10-Ethyl-3-(5-methyl-1,3,4-oxadiazol-2-yl)-10H-phenothia­zine

Pan, Y.-Z.; Wang, Y.-G.; Liu, J.-H.; Sun, L.-C.

doi:10.1107/S160053681200462X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o649

doi:10.1107/S160053681200462X

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10-Ethyl-3-(5-methyl-1,3,4-oxadiazol-2-yl)-10H-phenothiazine

Yu-Zhen Pan,^a You-Gui Wang,^a Jian-Hui Liu ^b ^* and Li-Cheng Sun ^b,^c ^*

^aCollege of Chemistry, Dalian University of Technology, 116024 Dalian, Liaoning, People's Republic of China, ^bState Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology, 116024 Dalian, Liaoning, People's Republic of China, and ^cDepartment of Chemistry, School of Chemical Science and Engineering, KTH Royal Institute of Technology, Stockholm 10044, Sweden
^*Correspondence e-mail: liujh@dlut.edu.cn, lichengs@kth.se

(Received 28 January 2012; accepted 3 February 2012; online 10 February 2012)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.039
wR(F²) = 0.107
S = 1.05
2554 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681200462X/is5065sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200462X/is5065Isup3.hkl

Supporting information file. DOI: 10.1107/S160053681200462X/is5065Isup3.cml

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2004) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

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.

10-Ethyl-3-(5-methyl-1,3,4-oxadiazol-2-yl)-10H-phenothiazine top

Crystal data top

C₁₇H₁₅N₃OS	Z = 2
M_r = 309.38	F(000) = 324
Triclinic, P1	D_x = 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 top

Bruker SMART APEX diffractometer	2554 independent reflections
Radiation source: fine-focus sealed tube	2217 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→9
T_min = 0.968, T_max = 0.979	k = −9→9
5348 measured reflections	l = −15→12

Refinement top

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(F_o²) + (0.0547P)² + 0.2148P] where P = (F_o² + 2F_c²)/3
2554 reflections	(Δ/σ)_max < 0.001
201 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₇H₁₅N₃OS	γ = 63.696 (3)°
M_r = 309.38	V = 731.92 (7) Å³
Triclinic, P1	Z = 2
a = 7.6752 (4) Å	Mo Kα radiation
b = 8.2913 (4) Å	µ = 0.23 mm⁻¹
c = 12.9469 (8) Å	T = 293 K
α = 84.870 (4)°	0.15 × 0.15 × 0.10 mm
β = 82.569 (4)°

Data collection top

Bruker SMART APEX diffractometer	2554 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2217 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.979	R_int = 0.020
5348 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.05	Δρ_max = 0.33 e Å⁻³
2554 reflections	Δρ_min = −0.28 e Å⁻³
201 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
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) top

	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) top

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)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅N₃OS
M_r	309.38
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.6752 (4), 8.2913 (4), 12.9469 (8)
α, β, γ (°)	84.870 (4), 82.569 (4), 63.696 (3)
V (Å³)	731.92 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.968, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	5348, 2554, 2217
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.107, 1.05
No. of reflections	2554
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.28

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), DIAMOND (Brandenburg & Putz, 2004) and SHELXTL (Sheldrick, 2008).

Acknowledgements

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.

References

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