Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015793/ob6076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015793/ob6076Isup2.hkl |
CCDC reference: 175995
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.033
- wR factor = 0.092
- Data-to-parameter ratio = 8.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Crystals of (I) were grown from an aqueous solution of a 2:1 stoichiometric ratio of β-alanine and nitric acid by slow evaporation.
All the H atoms were located and refined isotropically. The C—H and N—H bond lengths are 0.94 (2)–0.97 (2) and 0.87 (2)–0.89 (2) Å, respectively.
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.
Fig. 1. The molecular structure of (I) with the atom-numbering scheme and 50% probability displacement ellipsoids (Johnson, 1976). | |
Fig. 2. Packing diagram of (I) viewed down the b axis. |
2C3H7NO2·H+·NO3− | F(000) = 512 |
Mr = 241.21 | Dx = 1.516 Mg m−3 Dm = 1.502 Mg m−3 Dm measured by flotation using a mixture of carbon tetrachloride and xylene |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 19.791 (1) Å | Cell parameters from 25 reflections |
b = 5.3220 (3) Å | θ = 11.3–14.0° |
c = 10.974 (1) Å | µ = 0.14 mm−1 |
β = 113.923 (6)° | T = 293 K |
V = 1056.57 (13) Å3 | Needle, colorless |
Z = 4 | 0.6 × 0.4 × 0.2 mm |
Enraf-Nonius sealed tube diffractometer | 798 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.014 |
Graphite monochromator | θmax = 25.0°, θmin = 2.3° |
ω–2θ scans | h = 0→23 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→6 |
Tmin = 0.863, Tmax = 0.970 | l = −13→11 |
941 measured reflections | 3 standard reflections every 60 min |
914 independent reflections | intensity decay: none |
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 | All H-atom parameters refined |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0459P)2 + 0.682P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
914 reflections | Δρmax = 0.31 e Å−3 |
104 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.103 (7) |
2C3H7NO2·H+·NO3− | V = 1056.57 (13) Å3 |
Mr = 241.21 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.791 (1) Å | µ = 0.14 mm−1 |
b = 5.3220 (3) Å | T = 293 K |
c = 10.974 (1) Å | 0.6 × 0.4 × 0.2 mm |
β = 113.923 (6)° |
Enraf-Nonius sealed tube diffractometer | 798 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.014 |
Tmin = 0.863, Tmax = 0.970 | 3 standard reflections every 60 min |
941 measured reflections | intensity decay: none |
914 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.092 | All H-atom parameters refined |
S = 1.09 | Δρmax = 0.31 e Å−3 |
914 reflections | Δρmin = −0.18 e Å−3 |
104 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 | ||
O1A | 0.19302 (7) | 0.4346 (2) | 0.27700 (10) | 0.0452 (4) | |
O1B | 0.21345 (6) | 0.1038 (2) | 0.41024 (9) | 0.0381 (4) | |
H1B | 0.2500 | 0.2500 | 0.5000 | 0.116 (14)* | |
C11 | 0.18276 (8) | 0.2140 (3) | 0.29461 (14) | 0.0321 (4) | |
C12 | 0.13324 (9) | 0.0474 (3) | 0.18276 (14) | 0.0369 (4) | |
H12A | 0.0973 (11) | −0.033 (4) | 0.2091 (19) | 0.050 (5)* | |
H12B | 0.1631 (11) | −0.083 (4) | 0.1728 (18) | 0.045 (5)* | |
C13 | 0.09337 (9) | 0.1853 (3) | 0.05321 (15) | 0.0377 (4) | |
H13A | 0.0660 (10) | 0.324 (4) | 0.0621 (17) | 0.042 (5)* | |
H13B | 0.0597 (11) | 0.077 (4) | −0.015 (2) | 0.050 (5)* | |
N11 | 0.14535 (8) | 0.2912 (3) | −0.00011 (14) | 0.0389 (4) | |
H1A | 0.1805 (12) | 0.375 (4) | 0.062 (2) | 0.052 (5)* | |
H2B | 0.1670 (11) | 0.179 (4) | −0.0288 (19) | 0.055 (6)* | |
H3C | 0.1196 (13) | 0.386 (4) | −0.071 (2) | 0.061 (6)* | |
N1 | 0.5000 | 0.0750 (4) | 0.7500 | 0.0379 (5) | |
O1 | 0.45215 (7) | 0.1894 (3) | 0.65579 (12) | 0.0553 (4) | |
O2 | 0.5000 | −0.1571 (4) | 0.7500 | 0.0753 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0592 (8) | 0.0348 (7) | 0.0367 (6) | −0.0082 (5) | 0.0143 (5) | −0.0005 (5) |
O1B | 0.0423 (6) | 0.0377 (7) | 0.0277 (6) | −0.0011 (5) | 0.0074 (4) | 0.0007 (4) |
C11 | 0.0317 (7) | 0.0343 (9) | 0.0303 (8) | 0.0006 (6) | 0.0126 (6) | −0.0012 (6) |
C12 | 0.0394 (8) | 0.0352 (8) | 0.0318 (8) | −0.0027 (7) | 0.0100 (7) | −0.0014 (6) |
C13 | 0.0314 (8) | 0.0471 (10) | 0.0316 (8) | −0.0014 (7) | 0.0097 (6) | −0.0003 (7) |
N11 | 0.0390 (8) | 0.0441 (9) | 0.0320 (8) | −0.0008 (7) | 0.0127 (6) | −0.0002 (6) |
N1 | 0.0377 (10) | 0.0440 (11) | 0.0341 (9) | 0.000 | 0.0168 (8) | 0.000 |
O1 | 0.0497 (7) | 0.0541 (8) | 0.0507 (8) | 0.0099 (6) | 0.0086 (6) | 0.0069 (6) |
O2 | 0.0956 (16) | 0.0438 (11) | 0.0539 (12) | 0.000 | −0.0034 (11) | 0.000 |
O1A—C11 | 1.2204 (19) | C13—H13A | 0.94 (2) |
O1B—C11 | 1.3030 (17) | C13—H13B | 0.96 (2) |
O1B—H1B | 1.2333 (10) | N11—H1A | 0.87 (2) |
C11—C12 | 1.509 (2) | N11—H2B | 0.87 (2) |
C12—C13 | 1.507 (2) | N11—H3C | 0.89 (2) |
C12—H12A | 0.97 (2) | N1—O2 | 1.235 (3) |
C12—H12B | 0.94 (2) | N1—O1i | 1.2419 (15) |
C13—N11 | 1.486 (2) | N1—O1 | 1.2419 (15) |
C11—O1B—H1B | 112.62 (10) | N11—C13—H13B | 107.2 (12) |
O1A—C11—O1B | 123.06 (13) | C12—C13—H13B | 111.9 (12) |
O1A—C11—C12 | 122.09 (13) | H13A—C13—H13B | 107.4 (15) |
O1B—C11—C12 | 114.84 (13) | C13—N11—H1A | 110.2 (13) |
C13—C12—C11 | 113.58 (13) | C13—N11—H2B | 113.9 (14) |
C13—C12—H12A | 109.3 (11) | H1A—N11—H2B | 106.2 (19) |
C11—C12—H12A | 109.3 (12) | C13—N11—H3C | 108.4 (14) |
C13—C12—H12B | 111.1 (11) | H1A—N11—H3C | 113 (2) |
C11—C12—H12B | 107.1 (11) | H2B—N11—H3C | 105.5 (19) |
H12A—C12—H12B | 106.2 (16) | O2—N1—O1i | 119.35 (10) |
N11—C13—C12 | 112.02 (13) | O2—N1—O1 | 119.35 (10) |
N11—C13—H13A | 105.2 (11) | O1i—N1—O1 | 121.3 (2) |
C12—C13—H13A | 112.7 (11) | ||
O1A—C11—C12—C13 | −5.2 (2) | C11—C12—C13—N11 | 63.60 (19) |
O1B—C11—C12—C13 | 174.93 (13) |
Symmetry code: (i) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1B—H1B···O1Bii | 1.23 (1) | 1.23 (1) | 2.467 (2) | 180 |
N11—H1A···O1A | 0.87 (2) | 2.29 (2) | 2.8971 (18) | 126.5 (17) |
N11—H1A···O1Biii | 0.87 (2) | 2.34 (2) | 3.0517 (18) | 139.1 (17) |
N11—H2B···O1Biv | 0.87 (2) | 2.01 (3) | 2.877 (2) | 175 (2) |
N11—H3C···O1iii | 0.89 (2) | 2.10 (3) | 2.908 (2) | 150 (2) |
N11—H3C···O2v | 0.89 (2) | 2.40 (2) | 3.0779 (15) | 133.2 (18) |
Symmetry codes: (ii) −x+1/2, −y+1/2, −z+1; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x, −y, z−1/2; (v) x−1/2, y+1/2, z−1. |
Experimental details
Crystal data | |
Chemical formula | 2C3H7NO2·H+·NO3− |
Mr | 241.21 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 19.791 (1), 5.3220 (3), 10.974 (1) |
β (°) | 113.923 (6) |
V (Å3) | 1056.57 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.6 × 0.4 × 0.2 |
Data collection | |
Diffractometer | Enraf-Nonius sealed tube diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.863, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 941, 914, 798 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.092, 1.09 |
No. of reflections | 914 |
No. of parameters | 104 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.31, −0.18 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), SHELXL97.
O1A—C11 | 1.2204 (19) | N1—O2 | 1.235 (3) |
O1B—C11 | 1.3030 (17) | N1—O1 | 1.2419 (15) |
O1A—C11—C12—C13 | −5.2 (2) | C11—C12—C13—N11 | 63.60 (19) |
O1B—C11—C12—C13 | 174.93 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1B—H1B···O1Bi | 1.2333 (10) | 1.2333 (10) | 2.467 (2) | 180.0 |
N11—H1A···O1A | 0.87 (2) | 2.29 (2) | 2.8971 (18) | 126.5 (17) |
N11—H1A···O1Bii | 0.87 (2) | 2.34 (2) | 3.0517 (18) | 139.1 (17) |
N11—H2B···O1Biii | 0.87 (2) | 2.01 (3) | 2.877 (2) | 175 (2) |
N11—H3C···O1ii | 0.89 (2) | 2.10 (3) | 2.908 (2) | 150 (2) |
N11—H3C···O2iv | 0.89 (2) | 2.40 (2) | 3.0779 (15) | 133.2 (18) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x, −y, z−1/2; (iv) x−1/2, y+1/2, z−1. |
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In amino acid–inorganic acid complexes, when the number of H atoms liberated from the inorganic acid is less than the number of amino acids, the H atom is shared by two amino acids, resulting in short symmetric O—H···O hydrogen bonds, as evidenced in triglycine sulfate (Kay, 1977), leading to phase transitions. In order to look for similar compounds, a systematic study of the behaviour of hydrogen bonding in amino acid–inorganic acid complexes was undertaken. In this context, the crystal structure of L-phenylalanine L-phenylalaninium perchlorate (Srinivasan & Rajaram, 1997), hydrogen bis[L-lysinium (2+)] dichloride perchlorate (Srinivasan et al., 2001a), L-lysine L-lysinium dichloride nitrate (Srinivasan et al., 2001b), L-phenylalanine-nitric acid (2/1) (Srinivasan et al., 2001c) and bis(L-proline) hydrogen perchlorate (Pandiarajan et al., 2001) have been reported. A similar stucture, L-phenylalanine L-phenylalaninium formate, has been reported by Gorbitz & Etter (1992). As part of this programme, the crystal structure of β-alanine with nitric acid was undertaken to study the nature of the hydrogen bonding in the presence of an inorganic acid.
The asymmetric unit contains one β-alanine residue and a nitrate anion which lies on the twofold axis. The backbone conformation angles ψ1 and ψ2 are -5.2 (2) and 174.9 (1)°, respectively, for the alanine residue. The straight-chain conformation angle χ1 is in gauche I form [63.6 (2)°]. This tendency of twisting of the C—N bond is found in various amino acids (Lakshminarayanan et al., 1967).
The nitrate anion plays a vital role in forming hydrogen bonds with the alanine residue and stabilizing the structure. The H1B atom, which lies on a center of symmetry, links the two alanine residues through a strong symmetric O—H···O hydrogen bond [O1B···O1B(1/2 - x, 1/2 - y, 1 - z) 2.467 (2) Å]. The large Uiso value of H1B suggests that this atom may have positional or flip–flop disorder, leading to the switching of roles of the cation and zwitterion in a time-averaged equilibrium (Jeffrey & Saenger, 1991). A similar feature of short hydrogen bonding has been observed in L-phenylalanine L-phenylalaninium formate, L-phenylalanine L-phenylalaninium perchlorate, hydrogen bis[L-lysinium (2+)] dichloride perchlorate, L-lysine L-lysinium dichloride nitrate, L-phenylalanine-nitric acid (2/1) and bis(L-proline) hydrogen perchlorate. In these compounds, the hydrogen bond can be termed as a possible symmetric hydrogen bond. At low temperature, the crystal of (I) may go into non-centrosymmetric space group Cc, triggering a structural phase transition leading to interesting physical properties.
The O1 and O2 atoms of the nitrate anion, as acceptors, links the amino N atom in a three-centred hydrogen bond involving the alanine residue. This O2 atom of the nitrate anion, sitting on the twofold axis, links two symmetry-related β-alanine residues. A three-centred hydrogen bond is observed involving the alanine residue (amino N atom) and the carboxyl O1A (intramolecular hydrogen bond) and O1B (Z2 head-to-tail sequence) atoms. A glide-related head-to-tail sequence is observed, since N11—H2B···O1B(x, -y, z - 1/2) connects two glide-related amino acids (Vijayan, 1988).