1,2-Bis(4-methyl­benz­yl)diselane

Zhou, M.-Y.; Li, Y.-Q.; Zheng, W.-J.

doi:10.1107/S1600536812007726

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o985

doi:10.1107/S1600536812007726

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1,2-Bis(4-methylbenzyl)diselane

Mei-Yun Zhou,^a Yi-Qun Li ^a and Wen-Jie Zheng ^a ^*

^aDepartment of Chemistry, Jinan University, Guangzhou 510632, People's Republic of China
^*Correspondence e-mail: tzhwj@jnu.edu.cn

(Received 16 January 2012; accepted 21 February 2012; online 7 March 2012)

The title molecule, C₁₆H₁₈Se₂, features a diselenide bridge between two 4-methylbenzyl units, in which the central C—Se—Se—C torsion angle is 88.1 (3)°, while the two Se—Se—C—C fragments assume gauche conformations, with torsion angles of −51.8 (5) and 59.1 (4)°. The dihedral angle between the benzene rings is 78.9 (2)°.

Related literature

For applications of organoselenium compounds, see: Garud et al. (2007 ). For the synthesis of the title compound, see: Saravanan et al. (2003 ); Zhou et al. (2011 ). For related structures, see: Hua et al. (2010 ); Liu et al. (2006 ); Zhou et al. (2011).

Experimental

Crystal data

C₁₆H₁₈Se₂
M_r = 368.22
Monoclinic, P 2₁ /c
a = 5.8748 (7) Å
b = 11.5315 (11) Å
c = 22.794 (3) Å
β = 91.701 (9)°
V = 1543.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.77 mm⁻¹
T = 293 K
0.40 × 0.09 × 0.09 mm

Data collection

Agilent Xcalibur Sapphire3 Gemini Ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.469, T_max = 1.000
4989 measured reflections
2708 independent reflections
1806 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.111
S = 1.02
2708 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.91 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812007726/bh2412sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007726/bh2412Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812007726/bh2412Isup3.cml

checkCIF report

Comment top

Organoseleniums have been synthesized as anticancer agent, and for other medicinal applications, as well as biologically active substances exhibiting antiviral, antibacterial, antihypertensive, and fungicidal properties (Garud et al., 2007). In continuation of our work on the synthesis and structures of derivatives of selenium (Zhou et al., 2011), the title compound was prepared and its crystal structure is reported.

The title molecule (Fig. 1) features a diselenide bridge between two 4-methylbenzyl units. The central C—Se—Se—C torsion angle is 88.1 (3)°, while the two Se—Se—C—C fragments assume gauche conformations with values of -51.8 (5) and 59.1 (4)°. The dihedral angle between the two benzene rings is 78.9 (2)°. All bond lengths and angles are similar to those found in related structures (Hua et al., 2010; Liu et al., 2006; Zhou et al., 2011).

Related literature top

For potential applications of organoselenium compounds, see: Garud et al. (2007). For the synthesis of the title compound, see: Saravanan et al. (2003); Zhou et al. (2011). For related structures, see: Hua et al. (2010); Liu et al. (2006); Zhou et al. (2011).

Experimental top

Sodium borohydride (0.95 g, 25 mmol) was added to a vigorously stirred mixture of selenium powder (2.00 g, 25 mmol) and water (50 ml) at 0°C, then warmed to room temperature and stirred for 2 h. 1-(Bromomethyl)-4-methylbenzene (4.62 g, 25 mmol) was added to the mixture and stirred for 2 h. O₂ was passed through the solution slowly, for 2 h (Saravanan et al., 2003; Zhou et al., 2011). The mixture was extracted with ethyl acetate (200 ml) and washed three times with water (50 ml × 3) and dried over anhydrous sodium sulfate. The organic residue was further purified by silica gel column using dichloromethane as eluent. The solvent was then evaporated under vacuum and the solid residue was recrystallized from CH₃OH to afford yellow crystals of the title compound (yield: 3.73 g, 80.2%).

Structure description top

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); 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: publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of the title compound showing displacement ellipsoids at the 30% probability level.

1,2-Bis(4-methylbenzyl)diselane top

Crystal data top

C₁₆H₁₈Se₂	F(000) = 728
M_r = 368.22	D_x = 1.585 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 933 reflections
a = 5.8748 (7) Å	θ = 3.2–29.4°
b = 11.5315 (11) Å	µ = 4.77 mm⁻¹
c = 22.794 (3) Å	T = 293 K
β = 91.701 (9)°	Prism, yellow
V = 1543.5 (3) Å³	0.40 × 0.09 × 0.09 mm
Z = 4

Data collection top

Agilent Xcalibur Sapphire3 Gemini Ultra diffractometer	2708 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1806 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 16.0288 pixels mm^-1	θ_max = 25.0°, θ_min = 3.2°
ω scans	h = −4→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −7→13
T_min = 0.469, T_max = 1.000	l = −27→26
4989 measured reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.04P)²] where P = (F_o² + 2F_c²)/3
2708 reflections	(Δ/σ)_max = 0.001
165 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.91 e Å⁻³
0 constraints

Crystal data top

C₁₆H₁₈Se₂	V = 1543.5 (3) Å³
M_r = 368.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.8748 (7) Å	µ = 4.77 mm⁻¹
b = 11.5315 (11) Å	T = 293 K
c = 22.794 (3) Å	0.40 × 0.09 × 0.09 mm
β = 91.701 (9)°

Data collection top

Agilent Xcalibur Sapphire3 Gemini Ultra diffractometer	2708 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1806 reflections with I > 2σ(I)
T_min = 0.469, T_max = 1.000	R_int = 0.041
4989 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	Δρ_max = 0.39 e Å⁻³
2708 reflections	Δρ_min = −0.91 e Å⁻³
165 parameters

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

	x	y	z	U_iso*/U_eq
Se1	0.12002 (10)	0.36751 (6)	0.23758 (3)	0.0552 (2)
Se2	0.50760 (10)	0.39377 (5)	0.24250 (3)	0.0556 (2)
C10	0.4109 (9)	0.5942 (5)	0.1691 (3)	0.0429 (14)
C6	0.5077 (10)	0.1399 (6)	0.0874 (3)	0.0559 (17)
H6	0.6441	0.1495	0.0683	0.067*
C2	0.1859 (9)	0.2269 (5)	0.1334 (2)	0.0403 (14)
C7	0.3887 (9)	0.2363 (5)	0.1049 (2)	0.0476 (15)
H7	0.4468	0.3096	0.0973	0.057*
C3	0.1048 (9)	0.1154 (5)	0.1433 (3)	0.0500 (16)
H3	−0.0323	0.1057	0.1620	0.060*
C15	0.2026 (9)	0.6475 (5)	0.1722 (3)	0.0479 (15)
H15	0.1437	0.6645	0.2087	0.057*
C1	0.0609 (9)	0.3312 (5)	0.1532 (3)	0.0514 (16)
H1A	−0.1012	0.3190	0.1465	0.062*
H1B	0.1051	0.3973	0.1298	0.062*
C9	0.5378 (10)	0.5602 (5)	0.2243 (3)	0.0638 (19)
H9A	0.4812	0.6053	0.2567	0.077*
H9B	0.6977	0.5787	0.2204	0.077*
C13	0.1619 (11)	0.6539 (5)	0.0667 (3)	0.0590 (18)
C5	0.4281 (10)	0.0295 (5)	0.0978 (3)	0.0505 (16)
C14	0.0798 (9)	0.6759 (5)	0.1216 (3)	0.0528 (17)
H14	−0.0619	0.7109	0.1246	0.063*
C11	0.4962 (10)	0.5722 (5)	0.1137 (3)	0.0530 (17)
H11	0.6380	0.5373	0.1106	0.064*
C4	0.2230 (10)	0.0197 (5)	0.1258 (3)	0.0552 (17)
H4	0.1642	−0.0536	0.1330	0.066*
C12	0.3736 (12)	0.6015 (5)	0.0636 (3)	0.0617 (18)
H12	0.4334	0.5860	0.0271	0.074*
C8	0.5624 (11)	−0.0765 (6)	0.0797 (3)	0.084 (2)
H8A	0.4714	−0.1225	0.0529	0.126*
H8B	0.6022	−0.1217	0.1139	0.126*
H8C	0.6986	−0.0523	0.0610	0.126*
C16	0.0258 (13)	0.6855 (7)	0.0112 (3)	0.106 (3)
H16A	−0.1074	0.6374	0.0079	0.159*
H16B	0.1179	0.6735	−0.0223	0.159*
H16C	−0.0191	0.7654	0.0130	0.159*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.0591 (4)	0.0521 (4)	0.0554 (4)	−0.0040 (3)	0.0163 (3)	−0.0017 (3)
Se2	0.0581 (4)	0.0471 (4)	0.0609 (5)	0.0025 (3)	−0.0119 (3)	0.0037 (4)
C10	0.038 (3)	0.028 (3)	0.063 (4)	−0.004 (3)	−0.003 (3)	−0.001 (3)
C6	0.051 (4)	0.067 (4)	0.049 (4)	−0.005 (4)	0.004 (3)	−0.005 (4)
C2	0.041 (3)	0.037 (3)	0.042 (4)	−0.005 (3)	−0.012 (3)	0.005 (3)
C7	0.054 (4)	0.039 (3)	0.049 (4)	−0.005 (3)	0.002 (3)	0.000 (3)
C3	0.041 (3)	0.058 (4)	0.051 (4)	−0.006 (3)	−0.003 (3)	0.000 (3)
C15	0.057 (4)	0.036 (3)	0.052 (4)	0.001 (3)	0.010 (3)	−0.004 (3)
C1	0.047 (3)	0.047 (4)	0.060 (4)	0.003 (3)	−0.006 (3)	−0.002 (3)
C9	0.063 (4)	0.042 (4)	0.086 (5)	−0.010 (3)	−0.009 (4)	−0.004 (4)
C13	0.063 (4)	0.045 (4)	0.069 (5)	−0.016 (4)	−0.008 (4)	0.013 (4)
C5	0.060 (4)	0.046 (4)	0.044 (4)	0.003 (3)	−0.004 (3)	−0.009 (3)
C14	0.044 (3)	0.040 (4)	0.075 (5)	0.003 (3)	0.007 (3)	0.011 (4)
C11	0.051 (4)	0.035 (4)	0.074 (5)	0.001 (3)	0.015 (3)	0.002 (4)
C4	0.063 (4)	0.044 (4)	0.058 (5)	−0.010 (3)	−0.007 (3)	0.002 (4)
C12	0.082 (5)	0.046 (4)	0.058 (5)	−0.009 (4)	0.023 (4)	0.000 (4)
C8	0.098 (6)	0.061 (5)	0.092 (6)	0.010 (4)	0.001 (4)	−0.021 (5)
C16	0.113 (6)	0.127 (7)	0.077 (6)	−0.014 (6)	−0.031 (5)	0.034 (6)

Geometric parameters (Å, º) top

Se1—Se2	2.2964 (9)	C9—H9A	0.9700
Se1—C1	1.989 (6)	C9—H9B	0.9700
Se2—C9	1.973 (6)	C13—C14	1.377 (9)
C10—C15	1.373 (7)	C13—C12	1.386 (9)
C10—C9	1.496 (8)	C13—C16	1.521 (8)
C10—C11	1.396 (8)	C5—C4	1.385 (8)
C6—H6	0.9300	C5—C8	1.519 (8)
C6—C7	1.379 (7)	C14—H14	0.9300
C6—C5	1.379 (8)	C11—H11	0.9300
C2—C7	1.378 (7)	C11—C12	1.373 (8)
C2—C3	1.392 (7)	C4—H4	0.9300
C2—C1	1.487 (7)	C12—H12	0.9300
C7—H7	0.9300	C8—H8A	0.9600
C3—H3	0.9300	C8—H8B	0.9600
C3—C4	1.369 (8)	C8—H8C	0.9600
C15—H15	0.9300	C16—H16A	0.9600
C15—C14	1.383 (8)	C16—H16B	0.9600
C1—H1A	0.9700	C16—H16C	0.9600
C1—H1B	0.9700

