2-Carb­oxy-1-phenyl­ethanaminium perchlorate

Li, X.-Z.; Li, H.; Qu, Z.-R.

doi:10.1107/S1600536809016171

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1214

doi:10.1107/S1600536809016171

Open

access

2-Carboxy-1-phenylethanaminium perchlorate

Xiu-Zhi Li,^a Hui Li ^a and Zhi-Rong Qu ^a ^*

^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

(Received 25 April 2009; accepted 29 April 2009; online 7 May 2009)

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 crystal structure, 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

C₉H₁₂NO₂⁺·ClO₄⁻
M_r = 265.65
Orthorhombic, P b c a
a = 6.6583 (13) Å
b = 13.826 (3) Å
c = 24.300 (5) Å
V = 2237.0 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 294 K
0.45 × 0.35 × 0.12 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.863, T_max = 0.957
21012 measured reflections
2560 independent reflections
1966 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.110
S = 1.10
2560 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O3^iv	0.89	2.28	3.046 (3)	144
N1—H1A⋯O6^v	0.89	2.13	2.979 (3)	159
O1—H1⋯O2^vi	0.82	2.41	3.046 (2)	135
O1—H1⋯O4^vii	0.82	2.35	3.048 (3)	143
C8—H8⋯Cg1^viii	0.93	2.79	3.688 (3)	162
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) x-1, y-1, z; (iv) $[x-{\script{1\over 2}}, y-1, -z+{\script{1\over 2}}]$ ; (v) x, y-1, z; (vi) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (vii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (viii) $[-x-1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg1 is the centroid of the C4–C9 ring.

Data collection: CrystalClear (Rigaku/MSC, 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: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809016171/hk2675sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016171/hk2675Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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). Cg1 is the centroid of the C4–C9 ring.

Experimental top

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.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: 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).

Figures top

	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.

2-Carboxy-1-phenylethanaminium perchlorate top

Crystal data top

C₉H₁₂NO₂⁺·ClO₄⁻	F(000) = 1104
M_r = 265.65	D_x = 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

Data collection top

Rigaku SCXmini diffractometer	2560 independent reflections
Radiation source: fine-focus sealed tube	1966 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
CCD_Profile_fitting scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (Blessing, 1995)	h = −8→8
T_min = 0.863, T_max = 0.957	k = −17→17
21012 measured reflections	l = −31→31

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0351P)² + 1.6729P] where P = (F_o² + 2F_c²)/3
2560 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₉H₁₂NO₂⁺·ClO₄⁻	V = 2237.0 (8) Å³
M_r = 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

Data collection top

Rigaku SCXmini diffractometer	2560 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	1966 reflections with I > 2σ(I)
T_min = 0.863, T_max = 0.957	R_int = 0.058
21012 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.10	Δρ_max = 0.27 e Å⁻³
2560 reflections	Δρ_min = −0.37 e Å⁻³
156 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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···O3^iv	0.89	2.28	3.046 (3)	144
N1—H1A···O6^v	0.89	2.13	2.979 (3)	159
O1—H1···O2^vi	0.82	2.41	3.046 (2)	135
O1—H1···O4^vii	0.82	2.35	3.048 (3)	143
C8—H8···Cg1^viii	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⁻
M_r	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)
T_min, T_max	0.863, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	21012, 2560, 1966
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.37

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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···O3^iv	0.89	2.28	3.046 (3)	143.8
N1—H1A···O6^v	0.89	2.13	2.979 (3)	159.4
O1—H1···O2^vi	0.82	2.41	3.046 (2)	135.2
O1—H1···O4^vii	0.82	2.35	3.048 (3)	143.0
C8—H8···Cg1^viii	0.93	2.79	3.688 (3)	162.3

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