2-Chloro-3-(4-methyl­anilino)naph­tha­lene-1,4-dione

Gao, L.-J.; Liu, Y.

doi:10.1107/S1600536812045229

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3378

doi:10.1107/S1600536812045229

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2-Chloro-3-(4-methylanilino)naphthalene-1,4-dione

Li-Jiu Gao ^a and Yun Liu ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Xuzhou Normal University, Xuzhou, Jiangsu 221116, People's Republic of China
^*Correspondence e-mail: liu_yun3@sina.com.cn

(Received 14 August 2012; accepted 1 November 2012; online 17 November 2012)

In the title compound, C₁₇H₁₂ClNO₂, the naphthoquinone system is essentially planar [maximum deviation = 0.078 (2) Å] and makes a dihedral angle of 52.38 (7)° with the benzene ring. The crystal structure features N—H⋯O interactions.

Related literature

For the properties of substituted naphthoquinones, see: Batton et al. (2000 ); Monks et al. (1992 ). For standard bond lengths, see: Allen et al. (1987 ). For the structure of 2-hydroxyquinoxaline, see: Stępień et al. (1976 ).

Experimental

Crystal data

C₁₇H₁₂ClNO₂
M_r = 297.73
Orthorhombic, P n a 2₁
a = 12.1614 (10) Å
b = 22.4915 (18) Å
c = 5.0444 (4) Å
V = 1379.79 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 296 K
0.2 × 0.2 × 0.1 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995 ) T_min = 0.946, T_max = 0.972
15471 measured reflections
2479 independent reflections
2420 reflections with I > 2σ(I)
R_int = 0.036
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.119
S = 1.27
2479 reflections
195 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H⋯O2	0.70 (2)	2.23 (3)	2.611 (3)	116 (2)

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812045229/ds2213sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812045229/ds2213Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812045229/ds2213Isup3.cml

checkCIF report

Comment top

The substituted naphthoquinone have a diversity of biological activity and are playing an increasingly important role in developing new pharmaceuticals [Batton et al., 2000; Monks et al., 1992]. In our ongoing research work on the syntheses of amino-substituted naphthoquinones, we have prepared the title compound, (I), as one of the products. As part of this study, we have undertaken an X-ray crystallographic analysis of (I) in order to confirm its structure.

In the title compound, the bond lengths and angles of the title molecule (Fig. 1) are within normal ranges (Allen et al., 1987). The naphthoquinone ring[C1—C10] is essentially planar. The naphthoquinone ring makes the dihedral angle 52.38 (0.07) with the benzene ring [C11—C16]. Although atoms C9 and C11 attached to atom N are all of sp^2^ hybridization, their different environments cause slight differences in the N—C9, N—C11 bond lengths, and in the C9—N—H, C11—N—H angles (Table 1). The molecular packing is stabilized by intermolecular N—H···O hydrogen bonds (Table 2).

Related literature top

For the properties of substituted naphthoquinones, see: Batton et al. (2000); Monks et al. (1992). For standard bond lengths, see: Allen et al. (1987). For the structure of 2-hydroxyquinoxaline, see: Stępień et al. (1976).

Experimental top

To a stirred solution of naphthoquinone (1.0 eq) in 10 ml of acetonitrile, potassium carbonate (3.0 eq) was added. The mixture was stirred at room temperature for 5 min, followed by the addition of aniline (1.0 eq) and silver nitrate (0.1 mmol). The reaction mixture was refluxed for 10 h until complete consumption of starting material was observed on TLC. The reaction mixture was purified over silica gel (EtOAc/hexane)to afford the product in 96% yield.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Ellipsoid plot.
	Fig. 2. Packing diagram.

2-Chloro-3-(4-methylanilino)naphthalene-1,4-dione top

Crystal data top

C₁₇H₁₂ClNO₂	D_x = 1.433 Mg m⁻³
M_r = 297.73	Melting point: 475 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 25 reflections
a = 12.1614 (10) Å	θ = 9–12°
b = 22.4915 (18) Å	µ = 0.28 mm⁻¹
c = 5.0444 (4) Å	T = 296 K
V = 1379.79 (19) Å³	Block, red
Z = 4	0.2 × 0.2 × 0.1 mm
F(000) = 616

Data collection top

Enraf–Nonius CAD-4 diffractometer	2420 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 25.4°, θ_min = 1.8°
ω/2θ scans	h = −14→14
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995)	k = −26→27
T_min = 0.946, T_max = 0.972	l = −6→6
15471 measured reflections	3 standard reflections every 200 reflections
2479 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0725P)² + 0.1832P] where P = (F_o² + 2F_c²)/3
S = 1.27	(Δ/σ)_max = 0.001
2479 reflections	Δρ_max = 0.41 e Å⁻³
195 parameters	Δρ_min = −0.42 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.083 (7)

Crystal data top

C₁₇H₁₂ClNO₂	V = 1379.79 (19) Å³
M_r = 297.73	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 12.1614 (10) Å	µ = 0.28 mm⁻¹
b = 22.4915 (18) Å	T = 296 K
c = 5.0444 (4) Å	0.2 × 0.2 × 0.1 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	2420 reflections with I > 2σ(I)
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995)	R_int = 0.036
T_min = 0.946, T_max = 0.972	3 standard reflections every 200 reflections
15471 measured reflections	intensity decay: none
2479 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.27	Δρ_max = 0.41 e Å⁻³
2479 reflections	Δρ_min = −0.42 e Å⁻³
195 parameters

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. Flack parameter does not have any meaning here. Obviously anomalous contribution from Cl was not good enough to resolve the chirality.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.79748 (5)	0.74205 (2)	0.55999 (16)	0.0433 (2)
C10	1.05237 (17)	0.70460 (10)	0.0576 (6)	0.0407 (5)
C8	0.87671 (18)	0.71478 (10)	0.3028 (5)	0.0351 (5)
O1	0.73453 (13)	0.64787 (8)	0.1976 (5)	0.0514 (5)
C9	0.97837 (19)	0.73816 (10)	0.2467 (5)	0.0358 (5)
N	1.02703 (18)	0.78611 (10)	0.3494 (5)	0.0453 (6)
O2	1.14579 (14)	0.72164 (10)	0.0280 (5)	0.0623 (6)
C6	0.89985 (18)	0.63439 (10)	−0.0415 (5)	0.0378 (5)
C11	0.97909 (19)	0.83701 (11)	0.4684 (5)	0.0393 (5)
C7	0.82917 (18)	0.66522 (9)	0.1601 (5)	0.0376 (5)
C5	1.00808 (18)	0.65242 (10)	−0.0834 (5)	0.0395 (5)
C1	0.8574 (2)	0.58704 (11)	−0.1871 (6)	0.0497 (7)
H1A	0.7848	0.5752	−0.1626	0.060*
C12	1.0318 (2)	0.86289 (12)	0.6821 (6)	0.0480 (6)
H12A	1.0960	0.8463	0.7492	0.058*
C16	0.8851 (2)	0.86286 (12)	0.3654 (6)	0.0475 (6)
H16A	0.8502	0.8463	0.2191	0.057*
C3	1.0317 (2)	0.57524 (13)	−0.4066 (7)	0.0586 (7)
H3A	1.0758	0.5551	−0.5276	0.070*
C4	1.0739 (2)	0.62259 (13)	−0.2648 (6)	0.0522 (7)
H4A	1.1464	0.6345	−0.2908	0.063*
C15	0.8440 (2)	0.91351 (12)	0.4826 (7)	0.0522 (7)
H15A	0.7807	0.9306	0.4127	0.063*
C13	0.9881 (2)	0.91369 (14)	0.7954 (7)	0.0579 (8)
H13A	1.0236	0.9307	0.9400	0.069*
C14	0.8930 (3)	0.93989 (12)	0.6993 (7)	0.0572 (7)
C2	0.9233 (3)	0.55771 (12)	−0.3683 (7)	0.0582 (8)
H2A	0.8949	0.5260	−0.4651	0.070*
C17	0.8458 (3)	0.99422 (15)	0.8318 (9)	0.0829 (12)
H17A	0.7804	1.0064	0.7402	0.124*
H17B	0.8988	1.0258	0.8269	0.124*
H17C	0.8281	0.9851	1.0128	0.124*
H	1.082 (2)	0.7883 (12)	0.317 (6)	0.033 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0329 (3)	0.0546 (3)	0.0424 (3)	0.00269 (19)	0.0127 (3)	0.0028 (3)
C10	0.0276 (11)	0.0539 (11)	0.0407 (12)	−0.0004 (8)	0.0058 (10)	−0.0035 (12)
C8	0.0240 (10)	0.0460 (12)	0.0351 (11)	0.0060 (8)	0.0057 (9)	0.0038 (9)
O1	0.0278 (8)	0.0552 (10)	0.0712 (13)	−0.0061 (7)	0.0072 (9)	−0.0009 (9)
C9	0.0259 (11)	0.0456 (11)	0.0357 (12)	0.0016 (8)	0.0017 (10)	−0.0012 (9)
N	0.0226 (10)	0.0570 (13)	0.0564 (14)	−0.0033 (9)	0.0085 (10)	−0.0117 (10)
O2	0.0310 (9)	0.0820 (13)	0.0739 (15)	−0.0127 (8)	0.0194 (10)	−0.0292 (12)
C6	0.0329 (12)	0.0402 (10)	0.0402 (12)	0.0013 (9)	−0.0011 (9)	0.0046 (9)
C11	0.0294 (10)	0.0460 (11)	0.0425 (13)	−0.0028 (9)	0.0077 (10)	−0.0030 (10)
C7	0.0285 (10)	0.0397 (11)	0.0446 (13)	0.0014 (9)	0.0001 (9)	0.0085 (9)
C5	0.0321 (11)	0.0449 (11)	0.0414 (13)	0.0044 (9)	−0.0002 (10)	0.0000 (10)
C1	0.0414 (13)	0.0452 (13)	0.0626 (17)	−0.0036 (11)	−0.0045 (12)	0.0005 (12)
C12	0.0369 (13)	0.0566 (14)	0.0504 (15)	0.0004 (10)	0.0004 (12)	−0.0033 (12)
C16	0.0359 (12)	0.0593 (15)	0.0471 (14)	−0.0015 (11)	0.0023 (11)	0.0026 (12)
C3	0.0538 (15)	0.0609 (15)	0.0612 (18)	0.0056 (11)	0.0077 (15)	−0.0217 (15)
C4	0.0399 (13)	0.0591 (14)	0.0575 (17)	0.0010 (11)	0.0054 (13)	−0.0110 (13)
C15	0.0394 (13)	0.0534 (14)	0.0638 (19)	0.0082 (11)	0.0123 (13)	0.0158 (12)
C13	0.0569 (17)	0.0587 (16)	0.0581 (18)	−0.0068 (13)	0.0048 (15)	−0.0135 (13)
C14	0.0584 (17)	0.0481 (13)	0.0650 (19)	0.0006 (12)	0.0234 (15)	−0.0004 (13)
C2	0.0606 (17)	0.0498 (13)	0.0640 (19)	0.0001 (12)	−0.0094 (14)	−0.0143 (12)
C17	0.101 (3)	0.0615 (18)	0.086 (3)	0.0188 (19)	0.032 (2)	−0.0042 (18)

Geometric parameters (Å, º) top

Cl1—C8	1.728 (2)	C12—C13	1.383 (4)
C10—O2	1.208 (3)	C12—H12A	0.9300
C10—C5	1.474 (3)	C16—C15	1.377 (4)
C10—C9	1.513 (3)	C16—H16A	0.9300
C8—C9	1.373 (3)	C3—C4	1.382 (4)
C8—C7	1.447 (3)	C3—C2	1.389 (4)
O1—C7	1.230 (3)	C3—H3A	0.9300
C9—N	1.335 (3)	C4—H4A	0.9300
N—C11	1.418 (3)	C15—C14	1.379 (5)
N—H	0.69 (3)	C15—H15A	0.9300
C6—C1	1.393 (4)	C13—C14	1.386 (5)
C6—C5	1.393 (3)	C13—H13A	0.9300
C6—C7	1.501 (3)	C14—C17	1.506 (4)
C11—C12	1.382 (4)	C2—H2A	0.9300
C11—C16	1.383 (4)	C17—H17A	0.9600
C5—C4	1.389 (4)	C17—H17B	0.9600
C1—C2	1.383 (4)	C17—H17C	0.9600
C1—H1A	0.9300

O2—C10—C5	122.5 (2)	C13—C12—H12A	120.3
O2—C10—C9	118.6 (2)	C15—C16—C11	119.1 (3)
C5—C10—C9	118.94 (18)	C15—C16—H16A	120.4
C9—C8—C7	123.5 (2)	C11—C16—H16A	120.4
C9—C8—Cl1	121.39 (19)	C4—C3—C2	119.9 (3)
C7—C8—Cl1	115.08 (16)	C4—C3—H3A	120.0
N—C9—C8	129.0 (2)	C2—C3—H3A	120.0
N—C9—C10	112.6 (2)	C3—C4—C5	119.9 (3)
C8—C9—C10	118.3 (2)	C3—C4—H4A	120.0
C9—N—C11	129.4 (2)	C5—C4—H4A	120.0
C9—N—H	113 (2)	C16—C15—C14	122.6 (3)
C11—N—H	116 (2)	C16—C15—H15A	118.7
C1—C6—C5	119.5 (2)	C14—C15—H15A	118.7
C1—C6—C7	119.9 (2)	C12—C13—C14	121.8 (3)
C5—C6—C7	120.6 (2)	C12—C13—H13A	119.1
C12—C11—C16	119.9 (2)	C14—C13—H13A	119.1
C12—C11—N	118.6 (2)	C15—C14—C13	117.1 (3)
C16—C11—N	121.3 (2)	C15—C14—C17	122.4 (3)
O1—C7—C8	122.8 (2)	C13—C14—C17	120.5 (3)
O1—C7—C6	119.6 (2)	C1—C2—C3	120.4 (3)
C8—C7—C6	117.64 (19)	C1—C2—H2A	119.8
C4—C5—C6	120.3 (2)	C3—C2—H2A	119.8
C4—C5—C10	119.5 (2)	C14—C17—H17A	109.5
C6—C5—C10	120.2 (2)	C14—C17—H17B	109.5
C2—C1—C6	119.9 (2)	H17A—C17—H17B	109.5
C2—C1—H1A	120.1	C14—C17—H17C	109.5
C6—C1—H1A	120.1	H17A—C17—H17C	109.5
C11—C12—C13	119.5 (3)	H17B—C17—H17C	109.5
C11—C12—H12A	120.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H···O2	0.70 (2)	2.23 (3)	2.611 (3)	116 (2)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₂ClNO₂
M_r	297.73
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	12.1614 (10), 22.4915 (18), 5.0444 (4)
V (Å³)	1379.79 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.2 × 0.2 × 0.1

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (XCAD4; Harms & Wocadlo, 1995)
T_min, T_max	0.946, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	15471, 2479, 2420
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.119, 1.27
No. of reflections	2479
No. of parameters	195
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.42

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H···O2	0.70 (2)	2.23 (3)	2.611 (3)	116 (2)

Acknowledgements

The authors acknowledge the financial support of Xuzhou City (XZZD1213).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Batton, J. L., Trush, M. A., Penning, T. M., Dryhurst, G. & Monks, T. J. (2000). Chem. Res. Toxicol. 13, 135–160. Web of Science PubMed Google Scholar
Enraf–Nonius. (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Monks, T. J., Hanzlik, R. P., Cohen, G. M., Ross, D. & Graham, D. G. (1992). Toxicol. Appl. Pharmacol. 112, 2–16. CrossRef PubMed CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stępień, A., Grabowski, M. J., Cygler, M. & Wajsman, E. (1976). Acta Cryst. B32, 2048–2050. CSD CrossRef IUCr Journals Web of Science Google Scholar