Hydro­gen bis­[L-lysinium(2+)] dichloride perchlorate

In the title compound, 2C₆H₁₅N₂O₂⁺·H⁺·ClO₄⁻·2Cl⁻, the two mono- and dicationic lysinium mol­ecules are held together by strong O—H...O hydrogen bonds. Both the perchlorate and chloride anions link mol­ecules 1 and 2 through the α-amino and [epsilon]-amino groups into infinite chains along the a axis. The aggregation of the hydro­philic groups is along the z = 0 plane and that of hydro­phobic is along the z = plane. Mol­ecule 1 is engaged in a zigzag (Z1) head-to-tail sequence.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.069
• wR factor = 0.196
• Data-to-parameter ratio = 11.8

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           24.96
         From the CIF: _reflns_number_total               2905
         Count of symmetry unique reflns         2252
         Completeness (_total/calc)            129.00%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       653
         Fraction of Friedel pairs measured     0.290
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure

---

S1. Comment

Lysine is 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) and L-lysine semi maleate (Pratap et al., 2000) have been reported. In the present study, the analysis of lysine hydrochloride with perchloric acid, (I), was undertaken.

Both the lysinium molecules (1 and 2) in the asymmetric unit are cationic, with ε-amino groups accepting an H atom from hydrochloric acid. The H atom of the perchloric acid is liberated and bonded with the molecule 2 and as a result the perchloric acid exists as perchlorate anion. The lysinium molecules have two planar configurations, the carboxyl group and aliphatic chain terminating at the ε-amino group. The amino N atom deviates from the carboxyl plane by 0.164 (4) and 0.126 (4) Å in lysinium molecules 1 and 2, which corresponds to the twisting of the C—N bond out of the carboxyl group by -6.0 (6) and 5.7 (7)°, respectively in molecule 1 and 2. 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 is 112.6 and 117.1° in molecules 1 and 2, which is significantly greater than the tetrahedral value. However, the angle C^α—C^β—C^γ of 114.0 (4) and 117.4 (8)° for both the molecules 1 and 2 are appreciably large. Similar results are found in other amino acids and peptides, and this widening might be due to the steric effect of an atom hydrogen bonded to the NH₃⁺ group (Leung & Marsh, 1958). While molecule 1, as expected, has a fully extended conformation for the side chain [χ¹ = -163.2 (6)°, χ² = -178.2 (6)°, χ³ = 177.1 (7)° and χ⁴ = -177.5 (6)°], molecule 2 does not have a fully extended conformation [χ¹ = 70.9 (10)°, χ² = 179.2 (8)°, χ³ = -70.6 (14)° and χ⁴ = -169.8 (9)°; Pratap et al., 2000].

In the crystal, the molecules 1 and 2 are bonded through a strong O—H···O hydrogen bond between the carboxyl O atoms. Lysinium molecule 1 is engaged in a zigzag (Z1) head-to-tail sequence since N11—H11ⁱ···O1ⁱ [symmetry code: (i) x - 1/2, -y + 3/2, -z] connects two 2₁-related amino acids (Vijayan, 1988). The perchlorate anion links through the ε-amino group of four lysinium molecules extending in an infinite chain along the a axis. Both the chloride anions link the lysinium molecules 1 and 2 through the α-amino and ε-amino groups into infinite chains along the a axis. The Cl2 atom, as acceptor, links (i) two lysinium molecules 1, through their α-amino groups and (ii) the two lysinium molecules 2, through the ε-amino groups. Similarly the Cl3 atom links (i) the two lysinium molecules 1 through the ε-amino groups and (ii) the two lysinium molecules 2 through the α-amino groups. The hydrophobic groups aggregate along z = 1/4 plane and the hydrophilic groups along z = 0 plane.

S2. Experimental

The title compound was crystallized in an aqueous solution from a 2:1 stoichiometric ratio of L-lysine hydrochloride and perchloric acid. Colorless transparent and plate-like crystals were grown.

S3. Refinement

All H atoms were fixed by geometric constraints and were allowed to ride on the preceding atom. Intensities for 225 Friedel pairs were measured, resulting in a Flack parameter of 0.04 (15). Atoms C23, C24, C25 and C26 showed large displacement amplitudes with unusual C—C distances, indicating disorder. Since a satisfactory disorder model was not found, these atoms were refined by constraining the bond distances involving them.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Softwar; 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.

