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Acta Cryst. (2009). E65, o64    [ doi:10.1107/S1600536808040993 ]

2-Chloro-3-(4-chlorobenzamido)-1,4-naphthoquinone

Y. Brandy, R. J. Butcher, T. A. Adesiyun, S. Berhe and O. Bakare

Abstract top

The naphthoquinone ring is almost perpendicular [dihedral angle 71.02 (3)°] to the phenyl group of the title compound, C17H9Cl2NO3, while the dihedral angle between the amide group and the 4-chlorophenyl ring is 21.9 (2)°. The conformation of the N-H and C=O bonds are anti to each other. N-H...Cl hydrogen bonds link the molecules into chains in the a-axis direction. In addition, these chains are linked by weak intermolecular C-H...O interactions.

Comment top

The amido and imido derivatives of 3-chloro-1,4-naphthoquinone are well known for their anti-inflammatory, antiplatelet, antiallergic and anticancer activities (Lien et al., 1997; Huang et al., 2005; Bakare et al., 2003; Copeland et al., 2007). The title compound, 2-chloro-3-(p-chlorobenzamido)-1,4-naphthoquinone was obtained as an intermediate in the synthesis of some oxazolo-1,4-naphthoquinone and imido-substituted-1,4-naphthoquinone analogs.

The naphthoquinone ring is almost perpendicular to the phenyl group of the title compound C17H9Cl2NO3, while the dihedral angle betwen the amide group and the 4-chlorophenyl ring is 21.9 (2)° (Fig. 1). The conformation of the N—H and C=O bonds are anti to each other (Gowda, Kožíšek et al., 2008; Gowda, Tokarčík et al., 2008). N—H···Cl hydrogen bonds link the molecules into chains in the a direction. In addition, these chains are linked by weak intermolecular Ar—H···O interactions (Fig. 2, Table 1).

Related literature top

For similar structures see: Lien et al. (1997); Huang et al. (2005); Bakare et al. (2003); Copeland et al. (2007); Win et al. (2005); Rubin-Preminger et al. (2004). For related literature, see: Gowda, Kožíšek et al. (2008); Gowda, Tokarčík et al. (2008); van Oosten et al. (2008); Shen et al. (2008).

Experimental top

A mixture of 2-amino-3-chloro-1,4-naphthoquinone (213 mg, 1.03 mmol) and 4-chloro-benzoylchloride (2 ml) was refluxed for 2 1/2 h (powerstat setting at 70). The reaction mixture was cooled to room temperature. The precipitate was isolated by vacuum filtration and the yellow-grey solid was washed with diethyl ether. The crude was recrystallized from ethanol (20 ml) to obtain a yellow solid (67 mg, 18.8%). Crystals for x-ray study were obtained by recrystallization from methanol.

