Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801018128/wn6064sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801018128/wn6064Isup2.hkl |
CCDC reference: 176046
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- Disorder in solvent or counterion
- R factor = 0.062
- wR factor = 0.216
- Data-to-parameter ratio = 9.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 27.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was crystallized from an aqueous solution of β-alanine and perchloric acid in a 1:1 stoichiometric ratio by slow evaporation.
The perchlorate anion exhibits orientational disorder. The site-occupation factors for O1/O2/O3/O4 and O1'/O2'/O3'/O4' are 0.57 and 0.43, respectively. These O atoms were refined anisotropically with fixed site-occupation factors. All H atoms were fixed by geometric constraints using HFIX and allowed to ride on the attached atom.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.
C3H8NO2+·ClO4− | F(000) = 392 |
Mr = 189.55 | Dx = 1.697 Mg m−3 Dm = 1.690 Mg m−3 Dm measured by flotation using a mixture of carbon tetrachloride and xylene |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.024 (3) Å | Cell parameters from 25 reflections |
b = 7.556 (4) Å | θ = 6.4–13.6° |
c = 14.102 (4) Å | µ = 0.50 mm−1 |
β = 97.52 (4)° | T = 293 K |
V = 742.0 (5) Å3 | Needle, colorless |
Z = 4 | 0.3 × 0.2 × 0.1 mm |
Enraf-Nonis CAD-4 diffractometer | 1049 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 24.8°, θmin = 2.9° |
ω–2θ scans | h = −8→8 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→8 |
Tmin = 0.886, Tmax = 0.951 | l = 0→16 |
1521 measured reflections | 3 standard reflections every 60 min |
1297 independent reflections | intensity decay: none |
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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.216 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.1724P)2] where P = (Fo2 + 2Fc2)/3 |
1297 reflections | (Δ/σ)max = 0.001 |
136 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C3H8NO2+·ClO4− | V = 742.0 (5) Å3 |
Mr = 189.55 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.024 (3) Å | µ = 0.50 mm−1 |
b = 7.556 (4) Å | T = 293 K |
c = 14.102 (4) Å | 0.3 × 0.2 × 0.1 mm |
β = 97.52 (4)° |
Enraf-Nonis CAD-4 diffractometer | 1049 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.029 |
Tmin = 0.886, Tmax = 0.951 | 3 standard reflections every 60 min |
1521 measured reflections | intensity decay: none |
1297 independent reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.216 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.48 e Å−3 |
1297 reflections | Δρmin = −0.39 e Å−3 |
136 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 | Occ. (<1) | |
Cl1 | 0.13952 (11) | 0.24718 (8) | 0.63655 (6) | 0.0451 (5) | |
O1 | 0.066 (4) | 0.366 (2) | 0.5722 (12) | 0.205 (12) | 0.57 |
