organic compounds
[2,7-Dibutoxy-8-(4-fluorobenzoyl)naphthalen-1-yl](4-fluorophenyl)methanone
aDepartment of Organic and Polymer Materials Chemistry, Tokyo University of Agriculture & Technology (TUAT), Koganei, Tokyo 184.8588, Japan
*Correspondence e-mail: aokamoto@cc.tuat.ac.jp
In the title compound, C32H30F2O4, the benzene rings of the benzoyl groups make dihedral angles of 74.55 (6) and 74.39 (7)° with the naphthalene ring system. In the crystal, intra- and intermolecular C—H⋯π interactions are observed between the butoxy group and the aromatic rings. There are also C—H⋯F hydrogen bonds present that link the molecules into chains propagating along [010].
Related literature
For the electrophilic aromatic aroylation of 2,7-dimethoxynaphthalene, see: Okamoto & Yonezawa (2009); Okamoto et al. (2011, 2012). For the crystal structures of similar compounds, see: Sasagawa et al. (2011); Watanabe 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: PROCESS-AUTO; program(s) used to solve structure: Il Milione (Burla et al., 2007); 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/S1600536812044923/su2520sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812044923/su2520Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812044923/su2520Isup3.cml
The title compound was prepared by treating a mixture of 2,7-dibutoxynaphthalene (3.0 mmol, 817 mg) and 4-fluorobenzoic acid (6.6 mmol, 924 mg) with a phosphorus pentoxide—methanesulfonic acid mixture (P2O5—MsOH [1/10 w/w] 13.2 ml). After the reaction mixture had been stirred at 333 K for 1 h, the mixture was poured into ice-cold water and extracted with CHCl3. The organic layer thus obtained was dried over anhydrous MgSO4. The solvent was removed under reduced pressure to give a cake. The crude product was purified by recrystallization from CHCl3– hexane (v/v = 1:2) [39% isolated yield; M.p. 364.5–366 K]. HRMS (m/z): [M + H]+ calcd. for C32H31F2O4, 517.2190; found 517.2163. Block-like colourless crystals of the title compound, suitable for X-ray
were obtained by crystallization from hexane. Spectroscopic data for the title compound are available in the archived CIF.All the H atoms were included in calculated positions and treated as riding on their parent atoms: C—H = 0.95 (aromatic ), 0.98 (methyl), 0.99 (methylene) Å, with Uiso(H) = 1.2Ueq(C). The positions of methyl H atoms were rotationally optimized.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell
PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: Il Milione (Burla et al., 2007); 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).C32H30F2O4 | F(000) = 1088 |
Mr = 516.56 | Dx = 1.261 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54187 Å |
Hall symbol: -P 2ybc | Cell parameters from 45409 reflections |
a = 8.26012 (15) Å | θ = 3.5–68.2° |