Refinement top

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H = 0.95 Å, N—H = 0.88 Å and Uiso(H) = 1.2Ueq(C, N).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 20% probability level.
[Figure 2] Fig. 2. View of the packing viewed down the a axis. Dashed bonds show weak C—H···O interactions.
2-Chloro-3-(4-chlorobenzamido)-1,4-naphthoquinone top
Crystal data top
C17H9Cl2NO3F(000) = 704
Mr = 346.15Dx = 1.582 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4629 reflections
a = 5.6011 (2) Åθ = 4.6–32.5°
b = 8.7237 (3) ŵ = 0.46 mm−1
c = 29.7957 (9) ÅT = 200 K
β = 93.504 (3)°Plate, pale yellow
V = 1453.16 (8) Å30.49 × 0.41 × 0.12 mm
Z = 4
Data collection top
Oxford Diffraction Gemini R
diffractometer		4842 independent reflections
Radiation source: fine-focus sealed tube2832 reflections with I > 2σ(I)
graphiteRint = 0.035
Detector resolution: 10.5081 pixels mm-1θmax = 32.6°, θmin = 4.6°
φ and ω scansh = −8→8
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)		k = −12→12
Tmin = 0.887, Tmax = 1.000l = −44→44
13882 measured reflections
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters constrained
S = 0.93 w = 1/[σ2(Fo2) + (0.0416P)2]
where P = (Fo2 + 2Fc2)/3
4842 reflections(Δ/σ)max = 0.001
208 parametersΔρmax = 0.29 e Å−3
0 restraintsΔρmin = −0.36 e Å−3
Crystal data top
C17H9Cl2NO3V = 1453.16 (8) Å3
Mr = 346.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.6011 (2) ŵ = 0.46 mm−1
b = 8.7237 (3) ÅT = 200 K
c = 29.7957 (9) Å0.49 × 0.41 × 0.12 mm
β = 93.504 (3)°
Data collection top
Oxford Diffraction Gemini R
diffractometer		4842 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)		2832 reflections with I > 2σ(I)
Tmin = 0.887, Tmax = 1.000Rint = 0.035
13882 measured reflectionsθmax = 32.6°
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.086Δρmax = 0.29 e Å−3
S = 0.93Δρmin = −0.36 e Å−3
4842 reflectionsAbsolute structure: ?
208 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. (CrysAlis RED; Oxford Diffraction, 2007) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Cl10.42210 (6)0.13331 (4)0.298854 (11)0.02796 (10)
Cl2−0.42944 (7)−0.05032 (6)0.057164 (13)0.04852 (14)
O10.54644 (18)0.07511 (14)0.39281 (4)0.0401 (3)
O2−0.26101 (17)−0.20745 (14)0.33569 (3)0.0378 (3)
O30.31583 (17)−0.12832 (14)0.24103 (3)0.0364 (3)
N−0.02512 (19)−0.06128 (15)0.27365 (4)0.0273 (3)
H0A−0.1786−0.04150.26890.033*
C10.3653 (2)0.00688 (18)0.38026 (5)0.0275 (3)
C20.2705 (2)0.01309 (17)0.33244 (4)0.0251 (3)
C30.0712 (2)−0.06238 (17)0.31773 (4)0.0240 (3)
C4−0.0749 (2)−0.14777 (18)0.34975 (5)0.0264 (3)
C50.0144 (2)−0.15604 (18)0.39758 (5)0.0272 (3)
C6−0.1138 (3)−0.2369 (2)0.42817 (5)0.0391 (4)
H6A−0.2591−0.28640.41860.047*
C7−0.0289 (3)−0.2451 (3)0.47288 (5)0.0477 (5)
H7A−0.1169−0.30020.49390.057*
