1-Methyl-2,3-dihydro-1H-benzimidazole-2-selone

Mammadova, G.Z.; Matsulevich, Z.V.; Osmanov, V.K.; Borisov, A.V.; Khrustalev, V.N.

doi:10.1107/S1600536812013700

organic compounds

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Volume 68| Part 5| May 2012| Page o1381

doi:10.1107/S1600536812013700

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1-Methyl-2,3-dihydro-1H-benzimidazole-2-selone

Gunay Z. Mammadova,^a ^* Zhanna V. Matsulevich,^b Vladimir K. Osmanov,^b Alexander V. Borisov ^b and Victor N. Khrustalev ^c

^aBaku State University, Z. Khalilov St 23, Baku AZ-1148, Azerbaijan, ^bR.E. Alekseev Nizhny Novgorod State Technical University, 24 Minin St, Nizhny Novgorod, 603950, Russian Federation, and ^cX-Ray Structural Centre, A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov St, B-334, Moscow 119991, Russian Federation
^*Correspondence e-mail: gunka479@mail.ru

(Received 23 March 2012; accepted 29 March 2012; online 13 April 2012)

The title compound C₈H₈N₂Se, is the product of the reaction of 2-chloro-1-methylbenzimidazole with sodium hydroselenide. The molecule is almost planar (r.m.s. deviation = 0.041 Å) owing to the presence of the long chain of conjugated bonds (Se=C—NMe—C=C—C=C—C=C—NH). The C=Se bond length [1.838 (2) Å] corresponds well to those found in the close analogs and indicates its pronounced double-bond character. In the crystal, molecules form helicoidal chains along the b axis by means of N—H⋯Se hydrogen bonds.

Related literature

For selones as potential antithyroid drugs, see: Taurog et al. (1994 ); Roy & Mugesh (2005 , 2006 ); Roy et al. (2007 , 2011 ). For related compounds, see: Guziec & Guziec (1994 ); Husebye et al. (1997 ); Aydin et al. (1999 ); Akkurt et al. (2004 , 2011 ); Landry et al. (2006 ); Nakanishi et al. (2008 ); Mammadova et al. (2011 ). For hypervalent adducts of selones with dihalogens and interhalogens, see: Aragoni et al. (2001 ); Boyle & Godfrey (2001 ); Roy et al. (2011).

Experimental

Crystal data

C₈H₈N₂Se
M_r = 211.12
Monoclinic, P 2₁ /n
a = 9.9434 (13) Å
b = 5.8472 (8) Å
c = 13.6387 (18) Å
β = 95.360 (2)°
V = 789.50 (18) Å³
Z = 4
Mo Kα radiation
μ = 4.69 mm⁻¹
T = 100 K
0.24 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.399, T_max = 0.454
9470 measured reflections
2304 independent reflections
1941 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.068
S = 1.00
2304 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 1.10 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯Se1ⁱ	0.91	2.58	3.471 (2)	168
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812013700/rk2347sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013700/rk2347Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812013700/rk2347Isup3.cml

checkCIF report

Comment top

In the last years, the selone derivatives have attracted considerable attention owing to their antithyroid properties (Taurog et al., 1994; Roy & Mugesh, 2005, 2006; Roy et al., 2007, 2011) as well as selone-selenol tautomerism (Guziec & Guziec, 1994; Husebye et al., 1997; Landry et al., 2006; Mammadova et al., 2011). Moreover, they are used as substrates in the preparation of hypervalent adducts in reactions with dihalogens and interhalogens (Aydin et al., 1999; Aragoni et al., 2001; Boyle & Godfrey, 2001; Akkurt et al., 2004, 2011; Roy et al., 2011).

