The perchlorate salt of the novel diprotonated dinucleating ligand 1,3-bis­{[2-(2-pyridinio)eth­yl][2-(2-pyrid­yl)eth­yl]amino}benzene

In the title salt, 1,3-bis­{[2-(2-pyridinio)eth­yl][2-(2-pyrid­yl)ethyl]amino}benzene diperchlorate dihydrate, C₃₄H₃₈N₆²⁺·2ClO₄^-·2H₂O, the cation contains two ethyl­pyrid­yl and two ethyl­pyridinium pendant pairs anchored to the two N atoms of 1,3-phenyl­enediamine. The pyrid­yl and pyridinium N atoms are flanked by a mol­ecule of water through strong hydrogen-bonding inter­actions [N-H...O = 2.762 (6) and 2.758 (6) Å, and O-H...N = 2.834 (6) and 2.839 (6) Å]. The water mol­ecules have weak hydrogen-bonding inter­actions with the perchlorate anions as well. One of the perchlorate anions is severely disordered.

S1. Comment

Binucleating multidentate N,O-donor ligands, which can bind two metal ions in close proximity, have received considerable attention as synthetic models for the multinuclear metallobiosites involved in many catalytic transformations (Tshuva & Lippard, 2004). The hexadentate ligand 1,3-tetrakis{[2-(2-pyridyl)ethyl]amino}benzene, PD (Murthy et al., 1993), is one of these. An attempted synthesis of an iron(III)–oxo/hydroxo–acetato-bridged complex of PD by its reaction with ferric perchlorate Fe(ClO₄)₃.10H₂O, acetic acid and triethylamine (1:2:2:2 ratio) in ethanol gave a pale-yellow crystalline solid, at first thought to be an Fe complex. An X-ray diffraction study showed that the product did not contain Fe but was the title compound, [PDH₂]²⁺(ClO₄⁻)₂·2H₂O, (I), in which the two pyridyl groups, one on each amino N atom, are protonated. The selective protonation of these, as opposed to the aromatic ring-substituted amine N atoms, suggests that they are more basic, as expected. A similar protonated salt of a tetradentate aminoethylpyridyl ligand formed under identical reaction conditions has been reported previously (Britton et al., 1991). It is of interest that hydrogen-bonded tertiary aminopyridyl compounds are found to be antidotes for poisoning by organophosphorus compounds (Takeshi et al., 2002).

A view of the hydrogen-bonded structure of (I) and its atom-numbering scheme is shown in Fig. 1. The structure includes a [PDH₂]²⁺ dication, two perchlorate anions (one severely disordered) and two molecules of water. The packing diagram is given in Fig. 2. Compound (I) has two aromatic ring-substituted amine N atoms (N1 and N4) and four pyridyl N atoms (N2, N3, N5 and N6), of which two pyridyl N atoms are protonated (H3N and H5N). The amino N atoms, N1 and N4, are planar; the angles around them are close to 120°, indicating a π-delocalization of their lone pairs with the phenyl ring, which prevents their protonation or involvement in hydrogen bonds. In general, aminopyridyls are protonated in acidic solutions. In the present case, the protonation may be due to the acidic nature of the hydrated ferric perchlorate salt.

Notably, each pair of protonated pyridinium and non-protonated pyridyl groups trap a molecule of water (H₂O5 and H₂O6), one on each side, through strong hydrogen-bonding interactions (Table 1). The interactions are similar on both sides, with N3—H3N····O5 = 2.762 (6) and O5—H5B···N2 = 2.834 (6) Å, and N5—H5N····O6 = 2.758 (6) O6—H6B···N6 = 2.839 (6) Å]. These water molecules also have additional weak hydrogen-bonding interactions with perchlorate anions. A subtle difference in their interaction is apparent, as atom H5A on O5 interacts with two O atoms, while atom H6A interacts with only one of the O atoms of the perchlorate anions (Table 1). These factors appear to have an effect on the relative orientations of the pyridyl and pyridinium rings. Rings N6/C61–C65 and N5/C51–C55, with stronger hydrogen-bonding interactions with perchlorate, deviate from coplanarity (dihedral angle 28.2 °), while rings N2/C21–C25 and N3/C31–C35, with weaker perchlorate hydrogen-bonding interactions, are coplanar (dihedral angle 1.76 °). By contrast, in another similar instance, a hexadentate ligand with methylpyridyl pendants (Buchen et al., 1997), the two pyridine N atoms at each end of the molecule are mutually hydrogen bonded, with no intervening H₂O molecule. The reason for the difference in compound (I) may be due to the longer arm length of the pendants allowing the accommodation of a molecule of water. These two examples clearly exemplify the key role of structure on the type and nature of hydrogen-bonding interactions.

The C—C and C—N bond distances in (I) are very close to the corresponding values reported for an analogous ligand system (Buchen et al., 1997).

