Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014040/ob6065sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014040/ob6065Isup2.hkl |
CCDC reference: 172223
The title compound was crystallized from an aqueous solution of a 2:1 stoichiometric ratio of L-lysine hydrochloride and nitric acid by slow evaporation.
The nitrate O atoms are disordered due to the presence of pseudo-twofold symmetry. The site-occupation factors for O1/O2/O3 and O1'/O2'/O3'are 0.54 (1) and 0.46 (1). Since the geometry of these disordered atoms differ significantly from expected values, the DFIX constraint were used to fix the geometry of the nitrate anion as free variable. In the case of lysinium molecule II, atoms C23, C24, C25 and C26 showed large displacement amplitudes with unusual C—C distances, indicating disorder. Since this disorder cannot be explained satisfactorily, these atoms were refined using DFIX constraints. The H2 atom involved in the symmetric hydrogen bond was located and refined while all the other H atoms were fixed by geometric constraints using HFIX and were allowed to ride on the preceding 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.
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 a axis. |
2C6H15N2O2+·H+·NO3−·2Cl− | Dx = 1.341 Mg m−3 Dm = 1.333 Mg m−3 Dm measured by flotation |
Mr = 428.32 | Mo Kα radiation, λ = 0.71070 Å |
Orthorhombic, P212121 | Cell parameters from 20 reflections |
a = 4.9846 (2) Å | θ = 10.2–14.3° |
b = 20.604 (2) Å | µ = 0.35 mm−1 |
c = 20.663 (2) Å | T = 293 K |
V = 2122.1 (3) Å3 | Needles, colorless |
Z = 4 | 0.5 × 0.3 × 0.3 mm |
F(000) = 912 |
Enraf-Nonius sealed tube diffractometer | 1805 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.046 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω–2θ scans | h = −1→5 |
Absorption correction: ψ scan (North et al., 1968) | k = −2→24 |
Tmin = 0.883, Tmax = 0.901 | l = −2→24 |
3313 measured reflections | 3 standard reflections every 60 min |
2910 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)] = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.190 | w = 1/[σ2(Fo2) + (0.0869P)2 + 3.2345P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.002 |
2910 reflections | Δρmax = 0.53 e Å−3 |
270 parameters | Δρmin = −0.42 e Å−3 |
16 restraints | Absolute structure: Flack (1983), 714 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.2 (2) |
2C6H15N2O2+·H+·NO3−·2Cl− | V = 2122.1 (3) Å3 |
Mr = 428.32 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 4.9846 (2) Å | µ = 0.35 mm−1 |
