2-Amino­anilinium 2-carb­oxy­acetate

Feng, L.; Zhao, L.

doi:10.1107/S160053681102544X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1881

doi:10.1107/S160053681102544X

Open

access

2-Aminoanilinium 2-carboxyacetate

Li-ping Feng ^a ^* and Liang Zhao ^a

^aDepartment of Chemical & Environmental Engineering, Anyang Institute of Technology, Anyang 455000, People's Republic of China
^*Correspondence e-mail: ayitzhao@yahoo.com.cn

(Received 22 June 2011; accepted 28 June 2011; online 2 July 2011)

In the crystal structure of the title compound, C₆H₉N₂⁺·C₃H₃O₄⁻, all the amino H atoms are involved in intermolecular N—H⋯O hydrogen bonds, which link the ions into double chains parallel to [101]. In the anion, an intramolecular O—H⋯O hydrogen bond is observed.

Related literature

For background to pharmaceutical applications and growth of co-crystals, see: Almarsson & Zaworotko (2004 ); Blagden et al. (2008 ); Vishweshwar et al. (2006 ); Kapildev et al. (2011 ); Schultheiss & Newman (2009 ).

Experimental

Crystal data

C₆H₉N₂⁺·C₃H₃O₄⁻
M_r = 212.21
Monoclinic, P 2₁ /n
a = 12.735 (3) Å
b = 5.7448 (11) Å
c = 14.429 (3) Å
β = 107.38 (3)°
V = 1007.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.30 × 0.25 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
10297 measured reflections
2310 independent reflections
2027 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.129
S = 1.14
2310 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.89	1.90	2.7865 (17)	171
N1—H1B⋯O1ⁱⁱ	0.89	1.86	2.7420 (15)	170
N2—H2A⋯O3ⁱⁱⁱ	0.90	2.21	2.9693 (18)	142
N2—H2B⋯O2^iv	0.90	2.21	3.0988 (18)	169
N1—H1C⋯O2	0.89	2.25	2.9019 (15)	130
O4—H4⋯O2	0.82	1.67	2.4616 (15)	161
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+1.

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: SHELXTL .

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681102544X/rz2617sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681102544X/rz2617Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681102544X/rz2617Isup3.cml

checkCIF report

Comment top

Molecular co-crystals are becoming increasingly important within the pharmaceutical industry as an alternative source of new solid crystalline materials with the potential to provide optimal physical properties whilst retaining the chemical properties of the cocrystal components (Almarsson & Zaworotko, 2004; Blagden et al., 2008; Vishweshwar et al., 2006). Physicochemical properties such as the melting point, stability and solubility of an active pharmaceutical ingredient can be tuned through co-crystal formulation (Kapildev et al., 2011; Schultheiss & Newman, 2009). Co-crystal synthesis often relies on the acid-amide H-bonds interactions. Herein, we report the crystal structure of the title compound, 2-aminoanilinium 2-carboxyacetate.

The asymmetric unit of the title compound is composed of one 2-aminoanilinium cation and one 2-carboxyacetate anion (Fig. 1). The amine N1 atom is protonated and one of the carboxyl groups (C7/O1/O2) is deprotonated. The geometric parameters of the title compound are in the normal range. In the crystal structure, all the amino H atoms are involved in intermolecular N—H···O hydrogen bonding interactions with carboxylic O atoms, linking the ions into double chains parallel to the [101] direction (Table 1; Fig. 2). The conformation of the anion is stabilized by an intramolecular O—H···O hydrogen bond (Table 1).

Related literature top

For background to pharmaceutical applications and growth of co-crystals, see: Almarsson & Zaworotko (2004); Blagden et al. (2008); Vishweshwar et al. (2006); Kapildev et al. (2011); Schultheiss & Newman (2009).