b = 20.2309 (4) Å | µ = 0.75 mm−1 |
c = 16.5268 (3) Å | T = 193 K |
β = 99.918 (1)° | Block, colourless |
V = 2720.51 (9) Å3 | 0.60 × 0.50 × 0.50 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 4971 independent reflections |
Radiation source: rotating anode | 4715 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 10.000 pixels mm-1 | θmax = 68.2°, θmin = 3.5° |
ω scans | h = −9→9 |
Absorption correction: numerical (NUMABS; Higashi, 1999) | k = −24→24 |
Tmin = 0.661, Tmax = 0.705 | l = −19→19 |
50395 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)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0573P)2 + 1.0814P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
4971 reflections | Δρmax = 0.35 e Å−3 |
346 parameters | Δρmin = −0.41 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: 0.0198 (6) |
C32H30F2O4 | V = 2720.51 (9) Å3 |
Mr = 516.56 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 8.26012 (15) Å | µ = 0.75 mm−1 |
b = 20.2309 (4) Å | T = 193 K |
c = 16.5268 (3) Å | 0.60 × 0.50 × 0.50 mm |
β = 99.918 (1)° |
Rigaku R-AXIS RAPID diffractometer | 4971 independent reflections |
Absorption correction: numerical (NUMABS; Higashi, 1999) | 4715 reflections with I > 2σ(I) |
Tmin = 0.661, Tmax = 0.705 | Rint = 0.047 |
50395 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.35 e Å−3 |
4971 reflections | Δρmin = −0.41 e Å−3 |
346 parameters |
Experimental. Spectroscopic data for the title compound: 1HNMR δ (300 MHz, CDCl3): 0.68 (6H, t, J=7.5 Hz), 0.90–1.02 (4H, m), 1.27–1.36 (4H, m) 3.89 (4H, t, J=6.1 Hz), 7.04 (4H, t, J=8.5 Hz), 7.15 (2H, d, J=8.9 Hz), 7.75 (4H, dd, J=8.5, 5.1 Hz), 7.91 (2H, d, J=8.9 Hz) p.p.m. 13CNMR δ (75 MHz, CDCl3): 13.49, 18.63, 30.93, 68.55, 111.63, 114.93 (d, 2JC—F=21.6 Hz), 120.78, 125.28, 130.33, 131.49 (d, 3JC—F=7.9 Hz), 132.23, 135.68(d, 4JC—F=2.8 Hz), 155.94, 165.45(d, 1JC—F=253.5 Hz), 196.16 p.p.m. IR (KBr): 1659 (C═O), 1595, 1508, 1466 (Ar, naphthalene), 1236 (═C—O—C) cm-1. |
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 | ||
F1 | 1.2676 (2) | 0.02657 (7) | 0.89453 (9) | 0.1074 (6) | |
F2 | 0.04618 (12) | −0.02158 (5) | 0.58323 (6) | 0.0579 (3) | |
O1 | 0.56247 (13) | 0.14733 (5) | 0.77614 (7) | 0.0455 (3) | |
O2 | 0.72484 (11) | 0.12311 (5) | 0.61173 (6) | 0.0383 (3) | |
O3 | 0.84151 (15) | 0.25811 (5) | 0.87922 (6) | 0.0486 (3) | |
O4 | 0.44905 (13) | 0.20244 (5) | 0.46369 (6) | 0.0405 (3) | |
C1 | 0.71284 (15) | 0.24026 (6) | 0.74515 (8) | 0.0313 (3) | |
C2 | 0.78418 (17) | 0.28485 (7) | 0.80412 (9) | 0.0353 (3) | |
C3 | 0.79004 (17) | 0.35302 (7) | 0.78743 (9) | 0.0381 (3) | |
H3 | 0.8429 | 0.3827 | 0.8281 | 0.046* | |
C4 | 0.71875 (17) | 0.37570 (7) | 0.71201 (9) | 0.0376 (3) | |
H4 | 0.7208 | 0.4218 | 0.7010 | 0.045* | |
C5 | 0.56894 (17) | 0.35703 (7) | 0.57188 (10) | 0.0392 (3) | |
