2,6-Bis[bis(2-pyridiniomethyl)aminomethyl]-4-tert-butylphenol dichloride diperchlorate hydrate

The title compound, C₃₆H₄₄N₆O⁴⁺·2Cl⁻·2ClO₄⁻·0.132H₂O, is shown to be protonated at all the pyridine N atoms; the two chloride ions are hydrogen bonded to three pyridine N atoms and to the phenolic O atom of the same cation [Cl...N = 3.045 (2)–3.131 (2) Å and Cl...O = 2.938 (2) Å], and the remaining pyridine N atom is hydrogen bonded to the phenolic O atom [N...O = 2.861 (2) Å]. The mean value of the C—N—C angle of the protonated pyridine rings is 123.4 (1)°, which is significantly larger than that found for unprotonated pyridine rings.

S1. Comment

Compounds containing two transition metal ions have received considerable attention in the past two decades because of their potential reactivity in the activation of small molecules and catalysis of organic reactions, and as model systems for dimetallic enzymes (Reedijk, 1993; van der Beuken & Feringa, 1998). Several synthetic strategies for their preparation have been developed. These include self-asssembly methods, for example the spontaneous formation of dimetallic compounds with oxide and sulfide bridges, or the templated formation of suitable ditopic macrocyclic and acyclic ligands. The design of ligands containing two cavities suitable for metal binding is an important approach to a more controlled stepwise preparation of dimetallic compounds.

The title compound, bpbpH₅⁴⁺·2Cl^-·2ClO₄^-.0.132H₂O, (I), contains an example of such a preformed ditopic ligand. The compound bpbpH is an acyclic ditopic ligand precursor (it needs to be deprotonated in order to bind two metal ions); it has been used successfully by us for the preparation of dimetallic compounds. The ligand is normally septadentate, providing an amine and two pyridine donors to each metal ion in a dinuclear complex; the phenolate O atom `bridges' the two metal ions. The remaining coordination sphere of the metal ions is usually filled by small `exogenous' ligands, e.g. a typical formulation is [M₂(bpbp)(CH₃CO₂)₂](ClO₄)₂, M = a transition metal ion.

Interestingly bpbp^- shows a remarkable ability to stabilize mixed-metal and mixed-valent compounds (Ghiladi et al., 1997, 1999). In the attempted preparation of one such compound from an acidic solution, we isolated a small amount of a colourless crystalline product, which has been shown, by X-ray diffraction, to be the double salt (I). The ligand is protonated at the pyridine N atoms and not at the tertiary N atoms as might be expected from their acidities (cf. pK_a = 5.17 for pyridine and pK_a = 11.72 for triethylamine). We have also observed this preference for protonation at the pyridine N atoms in salts of trispicolylamine (tpa), i.e. in (H₃tpa)(SO₄)(NO₃) (Hazell et al., 1999) and in (H₃tpa)₂(HPO₄)(ClO₄)₄·2H₂O (Hazell & Toftlund, unpublished results).

The two Cl^- ions are both hydrogen bonded (Fig. 1) to three pyridine N atoms and to the phenolic O atom of the same cation [Cl···N = 3.045 (2)–3.131 (2) Å, Cl···O = 2.938 (2) Å]; the remaining pyridine N atom is hydrogen bonded to the phenolic O atom [N···O = 2.861 (2) Å].

Bond distances and angles are generally similar to those in bpbp complexes, the exception being that the C—N(py)—C angles are in the range 123.0 (2)–123.7 (2)°, whereas in both coordinated and non-coordinated pyridine groups this angle is less than 120°. Mean values from the Cambridge Structural Database (Allen & Kennard, 1993): 117.8° for non-coordinated pyridine (5255 observations mean standard uncertainty 0.03), 118.6° for pyridine coordinated to a metal atom (10000 observations, mean standard uncertainty 0.02) and 122.6° for pyridinium compounds (901 observations, mean standard uncertainty 0.07). The molecule is not as symmetric as might have been expected: C51—O1 is bent towards N1 and the torsion angle C51—C52—C57—N2 is 11.4° larger than C51—C56—C58—N1, distortions which may be caused by repusion between N41 and O1 [O1···N41 = 2.982 (2) Å]. This result is interesting with respect to the apparent propensity of bpbp^- to form unsymmetric dimetallic complexes, i.e. the incorporation of different metal ions in each cavity (Ghiladi et al.; 1997, 1999). A difference map showed a small peak which is interpreted as a partially occupied water site 2.62 (1) Å from one of the perchlorate O atoms.

