supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers Open access

is2542 scheme

Acta Cryst. (2010). E66, o1304    [ doi:10.1107/S1600536810015527 ]

(4-Chlorophenyl)(3,8-dibromo-2-hydroxy-7-methoxy-1-naphthyl)methanone

R. Mitsui, S. Watanabe, A. Nagasawa, A. Okamoto and N. Yonezawa

Abstract top

In the title compound, C18H11Br2ClO3, an intramolecular O-H...O=C hydrogen bond occurs, forming a six-membered ring. The naphthalene ring system and the benzene ring make a dihedral angle of 57.36 (9)°. The central carbonyl C-(C=O)-C group is twisted away from the naphthalene ring system and the benzene ring by 18.61 (15) and 26.25 (16)°, respectively. In the crystal structure, two intermolecular Br...Cl close contacts [3.4927 (7) and 3.4325 (7) Å] are observed.

Comment top

Recently, we reported the crystal structures of 1-aroylated 2,7-dimethoxynaphthalenes, 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene (Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa, 2008), (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (Mitsui, Nakaema, Noguchi & Yonezawa, 2008), (4-chlorophenyl)(2-ethoxy-7-methoxynaphthalen-1-yl)methanone (Mitsui et al., 2009), 1-bromo-8-(4-chlorobenzoyl)-7-hydroxy-2-methoxynaphthalene (Mitsui, Nakaema, Nagasawa et al., 2010) and (8-bromo-2,7-dimethoxy-1-naphthyl)(4-chlorophenyl)methanone (Mitsui, Nagasawa, Watanabe et al., 2010). As a part of our ongoing studies on the synthesis and crystal structure analysis of aroylated naphthalene derivatives, we prepared and analysed the structure of crystal of 2,5-dibromo-4-(4-chlorobenzoyl)-3-hydroxy-6-methoxynaphthalene, (I). The title compound was prepared by electrophilic aromatic bromination reaction of (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone with bromine.

An ORTEPIII (Burnett & Johnson, 1996) plot of (I) is shown in Fig. 1. In the molecule of (I), the intramolecular O—H···O═C hydrogen bond, which forms a six-membered ring including the C═O group and an edge of the naphthalene ring, is present (Table 1). The conformation of these groups resembles to that of (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (Mitsui, Nakaema, Noguchi & Yonezawa, 2008). Intriguingly, the central C═O group is twisted away from the naphthalene ring and the benzene ring, and the bromo group at 8-position of naphthalene is out of the least-squares plane of the naphthalene ring. The angles of the C═O bond vector against the least-squares plane of the naphthalene ring and the benzene ring are 18.61 (15) and 26.25 (16)°, respectively. The angle of the C9—Br1 bond vector against the least-squares plane of the naphthalene ring is 14.93 (7)°. This is presumably caused by release of the large steric repulsion brought about by the benzene ring and the bromo group on the naphthalene ring of (I).

In the crystal structure, the contact distances Br1···Cl1 and Br2···Cl1 are 3.4927 (7) and 3.4325 (7) Å, respectively (Fig. 2). These contacts are shorter than the sum of their van der Waals radii (3.60 Å), and the five atoms are arranged nearly linear [C9—Br1···Cl1 = 154.14 (6)°, C3—Br2···Cl1 = 165.35 (7)°], suggesting that there is a possibility for halogen interaction (Saruma & Desiraju, 1986; Pedireddi et al., 1994; Moorthy et al., 2002).

Related literature top

For related structures, see: Mitsui et al. (2009); Mitsui, Nakaema, Nagasawa et al. (2010); Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa (2008); Mitsui, Nakaema, Noguchi & Yonezawa (2008); Mitsui, Nagasawa, Watanabe et al. (2010). For information on halogen···halogen contacts, see: Moorthy et al. (2002); Pedireddi et al. (1994); Saruma & Desiraju (1986).

