Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680301136X/bt6285sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680301136X/bt6285Isup2.hkl |
CCDC reference: 214863
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).
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.
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.
C13H11Br3 | F(000) = 776 |
Mr = 406.95 | Dx = 2.109 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7316 (6) Å | Cell parameters from 7411 reflections |
b = 9.3716 (8) Å | θ = 2.4–30.5° |
c = 17.7245 (14) Å | µ = 9.41 mm−1 |
β = 93.835 (3)° | T = 133 K |
V = 1281.40 (18) Å3 | Tablet, colourless |
Z = 4 | 0.18 × 0.16 × 0.08 mm |
Bruker SMART 1000 CCD diffractometer | 3737 independent reflections |
Radiation source: fine-focus sealed tube | 2842 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.092 |
Detector resolution: 8.196 pixels mm-1 | θmax = 30.0°, θmin = 2.3° |
ω and ϕ scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −13→12 |
Tmin = 0.199, Tmax = 0.471 | l = −24→24 |
23006 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-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 parameters | Δρmax = 1.56 e Å−3 |
0 restraints | Δρmin = −0.69 e Å−3 |
C13H11Br3 | V = 1281.40 (18) Å3 |
Mr = 406.95 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.7316 (6) Å | µ = 9.41 mm−1 |
b = 9.3716 (8) Å | T = 133 K |
c = 17.7245 (14) Å | 0.18 × 0.16 × 0.08 mm |
β = 93.835 (3)° |
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 = 0.471 | Rint = 0.092 |
23006 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 0.97 | Δρmax = 1.56 e Å−3 |
3737 reflections | Δρmin = −0.69 e Å−3 |
145 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.22332 (5) | 0.93314 (4) | 0.49301 (2) | 0.03200 (11) | |
Br2 | −0.02500 (5) | 0.37769 (4) | 0.79090 (2) | 0.02826 (10) | |
Br3 | 0.54561 (5) | 0.50487 (4) | 0.807942 (19) | 0.02546 (10) | |
C1 | 0.3235 (4) | 0.6398 (3) | 0.47856 (17) | 0.0194 (6) | |
C2 | 0.2821 (5) | 0.5830 (4) | 0.40809 (18) | 0.0245 (7) | |
H2 | 0.3059 | 0.6365 | 0.3645 | 0.029* | |
C3 | 0.2050 (5) | 0.4471 (4) | 0.39913 (19) | 0.0261 (7) | |
H3 | 0.1771 | 0.4102 | 0.3499 | 0.031* | |
C4 | 0.1703 (4) | 0.3682 (3) | 0.46149 (18) | 0.0225 (7) | |
H4 | 0.1187 | 0.2766 | 0.4552 | 0.027* | |
C4A | 0.2108 (4) | 0.4219 (3) | 0.53516 (17) | 0.0178 (6) | |
C5 | 0.1761 (4) | 0.3431 (3) | 0.60060 (17) | 0.0199 (6) | |
H5 | 0.1247 | 0.2514 | 0.5946 | 0.024* | |
C6 | 0.2140 (4) | 0.3942 (3) | 0.67211 (17) | 0.0185 (6) | |
C7 | 0.2918 (4) | 0.5321 (3) | 0.68152 (17) | 0.0169 (6) | |
C8 | 0.3260 (4) | 0.6110 (3) | 0.61932 (17) | 0.0170 (6) | |
H8 | 0.3774 | 0.7025 | 0.6263 | 0.020* | |
C8A | 0.2868 (4) | 0.5599 (3) | 0.54399 (16) | 0.0157 (6) | |
C11 | 0.4028 (4) | 0.7859 (3) | 0.48407 (18) | 0.0227 (7) | |
H11A | 0.4666 | 0.8048 | 0.4385 | 0.027* | |
H11B | 0.4866 | 0.7904 | 0.5288 | 0.027* | |
C12 | 0.1749 (4) | 0.3049 (3) | 0.73826 (18) | 0.0232 (7) | |