O2 | 0.0861 (17) | 0.2379 (18) | 0.7242 (9) | 0.142 (5) | 0.57 |
O3 | 0.3261 (15) | 0.273 (2) | 0.6322 (7) | 0.178 (7) | 0.57 |
O4 | 0.1127 (18) | 0.0873 (11) | 0.5831 (7) | 0.122 (3) | 0.57 |
O1' | 0.117 (3) | 0.380 (2) | 0.5706 (14) | 0.113 (6) | 0.43 |
O2' | 0.1444 (14) | 0.3251 (11) | 0.7333 (8) | 0.074 (3) | 0.43 |
O3' | 0.316 (3) | 0.157 (3) | 0.6435 (11) | 0.197 (13) | 0.43 |
O4' | −0.016 (3) | 0.153 (4) | 0.6366 (11) | 0.236 (11) | 0.43 |
O1A | 0.6625 (3) | 0.9350 (3) | 0.58291 (18) | 0.0535 (7) | |
O1B | 0.4108 (4) | 0.7704 (3) | 0.5274 (2) | 0.0569 (8) | |
H12 | 0.3714 | 0.8640 | 0.5028 | 0.085* | |
C11 | 0.5775 (4) | 0.7949 (4) | 0.5755 (2) | 0.0401 (7) | |
C12 | 0.6627 (4) | 0.6308 (5) | 0.6248 (2) | 0.0509 (8) | |
H12A | 0.5684 | 0.5772 | 0.6603 | 0.061* | |
H12B | 0.6914 | 0.5465 | 0.5768 | 0.061* | |
C13 | 0.8431 (5) | 0.6667 (4) | 0.6921 (2) | 0.0512 (9) | |
H13A | 0.8164 | 0.7550 | 0.7386 | 0.061* | |
H13B | 0.8829 | 0.5591 | 0.7266 | 0.061* | |
N11 | 1.0036 (4) | 0.7311 (3) | 0.6404 (2) | 0.0487 (8) | |
H11A | 1.1073 | 0.7512 | 0.6824 | 0.073* | |
H11B | 0.9682 | 0.8308 | 0.6094 | 0.073* | |
H11C | 1.0304 | 0.6493 | 0.5987 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0484 (7) | 0.0417 (7) | 0.0469 (7) | 0.0035 (3) | 0.0124 (4) | 0.0032 (2) |
O1 | 0.40 (3) | 0.139 (13) | 0.076 (8) | 0.160 (16) | 0.024 (11) | −0.001 (8) |
O2 | 0.108 (7) | 0.243 (16) | 0.072 (5) | −0.013 (7) | 0.003 (4) | 0.003 (8) |
O3 | 0.096 (6) | 0.33 (2) | 0.092 (6) | −0.062 (8) | −0.049 (5) | 0.056 (8) |
O4 | 0.178 (9) | 0.084 (4) | 0.109 (6) | −0.025 (5) | 0.039 (7) | 0.003 (4) |
O1' | 0.184 (12) | 0.087 (10) | 0.072 (9) | −0.032 (9) | 0.031 (8) | 0.014 (7) |
O2' | 0.076 (6) | 0.081 (6) | 0.062 (4) | 0.017 (4) | −0.004 (4) | −0.015 (4) |
O3' | 0.195 (17) | 0.32 (3) | 0.090 (9) | 0.166 (19) | 0.081 (11) | 0.059 (13) |
O4' | 0.197 (16) | 0.37 (3) | 0.113 (11) | −0.163 (18) | −0.102 (12) | 0.075 (15) |
O1A | 0.0478 (14) | 0.0367 (12) | 0.0738 (16) | 0.0015 (9) | −0.0004 (11) | 0.0018 (10) |
O1B | 0.0460 (15) | 0.0408 (13) | 0.0805 (19) | −0.0022 (8) | −0.0042 (13) | 0.0109 (9) |
C11 | 0.0378 (15) | 0.0401 (14) | 0.0439 (16) | 0.0016 (13) | 0.0106 (12) | −0.0043 (13) |
C12 | 0.0535 (18) | 0.0421 (18) | 0.062 (2) | 0.0031 (14) | 0.0263 (14) | 0.0043 (13) |
C13 | 0.0537 (18) | 0.049 (2) | 0.0516 (18) | 0.0076 (14) | 0.0096 (14) | 0.0068 (12) |
N11 | 0.0452 (16) | 0.0476 (16) | 0.0522 (17) | 0.0052 (10) | 0.0026 (12) | 0.0012 (10) |
Cl1—O4' | 1.305 (14) | C11—C12 | 1.506 (4) |
Cl1—O1 | 1.333 (15) | C12—C13 | 1.505 (5) |
Cl1—O3 | 1.334 (11) | C12—H12A | 0.9700 |
Cl1—O2 | 1.339 (13) | C12—H12B | 0.9700 |
Cl1—O1' | 1.365 (17) | C13—N11 | 1.502 (4) |
Cl1—O3' | 1.410 (14) | C13—H13A | 0.9700 |
Cl1—O4 | 1.424 (9) | C13—H13B | 0.9700 |
Cl1—O2' | 1.483 (10) | N11—H11A | 0.8900 |
O1A—C11 | 1.213 (4) | N11—H11B | 0.8900 |