H5 | 0.5684 | 0.4033 | 0.5624 | 0.047* | |
C6 | 0.49959 (18) | 0.31636 (7) | 0.51018 (9) | 0.0393 (3) | |
H6 | 0.4501 | 0.3340 | 0.4586 | 0.047* | |
C7 | 0.50210 (16) | 0.24734 (7) | 0.52385 (8) | 0.0335 (3) | |
C8 | 0.56831 (15) | 0.22084 (6) | 0.59952 (8) | 0.0301 (3) | |
C9 | 0.64011 (15) | 0.26306 (6) | 0.66526 (8) | 0.0298 (3) | |
C10 | 0.64187 (16) | 0.33263 (7) | 0.64976 (9) | 0.0338 (3) | |
C11 | 0.69783 (18) | 0.17029 (7) | 0.77425 (8) | 0.0347 (3) | |
C12 | 0.8510 (2) | 0.13180 (7) | 0.80393 (9) | 0.0406 (4) | |
C13 | 0.8421 (3) | 0.07733 (8) | 0.85437 (11) | 0.0577 (5) | |
H13 | 0.7398 | 0.0643 | 0.8682 | 0.069* | |
C14 | 0.9857 (4) | 0.04188 (9) | 0.88456 (13) | 0.0755 (7) | |
H14 | 0.9821 | 0.0048 | 0.9194 | 0.091* | |
C15 | 1.1306 (3) | 0.06148 (10) | 0.86313 (13) | 0.0699 (6) | |
C16 | 1.1431 (2) | 0.11352 (10) | 0.81259 (12) | 0.0608 (5) | |
H16 | 1.2455 | 0.1251 | 0.7977 | 0.073* | |
C17 | 1.0016 (2) | 0.14922 (8) | 0.78338 (10) | 0.0462 (4) | |
H17 | 1.0078 | 0.1862 | 0.7487 | 0.055* | |
C18 | 0.58717 (16) | 0.14675 (6) | 0.60404 (8) | 0.0302 (3) | |
C19 | 0.43961 (16) | 0.10364 (6) | 0.59768 (8) | 0.0314 (3) | |
C20 | 0.45880 (19) | 0.03641 (7) | 0.58633 (10) | 0.0414 (3) | |
H20 | 0.5643 | 0.0193 | 0.5825 | 0.050* | |
C21 | 0.3262 (2) | −0.00605 (8) | 0.58051 (11) | 0.0492 (4) | |
H21 | 0.3386 | −0.0520 | 0.5717 | 0.059* | |
C22 | 0.17610 (19) | 0.02009 (8) | 0.58782 (9) | 0.0419 (4) | |
C23 | 0.15121 (18) | 0.08624 (8) | 0.59960 (9) | 0.0413 (3) | |
H23 | 0.0456 | 0.1027 | 0.6045 | 0.050* | |
C24 | 0.28524 (17) | 0.12828 (7) | 0.60418 (9) | 0.0369 (3) | |
H24 | 0.2714 | 0.1743 | 0.6118 | 0.044* | |
C25 | 0.88713 (18) | 0.29933 (7) | 0.94971 (9) | 0.0382 (3) | |
H25A | 0.7952 | 0.3289 | 0.9569 | 0.046* | |
H25B | 0.9836 | 0.3268 | 0.9438 | 0.046* | |
C26 | 0.92802 (18) | 0.25342 (8) | 1.02206 (9) | 0.0398 (3) | |
H26A | 0.8301 | 0.2261 | 1.0257 | 0.048* | |
H26B | 0.9522 | 0.2803 | 1.0728 | 0.048* | |
C27 | 1.07163 (19) | 0.20804 (9) | 1.01883 (10) | 0.0479 (4) | |
H27A | 1.1707 | 0.2349 | 1.0162 | 0.057* | |
H27B | 1.0486 | 0.1810 | 0.9682 | 0.057* | |
C28 | 1.1057 (3) | 0.16282 (13) | 1.09237 (14) | 0.0802 (7) | |
H28A | 1.0070 | 0.1369 | 1.0961 | 0.096* | |
H28B | 1.1359 | 0.1893 | 1.1424 | 0.096* | |
H28C | 1.1963 | 0.1329 | 1.0864 | 0.096* | |
C29 | 0.3849 (2) | 0.22518 (8) | 0.38231 (9) | 0.0450 (4) | |
H29A | 0.4614 | 0.2573 | 0.3640 | 0.054* | |
H29B | 0.2775 | 0.2471 | 0.3812 | 0.054* | |
C30 | 0.3653 (2) | 0.16535 (9) | 0.32649 (10) | 0.0513 (4) | |
H30A | 0.3280 | 0.1805 | 0.2693 | 0.062* | |
H30B | 0.4743 | 0.1444 | 0.3288 | 0.062* | |
C31 | 0.2476 (2) | 0.11429 (10) | 0.34659 (12) | 0.0576 (5) | |
H31A | 0.1405 | 0.1356 | 0.3485 | 0.069* | |
H31B | 0.2895 | 0.0961 | 0.4018 | 0.069* | |
C32 | 0.2216 (3) | 0.05793 (10) | 0.28513 (12) | 0.0640 (5) | |