Experimental top

A mixture of benzene-1,2-diamine (2.0 mmol), malonic acid (2.0 mmol) in distilled water (20 ml) was added into a 50 ml flask and refluxed for 5 hours, then cooled and filtrated. The solution was evaporated slowly in the air. Colourless block crystals suitable for X-ray analysis were obtained after one week.

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: SHELXTL (Sheldrick, 2008.

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the b axis, showing a double chain formed by intermolecular hydrogen bonds (dashed line). Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

2-Aminoanilinium 2-carboxyacetate top

Crystal data top

C₆H₉N₂⁺·C₃H₃O₄⁻	F(000) = 448
M_r = 212.21	D_x = 1.399 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2310 reflections
a = 12.735 (3) Å	θ = 1.9–27.5°
b = 5.7448 (11) Å	µ = 0.11 mm⁻¹
c = 14.429 (3) Å	T = 298 K
β = 107.38 (3)°	Block, colourless
V = 1007.4 (3) Å³	0.30 × 0.25 × 0.15 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	2310 independent reflections
Radiation source: fine-focus sealed tube	2027 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 1.9°
CCD profile fitting scans	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −7→7
T_min = 0.910, T_max = 1.000	l = −18→18
10297 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0733P)² + 0.1065P] where P = (F_o² + 2F_c²)/3
2310 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₆H₉N₂⁺·C₃H₃O₄⁻	V = 1007.4 (3) Å³
M_r = 212.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.735 (3) Å	µ = 0.11 mm⁻¹
b = 5.7448 (11) Å	T = 298 K
c = 14.429 (3) Å	0.30 × 0.25 × 0.15 mm
β = 107.38 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2310 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2027 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.026
10297 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.14	Δρ_max = 0.29 e Å⁻³
2310 reflections	Δρ_min = −0.25 e Å⁻³
137 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 > 2sigma(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
O2	0.61965 (7)	0.52957 (17)	0.59590 (7)	0.0380 (3)
N1	0.58132 (8)	0.80154 (19)	0.41942 (8)	0.0318 (3)
