supplementary materials


rk2398 scheme

Acta Cryst. (2013). E69, o678    [ doi:10.1107/S1600536813008829 ]

4-(4-Fluorobenzoyl)-3-phenyl-3,4-dihydronaphthalen-1(2H)-one

H. Zhang and Y.-M. Hu

Abstract top

In the title compound, C23H17FO2, the cyclohexenone ring has an envelope conformation, the flap atom being the C atom to which the phenyl ring is attached. The 4-fluorobenzoyl ring and the phenyl ring are inclined to one another by 28.77 (7)°, and by 52.00 (7) and 44.77 (7) °, respectively, to the aromatic ring fused to the cyclohexenone ring. In the crystal, molecules are linked via C-H...O hydrogen bonds, forming a two-dimensional network lying parallel to (100).

Comment top

Domino reaction as an important tool to construct structurally complicate molecule due to high atom economy and environmental benefits (Zhao et al., 2012). Pd-catalyzed cascade reactions have become an efficient protocol of modern organic synthesis chemistry (Wang et al., 2011; Yu et al., 2012). Condensed polycyclic compounds are playing increasingly important roles as synthetic building blocks, pharmacophores, and electroluminescence materials (Rixson et al., 2012). We have reported some novel cross-coupling reactions of aryl halides with the olefins and diynes (Hu et al., 2009; 2010). The reaction of bromobenzene with 1-(2-((4-fluorophenyl)ethynyl)phenyl)prop-2-en-1-one, in the presence of Pd(II) acetate and triphenylphosphine, in DMF at 418 K for 19 h, gave the unexpected title product.

The crystal structure data of molecule, C31H30N2O, reveals that all the bond lengths and angles have normal values. The titled molecule contains three phenyl ring and one six-membered carbon ring with a boat conformation. One phenyl ring and the cis-fused cyclohexene ring are common side. All the rings are not coplanar (Fig. 1). In the molecule there are two chiral carbon atoms, C9 and C10, but the crystal is a racemic system due to lacking of the chiral separation. In the crystal packing, there are weak intermolecular C–H···O interactions C14–H14···O1i which forms 1-D chain were formed between neighboring molecules along c axis (Fig. 2). Symmetry code: (i) x, -y+1/2, z-1/2.

Related literature top

For the domino reaction as an important tool in the construction of structurally complicated molecules, see: Zhao et al. (2012). For Pd-catalysed cascade reactions, see: Wang & Hu (2011); Yu & Hu (2012). For the use of condensed polycyclic compounds as synthetic building blocks, pharmacophores and electroluminescent materials, see: Rixson et al. (2012). For cross-coupling reactions of aryl halides with olefins and diynes, see: Hu et al. (2010, 2009).

Experimental top

An oven-dried Schlenk flask was evacuated, filled with nitrogen, and then charged with 1-(2-((4-fluorophenyl)ethynyl)phenyl)prop-2-en-1-one (2.51 g, 10 mmol), bromobenzene (1.72 g, 11 mmol), tributylamine (3 ml), PPh3 (52.5 mg, 0.2 mmol), Pd(OAc)2 (24 mg, 0.1 mol), and DMF (10 ml) to give a yellow solution. The reaction mixture was heated at 418 K with stirring. The reaction mixture was cooled to room temperature after 19 h and the resultant yellow-orange mixture was diluted with Et2O (10 ml). The mixture was washed with H2O (15 ml) and the aqueous layer was extracted with Et2O (20 ml). The combined organic layers were dried (MgSO4), filtered, and concentrated in vacuo. The crude product was purified by flash column chromatography on silica gel (petroleum ester : EtOAc = 9 : 1) and recrystalized from EtOAc, yield 2.45 g (71%). Colourless crystals suitable for X-ray diffraction were obtained by recrystallization from a solution of the title compound from ethyl acetate over a period of one week.

