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Acta Cryst. (2009). E65, o543    [ doi:10.1107/S1600536809004796 ]

(4-Chlorobenzoyl)(2-ethoxy-7-methoxynaphthalen-1-yl)methanone

R. Mitsui, K. Noguchi and N. Yonezawa

Abstract top

In the title compound, C20H17ClO3, the naphthalene and benzene rings form an interplanar angle of 83.30 (8)°. The conformation around the central C=O group is such that the C=O bond vector forms a larger angle to the plane of the naphthalene ring than to the plane of the benzene ring, viz. 55.8 (2)° versus 15.8 (2)°. The 4-chlorophenyl groups form a centrosymmetric [pi]-[pi] interaction, with a centroid-centroid distance of 3.829 (1) Å and a lateral offset of 1.758 Å. An intermolecular C-H...O interaction is formed between the 4-chlorophenyl group and the O atom of a neighbouring methoxy group, and two very weak C-H...[pi] contacts are present.

Comment top

Recently, we have reported the crystal structures of 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene and (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa, 2008; Mitsui, Nakaema, Noguchi & Yonezawa, 2008). As a part of our ongoing studies on the synthesis and crystal structure analyses of aroylated naphthalene derivatives, this paper reports the crystal structure of the title compound, prepared by ethylation of (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone with ethyl iodide.

In the molecule (Fig. 1), the interplanar angle between the benzene ring [C12–C17] and the naphthalene ring [C1–C10] is 83.30 (8)°. The C=O bond vector lies close to the mean plane of the benzene ring (angle 15.8 (2)°), but forms an angle of 55.77 (15)° to the plane of the naphthalene ring. The conformation of these groups is similar to 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene. On the other hand, the methoxy group is arranged toward the aroyl group [C20—O3—C8—C7 torsion angle = 177.7 (2)°] while that of the aforementioned related compound is arranged toward the naphthalene ring [-7.1 (3)°]. In both compounds, the C—O bond vector of the methoxy group lies approximately in the plane of the naphthalene ring [angle 4.2 (1)° in the title compound, 5.05 (9)° in the related compound].

In the crystal structure, the naphthalene rings interact with ethyl groups [C7···H18A = 2.87 Å, C7···H18B = 2.88 Å] and methyl groups [C5···H20B = 2.75 Å] of the adjacent molecule along the a axis (Fig. 2). The neighboring inversion-related ethyl groups interact with each other [H19C···H19C = 2.39 Å] along the c axis. The C=O groups interact with benzene rings [O1···H17 = 2.66 Å] along the b axis (Fig. 3). Adjacent 4-chlorophenyl groups related by crystallographic inversion centers are exactly antiparallel and the perpendicular distance between the mean planes of these groups is 3.402 (1) Å (Fig. 4). The centroid–centroid distance between the two antiparallel phenyl rings is 3.829 (1) Å and the lateral offset is 1.758 Å, indicating the presence of a π–π interaction. Moreover, molecules are linked by C—H···π interactions. The methyl group acts as a hydrogen-bond donor and the π system of the naphthalene ring [C1/C2/C3/C4/C5/C10 ring (with centroid Cg1)] of an adjacent molecule acts as an acceptor, viz. C20—H20B···π, C20—H20C···π (Fig. 2 and Table 1). Intermolecular C—H···O hydrogen bonds between the methoxy O and an H atom of the 4-chlorophenyl group of the adjacent molecule are also found along the c axis (C13—H13···O3i; Fig. 2 and Table 1).

Related literature top

For structures of closely related compounds, see: Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa (2008); Mitsui, Nakaema, Noguchi & Yonezawa (2008).

Experimental top

(4-Chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (0.13 g, 0.40 mmol) was dissolved in acetone (1.0 ml) and aqueous 0.8M NaOH (1.0 ml). EtI (0.31 g, 2.0 mmol) was added and the reaction mixture was heated at reflux for 6 h. Upon cooling to ambient temperature, the mixture was poured into H2O (5 ml) and CHCl3 (5 ml), and the aqueous layer was extracted with CHCl3 (3 × 5 ml). The combined organic layers were washed with brine (3 × 20 ml), and dried over MgSO4 overnight. The solvent was removed in vacuo and the crude material was purified by recrystallization from hexanes to give the title compound as colorless blocks (m.p. 365.5–366.0 K, yield 95 mg, 70%).

