organic compounds
{8-[4-(Bromomethyl)benzoyl]-2,7-dimethoxynaphthalen-1-yl}[4-(bromomethyl)phenyl]methanone
aDepartment of Organic and Polymer Materials Chemistry, Tokyo University of Agriculture & Technology, Koganei, Tokyo 184-8588, Japan
*Correspondence e-mail: aokamoto@cc.tuat.ac.jp
In the title compound, C28H22Br2O4, the two 4-bromomethylbenzoyl groups at the 1- and 8-positions of the naphthalene ring system are aligned almost antiparallel, the benzene rings forming a dihedral angle of 2.94 (16)°. The dihedral angles between the benzene rings and the naphthalene ring systems are 70.98 (13) and 72.89 (13)°. In the crystal, centrosymmetrically-related molecules are linked into dimeric units by intermolecular C—H⋯O interactions.
Related literature
For formation reactions of aroylated naphthalene compounds via electrophilic aromatic substitution of naphthalene derivatives, see: Okamoto & Yonezawa (2009). For the structures of closely related compounds, see: Muto et al. (2010); Nakaema et al. (2007, 2008); Watanabe, Nagasawa et al. (2010); Watanabe, Nakaema et al. (2010).
Experimental
Crystal data
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Refinement
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Data collection: PROCESS-AUTO (Rigaku, 1998); cell PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536811029151/rz2629sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811029151/rz2629Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811029151/rz2629Isup3.cml
To a 50 ml flask, 4-bromomethylbenzoic acid (22.0 mmol, 4.73 g) and phosphorus pentoxide–methanesulfonic acid (P2O5–MsOH, 40.0 ml) were placed and stirred at 333 K. To the mixture thus obtained, 2,7-dimethoxynaphthalene (10.0 mmol, 1.88 g) was added. After the reaction mixture was stirred at 333 K for 1 h, it was poured into ice-cold water (30 ml) and the mixture was extracted with CHCl3 (15 ml × 3). The combined extracts were washed with 2 M aqueous NaOH followed by washing with brine. The organic layers thus obtained were dried over anhydrous MgSO4. The solvent was removed under reduced pressure to give the crude product (81% yield), which was purified by
from CHCl3-hexane (1:1 v/v; 57% isolated yield). The isolated product was crystallized from acetone to give single-crystal.Spectroscopic Data:
1H NMR δ (300 MHz, CDCl3); 3.69 (6H, s), 4.49 (4H, s), 7.20 (2H, d, J = 9.0 Hz), 7.33 (4H, d, J = 8.0 Hz), 7.63 (4H, d, J = 8.0 Hz), 7.96 (2H, d, J = 9.0 Hz) p.p.m..
13C NMR δ (100 MHz, CDCl3); 32.7, 56.5, 111.4, 121.4, 125.6, 128.7, 129.5, 129.8, 132.2, 138.6, 141.9, 156.5, 196.1 p.p.m..