H32A | 0.3284 | 0.0404 | 0.2773 | 0.077* | |
H32B | 0.1616 | 0.0742 | 0.2325 | 0.077* | |
H32C | 0.1579 | 0.0228 | 0.3059 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.1195 (12) | 0.0818 (9) | 0.0989 (10) | 0.0636 (9) | −0.0436 (9) | −0.0190 (8) |
F2 | 0.0509 (6) | 0.0487 (5) | 0.0696 (7) | −0.0224 (4) | −0.0023 (5) | 0.0128 (5) |
O1 | 0.0498 (6) | 0.0446 (6) | 0.0423 (6) | −0.0115 (5) | 0.0087 (5) | −0.0009 (5) |
O2 | 0.0314 (5) | 0.0375 (5) | 0.0448 (6) | 0.0028 (4) | 0.0034 (4) | −0.0010 (4) |
O3 | 0.0672 (7) | 0.0353 (5) | 0.0363 (6) | 0.0048 (5) | −0.0103 (5) | −0.0082 (4) |
O4 | 0.0463 (6) | 0.0388 (5) | 0.0322 (5) | −0.0041 (4) | −0.0056 (4) | 0.0028 (4) |
C1 | 0.0283 (6) | 0.0300 (7) | 0.0351 (7) | 0.0008 (5) | 0.0040 (5) | −0.0022 (5) |
C2 | 0.0325 (7) | 0.0353 (7) | 0.0367 (7) | 0.0024 (5) | 0.0017 (6) | −0.0040 (6) |
C3 | 0.0348 (7) | 0.0335 (7) | 0.0450 (8) | −0.0030 (6) | 0.0040 (6) | −0.0093 (6) |
C4 | 0.0354 (7) | 0.0281 (7) | 0.0494 (8) | −0.0024 (5) | 0.0082 (6) | −0.0016 (6) |
C5 | 0.0373 (7) | 0.0292 (7) | 0.0501 (9) | −0.0004 (6) | 0.0048 (6) | 0.0070 (6) |
C6 | 0.0354 (7) | 0.0390 (8) | 0.0410 (8) | −0.0004 (6) | −0.0008 (6) | 0.0101 (6) |
C7 | 0.0267 (6) | 0.0365 (7) | 0.0360 (7) | −0.0029 (5) | 0.0016 (5) | 0.0016 (6) |
C8 | 0.0250 (6) | 0.0307 (7) | 0.0343 (7) | −0.0020 (5) | 0.0043 (5) | 0.0012 (5) |
C9 | 0.0238 (6) | 0.0306 (7) | 0.0350 (7) | −0.0009 (5) | 0.0054 (5) | −0.0002 (5) |
C10 | 0.0288 (6) | 0.0309 (7) | 0.0421 (8) | −0.0007 (5) | 0.0073 (6) | 0.0008 (6) |
C11 | 0.0439 (8) | 0.0330 (7) | 0.0262 (6) | −0.0036 (6) | 0.0030 (5) | −0.0040 (5) |
C12 | 0.0572 (9) | 0.0293 (7) | 0.0307 (7) | 0.0032 (6) | −0.0050 (6) | −0.0053 (6) |
C13 | 0.0858 (13) | 0.0362 (8) | 0.0443 (9) | −0.0033 (8) | −0.0083 (9) | 0.0017 (7) |
C14 | 0.124 (2) | 0.0338 (9) | 0.0534 (11) | 0.0130 (11) | −0.0264 (12) | 0.0031 (8) |
C15 | 0.0836 (15) | 0.0515 (11) | 0.0615 (12) | 0.0295 (11) | −0.0238 (11) | −0.0164 (9) |
C16 | 0.0592 (11) | 0.0634 (12) | 0.0534 (10) | 0.0226 (9) | −0.0078 (8) | −0.0186 (9) |
C17 | 0.0502 (9) | 0.0459 (9) | 0.0392 (8) | 0.0112 (7) | −0.0014 (7) | −0.0071 (7) |
C18 | 0.0312 (7) | 0.0328 (7) | 0.0253 (6) | 0.0001 (5) | 0.0012 (5) | −0.0007 (5) |
C19 | 0.0347 (7) | 0.0310 (7) | 0.0268 (6) | −0.0023 (5) | 0.0002 (5) | 0.0008 (5) |
C20 | 0.0403 (8) | 0.0338 (7) | 0.0491 (9) | 0.0004 (6) | 0.0046 (6) | −0.0003 (6) |
C21 | 0.0551 (10) | 0.0290 (7) | 0.0616 (10) | −0.0069 (7) | 0.0044 (8) | −0.0001 (7) |
C22 | 0.0418 (8) | 0.0389 (8) | 0.0416 (8) | −0.0143 (6) | −0.0025 (6) | 0.0077 (6) |
C23 | 0.0332 (7) | 0.0435 (8) | 0.0455 (8) | −0.0037 (6) | 0.0025 (6) | 0.0066 (6) |
C24 | 0.0355 (7) | 0.0315 (7) | 0.0422 (8) | −0.0007 (6) | 0.0029 (6) | 0.0014 (6) |
