4-(Carboxy­meth­oxy)anilinium bromide

Zhang, L.

doi:10.1107/S1600536810018726

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1573

doi:10.1107/S1600536810018726

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4-(Carboxymethoxy)anilinium bromide

Li Zhang ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fifazl@126.com

(Received 18 May 2010; accepted 19 May 2010; online 5 June 2010)

In the title hydrobromide salt, C₈H₁₀NO₃⁺·Br⁻, the positive charge resides on the N atom and the carboxyl –CO₂ end of the cation carries an H atom. In the crystal, N—H⋯Br, O—H⋯Br and N—H⋯O hydrogen bonds link the cations and anions, forming a ladder propagating along the a axis.

Related literature

For background to phase transition materials, see: Jain et al. (2008 ); Korfer & Fusee et al. (1988 ).

Experimental

Crystal data

C₈H₁₀NO₃⁺·Br⁻
M_r = 248.08
Monoclinic, P 2₁ /c
a = 6.0182 (12) Å
b = 9.6025 (19) Å
c = 16.514 (3) Å
β = 94.47 (3)°
V = 951.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.30 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.5, T_max = 0.5
9589 measured reflections
2178 independent reflections
1539 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.125
S = 0.80
2178 reflections
134 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.85 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯Br1	0.95 (4)	2.37 (5)	3.316 (3)	173 (4)
N1—H12⋯Br1ⁱ	0.99 (5)	2.47 (5)	3.317 (3)	144 (4)
N1—H13⋯O3ⁱⁱ	0.91 (4)	1.94 (4)	2.812 (4)	159 (3)
O2—H14⋯Br1ⁱⁱⁱ	0.78 (4)	2.46 (4)	3.223 (3)	165 (4)
Symmetry codes: (i) x+1, y, z; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810018726/ng2777sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810018726/ng2777Isup2.hkl

checkCIF report

Comment top

We are interested in the dielectric-ferroelectric materials. Recent studies have revealed that small molecular compounds which have one or more amidogens

probably have this kind of character(Jain et al., 2008 ; Korfer & Fusee et al., 1988). Thus, we want to find aromatic compounds containing amidogens having dielectric-ferroelectric properties. As part of our ongoing studies, we report here the crystal structure of the title compound, The dielectric constant of 2-(4-aminophenoxy) acetic acid bromide compound as a function of temperature indicates that the permittivity is basically temperature-independent, below the melting point (478k-480k) of the compound, the dielectric constant(4.51-8.33) as a function of temperature also goes smoothly, and there is no dielectric anomaly observed, so this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range.

The asymmetric unit of the title compound contains one 2-(4-aminophenoxy) acetic acid cation and one bromide anion(fig 1). The non-H atoms of the 2-(4-aminophenoxy) acetic acid are essentially coplanar. In the crystal structure, intermolecular N—H···Br hydrogen bonds link cations and anions to form one-dimensional ladder propagating wavily along the a axis direction(fig 2).

Related literature top

For background to phase transition materials, see: Jain et al. (2008); Korfer & Fusee et al. (1988)

Experimental top

ethyl 2-(4-aminophenoxy)acetate (1.95 g) and methanol(30 ml) were added to a round-bottomed flask with a magnetic stirrer bar, then hydrogen chloride(36%) 1.02 g was added into the mixture. The mixture was stirred for 4 h at room temperature. Colourless plate-like crystals of (I) were grown from an ethanol solution of the title compound by slow evaporation at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds.

4-(Carboxymethoxy)anilinium bromide top

Crystal data top

C₈H₁₀NO₃⁺·Br⁻	F(000) = 496
M_r = 248.08	D_x = 1.732 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 0 reflections
a = 6.0182 (12) Å	θ = 3.3–27.5°
b = 9.6025 (19) Å	µ = 4.30 mm⁻¹
c = 16.514 (3) Å	T = 293 K
β = 94.47 (3)°	Prism, colourless
V = 951.4 (3) Å³	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2178 independent reflections
Radiation source: fine-focus sealed tube	1539 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
T_min = 0.5, T_max = 0.5	l = −21→21
9589 measured reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 0.80	w = 1/[σ²(F_o²) + (0.0891P)² + 0.5552P] where P = (F_o² + 2F_c²)/3
2178 reflections	(Δ/σ)_max = 0.001
134 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.85 e Å⁻³

