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The first crystal structure determination of 1-bromo-2-(phenyl­selen­yl)benzene is presented. The mol­ecules form weak dimers through displaced parallel π-stacking inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S205698901500345X/lh5753sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205698901500345X/lh5753Isup2.hkl
Contains datablock I

cdx

Chemdraw file https://doi.org/10.1107/S205698901500345X/lh5753Isup3.cdx
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S205698901500345X/lh5753Isup4.cml
Supplementary material

CCDC reference: 1050354

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.017
  • wR factor = 0.042
  • Data-to-parameter ratio = 21.6

checkCIF/PLATON results

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Alert level G PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 17 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 0 ALERT level C = Check. Ensure it is not caused by an omission or oversight 1 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Chemical context top

Organoselenium compounds have been found to have diverse scientific applications. For instance, the anti­oxidant capabilities of the gluta­thione peroxidases has inspired the synthesis of selenium-containing enzyme mimetics for therapeutic use (Schewe, 1995), and examples are known of selenium-based conjugated materials exhibiting superconductivity (Jérome et al., 1980). Our research group is inter­ested in organoselenium compounds in the context of designing ligands for coordination to transition metals to generate catalytic complexes. This is an area of growing inter­est, as examples of selenium-containing catalysts with higher activity than the ubiquitous phosphine analogues are discovered (Kumar et al., 2012). The title compound represents a potentially valuable starting material for the synthesis of ligands containing –SePh donor groups, as the ortho Br atom provides a site of functionalization via, e.g. lithium halogen exchange followed by electrophile addition, or a metal-catalyzed cross-coupling reaction. Though previously prepared (Cristau et al., 1985), its structure has remained unreported.

Structural commentary top

The molecular structure of the title compound, (I), is depicted in Fig. 1. The asymmetric unit possesses one complete molecule, which features no significant disorder. The central Se atom exhibits a bent geometry [C1—Se1—C7 = 99.19 (6)°]. The two planes comprising the benzene and phenyl ring C atoms are twisted by 107.31 (5)° relative to each other. The Br and Se atoms are twisted with respect to the disubstituted benzene ring, as evidenced by displacements in opposite directions from the mean plane of the ring by 0.052 (2) and 0.129 (2) Å, respectively, and the torsion angle Br1—C2—C1—Se1 is 4.2 (1)°.

The Se—C distances of 1.9171 (14) and 1.9198 (14) Å are equal within experimental error. At 1.9044 (14) Å, the C—Br distance is measurably shorter than the Se—C bond lengths.

Supra­molecular features top

The closest intra­molecular Se···Br distance is 3.8013 (3) Å, which lies outside the sum of the van der Waals radii (3.75 Å) for these two elements (Bondi, 1964). The phenyl group of each molecule is associated with the same group on an adjacent molecule by a slipped π-stacking inter­action (Fig. 2). The two molecules in the dimeric units are situated about a crystallographic inversion centre. The centroid-to-centroid separation of the aromatic rings is 3.630 (1) Å, while the nearest centroid-to-plane distance is 3.378 (1) Å. Together, these are indicative of the slipped nature of the ππ inter­action. The ring separation is in the normal range (ca 3.3–3.8 Å) for π-stacked inter­actions (Janiak, 2000).

Database survey top

A search of the Cambridge Structural Database (CSD, Version 5.35; Groom & Allen, 2014) reveals 172 structures featuring two-coordinate aryl-substituted selenium centres. The mean bond angle of 98 (4)° and Se—C(aryl) distance of 1.92 (2) Å for these structures match well with the parameters observed for 1-bromo-2-(phenyl­selenyl)benzene.

Only two structures in the CSD feature the title compound as a substructure: bis­(2-bromo-4,5-di­meth­oxy­phenyl) selenide (SAKBIP; Schiffling and Klar, 1989) and 1,4-di­bromo-2,3,5,6-tetra­kis(phenyl­seleno)­benzene (MUHTOZ; Sato & Kanatomi, 2009). Both of these compounds exhibit similar twisted orientations of the two aromatic rings, but lack π-stacking secondary bonding inter­actions, presumably due to their highly substituted nature. By contrast, the structure of a less sterically crowded analogue, 1-bromo-8-(phenyl­selenyl)naphthalene (CIKPUI; Fuller et al., 2007), exhibits slipped π-stacking of the naphthalene rings.

Synthesis and crystallization top

1-Bromo-2-(phenyl­selenyl)benzene has been prepared in previous reports using several methodologies, including nickel(II)-catalyzed coupling of NaSePh with 1,2-di­bromo­benzene (Cristau et al., 1985) and the copper-catalyzed coupling of di­phenyl diselenide with 1-bromo-2-iodo­benzene (Dandapat et al., 2011), which is the procedure followed for this study (Figure 4). Purification via flash column chromatography with a silica stationary phase was conducted as reported. Though described by Dandapat et al. as being a `slightly brown oil,' we found that this compound was a nearly colourless liquid which slowly crystallized upon standing at room temperature. NMR spectoscopic analysis matched the reported data.

Though quite soluble in common solvents, including nonpolar solvents such as hexanes, in the highly lipophilic hexa­methyl­disiloxane we found this substance was more moderately soluble. It crystallized readily as transparent colourless crystals from a solution in this solvent upon storage at 273 K.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. No special considerations were needed for the refinement. H atoms were placed in calculated positions, with C—H = 0.95Å and Uiso(H) = 1.2Ueq(C) and treated in a riding-model approximation.

Related literature top

For related literature, see: Bondi (1964); Cristau et al. (1985); Dandapat et al. (2011); Fuller et al. (2007); Jérome et al. (1980); Janiak (2000); Kumar et al. (2012); Sato & Kanatomi (2009); Schewe (1995); Schiffling & Klar (1989). Groom & Allen (2014).

Computing details top

Data collection: APEX2 (Bruker 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, (I), showing 50% probabilty ellipsoids.
[Figure 2] Fig. 2. Slipped π-stacked dimers of 1-bromo-2-(phenylselenyl)benzene. Each molecule is related to the other by an inversion centre at the centre of the centroid–centroid line.
[Figure 3] Fig. 3. Packing diagram for (I), veiwed along the crystallographic b axis.
[Figure 4] Fig. 4. The synthetic route to 1-bromo-2-(phenylselenyl)benzene, (I).
1-Bromo-2-(phenylselenyl)benzene top
Crystal data top
C12H9BrSeF(000) = 600
Mr = 312.06Dx = 1.877 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.1171 (4) ÅCell parameters from 9910 reflections
b = 7.6028 (4) Åθ = 2.3–28.2°
c = 18.1345 (10) ŵ = 6.97 mm1
β = 99.2668 (6)°T = 173 K
V = 1104.52 (10) Å3Fragment, colourless
Z = 40.35 × 0.32 × 0.26 mm
Data collection top
Bruker APEXII CCD
diffractometer
2528 reflections with I > 2σ(I)
ω scansRint = 0.016
Absorption correction: numerical
(SADABS; Bruker, 2013)
θmax = 28.4°, θmin = 2.3°
Tmin = 0.205, Tmax = 0.361h = 1010
21749 measured reflectionsk = 1010
2742 independent reflectionsl = 2424
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.017H-atom parameters constrained
wR(F2) = 0.042 w = 1/[σ2(Fo2) + (0.0194P)2 + 0.5087P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2742 reflectionsΔρmax = 0.28 e Å3
127 parametersΔρmin = 0.45 e Å3
0 restraints
Crystal data top
C12H9BrSeV = 1104.52 (10) Å3
Mr = 312.06Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.1171 (4) ŵ = 6.97 mm1
b = 7.6028 (4) ÅT = 173 K
c = 18.1345 (10) Å0.35 × 0.32 × 0.26 mm
β = 99.2668 (6)°
Data collection top
Bruker APEXII CCD
diffractometer
2742 independent reflections
Absorption correction: numerical
(SADABS; Bruker, 2013)
2528 reflections with I > 2σ(I)
Tmin = 0.205, Tmax = 0.361Rint = 0.016
21749 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0170 restraints
wR(F2) = 0.042H-atom parameters constrained
S = 1.06Δρmax = 0.28 e Å3
2742 reflectionsΔρmin = 0.45 e Å3
127 parameters
Special details top

Experimental. The following wavelength and cell were deduced by SADABS from the direction cosines etc. They are given here for emergency use only: CELL 0.71074 8.140 7.626 18.183 89.999 99.279 90.004.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.37269 (2)0.33279 (2)0.26417 (2)0.03601 (5)
Se10.39491 (2)0.65383 (2)0.38572 (2)0.02860 (5)
C10.19202 (17)0.52181 (18)0.36221 (7)0.0237 (3)
C20.18210 (18)0.39017 (19)0.30840 (8)0.0266 (3)
C30.0361 (2)0.2971 (2)0.28518 (9)0.0349 (3)
H30.03230.20870.24790.042*
C40.1043 (2)0.3346 (2)0.31696 (10)0.0384 (4)
H40.20580.27350.30080.046*
C50.09621 (19)0.4610 (2)0.37222 (9)0.0341 (3)
H50.19180.48460.39470.041*
C60.05039 (18)0.55397 (19)0.39518 (8)0.0283 (3)
H60.05460.63990.43350.034*
C70.32416 (18)0.82409 (18)0.45228 (8)0.0255 (3)
C80.22331 (19)0.9649 (2)0.42396 (9)0.0315 (3)
H80.18490.97470.37180.038*
C90.17967 (19)1.0906 (2)0.47282 (10)0.0350 (3)
H90.10971.18610.45410.042*
C100.23779 (19)1.0773 (2)0.54880 (10)0.0343 (3)
H100.20741.16360.58200.041*
C110.3399 (2)0.9387 (2)0.57634 (9)0.0325 (3)
H110.38090.93110.62830.039*
C120.38282 (18)0.81058 (19)0.52816 (9)0.0283 (3)
H120.45180.71450.54710.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.03941 (9)0.04133 (10)0.02890 (8)0.00838 (7)0.01038 (6)0.00290 (6)
Se10.02379 (8)0.02797 (8)0.03495 (9)0.00057 (5)0.00750 (6)0.00292 (6)
C10.0245 (6)0.0210 (6)0.0253 (6)0.0015 (5)0.0034 (5)0.0045 (5)
C20.0294 (7)0.0261 (7)0.0244 (6)0.0041 (6)0.0045 (5)0.0030 (5)
C30.0418 (9)0.0299 (8)0.0310 (8)0.0032 (7)0.0002 (6)0.0033 (6)
C40.0322 (8)0.0352 (9)0.0460 (9)0.0086 (7)0.0010 (7)0.0016 (7)
C50.0274 (7)0.0312 (8)0.0449 (9)0.0010 (6)0.0098 (6)0.0047 (7)
C60.0292 (7)0.0230 (7)0.0340 (7)0.0014 (6)0.0089 (6)0.0009 (6)
C70.0228 (6)0.0208 (6)0.0332 (7)0.0020 (5)0.0049 (5)0.0010 (5)
C80.0296 (7)0.0279 (7)0.0350 (8)0.0009 (6)0.0004 (6)0.0023 (6)
C90.0281 (7)0.0251 (7)0.0504 (9)0.0042 (6)0.0023 (7)0.0019 (7)
C100.0305 (8)0.0280 (8)0.0457 (9)0.0021 (6)0.0105 (7)0.0069 (7)
C110.0338 (8)0.0325 (8)0.0313 (7)0.0031 (6)0.0057 (6)0.0008 (6)
C120.0274 (7)0.0233 (7)0.0339 (7)0.0006 (5)0.0038 (6)0.0047 (6)
Geometric parameters (Å, º) top
Br1—C21.9044 (14)C6—H60.9500