C25 | 0.0406 (8) | 0.0385 (8) | 0.0357 (7) | −0.0051 (6) | 0.0067 (6) | −0.0106 (6) |
C26 | 0.0393 (8) | 0.0463 (8) | 0.0343 (7) | −0.0035 (6) | 0.0076 (6) | −0.0082 (6) |
C27 | 0.0377 (8) | 0.0635 (10) | 0.0422 (8) | 0.0031 (7) | 0.0059 (6) | 0.0009 (7) |
C28 | 0.0728 (14) | 0.1043 (18) | 0.0640 (13) | 0.0279 (13) | 0.0127 (10) | 0.0292 (12) |
C29 | 0.0511 (9) | 0.0500 (9) | 0.0313 (7) | −0.0034 (7) | 0.0001 (6) | 0.0089 (6) |
C30 | 0.0527 (9) | 0.0664 (11) | 0.0341 (8) | −0.0017 (8) | 0.0054 (7) | 0.0011 (7) |
C31 | 0.0510 (10) | 0.0684 (12) | 0.0541 (10) | −0.0076 (8) | 0.0113 (8) | −0.0129 (9) |
C32 | 0.0810 (13) | 0.0589 (11) | 0.0475 (10) | −0.0034 (10) | −0.0018 (9) | −0.0066 (8) |
F1—C15 | 1.359 (2) | C18—C19 | 1.4876 (18) |
F2—C22 | 1.3566 (16) | C19—C20 | 1.386 (2) |
O1—C11 | 1.2160 (18) | C19—C24 | 1.3904 (19) |
O2—C18 | 1.2199 (16) | C20—C21 | 1.382 (2) |
O3—C2 | 1.3620 (17) | C20—H20 | 0.9500 |
O3—C25 | 1.4294 (16) | C21—C22 | 1.372 (2) |
O4—C7 | 1.3622 (17) | C21—H21 | 0.9500 |
O4—C29 | 1.4337 (17) | C22—C23 | 1.373 (2) |
C1—C2 | 1.3830 (19) | C23—C24 | 1.388 (2) |
C1—C9 | 1.4297 (19) | C23—H23 | 0.9500 |
C1—C11 | 1.5070 (19) | C24—H24 | 0.9500 |
C2—C3 | 1.409 (2) | C25—C26 | 1.506 (2) |
C3—C4 | 1.363 (2) | C25—H25A | 0.9900 |
C3—H3 | 0.9500 | C25—H25B | 0.9900 |
C4—C10 | 1.413 (2) | C26—C27 | 1.508 (2) |
C4—H4 | 0.9500 | C26—H26A | 0.9900 |
C5—C6 | 1.358 (2) | C26—H26B | 0.9900 |
C5—C10 | 1.413 (2) | C27—C28 | 1.508 (3) |
C5—H5 | 0.9500 | C27—H27A | 0.9900 |
C6—C7 | 1.414 (2) | C27—H27B | 0.9900 |
C6—H6 | 0.9500 | C28—H28A | 0.9800 |
C7—C8 | 1.3839 (19) | C28—H28B | 0.9800 |
C8—C9 | 1.4281 (18) | C28—H28C | 0.9800 |
C8—C18 | 1.5076 (18) | C29—C30 | 1.514 (2) |
C9—C10 | 1.4312 (19) | C29—H29A | 0.9900 |
C11—C12 | 1.495 (2) | C29—H29B | 0.9900 |
C12—C17 | 1.390 (2) | C30—C31 | 1.495 (3) |
C12—C13 | 1.391 (2) | C30—H30A | 0.9900 |
C13—C14 | 1.402 (3) | C30—H30B | 0.9900 |
C13—H13 | 0.9500 | C31—C32 | 1.517 (2) |
C14—C15 | 1.365 (4) | C31—H31A | 0.9900 |
C14—H14 | 0.9500 | C31—H31B | 0.9900 |
C15—C16 | 1.359 (3) | C32—H32A | 0.9800 |
C16—C17 | 1.388 (2) | C32—H32B | 0.9800 |
C16—H16 | 0.9500 | C32—H32C | 0.9800 |
C17—H17 | 0.9500 | ||
C2—O3—C25 | 120.83 (11) | C19—C20—H20 | 119.6 |
C7—O4—C29 | 119.42 (11) | C22—C21—C20 | 118.14 (14) |
C2—C1—C9 | 120.04 (12) | C22—C21—H21 | 120.9 |
C2—C1—C11 | 115.87 (12) | C20—C21—H21 | 120.9 |
C9—C1—C11 | 123.58 (12) | F2—C22—C21 | 118.27 (14) |
O3—C2—C1 | 114.97 (12) | F2—C22—C23 | 118.52 (14) |
O3—C2—C3 | 123.29 (13) | C21—C22—C23 | 123.22 (14) |
C1—C2—C3 | 121.69 (13) | C22—C23—C24 | 117.88 (14) |
C4—C3—C2 | 118.98 (13) | C22—C23—H23 | 121.1 |
C4—C3—H3 | 120.5 | C24—C23—H23 | 121.1 |
C2—C3—H3 | 120.5 | C23—C24—C19 | 120.64 (13) |
C3—C4—C10 | 121.83 (13) | C23—C24—H24 | 119.7 |
C3—C4—H4 | 119.1 | C19—C24—H24 | 119.7 |
C10—C4—H4 | 119.1 | O3—C25—C26 | 106.19 (12) |
C6—C5—C10 | 122.08 (13) | O3—C25—H25A | 110.5 |
C6—C5—H5 | 119.0 | C26—C25—H25A | 110.5 |
C10—C5—H5 | 119.0 | O3—C25—H25B | 110.5 |
C5—C6—C7 | 119.06 (13) | C26—C25—H25B | 110.5 |
C5—C6—H6 | 120.5 | H25A—C25—H25B | 108.7 |
C7—C6—H6 | 120.5 | C25—C26—C27 | 114.69 (12) |
O4—C7—C8 | 115.38 (12) | C25—C26—H26A | 108.6 |
O4—C7—C6 | 123.22 (12) | C27—C26—H26A | 108.6 |
C8—C7—C6 | 121.31 (13) | C25—C26—H26B | 108.6 |
C7—C8—C9 | 120.23 (12) | C27—C26—H26B | 108.6 |
C7—C8—C18 | 116.83 (12) | H26A—C26—H26B | 107.6 |
C9—C8—C18 | 122.08 (11) | C26—C27—C28 | 112.29 (15) |
C8—C9—C1 | 124.26 (12) | C26—C27—H27A | 109.1 |
C8—C9—C10 | 117.89 (12) | C28—C27—H27A | 109.1 |
C1—C9—C10 | 117.84 (12) | C26—C27—H27B | 109.1 |
C4—C10—C5 | 121.04 (13) | C28—C27—H27B | 109.1 |
C4—C10—C9 | 119.56 (13) | H27A—C27—H27B | 107.9 |
C5—C10—C9 | 119.39 (13) | C27—C28—H28A | 109.5 |
O1—C11—C12 | 121.51 (13) | C27—C28—H28B | 109.5 |
O1—C11—C1 | 119.57 (13) | H28A—C28—H28B | 109.5 |
C12—C11—C1 | 118.86 (12) | C27—C28—H28C | 109.5 |
C17—C12—C13 | 119.27 (16) | H28A—C28—H28C | 109.5 |
C17—C12—C11 | 122.02 (14) | H28B—C28—H28C | 109.5 |
C13—C12—C11 | 118.71 (16) | O4—C29—C30 | 107.38 (13) |
C12—C13—C14 | 119.3 (2) | O4—C29—H29A | 110.2 |
C12—C13—H13 | 120.3 | C30—C29—H29A | 110.2 |
C14—C13—H13 | 120.3 | O4—C29—H29B | 110.2 |
C15—C14—C13 | 119.01 (19) | C30—C29—H29B | 110.2 |
C15—C14—H14 | 120.5 | H29A—C29—H29B | 108.5 |
C13—C14—H14 | 120.5 | C31—C30—C29 | 115.01 (14) |
C16—C15—F1 | 119.4 (2) | C31—C30—H30A | 108.5 |
C16—C15—C14 | 123.20 (18) | C29—C30—H30A | 108.5 |
F1—C15—C14 | 117.4 (2) | C31—C30—H30B | 108.5 |
C15—C16—C17 | 117.9 (2) | C29—C30—H30B | 108.5 |
C15—C16—H16 | 121.0 | H30A—C30—H30B | 107.5 |
C17—C16—H16 | 121.0 | C30—C31—C32 | 113.15 (16) |
C16—C17—C12 | 121.23 (17) | C30—C31—H31A | 108.9 |
C16—C17—H17 | 119.4 | C32—C31—H31A | 108.9 |
C12—C17—H17 | 119.4 | C30—C31—H31B | 108.9 |
O2—C18—C19 | 121.02 (12) | C32—C31—H31B | 108.9 |
O2—C18—C8 | 118.77 (12) | H31A—C31—H31B | 107.8 |
C19—C18—C8 | 120.20 (11) | C31—C32—H32A | 109.5 |
C20—C19—C24 | 119.35 (13) | C31—C32—H32B | 109.5 |
C20—C19—C18 | 118.26 (13) | H32A—C32—H32B | 109.5 |
C24—C19—C18 | 122.38 (12) | C31—C32—H32C | 109.5 |
C21—C20—C19 | 120.76 (14) | H32A—C32—H32C | 109.5 |
C21—C20—H20 | 119.6 | H32B—C32—H32C | 109.5 |
C25—O3—C2—C1 | −167.14 (12) | O1—C11—C12—C17 | 163.03 (14) |
C25—O3—C2—C3 | 10.4 (2) | C1—C11—C12—C17 | −19.90 (19) |
C9—C1—C2—O3 | 176.55 (12) | O1—C11—C12—C13 | −17.7 (2) |
C11—C1—C2—O3 | 4.41 (18) | C1—C11—C12—C13 | 159.41 (13) |
C9—C1—C2—C3 | −1.0 (2) | C17—C12—C13—C14 | 1.1 (2) |
C11—C1—C2—C3 | −173.19 (13) | C11—C12—C13—C14 | −178.22 (15) |
O3—C2—C3—C4 | −175.24 (13) | C12—C13—C14—C15 | −0.5 (3) |
C1—C2—C3—C4 | 2.2 (2) | C13—C14—C15—C16 | −1.0 (3) |
C2—C3—C4—C10 | −1.2 (2) | C13—C14—C15—F1 | 179.03 (15) |