C1—Se1—Se2	102.67 (16)	H9A—C9—H9B	107.8
C9—Se2—Se1	102.31 (17)	C14—C13—C12	117.7 (6)
C15—C10—C9	119.7 (6)	C14—C13—C16	121.4 (6)
C15—C10—C11	118.2 (5)	C12—C13—C16	120.9 (7)
C11—C10—C9	122.0 (5)	C6—C5—C4	117.3 (6)
C7—C6—H6	119.4	C6—C5—C8	121.0 (6)
C7—C6—C5	121.1 (6)	C4—C5—C8	121.7 (6)
C5—C6—H6	119.4	C15—C14—H14	119.1
C7—C2—C3	117.0 (5)	C13—C14—C15	121.8 (6)
C7—C2—C1	121.4 (5)	C13—C14—H14	119.1
C3—C2—C1	121.6 (5)	C10—C11—H11	119.6
C6—C7—H7	119.1	C12—C11—C10	120.9 (6)
C2—C7—C6	121.7 (5)	C12—C11—H11	119.6
C2—C7—H7	119.1	C3—C4—C5	121.6 (6)
C2—C3—H3	119.4	C3—C4—H4	119.2
C4—C3—C2	121.2 (5)	C5—C4—H4	119.2
C4—C3—H3	119.4	C13—C12—H12	119.5
C10—C15—H15	119.8	C11—C12—C13	121.0 (6)
C10—C15—C14	120.4 (6)	C11—C12—H12	119.5
C14—C15—H15	119.8	C5—C8—H8A	109.5
Se1—C1—H1A	109.0	C5—C8—H8B	109.5
Se1—C1—H1B	109.0	C5—C8—H8C	109.5
C2—C1—Se1	112.9 (4)	H8A—C8—H8B	109.5
C2—C1—H1A	109.0	H8A—C8—H8C	109.5
C2—C1—H1B	109.0	H8B—C8—H8C	109.5
H1A—C1—H1B	107.8	C13—C16—H16A	109.5
Se2—C9—H9A	109.0	C13—C16—H16B	109.5
Se2—C9—H9B	109.0	C13—C16—H16C	109.5
C10—C9—Se2	112.7 (4)	H16A—C16—H16B	109.5
C10—C9—H9A	109.0	H16A—C16—H16C	109.5
C10—C9—H9B	109.0	H16B—C16—H16C	109.5

Se1—Se2—C9—C10	−51.8 (5)	C1—Se1—Se2—C9	88.1 (3)
Se2—Se1—C1—C2	59.1 (4)	C1—C2—C7—C6	178.8 (5)
C10—C15—C14—C13	−1.0 (9)	C1—C2—C3—C4	−178.8 (5)
C10—C11—C12—C13	0.1 (9)	C9—C10—C15—C14	−177.8 (5)
C6—C5—C4—C3	−0.8 (9)	C9—C10—C11—C12	178.2 (5)
C2—C3—C4—C5	0.1 (9)	C5—C6—C7—C2	0.0 (9)
C7—C6—C5—C4	0.7 (9)	C14—C13—C12—C11	0.4 (9)
C7—C6—C5—C8	−178.5 (5)	C11—C10—C15—C14	1.4 (8)
C7—C2—C3—C4	0.6 (8)	C11—C10—C9—Se2	−78.6 (6)
C7—C2—C1—Se1	−97.9 (6)	C12—C13—C14—C15	0.1 (9)
C3—C2—C7—C6	−0.7 (8)	C8—C5—C4—C3	178.5 (6)
C3—C2—C1—Se1	81.6 (6)	C16—C13—C14—C15	−180.0 (6)
C15—C10—C9—Se2	100.6 (6)	C16—C13—C12—C11	−179.6 (6)
C15—C10—C11—C12	−0.9 (9)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈Se₂
M_r	368.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.8748 (7), 11.5315 (11), 22.794 (3)
β (°)	91.701 (9)
V (Å³)	1543.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.77
Crystal size (mm)	0.40 × 0.09 × 0.09

Data collection
Diffractometer	Agilent Xcalibur Sapphire3 Gemini Ultra
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.469, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4989, 2708, 1806
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.111, 1.02
No. of reflections	2708
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.91

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Acknowledgements

This work was supported by grants from the National Natural Science Fund (Nos. 31000816 and 21071062).

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