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

Wang, L.; Xu, Y.; Guo, Z.; Wei, X.

doi:10.1107/S2414314617005326

organic compounds

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ISSN: 2414-3146

Volume 2| Part 4| April 2017| x170532

https://doi.org/10.1107/S2414314617005326

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

Liyun Wang,^a Ying Xu,^a Zhiqiang Guo ^b ^* and Xuehong Wei ^b

^aSchool of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, People's Republic of China, and ^bScientific Instrument Center, Shanxi University, Taiyuan 030006, People's Republic of China
^*Correspondence e-mail: gzq@sxu.edu.cn

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 23 March 2017; accepted 10 April 2017; online 18 April 2017)

In the title ebselen derivative, C₁₄H₁₁NOSe, the nine-membered benzisoselenazolyl ring system is approximately planar (r.m.s. deviation = 0.021 Å). The dihedral angle between its mean plane and that of the 3-methylphenyl ring is 5.37 (11)°. The five-membered isoselenazolyl ring is severely strained at the Se atom: Se—N = 1.889 (2) Å, Se—C_ar = 1.882 (3) Å and N—Se—C_ar = 83.30 (10)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds and short intermolecular Se⋯O contacts of 2.6917 (19) Å, forming chains along the c-axis direction. Neighbouring molecules are linked by offset π–π interactions [intercentroid distance = 3.535 (2) Å]. The chains are also linked by C—H⋯π interactions, forming a three-dimensional structure.

Keywords: crystal structure; ebselen analogue; benzisoselenazole; short Se⋯O contact; C—H⋯O hydrogen bonds; offset π–π interactions.

CCDC reference: 666227

Structure description

Ebselen (systematic name: 2-phenyl-1,2-benzoselenazol-3-one) is a synthetic organoselenium drug which has been reported to exhibit anti-inflammatory, anti-oxidant and cytoprotective activity (Mugesh & Singh, 2000 ; Mugesh et al., 2001a ,b ). We report herein on the synthesis and crystal structure of the 3-methylphenyl derivative of ebselen.

The molecular structure of the title compound is shown in Fig. 1. The nine-membered benzisoselenazolyl group is roughly planar (r.m.s. deviation = 0.021 Å). The dihedral angle between its mean plane and the 3-methylphenyl ring is 5.37 (11)°. This value is much smaller than that reported for N-(2-methylphenyl)-1,2-benzoselenazol-3(2H)-one (Zhu et al., 2013 ) in which the 2-methylphenyl ring is inclined to the benzisoselenazolyl ring system by 78.15 (11)°. In two polymorphs of ebselen, the corresponding dihedral angle is 24.24 (8)° for the monoclinic P2₁/c polymorph and 33.36 (12)° for the orthorhombic Pbca polymorph (Thomas et al., 2015 ). In the orthorhombic Pna2₁ polymorph of m-ebselenol (Thomas et al., 2015), the corresponding dihedral angle is 35.17 (12)°. The five-membered isoselenazolyl ring is severely strained at the Se atom: Se1—N1 = 1.889 (2) Å, Se1—C14 = 1.882 (3) Å, N1—Se1—C14 = 83.30 (10)°. These values are similar to those reported for the above mentioned compounds.

Figure 1
The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 25% probability level.

In the crystal, molecules are linked by C—H⋯O hydrogen bonds, and short Se1⋯Oⁱ contacts of 2.6917 (19) Å [symmetry code: (i) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ], forming chains along the c-axis direction (Table 1 and Fig. 2). Neighbouring molecules are linked by offset π–π interactions [Cg2⋯Cg4ⁱ = 3.535 (2) Å, Cg2 and Cg4 are the centroids of rings C1–C6 and Se1/N1/C8–C14, respectively, α = 5.37 (11)°, interplanar distances = 3.499 (1) and 3.466 (1) Å, slippage = 0.693 Å; symmetry code: (i) x, y − 1, z]. The chains are also linked by C—H⋯π interactions, forming a three-dimensional structure (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 and Cg3 are the centroids of rings C1–C6 and C9–C14, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O1ⁱ	0.93	2.38	3.057 (3)	129
C7—H7C⋯Cg2ⁱⁱ	0.96	2.97	3.926 (4)	176
C12—H12⋯Cg3ⁱⁱⁱ	0.93	2.74	3.535 (3)	144
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A view along the b axis of the crystal packing of the title compound. The C—H⋯O hydrogen bonds, Se⋯O contacts and C—H⋯π interactions are shown as dashed lines (see Table 1