S2. Experimental

Please give some indication of the method of preparation of the compound (reference?).

S3. Refinement

H atoms were located from a difference map, the phenolic H atom was refined isotropically, H atoms of the ligand were kept fixed at calculated positions (C—H = 0.95 Å) with U_iso = 1.2U_eq of the atom to which each is attached. H atoms of the water molecule were not included in the calculations.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SIR97 (Cascarano et al., 1996), KRYSTAL (Hazell, 1995); program(s) used to refine structure: modified ORFLS (Reference? 1962), KRYSTAL; molecular graphics: ORTEPIII (Burnett & Johnson, 1996), KRYSTAL; software used to prepare material for publication: KRYSTAL.

Figures

Fig. 1. View of (I) showing the hydrogen bonding. Displacement ellipsoids are shown at the 50% probability level; H atoms involved in hydrogen bonds are drawn as small circles of arbitrary radii; the other H atoms are ommitted.

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Crystal data

C36H44N6O^4+·2Cl^−·2ClO4^−·0.132H2O	F(000) = 1773.3
Mr = 848.97	Dx = 1.425 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5631 reflections
a = 20.376 (1) Å	θ = 1.9–29.8°
b = 13.0504 (8) Å	µ = 0.36 mm^−1
c = 15.8870 (9) Å	T = 120 K
β = 110.491 (1)°	Prism, colourless
V = 3957.4 (4) Å^3	0.40 × 0.24 × 0.10 mm
Z = 4

Data collection

Siemens SMART CCD diffractometer	10979 independent reflections
Radiation source: x-ray tube	6374 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.055
ω rotation scans with narrow frames	θmax = 29.8°, θmin = 1.9°
Absorption correction: integration (XPREP; Siemens, 1995)	h = −26→25
Tmin = 0.885, Tmax = 0.975	k = −17→18
39525 measured reflections	l = −22→21

Refinement

Refinement on F	0 constraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.033	1/{[σcs(F^2) + 1.03F^2]^1/2 - F|}^2 1/{[σcs(F^2) + 1.03F^2]^1/2 - F|}^2
wR(F^2) = 0.037	(Δ/σ)max = 0.002
S = 1.08	Δρmax = 0.40 (5) e Å^−3
6374 reflections	Δρmin = −0.46 (5) e Å^−3
506 parameters	Extinction correction: Becker & Coppens (1974) type 1 Lorentzian isotropic
0 restraints	Extinction coefficient: 150 (17)

Special details

Refinement. See_publ_section_exptl_refinement

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.53355 (3)	−0.15020 (4)	0.27732 (3)	0.0222 (3)
Cl2	−0.03101 (3)	−0.21425 (4)	0.36138 (3)	0.0202 (3)
Cl3	0.22969 (3)	−0.36994 (4)	0.49059 (3)	0.0220 (3)
Cl4	0.28673 (3)	−0.27507 (4)	0.25560 (3)	0.0247 (3)
O1	0.2192 (1)	−0.1475 (1)	0.3543 (1)	0.019 (1)
O2	0.6034 (1)	−0.1307 (1)	0.2773 (1)	0.032 (1)
O3	0.5266 (1)	−0.1068 (1)	0.3567 (1)	0.043 (1)
O4	0.5213 (1)	−0.2590 (1)	0.2742 (1)	0.032 (1)
O5	0.4839 (1)	−0.1028 (1)	0.1993 (1)	0.032 (1)
O6	−0.0123 (1)	−0.1193 (1)	0.4098 (1)	0.031 (1)
O7	0.0221 (1)	−0.2899 (1)	0.4014 (1)	0.043 (1)
O8	−0.0965 (1)	−0.2496 (1)	0.3661 (1)	0.034 (1)
O9	−0.0385 (1)	−0.1980 (1)	0.2693 (1)	0.039 (1)
N1	0.1265 (1)	−0.0691 (1)	0.1783 (1)	0.018 (1)
N2	0.3569 (1)	−0.1432 (1)	0.5299 (1)	0.017 (1)
N11	0.1118 (1)	−0.2636 (1)	0.2242 (1)	0.024 (1)
N21	0.2743 (1)	−0.0511 (1)	0.1946 (1)	0.020 (1)
N31	0.3723 (1)	−0.3489 (1)	0.4705 (1)	0.022 (1)
N41	0.2234 (1)	−0.1400 (1)	0.5437 (1)	0.019 (1)
C12	0.1126 (1)	−0.3566 (2)	0.2617 (1)	0.028 (1)
C13	0.0579 (1)	−0.4224 (2)	0.2237 (1)	0.028 (1)
C14	0.0031 (1)	−0.3907 (2)	0.1484 (1)	0.027 (1)
C15	0.0035 (1)	−0.2946 (2)	0.1127 (1)	0.025 (1)
C16	0.0594 (1)	−0.2301 (2)	0.1521 (1)	0.022 (1)
C17	0.0665 (1)	−0.1249 (2)	0.1173 (1)	0.025 (1)
C22	0.3442 (1)	−0.0413 (2)	0.2273 (1)	0.024 (1)
C23	0.3737 (1)	0.0544 (2)	0.2428 (1)	0.027 (1)
C24	0.3304 (1)	0.1389 (2)	0.2259 (1)	0.027 (1)
C25	0.2583 (1)	0.1262 (1)	0.1917 (1)	0.023 (1)
C26	0.2297 (1)	0.0292 (1)	0.1750 (1)	0.020 (1)
C27	0.1529 (1)	0.0078 (1)	0.1308 (1)	0.022 (1)
C32	0.3706 (1)	−0.4286 (2)	0.4171 (1)	0.028 (1)
C33	0.4259 (1)	−0.4490 (2)	0.3898 (1)	0.031 (1)
C34	0.4824 (1)	−0.3829 (2)	0.4164 (1)	0.033 (1)
C35	0.4822 (1)	−0.2995 (2)	0.4703 (1)	0.029 (1)
C36	0.4266 (1)	−0.2830 (1)	0.4987 (1)	0.021 (1)
C37	0.4229 (1)	−0.2004 (2)	0.5625 (1)	0.023 (1)
C42	0.1540 (1)	−0.1306 (2)	0.5246 (1)	0.021 (1)
C43	0.1280 (1)	−0.0434 (2)	0.5494 (1)	0.023 (1)
