L-Lysine L-lysinium dichloride nitrate

In the title compound, 2C₆H₁₅N₂O₂⁺·H⁺·NO₃⁻·2Cl⁻, both the monoprotonated lysinium mol­ecules are bonded through a strong, nearly symmetric, O—H...O hydrogen bond forming a dimer. The O...O distance is 2.425 (8) Å. Molecule I is engaged in a zigzag (Z1) head-to-tail sequence. Both chloride anions link mol­ecules I and II through the α- and [epsilon]-amino groups in an infinite chain along the a axis. The nitrate ion shows orientational disorder.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.012 Å
• Disorder in solvent or counterion
• R factor = 0.062
• wR factor = 0.190
• Data-to-parameter ratio = 10.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



PLAT_214  Alert B Atom >O2     (Anion/Solvent) ADP max/min Ratio       5.40


 Alert Level C:



PLAT_213  Alert C Atom  C23    has ADP max/min Ratio ...........       3.40

PLAT_302  Alert C Anion/Solvent Disorder .......................      33.00 Perc.

PLAT_360  Alert C Short  C(sp3)-C(sp3) Bond  C(23)  -   C(24)  =       1.37 Ang.

PLAT_360  Alert C Short  C(sp3)-C(sp3) Bond  C(25)  -   C(26)  =       1.39 Ang.

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           24.97
         From the CIF: _reflns_number_total               2910
         Count of symmetry unique reflns         2196
         Completeness (_total/calc)            132.51%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       714
         Fraction of Friedel pairs measured     0.325
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 4 Alert Level C = Please check

---

S1. Comment

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 C^α—C^β—C^γ, 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.

S2. Experimental

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.

S3. Refinement

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.

Computing details

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.

Figures

	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.

Bis (L-Lysinium(+)) hydrogen dichloride nitrate

Crystal data

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) Å^3	Needles, colorless
Z = 4	0.5 × 0.3 × 0.3 mm
F(000) = 912

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.190	w = 1/[σ^2(Fo^2) + (0.0869P)^2 + 3.2345P] where P = (Fo^2 + 2Fc^2)/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)

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	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O22—H2···O12^i	1.06 (11)	1.38 (11)	2.425 (8)	169 (9)
N11—H11A···O11^ii	0.89	1.98	2.821 (7)	157
N11—H11B···Cl1^i	0.89	2.40	3.283 (6)	171
N11—H11C···Cl1	0.89	2.49	3.367 (6)	168
N12—H12A···Cl2^iii	0.89	2.37	3.237 (7)	164
N12—H12B···O3^i	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···O2^iv	0.89	2.56	3.16 (3)	125
N12—H12C···Cl2^v	0.89	2.51	3.298 (7)	149
N21—H21A···Cl1^ii	0.89	2.38	3.260 (5)	172
N21—H21B···Cl2	0.89	2.36	3.221 (6)	163
N21—H21C···Cl2^i	0.89	2.33	3.215 (6)	173
N22—H22A···Cl1^vi	0.89	2.40	3.268 (8)	166
N22—H22B···O3^i	0.89	2.42	3.12 (3)	136
N22—H22B···O1^i	0.89	2.71	3.08 (3)	106
N22—H22C···Cl1^vii	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.