H1A	0.5336	0.8376	0.3623	0.048*
H1B	0.5997	0.9297	0.4552	0.048*
H1C	0.5506	0.6998	0.4500	0.048*
O4	0.78587 (8)	0.72834 (17)	0.69666 (7)	0.0407 (3)
H4	0.7231	0.6862	0.6670	0.061*
O3	0.94464 (8)	0.5435 (2)	0.74114 (7)	0.0458 (3)
O1	0.62897 (9)	0.1692 (2)	0.54632 (9)	0.0538 (3)
C1	0.67983 (9)	0.6987 (2)	0.40414 (8)	0.0286 (3)
C9	0.84796 (9)	0.5516 (2)	0.69323 (8)	0.0303 (3)
C7	0.67270 (10)	0.3478 (2)	0.58610 (8)	0.0320 (3)
C8	0.79755 (9)	0.3559 (2)	0.62487 (9)	0.0307 (3)
H8A	0.8226	0.2101	0.6580	0.037*
H8B	0.8263	0.3641	0.5698	0.037*
C6	0.77981 (11)	0.8061 (3)	0.44260 (10)	0.0390 (3)
H6A	0.7845	0.9435	0.4777	0.047*
N2	0.56773 (12)	0.3929 (3)	0.31118 (11)	0.0569 (4)
H2A	0.5601	0.2518	0.2828	0.068*
H2B	0.5078	0.4222	0.3303	0.068*
C2	0.66864 (11)	0.4931 (2)	0.35095 (9)	0.0342 (3)
C3	0.76464 (13)	0.3975 (3)	0.33892 (10)	0.0436 (4)
H3A	0.7607	0.2596	0.3043	0.052*
C4	0.86492 (13)	0.5041 (3)	0.37757 (12)	0.0515 (4)
H4A	0.9277	0.4369	0.3688	0.062*
C5	0.87378 (12)	0.7085 (3)	0.42893 (12)	0.0513 (4)
H5A	0.9418	0.7804	0.4542	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0268 (4)	0.0449 (5)	0.0408 (5)	0.0064 (4)	0.0079 (4)	0.0038 (4)
N1	0.0269 (5)	0.0348 (6)	0.0329 (5)	0.0024 (4)	0.0074 (4)	−0.0021 (4)
O4	0.0355 (5)	0.0373 (5)	0.0450 (5)	0.0022 (4)	0.0055 (4)	−0.0112 (4)
O3	0.0282 (5)	0.0568 (6)	0.0444 (6)	−0.0005 (4)	−0.0012 (4)	−0.0073 (5)
O1	0.0412 (6)	0.0616 (7)	0.0592 (7)	−0.0177 (5)	0.0160 (5)	−0.0293 (6)
C1	0.0259 (6)	0.0320 (6)	0.0282 (6)	0.0026 (4)	0.0085 (4)	0.0031 (4)
C9	0.0265 (6)	0.0365 (6)	0.0275 (6)	−0.0006 (5)	0.0075 (4)	0.0004 (5)
C7	0.0277 (6)	0.0421 (7)	0.0262 (5)	−0.0027 (5)	0.0082 (4)	−0.0023 (5)
C8	0.0274 (6)	0.0325 (6)	0.0324 (6)	0.0012 (5)	0.0092 (5)	−0.0031 (5)
C6	0.0319 (6)	0.0423 (7)	0.0414 (7)	−0.0037 (5)	0.0088 (5)	−0.0007 (6)
N2	0.0508 (8)	0.0546 (8)	0.0686 (9)	−0.0159 (6)	0.0229 (7)	−0.0303 (7)
C2	0.0384 (7)	0.0349 (7)	0.0314 (6)	0.0004 (5)	0.0134 (5)	0.0004 (5)
C3	0.0542 (9)	0.0426 (8)	0.0409 (7)	0.0124 (7)	0.0246 (6)	0.0031 (6)
C4	0.0425 (8)	0.0685 (11)	0.0513 (9)	0.0203 (7)	0.0259 (7)	0.0154 (8)
C5	0.0279 (7)	0.0690 (11)	0.0571 (9)	−0.0014 (7)	0.0128 (6)	0.0069 (8)

