5-Chloro-8-hydr­oxy-6-methyl-1,4-naphthoquinone

Tan, D.T.-C.; Osman, H.; Kamaruddin, A.H.; Jebas, S.R.; Fun, H.-K.

doi:10.1107/S1600536809010137

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages o871-o872

doi:10.1107/S1600536809010137

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5-Chloro-8-hydroxy-6-methyl-1,4-naphthoquinone

Daniel Teoh-Chuan Tan,^a Hasnah Osman,^a ‡ Azlina Harun Kamaruddin,^b Samuel Robinson Jebas ^c § and Hoong-Kun Fun ^c ^*

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bSchool of Chemical Engineering, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, Penang, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 17 March 2009; accepted 19 March 2009; online 25 March 2009)

The molecule of the title compound, C₁₁H₇ClO₃, is planar, with a maximum deviation of 0.0383 (10) Å from the naphthoquinone plane. An intramolecular O—H⋯O hydrogen bond generates an S(6) ring motif. The crystal packing is stabilized by intermolecular C—H⋯O hydrogen bonds. Short intramolecular Cl⋯O [2.8234 (8) Å] and O⋯O [2.5530 (11) Å], and intermolecular Cl⋯Cl [3.2777 (3) Å] contacts further stabilize the crystal structure.

Related literature

For the biological activity of the related compound 7-methyljuglone, see: Mahapatra et al. (2007 ); Van der Kooy & Meyer (2006 ). For the synthesis of 7-methyljuglone from the title compound, see: Musgrave & Skoyles (2001 ); Mahapatra et al. (2007). For bond-length data, see: Allen et al. (1987 ). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₁H₇ClO₃
M_r = 222.62
Monoclinic, C 2/c
a = 10.7546 (1) Å
b = 10.3104 (1) Å
c = 16.8370 (2) Å
β = 100.285 (1)°
V = 1836.96 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 100 K
0.30 × 0.21 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.891, T_max = 0.945
17328 measured reflections
4015 independent reflections
3356 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.109
S = 1.07
4015 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1O3⋯O2	0.86	1.73	2.5530 (11)	161
C2—H2A⋯O1ⁱ	0.93	2.51	3.4124 (12)	163
C3—H3A⋯O2ⁱⁱ	0.93	2.57	3.3000 (12)	136
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809010137/sj2597sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809010137/sj2597Isup2.hkl

checkCIF report

Comment top

5-Hydroxy-7-methyl-1,4-naphthoquinone (7-methyljuglone) has recently been reported to exhibit activity against mycobacterium tuberculosis (Van der Kooy & Meyer, 2006; Mahapatra et al., 2007). Naturally occurring 7-methyljuglone is synthesised from 8-chloro-5-hydroxy-7-methyl-1,4-naphthoquinone in high yield (Musgrave & Skoyles, 2001; Mahapatra et al., 2007). This paper reports the molecular structure of 8-chloro-5-hydroxy-7-methyl-1,4-naphthoquinone; the precursor to synthetic 7-methyljuglone.

The asymmetric unit of (I) consists of one molecule of 8-Chloro-5-hydroxy-7-methyl-1,4-naphthoquinone. The napthoquinone ring is essentially planar with the maximum deviation from planarity being 0.0383 (10) Å for atom C8. The bond lengths in (I) have normal values (Allen et al., 1987).

An intramolecular O–H···O hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995). The crystal packing is stabilized by intermolecular C–H···O hydrogen bonds (Table 2) (Fig 2). Short intramolecular Cl···O = 2.8234 (8) Å; O···O = 2.5530 (11)Å and intermolecular Cl···Clⁱ = 3.2777 (3) Å [symmetry code: (i) 1 - x, y, 3/2 - z] contacts further stabilize the crystal packing.

Related literature top

For the biological activity of the related compound 7-methyljuglone, see: Mahapatra et al. (2007); Van der Kooy & Meyer (2006). For the synthesis of 7-methyljuglone from the title compound, see: Musgrave & Skoyles (2001); Mahapatra et al. (2007). For bond-length data, see: Allen et al. (1987). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

The title compound was prepared from the Friedel-Crafts acylation of 4-chloro-3-methylphenol with maleic anhydride (Musgrave & Skoyles, 2001). Repeated Soxhlet extraction of the crude Friedel-Crafts product with n-hexane, and silica gel column chromatography purification [chloroform and n-hexane (1:9)] of the n-hexane extract afforded the title compound. Finally, slow evaporation of a n-hexane solution at 305 K gave single crystals of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom numbering scheme. The intramolecular H bond is drawn as a dashed line.
	Fig. 2. The crystal packing of the title compound, viewed along the c axis, showing dimer formation. Dashed lines indicate the hydrogen bonding.

5-Chloro-8-hydroxy-6-methyl-1,4-naphthoquinone top

Crystal data top

C₁₁H₇ClO₃	F(000) = 912
M_r = 222.62	D_x = 1.610 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6307 reflections
a = 10.7546 (1) Å	θ = 2.8–30.1°
b = 10.3104 (1) Å	µ = 0.40 mm⁻¹
c = 16.8370 (2) Å	T = 100 K
β = 100.285 (1)°	Block, red
V = 1836.96 (3) Å³	0.30 × 0.21 × 0.14 mm
Z = 8

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4015 independent reflections
Radiation source: fine-focus sealed tube	3356 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 35.1°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→17
T_min = 0.891, T_max = 0.945	k = −16→16
17328 measured reflections	l = −27→27

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0595P)² + 0.6106P] where P = (F_o² + 2F_c²)/3
4015 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₁H₇ClO₃	V = 1836.96 (3) Å³
M_r = 222.62	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 10.7546 (1) Å	µ = 0.40 mm⁻¹
b = 10.3104 (1) Å	T = 100 K
c = 16.8370 (2) Å	0.30 × 0.21 × 0.14 mm
β = 100.285 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4015 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3356 reflections with I > 2σ(I)
T_min = 0.891, T_max = 0.945	R_int = 0.031
17328 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.07	Δρ_max = 0.61 e Å⁻³
4015 reflections	Δρ_min = −0.35 e Å⁻³
137 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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

	x	y	z	U_iso*/U_eq
Cl1	0.60008 (2)	0.08776 (3)	0.687132 (14)	0.02314 (8)
O1	0.40351 (7)	0.18970 (8)	0.57005 (5)	0.02395 (16)
O2	0.64859 (7)	0.18264 (8)	0.31989 (4)	0.02085 (15)
O3	0.83772 (7)	0.06289 (8)	0.40048 (4)	0.02028 (14)
H1O3	0.7847	0.1042	0.3653	0.030*
C1	0.46492 (8)	0.18621 (9)	0.51561 (6)	0.01565 (16)
C2	0.40771 (9)	0.23850 (9)	0.43571 (6)	0.01789 (17)
H2A	0.3271	0.2743	0.4292	0.021*
C3	0.46720 (9)	0.23648 (9)	0.37229 (6)	0.01852 (17)
H3A	0.4275	0.2710	0.3232	0.022*
C4	0.59410 (9)	0.18056 (9)	0.37912 (5)	0.01556 (16)
C5	0.77541 (8)	0.06817 (8)	0.46273 (6)	0.01477 (15)
C6	0.83488 (8)	0.01527 (9)	0.53621 (6)	0.01568 (16)
H6A	0.9135	−0.0238	0.5394	0.019*
C7	0.77959 (8)	0.01969 (9)	0.60416 (5)	0.01563 (15)
C8	0.65972 (8)	0.07923 (9)	0.59849 (5)	0.01508 (15)
C9	0.59512 (8)	0.12905 (8)	0.52543 (5)	0.01356 (15)
C10	0.65466 (8)	0.12451 (8)	0.45647 (5)	0.01354 (15)
C11	0.84754 (10)	−0.03753 (11)	0.68182 (6)	0.02193 (19)
H11A	0.9265	−0.0738	0.6736	0.033*
H11B	0.7964	−0.1044	0.6993	0.033*
H11C	0.8632	0.0290	0.7222	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02101 (12)	0.03306 (14)	0.01720 (11)	0.00279 (9)	0.00841 (8)	0.00089 (8)
O1	0.0164 (3)	0.0311 (4)	0.0264 (4)	0.0055 (3)	0.0096 (3)	−0.0001 (3)
O2	0.0206 (3)	0.0258 (3)	0.0170 (3)	0.0004 (3)	0.0055 (3)	0.0009 (3)
O3	0.0172 (3)	0.0258 (3)	0.0200 (3)	0.0053 (3)	0.0093 (3)	0.0014 (3)
C1	0.0117 (3)	0.0146 (3)	0.0210 (4)	0.0004 (3)	0.0040 (3)	−0.0023 (3)
C2	0.0123 (4)	0.0162 (4)	0.0243 (4)	0.0018 (3)	0.0009 (3)	−0.0017 (3)
C3	0.0150 (4)	0.0188 (4)	0.0206 (4)	0.0015 (3)	0.0000 (3)	0.0006 (3)
C4	0.0146 (4)	0.0150 (3)	0.0170 (4)	−0.0012 (3)	0.0027 (3)	−0.0009 (3)
C5	0.0122 (3)	0.0152 (3)	0.0181 (4)	−0.0003 (3)	0.0058 (3)	−0.0017 (3)
C6	0.0115 (3)	0.0164 (4)	0.0193 (4)	0.0008 (3)	0.0034 (3)	−0.0012 (3)
C7	0.0126 (3)	0.0168 (4)	0.0171 (4)	−0.0006 (3)	0.0017 (3)	−0.0010 (3)
C8	0.0130 (3)	0.0174 (4)	0.0154 (4)	−0.0011 (3)	0.0043 (3)	−0.0013 (3)
C9	0.0103 (3)	0.0137 (3)	0.0172 (4)	−0.0002 (3)	0.0040 (3)	−0.0017 (3)
C10	0.0113 (3)	0.0141 (3)	0.0156 (3)	0.0001 (3)	0.0033 (3)	−0.0014 (3)
C11	0.0189 (4)	0.0279 (5)	0.0177 (4)	0.0024 (4)	−0.0001 (3)	0.0016 (3)

Geometric parameters (Å, º) top

Cl1—C8	1.7287 (9)	C5—C6	1.3980 (13)
O1—C1	1.2222 (12)	C5—C10	1.4092 (12)
O2—C4	1.2438 (11)	C6—C7	1.3812 (13)
O3—C5	1.3423 (11)	C6—H6A	0.9300
O3—H1O3	0.8581	C7—C8	1.4156 (13)
C1—C2	1.4777 (14)	C7—C11	1.5002 (13)
C1—C9	1.5008 (12)	C8—C9	1.3980 (13)
C2—C3	1.3393 (14)	C9—C10	1.4234 (12)
C2—H2A	0.9300	C11—H11A	0.9600
C3—C4	1.4670 (13)	C11—H11B	0.9600
C3—H3A	0.9300	C11—H11C	0.9600
C4—C10	1.4667 (13)

C5—O3—H1O3	99.0	C6—C7—C8	118.69 (8)
O1—C1—C2	118.62 (8)	C6—C7—C11	119.62 (8)
O1—C1—C9	123.19 (9)	C8—C7—C11	121.69 (8)
C2—C1—C9	118.18 (8)	C9—C8—C7	121.48 (8)
C3—C2—C1	122.65 (8)	C9—C8—Cl1	122.56 (7)
C3—C2—H2A	118.7	C7—C8—Cl1	115.95 (7)
C1—C2—H2A	118.7	C8—C9—C10	118.71 (8)
C2—C3—C4	120.92 (9)	C8—C9—C1	123.27 (8)
C2—C3—H3A	119.5	C10—C9—C1	118.02 (8)
C4—C3—H3A	119.5	C5—C10—C9	119.69 (8)
O2—C4—C10	121.37 (8)	C5—C10—C4	119.08 (8)
O2—C4—C3	119.69 (8)	C9—C10—C4	121.21 (8)
C10—C4—C3	118.94 (8)	C7—C11—H11A	109.5
O3—C5—C6	117.51 (8)	C7—C11—H11B	109.5
O3—C5—C10	122.69 (8)	H11A—C11—H11B	109.5
C6—C5—C10	119.80 (8)	C7—C11—H11C	109.5
C7—C6—C5	121.57 (8)	H11A—C11—H11C	109.5
C7—C6—H6A	119.2	H11B—C11—H11C	109.5
C5—C6—H6A	119.2

O1—C1—C2—C3	−178.75 (9)	O1—C1—C9—C8	−2.55 (14)
C9—C1—C2—C3	0.15 (13)	C2—C1—C9—C8	178.61 (8)
C1—C2—C3—C4	0.34 (14)	O1—C1—C9—C10	176.82 (9)
C2—C3—C4—O2	−178.28 (9)	C2—C1—C9—C10	−2.03 (12)
C2—C3—C4—C10	1.01 (14)	O3—C5—C10—C9	−178.76 (8)
O3—C5—C6—C7	178.08 (8)	C6—C5—C10—C9	1.06 (13)
C10—C5—C6—C7	−1.75 (13)	O3—C5—C10—C4	−0.34 (13)
C5—C6—C7—C8	0.12 (13)	C6—C5—C10—C4	179.48 (8)
C5—C6—C7—C11	−179.54 (9)	C8—C9—C10—C5	1.20 (13)
C6—C7—C8—C9	2.23 (13)	C1—C9—C10—C5	−178.19 (8)
C11—C7—C8—C9	−178.11 (9)	C8—C9—C10—C4	−177.18 (8)
C6—C7—C8—Cl1	−177.07 (7)	C1—C9—C10—C4	3.43 (12)
C11—C7—C8—Cl1	2.59 (12)	O2—C4—C10—C5	−2.09 (13)
C7—C8—C9—C10	−2.87 (13)	C3—C4—C10—C5	178.63 (8)
Cl1—C8—C9—C10	176.38 (7)	O2—C4—C10—C9	176.30 (8)
C7—C8—C9—C1	176.48 (8)	C3—C4—C10—C9	−2.98 (13)
Cl1—C8—C9—C1	−4.26 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O3···O2	0.86	1.73	2.5530 (11)	161
C2—H2A···O1ⁱ	0.93	2.51	3.4124 (12)	163
C3—H3A···O2ⁱⁱ	0.93	2.57	3.3000 (12)	136

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₇ClO₃
M_r	222.62
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	10.7546 (1), 10.3104 (1), 16.8370 (2)
β (°)	100.285 (1)
V (Å³)	1836.96 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.30 × 0.21 × 0.14

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.891, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	17328, 4015, 3356
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.808

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.109, 1.07
No. of reflections	4015
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.35

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), 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
O3—H1O3···O2	0.86	1.73	2.5530 (11)	161
C2—H2A···O1ⁱ	0.93	2.51	3.4124 (12)	163
C3—H3A···O2ⁱⁱ	0.93	2.57	3.3000 (12)	136

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, y, −z+1/2.

Footnotes

‡Additional Correspondence author e-mail: ohasnah@usm.my.

§Permanent address: Department of Physics, Karunya University, Karunya Nagar, Coimbatore 641114, India.

Acknowledgements

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post–doctoral research fellowship. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. HO and AHK thank the Malaysian Government for the FRGS fund (203/PKIMIA/671026). DT-CT thanks Universiti Sains Malaysia for financial support.

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