Ammonium 4-(4-carb­oxy­phen­oxy)benzoate

Li, H.-P.; Ng, S.W.

doi:10.1107/S1600536810048841

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3345

https://doi.org/10.1107/S1600536810048841

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Ammonium 4-(4-carboxyphenoxy)benzoate

He-Ping Li ^a and Seik Weng Ng ^b ^*

^aHenan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 18 November 2010; accepted 23 November 2010; online 27 November 2010)

The anions of the title salt, NH₄⁺·HO₂CC₆H₄–O–C₆H₄CO₂⁻, are linked by intermolecular –CO₂H⋯O₂C– hydrogen bonds, forming a polyanionic chain in the crystal; adjacent chains are connected through the ammonium cation into a layer structure, with the ammonium cation serving as hydrogen-bond donor to four carboxylate O atoms. The cation and anion both lie on special positions of 2 site symmetry. In the anion, the rings make a dihedral angle of 65.3 (1)°. The acid H atom is disordered about the special position.

Related literature

For the crystal structures of two modifications of oxy-4,4′-bis(benzoic acid), see: Dey & Desiraju (2005 ); Potts et al. (2007 ).

Experimental

Crystal data

NH₄⁺·C₁₄H₉O₅⁻
M_r = 275.25
Orthorhombic, P n n a
a = 6.1916 (1) Å
b = 28.5483 (6) Å
c = 7.1123 (1) Å
V = 1257.17 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.50 × 0.40 × 0.30 mm

Data collection

Bruker SMART APEX diffractometer
3444 measured reflections
1434 independent reflections
1279 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.146
S = 1.04
1434 reflections
102 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1ⁱ	0.84 (1)	1.70 (3)	2.490 (2)	156 (6)
N1—H11⋯O1ⁱ	0.88 (1)	2.14 (1)	2.962 (2)	155 (1)
N1—H12⋯O2	0.88 (1)	2.10 (2)	2.827 (1)	139 (2)
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y+1, z]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810048841/hg2754sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810048841/hg2754Isup2.hkl

checkCIF report

Comment top

We have been studying the co-crystals of carboxylic acids and amines. In the present study, the reaction of 4,4'-oxybis(benzoic acid) and tri-n-propylamine is expected to yield either the neutral co-crystal or the ammonium carboxylate. However, the amine has probably decomposed after being left in solution for several weeks. The product is ammonium hydrogen 4,4'-oxybis(benzoate) (Scheme I, Fig. 1). The non-hydrogen atoms of the benzoate portion of the anion nearly flat (r.m.s. deviation 0.10 Å); the two planes are aligned 65.3 (1) °. The anions are linked by an intermolecular –CO₂H···O₂C– hydrogen bond to form a polyanionic chain; adjacent chains are connected through the ammonium cation into a layer structure. The ammonium cation is hydrogen-bond donor to four carboxylate O atoms (Fig. 2). The cation and anion both lie on special positions of 2 site symmetry. The parent carboxylic acid itself crystallizes in two modifications (Dey & Desiraju, 2005; Potts et al., 2007).

Related literature top

For the crystal structures of two modifications of oxy-4,4'-bis(benzoic acid), see: Dey & Desiraju (2005); Potts et al. (2007).

Experimental top

4,4'-Oxybis(benzoic acid) (0.25 mmol, 0.065 g) was dissolved in a water-ethanol (50 ml/100 ml v/v) mixture. Tri-n-propylamine (33% aqueous solution) was added until the solution registered a neutral pH. The mixture was then set aside for a several weeks; colorless crystals were isolated.

Structure description top

For the crystal structures of two modifications of oxy-4,4'-bis(benzoic acid), see: Dey & Desiraju (2005); Potts et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [NH₄]⁺ [HO₂CC₆H₄–O–C₆H₄CO₂]^– at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Layer structure projected onto the unit cell.

