4,6-Dinitro­pyrogallol

Neis, C.; Merten, G.J.; Hegetschweiler, K.

doi:10.1107/S1600536812004771

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o695

doi:10.1107/S1600536812004771

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4,6-Dinitropyrogallol

Christian Neis,^a Günter J. Merten ^a and Kaspar Hegetschweiler ^a ^*

^aFachrichtung Chemie, Universität des Saarlandes, Postfach 151150, D-66041 Saarbrücken, Germany
^*Correspondence e-mail: hegetschweiler@mx.uni-saarland.de

(Received 25 January 2012; accepted 3 February 2012; online 17 February 2012)

In the title molecule, C₆H₄N₂O₇, the two nitro groups are tilted with respect to the aromatic ring by 11.2 (1) and 10.9 (1)°. All three hydroxy groups are involved in the formation of bifurcated intra- and intermolecular O—H⋯O hydrogen bonds. The crystal packing exhibits short O⋯O distances of 2.823 (2) Å between two O atoms of the nitro groups.

Related literature

The synthesis of the title compound has recently been reported by Merten et al. (2012 ). The importance of hydrogen bonding, π stacking and donor–acceptor interactions in solid-state structures and in solution has been reviewed by Schneider (2009 ). The crystal structure of dinitrophloroglucinol, a constitutional isomer of the title compound, has been described by Schweitzer et al. (2008 ). H atoms were treated as recommended by Müller et al. (2006 ).

Experimental

Crystal data

C₆H₄N₂O₇
M_r = 216.11
Monoclinic, P 2₁ /c
a = 6.7612 (14) Å
b = 10.878 (2) Å
c = 10.297 (2) Å
β = 92.75 (3)°
V = 756.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 200 K
0.60 × 0.22 × 0.20 mm

Data collection

Stoe IPDS image plate diffractometer
5824 measured reflections
1488 independent reflections
1326 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.089
S = 1.06
1488 reflections
146 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O3	0.85 (1)	2.14 (2)	2.6467 (14)	118 (2)
O2—H2O⋯O4ⁱ	0.85 (1)	2.27 (2)	2.9531 (14)	138 (2)
O1—H1O⋯O6	0.86 (2)	1.91 (2)	2.6359 (15)	141 (2)
O1—H1O⋯O6ⁱⁱ	0.86 (2)	2.46 (2)	3.1361 (15)	137 (2)
O3—H3O⋯O4	0.83 (2)	1.97 (2)	2.6357 (14)	137 (2)
O3—H3O⋯O7ⁱⁱⁱ	0.83 (2)	2.19 (2)	2.7658 (15)	127 (2)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x-1, -y+1, -z+1; (iii) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: IPDS Software (Stoe & Cie, 1997 ); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812004771/cv5241sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004771/cv5241Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812004771/cv5241Isup3.cml

checkCIF report

Comment top

As expected, the aromatic C₆-ring is planar (the positions of the six C atoms deviate from the mean plane by 0.0025 (8)–0.0196 (8) Å). The C₆-ring and the two nitro groups are also approximately coplanar, allowing significant π-delocalization. In the extended hydrogen bonding network all three phenolic hydroxy groups act as hydrogen donors and the nitro groups as hydrogen acceptors. The O atoms O1 and O6 of two neighbouring molecules form a planar, four-membered O1···O6···O1'···O6' ring with two bifurcated hydrogen bonds. Remarkably, the O6···O6' distance of 2.823 (2) Å (i.e. one of the diagonal of the corresponding parallelogram) is somewhat shorter than the sum of the van der Waals radii, although no direct hydrogen bond between these two atoms is operative. Some intermolecular C···C and C···O distances (C1···C1': 3.279 Å, C5···O2": 3.046 Å) are slightly shorter than the sum of the van der Waals radii and may be interpreted in terms of π-stacking or weak donor–acceptor interactions.

