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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1523–o1524.
Published online 2008 July 19. doi:  10.1107/S1600536808021594
PMCID: PMC2962149

5-Hydr­oxy-8-nitro-1,4-naphthoquinone

Abstract

The title compound, C10H5NO5, features an intra­molecular O—H(...)O hydrogen bond, forming a six-membered ring with an S(6) ring motif. The nitro group makes a dihedral angle of 71.66 (5)° with the plane of the benzene ring to which it is bound. The two rings are almost coplanar, with a dihedral angle of 4.44 (5)°. Short inter­molecular distances between the centroids of the six-membered rings [3.7188 (6)–3.8299 (6) Å] indicate the existence of π–π inter­actions. The inter­esting features of the crystal structure are the short inter­molecular O(...)O and O(...)N inter­actions. The crystal packing is stabilized by intra­molecular O—H(...)O and inter­molecular C—H(...)O (×3) hydrogen bonds, and C—H(...)π inter­actions.

Related literature

For related literature on hydrogen-bond motifs, see Bernstein et al. (1995 [triangle]). For values of bond lengths, see Allen et al. (1987 [triangle]). For related literature, see, for example: Guingant & Barreto (1987 [triangle]); Larsen et al. (1996 [triangle]); Krohn et al. (2004 [triangle]); Krohn et al. (2004 [triangle]); Cui et al. (2006 [triangle]); Anuradha et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1523-scheme1.jpg

Experimental

Crystal data

  • C10H5NO5
  • M r = 219.15
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1523-efi1.jpg
  • a = 8.6809 (2) Å
  • b = 8.4250 (2) Å
  • c = 12.1845 (3) Å
  • β = 93.946 (1)°
  • V = 889.02 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.14 mm−1
  • T = 100.0 (1) K
  • 0.35 × 0.14 × 0.13 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.900, T max = 0.982
  • 22792 measured reflections
  • 3028 independent reflections
  • 2493 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.119
  • S = 1.11
  • 3028 reflections
  • 165 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 [triangle]); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 [triangle]).

Table 1
Selected interatomic and centroid–centroid distances (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021594/at2591sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021594/at2591Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

HO thanks the Malaysian government for the FRGS fund (grant No. 203/PKIMIA/671026). DTCT thanks Universiti Sains Malaysia for financial support. HKF and RK thank the Malaysian government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

5-Hydroxy-1,4-naphthoquinone (juglone) and its 5-acetoxy-2-bromo analogue is the essential dienophile in the highly convergent and regiospecific Diels-Alder synthesis of ochromycinone (Guingant & Barreto, 1987; Larsen et al., 1996; Krohn et al., 2004) a type of natural anthraquinone which exhibits remarkable antibiotic and antitumour activities (Krohn et al., 2004; Cui et al., 2006). Our aim is to prepare aromatic ring substituted juglone analogues for the purpose of synthesizing new ochromycinone analogues. The title compound was prepared by the direct nitration of juglone with nickel(II) nitrate. The method outlined previously (Anuradha et al., 2006) predicted a ortho-nitro product. However the product that we obtained is a para-nitro product.

Compound (I), ( Fig. 1), features an intramolecular O—H···O hydrogen bond to form a six-membered ring, producing a S(6) ring motif (Bernstein et al., 1995). The bond lenghts and angles are within the normal ranges (Allen et al., 1987). The two phenyl rings are almost coplanar with the dihedral angle of 4.44 (5)°. The nitro group is not coplanar with the benzene ring and its orientation is indicated by the dihedral angle of 71.66 (5)° with the plane of the benzene ring to which it is bound. The short intermolecular distances between the centroids of six-membered rings [3.7188 (6) - 3.8299 (6) Å] prove existence of π–π interactions (Table 1). The interesting feature of the crystal structure is the short intermolecular O···O and O···N interactions (Table 1). The crystal packing,(Fig. 2), of the compound shows one-dimensional infinite chains along the b axis.The crystal packing is stabilized by the intramolecular O—H···O, intermolecular C—H···O hydrogen bonds, π–π, and C—H···π interactions.

Experimental

8-Nitro-5-hydroxy-1,4-naphthoquinone was prepared from 5-hydroxy-1,4-naphthoquinone by the protocol outlined by (Anuradha et al., 2006). Single crystals of 8-nitro-5-hydroxy-1,4-naphthoquinone was obtained by slow evaporation of a chloroform solution at 286 K° C.

Refinement

All of the H-atoms were located from the difference Fourier map and refined freely.

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering. Intramolecular hydrogen bond is drawn as a dashed line.
Fig. 2.
The crystal packing of (I) shows a one-dimensional infinite chain along the [010] direction when viewed down the a-axis. Intramolecular and intermolecular interactions are drawn as dashed lines.

