organic compounds
2-Carboxy-1-phenylethanaminium perchlorate
aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: quzr@seu.edu.cn
In the title compound, C9H12NO2+·ClO4−, an intramolecular N—H⋯O interaction results in the formation of a six-membered ring having a twisted chair conformation. In the intermolecular O—H⋯O, N—H⋯O and C—H⋯O interactions link the molecules into a network. A weak C—H⋯π interaction is also found.
Related literature
There has been an increased interest in the enantiomeric preparation of β-amino acids as precursors for the synthesis of novel biologically active compounds, see: Arki et al. (2004); Cohen et al. (2002); Zeller et al. (1965). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536809016171/hk2675sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809016171/hk2675Isup2.hkl
Under nitrogen protection, benzaldehyde (3.18 g, 30 mmol), malonic acid (5.00 g, 48 mmol) and ammonium acetate (6.00 g, 78 mmol) were added into a flask and refluxed for 10 h to yield a colorless precipitate. The crude product was obtained after filtration, then it was dissolved in ethanol/ perchloric acid (1:1), after slowly evaporating over a period of 4 d, colorless prism crystals of the title compound suitable for X-ray analysis were isolated.
H atoms were positioned geometrically with O-H = 0.82 Å (for OH), N-H = 0.89 Å (for NH3), C-H = 0.93, 0.98 and 0.97 Å, for aromatic, methine and methylene H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,O,N), where x = 1.5 for OH and NH3 H and x = 1.2 for all other H atoms.
Data collection: CrystalClear (Rigaku/MSC, 2005); cell
CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line. | |
Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. |
C9H12NO2+·ClO4− | F(000) = 1104 |
Mr = 265.65 | Dx = 1.578 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 1979 reflections |
a = 6.6583 (13) Å | θ = 3.1–27.5° |
b = 13.826 (3) Å | µ = 0.36 mm−1 |
c = 24.300 (5) Å | T = 294 K |
V = 2237.0 (8) Å3 | Prism, colorless |
Z = 8 | 0.45 × 0.35 × 0.12 mm |
Rigaku SCXmini diffractometer | 2560 independent reflections |
Radiation source: fine-focus sealed tube | 1966 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
CCD_Profile_fitting scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (Blessing, 1995) | h = −8→8 |
Tmin = 0.863, Tmax = 0.957 | k = −17→17 |
21012 measured reflections | l = −31→31 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0351P)2 + 1.6729P] where P = (Fo2 + 2Fc2)/3 |
2560 reflections | (Δ/σ)max < 0.001 |
156 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C9H12NO2+·ClO4− | V = 2237.0 (8) Å3 |
Mr = 265.65 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 6.6583 (13) Å | µ = 0.36 mm−1 |
b = 13.826 (3) Å | T = 294 K |
c = 24.300 (5) Å | 0.45 × 0.35 × 0.12 mm |
Rigaku SCXmini diffractometer | 2560 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 1966 reflections with I > 2σ(I) |
Tmin = 0.863, Tmax = 0.957 | Rint = 0.058 |
21012 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.27 e Å−3 |
2560 reflections | Δρmin = −0.37 e Å−3 |
156 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.99041 (8) | 0.97917 (4) | 0.32015 (2) | 0.03337 (17) | |
O1 | 0.9660 (3) | 0.30715 (14) | 0.32107 (7) | 0.0428 (5) | |
H1 | 1.0262 | 0.3182 | 0.2923 | 0.064* | |
O2 | 0.7570 (2) | 0.22973 (13) | 0.26501 (6) | 0.0365 (4) | |
O3 | 1.0688 (3) | 1.07288 (12) | 0.30762 (7) | 0.0439 (5) | |
O4 | 0.9012 (3) | 0.94103 (16) | 0.27168 (8) | 0.0630 (6) | |
O5 | 1.1483 (3) | 0.91952 (15) | 0.33824 (10) | 0.0649 (6) | |
O6 | 0.8413 (3) | 0.98786 (15) | 0.36203 (8) | 0.0584 (6) | |
N1 | 0.4988 (3) | 0.09957 (16) | 0.31532 (7) | 0.0349 (5) | |
H1A | 0.5772 | 0.0550 | 0.3307 | 0.052* | |
H1B | 0.5491 | 0.1165 | 0.2828 | 0.052* | |
H1C | 0.3759 | 0.0756 | 0.3107 | 0.052* | |
C1 | 0.8076 (3) | 0.25365 (17) | 0.31064 (9) | 0.0289 (5) | |
C2 | 0.6999 (3) | 0.22487 (17) | 0.36217 (9) | 0.0306 (5) | |
H2A | 0.6911 | 0.2806 | 0.3863 | 0.037* | |
H2B | 0.7778 | 0.1756 | 0.3810 | 0.037* | |
C3 | 0.4889 (3) | 0.18613 (17) | 0.35177 (9) | 0.0289 (5) | |
H3 | 0.4139 | 0.2364 | 0.3321 | 0.035* | |
C4 | 0.3749 (3) | 0.16333 (17) | 0.40392 (9) | 0.0310 (5) | |
C5 | 0.3897 (4) | 0.0760 (2) | 0.43014 (10) | 0.0464 (7) | |
H5 | 0.4766 | 0.0289 | 0.4167 | 0.056* | |
C6 | 0.2752 (5) | 0.0576 (2) | 0.47670 (12) | 0.0565 (8) | |
H6 | 0.2840 | −0.0023 | 0.4940 | 0.068* | |
C7 | 0.1499 (4) | 0.1267 (2) | 0.49722 (11) | 0.0537 (8) | |
H7 | 0.0739 | 0.1143 | 0.5286 | 0.064* | |
C8 | 0.1367 (4) | 0.2138 (2) | 0.47155 (11) | 0.0493 (7) | |
H8 | 0.0524 | 0.2613 | 0.4857 | 0.059* | |
C9 | 0.2472 (4) | 0.2322 (2) | 0.42480 (9) | 0.0390 (6) | |
H9 | 0.2352 | 0.2916 | 0.4072 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0277 (3) | 0.0306 (3) | 0.0418 (3) | −0.0002 (2) | 0.0000 (2) | 0.0054 (3) |
O1 | 0.0336 (10) | 0.0582 (12) | 0.0365 (9) | −0.0188 (8) | 0.0033 (8) | −0.0024 (9) |
O2 | 0.0335 (9) | 0.0489 (10) | 0.0270 (8) | −0.0081 (8) | 0.0018 (7) | −0.0040 (7) |
O3 | 0.0422 (10) | 0.0332 (10) | 0.0564 (11) | −0.0080 (8) | −0.0014 (9) | 0.0095 (8) |
O4 | 0.0594 (13) | 0.0684 (14) | 0.0612 (13) | −0.0217 (11) | −0.0103 (11) | −0.0133 (11) |
O5 | 0.0553 (13) | 0.0554 (13) | 0.0841 (15) | 0.0219 (11) | −0.0044 (12) | 0.0233 (11) |
O6 | 0.0517 (12) | 0.0644 (13) | 0.0591 (12) | 0.0037 (10) | 0.0210 (10) | 0.0119 (11) |
N1 | 0.0307 (11) | 0.0439 (12) | 0.0300 (10) | −0.0085 (9) | 0.0019 (9) | −0.0045 (9) |
C1 | 0.0242 (11) | 0.0291 (12) | 0.0333 (12) | 0.0002 (9) | 0.0011 (9) | −0.0020 (10) |
C2 | 0.0296 (12) | 0.0359 (13) | 0.0262 (11) | −0.0056 (10) | −0.0013 (9) | −0.0024 (10) |
C3 | 0.0253 (11) | 0.0355 (13) | 0.0259 (11) | 0.0009 (10) | 0.0013 (9) | −0.0003 (9) |
C4 | 0.0238 (11) | 0.0435 (14) | 0.0256 (11) | −0.0039 (10) | −0.0005 (9) | 0.0008 (10) |
C5 | 0.0485 (16) | 0.0501 (16) | 0.0406 (14) | 0.0037 (13) | 0.0071 (13) | 0.0065 (13) |
C6 | 0.066 (2) | 0.0596 (19) | 0.0435 (16) | −0.0121 (16) | 0.0047 (15) | 0.0180 (14) |
C7 | 0.0425 (16) | 0.085 (2) | 0.0339 (14) | −0.0167 (16) | 0.0088 (12) | 0.0037 (15) |
C8 | 0.0388 (15) | 0.073 (2) | 0.0363 (14) | 0.0045 (14) | 0.0094 (12) | −0.0057 (14) |
C9 | 0.0323 (12) | 0.0520 (16) | 0.0326 (12) | 0.0016 (11) | 0.0003 (11) | 0.0012 (12) |
Cl1—O5 | 1.4067 (19) | C3—N1 | 1.490 (3) |
Cl1—O4 | 1.421 (2) | C3—C4 | 1.510 (3) |
Cl1—O6 | 1.4269 (19) | C3—H3 | 0.9800 |
Cl1—O3 | 1.4297 (18) | C4—C5 | 1.369 (3) |
O1—H1 | 0.8200 | C4—C9 | 1.373 (3) |
N1—H1A | 0.8900 | C5—C6 | 1.388 (4) |
N1—H1B | 0.8900 | C5—H5 | 0.9300 |
N1—H1C | 0.8900 | C6—C7 | 1.363 (4) |
C1—O2 | 1.205 (3) | C6—H6 | 0.9300 |
C1—O1 | 1.313 (3) | C7—C8 | 1.359 (4) |
C1—C2 | 1.497 (3) | C7—H7 | 0.9300 |
C2—C3 | 1.524 (3) | C8—C9 | 1.377 (3) |
C2—H2A | 0.9700 | C8—H8 | 0.9300 |
C2—H2B | 0.9700 | C9—H9 | 0.9300 |
O5—Cl1—O4 | 110.73 (15) | N1—C3—C2 | 109.89 (18) |
O5—Cl1—O6 | 110.28 (13) | C4—C3—C2 | 113.42 (18) |
O4—Cl1—O6 | 109.36 (13) | N1—C3—H3 | 107.5 |
O5—Cl1—O3 | 108.97 (12) | C4—C3—H3 | 107.5 |
O4—Cl1—O3 | 108.21 (12) | C2—C3—H3 | 107.5 |
O6—Cl1—O3 | 109.25 (12) | C5—C4—C9 | 119.0 (2) |
C1—O1—H1 | 109.5 | C5—C4—C3 | 122.6 (2) |
C3—N1—H1A | 109.5 | C9—C4—C3 | 118.5 (2) |
C3—N1—H1B | 109.5 | C4—C5—C6 | 120.1 (3) |
C3—N1—H1C | 109.5 | C4—C5—H5 | 120.0 |
H1A—N1—H1B | 109.5 | C6—C5—H5 | 120.0 |
H1A—N1—H1C | 109.5 | C7—C6—C5 | 120.4 (3) |
H1B—N1—H1C | 109.5 | C7—C6—H6 | 119.8 |
O2—C1—O1 | 123.8 (2) | C5—C6—H6 | 119.8 |
O2—C1—C2 | 124.2 (2) | C8—C7—C6 | 119.5 (3) |
O1—C1—C2 | 111.91 (19) | C8—C7—H7 | 120.2 |
C1—C2—C3 | 113.35 (18) | C6—C7—H7 | 120.2 |
C1—C2—H2A | 108.9 | C7—C8—C9 | 120.5 (3) |
C3—C2—H2A | 108.9 | C7—C8—H8 | 119.7 |
C1—C2—H2B | 108.9 | C9—C8—H8 | 119.7 |
C3—C2—H2B | 108.9 | C4—C9—C8 | 120.5 (3) |
H2A—C2—H2B | 107.7 | C4—C9—H9 | 119.7 |
N1—C3—C4 | 110.68 (19) | C8—C9—H9 | 119.7 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2 | 0.89 | 2.13 | 2.773 (3) | 128 |
C9—H9···O5i | 0.93 | 2.56 | 3.409 (3) | 152 |
C3—H3···O5i | 0.98 | 2.57 | 3.370 (3) | 139 |
C3—H3···O2ii | 0.98 | 2.58 | 3.286 (3) | 129 |
N1—H1C···O3iii | 0.89 | 2.05 | 2.892 (3) | 158 |
N1—H1B···O3iv | 0.89 | 2.28 | 3.046 (3) | 144 |
N1—H1A···O6v | 0.89 | 2.13 | 2.979 (3) | 159 |
O1—H1···O2vi | 0.82 | 2.41 | 3.046 (2) | 135 |
O1—H1···O4vii | 0.82 | 2.35 | 3.048 (3) | 143 |
C8—H8···Cg1viii | 0.93 | 2.79 | 3.688 (3) | 162 |
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x−1/2, y, −z+1/2; (iii) x−1, y−1, z; (iv) x−1/2, y−1, −z+1/2; (v) x, y−1, z; (vi) x+1/2, y, −z+1/2; (vii) −x+2, y−1/2, −z+1/2; (viii) −x−1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H12NO2+·ClO4− |
Mr | 265.65 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 294 |
a, b, c (Å) | 6.6583 (13), 13.826 (3), 24.300 (5) |
V (Å3) | 2237.0 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.45 × 0.35 × 0.12 |
Data collection | |
Diffractometer | Rigaku SCXmini diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.863, 0.957 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21012, 2560, 1966 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.110, 1.10 |
No. of reflections | 2560 |
No. of parameters | 156 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.37 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2 | 0.89 | 2.13 | 2.773 (3) | 128.1 |
C9—H9···O5i | 0.93 | 2.56 | 3.409 (3) | 152.4 |
C3—H3···O5i | 0.98 | 2.57 | 3.370 (3) | 138.8 |
C3—H3···O2ii | 0.98 | 2.58 | 3.286 (3) | 128.8 |
N1—H1C···O3iii | 0.89 | 2.05 | 2.892 (3) | 158.4 |
N1—H1B···O3iv | 0.89 | 2.28 | 3.046 (3) | 143.8 |
N1—H1A···O6v | 0.89 | 2.13 | 2.979 (3) | 159.4 |
O1—H1···O2vi | 0.82 | 2.41 | 3.046 (2) | 135.2 |
O1—H1···O4vii | 0.82 | 2.35 | 3.048 (3) | 143.0 |
C8—H8···Cg1viii | 0.93 | 2.79 | 3.688 (3) | 162.3 |
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x−1/2, y, −z+1/2; (iii) x−1, y−1, z; (iv) x−1/2, y−1, −z+1/2; (v) x, y−1, z; (vi) x+1/2, y, −z+1/2; (vii) −x+2, y−1/2, −z+1/2; (viii) −x−1, y+1/2, −z+1/2. |
Acknowledgements
This work was supported by the Technical Fund Financing Projects (grant Nos. 9207042464 and 9207041482) from Southeast University to ZRQ.
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Arki, A., Tourwe, D., Solymar, M., Fueloep, F., Armstrong, D. W. & Peter, A. (2004). Chromatographia, 60, S43–54. Web of Science CrossRef CAS Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Cohen, J. H., Abdel-Magid, A. F., Almond, H. R. Jr & Maryanoff, C. A. (2002). Tetrahedron Lett. 43, 1977–1981. Web of Science CrossRef CAS Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zeller, E. A., Ramachander, G., Fleisher, G. A., Ishimaru, T. & Zeller, V. (1965). Biochem. J. 95, 262–269. PubMed CAS Web of Science Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
β-Amino acids are important molecules, due to their pharmacological properties. Recently, there has been an increased interest in the enantiomeric preparations of β-amino acids, as precursors for the synthesis of novel biologically active compounds (Arki et al., 2004; Cohen et al., 2002; Zeller et al., 1965). We report herein the crystal structure of the title compound.
The asymmetric unit of the title compound contains one cation and one anion (Fig.1 ), in which the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C4-C9) is, of course, planar. Intramolecular N-H···O interaction results in the formation of a six-membered ring B (O2/N1/C1-C3/H1B) having twisted conformation.
In the crystal structure, intermolecular O-H···O, N-H···O and C-H···O interactions (Table 1) link the molecules into a network (Fig. 2), in which they may be effective in the stabilization of the structure. There also exists a weak C—H···π interaction (Table 1).