S2. Experimental

The reaction of the binucleating ligand 1,3-tetrakis{[2-(2-pyridyl)ethyl]amino}benzene, PD, and ferric perchlorate decahydrate, Fe(ClO₄)₃.10H₂O, in the presence of acetic acid and triethylamine (1:2:2:2 molar? ratio) in ethanol resulted in the formation of the title salt, (I), as pale-yellow needles in 86% yield. UV–vis [MeOH, λmax, nm (ε, LM⁻¹cm⁻¹)]: 305 (632); IR (Nujol, cm⁻¹): 3488 (s, H₂O), 1100 (s, ClO₄⁻); ¹H NMR (CD₃NO₂, 400 MHz, δ, p.p.m.): 3.42 (overlapping triplets, 8H, CH₂), 3.92 (overlapping triplets, 8H, CH₂py), 5.4 (s, b, –NH), 6.58 (d, 2H), 7.20 (s, 1H), 7.99–8.01 (m, 9H), 8.54 (t, 4H, 4-pyridyl), 8.68 (d, 4H, 6-pyridinium/pyridyl). Crystals suitable for X-ray diffraction were obtained from the original sample.

S3. Refinement

H atoms attached to aromatic C atoms were fixed at C—H distances of 0.93 Å, while those attached to aliphatic methylene C atoms were fixed at C—H distances of 0.97 Å, and they were all refined using a riding-model approximation, with U_iso(H) = 1.2U_eq(C). H atoms attached to the pyridyl N atoms (N3 and N5) were identified from the difference maps and refined isotropically. The Fourier map gave a set of eight disordered positions for the O atoms of one of the perchlorate anions (Cl2O₄⁻). Initially, four of those peaks satisfying nearly tetrahedral geometry were assigned as O atoms (O7, O8, O9 and O10) with partial site occupancy. Refinement, and hence the subsequent difference map, showed three more O-atom positions (O7', O9' and O10'). Thus, atom O8 was found common to two approximate tetrahedra. The constrained refinements were performed on these partial positions such that the atoms of the two tetrahedra remained in chemically meaningful positions. Two common occupancy factors were given to each disordered set with the sum constrained to 1. The H atoms of the two water molecules were located in a difference map and their positions were fixed during the refinement such that they remained in chemically meaningful positions. Both the water molecules are hydrogen bonded to pyridine N atoms and perchlorate O atoms. Atom H6A of water molecule H₂O6, which is hydrogen-bonded to the disordered perchlorate group Cl2O₄⁻, is also disordered; its position was fixed at a geometrically meaningful position and was not refined.

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995) in WinGX (Farrugia, 1999); program(s) used to solve structure: SIR92 in WinGX (Altomare et al., 1994) in WinGX; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and WinGX.

Figures

	Fig. 1. The crystal structure of the [PDH2]^2+ cation of (I), showing the intramolecular hydrogen bonding (dashed lines) and the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms bonded to C atoms have been omitted for clarity. The perchlorate anions are not shown.
	Fig. 2. A partial packing diagram for (I). Disordered O-atom positions about Cl2 are shown. Selected atoms are labelled. Hydrogen bonds are shown as dashed lines.

1,3-bis{[2-(2-pyridinio)ethyl][2-(2-pyridyl)ethyl]amino}benzene diperchlorate dihydrate

Crystal data

C34H38N6^2+·2ClO4^−·2H2O	Z = 2
Mr = 765.64	F(000) = 804
Triclinic, P1	Dx = 1.394 Mg m^−3
a = 9.264 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.937 (6) Å	Cell parameters from 25 reflections
c = 20.751 (8) Å	θ = 10–15°
α = 78.28 (4)°	µ = 0.24 mm^−1
β = 87.01 (3)°	T = 293 K
γ = 77.31 (4)°	Needle, pale yellow
V = 1824.6 (15) Å^3	0.3 × 0.2 × 0.2 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	3517 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968). Number of ψ-scan sets used was 5. θ correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.	k = −11→11
Tmin = 0.946, Tmax = 1.000	l = −24→24
6833 measured reflections	2 standard reflections every 60 min
6397 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.212	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.1022P)^2 + 1.7559P] where P = (Fo^2 + 2Fc^2)/3
6397 reflections	(Δ/σ)max < 0.001
518 parameters	Δρmax = 0.57 e Å^−3
94 restraints	Δρmin = −0.43 e Å^−3