The title compound - 1-methyl-2,3-dihydro-1H-benzimidazole-2-selone, I was obtained by a reaction of 2-chloro-1-methylbenzimidazole with sodium hydroselenide (Fig. 1). The molecule of I is almost planar (r.m.s. deviation = 0.041Å) owing to the presence of the long chain of conjugated bonds (Se═C—NMe—C═C—C═C—C═C—NH) (Fig. 2). The length of the C═Se bond (1.838 (2)Å) corresponds well to those found in the closer analogs of I - 1,3-dimethylbenzimidazole-2-selone (1.825 (7)Å) (Aydin et al., 1999), 1-ethyl-3-(2-phenylethyl)benzimidazole-2-selone (1.829 (3)Å) (Akkurt et al., 2004) and 1,3-bis(3-phenylpropyl)-1H-1,3-benzimidazole-2(3H)-selone (1.828 (2)Å) (Akkurt et al., 2011) indicating its pronounced double character.

In the crystal, molecules form helicoidal chains along the b axis by means of intermolecular N—H···Seⁱ hydrogen bonds (Fig. 3, Table 1). Symmetry code: (i) -x+1/2, y+1/2, -z+3/2.

Related literature top

For selones as potential antithyroid drugs, see: Taurog et al. (1994); Roy & Mugesh (2005, 2006); Roy et al. (2007, 2011). For related compounds, see: Guziec & Guziec (1994); Husebye et al. (1997); Aydin et al. (1999); Akkurt et al. (2004, 2011); Landry et al. (2006); Nakanishi et al. (2008); Mammadova et al. (2011). For hypervalent adducts of selones with dihalogens and interhalogens, see: Aragoni et al. (2001); Boyle & Godfrey (2001); Roy et al. (2011).

Experimental top

A solution of NaBH₄ (3.83 g, 100.0 mmol) in water (25 ml) was added to a suspension of selenium (3.77 g, 47.7 mmol) in water (30 ml) with stirring at room temperature under argon. After 15 min, a solution of 2-chloro-1-methylbenzimidazole (6.60 g, 39.6 mmol) in C₂H₅OH (25 ml) was added. The resulting mixture was refluxed for 5 h. At the end of the reaction the solvents were evaporated in vacuo, and formed precipitate was extracted with CH₂Cl₂. Then the extract was dried over MgSO₄. Further crystallization from CH₂Cl₂ gives the selone I as colourless crystals. Yield is 7.81 g (93%). M.p. = 470-471 K. IR(KBr), ν/cm^-1: 3095, 1618, 1438, 1382, 11330, 1223, 1091, 746, 709. ¹H NMR (DMSO-d₆, 600 MHz, 303 K): δ = 3.63 (s, 3H, Me), 7.15 (t, 1H, H6, J = 7.1), 7.19 (t, 1H, H5, J = 7.1), 7.37 (d, 1H, H4, J = 7.1), 7.43 (d, 1H, H7, J = 7.1), 13.25 (s, 1H, H3). Anal. Calc. for C₈H₈N₂Se: C, 45.53; H, 3.82; N, 13.27. Found: C, 45.43; H, 2.78; N, 13.19.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Reaction of 2-chloro-1-methylbenzimidazole with sodium hydroselenide.
	Fig. 2. Molecular structure of I with the atom numbering scheme. Displacement ellipsoids are shown at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 3. The helicoidal chains of I along the b axis. Dashed lines indicate the intermolecular N–H···Se hydrogen bonds.

1-Methyl-2,3-dihydro-1H-benzimidazole-2-selone top

Crystal data top

C₈H₈N₂Se	F(000) = 416
M_r = 211.12	D_x = 1.776 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3916 reflections
a = 9.9434 (13) Å	θ = 2.4–32.5°
b = 5.8472 (8) Å	µ = 4.69 mm⁻¹
c = 13.6387 (18) Å	T = 100 K
β = 95.360 (2)°	Prism, yellow
V = 789.50 (18) Å³	0.24 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2304 independent reflections
Radiation source: fine-focus sealed tube	1941 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ– and ω–scans	θ_max = 30.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −13→13
T_min = 0.399, T_max = 0.454	k = −8→8
9470 measured reflections	l = −19→19