Crystal data top

C₈H₁₀NO₃⁺·Br⁻	V = 951.4 (3) Å³
M_r = 248.08	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.0182 (12) Å	µ = 4.30 mm⁻¹
b = 9.6025 (19) Å	T = 293 K
c = 16.514 (3) Å	0.40 × 0.30 × 0.20 mm
β = 94.47 (3)°

Data collection top

Rigaku SCXmini diffractometer	2178 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1539 reflections with I > 2σ(I)
T_min = 0.5, T_max = 0.5	R_int = 0.062
9589 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 0.80	Δρ_max = 0.27 e Å⁻³
2178 reflections	Δρ_min = −0.85 e Å⁻³
134 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Br1	0.41951 (5)	0.75195 (3)	0.28076 (2)	0.04135 (18)
N1	0.9214 (5)	0.6075 (4)	0.29003 (18)	0.0390 (7)
O1	1.0375 (4)	0.1877 (3)	0.52465 (15)	0.0447 (6)
C4	0.7915 (5)	0.4697 (3)	0.40446 (19)	0.0329 (7)
H4A	0.6621	0.5230	0.4021	0.039*
C5	0.9527 (5)	0.4943 (3)	0.35062 (19)	0.0313 (7)
O2	1.3878 (4)	−0.0723 (3)	0.61539 (16)	0.0435 (6)
C7	1.1796 (5)	0.3112 (4)	0.4098 (2)	0.0336 (7)
H7A	1.3085	0.2575	0.4118	0.040*
C8	1.2172 (5)	0.0143 (4)	0.6064 (2)	0.0349 (7)
O3	1.0656 (4)	0.0186 (3)	0.64965 (16)	0.0521 (7)
C10	0.8249 (5)	0.3660 (3)	0.46127 (19)	0.0344 (7)
H10A	0.7177	0.3483	0.4976	0.041*
C11	1.1450 (5)	0.4159 (3)	0.35252 (19)	0.0351 (7)
H11A	1.2507	0.4332	0.3156	0.042*
C12	1.0192 (6)	0.2874 (3)	0.4644 (2)	0.0314 (7)
C13	1.2343 (5)	0.1059 (3)	0.53319 (19)	0.0367 (7)
H13A	1.3646	0.1654	0.5407	0.044*
H13B	1.2472	0.0495	0.4851	0.044*
H11	0.780 (7)	0.650 (5)	0.292 (3)	0.080 (14)*
H12	1.032 (7)	0.683 (5)	0.299 (3)	0.076 (14)*
H13	0.931 (6)	0.564 (4)	0.241 (3)	0.063 (13)*
H14	1.371 (6)	−0.113 (4)	0.656 (2)	0.052 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0343 (3)	0.0443 (3)	0.0452 (3)	0.00119 (14)	0.00119 (17)	−0.00404 (14)
N1	0.0360 (17)	0.0490 (19)	0.0323 (17)	0.0081 (14)	0.0056 (13)	0.0041 (14)
O1	0.0443 (14)	0.0448 (14)	0.0472 (16)	0.0106 (12)	0.0167 (11)	0.0142 (12)
C4	0.0282 (16)	0.0339 (17)	0.0367 (18)	−0.0005 (14)	0.0039 (13)	−0.0070 (14)
C5	0.0325 (16)	0.0333 (17)	0.0276 (16)	0.0002 (13)	−0.0002 (13)	−0.0009 (13)
O2	0.0461 (15)	0.0446 (15)	0.0407 (15)	0.0091 (12)	0.0089 (11)	0.0073 (12)
C7	0.0310 (17)	0.0349 (17)	0.0354 (18)	0.0039 (14)	0.0065 (13)	−0.0032 (14)
C8	0.0360 (17)	0.0345 (17)	0.0338 (18)	−0.0002 (15)	0.0001 (14)	−0.0032 (14)
O3	0.0454 (14)	0.0727 (19)	0.0403 (15)	0.0104 (14)	0.0163 (12)	0.0135 (13)
C10	0.0267 (15)	0.0396 (18)	0.0380 (18)	−0.0051 (14)	0.0085 (13)	−0.0043 (14)
C11	0.0313 (16)	0.0411 (18)	0.0342 (17)	0.0028 (14)	0.0104 (13)	−0.0009 (14)
C12	0.0320 (16)	0.0307 (15)	0.0317 (18)	−0.0029 (14)	0.0038 (13)	−0.0019 (13)
C13	0.0374 (18)	0.0396 (18)	0.0336 (18)	0.0029 (15)	0.0065 (14)	0.0040 (14)

Geometric parameters (Å, º) top

N1—C5	1.479 (4)	O2—H14	0.78 (4)
N1—H11	0.95 (4)	C7—C12	1.390 (4)
N1—H12	0.99 (5)	C7—C11	1.385 (5)
N1—H13	0.91 (4)	C7—H7A	0.9300
O1—C12	1.379 (4)	C8—O3	1.202 (4)
O1—C13	1.419 (4)	C8—C13	1.505 (4)
C4—C10	1.372 (4)	C10—C12	1.389 (5)
C4—C5	1.386 (4)	C10—H10A	0.9300
C4—H4A	0.9300	C11—H11A	0.9300
C5—C11	1.379 (4)	C13—H13A	0.9700
O2—C8	1.321 (4)	C13—H13B	0.9700

C5—N1—H11	111 (3)	O3—C8—C13	124.1 (3)
C5—N1—H12	112 (3)	O2—C8—C13	110.9 (3)
H11—N1—H12	106 (4)	C4—C10—C12	119.9 (3)
C5—N1—H13	105 (3)	C4—C10—H10A	120.1
H11—N1—H13	111 (4)	C12—C10—H10A	120.1
H12—N1—H13	112 (3)	C5—C11—C7	119.5 (3)
C12—O1—C13	118.4 (2)	C5—C11—H11A	120.2
C10—C4—C5	119.3 (3)	C7—C11—H11A	120.2
C10—C4—H4A	120.3	O1—C12—C7	124.2 (3)
C5—C4—H4A	120.3	O1—C12—C10	115.1 (3)
C11—C5—C4	121.3 (3)	C7—C12—C10	120.8 (3)
C11—C5—N1	118.6 (3)	O1—C13—C8	107.1 (3)
C4—C5—N1	120.0 (3)	O1—C13—H13A	110.3
C8—O2—H14	105 (3)	C8—C13—H13A	110.3
C12—C7—C11	119.2 (3)	O1—C13—H13B	110.3
C12—C7—H7A	120.4	C8—C13—H13B	110.3
C11—C7—H7A	120.4	H13A—C13—H13B	108.5
O3—C8—O2	125.0 (3)

C10—C4—C5—C11	0.6 (5)	C11—C7—C12—O1	−179.0 (3)
C10—C4—C5—N1	−178.8 (3)	C11—C7—C12—C10	0.8 (5)
C5—C4—C10—C12	0.2 (5)	C4—C10—C12—O1	178.9 (3)
C4—C5—C11—C7	−0.6 (5)	C4—C10—C12—C7	−0.9 (5)
N1—C5—C11—C7	178.7 (3)	C12—O1—C13—C8	175.9 (3)
C12—C7—C11—C5	0.0 (5)	O3—C8—C13—O1	−3.0 (5)
C13—O1—C12—C7	1.6 (5)	O2—C8—C13—O1	175.7 (3)
C13—O1—C12—C10	−178.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···Br1	0.95 (4)	2.37 (5)	3.316 (3)	173 (4)
N1—H12···Br1ⁱ	0.99 (5)	2.47 (5)	3.317 (3)	144 (4)
N1—H13···O3ⁱⁱ	0.91 (4)	1.94 (4)	2.812 (4)	159 (3)
O2—H14···Br1ⁱⁱⁱ	0.78 (4)	2.46 (4)	3.223 (3)	165 (4)

Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z−1/2; (iii) x+1, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₀NO₃⁺·Br⁻
M_r	248.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.0182 (12), 9.6025 (19), 16.514 (3)
β (°)	94.47 (3)
V (Å³)	951.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.30
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.5, 0.5
No. of measured, independent and observed [I > 2σ(I)] reflections	9589, 2178, 1539
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.125, 0.80
No. of reflections	2178
No. of parameters	134
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.85

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···Br1	0.95 (4)	2.37 (5)	3.316 (3)	173 (4)
N1—H12···Br1ⁱ	0.99 (5)	2.47 (5)	3.317 (3)	144 (4)
N1—H13···O3ⁱⁱ	0.91 (4)	1.94 (4)	2.812 (4)	159 (3)
O2—H14···Br1ⁱⁱⁱ	0.78 (4)	2.46 (4)	3.223 (3)	165 (4)

Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z−1/2; (iii) x+1, −y+1/2, z+1/2.

Acknowledgements

The author is grateful to the starter fund of Southeast University for the purchase of the diffractometer.

References

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Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar