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Acta Cryst. (2008). E64, o593    [ doi:10.1107/S1600536807068006 ]

2,3-Bis(2-chlorobenzyl)naphthalene-1,4-dione

S. Huang, Z.-S. Huang, L.-Q. Gu, Z. Zhou and S. W. Ng

Abstract top

The title disubstituted naphthalene-1,4-dione, C24H16Cl2O2, has the two chlorobenzyl substituents related by a non-crystallographic twofold rotation axis, generating a chiral conformation; both enantiomers are present. The two chlorobenzene rings are nearly perpendicular to the fused ring system, making angles of 88.8 (1) and 77.5 (1)° with it.

Related literature top

2,3-Bis(2-chlorobenzyl)naphthalene-1,4-dione was the unexpected product in the attempted synthesis of 2-(2-chlorobenzyl)naphthalene-1,4-dione by a free-radical alkylation (see Boehm et al., 1981; Chen et al., 2005; Tsai et al., 2001). Although the title dichloro compound has not been reported, 2,3-dibenzylnaphthalene-1,4-dione has been known for a long time (Baxter & Sanders, 1974; Chen et al., 2005; Oettmeier et al., 1986; Sharma & Torssell, 1978; Yamago et al., 2002). This class of compounds exhibits antitumour activity (Driscoll, 1974; Driscoll et al., 1974).

Experimental top

The title compound (I) was synthesized by using a modification of the procedure by Boehm et al. (1981). 1,4-Naphthoquinone (4 g, 25.3 mmol), 2-(2-chlorophenyl)acetic acid (8.60 g, 50.6 mmol), and silver nitrate (2.13 g, 12.6 mmol) in acetonitrile (60 ml) were heated to 353 K. A solution of ammonium peroxydisulfate in 30 ml water was added dropwise within 30 min. The mixture was then refluxed for another 2 h. The solution was concentrated to give a brown solid. The crude product was purified by column chromatography (silica gel, 1:2 dichloromethane:petroleum ether) to give yellow solid in 40% yield. Single crystals of (I) were obtained by slow evaporation of a 1:2 dichloromethane:petroleum ether (50 ml) solution.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with 50% probability ellipsoids for the non-H atoms.
2,3-Bis(2-chlorobenzyl)naphthalene-1,4-dione top
Crystal data top
C24H16Cl2O2F000 = 840
Mr = 407.27Dx = 1.418 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6278 reflections
a = 9.998 (1) Åθ = 2.2–27.5º
b = 10.272 (1) ŵ = 0.36 mm−1
c = 18.804 (2) ÅT = 295 (2) K
β = 99.071 (1)ºBlock, yellow
V = 1907.1 (3) Å30.5 × 0.5 × 0.5 mm
Z = 4
Data collection top
Bruker SMART area-detector
diffractometer		2921 reflections with I > 2σ(I)
Radiation source: medium-focus sealed tubeRint = 0.035
Monochromator: graphiteθmax = 27.5º
T = 295(2) Kθmin = 2.2º
φ and ω scansh = −12→12
Absorption correction: nonek = −13→13
12440 measured reflectionsl = −24→11
4366 independent 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)] = 0.044H-atom parameters constrained
wR(F2) = 0.131  w = 1/[σ2(Fo2) + (0.0628P)2 + 0.3578P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
4366 reflectionsΔρmax = 0.18 e Å−3
253 parametersΔρmin = −0.42 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C24H16Cl2O2V = 1907.1 (3) Å3
Mr = 407.27Z = 4
Monoclinic, P21/nMo Kα
a = 9.998 (1) ŵ = 0.36 mm−1
b = 10.272 (1) ÅT = 295 (2) K
c = 18.804 (2) Å0.5 × 0.5 × 0.5 mm
β = 99.071 (1)º
Data collection top
Bruker SMART area-detector
diffractometer		4366 independent reflections
Absorption correction: none2921 reflections with I > 2σ(I)
12440 measured reflectionsRint = 0.035
Refinement top
R[F2 > 2σ(F2)] = 0.044253 parameters
wR(F2) = 0.131H-atom parameters constrained
S = 1.02Δρmax = 0.18 e Å−3
4366 reflectionsΔρmin = −0.42 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.53007 (6)0.55702 (6)0.66580 (4)0.0779 (2)
Cl2−0.07641 (7)0.55387 (6)0.39047 (4)0.0856 (2)
O10.48173 (15)1.00324 (15)0.60292 (8)0.0693 (4)
O20.03492 (16)1.00716 (16)0.40921 (9)0.0763 (5)
C10.39509 (19)0.64277 (17)0.69086 (10)0.0508 (5)
C20.3610 (3)0.6185 (2)0.75798 (11)0.0707 (7)
H20.41080.55890.78870.085*
C30.2548 (3)0.6819 (2)0.77899 (13)0.0821 (8)
H30.23170.66580.82420.099*
C40.1817 (3)0.7694 (2)0.73391 (13)0.0743 (7)
H40.10810.81180.74810.089*
C50.2169 (2)0.79478 (19)0.66737 (10)0.0550 (5)
H50.16670.85500.63730.066*
C60.32481 (18)0.73306 (16)0.64433 (9)0.0438 (4)
C70.3679 (2)0.76083 (18)0.57207 (10)0.0524 (5)
H7A0.46580.76880.57890.063*
H7B0.34310.68710.54050.063*
C80.30674 (17)0.88202 (17)0.53547 (9)0.0426 (4)
C90.37930 (17)1.00544 (18)0.55815 (9)0.0438 (4)
C100.32835 (17)1.12940 (16)0.52474 (9)0.0422 (4)
C110.39225 (19)1.24608 (19)0.54606 (11)0.0555 (5)
H110.46501.24690.58360.067*
C120.3487 (2)1.3603 (2)0.51213 (14)0.0698 (6)