Experimental top

To a solution of (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (313 mg, 1.00 mmol) in chloroform (5 ml) was added Br2 (483 mg, 3.03 mmol) drop-wise. The reaction mixture was heated at reflux for 2 h, then poured into aqueous 2 M Na2S2O3 (10 ml), and the aqueous layer was extracted with CHCl3 (3 × 10 ml). The combined organic layers were washed with 2 M Na2S2O3 (3 × 30 ml) and brine (3 × 30 ml), and dried over MgSO4 overnight. The solvent was removed in vacuo and the crude material was purified by column chromatography (silica gel, CHCl3) to give the title compound (yield 306 mg, 65%). Single crystals suitable for X-ray diffraction analysis were obtained from CHCl3 as yellow blocks (m.p. 455.0–455.5 K).

Spectroscopic Data: 1H NMR (300 MHz, CDCl3) δ 8.10 (s, 1H), 8.04 (s, 1H), 7.75 (d, 1H), 7.58 (d, 2H), 7.31 (d, 2H), 7.17 (d, 1H), 3.95 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 195.6, 156.3, 152.6, 139.3, 138.3, 134.9, 132.4, 130.3, 129.1, 128.8, 125.8, 118.1, 112.2, 110.5, 105.9, 56.9; IR (KBr): 1670, 1607, 1587, 1495, 1276, 1215, 1096, 782; HRMS (m/z): [M + H]+ calcd for C18H12Br2ClO3, 468.8842 found, 468.8839. Anal. Calcd for C18H11Br2ClO3: C 45.95, H 2.36. Found: C 46.23, H 2.39.