Related literature top

The synthesis of the title compound has recently been reported by Merten et al. (2012). The importance of hydrogen bonding, π stacking and donor–acceptor interactions in solid-state structures and in solution has been reviewed by Schneider (2009). The crystal structure of dinitrophloroglucinol, a diastereomer of the title compound, has been described by Schweitzer et al. (2008). H atoms were treated as recommended by Müller et al. (2006).

Experimental top

The title compound has been prepared by nitration of pyrogallol-triacetate. ¹H NMR ([D₆]acetone): δ (p.p.m.) = 8.51. ¹³C NMR ([D₆]acetone): δ (p.p.m.) = 114.4, 128.7, 136.6, 148.8. Elemental analysis calculated for C₆H₄N₂O₇ (%): C 33.35, H 1.87, N 12.96; found (%): C 33.19, H 2.24, N 12.83. Single crystals were obtained directly from the reaction mixture at 278 K.

Computing details top

Data collection: IPDS Software (Stoe & Cie, 1997); cell refinement: IPDS Software (Stoe & Cie, 1997); data reduction: IPDS Software (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Section of the hydrogen bonding network, showing bifurcated hydrogen bonds for all three hydroxy groups (displacement ellipsoids are drawn at the 50% probability level).

4,6-Dinitrobenzene-1,2,3-triol top

Crystal data top

C₆H₄N₂O₇	Z = 4
M_r = 216.11	F(000) = 440
Monoclinic, P2₁/c	D_x = 1.898 Mg m⁻³
a = 6.7612 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.878 (2) Å	µ = 0.18 mm⁻¹
c = 10.297 (2) Å	T = 200 K
β = 92.75 (3)°	Prism, light brown
V = 756.5 (3) Å³	0.60 × 0.22 × 0.20 mm

Data collection top

Stoe IPDS image plate diffractometer	1326 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.059
Graphite monochromator	θ_max = 26.0°, θ_min = 2.7°
ϕ scans	h = −8→8
5824 measured reflections	k = −13→13
1488 independent reflections	l = −12→12

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)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0484P)² + 0.1574P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1488 reflections	Δρ_max = 0.31 e Å⁻³
146 parameters	Δρ_min = −0.23 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.093 (9)

Crystal data top

C₆H₄N₂O₇	V = 756.5 (3) Å³
M_r = 216.11	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.7612 (14) Å	µ = 0.18 mm⁻¹
b = 10.878 (2) Å	T = 200 K
c = 10.297 (2) Å	0.60 × 0.22 × 0.20 mm
β = 92.75 (3)°

Data collection top

Stoe IPDS image plate diffractometer	1326 reflections with I > 2σ(I)
5824 measured reflections	R_int = 0.059
1488 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	3 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.31 e Å⁻³
1488 reflections	Δρ_min = −0.23 e Å⁻³
146 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.

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

	x	y	z	U_iso*/U_eq
C5	0.03683 (18)	0.22251 (11)	0.46470 (11)	0.0173 (3)
H5	0.0181	0.1542	0.5203	0.021*
C2	0.09313 (18)	0.42549 (12)	0.30137 (11)	0.0176 (3)
C6	−0.10033 (17)	0.31771 (12)	0.45731 (11)	0.0166 (3)
C1	−0.07860 (17)	0.42018 (11)	0.37270 (11)	0.0168 (3)
C4	0.20152 (17)	0.22875 (11)	0.38968 (11)	0.0167 (3)
C3	0.23403 (17)	0.33087 (12)	0.30757 (11)	0.0176 (3)
O2	0.11938 (14)	0.52556 (9)	0.22378 (9)	0.0253 (3)
H2O	0.235 (2)	0.5179 (17)	0.1964 (17)	0.038*
O1	−0.20607 (13)	0.51466 (9)	0.35774 (9)	0.0228 (3)
H1O	−0.310 (2)	0.4983 (17)	0.3996 (17)	0.034*
O3	0.38713 (14)	0.34789 (10)	0.23055 (10)	0.0265 (3)
H3O	0.467 (3)	0.2905 (15)	0.2362 (18)	0.040*
N4	0.34037 (15)	0.12578 (10)	0.39485 (10)	0.0184 (3)
N6	−0.26572 (15)	0.31109 (10)	0.54231 (10)	0.0195 (3)
O4	0.50228 (13)	0.14010 (9)	0.34200 (9)	0.0250 (3)
O5	0.29368 (14)	0.03088 (9)	0.44938 (9)	0.0259 (3)
O6	−0.40392 (14)	0.38686 (10)	0.52605 (9)	0.0288 (3)
O7	−0.26491 (15)	0.23213 (9)	0.62784 (10)	0.0289 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C5	0.0202 (6)	0.0161 (6)	0.0156 (5)	−0.0017 (5)	0.0016 (4)	−0.0004 (5)
C2	0.0208 (6)	0.0168 (6)	0.0152 (6)	−0.0010 (5)	0.0011 (4)	0.0022 (4)
C6	0.0159 (6)	0.0189 (6)	0.0154 (6)	−0.0021 (5)	0.0029 (4)	−0.0024 (4)
C1	0.0179 (6)	0.0171 (6)	0.0151 (6)	0.0020 (5)	−0.0010 (4)	−0.0027 (4)
C4	0.0189 (6)	0.0150 (6)	0.0162 (6)	0.0017 (4)	0.0007 (5)	−0.0014 (4)
C3	0.0165 (6)	0.0208 (6)	0.0158 (6)	−0.0009 (5)	0.0025 (4)	−0.0013 (5)
O2	0.0246 (5)	0.0238 (5)	0.0283 (5)	0.0039 (4)	0.0084 (4)	0.0113 (4)
O1	0.0209 (5)	0.0231 (5)	0.0247 (5)	0.0065 (4)	0.0048 (4)	0.0036 (4)
O3	0.0227 (5)	0.0280 (6)	0.0300 (5)	0.0065 (4)	0.0135 (4)	0.0090 (4)
N4	0.0199 (5)	0.0191 (6)	0.0163 (5)	0.0019 (4)	0.0011 (4)	−0.0012 (4)
N6	0.0189 (5)	0.0196 (6)	0.0204 (5)	−0.0016 (4)	0.0041 (4)	−0.0027 (4)
O4	0.0208 (5)	0.0265 (5)	0.0284 (5)	0.0056 (4)	0.0084 (4)	0.0003 (4)
O5	0.0306 (5)	0.0186 (5)	0.0288 (5)	0.0030 (4)	0.0040 (4)	0.0062 (4)
O6	0.0214 (5)	0.0345 (6)	0.0314 (5)	0.0085 (4)	0.0091 (4)	0.0023 (4)
O7	0.0319 (5)	0.0252 (5)	0.0310 (5)	0.0009 (4)	0.0155 (4)	0.0071 (4)

Geometric parameters (Å, º) top

C5—C4	1.3870 (17)	C4—N4	1.4609 (16)
C5—C6	1.3898 (17)	C3—O3	1.3467 (15)
C5—H5	0.9500	O2—H2O	0.846 (14)
C2—O2	1.3669 (15)	O1—H1O	0.859 (15)
C2—C3	1.4019 (18)	O3—H3O	0.827 (15)
C2—C1	1.4046 (17)	N4—O5	1.2237 (15)
C6—C1	1.4267 (17)	N4—O4	1.2554 (14)
C6—N6	1.4545 (15)	N6—O7	1.2301 (15)
C1—O1	1.3454 (15)	N6—O6	1.2512 (15)
C4—C3	1.4195 (18)

C4—C5—C6	118.97 (11)	C5—C4—N4	118.28 (11)
C4—C5—H5	120.5	O3—C3—C2	114.34 (11)
C6—C5—H5	120.5	O3—C3—C4	127.14 (12)
O2—C2—C3	120.29 (11)	C2—C3—C4	118.51 (11)
O2—C2—C1	118.18 (11)	C2—O2—H2O	105.3 (13)
C3—C2—C1	121.53 (11)	C1—O1—H1O	108.5 (13)
C5—C6—C1	121.85 (11)	C3—O3—H3O	111.9 (13)
C5—C6—N6	117.42 (11)	O5—N4—O4	123.58 (11)
C1—C6—N6	120.71 (11)	O5—N4—C4	118.95 (11)
O1—C1—C2	116.73 (11)	O4—N4—C4	117.47 (10)
O1—C1—C6	125.64 (11)	O7—N6—O6	122.24 (11)
C2—C1—C6	117.61 (11)	O7—N6—C6	119.22 (11)
C5—C4—C3	121.43 (11)	O6—N6—C6	118.54 (10)

C4—C5—C6—C1	1.40 (18)	O2—C2—C3—C4	179.79 (11)
C4—C5—C6—N6	−176.90 (10)	C1—C2—C3—C4	−0.88 (18)
O2—C2—C1—O1	0.65 (16)	C5—C4—C3—O3	179.92 (11)
C3—C2—C1—O1	−178.70 (11)	N4—C4—C3—O3	−1.37 (19)
O2—C2—C1—C6	−177.52 (10)	C5—C4—C3—C2	−1.28 (18)
C3—C2—C1—C6	3.13 (17)	N4—C4—C3—C2	177.43 (10)
C5—C6—C1—O1	178.59 (11)	C5—C4—N4—O5	10.41 (16)
N6—C6—C1—O1	−3.17 (18)	C3—C4—N4—O5	−168.34 (11)
C5—C6—C1—C2	−3.43 (17)	C5—C4—N4—O4	−169.81 (10)
N6—C6—C1—C2	174.81 (10)	C3—C4—N4—O4	11.44 (16)
C6—C5—C4—C3	1.01 (18)	C5—C6—N6—O7	9.35 (16)
C6—C5—C4—N4	−177.72 (10)	C1—C6—N6—O7	−168.96 (11)
O2—C2—C3—O3	−1.27 (17)	C5—C6—N6—O6	−171.03 (10)
C1—C2—C3—O3	178.07 (10)	C1—C6—N6—O6	10.65 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O3	0.85 (1)	2.14 (2)	2.6467 (14)	118 (2)
O2—H2O···O4ⁱ	0.85 (1)	2.27 (2)	2.9531 (14)	138 (2)
O1—H1O···O6	0.86 (2)	1.91 (2)	2.6359 (15)	141 (2)
O1—H1O···O6ⁱⁱ	0.86 (2)	2.46 (2)	3.1361 (15)	137 (2)
O3—H3O···O4	0.83 (2)	1.97 (2)	2.6357 (14)	137 (2)
O3—H3O···O7ⁱⁱⁱ	0.83 (2)	2.19 (2)	2.7658 (15)	127 (2)

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

Experimental details

Crystal data
Chemical formula	C₆H₄N₂O₇
M_r	216.11
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	6.7612 (14), 10.878 (2), 10.297 (2)
β (°)	92.75 (3)
V (Å³)	756.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.60 × 0.22 × 0.20

Data collection
Diffractometer	Stoe IPDS image plate diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5824, 1488, 1326
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.089, 1.06
No. of reflections	1488
No. of parameters	146
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.23

Computer programs: IPDS Software (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2011).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O3	0.846 (14)	2.138 (18)	2.6467 (14)	118.4 (15)
O2—H2O···O4ⁱ	0.846 (14)	2.271 (16)	2.9531 (14)	137.9 (16)
O1—H1O···O6	0.859 (15)	1.910 (16)	2.6359 (15)	141.3 (17)
O1—H1O···O6ⁱⁱ	0.859 (15)	2.457 (17)	3.1361 (15)	136.5 (16)
O3—H3O···O4	0.827 (15)	1.973 (17)	2.6357 (14)	136.6 (17)
O3—H3O···O7ⁱⁱⁱ	0.827 (15)	2.187 (17)	2.7658 (15)	127.2 (16)

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

Acknowledgements

The authors thank Dr Volker Huch (Universität des Saarlandes) for the collection of the data set.

References

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