The Se⋯O distance in N-(2-methylphenyl)-1,2-benzoselenazol-3(2H)-one (Zhu et al., 2013) is 2.733 (3) Å. In the two polymorphs of ebselen mentioned above the Se⋯O contacts are slightly shorter at 2.533 (2) and 2.522 (2) Å.

Synthesis and crystallization

The title compound was prepared following a modified literature procedure (Zhu et al., 2013). A solution of 2-(chloroseleno)benzoyl chloride (0.76 g, 3 mmol) in dry acetonitrile (20 ml) was added dropwise to a solution of 3-methylaniline (0.322 g, 3 mmol) and triethylamine in dry acetonitrile (20 ml) at room temperature. The reaction mixture was stirred at room temperature for about 5 h and the solvent was evaporated in vacuo. The precipitate was recrystallized to obtain colourless block-like crystals (yield 55%, m.p. 426–427 K).

¹H NMR (CDCl₃): δ 2.38 (s, 3 H, CH₃), 7.08–7.10 (d, ³J = 7.3 Hz, 1 H, H—C11), 7.27–7.32 (t, ³J = 8.3 Hz, 1 H, H—C10), 7.38–7.45 (m, 3 H, H—C2, C9, C13), 7.59–7.70 (m, 2 H, H—C3, C4)), 8.10–8.12 (d, ³J = 7.8 Hz, 1 H, H—C5); ¹³C NMR: δ 24.1 (CH₃), 125.3 (C9), 126.6 (C13), 128.8 (C11), 129.2 (C10), 130.4 (C2), 131.6 (C4), 131.8 (C5), 132.0 (C3), 135.1 (C1), 140.6 (C12), 141.6 (C6), 142.0 (C8), 168.5 (C=O); ⁷⁷Se NMR: δ 961. Analysis calculated for C₁₄H₁₁NOSe: C, 58.34; H, 3.85; N, 4.86%. Found: C, 58.20; H, 3.90; N, 4.77%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₁NOSe
M_r	288.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	15.561 (4), 5.9415 (16), 12.471 (3)
β (°)	92.799 (3)
V (Å³)	1151.6 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.24
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001 )
T_min, T_max	0.563, 0.737
No. of measured, independent and observed [I > 2σ(I)] reflections	4482, 2015, 1728
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.073, 1.05
No. of reflections	2015
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.21
Computer programs: SMART and SAINT (Bruker, 2001), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2009 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 666227

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617005326/su4145sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2414314617005326/su4145Isup2.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