IR (KBr); 1666 (C=O), 1606 (Ar), 1510 (Ar) cm-1. C28H22O4Br2; Calcd. C, 57.76; H, 3.81 found C, 57.81; H, 4.01. m.p. = 239.0–245.0 K
All H atoms were found in a difference map and were subsequently refined as riding atoms, with C—H = 0.95 (aromatic) and 0.98 (methyl) Å, and with Uĩso(H) = 1.2 Ueq(C).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell
PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C28H22Br2O4 | F(000) = 1168 |
Mr = 582.28 | Dx = 1.626 Mg m−3 |
Monoclinic, P21/n | Melting point = 239.0–245.0 K |
Hall symbol: -P 2yn | Cu Kα radiation, λ = 1.54187 Å |
a = 11.5948 (2) Å | Cell parameters from 30055 reflections |
b = 8.37239 (15) Å | θ = 3.6–68.2° |
c = 24.5352 (5) Å | µ = 4.60 mm−1 |
β = 92.617 (1)° | T = 193 K |
V = 2379.29 (8) Å3 | Block, yellow |
Z = 4 | 0.50 × 0.40 × 0.20 mm |
Rigaku R-AXIS RAPID diffractometer | 4319 independent reflections |
Radiation source: rotating anode | 3916 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
Detector resolution: 10.000 pixels mm-1 | θmax = 68.2°, θmin = 3.6° |
ω scans | h = −13→13 |
Absorption correction: numerical (NUMABS; Higashi, 1999) | k = −10→10 |
Tmin = 0.207, Tmax = 0.460 | l = −29→29 |
41450 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0277P)2 + 4.5808P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max < 0.001 |
4319 reflections | Δρmax = 0.85 e Å−3 |
310 parameters | Δρmin = −0.59 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00183 (10) |
C28H22Br2O4 | V = 2379.29 (8) Å3 |
Mr = 582.28 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 11.5948 (2) Å | µ = 4.60 mm−1 |
b = 8.37239 (15) Å | T = 193 K |
c = 24.5352 (5) Å | 0.50 × 0.40 × 0.20 mm |
β = 92.617 (1)° |
Rigaku R-AXIS RAPID diffractometer | 4319 independent reflections |
Absorption correction: numerical (NUMABS; Higashi, 1999) | 3916 reflections with I > 2σ(I) |
Tmin = 0.207, Tmax = 0.460 | Rint = 0.079 |
41450 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.85 e Å−3 |
4319 reflections | Δρmin = −0.59 e Å−3 |
310 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. |
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 | −0.15947 (4) | 0.20415 (5) | 0.241294 (16) | 0.04354 (16) | |
Br2 | −0.11445 (4) | 0.28738 (5) | −0.255555 (15) | 0.04200 (15) | |
O1 | 0.1773 (2) | 0.4762 (3) | 0.01077 (9) | 0.0310 (5) | |
O2 | 0.1901 (2) | 0.0544 (3) | 0.00410 (9) | 0.0317 (5) | |
O3 | 0.33170 (19) | 0.5296 (3) | 0.13097 (9) | 0.0331 (6) | |
O4 | 0.3673 (2) | 0.0170 (3) | −0.10273 (9) | 0.0352 (6) | |
