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The title compound, C13H11Br3, has a planar framework of C atoms with no distortion towards helicity. The two adjacent bromine substituents point to opposite sides of the ring system. Two bromine–bromine contacts, with distances less than twice the van der Waals radius, link the mol­ecules to form ribbons parallel to the a axis. Weak C—H...Br hydrogen bonds and partial ring stacking complete the crystal packing.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680301136X/bt6285sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680301136X/bt6285Isup2.hkl
Contains datablock I

CCDC reference: 214863

Key indicators

  • Single-crystal X-ray study
  • T = 133 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.037
  • wR factor = 0.094
  • Data-to-parameter ratio = 25.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The title compound, (I), was synthesized as a potential precursor to naphthalenophanes (see, for example, Kuś & Jones, 2000).

The molecular structure of (I) is presented in Fig. 1. Bond lengths and angles may be regarded as normal. The naphthalene framework is planar (r.m.s. deviation 0.004 Å for all 11 C atoms); the level of substitution is thus not great enough to promote helicity, in contrast to the octakis-substituted analogue (Siman et al., 2003). The bromomethyl groups are approximately perpendicular to the ring system (torsion angles in Table 1), with atoms Br1 and Br2 on one side of the plane, Br3 on the other.

The crystal packing involves two main types of interaction, weak C—H···Br hydrogen bonds and Br···Br interactions. Details of the H bonds are given in Table 2; none of the H···Br distances is especially short, and two have narrow angles (<120°) at hydrogen. The Br···Br contacts, Br1···Br1v 3.6974 (8) and Br2···Br3vi 3.5591 (6) Å [symmetry codes: (v) −x, 2 − y, 1 − z; (vi) −1 + x, y, z] may be compared with the double van der Waals radius of 3.7 Å (Bondi, 1964). There is also a longer contact Br1···Br3i of 3.9048 (6) Å [symmetry code: (i) please supply]. The first two are established as `type II' and the third contact as `type I' in the classification of Pedireddi et al. (1994) by the angles at bromine: 155.30 (10)° (× 2, by symmetry), 156.59 (10) and 147.56 (9)°, and 84.90 (10) and 142.03 (9)°, respectively.

The effect of the two shortest Br···Br contacts is to link the molecules to form highly corrugated ribbons (Fig. 2) with overall direction parallel to the x axis. The hydrogen bonds (not shown) then link the ribbons in the z direction to establish the final three-dimensional packing, which also involves partial stacking (incomplete overlap in projection) of the ring systems.

Experimental top

The title material was synthesized from 1,6,7-trimethylnaphthalene (Ried & Bodem, 1958) and recrystallized from ethanol/dichloromethane (1:2 v/v). 1H NMR data (300 MHz, CDCl3, TMS, p.p.m.): δ 4.87 (s, 2H), 4.91 (s, 2H), 4.92 (s, 2H), 7.43 (t, 1H), 7.55 (d, 1H), 7.79 (d, 1H), 7.89 (s, 1H) and 8.14 (s, 1H).