O1B—C11 | 1.287 (4) | N11—H11C | 0.8900 |
O1B—H12 | 0.8200 | ||
O4'—Cl1—O1 | 96.7 (15) | O1'—Cl1—O2' | 108.7 (9) |
O4'—Cl1—O3 | 155.2 (17) | O3'—Cl1—O2' | 102.4 (9) |
O1—Cl1—O3 | 99.6 (12) | O4—Cl1—O2' | 144.1 (6) |
O4'—Cl1—O2 | 68.6 (11) | C11—O1B—H12 | 109.5 |
O1—Cl1—O2 | 122.1 (10) | O1A—C11—O1B | 125.0 (3) |
O3—Cl1—O2 | 116.4 (6) | O1A—C11—C12 | 121.2 (3) |
O4'—Cl1—O1' | 112.4 (12) | O1B—C11—C12 | 113.8 (3) |
O1—Cl1—O1' | 16.2 (17) | C13—C12—C11 | 113.2 (3) |
O3—Cl1—O1' | 83.5 (11) | C13—C12—H12A | 108.9 |
O2—Cl1—O1' | 130.2 (11) | C11—C12—H12A | 108.9 |
O4'—Cl1—O3' | 117.7 (18) | C13—C12—H12B | 108.9 |
O1—Cl1—O3' | 129.5 (12) | C11—C12—H12B | 108.9 |
O3—Cl1—O3' | 38.1 (12) | H12A—C12—H12B | 107.8 |
O2—Cl1—O3' | 105.1 (8) | N11—C13—C12 | 112.0 (3) |
O1'—Cl1—O3' | 115.3 (12) | N11—C13—H13A | 109.2 |
O4'—Cl1—O4 | 58.9 (14) | C12—C13—H13A | 109.2 |
O1—Cl1—O4 | 101.5 (9) | N11—C13—H13B | 109.2 |
O3—Cl1—O4 | 99.4 (8) | C12—C13—H13B | 109.2 |
O2—Cl1—O4 | 114.2 (7) | H13A—C13—H13B | 107.9 |
O1'—Cl1—O4 | 105.6 (10) | C13—N11—H11A | 109.5 |
O3'—Cl1—O4 | 71.3 (11) | C13—N11—H11B | 109.5 |
O4'—Cl1—O2' | 97.7 (12) | H11A—N11—H11B | 109.5 |
O1—Cl1—O2' | 108.6 (7) | C13—N11—H11C | 109.5 |
O3—Cl1—O2' | 94.6 (7) | H11A—N11—H11C | 109.5 |
O2—Cl1—O2' | 31.5 (6) | H11B—N11—H11C | 109.5 |
O1A—C11—C12—C13 | 8.0 (4) | C11—C12—C13—N11 | −65.0 (3) |
O1B—C11—C12—C13 | −171.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1B—H12···O1Ai | 0.82 | 1.94 | 2.726 (3) | 161 |
N11—H11A···O2ii | 0.89 | 2.37 | 3.243 (12) | 165 |
N11—H11A···O2′ii | 0.89 | 2.06 | 2.939 (10) | 172 |
N11—H11A···O3ii | 0.89 | 2.60 | 3.288 (9) | 135 |
N11—H11A···O3′ii | 0.89 | 2.55 | 3.19 (2) | 130 |
N11—H11B···O4iii | 0.89 | 2.24 | 2.941 (9) | 135 |
N11—H11B···O4′iii | 0.89 | 2.46 | 3.19 (3) | 139 |
N11—H11B···O1A | 0.89 | 2.27 | 2.875 (3) | 125 |
N11—H11C···O1iv | 0.89 | 2.19 | 2.971 (15) | 146 |
N11—H11C···O1′iv | 0.89 | 2.17 | 2.97 (2) | 149 |
N11—H11C···O1v | 0.89 | 2.42 | 3.064 (17) | 129 |
N11—H11C···O1′v | 0.89 | 2.49 | 3.10 (2) | 127 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x+1, y+1, z; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C3H8NO2+·ClO4− |
Mr | 189.55 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.024 (3), 7.556 (4), 14.102 (4) |
β (°) | 97.52 (4) |
V (Å3) | 742.0 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.50 |
Crystal size (mm) | 0.3 × 0.2 × 0.1 |
Data collection | |
Diffractometer | Enraf-Nonis CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.886, 0.951 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1521, 1297, 1049 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.591 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.216, 1.12 |
No. of reflections | 1297 |
No. of parameters | 136 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.39 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), SHELXL97.