C1 | 0.3426 (3) | 0.3654 (4) | 0.05473 (12) | 0.0229 (6) | |
C2 | 0.3998 (3) | 0.4487 (4) | 0.09594 (12) | 0.0268 (7) | |
C3 | 0.5212 (3) | 0.4562 (4) | 0.10035 (13) | 0.0300 (7) | |
H3 | 0.5592 | 0.5116 | 0.1298 | 0.036* | |
C4 | 0.5834 (3) | 0.3832 (4) | 0.06193 (13) | 0.0296 (7) | |
H4 | 0.6651 | 0.3932 | 0.0637 | 0.035* | |
C5 | 0.5291 (3) | 0.2925 (4) | 0.01916 (13) | 0.0262 (7) | |
C6 | 0.5961 (3) | 0.2128 (4) | −0.01911 (14) | 0.0301 (7) | |
H6 | 0.6779 | 0.2216 | −0.0163 | 0.036* | |
C7 | 0.5455 (3) | 0.1239 (4) | −0.05987 (14) | 0.0312 (7) | |
H7 | 0.5916 | 0.0719 | −0.0855 | 0.037* | |
C8 | 0.4242 (3) | 0.1090 (4) | −0.06393 (13) | 0.0277 (7) | |
C9 | 0.3552 (3) | 0.1836 (4) | −0.02723 (12) | 0.0234 (7) | |
C10 | 0.4066 (3) | 0.2799 (4) | 0.01571 (12) | 0.0230 (6) | |
C11 | 0.2132 (3) | 0.3889 (4) | 0.04739 (12) | 0.0234 (6) | |
C12 | 0.1329 (3) | 0.3064 (4) | 0.08379 (12) | 0.0230 (6) | |
C13 | 0.1743 (3) | 0.2117 (4) | 0.12720 (12) | 0.0256 (7) | |
H13 | 0.2551 | 0.1999 | 0.1342 | 0.031* | |
C14 | 0.0980 (3) | 0.1351 (4) | 0.15989 (13) | 0.0294 (7) | |
H14 | 0.1267 | 0.0730 | 0.1899 | 0.035* | |
C15 | −0.0205 (3) | 0.1477 (4) | 0.14942 (13) | 0.0280 (7) | |
C16 | −0.0608 (3) | 0.2401 (4) | 0.10524 (14) | 0.0310 (7) | |
H16 | −0.1416 | 0.2481 | 0.0972 | 0.037* | |
C17 | 0.0147 (3) | 0.3201 (4) | 0.07308 (13) | 0.0269 (7) | |
H17 | −0.0141 | 0.3844 | 0.0436 | 0.032* | |
C18 | 0.2281 (3) | 0.1422 (4) | −0.03013 (12) | 0.0244 (7) | |
C19 | 0.1506 (3) | 0.2140 (4) | −0.07415 (12) | 0.0247 (7) | |
C20 | 0.1954 (3) | 0.3069 (4) | −0.11521 (13) | 0.0264 (7) | |
H20 | 0.2764 | 0.3231 | −0.1161 | 0.032* | |
C21 | 0.1222 (3) | 0.3757 (4) | −0.15465 (13) | 0.0282 (7) | |
H21 | 0.1534 | 0.4372 | −0.1830 | 0.034* | |
C22 | 0.0038 (3) | 0.3556 (4) | −0.15305 (13) | 0.0269 (7) | |
C23 | −0.0412 (3) | 0.2637 (4) | −0.11166 (14) | 0.0303 (7) | |
H23 | −0.1223 | 0.2499 | −0.1103 | 0.036* | |
C24 | 0.0318 (3) | 0.1926 (4) | −0.07264 (13) | 0.0290 (7) | |
H24 | 0.0007 | 0.1290 | −0.0448 | 0.035* | |
C25 | 0.3876 (3) | 0.6214 (5) | 0.17364 (14) | 0.0388 (9) | |
H25A | 0.4311 | 0.5499 | 0.1986 | 0.047* | |
H25B | 0.3294 | 0.6790 | 0.1937 | 0.047* | |
H25C | 0.4404 | 0.6981 | 0.1579 | 0.047* | |
C26 | 0.4333 (3) | −0.0513 (5) | −0.14481 (14) | 0.0388 (9) | |
H26A | 0.4684 | 0.0343 | −0.1657 | 0.047* | |
H26B | 0.3825 | −0.1154 | −0.1692 | 0.047* | |
H26C | 0.4941 | −0.1195 | −0.1283 | 0.047* | |