b = 20.604 (2) Å | T = 293 K |
c = 20.663 (2) Å | 0.5 × 0.3 × 0.3 mm |
Enraf-Nonius sealed tube diffractometer | 1805 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.046 |
Tmin = 0.883, Tmax = 0.901 | 3 standard reflections every 60 min |
3313 measured reflections | intensity decay: none |
2910 independent reflections |
R[F2 > 2σ(F2)] = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.190 | Δρmax = 0.53 e Å−3 |
S = 1.03 | Δρmin = −0.42 e Å−3 |
2910 reflections | Absolute structure: Flack (1983), 714 Friedel pairs |
270 parameters | Absolute structure parameter: 0.2 (2) |
16 restraints |
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) | |
N1 | 0.262 (3) | 0.3115 (5) | 0.4110 (4) | 0.105 (4) | |
O1 | 0.307 (5) | 0.2948 (14) | 0.3554 (9) | 0.132 (12) | 0.536 (14) |
O2 | 0.426 (7) | 0.3066 (16) | 0.4505 (13) | 0.39 (4) | 0.536 (14) |
O3 | 0.020 (5) | 0.2971 (10) | 0.4253 (10) | 0.28 (3) | 0.536 (14) |
O1' | 0.241 (5) | 0.2826 (8) | 0.3629 (6) | 0.047 (4) | 0.464 (14) |
O2' | 0.268 (3) | 0.2999 (6) | 0.4668 (5) | 0.044 (4) | 0.464 (14) |
O3' | 0.294 (5) | 0.3749 (6) | 0.4049 (8) | 0.132 (9) | 0.464 (14) |
Cl1 | 0.2235 (4) | 0.67394 (7) | 0.68813 (7) | 0.0394 (4) | |
Cl2 | 0.2349 (4) | 0.65481 (10) | 0.15174 (8) | 0.0596 (6) | |
O11 | 0.3233 (9) | 0.7006 (2) | 0.5069 (2) | 0.0424 (12) | |
O12 | 0.4692 (13) | 0.6191 (3) | 0.4466 (3) | 0.0716 (19) | |
C11 | 0.4836 (13) | 0.6575 (3) | 0.4945 (3) | 0.0343 (15) | |
C12 | 0.7287 (15) | 0.6471 (3) | 0.5372 (3) | 0.0325 (14) | |
H12 | 0.8907 | 0.6493 | 0.5104 | 0.039* | |
N11 | 0.7347 (13) | 0.7003 (2) | 0.5849 (2) | 0.0360 (12) | |
H11A | 0.7420 | 0.7382 | 0.5643 | 0.054* | |
H11B | 0.8784 | 0.6961 | 0.6101 | 0.054* | |
H11C | 0.5871 | 0.6988 | 0.6091 | 0.054* | |
C13 | 0.7230 (19) | 0.5813 (3) | 0.5729 (3) | 0.0482 (18) | |
H13A | 0.8561 | 0.5819 | 0.6072 | 0.058* | |
H13B | 0.5484 | 0.5756 | 0.5929 | 0.058* | |
C14 | 0.777 (3) | 0.5250 (3) | 0.5296 (4) | 0.068 (2) | |
H14A | 0.9538 | 0.5299 | 0.5107 | 0.081* | |
H14B | 0.6472 | 0.5251 | 0.4946 | 0.081* | |
C15 | 0.763 (2) | 0.4599 (3) | 0.5644 (3) | 0.061 (2) | |
H15A | 0.9035 | 0.4577 | 0.5969 | 0.073* | |
H15B | 0.5916 | 0.4559 | 0.5863 | 0.073* | |
C16 | 0.795 (2) | 0.4064 (3) | 0.5188 (4) | 0.066 (2) | |
H16A | 0.9683 | 0.4101 | 0.4980 | 0.079* | |
H16B | 0.6582 | 0.4101 | 0.4855 | 0.079* | |
N12 | 0.7732 (15) | 0.3421 (2) | 0.5495 (3) | 0.0499 (15) | |
H12A | 0.8843 | 0.3401 | 0.5832 | 0.075* | |