Geometric parameters (Å, º) top

O2—C7	1.2742 (16)	C8—H8A	0.9700
N1—C1	1.4618 (15)	C8—H8B	0.9700
N1—H1A	0.8900	C6—C5	1.388 (2)
N1—H1B	0.8900	C6—H6A	0.9300
N1—H1C	0.8900	N2—C2	1.3679 (19)
O4—C9	1.2969 (16)	N2—H2A	0.9003
O4—H4	0.8221	N2—H2B	0.9008
O3—C9	1.2195 (15)	C2—C3	1.3978 (19)
O1—C7	1.2253 (17)	C3—C4	1.375 (2)
C1—C6	1.3737 (18)	C3—H3A	0.9300
C1—C2	1.3924 (18)	C4—C5	1.375 (3)
C9—C8	1.5069 (17)	C4—H4A	0.9300
C7—C8	1.5205 (17)	C5—H5A	0.9300

C1—N1—H1A	109.5	C7—C8—H8B	108.0
C1—N1—H1B	109.5	H8A—C8—H8B	107.2
H1A—N1—H1B	109.5	C1—C6—C5	119.72 (14)
C1—N1—H1C	109.5	C1—C6—H6A	120.1
H1A—N1—H1C	109.5	C5—C6—H6A	120.1
H1B—N1—H1C	109.5	C2—N2—H2A	122.0
C9—O4—H4	105.0	C2—N2—H2B	124.6
C6—C1—C2	122.23 (12)	H2A—N2—H2B	108.7
C6—C1—N1	119.42 (12)	N2—C2—C1	121.12 (12)
C2—C1—N1	118.34 (11)	N2—C2—C3	121.96 (13)
O3—C9—O4	122.15 (12)	C1—C2—C3	116.91 (13)
O3—C9—C8	120.19 (12)	C4—C3—C2	121.01 (14)
O4—C9—C8	117.62 (10)	C4—C3—H3A	119.5
O1—C7—O2	123.81 (12)	C2—C3—H3A	119.5
O1—C7—C8	118.48 (12)	C5—C4—C3	121.04 (13)
O2—C7—C8	117.71 (11)	C5—C4—H4A	119.5
C9—C8—C7	117.25 (10)	C3—C4—H4A	119.5
C9—C8—H8A	108.0	C4—C5—C6	119.08 (14)
C7—C8—H8A	108.0	C4—C5—H5A	120.5
C9—C8—H8B	108.0	C6—C5—H5A	120.5

O3—C9—C8—C7	165.75 (12)	C6—C1—C2—C3	0.67 (19)
O4—C9—C8—C7	−16.10 (16)	N1—C1—C2—C3	−179.06 (11)
O1—C7—C8—C9	−165.98 (12)	N2—C2—C3—C4	178.41 (14)
O2—C7—C8—C9	14.93 (16)	C1—C2—C3—C4	−0.5 (2)
C2—C1—C6—C5	−0.2 (2)	C2—C3—C4—C5	−0.2 (2)
N1—C1—C6—C5	179.56 (12)	C3—C4—C5—C6	0.8 (2)
C6—C1—C2—N2	−178.23 (14)	C1—C6—C5—C4	−0.6 (2)
N1—C1—C2—N2	2.05 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.89	1.90	2.7865 (17)	171
N1—H1B···O1ⁱⁱ	0.89	1.86	2.7420 (15)	170
N2—H2A···O3ⁱⁱⁱ	0.90	2.21	2.9693 (18)	142
N2—H2B···O2^iv	0.90	2.21	3.0988 (18)	169
N1—H1C···O2	0.89	2.25	2.9019 (15)	130
O4—H4···O2	0.82	1.67	2.4616 (15)	161

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x, y+1, z; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₃H₃O₄⁻
M_r	212.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	12.735 (3), 5.7448 (11), 14.429 (3)
β (°)	107.38 (3)
V (Å³)	1007.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.25 × 0.15

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10297, 2310, 2027
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.129, 1.14
No. of reflections	2310
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.25

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.89	1.90	2.7865 (17)	171
N1—H1B···O1ⁱⁱ	0.89	1.86	2.7420 (15)	170
N2—H2A···O3ⁱⁱⁱ	0.90	2.21	2.9693 (18)	142
N2—H2B···O2^iv	0.90	2.21	3.0988 (18)	169
N1—H1C···O2	0.89	2.25	2.9019 (15)	130
O4—H4···O2	0.82	1.67	2.4616 (15)	161

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x, y+1, z; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1, −y+1, −z+1.

Acknowledgements

This work was supported by the start-up fund of Anyang Institute of Technology, China.

References

Almarsson, O. & Zaworotko, M. J. (2004). Chem. Commun. 17, 1889–1896. Web of Science CrossRef Google Scholar
Blagden, N., Berry, D. J., Parkin, A., Javed, H., Ibrahim, A., Gavan, P. T., De Matos, L. L. & Seaton, C. C. (2008). New J. Chem. 32, 1659–1672. Web of Science CSD CrossRef CAS Google Scholar
Kapildev, K. A., Nitin, G. T. & Raj, S. (2011). Mol. Pharm. 8, 982–989. Web of Science PubMed Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Schultheiss, N. & Newman, A. (2009). Cryst. Growth Des. 9, 2950–2967. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vishweshwar, P., McMahon, J. A., Bis, J. A. & Zaworotko, M. J. (2006). J. Pharm. Sci. 95, 499–516. Web of Science CrossRef PubMed CAS Google Scholar