Refinement top

All H atoms were located in a difference Fourier map and were subsequently refined as riding atoms, with O—H = 0.833 Å, C—H = 0.95 Å (aromatic) and 0.98 Å (methyl) Å, and with Uiso(H) = 1.2Ueq(O, 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. The molecular structure of compound (I), showing 50% probability displacement ellipsoids. The intramolecular hydrogen bond is shown as a dashed line.
[Figure 2] Fig. 2. Partial crystal packing diagram of compound (I), viewed down the b axis. Halogen-halogen interactions are shown as dashed lines.
(4-Chlorophenyl)(3,8-dibromo-2-hydroxy-7-methoxy-1-naphthyl)methanone top
Crystal data top
C18H11Br2ClO3F(000) = 920
Mr = 470.54Dx = 1.893 Mg m−3
Monoclinic, P21/cMelting point = 455.0–455.5 K
Hall symbol: -P 2ybcCu Kα radiation, λ = 1.54187 Å
a = 12.1513 (2) ÅCell parameters from 28732 reflections
b = 10.06343 (18) Åθ = 3.3–68.2°
c = 13.8936 (3) ŵ = 7.85 mm−1
β = 103.675 (1)°T = 193 K
V = 1650.79 (5) Å3Block, yellow
Z = 40.30 × 0.25 × 0.20 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3022 independent reflections
Radiation source: rotating anode2940 reflections with I > 2σ(I)
graphiteRint = 0.068
Detector resolution: 10.00 pixels mm-1θmax = 68.3°, θmin = 3.7°
ω scansh = −14→14
Absorption correction: numerical
(NUMABS; Higashi, 1999)		k = −12→12
Tmin = 0.189, Tmax = 0.308l = −16→16
29373 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)] = 0.028H-atom parameters constrained
wR(F2) = 0.076 w = 1/[σ2(Fo2) + (0.0457P)2 + 0.9314P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
3022 reflectionsΔρmax = 0.60 e Å−3
219 parametersΔρmin = −0.64 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0162 (4)
Crystal data top
C18H11Br2ClO3V = 1650.79 (5) Å3
Mr = 470.54Z = 4
Monoclinic, P21/cCu Kα radiation
a = 12.1513 (2) ŵ = 7.85 mm−1
b = 10.06343 (18) ÅT = 193 K
c = 13.8936 (3) Å0.30 × 0.25 × 0.20 mm
β = 103.675 (1)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3022 independent reflections
Absorption correction: numerical
(NUMABS; Higashi, 1999)		2940 reflections with I > 2σ(I)
Tmin = 0.189, Tmax = 0.308Rint = 0.068
29373 measured reflectionsθmax = 68.3°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.076Δρmax = 0.60 e Å−3
S = 1.11Δρmin = −0.64 e Å−3
3022 reflectionsAbsolute structure: ?
219 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Br10.348845 (18)0.93221 (2)0.140206 (18)0.02724 (13)
Br2−0.250748 (19)0.77531 (3)0.077383 (18)0.03487 (13)
Cl10.49341 (5)0.85290 (6)0.59621 (4)0.03239 (17)
O10.18770 (16)0.61119 (18)0.17108 (14)0.0377 (4)
O2−0.02937 (15)0.63660 (18)0.11024 (13)0.0357 (4)
H2O0.03290.59820.11980.043*
O30.33774 (13)1.21262 (15)0.17994 (12)0.0256 (3)
C10.09899 (18)0.8215 (2)0.14949 (15)0.0222 (4)
C2−0.0097 (2)0.7676 (2)0.11910 (17)0.0264 (5)
C3−0.10526 (18)0.8529 (3)0.10204 (16)0.0268 (5)
C4−0.09270 (18)0.9868 (3)0.10944 (16)0.0268 (5)
H4−0.15791.04170.10040.032*
C50.01632 (18)1.0458 (2)0.13047 (16)0.0232 (5)
C60.02945 (19)1.1856 (2)0.13389 (17)0.0266 (5)
H6−0.03611.24020.12170.032*
C70.1339 (2)1.2440 (2)0.15434 (17)0.0259 (5)
H70.14081.33770.16170.031*
C80.23139 (18)1.1645 (2)0.16441 (15)0.0216 (4)
C90.21941 (17)1.0276 (2)0.15487 (15)0.0198 (4)
C100.11426 (18)0.9635 (2)0.14633 (15)0.0203 (4)
C110.18698 (19)0.7270 (2)0.20076 (17)0.0249 (5)
C120.26347 (18)0.7639 (2)0.29783 (17)0.0229 (5)
C130.23528 (18)0.8631 (2)0.35778 (16)0.0238 (5)
H130.16780.91310.33510.029*
C140.30470 (19)0.8895 (2)0.45010 (17)0.0261 (5)
H140.28460.95590.49140.031*
C150.40403 (18)0.8174 (2)0.48129 (16)0.0242 (5)
C160.43420 (19)0.7176 (2)0.42328 (18)0.0278 (5)
H160.50240.66890.44580.033*
C170.36288 (19)0.6908 (2)0.33217 (18)0.0268 (5)
H170.38160.62170.29220.032*
C180.3525 (2)1.3542 (2)0.18675 (19)0.0318 (5)
H18A0.43261.37600.19360.038*
H18B0.32791.38730.24460.038*
H18C0.30711.39600.12670.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01855 (17)0.02555 (19)0.04042 (19)0.00433 (8)0.01259 (11)0.00170 (9)
Br20.01849 (17)0.0547 (2)0.02984 (18)−0.01184 (10)0.00254 (11)0.00019 (10)
Cl10.0229 (3)0.0404 (4)0.0307 (3)−0.0019 (2)0.0000 (2)−0.0010 (2)
O10.0354 (10)0.0239 (9)0.0482 (11)0.0019 (7)−0.0014 (8)−0.0083 (8)
O20.0278 (9)0.0311 (10)0.0447 (10)−0.0081 (7)0.0016 (7)−0.0024 (8)
O30.0196 (8)0.0220 (8)0.0346 (9)−0.0022 (6)0.0050 (6)−0.0014 (6)