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

Crystal data top

C₁₄H₁₁NOSe	F(000) = 576
M_r = 288.20	D_x = 1.662 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.561 (4) Å	Cell parameters from 2393 reflections
b = 5.9415 (16) Å	θ = 2.6–27.1°
c = 12.471 (3) Å	µ = 3.24 mm⁻¹
β = 92.799 (3)°	T = 293 K
V = 1151.6 (5) Å³	Block, colorless
Z = 4	0.20 × 0.10 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1728 reflections with I > 2σ(I)
phi and ω scans	R_int = 0.021
Absorption correction: multi-scan (SADABS; Bruker, 2001)	θ_max = 25.0°, θ_min = 2.6°
T_min = 0.563, T_max = 0.737	h = −18→16
4482 measured reflections	k = −6→7
2015 independent reflections	l = −9→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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0422P)² + 0.1339P] where P = (F_o² + 2F_c²)/3
2015 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Se1	0.77312 (2)	0.16715 (4)	0.66672 (2)	0.03852 (12)
N1	0.75687 (14)	0.0480 (3)	0.80472 (15)	0.0362 (5)
O1	0.79688 (14)	0.1110 (3)	0.98233 (14)	0.0527 (5)
C1	0.70239 (17)	−0.1434 (4)	0.8143 (2)	0.0350 (6)
C2	0.69338 (19)	−0.2532 (5)	0.9106 (2)	0.0488 (7)
H2	0.7217	−0.2012	0.9731	0.059*
C3	0.6413 (2)	−0.4427 (5)	0.9123 (3)	0.0610 (9)
H3	0.6353	−0.5184	0.9768	0.073*
C4	0.5983 (2)	−0.5212 (5)	0.8206 (3)	0.0554 (8)
H4	0.5637	−0.6484	0.8240	0.066*
C5	0.60614 (19)	−0.4142 (5)	0.7252 (2)	0.0473 (7)
C6	0.65794 (18)	−0.2238 (5)	0.7229 (2)	0.0437 (7)
H6	0.6630	−0.1480	0.6583	0.052*
C7	0.5604 (2)	−0.4993 (6)	0.6237 (2)	0.0652 (9)
H7A	0.5975	−0.6005	0.5876	0.098*
H7B	0.5457	−0.3745	0.5775	0.098*
H7C	0.5090	−0.5772	0.6414	0.098*
C8	0.79923 (18)	0.1616 (4)	0.8870 (2)	0.0378 (6)
C9	0.84756 (17)	0.3536 (4)	0.8470 (2)	0.0393 (6)
C10	0.89553 (18)	0.5007 (5)	0.9122 (2)	0.0458 (7)
H10	0.9003	0.4780	0.9861	0.055*
C11	0.93588 (19)	0.6799 (4)	0.8671 (2)	0.0491 (7)
H11	0.9684	0.7785	0.9105	0.059*
C12	0.92841 (18)	0.7147 (5)	0.7574 (2)	0.0480 (7)
H12	0.9556	0.8380	0.7280	0.058*
C13	0.88175 (18)	0.5709 (5)	0.6909 (2)	0.0432 (6)
H13	0.8772	0.5948	0.6171	0.052*
C14	0.84146 (16)	0.3887 (4)	0.7370 (2)	0.0359 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.0507 (2)	0.03956 (18)	0.02478 (17)	0.00204 (11)	−0.00299 (12)	−0.00034 (10)
N1	0.0476 (12)	0.0378 (12)	0.0228 (11)	0.0000 (10)	−0.0027 (9)	−0.0011 (9)
O1	0.0817 (15)	0.0527 (11)	0.0234 (10)	−0.0107 (11)	−0.0015 (9)	−0.0023 (8)
C1	0.0394 (14)	0.0344 (14)	0.0312 (13)	0.0040 (11)	0.0013 (11)	−0.0033 (10)
C2	0.0575 (19)	0.0522 (16)	0.0360 (16)	−0.0063 (15)	−0.0042 (13)	0.0012 (14)
C3	0.075 (2)	0.0583 (19)	0.0489 (19)	−0.0152 (17)	−0.0015 (16)	0.0136 (15)
C4	0.0557 (19)	0.0503 (17)	0.060 (2)	−0.0135 (15)	−0.0011 (15)	0.0002 (15)
C5	0.0476 (17)	0.0471 (15)	0.0464 (18)	0.0019 (13)	−0.0051 (13)	−0.0098 (13)
C6	0.0498 (17)	0.0475 (15)	0.0334 (15)	−0.0029 (13)	−0.0025 (12)	−0.0023 (12)
C7	0.064 (2)	0.069 (2)	0.061 (2)	−0.0125 (17)	−0.0090 (16)	−0.0188 (17)
C8	0.0503 (16)	0.0372 (14)	0.0255 (13)	0.0043 (11)	−0.0038 (11)	−0.0027 (11)
C9	0.0407 (15)	0.0417 (15)	0.0355 (15)	0.0045 (12)	0.0009 (11)	−0.0040 (11)
C10	0.0508 (16)	0.0510 (16)	0.0352 (15)	−0.0011 (14)	−0.0023 (12)	−0.0053 (13)
C11	0.0471 (17)	0.0473 (16)	0.0524 (19)	−0.0062 (13)	−0.0032 (14)	−0.0103 (13)
C12	0.0440 (16)	0.0411 (15)	0.059 (2)	0.0015 (13)	0.0015 (14)	0.0054 (13)
C13	0.0459 (16)	0.0468 (15)	0.0367 (15)	0.0030 (13)	0.0007 (12)	0.0068 (12)
C14	0.0383 (14)	0.0378 (13)	0.0313 (14)	0.0072 (11)	−0.0028 (11)	−0.0027 (11)

