Crystal structure of ammonium (3,5-di-chloro-phen-oxy)acetate hemihydrate.

In the structure of the title hydrated salt, NH4 (+)·C8H5Cl2O3 (-)·0.5H2O, where the anion derives from (3,5-di-chloro-phen-oxy)acetic acid, the ammonium cation is involved in extensive N-H⋯O hydrogen bonding with both carboxyl-ate and ether O-atom acceptors giving sheet structures lying parallel to (100). The water mol-ecule of solvation lies on a crystallographic twofold rotation axis and is involved in intra-sheet O-H⋯Ocarboxyl-ate hydrogen-bonding inter-actions. In the anion, the oxoacetate side chain assumes an antiperiplanar conformation with the defining C-O-C-C torsion angle = -171.33 (15)°.

Related literature

For background on the phen­oxy­acetic acid herbicides, see: Zumdahl (2010 ▸). For examples of structures of a tryptaminium salt and a co-crystalline adduct with (3,5-di­chloro­phen­oxy)acetic acid, see: Smith & Lynch (2015 ▸); Lynch et al. (2003 ▸). For the structures of ammonium salts of other phen­oxy­acetic acids, see: Liu et al. (2009 ▸); Smith (2014 ▸).

Experimental

Crystal data

NH4 +·C8H5Cl2O3 −·0.5H2O

M = 247.07

Monoclinic,

a = 39.818 (3) Å

b = 4.3440 (4) Å

c = 12.7211 (8) Å

β = 98.098 (5)°

V = 2178.4 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.58 mm−1

T = 200 K

0.40 × 0.12 × 0.05 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▸) T min = 0.948, T max = 0.980

6680 measured reflections

2146 independent reflections

1832 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.084

S = 1.08

2146 reflections

147 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.28 e Å−3

Data collection: CrysAlis PRO (Agilent, 2013 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸) within WinGX (Farrugia, 2012 ▸); molecular graphics: PLATON (Spek, 2009 ▸); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015016345/nk2232sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016345/nk2232Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015016345/nk2232Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015016345/nk2232fig1.tif

The mol­ecular configuration and atom-numbering scheme for the title hemi-hydrate salt, with non-H atoms shown as 40% probability ellipsoids. The water mol­ecule lies on a twofold rotation axis and inter-species hydrogen bonds are shown as dashed lines.

Click here for additional data file.

b . DOI: 10.1107/S2056989015016345/nk2232fig2.tif

The two-dimensional sheet structure viewed along the b axis, with intra­molecular hydrogen bonds shown as dashed lines. For symmetry codes, see Table 1.

CCDC reference: 1421868

Additional supporting information: crystallographic information; 3D view; checkCIF report

NH4+·C8H5Cl2O3−·0.5H2O	F(000) = 1016
Mr = 247.07	Dx = 1.507 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2066 reflections
a = 39.818 (3) Å	θ = 4.1–28.7°
b = 4.3440 (4) Å	µ = 0.58 mm−1
c = 12.7211 (8) Å	T = 200 K
β = 98.098 (5)°	Prism, colourless
V = 2178.4 (3) Å3	0.40 × 0.12 × 0.05 mm
Z = 8

Oxford Diffraction Gemini-S CCD-detector diffractometer	2146 independent reflections
Radiation source: Enhance (Mo) X-ray source	1832 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.1°
ω scans	h = −48→39
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −3→5
Tmin = 0.948, Tmax = 0.980	l = −15→15
6680 measured reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.034P)2 + 1.220P] where P = (Fo2 + 2Fc2)/3
2146 reflections	(Δ/σ)max = 0.002
147 parameters	Δρmax = 0.21 e Å−3
5 restraints	Δρmin = −0.28 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