C80.1823 (3)−0.1737 (2)0.48705 (5)0.0477 (5)
H8A0.2390−0.17940.51770.057*
C90.3111 (3)−0.0940 (2)0.45660 (5)0.0391 (4)
H9A0.4574−0.04590.46630.047*
C100.2273 (2)−0.08383 (18)0.41170 (5)0.0287 (3)
C110.1070 (3)−0.08964 (17)0.23680 (5)0.0263 (3)
C12−0.0252 (2)−0.07098 (17)0.19218 (4)0.0245 (3)
C13−0.2316 (2)0.01736 (18)0.18635 (5)0.0277 (3)
H13A−0.28820.07260.21100.033*
C14−0.3550 (3)0.02492 (19)0.14462 (5)0.0315 (3)
H14A−0.49660.08460.14060.038*
C15−0.2697 (3)−0.05531 (19)0.10907 (5)0.0307 (3)
C16−0.0608 (3)−0.1395 (2)0.11357 (5)0.0319 (3)
H16A−0.0020−0.19130.08850.038*
C170.0618 (3)−0.14706 (19)0.15551 (5)0.0295 (3)
H17A0.2058−0.20450.15920.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.02827 (17)0.0286 (2)0.02758 (17)−0.00541 (15)0.00608 (13)0.00212 (15)
Cl20.0514 (2)0.0680 (4)0.02503 (18)0.0176 (2)−0.00744 (17)−0.0029 (2)
O10.0364 (6)0.0500 (8)0.0334 (6)−0.0141 (6)−0.0034 (5)−0.0042 (5)
O20.0321 (5)0.0490 (8)0.0318 (6)−0.0152 (5)−0.0010 (5)0.0023 (5)
O30.0328 (6)0.0476 (8)0.0288 (5)0.0120 (5)0.0007 (4)−0.0072 (5)
N0.0240 (6)0.0383 (8)0.0196 (5)0.0012 (5)0.0019 (5)0.0013 (5)
C10.0266 (7)0.0307 (9)0.0253 (7)−0.0004 (6)0.0021 (6)−0.0031 (6)
C20.0272 (7)0.0247 (8)0.0239 (7)0.0006 (6)0.0058 (6)−0.0012 (6)
C30.0252 (6)0.0278 (8)0.0192 (6)0.0026 (6)0.0028 (5)−0.0013 (6)
C40.0278 (7)0.0268 (8)0.0248 (7)−0.0014 (6)0.0030 (6)−0.0008 (6)
C50.0294 (7)0.0302 (9)0.0220 (6)0.0000 (6)0.0023 (6)0.0005 (6)
C60.0374 (8)0.0517 (12)0.0286 (7)−0.0087 (8)0.0041 (7)0.0049 (8)
C70.0502 (10)0.0654 (14)0.0282 (8)−0.0078 (9)0.0083 (7)0.0117 (9)
C80.0532 (10)0.0680 (15)0.0214 (7)0.0003 (10)−0.0008 (7)0.0049 (8)
C90.0374 (8)0.0562 (12)0.0232 (7)−0.0047 (8)−0.0026 (6)−0.0018 (7)
C100.0296 (7)0.0348 (9)0.0218 (6)0.0004 (6)0.0023 (6)−0.0028 (6)
C110.0306 (7)0.0258 (8)0.0228 (7)0.0018 (6)0.0033 (6)−0.0012 (6)
C120.0275 (7)0.0260 (8)0.0201 (6)−0.0020 (6)0.0034 (5)0.0002 (6)
C130.0321 (7)0.0282 (8)0.0233 (7)0.0034 (6)0.0060 (6)−0.0017 (6)
C140.0293 (7)0.0361 (9)0.0291 (7)0.0071 (7)0.0022 (6)0.0014 (7)
C150.0359 (8)0.0359 (9)0.0202 (6)0.0015 (7)−0.0008 (6)0.0018 (7)
C160.0347 (8)0.0400 (10)0.0215 (7)0.0064 (7)0.0051 (6)−0.0032 (7)
C170.0292 (7)0.0348 (9)0.0246 (7)0.0052 (6)0.0035 (6)−0.0009 (6)
Geometric parameters (Å, °) top
Cl1—C21.7105 (15)C7—C81.380 (2)
Cl2—C151.7394 (14)C7—H7A0.9500
O1—C11.2154 (17)C8—C91.381 (2)
O2—C41.2166 (16)C8—H8A0.9500
O3—C111.2167 (16)C9—C101.3932 (19)
N—C111.3834 (18)C9—H9A0.9500
N—C31.3890 (15)C11—C121.4905 (19)
N—H0A0.8800C12—C171.392 (2)
C1—C101.480 (2)C12—C131.392 (2)
C1—C21.4907 (18)C13—C141.3867 (19)
C2—C31.3461 (19)C13—H13A0.9500
C3—C41.494 (2)C14—C151.379 (2)
C4—C51.4829 (19)C14—H14A0.9500
C5—C61.387 (2)C15—C161.381 (2)
C5—C101.391 (2)C16—C171.3903 (19)