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: difference Fourier map
wR(F²) = 0.068	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0345P)² + 0.745P] where P = (F_o² + 2F_c²)/3
2304 reflections	(Δ/σ)_max = 0.001
101 parameters	Δρ_max = 1.10 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₈H₈N₂Se	V = 789.50 (18) Å³
M_r = 211.12	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.9434 (13) Å	µ = 4.69 mm⁻¹
b = 5.8472 (8) Å	T = 100 K
c = 13.6387 (18) Å	0.24 × 0.20 × 0.20 mm
β = 95.360 (2)°

Data collection top

Bruker APEXII CCD diffractometer	2304 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1941 reflections with I > 2σ(I)
T_min = 0.399, T_max = 0.454	R_int = 0.030
9470 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.00	Δρ_max = 1.10 e Å⁻³
2304 reflections	Δρ_min = −0.28 e Å⁻³
101 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Se1	0.26128 (2)	1.12016 (4)	0.878637 (16)	0.02213 (7)
N1	0.47551 (17)	0.8571 (3)	0.80856 (13)	0.0200 (3)
C2	0.3951 (2)	1.0457 (4)	0.79997 (16)	0.0203 (4)
N3	0.43002 (18)	1.1660 (3)	0.72130 (13)	0.0209 (3)
H3N	0.3892	1.2987	0.7005	0.025*
C3A	0.5294 (2)	1.0505 (4)	0.67611 (16)	0.0206 (4)
C4	0.5950 (2)	1.0978 (4)	0.59324 (16)	0.0224 (4)
H4	0.5785	1.2350	0.5568	0.027*
C5	0.6860 (2)	0.9352 (4)	0.56600 (17)	0.0242 (4)
H5	0.7320	0.9611	0.5090	0.029*
C6	0.7122 (2)	0.7339 (4)	0.62006 (16)	0.0240 (4)
H6	0.7745	0.6260	0.5986	0.029*
C7	0.6488 (2)	0.6890 (4)	0.70443 (16)	0.0220 (4)
H7	0.6674	0.5539	0.7419	0.026*
C7A	0.5571 (2)	0.8506 (3)	0.73148 (15)	0.0200 (4)
C8	0.4688 (2)	0.6817 (4)	0.88271 (17)	0.0255 (4)
H8A	0.4578	0.7533	0.9464	0.038*
H8B	0.5524	0.5919	0.8876	0.038*
H8C	0.3918	0.5810	0.8644	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.02158 (11)	0.02058 (11)	0.02486 (11)	−0.00119 (8)	0.00548 (7)	−0.00250 (8)
N1	0.0202 (8)	0.0177 (8)	0.0225 (8)	−0.0010 (6)	0.0030 (6)	0.0026 (6)
C2	0.0191 (9)	0.0196 (9)	0.0219 (9)	−0.0018 (7)	0.0011 (7)	−0.0011 (7)
N3	0.0219 (8)	0.0174 (8)	0.0236 (8)	0.0020 (6)	0.0037 (6)	0.0018 (6)
C3A	0.0195 (9)	0.0184 (9)	0.0236 (10)	−0.0006 (7)	0.0007 (7)	0.0000 (7)
C4	0.0227 (9)	0.0221 (10)	0.0222 (9)	−0.0013 (8)	0.0017 (7)	0.0027 (8)
C5	0.0231 (10)	0.0272 (11)	0.0227 (10)	−0.0019 (8)	0.0037 (8)	−0.0019 (8)
C6	0.0204 (10)	0.0242 (10)	0.0274 (11)	0.0021 (8)	0.0029 (8)	−0.0023 (8)
C7	0.0200 (9)	0.0192 (9)	0.0263 (10)	0.0007 (7)	0.0005 (8)	−0.0008 (8)
C7A	0.0184 (9)	0.0199 (9)	0.0216 (9)	−0.0015 (7)	0.0009 (7)	−0.0005 (7)
C8	0.0258 (10)	0.0237 (10)	0.0275 (11)	0.0005 (8)	0.0058 (8)	0.0063 (8)

