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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2544.
Published online 2010 September 11. doi:  10.1107/S1600536810035415
PMCID: PMC2983309

2-Amino-4-nitro­phenol monohydrate

Abstract

The title compound, C6H6N2O3·H2O, crystallizes with two formula units in the asymmetric unit. The mol­ecules are essentially planar with the nitro groups twisted slightly out of the ring planes [maximum deviations from the ring plane of 0.13 (2) and 0.22 (2) Å in the two mol­ecules]. The respective O—N—C—C torsion angles are 6.0 (4) and 12.5 (4)°. In the crystal structure, mol­ecules are linked by inter­molecular N—H(...)O, C—H(...)O, O—H(...)O and O—H(...)N inter­actions into a three-dimensional network.

Related literature

For the use of nitro­aromatics as inter­mediates in explosives, dyestuffs, pesticides and organic synthesis, see: Yan et al. (2006 [triangle]). For the occurrence of nitro­aromatics in industrial wastes and as direct pollutants in the environment, see: Yan et al. (2006 [triangle]); Soojhawon et al. (2005 [triangle]). For related structures, see: Tanak et al. (2010 [triangle]); Bi et al. (2009 [triangle]); Garden et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2544-scheme1.jpg

Experimental

Crystal data

  • C6H6N2O3·H2O
  • M r = 172.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2544-efi1.jpg
  • a = 7.539 (5) Å
  • b = 21.436 (5) Å
  • c = 9.714 (5) Å
  • β = 99.328 (5)°
  • V = 1549.1 (13) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.13 mm−1
  • T = 296 K
  • 0.62 × 0.30 × 0.05 mm

Data collection

  • Stoe IPDS II diffractometer
  • Absorption correction: integration (X-RED32; Stoe & Cie, 2002 [triangle]) T min = 0.578, T max = 0.892
  • 8719 measured reflections
  • 3031 independent reflections
  • 1598 reflections with I > 2σ(I)
  • R int = 0.069

Refinement

  • R[F 2 > 2σ(F 2)] = 0.054
  • wR(F 2) = 0.116
  • S = 0.98
  • 3031 reflections
  • 242 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 [triangle]); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810035415/bt5342sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035415/bt5342Isup2.hkl

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

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant No. F279 of the University Research Fund).

supplementary crystallographic information

Comment

Nitroaromatics are widely used either as materials or as intermediates in explosives, dyestuffs, pesticides and organic synthesis (Yan et al., 2006). Nitroaromatics occur as industrial wastes and direct pollutants in the environment, and are relatively soluble in water and detectable in rivers, ponds and soil (Yan et al., 2006; Soojhawon et al., 2005).

There is two independent molecules in the asymmetric unit of the title compound (I, Fig. 1). The bond lengths and angles in (I) have normal values, and are comparable with those in the related structures (Tanak et al., 2010; Bi et al., 2009; Garden et al., 2004). The aromatic ring systems are almost planar with the maximum deviation, 0.13 (2) Å for atom O1 in the ring system C1—C6 and -0.22 (2) Å for atom O4 in the ring system C7—C12.

In the crystal structure, the molecules are linked by intermolecular N—H···O, C—H···O, O—H···O and O—H···N interactions (see Table I) into a three-dimensional network.

Experimental

The commercially available compound (Acros organics) was recrystallized from ethanol.

Refinement

C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The position of the H4, H5, H10, H11, H13, H14, H15 and H16 atoms were obtained from a difference map and these atoms were freely refined. The H atoms of the hydroxyl groups were refined using a riding model with O-H = 0.82Å and Uiso(H) = 1.5Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound, showing the atom-numbering scheme and 50% probability diplacement ellipsoids.
Fig. 2.
The crystal packing of the title compound.