H12B | 0.8167 | 0.3115 | 0.5210 | 0.075* | |
H12C | 0.6056 | 0.3358 | 0.5630 | 0.075* | |
O21 | 1.1690 (10) | 0.6936 (2) | 0.3192 (3) | 0.0530 (14) | |
O22 | 1.0639 (13) | 0.6106 (3) | 0.3822 (3) | 0.0726 (19) | |
H2 | 1.23 (2) | 0.618 (4) | 0.414 (4) | 0.09 (3)* | |
C21 | 1.0223 (15) | 0.6493 (4) | 0.3352 (3) | 0.0441 (18) | |
C22 | 0.7638 (17) | 0.6343 (3) | 0.2998 (3) | 0.0428 (16) | |
H22 | 0.6122 | 0.6387 | 0.3297 | 0.051* | |
N21 | 0.7356 (14) | 0.6821 (2) | 0.2464 (2) | 0.0404 (13) | |
H21A | 0.7493 | 0.7222 | 0.2623 | 0.061* | |
H21B | 0.5762 | 0.6773 | 0.2276 | 0.061* | |
H21C | 0.8646 | 0.6757 | 0.2173 | 0.061* | |
C23 | 0.764 (3) | 0.5646 (4) | 0.2701 (5) | 0.103 (4) | |
H23A | 0.6181 | 0.5628 | 0.2391 | 0.123* | |
H23B | 0.9292 | 0.5599 | 0.2459 | 0.123* | |
C24 | 0.741 (5) | 0.5114 (5) | 0.3091 (6) | 0.131 (5) | |
H24A | 0.5666 | 0.5122 | 0.3301 | 0.157* | |
H24B | 0.8767 | 0.5135 | 0.3426 | 0.157* | |
C25 | 0.771 (3) | 0.4458 (4) | 0.2714 (6) | 0.101 (4) | |
H25A | 0.6238 | 0.4402 | 0.2413 | 0.121* | |
H25B | 0.9380 | 0.4455 | 0.2472 | 0.121* | |
C26 | 0.771 (3) | 0.3959 (7) | 0.3170 (5) | 0.138 (6) | |
H26A | 0.9278 | 0.4008 | 0.3444 | 0.166* | |
H26B | 0.6139 | 0.4007 | 0.3442 | 0.166* | |
N22 | 0.7720 (17) | 0.3334 (3) | 0.2914 (3) | 0.0698 (19) | |
H22A | 0.6222 | 0.3270 | 0.2688 | 0.105* | |
H22B | 0.7807 | 0.3046 | 0.3235 | 0.105* | |
H22C | 0.9134 | 0.3286 | 0.2656 | 0.105* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.165 (12) | 0.075 (7) | 0.074 (8) | 0.000 (10) | 0.017 (10) | 0.027 (6) |
O1 | 0.069 (15) | 0.18 (2) | 0.15 (2) | −0.042 (13) | 0.050 (12) | 0.007 (16) |
O2 | 0.68 (9) | 0.18 (3) | 0.31 (4) | −0.11 (4) | −0.42 (6) | 0.05 (3) |
O3 | 0.71 (8) | 0.073 (12) | 0.073 (12) | −0.06 (3) | 0.13 (3) | −0.013 (10) |
O1' | 0.044 (10) | 0.058 (8) | 0.038 (7) | −0.001 (9) | −0.010 (8) | −0.023 (6) |
O2' | 0.039 (7) | 0.058 (7) | 0.034 (6) | 0.003 (8) | 0.007 (7) | −0.022 (6) |
O3' | 0.17 (2) | 0.078 (12) | 0.145 (15) | −0.019 (15) | 0.014 (19) | 0.009 (10) |
Cl1 | 0.0347 (9) | 0.0437 (8) | 0.0398 (8) | −0.0026 (9) | −0.0009 (9) | −0.0006 (7) |
Cl2 | 0.0344 (10) | 0.0997 (15) | 0.0449 (9) | −0.0028 (14) | 0.0008 (10) | −0.0061 (9) |
O11 | 0.031 (3) | 0.043 (3) | 0.053 (3) | 0.002 (2) | −0.008 (2) | 0.006 (2) |
O12 | 0.060 (4) | 0.098 (5) | 0.057 (3) | 0.028 (4) | −0.029 (3) | −0.028 (3) |
C11 | 0.024 (3) | 0.039 (4) | 0.039 (4) | 0.000 (3) | 0.000 (3) | 0.002 (3) |
C12 | 0.031 (4) | 0.034 (3) | 0.032 (3) | −0.009 (4) | 0.001 (3) | 0.003 (2) |
N11 | 0.038 (3) | 0.032 (2) | 0.038 (3) | −0.002 (4) | −0.007 (4) | 0.003 (2) |
C13 | 0.058 (5) | 0.041 (4) | 0.046 (4) | 0.003 (5) | −0.012 (5) | 0.002 (3) |
C14 | 0.103 (8) | 0.044 (4) | 0.056 (4) | 0.007 (7) | 0.004 (7) | 0.003 (3) |
C15 | 0.079 (6) | 0.049 (4) | 0.054 (4) | −0.001 (6) | 0.002 (6) | 0.003 (3) |
C16 | 0.088 (7) | 0.052 (4) | 0.056 (4) | 0.004 (6) | −0.012 (6) | 0.007 (3) |
N12 | 0.056 (4) | 0.042 (3) | 0.052 (3) | −0.001 (4) | 0.000 (4) | 0.001 (2) |
O21 | 0.036 (3) | 0.051 (3) | 0.071 (3) | −0.007 (3) | −0.015 (3) | −0.009 (3) |
O22 | 0.061 (4) | 0.093 (5) | 0.065 (4) | −0.017 (4) | −0.030 (3) | 0.019 (4) |
C21 | 0.040 (4) | 0.050 (4) | 0.042 (4) | 0.011 (4) | −0.011 (3) | −0.013 (4) |
C22 | 0.035 (4) | 0.046 (3) | 0.048 (4) | −0.008 (4) | −0.009 (4) | 0.002 (3) |
N21 | 0.034 (3) | 0.044 (3) | 0.043 (3) | 0.006 (4) | −0.003 (3) | −0.008 (2) |
C23 | 0.130 (10) | 0.055 (5) | 0.123 (8) | −0.059 (8) | −0.080 (9) | 0.031 (5) |
C24 | 0.171 (14) | 0.103 (8) | 0.120 (8) | −0.033 (12) | 0.009 (14) | −0.005 (7) |
C25 | 0.074 (7) | 0.069 (6) | 0.161 (11) | −0.005 (7) | −0.044 (9) | −0.050 (7) |
C26 | 0.127 (12) | 0.183 (13) | 0.104 (9) | 0.067 (14) | −0.049 (11) | −0.064 (10) |
N22 | 0.052 (4) | 0.102 (5) | 0.056 (4) | 0.013 (6) | 0.002 (4) | −0.006 (4) |
N1—O1' | 1.162 (12) | N12—H12B | 0.8900 |
N1—O2 | 1.163 (16) | N12—H12C | 0.8900 |
N1—O2' | 1.178 (13) | O21—C21 | 1.217 (9) |
N1—O1 | 1.221 (15) | O22—C21 | 1.274 (9) |
N1—O3 | 1.276 (19) | O22—H2 | 1.06 (11) |
N1—O3' | 1.323 (14) | C21—C22 | 1.514 (11) |
O11—C11 | 1.223 (7) | C22—N21 | 1.486 (7) |
O12—C11 | 1.267 (8) | C22—C23 | 1.561 (10) |
C11—C12 | 1.522 (9) | C22—H22 | 0.9800 |
C12—N11 | 1.476 (7) | N21—H21A | 0.8900 |
C12—C13 | 1.544 (8) | N21—H21B | 0.8900 |
C12—H12 | 0.9800 | N21—H21C | 0.8900 |
N11—H11A | 0.8900 | C23—C24 | 1.366 (11) |
N11—H11B | 0.8900 | C23—H23A | 0.9700 |
N11—H11C | 0.8900 | C23—H23B | 0.9700 |
C13—C14 | 1.490 (9) | C24—C25 | 1.566 (13) |
C13—H13A | 0.9700 | C24—H24A | 0.9700 |
C13—H13B | 0.9700 | C24—H24B | 0.9700 |
C14—C15 | 1.524 (9) | C25—C26 | 1.394 (14) |
C14—H14A | 0.9700 | C25—H25A | 0.9700 |
C14—H14B | 0.9700 | C25—H25B | 0.9700 |
C15—C16 | 1.458 (10) | C26—N22 | 1.392 (13) |
C15—H15A | 0.9700 | C26—H26A | 0.9700 |
C15—H15B | 0.9700 | C26—H26B | 0.9700 |
C16—N12 | 1.474 (8) | N22—H22A | 0.8900 |
C16—H16A | 0.9700 | N22—H22B | 0.8900 |
C16—H16B | 0.9700 | N22—H22C | 0.8900 |
N12—H12A | 0.8900 | ||
O1'—N1—O2 | 128 (2) | H16A—C16—H16B | 107.8 |
O1'—N1—O2' | 137.3 (13) | C16—N12—H12A | 109.5 |
O2—N1—O2' | 44 (2) | C16—N12—H12B | 109.5 |
O1'—N1—O1 | 21.3 (18) | H12A—N12—H12B | 109.5 |
O2—N1—O1 | 120 (2) | C16—N12—H12C | 109.5 |
O2'—N1—O1 | 149 (2) | H12A—N12—H12C | 109.5 |
O1'—N1—O3 | 89.7 (18) | H12B—N12—H12C | 109.5 |
O2—N1—O3 | 119.0 (17) | C21—O22—H2 | 120 (5) |
O2'—N1—O3 | 75.6 (14) | O21—C21—O22 | 125.4 (7) |
O1—N1—O3 | 109.1 (15) | O21—C21—C22 | 122.2 (7) |
O1'—N1—O3' | 115.8 (12) | O22—C21—C22 | 112.3 (7) |
O2—N1—O3' | 94 (2) | N21—C22—C21 | 107.7 (6) |
O2'—N1—O3' | 106.8 (11) | N21—C22—C23 | 108.6 (5) |
O1—N1—O3' | 99.6 (18) | C21—C22—C23 | 112.2 (7) |
O3—N1—O3' | 111.6 (19) | N21—C22—H22 | 109.5 |
O11—C11—O12 | 125.4 (6) | C21—C22—H22 | 109.5 |
O11—C11—C12 | 120.3 (6) | C23—C22—H22 | 109.5 |
O12—C11—C12 | 114.2 (6) | C22—N21—H21A | 109.5 |
N11—C12—C11 | 107.4 (6) | C22—N21—H21B | 109.5 |
N11—C12—C13 | 109.5 (4) | H21A—N21—H21B | 109.5 |
C11—C12—C13 | 112.7 (6) | C22—N21—H21C | 109.5 |
N11—C12—H12 | 109.1 | H21A—N21—H21C | 109.5 |
C11—C12—H12 | 109.1 | H21B—N21—H21C | 109.5 |
C13—C12—H12 | 109.1 | C24—C23—C22 | 120.5 (9) |
C12—N11—H11A | 109.5 | C24—C23—H23A | 107.2 |
C12—N11—H11B | 109.5 | C22—C23—H23A | 107.2 |
H11A—N11—H11B | 109.5 | C24—C23—H23B | 107.2 |
C12—N11—H11C | 109.5 | C22—C23—H23B | 107.2 |
H11A—N11—H11C | 109.5 | H23A—C23—H23B | 106.8 |
H11B—N11—H11C | 109.5 | C23—C24—C25 | 113.1 (11) |
C14—C13—C12 | 113.1 (6) | C23—C24—H24A | 109.0 |
C14—C13—H13A | 109.0 | C25—C24—H24A | 109.0 |
C12—C13—H13A | 109.0 | C23—C24—H24B | 109.0 |
C14—C13—H13B | 109.0 | C25—C24—H24B | 109.0 |
C12—C13—H13B | 109.0 | H24A—C24—H24B | 107.8 |
H13A—C13—H13B | 107.8 | C26—C25—C24 | 107.5 (11) |
C13—C14—C15 | 113.1 (6) | C26—C25—H25A | 110.2 |
C13—C14—H14A | 108.9 | C24—C25—H25A | 110.2 |
C15—C14—H14A | 108.9 | C26—C25—H25B | 110.2 |
C13—C14—H14B | 109.0 | C24—C25—H25B | 110.2 |
C15—C14—H14B | 109.0 | H25A—C25—H25B | 108.5 |
H14A—C14—H14B | 107.8 | N22—C26—C25 | 115.2 (9) |
C16—C15—C14 | 110.7 (6) | N22—C26—H26A | 108.5 |
C16—C15—H15A | 109.5 | C25—C26—H26A | 108.5 |
C14—C15—H15A | 109.5 | N22—C26—H26B | 108.5 |
C16—C15—H15B | 109.5 | C25—C26—H26B | 108.5 |
C14—C15—H15B | 109.5 | H26A—C26—H26B | 107.5 |
H15A—C15—H15B | 108.1 | C26—N22—H22A | 109.5 |
C15—C16—N12 | 113.1 (6) | C26—N22—H22B | 109.5 |
C15—C16—H16A | 109.0 | H22A—N22—H22B | 109.5 |
N12—C16—H16A | 109.0 | C26—N22—H22C | 109.5 |
C15—C16—H16B | 109.0 | H22A—N22—H22C | 109.5 |
N12—C16—H16B | 109.0 | H22B—N22—H22C | 109.5 |
O11—C11—C12—N11 | −6.1 (8) | O21—C21—C22—N21 | −0.1 (9) |
O12—C11—C12—N11 | 172.7 (6) | O22—C21—C22—N21 | 179.9 (6) |
O11—C11—C12—C13 | 114.6 (7) | O21—C21—C22—C23 | 119.3 (8) |
O12—C11—C12—C13 | −66.7 (8) | O22—C21—C22—C23 | −60.7 (9) |
N11—C12—C13—C14 | −167.4 (9) | N21—C22—C23—C24 | −168.7 (15) |
C11—C12—C13—C14 | 73.2 (10) | C21—C22—C23—C24 | 72.5 (18) |
C12—C13—C14—C15 | −178.3 (9) | C22—C23—C24—C25 | −174.6 (12) |
C13—C14—C15—C16 | 175.1 (11) | C23—C24—C25—C26 | 174.1 (17) |
C14—C15—C16—N12 | −178.0 (9) | C24—C25—C26—N22 | 174.3 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O22—H2···O12i | 1.06 (11) | 1.38 (11) | 2.425 (8) | 169 (9) |
N11—H11A···O11ii | 0.89 | 1.98 | 2.821 (7) | 157 |
N11—H11B···Cl1i | 0.89 | 2.40 | 3.283 (6) | 171 |
N11—H11C···Cl1 | 0.89 | 2.49 | 3.367 (6) | 168 |
N12—H12A···Cl2iii | 0.89 | 2.37 | 3.237 (7) | 164 |
N12—H12B···O3i | 0.89 | 2.24 | 2.994 (18) | 142 |
N12—H12B···O2′iv | 0.89 | 2.32 | 2.945 (14) | 127 |
N12—H12B···O2′i | 0.89 | 2.52 | 3.124 (14) | 125 |
N12—H12B···O2iv | 0.89 | 2.56 | 3.16 (3) | 125 |
N12—H12C···Cl2v | 0.89 | 2.51 | 3.298 (7) | 149 |
N21—H21A···Cl1ii | 0.89 | 2.38 | 3.260 (5) | 172 |
N21—H21B···Cl2 | 0.89 | 2.36 | 3.221 (6) | 163 |
N21—H21C···Cl2i | 0.89 | 2.33 | 3.215 (6) | 173 |
N22—H22A···Cl1vi | 0.89 | 2.40 | 3.268 (8) | 166 |
N22—H22B···O3i | 0.89 | 2.42 | 3.12 (3) | 136 |
N22—H22B···O1i | 0.89 | 2.71 | 3.08 (3) | 106 |
N22—H22C···Cl1vii | 0.89 | 2.42 | 3.302 (8) | 173 |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+3/2, −z+1; (iii) −x+3/2, −y+1, z+1/2; (iv) x+1/2, −y+1/2, −z+1; (v) −x+1/2, −y+1, z+1/2; (vi) −x+1/2, −y+1, z−1/2; (vii) −x+3/2, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | 2C6H15N2O2+·H+·NO3−·2Cl− |
Mr | 428.32 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 4.9846 (2), 20.604 (2), 20.663 (2) |
V (Å3) | 2122.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.5 × 0.3 × 0.3 |
Data collection | |
Diffractometer | Enraf-Nonius sealed tube diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.883, 0.901 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3313, 2910, 1805 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.190, 1.03 |
No. of reflections | 2910 |
No. of parameters | 270 |
No. of restraints | 16 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.53, −0.42 |
Absolute structure | Flack (1983), 714 Friedel pairs |
Absolute structure parameter | 0.2 (2) |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), SHELXL97.
O11—C11 | 1.223 (7) | O21—C21 | 1.217 (9) |
O12—C11 | 1.267 (8) | O22—C21 | 1.274 (9) |
O11—C11—C12—N11 | −6.1 (8) | O21—C21—C22—N21 | −0.1 (9) |
N11—C12—C13—C14 | −167.4 (9) | N21—C22—C23—C24 | −168.7 (15) |
C12—C13—C14—C15 | −178.3 (9) | C22—C23—C24—C25 | −174.6 (12) |
C13—C14—C15—C16 | 175.1 (11) | C23—C24—C25—C26 | 174.1 (17) |
C14—C15—C16—N12 | −178.0 (9) | C24—C25—C26—N22 | 174.3 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O22—H2···O12i | 1.06 (11) | 1.38 (11) | 2.425 (8) | 169 (9) |
N11—H11A···O11ii | 0.89 | 1.98 | 2.821 (7) | 157.3 |
N11—H11B···Cl1i | 0.89 | 2.40 | 3.283 (6) | 171.2 |
N11—H11C···Cl1 | 0.89 | 2.49 | 3.367 (6) | 167.5 |
N12—H12A···Cl2iii | 0.89 | 2.37 | 3.237 (7) | 164.4 |
N12—H12B···O3i | 0.89 | 2.24 | 2.994 (18) | 142.1 |
N12—H12B···O2'iv | 0.89 | 2.32 | 2.945 (14) | 127.0 |
N12—H12B···O2'i | 0.89 | 2.52 | 3.124 (14) | 125.3 |
N12—H12B···O2iv | 0.89 | 2.56 | 3.16 (3) | 124.9 |
N12—H12C···Cl2v | 0.89 | 2.51 | 3.298 (7) | 148.6 |
N21—H21A···Cl1ii | 0.89 | 2.38 | 3.260 (5) | 171.6 |
N21—H21B···Cl2 | 0.89 | 2.36 | 3.221 (6) | 162.9 |
N21—H21C···Cl2i | 0.89 | 2.33 | 3.215 (6) | 173.0 |
N22—H22A···Cl1vi | 0.89 | 2.40 | 3.268 (8) | 165.6 |
N22—H22B···O3i | 0.89 | 2.42 | 3.12 (3) | 135.5 |
N22—H22B···O1i | 0.89 | 2.71 | 3.08 (3) | 106.1 |
N22—H22C···Cl1vii | 0.89 | 2.42 | 3.302 (8) | 173.2 |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+3/2, −z+1; (iii) −x+3/2, −y+1, z+1/2; (iv) x+1/2, −y+1/2, −z+1; (v) −x+1/2, −y+1, z+1/2; (vi) −x+1/2, −y+1, z−1/2; (vii) −x+3/2, −y+1, z−1/2. |
Lysine is the one of the four amino acids having basic side chains. The crystal structure of L-lysine monohydrochloride dihydrate (Wright & Marsh, 1962; Koetzle et al., 1972), L-lysine sulfate (Capasso et al., 1983), L-lysine semimaleate (Pratap et al., 2000) and hydrogen bis[L-lysinium(+)] dichloride perchlorate (Srinivasan et al., 2001) have been reported. The crystal structure of lysine hydrochloride with nitric acid, (I), was undertaken to study the effects of hydrogen bonding due to the presence of inorganic acids.