C10.0185 (10)0.0247 (12)0.0229 (10)−0.0011 (9)0.0038 (8)−0.0019 (8)
C20.0249 (12)0.0304 (13)0.0228 (11)−0.0053 (9)0.0034 (9)−0.0009 (9)
C30.0150 (10)0.0423 (14)0.0219 (10)−0.0054 (9)0.0021 (8)0.0000 (9)
C40.0175 (10)0.0387 (14)0.0246 (11)0.0029 (9)0.0056 (8)0.0001 (9)
C50.0175 (10)0.0325 (12)0.0198 (10)0.0035 (9)0.0050 (8)0.0004 (9)
C60.0202 (11)0.0305 (12)0.0291 (11)0.0085 (9)0.0059 (9)0.0008 (9)
C70.0259 (12)0.0236 (12)0.0277 (11)0.0041 (9)0.0054 (9)−0.0021 (9)
C80.0194 (10)0.0262 (12)0.0193 (9)−0.0001 (8)0.0046 (8)−0.0011 (8)
C90.0156 (10)0.0228 (11)0.0213 (10)0.0045 (8)0.0049 (8)0.0003 (8)
C100.0180 (10)0.0242 (11)0.0181 (9)0.0016 (8)0.0033 (8)−0.0017 (8)
C110.0216 (11)0.0221 (12)0.0309 (12)−0.0018 (9)0.0063 (9)−0.0011 (9)
C120.0195 (10)0.0206 (11)0.0292 (11)−0.0014 (8)0.0072 (9)0.0036 (8)
C130.0176 (10)0.0246 (12)0.0301 (11)0.0014 (8)0.0075 (9)0.0034 (9)
C140.0224 (11)0.0285 (12)0.0282 (11)0.0011 (9)0.0077 (9)0.0002 (9)
C150.0188 (10)0.0283 (12)0.0243 (10)−0.0046 (9)0.0031 (8)0.0024 (9)
C160.0191 (11)0.0291 (13)0.0352 (12)0.0035 (9)0.0063 (9)0.0051 (9)
C170.0235 (11)0.0243 (12)0.0333 (12)0.0019 (9)0.0079 (9)−0.0004 (9)
C180.0331 (13)0.0233 (12)0.0387 (13)−0.0066 (10)0.0075 (10)−0.0012 (10)
Geometric parameters (Å, °) top
Br1—C91.894 (2)C7—C81.408 (3)
Br2—C31.888 (2)C7—H70.9500
Cl1—C151.743 (2)C8—C91.388 (3)
O1—C111.237 (3)C9—C101.411 (3)
O2—C21.340 (3)C11—C121.492 (3)
O2—H2O0.8326C12—C131.394 (3)
O3—C81.349 (3)C12—C171.398 (3)
O3—C181.437 (3)C13—C141.384 (3)
C1—C21.398 (3)C13—H130.9500
C1—C101.443 (3)C14—C151.387 (3)
C1—C111.481 (3)C14—H140.9500
C2—C31.418 (3)C15—C161.390 (3)
C3—C41.357 (4)C16—C171.381 (3)
C4—C51.418 (3)C16—H160.9500
C4—H40.9500C17—H170.9500
C5—C61.415 (3)C18—H18A0.9800
C5—C101.424 (3)C18—H18B0.9800
C6—C71.366 (3)C18—H18C0.9800
C6—H60.9500
C2—O2—H2O107.9C9—C10—C1124.8 (2)
C8—O3—C18117.81 (18)C5—C10—C1118.17 (19)
C2—C1—C10119.6 (2)O1—C11—C1120.4 (2)
C2—C1—C11114.8 (2)O1—C11—C12118.9 (2)
C10—C1—C11124.52 (19)C1—C11—C12119.97 (19)
O2—C2—C1123.0 (2)C13—C12—C17119.2 (2)
O2—C2—C3117.3 (2)C13—C12—C11122.0 (2)
C1—C2—C3119.6 (2)C17—C12—C11118.7 (2)
C4—C3—C2121.0 (2)C14—C13—C12120.6 (2)
C4—C3—Br2120.53 (18)C14—C13—H13119.7
C2—C3—Br2118.32 (18)C12—C13—H13119.7
C3—C4—C5121.0 (2)C13—C14—C15118.9 (2)
C3—C4—H4119.5C13—C14—H14120.5
C5—C4—H4119.5C15—C14—H14120.5
C6—C5—C4121.0 (2)C14—C15—C16121.7 (2)
C6—C5—C10119.3 (2)C14—C15—Cl1119.13 (18)
C4—C5—C10119.6 (2)C16—C15—Cl1119.13 (18)
C7—C6—C5121.8 (2)C17—C16—C15118.6 (2)
C7—C6—H6119.1C17—C16—H16120.7
C5—C6—H6119.1C15—C16—H16120.7
C6—C7—C8119.6 (2)C16—C17—C12120.9 (2)
C6—C7—H7120.2C16—C17—H17119.5
C8—C7—H7120.2C12—C17—H17119.5
O3—C8—C9116.51 (19)O3—C18—H18A109.5
O3—C8—C7124.3 (2)O3—C18—H18B109.5
C9—C8—C7119.2 (2)H18A—C18—H18B109.5
C8—C9—C10122.30 (19)O3—C18—H18C109.5
C8—C9—Br1116.24 (16)H18A—C18—H18C109.5
C10—C9—Br1121.15 (17)H18B—C18—H18C109.5
C9—C10—C5117.0 (2)
C10—C1—C2—O2172.9 (2)C6—C5—C10—C9−6.2 (3)
C11—C1—C2—O2−18.3 (3)C4—C5—C10—C9172.45 (18)
C10—C1—C2—C3−10.9 (3)C6—C5—C10—C1175.64 (19)
C11—C1—C2—C3157.8 (2)C4—C5—C10—C1−5.7 (3)
O2—C2—C3—C4−180.0 (2)C2—C1—C10—C9−166.1 (2)
C1—C2—C3—C43.7 (3)C11—C1—C10—C926.3 (3)
O2—C2—C3—Br24.2 (3)C2—C1—C10—C511.9 (3)
C1—C2—C3—Br2−172.17 (16)C11—C1—C10—C5−155.7 (2)
C2—C3—C4—C52.6 (3)C2—C1—C11—O140.3 (3)
Br2—C3—C4—C5178.36 (16)C10—C1—C11—O1−151.6 (2)
C3—C4—C5—C6177.2 (2)C2—C1—C11—C12−129.7 (2)
C3—C4—C5—C10−1.5 (3)C10—C1—C11—C1238.5 (3)
C4—C5—C6—C7179.8 (2)O1—C11—C12—C13−149.6 (2)
C10—C5—C6—C7−1.6 (3)C1—C11—C12—C1320.5 (3)
C5—C6—C7—C85.3 (3)O1—C11—C12—C1726.3 (3)
C18—O3—C8—C9177.92 (19)C1—C11—C12—C17−163.6 (2)
C18—O3—C8—C70.1 (3)C17—C12—C13—C140.1 (3)
C6—C7—C8—O3176.8 (2)C11—C12—C13—C14176.0 (2)
C6—C7—C8—C9−1.0 (3)C12—C13—C14—C151.3 (3)
O3—C8—C9—C10174.84 (18)C13—C14—C15—C16−1.5 (3)
C7—C8—C9—C10−7.2 (3)C13—C14—C15—Cl1178.49 (17)
O3—C8—C9—Br1−11.4 (2)C14—C15—C16—C170.2 (3)
C7—C8—C9—Br1166.54 (16)Cl1—C15—C16—C17−179.73 (18)
C8—C9—C10—C510.7 (3)C15—C16—C17—C121.2 (3)
Br1—C9—C10—C5−162.76 (15)C13—C12—C17—C16−1.4 (3)
C8—C9—C10—C1−171.3 (2)C11—C12—C17—C16−177.4 (2)
Br1—C9—C10—C115.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···O10.831.852.585 (3)146
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···O10.831.852.585 (3)146
Acknowledgements top