C44	0.1741 (1)	0.0331 (2)	0.5943 (1)	0.026 (1)
C45	0.2450 (1)	0.0211 (2)	0.6119 (1)	0.023 (1)
C46	0.2698 (1)	−0.0674 (1)	0.5856 (1)	0.018 (1)
C47	0.3458 (1)	−0.0889 (1)	0.6046 (1)	0.020 (1)
C51	0.2305 (1)	−0.0440 (1)	0.3669 (1)	0.015 (1)
C52	0.2948 (1)	−0.0040 (1)	0.4207 (1)	0.016 (1)
C53	0.2996 (1)	0.1016 (1)	0.4371 (1)	0.017 (1)
C54	0.2425 (1)	0.1677 (1)	0.4014 (1)	0.016 (1)
C55	0.1803 (1)	0.1242 (1)	0.3433 (1)	0.016 (1)
C56	0.1737 (1)	0.0204 (1)	0.3242 (1)	0.016 (1)
C57	0.3587 (1)	−0.0711 (1)	0.4586 (1)	0.019 (1)
C58	0.1093 (1)	−0.0230 (1)	0.2536 (1)	0.019 (1)
C59	0.2457 (1)	0.2829 (1)	0.4214 (1)	0.019 (1)
C60	0.2368 (1)	0.3437 (2)	0.3350 (1)	0.027 (1)
C61	0.3150 (1)	0.3140 (2)	0.4932 (1)	0.027 (1)
C62	0.1854 (1)	0.3121 (2)	0.4540 (1)	0.029 (1)
O10	0.9244 (7)	0.0260 (10)	0.0858 (8)	0.043 (5)*	0.132 (5)
HO1	0.249 (1)	−0.178 (2)	0.341 (2)	0.043 (8)*
HN11	0.1506	−0.2193	0.2506	0.029*
HN21	0.2551	−0.1182	0.1846	0.025*
HN31	0.3335	−0.3381	0.4895	0.026*
HN41	0.2405	−0.2014	0.5266	0.022*
H12	0.1507	−0.3761	0.3138	0.033*
H13	0.0576	−0.4885	0.2486	0.034*
H14	−0.0352	−0.4356	0.1210	0.033*
H15	−0.0345	−0.2729	0.0613	0.029*
H17a	0.0722	−0.1316	0.0607	0.030*
H17b	0.0250	−0.0871	0.1102	0.030*
H22	0.3732	−0.1005	0.2397	0.028*
H23	0.4232	0.0624	0.2648	0.032*
H24	0.3499	0.2057	0.2378	0.033*
H25	0.2285	0.1845	0.1796	0.027*
H27a	0.1279	0.0699	0.1284	0.026*
H27b	0.1447	−0.0161	0.0715	0.026*
H32	0.3304	−0.4716	0.3978	0.033*
H33	0.4255	−0.5071	0.3536	0.037*
H34	0.5213	−0.3946	0.3978	0.039*
H35	0.5207	−0.2533	0.4877	0.034*
H37a	0.4275	−0.2310	0.6185	0.028*
H37b	0.4605	−0.1540	0.5704	0.028*
H42	0.1232	−0.1841	0.4941	0.025*
H43	0.0790	−0.0355	0.5359	0.028*
H44	0.1571	0.0935	0.6130	0.031*
H45	0.2768	0.0737	0.6420	0.028*
H47a	0.3705	−0.0258	0.6142	0.025*
H47b	0.3632	−0.1298	0.6572	0.025*
H53	0.3433	0.1295	0.4739	0.020*
H55	0.1411	0.1675	0.3160	0.019*
H57a	0.3636	−0.1102	0.4107	0.022*
H57b	0.3983	−0.0279	0.4830	0.022*
H58a	0.0897	−0.0742	0.2802	0.023*