H12A | 0.2782 | 0.3019 | 0.7744 | 0.028* | |
H12B | 0.1500 | 0.2061 | 0.7209 | 0.028* | |
C13 | 0.3354 (4) | 0.5945 (3) | 0.75783 (17) | 0.0195 (6) | |
H13A | 0.2364 | 0.5807 | 0.7897 | 0.023* | |
H13B | 0.3550 | 0.6984 | 0.7528 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0294 (2) | 0.01728 (17) | 0.0487 (2) | 0.00271 (13) | −0.00223 (16) | −0.00067 (15) |
Br2 | 0.0244 (2) | 0.0310 (2) | 0.03027 (18) | −0.00130 (14) | 0.00875 (14) | 0.00442 (14) |
Br3 | 0.02430 (19) | 0.02515 (18) | 0.02624 (17) | 0.00265 (13) | −0.00353 (13) | −0.00019 (13) |
C1 | 0.0177 (16) | 0.0183 (14) | 0.0224 (14) | 0.0040 (11) | 0.0033 (12) | 0.0025 (12) |
C2 | 0.0279 (19) | 0.0257 (17) | 0.0201 (15) | 0.0053 (13) | 0.0029 (13) | 0.0027 (13) |
C3 | 0.032 (2) | 0.0270 (17) | 0.0186 (14) | 0.0066 (14) | −0.0028 (13) | −0.0064 (13) |
C4 | 0.0246 (18) | 0.0161 (14) | 0.0266 (16) | 0.0027 (12) | −0.0009 (13) | −0.0050 (12) |
C4A | 0.0192 (16) | 0.0138 (14) | 0.0208 (14) | 0.0032 (11) | 0.0031 (12) | −0.0015 (11) |
C5 | 0.0200 (16) | 0.0146 (14) | 0.0251 (15) | −0.0010 (11) | 0.0015 (12) | 0.0005 (12) |
C6 | 0.0189 (16) | 0.0144 (14) | 0.0228 (14) | 0.0022 (11) | 0.0057 (12) | 0.0030 (11) |
C7 | 0.0165 (16) | 0.0147 (13) | 0.0198 (14) | 0.0024 (11) | 0.0028 (11) | −0.0023 (11) |
C8 | 0.0155 (15) | 0.0142 (13) | 0.0212 (14) | −0.0007 (11) | 0.0010 (11) | −0.0030 (11) |
C8A | 0.0158 (15) | 0.0128 (13) | 0.0183 (14) | 0.0030 (10) | 0.0005 (11) | −0.0001 (11) |
C11 | 0.0220 (17) | 0.0202 (15) | 0.0262 (16) | 0.0004 (12) | 0.0051 (13) | 0.0056 (12) |
C12 | 0.0232 (17) | 0.0198 (15) | 0.0271 (16) | −0.0006 (13) | 0.0061 (13) | 0.0026 (13) |
C13 | 0.0231 (17) | 0.0164 (14) | 0.0188 (14) | 0.0024 (12) | 0.0003 (12) | 0.0006 (11) |
Br1—C11 | 1.971 (3) | C7—C8 | 1.368 (4) |
Br2—C12 | 1.979 (3) | C7—C13 | 1.491 (4) |
Br3—C13 | 1.986 (3) | C8—C8A | 1.431 (4) |
C1—C2 | 1.376 (4) | C2—H2 | 0.9500 |
C1—C8A | 1.425 (4) | C3—H3 | 0.9500 |
C1—C11 | 1.501 (4) | C4—H4 | 0.9500 |
C2—C3 | 1.411 (5) | C5—H5 | 0.9500 |
C3—C4 | 1.371 (5) | C8—H8 | 0.9500 |
C4—C4A | 1.415 (4) | C11—H11A | 0.9900 |
C4A—C5 | 1.416 (4) | C11—H11B | 0.9900 |
C4A—C8A | 1.425 (4) | C12—H12A | 0.9900 |
C5—C6 | 1.368 (4) | C12—H12B | 0.9900 |
C6—C7 | 1.431 (4) | C13—H13A | 0.9900 |
C6—C12 | 1.488 (4) | C13—H13B | 0.9900 |
C2—C1—C8A | 119.3 (3) | C3—C2—H2 | 119.3 |
C2—C1—C11 | 118.8 (3) | C4—C3—H3 | 120.0 |
C8A—C1—C11 | 121.9 (3) | C2—C3—H3 | 120.0 |
C1—C2—C3 | 121.5 (3) | C3—C4—H4 | 119.7 |
C4—C3—C2 | 120.0 (3) | C4A—C4—H4 | 119.7 |
C3—C4—C4A | 120.6 (3) | C6—C5—H5 | 118.8 |
C4—C4A—C5 | 121.9 (3) | C4A—C5—H5 | 118.8 |
C4—C4A—C8A | 119.3 (3) | C7—C8—H8 | 119.0 |
C5—C4A—C8A | 118.9 (3) | C8A—C8—H8 | 119.0 |
C6—C5—C4A | 122.4 (3) | C1—C11—H11A | 109.5 |
C5—C6—C7 | 119.1 (3) | Br1—C11—H11A | 109.5 |
C5—C6—C12 | 119.4 (3) | C1—C11—H11B | 109.5 |
C7—C6—C12 | 121.5 (3) | Br1—C11—H11B | 109.5 |
C8—C7—C6 | 119.8 (3) | H11A—C11—H11B | 108.0 |
C8—C7—C13 | 118.4 (3) | C6—C12—H12A | 109.1 |
