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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2756.
Published online 2009 October 17. doi:  10.1107/S1600536809041397
PMCID: PMC2971118

2,2′-(4,6-Dinitro-1,3-phenyl­enedi­oxy)diacetic acid dihydrate

Abstract

In the title compound, C10H8N2O10·2H2O, the skeleton of the dicarboxylic acid mol­ecule is approximately planar, the largest deviation being 0.477 (1) Å for an O atom of a nitro group; this nitro group is twisted out of the plane of the ring by 24.6 (1)°. Adjacent mol­ecules are linked by O—H(...)O hydrogen bonds, which connect the dicarboxylic acid and water mol­ecules into a three-dimensional supra­molecular network.

Related literature

For general background to flexible aromatic carboxylic acids, see: Coronado et al. (2000 [triangle]). For the synthesis and related structures, see: Gao et al. (2006 [triangle]) Ma et al. (2009 [triangle])

An external file that holds a picture, illustration, etc.
Object name is e-65-o2756-scheme1.jpg

Experimental

Crystal data

  • C10H8N2O10·2H2O
  • M r = 352.22
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2756-efi1.jpg
  • a = 8.4438 (17) Å
  • b = 16.049 (3) Å
  • c = 10.539 (2) Å
  • β = 93.13 (3)°
  • V = 1426.0 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.16 mm−1
  • T = 291 K
  • 0.19 × 0.18 × 0.17 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.972, T max = 0.974
  • 10898 measured reflections
  • 2461 independent reflections
  • 2059 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.130
  • S = 1.06
  • 2461 reflections
  • 217 parameters
  • H-atom parameters constrained
  • Δρmax = 0.60 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809041397/ng2661sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809041397/ng2661Isup2.hkl

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

Acknowledgments

The authors thank Heilongjiang University for supporting this study.

supplementary crystallographic information

Comment

Flexible aromatic carboxylic acid with oxygen is a kind of biological activity of the organic carboxylic acid, not only in agriculture, such as plant growth regulators and herbicides it is applied, but also it is important to the synthesis of some organic medicine centre body. Compared with other rigid carboxylic acid ligands, such flexible aromatic carboxylic acid have highly plasticity and spatial configuration of, so it provides a rich and colorful way to identify and assemble for constructing a novel topological network structure with the special physical and chemical properties (Coronado et al., 2000; Gao et al., 2006). In this paper, we report the synthesis and crystal structures of a new flexible aromatic carboxylic acid compound.

In the crystal structure, the skeletons of the dicarboxylic acid molecule is approximately co-planar with the largest deviation being 0.477 (1) Å from O7 of one twisty nitro group [dihedral angles = 24.6 (1)°] (Figure 1).

There are six symmetry-independent 'active' H atoms in the crystal structure, all of them participate in hydrogen bonds, which link the dicarboxylic acid and water molecules into a three-dimensional supramolecular network (Figure 2, Table 1).

Experimental

The synthesis of target product is as follows: chlorine acetic acid (51.6 g, 0.54 mol), sodalye (36.3 g, 0.90 mol) and resorcinol (20 g, 0.18 mol) were dissolved into 200 ml distilled water with stirring. The mixture was heated to refluxed for 6 h, then the pH value was adjusted to about 2.0 by using 3 M hydrochloric acid. After cooling to the room temperature, 10.8 g (27%) yellow precipitate was obtained. The 10.8 g above yellow product was dissolved into 100 ml concentrated sulfuric acid with stirring, and then the mixture of nitric acid (9.45 g, 0.15 mol) and sulfuric acid (20.58 g, 0.21 mol) was dropped into the above solution with keeping the reaction temperature under 0° C for 1 h. Then the rection solution is stirred about 5h at room temperature. The mixture was poured into 500 ml water solution, the crude product were obtained (37%). The product was suitable for X-ray test obtained by recrystallization from water solution.

Refinement

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic), C—H = 0.97 Å (methylene), and with Uiso(H) = 1.2Ueq(C). Water and Carboxylic H atoms were initially located in a difference Fourier map, but they were treated as riding on their parent atoms with O—H = 0.85 Å and with with Uiso(H) = 1.5 Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms.
Fig. 2.
A partial packing view, showing the three-dimensional supramolecular network. Dashed lines indicate the hydrogen-bonding interactions and no involving H atoms have been omitted.

Crystal data

C10H8N2O10·2H2OF(000) = 728
Mr = 352.22Dx = 1.641 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 10730 reflections
a = 8.4438 (17) Åθ = 3.0–27.6°
b = 16.049 (3) ŵ = 0.16 mm1
c = 10.539 (2) ÅT = 291 K
β = 93.13 (3)°Block, colorless
V = 1426.0 (5) Å30.19 × 0.18 × 0.17 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer2461 independent reflections
Radiation source: fine-focus sealed tube2059 reflections with I > 2σ(I)
graphiteRint = 0.021
ω scansθmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −10→10
Tmin = 0.972, Tmax = 0.974k = −18→19
10898 measured reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0711P)2 + 0.5856P] where P = (Fo2 + 2Fc2)/3
2461 reflections(Δ/σ)max < 0.001
217 parametersΔρmax = 0.60 e Å3
0 restraintsΔρmin = −0.25 e Å3

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
C10.5107 (2)0.77890 (11)0.61383 (18)0.0337 (4)
C20.3605 (2)0.76229 (11)0.65578 (19)0.0361 (4)
H20.32610.70730.65890.043*
C30.2606 (2)0.82504 (11)0.69305 (17)0.0329 (4)
C40.3158 (2)0.90822 (12)0.68891 (18)0.0350 (4)
C50.4650 (2)0.92555 (11)0.65097 (18)0.0362 (4)
H50.50070.98040.65110.043*
C60.5625 (2)0.86256 (12)0.61261 (17)0.0347 (4)
C70.5601 (2)0.63511 (12)0.5756 (2)0.0411 (5)
H7A0.47290.62560.51350.049*
H7B0.52560.62020.65890.049*
C80.7010 (2)0.58376 (13)0.54410 (19)0.0403 (5)
C90.0654 (2)0.72769 (11)0.7455 (2)0.0394 (5)
H9A0.14100.69750.80070.047*
H9B0.05920.70060.66310.047*
C10−0.0949 (2)0.72744 (12)0.80110 (18)0.0356 (4)
N10.2172 (2)0.97868 (10)0.72076 (18)0.0455 (4)
N20.7145 (2)0.88676 (11)0.56748 (17)0.0419 (4)
O10.60775 (16)0.72016 (8)0.57395 (15)0.0444 (4)
O20.6797 (2)0.50642 (10)0.5751 (2)0.0691 (6)
H100.76500.47960.56550.104*
O30.8147 (2)0.61073 (11)0.4960 (2)0.0658 (5)
O40.11529 (16)0.81155 (8)0.73285 (14)0.0411 (4)
O5−0.17145 (17)0.78783 (9)0.82313 (16)0.0507 (4)
O6−0.13690 (18)0.65015 (9)0.82352 (16)0.0517 (4)
H6−0.22750.64720.85460.077*
O70.0758 (2)0.97067 (11)0.7144 (3)0.0895 (8)
O80.2816 (2)1.04435 (10)0.7480 (2)0.0735 (6)
O90.7504 (2)0.96008 (10)0.5705 (2)0.0785 (6)
O100.8007 (2)0.83474 (11)0.5236 (2)0.0708 (6)
O120.8696 (2)0.38512 (11)0.53639 (19)0.0681 (5)
H110.96900.39120.53120.102*
H120.84030.34860.58860.102*
O11−0.41411 (19)0.62047 (11)0.90755 (19)0.0658 (5)
H15−0.48800.64550.94370.099*
H14−0.43720.56960.89380.099*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0292 (10)0.0329 (10)0.0396 (10)−0.0014 (7)0.0066 (7)−0.0016 (8)
C20.0316 (10)0.0276 (9)0.0500 (11)−0.0041 (7)0.0097 (8)−0.0008 (8)
C30.0278 (9)0.0306 (9)0.0406 (9)−0.0009 (7)0.0058 (7)0.0007 (8)
C40.0348 (10)0.0284 (9)0.0421 (10)0.0001 (7)0.0048 (8)0.0011 (8)
C50.0387 (11)0.0282 (9)0.0419 (10)−0.0061 (8)0.0029 (8)0.0038 (8)
C60.0292 (10)0.0357 (10)0.0394 (10)−0.0059 (8)0.0037 (7)0.0029 (8)
C70.0317 (10)0.0316 (10)0.0609 (12)−0.0027 (8)0.0118 (9)−0.0036 (9)
C80.0323 (10)0.0401 (11)0.0492 (11)−0.0007 (8)0.0087 (8)−0.0063 (9)
C90.0355 (11)0.0279 (9)0.0563 (12)−0.0013 (8)0.0160 (9)−0.0007 (8)
C100.0315 (10)0.0360 (10)0.0398 (10)−0.0018 (8)0.0067 (8)−0.0027 (8)
N10.0459 (11)0.0298 (9)0.0621 (11)0.0026 (7)0.0157 (8)0.0040 (8)
N20.0323 (9)0.0402 (10)0.0539 (10)−0.0082 (7)0.0071 (7)0.0044 (8)
O10.0322 (7)0.0332 (7)0.0699 (10)−0.0040 (6)0.0209 (7)−0.0073 (7)
O20.0519 (10)0.0419 (9)0.1163 (15)0.0113 (7)0.0309 (10)0.0068 (9)
O30.0457 (10)0.0585 (10)0.0968 (13)0.0050 (8)0.0355 (9)0.0015 (9)
O40.0300 (7)0.0279 (7)0.0669 (9)−0.0009 (5)0.0168 (6)0.0000 (6)
O50.0364 (8)0.0441 (8)0.0733 (10)0.0032 (6)0.0183 (7)−0.0047 (7)
O60.0414 (8)0.0395 (8)0.0765 (10)−0.0070 (6)0.0258 (7)0.0029 (7)
O70.0444 (11)0.0385 (9)0.189 (2)0.0076 (8)0.0335 (13)0.0009 (11)
O80.0688 (12)0.0327 (9)0.1204 (16)−0.0043 (8)0.0192 (11)−0.0199 (9)
O90.0521 (11)0.0445 (10)0.1419 (19)−0.0196 (8)0.0315 (11)−0.0013 (10)
O100.0527 (10)0.0550 (10)0.1092 (15)−0.0120 (8)0.0448 (10)−0.0093 (10)
O120.0514 (10)0.0634 (11)0.0912 (13)0.0040 (8)0.0191 (9)0.0121 (9)
O110.0462 (10)0.0549 (10)0.0995 (14)−0.0074 (8)0.0323 (9)−0.0081 (9)

Geometric parameters (Å, °)

C1—O11.332 (2)C8—O21.298 (3)
C1—C21.392 (3)C9—O41.419 (2)
C1—C61.412 (3)C9—C101.504 (3)
C2—C31.384 (3)C9—H9A0.9700
C2—H20.9300C9—H9B0.9700
C3—O41.336 (2)C10—O51.195 (2)
C3—C41.415 (3)C10—O61.315 (2)
C4—C51.371 (3)N1—O71.200 (2)
C4—N11.454 (3)N1—O81.213 (2)
C5—C61.379 (3)N2—O91.215 (2)
C5—H50.9300N2—O101.216 (2)
C6—N21.446 (2)O2—H100.8500
C7—O11.423 (2)O6—H60.8500
C7—C81.499 (3)O12—H110.8500
C7—H7A0.9700O12—H120.8500
C7—H7B0.9700O11—H150.8500
C8—O31.191 (3)O11—H140.8500
O1—C1—C2123.49 (17)O3—C8—O2125.5 (2)
O1—C1—C6118.27 (16)O3—C8—C7124.2 (2)
C2—C1—C6118.24 (17)O2—C8—C7110.32 (17)
C3—C2—C1122.07 (17)O4—C9—C10108.50 (15)
C3—C2—H2119.0O4—C9—H9A110.0
C1—C2—H2119.0C10—C9—H9A110.0
O4—C3—C2123.74 (16)O4—C9—H9B110.0
O4—C3—C4118.18 (16)C10—C9—H9B110.0
C2—C3—C4118.08 (17)H9A—C9—H9B108.4
C5—C4—C3120.65 (17)O5—C10—O6125.20 (18)
C5—C4—N1117.14 (17)O5—C10—C9125.55 (18)
C3—C4—N1122.19 (17)O6—C10—C9109.24 (16)
C4—C5—C6120.67 (17)O7—N1—O8122.56 (19)
C4—C5—H5119.7O7—N1—C4118.99 (18)
C6—C5—H5119.7O8—N1—C4118.39 (18)
C5—C6—C1120.27 (17)O9—N2—O10121.43 (18)
C5—C6—N2117.05 (17)O9—N2—C6118.43 (18)
C1—C6—N2122.64 (17)O10—N2—C6120.08 (17)
O1—C7—C8107.23 (15)C1—O1—C7119.71 (15)
O1—C7—H7A110.3C8—O2—H10109.0
C8—C7—H7A110.3C3—O4—C9117.76 (14)
O1—C7—H7B110.3C10—O6—H6112.3
C8—C7—H7B110.3H11—O12—H12116.4
H7A—C7—H7B108.5H15—O11—H14111.3

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H10···O120.851.792.569 (2)152
O6—H6···O110.851.752.592 (2)169
O12—H11···O3i0.851.862.707 (2)171
O12—H12···O5ii0.852.002.775 (2)152
O11—H15···O10iii0.852.042.852 (2)160
O11—H14···O7iv0.852.253.017 (3)151
O11—H14···O9ii0.852.382.925 (2)123

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2661).

References

  • Coronado, E., Galan-Mascaros, J. R., Comez-Garcia, C. J., Ensling, J. & Gutlich, P. (2000). Chem. Eur. J.6, 552–563. [PubMed]
  • Gao, J.-S., Hou, G.-F., Yu, Y.-H., Hou, Y.-J. & Li, G.-M. (2006). Acta Cryst. E62, m2685–m2687.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Ma, D.-S., Zhang, X.-M., Zhang, H., Mu, D. & Hou, G.-F. (2009). Acta Cryst. E65, o2456. [PMC free article] [PubMed]
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalClear Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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