Geometric parameters (Å, º) top

Se1—C14	1.882 (3)	C6—H6	0.9300
Se1—N1	1.889 (2)	C7—H7A	0.9600
N1—C8	1.370 (3)	C7—H7B	0.9600
N1—C1	1.427 (3)	C7—H7C	0.9600
O1—C8	1.229 (3)	C8—C9	1.467 (4)
C1—C2	1.379 (4)	C9—C14	1.386 (4)
C1—C6	1.389 (4)	C9—C10	1.387 (4)
C2—C3	1.388 (4)	C10—C11	1.370 (4)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.377 (4)	C11—C12	1.383 (4)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.360 (4)	C12—C13	1.373 (4)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.390 (4)	C13—C14	1.390 (4)
C5—C7	1.508 (4)	C13—H13	0.9300

C14—Se1—N1	86.30 (10)	C5—C7—H7C	109.5
C8—N1—C1	126.6 (2)	H7A—C7—H7C	109.5
C8—N1—Se1	114.61 (17)	H7B—C7—H7C	109.5
C1—N1—Se1	118.78 (15)	O1—C8—N1	124.6 (2)
C2—C1—C6	118.9 (3)	O1—C8—C9	123.9 (2)
C2—C1—N1	122.4 (2)	N1—C8—C9	111.4 (2)
C6—C1—N1	118.7 (2)	C14—C9—C10	119.6 (2)
C1—C2—C3	118.8 (3)	C14—C9—C8	116.2 (2)
C1—C2—H2	120.6	C10—C9—C8	124.2 (2)
C3—C2—H2	120.6	C11—C10—C9	119.5 (3)
C4—C3—C2	121.5 (3)	C11—C10—H10	120.2
C4—C3—H3	119.3	C9—C10—H10	120.2
C2—C3—H3	119.3	C10—C11—C12	120.3 (3)
C5—C4—C3	120.5 (3)	C10—C11—H11	119.9
C5—C4—H4	119.7	C12—C11—H11	119.9
C3—C4—H4	119.7	C13—C12—C11	121.4 (3)
C4—C5—C6	118.3 (3)	C13—C12—H12	119.3
C4—C5—C7	121.3 (3)	C11—C12—H12	119.3
C6—C5—C7	120.4 (3)	C12—C13—C14	118.1 (3)
C1—C6—C5	122.0 (3)	C12—C13—H13	121.0
C1—C6—H6	119.0	C14—C13—H13	121.0
C5—C6—H6	119.0	C9—C14—C13	121.1 (2)
C5—C7—H7A	109.5	C9—C14—Se1	111.45 (19)
C5—C7—H7B	109.5	C13—C14—Se1	127.5 (2)
H7A—C7—H7B	109.5

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg3 are the centroids of rings C1–C6 and C9–C14, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1ⁱ	0.93	2.38	3.057 (3)	129
C7—H7C···Cg2ⁱⁱ	0.96	2.97	3.926 (4)	176
C12—H12···Cg3ⁱⁱⁱ	0.93	2.74	3.535 (3)	144

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+2, y+1/2, −z+3/2.

Funding information

Funding for this research was provided by: Special Fund for Agro-scientific Research in the Public Interest (award No. 201303106).

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Structure description

Synthesis and crystallization

Refinement

Structural data

Funding information

References

organic compounds

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