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Acta Cryst. (2010). E66, o2579    [ doi:10.1107/S1600536810036676 ]

1,2-Bis(2-bromobenzyl)diselane

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

Abstract top

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.

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.

Refinement top

All H atoms were included in calculated positions and refined as riding atoms with U\ĩso\~(H) = 1.5 U\~eq\~. The highest peak in the difference map is 1.12 Å from atom Se2.

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
[Figure 1] Fig. 1. Anisotropic displacement ellipsoid plot of the title compound.
1,2-Bis(2-bromobenzyl)diselane top
Crystal data top
C14H12Br2Se2F(000) = 936.00
Mr = 497.98Dx = 2.238 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ynCell parameters from 4976 reflections
a = 10.873 (3) Åθ = 2.0–26.4°
b = 9.002 (2) ŵ = 10.41 mm−1
c = 15.714 (4) ÅT = 125 K
β = 106.102 (6)°Prism, colorless
V = 1477.9 (6) Å30.15 × 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-1Rint = 0.058
ω scansθmax = 26.4°
Absorption correction: multi-scan
CrystalClear (Rigaku Americas and Rigaku, 2009)		h = −9→13
Tmin = 0.153, Tmax = 0.392k = −11→9
9089 measured reflectionsl = −16→19
3124 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082H-atom parameters constrained
S = 1.22 w = 1/[σ2(Fo2) + (0.0253P)2 + 2.0566P]
where P = (Fo2 + 2Fc2)/3
2939 reflections(Δ/σ)max = 0.001
163 parametersΔρmax = 0.76 e Å−3
0 restraintsΔρmin = −0.61 e Å−3
Primary atom site location: structure-invariant direct methods
Crystal data top
C14H12Br2Se2V = 1477.9 (6) Å3
Mr = 497.98Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.873 (3) ŵ = 10.41 mm−1
b = 9.002 (2) ÅT = 125 K
c = 15.714 (4) Å0.15 × 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)
Tmin = 0.153, Tmax = 0.392Rint = 0.058
9089 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.082Δρmax = 0.76 e Å−3
S = 1.22Δρmin = −0.61 e Å−3
2939 reflectionsAbsolute structure: ?
163 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
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)0.76950.40970.34990.029*
H(1b)0.85820.53590.32610.029*
H(4)0.97220.82990.58250.033*
H(5)0.91190.68020.68660.038*
H(6)0.80590.45620.64200.033*
H(7)0.75230.38520.49430.029*
H(8a)0.46480.75610.48660.030*
H(8b)0.61320.74600.49070.030*
H(11)0.31981.16350.29910.035*
H(12)0.51231.27400.29280.043*
H(13)0.70591.15810.35850.044*
H(14)0.70960.93120.42970.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
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, °) top
Br1—C31.911 (4)C6—H60.9500
Br2—C101.899 (5)C7—H70.9500
Se1—C11.987 (5)C8—C91.498 (6)
Se1—Se22.3034 (8)C8—H8A0.9900
Se2—C81.986 (5)C8—H8B0.9900
C1—C21.487 (6)C9—C141.389 (7)
C1—H1A0.9900C9—C101.389 (7)
C1—H1B0.9900C10—C111.385 (6)
C2—C31.391 (6)C11—C121.389 (8)
C2—C71.398 (6)C11—H110.9500
C3—C41.384 (7)C12—C131.371 (8)
C4—C51.389 (7)C12—H120.9500
C4—H40.9500C13—C141.385 (7)
C5—C61.383 (7)C13—H130.9500
C5—H50.9500C14—H140.9500
C6—C71.382 (7)
C1—Se1—Se2103.36 (13)C2—C7—H7119.3
C8—Se2—Se1102.41 (14)C9—C8—Se2113.4 (3)
C2—C1—Se1112.3 (3)C9—C8—H8A108.9
C2—C1—H1A109.1Se2—C8—H8A108.9
Se1—C1—H1A109.1C9—C8—H8B108.9
C2—C1—H1B109.1Se2—C8—H8B108.9
Se1—C1—H1B109.1H8A—C8—H8B107.7
H1A—C1—H1B107.9C14—C9—C10117.1 (4)
C3—C2—C7116.7 (4)C14—C9—C8118.9 (5)
C3—C2—C1123.6 (4)C10—C9—C8124.0 (4)
C7—C2—C1119.6 (4)C11—C10—C9122.2 (5)
C4—C3—C2122.8 (4)C11—C10—Br2117.3 (4)
C4—C3—Br1117.3 (3)C9—C10—Br2120.5 (3)
C2—C3—Br1119.8 (3)C10—C11—C12118.9 (5)
C3—C4—C5118.8 (5)C10—C11—H11120.6
C3—C4—H4120.6C12—C11—H11120.6
C5—C4—H4120.6C13—C12—C11120.2 (5)
C6—C5—C4119.9 (5)C13—C12—H12119.9
C6—C5—H5120.1C11—C12—H12119.9
C4—C5—H5120.1C12—C13—C14119.9 (5)
C7—C6—C5120.3 (4)C12—C13—H13120.0
C7—C6—H6119.8C14—C13—H13120.0
C5—C6—H6119.8C13—C14—C9121.6 (5)
C6—C7—C2121.4 (4)C13—C14—H14119.2
C6—C7—H7119.3C9—C14—H14119.2
C1—Se1—Se2—C888.8 (2)Se1—Se2—C8—C955.2 (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—C1078.0 (5)
Se1—C1—C2—C799.9 (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—C4176.9 (4)C14—C9—C10—Br2−178.7 (3)
C7—C2—C3—Br1−179.8 (3)C8—C9—C10—Br22.2 (6)
C1—C2—C3—Br1−2.4 (6)C9—C10—C11—C121.7 (7)
C2—C3—C4—C5−0.3 (7)Br2—C10—C11—C12179.8 (3)
Br1—C3—C4—C5179.0 (4)C10—C11—C12—C13−1.4 (7)
C3—C4—C5—C61.2 (8)C11—C12—C13—C140.2 (7)
C4—C5—C6—C7−1.3 (8)C12—C13—C14—C90.8 (7)
C5—C6—C7—C20.5 (8)C10—C9—C14—C13−0.5 (7)
C3—C2—C7—C60.4 (7)C8—C9—C14—C13178.6 (4)
C1—C2—C7—C6−177.1 (4)
Table 1
Selected geometric parameters (Å, °) top
Se1—C11.987 (5)Se2—C81.986 (5)
Se1—Se22.3034 (8)
C1—Se1—Se2—C888.8 (2)
references
References top

Aucott, S. M., Milton, H. L., Robertson, S. D., Slawin, A. M. Z. & Woollins, J. D. (2004). Heteroat. Chem. 15, 531–542.

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.

Lari, A., Rominger, F. & Gleiter, R. (2009). Acta Cryst. C65, o400–o403.

Rigaku Americas and Rigaku (2009). CrystalClear. Rigaku Americas, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.

Rigaku Americas and Rigaku (2010). CrystalStructure. Rigaku Americas, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.