Refinement top

H atoms were included using a riding model with fixed C—H bond lengths of 0.95 (sp2 carbon) or 0.99 Å (methylene). Uiso(H) values were fixed at 1.2Ueq of the parent atom.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecule of the title compound in the crystal. Ellipsoids represent 50% probability levels. The H-atom radius is arbitrary.
[Figure 2] Fig. 2. Packing diagram of the title compound, viewed perpendicular to the xy plane. Br···Br interactions are indicated by dashed lines. H atoms have been omitted.
1,6,7-Tris(bromomethyl)naphthalene top
Crystal data top
C13H11Br3F(000) = 776
Mr = 406.95Dx = 2.109 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.7316 (6) ÅCell parameters from 7411 reflections
b = 9.3716 (8) Åθ = 2.4–30.5°
c = 17.7245 (14) ŵ = 9.41 mm1
β = 93.835 (3)°T = 133 K
V = 1281.40 (18) Å3Tablet, colourless
Z = 40.18 × 0.16 × 0.08 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer
3737 independent reflections
Radiation source: fine-focus sealed tube2842 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.092
Detector resolution: 8.196 pixels mm-1θmax = 30.0°, θmin = 2.3°
ω and ϕ scansh = 1010
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
k = 1312
Tmin = 0.199, Tmax = 0.471l = 2424
23006 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0518P)2]
where P = (Fo2 + 2Fc2)/3
3737 reflections(Δ/σ)max = 0.001
145 parametersΔρmax = 1.56 e Å3
0 restraintsΔρmin = 0.69 e Å3
Crystal data top
C13H11Br3V = 1281.40 (18) Å3
Mr = 406.95Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.7316 (6) ŵ = 9.41 mm1
b = 9.3716 (8) ÅT = 133 K
c = 17.7245 (14) Å0.18 × 0.16 × 0.08 mm
β = 93.835 (3)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
3737 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
2842 reflections with I > 2σ(I)
Tmin = 0.199, Tmax = 0.471Rint = 0.092
23006 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.094H-atom parameters constrained
S = 0.97Δρmax = 1.56 e Å3
3737 reflectionsΔρmin = 0.69 e Å3
145 parameters
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.

Non-bonded Distances etc.

3.9048 (0.0006) Br1 - Br3_$1 3.6974 (0.0008) Br1 - Br1_$5 3.5591 (0.0006) Br2 - Br3_$6

155.30 (0.10) C11 - Br1 - Br1_$5 84.90 (0.10) C11 - Br1 - Br3_$1 142.03 (0.09) Br1 - Br3_$1 - C13_$1 156.59 (0.10) C12 - Br2 - Br3_$6 147.56 (0.09) Br2 - Br3_$6 - C13_$6

Operators for generating equivalent atoms:

$1 − x + 1, y + 1/2, −z + 3/2 $5 − x, −y + 2, −z + 1 $6 x − 1, y, z

=============================================================================

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

− 7.0419 (0.0023) x + 3.8686 (0.0060) y + 0.9728 (0.0083) z = 0.6703 (0.0067)

* −0.0080 (0.0028) C1 * −0.0042 (0.0029) C2 * 0.0040 (0.0029) C3 * 0.0036 (0.0028) C4 * 0.0010 (0.0029) C5 * 0.0018 (0.0029) C6 * −0.0037 (0.0028) C7 * 0.0001 (0.0028) C8 * 0.0046 (0.0024) C11 * −0.0043 (0.0027) C12 * 0.0051 (0.0026) C13 1.8467 (0.0026) Br1 1.7364 (0.0022) Br2 − 1.7733 (0.0023) Br3