Figures

	Fig. 1. The structure of (I) showing the atomic numbering scheme and 50% probability displacement ellipsoids (Johnson, 1976).
	Fig. 2. Packing of the molecules viewed down the a axis.

Hydrogen bis[L-lysinium(2+)] dichloride perchlorate

Crystal data

C6H15N2O2^+·C6H16N2O2^2+·ClO4^−·2Cl^−	Dx = 1.415 Mg m^−3 Dm = 1.413 Mg m^−3 Dm measured by flotation in a mixture of carbon tetrachloride and xylene
Mr = 465.76	Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 5.0264 (6) Å	θ = 11.3–13.2°
b = 20.822 (2) Å	µ = 0.46 mm^−1
c = 20.897 (2) Å	T = 293 K
V = 2187.1 (4) Å^3	Plates, colorless
Z = 4	0.5 × 0.4 × 0.25 mm
F(000) = 984

Data collection

Enraf-Nonius sealed tube diffractometer	2427 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.069
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
ω–2θ scans	h = −1→5
Absorption correction: ψ scan (North et al., 1968)	k = −1→24
Tmin = 0.859, Tmax = 0.891	l = −2→24
3207 measured reflections	3 standard reflections every 60 min
2905 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.069	w = 1/[σ^2(Fo^2) + (0.1519P)^2 + 0.4185P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.196	(Δ/σ)max = 0.003
S = 1.06	Δρmax = 0.66 e Å^−3
2905 reflections	Δρmin = −0.63 e Å^−3
246 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.007 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.04 (15)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	−0.0066 (3)	0.33860 (6)	0.06838 (6)	0.0421 (4)
O1	−0.2886 (10)	0.3365 (2)	0.0633 (2)	0.0645 (13)
O2	0.0674 (14)	0.3478 (3)	0.1339 (2)	0.0854 (18)
O3	0.0871 (12)	0.3909 (2)	0.0316 (3)	0.0768 (16)
O4	0.0980 (12)	0.2793 (2)	0.0460 (2)	0.0676 (14)
Cl2	0.0394 (3)	0.56229 (6)	0.07556 (6)	0.0423 (4)
Cl3	0.9666 (3)	0.59640 (7)	0.39898 (8)	0.0517 (4)
O1A	0.9527 (8)	0.74050 (17)	0.04852 (17)	0.0439 (9)
O1B	0.8200 (10)	0.7997 (2)	0.1309 (2)	0.0629 (14)
C11	0.7972 (11)	0.7542 (2)	0.0923 (3)	0.0351 (12)
C12	0.5500 (11)	0.7139 (2)	0.1012 (2)	0.0328 (11)
H12	0.3947	0.7423	0.0994	0.039*
N11	0.5304 (10)	0.66688 (18)	0.04750 (19)	0.0380 (10)
H11A	0.5326	0.6878	0.0104	0.057*
H11B	0.3793	0.6449	0.0510	0.057*
H11C	0.6677	0.6399	0.0492	0.057*
C13	0.5451 (14)	0.6777 (2)	0.1654 (2)	0.0382 (12)
H13A	0.4126	0.6440	0.1630	0.046*
H13B	0.7168	0.6575	0.1719	0.046*
C14	0.4845 (18)	0.7196 (3)	0.2220 (2)	0.0540 (16)
H14A	0.3101	0.7387	0.2163	0.065*
H14B	0.6137	0.7541	0.2238	0.065*
C15	0.4894 (16)	0.6829 (3)	0.2855 (2)	0.0474 (14)
H15A	0.3530	0.6500	0.2852	0.057*
H15B	0.6606	0.6622	0.2908	0.057*
C16	0.4418 (17)	0.7279 (3)	0.3394 (2)	0.0524 (17)
H16A	0.5733	0.7620	0.3377	0.063*
H16B	0.2678	0.7474	0.3342	0.063*
N12	0.4549 (11)	0.6967 (2)	0.40304 (19)	0.0417 (11)
H12A	0.4254	0.7258	0.4334	0.063*
H12B	0.6153	0.6794	0.4086	0.063*
H12C	0.3318	0.6660	0.4054	0.063*
O2A	0.8894 (9)	0.4279 (2)	0.4440 (2)	0.0543 (11)
