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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1905.
Published online 2009 July 18. doi:  10.1107/S1600536809026919
PMCID: PMC2977423

Ammonium 2-(2,4-dichloro­phen­oxy)acetate hemihydrate

Abstract

The title compound, NH4 +·C8H7Cl2O6 ·0.5H2O, was prepared by the reaction of 2-(2,4-dichloro­phen­oxy)­acetic acid and ammonia in water at 367 K. The mol­ecular structure and packing are stabilized by N—H(...)O and O—H(...)O inter­molecular hydrogen-bond inter­actions.

Related literature

For the biological activity of 2-(2,4-dichloro­phen­oxy)acetic acid, see: Lv et al. (1998 [triangle]). Due to their versatile bonding modes with metal ions, they have also been used in the synthesis of mononuclear monomeric (Gao et al., 2004a [triangle]; Psomas et al., 2000 [triangle]) and polymeric complexes (Liu et al., 2004 [triangle]; Gao et al., 2004b [triangle], 2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1905-scheme1.jpg

Experimental

Crystal data

  • NH4 +·C8H5Cl2O3 ·0.5H2O
  • M r = 247.07
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1905-efi1.jpg
  • a = 37.738 (8) Å
  • b = 4.3889 (9) Å
  • c = 12.900 (3) Å
  • β = 103.83 (3)°
  • V = 2074.7 (8) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.61 mm−1
  • T = 293 K
  • 0.15 × 0.12 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: none
  • 9447 measured reflections
  • 2385 independent reflections
  • 2216 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.023
  • wR(F 2) = 0.060
  • S = 1.07
  • 2385 reflections
  • 137 parameters
  • 90 restraints
  • H-atom parameters constrained
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; 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: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809026919/at2826sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026919/at2826Isup2.hkl

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

Acknowledgments

The authors thank the Science Foundation of Shandong Province (No. Y2008B30) and the Youth Foundation of Weifang University (No. 2009Z18).

supplementary crystallographic information

Comment

2-(2,4-Dichlorophenoxy)acetic acid is one of the important biologically active compounds that have been commonly used in herbicides and plant growth substances (Lv et al., 1998). Due to their versatile bonding modes with metal ions, they have also been used in the synthesis of mononuclear monomeric (Gao et al., 2004a; Psomas et al., 2000) and polymeric complexes (Liu et al., 2004; Gao et al., 2004b, 2005). We synthesized the title compound, (I), and report here its crystal structure.

In the crystal structure of (I) (Fig. 1), all the non-H atoms of 2-(2,4-dichlorophenoxy)acetic acid are in the same plane, with the maximum deviation being 0.146Å for atom O3.

Experimental

A mixture of 2-(2,4-dichlorophenoxy)acetic acid (4.42 g, 0.02 mol) and ammonia (1.0 ml, 0.02 mol) was stirred with water (50 ml) at 367 K for 2 h. Single crystals suitable for X-ray measurements were obtained by recrystallization from acetone and ethanol (1:1) at room temperature.

Refinement

The H atoms of the water molecule were found from a difference Fourier map and refined freely. The remaining H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H and N—H distances of 0.93–0.96 and 0.86Å, respectively, and with Uiso(H)=1.2–1.5Ueq(C,N).

Figures

Fig. 1.
The molecular structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
The crystal packing of (I), viewed along b axis. Hydrogen bonds are indicated by dashed lines.

Crystal data

NH4+·C8H5Cl2O3·0.5H2OF(000) = 1016
Mr = 247.07Dx = 1.582 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2216 reflections
a = 37.738 (8) Åθ = 3.2–27.5°
b = 4.3889 (9) ŵ = 0.61 mm1
c = 12.900 (3) ÅT = 293 K
β = 103.83 (3)°Bar, colourless
V = 2074.7 (8) Å30.15 × 0.12 × 0.10 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer2216 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.026
graphiteθmax = 27.5°, θmin = 3.2°
[var phi] and ω scansh = −48→48
9447 measured reflectionsk = −5→5
2385 independent reflectionsl = −16→16

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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0294P)2 + 1.6158P] where P = (Fo2 + 2Fc2)/3
2385 reflections(Δ/σ)max < 0.001
137 parametersΔρmax = 0.38 e Å3
90 restraintsΔρmin = −0.19 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
Cl20.252351 (7)0.68291 (7)0.14126 (2)0.01935 (8)
Cl10.120306 (7)0.46470 (7)0.21755 (2)0.01934 (8)
O30.04445 (2)−0.21277 (17)−0.01018 (6)0.01408 (16)
O20.05453 (2)−0.41964 (18)−0.15912 (6)0.01545 (16)
O10.10714 (2)0.10909 (18)0.02392 (6)0.01371 (16)
C40.14091 (3)0.2393 (2)0.04524 (8)0.0119 (2)
C60.18475 (3)0.5588 (2)0.16711 (8)0.0146 (2)
H6A0.19100.67740.22850.018*
C70.09822 (3)−0.0753 (2)−0.07012 (8)0.0122 (2)
H7A0.1178−0.2195−0.06870.015*
H7B0.09610.0534−0.13240.015*
C30.16595 (3)0.2075 (2)−0.01809 (9)0.0141 (2)
H3A0.15980.0924−0.08030.017*
C80.06265 (3)−0.2485 (2)−0.07926 (8)0.0113 (2)
C50.15090 (3)0.4193 (2)0.13763 (8)0.0130 (2)
C20.20009 (3)0.3460 (3)0.01088 (9)0.0152 (2)
H2A0.21660.3227−0.03160.018*
C10.20925 (3)0.5183 (2)0.10313 (9)0.0142 (2)
N10.03308 (2)0.2772 (2)0.11575 (7)0.01333 (18)
O1W0.0000−0.1574 (3)0.25000.0237 (3)
H1A0.03990.29020.18240.024 (4)*
H1B0.03780.44140.08720.024 (4)*
H1WA−0.0158−0.27970.21540.044 (5)*
H1C0.00930.25770.09970.029 (4)*
H1D0.04230.11900.08530.029 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl20.01261 (13)0.02457 (15)0.02073 (14)−0.00724 (10)0.00367 (10)−0.00251 (10)
Cl10.01548 (13)0.02906 (16)0.01553 (13)−0.00433 (11)0.00777 (10)−0.00675 (10)
O30.0133 (3)0.0140 (4)0.0165 (4)−0.0013 (3)0.0066 (3)−0.0002 (3)
O20.0164 (4)0.0157 (4)0.0137 (4)−0.0026 (3)0.0024 (3)−0.0021 (3)
O10.0108 (3)0.0175 (4)0.0137 (4)−0.0038 (3)0.0047 (3)−0.0044 (3)
C40.0099 (4)0.0119 (5)0.0134 (5)−0.0002 (4)0.0019 (4)0.0022 (4)
C60.0150 (5)0.0155 (5)0.0125 (5)−0.0014 (4)0.0013 (4)−0.0006 (4)
C70.0119 (5)0.0132 (5)0.0121 (5)−0.0014 (4)0.0042 (4)−0.0020 (4)
C30.0137 (5)0.0150 (5)0.0140 (5)−0.0012 (4)0.0040 (4)−0.0013 (4)
C80.0101 (4)0.0101 (4)0.0130 (5)0.0014 (4)0.0016 (4)0.0033 (4)
C50.0125 (5)0.0154 (5)0.0121 (5)0.0007 (4)0.0048 (4)0.0012 (4)
C20.0130 (5)0.0171 (5)0.0170 (5)−0.0006 (4)0.0064 (4)0.0010 (4)
C10.0102 (5)0.0151 (5)0.0167 (5)−0.0028 (4)0.0019 (4)0.0021 (4)
N10.0131 (4)0.0134 (4)0.0143 (4)−0.0009 (3)0.0050 (3)0.0001 (3)
O1W0.0199 (6)0.0128 (5)0.0358 (7)0.0000.0014 (5)0.000

Geometric parameters (Å, °)

Cl2—C11.7400 (11)C7—H7A0.9700
Cl1—C51.7336 (12)C7—H7B0.9700
O3—C81.2584 (13)C3—C21.3924 (15)
O2—C81.2523 (13)C3—H3A0.9300
O1—C41.3635 (13)C2—C11.3824 (16)
O1—C71.4298 (12)C2—H2A0.9300
C4—C31.3962 (15)N1—H1A0.8385
C4—C51.4042 (15)N1—H1B0.8474
C6—C51.3851 (15)N1—H1C0.8757
C6—C11.3901 (16)N1—H1D0.9069
C6—H6A0.9300O1W—H1WA0.8458
C7—C81.5225 (14)
C4—O1—C7115.30 (8)O2—C8—C7113.65 (9)
O1—C4—C3124.81 (10)O3—C8—C7120.22 (9)
O1—C4—C5117.10 (9)C6—C5—C4121.65 (10)
C3—C4—C5118.09 (10)C6—C5—Cl1119.18 (8)
C5—C6—C1118.74 (10)C4—C5—Cl1119.17 (8)
C5—C6—H6A120.6C1—C2—C3119.65 (10)
C1—C6—H6A120.6C1—C2—H2A120.2
O1—C7—C8111.88 (9)C3—C2—H2A120.2
O1—C7—H7A109.2C2—C1—C6121.08 (10)
C8—C7—H7A109.2C2—C1—Cl2119.67 (9)
O1—C7—H7B109.2C6—C1—Cl2119.24 (9)
C8—C7—H7B109.2H1A—N1—H1B110.0
H7A—C7—H7B107.9H1A—N1—H1C107.2
C2—C3—C4120.77 (10)H1B—N1—H1C106.9
C2—C3—H3A119.6H1A—N1—H1D116.2
C4—C3—H3A119.6H1B—N1—H1D108.7
O2—C8—O3126.13 (10)H1C—N1—H1D107.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1···O2i0.851.973.2969 (15)169.9
N1—H1A···O2i0.842.072.8908 (14)168
N1—H1B···O3ii0.852.022.8578 (13)168
N1—H1C···O3iii0.882.092.9310 (15)161

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2826).

References

  • Bruker (1997). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Gao, S., Liu, J.-W., Huo, L.-H. & Zhao, H. (2005). Acta Cryst. C61, m348–m350. [PubMed]
  • Gao, S., Liu, J.-W., Huo, L.-H., Zhao, H. & Zhao, J.-G. (2004a). Acta Cryst. E60, m622–m624.
  • Gao, S., Liu, J.-W., Huo, L.-H., Zhao, H. & Zhao, J.-G. (2004b). Acta Cryst. E60, m1875–m1877.
  • Liu, J. W., Huo, L. H., Gao, S., Zhao, H., Zhu, Z. B. & Zhao, J. G. (2004). Wuji Huaxue Xuebao, 20, 707–710.
  • Lv, F. T. (1998). Chem. Agent 20, 179–182.
  • Psomas, G., Raptopoulou, C. P., Iordanidis, L., Dendrinou-Samara, C., Tangoulis, V. & Kessissoglou, D. P. (2000). Inorg. Chem.39, 3042–3048. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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