H58b	0.0761	0.0304	0.2308	0.023*
H60a	0.2388	0.4151	0.3474	0.032*
H60b	0.1927	0.3276	0.2907	0.032*
H60c	0.2732	0.3259	0.3134	0.032*
H61a	0.3170	0.3854	0.5056	0.032*
H61b	0.3522	0.2967	0.4729	0.032*
H61c	0.3203	0.2775	0.5469	0.032*
H62a	0.1875	0.3835	0.4664	0.034*
H62b	0.1898	0.2749	0.5071	0.034*
H62c	0.1419	0.2961	0.4087	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0193 (3)	0.0198 (2)	0.0263 (3)	−0.0036 (2)	0.0063 (2)	−0.0038 (2)
Cl2	0.0178 (3)	0.0205 (2)	0.0205 (2)	−0.0006 (2)	0.0044 (2)	−0.0034 (2)
Cl3	0.0240 (3)	0.0208 (2)	0.0213 (2)	−0.0048 (2)	0.0079 (2)	0.0004 (2)
Cl4	0.0310 (3)	0.0204 (3)	0.0229 (3)	0.0062 (2)	0.0097 (2)	−0.0013 (2)
O1	0.022 (1)	0.014 (1)	0.023 (1)	0.001 (1)	0.008 (1)	−0.002 (1)
O2	0.018 (1)	0.027 (1)	0.049 (1)	−0.003 (1)	0.009 (1)	−0.006 (1)
O3	0.055 (1)	0.046 (1)	0.036 (1)	−0.015 (1)	0.025 (1)	−0.017 (1)
O4	0.035 (1)	0.020 (1)	0.039 (1)	−0.007 (1)	0.009 (1)	0.000 (1)
O5	0.025 (1)	0.029 (1)	0.037 (1)	0.005 (1)	0.006 (1)	0.005 (1)
O6	0.035 (1)	0.022 (1)	0.032 (1)	−0.008 (1)	0.006 (1)	−0.009 (1)
O7	0.036 (1)	0.036 (1)	0.048 (1)	0.017 (1)	0.002 (1)	0.001 (1)
O8	0.028 (1)	0.029 (1)	0.049 (1)	−0.009 (1)	0.018 (1)	−0.005 (1)
O9	0.046 (1)	0.051 (1)	0.024 (1)	−0.003 (1)	0.017 (1)	−0.003 (1)
N1	0.019 (1)	0.017 (1)	0.017 (1)	−0.001 (1)	0.004 (1)	−0.003 (1)
N2	0.014 (1)	0.017 (1)	0.017 (1)	0.002 (1)	0.003 (1)	0.002 (1)
N11	0.019 (1)	0.021 (1)	0.027 (1)	−0.005 (1)	0.003 (1)	−0.005 (1)
N21	0.021 (1)	0.020 (1)	0.021 (1)	0.001 (1)	0.008 (1)	−0.002 (1)
N31	0.022 (1)	0.021 (1)	0.022 (1)	0.002 (1)	0.008 (1)	0.002 (1)
N41	0.020 (1)	0.019 (1)	0.017 (1)	−0.002 (1)	0.007 (1)	0.000 (1)
C12	0.030 (1)	0.024 (1)	0.028 (1)	−0.001 (1)	0.007 (1)	0.000 (1)
C13	0.034 (1)	0.025 (1)	0.031 (1)	−0.007 (1)	0.016 (1)	−0.005 (1)
C14	0.024 (1)	0.031 (1)	0.032 (1)	−0.008 (1)	0.016 (1)	−0.013 (1)
C15	0.019 (1)	0.030 (1)	0.025 (1)	−0.001 (1)	0.008 (1)	−0.010 (1)
C16	0.019 (1)	0.025 (1)	0.022 (1)	0.001 (1)	0.007 (1)	−0.007 (1)
C17	0.022 (1)	0.024 (1)	0.022 (1)	0.000 (1)	0.000 (1)	−0.006 (1)
C22	0.021 (1)	0.028 (1)	0.024 (1)	0.003 (1)	0.011 (1)	−0.001 (1)
C23	0.024 (1)	0.031 (1)	0.028 (1)	−0.003 (1)	0.013 (1)	−0.001 (1)
C24	0.031 (1)	0.025 (1)	0.030 (1)	−0.006 (1)	0.016 (1)	−0.001 (1)
C25	0.029 (1)	0.021 (1)	0.022 (1)	0.003 (1)	0.014 (1)	0.004 (1)
C26	0.023 (1)	0.024 (1)	0.015 (1)	0.004 (1)	0.010 (1)	0.002 (1)
C27	0.023 (1)	0.022 (1)	0.019 (1)	0.003 (1)	0.006 (1)	0.001 (1)
C32	0.035 (1)	0.018 (1)	0.027 (1)	−0.002 (1)	0.007 (1)	0.001 (1)
C33	0.041 (1)	0.024 (1)	0.029 (1)	0.011 (1)	0.013 (1)	0.002 (1)
C34	0.033 (1)	0.033 (1)	0.038 (1)	0.016 (1)	0.020 (1)	0.013 (1)
C35	0.023 (1)	0.026 (1)	0.037 (1)	0.004 (1)	0.011 (1)	0.007 (1)
C36	0.019 (1)	0.017 (1)	0.023 (1)	0.003 (1)	0.003 (1)	0.007 (1)
C37	0.018 (1)	0.021 (1)	0.026 (1)	0.001 (1)	0.001 (1)	0.001 (1)
C42	0.018 (1)	0.026 (1)	0.019 (1)	−0.006 (1)	0.006 (1)	0.000 (1)
C43	0.019 (1)	0.031 (1)	0.021 (1)	−0.001 (1)	0.008 (1)	−0.001 (1)
C44	0.025 (1)	0.026 (1)	0.028 (1)	0.000 (1)	0.013 (1)	−0.006 (1)
C45	0.024 (1)	0.023 (1)	0.024 (1)	−0.005 (1)	0.009 (1)	−0.006 (1)
C46	0.019 (1)	0.020 (1)	0.014 (1)	−0.004 (1)	0.006 (1)	0.001 (1)
C47	0.019 (1)	0.023 (1)	0.018 (1)	−0.003 (1)	0.004 (1)	0.000 (1)
C51	0.018 (1)	0.015 (1)	0.015 (1)	−0.001 (1)	0.008 (1)	0.000 (1)
C52	0.016 (1)	0.019 (1)	0.015 (1)	0.002 (1)	0.006 (1)	0.003 (1)
C53	0.016 (1)	0.019 (1)	0.017 (1)	−0.003 (1)	0.006 (1)	0.000 (1)
C54	0.018 (1)	0.017 (1)	0.017 (1)	0.000 (1)	0.009 (1)	0.000 (1)
C55	0.016 (1)	0.016 (1)	0.016 (1)	0.002 (1)	0.007 (1)	0.000 (1)
C56	0.015 (1)	0.018 (1)	0.015 (1)	−0.001 (1)	0.006 (1)	−0.001 (1)
C57	0.017 (1)	0.019 (1)	0.020 (1)	0.000 (1)	0.007 (1)	0.001 (1)
C58	0.017 (1)	0.018 (1)	0.021 (1)	0.000 (1)	0.005 (1)	−0.002 (1)
C59	0.020 (1)	0.015 (1)	0.021 (1)	−0.001 (1)	0.006 (1)	−0.002 (1)
C60	0.030 (1)	0.018 (1)	0.028 (1)	−0.003 (1)	0.005 (1)	0.001 (1)
C61	0.026 (1)	0.020 (1)	0.029 (1)	−0.003 (1)	0.003 (1)	−0.005 (1)
C62	0.029 (1)	0.023 (1)	0.035 (1)	−0.001 (1)	0.012 (1)	−0.010 (1)

Geometric parameters (Å, º)

Cl1—O2	1.447 (1)	C55—C56	1.384 (3)
Cl1—O3	1.434 (2)	C56—C58	1.508 (3)
Cl1—O4	1.439 (2)	C59—C61	1.527 (3)
Cl1—O5	1.437 (2)	C59—C62	1.539 (3)
Cl2—O6	1.438 (1)	C59—C60	1.540 (3)
Cl2—O7	1.438 (2)	O1—HO1	0.81 (2)
Cl2—O8	1.439 (2)	N11—HN11	0.950
Cl2—O9	1.432 (2)	N21—HN21	0.950
O1—C51	1.373 (2)	N31—HN31	0.950
N1—C17	1.461 (2)	N41—HN41	0.950
N1—C27	1.467 (3)	C53—H53	0.950
N1—C58	1.487 (2)	C55—H55	0.950
N2—C37	1.465 (2)	C57—H57a	0.950
N2—C47	1.467 (2)	C57—H57b	0.950
N2—C57	1.483 (2)	C58—H58a	0.950
N11—C12	1.349 (3)	C58—H58b	0.950
N11—C16	1.337 (3)	C12—H12	0.950
N21—C22	1.341 (3)	C13—H13	0.950
N21—C26	1.350 (3)	C14—H14	0.950
N31—C32	1.335 (3)	C15—H15	0.950
N31—C36	1.348 (3)	C17—H17a	0.950
N41—C42	1.345 (2)	C17—H17b	0.950
N41—C46	1.339 (2)	C22—H22	0.950
C12—C13	1.370 (3)	C23—H23	0.950
C13—C14	1.385 (3)	C24—H24	0.950
C14—C15	1.378 (3)	C25—H25	0.950
C15—C16	1.378 (3)	C27—H27a	0.950
C16—C17	1.505 (3)	C27—H27b	0.950
C22—C23	1.371 (3)	C32—H32	0.950
C23—C24	1.380 (3)	C33—H33	0.950
C24—C25	1.386 (3)	C34—H34	0.950
C25—C26	1.381 (3)	C35—H35	0.950
C26—C27	1.500 (3)	C37—H37a	0.950
C32—C33	1.370 (3)	C37—H37b	0.950
C33—C34	1.381 (3)	C42—H42	0.950
C34—C35	1.386 (3)	C43—H43	0.950
C35—C36	1.376 (3)	C44—H44	0.950
C36—C37	1.499 (3)	C45—H45	0.950
C42—C43	1.370 (3)	C47—H47a	0.950
C43—C44	1.386 (3)	C47—H47b	0.950
C44—C45	1.381 (3)	C60—H60a	0.950
C45—C46	1.382 (3)	C60—H60b	0.950
C46—C47	1.496 (3)	C60—H60c	0.950
C51—C52	1.391 (3)	C61—H61a	0.950
C51—C56	1.399 (3)	C61—H61b	0.950
C52—C53	1.400 (3)	C61—H61c	0.950
C52—C57	1.508 (3)	C62—H62a	0.950
C53—C54	1.399 (3)	C62—H62b	0.950
C54—C55	1.400 (3)	C62—H62c	0.950
C54—C59	1.533 (3)
O7^i···O10	2.617 (13)	O1···N1	2.955 (2)
O1···N41	2.982 (2)	O1···N2	3.192 (2)
O2—Cl1—O3	109.3 (1)	C54—C53—H53	118.7
O2—Cl1—O4	109.39 (9)	C52—C53—H53	118.7
O2—Cl1—O5	108.72 (9)	C56—C55—H55	118.8
O3—Cl1—O4	110.5 (1)	C54—C55—H55	118.8
O3—Cl1—O5	109.4 (1)	H57a—C57—H57b	109.5
O4—Cl1—O5	109.49 (9)	N2—C57—H57a	108.0
O6—Cl2—O7	109.7 (1)	C52—C57—H57a	108.0
O6—Cl2—O8	109.02 (9)	N2—C57—H57b	108.0
O6—Cl2—O9	109.4 (1)	C52—C57—H57b	108.0
O7—Cl2—O8	109.0 (1)	H58a—C58—H58b	109.5
O7—Cl2—O9	110.4 (1)	N1—C58—H58a	109.0
O8—Cl2—O9	109.3 (1)	C56—C58—H58a	109.0
C17—N1—C27	111.9 (2)	N1—C58—H58b	109.0
C58—N1—C17	110.9 (2)	C56—C58—H58b	109.0
C58—N1—C27	111.6 (1)	N11—C12—H12	120.4
C37—N2—C47	110.1 (1)	C13—C12—H12	120.4
C57—N2—C37	109.1 (1)	C12—C13—H13	120.7
C57—N2—C47	111.3 (1)	C14—C13—H13	120.7
C12—N11—C16	123.7 (2)	C15—C14—H14	119.7
C22—N21—C26	123.6 (2)	C13—C14—H14	119.7
C32—N31—C36	123.0 (2)	C16—C15—H15	120.2
C42—N41—C46	123.4 (2)	C14—C15—H15	120.2
N11—C12—C13	119.2 (2)	H17a—C17—H17b	109.5
C12—C13—C14	118.7 (2)	N1—C17—H17a	108.8
C13—C14—C15	120.5 (2)	C16—C17—H17a	108.8