Crystal data

C10H5NO5F000 = 448
Mr = 219.15Dx = 1.637 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5257 reflections
a = 8.6809 (2) Åθ = 2.8–31.8º
b = 8.4250 (2) ŵ = 0.14 mm1
c = 12.1845 (3) ÅT = 100.0 (1) K
β = 93.9460 (10)ºBlock, brown
V = 889.02 (4) Å30.35 × 0.14 × 0.13 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer3028 independent reflections
Radiation source: fine-focus sealed tube2493 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.041
T = 100.0(1) Kθmax = 31.8º
[var phi] and ω scansθmin = 2.8º
Absorption correction: multi-scan(SADABS; Bruker, 2005)h = −12→12
Tmin = 0.901, Tmax = 0.982k = −12→12
22792 measured reflectionsl = −18→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.119  w = 1/[σ2(Fo2) + (0.0671P)2 + 0.1177P] where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
3028 reflectionsΔρmax = 0.50 e Å3
165 parametersΔρmin = −0.22 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.
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)

xyzUiso*/Ueq
O10.60929 (9)0.14448 (9)0.47684 (6)0.01684 (17)
O20.70729 (9)0.29533 (9)0.65117 (6)0.01718 (17)
O31.13635 (9)−0.14728 (9)0.74975 (6)0.01826 (17)
O40.97394 (10)−0.42986 (9)0.67891 (6)0.02146 (19)
O51.11804 (9)−0.37894 (9)0.54429 (6)0.01912 (18)
N11.01058 (10)−0.34927 (10)0.60140 (7)0.01427 (18)
C10.71200 (11)0.03181 (12)0.50785 (8)0.01280 (18)
C20.71889 (11)−0.10405 (12)0.44177 (8)0.01457 (19)
C30.81830 (11)−0.22605 (12)0.47321 (8)0.01431 (19)
C40.91370 (11)−0.21081 (11)0.56968 (8)0.01219 (18)
C50.91680 (11)−0.07504 (11)0.63367 (7)0.01156 (18)
C61.03288 (11)−0.05166 (12)0.72840 (8)0.01326 (19)
C71.02414 (12)0.09636 (13)0.79222 (8)0.0172 (2)
C80.91880 (12)0.20847 (12)0.76649 (8)0.0168 (2)
C90.80517 (11)0.19086 (12)0.67159 (8)0.01387 (19)
C100.81225 (11)0.04769 (11)0.60319 (8)0.01189 (18)
H80.9139 (16)0.3051 (18)0.8063 (12)0.022 (4)*
H20.6513 (17)−0.1106 (19)0.3752 (12)0.025 (4)*
H30.8222 (16)−0.3231 (18)0.4307 (12)0.020 (3)*
H71.1034 (18)0.1097 (19)0.8530 (13)0.029 (4)*
H1O10.620 (2)0.223 (2)0.5255 (16)0.049 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0161 (3)0.0151 (4)0.0187 (4)0.0031 (3)−0.0031 (3)0.0017 (3)
O20.0197 (4)0.0144 (4)0.0176 (3)0.0040 (3)0.0029 (3)0.0005 (3)
O30.0190 (4)0.0170 (4)0.0179 (3)0.0025 (3)−0.0051 (3)0.0005 (3)
O40.0285 (4)0.0150 (4)0.0210 (4)0.0010 (3)0.0023 (3)0.0054 (3)
O50.0161 (3)0.0181 (4)0.0234 (4)0.0026 (3)0.0032 (3)−0.0025 (3)
N10.0159 (4)0.0110 (4)0.0155 (4)−0.0001 (3)−0.0015 (3)−0.0010 (3)
C10.0114 (4)0.0132 (4)0.0136 (4)0.0000 (3)−0.0003 (3)0.0021 (3)
C20.0142 (4)0.0156 (5)0.0135 (4)−0.0011 (3)−0.0018 (3)−0.0004 (3)
C30.0152 (4)0.0138 (4)0.0138 (4)−0.0011 (3)0.0000 (3)−0.0021 (3)
C40.0122 (4)0.0110 (4)0.0133 (4)0.0007 (3)0.0005 (3)0.0008 (3)
C50.0120 (4)0.0112 (4)0.0114 (4)−0.0010 (3)0.0002 (3)−0.0001 (3)
C60.0143 (4)0.0130 (4)0.0122 (4)−0.0011 (3)−0.0012 (3)0.0005 (3)
C70.0203 (5)0.0157 (5)0.0150 (4)−0.0008 (4)−0.0030 (3)−0.0026 (4)
C80.0204 (5)0.0144 (5)0.0153 (4)−0.0006 (4)−0.0005 (3)−0.0035 (3)
C90.0155 (4)0.0123 (4)0.0141 (4)−0.0002 (3)0.0031 (3)0.0002 (3)
C100.0123 (4)0.0110 (4)0.0124 (4)0.0001 (3)0.0011 (3)0.0004 (3)

Geometric parameters (Å, °)

O1—C11.3388 (11)C3—C41.3964 (13)
O1—H1O10.89 (2)C3—H30.970 (15)
O2—C91.2367 (12)C4—C51.3836 (13)
O3—C61.2211 (12)C5—C101.4087 (13)
O4—N11.2229 (11)C5—C61.4921 (13)
O5—N11.2274 (11)C6—C71.4744 (14)
N1—C41.4741 (12)C7—C81.3369 (15)
C1—C21.4031 (14)C7—H70.982 (16)
C1—C101.4091 (13)C8—C91.4748 (14)
C2—C31.3793 (14)C8—H80.950 (15)
C2—H20.969 (15)C9—C101.4699 (13)
Cg1···Cg2i3.7188 (6)O5···O5ii3.0367 (11)
Cg1···Cg2i3.8299 (6)O5···N1ii3.0608 (11)
O2···O5i2.9940 (11)
C1—O1—H1O1107.7 (12)C4—C5—C6122.07 (8)
O4—N1—O5124.96 (9)C10—C5—C6119.72 (8)
O4—N1—C4117.90 (8)O3—C6—C7120.63 (9)
O5—N1—C4117.04 (8)O3—C6—C5121.69 (9)
O1—C1—C2118.06 (8)C7—C6—C5117.58 (8)
O1—C1—C10121.79 (9)C8—C7—C6122.22 (9)
C2—C1—C10120.15 (9)C8—C7—H7121.9 (10)
C3—C2—C1119.94 (9)C6—C7—H7115.8 (9)
C3—C2—H2121.4 (9)C7—C8—C9121.51 (9)
C1—C2—H2118.6 (9)C7—C8—H8122.7 (9)
C2—C3—C4119.26 (9)C9—C8—H8115.8 (9)
C2—C3—H3121.6 (9)O2—C9—C10121.66 (9)
C4—C3—H3119.1 (9)O2—C9—C8119.96 (9)
C5—C4—C3122.53 (9)C10—C9—C8118.38 (9)
C5—C4—N1121.19 (8)C5—C10—C1119.86 (9)
C3—C4—N1116.27 (8)C5—C10—C9120.27 (8)
C4—C5—C10118.10 (8)C1—C10—C9119.86 (9)
O1—C1—C2—C3−177.19 (9)O3—C6—C7—C8175.40 (10)
C10—C1—C2—C33.41 (15)C5—C6—C7—C8−1.17 (15)
C1—C2—C3—C4−1.45 (15)C6—C7—C8—C9−0.45 (16)
C2—C3—C4—C5−2.37 (15)C7—C8—C9—O2178.62 (10)
C2—C3—C4—N1176.71 (9)C7—C8—C9—C10−1.51 (15)
O4—N1—C4—C572.88 (12)C4—C5—C10—C1−2.00 (14)
O5—N1—C4—C5−110.47 (10)C6—C5—C10—C1174.21 (8)
O4—N1—C4—C3−106.21 (10)C4—C5—C10—C9176.79 (8)
O5—N1—C4—C370.44 (11)C6—C5—C10—C9−7.00 (14)
C3—C4—C5—C104.07 (14)O1—C1—C10—C5178.97 (9)
N1—C4—C5—C10−174.97 (8)C2—C1—C10—C5−1.65 (14)
C3—C4—C5—C6−172.05 (9)O1—C1—C10—C90.17 (14)
N1—C4—C5—C68.92 (14)C2—C1—C10—C9179.56 (9)
C4—C5—C6—O34.45 (15)O2—C9—C10—C5−174.82 (9)
C10—C5—C6—O3−171.60 (9)C8—C9—C10—C55.31 (14)
C4—C5—C6—C7−179.01 (9)O2—C9—C10—C13.97 (15)
C10—C5—C6—C74.94 (13)C8—C9—C10—C1−175.90 (9)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1O1···O20.889 (18)1.769 (19)2.5695 (10)148.5 (16)
C2—H2···O3iii0.969 (15)2.547 (16)3.1853 (12)123.4 (12)
C3—H3···O5ii0.970 (15)2.577 (15)3.3827 (13)140.6 (11)
C7—H7···O1iv0.982 (16)2.561 (16)3.1851 (13)121.4 (12)
C8—H8···Cg1v0.950 (15)2.976 (14)3.6548 (11)129.5 (11)

Symmetry codes: (iii) x−1/2, −y−1/2, z−1/2; (ii) −x+2, −y−1, −z+1; (iv) x+1/2, −y+1/2, z+1/2; (v) −x+3/2, y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2591).

References

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  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cui, J. R., Jian, Y. J., Wu, Y. K. & Wang, S. M. (2006). Chin. J. Chem.24, 1163–1169.
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  • Krohn, K., Sohrab, M. H. & Flörke, U. (2004). Tetrahedron Asymmetry15, 713–718.
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