Geometric parameters (Å, º) top

Se1—C2	1.838 (2)	C4—H4	0.9500
N1—C2	1.361 (3)	C5—C6	1.400 (3)
N1—C7A	1.387 (3)	C5—H5	0.9500
N1—C8	1.446 (3)	C6—C7	1.388 (3)
C2—N3	1.355 (3)	C6—H6	0.9500
N3—C3A	1.388 (3)	C7—C7A	1.387 (3)
N3—H3N	0.9090	C7—H7	0.9500
C3A—C4	1.385 (3)	C8—H8A	0.9800
C3A—C7A	1.405 (3)	C8—H8B	0.9800
C4—C5	1.387 (3)	C8—H8C	0.9800

C2—N1—C7A	109.74 (17)	C6—C5—H5	119.0
C2—N1—C8	124.74 (18)	C7—C6—C5	121.3 (2)
C7A—N1—C8	125.35 (18)	C7—C6—H6	119.4
N3—C2—N1	107.24 (18)	C5—C6—H6	119.4
N3—C2—Se1	126.35 (16)	C7A—C7—C6	116.9 (2)
N1—C2—Se1	126.40 (16)	C7A—C7—H7	121.5
C2—N3—C3A	110.20 (18)	C6—C7—H7	121.5
C2—N3—H3N	123.4	C7—C7A—N1	131.8 (2)
C3A—N3—H3N	126.3	C7—C7A—C3A	121.6 (2)
C4—C3A—N3	132.4 (2)	N1—C7A—C3A	106.60 (18)
C4—C3A—C7A	121.4 (2)	N1—C8—H8A	109.5
N3—C3A—C7A	106.12 (18)	N1—C8—H8B	109.5
C3A—C4—C5	116.8 (2)	H8A—C8—H8B	109.5
C3A—C4—H4	121.6	N1—C8—H8C	109.5
C5—C4—H4	121.6	H8A—C8—H8C	109.5
C4—C5—C6	121.9 (2)	H8B—C8—H8C	109.5
C4—C5—H5	119.0

C7A—N1—C2—N3	−3.4 (2)	C5—C6—C7—C7A	1.1 (3)
C8—N1—C2—N3	−178.94 (19)	C6—C7—C7A—N1	178.4 (2)
C7A—N1—C2—Se1	175.35 (15)	C6—C7—C7A—C3A	0.0 (3)
C8—N1—C2—Se1	−0.2 (3)	C2—N1—C7A—C7	−175.6 (2)
N1—C2—N3—C3A	2.5 (2)	C8—N1—C7A—C7	−0.1 (4)
Se1—C2—N3—C3A	−176.20 (15)	C2—N1—C7A—C3A	2.9 (2)
C2—N3—C3A—C4	178.0 (2)	C8—N1—C7A—C3A	178.45 (19)
C2—N3—C3A—C7A	−0.7 (2)	C4—C3A—C7A—C7	−1.5 (3)
N3—C3A—C4—C5	−176.7 (2)	N3—C3A—C7A—C7	177.40 (19)
C7A—C3A—C4—C5	1.9 (3)	C4—C3A—C7A—N1	179.74 (19)
C3A—C4—C5—C6	−0.8 (3)	N3—C3A—C7A—N1	−1.3 (2)
C4—C5—C6—C7	−0.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···Se1ⁱ	0.91	2.58	3.471 (2)	168

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

Experimental details

Crystal data
Chemical formula	C₈H₈N₂Se
M_r	211.12
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.9434 (13), 5.8472 (8), 13.6387 (18)
β (°)	95.360 (2)
V (Å³)	789.50 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.69
Crystal size (mm)	0.24 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.399, 0.454
No. of measured, independent and observed [I > 2σ(I)] reflections	9470, 2304, 1941
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.068, 1.00
No. of reflections	2304
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.10, −0.28

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···Se1ⁱ	0.91	2.58	3.471 (2)	168

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

Acknowledgements

We thank Professor Abel M. Maharramov for fruitful discussions and help in this work.

References

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