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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o1912.
Published online 2008 September 13. doi:  10.1107/S1600536808028080
PMCID: PMC2959423

(1S,3R)-3-Ammonio­cyclo­hexa­necarboxyl­ate

Abstract

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 [triangle]); Ávila et al. (2004 [triangle]); Fábián et al. (2005 [triangle]); Granja (2004 [triangle]); Hu et al. (2006 [triangle]); Schousboe (2000 [triangle]).

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Object name is e-64-o1912-scheme1.jpg

Experimental

Crystal data

  • C7H13NO2
  • M r = 143.18
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1912-efi4.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.093
  • S = 0.97
  • 1107 reflections
  • 92 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 1999 [triangle]); cell refinement: SAINT-Plus (Bruker, 1999 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808028080/wn2278sup1.cif

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

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

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Carbon-bound H atoms were positioned geometrically and were treated as riding on their parent atoms, with C—H distances in the range 0.97–0.98 Å, with Uiso(H) = 1.2 times Ueq of the parent atom. H atoms attached to N1 were located in difference Fourier maps and refined initially with distance restraints of 0.89 Å. They were then repositioned geometrically and refined as riding, with N—H = 0.89 Å and with Uiso(H) = 1.5 times Ueq(N). In the absence of significant anomalous scattering effects, Friedel pairs were merged.

Figures

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 ...
Fig. 3.
A crystal packing diagram, viewed down the a axis, showing the layer architecture.

Crystal data

C7H13NO2F(000) = 312
Mr = 143.18Dx = 1.250 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 31 reflections
a = 5.513 (1) Åθ = 4.9–13.6°
b = 6.1282 (9) ŵ = 0.09 mm1
c = 22.518 (4) ÅT = 293 K
V = 760.8 (2) Å3Block, colourless
Z = 40.48 × 0.38 × 0.30 mm

Data collection

Bruker SMART 1K area-detector diffractometer1107 independent reflections
Radiation source: fine-focus sealed tube891 reflections with I > 2σ(I)
graphiteRint = 0.013
[var phi] and ω scansθmax = 28.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = 0→7
Tmin = 0.958, Tmax = 0.973k = 0→8
1150 measured reflectionsl = −1→29

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 0.97w = 1/[σ2(Fo2) + (0.057P)2] where P = (Fo2 + 2Fc2)/3
1107 reflections(Δ/σ)max < 0.001
92 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = −0.20 e Å3

Special details

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)

xyzUiso*/Ueq
C10.2478 (4)0.3817 (3)0.08035 (7)0.0282 (4)
H1A0.39250.46960.07500.034*
H1B0.20110.32370.04190.034*
C20.0440 (3)0.5232 (3)0.10484 (8)0.0262 (4)
H2−0.10340.43460.10770.031*
C30.1066 (4)0.6102 (3)0.16649 (8)0.0339 (5)
H3A0.24660.70550.16390.041*
H3B−0.02850.69460.18180.041*
C40.1614 (4)0.4219 (3)0.20854 (8)0.0369 (5)
H4A0.20690.47960.24710.044*
H4B0.01660.33400.21370.044*
C50.3656 (4)0.2795 (3)0.18478 (8)0.0347 (5)
H5A0.39260.15800.21160.042*
H5B0.51410.36410.18270.042*
C60.3023 (3)0.1930 (3)0.12313 (7)0.0265 (4)
H60.15260.10800.12710.032*
C70.4929 (3)0.0418 (3)0.09604 (9)0.0303 (4)
N1−0.0035 (3)0.7099 (2)0.06373 (6)0.0293 (4)
H1C0.12900.79230.06100.044*
H1D−0.12560.78970.07780.044*
H1E−0.04220.65880.02800.044*
O10.4251 (3)−0.0725 (2)0.05224 (6)0.0405 (4)
O20.6983 (3)0.0343 (3)0.11737 (8)0.0611 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0320 (10)0.0277 (9)0.0249 (8)0.0087 (9)0.0012 (7)−0.0031 (7)
C20.0268 (9)0.0234 (8)0.0285 (8)0.0039 (8)0.0018 (8)−0.0017 (7)
C30.0454 (12)0.0292 (9)0.0271 (9)0.0112 (10)0.0044 (9)−0.0050 (8)
C40.0503 (12)0.0357 (10)0.0247 (8)0.0060 (11)0.0034 (9)−0.0002 (9)
C50.0402 (11)0.0347 (10)0.0291 (9)0.0074 (10)−0.0035 (9)0.0004 (9)
C60.0239 (9)0.0228 (8)0.0329 (9)0.0036 (8)0.0014 (8)−0.0014 (8)
C70.0300 (9)0.0212 (8)0.0397 (10)0.0031 (9)0.0059 (9)0.0012 (9)
N10.0322 (8)0.0287 (7)0.0271 (7)0.0101 (8)−0.0014 (7)−0.0030 (7)
O10.0442 (8)0.0393 (8)0.0379 (8)0.0026 (8)0.0110 (6)−0.0114 (7)
O20.0320 (8)0.0617 (11)0.0896 (13)0.0192 (9)−0.0095 (8)−0.0294 (11)