Rms deviation of fitted atoms = 0.0042

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
Br10.22332 (5)0.93314 (4)0.49301 (2)0.03200 (11)
Br20.02500 (5)0.37769 (4)0.79090 (2)0.02826 (10)
Br30.54561 (5)0.50487 (4)0.807942 (19)0.02546 (10)
C10.3235 (4)0.6398 (3)0.47856 (17)0.0194 (6)
C20.2821 (5)0.5830 (4)0.40809 (18)0.0245 (7)
H20.30590.63650.36450.029*
C30.2050 (5)0.4471 (4)0.39913 (19)0.0261 (7)
H30.17710.41020.34990.031*
C40.1703 (4)0.3682 (3)0.46149 (18)0.0225 (7)
H40.11870.27660.45520.027*
C4A0.2108 (4)0.4219 (3)0.53516 (17)0.0178 (6)
C50.1761 (4)0.3431 (3)0.60060 (17)0.0199 (6)
H50.12470.25140.59460.024*
C60.2140 (4)0.3942 (3)0.67211 (17)0.0185 (6)
C70.2918 (4)0.5321 (3)0.68152 (17)0.0169 (6)
C80.3260 (4)0.6110 (3)0.61932 (17)0.0170 (6)
H80.37740.70250.62630.020*
C8A0.2868 (4)0.5599 (3)0.54399 (16)0.0157 (6)
C110.4028 (4)0.7859 (3)0.48407 (18)0.0227 (7)
H11A0.46660.80480.43850.027*
H11B0.48660.79040.52880.027*
C120.1749 (4)0.3049 (3)0.73826 (18)0.0232 (7)
H12A0.27820.30190.77440.028*
H12B0.15000.20610.72090.028*
C130.3354 (4)0.5945 (3)0.75783 (17)0.0195 (6)
H13A0.23640.58070.78970.023*
H13B0.35500.69840.75280.023*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0294 (2)0.01728 (17)0.0487 (2)0.00271 (13)0.00223 (16)0.00067 (15)
Br20.0244 (2)0.0310 (2)0.03027 (18)0.00130 (14)0.00875 (14)0.00442 (14)
Br30.02430 (19)0.02515 (18)0.02624 (17)0.00265 (13)0.00353 (13)0.00019 (13)
C10.0177 (16)0.0183 (14)0.0224 (14)0.0040 (11)0.0033 (12)0.0025 (12)
C20.0279 (19)0.0257 (17)0.0201 (15)0.0053 (13)0.0029 (13)0.0027 (13)
C30.032 (2)0.0270 (17)0.0186 (14)0.0066 (14)0.0028 (13)0.0064 (13)
C40.0246 (18)0.0161 (14)0.0266 (16)0.0027 (12)0.0009 (13)0.0050 (12)
C4A0.0192 (16)0.0138 (14)0.0208 (14)0.0032 (11)0.0031 (12)0.0015 (11)
C50.0200 (16)0.0146 (14)0.0251 (15)0.0010 (11)0.0015 (12)0.0005 (12)
C60.0189 (16)0.0144 (14)0.0228 (14)0.0022 (11)0.0057 (12)0.0030 (11)
C70.0165 (16)0.0147 (13)0.0198 (14)0.0024 (11)0.0028 (11)0.0023 (11)
C80.0155 (15)0.0142 (13)0.0212 (14)0.0007 (11)0.0010 (11)0.0030 (11)
C8A0.0158 (15)0.0128 (13)0.0183 (14)0.0030 (10)0.0005 (11)0.0001 (11)
C110.0220 (17)0.0202 (15)0.0262 (16)0.0004 (12)0.0051 (13)0.0056 (12)
C120.0232 (17)0.0198 (15)0.0271 (16)0.0006 (13)0.0061 (13)0.0026 (13)
C130.0231 (17)0.0164 (14)0.0188 (14)0.0024 (12)0.0003 (12)0.0006 (11)
Geometric parameters (Å, º) top
Br1—C111.971 (3)C7—C81.368 (4)
Br2—C121.979 (3)C7—C131.491 (4)
Br3—C131.986 (3)C8—C8A1.431 (4)
C1—C21.376 (4)C2—H20.9500
C1—C8A1.425 (4)C3—H30.9500
C1—C111.501 (4)C4—H40.9500
C2—C31.411 (5)C5—H50.9500
C3—C41.371 (5)C8—H80.9500
C4—C4A1.415 (4)C11—H11A0.9900
C4A—C51.416 (4)C11—H11B0.9900
C4A—C8A1.425 (4)C12—H12A0.9900
C5—C61.368 (4)C12—H12B0.9900
C6—C71.431 (4)C13—H13A0.9900
C6—C121.488 (4)C13—H13B0.9900
C2—C1—C8A119.3 (3)C3—C2—H2119.3
C2—C1—C11118.8 (3)C4—C3—H3120.0
C8A—C1—C11121.9 (3)C2—C3—H3120.0
C1—C2—C3121.5 (3)C3—C4—H4119.7