H120.39201.43820.52660.084*
C130.2408 (2)1.3596 (2)0.45657 (15)0.0745 (7)
H130.21311.43680.43300.089*
C140.1739 (2)1.2458 (2)0.43582 (12)0.0618 (5)
H140.10021.24650.39880.074*
C150.21608 (18)1.12966 (17)0.47002 (9)0.0447 (4)
C160.14175 (18)1.00724 (18)0.45086 (9)0.0476 (4)
C170.19512 (18)0.88289 (17)0.48466 (9)0.0443 (4)
C180.1139 (2)0.76407 (19)0.45892 (11)0.0566 (5)
H18A0.01850.78350.45740.068*
H18B0.13720.69460.49360.068*
C190.13550 (17)0.71606 (17)0.38532 (10)0.0466 (4)
C200.23605 (19)0.76496 (19)0.35008 (10)0.0542 (5)
H200.29380.82900.37240.065*
C210.2529 (2)0.7209 (2)0.28236 (12)0.0675 (6)
H210.32110.75550.25970.081*
C220.1689 (3)0.6263 (3)0.24877 (13)0.0762 (7)
H220.18040.59650.20340.091*
C230.0682 (2)0.5759 (2)0.28197 (13)0.0694 (6)
H230.01080.51210.25920.083*
C240.05248 (19)0.62039 (18)0.34967 (11)0.0553 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0746 (4)0.0631 (4)0.0901 (5)0.0227 (3)−0.0056 (3)0.0124 (3)
Cl20.0785 (4)0.0736 (4)0.1006 (5)−0.0274 (3)0.0012 (3)0.0022 (3)
O10.0628 (9)0.0722 (10)0.0629 (9)0.0011 (7)−0.0211 (7)0.0104 (7)
O20.0696 (9)0.0745 (10)0.0715 (10)0.0136 (8)−0.0305 (8)−0.0104 (8)
C10.0583 (11)0.0404 (9)0.0490 (10)−0.0050 (8)−0.0064 (9)0.0029 (8)
C20.1079 (19)0.0510 (12)0.0466 (12)−0.0113 (12)−0.0080 (12)0.0110 (10)
C30.134 (2)0.0653 (15)0.0519 (13)−0.0148 (16)0.0309 (14)0.0074 (11)
C40.0997 (18)0.0636 (14)0.0682 (14)−0.0003 (13)0.0402 (13)0.0038 (11)
C50.0640 (12)0.0510 (11)0.0520 (11)0.0054 (9)0.0157 (9)0.0062 (9)
C60.0519 (10)0.0376 (8)0.0399 (9)−0.0032 (7)0.0012 (7)0.0009 (7)
C70.0638 (11)0.0465 (10)0.0479 (10)0.0142 (9)0.0118 (9)0.0056 (8)
C80.0507 (10)0.0447 (10)0.0333 (8)0.0093 (8)0.0100 (7)0.0031 (7)
C90.0442 (9)0.0532 (10)0.0332 (8)0.0052 (8)0.0037 (7)0.0011 (7)
C100.0453 (9)0.0439 (9)0.0385 (9)0.0045 (7)0.0102 (7)−0.0013 (7)
C110.0516 (10)0.0549 (11)0.0603 (12)−0.0011 (9)0.0097 (9)−0.0046 (9)
C120.0709 (14)0.0443 (11)0.0967 (18)−0.0021 (10)0.0214 (13)−0.0018 (11)
C130.0813 (15)0.0472 (12)0.0973 (18)0.0131 (11)0.0211 (14)0.0212 (12)
C140.0621 (12)0.0606 (13)0.0610 (12)0.0173 (10)0.0050 (10)0.0161 (10)
C150.0478 (9)0.0467 (10)0.0397 (9)0.0097 (8)0.0073 (7)0.0034 (7)
C160.0505 (10)0.0539 (11)0.0359 (9)0.0089 (8)−0.0009 (8)−0.0028 (8)
C170.0509 (10)0.0465 (10)0.0365 (9)0.0017 (8)0.0097 (7)−0.0027 (7)
C180.0641 (12)0.0530 (11)0.0531 (11)−0.0076 (9)0.0101 (9)−0.0038 (9)
C190.0468 (9)0.0418 (9)0.0476 (10)0.0059 (8)−0.0036 (8)−0.0018 (8)
C200.0497 (10)0.0586 (11)0.0514 (11)0.0030 (9)−0.0007 (9)−0.0095 (9)
C210.0657 (13)0.0817 (16)0.0549 (12)0.0107 (12)0.0092 (10)−0.0092 (11)
C220.0836 (16)0.0850 (17)0.0555 (13)0.0203 (14)−0.0027 (12)−0.0212 (12)
C230.0766 (15)0.0565 (12)0.0658 (14)0.0061 (11)−0.0176 (12)−0.0163 (11)
C240.0538 (11)0.0436 (10)0.0626 (12)0.0045 (8)−0.0089 (9)−0.0003 (9)
Geometric parameters (Å, °) top
Cl1—C11.738 (2)C11—H110.9300
Cl2—C241.740 (2)C12—C131.379 (3)
O1—C91.219 (2)C12—H120.9300
O2—C161.221 (2)C13—C141.372 (3)
C1—C21.381 (3)C13—H130.9300
C1—C61.388 (2)C14—C151.389 (3)
C2—C31.357 (3)C14—H140.9300
C2—H20.9300C15—C161.476 (3)
C3—C41.365 (3)C16—C171.488 (2)
C3—H30.9300C17—C181.503 (3)
C4—C51.377 (3)C18—C191.516 (3)
C4—H40.9300C18—H18A0.9700
C5—C61.379 (3)C18—H18B0.9700
C5—H50.9300C19—C201.383 (3)
C6—C71.516 (2)C19—C241.389 (2)
C7—C81.505 (2)C20—C211.386 (3)
C7—H7A0.9700C20—H200.9300
C7—H7B0.9700C21—C221.371 (3)