Spectroscopic Data: 1H NMR (300 MHz, CDCl3) δ 7.83 (d, 1H), 7.77 (d, 2H), 7.70 (d, 1H), 7.38 (d, 2H), 7.11 (d, 1H), 7.02 (dd, 1H), 6.86 (d, 1H), 4.05 (q, 2H), 3.74 (s, 3H), 1.10 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 196.8, 159.1, 154.8, 139.4, 137.1, 133.2, 131.3, 130.7, 129.7, 128.7, 124.5, 121.7, 117.2, 111.5, 102.3, 65.0, 55.2, 14.6; IR (KBr): 1671, 1624, 1582, 1511, 1464, 1249, 1227, 1046; HRMS (m/z): [M + H]+ calcd for C20H18ClO3, 341.0945; found, 341.0903.

Refinement top

Rigid bond restraints were applied to the Uij values of the naphthalene ring (C4—C7) (5 restraints with the DELU command in SHELXL97). Further restraints were used to generate similar Uij values for the atoms of naphthalene ring (18 restraints with the SIMU command in SHELXL97). All H atoms were visible in difference maps but were subsequently placed in calculated positions and refined as riding, with C—H = 0.95 (aromatic), 0.98 (methyl) and 0.99 (methylene) Å, and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. Molecular structure with displacement ellipsoids at 30% probability for non-H atoms.
[Figure 2] Fig. 2. Packing diagram viewed down the b axis. Van der Waals, C—H···π and C—H···O interactions are shown as black, red and green dashed lines, respectively.
[Figure 3] Fig. 3. Partial packing diagram viewed down the a axis. Van der Waals interactions are shown as dashed lines.
[Figure 4] Fig. 4. Side-on view of the π–π interaction.
(4-Chlorobenzoyl)(2-ethoxy-7-methoxynaphthalen-1-yl)methanone top
Crystal data top
C20H17ClO3F(000) = 712
Mr = 340.79Dx = 1.330 Mg m−3
Monoclinic, P21/cMelting point = 365.5–366.0 K
Hall symbol: -P 2ybcCu Kα radiation, λ = 1.54187 Å
a = 7.26434 (13) ÅCell parameters from 26200 reflections
b = 20.8849 (4) Åθ = 3.9–68.1°
c = 12.2094 (2) ŵ = 2.11 mm−1
β = 113.201 (1)°T = 193 K
V = 1702.55 (5) Å3Block, colorless
Z = 40.40 × 0.30 × 0.20 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3104 independent reflections
Radiation source: rotating anode2544 reflections with I > 2σ(I)
graphiteRint = 0.023
Detector resolution: 10.00 pixels mm-1θmax = 68.1°, θmin = 4.2°
ω scansh = −8→8
Absorption correction: numerical
(NUMABS; Higashi, 1999)		k = −25→25
Tmin = 0.542, Tmax = 0.656l = −14→14
30947 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.120 w = 1/[σ2(Fo2) + (0.0592P)2 + 0.3688P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
3104 reflectionsΔρmax = 0.27 e Å−3
218 parametersΔρmin = −0.28 e Å−3
23 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0020 (3)
Crystal data top
C20H17ClO3V = 1702.55 (5) Å3
Mr = 340.79Z = 4
Monoclinic, P21/cCu Kα radiation
a = 7.26434 (13) ŵ = 2.11 mm−1
b = 20.8849 (4) ÅT = 193 K
c = 12.2094 (2) Å0.40 × 0.30 × 0.20 mm
β = 113.201 (1)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3104 independent reflections
Absorption correction: numerical
(NUMABS; Higashi, 1999)		2544 reflections with I > 2σ(I)
Tmin = 0.542, Tmax = 0.656Rint = 0.023
30947 measured reflectionsθmax = 68.1°
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.120Δρmax = 0.27 e Å−3
S = 1.10Δρmin = −0.28 e Å−3
3104 reflectionsAbsolute structure: ?
218 parametersFlack parameter: ?
23 restraintsRogers parameter: ?
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.

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
Cl11.10278 (9)0.57118 (2)0.30495 (5)0.0781 (2)
O10.4618 (2)0.39338 (6)0.45026 (12)0.0659 (4)
O20.3297 (2)0.37751 (7)0.15066 (12)0.0756 (4)
O30.9489 (2)0.19765 (7)0.67286 (15)0.0765 (4)
C10.5171 (3)0.31905 (9)0.31945 (17)0.0566 (4)
C20.4068 (3)0.31950 (10)0.19824 (18)0.0656 (5)
C30.3762 (3)0.26240 (12)0.1314 (2)0.0767 (6)
H30.30190.26280.04760.092*
C40.4553 (3)0.20662 (11)0.1892 (2)0.0784 (7)
H40.43260.16810.14430.094*
C50.5692 (3)0.20400 (9)0.3128 (2)0.0671 (5)
C60.6600 (4)0.14645 (10)0.3747 (3)0.0794 (7)
H60.63490.10720.33210.095*
C70.7796 (4)0.14653 (10)0.4912 (3)0.0785 (6)
H70.83670.10750.52960.094*
C80.8208 (3)0.20409 (9)0.5568 (2)0.0665 (5)
C90.7332 (3)0.26027 (8)0.50295 (18)0.0572 (4)
H90.75890.29870.54820.069*
C100.6044 (3)0.26155 (8)0.38026 (18)0.0579 (5)
C110.5461 (3)0.38232 (8)0.38384 (15)0.0536 (4)
C120.6830 (3)0.42954 (8)0.36347 (15)0.0505 (4)
C130.8197 (3)0.40999 (8)0.31679 (16)0.0547 (4)
H130.82350.36630.29630.066*
C140.9509 (3)0.45307 (9)0.29947 (16)0.0587 (4)
H141.04530.43930.26840.070*
C150.9411 (3)0.51637 (8)0.32839 (15)0.0569 (4)
C160.8073 (3)0.53732 (9)0.37524 (16)0.0599 (5)
H160.80320.58120.39450.072*
C170.6795 (3)0.49384 (8)0.39383 (16)0.0569 (4)
H170.58870.50770.42750.068*
C180.2883 (4)0.38987 (15)0.0278 (2)0.0872 (7)
H18A0.16160.3689−0.02420.105*
H18B0.39800.37350.00670.105*
C190.2714 (5)0.46071 (17)0.0136 (3)0.1199 (11)
H19A0.24280.4720−0.06950.144*
H19B0.39760.48060.06580.144*
H19C0.16260.47610.03500.144*
C201.0050 (3)0.25362 (11)0.7447 (2)0.0754 (6)
H20A1.09700.24200.82560.090*
H20B0.88530.27380.74760.090*
H20C1.07150.28370.71050.090*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0934 (4)0.0670 (3)0.0780 (4)−0.0205 (3)0.0382 (3)0.0047 (2)
O10.0784 (9)0.0658 (8)0.0721 (8)0.0068 (7)0.0496 (7)0.0002 (6)
O20.0841 (10)0.0855 (10)0.0595 (8)−0.0073 (8)0.0306 (7)0.0064 (7)
O30.0712 (9)0.0656 (9)0.1016 (11)0.0101 (7)0.0435 (9)0.0261 (8)
C10.0633 (11)0.0567 (10)0.0629 (11)−0.0068 (8)0.0390 (9)−0.0048 (8)
C20.0665 (12)0.0731 (13)0.0699 (12)−0.0139 (10)0.0406 (10)−0.0083 (10)
C30.0749 (14)0.0969 (17)0.0735 (13)−0.0280 (12)0.0457 (11)−0.0229 (12)
C40.0799 (14)0.0744 (14)0.1077 (17)−0.0300 (12)0.0658 (14)−0.0359 (13)
C50.0698 (12)0.0585 (11)0.0970 (15)−0.0162 (9)0.0586 (12)−0.0188 (10)
C60.0850 (15)0.0482 (11)0.138 (2)−0.0128 (10)0.0796 (16)−0.0187 (12)
C70.0798 (15)0.0507 (11)0.128 (2)0.0019 (10)0.0655 (15)0.0056 (12)
C80.0659 (12)0.0546 (11)0.1001 (16)0.0007 (9)0.0554 (12)0.0089 (10)
C90.0637 (11)0.0479 (9)0.0766 (12)0.0002 (8)0.0453 (10)0.0028 (8)
C100.0628 (11)0.0496 (9)0.0820 (12)−0.0056 (8)0.0507 (10)−0.0057 (8)
C110.0607 (10)0.0541 (10)0.0527 (9)0.0091 (8)0.0295 (8)0.0040 (7)
C120.0617 (10)0.0464 (9)0.0483 (9)0.0066 (7)0.0270 (8)0.0026 (7)
C130.0677 (11)0.0456 (9)0.0600 (10)0.0003 (8)0.0351 (9)−0.0031 (7)
C140.0658 (11)0.0593 (10)0.0589 (10)−0.0008 (8)0.0332 (9)−0.0021 (8)
C150.0676 (11)0.0525 (9)0.0491 (9)−0.0038 (8)0.0213 (8)0.0060 (7)
C160.0758 (12)0.0439 (9)0.0585 (10)0.0067 (8)0.0247 (9)0.0043 (7)
C170.0691 (11)0.0508 (9)0.0550 (9)0.0120 (8)0.0290 (9)0.0019 (7)
C180.0657 (13)0.134 (2)0.0608 (12)−0.0117 (13)0.0243 (10)0.0111 (13)
C190.119 (2)0.142 (3)0.0847 (18)−0.014 (2)0.0247 (16)0.0474 (18)
C200.0702 (13)0.0782 (14)0.0890 (15)0.0106 (11)0.0434 (12)0.0189 (12)
Geometric parameters (Å, °) top
Cl1—C151.7426 (19)C9—H90.950
O1—C111.215 (2)C11—C121.490 (3)
O2—C21.365 (3)C12—C131.387 (2)
O2—C181.432 (3)C12—C171.396 (2)
O3—C81.361 (3)C13—C141.386 (3)
O3—C201.421 (3)C13—H130.950
C1—C21.378 (3)C14—C151.377 (3)
C1—C101.423 (3)C14—H140.950
C1—C111.509 (2)C15—C161.379 (3)
C2—C31.413 (3)C16—C171.380 (3)
C3—C41.366 (4)C16—H160.950
C3—H30.950C17—H170.950
C4—C51.408 (3)C18—C191.489 (4)
C4—H40.950C18—H18A0.990
C5—C101.422 (3)C18—H18B0.990
C5—C61.435 (3)C19—H19A0.980
C6—C71.343 (3)C19—H19B0.980
C6—H60.950C19—H19C0.980
C7—C81.410 (3)C20—H20A0.980
C7—H70.950C20—H20B0.980
C8—C91.373 (3)C20—H20C0.980
C9—C101.420 (3)
C2—O2—C18119.19 (18)C13—C12—C11120.47 (15)
C8—O3—C20118.27 (16)C17—C12—C11120.62 (16)
C2—C1—C10121.15 (17)C14—C13—C12121.21 (16)
C2—C1—C11117.15 (17)C14—C13—H13119.4
C10—C1—C11121.68 (16)C12—C13—H13119.4
O2—C2—C1115.52 (17)C15—C14—C13118.40 (17)
O2—C2—C3124.0 (2)C15—C14—H14120.8
C1—C2—C3120.5 (2)C13—C14—H14120.8
C4—C3—C2118.9 (2)C14—C15—C16121.81 (17)
C4—C3—H3120.6C14—C15—Cl1118.81 (15)
C2—C3—H3120.6C16—C15—Cl1119.38 (14)
C3—C4—C5122.49 (19)C15—C16—C17119.29 (17)
C3—C4—H4118.8C15—C16—H16120.4
C5—C4—H4118.8C17—C16—H16120.4
C4—C5—C10118.9 (2)C16—C17—C12120.37 (17)
C4—C5—C6123.5 (2)C16—C17—H17119.8
C10—C5—C6117.6 (2)C12—C17—H17119.8
C7—C6—C5121.9 (2)O2—C18—C19106.0 (2)
C7—C6—H6119.1O2—C18—H18A110.5
C5—C6—H6119.1C19—C18—H18A110.5
C6—C7—C8120.4 (2)O2—C18—H18B110.5