O2B	0.7688 (11)	0.3629 (2)	0.3642 (3)	0.0720 (15)
H2B	0.9136	0.3459	0.3705	0.108*
C21	0.7396 (12)	0.4105 (3)	0.4026 (3)	0.0434 (14)
C22	0.4759 (13)	0.4451 (3)	0.3905 (3)	0.0466 (13)
H22	0.3371	0.4162	0.4065	0.056*
N21	0.4670 (10)	0.50247 (19)	0.43230 (19)	0.0393 (10)
H21A	0.3147	0.5233	0.4260	0.059*
H21B	0.6029	0.5282	0.4229	0.059*
H21C	0.4781	0.4903	0.4731	0.059*
C23	0.4111 (18)	0.4566 (5)	0.3217 (3)	0.081 (3)
H23A	0.3825	0.4152	0.3015	0.097*
H23B	0.2439	0.4798	0.3198	0.097*
C24	0.605 (2)	0.4917 (6)	0.2837 (4)	0.110 (4)
H24A	0.7726	0.4688	0.2861	0.132*
H24B	0.6316	0.5333	0.3036	0.132*
C25	0.542 (2)	0.5027 (4)	0.2138 (3)	0.088 (3)
H25A	0.3654	0.5215	0.2113	0.105*
H25B	0.6658	0.5345	0.1977	0.105*
C26	0.548 (2)	0.4481 (4)	0.1706 (4)	0.090 (3)
H26A	0.4017	0.4197	0.1809	0.108*
H26B	0.7124	0.4246	0.1776	0.108*
N22	0.5305 (11)	0.4663 (2)	0.1010 (3)	0.0574 (13)
H22A	0.5344	0.4310	0.0771	0.086*
H22B	0.6674	0.4914	0.0908	0.086*
H22C	0.3791	0.4874	0.0940	0.086*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0409 (8)	0.0416 (6)	0.0438 (7)	−0.0021 (7)	−0.0018 (7)	−0.0010 (5)
O1	0.043 (3)	0.068 (3)	0.082 (3)	−0.004 (2)	−0.001 (3)	0.007 (3)
O2	0.081 (4)	0.120 (4)	0.055 (3)	0.020 (4)	−0.011 (3)	−0.026 (3)
O3	0.074 (4)	0.063 (3)	0.093 (4)	−0.019 (3)	0.002 (3)	0.025 (3)
O4	0.076 (4)	0.057 (2)	0.070 (3)	0.016 (3)	−0.007 (3)	−0.016 (2)
Cl2	0.0366 (7)	0.0418 (6)	0.0486 (7)	0.0002 (6)	−0.0027 (6)	−0.0024 (5)
Cl3	0.0318 (7)	0.0417 (6)	0.0818 (10)	0.0003 (6)	−0.0041 (8)	−0.0018 (6)
O1A	0.034 (2)	0.054 (2)	0.0436 (18)	−0.009 (2)	0.0037 (19)	0.0024 (17)
O1B	0.059 (3)	0.049 (2)	0.081 (3)	−0.027 (2)	0.021 (3)	−0.024 (2)
C11	0.032 (3)	0.035 (3)	0.038 (2)	−0.001 (2)	−0.002 (2)	0.008 (2)
C12	0.030 (3)	0.033 (2)	0.035 (2)	0.000 (2)	−0.001 (3)	0.0008 (19)
N11	0.039 (3)	0.041 (2)	0.0341 (19)	−0.007 (2)	0.000 (2)	0.0036 (17)
C13	0.043 (3)	0.034 (2)	0.038 (2)	−0.002 (3)	0.003 (3)	0.0038 (19)
C14	0.070 (5)	0.052 (3)	0.040 (2)	0.001 (4)	0.011 (4)	0.001 (2)
C15	0.058 (4)	0.044 (3)	0.040 (3)	0.003 (3)	0.000 (3)	0.000 (2)
C16	0.073 (5)	0.044 (3)	0.041 (3)	−0.001 (3)	−0.002 (3)	0.004 (2)
N12	0.045 (3)	0.044 (2)	0.0361 (19)	0.001 (2)	−0.002 (2)	−0.0031 (18)
O2A	0.037 (2)	0.072 (3)	0.054 (2)	0.011 (2)	−0.005 (2)	0.012 (2)
O2B	0.046 (3)	0.056 (3)	0.114 (4)	0.019 (2)	−0.008 (3)	−0.023 (3)
C21	0.032 (3)	0.043 (3)	0.055 (3)	0.002 (3)	0.010 (3)	0.016 (3)
C22	0.037 (3)	0.047 (3)	0.056 (3)	0.008 (3)	0.000 (3)	−0.001 (2)
N21	0.031 (2)	0.043 (2)	0.043 (2)	0.009 (2)	−0.003 (2)	0.0058 (18)
C23	0.074 (6)	0.112 (6)	0.055 (4)	0.043 (6)	−0.009 (4)	−0.003 (4)
C24	0.082 (7)	0.123 (8)	0.125 (8)	0.006 (7)	−0.018 (7)	0.037 (7)
C25	0.097 (7)	0.086 (5)	0.081 (5)	0.016 (6)	0.001 (6)	0.026 (4)
C26	0.066 (5)	0.070 (5)	0.134 (8)	0.003 (5)	−0.011 (6)	0.042 (5)
N22	0.039 (3)	0.053 (3)	0.080 (3)	0.005 (3)	−0.010 (3)	−0.012 (3)