C27 | −0.1034 (3) | 0.0618 (4) | 0.18381 (15) | 0.0362 (8) | |
H27A | −0.0648 | −0.0323 | 0.2009 | 0.043* | |
H27B | −0.1697 | 0.0235 | 0.1605 | 0.043* | |
C28 | −0.0739 (3) | 0.4356 (4) | −0.19505 (14) | 0.0346 (8) | |
H28A | −0.0348 | 0.5307 | −0.2095 | 0.041* | |
H28B | −0.1452 | 0.4717 | −0.1780 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0452 (3) | 0.0507 (3) | 0.0359 (2) | −0.00291 (18) | 0.01501 (18) | −0.00418 (17) |
Br2 | 0.0488 (3) | 0.0514 (3) | 0.0252 (2) | 0.00179 (18) | −0.00500 (16) | −0.00459 (16) |
O1 | 0.0332 (13) | 0.0350 (13) | 0.0247 (11) | 0.0049 (10) | −0.0006 (9) | 0.0078 (10) |
O2 | 0.0350 (13) | 0.0305 (12) | 0.0299 (12) | −0.0011 (10) | 0.0063 (10) | 0.0043 (10) |
O3 | 0.0292 (12) | 0.0422 (14) | 0.0282 (12) | −0.0060 (11) | 0.0036 (10) | −0.0113 (10) |
O4 | 0.0355 (13) | 0.0374 (14) | 0.0330 (13) | 0.0077 (11) | 0.0051 (10) | −0.0102 (10) |
C1 | 0.0228 (16) | 0.0245 (16) | 0.0212 (15) | −0.0007 (13) | 0.0016 (12) | 0.0044 (12) |
C2 | 0.0308 (17) | 0.0280 (16) | 0.0217 (15) | −0.0033 (14) | 0.0027 (13) | 0.0043 (13) |
C3 | 0.0293 (18) | 0.0342 (18) | 0.0260 (16) | −0.0056 (14) | −0.0037 (14) | 0.0040 (14) |
C4 | 0.0224 (16) | 0.0318 (18) | 0.0342 (18) | −0.0024 (14) | −0.0021 (14) | 0.0111 (14) |
C5 | 0.0260 (17) | 0.0268 (16) | 0.0260 (16) | 0.0040 (13) | 0.0017 (13) | 0.0100 (13) |
C6 | 0.0246 (17) | 0.0317 (18) | 0.0344 (18) | 0.0068 (14) | 0.0048 (14) | 0.0100 (14) |
C7 | 0.0321 (18) | 0.0313 (18) | 0.0310 (17) | 0.0094 (15) | 0.0091 (14) | 0.0083 (14) |
C8 | 0.0334 (18) | 0.0258 (16) | 0.0242 (16) | 0.0053 (14) | 0.0021 (13) | 0.0057 (13) |
C9 | 0.0255 (16) | 0.0217 (15) | 0.0231 (15) | 0.0039 (12) | 0.0025 (13) | 0.0052 (12) |
C10 | 0.0236 (16) | 0.0227 (15) | 0.0225 (15) | 0.0009 (12) | 0.0000 (12) | 0.0073 (12) |
C11 | 0.0271 (16) | 0.0233 (15) | 0.0197 (15) | 0.0028 (13) | −0.0014 (12) | −0.0040 (12) |
C12 | 0.0258 (16) | 0.0225 (15) | 0.0208 (15) | 0.0015 (12) | 0.0028 (12) | −0.0040 (12) |
C13 | 0.0227 (16) | 0.0304 (17) | 0.0237 (16) | 0.0000 (13) | −0.0009 (13) | −0.0007 (13) |
C14 | 0.0346 (19) | 0.0290 (17) | 0.0245 (16) | −0.0020 (14) | 0.0003 (14) | 0.0006 (13) |
C15 | 0.0312 (18) | 0.0248 (16) | 0.0287 (17) | −0.0027 (14) | 0.0078 (14) | −0.0078 (13) |
C16 | 0.0235 (17) | 0.0353 (18) | 0.0343 (18) | 0.0014 (14) | 0.0023 (14) | −0.0061 (14) |
C17 | 0.0247 (17) | 0.0308 (17) | 0.0252 (16) | 0.0026 (13) | −0.0002 (13) | −0.0016 (13) |
C18 | 0.0292 (17) | 0.0212 (15) | 0.0230 (15) | 0.0005 (13) | 0.0031 (13) | −0.0034 (12) |
