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

Liu, H.-L.; Guo, S.-H.; Li, Y.-Y.; Jian, F.-F.

doi:10.1107/S1600536809026919

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1905

doi:10.1107/S1600536809026919

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

Hui-Lian Liu,^a Shu-Hua Guo,^a Yun-Ying Li ^b and Fang-Fang Jian ^c ^*

^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 ). 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

Crystal data

NH₄⁺·C₈H₅Cl₂O₃⁻·0.5H₂O
M_r = 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)
R_int = 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
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

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

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

checkCIF report

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.

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

	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.

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

Crystal data top

NH₄⁺·C₈H₅Cl₂O₃⁻·0.5H₂O	F(000) = 1016
M_r = 247.07	D_x = 1.582 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2216 reflections
a = 37.738 (8) Å	θ = 3.2–27.5°
b = 4.3889 (9) Å	µ = 0.61 mm⁻¹
c = 12.900 (3) Å	T = 293 K
β = 103.83 (3)°	Bar, colourless
V = 2074.7 (8) Å³	0.15 × 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 tube	R_int = 0.026
Graphite monochromator	θ_max = 27.5°, θ_min = 3.2°
ϕ and ω scans	h = −48→48
9447 measured reflections	k = −5→5
2385 independent reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.060	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0294P)² + 1.6158P] where P = (F_o² + 2F_c²)/3
2385 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.38 e Å⁻³
90 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

NH₄⁺·C₈H₅Cl₂O₃⁻·0.5H₂O	V = 2074.7 (8) Å³
M_r = 247.07	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 37.738 (8) Å	µ = 0.61 mm⁻¹
b = 4.3889 (9) Å	T = 293 K
c = 12.900 (3) Å	0.15 × 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 reflections	R_int = 0.026
2385 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	90 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.07	Δρ_max = 0.38 e Å⁻³
2385 reflections	Δρ_min = −0.19 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cl2	0.252351 (7)	0.68291 (7)	0.14126 (2)	0.01935 (8)
Cl1	0.120306 (7)	0.46470 (7)	0.21755 (2)	0.01934 (8)
O3	0.04445 (2)	−0.21277 (17)	−0.01018 (6)	0.01408 (16)
O2	0.05453 (2)	−0.41964 (18)	−0.15912 (6)	0.01545 (16)
O1	0.10714 (2)	0.10909 (18)	0.02392 (6)	0.01371 (16)
C4	0.14091 (3)	0.2393 (2)	0.04524 (8)	0.0119 (2)
C6	0.18475 (3)	0.5588 (2)	0.16711 (8)	0.0146 (2)
H6A	0.1910	0.6774	0.2285	0.018*
C7	0.09822 (3)	−0.0753 (2)	−0.07012 (8)	0.0122 (2)
H7A	0.1178	−0.2195	−0.0687	0.015*
H7B	0.0961	0.0534	−0.1324	0.015*
C3	0.16595 (3)	0.2075 (2)	−0.01809 (9)	0.0141 (2)
H3A	0.1598	0.0924	−0.0803	0.017*
C8	0.06265 (3)	−0.2485 (2)	−0.07926 (8)	0.0113 (2)
C5	0.15090 (3)	0.4193 (2)	0.13763 (8)	0.0130 (2)
C2	0.20009 (3)	0.3460 (3)	0.01088 (9)	0.0152 (2)
H2A	0.2166	0.3227	−0.0316	0.018*
C1	0.20925 (3)	0.5183 (2)	0.10313 (9)	0.0142 (2)
N1	0.03308 (2)	0.2772 (2)	0.11575 (7)	0.01333 (18)
O1W	0.0000	−0.1574 (3)	0.2500	0.0237 (3)
H1A	0.0399	0.2902	0.1824	0.024 (4)*
H1B	0.0378	0.4414	0.0872	0.024 (4)*
H1WA	−0.0158	−0.2797	0.2154	0.044 (5)*
H1C	0.0093	0.2577	0.0997	0.029 (4)*
H1D	0.0423	0.1190	0.0853	0.029 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl2	0.01261 (13)	0.02457 (15)	0.02073 (14)	−0.00724 (10)	0.00367 (10)	−0.00251 (10)
Cl1	0.01548 (13)	0.02906 (16)	0.01553 (13)	−0.00433 (11)	0.00777 (10)	−0.00675 (10)
O3	0.0133 (3)	0.0140 (4)	0.0165 (4)	−0.0013 (3)	0.0066 (3)	−0.0002 (3)
O2	0.0164 (4)	0.0157 (4)	0.0137 (4)	−0.0026 (3)	0.0024 (3)	−0.0021 (3)
O1	0.0108 (3)	0.0175 (4)	0.0137 (4)	−0.0038 (3)	0.0047 (3)	−0.0044 (3)
C4	0.0099 (4)	0.0119 (5)	0.0134 (5)	−0.0002 (4)	0.0019 (4)	0.0022 (4)
C6	0.0150 (5)	0.0155 (5)	0.0125 (5)	−0.0014 (4)	0.0013 (4)	−0.0006 (4)
C7	0.0119 (5)	0.0132 (5)	0.0121 (5)	−0.0014 (4)	0.0042 (4)	−0.0020 (4)
C3	0.0137 (5)	0.0150 (5)	0.0140 (5)	−0.0012 (4)	0.0040 (4)	−0.0013 (4)
C8	0.0101 (4)	0.0101 (4)	0.0130 (5)	0.0014 (4)	0.0016 (4)	0.0033 (4)
C5	0.0125 (5)	0.0154 (5)	0.0121 (5)	0.0007 (4)	0.0048 (4)	0.0012 (4)
C2	0.0130 (5)	0.0171 (5)	0.0170 (5)	−0.0006 (4)	0.0064 (4)	0.0010 (4)
C1	0.0102 (5)	0.0151 (5)	0.0167 (5)	−0.0028 (4)	0.0019 (4)	0.0021 (4)
N1	0.0131 (4)	0.0134 (4)	0.0143 (4)	−0.0009 (3)	0.0050 (3)	0.0001 (3)
O1W	0.0199 (6)	0.0128 (5)	0.0358 (7)	0.000	0.0014 (5)	0.000

