Coordination and hydrogen-bonding assemblies in hybrid reaction products between 5,10,15,20-tetra-4-pyrid­ylporphyrin and dysprosium trinitrate hexa­hydrate

Reactions of the title free-base porphyrin compound (TPyP) with dysprosium trinitrate hexa­hydrate in different crystallization environments yielded two solid products, viz. [μ-5,15-bis­(pyridin-1-ium-4-yl)-10,20-di-4-pyridyl­porphyrin]bis­[aqua­tetra­nitratodysprosium(III)] benzene solvate, [Dy₂(NO₃)₈(C₄₀H₂₈N₈)(H₂O)₂]·C₆H₆, (I), and 5,10,15,20-tetra­kis­(pyridin-1-ium-4-yl)porphyrin penta­aqua­dinitratodysprosate(III) penta­nitrate diethanol solvate dihydrate, (C₄₀H₃₀N₈)[Dy(NO₃)₂(H₂O)₅](NO₃)₅·2C₂H₆O·2H₂O, (II). Compound (I) represents a 2:1 metal–porphyrin coordinated complex, which lies across a centre of inversion. Two trans-related pyridyl groups are involved in Dy coordination. The two other pyridyl substituents are protonated and involved in inter­molecular hydrogen bonding along with the metal-coordinated water and nitrate ligands. Compound (II) represents an extended hydrogen-bonded assembly between the tetra­kis­(pyridin-1-ium-4-yl)porphyrin tetra­cation, the [Dy(NO₃)₂(H₂O)₅]⁺ cation and the free nitrate ions, as well as the ethanol and water solvent molecules. This report provides the first structural characterization of the exocyclic dysprosium complex with tetra­pyridyl­porphyrin. It also demonstrates that charge balance can be readily achieved by protonation of the peripheral pyridyl functions, which then enhances their capacity in hydrogen bonding as H-atom donors rather than H-atom acceptors.

S1. Comment

The tetra(4-pyridyl)porphyrin ligand (TPyP) is characterized by rigid square-planar geometry, bears multiple diverging molecular recognition sites for metal coordination as well as hydrogen bonding, and consequently reveals an extraordinarily rich supramolecular chemistry. Of particular interest is the coordination polymerization of this scaffold through exocyclic metal ion connectors. A survey of the literature indicates that the TPyP moiety provides an excellent building block for the formation of extended hybrid coordination polymers of diverse topologies when reacted with exocyclic transition metal ion connectors such as Ag (e.g. Carlucci et al., 2003), Cd (e.g. Zheng et al., 2007), Cu (e.g. Ohmura et al., 2006), Fe (Hagrman et al., 1999), Hg and Pb (Sharma et al., 1999) ions. Structures with exocyclic coordination to the TPyP macroring of selected transition metals in discrete complexes have been reported as well (e.g. Kon et al., 2006). Only a few coordination polymers and molecular complexes of lanthanoid (Ln) ions with simple bipyridyl ligands are known (Sharma & Rogers, 1999), but analogous compounds with the TPyP unit have not been explored until recently. This could be due to the oxophilic nature of the lanthanoid ions and their much lower tendency to coordinate to aromatic pyridyl sites. In recent studies newer types of framework solids were obtained (Lipstman & Goldberg, 2010) by reacting the TPyP with various aqua nitrate salts of lanthanoid f-metals. Those materials are characterized by open architectures of three-dimensional connectivity, which are sustained either by a combination of coordination polymerization in one direction and hydrogen bonding in the other directions, or by hydrogen-bonding interactions between the organic and inorganic components in all three dimensions. Direct coordination bonding between a lanthanoid ion and the pyridyl sites of TPyP has been observed thus far for La, Nd, Sm, Gd and Tb ions (Lipstman & Goldberg, 2009, 2010). Direct insertion of the lanthanoids into the centre of the porphyrin core is unlikely due to the relatively large size of these ions. Only a small number of double-decker-type compounds in which the Ln ions are sandwiched between, and coordinated by, the central pyrrole rings of two TPyPs has been observed (Ikeda et al., 2000).

