1,2-Bis(2-bromo­benz­yl)diselane

Hua, G.; Fuller, A.L.; Slawin, A.M.Z.; Woollins, J.D.

doi:10.1107/S1600536810036676

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2579

doi:10.1107/S1600536810036676

Open

access

1,2-Bis(2-bromobenzyl)diselane

Guoxiong Hua,^a Amy L. Fuller,^a Alexandra M. Z. Slawin ^a ^* and J. Derek Woollins ^a

^aDepartment of Chemistry, University of St Andrews, St Andrews KY16 9ST, Scotland
^*Correspondence e-mail: amzs@st-and.ac.uk

(Received 12 September 2010; accepted 13 September 2010; online 18 September 2010)

In the title compound, C₁₄H₁₂Br₂Se₂, the Se—Se bond length [2.3034 (9) Å] is similar to those in diphenyl diselenide [2.3066 (7) and 2.3073 (10) Å] and shorter than that in 1,8-diselenonaphthalene [2.0879 (8)Å]. The molecule adopts a classical gauche conformation.

Related literature

Related structures are: diphenyl diselenide (Fuller et al., 2010 ); di(2-bromomethyl)phenyldiselenide (Lari et al., 2009 ) and 1,8 diseleno-naphthalene (Aucott et al., 2004 ).

Experimental

Crystal data

C₁₄H₁₂Br₂Se₂
M_r = 497.98
Monoclinic, P 2₁ /n
a = 10.873 (3) Å
b = 9.002 (2) Å
c = 15.714 (4) Å
β = 106.102 (6)°
V = 1477.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 10.41 mm⁻¹
T = 125 K
0.15 × 0.09 × 0.09 mm

Data collection

Rigaku Saturn70 CCD diffractometer
Absorption correction: multi-scan CrystalClear (Rigaku Americas and Rigaku, 2009 ) T_min = 0.153, T_max = 0.392
9089 measured reflections
3124 independent reflections
2671 reflections with F² > 2σ(F²)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.082
S = 1.22
2939 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Se1—C1	1.987 (5)
Se1—Se2	2.3034 (8)
Se2—C8	1.986 (5)

C1—Se1—Se2—C8	88.8 (2)

Data collection: CrystalClear (Rigaku Americas and Rigaku, 2009); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku Americas and Rigaku, 2010 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036676/bt5357sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810036676/bt5357Isup2.hkl

checkCIF report

Comment top

We have recently reported (Fuller et al., 2010) on the remarkable crystallization of PhSeSePh as one isomer. Here, the title compound (figure 1) is obtained as a mixture of both hands, the Se—Se bondlength, 2.3034 (9), is similar to that in diphenyldiselenide [2.3066 (7), 2.3073 (10) Å; Fuller et al., 2010] and shorter than that in 1,8-diselenonaphthalene [2.0879 (8)Å; Aucott et al., 2004).

Related literature top

Related structures are: diphenyl diselenide (Fuller et al., 2010); di(2-bromomethyl)phenyldiselenide (Lari et al., 2009) and 1,8 diseleno-naphthalene (Aucott et al., 2004).

Experimental top

To a solution of 2-bromobenzyl bromide (15.0 g, 60 mmol) in 150 ml of dry ethanol was added potassium selenocyanate (9.5 g, 65.0 mmol) at ambient temperature. The mixture was stirred for 2 h. Then an equeous solution of NaOH (4.8 g, 120 mmol in 200 ml of water) was added to the mixture and was continued stirring for another 2 h. After extracted by dichloromethane (300 ml) and washed three times with water (100 mLx3), the organic layer was dried over MgSO₄ overnight. The organic residue was further purified by silica gel column (dichloromethane as eluent) to give a bright yellow solid (14.5 g) in 97% yield. Selected IR (KBr, cm^-1): 2985(w), 1563(m), 1469(m), 1436(m), 1413(m), 1334(m), 1170(m), 1022(s), 755(versus), 718(m), 657(m), 589(m). ¹H NMR (CD₂Cl₂, d), 7.54 (dd, J(H,H) = 8.0 Hz, 2H, ArH), 7.29–7.09 (m, 6H, ArH), 4.00 (s, 4H, CH₂) p.p.m.. ¹³C NMR (CD₂Cl₂, d), 138.6, 133.1, 131.0, 128.9, 127.5, 124.3, 33.4 p.p.m.. ⁷⁷Se NMR (CD₂Cl₂, d), 398.6 p.p.m.. MS (EI⁺, m/z), 498 [M]⁺. Accurate mass measurement [EI⁺, m/z]: 489.7664 [M]⁺, calculated mass for C₁₄H₁₂Br₂⁷⁶Se₂: 489.7685. Anal. Calcd. for C₁₄H₁₂Br₂Se₂: C, 33.78; H, 2.43. Found: C, 33.92; H, 2.62.

Computing details top

Data collection: CrystalClear (Rigaku Americas and Rigaku, 2009); cell refinement: CrystalClear (Rigaku Americas and Rigaku, 2009); data reduction: CrystalClear (Rigaku Americas and Rigaku, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku Americas and Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku Americas and Rigaku, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot of the title compound.

1,2-Bis(2-bromobenzyl)diselane top

Crystal data top

C₁₄H₁₂Br₂Se₂	F(000) = 936.00
M_r = 497.98	D_x = 2.238 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2yn	Cell parameters from 4976 reflections
a = 10.873 (3) Å	θ = 2.0–26.4°
b = 9.002 (2) Å	µ = 10.41 mm⁻¹
c = 15.714 (4) Å	T = 125 K
β = 106.102 (6)°	Prism, colorless
V = 1477.9 (6) Å³	0.15 × 0.09 × 0.09 mm
Z = 4

Data collection top

Rigaku Saturn70 CCD diffractometer	2671 reflections with F² > 2σ(F²)
Detector resolution: 14.629 pixels mm^-1	R_int = 0.058
ω scans	θ_max = 26.4°
Absorption correction: multi-scan CrystalClear (Rigaku Americas and Rigaku, 2009)	h = −9→13
T_min = 0.153, T_max = 0.392	k = −11→9
9089 measured reflections	l = −16→19
3124 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 1.22	w = 1/[σ²(F_o²) + (0.0253P)² + 2.0566P] where P = (F_o² + 2F_c²)/3
2939 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.76 e Å⁻³
0 restraints	Δρ_min = −0.61 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₄H₁₂Br₂Se₂	V = 1477.9 (6) Å³
M_r = 497.98	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.873 (3) Å	µ = 10.41 mm⁻¹
b = 9.002 (2) Å	T = 125 K
c = 15.714 (4) Å	0.15 × 0.09 × 0.09 mm
β = 106.102 (6)°

Data collection top

Rigaku Saturn70 CCD diffractometer	3124 independent reflections
Absorption correction: multi-scan CrystalClear (Rigaku Americas and Rigaku, 2009)	2671 reflections with F² > 2σ(F²)
T_min = 0.153, T_max = 0.392	R_int = 0.058
9089 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.22	Δρ_max = 0.76 e Å⁻³
2939 reflections	Δρ_min = −0.61 e Å⁻³
163 parameters

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
Br(1)	0.94202 (5)	0.82306 (5)	0.39444 (3)	0.02997 (15)
Br(2)	0.24435 (5)	0.89337 (5)	0.36824 (4)	0.03177 (15)
Se(1)	0.63257 (5)	0.62609 (5)	0.28455 (3)	0.02562 (14)
Se(2)	0.48881 (5)	0.58891 (5)	0.36604 (3)	0.02668 (14)
C(1)	0.7876 (5)	0.5176 (5)	0.3532 (3)	0.0245 (10)
C(2)	0.8288 (5)	0.5639 (5)	0.4477 (3)	0.0213 (10)
C(3)	0.8944 (5)	0.6951 (5)	0.4770 (3)	0.0222 (10)
C(4)	0.9269 (5)	0.7397 (5)	0.5647 (3)	0.0275 (11)
C(5)	0.8920 (5)	0.6504 (6)	0.6263 (3)	0.0313 (11)
C(6)	0.8282 (5)	0.5183 (5)	0.5996 (3)	0.0279 (11)
C(7)	0.7967 (5)	0.4760 (5)	0.5117 (3)	0.0241 (10)
C(8)	0.5260 (5)	0.7583 (5)	0.4503 (3)	0.0247 (10)
C(9)	0.5175 (5)	0.9065 (5)	0.4057 (3)	0.0223 (10)
C(10)	0.4031 (5)	0.9784 (5)	0.3655 (3)	0.0217 (10)
C(11)	0.3992 (6)	1.1154 (5)	0.3247 (3)	0.0289 (12)
C(12)	0.5135 (6)	1.1812 (5)	0.3217 (3)	0.0359 (14)
C(13)	0.6279 (6)	1.1126 (5)	0.3605 (4)	0.0364 (14)
C(14)	0.6297 (5)	0.9771 (5)	0.4025 (3)	0.0298 (11)
H(1a)	0.7695	0.4097	0.3499	0.029*
H(1b)	0.8582	0.5359	0.3261	0.029*
H(4)	0.9722	0.8299	0.5825	0.033*
H(5)	0.9119	0.6802	0.6866	0.038*
H(6)	0.8059	0.4562	0.6420	0.033*
H(7)	0.7523	0.3852	0.4943	0.029*
H(8a)	0.4648	0.7561	0.4866	0.030*
H(8b)	0.6132	0.7460	0.4907	0.030*
H(11)	0.3198	1.1635	0.2991	0.035*
H(12)	0.5123	1.2740	0.2928	0.043*
H(13)	0.7059	1.1581	0.3585	0.044*
H(14)	0.7096	0.9312	0.4297	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br(1)	0.0302 (3)	0.0269 (3)	0.0381 (3)	−0.0038 (2)	0.0184 (3)	0.0042 (2)
Br(2)	0.0225 (3)	0.0318 (3)	0.0397 (3)	−0.0011 (2)	0.0065 (2)	−0.0027 (2)
Se(1)	0.0286 (3)	0.0285 (3)	0.0192 (2)	0.0043 (2)	0.0057 (2)	−0.00085 (18)
Se(2)	0.0256 (3)	0.0213 (2)	0.0342 (3)	−0.00192 (19)	0.0101 (2)	−0.00485 (19)
C(1)	0.022 (3)	0.022 (2)	0.030 (3)	0.003 (2)	0.007 (2)	0.0001 (19)
C(2)	0.019 (3)	0.020 (2)	0.026 (2)	0.0021 (19)	0.008 (2)	0.0020 (18)
C(3)	0.018 (3)	0.022 (2)	0.029 (3)	0.0021 (19)	0.010 (2)	0.0044 (19)
C(4)	0.023 (3)	0.030 (2)	0.029 (3)	−0.004 (2)	0.007 (2)	0.000 (2)
C(5)	0.028 (3)	0.041 (3)	0.021 (3)	0.000 (2)	0.000 (2)	0.001 (2)
C(6)	0.026 (3)	0.030 (2)	0.028 (3)	0.002 (2)	0.007 (2)	0.010 (2)
C(7)	0.020 (3)	0.020 (2)	0.031 (3)	−0.0019 (19)	0.004 (2)	0.0018 (19)
C(8)	0.023 (3)	0.028 (2)	0.022 (2)	0.006 (2)	0.005 (2)	−0.0009 (19)
C(9)	0.026 (3)	0.021 (2)	0.022 (2)	−0.0023 (19)	0.010 (2)	−0.0063 (18)
C(10)	0.025 (3)	0.022 (2)	0.020 (2)	−0.0031 (19)	0.008 (2)	−0.0052 (18)
C(11)	0.040 (3)	0.023 (2)	0.025 (3)	0.004 (2)	0.011 (2)	−0.0035 (19)
C(12)	0.065 (4)	0.020 (2)	0.032 (3)	−0.004 (3)	0.029 (3)	−0.005 (2)
C(13)	0.045 (4)	0.029 (3)	0.045 (3)	−0.015 (3)	0.028 (3)	−0.015 (2)
C(14)	0.025 (3)	0.032 (3)	0.035 (3)	−0.002 (2)	0.013 (2)	−0.011 (2)

Geometric parameters (Å, º) top

Br1—C3	1.911 (4)	C6—H6	0.9500
Br2—C10	1.899 (5)	C7—H7	0.9500
Se1—C1	1.987 (5)	C8—C9	1.498 (6)
Se1—Se2	2.3034 (8)	C8—H8A	0.9900
Se2—C8	1.986 (5)	C8—H8B	0.9900
C1—C2	1.487 (6)	C9—C14	1.389 (7)
C1—H1A	0.9900	C9—C10	1.389 (7)
C1—H1B	0.9900	C10—C11	1.385 (6)
C2—C3	1.391 (6)	C11—C12	1.389 (8)
C2—C7	1.398 (6)	C11—H11	0.9500
C3—C4	1.384 (7)	C12—C13	1.371 (8)
C4—C5	1.389 (7)	C12—H12	0.9500
C4—H4	0.9500	C13—C14	1.385 (7)
C5—C6	1.383 (7)	C13—H13	0.9500
C5—H5	0.9500	C14—H14	0.9500
C6—C7	1.382 (7)

