N-(2-Methyl­phen­yl)-1,2-benzoselen­azol-3(2H)-one

Zhu, X.; Xu, Y.; Han, H.; Guo, Z.; Wei, X.

doi:10.1107/S1600536813024744

organic compounds

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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Page o1538

doi:10.1107/S1600536813024744

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N-(2-Methylphenyl)-1,2-benzoselenazol-3(2H)-one

Xu Zhu,^a Ying Xu,^a Hongfei Han,^b ^* Zhiqiang Guo ^c and Xuehong Wei ^a

^aThe School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, People's Republic of China, ^bDepartment of Chemistry, Taiyuan Normal University, Taiyuan 030031, People's Republic of China, and ^cInstitute of Applied Chemistry, Shanxi University, Taiyuan 030006, People's Republic of China
^*Correspondence e-mail: hfhan001@163.com;_gzq@sxu.edu.cn

(Received 20 August 2013; accepted 5 September 2013; online 12 September 2013)

In the title Ebselen [systematic name: (2-phenyl-1,2-benzoisoselenazol-3-(2H)-one)] analogue, C₁₄H₁₁NOSe, the benzisoselenazolyl moiety (r.m.s. deviation = 0.0209 Å) is nearly perpendicular to the N-arenyl ring, making a dihedral angle of 78.15 (11)°. In the crystal, molecules are linked by C—H⋯O and Se⋯O interactions into chains along the c-axis direction. The Se⋯O distance [2.733 (3) Å] is longer than that in Ebselen (2.571 (3) Å].

Related literature

For general background to the properties of Ebselen, see: Bhabak & Mugesh (2010 ); Mugesh et al. (2001a ,b ); Mugesh & Singh (2000 ); Engman (1989 ); Parnham & Graf (1991 ). For related structures, see: Balkrishna et al. (2010 ); Bhabak & Mugesh (2007 ); Chang et al. (2003 ); Dupont et al. (1990 ).

Experimental

Crystal data

C₁₄H₁₁NOSe
M_r = 288.20
Monoclinic, P 2₁ /n
a = 7.7319 (14) Å
b = 13.491 (2) Å
c = 11.913 (2) Å
β = 102.625 (3)°
V = 1212.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.08 mm⁻¹
T = 273 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.459, T_max = 0.578
4948 measured reflections
2133 independent reflections
1840 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.095
S = 1.10
2133 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Oⁱ	0.93	2.45	3.132 (4)	130
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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, New_Global_Publ_Block. DOI: 10.1107/S1600536813024744/bg2515sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813024744/bg2515Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813024744/bg2515Isup3.cml

checkCIF report

Comment top

Organoselenium compounds play a very important role in biological and relevant processes. Among them, Ebselen (2-phenyl-1, 2-benzoisoselenazol-3-(2H)-one) shows anti-inflammatory, anti-atherosclerotic and cytoprotective properties, and has been used as the most active mimic of GPx (glutathione peroxidase). In the past decade, a number of Ebselen analogues were synthesized and their pharmacological activities were thoroughly studied toward a better understanding of the pharmacology of Ebselen. Furthermore, structurally well defined Ebselen analogues with substituents on N-phenyl ring are still rare. Mugesh and co-workers reported several of this kind of Ebselen analogues (Mugesh and Singh, 2000; Mugesh et al., 2001a, 2001b) which exhibited much higher GPx catalytic activity than that of Ebselen when GSH was used as the co-substrate.

The molecular structure of the title compound is shown in Fig.1. The molecules in the crystal are linked by C-H···O (C2-H2···O[1/2+x,3/2-y,1/2+z]; H···O: 2.45Å; C···O: 3.132 (4)Å, C-H···O: 130°) and Se···O interactions, forming chains along c. The Se···O distance (2.733 (3) Å) is longer than that in Ebselen (2.571 (3) Å, Dupont et al., 1990). The nine-membered benzisoselenazolyl group, which is similar as that of Ebselen, lies on a plane (r.m.s.d. = 0.0209). The dihedral angle between the planes of benzisoselenazolyl group and the N-arenyl ring is 78.15 (11)°, which is much wider than that in Ebselen (33.39 (13)°). The five-membered isoselenazolyl ring is severely strained at the Se atom, the bond length of Se—N [1.876 (3) Å] being shorter than the one in Ebselen [1.896 (3)], while the Se—C1 distance [1.894 (4) Å] and the N—Se—C1 bond angle [85.13 (14) °] are similar to those in Ebselen (1.892 (4)Å and 85.84 (15) °, respectively).

Related literature top

For general background to the properties of Ebselen, see: Bhabak & Mugesh (2010); Mugesh et al. (2001a,b); Mugesh & Singh (2000); Engman (1989); Parnham & Graf (1991). For related structures, see: Balkrishna et al. (2010); Bhabak & Mugesh (2007); Chang et al. (2003); Dupont et al. (1990).

Experimental top

A solution of 2-(chloroseleno)benzoyl chloride (1.27 g, 5 mmol) in dry acetonitrile (25 ml) was added (dropwise and at room temperature ) to a solution of 2-methylaniline (0.536 g, 5 mmol) and triethylamine in dry acetonitrile (15 ml) while stirring during 30 min. The reaction mixture was then further stirred at room temperature for about 5 h and the solvent was evaporated in vacuo. The precipitate was filtered off and dried to obtain a yellow solid that was purified in an active neutral alumina column, by using ethyl acetate and chloroform (1:2) as eluent. The resulting yellow compound was recrystallized to obtain yellow blocks for X-ray diffraction analysis. Yield, 79%. mp 175- 176 ^oC (173 - 174 ^oC ¹¹). ¹H NMR (CDCl₃): δ 2.23 (s, 3 H, CH₃), 7.28–7.34 (m, 4 H, H—C2, C10, C11, C12), 7.45–7.50 (t, ³J = 7.0 Hz, 1 H, H—C4), 7.62–7.72 (m, 2 H, H—C3, C13), 8.12–8.13 (d, ³J = 7.8 Hz, 1 H, H—C5); ¹³C NMR: δ 20.9 (CH₃), 126.7 (C13), 129.1 (C11), 129.6 (C12), 129.8 (C10), 131.8 (C2), 132.1 (C4), 133.9 (C5), 134.4 (C3), 135.1 (C1), 139.4 (C9), 140.3 (C6), 141.6 (C8), 168.4 (C=O); ⁷⁷Se NMR: δ 961. Anal. Calc. For C₁₄H₁₁NOSe: C, 58.34; H, 3.85; N, 4.86%. Found: C, 58.24; H, 3.81; N, 4.50%.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, showing the atom–numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.