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)
C1	0.6496 (5)	0.4208 (4)	0.7296 (2)	0.0416 (10)
C2	0.6481 (5)	0.2957 (4)	0.7743 (2)	0.0422 (10)
H2	0.5711	0.2501	0.7728	0.051*
C3	0.7591 (5)	0.2365 (4)	0.8214 (2)	0.0402 (10)
C4	0.8700 (5)	0.3105 (5)	0.8246 (2)	0.0486 (11)
H4	0.9436	0.2754	0.8562	0.058*
C5	0.8703 (5)	0.4344 (5)	0.7813 (2)	0.0514 (12)
H5	0.9449	0.4821	0.7841	0.062*
C6	0.7634 (5)	0.4910 (5)	0.7335 (2)	0.0479 (11)
H6	0.7671	0.5746	0.7043	0.058*
C21	0.4155 (7)	0.8555 (6)	0.4437 (3)	0.0690 (15)
H21	0.3210	0.8747	0.4263	0.083*
C22	0.5059 (9)	0.9416 (6)	0.4180 (3)	0.0767 (18)
H22	0.4749	1.0173	0.3836	0.092*
C23	0.6457 (8)	0.9154 (6)	0.4437 (3)	0.0801 (19)
H23	0.7114	0.9726	0.4268	0.096*
C24	0.6867 (6)	0.8014 (6)	0.4955 (3)	0.0664 (15)
H24	0.7798	0.7824	0.5143	0.080*
C25	0.5878 (6)	0.7174 (5)	0.5184 (2)	0.0507 (12)
C26	0.6243 (6)	0.5910 (5)	0.5740 (3)	0.0608 (14)
H26A	0.7286	0.5734	0.5840	0.073*
H26B	0.6065	0.5092	0.5595	0.073*
C27	0.5344 (5)	0.6089 (5)	0.6364 (2)	0.0489 (12)
H27A	0.5723	0.6720	0.6579	0.059*
H27B	0.4324	0.6522	0.6246	0.059*
C31	0.0203 (6)	0.3555 (6)	0.5922 (3)	0.0619 (14)
H31	−0.0200	0.3975	0.5510	0.074*
C32	−0.0215 (6)	0.2390 (6)	0.6269 (3)	0.0675 (15)
H32	−0.0899	0.2003	0.6095	0.081*
C33	0.0378 (6)	0.1790 (6)	0.6873 (3)	0.0660 (15)
H33	0.0098	0.0991	0.7116	0.079*
C34	0.1387 (6)	0.2367 (5)	0.7123 (3)	0.0592 (13)
H34	0.1800	0.1947	0.7534	0.071*
C35	0.1798 (5)	0.3560 (5)	0.6774 (2)	0.0490 (12)
C36	0.2874 (6)	0.4286 (5)	0.7004 (2)	0.0547 (13)
H36A	0.2985	0.3992	0.7478	0.066*
H36B	0.2492	0.5295	0.6906	0.066*
C37	0.4379 (5)	0.3942 (5)	0.6672 (2)	0.0506 (12)
H37A	0.4810	0.2948	0.6812	0.061*
H37B	0.4248	0.4128	0.6199	0.061*
C51	1.1883 (7)	−0.3575 (6)	0.9881 (3)	0.0696 (16)
H51	1.1649	−0.4438	1.0061	0.083*
C52	1.3124 (6)	−0.3268 (6)	1.0073 (3)	0.0721 (16)
H52	1.3741	−0.3905	1.0387	0.087*
C53	1.3458 (6)	−0.1993 (6)	0.9794 (3)	0.0668 (15)
H53	1.4320	−0.1767	0.9909	0.080*
C54	1.2511 (6)	−0.1059 (5)	0.9345 (3)	0.0563 (13)
H54	1.2726	−0.0188	0.9164	0.068*
C55	1.1264 (5)	−0.1380 (5)	0.9158 (2)	0.0450 (11)
C56	1.0150 (5)	−0.0426 (5)	0.8687 (2)	0.0527 (12)
H56A	0.9791	−0.0970	0.8416	0.063*
H56B	1.0615	0.0258	0.8400	0.063*
C57	0.8832 (5)	0.0351 (5)	0.9052 (2)	0.0482 (11)
H57A	0.8515	−0.0330	0.9404	0.058*
H57B	0.9173	0.1023	0.9253	0.058*
C61	0.4943 (7)	−0.3488 (6)	0.8381 (3)	0.0731 (16)
H61	0.5149	−0.4380	0.8648	0.088*
C62	0.3684 (7)	−0.3114 (7)	0.8025 (3)	0.0756 (17)
H62	0.3049	−0.3727	0.8045	0.091*
C63	0.3382 (7)	−0.1804 (8)	0.7636 (3)	0.0790 (18)
H63	0.2521	−0.1502	0.7388	0.095*
C64	0.4360 (6)	−0.0935 (6)	0.7612 (3)	0.0635 (14)
H64	0.4169	−0.0045	0.7344	0.076*
C65	0.5623 (6)	−0.1386 (5)	0.7987 (2)	0.0515 (12)
C66	0.6707 (6)	−0.0483 (5)	0.7993 (2)	0.0556 (13)
H66A	0.6624	0.0212	0.7586	0.067*
H66B	0.7701	−0.1061	0.8012	0.067*
C67	0.6463 (5)	0.0273 (5)	0.8578 (2)	0.0474 (11)
H67A	0.5494	0.0899	0.8536	0.057*
H67B	0.6454	−0.0425	0.8979	0.057*
N1	0.5386 (5)	0.4760 (4)	0.6827 (2)	0.0557 (11)
N2	0.4523 (5)	0.7435 (4)	0.4928 (2)	0.0582 (11)
N3	0.1199 (4)	0.4102 (5)	0.6173 (2)	0.0528 (10)
N4	0.7558 (4)	0.1091 (4)	0.86469 (18)	0.0455 (9)
N5	1.0986 (5)	−0.2650 (4)	0.9436 (2)	0.0567 (11)
N6	0.5919 (5)	−0.2661 (4)	0.8376 (2)	0.0615 (11)
O1	0.0048 (7)	0.7770 (8)	0.7199 (3)	0.160 (3)
O2	−0.1565 (7)	0.9274 (7)	0.6492 (3)	0.163 (3)
O3	−0.0544 (6)	0.7073 (5)	0.6282 (3)	0.126 (2)
O4	0.0881 (7)	0.8688 (7)	0.6189 (4)	0.166 (3)
O5	0.1939 (5)	0.6395 (4)	0.5337 (2)	0.0660 (10)
O6	0.8706 (5)	−0.3617 (4)	0.9008 (2)	0.0875 (13)
O8	0.2719 (5)	0.2284 (4)	0.86017 (18)	0.0859 (13)
O7	0.1464 (10)	0.2502 (10)	0.9534 (4)	0.089 (3)	0.494 (4)
O9	0.3684 (9)	0.3198 (11)	0.9375 (5)	0.119 (5)	0.494 (4)
O10	0.1684 (9)	0.4420 (7)	0.8782 (5)	0.094 (4)	0.494 (4)
O7'	0.2776 (17)	0.1994 (10)	0.9721 (4)	0.138 (5)	0.506 (4)
O9'	0.3638 (11)	0.3796 (11)	0.9088 (6)	0.125 (6)	0.506 (4)
O10'	0.1132 (9)	0.3894 (15)	0.9143 (8)	0.216 (12)	0.506 (4)
Cl1	−0.03294 (17)	0.82241 (15)	0.65273 (8)	0.0741 (5)
Cl2	0.24922 (15)	0.30465 (14)	0.91146 (7)	0.0628 (4)
H3N	0.135 (5)	0.495 (6)	0.590 (3)	0.061 (15)*
H5N	1.023 (7)	−0.291 (6)	0.933 (3)	0.08 (2)*
H5B	0.281 (3)	0.663 (6)	0.522 (3)	0.11 (3)*
H5A	0.130 (6)	0.709 (5)	0.548 (4)	0.16 (4)*
H6A	0.8827	−0.4502	0.8943	0.180*
H6B	0.777 (3)	−0.314 (4)	0.893 (5)	0.20 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.041 (2)	0.036 (2)	0.045 (3)	−0.006 (2)	−0.004 (2)	−0.004 (2)
C2	0.039 (2)	0.038 (2)	0.050 (3)	−0.013 (2)	−0.005 (2)	−0.003 (2)
C3	0.037 (2)	0.036 (2)	0.047 (3)	−0.0081 (19)	−0.004 (2)	−0.005 (2)
C4	0.041 (3)	0.049 (3)	0.056 (3)	−0.010 (2)	−0.009 (2)	−0.008 (2)
C5	0.048 (3)	0.047 (3)	0.062 (3)	−0.020 (2)	−0.002 (2)	−0.006 (2)
C6	0.050 (3)	0.037 (2)	0.054 (3)	−0.013 (2)	−0.006 (2)	0.003 (2)
C21	0.088 (4)	0.060 (3)	0.052 (3)	−0.010 (3)	−0.010 (3)	0.000 (3)
C22	0.115 (6)	0.058 (4)	0.049 (3)	−0.014 (4)	0.011 (4)	0.000 (3)
C23	0.108 (5)	0.065 (4)	0.072 (4)	−0.039 (4)	0.039 (4)	−0.014 (3)
C24	0.064 (3)	0.069 (4)	0.068 (4)	−0.018 (3)	0.009 (3)	−0.015 (3)
C25	0.057 (3)	0.046 (3)	0.048 (3)	−0.011 (2)	0.008 (2)	−0.011 (2)
C26	0.059 (3)	0.051 (3)	0.064 (3)	0.000 (2)	−0.002 (3)	−0.004 (3)
C27	0.055 (3)	0.037 (2)	0.050 (3)	−0.008 (2)	−0.009 (2)	0.003 (2)
C31	0.056 (3)	0.069 (4)	0.059 (3)	−0.013 (3)	−0.014 (3)	−0.006 (3)
C32	0.054 (3)	0.075 (4)	0.077 (4)	−0.025 (3)	−0.011 (3)	−0.010 (3)
