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ISSN: 2056-9890

Ammonium 4-(4-carb­­oxy­phen­­oxy)benzoate

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[Dey, A. & Desiraju, G. R. (2005). Chem. Commun. pp. 2486-2488.]); Potts et al. (2007[Potts, S., Bredenkamp, M. W. & Gertenbach, J.-A. (2007). Acta Cryst. E63, o2887.]).

[Scheme 1]

Experimental

Crystal data
  • NH4+·C14H9O5

  • Mr = 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)

  • Rint = 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

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.42 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 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: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C–H 0.93 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Ueq(C).

The acid and ammonium H-atoms were located in a difference Fourier map, and were refined with distance restraints of O–H 0.84±0.01 and N–H 0.88±0.01 Å. The temperature factor of the acid H atom was refined whereas that of the ammonium H atoms were tied by a factor of 1.2 times. For the ammonium H-atoms, because the N atom lies on a special position, the H···H distance was restrained to 1.43±0.01 Å.

Structure description 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).

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
[Figure 1] 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.
[Figure 2] Fig. 2. Layer structure projected onto the unit cell.
Ammonium 4-(4-carboxyphenoxy)benzoate top
Crystal data top
NH4+·C14H9O5F(000) = 576
Mr = 275.25Dx = 1.454 Mg m3
Orthorhombic, PnnaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2bcCell parameters from 2311 reflections
a = 6.1916 (1) Åθ = 2.9–27.6°
b = 28.5483 (6) ŵ = 0.11 mm1
c = 7.1123 (1) ÅT = 293 K
V = 1257.17 (4) Å3Block, colorless
Z = 40.50 × 0.40 × 0.30 mm
Data collection top
Bruker SMART APEX
diffractometer
1279 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.014
Graphite monochromatorθmax = 27.5°, θmin = 2.9°
ω scansh = 68
3444 measured reflectionsk = 3629
1434 independent reflectionsl = 95
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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0922P)2 + 0.4317P]
where P = (Fo2 + 2Fc2)/3
1434 reflections(Δ/σ)max = 0.001
102 parametersΔρmax = 0.30 e Å3
6 restraintsΔρmin = 0.42 e Å3
Crystal data top
NH4+·C14H9O5V = 1257.17 (4) Å3
Mr = 275.25Z = 4
Orthorhombic, PnnaMo Kα radiation
a = 6.1916 (1) ŵ = 0.11 mm1
b = 28.5483 (6) ÅT = 293 K
c = 7.1123 (1) Å0.50 × 0.40 × 0.30 mm
Data collection top
Bruker SMART APEX
diffractometer
1279 reflections with I > 2σ(I)
3444 measured reflectionsRint = 0.014
1434 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0496 restraints
wR(F2) = 0.146H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.30 e Å3
1434 reflectionsΔρmin = 0.42 e Å3
102 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.83559 (19)0.46053 (3)0.15346 (17)0.0429 (4)
H10.748 (8)0.4828 (15)0.140 (6)0.10 (2)*0.50
O20.5981 (2)0.43933 (4)0.37136 (18)0.0536 (4)
O31.1215 (2)0.25000.25000.0325 (4)
C10.7477 (2)0.43024 (5)0.26451 (19)0.0320 (3)
C20.8424 (2)0.38203 (4)0.25651 (17)0.0266 (3)
C30.7341 (2)0.34508 (5)0.34202 (18)0.0302 (3)
H30.60340.35060.40260.036*
C40.8184 (2)0.30004 (5)0.33813 (18)0.0304 (3)
H40.74500.27540.39500.036*
C51.0136 (2)0.29244 (4)0.24811 (16)0.0254 (3)
