(1S,3R)-3-Ammonio­cyclo­hexa­necarboxyl­ate

Hu, Y.; Sun, X.X.; Guo, Y.; Tuo, X.

doi:10.1107/S1600536808028080

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1912

doi:10.1107/S1600536808028080

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(1S,3R)-3-Ammoniocyclohexanecarboxylate

Yu Hu,^a ^* XiaoXia Sun,^b Ying Guo ^a and Xun Tuo ^a

^aExperimental Chemistry Center, Nanchang University, Nanchang 330031, People's Republic of China, and ^bJiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University, Nanchang 330013, People's Republic of China
^*Correspondence e-mail: huyu@ncu.edu.cn

(Received 25 August 2008; accepted 3 September 2008; online 13 September 2008)

The title γ-aminobutyric acid, C₇H₁₃NO₂, exists as a zwitterion. The crystal structure is stabilized by a network of intermolecular N—H⋯O hydrogen bonds, forming a two-dimensional bilayer. An intermolecular C—H⋯O hydrogen bond is also observed.

Related literature

For related literature, see: Allan et al. (1981 ); Ávila et al. (2004 ); Fábián et al. (2005 ); Granja (2004 ); Hu et al. (2006 ); Schousboe (2000 ).

Experimental

Crystal data

C₇H₁₃NO₂
M_r = 143.18
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.5130 (10) Å
b = 6.1282 (9) Å
c = 22.518 (4) Å
V = 760.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.48 × 0.38 × 0.30 mm

Data collection

Bruker SMART 1K area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.958, T_max = 0.973
1150 measured reflections
1107 independent reflections
891 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.093
S = 0.97
1107 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O1ⁱ	0.89	1.84	2.725 (2)	172
N1—H1D⋯O2ⁱⁱ	0.89	2.00	2.849 (2)	160
N1—H1E⋯O1ⁱⁱⁱ	0.89	1.89	2.772 (2)	170
C6—H6⋯O2^iv	0.98	2.55	3.472 (2)	156
Symmetry codes: (i) x, y+1, z; (ii) x-1, y+1, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iv) x-1, y, z.

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; 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/S1600536808028080/wn2278sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808028080/wn2278Isup2.hkl

checkCIF report

Comment top

The importance of the inhibitory neurotransmitter, γ-aminobutyric acid (GABA), in certain neurological and psychiatric disorders has become generally accepted (Schousboe et al., 2000). As an analogue of GABA, 3-aminocyclohexanecarboxylic acid has been investigated in structure–activity studies of conformationally restricted analogues (Allan et al., 1981). From another point of view, self-assembling peptide nanotubes, which contain 3-aminocyclohexanecarboxylic acid, have structural and functional properties that may be suitable for various applications in biology and material science (Granja, 2004). The structure of 1S,3R-3-aminocyclohexanecarboxylic acid was elucidated by spectroscopic analysis. Here we report its crystal structure.

The X-ray crystallographic study confirms the molecular structure previously proposed on the basis of spectroscopic data. The title compound exists as a zwitterion, containing an ammonium group and a carboxylate group (Fig. 1) and amino acid units are linked, in a head-to-tail fashion, by hydrogen bonds (Fig. 2 and Table 1); this is very often observed in the crystal structures of amino acids (Ávila et al., 2004; Fábián et al., 2005). The hydrogen bonds result in a two-dimensional bilayer structure parallel to the bc plane (Fig. 3).

Related literature top

For related literature, see: Allan et al. (1981); Ávila et al. (2004); Fábián et al. (2005); Granja (2004); Hu et al. (2006); Schousboe (2000).

Experimental top

1S,3R-3-amino-cyclohexanecarboxylic acid was synthesized and resolved from 3-cyclohexenecarboxylic acid (Hu et al., 2006). Its identity was confirmed by NMR and HRMS. ¹H NMR in D₂O (300 MHz): 3.19–3.26 (m, 1H), 2.16–2.28 (m, 2H), 1.89–2.03 (m, 3H), 1.27–1.50 (m, 4H). ¹³C NMR in D₂O (75 MHz): 183.96, 49.91, 45.02, 33.55, 29.89, 28.48, 23.30 HRMS calcd for C₇H₁₂NO₂ 142.0863, found 142.0859. Single crystals suitable for X-ray diffraction analysis were obtained by the slow diffusion of acetone into an aqueous solution of the title compound.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); 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. A view of the molecular structure of the title compound, with anisotropic displacement parameters drawn at the 50% probability level. H atoms are represented by spheres of arbitrary radius.
	Fig. 2. A view of the hydrogen-bonded molecular strands (dashed lines). The strands are aligned parallel to the crystallographic b axis. H atoms not involved in hydrogen bonding have been omitted for clarity. Symmetry codes: () x-1,1 + y,z; () x,y-1,z; (#)x,1 + y,z; (##) 2 + x,y-1,z; ($)x-1/2,1/2 - y,-z; ($$) 1/2 + x,1/2 - y*,-z
	Fig. 3. A crystal packing diagram, viewed down the a axis, showing the layer architecture.

(1S,3R)-3-Ammoniocyclohexanecarboxylate top

Crystal data top

C₇H₁₃NO₂	F(000) = 312
M_r = 143.18	D_x = 1.250 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 31 reflections
a = 5.513 (1) Å	θ = 4.9–13.6°
b = 6.1282 (9) Å	µ = 0.09 mm⁻¹
c = 22.518 (4) Å	T = 293 K
V = 760.8 (2) Å³	Block, colourless
Z = 4	0.48 × 0.38 × 0.30 mm

Data collection top

Bruker SMART 1K area-detector diffractometer	1107 independent reflections
Radiation source: fine-focus sealed tube	891 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ϕ and ω scans	θ_max = 28.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = 0→7
T_min = 0.958, T_max = 0.973	k = 0→8
1150 measured reflections	l = −1→29

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.057P)²] where P = (F_o² + 2F_c²)/3
1107 reflections	(Δ/σ)_max < 0.001
92 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₇H₁₃NO₂	V = 760.8 (2) Å³
M_r = 143.18	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.513 (1) Å	µ = 0.09 mm⁻¹
b = 6.1282 (9) Å	T = 293 K
c = 22.518 (4) Å	0.48 × 0.38 × 0.30 mm

Data collection top

Bruker SMART 1K area-detector diffractometer	1107 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	891 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.973	R_int = 0.013
1150 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 0.97	Δρ_max = 0.15 e Å⁻³
1107 reflections	Δρ_min = −0.20 e Å⁻³
92 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
C1	0.2478 (4)	0.3817 (3)	0.08035 (7)	0.0282 (4)
H1A	0.3925	0.4696	0.0750	0.034*
H1B	0.2011	0.3237	0.0419	0.034*
C2	0.0440 (3)	0.5232 (3)	0.10484 (8)	0.0262 (4)
H2	−0.1034	0.4346	0.1077	0.031*
C3	0.1066 (4)	0.6102 (3)	0.16649 (8)	0.0339 (5)
H3A	0.2466	0.7055	0.1639	0.041*
H3B	−0.0285	0.6946	0.1818	0.041*
C4	0.1614 (4)	0.4219 (3)	0.20854 (8)	0.0369 (5)
H4A	0.2069	0.4796	0.2471	0.044*
H4B	0.0166	0.3340	0.2137	0.044*
C5	0.3656 (4)	0.2795 (3)	0.18478 (8)	0.0347 (5)
H5A	0.3926	0.1580	0.2116	0.042*
H5B	0.5141	0.3641	0.1827	0.042*
C6	0.3023 (3)	0.1930 (3)	0.12313 (7)	0.0265 (4)
H6	0.1526	0.1080	0.1271	0.032*
C7	0.4929 (3)	0.0418 (3)	0.09604 (9)	0.0303 (4)
N1	−0.0035 (3)	0.7099 (2)	0.06373 (6)	0.0293 (4)
H1C	0.1290	0.7923	0.0610	0.044*
H1D	−0.1256	0.7897	0.0778	0.044*
H1E	−0.0422	0.6588	0.0280	0.044*
O1	0.4251 (3)	−0.0725 (2)	0.05224 (6)	0.0405 (4)
O2	0.6983 (3)	0.0343 (3)	0.11737 (8)	0.0611 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0320 (10)	0.0277 (9)	0.0249 (8)	0.0087 (9)	0.0012 (7)	−0.0031 (7)
C2	0.0268 (9)	0.0234 (8)	0.0285 (8)	0.0039 (8)	0.0018 (8)	−0.0017 (7)
C3	0.0454 (12)	0.0292 (9)	0.0271 (9)	0.0112 (10)	0.0044 (9)	−0.0050 (8)
C4	0.0503 (12)	0.0357 (10)	0.0247 (8)	0.0060 (11)	0.0034 (9)	−0.0002 (9)
C5	0.0402 (11)	0.0347 (10)	0.0291 (9)	0.0074 (10)	−0.0035 (9)	0.0004 (9)
C6	0.0239 (9)	0.0228 (8)	0.0329 (9)	0.0036 (8)	0.0014 (8)	−0.0014 (8)
C7	0.0300 (9)	0.0212 (8)	0.0397 (10)	0.0031 (9)	0.0059 (9)	0.0012 (9)
N1	0.0322 (8)	0.0287 (7)	0.0271 (7)	0.0101 (8)	−0.0014 (7)	−0.0030 (7)
O1	0.0442 (8)	0.0393 (8)	0.0379 (8)	0.0026 (8)	0.0110 (6)	−0.0114 (7)
O2	0.0320 (8)	0.0617 (11)	0.0896 (13)	0.0192 (9)	−0.0095 (8)	−0.0294 (11)

Geometric parameters (Å, º) top

C1—C2	1.523 (2)	C4—H4B	0.9700
C1—C6	1.535 (2)	C5—C6	1.526 (2)
C1—H1A	0.9700	C5—H5A	0.9700
C1—H1B	0.9700	C5—H5B	0.9700
C2—N1	1.495 (2)	C6—C7	1.528 (2)
C2—C3	1.527 (2)	C6—H6	0.9800
C2—H2	0.9800	C7—O2	1.231 (2)
C3—C4	1.523 (3)	C7—O1	1.266 (2)
C3—H3A	0.9700	N1—H1C	0.8900
C3—H3B	0.9700	N1—H1D	0.8900
C4—C5	1.522 (3)	N1—H1E	0.8900
C4—H4A	0.9700

C2—C1—C6	110.26 (14)	H4A—C4—H4B	108.0
C2—C1—H1A	109.6	C4—C5—C6	110.48 (16)
C6—C1—H1A	109.6	C4—C5—H5A	109.6
C2—C1—H1B	109.6	C6—C5—H5A	109.6
C6—C1—H1B	109.6	C4—C5—H5B	109.6
H1A—C1—H1B	108.1	C6—C5—H5B	109.6
N1—C2—C1	109.94 (14)	H5A—C5—H5B	108.1
N1—C2—C3	109.61 (14)	C5—C6—C7	114.62 (15)
C1—C2—C3	111.20 (15)	C5—C6—C1	110.72 (15)
N1—C2—H2	108.7	C7—C6—C1	109.93 (14)
C1—C2—H2	108.7	C5—C6—H6	107.1
C3—C2—H2	108.7	C7—C6—H6	107.1
C4—C3—C2	110.22 (15)	C1—C6—H6	107.1
C4—C3—H3A	109.6	O2—C7—O1	123.73 (19)
C2—C3—H3A	109.6	O2—C7—C6	119.95 (18)
C4—C3—H3B	109.6	O1—C7—C6	116.32 (17)
C2—C3—H3B	109.6	C2—N1—H1C	109.5
H3A—C3—H3B	108.1	C2—N1—H1D	109.5
C5—C4—C3	111.27 (15)	H1C—N1—H1D	109.5
C5—C4—H4A	109.4	C2—N1—H1E	109.5
C3—C4—H4A	109.4	H1C—N1—H1E	109.5
C5—C4—H4B	109.4	H1D—N1—H1E	109.5
C3—C4—H4B	109.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1ⁱ	0.89	1.84	2.725 (2)	172
N1—H1D···O2ⁱⁱ	0.89	2.00	2.849 (2)	160
N1—H1E···O1ⁱⁱⁱ	0.89	1.89	2.772 (2)	170
C6—H6···O2^iv	0.98	2.55	3.472 (2)	156

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

Experimental details

Crystal data
Chemical formula	C₇H₁₃NO₂
M_r	143.18
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	5.513 (1), 6.1282 (9), 22.518 (4)
V (Å³)	760.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.48 × 0.38 × 0.30

Data collection
Diffractometer	Bruker SMART 1K area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.958, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	1150, 1107, 891
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.093, 0.97
No. of reflections	1107
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.20

Computer programs: SMART (Bruker, 1999), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1ⁱ	0.89	1.84	2.725 (2)	172.0
N1—H1D···O2ⁱⁱ	0.89	2.00	2.849 (2)	159.9
N1—H1E···O1ⁱⁱⁱ	0.89	1.89	2.772 (2)	170.3
C6—H6···O2^iv	0.98	2.55	3.472 (2)	155.7

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

Acknowledgements

This work was supported by the Science Fund of the Education Office of Jiangxi, China [(2007)279].

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