C33	0.070 (4)	0.062 (3)	0.070 (4)	−0.029 (3)	0.004 (3)	−0.007 (3)
C34	0.066 (3)	0.061 (3)	0.048 (3)	−0.018 (3)	0.000 (3)	0.000 (3)
C35	0.049 (3)	0.050 (3)	0.048 (3)	−0.009 (2)	−0.002 (2)	−0.010 (2)
C36	0.071 (3)	0.049 (3)	0.045 (3)	−0.017 (3)	−0.003 (2)	−0.007 (2)
C37	0.055 (3)	0.047 (3)	0.047 (3)	−0.014 (2)	−0.013 (2)	0.003 (2)
C51	0.070 (4)	0.046 (3)	0.079 (4)	−0.004 (3)	−0.007 (3)	0.013 (3)
C52	0.061 (4)	0.069 (4)	0.071 (4)	0.007 (3)	−0.022 (3)	0.003 (3)
C53	0.050 (3)	0.071 (4)	0.079 (4)	−0.007 (3)	−0.015 (3)	−0.017 (3)
C54	0.054 (3)	0.048 (3)	0.064 (3)	−0.009 (2)	−0.002 (3)	−0.008 (3)
C55	0.043 (3)	0.044 (3)	0.043 (3)	−0.002 (2)	0.000 (2)	−0.004 (2)
C56	0.052 (3)	0.057 (3)	0.042 (3)	−0.007 (2)	−0.002 (2)	0.002 (2)
C57	0.049 (3)	0.045 (3)	0.044 (3)	−0.005 (2)	−0.007 (2)	0.003 (2)
C61	0.099 (5)	0.053 (3)	0.074 (4)	−0.032 (3)	0.003 (4)	−0.011 (3)
C62	0.087 (5)	0.084 (5)	0.075 (4)	−0.046 (4)	0.009 (4)	−0.034 (4)
C63	0.058 (4)	0.112 (6)	0.080 (4)	−0.021 (4)	−0.005 (3)	−0.041 (4)
C64	0.063 (3)	0.065 (3)	0.058 (3)	−0.009 (3)	−0.007 (3)	−0.004 (3)
C65	0.056 (3)	0.049 (3)	0.050 (3)	−0.014 (2)	0.004 (2)	−0.010 (2)
C66	0.056 (3)	0.053 (3)	0.057 (3)	−0.017 (2)	0.004 (2)	−0.005 (2)
C67	0.047 (3)	0.039 (2)	0.052 (3)	−0.009 (2)	−0.001 (2)	0.000 (2)
N1	0.063 (3)	0.045 (2)	0.057 (3)	−0.022 (2)	−0.023 (2)	0.0138 (19)
N2	0.066 (3)	0.052 (2)	0.054 (3)	−0.015 (2)	0.000 (2)	−0.002 (2)
N3	0.052 (3)	0.050 (2)	0.053 (3)	−0.011 (2)	−0.007 (2)	−0.001 (2)
N4	0.043 (2)	0.040 (2)	0.050 (2)	−0.0096 (17)	−0.0092 (18)	0.0024 (17)
N5	0.049 (3)	0.051 (3)	0.067 (3)	−0.014 (2)	−0.006 (2)	−0.001 (2)
N6	0.074 (3)	0.046 (2)	0.064 (3)	−0.016 (2)	−0.010 (2)	−0.004 (2)
O1	0.122 (5)	0.240 (8)	0.104 (4)	−0.027 (5)	−0.044 (4)	−0.005 (5)
O2	0.143 (5)	0.148 (5)	0.155 (6)	0.057 (5)	−0.020 (4)	−0.022 (5)
O3	0.139 (5)	0.103 (4)	0.166 (5)	−0.068 (4)	0.037 (4)	−0.061 (4)
O4	0.173 (6)	0.145 (5)	0.216 (7)	−0.109 (5)	0.091 (5)	−0.056 (5)
O5	0.069 (3)	0.065 (2)	0.063 (2)	−0.021 (2)	0.000 (2)	−0.001 (2)
O6	0.088 (3)	0.064 (2)	0.109 (4)	−0.023 (2)	−0.029 (3)	0.001 (2)
O8	0.103 (3)	0.082 (3)	0.070 (3)	−0.006 (2)	−0.002 (2)	−0.021 (2)
O7	0.070 (6)	0.141 (10)	0.055 (5)	−0.030 (6)	0.019 (5)	−0.016 (6)
O9	0.074 (7)	0.125 (11)	0.156 (12)	−0.015 (7)	−0.079 (8)	−0.006 (9)
O10	0.068 (8)	0.040 (4)	0.167 (10)	−0.003 (5)	−0.022 (7)	−0.009 (5)
O7'	0.249 (17)	0.123 (9)	0.059 (6)	−0.099 (11)	−0.016 (8)	0.010 (6)
O9'	0.111 (10)	0.089 (8)	0.182 (14)	−0.067 (8)	−0.027 (9)	0.011 (9)
O10'	0.038 (7)	0.26 (2)	0.39 (3)	0.049 (11)	−0.057 (12)	−0.23 (2)
Cl1	0.0699 (10)	0.0576 (8)	0.0967 (12)	−0.0151 (7)	−0.0055 (8)	−0.0164 (8)
Cl2	0.0571 (8)	0.0628 (8)	0.0732 (9)	−0.0211 (7)	−0.0009 (7)	−0.0153 (7)