C6—C7—C13 | 121.8 (3) | Br2—C12—H12A | 109.1 |
C7—C8—C8A | 122.1 (3) | C6—C12—H12B | 109.1 |
C1—C8A—C4A | 119.4 (3) | Br2—C12—H12B | 109.1 |
C1—C8A—C8 | 122.9 (3) | H12A—C12—H12B | 107.8 |
C4A—C8A—C8 | 117.8 (3) | C7—C13—H13A | 109.3 |
C1—C11—Br1 | 110.9 (2) | Br3—C13—H13A | 109.3 |
C6—C12—Br2 | 112.5 (2) | C7—C13—H13B | 109.3 |
C7—C13—Br3 | 111.6 (2) | Br3—C13—H13B | 109.3 |
C1—C2—H2 | 119.3 | H13A—C13—H13B | 108.0 |
C8A—C1—C2—C3 | −0.4 (5) | C2—C1—C8A—C4A | 1.1 (5) |
C11—C1—C2—C3 | −179.1 (3) | C11—C1—C8A—C4A | 179.7 (3) |
C1—C2—C3—C4 | −0.2 (5) | C2—C1—C8A—C8 | 179.9 (3) |
C2—C3—C4—C4A | 0.1 (5) | C11—C1—C8A—C8 | −1.5 (5) |
C3—C4—C4A—C5 | 179.8 (3) | C4—C4A—C8A—C1 | −1.2 (5) |
C3—C4—C4A—C8A | 0.6 (5) | C5—C4A—C8A—C1 | 179.5 (3) |
C4—C4A—C5—C6 | −179.7 (3) | C4—C4A—C8A—C8 | 180.0 (3) |
C8A—C4A—C5—C6 | −0.5 (5) | C5—C4A—C8A—C8 | 0.7 (4) |
C4A—C5—C6—C7 | −0.1 (5) | C7—C8—C8A—C1 | −179.2 (3) |
C4A—C5—C6—C12 | −179.6 (3) | C7—C8—C8A—C4A | −0.4 (4) |
C5—C6—C7—C8 | 0.5 (5) | C2—C1—C11—Br1 | 93.4 (3) |
C12—C6—C7—C8 | 179.9 (3) | C8A—C1—C11—Br1 | −85.2 (3) |
C5—C6—C7—C13 | 179.6 (3) | C5—C6—C12—Br2 | −107.6 (3) |
C12—C6—C7—C13 | −0.9 (5) | C7—C6—C12—Br2 | 72.9 (4) |
C6—C7—C8—C8A | −0.2 (5) | C8—C7—C13—Br3 | −105.4 (3) |
C13—C7—C8—C8A | −179.4 (3) | C6—C7—C13—Br3 | 75.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···Br3i | 0.95 | 3.11 | 4.013 (3) | 160 |
C11—H11A···Br3ii | 0.99 | 3.02 | 3.908 (3) | 150 |
C13—H13B···Br2iii | 0.99 | 3.11 | 3.643 (3) | 115 |
C12—H12B···Br3iv | 0.99 | 3.09 | 3.672 (3) | 119 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+3/2, z−1/2; (iii) −x, y+1/2, −z+3/2; (iv) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C13H11Br3 |
Mr | 406.95 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 133 |
a, b, c (Å) | 7.7316 (6), 9.3716 (8), 17.7245 (14) |
β (°) | 93.835 (3) |
V (Å3) | 1281.40 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 9.41 |
Crystal size (mm) | 0.18 × 0.16 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.199, 0.471 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23006, 3737, 2842 |
Rint | 0.092 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.094, 0.97 |
No. of reflections | 3737 |
No. of parameters | 145 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.56, −0.69 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
Br1—C11 | 1.971 (3) | Br3—C13 | 1.986 (3) |
Br2—C12 | 1.979 (3) | ||
C1—C11—Br1 | 110.9 (2) | C7—C13—Br3 | 111.6 (2) |
C6—C12—Br2 | 112.5 (2) | ||
C2—C1—C11—Br1 | 93.4 (3) | C6—C7—C13—Br3 | 75.4 (3) |
C7—C6—C12—Br2 | 72.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···Br3i | 0.95 | 3.11 | 4.013 (3) | 160 |
C11—H11A···Br3ii | 0.99 | 3.02 | 3.908 (3) | 150 |
C13—H13B···Br2iii | 0.99 | 3.11 | 3.643 (3) | 115 |
C12—H12B···Br3iv | 0.99 | 3.09 | 3.672 (3) | 119 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+3/2, z−1/2; (iii) −x, y+1/2, −z+3/2; (iv) −x+1, y−1/2, −z+3/2. |
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.