2-Amino­anilinium benzoate

Zhang, Y.

doi:10.1107/S1600536810048208

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3296

https://doi.org/10.1107/S1600536810048208

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2-Aminoanilinium benzoate

Yan-wei Zhang ^a ^*

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

(Received 17 November 2010; accepted 18 November 2010; online 24 November 2010)

In the crystal of the title molecular salt, C₆H₉N₂⁺·C₇H₅O₂⁻, the cations and anions are linked by N—H⋯O hydrogen bonds, buiding an R₂²(9) ring. Futher N—H⋯O hydrogen bonds generate chains, which develop parallel to the a axis through the formation of R₄³(10) rings.,

Related literature

For the properties of amino compounds, see: Fu et al. (2009 ); Aminabhavi et al. (1986 ); Dai & Fu (2008a ,b ). For hydrogen-bond motifs, see: Etter (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₆H₉N₂⁺·C₇H₅O₂⁻
M_r = 230.26
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.0211 (12) Å
b = 12.237 (2) Å
c = 16.639 (3) Å
V = 1226.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.30 × 0.15 × 0.10 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.970, T_max = 1.000
12656 measured reflections
1638 independent reflections
1133 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.118
S = 1.08
1638 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O1	0.89	1.83	2.699 (3)	166
N2—H2A⋯O2	1.00	2.16	3.093 (3)	155
N1—H1B⋯O1ⁱ	0.89	1.94	2.815 (3)	168
N1—H1A⋯O2ⁱⁱ	0.89	1.90	2.753 (3)	161
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

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: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810048208/dn2626sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810048208/dn2626Isup2.hkl

checkCIF report

Comment top

The amino derivatives have found wide range of applications in material science, such as magnetic, fluorescent and dielectric behaviors. And there has been an increased interest in the preparation of amino coordination compound (Aminabhavi et al., 1986; Dai & Fu 2008a; Dai & Fu 2008b; Fu, et al. 2009). As an extension on the structural characterization, we report here the crystal structure of the title compound 2-aminoanilinium benzoate.

The asymmetrical unit of the title compound consists of one benzene-1,2-diamine cation and one benzoic acid anion linked by N-H···O hydrogen bonds buiding a R₂²(9) ring (Etter, 1990, Bernstein et al., 1995) (Fig.1; Table 1). As expected The carboxyl acid group has protonated one of the amine N atom.

N—H···O hydrogen bonds generate chains which develop parallel to the a axis through the formation of R₃⁴(10) ring (Etter, 1990; Bernstein et al., 1995)(Fig. 2; Table 1).

Related literature top

For the properties of amino compounds, see: Fu et al. (2009); Aminabhavi et al. (1986); Dai & Fu (2008a,b). For hydrogen-bond motifs, see: Etter (1990); Bernstein et al. (1995).

Experimental top

A mixture of benzene-1,2-diamine (0.1 mmol) and benzoic acid (0.1 mmol) was dissolved in ethanol (20 ml). The solution was allowed to evaporate to obtain colourless block-shaped crystals of the title compound.

Structure description top

N—H···O hydrogen bonds generate chains which develop parallel to the a axis through the formation of R₃⁴(10) ring (Etter, 1990; Bernstein et al., 1995)(Fig. 2; Table 1).

For the properties of amino compounds, see: Fu et al. (2009); Aminabhavi et al. (1986); Dai & Fu (2008a,b). For hydrogen-bond motifs, see: Etter (1990); Bernstein et al. (1995).

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: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. H bonds are shown as dashed lines.
	Fig. 2. Partial packing view of the title compound showing the formation of the chain through the R₃⁴(10) rings. H atoms not involved in hydrogen bonding have been omitted for clarity. H bonds are shown as dashed lines. [Symmetry codes: (i) -x-1, y+3/2, -z+3/2; (ii) -x, y+3/2, -z+3/2]

2-Aminoanilinium benzoate top

Crystal data top

C₆H₉N₂⁺·C₇H₅O₂⁻	F(000) = 488
M_r = 230.26	D_x = 1.247 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2805 reflections
a = 6.0211 (12) Å	θ = 3.3–27.5°
b = 12.237 (2) Å	µ = 0.09 mm⁻¹
c = 16.639 (3) Å	T = 298 K
V = 1226.0 (4) Å³	Block, colourless
Z = 4	0.30 × 0.15 × 0.10 mm

Data collection top

Rigaku Mercury2 diffractometer	1638 independent reflections
Radiation source: fine-focus sealed tube	1133 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
CCD profile fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
T_min = 0.970, T_max = 1.000	l = −21→21
12656 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0536P)² + 0.0477P] where P = (F_o² + 2F_c²)/3
1638 reflections	(Δ/σ)_max = 0.002
155 parameters	Δρ_max = 0.11 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₆H₉N₂⁺·C₇H₅O₂⁻	V = 1226.0 (4) Å³
M_r = 230.26	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.0211 (12) Å	µ = 0.09 mm⁻¹
b = 12.237 (2) Å	T = 298 K
c = 16.639 (3) Å	0.30 × 0.15 × 0.10 mm

Data collection top

Rigaku Mercury2 diffractometer	1638 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1133 reflections with I > 2σ(I)
T_min = 0.970, T_max = 1.000	R_int = 0.053
12656 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.08	Δρ_max = 0.11 e Å⁻³
1638 reflections	Δρ_min = −0.16 e Å⁻³
155 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
N1	0.7176 (3)	0.63438 (15)	0.49671 (11)	0.0429 (5)
H1A	0.8339	0.6156	0.5267	0.064*
H1B	0.6171	0.6679	0.5272	0.064*
H1C	0.7617	0.6793	0.4578	0.064*
N2	0.3415 (4)	0.65071 (19)	0.39767 (14)	0.0658 (7)
H2A	0.4535	0.7109	0.3927	0.099*
H2B	0.2137	0.6471	0.3597	0.099*
C1	0.4321 (4)	0.5481 (2)	0.41353 (14)	0.0475 (6)
C2	0.6195 (4)	0.53644 (19)	0.46122 (13)	0.0417 (6)
C3	0.7065 (5)	0.4356 (2)	0.47948 (17)	0.0601 (8)
H3	0.8326	0.4301	0.5115	0.072*
C4	0.6058 (8)	0.3428 (2)	0.4501 (2)	0.0846 (11)
H4	0.6638	0.2743	0.4619	0.101*
C5	0.4195 (8)	0.3522 (3)	0.4032 (2)	0.0845 (10)
H5	0.3511	0.2895	0.3836	0.101*
C6	0.3325 (6)	0.4528 (3)	0.38492 (18)	0.0706 (9)
H6	0.2059	0.4576	0.3531	0.085*
O1	0.8819 (3)	0.79093 (13)	0.39910 (9)	0.0512 (5)
O2	0.5619 (3)	0.87900 (18)	0.39486 (13)	0.0749 (7)
C7	0.7644 (4)	0.8731 (2)	0.38177 (14)	0.0450 (6)
C8	0.8786 (4)	0.9670 (2)	0.34141 (13)	0.0416 (6)
C9	0.7821 (6)	1.0692 (2)	0.33900 (17)	0.0630 (8)
H9	0.6427	1.0799	0.3618	0.076*
C10	0.8903 (8)	1.1555 (3)	0.3032 (2)	0.0858 (11)
H10	0.8253	1.2244	0.3029	0.103*
C11	1.0919 (8)	1.1402 (3)	0.2682 (2)	0.0893 (12)
H11	1.1642	1.1986	0.2438	0.107*
C12	1.1892 (5)	1.0385 (3)	0.26864 (17)	0.0764 (10)
H12	1.3254	1.0278	0.2435	0.092*
C13	1.0847 (4)	0.9529 (2)	0.30625 (14)	0.0535 (7)
H13	1.1531	0.8848	0.3081	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0360 (10)	0.0443 (11)	0.0485 (11)	0.0012 (10)	−0.0044 (9)	0.0033 (9)
N2	0.0584 (14)	0.0684 (15)	0.0706 (15)	0.0104 (13)	−0.0274 (14)	−0.0004 (12)
C1	0.0447 (14)	0.0537 (16)	0.0441 (13)	−0.0013 (14)	−0.0019 (12)	−0.0034 (12)
C2	0.0403 (13)	0.0442 (13)	0.0405 (12)	−0.0028 (13)	0.0009 (12)	−0.0013 (11)
C3	0.070 (2)	0.0463 (15)	0.0638 (17)	0.0067 (16)	−0.0119 (16)	0.0006 (14)
C4	0.117 (3)	0.0464 (17)	0.090 (2)	0.004 (2)	−0.018 (3)	−0.0056 (16)
C5	0.117 (3)	0.057 (2)	0.080 (2)	−0.022 (2)	−0.015 (2)	−0.0091 (17)
C6	0.073 (2)	0.077 (2)	0.0612 (17)	−0.0195 (18)	−0.0146 (17)	−0.0081 (16)
O1	0.0547 (11)	0.0483 (10)	0.0506 (10)	−0.0027 (9)	0.0006 (10)	0.0044 (8)
O2	0.0383 (10)	0.1060 (17)	0.0804 (14)	−0.0014 (11)	0.0130 (11)	0.0259 (13)
C7	0.0371 (13)	0.0587 (16)	0.0393 (13)	−0.0023 (14)	0.0003 (11)	0.0004 (13)
C8	0.0395 (13)	0.0518 (14)	0.0334 (11)	0.0025 (13)	−0.0023 (11)	0.0032 (11)
C9	0.0675 (19)	0.0622 (18)	0.0592 (16)	0.0089 (17)	−0.0015 (16)	0.0070 (15)
C10	0.125 (3)	0.0573 (18)	0.075 (2)	−0.001 (2)	−0.013 (3)	0.0192 (17)
C11	0.109 (3)	0.095 (3)	0.063 (2)	−0.046 (3)	−0.016 (2)	0.032 (2)
C12	0.058 (2)	0.117 (3)	0.0539 (17)	−0.022 (2)	0.0012 (15)	0.022 (2)
C13	0.0426 (14)	0.0721 (18)	0.0458 (14)	−0.0039 (15)	0.0010 (13)	0.0107 (13)

Geometric parameters (Å, º) top

N1—C2	1.461 (3)	C6—H6	0.9300
N1—H1A	0.8900	O1—C7	1.263 (3)
N1—H1B	0.8900	O2—C7	1.241 (3)
N1—H1C	0.8900	C7—C8	1.499 (3)
N2—C1	1.394 (3)	C8—C9	1.379 (4)
N2—H2A	1.0021	C8—C13	1.383 (4)
N2—H2B	0.9968	C9—C10	1.376 (5)
C1—C2	1.387 (4)	C9—H9	0.9300
C1—C6	1.395 (4)	C10—C11	1.359 (6)
C2—C3	1.375 (3)	C10—H10	0.9300
C3—C4	1.377 (4)	C11—C12	1.375 (5)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.371 (6)	C12—C13	1.373 (4)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.373 (5)	C13—H13	0.9300
C5—H5	0.9300

C2—N1—H1A	109.5	C5—C6—C1	120.7 (3)
C2—N1—H1B	109.5	C5—C6—H6	119.7
H1A—N1—H1B	109.5	C1—C6—H6	119.7
C2—N1—H1C	109.5	O2—C7—O1	123.9 (3)
H1A—N1—H1C	109.5	O2—C7—C8	119.0 (3)
H1B—N1—H1C	109.5	O1—C7—C8	117.1 (2)
C1—N2—H2A	114.5	C9—C8—C13	118.7 (3)
C1—N2—H2B	112.5	C9—C8—C7	121.0 (2)
H2A—N2—H2B	120.0	C13—C8—C7	120.3 (2)
C2—C1—N2	121.3 (2)	C10—C9—C8	120.6 (3)
C2—C1—C6	117.3 (2)	C10—C9—H9	119.7
N2—C1—C6	121.4 (2)	C8—C9—H9	119.7
C3—C2—C1	121.9 (2)	C11—C10—C9	120.2 (3)
C3—C2—N1	119.6 (2)	C11—C10—H10	119.9
C1—C2—N1	118.4 (2)	C9—C10—H10	119.9
C2—C3—C4	119.6 (3)	C10—C11—C12	120.2 (3)
C2—C3—H3	120.2	C10—C11—H11	119.9
C4—C3—H3	120.2	C12—C11—H11	119.9
C5—C4—C3	119.6 (3)	C13—C12—C11	119.9 (3)
C5—C4—H4	120.2	C13—C12—H12	120.1
C3—C4—H4	120.2	C11—C12—H12	120.1
C4—C5—C6	120.9 (3)	C12—C13—C8	120.5 (3)
C4—C5—H5	119.6	C12—C13—H13	119.7
C6—C5—H5	119.6	C8—C13—H13	119.7

N2—C1—C2—C3	177.9 (2)	O1—C7—C8—C9	−163.0 (2)
C6—C1—C2—C3	0.5 (4)	O2—C7—C8—C13	−162.2 (2)
N2—C1—C2—N1	1.7 (4)	O1—C7—C8—C13	16.5 (3)
C6—C1—C2—N1	−175.7 (2)	C13—C8—C9—C10	−0.8 (4)
C1—C2—C3—C4	−0.2 (4)	C7—C8—C9—C10	178.7 (3)
N1—C2—C3—C4	176.0 (3)	C8—C9—C10—C11	1.5 (5)
C2—C3—C4—C5	−0.3 (5)	C9—C10—C11—C12	−0.3 (5)
C3—C4—C5—C6	0.3 (6)	C10—C11—C12—C13	−1.5 (5)
C4—C5—C6—C1	0.1 (5)	C11—C12—C13—C8	2.2 (4)
C2—C1—C6—C5	−0.5 (4)	C9—C8—C13—C12	−1.0 (4)
N2—C1—C6—C5	−177.8 (3)	C7—C8—C13—C12	179.5 (2)
O2—C7—C8—C9	18.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1	0.89	1.83	2.699 (3)	166
N2—H2A···O2	1.00	2.16	3.093 (3)	155
N1—H1B···O1ⁱ	0.89	1.94	2.815 (3)	168
N1—H1A···O2ⁱⁱ	0.89	1.90	2.753 (3)	161

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

Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₇H₅O₂⁻
M_r	230.26
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	6.0211 (12), 12.237 (2), 16.639 (3)
V (Å³)	1226.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.15 × 0.10

Data collection
Diffractometer	Rigaku Mercury2
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.970, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12656, 1638, 1133
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.118, 1.08
No. of reflections	1638
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.16

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1	0.89	1.83	2.699 (3)	165.5
N2—H2A···O2	1.00	2.16	3.093 (3)	154.5
N1—H1B···O1ⁱ	0.89	1.94	2.815 (3)	167.6
N1—H1A···O2ⁱⁱ	0.89	1.90	2.753 (3)	161.3

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

Acknowledgements

This work was supported by a start-up grant from Anyang Institute of Technology.

References

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