C6—C7—H7119.8C19—C18—H18B110.5
C8—C7—H7119.8H18A—C18—H18B108.7
O3—C8—C9125.51 (19)C18—C19—H19A109.5
O3—C8—C7114.35 (19)C18—C19—H19B109.5
C9—C8—C7120.1 (2)H19A—C19—H19B109.5
C8—C9—C10120.65 (18)C18—C19—H19C109.5
C8—C9—H9119.7H19A—C19—H19C109.5
C10—C9—H9119.7H19B—C19—H19C109.5
C9—C10—C5119.24 (18)O3—C20—H20A109.5
C9—C10—C1122.64 (16)O3—C20—H20B109.5
C5—C10—C1118.02 (19)H20A—C20—H20B109.5
O1—C11—C12122.05 (16)O3—C20—H20C109.5
O1—C11—C1120.71 (16)H20A—C20—H20C109.5
C12—C11—C1117.24 (14)H20B—C20—H20C109.5
C13—C12—C17118.90 (16)
C18—O2—C2—C1154.21 (17)C6—C5—C10—C1179.21 (16)
C18—O2—C2—C3−26.8 (3)C2—C1—C10—C9174.41 (16)
C10—C1—C2—O2179.52 (15)C11—C1—C10—C9−3.8 (3)
C11—C1—C2—O2−2.2 (2)C2—C1—C10—C5−2.0 (3)
C10—C1—C2—C30.5 (3)C11—C1—C10—C5179.83 (16)
C11—C1—C2—C3178.82 (16)C2—C1—C11—O1109.0 (2)
O2—C2—C3—C4−177.90 (18)C10—C1—C11—O1−72.7 (2)
C1—C2—C3—C41.0 (3)C2—C1—C11—C12−71.7 (2)
C2—C3—C4—C5−1.1 (3)C10—C1—C11—C12106.57 (18)
C3—C4—C5—C10−0.4 (3)O1—C11—C12—C13161.18 (18)
C3—C4—C5—C6−177.56 (19)C1—C11—C12—C13−18.1 (2)
C4—C5—C6—C7175.11 (19)O1—C11—C12—C17−17.2 (3)
C10—C5—C6—C7−2.1 (3)C1—C11—C12—C17163.60 (16)
C5—C6—C7—C8−0.4 (3)C17—C12—C13—C14−0.3 (3)
C20—O3—C8—C9−2.8 (3)C11—C12—C13—C14−178.72 (16)
C20—O3—C8—C7177.68 (16)C12—C13—C14—C15−0.8 (3)
C6—C7—C8—O3−178.08 (17)C13—C14—C15—C161.0 (3)
C6—C7—C8—C92.3 (3)C13—C14—C15—Cl1−179.07 (14)
O3—C8—C9—C10178.81 (16)C14—C15—C16—C170.0 (3)
C7—C8—C9—C10−1.7 (3)Cl1—C15—C16—C17−179.94 (14)
C8—C9—C10—C5−0.9 (3)C15—C16—C17—C12−1.2 (3)
C8—C9—C10—C1−177.22 (16)C13—C12—C17—C161.4 (3)
C4—C5—C10—C9−174.63 (16)C11—C12—C17—C16179.72 (16)
C6—C5—C10—C92.7 (2)C2—O2—C18—C19−162.1 (2)
C4—C5—C10—C11.9 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C20—H20B···Cg1i0.983.023.821 (3)140
C20—H20C···Cg1ii0.983.013.477 (3)110
C13—H13···O3iii0.952.443.213 (2)138
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x+1, −y+1/2, z+1/2; (iii) x, −y+1/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C20—H20B···Cg1i0.983.023.821 (3)140
C20—H20C···Cg1ii0.983.013.477 (3)110
C13—H13···O3iii0.952.443.213 (2)138
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x+1, −y+1/2, z+1/2; (iii) x, −y+1/2, z−1/2.
Acknowledgements top

This work was financially supported by Seiki Kogyo Co. Ltd, Tokorozawa, Saitama, Japan.

references
References top

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