C6—C71.389 (2)C16—H16A0.9500
C6—H6A0.9500C17—H17A0.9500
C11—N—C3123.62 (11)C8—C9—C10120.27 (15)
C11—N—H0A118.2C8—C9—H9A119.9
C3—N—H0A118.2C10—C9—H9A119.9
O1—C1—C10121.71 (13)C5—C10—C9119.60 (14)
O1—C1—C2121.20 (14)C5—C10—C1121.47 (12)
C10—C1—C2117.08 (12)C9—C10—C1118.91 (13)
C3—C2—C1122.21 (13)O3—C11—N121.65 (12)
C3—C2—Cl1122.74 (11)O3—C11—C12123.01 (13)
C1—C2—Cl1114.90 (10)N—C11—C12115.34 (12)
C2—C3—N124.82 (13)C17—C12—C13119.63 (12)
C2—C3—C4120.79 (12)C17—C12—C11118.00 (12)
N—C3—C4114.27 (12)C13—C12—C11122.36 (12)
O2—C4—C5122.80 (13)C14—C13—C12120.19 (13)
O2—C4—C3119.01 (12)C14—C13—H13A119.9
C5—C4—C3118.19 (12)C12—C13—H13A119.9
C6—C5—C10120.03 (13)C15—C14—C13119.16 (13)
C6—C5—C4119.89 (13)C15—C14—H14A120.4
C10—C5—C4120.08 (13)C13—C14—H14A120.4
C5—C6—C7119.71 (15)C14—C15—C16121.78 (13)
C5—C6—H6A120.1C14—C15—Cl2119.11 (11)
C7—C6—H6A120.1C16—C15—Cl2119.11 (11)
C8—C7—C6120.49 (16)C15—C16—C17118.79 (14)
C8—C7—H7A119.8C15—C16—H16A120.6
C6—C7—H7A119.8C17—C16—H16A120.6
C7—C8—C9119.89 (14)C16—C17—C12120.37 (13)
C7—C8—H8A120.1C16—C17—H17A119.8
C9—C8—H8A120.1C12—C17—H17A119.8
O1—C1—C2—C3179.54 (14)C6—C5—C10—C1−178.31 (15)
C10—C1—C2—C3−1.3 (2)C4—C5—C10—C12.1 (2)
O1—C1—C2—Cl1−4.8 (2)C8—C9—C10—C5−0.8 (3)
C10—C1—C2—Cl1174.35 (11)C8—C9—C10—C1177.93 (16)
C1—C2—C3—N−179.82 (14)O1—C1—C10—C5177.09 (15)
Cl1—C2—C3—N4.8 (2)C2—C1—C10—C5−2.0 (2)
C1—C2—C3—C44.4 (2)O1—C1—C10—C9−1.6 (2)
Cl1—C2—C3—C4−170.99 (11)C2—C1—C10—C9179.29 (14)
C11—N—C3—C249.6 (2)C3—N—C11—O35.2 (2)
C11—N—C3—C4−134.37 (14)C3—N—C11—C12−175.37 (13)
C2—C3—C4—O2175.91 (14)O3—C11—C12—C1721.9 (2)
N—C3—C4—O2−0.3 (2)N—C11—C12—C17−157.54 (14)
C2—C3—C4—C5−4.1 (2)O3—C11—C12—C13−159.00 (15)
N—C3—C4—C5179.64 (12)N—C11—C12—C1321.6 (2)
O2—C4—C5—C61.2 (2)C17—C12—C13—C142.4 (2)
C3—C4—C5—C6−178.73 (15)C11—C12—C13—C14−176.72 (14)
O2—C4—C5—C10−179.23 (15)C12—C13—C14—C15−0.4 (2)
C3—C4—C5—C100.8 (2)C13—C14—C15—C16−1.9 (2)
C10—C5—C6—C70.1 (3)C13—C14—C15—Cl2178.10 (12)
C4—C5—C6—C7179.64 (16)C14—C15—C16—C172.1 (2)
C5—C6—C7—C8−0.2 (3)Cl2—C15—C16—C17−177.92 (13)
C6—C7—C8—C9−0.3 (3)C15—C16—C17—C120.0 (2)
C7—C8—C9—C100.7 (3)C13—C12—C17—C16−2.2 (2)
C6—C5—C10—C90.4 (2)C11—C12—C17—C16176.94 (14)
C4—C5—C10—C9−179.17 (15)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N—H0A···Cl1i0.882.893.6491 (12)145
C14—H14A···O2ii0.952.403.2517 (19)149
Symmetry codes: (i) x−1, y, z; (ii) −x−1, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N—H0A···Cl1i0.882.893.6491 (12)145
C14—H14A···O2ii0.952.403.2517 (19)149
Symmetry codes: (i) x−1, y, z; (ii) −x−1, y+1/2, −z+1/2.
Acknowledgements top

RJBacknowledges the Laboratory for the Structure of Matter at the Naval Research Laboratory for access to their diffractometers.

references
References top

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