Within the context of our continuing investigations on porphyrin framework solids (Goldberg, 2008) and on the supramolecular hybrid assemblies of the TPyP with lanthanoid ions, we describe here the structures of two new solid products, (I) and (II), obtained by reacting the porphyrin ligand with dysprosium nitrate hexahydrate, Dy^III(NO₃)₃.6(H₂O), in different crystallization conditions. It should be noticed that the large excess of the aqua nitrate salt in the reaction creates acidic conditions which promote protonation of the TPyP Lewis base, accompanied by insertion of additional nitrate ions into the solid products. This has been observed in earlier studies of the tetranitrato lanthanide complexes with TPyP (Lipstman & Goldberg, 2009, 2010) as well as with 4,4'-bipyridine (Sharma & Rogers, 1999). Compound (I) provides another example of this. Here, two trans-related pyridyl groups of the TPyP component become protonated, while the other two pyridyl functions engage in coordinative bonds with two Dy metal centres. The ORTEP structure of this product, [Dy³⁺(NO₃^-)₄(H₂O)]₂.(TPyPH₂)²⁺, is illustrated in Fig. 1. The porphyrin core in the formed metallo-organic complex is essentially planar. The Dy ion doubly coordinates to the four nitrate ions and singly to a water molecule (Table 1), being thus characterized by a coordination number of 9 (typical of lanthanoid metal ions in their most common oxidation state of 3+). The crystal packing of (I) involves hydrogen-bonding interactions between neighbouring units of the complex, utilizing the water ligand and pyridinium fragments as H-atom donors and the metal-coordinated nitrate ions as H-atom acceptors (Table 2). It reveals columnar organization of the organic and inorganic components along the a axis of the crystal (Fig. 2). The porphyrin entities are stacked along a in an offset-stacked manner, as commonly observed in a large variety of tetraarylporphyrin compounds (Byrn et al., 1993). The interstitial voids between the porphyrin columns entrap disordered molecules of the benzene crystallization solvent. The inorganic [Dy³⁺(NO₃^-)₄(H₂O)] components displaced along the a axis at (x,1/2,0) are hydrogen bonded to one another across inversion centres at (0,1/2,0) and (1/2,1/2,0); the (TPyPH₂)²⁺ entity located across the inversion centre at (1/2,1/2,1/2) takes part in hydrogen bonding with adjacent units of the coordination complex near the (1,1,0) and (0,0,1) corners of the unit cell (Table 2).

In more acidic conditions, due to the presence of benzenetricarboxylic acid in the crystallization mixture, a full protonation of the peripheral pyridyl groups of the TPyP has occurred in compound (II). Moreover, in such conditions the basic nitrate anions have comparable tendency to be present in either a free or a metal-coordinated state, due to the competing ion-pairing and coordination interactions. In an aqueous protic environment this leads also to crystallization of the product in a solvated form of complex composition: [Dy³⁺(NO₃^-)₂(H₂O)₅].(TPyPH₄)⁴⁺.5(NO₃^-).2EtOH.2H₂O (Fig. 3). The Dy ion in (II) is also nine-coordinate, linking singly to five molecules of water and doubly to two nitrate ions (Table 3). Given the large number of potential O—H and N—H H-atom donor and the nitrate H-atom acceptor sites, the supramolecular organization in this structure is netted by a large number of O—H···O and N—H···O hydrogen bonds (Table 4). Fig. 4 illustrates the hydrogen-bonded crystal packing of (II). It also shows that the protonated pyridyl sites of the (TPyPH₄)⁴⁺ residue are not available for metal coordination, being involved in charge-assisted hydrogen bonds with the surrounding nitrate ions and water molecules. The conformation of the porphyrin macrocycle in (II) is essentially planar. The observed crystal packing exhibit segregated zones of the porphyrin and the metal-complex fragment parallel to the (ac) plane of the crystal, the former being centred at y = 0 and the latter clustering around y = 1/2.

In summary, we report here on yet another example of previously rarely observed direct exocyclic coordination adducts of TPyP and lanthanoid ions (Lipstman & Goldberg, 2009, 2010). Structures in which the TPyP entity is involved in supramolecular hydrogen bonding through their pyridyl groups are also scarce (Koner & Goldberg, 2009, 2010; Langford & Woodward, 2007; Kim et al., 2005). While it is expected in crystal engineering that the pyridyl N sites will normally engage in hydrogen bonds as H-atom acceptors with complementary H-atom donors, in structures (I) and (II) the protonated pyridyl sites adopt and [an?] opposite H-atom donating function.