N-(2-Methylphenyl)-1,2-benzoselenazol-3(2H)-one top

Crystal data top

C₁₄H₁₁NOSe	Z = 4
M_r = 288.20	F(000) = 576
Monoclinic, P2₁/n	D_x = 1.579 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 7.7319 (14) Å	µ = 3.08 mm⁻¹
b = 13.491 (2) Å	T = 273 K
c = 11.913 (2) Å	Plate, yellow
β = 102.625 (3)°	0.30 × 0.20 × 0.20 mm
V = 1212.6 (4) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2133 independent reflections
Radiation source: fine-focus sealed tube	1840 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
phi and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→9
T_min = 0.459, T_max = 0.578	k = −15→16
4948 measured reflections	l = −13→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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0461P)² + 0.4966P] where P = (F_o² + 2F_c²)/3
2133 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₄H₁₁NOSe	V = 1212.6 (4) Å³
M_r = 288.20	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.7319 (14) Å	µ = 3.08 mm⁻¹
b = 13.491 (2) Å	T = 273 K
c = 11.913 (2) Å	0.30 × 0.20 × 0.20 mm
β = 102.625 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2133 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1840 reflections with I > 2σ(I)
T_min = 0.459, T_max = 0.578	R_int = 0.026
4948 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.10	Δρ_max = 0.52 e Å⁻³
2133 reflections	Δρ_min = −0.27 e Å⁻³
155 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
Se	1.09550 (5)	0.78392 (3)	0.72071 (3)	0.04308 (16)
N	0.9365 (4)	0.8320 (2)	0.5900 (2)	0.0409 (7)
O	0.8278 (4)	0.8041 (2)	0.3987 (2)	0.0515 (7)
C1	1.1450 (5)	0.6833 (3)	0.6215 (3)	0.0397 (9)
C2	1.2625 (5)	0.6048 (3)	0.6512 (3)	0.0510 (10)
H2	1.3234	0.5952	0.7269	0.061*
C3	1.2857 (6)	0.5417 (3)	0.5648 (4)	0.0621 (12)
H3	1.3649	0.4892	0.5825	0.074*
C4	1.1934 (6)	0.5548 (4)	0.4520 (4)	0.0656 (12)
H4	1.2105	0.5111	0.3951	0.079*
C5	1.0771 (6)	0.6323 (3)	0.4247 (3)	0.0550 (11)
H5	1.0157	0.6415	0.3491	0.066*
C6	1.0513 (5)	0.6967 (3)	0.5096 (3)	0.0407 (9)
C7	0.9274 (5)	0.7807 (3)	0.4903 (3)	0.0412 (9)
C8	0.8145 (5)	0.9075 (3)	0.6062 (3)	0.0403 (9)
C9	0.6444 (5)	0.8811 (3)	0.6142 (3)	0.0489 (10)
C10	0.5347 (6)	0.9574 (4)	0.6363 (3)	0.0626 (12)
H10	0.4197	0.9423	0.6423	0.075*
C11	0.5907 (8)	1.0532 (4)	0.6493 (4)	0.0677 (14)
H11	0.5142	1.1022	0.6643	0.081*
C12	0.7594 (8)	1.0778 (3)	0.6403 (4)	0.0682 (13)
H12	0.7974	1.1433	0.6494	0.082*
C13	0.8721 (6)	1.0048 (3)	0.6179 (3)	0.0525 (10)
H13	0.9861	1.0209	0.6107	0.063*
C14	0.5808 (7)	0.7763 (3)	0.6001 (5)	0.0706 (14)
H14A	0.5574	0.7586	0.5202	0.106*
H14B	0.4741	0.7699	0.6282	0.106*
H14C	0.6701	0.7332	0.6429	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se	0.0454 (3)	0.0501 (3)	0.0297 (2)	0.00016 (19)	−0.00047 (16)	−0.00060 (16)
N	0.0423 (17)	0.0472 (17)	0.0286 (16)	0.0005 (15)	−0.0025 (13)	0.0000 (13)
O	0.0548 (17)	0.0605 (17)	0.0323 (14)	0.0018 (14)	−0.0057 (13)	0.0014 (12)
C1	0.039 (2)	0.047 (2)	0.0308 (19)	−0.0045 (17)	0.0041 (16)	−0.0007 (16)
C2	0.052 (2)	0.054 (2)	0.042 (2)	0.005 (2)	−0.0005 (19)	0.0055 (19)
C3	0.063 (3)	0.062 (3)	0.058 (3)	0.014 (2)	0.007 (2)	−0.002 (2)
C4	0.073 (3)	0.070 (3)	0.053 (3)	0.010 (3)	0.011 (2)	−0.015 (2)
C5	0.061 (3)	0.065 (3)	0.037 (2)	0.002 (2)	0.0058 (19)	−0.003 (2)
C6	0.043 (2)	0.046 (2)	0.0316 (19)	−0.0042 (17)	0.0047 (17)	0.0005 (16)
C7	0.040 (2)	0.047 (2)	0.034 (2)	−0.0079 (18)	0.0030 (17)	0.0010 (16)
C8	0.043 (2)	0.047 (2)	0.0281 (18)	0.0034 (18)	0.0023 (16)	0.0016 (16)
C9	0.048 (2)	0.062 (3)	0.036 (2)	0.003 (2)	0.0066 (18)	0.0096 (18)
C10	0.053 (3)	0.094 (4)	0.041 (2)	0.016 (3)	0.012 (2)	0.013 (2)
C11	0.091 (4)	0.070 (3)	0.042 (2)	0.032 (3)	0.015 (2)	−0.001 (2)
C12	0.104 (4)	0.050 (3)	0.047 (3)	0.005 (3)	0.009 (3)	−0.005 (2)
C13	0.059 (3)	0.056 (3)	0.040 (2)	−0.008 (2)	0.004 (2)	−0.0039 (19)
C14	0.061 (3)	0.070 (3)	0.081 (4)	−0.017 (3)	0.016 (3)	0.014 (3)