The authors would like to express their gratitude to Professor Keiichi Noguchi for technical advice. This work was partially supported by the Ogasawara Foundation for the Promotion of Science & Engineering, Tokyo, Japan.

references
References top

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388.

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory. Tennessee, USA.

Higashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan.

Mitsui, R., Nagasawa, A., Watanabe, S., Okamoto, A. & Yonezawa, N. (2010). Acta Cryst. E66, o873.

Mitsui, R., Nakaema, K., Nagasawa, A., Noguchi, K. & Yonezawa, N. (2010). Acta Cryst. E66, o676.

Mitsui, R., Nakaema, K., Noguchi, K., Okamoto, A. & Yonezawa, N. (2008). Acta Cryst. E64, o1278.

Mitsui, R., Nakaema, K., Noguchi, K. & Yonezawa, N. (2008). Acta Cryst. E64, o2497.

Mitsui, R., Noguchi, K. & Yonezawa, N. (2009). Acta Cryst. E65, o543.

Moorthy, J. N., Natarajan, R., Mal, P. & Venugopalan, P. (2002). J. Am. Chem. Soc. 124, 6530–6531.

Pedireddi, V. R., Shekhar Reddy, D., Satish Goud, B., Craig, D. C., Rae, A. D. & Desiraju, G. R. (1994). J. Chem. Soc. Perkin Trans. 2, pp. 2353–2359.

Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.

Saruma, J. A. R. & Desiraju, G. R. (1986). Acc. Chem. Res. 19, 222–228.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.