Geometric parameters (Å, º)

C1—C2	1.394 (6)	C52—C53	1.375 (8)
C1—N1	1.395 (6)	C52—H52	0.9300
C1—C6	1.399 (6)	C53—C54	1.369 (7)
C2—C3	1.402 (6)	C53—H53	0.9300
C2—H2	0.9300	C54—C55	1.359 (7)
C3—C4	1.399 (6)	C54—H54	0.9300
C3—N4	1.401 (5)	C55—N5	1.351 (6)
C4—C5	1.370 (6)	C55—C56	1.489 (6)
C4—H4	0.9300	C56—C57	1.544 (7)
C5—C6	1.383 (6)	C56—H56A	0.9700
C5—H5	0.9300	C56—H56B	0.9700
C6—H6	0.9300	C57—N4	1.453 (6)
C21—C22	1.342 (8)	C57—H57A	0.9700
C21—N2	1.343 (6)	C57—H57B	0.9700
C21—H21	0.9300	C61—N6	1.347 (7)
C22—C23	1.377 (9)	C61—C62	1.353 (9)
C22—H22	0.9300	C61—H61	0.9300
C23—C24	1.394 (8)	C62—C63	1.364 (9)
C23—H23	0.9300	C62—H62	0.9300
C24—C25	1.375 (7)	C63—C64	1.375 (8)
C24—H24	0.9300	C63—H63	0.9300
C25—N2	1.340 (6)	C64—C65	1.378 (7)
C25—C26	1.512 (7)	C64—H64	0.9300
C26—C27	1.523 (7)	C65—N6	1.337 (6)
C26—H26A	0.9700	C65—C66	1.488 (7)
C26—H26B	0.9700	C66—C67	1.536 (7)
C27—N1	1.461 (5)	C66—H66A	0.9700
C27—H27A	0.9700	C66—H66B	0.9700
C27—H27B	0.9700	C67—N4	1.461 (6)
C31—N3	1.344 (6)	C67—H67A	0.9700
C31—C32	1.355 (8)	C67—H67B	0.9700
C31—H31	0.9300	N3—H3N	0.95 (5)
C32—C33	1.362 (7)	N5—H5N	0.85 (6)
C32—H32	0.9300	O1—Cl1	1.412 (5)
C33—C34	1.371 (7)	O2—Cl1	1.363 (5)
C33—H33	0.9300	O3—Cl1	1.398 (4)
C34—C35	1.377 (7)	O4—Cl1	1.406 (5)
C34—H34	0.9300	O5—H5B	0.90 (4)
C35—N3	1.348 (6)	O5—H5A	0.90 (4)
C35—C36	1.500 (7)	O6—H6A	0.90
C36—C37	1.524 (7)	O6—H6B	0.90 (4)
C36—H36A	0.9700	O8—Cl2	1.409 (4)
C36—H36B	0.9700	O7—Cl2	1.380 (6)
C37—N1	1.452 (6)	O9—Cl2	1.305 (7)
C37—H37A	0.9700	O10—Cl2	1.457 (7)
C37—H37B	0.9700	O7'—Cl2	1.457 (8)
C51—N5	1.337 (7)	O9'—Cl2	1.417 (8)
C51—C52	1.351 (8)	O10'—Cl2	1.359 (8)
C51—H51	0.9300
C2—C1—N1	120.6 (4)	C52—C53—H53	120.3
C2—C1—C6	118.7 (4)	C55—C54—C53	121.3 (5)
N1—C1—C6	120.7 (4)	C55—C54—H54	119.3
C1—C2—C3	122.0 (4)	C53—C54—H54	119.3
C1—C2—H2	119.0	N5—C55—C54	117.5 (4)
C3—C2—H2	119.0	N5—C55—C56	117.2 (4)
C4—C3—N4	121.6 (4)	C54—C55—C56	125.3 (4)
C4—C3—C2	117.9 (4)	C55—C56—C57	111.4 (4)
N4—C3—C2	120.5 (4)	C55—C56—H56A	109.3
C5—C4—C3	120.1 (4)	C57—C56—H56A	109.3
C5—C4—H4	120.0	C55—C56—H56B	109.3
C3—C4—H4	120.0	C57—C56—H56B	109.3
C4—C5—C6	122.2 (4)	H56A—C56—H56B	108.0
C4—C5—H5	118.9	N4—C57—C56	115.4 (4)
C6—C5—H5	118.9	N4—C57—H57A	108.4
C5—C6—C1	119.2 (4)	C56—C57—H57A	108.4
C5—C6—H6	120.4	N4—C57—H57B	108.4