Geometric parameters (Å, º) top

Se—N	1.876 (3)	C6—C7	1.470 (5)
Se—C1	1.894 (4)	C8—C13	1.384 (5)
N—C7	1.364 (5)	C8—C9	1.386 (5)
N—C8	1.429 (5)	C9—C10	1.394 (6)
O—C7	1.231 (4)	C9—C14	1.494 (6)
C1—C6	1.383 (5)	C10—C11	1.361 (7)
C1—C2	1.389 (5)	C10—H10	0.9300
C2—C3	1.377 (6)	C11—C12	1.373 (7)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.388 (6)	C12—C13	1.380 (6)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.371 (6)	C13—H13	0.9300
C4—H4	0.9300	C14—H14A	0.9600
C5—C6	1.380 (5)	C14—H14B	0.9600
C5—H5	0.9300	C14—H14C	0.9600

N—Se—C1	85.13 (14)	C13—C8—C9	121.7 (4)
C7—N—C8	124.7 (3)	C13—C8—N	118.9 (4)
C7—N—Se	116.6 (2)	C9—C8—N	119.4 (3)
C8—N—Se	117.8 (2)	C8—C9—C10	116.7 (4)
C6—C1—C2	121.4 (4)	C8—C9—C14	121.9 (4)
C6—C1—Se	111.9 (3)	C10—C9—C14	121.3 (4)
C2—C1—Se	126.7 (3)	C11—C10—C9	122.0 (5)
C3—C2—C1	117.7 (4)	C11—C10—H10	119.0
C3—C2—H2	121.1	C9—C10—H10	119.0
C1—C2—H2	121.1	C10—C11—C12	120.4 (5)
C2—C3—C4	121.5 (4)	C10—C11—H11	119.8
C2—C3—H3	119.3	C12—C11—H11	119.8
C4—C3—H3	119.3	C11—C12—C13	119.5 (4)
C5—C4—C3	119.9 (4)	C11—C12—H12	120.2
C5—C4—H4	120.1	C13—C12—H12	120.2
C3—C4—H4	120.1	C12—C13—C8	119.6 (4)
C4—C5—C6	119.9 (4)	C12—C13—H13	120.2
C4—C5—H5	120.1	C8—C13—H13	120.2
C6—C5—H5	120.1	C9—C14—H14A	109.5
C5—C6—C1	119.7 (4)	C9—C14—H14B	109.5
C5—C6—C7	124.3 (3)	H14A—C14—H14B	109.5
C1—C6—C7	116.0 (3)	C9—C14—H14C	109.5
O—C7—N	123.0 (4)	H14A—C14—H14C	109.5
O—C7—C6	126.7 (3)	H14B—C14—H14C	109.5
N—C7—C6	110.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Oⁱ	0.93	2.45	3.132 (4)	130

Symmetry code: (i) x+1/2, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Oⁱ	0.93	2.45	3.132 (4)	130

Symmetry code: (i) x+1/2, −y+3/2, z+1/2.

Acknowledgements

We thank the NSFC (20772074; 31070295), SXNSFC (2008011021; 2008012013–2; 2011021011–1) and the Research Project Supported by the Shanxi Scholarship Council of China for financial support.

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