2,4-Dinitro-1-naphthol

In the title compound, C₁₀H₆N₂O₅, the two fused rings are almost co-planar, with an r.m.s. deviation of 0.0163 Å. The nitro groups are oriented at dihedral angles of 2.62 (11) and 44.69 (11)° with respect to the plane of the parent fused rings. Intra­molecular O—H...O and C—H...O hydrogen bonds complete S(6) ring motifs. In the crystal, mol­ecules are linked into chains along [101] by inter­molecular O—H...O hydrogen bonds. π–π inter­actions [centroid–centroid distances = 3.6296 (15), 3.8104 (15) and 3.6513 (14) Å] might play a role in stabilizing the structure.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.042
• wR factor = 0.119
• Data-to-parameter ratio = 10.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.597          7

Alert level G
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Estrogens have been found to have maintenance effects on bone, brain, skin, cardiovascular system (Schwartz et al., 1995). In spite of their beneficial biological effects, estrogens are suspected to have relationship with the risk of cancer and thromboemetic diseases (O'Donnell et al., 2001). The title compound was obtained as an interesting side product while synthesizing substituted 1-tetralone as AB ring of the estrogen skeleton which will bear substituent at positions not found in nature.

The title compound (I) is related to the published crystal structures of 1-naphthalenol (Rozycka-Sokolowska et al., 2004) and hydroxonium 2,4-dinitro-1-hydroxy-7-sulfonatonaphthalene monohydrate (Filipenko et al., 2001).

In (I), the two fused rings (C1—C10) are neraly planar with the largest deviation being 0.033 (2)Å at C10 (Fig. 1). The hydroxyl O5 atom is only deviating by 0.129 (2)Å from the mean plane. Owing to the intramolecular O5–H···O4 hydrogen bond (Table 1), the O3 and O4 atoms are only slightly displaced from the mean plane of the fused rings by -0.074 (2)Å and 0.023 (2) Å, respectively. The other nitro group is twisted by 44.72 (12)° with respect to the fused rings.

Strong intramolecular H-bondings of O—H···O and C—H···O types (Table 1, Fig. 1) complete S(6) ring motifs (Bernstein et al., 1995). The molecules are stabilized in the form of polymeric chains due to intermolecular O—H···O hydrogen bonds (Table 1, Fig. 2). Slippest weak π–π interactions (Table 2) might play a role in stabilizing the packing.

Related literature

For background to estrogens, see: Schwartz et al. (1995); O'Donnell et al. (2001). For related structures, see: Filipenko et al. (2001); Rozycka-Sokolowska et al. (2004). For graph-set notation, see: Bernstein et al. (1995). For π–π interactions, see: Janiak (2000).

S2. Experimental

The 1-tetralone (1 ml, 1.1 g, 1 eq) was added to a chilled and well stirred nitrating mixture containing H₂SO₄ (2 ml, 0.57 g, 2 eq) and HNO₃ (0.5 ml, 0.7 g, 1.5 eq). The reaction mixture was then neutralized and extracted with EtOAc (3 × 25 ml) and the combined organic extract was dried over anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography and the title compound (I) was obtained as dull brown crystalline solid in 61–79^th fraction (20 ml each) using 2.5% CHCl₃ (3 × 500 ml) as mobile phase. Yield: 15%.

S3. Refinement

The H-atoms were positioned geometrically with (O–H = 0.82, C–H = 0.93 Å) and treated as riding with U_iso(H) = 1.2U_eq(C, O).

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures

	Fig. 1. View of the title compound with the atom numbering scheme. The thermal ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii. The dotted line indicate the intramolecular H-bond.
	Fig. 2. The partial packing (PLATON; Spek, 2009) which shows that molecules form polymeric chains.