Geometric parameters (Å, º) top

Cl2—C1	1.7400 (11)	C7—H7A	0.9700
Cl1—C5	1.7336 (12)	C7—H7B	0.9700
O3—C8	1.2584 (13)	C3—C2	1.3924 (15)
O2—C8	1.2523 (13)	C3—H3A	0.9300
O1—C4	1.3635 (13)	C2—C1	1.3824 (16)
O1—C7	1.4298 (12)	C2—H2A	0.9300
C4—C3	1.3962 (15)	N1—H1A	0.8385
C4—C5	1.4042 (15)	N1—H1B	0.8474
C6—C5	1.3851 (15)	N1—H1C	0.8757
C6—C1	1.3901 (16)	N1—H1D	0.9069
C6—H6A	0.9300	O1W—H1WA	0.8458
C7—C8	1.5225 (14)

C4—O1—C7	115.30 (8)	O2—C8—C7	113.65 (9)
O1—C4—C3	124.81 (10)	O3—C8—C7	120.22 (9)
O1—C4—C5	117.10 (9)	C6—C5—C4	121.65 (10)
C3—C4—C5	118.09 (10)	C6—C5—Cl1	119.18 (8)
C5—C6—C1	118.74 (10)	C4—C5—Cl1	119.17 (8)
C5—C6—H6A	120.6	C1—C2—C3	119.65 (10)
C1—C6—H6A	120.6	C1—C2—H2A	120.2
O1—C7—C8	111.88 (9)	C3—C2—H2A	120.2
O1—C7—H7A	109.2	C2—C1—C6	121.08 (10)
C8—C7—H7A	109.2	C2—C1—Cl2	119.67 (9)
O1—C7—H7B	109.2	C6—C1—Cl2	119.24 (9)
C8—C7—H7B	109.2	H1A—N1—H1B	110.0
H7A—C7—H7B	107.9	H1A—N1—H1C	107.2
C2—C3—C4	120.77 (10)	H1B—N1—H1C	106.9
C2—C3—H3A	119.6	H1A—N1—H1D	116.2
C4—C3—H3A	119.6	H1B—N1—H1D	108.7
O2—C8—O3	126.13 (10)	H1C—N1—H1D	107.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2; (ii) x, y+1, z; (iii) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	NH₄⁺·C₈H₅Cl₂O₃⁻·0.5H₂O
M_r	247.07
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	37.738 (8), 4.3889 (9), 12.900 (3)
β (°)	103.83 (3)
V (Å³)	2074.7 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9447, 2385, 2216
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.060, 1.07
No. of reflections	2385
No. of parameters	137
No. of restraints	90
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
O1W—H1···O2ⁱ	0.85	1.97	3.2969 (15)	169.9
N1—H1A···O2ⁱ	0.84	2.07	2.8908 (14)	167.8
N1—H1B···O3ⁱⁱ	0.85	2.02	2.8578 (13)	167.9
N1—H1C···O3ⁱⁱⁱ	0.88	2.09	2.9310 (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

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