C1—C6—H6	120.4	C56—C57—H57B	108.4
C22—C21—N2	124.4 (6)	H57A—C57—H57B	107.5
C22—C21—H21	117.8	N6—C61—C62	124.6 (6)
N2—C21—H21	117.8	N6—C61—H61	117.7
C21—C22—C23	118.4 (6)	C62—C61—H61	117.7
C21—C22—H22	120.8	C61—C62—C63	117.6 (6)
C23—C22—H22	120.8	C61—C62—H62	121.2
C22—C23—C24	118.7 (6)	C63—C62—H62	121.2
C22—C23—H23	120.7	C62—C63—C64	119.5 (6)
C24—C23—H23	120.7	C62—C63—H63	120.2
C25—C24—C23	119.1 (6)	C64—C63—H63	120.2
C25—C24—H24	120.4	C63—C64—C65	119.8 (5)
C23—C24—H24	120.4	C63—C64—H64	120.1
N2—C25—C24	121.7 (5)	C65—C64—H64	120.1
N2—C25—C26	115.9 (4)	N6—C65—C64	121.0 (5)
C24—C25—C26	122.4 (5)	N6—C65—C66	116.6 (5)
C25—C26—C27	113.4 (4)	C64—C65—C66	122.3 (5)
C25—C26—H26A	108.9	C65—C66—C67	112.3 (4)
C27—C26—H26A	108.9	C65—C66—H66A	109.1
C25—C26—H26B	108.9	C67—C66—H66A	109.1
C27—C26—H26B	108.9	C65—C66—H66B	109.1
H26A—C26—H26B	107.7	C67—C66—H66B	109.1
N1—C27—C26	113.0 (4)	H66A—C66—H66B	107.9
N1—C27—H27A	109.0	N4—C67—C66	115.5 (4)
C26—C27—H27A	109.0	N4—C67—H67A	108.4
N1—C27—H27B	109.0	C66—C67—H67A	108.4
C26—C27—H27B	109.0	N4—C67—H67B	108.4
H27A—C27—H27B	107.8	C66—C67—H67B	108.4
N3—C31—C32	120.0 (5)	H67A—C67—H67B	107.5
N3—C31—H31	120.0	C1—N1—C37	122.5 (4)
C32—C31—H31	120.0	C1—N1—C27	122.1 (4)
C31—C32—C33	119.3 (5)	C37—N1—C27	114.3 (4)
C31—C32—H32	120.3	C25—N2—C21	117.6 (5)
C33—C32—H32	120.3	C31—N3—C35	122.8 (5)
C32—C33—C34	119.9 (5)	C31—N3—H3N	112 (3)
C32—C33—H33	120.1	C35—N3—H3N	125 (3)
C34—C33—H33	120.1	C3—N4—C57	120.4 (4)
C33—C34—C35	120.8 (5)	C3—N4—C67	121.2 (4)
C33—C34—H34	119.6	C57—N4—C67	116.2 (4)
C35—C34—H34	119.6	C51—N5—C55	122.5 (5)
N3—C35—C34	117.2 (4)	C51—N5—H5N	117 (4)
N3—C35—C36	117.7 (4)	C55—N5—H5N	121 (4)
C34—C35—C36	125.1 (4)	C65—N6—C61	117.4 (5)
C35—C36—C37	111.1 (4)	H5B—O5—H5A	112 (5)
C35—C36—H36A	109.4	H6A—O6—H6B	111
C37—C36—H36A	109.4	O2—Cl1—O3	113.1 (4)
C35—C36—H36B	109.4	O2—Cl1—O4	112.4 (5)
C37—C36—H36B	109.4	O3—Cl1—O4	107.8 (4)
H36A—C36—H36B	108.0	O2—Cl1—O1	107.0 (5)
N1—C37—C36	112.1 (4)	O3—Cl1—O1	108.6 (4)
N1—C37—H37A	109.2	O4—Cl1—O1	107.8 (5)
C36—C37—H37A	109.2	O9—Cl2—O7	117.6 (5)
N1—C37—H37B	109.2	O9—Cl2—O8	116.0 (5)
C36—C37—H37B	109.2	O10'—Cl2—O8	116.0 (5)
H37A—C37—H37B	107.9	O7—Cl2—O8	106.0 (4)
N5—C51—C52	120.7 (5)	O10'—Cl2—O9'	111.8 (5)
N5—C51—H51	119.6	O8—Cl2—O9'	108.6 (5)
C52—C51—H51	119.6	O9—Cl2—O10	109.0 (5)
