5-Methyl­benzo[d][2,1,3]selena­diazole

Ouahine, H.; Ait Ali, M.; El Firdoussi, L.; Spannenberg, A.

doi:10.1107/S2414314617002267

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170226

https://doi.org/10.1107/S2414314617002267

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5-Methylbenzo[d][2,1,3]selenadiazole

Halima Ouahine,^a Mustapha Ait Ali,^a Larbi El Firdoussi ^a ^* and Anke Spannenberg ^b

^aEquipe de Chimie de Coordination et de Catalyse, Département de Chimie, Faculté des Sciences Semlalia, BP 2390, 40001 Marrakech, Morocco, and ^bLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
^*Correspondence e-mail: elfirdoussi@uca.ma

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 7 February 2017; accepted 10 February 2017; online 17 February 2017)

In the crystal of the title compound, C₇H₆N₂Se, the molecules are arranged in rods along the b-axis direction and form dimeric units due to intermolecular Se⋯N contacts of 2.982 (2) Å. The molecules are further linked by weak π–π stacking interactions between the 2,1,3-selenadiazole and six-membered aromatic rings [centroid–centroid distance = 3.8509 (11) Å and ring slippage = 1.539 (3) Å].

Keywords: crystal structure; selenadiazole; Se⋯N contacts; π–π interactions.

CCDC reference: 1532046

Structure description

Organoselenium compounds are commonly found to be efficient catalysts in a variety of organic reactions, for example, the allylic chlorination of terpenic olefins (Boualy et al., 2016 ). Various selenoheterocyclic compounds are widely employed as ligands in asymmetric syntheses (Zhou et al., 2005 ). They are also used as structure motifs in bioactive molecules, such as antioxidants, anti-inflammatory agents, cytokine inducers, enzyme inhibitors, antitumor and anticancer agents (Mlochowski et al., 2007 ; Mugesh et al., 2001 ; Osajda et al., 2001 ).

The molecule of the title compound (Fig. 1) is almost planar [r.m.s. deviation for the non-H atoms = 0.008 Å; maximum deviation = 0.012 (2) Å for atom C5]. In the crystal, molecules are arranged in rods along the b axis. As found for 4,5,6,7-tetramethyl-2,1,3-benzoselenadiazole and their co-crystals, intermolecular Se⋯N interactions are also observed (Eichstaedt et al., 2016 ), forming dimeric units. The Se⋯N distance in the title compound is 2.982 (2) Å. The dimers are further linked by weak π–π stacking interactions between the 2,1,3-selenadiazole and the six-membered aromatic rings [centroid–centroid distance = 3.8509 (11) Å and ring slippage = 1.539 (3) Å] (Fig. 2).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Figure 2
Packing diagram of the title compound, showing Se⋯N contacts and π–π stacking interactions as dotted lines. Displacement ellipsoids are drawn at the 30% probability level. For clarity, H atoms have been omitted.

Synthesis and crystallization

4-Methyl-o-phenylenediamine (0.25 g, 2.04 mmol) and SeO₂ (0.22 g, 1.96 mmol) were dissolved in 5 ml of N,N-dimethylformamide. After stirring for 24 h at room temperature, the reaction mixture was diluted with 30 ml of water and extracted three times with 20 ml of ethyl acetate. The organic phase was dried over MgSO₄ and evaporated under vacuum. The pure product was isolated by column chromatography on silica gel using hexane/ethyl acetate (90:10 v/v) as eluent (yield 81%). Colourless crystals were obtained by slow evaporation of a chloroform solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were placed geometrically and refined using a riding-atom approximation, with C—H = 0.95–0.98 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl H atoms. A rotating model was used for the methyl groups.

Table 1
Experimental details

Crystal data
Chemical formula	C₇H₆N₂Se
M_r	197.10
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	10.2436 (8), 4.7669 (4), 14.1543 (11)
β (°)	96.6007 (16)
V (Å³)	686.58 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	5.38
Crystal size (mm)	0.53 × 0.13 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.41, 0.66
No. of measured, independent and observed [I > 2σ(I)] reflections	9766, 1666, 1551
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.066, 1.05
No. of reflections	1666
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.54
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2013 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1532046

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002267/rz4011sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002267/rz4011Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617002267/rz4011Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

5-Methylbenzo[d][2,1,3]selenadiazole top

Crystal data top

C₇H₆N₂Se	F(000) = 384
M_r = 197.10	D_x = 1.907 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.2436 (8) Å	Cell parameters from 6123 reflections
b = 4.7669 (4) Å	θ = 2.9–30.5°
c = 14.1543 (11) Å	µ = 5.38 mm⁻¹
β = 96.6007 (16)°	T = 150 K
V = 686.58 (10) Å³	Needle, colourless
Z = 4	0.53 × 0.13 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	1666 independent reflections
Radiation source: fine-focus sealed tube	1551 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm^-1	R_int = 0.029
φ and ω scans	θ_max = 28.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −12→13
T_min = 0.41, T_max = 0.66	k = −6→6
9766 measured reflections	l = −18→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0423P)² + 0.3807P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
1666 reflections	Δρ_max = 0.45 e Å⁻³
92 parameters	Δρ_min = −0.54 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
C1	0.65487 (18)	0.4128 (4)	0.91555 (13)	0.0175 (3)
C2	0.62888 (18)	0.5312 (4)	0.82258 (13)	0.0201 (4)
H2	0.5533	0.4764	0.7815	0.024*
C3	0.71401 (19)	0.7236 (4)	0.79367 (13)	0.0205 (4)
H3	0.6957	0.8033	0.7321	0.025*
C4	0.83091 (18)	0.8116 (4)	0.85274 (14)	0.0181 (4)
C5	0.85896 (18)	0.7016 (4)	0.94160 (14)	0.0196 (4)
H5	0.9363	0.7576	0.9806	0.024*
C6	0.77171 (18)	0.5015 (4)	0.97612 (13)	0.0179 (4)
C7	0.91893 (19)	1.0247 (4)	0.81370 (14)	0.0223 (4)
H7A	0.8820	1.2127	0.8195	0.033*
H7B	0.9256	0.9838	0.7466	0.033*
H7C	1.0065	1.0163	0.8496	0.033*
N1	0.57862 (16)	0.2254 (4)	0.95243 (12)	0.0206 (3)
N2	0.79010 (18)	0.3861 (4)	1.06228 (12)	0.0228 (3)
Se1	0.65506 (2)	0.15213 (4)	1.07010 (2)	0.02169 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0185 (8)	0.0160 (8)	0.0182 (8)	0.0025 (7)	0.0036 (7)	−0.0014 (7)
C2	0.0198 (9)	0.0220 (9)	0.0181 (8)	−0.0001 (7)	0.0000 (7)	−0.0012 (7)
C3	0.0238 (9)	0.0198 (9)	0.0177 (8)	0.0025 (7)	0.0021 (7)	−0.0001 (7)
C4	0.0187 (9)	0.0153 (8)	0.0209 (9)	0.0020 (6)	0.0052 (7)	−0.0028 (7)
C5	0.0195 (9)	0.0187 (9)	0.0204 (9)	−0.0008 (7)	0.0010 (7)	−0.0026 (7)
C6	0.0200 (8)	0.0168 (9)	0.0169 (8)	0.0020 (6)	0.0023 (6)	−0.0015 (6)
C7	0.0256 (9)	0.0171 (9)	0.0251 (9)	−0.0012 (7)	0.0068 (7)	−0.0007 (7)
N1	0.0199 (8)	0.0216 (8)	0.0206 (8)	0.0006 (6)	0.0043 (6)	−0.0006 (6)
N2	0.0249 (9)	0.0236 (8)	0.0197 (8)	−0.0009 (6)	0.0009 (6)	0.0018 (6)
Se1	0.02535 (14)	0.02166 (14)	0.01885 (13)	0.00117 (6)	0.00588 (8)	0.00329 (6)

Geometric parameters (Å, º) top

C1—N1	1.332 (3)	C5—C6	1.431 (3)
C1—C2	1.429 (3)	C5—H5	0.9500
C1—C6	1.453 (3)	C6—N2	1.331 (2)
C2—C3	1.361 (3)	C7—H7A	0.9800
C2—H2	0.9500	C7—H7B	0.9800
C3—C4	1.442 (3)	C7—H7C	0.9800
C3—H3	0.9500	N1—Se1	1.7916 (17)
C4—C5	1.363 (3)	N2—Se1	1.7902 (18)
C4—C7	1.505 (3)

N1—C1—C2	124.78 (18)	C6—C5—H5	120.1
N1—C1—C6	116.39 (17)	N2—C6—C5	124.06 (17)
C2—C1—C6	118.83 (17)	N2—C6—C1	116.14 (17)
C3—C2—C1	119.04 (18)	C5—C6—C1	119.80 (17)
C3—C2—H2	120.5	C4—C7—H7A	109.5
C1—C2—H2	120.5	C4—C7—H7B	109.5
C2—C3—C4	122.69 (18)	H7A—C7—H7B	109.5
C2—C3—H3	118.7	C4—C7—H7C	109.5
C4—C3—H3	118.7	H7A—C7—H7C	109.5
C5—C4—C3	119.75 (18)	H7B—C7—H7C	109.5
C5—C4—C7	121.81 (18)	C1—N1—Se1	106.37 (13)
C3—C4—C7	118.44 (17)	C6—N2—Se1	106.57 (13)
C4—C5—C6	119.87 (18)	N2—Se1—N1	94.54 (8)
C4—C5—H5	120.1

N1—C1—C2—C3	179.25 (18)	C2—C1—C6—N2	179.36 (17)
C6—C1—C2—C3	−0.1 (3)	N1—C1—C6—C5	179.78 (17)
C1—C2—C3—C4	0.7 (3)	C2—C1—C6—C5	−0.8 (3)
C2—C3—C4—C5	−0.4 (3)	C2—C1—N1—Se1	−179.30 (15)
C2—C3—C4—C7	179.66 (18)	C6—C1—N1—Se1	0.1 (2)
C3—C4—C5—C6	−0.6 (3)	C5—C6—N2—Se1	−179.85 (15)
C7—C4—C5—C6	179.39 (17)	C1—C6—N2—Se1	0.0 (2)
C4—C5—C6—N2	−179.01 (18)	C6—N2—Se1—N1	0.04 (14)
C4—C5—C6—C1	1.1 (3)	C1—N1—Se1—N2	−0.09 (14)
N1—C1—C6—N2	−0.1 (3)

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