C10—C5—C6—C7 | −0.8 (2) | F1—C15—C16—C17 | −178.29 (15) |
C29—O4—C7—C8 | −177.39 (12) | C14—C15—C16—C17 | 1.7 (3) |
C29—O4—C7—C6 | −0.9 (2) | C15—C16—C17—C12 | −1.0 (2) |
C5—C6—C7—O4 | −173.93 (13) | C13—C12—C17—C16 | −0.4 (2) |
C5—C6—C7—C8 | 2.4 (2) | C11—C12—C17—C16 | 178.95 (14) |
O4—C7—C8—C9 | 174.85 (11) | C7—C8—C18—O2 | 108.25 (14) |
C6—C7—C8—C9 | −1.7 (2) | C9—C8—C18—O2 | −61.18 (17) |
O4—C7—C8—C18 | 5.22 (17) | C7—C8—C18—C19 | −70.66 (16) |
C6—C7—C8—C18 | −171.35 (12) | C9—C8—C18—C19 | 119.90 (13) |
C7—C8—C9—C1 | −179.36 (12) | O2—C18—C19—C20 | −11.03 (19) |
C18—C8—C9—C1 | −10.28 (19) | C8—C18—C19—C20 | 167.86 (13) |
C7—C8—C9—C10 | −0.46 (18) | O2—C18—C19—C24 | 167.79 (13) |
C18—C8—C9—C10 | 168.62 (12) | C8—C18—C19—C24 | −13.32 (19) |
C2—C1—C9—C8 | 177.88 (12) | C24—C19—C20—C21 | 0.7 (2) |
C11—C1—C9—C8 | −10.6 (2) | C18—C19—C20—C21 | 179.59 (14) |
C2—C1—C9—C10 | −1.01 (18) | C19—C20—C21—C22 | −1.2 (2) |
C11—C1—C9—C10 | 170.50 (12) | C20—C21—C22—F2 | −179.14 (14) |
C3—C4—C10—C5 | −179.85 (13) | C20—C21—C22—C23 | 0.8 (3) |
C3—C4—C10—C9 | −0.9 (2) | F2—C22—C23—C24 | 179.99 (13) |
C6—C5—C10—C4 | 177.59 (14) | C21—C22—C23—C24 | 0.1 (2) |
C6—C5—C10—C9 | −1.4 (2) | C22—C23—C24—C19 | −0.5 (2) |
C8—C9—C10—C4 | −177.00 (12) | C20—C19—C24—C23 | 0.2 (2) |
C1—C9—C10—C4 | 1.96 (18) | C18—C19—C24—C23 | −178.65 (13) |
C8—C9—C10—C5 | 1.97 (18) | C2—O3—C25—C26 | 174.59 (12) |
C1—C9—C10—C5 | −179.06 (12) | O3—C25—C26—C27 | 62.58 (16) |
C2—C1—C11—O1 | 112.36 (15) | C25—C26—C27—C28 | −179.43 (16) |
C9—C1—C11—O1 | −59.48 (18) | C7—O4—C29—C30 | 170.00 (12) |
C2—C1—C11—C12 | −64.77 (16) | O4—C29—C30—C31 | 61.91 (19) |
C9—C1—C11—C12 | 123.39 (14) | C29—C30—C31—C32 | 175.40 (16) |
Cg1 and Cg2 are the centroids of the C12–C17 and C5–C10 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C27—H27B···Cg1 | 0.99 | 2.79 | 3.7754 (19) | 175 |
C26—H26A···Cg2i | 0.99 | 2.54 | 3.4239 (16) | 145 |
C3—H3···F2ii | 0.95 | 2.50 | 3.4408 (17) | 169 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C32H30F2O4 |
Mr | 516.56 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 193 |
a, b, c (Å) | 8.26012 (15), 20.2309 (4), 16.5268 (3) |
β (°) | 99.918 (1) |
V (Å3) | 2720.51 (9) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.75 |
Crystal size (mm) | 0.60 × 0.50 × 0.50 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Numerical (NUMABS; Higashi, 1999) |
Tmin, Tmax | 0.661, 0.705 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 50395, 4971, 4715 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.116, 1.03 |
No. of reflections | 4971 |
No. of parameters | 346 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.41 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), Il Milione (Burla et al., 2007), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996).