Ammonium 4-(4-carboxyphenoxy)benzoate top

Crystal data top

NH₄⁺·C₁₄H₉O₅⁻	F(000) = 576
M_r = 275.25	D_x = 1.454 Mg m⁻³
Orthorhombic, Pnna	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2bc	Cell parameters from 2311 reflections
a = 6.1916 (1) Å	θ = 2.9–27.6°
b = 28.5483 (6) Å	µ = 0.11 mm⁻¹
c = 7.1123 (1) Å	T = 293 K
V = 1257.17 (4) Å³	Block, colorless
Z = 4	0.50 × 0.40 × 0.30 mm

Data collection top

Bruker SMART APEX diffractometer	1279 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.014
Graphite monochromator	θ_max = 27.5°, θ_min = 2.9°
ω scans	h = −6→8
3444 measured reflections	k = −36→29
1434 independent reflections	l = −9→5

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0922P)² + 0.4317P] where P = (F_o² + 2F_c²)/3
1434 reflections	(Δ/σ)_max = 0.001
102 parameters	Δρ_max = 0.30 e Å⁻³
6 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

NH₄⁺·C₁₄H₉O₅⁻	V = 1257.17 (4) Å³
M_r = 275.25	Z = 4
Orthorhombic, Pnna	Mo Kα radiation
a = 6.1916 (1) Å	µ = 0.11 mm⁻¹
b = 28.5483 (6) Å	T = 293 K
c = 7.1123 (1) Å	0.50 × 0.40 × 0.30 mm

Data collection top

Bruker SMART APEX diffractometer	1279 reflections with I > 2σ(I)
3444 measured reflections	R_int = 0.014
1434 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	6 restraints
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.30 e Å⁻³
1434 reflections	Δρ_min = −0.42 e Å⁻³
102 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.83559 (19)	0.46053 (3)	0.15346 (17)	0.0429 (4)
H1	0.748 (8)	0.4828 (15)	0.140 (6)	0.10 (2)*	0.50
O2	0.5981 (2)	0.43933 (4)	0.37136 (18)	0.0536 (4)
O3	1.1215 (2)	0.2500	0.2500	0.0325 (4)
C1	0.7477 (2)	0.43024 (5)	0.26451 (19)	0.0320 (3)
C2	0.8424 (2)	0.38203 (4)	0.25651 (17)	0.0266 (3)
C3	0.7341 (2)	0.34508 (5)	0.34202 (18)	0.0302 (3)
H3	0.6034	0.3506	0.4026	0.036*
C4	0.8184 (2)	0.30004 (5)	0.33813 (18)	0.0304 (3)
H4	0.7450	0.2754	0.3950	0.036*
C5	1.0136 (2)	0.29244 (4)	0.24811 (16)	0.0254 (3)
C6	1.1244 (2)	0.32879 (5)	0.16242 (18)	0.0292 (3)
H6	1.2555	0.3232	0.1027	0.035*
C7	1.0374 (2)	0.37357 (4)	0.16673 (18)	0.0298 (3)
H7	1.1105	0.3981	0.1089	0.036*
N1	0.2500	0.5000	0.2884 (4)	0.0503 (5)
H11	0.3506 (16)	0.5123 (6)	0.2161 (16)	0.060*
H12	0.308 (3)	0.4771 (5)	0.355 (2)	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0450 (7)	0.0203 (5)	0.0633 (8)	0.0051 (4)	0.0098 (5)	0.0037 (4)
O2	0.0553 (8)	0.0374 (6)	0.0681 (8)	0.0191 (5)	0.0230 (6)	0.0050 (5)
O3	0.0327 (7)	0.0164 (6)	0.0485 (8)	0.000	0.000	−0.0001 (5)
C1	0.0339 (7)	0.0233 (6)	0.0387 (7)	0.0044 (5)	−0.0013 (5)	−0.0041 (5)
C2	0.0321 (7)	0.0194 (6)	0.0284 (6)	0.0019 (5)	−0.0005 (5)	−0.0016 (4)
C3	0.0309 (7)	0.0269 (7)	0.0329 (7)	0.0015 (5)	0.0058 (5)	−0.0014 (5)
C4	0.0366 (7)	0.0223 (6)	0.0323 (7)	−0.0030 (5)	0.0062 (5)	0.0024 (5)
C5	0.0328 (7)	0.0167 (6)	0.0266 (6)	0.0011 (4)	−0.0016 (5)	−0.0020 (4)
C6	0.0308 (7)	0.0219 (6)	0.0350 (7)	0.0006 (5)	0.0070 (5)	−0.0013 (5)
C7	0.0360 (8)	0.0183 (6)	0.0352 (7)	−0.0012 (5)	0.0062 (5)	0.0019 (4)
N1	0.0342 (10)	0.0516 (12)	0.0651 (13)	0.0082 (9)	0.000	0.000

