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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2579.
Published online 2010 September 18. doi:  10.1107/S1600536810036676
PMCID: PMC2983184

1,2-Bis(2-bromo­benz­yl)diselane

Abstract

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 [triangle]); di(2-bromo­meth­yl)phenyl­diselenide (Lari et al., 2009 [triangle]) and 1,8 diseleno-naphthalene (Aucott et al., 2004 [triangle]).

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Object name is e-66-o2579-scheme1.jpg

Experimental

Crystal data

  • C14H12Br2Se2
  • M r = 497.98
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2579-efi1.jpg
  • 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 [triangle]) T min = 0.153, T max = 0.392
  • 9089 measured reflections
  • 3124 independent reflections
  • 2671 reflections with F 2 > 2σ(F 2)
  • R int = 0.058

Refinement

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

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

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

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

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.

Figures

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

Crystal data

C14H12Br2Se2F(000) = 936.00
Mr = 497.98Dx = 2.238 Mg m3
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 mm1
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

Rigaku Saturn70 CCD diffractometer2671 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

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 = 1.22w = 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 Å3
0 restraintsΔρmin = −0.61 e Å3
Primary atom site location: structure-invariant direct methods

Special details

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)

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)

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, °)

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)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5357).

References

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography