated by intermolecular interactions of hydrogen bond between the O1A atom of sulfoxide and H atom H5 of the aromatic ring. On the other hand, π–π contacts between the aromatic rings [centroid to centroid distances = 3.7547 (15) and 3.9577 (15) Å ] in parallel accumulation may further stabilize the crystal structure.