Cg1 and Cg2 are the centroids of the C12–C17 and C5–C10 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C27—H27B···Cg1 | 0.99 | 2.79 | 3.7754 (19) | 175 |
C26—H26A···Cg2i | 0.99 | 2.54 | 3.4239 (16) | 145 |
C3—H3···F2ii | 0.95 | 2.50 | 3.4408 (17) | 169 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y+1/2, −z+3/2. |
Acknowledgements
The authors express their gratitude to Professor Keiichi Noguchi, Instrumentation Analysis Center, Tokyo University of Agriculture and Technology, for his technical advice. This work was partially supported by the Ogasawara Foundation for the Promotion of Science & Engineering, Tokyo, Japan.
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 studies on electrophilic aromatic aroylation of 2,7-dimethoxynaphthalene, peri-aroylnaphthalene compounds have proven to be formed regioselectively with the aid of suitable acidic mediators (Okamoto & Yonezawa, 2009; Okamoto, Mitsui et al., 2011). In one application, the authors have integrated the resulting molecular unit to a poly(ether ketone) backbone via nucleophilic aromatic substitution polycondensation (Okamoto et al., 2012). The poly(ether ketone)s composed of 1,8-diaroylenenaphthalene units show unique thermal properties and solubility for organic solvents. These curious features of the polymers can be explained on the basis of the structural features of the 1,8-diaroylene naphthalene units. Under these circumstances, the authors have undertaken the X-ray crystal structural study of several 1,8-diaroylated naphthalene analogues, exemplified by (2,7-dimethoxynaphthalene-1,8-diyl)bis(4-fluorophenyl)dimethanone (Watanabe et al., 2010) and [8-(4-butoxybenzoyl)-2,7-dimethoxy- naphthalen-1-yl](4-butoxyphenyl)-methanone (Sasagawa et al., 2011). These molecules have essentially the same non-coplanar features. The aroyl groups at the 1,8-positions of the naphthalene rings in these molecules are twisted and bonded in an almost perpendicular fashion, but the benzene ring moieties of the aroyl groups tilt slightly toward the exo sides of the naphthalene rings. As a part of our continuous studies on the molecular structures of this kind of homologous molecules, the X-ray crystal structure of the title compound is presented herein.
The molecular structure of the title compound is displayed in Fig. 1. Two benzoyl groups at the 1,8-positions of the naphthalene ring are situated in opposite directions, with an anti orientation. The benzene rings of the benzoyl groups make dihedral angles with the naphthalene ring system of 74.55 (6) and 74.39 (7)°, respectively. The dihedral angle between these benzene rings is 44.61 (8)°.
In the crystal structure, the molecular packing of the title compound is stabilized mainly by two types of C—H···π interactions: a) an intramolecular C—H···π interaction between the benzene ring of the aroyl group (C12—C17; Cg1) and one methylene H atom (H27B) of the butoxy group (C27—H27B···Cg1= 2.79 Å; Fig. 2 and Table 1); and b) an intermolecular C—H···π interaction between the centroid of the C5—C10 ring (Cg2) and one methylene H atom (H26A) of the butoxy group (C26—H26A···Cg2i= 2.54 Å; Fig. 2 and Table 1). There is also a C-H···F hydrogen bond present (Table 1) that links the molecules to form chains propagating along the b axis direction.