Geometric parameters (Å, º) top

O1—C1	1.2914 (18)	C3—H3	0.9300
O1—H1	0.841 (10)	C4—C5	1.385 (2)
O2—C1	1.2260 (18)	C4—H4	0.9300
O3—C5ⁱ	1.3833 (13)	C5—C6	1.3852 (18)
O3—C5	1.3833 (13)	C6—C7	1.3876 (17)
C1—C2	1.4973 (17)	C6—H6	0.9300
C2—C7	1.3867 (19)	C7—H7	0.9300
C2—C3	1.3902 (18)	N1—H11	0.881 (7)
C3—C4	1.3880 (18)	N1—H12	0.882 (8)

C1—O1—H1	108 (4)	C5—C4—H4	120.6
C5ⁱ—O3—C5	122.29 (15)	C3—C4—H4	120.6
O2—C1—O1	123.76 (13)	O3—C5—C4	123.65 (11)
O2—C1—C2	120.94 (13)	O3—C5—C6	114.94 (12)
O1—C1—C2	115.30 (12)	C4—C5—C6	121.19 (11)
C7—C2—C3	119.32 (11)	C5—C6—C7	119.25 (12)
C7—C2—C1	121.23 (12)	C5—C6—H6	120.4
C3—C2—C1	119.45 (12)	C7—C6—H6	120.4
C4—C3—C2	120.83 (12)	C2—C7—C6	120.55 (12)
C4—C3—H3	119.6	C2—C7—H7	119.7
C2—C3—H3	119.6	C6—C7—H7	119.7
C5—C4—C3	118.86 (12)	H11—N1—H12	108.6 (10)

O2—C1—C2—C7	−166.60 (14)	C5ⁱ—O3—C5—C6	−151.57 (12)
O1—C1—C2—C7	12.97 (19)	C3—C4—C5—O3	174.06 (11)
O2—C1—C2—C3	12.8 (2)	C3—C4—C5—C6	−0.17 (19)
O1—C1—C2—C3	−167.60 (13)	O3—C5—C6—C7	−174.86 (10)
C7—C2—C3—C4	−0.1 (2)	C4—C5—C6—C7	−0.15 (19)
C1—C2—C3—C4	−179.57 (12)	C3—C2—C7—C6	−0.20 (19)
C2—C3—C4—C5	0.3 (2)	C1—C2—C7—C6	179.23 (12)
C5ⁱ—O3—C5—C4	33.86 (10)	C5—C6—C7—C2	0.3 (2)

Symmetry code: (i) x, −y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱⁱ	0.84 (1)	1.70 (3)	2.490 (2)	156 (6)
N1—H11···O1ⁱⁱ	0.88 (1)	2.14 (1)	2.962 (2)	155 (1)
N1—H12···O2	0.88 (1)	2.10 (2)	2.827 (1)	139 (2)

Symmetry code: (ii) −x+3/2, −y+1, z.

Experimental details

Crystal data
Chemical formula	NH₄⁺·C₁₄H₉O₅⁻
M_r	275.25
Crystal system, space group	Orthorhombic, Pnna
Temperature (K)	293
a, b, c (Å)	6.1916 (1), 28.5483 (6), 7.1123 (1)
V (Å³)	1257.17 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.50 × 0.40 × 0.30

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3444, 1434, 1279
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.146, 1.04
No. of reflections	1434
No. of parameters	102
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.42

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.84 (1)	1.70 (3)	2.490 (2)	156 (6)
N1—H11···O1ⁱ	0.88 (1)	2.14 (1)	2.962 (2)	155 (1)
N1—H12···O2	0.88 (1)	2.10 (2)	2.827 (1)	139 (2)

Symmetry code: (i) −x+3/2, −y+1, z.

Acknowledgements

We thank Dr Yun-Xia Yang of Northeast Normal University for the diffraction measurements, and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
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