C1—Se1—Se2	103.36 (13)	C2—C7—H7	119.3
C8—Se2—Se1	102.41 (14)	C9—C8—Se2	113.4 (3)
C2—C1—Se1	112.3 (3)	C9—C8—H8A	108.9
C2—C1—H1A	109.1	Se2—C8—H8A	108.9
Se1—C1—H1A	109.1	C9—C8—H8B	108.9
C2—C1—H1B	109.1	Se2—C8—H8B	108.9
Se1—C1—H1B	109.1	H8A—C8—H8B	107.7
H1A—C1—H1B	107.9	C14—C9—C10	117.1 (4)
C3—C2—C7	116.7 (4)	C14—C9—C8	118.9 (5)
C3—C2—C1	123.6 (4)	C10—C9—C8	124.0 (4)
C7—C2—C1	119.6 (4)	C11—C10—C9	122.2 (5)
C4—C3—C2	122.8 (4)	C11—C10—Br2	117.3 (4)
C4—C3—Br1	117.3 (3)	C9—C10—Br2	120.5 (3)
C2—C3—Br1	119.8 (3)	C10—C11—C12	118.9 (5)
C3—C4—C5	118.8 (5)	C10—C11—H11	120.6
C3—C4—H4	120.6	C12—C11—H11	120.6
C5—C4—H4	120.6	C13—C12—C11	120.2 (5)
C6—C5—C4	119.9 (5)	C13—C12—H12	119.9
C6—C5—H5	120.1	C11—C12—H12	119.9
C4—C5—H5	120.1	C12—C13—C14	119.9 (5)
C7—C6—C5	120.3 (4)	C12—C13—H13	120.0
C7—C6—H6	119.8	C14—C13—H13	120.0
C5—C6—H6	119.8	C13—C14—C9	121.6 (5)
C6—C7—C2	121.4 (4)	C13—C14—H14	119.2
C6—C7—H7	119.3	C9—C14—H14	119.2

C1—Se1—Se2—C8	88.8 (2)	Se1—Se2—C8—C9	55.2 (4)
Se2—Se1—C1—C2	−53.2 (3)	Se2—C8—C9—C14	−101.0 (4)
Se1—C1—C2—C3	−77.5 (5)	Se2—C8—C9—C10	78.0 (5)
Se1—C1—C2—C7	99.9 (4)	C14—C9—C10—C11	−0.8 (6)
C7—C2—C3—C4	−0.5 (7)	C8—C9—C10—C11	−179.8 (4)
C1—C2—C3—C4	176.9 (4)	C14—C9—C10—Br2	−178.7 (3)
C7—C2—C3—Br1	−179.8 (3)	C8—C9—C10—Br2	2.2 (6)
C1—C2—C3—Br1	−2.4 (6)	C9—C10—C11—C12	1.7 (7)
C2—C3—C4—C5	−0.3 (7)	Br2—C10—C11—C12	179.8 (3)
Br1—C3—C4—C5	179.0 (4)	C10—C11—C12—C13	−1.4 (7)
C3—C4—C5—C6	1.2 (8)	C11—C12—C13—C14	0.2 (7)
C4—C5—C6—C7	−1.3 (8)	C12—C13—C14—C9	0.8 (7)
C5—C6—C7—C2	0.5 (8)	C10—C9—C14—C13	−0.5 (7)
C3—C2—C7—C6	0.4 (7)	C8—C9—C14—C13	178.6 (4)
C1—C2—C7—C6	−177.1 (4)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂Br₂Se₂
M_r	497.98
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	125
a, b, c (Å)	10.873 (3), 9.002 (2), 15.714 (4)
β (°)	106.102 (6)
V (Å³)	1477.9 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	10.41
Crystal size (mm)	0.15 × 0.09 × 0.09

Data collection
Diffractometer	Rigaku Saturn70 CCD diffractometer
Absorption correction	Multi-scan CrystalClear (Rigaku Americas and Rigaku, 2009)
T_min, T_max	0.153, 0.392
No. of measured, independent and observed [F² > 2σ(F²)] reflections	9089, 3124, 2671
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.082, 1.22
No. of reflections	2939
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.76, −0.61

Computer programs: CrystalClear (Rigaku Americas and Rigaku, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku Americas and Rigaku, 2010).

Selected geometric parameters (Å, º) top

Se1—C1	1.987 (5)	Se2—C8	1.986 (5)
Se1—Se2	2.3034 (8)

C1—Se1—Se2—C8	88.8 (2)

References

Aucott, S. M., Milton, H. L., Robertson, S. D., Slawin, A. M. Z. & Woollins, J. D. (2004). Heteroat. Chem. 15, 531–542. Web of Science CSD CrossRef Google Scholar
Fuller, A. L., Scott-Hayward, L. A. S., Li, Y., Bühl, M., Slawin, A. M. Z. & Woollins, J. D. (2010). J. Am. Chem. Soc. 132, 5799–5802. Web of Science CSD CrossRef CAS PubMed Google Scholar
Lari, A., Rominger, F. & Gleiter, R. (2009). Acta Cryst. C65, o400–o403. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku Americas and Rigaku (2009). CrystalClear. Rigaku Americas, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku Americas and Rigaku (2010). CrystalStructure. Rigaku Americas, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar