10-Acetyl-10H-phenothia­zine 5-oxide

Wang, Q.; Yang, L.; Xu, Z.; Sun, Y.

doi:10.1107/S1600536809028487

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1978

doi:10.1107/S1600536809028487

Open

access

10-Acetyl-10H-phenothiazine 5-oxide

Qiang Wang,^a ^* Lei Yang,^a Zhouqing Xu ^a and Yanchun Sun ^b

^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

(Received 24 June 2009; accepted 19 July 2009; online 25 July 2009)

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

C₁₄H₁₁NO₂S
M_r = 257.30
Monoclinic, P 2₁ /n
a = 8.1244 (1) Å
b = 14.1787 (2) Å
c = 10.7576 (1) Å
β = 100.963 (1)°
V = 1216.59 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 296 K
0.20 × 0.14 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.950, T_max = 0.967
11538 measured reflections
3067 independent reflections
2404 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.127
S = 1.09
3067 reflections
174 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2003 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028487/bh2235sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809028487/bh2235Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: 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).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines, viewed down the a axis.

10-Acetyl-10H-phenothiazine 5-oxide top

Crystal data top

C₁₄H₁₁NO₂S	F(000) = 536
M_r = 257.30	D_x = 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

Data collection top

Bruker APEXII CCD area-detector diffractometer	3067 independent reflections
Radiation source: fine-focus sealed tube	2404 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 28.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→10
T_min = 0.950, T_max = 0.967	k = −18→18
11538 measured reflections	l = −14→14

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0506P)² + 0.5122P] where P = (F_o² + 2F_c²)/3
3067 reflections	(Δ/σ)_max = 0.001
174 parameters	Δρ_max = 0.34 e Å⁻³
2 restraints	Δρ_min = −0.24 e Å⁻³
0 constraints

Crystal data top

C₁₄H₁₁NO₂S	V = 1216.59 (3) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3067 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2404 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.967	R_int = 0.019
11538 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	2 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.09	Δρ_max = 0.34 e Å⁻³
3067 reflections	Δρ_min = −0.24 e Å⁻³
174 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.950, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	11538, 3067, 2404
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.24

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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