C8—C171.350 (2)C21—H210.9300
C8—C91.489 (3)C22—C231.367 (3)
C9—C101.475 (2)C22—H220.9300
C10—C111.387 (3)C23—C241.385 (3)
C10—C151.398 (2)C23—H230.9300
C11—C121.373 (3)
C2—C1—C6121.6 (2)C14—C13—C12120.6 (2)
C2—C1—Cl1118.05 (16)C14—C13—H13119.7
C6—C1—Cl1120.36 (15)C12—C13—H13119.7
C3—C2—C1119.8 (2)C13—C14—C15120.1 (2)
C3—C2—H2120.1C13—C14—H14120.0
C1—C2—H2120.1C15—C14—H14120.0
C2—C3—C4120.1 (2)C14—C15—C10119.49 (18)
C2—C3—H3119.9C14—C15—C16120.95 (17)
C4—C3—H3119.9C10—C15—C16119.53 (15)
C3—C4—C5120.0 (2)O2—C16—C15120.86 (17)
C3—C4—H4120.0O2—C16—C17119.48 (18)
C5—C4—H4120.0C15—C16—C17119.62 (15)
C4—C5—C6121.55 (19)C8—C17—C16120.59 (16)
C4—C5—H5119.2C8—C17—C18124.53 (16)
C6—C5—H5119.2C16—C17—C18114.86 (16)
C5—C6—C1116.92 (17)C17—C18—C19114.23 (16)
C5—C6—C7122.83 (16)C17—C18—H18A108.7
C1—C6—C7120.25 (16)C19—C18—H18A108.7
C8—C7—C6114.41 (15)C17—C18—H18B108.7
C8—C7—H7A108.7C19—C18—H18B108.7
C6—C7—H7A108.7H18A—C18—H18B107.6
C8—C7—H7B108.7C20—C19—C24116.75 (18)
C6—C7—H7B108.7C20—C19—C18122.56 (16)
H7A—C7—H7B107.6C24—C19—C18120.68 (18)
C17—C8—C9120.54 (15)C19—C20—C21121.61 (19)
C17—C8—C7124.07 (17)C19—C20—H20119.2
C9—C8—C7115.39 (15)C21—C20—H20119.2
O1—C9—C10120.42 (17)C22—C21—C20120.0 (2)
O1—C9—C8120.02 (17)C22—C21—H21120.0
C10—C9—C8119.54 (15)C20—C21—H21120.0
C11—C10—C15119.39 (16)C23—C22—C21120.0 (2)
C11—C10—C9120.69 (16)C23—C22—H22120.0
C15—C10—C9119.90 (15)C21—C22—H22120.0
C12—C11—C10120.40 (19)C22—C23—C24119.5 (2)
C12—C11—H11119.8C22—C23—H23120.2
C10—C11—H11119.8C24—C23—H23120.2
C11—C12—C13120.0 (2)C19—C24—C23122.1 (2)
C11—C12—H12120.0C19—C24—Cl2119.53 (16)
C13—C12—H12120.0C23—C24—Cl2118.37 (16)
C6—C1—C2—C31.4 (3)C9—C10—C15—C14−176.07 (17)
Cl1—C1—C2—C3−178.88 (18)C11—C10—C15—C16−175.53 (16)
C1—C2—C3—C40.0 (4)C9—C10—C15—C165.7 (2)
C2—C3—C4—C5−0.9 (4)C14—C15—C16—O2−6.5 (3)
C3—C4—C5—C60.4 (4)C10—C15—C16—O2171.68 (18)
C4—C5—C6—C10.9 (3)C14—C15—C16—C17175.61 (17)
C4—C5—C6—C7−178.7 (2)C10—C15—C16—C17−6.2 (3)
C2—C1—C6—C5−1.8 (3)C9—C8—C17—C16−0.6 (2)
Cl1—C1—C6—C5178.44 (14)C7—C8—C17—C16−179.65 (16)
C2—C1—C6—C7177.85 (18)C9—C8—C17—C18−179.10 (16)
Cl1—C1—C6—C7−1.9 (2)C7—C8—C17—C181.8 (3)
C5—C6—C7—C814.0 (3)O2—C16—C17—C8−174.32 (18)
C1—C6—C7—C8−165.61 (16)C15—C16—C17—C83.6 (3)
C6—C7—C8—C17−96.4 (2)O2—C16—C17—C184.4 (3)
C6—C7—C8—C984.5 (2)C15—C16—C17—C18−177.76 (16)
C17—C8—C9—O1−178.37 (17)C8—C17—C18—C19−104.7 (2)
C7—C8—C9—O10.8 (2)C16—C17—C18—C1976.7 (2)
C17—C8—C9—C100.1 (2)C17—C18—C19—C209.4 (3)
C7—C8—C9—C10179.22 (15)C17—C18—C19—C24−169.87 (16)
O1—C9—C10—C11−3.0 (3)C24—C19—C20—C210.2 (3)
C8—C9—C10—C11178.54 (16)C18—C19—C20—C21−179.10 (18)
O1—C9—C10—C15175.71 (17)C19—C20—C21—C22−0.2 (3)
C8—C9—C10—C15−2.7 (2)C20—C21—C22—C230.3 (3)
C15—C10—C11—C12−2.2 (3)C21—C22—C23—C24−0.4 (3)
C9—C10—C11—C12176.55 (18)C20—C19—C24—C23−0.3 (3)
C10—C11—C12—C130.1 (3)C18—C19—C24—C23179.01 (18)
C11—C12—C13—C141.6 (4)C20—C19—C24—Cl2179.97 (14)
C12—C13—C14—C15−1.1 (3)C18—C19—C24—Cl2−0.7 (2)
C13—C14—C15—C10−1.1 (3)C22—C23—C24—C190.4 (3)
C13—C14—C15—C16177.1 (2)C22—C23—C24—Cl2−179.87 (17)
C11—C10—C15—C142.7 (3)
Acknowledgements top

The authors are indebted to the National Natural Science Foundation of China (grant No. 30701050), the Guangdong Provincial Science Foundation (grant No. 7301303) and the University of Malaya for supporting this study.

references
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