C19 | 0.0292 (17) | 0.0242 (16) | 0.0208 (15) | 0.0007 (13) | 0.0007 (13) | −0.0050 (12) |
C20 | 0.0246 (17) | 0.0265 (16) | 0.0282 (16) | 0.0004 (13) | 0.0027 (13) | −0.0023 (13) |
C21 | 0.0351 (19) | 0.0256 (16) | 0.0241 (16) | −0.0001 (14) | 0.0018 (13) | −0.0017 (13) |
C22 | 0.0304 (17) | 0.0236 (16) | 0.0264 (16) | 0.0021 (13) | −0.0012 (13) | −0.0077 (13) |
C23 | 0.0236 (17) | 0.0351 (19) | 0.0322 (18) | 0.0005 (14) | 0.0021 (14) | −0.0067 (14) |
C24 | 0.0294 (18) | 0.0326 (18) | 0.0252 (16) | −0.0026 (14) | 0.0040 (14) | −0.0028 (13) |
C25 | 0.044 (2) | 0.047 (2) | 0.0257 (17) | −0.0160 (18) | 0.0029 (15) | −0.0096 (16) |
C26 | 0.052 (2) | 0.0338 (19) | 0.0317 (19) | 0.0043 (17) | 0.0130 (16) | −0.0044 (15) |
C27 | 0.038 (2) | 0.0310 (18) | 0.041 (2) | −0.0066 (15) | 0.0120 (16) | −0.0063 (15) |
C28 | 0.0372 (19) | 0.0322 (18) | 0.0336 (18) | 0.0039 (15) | −0.0053 (15) | −0.0060 (15) |
Br1—C27 | 1.979 (3) | C14—C15 | 1.390 (5) |
Br2—C28 | 1.975 (3) | C14—H14 | 0.9500 |
O1—C11 | 1.216 (4) | C15—C16 | 1.395 (5) |
O2—C18 | 1.214 (4) | C15—C27 | 1.492 (5) |
O3—C2 | 1.372 (4) | C16—C17 | 1.379 (5) |
O3—C25 | 1.430 (4) | C16—H16 | 0.9500 |
O4—C8 | 1.370 (4) | C17—H17 | 0.9500 |
O4—C26 | 1.432 (4) | C18—C19 | 1.499 (4) |
C1—C2 | 1.374 (4) | C19—C20 | 1.392 (5) |
C1—C10 | 1.430 (4) | C19—C24 | 1.392 (5) |
C1—C11 | 1.516 (4) | C20—C21 | 1.383 (4) |
C2—C3 | 1.409 (5) | C20—H20 | 0.9500 |
C3—C4 | 1.357 (5) | C21—C22 | 1.386 (5) |
C3—H3 | 0.9500 | C21—H21 | 0.9500 |
C4—C5 | 1.419 (5) | C22—C23 | 1.395 (5) |
C4—H4 | 0.9500 | C22—C28 | 1.496 (4) |
C5—C6 | 1.413 (5) | C23—C24 | 1.383 (5) |
C5—C10 | 1.423 (4) | C23—H23 | 0.9500 |
C6—C7 | 1.358 (5) | C24—H24 | 0.9500 |
C6—H6 | 0.9500 | C25—H25A | 0.9800 |
C7—C8 | 1.411 (5) | C25—H25B | 0.9800 |
C7—H7 | 0.9500 | C25—H25C | 0.9800 |
C8—C9 | 1.380 (4) | C26—H26A | 0.9800 |
C9—C10 | 1.434 (4) | C26—H26B | 0.9800 |
C9—C18 | 1.513 (4) | C26—H26C | 0.9800 |
C11—C12 | 1.489 (4) | C27—H27A | 0.9900 |
C12—C17 | 1.388 (4) | C27—H27B | 0.9900 |
C12—C13 | 1.396 (4) | C28—H28A | 0.9900 |
C13—C14 | 1.379 (5) | C28—H28B | 0.9900 |
C13—H13 | 0.9500 | ||
C2—O3—C25 | 118.0 (3) | C15—C16—H16 | 119.5 |
C8—O4—C26 | 118.0 (3) | C16—C17—C12 | 119.9 (3) |
C2—C1—C10 | 119.9 (3) | C16—C17—H17 | 120.0 |
C2—C1—C11 | 117.6 (3) | C12—C17—H17 | 120.0 |
C10—C1—C11 | 121.8 (3) | O2—C18—C19 | 121.1 (3) |
O3—C2—C1 | 116.1 (3) | O2—C18—C9 | 119.3 (3) |
O3—C2—C3 | 122.1 (3) | C19—C18—C9 | 119.5 (3) |
C1—C2—C3 | 121.8 (3) | C20—C19—C24 | 119.6 (3) |
C4—C3—C2 | 119.1 (3) | C20—C19—C18 | 121.0 (3) |
C4—C3—H3 | 120.4 | C24—C19—C18 | 119.4 (3) |
C2—C3—H3 | 120.4 | C21—C20—C19 | 120.1 (3) |
C3—C4—C5 | 121.6 (3) | C21—C20—H20 | 119.9 |
C3—C4—H4 | 119.2 | C19—C20—H20 | 119.9 |
C5—C4—H4 | 119.2 | C20—C21—C22 | 120.4 (3) |
C6—C5—C4 | 120.4 (3) | C20—C21—H21 | 119.8 |
C6—C5—C10 | 120.2 (3) | C22—C21—H21 | 119.8 |
C4—C5—C10 | 119.4 (3) | C21—C22—C23 | 119.5 (3) |
C7—C6—C5 | 121.1 (3) | C21—C22—C28 | 119.5 (3) |
C7—C6—H6 | 119.5 | C23—C22—C28 | 121.0 (3) |
C5—C6—H6 | 119.5 | C24—C23—C22 | 120.3 (3) |
C6—C7—C8 | 119.8 (3) | C24—C23—H23 | 119.9 |
C6—C7—H7 | 120.1 | C22—C23—H23 | 119.9 |
C8—C7—H7 | 120.1 | C23—C24—C19 | 120.1 (3) |
O4—C8—C9 | 115.7 (3) | C23—C24—H24 | 120.0 |
O4—C8—C7 | 123.0 (3) | C19—C24—H24 | 120.0 |
C9—C8—C7 | 121.3 (3) | O3—C25—H25A | 109.5 |
C8—C9—C10 | 120.0 (3) | O3—C25—H25B | 109.5 |
C8—C9—C18 | 117.2 (3) | H25A—C25—H25B | 109.5 |
C10—C9—C18 | 122.3 (3) | O3—C25—H25C | 109.5 |
C5—C10—C1 | 118.1 (3) | H25A—C25—H25C | 109.5 |
C5—C10—C9 | 117.7 (3) | H25B—C25—H25C | 109.5 |
C1—C10—C9 | 124.2 (3) | O4—C26—H26A | 109.5 |
O1—C11—C12 | 121.3 (3) | O4—C26—H26B | 109.5 |
O1—C11—C1 | 118.0 (3) | H26A—C26—H26B | 109.5 |
C12—C11—C1 | 120.7 (3) | O4—C26—H26C | 109.5 |
C17—C12—C13 | 119.6 (3) | H26A—C26—H26C | 109.5 |
C17—C12—C11 | 119.1 (3) | H26B—C26—H26C | 109.5 |
C13—C12—C11 | 121.3 (3) | C15—C27—Br1 | 110.7 (2) |
C14—C13—C12 | 120.0 (3) | C15—C27—H27A | 109.5 |
C14—C13—H13 | 120.0 | Br1—C27—H27A | 109.5 |
C12—C13—H13 | 120.0 | C15—C27—H27B | 109.5 |
C13—C14—C15 | 120.8 (3) | Br1—C27—H27B | 109.5 |
C13—C14—H14 | 119.6 | H27A—C27—H27B | 108.1 |
C15—C14—H14 | 119.6 | C22—C28—Br2 | 110.6 (2) |
C14—C15—C16 | 118.6 (3) | C22—C28—H28A | 109.5 |
C14—C15—C27 | 121.0 (3) | Br2—C28—H28A | 109.5 |
C16—C15—C27 | 120.3 (3) | C22—C28—H28B | 109.5 |
C17—C16—C15 | 121.0 (3) | Br2—C28—H28B | 109.5 |
C17—C16—H16 | 119.5 | H28A—C28—H28B | 108.1 |
C25—O3—C2—C1 | −178.4 (3) | C10—C1—C11—C12 | 110.7 (3) |
C25—O3—C2—C3 | −1.2 (5) | O1—C11—C12—C17 | 4.9 (4) |
C10—C1—C2—O3 | 178.9 (3) | C1—C11—C12—C17 | −174.7 (3) |
C11—C1—C2—O3 | 8.1 (4) | O1—C11—C12—C13 | −177.3 (3) |
C10—C1—C2—C3 | 1.6 (5) | C1—C11—C12—C13 | 3.1 (4) |
C11—C1—C2—C3 | −169.1 (3) | C17—C12—C13—C14 | −1.4 (5) |
O3—C2—C3—C4 | −175.0 (3) | C11—C12—C13—C14 | −179.2 (3) |
C1—C2—C3—C4 | 2.1 (5) | C12—C13—C14—C15 | 1.6 (5) |
C2—C3—C4—C5 | −3.5 (5) | C13—C14—C15—C16 | −0.3 (5) |
C3—C4—C5—C6 | −177.6 (3) | C13—C14—C15—C27 | 178.4 (3) |
C3—C4—C5—C10 | 1.2 (5) | C14—C15—C16—C17 | −1.2 (5) |
C4—C5—C6—C7 | 179.2 (3) | C27—C15—C16—C17 | −180.0 (3) |
C10—C5—C6—C7 | 0.4 (5) | C15—C16—C17—C12 | 1.4 (5) |
C5—C6—C7—C8 | −0.7 (5) | C13—C12—C17—C16 | −0.1 (5) |
C26—O4—C8—C9 | 174.4 (3) | C11—C12—C17—C16 | 177.8 (3) |
C26—O4—C8—C7 | −7.7 (4) | C8—C9—C18—O2 | 104.4 (3) |
C6—C7—C8—O4 | −177.7 (3) | C10—C9—C18—O2 | −67.8 (4) |
C6—C7—C8—C9 | 0.1 (5) | C8—C9—C18—C19 | −77.4 (4) |
O4—C8—C9—C10 | 178.7 (3) | C10—C9—C18—C19 | 110.3 (3) |
C7—C8—C9—C10 | 0.7 (5) | O2—C18—C19—C20 | −176.1 (3) |
O4—C8—C9—C18 | 6.3 (4) | C9—C18—C19—C20 | 5.7 (4) |
C7—C8—C9—C18 | −171.7 (3) | O2—C18—C19—C24 | 6.4 (5) |
C6—C5—C10—C1 | −178.7 (3) | C9—C18—C19—C24 | −171.7 (3) |
C4—C5—C10—C1 | 2.4 (4) | C24—C19—C20—C21 | −0.8 (5) |
C6—C5—C10—C9 | 0.5 (4) | C18—C19—C20—C21 | −178.3 (3) |
C4—C5—C10—C9 | −178.4 (3) | C19—C20—C21—C22 | 1.3 (5) |
C2—C1—C10—C5 | −3.8 (4) | C20—C21—C22—C23 | −0.8 (5) |
C11—C1—C10—C5 | 166.6 (3) | C20—C21—C22—C28 | 178.0 (3) |
C2—C1—C10—C9 | 177.0 (3) | C21—C22—C23—C24 | −0.3 (5) |
C11—C1—C10—C9 | −12.6 (5) | C28—C22—C23—C24 | −179.0 (3) |
C8—C9—C10—C5 | −1.0 (4) | C22—C23—C24—C19 | 0.8 (5) |
C18—C9—C10—C5 | 171.0 (3) | C20—C19—C24—C23 | −0.2 (5) |
C8—C9—C10—C1 | 178.2 (3) | C18—C19—C24—C23 | 177.3 (3) |
C18—C9—C10—C1 | −9.8 (5) | C14—C15—C27—Br1 | 96.1 (3) |
C2—C1—C11—O1 | 101.7 (3) | C16—C15—C27—Br1 | −85.1 (3) |
C10—C1—C11—O1 | −68.9 (4) | C21—C22—C28—Br2 | 95.9 (3) |
C2—C1—C11—C12 | −78.7 (4) | C23—C22—C28—Br2 | −85.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17···O1i | 0.95 | 2.55 | 3.417 (4) | 152 |
C28—H28B···O3i | 0.99 | 2.50 | 3.453 (4) | 162 |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C28H22Br2O4 |
Mr | 582.28 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 193 |
a, b, c (Å) | 11.5948 (2), 8.37239 (15), 24.5352 (5) |
β (°) | 92.617 (1) |
V (Å3) | 2379.29 (8) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 4.60 |
Crystal size (mm) | 0.50 × 0.40 × 0.20 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Numerical (NUMABS; Higashi, 1999) |
Tmin, Tmax | 0.207, 0.460 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 41450, 4319, 3916 |
Rint | 0.079 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.103, 1.14 |
No. of reflections | 4319 |
No. of parameters | 310 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.85, −0.59 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996).
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17···O1i | 0.95 | 2.55 | 3.417 (4) | 152 |
C28—H28B···O3i | 0.99 | 2.50 | 3.453 (4) | 162 |
Symmetry code: (i) −x, −y+1, −z. |
Acknowledgements
The authors would express their gratitude to Master Yuichi Kato and Mr Toyokazu Muto, Department of Organic and Polymer Materials Chemistry, Graduate School, Tokyo University of Agriculture & Technology, and Professor Keiichi Noguchi, Instrumentation Analysis Center, Tokyo University of Agriculture & Technology, for their technical advice.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
In the course of our study on selective electrophilic aromatic aroylation of the naphthalene core, 1,8-diaroylnaphthalene compounds have proved to be formed regioselectively by the aid of a suitable acidic mediator (Okamoto & Yonezawa, 2009). Recently, we reported the X-ray crystal structures of 1,8-diaroylated 2,7-dimethoxynaphthalene derivatives such as 1,8-bis(4-chlorobenzoyl)-2,7-dimethoxynaphthalene (Nakaema et al., 2007), 1,8-dibenzoyl-2,7-dimethoxynaphthalene (Nakaema et al., 2008), bis(4-bromophenyl)(2,7-dimethoxynaphthalene-1,8-diyl)dimethanone (Watanabe, Nakaema et al., 2010), (2,7-dimethoxynaphthalene-1,8-diyl)bis(4-fluorophenyl)dimethanone [1,8-bis(4-fluorobenzoyl)-2,7-dimethoxynaphthalene] (Watanabe, Nagasawa et al., 2010), and 1,8-bis(4-methylbenzoyl)-2,7-dimethoxynaphthalene (Muto et al., 2010). The aroyl groups in these compounds are attached to the naphthalene rings in an almost parallel fashion and oriented in opposite direction. As a part of our ongoing studies on the molecular structures of homologous aroylated 2,7-dimethoxynaphthalene molecules, the X-ray crystal structure of the title compound, bis(4-bromomethylbenzoylated) 2,7-dimethoxynaphthalene, is discussed in this article.
The molecular structure of the title compound is displayed in Fig 1. The two 4-bromomethylbenzoyl groups are twisted away from the attaching naphthalene ring and situated in anti orientation. The dihedral angle between the planes of the benzene rings is 2.94 (16)°. On the other hand, the dihedral angles of the benzene rings with the naphthalene ring system are 70.98 (13) and 72.89 (13)°, respectively. The torsion angles between the carbonyl groups and the naphthalene ring [C10—C1—C11—O1 = -68.9 (4)° and C10—C9—C18—O2 = -67.8 (4)°] are larger than those between the carbonyl groups and the benzene rings [O1—C11—C12—C13 = -177.3 (3)° and O2—C18—C19—C20 = -176.1 (3)°].
In the crystal packing, C—H···O hydrogen bonds between the oxygen atoms of the carbonyl groups and the hydrogen atoms of the benzene rings and between the oxygen atoms of the methoxy groups and the hydrogen atoms of the bromomethyl groups are also observed (Table 1), resulting in the formation of supramolecular dimeric units (Fig. 2) having crystallographic inversion centre.