Crystal data

C6H6N2O3·H2OF(000) = 720
Mr = 172.14Dx = 1.476 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 7016 reflections
a = 7.539 (5) Åθ = 1.9–27.3°
b = 21.436 (5) ŵ = 0.13 mm1
c = 9.714 (5) ÅT = 296 K
β = 99.328 (5)°Prism, yellow
V = 1549.1 (13) Å30.62 × 0.30 × 0.05 mm
Z = 8

Data collection

Stoe IPDS II diffractometer3031 independent reflections
Radiation source: fine-focus sealed tube1598 reflections with I > 2σ(I)
graphiteRint = 0.069
Detector resolution: 6.67 pixels mm-1θmax = 26.0°, θmin = 1.9°
rotation method scansh = −7→9
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)k = −26→26
Tmin = 0.578, Tmax = 0.892l = −11→11
8719 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116w = 1/[σ2(Fo2) + (0.0426P)2] where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
3031 reflectionsΔρmax = 0.17 e Å3
242 parametersΔρmin = −0.21 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0063 (11)

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 (Å2)

xyzUiso*/Ueq
O30.6819 (3)0.50238 (8)0.1354 (2)0.0700 (6)
H10.70780.47270.18820.105*
C110.4215 (3)0.62410 (11)0.4251 (3)0.0524 (7)
O60.3203 (3)0.52487 (8)0.3513 (2)0.0738 (6)
H70.26340.50610.28490.111*
C40.7466 (3)0.55594 (11)0.2003 (3)0.0525 (7)
C50.7094 (3)0.61040 (11)0.1216 (3)0.0521 (6)
C120.4337 (3)0.68701 (11)0.4013 (3)0.0534 (7)
H120.49500.71290.46990.064*
O80.7879 (3)0.39992 (9)0.2795 (3)0.0796 (7)
C20.9053 (4)0.61399 (12)0.3917 (3)0.0581 (7)
H20.97020.61580.48160.070*
C100.3296 (3)0.58634 (11)0.3190 (3)0.0540 (7)
N40.4880 (4)0.59777 (11)0.5561 (3)0.0661 (7)
N20.6190 (4)0.60576 (11)−0.0165 (3)0.0656 (7)
C10.8706 (4)0.66709 (11)0.3123 (3)0.0543 (7)
C60.7737 (4)0.66635 (11)0.1799 (3)0.0567 (7)
H60.75150.70330.12990.068*
O11.0411 (4)0.72657 (11)0.4830 (3)0.0981 (8)
C30.8408 (4)0.55795 (12)0.3337 (3)0.0580 (7)
H30.86120.52140.38530.070*
N30.3654 (4)0.77812 (11)0.2558 (3)0.0690 (7)
N10.9413 (4)0.72598 (12)0.3708 (3)0.0744 (8)
C90.2545 (4)0.61152 (12)0.1923 (3)0.0612 (7)
H90.19660.58580.12190.073*
C80.2650 (4)0.67473 (12)0.1700 (3)0.0614 (7)
H80.21260.69220.08560.074*
C70.3544 (4)0.71151 (11)0.2748 (3)0.0540 (7)
O50.4692 (4)0.80874 (9)0.3407 (3)0.0955 (8)
O40.2702 (3)0.80249 (9)0.1563 (3)0.0911 (8)
O20.9015 (4)0.77391 (10)0.3045 (3)0.1136 (10)
O70.1271 (4)0.45374 (12)0.1652 (4)0.1135 (11)
H110.513 (6)0.558 (2)0.552 (5)0.170*
H50.544 (7)0.574 (2)−0.025 (5)0.170*
H100.584 (7)0.620 (2)0.603 (5)0.170*
H40.564 (7)0.641 (2)−0.048 (5)0.170*
H150.808 (7)0.368 (2)0.243 (6)0.170*
H160.686 (7)0.394 (2)0.327 (5)0.170*
H130.201 (7)0.432 (2)0.122 (6)0.170*
H140.055 (7)0.431 (2)0.188 (6)0.170*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O30.0838 (15)0.0491 (10)0.0692 (13)−0.0074 (9)−0.0118 (11)0.0001 (10)
C110.0552 (17)0.0446 (14)0.0573 (18)0.0031 (11)0.0091 (13)0.0025 (13)
O60.0843 (16)0.0441 (10)0.0885 (15)−0.0017 (9)0.0006 (11)−0.0001 (10)
C40.0559 (17)0.0441 (14)0.0555 (18)−0.0012 (12)0.0031 (13)−0.0018 (14)
C50.0512 (16)0.0507 (14)0.0534 (17)0.0033 (12)0.0056 (13)−0.0005 (14)
C120.0575 (18)0.0436 (14)0.0573 (18)0.0006 (11)0.0038 (13)0.0024 (13)
O80.0979 (19)0.0521 (11)0.0887 (18)0.0038 (11)0.0145 (13)0.0065 (11)
C20.0568 (17)0.0612 (17)0.0530 (17)0.0036 (13)−0.0011 (13)−0.0075 (15)
C100.0549 (18)0.0402 (13)0.068 (2)0.0042 (11)0.0126 (14)0.0023 (14)
N40.0814 (19)0.0477 (12)0.0641 (17)0.0015 (12)−0.0041 (13)0.0101 (13)
N20.0727 (18)0.0609 (14)0.0581 (16)0.0057 (12)−0.0050 (13)0.0039 (13)
C10.0514 (16)0.0478 (14)0.064 (2)−0.0011 (12)0.0099 (14)−0.0135 (14)
C60.0570 (17)0.0458 (14)0.068 (2)0.0048 (12)0.0128 (15)0.0029 (15)
O10.0942 (18)0.0970 (17)0.0998 (19)−0.0290 (13)0.0057 (15)−0.0430 (16)
C30.0661 (19)0.0492 (14)0.0557 (19)0.0042 (12)0.0007 (14)0.0026 (13)
N30.0799 (19)0.0529 (14)0.0747 (19)0.0083 (13)0.0136 (15)0.0146 (15)
N10.0694 (19)0.0599 (17)0.096 (2)−0.0080 (13)0.0205 (17)−0.0282 (17)
C90.0613 (18)0.0606 (16)0.0597 (18)0.0016 (13)0.0039 (14)−0.0047 (15)
C80.0599 (19)0.0641 (17)0.0594 (19)0.0103 (14)0.0075 (14)0.0096 (15)
C70.0526 (17)0.0459 (13)0.0635 (19)0.0067 (12)0.0097 (14)0.0088 (14)
O50.122 (2)0.0524 (12)0.104 (2)−0.0134 (12)−0.0068 (16)0.0133 (13)
O40.1057 (19)0.0673 (13)0.0949 (18)0.0214 (12)−0.0002 (14)0.0300 (13)
O20.137 (2)0.0485 (13)0.149 (3)−0.0033 (13)0.0030 (19)−0.0150 (15)
O70.105 (2)0.0883 (18)0.156 (3)−0.0325 (14)0.0474 (18)−0.0539 (18)

Geometric parameters (Å, °)

O3—C41.361 (3)N4—H110.88 (5)
O3—H10.8200N4—H100.92 (5)
C11—C121.374 (3)N2—H50.89 (5)
C11—C101.402 (4)N2—H40.89 (5)
C11—N41.408 (4)C1—C61.372 (4)
O6—C101.359 (3)C1—N11.450 (3)
O6—H70.8200C6—H60.9300
C4—C31.374 (4)O1—N11.219 (4)
C4—C51.398 (3)C3—H30.9300
C5—C61.380 (3)N3—O41.223 (3)
C5—N21.406 (4)N3—O51.230 (3)
C12—C71.380 (4)N3—C71.444 (3)
C12—H120.9300N1—O21.224 (3)
O8—H150.80 (5)C9—C81.377 (4)
O8—H160.96 (5)C9—H90.9300
C2—C11.376 (4)C8—C71.374 (4)
C2—C31.382 (4)C8—H80.9300
C2—H20.9300O7—H130.89 (5)
C10—C91.378 (4)O7—H140.78 (5)
C4—O3—H1109.5H5—N2—H4112 (4)
C12—C11—C10118.8 (2)C6—C1—C2122.7 (2)
C12—C11—N4121.5 (3)C6—C1—N1118.9 (3)
C10—C11—N4119.6 (2)C2—C1—N1118.4 (3)
C10—O6—H7109.5C1—C6—C5119.5 (2)
O3—C4—C3123.7 (2)C1—C6—H6120.2
O3—C4—C5115.2 (2)C5—C6—H6120.2
C3—C4—C5121.1 (2)C4—C3—C2120.4 (3)
C6—C5—C4118.4 (2)C4—C3—H3119.8
C6—C5—N2122.5 (2)C2—C3—H3119.8
C4—C5—N2119.0 (2)O4—N3—O5122.0 (2)
C11—C12—C7119.5 (3)O4—N3—C7119.0 (3)
C11—C12—H12120.3O5—N3—C7119.1 (3)
C7—C12—H12120.3O1—N1—O2121.6 (3)
H15—O8—H16109 (4)O1—N1—C1119.6 (3)
C1—C2—C3117.9 (2)O2—N1—C1118.7 (3)
C1—C2—H2121.1C8—C9—C10120.0 (3)
C3—C2—H2121.1C8—C9—H9120.0
O6—C10—C9123.9 (3)C10—C9—H9120.0
O6—C10—C11115.3 (2)C7—C8—C9118.8 (3)
C9—C10—C11120.9 (2)C7—C8—H8120.6
C11—N4—H11113 (3)C9—C8—H8120.6
C11—N4—H10112 (3)C8—C7—C12122.0 (2)
H11—N4—H10112 (4)C8—C7—N3120.3 (3)
C5—N2—H5110 (3)C12—C7—N3117.7 (3)
C5—N2—H4113 (3)H13—O7—H14109 (5)
O3—C4—C5—C6−178.9 (2)C5—C4—C3—C2−1.8 (4)
C3—C4—C5—C61.6 (4)C1—C2—C3—C40.6 (4)
O3—C4—C5—N2−3.1 (4)C6—C1—N1—O1−173.4 (3)
C3—C4—C5—N2177.4 (3)C2—C1—N1—O16.0 (4)
C10—C11—C12—C70.6 (4)C6—C1—N1—O25.2 (4)
N4—C11—C12—C7−175.0 (2)C2—C1—N1—O2−175.4 (3)
C12—C11—C10—O6−178.8 (2)O6—C10—C9—C8177.8 (2)
N4—C11—C10—O6−3.2 (4)C11—C10—C9—C8−1.7 (4)
C12—C11—C10—C90.8 (4)C10—C9—C8—C71.3 (4)
N4—C11—C10—C9176.4 (3)C9—C8—C7—C120.0 (4)
C3—C2—C1—C60.8 (4)C9—C8—C7—N3−179.0 (2)
C3—C2—C1—N1−178.6 (2)C11—C12—C7—C8−1.0 (4)
C2—C1—C6—C5−0.9 (4)C11—C12—C7—N3178.0 (2)
N1—C1—C6—C5178.4 (2)O4—N3—C7—C812.1 (4)
C4—C5—C6—C1−0.3 (4)O5—N3—C7—C8−168.4 (3)
N2—C5—C6—C1−175.9 (3)O4—N3—C7—C12−166.9 (3)
O3—C4—C3—C2178.7 (2)O5—N3—C7—C1212.5 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H4···O2i0.89 (5)2.51 (5)3.382 (3)165 (4)
N2—H5···O3ii0.89 (5)2.47 (5)3.317 (3)159 (4)
N4—H10···O4iii0.92 (5)2.18 (5)3.062 (3)159 (4)
N4—H11···O6iv0.88 (5)2.28 (5)3.064 (3)147 (4)
O7—H13···N2ii0.89 (5)2.00 (5)2.877 (4)172 (5)
O7—H14···O8v0.78 (5)2.43 (5)3.166 (4)158 (5)
O8—H15···O2vi0.80 (5)2.55 (5)3.102 (3)127 (4)
O8—H15···O5vi0.80 (5)2.35 (5)3.038 (3)144 (5)
O8—H16···N4iv0.96 (5)1.88 (5)2.821 (4)164 (4)
C6—H6···O1i0.932.473.304 (4)150
C12—H12···O4iii0.932.543.254 (4)133
O3—H1···O80.821.852.657 (3)169
O6—H7···O70.821.812.619 (4)168

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5342).

References

  • Bi, S., Wu, Y.-Z., Zhou, Y.-X., Tang, J.-G. & Guo, C. (2009). Acta Cryst. E65, o1378. [PMC free article] [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Garden, S. J., da Cunha, F. R., Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2004). Acta Cryst. C60, o12–o14. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Soojhawon, I., Lokhande, P. D., Kodam, K. M. & Gawai, K. R. (2005). Enz. Microb. Technol.37, 527–533.
  • Stoe & Cie (2002). X-AREA and X-RED32 Stoe & Cie, Darmstadt, Germany.
  • Tanak, H., Macit, M., Yavuz, M. & Işık, Ş. (2009). Acta Cryst. E65, o3056–o3057. [PMC free article] [PubMed]
  • Yan, X. F., Xiao, H. M., Gong, X. D. & Ju, X. H. (2006). J. Mol. Struct. (THEOCHEM), 764, 141–148.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography