Acta Cryst. (2009). E65, o245 [ doi:10.1107/S1600536808044243 ]
The crystal structure of the title compound, C7H14NO2+·Cl-, was reported previously [Chacko, Srinivasan & Zand (1975). J. Cryst. Mol. Struct. 5, 353-357] from Weissenberg photographic data with R = 0.113. It has now been redetermined, providing a significant increase in the precision of the derived geometric parameters, viz. mean ![[sigma]](/logos/entities/sigma_rmgif.gif)
(C-C) = 0.003 Å in the present work compared with 0.021 Å for the previous work. The complete cation is generated by crystallographic mirrror symmetry, with three C atoms, two O atoms and the N atom lying on the reflecting plane; the chloride anion also has m site symmetry. The crystal structure is established by a two-dimensional network of O-H
Cl and N-HCl hydrogen bonds, generating C12(4) and C12(7) chains, and R24(8) and R24(14) rings.
1-Amino-cyclohexanecarboxylic acid and hydrochloric acid in equal molar ratio were mixed together with enough water, and heated to a temperature where a clear solution was obtained. Colorless crystals of (I) suitable for X-ray diffraction analysis were grown by slow evaporation of this solution.
All H atoms were located in a difference map and their positions were freely refined, with the Uiso(H) values set at 1.2Ueq(carrier C), 1.5Ueq(carrier O) and 1.5Ueq(carrier N), respectively.
Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: PLATON (Spek, 2003) and publCIF (Westrip, 2009).
![[Figure 1]](./bh2212fig1thm.gif)
| Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms. |
![[Figure 2]](./bh2212fig2thm.gif)
| Fig. 2. A partial packing view of (I). Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. Symmetry codes: (i) x, y, z - 1; (ii) 1 - x, y - 1/2, 1 - z. |
| C7H14NO2+·Cl− | F(000) = 192 |
| Mr = 179.64 | Dx = 1.364 Mg m−3 |
| Monoclinic, P21/m | Mo Kα radiation, λ = 0.71070 Å |
| Hall symbol: -P 2yb | Cell parameters from 1650 reflections |
| a = 7.382 (3) Å | θ = 2.2–27.2° |
| b = 6.357 (2) Å | µ = 0.39 mm−1 |
| c = 9.374 (3) Å | T = 298 K |
| β = 96.239 (10)° | Block, colourless |
| V = 437.3 (3) Å3 | 0.31 × 0.27 × 0.18 mm |
| Z = 2 |
| Rigaku AFC-7S Mercury diffractometer | 845 independent reflections |
| Radiation source: Normal-focus sealed tube | 789 reflections with I > 2σ(I) |
| graphite | Rint = 0.023 |
| Detector resolution: 14.6306 pixels mm-1 | θmax = 25.0°, θmin = 2.2° |
| ω scans | h = −8→8 |
| Absorption correction: multi-scan (Jacobson, 1998) | k = −6→7 |
| Tmin = 0.880, Tmax = 0.930 | l = −11→11 |
| 4638 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.047P)2 + 0.1831P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max < 0.001 |
| 845 reflections | Δρmax = 0.18 e Å−3 |
| 85 parameters | Δρmin = −0.15 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 constraints | Extinction coefficient: 0.042 (10) |
| Primary atom site location: structure-invariant direct methods |
| C7H14NO2+·Cl− | V = 437.3 (3) Å3 |
| Mr = 179.64 | Z = 2 |
| Monoclinic, P21/m | Mo Kα radiation |
| a = 7.382 (3) Å | µ = 0.39 mm−1 |
| b = 6.357 (2) Å | T = 298 K |
| c = 9.374 (3) Å | 0.31 × 0.27 × 0.18 mm |
| β = 96.239 (10)° |