Se1—C11.9171 (14)C7—C81.395 (2)
Se1—C71.9198 (14)C7—C121.386 (2)
C1—C21.391 (2)C8—H80.9500
C1—C61.4001 (19)C8—C91.387 (2)
C2—C31.386 (2)C9—H90.9500
C3—H30.9500C9—C101.386 (2)
C3—C41.387 (2)C10—H100.9500
C4—H40.9500C10—C111.384 (2)
C4—C51.383 (2)C11—H110.9500
C5—H50.9500C11—C121.390 (2)
C5—C61.389 (2)C12—H120.9500
C1—Se1—C799.19 (6)C8—C7—Se1120.23 (11)
C2—C1—Se1118.90 (10)C12—C7—Se1118.99 (11)
C2—C1—C6117.80 (13)C12—C7—C8120.67 (14)
C6—C1—Se1123.27 (11)C7—C8—H8120.4
C1—C2—Br1120.07 (11)C9—C8—C7119.25 (14)
C3—C2—Br1117.89 (11)C9—C8—H8120.4
C3—C2—C1122.04 (14)C8—C9—H9119.9
C2—C3—H3120.4C10—C9—C8120.25 (15)
C2—C3—C4119.24 (15)C10—C9—H9119.9
C4—C3—H3120.4C9—C10—H10119.9
C3—C4—H4120.1C11—C10—C9120.16 (15)
C5—C4—C3119.82 (15)C11—C10—H10119.9
C5—C4—H4120.1C10—C11—H11119.9
C4—C5—H5119.7C10—C11—C12120.22 (15)
C4—C5—C6120.64 (15)C12—C11—H11119.9
C6—C5—H5119.7C7—C12—C11119.45 (14)
C1—C6—H6119.8C7—C12—H12120.3
C5—C6—C1120.39 (14)C11—C12—H12120.3
C5—C6—H6119.8
Br1—C2—C3—C4179.31 (12)C4—C5—C6—C10.5 (2)
Se1—C1—C2—Br14.17 (16)C6—C1—C2—Br1177.44 (10)
Se1—C1—C2—C3175.83 (12)C6—C1—C2—C32.6 (2)
Se1—C1—C6—C5175.87 (11)C7—C8—C9—C100.9 (2)
Se1—C7—C8—C9177.21 (12)C8—C7—C12—C110.2 (2)
Se1—C7—C12—C11176.40 (11)C8—C9—C10—C110.1 (2)
C1—C2—C3—C40.7 (2)C9—C10—C11—C121.0 (2)
C2—C1—C6—C52.4 (2)C10—C11—C12—C70.8 (2)
C2—C3—C4—C51.3 (2)C12—C7—C8—C91.1 (2)
C3—C4—C5—C61.4 (3)

Experimental details

Crystal data
Chemical formulaC12H9BrSe
Mr312.06
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)8.1171 (4), 7.6028 (4), 18.1345 (10)
β (°) 99.2668 (6)
V3)1104.52 (10)
Z4
Radiation typeMo Kα
µ (mm1)6.97
Crystal size (mm)0.35 × 0.32 × 0.26
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionNumerical
(SADABS; Bruker, 2013)
Tmin, Tmax0.205, 0.361
No. of measured, independent and
observed [I > 2σ(I)] reflections
21749, 2742, 2528
Rint0.016
(sin θ/λ)max1)0.669
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.017, 0.042, 1.06
No. of reflections2742
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.45

Computer programs: APEX2 (Bruker 2013), SAINT (Bruker, 2013), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009).

 

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