Refinement top

All H atoms were positioned geometrically and refined using a riding model with C–H = 0.93Å-0.98Å with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
[Figure 2] Fig. 2. A view of 1-D chain along c axis. Symmetry codes: (i) x, -y+1/2, z-1/2; (ii) x, -y+1/2, z+1/2.
[Figure 3] Fig. 3. A view of the cell paking down b axis.
4-(4-Fluorobenzoyl)-3-phenyl-3,4-dihydronaphthalen-1(2H)-one top
Crystal data top
C23H17FO2F(000) = 720
Mr = 344.37Dx = 1.325 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2731 reflections
a = 8.0063 (6) Åθ = 2.1–23.6°
b = 10.6688 (8) ŵ = 0.09 mm1
c = 20.3796 (15) ÅT = 295 K
β = 97.458 (1)°Block, colourless
V = 1726.1 (2) Å30.35 × 0.32 × 0.29 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer
3987 independent reflections
Radiation source: sealed tube3176 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
φ– and ω–scansθmax = 27.6°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1010
Tmin = 0.969, Tmax = 0.974k = 1313
14632 measured reflectionsl = 2624
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.05P)2 + 0.44P]
where P = (Fo2 + 2Fc2)/3
3987 reflections(Δ/σ)max < 0.001
235 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C23H17FO2V = 1726.1 (2) Å3
Mr = 344.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.0063 (6) ŵ = 0.09 mm1
b = 10.6688 (8) ÅT = 295 K
c = 20.3796 (15) Å0.35 × 0.32 × 0.29 mm
β = 97.458 (1)°
Data collection top
Bruker SMART APEX CCD
diffractometer
3987 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
3176 reflections with I > 2σ(I)
Tmin = 0.969, Tmax = 0.974Rint = 0.025
14632 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.117Δρmax = 0.23 e Å3
S = 1.03Δρmin = 0.28 e Å3
3987 reflectionsAbsolute structure: ?
235 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
C11.2122 (2)0.13272 (15)0.42049 (7)0.0558 (4)
H11.19400.09400.45980.067*
C21.3639 (2)0.18874 (18)0.41545 (8)0.0638 (5)
H21.44790.18900.45150.077*
C31.39238 (19)0.24486 (16)0.35687 (8)0.0590 (4)
H31.49570.28260.35360.071*
C41.26809 (17)0.24528 (14)0.30301 (7)0.0474 (3)
H41.28920.28200.26350.057*
C51.11203 (16)0.19136 (12)0.30728 (6)0.0380 (3)
C61.08446 (17)0.13349 (12)0.36657 (6)0.0429 (3)
C70.92053 (19)0.07364 (12)0.37339 (6)0.0447 (3)
C80.78176 (17)0.08569 (13)0.31679 (7)0.0450 (3)
H8A0.67490.09030.33430.054*
H8B0.78000.01090.28960.054*
C90.79881 (15)0.19977 (12)0.27346 (6)0.0379 (3)
H90.79630.27340.30210.045*
C100.97521 (15)0.19869 (11)0.24892 (6)0.0346 (3)
H100.98880.27750.22550.041*
C110.98542 (16)0.09084 (11)0.20047 (6)0.0362 (3)
C120.92979 (15)0.11179 (11)0.12871 (6)0.0363 (3)
C130.93535 (19)0.22788 (13)0.09884 (7)0.0466 (3)
H130.97600.29660.12410.056*
C140.8814 (2)0.24341 (16)0.03199 (7)0.0573 (4)
H140.88790.32100.01170.069*
C150.8189 (2)0.14184 (17)0.00295 (7)0.0574 (4)
C160.8094 (2)0.02478 (18)0.02434 (8)0.0660 (5)
H160.76480.04260.00110.079*
C170.8681 (2)0.00996 (14)0.09066 (7)0.0522 (4)
H170.86620.06890.11000.063*
C180.65496 (16)0.21523 (12)0.21773 (6)0.0400 (3)
C190.62893 (18)0.33103 (14)0.18694 (8)0.0496 (3)
H190.69770.39830.20160.060*
C200.5021 (2)0.34751 (17)0.13476 (8)0.0608 (4)
H200.48770.42520.11410.073*
C210.3973 (2)0.24981 (19)0.11325 (8)0.0655 (5)
H210.31200.26120.07820.079*
C220.4193 (2)0.13585 (18)0.14369 (9)0.0648 (5)
H220.34750.06980.12970.078*
C230.54788 (19)0.11786 (15)0.19539 (8)0.0524 (4)
H230.56240.03950.21530.063*
F10.76491 (16)0.15640 (12)0.06863 (5)0.0895 (4)
O10.89843 (17)0.01466 (11)0.42256 (5)0.0676 (3)
O21.02932 (15)0.01260 (9)0.22076 (5)0.0544 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0642 (10)0.0602 (9)0.0388 (8)0.0110 (7)0.0090 (7)0.0028 (6)
C20.0542 (9)0.0783 (11)0.0523 (9)0.0133 (8)0.0180 (7)0.0134 (8)
C30.0405 (7)0.0705 (10)0.0628 (10)0.0041 (7)0.0052 (7)0.0164 (8)
C40.0418 (7)0.0519 (8)0.0474 (8)0.0032 (6)0.0013 (6)0.0090 (6)
C50.0411 (6)0.0355 (6)0.0356 (6)0.0058 (5)0.0025 (5)0.0072 (5)
C60.0510 (8)0.0405 (7)0.0349 (6)0.0072 (6)0.0033 (5)0.0044 (5)
C70.0633 (9)0.0361 (7)0.0339 (7)0.0038 (6)0.0028 (6)0.0010 (5)
C80.0474 (7)0.0448 (7)0.0424 (7)0.0022 (6)0.0048 (6)0.0037 (6)
C90.0398 (6)0.0359 (6)0.0370 (6)0.0018 (5)0.0014 (5)0.0020 (5)
C100.0396 (6)0.0301 (6)0.0327 (6)0.0003 (5)0.0004 (5)0.0008 (4)
C110.0406 (6)0.0316 (6)0.0353 (6)0.0001 (5)0.0007 (5)0.0007 (5)
C120.0383 (6)0.0373 (6)0.0329 (6)0.0014 (5)0.0028 (5)0.0008 (5)
C130.0598 (8)0.0407 (7)0.0382 (7)0.0004 (6)0.0020 (6)0.0027 (5)
C140.0731 (10)0.0558 (9)0.0422 (8)0.0100 (8)0.0050 (7)0.0127 (7)
C150.0601 (9)0.0781 (11)0.0311 (7)0.0101 (8)0.0048 (6)0.0025 (7)
C160.0846 (12)0.0691 (11)0.0407 (8)0.0139 (9)0.0061 (8)0.0110 (7)
C170.0715 (10)0.0449 (8)0.0387 (7)0.0079 (7)0.0013 (7)0.0022 (6)
C180.0362 (6)0.0441 (7)0.0395 (7)0.0054 (5)0.0036 (5)0.0030 (5)
C190.0455 (7)0.0466 (8)0.0550 (8)0.0065 (6)0.0002 (6)0.0026 (6)
C200.0554 (9)0.0670 (10)0.0586 (10)0.0192 (8)0.0014 (7)0.0122 (8)
C210.0489 (9)0.0930 (13)0.0505 (9)0.0118 (9)0.0088 (7)0.0001 (9)
C220.0524 (9)0.0777 (12)0.0597 (10)0.0067 (8)0.0104 (7)0.0119 (9)
C230.0505 (8)0.0510 (8)0.0533 (8)0.0019 (6)0.0032 (6)0.0033 (7)
F10.1108 (9)0.1147 (9)0.0360 (5)0.0106 (7)0.0174 (5)0.0072 (5)
O10.0949 (9)0.0638 (7)0.0418 (6)0.0137 (6)0.0003 (6)0.0132 (5)
O20.0832 (8)0.0338 (5)0.0426 (5)0.0118 (5)0.0052 (5)0.0003 (4)
Geometric parameters (Å, º) top
C1—C21.369 (2)C11—C121.4892 (17)
C1—C61.4009 (19)C12—C131.3834 (18)
C1—H10.9300C12—C171.3880 (18)
C2—C31.381 (3)C13—C141.3846 (19)
C2—H20.9300C13—H130.9300
C3—C41.3825 (19)C14—C151.356 (2)
C3—H30.9300C14—H140.9300
C4—C51.3885 (19)C15—F11.3610 (17)
C4—H40.9300C15—C161.373 (2)
C5—C61.3997 (19)C16—C171.381 (2)
C5—C101.5108 (16)C16—H160.9300
C6—C71.482 (2)C17—H170.9300
C7—O11.2154 (17)C18—C231.3857 (19)
C7—C81.4996 (19)C18—C191.3891 (19)
C8—C91.5203 (18)C19—C201.383 (2)
C8—H8A0.9700C19—H190.9300
C8—H8B0.9700C20—C211.374 (3)
C9—C181.5180 (17)C20—H200.9300
C9—C101.5583 (17)C21—C221.366 (3)
C9—H90.9800C21—H210.9300
C10—C111.5253 (16)C22—C231.388 (2)
C10—H100.9800C22—H220.9300
C11—O21.2144 (15)C23—H230.9300
C2—C1—C6120.20 (15)O2—C11—C12120.48 (11)
C2—C1—H1119.9O2—C11—C10120.17 (11)
C6—C1—H1119.9C12—C11—C10119.22 (10)
C1—C2—C3120.11 (14)C13—C12—C17118.97 (12)
C1—C2—H2119.9C13—C12—C11122.95 (11)
C3—C2—H2119.9C17—C12—C11118.07 (11)
C2—C3—C4120.35 (15)C12—C13—C14121.09 (14)
C2—C3—H3119.8C12—C13—H13119.5
C4—C3—H3119.8C14—C13—H13119.5
C3—C4—C5120.65 (14)C15—C14—C13117.89 (15)
C3—C4—H4119.7C15—C14—H14121.1
C5—C4—H4119.7C13—C14—H14121.1
C4—C5—C6118.74 (12)C14—C15—F1118.27 (15)
C4—C5—C10119.71 (12)C14—C15—C16123.37 (14)
C6—C5—C10121.53 (12)F1—C15—C16118.35 (15)
C5—C6—C1119.92 (13)C15—C16—C17118.08 (15)
C5—C6—C7120.78 (11)C15—C16—H16121.0
C1—C6—C7119.29 (13)C17—C16—H16121.0
O1—C7—C6121.72 (13)C16—C17—C12120.56 (14)
O1—C7—C8120.39 (14)C16—C17—H17119.7
C6—C7—C8117.88 (11)C12—C17—H17119.7
C7—C8—C9113.70 (11)C23—C18—C19117.92 (13)
C7—C8—H8A108.8C23—C18—C9122.78 (12)
C9—C8—H8A108.8C19—C18—C9119.30 (12)
C7—C8—H8B108.8C20—C19—C18120.83 (15)
C9—C8—H8B108.8C20—C19—H19119.6
H8A—C8—H8B107.7C18—C19—H19119.6
C18—C9—C8113.89 (11)C21—C20—C19120.40 (16)
C18—C9—C10113.07 (10)C21—C20—H20119.8
C8—C9—C10109.51 (10)C19—C20—H20119.8
C18—C9—H9106.6C22—C21—C20119.56 (15)
C8—C9—H9106.6C22—C21—H21120.2
C10—C9—H9106.6C20—C21—H21120.2
C5—C10—C11112.10 (10)C21—C22—C23120.46 (16)
C5—C10—C9110.03 (10)C21—C22—H22119.8
C11—C10—C9109.89 (10)C23—C22—H22119.8
C5—C10—H10108.2C18—C23—C22120.82 (15)
C11—C10—H10108.2C18—C23—H23119.6
C9—C10—H10108.2C22—C23—H23119.6
C6—C1—C2—C30.8 (2)C5—C10—C11—C12148.71 (11)
C1—C2—C3—C40.2 (3)C9—C10—C11—C1288.60 (13)
C2—C3—C4—C51.1 (2)O2—C11—C12—C13156.49 (14)
C3—C4—C5—C61.8 (2)C10—C11—C12—C1327.68 (18)
C3—C4—C5—C10176.91 (12)O2—C11—C12—C1724.2 (2)
C4—C5—C6—C11.10 (19)C10—C11—C12—C17151.59 (12)
C10—C5—C6—C1177.54 (12)C17—C12—C13—C140.3 (2)
C4—C5—C6—C7179.46 (12)C11—C12—C13—C14179.61 (13)
C10—C5—C6—C71.90 (18)C12—C13—C14—C151.7 (2)
C2—C1—C6—C50.2 (2)C13—C14—C15—F1179.74 (15)
C2—C1—C6—C7179.26 (14)C13—C14—C15—C161.2 (3)
C5—C6—C7—O1174.25 (13)C14—C15—C16—C170.5 (3)
C1—C6—C7—O16.3 (2)F1—C15—C16—C17178.48 (15)
C5—C6—C7—C84.57 (18)C15—C16—C17—C121.9 (3)
C1—C6—C7—C8174.87 (13)C13—C12—C17—C161.5 (2)
O1—C7—C8—C9156.38 (13)C11—C12—C17—C16177.80 (14)
C6—C7—C8—C924.80 (17)C8—C9—C18—C2318.97 (18)
C7—C8—C9—C18177.69 (11)C10—C9—C18—C23106.89 (15)
C7—C8—C9—C1054.60 (14)C8—C9—C18—C19161.63 (12)
C4—C5—C10—C1187.24 (14)C10—C9—C18—C1972.51 (15)
C6—C5—C10—C1194.14 (14)C23—C18—C19—C201.3 (2)
C4—C5—C10—C9150.15 (12)C9—C18—C19—C20178.14 (13)
C6—C5—C10—C928.47 (15)C18—C19—C20—C211.2 (2)
C18—C9—C10—C5176.40 (10)C19—C20—C21—C220.1 (3)
C8—C9—C10—C555.42 (13)C20—C21—C22—C230.9 (3)
C18—C9—C10—C1159.70 (13)C19—C18—C23—C220.2 (2)
C8—C9—C10—C1168.48 (13)C9—C18—C23—C22179.17 (14)
C5—C10—C11—O235.45 (17)C21—C22—C23—C180.9 (3)
C9—C10—C11—O287.23 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O1i0.932.533.425 (2)161
C10—H10···O2ii0.982.513.1427 (15)123
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O1i0.932.533.425 (2)161
C10—H10···O2ii0.982.513.1427 (15)123
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+2, y+1/2, z+1/2.
Acknowledgements top

We thank the National Science Foundation of China (project Nos. 21272005 and 21072003) for financial support of this work.

references
References top

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