A pseudo-non-crystallographic twofold axis is observed near (1/4, y, 0.41) for both the chloride anions and lysinium cations. The N atom of the nitrate group lies on this pseudo-twofold axis. The existence of pseudosymmetry is responsible for two possible orientation of the nitrate O atom and hence the large deviation from the nearly trigonal symmetry.
The asymmetric part contains two crystallographically independent lysinium residues (I and II). The lysinium cations are characterized by two planar configurations, viz. the carboxylate group and the aliphatic side chain terminating at the ε-amino group. The straight chain conformation angle ψ1 is -6.1 (8) and -0.1 (9)° for lysinium residues I and II, respectively. This tendency of twisting of the C—N bond is found in various amino acids (Lakshminarayanan et al., 1967). The average value of the four C—C—C angles for both molecules I and II are 112.4 (6) and 113.3 (11)°, significantly greater than the tetrahedral value. However, the angle Cα—Cβ—Cγ, 113.1 (6) and 120.5 (11)° for the molecules I and II, are appreciably larger than the other three. The widening of this angle might be due to the steric effect of an atom hydrogen bonded to the NH3+ group also found in other amino acids and peptides (Leung & Marsh, 1958). Molecules I and II have a fully extended side-chain conformation [χ1 = -167.3 (9) and -168.7 (15)°, χ2 = -178.2 (9) and -174.5 (12)°, χ3 = 174.9 (11) and 174.2 (17)°, and χ4 = -178.0 (9) and 174.2 (14)°, respectively].
Both the lysinium molecules (I and II) are cationic, with ε-amino groups accepting an H atom. The two lysinium molecules are bonded with a strong O—H···O hydrogen bond [O22···O12 2.425 (8) Å]. The equality of the C—O distances of molecules I and II within significant limits [1.223 (7) and 1.217 (9) Å, and 1.267 (8) and 1.274 (9) Å] suggests that hydrogen linking I and II are equally shared by I and II. Hence, this hydrogen bond may be termed as a symmetric hydrogen bond, since the two cations are related by non-crystallographic pseudo-twofold symmetry and the H atom is on the pseudo-axis. The O12—H2 and O22—H2 distances [1.06 (11) and 1.38 (11) Å] are nearly equal within significant limits. Hence, the symmetric hydrogen-bonded lysinium dimer thus formed carries a net positive charge, as found in L-phenylalanine L-phenylalaninium perchlorate (Srinivasan & Rajaram, 1997).
A zigzag (Z1) head-to-tail sequence is engaged in molecule I, since the N11—H11A···O11(1/2 + x, 3/2 - y, 1 - z) bond connects two 21-related amino acids (Vijayan, 1988). But in the case of lysinium molecule II, the α-amino group have hydrogen bonds with chloride anions only. The chloride anion (Cl1) links the α-amino nitrogen of lysinium molecule I through a hydrogen bond in an infinite chain running along the a axis and chloride anion Cl2 links the ε-amino nitrogen in an infinite chain along the a axis. Similarly, in lysinium molecule II, the α-N atom is linked by chloride anion Cl2 through a hydrogen bond in an infinite chain along the a axis and the ε-amino nitrogen is linked by chloride anion Cl1 in an infinite chain along the a axis. Besides this, the nitrate anion links the ε-amino N atoms of both molecules I and II.
As shown in Fig. 2, the two hydrophilic layers about the y = 1/4 plane are connected by hydrogen bonds involving nitrate and chloride anions. The aggregation of the hydrophilic double layers are interspersed by the hydrophobic side chain across the y = 1/2 plane.