Abstract
In the title compound, C17H15N3OS, the phenothiazine ring system is slightly bent, with a dihedral angle of 13.68 (7)° between the benzene rings. The dihedral angle between the oxadiazole ring and the adjacent benzene ring is 7.72 (7)°. In the crystal, a π–π interaction with a centroid–centroid distance of 3.752 (2) Å is observed between the benzene rings of neighbouring molecules.
Related literature
For general background to phenothiazine derivatives, see: Kim et al. (2011 ▶); Hagfeldt et al. (2010 ▶). For related structures, see: Chu & Van der Helm (1975 ▶); Hdii et al. (1998 ▶); Li, Hu et al. (2009 ▶); Li, Lv et al. (2009 ▶); Yu et al. (2011 ▶).
Experimental
Crystal data
C17H15N3OS
M r = 309.38
Triclinic,
a = 7.6752 (4) Å
b = 8.2913 (4) Å
c = 12.9469 (8) Å
α = 84.870 (4)°
β = 82.569 (4)°
γ = 63.696 (3)°
V = 731.92 (7) Å3
Z = 2
Mo Kα radiation
μ = 0.23 mm−1
T = 293 K
0.15 × 0.15 × 0.10 mm
Data collection
Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.968, T max = 0.979
5348 measured reflections
2554 independent reflections
2217 reflections with I > 2σ(I)
R int = 0.020
Refinement
R[F 2 > 2σ(F 2)] = 0.039
wR(F 2) = 0.107
S = 1.05
2554 reflections
201 parameters
H-atom parameters constrained
Δρmax = 0.33 e Å−3
Δρmin = −0.28 e Å−3
Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg & Putz, 2004 ▶) and SHELXTL; software used to prepare material for publication: SHELXTL.
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681200462X/is5065sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681200462X/is5065Isup3.hkl
Supplementary material file. DOI: 10.1107/S160053681200462X/is5065Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank the China Natural Science Foundation (grant No. 21120102036) and the National Basic Research Program of China (grant No. 2009CB220009) for financial support.
supplementary crystallographic information
Comment
The derivatives of phenothiazine are a series important chemical intermediates in design of the dye-sensitized solar cells (DSSCs) (Kim et al., 2011; Hagfeldt et al., 2010). As part of our interest in these materials, here we report the crystal structure of the title compound C17H15N3OS.
The title molecule is in a nonlplanar butterfly conformation with a dihedral angle of 13.68 (7)° between two benzene rings (Fig. 1). The crystal packing exhibits a π–π interaction with a centroid-centroid distance of 3.752 (2) Å between the benzene rings from the neighbouring molecules.
Experimental
A solution of 5-[3-(10-ethyl)phenothiazyl]-tetrazole (500 mg, 1.69 mmol) in 10 ml acetic anhydride was heated to reflux and stirred for 1 h. The excess acetic anhydride was evaporated and the residue solid was extracted three times with dichloromethane. Then the organic layer was washed with water and dried with anhydrous sodium sulfate. After removal of the solvent, the crude product was purified by chromatography on a silica gel column using dichloromethane-ethyl acetate (v/v = 10:1) as eluent and isolated as a yellow powder. Yield: 472 mg (90%). The yellow single crystals suitable for X-ray diffraction were obtained after several days by slow evaporation of a mixture solution of dichloromethane and petroleum ether.
Refinement
H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and treated as riding atoms, with Uiso(H) = 1.2 or 1.5Ueq(C).
Figures
Fig. 1.
The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
Crystal data
| C17H15N3OS | Z = 2 |
| Mr = 309.38 | F(000) = 324 |
| Triclinic, P1 | Dx = 1.404 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.6752 (4) Å | Cell parameters from 2708 reflections |
| b = 8.2913 (4) Å | θ = 3.0–31.6° |
| c = 12.9469 (8) Å | µ = 0.23 mm−1 |
| α = 84.870 (4)° | T = 293 K |
| β = 82.569 (4)° | Block, yellow |
| γ = 63.696 (3)° | 0.15 × 0.15 × 0.10 mm |
| V = 731.92 (7) Å3 |
Data collection
| Bruker SMART APEX diffractometer | 2554 independent reflections |
| Radiation source: fine-focus sealed tube | 2217 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.020 |
| φ and ω scans | θmax = 25.0°, θmin = 2.7° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −9→9 |
| Tmin = 0.968, Tmax = 0.979 | k = −9→9 |
| 5348 measured reflections | l = −15→12 |
Refinement
| 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.107 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0547P)2 + 0.2148P] where P = (Fo2 + 2Fc2)/3 |
| 2554 reflections | (Δ/σ)max < 0.001 |
| 201 parameters | Δρmax = 0.33 e Å−3 |
| 0 restraints | Δρmin = −0.28 e Å−3 |
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 | ||
| S1 | 0.37243 (8) | 0.17365 (6) | 0.11098 (4) | 0.05078 (19) | |
| O1 | 0.39396 (19) | 0.69128 (15) | −0.27750 (9) | 0.0430 (3) | |
| C12 | 0.2887 (2) | 0.3831 (2) | 0.04285 (13) | 0.0353 (4) | |
| N1 | 0.0965 (2) | 0.54971 (18) | 0.19818 (11) | 0.0410 (4) | |
| C10 | 0.3234 (3) | 0.5423 (2) | −0.11819 (13) | 0.0388 (4) | |
| C6 | 0.0893 (3) | 0.3994 (2) | 0.25572 (13) | 0.0376 (4) | |
| C7 | 0.1642 (2) | 0.5454 (2) | 0.09210 (13) | 0.0371 (4) | |
| C1 | 0.2039 (3) | 0.2227 (2) | 0.22245 (13) | 0.0377 (4) | |
| N2 | 0.5266 (2) | 0.3956 (2) | −0.27726 (12) | 0.0460 (4) | |
| C13 | 0.4168 (3) | 0.5350 (2) | −0.22376 (13) | 0.0388 (4) | |
| C11 | 0.3653 (3) | 0.3829 (2) | −0.05932 (13) | 0.0382 (4) | |
| H11 | 0.4470 | 0.2736 | −0.0898 | 0.046* | |
| C9 | 0.1961 (3) | 0.7029 (2) | −0.07199 (14) | 0.0452 (5) | |
| H9 | 0.1633 | 0.8110 | −0.1103 | 0.054* | |
| C5 | −0.0285 (3) | 0.4198 (2) | 0.34965 (14) | 0.0450 (4) | |
| H5 | −0.1070 | 0.5351 | 0.3734 | 0.054* | |
| C15 | 0.0098 (3) | 0.7238 (2) | 0.24919 (15) | 0.0454 (5) | |
| H15A | 0.0783 | 0.7936 | 0.2189 | 0.054* | |
| H15B | 0.0307 | 0.7016 | 0.3224 | 0.054* | |
| N3 | 0.5841 (2) | 0.4600 (2) | −0.37384 (12) | 0.0477 (4) | |
| C8 | 0.1174 (3) | 0.7040 (2) | 0.03038 (14) | 0.0453 (5) | |
| H8 | 0.0307 | 0.8133 | 0.0592 | 0.054* | |
| C2 | 0.1976 (3) | 0.0770 (2) | 0.28143 (15) | 0.0462 (5) | |
| H2 | 0.2731 | −0.0388 | 0.2577 | 0.055* | |
| C14 | 0.5034 (3) | 0.6320 (2) | −0.36985 (13) | 0.0424 (4) | |
| C4 | −0.0320 (3) | 0.2730 (3) | 0.40882 (15) | 0.0498 (5) | |
| H4 | −0.1109 | 0.2908 | 0.4716 | 0.060* | |
| C16 | −0.2063 (3) | 0.8351 (3) | 0.24062 (18) | 0.0573 (6) | |
| H16A | −0.2300 | 0.8537 | 0.1685 | 0.086* | |
| H16B | −0.2488 | 0.9493 | 0.2713 | 0.086* | |
| H16C | −0.2773 | 0.7728 | 0.2766 | 0.086* | |
| C3 | 0.0812 (3) | 0.1007 (3) | 0.37469 (16) | 0.0521 (5) | |
| H3 | 0.0790 | 0.0020 | 0.4140 | 0.063* | |
| C17 | 0.5164 (4) | 0.7672 (3) | −0.44929 (15) | 0.0558 (5) | |
| H17A | 0.5952 | 0.8184 | −0.4272 | 0.084* | |
| H17B | 0.3878 | 0.8606 | −0.4578 | 0.084* | |
| H17C | 0.5748 | 0.7102 | −0.5145 | 0.084* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0589 (3) | 0.0257 (3) | 0.0468 (3) | −0.0033 (2) | 0.0067 (2) | 0.00176 (18) |
| O1 | 0.0540 (8) | 0.0336 (6) | 0.0387 (7) | −0.0177 (6) | −0.0011 (6) | 0.0001 (5) |
| C12 | 0.0363 (9) | 0.0266 (8) | 0.0403 (9) | −0.0112 (7) | −0.0049 (7) | 0.0004 (7) |
| N1 | 0.0469 (9) | 0.0259 (7) | 0.0425 (8) | −0.0103 (6) | 0.0023 (7) | −0.0035 (6) |
| C10 | 0.0405 (10) | 0.0356 (9) | 0.0403 (9) | −0.0169 (8) | −0.0050 (8) | 0.0008 (7) |
| C6 | 0.0380 (9) | 0.0298 (9) | 0.0413 (9) | −0.0111 (7) | −0.0060 (7) | −0.0005 (7) |
| C7 | 0.0352 (9) | 0.0287 (8) | 0.0438 (9) | −0.0110 (7) | −0.0022 (7) | −0.0016 (7) |
| C1 | 0.0412 (10) | 0.0304 (9) | 0.0393 (9) | −0.0134 (7) | −0.0066 (7) | 0.0008 (7) |
| N2 | 0.0514 (10) | 0.0370 (8) | 0.0437 (8) | −0.0154 (7) | −0.0002 (7) | 0.0004 (7) |
| C13 | 0.0407 (10) | 0.0325 (9) | 0.0427 (9) | −0.0156 (8) | −0.0067 (8) | 0.0023 (7) |
| C11 | 0.0393 (10) | 0.0281 (8) | 0.0430 (9) | −0.0103 (7) | −0.0039 (8) | −0.0048 (7) |
| C9 | 0.0492 (11) | 0.0290 (9) | 0.0492 (10) | −0.0119 (8) | −0.0024 (9) | 0.0070 (8) |
| C5 | 0.0437 (10) | 0.0377 (10) | 0.0460 (10) | −0.0118 (8) | 0.0002 (8) | −0.0035 (8) |
| C15 | 0.0516 (11) | 0.0325 (9) | 0.0502 (10) | −0.0170 (8) | −0.0002 (9) | −0.0068 (8) |
| N3 | 0.0526 (10) | 0.0434 (9) | 0.0423 (8) | −0.0181 (8) | 0.0011 (7) | −0.0023 (7) |
| C8 | 0.0472 (11) | 0.0268 (9) | 0.0505 (11) | −0.0078 (8) | 0.0020 (9) | −0.0011 (7) |
| C2 | 0.0545 (12) | 0.0309 (9) | 0.0496 (10) | −0.0158 (8) | −0.0053 (9) | 0.0009 (8) |
| C14 | 0.0471 (11) | 0.0425 (10) | 0.0374 (9) | −0.0197 (8) | −0.0031 (8) | −0.0014 (7) |
| C4 | 0.0507 (12) | 0.0497 (11) | 0.0452 (10) | −0.0212 (10) | 0.0014 (9) | 0.0039 (9) |
| C16 | 0.0530 (12) | 0.0355 (10) | 0.0696 (13) | −0.0089 (9) | 0.0043 (10) | −0.0056 (9) |
| C3 | 0.0612 (13) | 0.0424 (10) | 0.0523 (11) | −0.0249 (10) | −0.0033 (10) | 0.0093 (9) |
| C17 | 0.0736 (15) | 0.0516 (12) | 0.0451 (11) | −0.0321 (11) | −0.0024 (10) | 0.0049 (9) |
Geometric parameters (Å, º)
| S1—C1 | 1.7541 (17) | C9—H9 | 0.9300 |
| S1—C12 | 1.7583 (17) | C5—C4 | 1.388 (3) |
| O1—C14 | 1.362 (2) | C5—H5 | 0.9300 |
| O1—C13 | 1.365 (2) | C15—C16 | 1.512 (3) |
| C12—C11 | 1.376 (2) | C15—H15A | 0.9700 |
| C12—C7 | 1.409 (2) | C15—H15B | 0.9700 |
| N1—C7 | 1.402 (2) | N3—C14 | 1.282 (2) |
| N1—C6 | 1.413 (2) | C8—H8 | 0.9300 |
| N1—C15 | 1.472 (2) | C2—C3 | 1.379 (3) |
| C10—C9 | 1.387 (2) | C2—H2 | 0.9300 |
| C10—C11 | 1.392 (2) | C14—C17 | 1.480 (2) |
| C10—C13 | 1.452 (2) | C4—C3 | 1.380 (3) |
| C6—C5 | 1.394 (2) | C4—H4 | 0.9300 |
| C6—C1 | 1.407 (2) | C16—H16A | 0.9600 |
| C7—C8 | 1.402 (2) | C16—H16B | 0.9600 |
| C1—C2 | 1.387 (2) | C16—H16C | 0.9600 |
| N2—C13 | 1.287 (2) | C3—H3 | 0.9300 |
| N2—N3 | 1.411 (2) | C17—H17A | 0.9600 |
| C11—H11 | 0.9300 | C17—H17B | 0.9600 |
| C9—C8 | 1.383 (2) | C17—H17C | 0.9600 |
| C1—S1—C12 | 101.74 (8) | N1—C15—H15A | 108.5 |
| C14—O1—C13 | 102.81 (13) | C16—C15—H15A | 108.5 |
| C11—C12—C7 | 121.19 (15) | N1—C15—H15B | 108.5 |
| C11—C12—S1 | 116.40 (12) | C16—C15—H15B | 108.5 |
| C7—C12—S1 | 122.15 (13) | H15A—C15—H15B | 107.5 |
| C7—N1—C6 | 123.14 (14) | C14—N3—N2 | 106.14 (14) |
| C7—N1—C15 | 118.30 (14) | C9—C8—C7 | 122.01 (16) |
| C6—N1—C15 | 118.23 (14) | C9—C8—H8 | 119.0 |
| C9—C10—C11 | 118.04 (16) | C7—C8—H8 | 119.0 |
| C9—C10—C13 | 122.68 (16) | C3—C2—C1 | 121.15 (17) |
| C11—C10—C13 | 119.26 (15) | C3—C2—H2 | 119.4 |
| C5—C6—C1 | 117.04 (16) | C1—C2—H2 | 119.4 |
| C5—C6—N1 | 121.22 (15) | N3—C14—O1 | 112.57 (15) |
| C1—C6—N1 | 121.73 (15) | N3—C14—C17 | 129.09 (17) |
| C8—C7—N1 | 121.38 (15) | O1—C14—C17 | 118.33 (16) |
| C8—C7—C12 | 116.46 (15) | C3—C4—C5 | 120.19 (17) |
| N1—C7—C12 | 122.11 (15) | C3—C4—H4 | 119.9 |
| C2—C1—C6 | 120.68 (16) | C5—C4—H4 | 119.9 |
| C2—C1—S1 | 116.70 (13) | C15—C16—H16A | 109.5 |
| C6—C1—S1 | 122.48 (13) | C15—C16—H16B | 109.5 |
| C13—N2—N3 | 106.45 (14) | H16A—C16—H16B | 109.5 |
| N2—C13—O1 | 112.02 (15) | C15—C16—H16C | 109.5 |
| N2—C13—C10 | 128.50 (16) | H16A—C16—H16C | 109.5 |
| O1—C13—C10 | 119.47 (15) | H16B—C16—H16C | 109.5 |
| C12—C11—C10 | 121.51 (15) | C2—C3—C4 | 119.06 (17) |
| C12—C11—H11 | 119.2 | C2—C3—H3 | 120.5 |
| C10—C11—H11 | 119.2 | C4—C3—H3 | 120.5 |
| C8—C9—C10 | 120.70 (16) | C14—C17—H17A | 109.5 |
| C8—C9—H9 | 119.6 | C14—C17—H17B | 109.5 |
| C10—C9—H9 | 119.6 | H17A—C17—H17B | 109.5 |
| C4—C5—C6 | 121.87 (17) | C14—C17—H17C | 109.5 |
| C4—C5—H5 | 119.1 | H17A—C17—H17C | 109.5 |
| C6—C5—H5 | 119.1 | H17B—C17—H17C | 109.5 |
| N1—C15—C16 | 114.91 (16) |
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS5065).
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681200462X/is5065sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681200462X/is5065Isup3.hkl
Supplementary material file. DOI: 10.1107/S160053681200462X/is5065Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report