| Rigaku AFC-7S Mercury diffractometer | 845 independent reflections |
| Absorption correction: multi-scan (Jacobson, 1998) | 789 reflections with I > 2σ(I) |
| Tmin = 0.880, Tmax = 0.930 | Rint = 0.023 |
| 4638 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.088 | Δρmax = 0.18 e Å−3 |
| S = 1.01 | Δρmin = −0.15 e Å−3 |
| 845 reflections | Absolute structure: ? |
| 85 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| Cl | 0.41343 (8) | 0.2500 | 0.64377 (6) | 0.0414 (3) | |
| O2 | 0.5446 (2) | 0.2500 | 0.04758 (18) | 0.0511 (5) | |
| O1 | 0.2629 (3) | 0.2500 | −0.06850 (18) | 0.0528 (5) | |
| H1 | 0.324 (5) | 0.2500 | −0.146 (4) | 0.079* | |
| N1 | 0.4370 (3) | 0.2500 | 0.3054 (2) | 0.0343 (5) | |
| H1A | 0.506 (3) | 0.138 (3) | 0.300 (2) | 0.051* | |
| H1B | 0.398 (4) | 0.2500 | 0.393 (3) | 0.051* | |
| C1 | 0.2863 (3) | 0.2500 | 0.1837 (2) | 0.0292 (5) | |
| C2 | 0.1715 (2) | 0.4484 (3) | 0.19289 (19) | 0.0408 (5) | |
| H2A | 0.251 (3) | 0.566 (3) | 0.1923 (19) | 0.049* | |
| H2B | 0.090 (3) | 0.452 (3) | 0.107 (2) | 0.049* | |
| C3 | 0.0597 (3) | 0.4450 (4) | 0.3193 (2) | 0.0539 (6) | |
| H3A | 0.140 (3) | 0.449 (4) | 0.409 (2) | 0.065* | |
| H3B | −0.018 (3) | 0.571 (4) | 0.315 (2) | 0.065* | |
| C4 | −0.0557 (4) | 0.2500 | 0.3201 (3) | 0.0626 (9) | |
| H4A | −0.145 (5) | 0.2500 | 0.232 (4) | 0.075* | |
| H4B | −0.148 (5) | 0.2500 | 0.397 (4) | 0.075* | |
| C5 | 0.3819 (3) | 0.2500 | 0.0475 (2) | 0.0358 (5) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl | 0.0457 (4) | 0.0544 (4) | 0.0238 (4) | 0.000 | 0.0025 (2) | 0.000 |
| O2 | 0.0359 (10) | 0.0837 (14) | 0.0345 (10) | 0.000 | 0.0078 (7) | 0.000 |
| O1 | 0.0443 (11) | 0.0932 (15) | 0.0205 (9) | 0.000 | 0.0023 (7) | 0.000 |
| N1 | 0.0335 (11) | 0.0449 (12) | 0.0238 (10) | 0.000 | −0.0002 (8) | 0.000 |
| C1 | 0.0303 (11) | 0.0355 (12) | 0.0211 (11) | 0.000 | −0.0004 (8) | 0.000 |
| C2 | 0.0439 (10) | 0.0402 (10) | 0.0373 (10) | 0.0074 (8) | −0.0004 (8) | 0.0024 (7) |
| C3 | 0.0497 (11) | 0.0707 (14) | 0.0412 (10) | 0.0221 (10) | 0.0052 (9) | −0.0058 (10) |
| C4 | 0.0386 (15) | 0.105 (3) | 0.0449 (17) | 0.000 | 0.0076 (13) | 0.000 |
| C5 | 0.0385 (13) | 0.0425 (13) | 0.0262 (12) | 0.000 | 0.0025 (10) | 0.000 |
| O2—C5 | 1.201 (3) | C2—C3 | 1.516 (3) |
| O1—C5 | 1.322 (3) | C2—H2A | 0.95 (2) |
| O1—H1 | 0.89 (4) | C2—H2B | 0.95 (2) |
| N1—C1 | 1.504 (3) | C3—C4 | 1.505 (3) |
| N1—H1A | 0.88 (2) | C3—H3A | 0.97 (2) |
| N1—H1B | 0.90 (3) | C3—H3B | 0.98 (2) |
| C1—C5 | 1.524 (3) | C4—H4A | 0.99 (3) |
| C1—C2 | 1.528 (2) | C4—H4B | 1.05 (4) |
| C5—O1—H1 | 109 (2) | C4—C3—C2 | 111.85 (19) |
| C1—N1—H1A | 110.2 (13) | C4—C3—H3A | 107.9 (13) |
| C1—N1—H1B | 114.0 (18) | C2—C3—H3A | 109.9 (12) |
| H1A—N1—H1B | 107.1 (16) | C4—C3—H3B | 110.2 (13) |
| N1—C1—C5 | 105.28 (18) | C2—C3—H3B | 108.4 (13) |
| N1—C1—C2 | 109.04 (12) | H3A—C3—H3B | 108.5 (17) |
| C5—C1—C2 | 110.97 (12) | C3—C4—H4A | 108.6 (10) |
| C3—C2—C1 | 112.64 (16) | C3—C4—H4B | 114.6 (8) |
| C3—C2—H2A | 113.8 (11) | H4A—C4—H4B | 99 (3) |
| C1—C2—H2A | 107.7 (12) | O2—C5—O1 | 125.2 (2) |
| C3—C2—H2B | 108.3 (11) | O2—C5—C1 | 123.6 (2) |
| C1—C2—H2B | 105.8 (12) | O1—C5—C1 | 111.2 (2) |
| H2A—C2—H2B | 108.2 (16) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1B···Cl | 0.90 (3) | 2.34 (3) | 3.196 (2) | 158 (2) |
| N1—H1A···Cli | 0.88 (2) | 2.58 (2) | 3.3816 (13) | 152.4 (17) |
| O1—H1···Clii | 0.89 (4) | 2.15 (4) | 3.027 (2) | 168 (3) |
| Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x, y, z−1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1B···Cl | 0.90 (3) | 2.34 (3) | 3.196 (2) | 158 (2) |
| N1—H1A···Cli | 0.88 (2) | 2.58 (2) | 3.3816 (13) | 152.4 (17) |
| O1—H1···Clii | 0.89 (4) | 2.15 (4) | 3.027 (2) | 168 (3) |
| Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x, y, z−1. |
This work was supported by CDCHT-ULA (grant Nos. C-1618-08-A, C-1615-08-B and C-1620-08-08-Em) and FONACIT (grant No. LAB-97000821).
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Chacko, K. K., Srinivasan, R. & Zand, R. (1971). J. Cryst. Mol. Struct. 1, 261–269.
Chacko, K. K., Srinivasan, R. & Zand, R. (1975). J. Cryst. Mol. Struct. 5, 353–357.
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126.
Jacobson, R. (1998). Private communication to Rigaku Corporation, Tokyo, Japan.
Rigaku (2002). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.
Rodríguez-Ropero, F., Zanuy, D., Casanovas, J., Nussinov, R. & Alemán, C. (2008). J. Chem. Inf. Model. 48, 333–343.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
Valle, G., Crisma, M., Toniolo, C., Sen, N., Sukumar, M. & Balaram, P. (1988). J. Chem. Soc. Perkin Trans. 2, pp. 393–398.
Westrip, S. P. (2009). publCIF. In preparation.
1-Amino-cyclohexanecarboxylic acid is a promising amino acid candidate to serve as basic piece in redesigned protein motifs which constitute the basic modules in synthetic nanoconstructs (Rodríguez-Ropero et al., 2008). It structure was reported by Valle et al. (1988). The title compound, (I), 1-amino-cyclohexanecarboxylic acid hydrochloride, C7H14NO2+.Cl-, was first reported in the noncentric space group P21 (Chacko et al., 1971) and later reported in the centrosymmetric space group P21/m (Chacko et al., 1975) with R = 0.113. The present paper reports a redetermination of the crystal structure of (I), with greater precision and accuracy. Both, the cation and anion are located on a mirror plane, which confirms the space group P21/m instead of P21. In this compound, the cyclohexane ring adopts a chair conformation, with the ammonium and carboxylate groups in axial and equatorial positions, respectively (Cremer & Pople, 1975), while the pure amino acid has an opposite conformation (Valle et al., 1988). In (I), 1-amino-cyclohexanecarboxylic acid is protonated and is linked to the Cl- anion by a O—H···Cl hydrogen bond (Fig. 1, Table 1). The hydrogen bonds O1—H1···Cl1 (x, y, z - 1) and N1—H1B···Cl1 (1 - x, y - 1/2, 1 - z) form infinite chains running along the [001] direction (Fig. 2) and may be described in graph-set notation as C12(7) (Etter, 1990). The intramolecular hydrogen bonds N1—H1A···Cl1 form infinite chains, with graph-set C12(4), running along the b cell axis. The combination of these interactions produces rings with graph-set R24(8) and R24(14), parallel to the bc plane (Fig. 2).