O1A—C11 | 1.213 (4) | O1B—C11 | 1.287 (4) |
O1A—C11—C12—C13 | 8.0 (4) | C11—C12—C13—N11 | −65.0 (3) |
O1B—C11—C12—C13 | −171.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1B—H12···O1Ai | 0.82 | 1.94 | 2.726 (3) | 161 |
N11—H11A···O2ii | 0.89 | 2.37 | 3.243 (12) | 165 |
N11—H11A···O2'ii | 0.89 | 2.06 | 2.939 (10) | 172 |
N11—H11A···O3ii | 0.89 | 2.60 | 3.288 (9) | 135 |
N11—H11A···O3'ii | 0.89 | 2.55 | 3.19 (2) | 130 |
N11—H11B···O4iii | 0.89 | 2.24 | 2.941 (9) | 135 |
N11—H11B···O4'iii | 0.89 | 2.46 | 3.19 (3) | 139 |
N11—H11B···O1A | 0.89 | 2.27 | 2.875 (3) | 125 |
N11—H11C···O1iv | 0.89 | 2.19 | 2.971 (15) | 146 |
N11—H11C···O1'iv | 0.89 | 2.17 | 2.97 (2) | 149 |
N11—H11C···O1v | 0.89 | 2.42 | 3.064 (17) | 129 |
N11—H11C···O1'v | 0.89 | 2.49 | 3.10 (2) | 127 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x+1, y+1, z; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1. |
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Alanine is the second simplest amino acid, but the most common in proteins. β-Alanine is the only naturally occurring β-amino acid. The crystal structure of L-alanine (Lehmann et al., 1972), L-alanine hydrochloride (Di Blasio et al., 1977), β-alanine (Papavinasam et al., 1986), bis(DL-alanine) phosphate (Averbuch-Pouchot et al., 1988), DL-alanine nitrate (Asath Bahadur & Rajaram, 1995) and bis (β-alanine) hydrogen nitrate (Sridhar et al., 2001) have been reported. In the present investigation, β-alanine was reacted with perchloric acid to produe the title compound (I) which was investigated to study the conformation and hydrogen bonds in the presence of an inorganic acid.
The asymmetric unit of (I) consists of one β-alaninium residue and a perchlorate anion. The backbone conformation angles ψ1 and ψ2 are 8.0 (4) and -171.5 (3)°, respectively, for the alaninium residue. The straight-chain conformation angle χ1 is in the gauche II form [-65.0 (3)°].
In the perchlorate anion, all the O atoms are found to have orientational disorder. This leads to considerable variations in the Cl—O bond distances and the tetrahedral symmetry of the anion.
In biological molecules, such as amino acids, hydrogen bonds play an important role. In the present structure, a normal O—H···O hydrogen bond (2.726 Å) is observed which forms a dimer between the carboxylic acid groups of two β-alaninium residues related by an inversion center. The hydrogen bonds that exist between the perchlorate anion and the alaninium residue play an important role in stabilizing the structure. The amino N atom is also involved in a chelated three-centered hydrogen bond with acceptor O atoms (O2 and O3) of the perchlorate anion. The amino N atom is also found to be engaged in a three-centered hydrogen bond, with (i) the carboxyl atom O1A (intramolecular hydrogen bond) and atom O4 of the perchlorate anion and (ii) two O atoms of the perchlorate anions across a center of inversion, forming infinite chains. The presence of the three-centered hydrogen bond is due to an excess of acceptors over donors or proton deficiency (Jeffrey & Saenger, 1991).