2,4-Dinitro-1-naphthol

Crystal data

C10H6N2O5	F(000) = 480
Mr = 234.17	Dx = 1.647 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1058 reflections
a = 7.0512 (10) Å	θ = 2.5–25.1°
b = 16.3541 (19) Å	µ = 0.14 mm^−1
c = 8.7988 (10) Å	T = 296 K
β = 111.452 (6)°	Needle, brown
V = 944.4 (2) Å^3	0.32 × 0.14 × 0.12 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer	1684 independent reflections
Radiation source: fine-focus sealed tube	1058 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 8.20 pixels mm^-1	θmax = 25.1°, θmin = 2.5°
ω scans	h = −7→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −19→19
Tmin = 0.978, Tmax = 0.982	l = −10→10
6868 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.059P)^2] where P = (Fo^2 + 2Fc^2)/3
1684 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.3884 (3)	0.45828 (13)	0.10925 (19)	0.0656 (6)
O2	0.6120 (3)	0.36519 (11)	0.1294 (2)	0.0663 (6)
O3	0.8511 (3)	0.26242 (11)	0.6881 (2)	0.0762 (7)
O4	1.0038 (3)	0.34485 (11)	0.8845 (2)	0.0735 (6)
O5	0.9984 (3)	0.49989 (10)	0.83341 (16)	0.0500 (5)
H5A	1.0356	0.4587	0.8896	0.060*
N1	0.5444 (3)	0.42063 (12)	0.1860 (2)	0.0441 (5)
N2	0.8995 (3)	0.33110 (13)	0.7401 (3)	0.0497 (6)
C1	0.8052 (3)	0.54453 (12)	0.5693 (2)	0.0313 (5)
C2	0.8467 (4)	0.62585 (14)	0.6216 (3)	0.0415 (6)
H2	0.9197	0.6370	0.7312	0.050*
C3	0.7809 (4)	0.68880 (14)	0.5131 (3)	0.0465 (7)
H3	0.8077	0.7426	0.5489	0.056*
C4	0.6744 (4)	0.67246 (15)	0.3500 (3)	0.0487 (7)
H4	0.6329	0.7157	0.2766	0.058*
C5	0.6283 (4)	0.59409 (15)	0.2936 (3)	0.0419 (6)
H5	0.5557	0.5848	0.1832	0.050*
C6	0.6905 (3)	0.52753 (13)	0.4024 (2)	0.0313 (5)
C7	0.6553 (3)	0.44389 (13)	0.3569 (2)	0.0334 (5)
C8	0.7224 (3)	0.38182 (13)	0.4646 (2)	0.0373 (6)
H8	0.6948	0.3279	0.4299	0.045*
C9	0.8335 (3)	0.39941 (13)	0.6284 (2)	0.0354 (6)
C10	0.8816 (3)	0.47868 (13)	0.6824 (2)	0.0345 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0468 (12)	0.0892 (14)	0.0412 (10)	0.0043 (11)	−0.0071 (9)	−0.0067 (9)
O2	0.0875 (16)	0.0570 (12)	0.0489 (11)	0.0026 (11)	0.0184 (10)	−0.0192 (9)
O3	0.110 (2)	0.0391 (11)	0.0731 (13)	−0.0007 (11)	0.0256 (12)	0.0117 (9)
O4	0.0881 (16)	0.0695 (13)	0.0441 (11)	−0.0059 (11)	0.0017 (11)	0.0225 (9)
O5	0.0560 (12)	0.0565 (10)	0.0260 (9)	−0.0001 (9)	0.0012 (8)	0.0046 (7)
N1	0.0459 (14)	0.0488 (12)	0.0320 (11)	−0.0085 (11)	0.0075 (10)	−0.0052 (9)
N2	0.0521 (15)	0.0483 (14)	0.0490 (13)	0.0019 (11)	0.0190 (11)	0.0158 (10)
C1	0.0258 (13)	0.0386 (12)	0.0291 (11)	0.0020 (10)	0.0096 (9)	−0.0002 (9)
C2	0.0405 (15)	0.0446 (14)	0.0385 (13)	−0.0023 (11)	0.0132 (11)	−0.0055 (11)
C3	0.0493 (17)	0.0376 (14)	0.0519 (15)	0.0043 (12)	0.0175 (13)	0.0013 (11)
C4	0.0490 (17)	0.0448 (15)	0.0489 (15)	0.0094 (12)	0.0139 (13)	0.0142 (12)
C5	0.0368 (15)	0.0526 (15)	0.0317 (12)	0.0054 (12)	0.0070 (10)	0.0065 (11)
C6	0.0235 (12)	0.0401 (12)	0.0298 (11)	0.0026 (10)	0.0093 (9)	0.0016 (9)
C7	0.0267 (13)	0.0435 (13)	0.0272 (11)	−0.0026 (10)	0.0066 (9)	−0.0030 (10)
C8	0.0347 (14)	0.0384 (13)	0.0388 (13)	−0.0021 (11)	0.0137 (11)	−0.0017 (10)
C9	0.0337 (14)	0.0404 (13)	0.0321 (12)	0.0021 (10)	0.0120 (10)	0.0083 (10)
C10	0.0307 (13)	0.0474 (14)	0.0247 (11)	0.0008 (11)	0.0093 (10)	0.0021 (10)

Geometric parameters (Å, º)

O1—N1	1.225 (2)	C2—H2	0.9300
O2—N1	1.213 (2)	C3—C4	1.381 (3)
O3—N2	1.214 (3)	C3—H3	0.9300
O4—N2	1.234 (3)	C4—C5	1.370 (3)
O5—C10	1.328 (2)	C4—H4	0.9300
O5—H5A	0.8200	C5—C6	1.409 (3)
N1—C7	1.469 (3)	C5—H5	0.9300
N2—C9	1.448 (3)	C6—C7	1.421 (3)
C1—C2	1.403 (3)	C7—C8	1.351 (3)
C1—C6	1.421 (3)	C8—C9	1.395 (3)
C1—C10	1.431 (3)	C8—H8	0.9300
C2—C3	1.365 (3)	C9—C10	1.380 (3)
C10—O5—H5A	109.5	C4—C5—C6	120.2 (2)
O2—N1—O1	123.9 (2)	C4—C5—H5	119.9
O2—N1—C7	118.2 (2)	C6—C5—H5	119.9
O1—N1—C7	117.9 (2)	C5—C6—C7	124.98 (19)
O3—N2—O4	122.4 (2)	C5—C6—C1	118.0 (2)
O3—N2—C9	118.8 (2)	C7—C6—C1	117.00 (19)
O4—N2—C9	118.8 (2)	C8—C7—C6	123.06 (19)
C2—C1—C6	119.75 (19)	C8—C7—N1	116.25 (19)
C2—C1—C10	120.33 (19)	C6—C7—N1	120.68 (18)
C6—C1—C10	119.90 (19)	C7—C8—C9	119.3 (2)
C3—C2—C1	120.6 (2)	C7—C8—H8	120.3
C3—C2—H2	119.7	C9—C8—H8	120.3
C1—C2—H2	119.7	C10—C9—C8	121.60 (19)
C2—C3—C4	119.8 (2)	C10—C9—N2	120.89 (19)
C2—C3—H3	120.1	C8—C9—N2	117.5 (2)
C4—C3—H3	120.1	O5—C10—C9	125.07 (19)
C5—C4—C3	121.6 (2)	O5—C10—C1	115.92 (19)
C5—C4—H4	119.2	C9—C10—C1	119.00 (18)
C3—C4—H4	119.2
C6—C1—C2—C3	−1.1 (3)	O1—N1—C7—C6	−44.9 (3)
C10—C1—C2—C3	177.5 (2)	C6—C7—C8—C9	−0.7 (3)
C1—C2—C3—C4	−0.7 (4)	N1—C7—C8—C9	178.4 (2)
C2—C3—C4—C5	1.5 (4)	C7—C8—C9—C10	−1.9 (3)
C3—C4—C5—C6	−0.4 (4)	C7—C8—C9—N2	179.0 (2)
C4—C5—C6—C7	−178.5 (2)	O3—N2—C9—C10	178.8 (2)
C4—C5—C6—C1	−1.4 (3)	O4—N2—C9—C10	−1.5 (3)
C2—C1—C6—C5	2.1 (3)	O3—N2—C9—C8	−2.1 (3)
C10—C1—C6—C5	−176.42 (19)	O4—N2—C9—C8	177.6 (2)
C2—C1—C6—C7	179.44 (19)	C8—C9—C10—O5	−175.0 (2)
C10—C1—C6—C7	0.9 (3)	N2—C9—C10—O5	4.1 (3)
C5—C6—C7—C8	178.2 (2)	C8—C9—C10—C1	3.8 (3)
C1—C6—C7—C8	1.1 (3)	N2—C9—C10—C1	−177.11 (19)
C5—C6—C7—N1	−0.8 (3)	C2—C1—C10—O5	−2.9 (3)
C1—C6—C7—N1	−177.9 (2)	C6—C1—C10—O5	175.7 (2)
O2—N1—C7—C8	−43.7 (3)	C2—C1—C10—C9	178.2 (2)
O1—N1—C7—C8	136.1 (2)	C6—C1—C10—C9	−3.2 (3)
O2—N1—C7—C6	135.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O1^i	0.82	2.53	3.006 (3)	118
O5—H5A···O4	0.82	1.87	2.573 (2)	142
O5—H5A···N2	0.82	2.47	2.892 (3)	113
C5—H5···O1	0.93	2.35	2.902 (3)	118

Symmetry code: (i) x+1, y, z+1.