C4—C3—C2120.0 (3)C4A—C4—H4119.7
C3—C4—C4A120.6 (3)C6—C5—H5118.8
C4—C4A—C5121.9 (3)C4A—C5—H5118.8
C4—C4A—C8A119.3 (3)C7—C8—H8119.0
C5—C4A—C8A118.9 (3)C8A—C8—H8119.0
C6—C5—C4A122.4 (3)C1—C11—H11A109.5
C5—C6—C7119.1 (3)Br1—C11—H11A109.5
C5—C6—C12119.4 (3)C1—C11—H11B109.5
C7—C6—C12121.5 (3)Br1—C11—H11B109.5
C8—C7—C6119.8 (3)H11A—C11—H11B108.0
C8—C7—C13118.4 (3)C6—C12—H12A109.1
C6—C7—C13121.8 (3)Br2—C12—H12A109.1
C7—C8—C8A122.1 (3)C6—C12—H12B109.1
C1—C8A—C4A119.4 (3)Br2—C12—H12B109.1
C1—C8A—C8122.9 (3)H12A—C12—H12B107.8
C4A—C8A—C8117.8 (3)C7—C13—H13A109.3
C1—C11—Br1110.9 (2)Br3—C13—H13A109.3
C6—C12—Br2112.5 (2)C7—C13—H13B109.3
C7—C13—Br3111.6 (2)Br3—C13—H13B109.3
C1—C2—H2119.3H13A—C13—H13B108.0
C8A—C1—C2—C30.4 (5)C2—C1—C8A—C4A1.1 (5)
C11—C1—C2—C3179.1 (3)C11—C1—C8A—C4A179.7 (3)
C1—C2—C3—C40.2 (5)C2—C1—C8A—C8179.9 (3)
C2—C3—C4—C4A0.1 (5)C11—C1—C8A—C81.5 (5)
C3—C4—C4A—C5179.8 (3)C4—C4A—C8A—C11.2 (5)
C3—C4—C4A—C8A0.6 (5)C5—C4A—C8A—C1179.5 (3)
C4—C4A—C5—C6179.7 (3)C4—C4A—C8A—C8180.0 (3)
C8A—C4A—C5—C60.5 (5)C5—C4A—C8A—C80.7 (4)
C4A—C5—C6—C70.1 (5)C7—C8—C8A—C1179.2 (3)
C4A—C5—C6—C12179.6 (3)C7—C8—C8A—C4A0.4 (4)
C5—C6—C7—C80.5 (5)C2—C1—C11—Br193.4 (3)
C12—C6—C7—C8179.9 (3)C8A—C1—C11—Br185.2 (3)
C5—C6—C7—C13179.6 (3)C5—C6—C12—Br2107.6 (3)
C12—C6—C7—C130.9 (5)C7—C6—C12—Br272.9 (4)
C6—C7—C8—C8A0.2 (5)C8—C7—C13—Br3105.4 (3)
C13—C7—C8—C8A179.4 (3)C6—C7—C13—Br375.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···Br3i0.953.114.013 (3)160
C11—H11A···Br3ii0.993.023.908 (3)150
C13—H13B···Br2iii0.993.113.643 (3)115
C12—H12B···Br3iv0.993.093.672 (3)119
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x, y+3/2, z1/2; (iii) x, y+1/2, z+3/2; (iv) x+1, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC13H11Br3
Mr406.95
Crystal system, space groupMonoclinic, P21/c
Temperature (K)133
a, b, c (Å)7.7316 (6), 9.3716 (8), 17.7245 (14)
β (°) 93.835 (3)
V3)1281.40 (18)
Z4
Radiation typeMo Kα
µ (mm1)9.41
Crystal size (mm)0.18 × 0.16 × 0.08
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.199, 0.471
No. of measured, independent and
observed [I > 2σ(I)] reflections
23006, 3737, 2842
Rint0.092
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.094, 0.97
No. of reflections3737
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.56, 0.69

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.

Selected geometric parameters (Å, º) top
Br1—C111.971 (3)Br3—C131.986 (3)
Br2—C121.979 (3)
C1—C11—Br1110.9 (2)C7—C13—Br3111.6 (2)
C6—C12—Br2112.5 (2)
C2—C1—C11—Br193.4 (3)C6—C7—C13—Br375.4 (3)
C7—C6—C12—Br272.9 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···Br3i0.953.114.013 (3)160
C11—H11A···Br3ii0.993.023.908 (3)150
C13—H13B···Br2iii0.993.113.643 (3)115
C12—H12B···Br3iv0.993.093.672 (3)119
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x, y+3/2, z1/2; (iii) x, y+1/2, z+3/2; (iv) x+1, y1/2, z+3/2.
 

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