C61.1244 (2)0.32879 (5)0.16242 (18)0.0292 (3)
H61.25550.32320.10270.035*
C71.0374 (2)0.37357 (4)0.16673 (18)0.0298 (3)
H71.11050.39810.10890.036*
N10.25000.50000.2884 (4)0.0503 (5)
H110.3506 (16)0.5123 (6)0.2161 (16)0.060*
H120.308 (3)0.4771 (5)0.355 (2)0.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0450 (7)0.0203 (5)0.0633 (8)0.0051 (4)0.0098 (5)0.0037 (4)
O20.0553 (8)0.0374 (6)0.0681 (8)0.0191 (5)0.0230 (6)0.0050 (5)
O30.0327 (7)0.0164 (6)0.0485 (8)0.0000.0000.0001 (5)
C10.0339 (7)0.0233 (6)0.0387 (7)0.0044 (5)0.0013 (5)0.0041 (5)
C20.0321 (7)0.0194 (6)0.0284 (6)0.0019 (5)0.0005 (5)0.0016 (4)
C30.0309 (7)0.0269 (7)0.0329 (7)0.0015 (5)0.0058 (5)0.0014 (5)
C40.0366 (7)0.0223 (6)0.0323 (7)0.0030 (5)0.0062 (5)0.0024 (5)
C50.0328 (7)0.0167 (6)0.0266 (6)0.0011 (4)0.0016 (5)0.0020 (4)
C60.0308 (7)0.0219 (6)0.0350 (7)0.0006 (5)0.0070 (5)0.0013 (5)
C70.0360 (8)0.0183 (6)0.0352 (7)0.0012 (5)0.0062 (5)0.0019 (4)
N10.0342 (10)0.0516 (12)0.0651 (13)0.0082 (9)0.0000.000
Geometric parameters (Å, º) top
O1—C11.2914 (18)C3—H30.9300
O1—H10.841 (10)C4—C51.385 (2)
O2—C11.2260 (18)C4—H40.9300
O3—C5i1.3833 (13)C5—C61.3852 (18)
O3—C51.3833 (13)C6—C71.3876 (17)
C1—C21.4973 (17)C6—H60.9300
C2—C71.3867 (19)C7—H70.9300
C2—C31.3902 (18)N1—H110.881 (7)
C3—C41.3880 (18)N1—H120.882 (8)
C1—O1—H1108 (4)C5—C4—H4120.6
C5i—O3—C5122.29 (15)C3—C4—H4120.6
O2—C1—O1123.76 (13)O3—C5—C4123.65 (11)
O2—C1—C2120.94 (13)O3—C5—C6114.94 (12)
O1—C1—C2115.30 (12)C4—C5—C6121.19 (11)
C7—C2—C3119.32 (11)C5—C6—C7119.25 (12)
C7—C2—C1121.23 (12)C5—C6—H6120.4
C3—C2—C1119.45 (12)C7—C6—H6120.4
C4—C3—C2120.83 (12)C2—C7—C6120.55 (12)
C4—C3—H3119.6C2—C7—H7119.7
C2—C3—H3119.6C6—C7—H7119.7
C5—C4—C3118.86 (12)H11—N1—H12108.6 (10)
O2—C1—C2—C7166.60 (14)C5i—O3—C5—C6151.57 (12)
O1—C1—C2—C712.97 (19)C3—C4—C5—O3174.06 (11)
O2—C1—C2—C312.8 (2)C3—C4—C5—C60.17 (19)
O1—C1—C2—C3167.60 (13)O3—C5—C6—C7174.86 (10)
C7—C2—C3—C40.1 (2)C4—C5—C6—C70.15 (19)
C1—C2—C3—C4179.57 (12)C3—C2—C7—C60.20 (19)
C2—C3—C4—C50.3 (2)C1—C2—C7—C6179.23 (12)
C5i—O3—C5—C433.86 (10)C5—C6—C7—C20.3 (2)
Symmetry code: (i) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O1ii0.84 (1)1.70 (3)2.490 (2)156 (6)
N1—H11···O1ii0.88 (1)2.14 (1)2.962 (2)155 (1)
N1—H12···O20.88 (1)2.10 (2)2.827 (1)139 (2)
Symmetry code: (ii) x+3/2, y+1, z.

Experimental details

Crystal data
Chemical formulaNH4+·C14H9O5
Mr275.25
Crystal system, space groupOrthorhombic, Pnna
Temperature (K)293
a, b, c (Å)6.1916 (1), 28.5483 (6), 7.1123 (1)
V3)1257.17 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.50 × 0.40 × 0.30
Data collection
DiffractometerBruker SMART APEX
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3444, 1434, 1279
Rint0.014
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.146, 1.04
No. of reflections1434
No. of parameters102
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O1—H1···O1i0.84 (1)1.70 (3)2.490 (2)156 (6)
N1—H11···O1i0.88 (1)2.14 (1)2.962 (2)155 (1)
N1—H12···O20.88 (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

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDey, A. & Desiraju, G. R. (2005). Chem. Commun. pp. 2486–2488.  Web of Science CSD CrossRef Google Scholar
First citationPotts, S., Bredenkamp, M. W. & Gertenbach, J.-A. (2007). Acta Cryst. E63, o2887.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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