2-Amino-anilinium 2-carb-oxy-acetate.

In the crystal structure of the title compound, C(6)H(9)N(2) (+)·C(3)H(3)O(4) (-), all the amino H atoms are involved in inter-molecular N-H⋯O hydrogen bonds, which link the ions into double chains parallel to [101]. In the anion, an intra-molecular 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 = 212.21

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.129

S = 1.14

2310 reflections

137 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.25 e Å−3

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 .

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681102544X/rz2617sup1.cif

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

Supplementary material file. DOI: 10.1107/S160053681102544X/rz2617Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H9N2+·C3H3O4−	F(000) = 448
Mr = 212.21	Dx = 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

Rigaku Mercury2 diffractometer	2310 independent reflections
Radiation source: fine-focus sealed tube	2027 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 1.9°
CCD profile fitting scans	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −7→7
Tmin = 0.910, Tmax = 1.000	l = −18→18
10297 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0733P)2 + 0.1065P] where P = (Fo2 + 2Fc2)/3
2310 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O2iv	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

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⋯O2iv	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) ; (ii) ; (iii) ; (iv) .