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ISSN: 2056-9890

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

aMicroscale Science Institute, Biology Department, Weifang University, Weifang 261061, People's Republic of China, bThe 7th Middle School, Weifang 261061, People's Republic of China, and cMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China
*Correspondence e-mail: ffjian2008@163.com

(Received 19 June 2009; accepted 9 July 2009; online 18 July 2009)

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[Lv, F. T. (1998). Chem. Agent. 20, 179-182.]). Due to their versatile bonding modes with metal ions, they have also been used in the synthesis of mononuclear monomeric (Gao et al., 2004a[Gao, S., Liu, J.-W., Huo, L.-H., Zhao, H. & Zhao, J.-G. (2004a). Acta Cryst. E60, m622-m624.]; Psomas et al., 2000[Psomas, G., Raptopoulou, C. P., Iordanidis, L., Dendrinou-Samara, C., Tangoulis, V. & Kessissoglou, D. P. (2000). Inorg. Chem. 39, 3042-3048.]) and polymeric complexes (Liu et al., 2004[Liu, J. W., Huo, L. H., Gao, S., Zhao, H., Zhu, Z. B. & Zhao, J. G. (2004). Wuji Huaxue Xuebao, 20, 707-710.]; Gao et al., 2004b[Gao, S., Liu, J.-W., Huo, L.-H., Zhao, H. & Zhao, J.-G. (2004b). Acta Cryst. E60, m1875-m1877.], 2005[Gao, S., Liu, J.-W., Huo, L.-H. & Zhao, H. (2005). Acta Cryst. C61, m348-m350.]).

[Scheme 1]

Experimental

Crystal data
  • NH4+·C8H5Cl2O3·0.5H2O

  • Mr = 247.07

  • Monoclinic, C 2/c

  • 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)

  • Rint = 0.026

Refinement
  • R[F2 > 2σ(F2)] = 0.023

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1W—H1⋯O2i 0.85 1.97 3.2969 (15) 170
N1—H1A⋯O2i 0.84 2.07 2.8908 (14) 168
N1—H1B⋯O3ii 0.85 2.02 2.8578 (13) 168
N1—H1C⋯O3iii 0.88 2.09 2.9310 (15) 161
Symmetry codes: (i) [x, -y, z+{\script{1\over 2}}]; (ii) x, y+1, z; (iii) -x, -y, -z.

Data collection: SMART (Bruker, 1997[Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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.

Related literature top

For the biological activity, see: related literature, see: 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).

Experimental top

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 top

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).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The crystal packing of (I), viewed along b axis. Hydrogen bonds are indicated by dashed lines.
Ammonium 2-(2,4-dichlorophenoxy)acetate hemihydrate top
Crystal data top
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 top
Bruker SMART CCD area-detector
diffractometer
2216 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.026
Graphite monochromatorθmax = 27.5°, θmin = 3.2°
ϕ and ω scansh = 4848
9447 measured reflectionsk = 55
2385 independent reflectionsl = 1616
Refinement top
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 = 1.07 w = 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
Crystal data top
NH4+·C8H5Cl2O3·0.5H2OV = 2074.7 (8) Å3
Mr = 247.07Z = 8
Monoclinic, C2/cMo Kα radiation
a = 37.738 (8) ŵ = 0.61 mm1
b = 4.3889 (9) ÅT = 293 K
c = 12.900 (3) Å0.15 × 0.12 × 0.10 mm
β = 103.83 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2216 reflections with I > 2σ(I)
9447 measured reflectionsRint = 0.026
2385 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02390 restraints
wR(F2) = 0.060H-atom parameters constrained
S = 1.07Δρmax = 0.38 e Å3
2385 reflectionsΔρmin = 0.19 e Å3
137 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
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)
H7A0.11780.21950.06870.015*
H7B0.09610.05340.13240.015*
C30.16595 (3)0.2075 (2)0.01809 (9)0.0141 (2)
H3A0.15980.09240.08030.017*
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)
H2A0.21660.32270.03160.018*
C10.20925 (3)0.5183 (2)0.10313 (9)0.0142 (2)
N10.03308 (2)0.2772 (2)0.11575 (7)0.01333 (18)
O1W0.00000.1574 (3)0.25000.0237 (3)
H1A0.03990.29020.18240.024 (4)*
H1B0.03780.44140.08720.024 (4)*
H1WA0.01580.27970.21540.044 (5)*
H1C0.00930.25770.09970.029 (4)*
H1D0.04230.11900.08530.029 (4)*
Atomic displacement parameters (Å2) top
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, º) top
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, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···O2i0.851.973.2969 (15)170
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.

Experimental details

Crystal data
Chemical formulaNH4+·C8H5Cl2O3·0.5H2O
Mr247.07
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)37.738 (8), 4.3889 (9), 12.900 (3)
β (°) 103.83 (3)
V3)2074.7 (8)
Z8
Radiation typeMo Kα
µ (mm1)0.61
Crystal size (mm)0.15 × 0.12 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
9447, 2385, 2216
Rint0.026
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.060, 1.07
No. of reflections2385
No. of parameters137
No. of restraints90
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.19

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···O2i0.851.973.2969 (15)169.9
N1—H1A···O2i0.842.072.8908 (14)167.8
N1—H1B···O3ii0.852.022.8578 (13)167.9
N1—H1C···O3iii0.882.092.9310 (15)160.8
Symmetry codes: (i) x, y, z+1/2; (ii) x, y+1, z; (iii) x, y, z.
 

Acknowledgements

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

References

First citationBruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationGao, S., Liu, J.-W., Huo, L.-H. & Zhao, H. (2005). Acta Cryst. C61, m348–m350.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationGao, S., Liu, J.-W., Huo, L.-H., Zhao, H. & Zhao, J.-G. (2004a). Acta Cryst. E60, m622–m624.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationGao, S., Liu, J.-W., Huo, L.-H., Zhao, H. & Zhao, J.-G. (2004b). Acta Cryst. E60, m1875–m1877.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLiu, J. W., Huo, L. H., Gao, S., Zhao, H., Zhu, Z. B. & Zhao, J. G. (2004). Wuji Huaxue Xuebao, 20, 707–710.  Google Scholar
First citationLv, F. T. (1998). Chem. Agent. 20, 179–182.  Google Scholar
First citationPsomas, G., Raptopoulou, C. P., Iordanidis, L., Dendrinou-Samara, C., Tangoulis, V. & Kessissoglou, D. P. (2000). Inorg. Chem. 39, 3042–3048.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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