Geometric parameters (Å, º)

Cl1—O3	1.413 (5)	N12—H12C	0.89
Cl1—O1	1.422 (5)	O2A—C21	1.203 (7)
Cl1—O4	1.421 (4)	O2B—C21	1.284 (8)
Cl1—O2	1.431 (5)	O2B—H2B	0.82
O1A—C11	1.236 (7)	C21—C22	1.529 (8)
O1B—C11	1.250 (7)	C22—N21	1.481 (7)
C11—C12	1.511 (8)	C22—C23	1.493 (9)
C12—N11	1.492 (6)	C22—H22	0.98
C12—C13	1.539 (6)	N21—H21A	0.89
C12—H12	0.98	N21—H21B	0.89
N11—H11A	0.89	N21—H21C	0.89
N11—H11B	0.89	C23—C24	1.454 (9)
N11—H11C	0.89	C23—H23A	0.97
C13—C14	1.501 (7)	C23—H23B	0.97
C13—H13A	0.97	C24—C25	1.513 (9)
C13—H13B	0.97	C24—H24A	0.97
C14—C15	1.530 (7)	C24—H24B	0.97
C14—H14A	0.97	C25—C26	1.452 (9)
C14—H14B	0.97	C25—H25A	0.97
C15—C16	1.485 (7)	C25—H25B	0.97
C15—H15A	0.97	C26—N22	1.506 (10)
C15—H15B	0.97	C26—H26A	0.97
C16—N12	1.482 (6)	C26—H26B	0.97
C16—H16A	0.97	N22—H22A	0.89
C16—H16B	0.97	N22—H22B	0.89
N12—H12A	0.89	N22—H22C	0.89
N12—H12B	0.89
O3—Cl1—O1	108.4 (3)	H12A—N12—H12C	109.5
O3—Cl1—O4	111.5 (3)	H12B—N12—H12C	109.5
O1—Cl1—O4	108.5 (3)	C21—O2B—H2B	109.5
O3—Cl1—O2	109.2 (4)	O2A—C21—O2B	127.7 (6)
O1—Cl1—O2	109.6 (4)	O2A—C21—C22	121.3 (5)
O4—Cl1—O2	109.5 (3)	O2B—C21—C22	111.0 (6)
O1A—C11—O1B	126.5 (5)	N21—C22—C23	115.6 (5)
O1A—C11—C12	118.9 (5)	N21—C22—C21	108.0 (5)
O1B—C11—C12	114.6 (5)	C23—C22—C21	115.1 (5)
N11—C12—C11	109.0 (4)	N21—C22—H22	105.8
N11—C12—C13	109.5 (4)	C23—C22—H22	105.8
C11—C12—C13	113.1 (4)	C21—C22—H22	105.8
N11—C12—H12	108.4	C22—N21—H21A	109.5
C11—C12—H12	108.4	C22—N21—H21B	109.5
C13—C12—H12	108.4	H21A—N21—H21B	109.5
C12—N11—H11A	109.5	C22—N21—H21C	109.5
C12—N11—H11B	109.5	H21A—N21—H21C	109.5
H11A—N11—H11B	109.5	H21B—N21—H21C	109.5
C12—N11—H11C	109.5	C24—C23—C22	117.4 (8)
H11A—N11—H11C	109.5	C24—C23—H23A	107.9
H11B—N11—H11C	109.5	C22—C23—H23A	107.9
C14—C13—C12	114.0 (4)	C24—C23—H23B	107.9
C14—C13—H13A	108.7	C22—C23—H23B	107.9
C12—C13—H13A	108.7	H23A—C23—H23B	107.2
C14—C13—H13B	108.7	C23—C24—C25	117.6 (9)
C12—C13—H13B	108.7	C23—C24—H24A	107.9
H13A—C13—H13B	107.6	C25—C24—H24A	107.9
C13—C14—C15	113.0 (5)	C23—C24—H24B	107.9
C13—C14—H14A	109.0	C25—C24—H24B	107.9