C14—C15—C16	119.5 (2)	N1—C17—H17b	108.8
N11—C16—C15	118.4 (2)	C16—C17—H17b	108.8
N11—C16—C17	117.5 (2)	N21—C22—H22	120.1
C15—C16—C17	124.1 (2)	C23—C22—H22	120.1
N1—C17—C16	112.1 (2)	C22—C23—H23	120.6
N21—C22—C23	119.7 (2)	C24—C23—H23	120.6
C22—C23—C24	118.8 (2)	C23—C24—H24	120.0
C23—C24—C25	120.0 (2)	C25—C24—H24	120.0
C24—C25—C26	120.2 (2)	C26—C25—H25	119.9
N21—C26—C25	117.6 (2)	C24—C25—H25	119.9
N21—C26—C27	118.1 (2)	H27a—C27—H27b	109.5
C25—C26—C27	124.1 (2)	N1—C27—H27a	108.5
N1—C27—C26	113.4 (2)	C26—C27—H27a	108.5
N31—C32—C33	120.8 (2)	N1—C27—H27b	108.5
C32—C33—C34	118.2 (2)	C26—C27—H27b	108.5
C33—C34—C35	119.8 (2)	N31—C32—H32	119.6
C34—C35—C36	120.4 (2)	C33—C32—H32	119.6
N31—C36—C35	117.8 (2)	C32—C33—H33	120.9
N31—C36—C37	117.0 (2)	C34—C33—H33	120.9
C35—C36—C37	125.1 (2)	C33—C34—H34	120.1
N2—C37—C36	112.6 (2)	C35—C34—H34	120.1
N41—C42—C43	119.5 (2)	C36—C35—H35	119.8
C42—C43—C44	119.1 (2)	C34—C35—H35	119.8
C43—C44—C45	119.7 (2)	H37a—C37—H37b	109.5
C44—C45—C46	120.0 (2)	N2—C37—H37a	108.7
N41—C46—C45	118.3 (2)	C36—C37—H37a	108.7
N41—C46—C47	117.9 (2)	N2—C37—H37b	108.7
C45—C46—C47	123.8 (2)	C36—C37—H37b	108.7
N2—C47—C46	111.7 (2)	N41—C42—H42	120.2
O1—C51—C52	122.2 (2)	C43—C42—H42	120.2
O1—C51—C56	116.9 (2)	C42—C43—H43	120.5
C52—C51—C56	120.9 (2)	C44—C43—H43	120.5
C51—C52—C53	118.2 (2)	C45—C44—H44	120.2
C51—C52—C57	121.5 (2)	C43—C44—H44	120.1
C53—C52—C57	120.2 (2)	C44—C45—H45	120.0
C52—C53—C54	122.5 (2)	C46—C45—H45	120.0
C53—C54—C55	116.7 (2)	H47a—C47—H47b	109.5
C53—C54—C59	123.4 (2)	N2—C47—H47a	108.9
C55—C54—C59	119.8 (2)	C46—C47—H47a	108.9
C54—C55—C56	122.5 (2)	N2—C47—H47b	108.9
C51—C56—C55	118.8 (2)	C46—C47—H47b	108.9
C55—C56—C58	121.5 (2)	H60a—C60—H60b	109.4
C51—C56—C58	119.5 (2)	H60a—C60—H60c	109.4
N2—C57—C52	115.2 (2)	C59—C60—H60a	109.7
N1—C58—C56	111.2 (2)	H60b—C60—H60c	109.5
C54—C59—C61	112.2 (2)	C59—C60—H60b	109.4
C61—C59—C62	108.7 (2)	C59—C60—H60c	109.4
C60—C59—C61	108.6 (2)	H61a—C61—H61b	108.8
C54—C59—C62	109.4 (2)	H61a—C61—H61c	108.8
C54—C59—C60	109.7 (2)	C59—C61—H61a	112.2
C60—C59—C62	108.2 (2)	H61b—C61—H61c	109.5
C51—O1—HO1	115 (2)	C59—C61—H61b	108.8
C16—N11—HN11	118.2	C59—C61—H61c	108.8
C12—N11—HN11	118.1	H62a—C62—H62b	109.5
C22—N21—HN21	118.2	H62a—C62—H62c	109.5
C26—N21—HN21	118.2	C59—C62—H62a	109.4
C32—N31—HN31	118.5	H62b—C62—H62c	109.5
C36—N31—HN31	118.5	C59—C62—H62b	109.5
C46—N41—HN41	118.3	C59—C62—H62c	109.5
C42—N41—HN41	118.3
C51—C52—C57—N2	−70.3 (2)	C51—C56—C58—N1	−58.9 (2)

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—HN11···O1	0.95	1.98	2.861 (2)	152.8
N21—HN21···Cl4	0.95	2.32	3.062 (2)	134.8
N31—HN31···Cl3	0.95	2.16	3.045 (2)	154.1
N41—HN41···Cl3	0.95	2.26	3.131 (2)	151.5
O1—HO1···Cl4	0.81 (2)	2.18 (3)	2.938 (2)	155 (2)