	x	y	z	Uiso*/Ueq
Cl3	0.66552 (1)	1.11332 (13)	0.31644 (4)	0.0401 (2)
Cl5	0.72836 (1)	0.45912 (16)	0.64617 (5)	0.0517 (2)
O11	0.59904 (3)	0.5049 (3)	0.55326 (10)	0.0340 (4)
O13	0.53963 (3)	0.2408 (3)	0.56560 (10)	0.0325 (4)
O14	0.55624 (4)	0.0775 (3)	0.73120 (11)	0.0384 (5)
C1	0.63101 (4)	0.5896 (4)	0.53513 (14)	0.0268 (5)
C2	0.63218 (5)	0.7850 (4)	0.44879 (14)	0.0282 (6)
C3	0.66354 (5)	0.8742 (4)	0.42535 (14)	0.0288 (6)
C4	0.69369 (5)	0.7798 (5)	0.48405 (15)	0.0338 (6)
C5	0.69140 (5)	0.5888 (5)	0.56904 (15)	0.0322 (6)
C6	0.66063 (4)	0.4896 (5)	0.59619 (14)	0.0280 (6)
C12	0.59684 (5)	0.3252 (5)	0.64620 (14)	0.0314 (6)
C13	0.56109 (4)	0.2087 (4)	0.64708 (14)	0.0274 (6)
O1W	0.50000	−0.3034 (5)	0.75000	0.0456 (8)
N1	0.53131 (4)	0.7283 (5)	0.41888 (14)	0.0332 (6)
H2	0.61190	0.85480	0.40720	0.0340*
H4	0.71500	0.84390	0.46650	0.0410*
H6	0.65990	0.35670	0.65510	0.0340*
H121	0.60370	0.45230	0.71020	0.0380*
H122	0.61260	0.14830	0.64820	0.0380*
H1W	0.5153 (5)	−0.185 (5)	0.7335 (17)	0.0400*
H11	0.5403 (5)	0.568 (4)	0.4560 (15)	0.0320*
H12	0.5089 (4)	0.732 (5)	0.4100 (15)	0.0320*
H13	0.5406 (5)	0.744 (5)	0.3632 (13)	0.0320*
H14	0.5370 (5)	0.904 (4)	0.4539 (15)	0.0320*

	U11	U22	U33	U12	U13	U23
Cl3	0.0507 (3)	0.0386 (3)	0.0329 (3)	−0.0105 (2)	0.0122 (2)	0.0034 (2)
Cl5	0.0240 (3)	0.0735 (5)	0.0549 (4)	−0.0024 (3)	−0.0035 (2)	0.0113 (3)
O11	0.0217 (7)	0.0486 (9)	0.0323 (7)	−0.0008 (6)	0.0055 (5)	0.0128 (6)
O13	0.0252 (7)	0.0387 (8)	0.0330 (7)	−0.0004 (6)	0.0020 (6)	0.0037 (6)
O14	0.0370 (8)	0.0504 (9)	0.0298 (7)	−0.0067 (7)	0.0112 (6)	0.0059 (7)
C1	0.0240 (9)	0.0309 (10)	0.0264 (9)	−0.0031 (8)	0.0066 (7)	−0.0046 (8)
C2	0.0278 (10)	0.0319 (11)	0.0250 (9)	0.0002 (8)	0.0040 (7)	−0.0012 (8)
C3	0.0361 (11)	0.0264 (10)	0.0253 (9)	−0.0054 (8)	0.0096 (8)	−0.0051 (8)
C4	0.0283 (10)	0.0386 (12)	0.0361 (11)	−0.0098 (9)	0.0098 (8)	−0.0058 (9)
C5	0.0239 (10)	0.0391 (12)	0.0326 (11)	−0.0020 (9)	0.0002 (8)	−0.0054 (9)
C6	0.0257 (10)	0.0334 (11)	0.0250 (9)	−0.0020 (8)	0.0035 (7)	−0.0001 (8)
C12	0.0280 (10)	0.0420 (12)	0.0239 (9)	−0.0028 (9)	0.0024 (7)	0.0062 (8)
C13	0.0265 (10)	0.0294 (10)	0.0277 (10)	0.0032 (8)	0.0088 (8)	−0.0016 (8)
O1W	0.0348 (12)	0.0361 (13)	0.0660 (15)	0.0000	0.0073 (11)	0.0000
N1	0.0282 (9)	0.0392 (11)	0.0325 (10)	0.0027 (8)	0.0050 (7)	0.0076 (8)