Geometric parameters (Å, °)

C1—C21.523 (2)C4—H4B0.9700
C1—C61.535 (2)C5—C61.526 (2)
C1—H1A0.9700C5—H5A0.9700
C1—H1B0.9700C5—H5B0.9700
C2—N11.495 (2)C6—C71.528 (2)
C2—C31.527 (2)C6—H60.9800
C2—H20.9800C7—O21.231 (2)
C3—C41.523 (3)C7—O11.266 (2)
C3—H3A0.9700N1—H1C0.8900
C3—H3B0.9700N1—H1D0.8900
C4—C51.522 (3)N1—H1E0.8900
C4—H4A0.9700
C2—C1—C6110.26 (14)H4A—C4—H4B108.0
C2—C1—H1A109.6C4—C5—C6110.48 (16)
C6—C1—H1A109.6C4—C5—H5A109.6
C2—C1—H1B109.6C6—C5—H5A109.6
C6—C1—H1B109.6C4—C5—H5B109.6
H1A—C1—H1B108.1C6—C5—H5B109.6
N1—C2—C1109.94 (14)H5A—C5—H5B108.1
N1—C2—C3109.61 (14)C5—C6—C7114.62 (15)
C1—C2—C3111.20 (15)C5—C6—C1110.72 (15)
N1—C2—H2108.7C7—C6—C1109.93 (14)
C1—C2—H2108.7C5—C6—H6107.1
C3—C2—H2108.7C7—C6—H6107.1
C4—C3—C2110.22 (15)C1—C6—H6107.1
C4—C3—H3A109.6O2—C7—O1123.73 (19)
C2—C3—H3A109.6O2—C7—C6119.95 (18)
C4—C3—H3B109.6O1—C7—C6116.32 (17)
C2—C3—H3B109.6C2—N1—H1C109.5
H3A—C3—H3B108.1C2—N1—H1D109.5
C5—C4—C3111.27 (15)H1C—N1—H1D109.5
C5—C4—H4A109.4C2—N1—H1E109.5
C3—C4—H4A109.4H1C—N1—H1E109.5
C5—C4—H4B109.4H1D—N1—H1E109.5
C3—C4—H4B109.4

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1C···O1i0.891.842.725 (2)172.
N1—H1D···O2ii0.892.002.849 (2)160.
N1—H1E···O1iii0.891.892.772 (2)170.
C6—H6···O2iv0.982.553.472 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WN2278).

References

  • Allan, R. D., Johnston, G. A. R. & Twitchin, B. (1981). Aust. J. Chem.34, 2231–2236.
  • Ávila, E. E., Mora, A. J., Delgado, G. E., Ramírez, B. M., Bahsas, A. & Koteich, S. (2004). Acta Cryst. C60, o759–o761. [PubMed]
  • Bruker (1999). SMART and SAINT-Plus Bruker AXS Inc, Madison, Wisconsin, USA.
  • Fábián, L., Kálmán, A., Argay, G., Bernáth, G. & Gyarmati, Z. Cs. (2005). Cryst. Growth Des.5, 773–782.
  • Granja, J. R. (2004). Intl Patent WO 2 004 052 916.
  • Hu, Y., Yu, S. L., Yang, Y. J., Zhu, J. & Deng, J. G. (2006). Chin. J. Chem.24, 795–799.
  • Schousboe, A. (2000). Neurochem. Res.25, 1241–1244. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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