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Acta Cryst. (2009). E65, o1327    [ doi:10.1107/S1600536809018066 ]

2,5-Bis(bromomethyl)biphenyl

P. Kus, A. Zemanek and P. G. Jones

Abstract top

In the title compound, C14H12Br2, the Br atoms lie on opposite sides of their ring plane. The biphenyl interplanar angle is 53.52 (8)°. The packing is characterized by several H...Br contacts to each Br atom, but at long distances of 3.07-3.43 Å.

Comment top

We are interested in the structures of bromomethyl-substituted aromatic ring systems, compounds that are often used as synthestic intermediates; e.g. various bromomethylbenzenes (Jones & Kuś, 2007), 2,2"- and 2',5'- bis(bromomethyl)-p-terphenyl (Jones & Kuś, 2005; Jones et al., 2007). The packing patterns are often characterized by secondary interactions such as C—H···Br, Br···Br and C—H···π.

As a part of the synthesis of phenyl derivatives of [2.2]paracyclophane (Czuchajowski & Zemanek 1990), 2,5-di(bromomethyl)biphenyl (1) was obtained by bromination of 2,5-dimethylbiphenyl. Here we present its structure (Fig. 1).

Bond lengths and angles may be regarded as normal (e.g. the single bond between the rings is 1.486 (4) Å; ring angles at the substituted atoms C1, C2, C5 are all about 1° less than the ideal 120°). The interplanar angle is 53.52 (8)°. The bromomethyl groups adopt an anti-conformation whereby Br1 and Br2 lie out of their ring plane by 1.680 (4) and -1.736 (4) Å; associated torsion angles are C3—C2—C7—Br1 - 77.2 (3) and C4—C5—C8—Br2 - 87.9 (3)°. A similar conformation was observed in 2,6-di(bromomethyl)biphenyl (Obrey et al., 2002), whereas 2',5'-di(bromomethyl)-p-terphenyl adopts a syn-conformation (Jones et al. 2007).

The packing (Fig. 2) appears at first sight to be characterized by an almost total lack of secondary contacts. The shortest H···Br contact is H12···Br1 3.07 Å (operator 0.5 - x,-1/2 + y,0.5 - z) and there are no other H···Br < 3.19 Å; there are no Br···Br contacts < 4.2 Å and no H···π contacts < 2.95 Å (and these with very narrow angles). Both bromine atoms however are situated in a pocket surrounded by several H atoms; Br1 by six H at distances of 3.07–3.43, Br2 by eight H from 3.20–3.43 Å. This corresponds to the phenomenon of tertiary contacts as postulated by Du Mont et al. (2008).

Related literature top

For the structures of bromomethyl-substituted aromatic ring systems, see: Jones & Kuś (2005, 2007); Jones et al. (2007). For the synthesis, see: Czuchajowski & Zemanek (1990); For a related structure with a similar conformation, see: Obrey et al. (2002). For the phenomenon of tertiary contacts, see: Du Mont et al. (2008);

Experimental top

The title compound was obtained from 2,5-dimethylbiphenyl according to the method of Czuchajowski & Zemanek (1990). The analytical and spectroscopic data are consistent with the literature. Single crystals were grown by slow evaporation of a hexane solution. NMR data for (1): 1H NMR (CDCl3, 400 MHz): δ 7.52 (d, 1H), 7.50–7.39 (m, 6H), 7.29 (d, 1H), 4.50 (s, 2H), 4.44(s, 2H); 13C NMR (100 MHz): δ 142.54, 139.57, 138.07, 135.46, 131.53, 131.03, 128.94, 128.61, 128.44, 127.77, 32.75, 31.58.

Refinement top

H atoms were included at calculated positions and refined using a riding model, with fixed C—H bond lengths of 0.95 Å (CH, aromatic) or 0.99 Å (CH2) Å; Uiso(H) values were fixed at 1.2Ueq of the parent C atom. Largest difference peaks of ±1.0 e Å-3 near the bromine atoms may be attributed to residual absorption errors.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The title compound in the crystal. Displacement ellipsoids represent 50% probability levels.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed parallel to the short b axis.
2,5-Bis(bromomethyl)biphenyl top
Crystal data top
C14H12Br2F000 = 1328
Mr = 340.06Dx = 1.799 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
a = 33.084 (4) ÅCell parameters from 6730 reflections
b = 4.3354 (6) Åθ = 2.3–28.8º
c = 18.017 (2) ŵ = 6.43 mm−1
β = 103.702 (4)ºT = 133 K
V = 2510.7 (5) Å3Prism, colourless
Z = 80.25 × 0.10 × 0.10 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		3120 independent reflections
Radiation source: fine-focus sealed tube2518 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.040
Detector resolution: 8.192 pixels mm-1θmax = 28.3º
T = 133 Kθmin = 1.3º
φ and ω scansh = −44→44
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		k = −5→5
Tmin = 0.316, Tmax = 0.566l = −24→24
18269 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.085  w = 1/[σ2(Fo2) + (0.0515P)2 + 1.9201P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3120 reflectionsΔρmax = 1.00 e Å−3
145 parametersΔρmin = −1.00 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C14H12Br2V = 2510.7 (5) Å3
Mr = 340.06Z = 8
Monoclinic, C2/cMo Kα
a = 33.084 (4) ŵ = 6.43 mm−1
b = 4.3354 (6) ÅT = 133 K
c = 18.017 (2) Å0.25 × 0.10 × 0.10 mm
β = 103.702 (4)º
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		3120 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		2518 reflections with I > 2σ(I)
Tmin = 0.316, Tmax = 0.566Rint = 0.040
18269 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031145 parameters
wR(F2) = 0.085H-atom parameters constrained
S = 1.05Δρmax = 1.00 e Å−3
3120 reflectionsΔρmin = −1.00 e Å−3
Special details top

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.219743 (8)0.60712 (7)0.152339 (16)0.02600 (10)
Br2−0.025878 (8)0.25836 (8)0.108852 (19)0.03229 (11)
C10.11964 (8)0.5306 (6)0.22477 (14)0.0176 (5)
C20.13425 (8)0.6193 (6)0.16080 (15)0.0179 (5)
C30.11266 (8)0.5205 (7)0.08827 (15)0.0209 (5)
H30.12190.58560.04470.025*
C40.07831 (9)0.3310 (7)0.07839 (17)0.0244 (6)
H40.06470.26210.02870.029*
C50.06355 (8)0.2407 (6)0.14127 (17)0.0222 (6)
C60.08387 (8)0.3445 (7)0.21324 (16)0.0209 (6)
H60.07330.28830.25600.025*
C70.17006 (8)0.8325 (7)0.16619 (16)0.0211 (6)
H7A0.17650.93470.21680.025*
H7B0.16250.99420.12650.025*
C80.02710 (8)0.0280 (7)0.13151 (19)0.0304 (7)
H8A0.0294−0.09370.17880.037*
H8B0.0273−0.11760.08930.037*
C110.14006 (8)0.6257 (7)0.30405 (14)0.0187 (5)
C120.18247 (9)0.5758 (7)0.33539 (16)0.0247 (6)
H120.19890.47830.30560.030*
C130.20058 (9)0.6669 (8)0.40922 (17)0.0300 (7)
H130.22930.62880.43000.036*
C140.17707 (10)0.8145 (8)0.45354 (17)0.0306 (7)
H140.18980.88220.50380.037*
C150.13489 (9)0.8614 (8)0.42342 (16)0.0279 (7)
H150.11860.96150.45320.033*
C160.11642 (9)0.7626 (7)0.34998 (16)0.0225 (6)
H160.08730.78830.33060.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01373 (14)0.03068 (18)0.03439 (16)−0.00368 (11)0.00730 (10)−0.00446 (13)
Br20.01203 (15)0.0309 (2)0.0514 (2)−0.00186 (11)0.00244 (12)0.00305 (14)
C10.0114 (11)0.0171 (13)0.0231 (12)0.0036 (10)0.0018 (9)0.0018 (11)
C20.0130 (11)0.0162 (13)0.0236 (12)0.0016 (10)0.0027 (9)0.0000 (11)
C30.0177 (12)0.0208 (14)0.0234 (12)0.0028 (11)0.0036 (10)0.0026 (11)
C40.0165 (13)0.0260 (15)0.0273 (14)0.0032 (11)−0.0013 (10)−0.0023 (12)
C50.0120 (12)0.0158 (14)0.0371 (15)0.0029 (10)0.0025 (11)−0.0001 (12)
C60.0135 (12)0.0208 (14)0.0278 (13)0.0025 (10)0.0033 (10)0.0051 (11)
C70.0174 (13)0.0201 (14)0.0264 (13)0.0016 (11)0.0064 (10)0.0013 (11)
C80.0137 (13)0.0213 (15)0.0528 (19)0.0011 (12)0.0009 (12)0.0013 (14)
C110.0139 (12)0.0221 (14)0.0194 (12)0.0007 (10)0.0027 (9)0.0045 (11)
C120.0162 (13)0.0326 (17)0.0252 (13)0.0037 (12)0.0049 (10)−0.0003 (12)
C130.0156 (13)0.045 (2)0.0266 (14)0.0033 (13)−0.0003 (11)0.0033 (14)
C140.0276 (16)0.0415 (19)0.0209 (13)−0.0006 (14)0.0018 (11)0.0002 (13)
C150.0260 (15)0.0366 (18)0.0233 (13)0.0043 (13)0.0104 (11)0.0026 (13)
C160.0174 (13)0.0252 (16)0.0254 (13)0.0055 (11)0.0059 (10)0.0057 (12)
Geometric parameters (Å, °) top
Br1—C71.978 (3)C14—C151.387 (4)
Br2—C81.974 (3)C15—C161.387 (4)
C1—C21.405 (4)C3—H30.9500
C1—C61.407 (4)C4—H40.9500
C1—C111.486 (4)C6—H60.9500
C2—C31.400 (4)C7—H7A0.9900
C2—C71.487 (4)C7—H7B0.9900
C3—C41.379 (4)C8—H8A0.9900
C4—C51.392 (4)C8—H8B0.9900
C5—C61.387 (4)C12—H120.9500
C5—C81.495 (4)C13—H130.9500
C11—C161.398 (4)C14—H140.9500
C11—C121.400 (4)C15—H150.9500
C12—C131.381 (4)C16—H160.9500
C13—C141.395 (4)
C2—C1—C6118.5 (2)C3—C4—H4120.0
C2—C1—C11123.1 (2)C5—C4—H4120.0
C6—C1—C11118.4 (2)C5—C6—H6119.0
C3—C2—C1118.9 (2)C1—C6—H6119.0
C3—C2—C7118.3 (2)C2—C7—H7A109.4
C1—C2—C7122.7 (2)Br1—C7—H7A109.4
C4—C3—C2121.7 (3)C2—C7—H7B109.4
C3—C4—C5120.0 (3)Br1—C7—H7B109.4
C6—C5—C4119.0 (3)H7A—C7—H7B108.0
C6—C5—C8120.6 (3)C5—C8—H8A109.4
C4—C5—C8120.4 (3)Br2—C8—H8A109.4
C5—C6—C1121.9 (3)C5—C8—H8B109.4
C2—C7—Br1111.0 (2)Br2—C8—H8B109.4
C5—C8—Br2111.4 (2)H8A—C8—H8B108.0
C16—C11—C12118.3 (3)C13—C12—H12119.7
C16—C11—C1119.7 (2)C11—C12—H12119.7
C12—C11—C1121.9 (2)C12—C13—H13119.7
C13—C12—C11120.6 (3)C14—C13—H13119.7
C12—C13—C14120.6 (3)C15—C14—H14120.4
C15—C14—C13119.3 (3)C13—C14—H14120.4
C14—C15—C16120.2 (3)C14—C15—H15119.9
C15—C16—C11120.9 (3)C16—C15—H15119.9
C4—C3—H3119.1C15—C16—H16119.5
C2—C3—H3119.1C11—C16—H16119.5
C6—C1—C2—C30.2 (4)C6—C5—C8—Br293.8 (3)
C11—C1—C2—C3−179.4 (3)C4—C5—C8—Br2−87.9 (3)
C6—C1—C2—C7175.8 (3)C2—C1—C11—C16128.0 (3)
C11—C1—C2—C7−3.8 (4)C6—C1—C11—C16−51.6 (4)
C1—C2—C3—C4−2.1 (4)C2—C1—C11—C12−53.6 (4)
C7—C2—C3—C4−177.8 (3)C6—C1—C11—C12126.8 (3)
C2—C3—C4—C51.9 (4)C16—C11—C12—C13−1.6 (4)
C3—C4—C5—C60.1 (4)C1—C11—C12—C13179.9 (3)
C3—C4—C5—C8−178.2 (3)C11—C12—C13—C14−1.0 (5)
C4—C5—C6—C1−1.9 (4)C12—C13—C14—C151.8 (5)
C8—C5—C6—C1176.3 (3)C13—C14—C15—C16−0.1 (5)
C2—C1—C6—C51.8 (4)C14—C15—C16—C11−2.5 (5)
C11—C1—C6—C5−178.6 (3)C12—C11—C16—C153.3 (4)
C3—C2—C7—Br1−77.2 (3)C1—C11—C16—C15−178.2 (3)
C1—C2—C7—Br1107.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7B···Br1i0.993.233.773 (3)116
C12—H12···Br1ii0.953.073.782 (3)133
C13—H13···Br1ii0.953.373.931 (3)120
C13—H13···Br1iii0.953.243.634 (3)107
C14—H14···Br1iv0.953.373.971 (3)123
C14—H14···Br1v0.953.434.326 (3)157
C4—H4···Br2vi0.953.374.260 (3)156
C4—H4···Br2vii0.953.263.845 (3)122
C6—H6···Br2viii0.953.204.124 (3)166
C8—H8B···Br2ix0.993.293.746 (3)110
C8—H8A···Br2ix0.993.433.746 (3)101
C15—H15···Br2x0.953.273.913 (3)127
C16—H16···Br2viii0.953.413.918 (3)116
C16—H16···Br2x0.953.243.898 (3)128
Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x, −y+1, z+1/2; (v) x, −y+2, z+1/2; (vi) −x, −y, −z; (vii) −x, −y+1, −z; (viii) −x, y, −z+1/2; (ix) x, y−1, z; (x) −x, y+1, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7B···Br1i0.993.233.773 (3)116
C12—H12···Br1ii0.953.073.782 (3)133
C13—H13···Br1ii0.953.373.931 (3)120
C13—H13···Br1iii0.953.243.634 (3)107
C14—H14···Br1iv0.953.373.971 (3)123
C14—H14···Br1v0.953.434.326 (3)157
C4—H4···Br2vi0.953.374.260 (3)156
C4—H4···Br2vii0.953.263.845 (3)122
C6—H6···Br2viii0.953.204.124 (3)166
C8—H8B···Br2ix0.993.293.746 (3)110
C8—H8A···Br2ix0.993.433.746 (3)101
C15—H15···Br2x0.953.273.913 (3)127
C16—H16···Br2viii0.953.413.918 (3)116
C16—H16···Br2x0.953.243.898 (3)128
Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x, −y+1, z+1/2; (v) x, −y+2, z+1/2; (vi) −x, −y, −z; (vii) −x, −y+1, −z; (viii) −x, y, −z+1/2; (ix) x, y−1, z; (x) −x, y+1, −z+1/2.
references
References top

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Obrey, S. J., Bott, S. G. & Barron, A. R. (2002). J. Chem. Crystallogr. 32, 205–207.

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

Siemens (1994). XP. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.