C15—C14—H14A	109.0	H24A—C24—H24B	107.2
C13—C14—H14B	109.0	C26—C25—C24	118.4 (8)
C15—C14—H14B	109.0	C26—C25—H25A	107.7
H14A—C14—H14B	107.8	C24—C25—H25A	107.7
C16—C15—C14	110.0 (5)	C26—C25—H25B	107.7
C16—C15—H15A	109.7	C24—C25—H25B	107.7
C14—C15—H15A	109.7	H25A—C25—H25B	107.1
C16—C15—H15B	109.7	C25—C26—N22	113.7 (6)
C14—C15—H15B	109.7	C25—C26—H26A	108.8
H15A—C15—H15B	108.2	N22—C26—H26A	108.8
N12—C16—C15	113.4 (4)	C25—C26—H26B	108.8
N12—C16—H16A	108.9	N22—C26—H26B	108.8
C15—C16—H16A	108.9	H26A—C26—H26B	107.7
N12—C16—H16B	108.9	C26—N22—H22A	109.5
C15—C16—H16B	108.9	C26—N22—H22B	109.5
H16A—C16—H16B	107.7	H22A—N22—H22B	109.5
C16—N12—H12A	109.5	C26—N22—H22C	109.5
C16—N12—H12B	109.5	H22A—N22—H22C	109.5
H12A—N12—H12B	109.5	H22B—N22—H22C	109.5
C16—N12—H12C	109.5
O1A—C11—C12—N11	−6.0 (6)	O2A—C21—C22—N21	5.7 (7)
O1B—C11—C12—N11	173.1 (5)	O2B—C21—C22—N21	−175.0 (5)
O1A—C11—C12—C13	116.0 (5)	O2A—C21—C22—C23	136.5 (7)
O1B—C11—C12—C13	−64.9 (6)	O2B—C21—C22—C23	−44.3 (8)
N11—C12—C13—C14	−163.2 (6)	N21—C22—C23—C24	70.9 (10)
C11—C12—C13—C14	75.0 (7)	C21—C22—C23—C24	−56.0 (10)
C12—C13—C14—C15	−178.2 (6)	C22—C23—C24—C25	179.2 (8)
C13—C14—C15—C16	177.1 (7)	C23—C24—C25—C26	−70.6 (14)
C14—C15—C16—N12	−177.5 (6)	C24—C25—C26—N22	−169.8 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2B—H2B···O1B^i	0.82	1.65	2.453 (7)	166
N11—H11A···O1A^ii	0.89	1.98	2.810 (5)	156
N11—H11B···Cl2	0.89	2.48	3.343 (5)	164
N11—H11C···Cl2^iii	0.89	2.53	3.410 (5)	170
N12—H12A···O4^iv	0.89	2.36	3.041 (6)	134
N12—H12A···O1^v	0.89	2.41	3.109 (7)	136
N12—H12B···Cl3	0.89	2.48	3.314 (5)	156
N12—H12C···Cl3^vi	0.89	2.34	3.223 (5)	170
N21—H21A···Cl3^vi	0.89	2.39	3.261 (4)	168
N21—H21B···Cl3	0.89	2.37	3.258 (5)	179
N21—H21C···Cl2^iv	0.89	2.41	3.284 (4)	168
N22—H22A···O1^iii	0.89	2.18	2.958 (6)	146
N22—H22A···O3	0.89	2.58	3.088 (8)	117
N22—H22B···Cl2^iii	0.89	2.40	3.289 (6)	174
N22—H22C···Cl2	0.89	2.34	3.220 (5)	168

Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x−1/2, −y+3/2, −z; (iii) x+1, y, z; (iv) −x+1/2, −y+1, z+1/2; (v) −x, y+1/2, −z+1/2; (vi) x−1, y, z.