Cl3—C3	1.7423 (18)	C1—C6	1.387 (2)
Cl5—C5	1.743 (2)	C1—C2	1.394 (2)
O11—C1	1.375 (2)	C2—C3	1.380 (3)
O11—C12	1.430 (2)	C3—C4	1.384 (3)
O13—C13	1.255 (2)	C4—C5	1.376 (3)
O14—C13	1.251 (2)	C5—C6	1.388 (3)
O1W—H1Wi	0.85 (2)	C12—C13	1.512 (3)
O1W—H1W	0.85 (2)	C2—H2	0.9500
N1—H13	0.847 (18)	C4—H4	0.9500
N1—H12	0.884 (16)	C6—H6	0.9500
N1—H11	0.888 (18)	C12—H122	0.9900
N1—H14	0.897 (18)	C12—H121	0.9900
C1—O11—C12	116.79 (14)	C4—C5—C6	122.78 (18)
H1W—O1W—H1Wi	105 (2)	C1—C6—C5	118.31 (17)
H12—N1—H13	116.4 (18)	O11—C12—C13	110.87 (15)
H12—N1—H14	103.2 (19)	O13—C13—C12	119.27 (15)
H11—N1—H12	114.0 (19)	O13—C13—O14	126.01 (16)
H11—N1—H13	108.5 (19)	O14—C13—C12	114.68 (16)
H13—N1—H14	103.7 (19)	C3—C2—H2	121.00
H11—N1—H14	110.4 (17)	C1—C2—H2	121.00
C2—C1—C6	120.77 (16)	C5—C4—H4	121.00
O11—C1—C6	123.80 (16)	C3—C4—H4	122.00
O11—C1—C2	115.43 (15)	C1—C6—H6	121.00
C1—C2—C3	118.23 (17)	C5—C6—H6	121.00
Cl3—C3—C2	118.89 (14)	O11—C12—H121	109.00
Cl3—C3—C4	118.22 (15)	O11—C12—H122	109.00
C2—C3—C4	122.89 (17)	C13—C12—H121	109.00
C3—C4—C5	117.02 (18)	C13—C12—H122	110.00
Cl5—C5—C4	119.54 (16)	H121—C12—H122	108.00
Cl5—C5—C6	117.68 (15)
C12—O11—C1—C2	−175.05 (16)	Cl3—C3—C4—C5	−179.42 (15)
C12—O11—C1—C6	5.6 (3)	C2—C3—C4—C5	0.0 (3)
C1—O11—C12—C13	−171.33 (15)	C3—C4—C5—Cl5	179.67 (15)
O11—C1—C2—C3	−178.93 (15)	C3—C4—C5—C6	0.5 (3)
C6—C1—C2—C3	0.5 (3)	Cl5—C5—C6—C1	−179.64 (15)
O11—C1—C6—C5	179.27 (17)	C4—C5—C6—C1	−0.4 (3)
C2—C1—C6—C5	−0.1 (3)	O11—C12—C13—O13	9.5 (2)
C1—C2—C3—Cl3	178.97 (13)	O11—C12—C13—O14	−172.65 (15)
C1—C2—C3—C4	−0.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O14	0.85 (2)	1.99 (2)	2.822 (2)	166 (2)
N1—H11···O11	0.89 (2)	2.50 (2)	3.137 (2)	129 (2)
N1—H11···O13	0.89 (2)	1.99 (2)	2.811 (2)	153 (2)
N1—H12···O13ii	0.88 (2)	2.00 (2)	2.862 (2)	164 (2)
N1—H13···O14iii	0.85 (2)	2.03 (2)	2.840 (2)	161 (2)
N1—H14···O13iv	0.90 (2)	2.03 (2)	2.894 (2)	161 (2)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1WH1WO14	0.85(2)	1.99(2)	2.822(2)	166(2)
N1H11O11	0.89(2)	2.50(2)	3.137(2)	129(2)
N1H11O13	0.89(2)	1.99(2)	2.811(2)	153(2)
N1H12O13i	0.88(2)	2.00(2)	2.862(2)	164(2)
N1H13O14ii	0.85(2)	2.03(2)	2.840(2)	161(2)
N1H14O13iii	0.90(2)	2.03(2)	2.894(2)	161(2)

Symmetry codes: (i) ; (ii) ; (iii) .