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ISSN: 2056-9890

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

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[Bhabak, K. P. & Mugesh, G. (2010). Acc. Chem. Res, 43, 1408-1419.]); Mugesh et al. (2001a[Mugesh, G., Mont, W. W. & Sies, H. (2001a). Chem. Rev. 101, 2125-2180.],b[Mugesh, G., Panda, A. & Singh, H. B. (2001b). J. Am. Chem. Soc. 123, 839-850.]); Mugesh & Singh (2000[Mugesh, G. & Singh, H. B. (2000). Chem. Soc. Rev. 29, 347-357.]); Engman (1989[Engman, L. (1989). J. Org. Chem. 54, 2964-2966.]); Parnham & Graf (1991[Parnham, M. J. & Graf, E. (1991). Prog. Drug Res. 36, 9-47.]). For related structures, see: Balkrishna et al. (2010[Balkrishna, S. J., Bhakuni, B. S., Chopra, D. & Kumar, S. (2010). Org. Lett. 12, 5394-5397.]); Bhabak & Mugesh (2007[Bhabak, K. P. & Mugesh, G. (2007). Chem. Eur. J. 13, 4594-4601.]); Chang et al. (2003[Chang, T. C., Huang, M. L., Hsu, W. L., Hwang, J. M. & Hsu, L. Y. (2003). Chem. Pharm. Bull. 51, 1413-1416.]); Dupont et al. (1990[Dupont, L., Dideberg, O. & Jacquemin, P. (1990). Acta Cryst. C46, 484-486.]).

[Scheme 1]

Experimental

Crystal data
  • C14H11NOSe

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.459, Tmax = 0.578

  • 4948 measured reflections

  • 2133 independent reflections

  • 1840 reflections with I > 2σ(I)

  • Rint = 0.026

Refinement
  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.095

  • S = 1.10

  • 2133 reflections

  • 155 parameters

  • H-atom parameters constrained

  • Δρmax = 0.52 e Å−3

  • Δρmin = −0.27 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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%.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically(C—H = 0.93–0.96 Å), and refined as riding with Uiso(H) = 1.2Ueq of the adjacent carbon atom (1.5Ueq for methyl H atoms).

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
[Figure 1] 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
C14H11NOSeZ = 4
Mr = 288.20F(000) = 576
Monoclinic, P21/nDx = 1.579 Mg m3
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 7.7319 (14) ŵ = 3.08 mm1
b = 13.491 (2) ÅT = 273 K
c = 11.913 (2) ÅPlate, 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 tube1840 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
phi and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 79
Tmin = 0.459, Tmax = 0.578k = 1516
4948 measured reflectionsl = 1314
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0461P)2 + 0.4966P]
where P = (Fo2 + 2Fc2)/3
2133 reflections(Δ/σ)max < 0.001
155 parametersΔρmax = 0.52 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C14H11NOSeV = 1212.6 (4) Å3
Mr = 288.20Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.7319 (14) ŵ = 3.08 mm1
b = 13.491 (2) ÅT = 273 K
c = 11.913 (2) Å0.30 × 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)
Tmin = 0.459, Tmax = 0.578Rint = 0.026
4948 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.095H-atom parameters constrained
S = 1.10Δρmax = 0.52 e Å3
2133 reflectionsΔρmin = 0.27 e Å3
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
xyzUiso*/Ueq
Se1.09550 (5)0.78392 (3)0.72071 (3)0.04308 (16)
N0.9365 (4)0.8320 (2)0.5900 (2)0.0409 (7)
O0.8278 (4)0.8041 (2)0.3987 (2)0.0515 (7)
C11.1450 (5)0.6833 (3)0.6215 (3)0.0397 (9)
C21.2625 (5)0.6048 (3)0.6512 (3)0.0510 (10)
H21.32340.59520.72690.061*
C31.2857 (6)0.5417 (3)0.5648 (4)0.0621 (12)
H31.36490.48920.58250.074*
C41.1934 (6)0.5548 (4)0.4520 (4)0.0656 (12)
H41.21050.51110.39510.079*
C51.0771 (6)0.6323 (3)0.4247 (3)0.0550 (11)
H51.01570.64150.34910.066*
C61.0513 (5)0.6967 (3)0.5096 (3)0.0407 (9)
C70.9274 (5)0.7807 (3)0.4903 (3)0.0412 (9)
C80.8145 (5)0.9075 (3)0.6062 (3)0.0403 (9)
C90.6444 (5)0.8811 (3)0.6142 (3)0.0489 (10)
C100.5347 (6)0.9574 (4)0.6363 (3)0.0626 (12)
H100.41970.94230.64230.075*
C110.5907 (8)1.0532 (4)0.6493 (4)0.0677 (14)
H110.51421.10220.66430.081*
C120.7594 (8)1.0778 (3)0.6403 (4)0.0682 (13)
H120.79741.14330.64940.082*
C130.8721 (6)1.0048 (3)0.6179 (3)0.0525 (10)
H130.98611.02090.61070.063*
C140.5808 (7)0.7763 (3)0.6001 (5)0.0706 (14)
H14A0.55740.75860.52020.106*
H14B0.47410.76990.62820.106*
H14C0.67010.73320.64290.106*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Se0.0454 (3)0.0501 (3)0.0297 (2)0.00016 (19)0.00047 (16)0.00060 (16)
N0.0423 (17)0.0472 (17)0.0286 (16)0.0005 (15)0.0025 (13)0.0000 (13)
O0.0548 (17)0.0605 (17)0.0323 (14)0.0018 (14)0.0057 (13)0.0014 (12)
C10.039 (2)0.047 (2)0.0308 (19)0.0045 (17)0.0041 (16)0.0007 (16)
C20.052 (2)0.054 (2)0.042 (2)0.005 (2)0.0005 (19)0.0055 (19)
C30.063 (3)0.062 (3)0.058 (3)0.014 (2)0.007 (2)0.002 (2)
C40.073 (3)0.070 (3)0.053 (3)0.010 (3)0.011 (2)0.015 (2)
C50.061 (3)0.065 (3)0.037 (2)0.002 (2)0.0058 (19)0.003 (2)
C60.043 (2)0.046 (2)0.0316 (19)0.0042 (17)0.0047 (17)0.0005 (16)
C70.040 (2)0.047 (2)0.034 (2)0.0079 (18)0.0030 (17)0.0010 (16)
C80.043 (2)0.047 (2)0.0281 (18)0.0034 (18)0.0023 (16)0.0016 (16)
C90.048 (2)0.062 (3)0.036 (2)0.003 (2)0.0066 (18)0.0096 (18)
C100.053 (3)0.094 (4)0.041 (2)0.016 (3)0.012 (2)0.013 (2)
C110.091 (4)0.070 (3)0.042 (2)0.032 (3)0.015 (2)0.001 (2)
C120.104 (4)0.050 (3)0.047 (3)0.005 (3)0.009 (3)0.005 (2)
C130.059 (3)0.056 (3)0.040 (2)0.008 (2)0.004 (2)0.0039 (19)
C140.061 (3)0.070 (3)0.081 (4)0.017 (3)0.016 (3)0.014 (3)
Geometric parameters (Å, º) top
Se—N1.876 (3)C6—C71.470 (5)
Se—C11.894 (4)C8—C131.384 (5)
N—C71.364 (5)C8—C91.386 (5)
N—C81.429 (5)C9—C101.394 (6)
O—C71.231 (4)C9—C141.494 (6)
C1—C61.383 (5)C10—C111.361 (7)
C1—C21.389 (5)C10—H100.9300
C2—C31.377 (6)C11—C121.373 (7)
C2—H20.9300C11—H110.9300
C3—C41.388 (6)C12—C131.380 (6)
C3—H30.9300C12—H120.9300
C4—C51.371 (6)C13—H130.9300
C4—H40.9300C14—H14A0.9600
C5—C61.380 (5)C14—H14B0.9600
C5—H50.9300C14—H14C0.9600
N—Se—C185.13 (14)C13—C8—C9121.7 (4)
C7—N—C8124.7 (3)C13—C8—N118.9 (4)
C7—N—Se116.6 (2)C9—C8—N119.4 (3)
C8—N—Se117.8 (2)C8—C9—C10116.7 (4)
C6—C1—C2121.4 (4)C8—C9—C14121.9 (4)
C6—C1—Se111.9 (3)C10—C9—C14121.3 (4)
C2—C1—Se126.7 (3)C11—C10—C9122.0 (5)
C3—C2—C1117.7 (4)C11—C10—H10119.0
C3—C2—H2121.1C9—C10—H10119.0
C1—C2—H2121.1C10—C11—C12120.4 (5)
C2—C3—C4121.5 (4)C10—C11—H11119.8
C2—C3—H3119.3C12—C11—H11119.8
C4—C3—H3119.3C11—C12—C13119.5 (4)
C5—C4—C3119.9 (4)C11—C12—H12120.2
C5—C4—H4120.1C13—C12—H12120.2
C3—C4—H4120.1C12—C13—C8119.6 (4)
C4—C5—C6119.9 (4)C12—C13—H13120.2
C4—C5—H5120.1C8—C13—H13120.2
C6—C5—H5120.1C9—C14—H14A109.5
C5—C6—C1119.7 (4)C9—C14—H14B109.5
C5—C6—C7124.3 (3)H14A—C14—H14B109.5
C1—C6—C7116.0 (3)C9—C14—H14C109.5
O—C7—N123.0 (4)H14A—C14—H14C109.5
O—C7—C6126.7 (3)H14B—C14—H14C109.5
N—C7—C6110.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Oi0.932.453.132 (4)130
Symmetry code: (i) x+1/2, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Oi0.932.453.132 (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.

References

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