C51—C52—C53	118.6 (5)	O7—Cl2—O10	104.5 (4)
C51—C52—H52	120.7	O8—Cl2—O10	101.9 (4)
C53—C52—H52	120.7	O10'—Cl2—O7'	110.0 (6)
C54—C53—C52	119.4 (5)	O8—Cl2—O7'	105.6 (4)
C54—C53—H53	120.3	O9'—Cl2—O7'	104.0 (5)
N1—C1—C2—C3	179.1 (4)	C61—C62—C63—C64	0.9 (9)
C6—C1—C2—C3	−1.9 (7)	C62—C63—C64—C65	−0.9 (9)
C1—C2—C3—C4	2.9 (7)	C63—C64—C65—N6	0.1 (8)
C1—C2—C3—N4	−178.7 (4)	C63—C64—C65—C66	−178.8 (5)
N4—C3—C4—C5	179.7 (4)	N6—C65—C66—C67	−81.9 (6)
C2—C3—C4—C5	−1.9 (7)	C64—C65—C66—C67	97.0 (6)
C3—C4—C5—C6	0.0 (7)	C65—C66—C67—N4	175.3 (4)
C4—C5—C6—C1	1.0 (7)	C2—C1—N1—C37	−14.8 (7)
C2—C1—C6—C5	0.0 (7)	C6—C1—N1—C37	166.2 (4)
N1—C1—C6—C5	178.9 (4)	C2—C1—N1—C27	178.2 (4)
N2—C21—C22—C23	−0.6 (9)	C6—C1—N1—C27	−0.7 (7)
C21—C22—C23—C24	−0.5 (9)	C36—C37—N1—C1	101.1 (5)
C22—C23—C24—C25	1.2 (8)	C36—C37—N1—C27	−91.0 (5)
C23—C24—C25—N2	−0.9 (8)	C26—C27—N1—C1	87.4 (6)
C23—C24—C25—C26	179.4 (5)	C26—C27—N1—C37	−80.6 (5)
N2—C25—C26—C27	−67.4 (6)	C24—C25—N2—C21	−0.1 (7)
C24—C25—C26—C27	112.3 (6)	C26—C25—N2—C21	179.5 (4)
C25—C26—C27—N1	163.9 (4)	C22—C21—N2—C25	1.0 (8)
N3—C31—C32—C33	0.4 (9)	C32—C31—N3—C35	−1.5 (8)
C31—C32—C33—C34	−0.1 (9)	C34—C35—N3—C31	2.2 (7)
C32—C33—C34—C35	0.9 (9)	C36—C35—N3—C31	−178.7 (5)
C33—C34—C35—N3	−1.9 (8)	C4—C3—N4—C57	−12.8 (6)
C33—C34—C35—C36	179.1 (5)	C2—C3—N4—C57	168.9 (4)
N3—C35—C36—C37	−76.6 (5)	C4—C3—N4—C67	−175.3 (4)
C34—C35—C36—C37	102.4 (6)	C2—C3—N4—C67	6.3 (6)
C35—C36—C37—N1	173.2 (4)	C56—C57—N4—C3	−75.1 (5)
N5—C51—C52—C53	−0.9 (9)	C56—C57—N4—C67	88.3 (5)
C51—C52—C53—C54	1.7 (9)	C66—C67—N4—C3	72.6 (5)
C52—C53—C54—C55	−1.5 (8)	C66—C67—N4—C57	−90.6 (5)
C53—C54—C55—N5	0.6 (7)	C52—C51—N5—C55	0.0 (9)
C53—C54—C55—C56	178.3 (5)	C54—C55—N5—C51	0.2 (7)
N5—C55—C56—C57	81.0 (5)	C56—C55—N5—C51	−177.8 (5)
C54—C55—C56—C57	−96.7 (6)	C64—C65—N6—C61	0.6 (8)
C55—C56—C57—N4	−168.5 (4)	C66—C65—N6—C61	179.5 (5)
N6—C61—C62—C63	−0.3 (9)	C62—C61—N6—C65	−0.5 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O5	0.95 (5)	1.82 (5)	2.762 (6)	170 (5)
N5—H5N···O6	0.85 (6)	1.91 (6)	2.758 (6)	172 (6)
O5—H5B···N2	0.90 (4)	1.95 (4)	2.834 (6)	172 (6)
O5—H5A···O3	0.90 (4)	2.32 (5)	2.996 (7)	132 (6)
O5—H5A···O4	0.90 (4)	2.33 (5)	3.123 (8)	147 (7)
O6—H6A···O10′^i	0.90	2.37	2.931 (10)	121
O6—H6B···N6	0.90 (4)	2.02 (4)	2.839 (6)	150 (7)

Symmetry code: (i) x+1, y−1, z.