Related literature

For related literature, see: Byrn et al. (1993); Carlucci et al. (2003); Goldberg (2008); Hagrman et al. (1999); Ikeda et al. (2000); Kim et al. (2005); Kon et al. (2006); Koner & Goldberg (2009, 2010); Langford & Woodward (2007); Lipstman & Goldberg (2009, 2010); Sharma & Rogers (1999); Sharma, Broker, Huddleston, Baldwin, Metzger & Rogers (1999); Spek (2009); Zheng et al. (2007).

S2. Experimental

The porphyrin and lanthanoid salt reagents as well as all solvents were obtained commercially. Compound (I) was obtained by dissolving dysprosium(III) trinitrate hexahydrate (1.24 mmol) and TPyP (0.046 mmol) in a mixture of ethanol (6 ml) and o-dichlorobenzene (8 ml). This solution was refluxed overnight and filtered. Then it was placed in a tube and covered carefully with a layer of benzene in order to induce crystallization of the product by slow diffusion of benzene into the mother solution. Nice purple prisms of the solid material, (I), were obtained after 5 months. Compound (II) was obtained in more acidic conditions by dissolving Dy(NO₃)₃.6(H₂O) (0.607 mmol), TPyP (0.026 mmol) and 1,3.5-benzenetricarboxylic acid (0.030 mmol) in a mixture of ethanol (12 ml) and o-dichlorobenzene (12 ml). The resulting solution was refluxed for 12 h, filtered and left for crystallization by slow evaporation. Diffraction quality crystals of (II) appeared at the bottom of the tube after 40 d.

S3. Refinement

The H atoms bound to C atoms were located in calculated positions, and were constrained to ride on their parent atoms with C—H distances of 0.95 and 0.98 Å and with U_iso(H) = 1.2 or 1.5 U_eq(C). Those bound to O and N atoms were either located in difference Fourier maps or placed in calculated positions to correspond to idealized hydrogen-bonding geometries, with O—H and N—H distances within the range of 0.83–1.03 Å and 0.85–0.96 Å, respectively. Their atomic positions were not refined, and they were constrained to ride on their parent atoms with U_iso(H) = 1.5 U_eq(carrier). In (I), the benzene crystallization solvent trapped in the crystal lattice was found to be severely disordered such that it could not be reliably modelled as discrete atoms. It is located on, and disordered about, the centre of inversion at (0,0,1/2). For the final refinement its contribution to the diffraction pattern was subtracted by the Squeeze procedure, using PLATON (Spek, 2009). In (II) the two H atoms bound to N within the porphyrin core could not be located reliably. As some residual electron density was observed near all the pyrrole N atoms, the H atoms bound to them were assumed to be disordered between the four pyrrole rings, and accordingly they were placed in calculated positions with N—H distances of 0.88 Å andU_iso(H) = 1.2 U_eq(N).

Computing details

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-III (Burnett & Johnson, 1996), Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of compound (I), showing the atom-labelling scheme. Molecules of this complex are located across centres of inversion, and only the unique atoms of the asymmetric unit are labelled. The atom ellipsoids represent thermal displacement parameters at the 50% probability level at circa 110 K. The H atoms and the disordered benzene solvent have been omitted.
	Fig. 2. The crystal packing of (I) projected down the a axis of the unit cell. Note the separate columns of the organic and inorganic components of this structure. The intermolecular hydrogen bonds are depicted by dashed lines. Wireframe illustration; only the Dy ions and the coordinated water ligand are shown as small spheres. The benzene solvent located on, and disordered about, the inversion centre at (0,0,1/2) has been omitted.
	Fig. 3. The molecular structure of compound (II), showing the atom-labeling scheme. The atom ellipsoids represent thermal displacement parameters at the 50% probability level at circa 110 K. The H atoms are omitted. In order to avoid severe overcrowding the upper and lower parts of this figure were drawn and labelled separately. Consequently, only hydrogen bonds between the component species within each part are shown (dashed lines); all hydrogen-bonding interactions are listed in Table 4.
	Fig. 4. Ball-and-stick representation of the crystal packing in (II), dashed lines indicating the hydrogen bonding between the component species. Note the segregation between the porphyrin and the Dy complex zones in the crystal. H atoms have been omitted.

(I) [µ-5,15-bis(pyridin-1-ium-4-yl)-10,20-di-4- pyridylporphyrin]bis[aquatetranitratodysprosium(III)] benzene solvate

Crystal data

[Dy2(NO3)8(C40H28N8)(H2O)2]·C6H6	Z = 1
Mr = 1477.82	F(000) = 724
Triclinic, P1	Dx = 1.644 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7897 (2) Å	Cell parameters from 4507 reflections
b = 12.2577 (2) Å	θ = 1.4–27.1°
c = 17.2316 (5) Å	µ = 2.58 mm^−1
α = 70.1447 (10)°	T = 110 K
β = 89.341 (1)°	Prism, purple
γ = 75.3827 (16)°	0.15 × 0.10 × 0.05 mm
V = 1492.45 (6) Å^3

Data collection

Nonius KappaCCD diffractometer	6457 independent reflections
Radiation source: fine-focus sealed tube	5074 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
Detector resolution: 12.8 pixels mm^-1	θmax = 27.1°, θmin = 1.8°
1 deg. ϕ and ω scans	h = 0→9
Absorption correction: multi-scan (Blessing, 1995)	k = −14→15
Tmin = 0.699, Tmax = 0.882	l = −21→22
13999 measured reflections

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0346P)^2] where P = (Fo^2 + 2Fc^2)/3
6457 reflections	(Δ/σ)max = 0.001
379 parameters	Δρmax = 1.36 e Å^−3
0 restraints	Δρmin = −1.03 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.

The structure contains also severely disordered benzene crystallization solvent, which could not be reliably modeled by discrete atoms. It is located on, and disordered about, crystallographic centers of inversion. Its contribution to the diffraction data was subtracted by the Squeeze procedure, using the PLATON software (Spek, 2003).

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

	x	y	z	Uiso*/Ueq
C1	0.2728 (6)	0.3326 (4)	0.5960 (3)	0.0215 (10)
C2	0.1662 (6)	0.2578 (4)	0.5839 (3)	0.0281 (11)
H2	0.1204	0.2019	0.6260	0.034*
C3	0.1440 (6)	0.2823 (4)	0.5014 (3)	0.0271 (11)
H3	0.0797	0.2459	0.4755	0.033*
C4	0.2331 (6)	0.3720 (4)	0.4594 (3)	0.0220 (10)
C5	0.2514 (6)	0.4171 (4)	0.3747 (3)	0.0220 (10)
C6	0.3575 (6)	0.4952 (4)	0.3365 (3)	0.0217 (10)
C7	0.3675 (6)	0.5434 (4)	0.2473 (3)	0.0254 (10)
H7	0.3058	0.5286	0.2063	0.031*
C8	0.4819 (6)	0.6134 (4)	0.2342 (3)	0.0254 (10)
H8	0.5163	0.6571	0.1822	0.031*
C9	0.5422 (6)	0.6086 (4)	0.3152 (3)	0.0199 (9)
C10	0.6628 (6)	0.6701 (4)	0.3280 (3)	0.0191 (9)
N11	0.3067 (5)	0.4004 (3)	0.5196 (2)	0.0212 (8)
H11	0.3750	0.4526	0.5076	0.025*
N12	0.4651 (5)	0.5359 (3)	0.3765 (2)	0.0205 (8)
C13	0.1588 (6)	0.3734 (4)	0.3204 (2)	0.0209 (10)
C14	−0.0246 (6)	0.3881 (4)	0.3172 (3)	0.0225 (10)
H14	−0.0958	0.4252	0.3512	0.027*
C15	−0.1021 (6)	0.3477 (4)	0.2637 (3)	0.0227 (10)
H15	−0.2272	0.3584	0.2621	0.027*
N16	−0.0094 (5)	0.2942 (3)	0.2139 (2)	0.0233 (8)
C17	0.1668 (6)	0.2796 (4)	0.2181 (3)	0.0265 (10)
H17	0.2351	0.2426	0.1833	0.032*
C18	0.2552 (6)	0.3157 (4)	0.2707 (3)	0.0253 (10)
H18	0.3811	0.3009	0.2726	0.030*
C19	0.7268 (6)	0.7483 (4)	0.2522 (2)	0.0201 (9)
C20	0.6045 (7)	0.8425 (4)	0.1943 (3)	0.0275 (11)
H20	0.4817	0.8591	0.2036	0.033*
C21	0.6621 (8)	0.9121 (4)	0.1229 (3)	0.0339 (12)
H21	0.5789	0.9760	0.0824	0.041*
N22	0.8335 (7)	0.8890 (4)	0.1112 (2)	0.0390 (12)
H22	0.8677	0.9348	0.0656	0.047*
C23	0.9597 (8)	0.7988 (5)	0.1657 (3)	0.0381 (14)
H23	1.0816	0.7850	0.1548	0.046*
C24	0.9062 (7)	0.7274 (4)	0.2375 (3)	0.0301 (11)
H24	0.9920	0.6640	0.2769	0.036*
Dy1	−0.16769 (3)	0.254801 (19)	0.101320 (13)	0.02266 (8)
O25	−0.2795 (4)	0.4577 (3)	0.08919 (18)	0.0258 (7)
H25A	−0.3644	0.5114	0.0450	0.031*
H25B	−0.2001	0.5031	0.0936	0.031*
N26	−0.4919 (5)	0.2577 (3)	0.0150 (2)	0.0263 (9)
O27	−0.4881 (4)	0.3514 (3)	0.03221 (19)	0.0286 (7)
O28	−0.3643 (4)	0.1658 (3)	0.0483 (2)	0.0290 (7)
O29	−0.6091 (4)	0.2586 (3)	−0.0314 (2)	0.0338 (8)
N30	−0.0376 (5)	0.3841 (3)	−0.0494 (2)	0.0259 (9)
O31	−0.1794 (4)	0.3517 (3)	−0.04998 (18)	0.0281 (8)
O32	0.0434 (4)	0.3574 (3)	0.02102 (18)	0.0284 (8)
O33	0.0176 (5)	0.4394 (3)	−0.11420 (19)	0.0324 (8)
N34	0.1371 (5)	0.0616 (3)	0.0877 (2)	0.0263 (9)
O35	−0.0091 (4)	0.1066 (3)	0.04046 (18)	0.0240 (7)
O36	0.1508 (5)	0.1072 (3)	0.14148 (19)	0.0334 (8)
O37	0.2524 (5)	−0.0201 (3)	0.0783 (2)	0.0372 (8)
N38	−0.2955 (6)	0.1028 (4)	0.2415 (2)	0.0327 (10)
O39	−0.3617 (4)	0.2172 (3)	0.2115 (2)	0.0303 (8)
O40	−0.1591 (5)	0.0617 (3)	0.20781 (19)	0.0309 (8)
O41	−0.3601 (6)	0.0392 (3)	0.2978 (2)	0.0551 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.021 (2)	0.023 (2)	0.019 (2)	−0.009 (2)	0.0011 (18)	−0.0049 (19)
C2	0.030 (3)	0.031 (3)	0.024 (3)	−0.016 (2)	−0.002 (2)	−0.006 (2)
C3	0.033 (3)	0.033 (3)	0.019 (2)	−0.019 (2)	0.000 (2)	−0.007 (2)
C4	0.024 (2)	0.024 (2)	0.018 (2)	−0.009 (2)	−0.0048 (18)	−0.0051 (19)
C5	0.021 (2)	0.025 (2)	0.022 (2)	−0.010 (2)	−0.0013 (19)	−0.008 (2)
C6	0.023 (2)	0.024 (2)	0.017 (2)	−0.004 (2)	−0.0041 (18)	−0.0064 (19)
C7	0.032 (3)	0.030 (2)	0.018 (2)	−0.015 (2)	0.0002 (19)	−0.009 (2)
C8	0.034 (3)	0.031 (3)	0.014 (2)	−0.017 (2)	0.0044 (19)	−0.005 (2)
C9	0.019 (2)	0.026 (2)	0.015 (2)	−0.007 (2)	0.0016 (18)	−0.0074 (19)
C10	0.018 (2)	0.019 (2)	0.018 (2)	−0.0074 (19)	0.0020 (18)	−0.0021 (18)
N11	0.026 (2)	0.0253 (19)	0.0144 (18)	−0.0142 (17)	−0.0008 (15)	−0.0045 (16)
N12	0.022 (2)	0.0233 (19)	0.0176 (19)	−0.0106 (17)	0.0006 (15)	−0.0060 (16)
C13	0.032 (3)	0.021 (2)	0.009 (2)	−0.012 (2)	−0.0020 (18)	−0.0008 (18)
C14	0.029 (3)	0.023 (2)	0.015 (2)	−0.009 (2)	−0.0044 (18)	−0.0028 (18)
C15	0.025 (2)	0.021 (2)	0.018 (2)	−0.007 (2)	−0.0052 (19)	−0.0007 (19)
N16	0.024 (2)	0.026 (2)	0.020 (2)	−0.0082 (18)	−0.0018 (16)	−0.0076 (17)
C17	0.030 (3)	0.028 (3)	0.023 (2)	−0.010 (2)	0.001 (2)	−0.010 (2)
C18	0.023 (2)	0.029 (2)	0.025 (2)	−0.010 (2)	−0.0009 (19)	−0.009 (2)
C19	0.032 (3)	0.017 (2)	0.013 (2)	−0.012 (2)	0.0001 (18)	−0.0046 (18)
C20	0.037 (3)	0.027 (2)	0.021 (2)	−0.016 (2)	−0.004 (2)	−0.006 (2)
C21	0.051 (4)	0.027 (3)	0.028 (3)	−0.019 (3)	−0.007 (2)	−0.009 (2)
N22	0.073 (4)	0.045 (3)	0.013 (2)	−0.042 (3)	0.012 (2)	−0.009 (2)
C23	0.049 (3)	0.048 (3)	0.040 (3)	−0.036 (3)	0.024 (3)	−0.029 (3)
C24	0.033 (3)	0.030 (3)	0.031 (3)	−0.016 (2)	0.006 (2)	−0.011 (2)
Dy1	0.02996 (13)	0.02089 (12)	0.01821 (12)	−0.00914 (9)	−0.00270 (8)	−0.00626 (8)
O25	0.0329 (19)	0.0191 (15)	0.0244 (17)	−0.0080 (14)	−0.0076 (14)	−0.0053 (13)
N26	0.034 (2)	0.023 (2)	0.025 (2)	−0.0110 (19)	0.0028 (18)	−0.0095 (17)
O27	0.036 (2)	0.0220 (16)	0.0297 (18)	−0.0087 (15)	−0.0054 (15)	−0.0102 (14)
O28	0.0300 (19)	0.0202 (16)	0.0353 (19)	−0.0051 (15)	−0.0038 (15)	−0.0087 (15)
O29	0.032 (2)	0.043 (2)	0.0336 (19)	−0.0151 (17)	−0.0078 (15)	−0.0182 (16)
N30	0.037 (2)	0.023 (2)	0.021 (2)	−0.0115 (19)	−0.0024 (18)	−0.0080 (17)
O31	0.038 (2)	0.0290 (17)	0.0205 (17)	−0.0191 (16)	−0.0021 (14)	−0.0057 (14)
O32	0.0352 (19)	0.0348 (18)	0.0200 (17)	−0.0169 (16)	−0.0023 (14)	−0.0100 (14)
O33	0.045 (2)	0.0335 (19)	0.0203 (18)	−0.0207 (17)	−0.0006 (15)	−0.0042 (15)
N34	0.034 (2)	0.026 (2)	0.020 (2)	−0.013 (2)	0.0033 (17)	−0.0069 (17)
O35	0.0229 (17)	0.0293 (17)	0.0198 (16)	−0.0099 (14)	−0.0015 (13)	−0.0062 (14)
O36	0.043 (2)	0.0372 (19)	0.0256 (18)	−0.0091 (17)	−0.0041 (15)	−0.0191 (16)
O37	0.036 (2)	0.037 (2)	0.038 (2)	−0.0006 (18)	0.0024 (17)	−0.0190 (17)
N38	0.048 (3)	0.030 (2)	0.023 (2)	−0.017 (2)	0.004 (2)	−0.0086 (19)
O39	0.035 (2)	0.0256 (18)	0.0314 (19)	−0.0088 (16)	0.0056 (15)	−0.0102 (15)
O40	0.041 (2)	0.0237 (17)	0.0227 (17)	−0.0044 (16)	−0.0004 (16)	−0.0045 (14)
O41	0.084 (3)	0.043 (2)	0.037 (2)	−0.030 (2)	0.027 (2)	−0.0030 (19)

Geometric parameters (Å, º)

C1—N11	1.361 (5)	C20—C21	1.382 (7)
C1—C10^i	1.395 (6)	C20—H20	0.9500
C1—C2	1.447 (6)	C21—N22	1.321 (7)
C2—C3	1.354 (6)	C21—H21	0.9500
C2—H2	0.9500	N22—C23	1.356 (7)
C3—C4	1.431 (6)	N22—H22	0.8800
C3—H3	0.9500	C23—C24	1.380 (7)
C4—N11	1.374 (5)	C23—H23	0.9500
C4—C5	1.393 (6)	C24—H24	0.9500
C5—C6	1.412 (6)	Dy1—O25	2.355 (3)
C5—C13	1.495 (5)	Dy1—O39	2.406 (3)
C6—N12	1.373 (5)	Dy1—O28	2.434 (3)
C6—C7	1.457 (6)	Dy1—O40	2.439 (3)
C7—C8	1.352 (6)	Dy1—O32	2.451 (3)
C7—H7	0.9500	Dy1—O35	2.462 (3)
C8—C9	1.456 (6)	Dy1—O31	2.462 (3)
C8—H8	0.9500	Dy1—O27	2.582 (3)
C9—N12	1.374 (5)	Dy1—O36	2.613 (4)
C9—C10	1.404 (6)	Dy1—N38	2.850 (4)
C10—C1^i	1.395 (6)	Dy1—N30	2.870 (4)
C10—C19	1.499 (6)	O25—H25A	0.9496
N11—H11	0.9023	O25—H25B	0.9496
C13—C18	1.388 (6)	N26—O29	1.216 (4)
C13—C14	1.394 (6)	N26—O28	1.263 (5)
C14—C15	1.391 (5)	N26—O27	1.287 (4)
C14—H14	0.9500	N30—O33	1.230 (5)
C15—N16	1.348 (6)	N30—O31	1.266 (5)
C15—H15	0.9500	N30—O32	1.273 (4)
N16—C17	1.338 (6)	N34—O37	1.220 (5)
N16—Dy1	2.551 (3)	N34—O36	1.252 (4)
C17—C18	1.389 (6)	N34—O35	1.290 (5)
C17—H17	0.9500	N38—O41	1.214 (5)
C18—H18	0.9500	N38—O40	1.278 (5)
C19—C20	1.386 (6)	N38—O39	1.284 (5)
C19—C24	1.393 (7)
N11—C1—C10^i	126.8 (4)	O32—Dy1—O35	78.50 (10)
N11—C1—C2	107.1 (4)	O25—Dy1—O31	80.06 (10)
C10^i—C1—C2	126.1 (4)	O39—Dy1—O31	140.67 (11)
C3—C2—C1	107.1 (4)	O28—Dy1—O31	76.14 (10)
C3—C2—H2	126.4	O40—Dy1—O31	141.44 (10)
C1—C2—H2	126.4	O32—Dy1—O31	52.24 (9)
C2—C3—C4	109.0 (4)	O35—Dy1—O31	70.49 (10)
C2—C3—H3	125.5	O25—Dy1—N16	70.85 (11)
C4—C3—H3	125.5	O39—Dy1—N16	78.07 (11)
N11—C4—C5	126.3 (4)	O28—Dy1—N16	155.05 (11)
N11—C4—C3	106.4 (4)	O40—Dy1—N16	85.02 (11)
C5—C4—C3	127.2 (4)	O32—Dy1—N16	79.31 (10)
C4—C5—C6	125.6 (4)	O35—Dy1—N16	120.20 (11)
C4—C5—C13	117.1 (3)	O31—Dy1—N16	128.62 (10)
C6—C5—C13	117.3 (4)	O25—Dy1—O27	66.05 (9)
N12—C6—C5	125.9 (4)	O39—Dy1—O27	73.92 (11)
N12—C6—C7	110.5 (3)	O28—Dy1—O27	50.84 (10)
C5—C6—C7	123.6 (3)	O40—Dy1—O27	108.53 (10)
C8—C7—C6	106.7 (4)	O32—Dy1—O27	111.46 (10)
C8—C7—H7	126.7	O35—Dy1—O27	109.73 (9)
C6—C7—H7	126.7	O31—Dy1—O27	66.75 (11)
C7—C8—C9	106.7 (4)	N16—Dy1—O27	130.06 (11)
C7—C8—H8	126.7	O25—Dy1—O36	132.39 (10)
C9—C8—H8	126.7	O39—Dy1—O36	112.77 (11)
N12—C9—C10	125.3 (4)	O28—Dy1—O36	110.00 (10)
N12—C9—C8	110.5 (3)	O40—Dy1—O36	66.18 (11)
C10—C9—C8	124.2 (4)	O32—Dy1—O36	71.78 (11)
C1^i—C10—C9	126.6 (4)	O35—Dy1—O36	50.15 (9)
C1^i—C10—C19	116.5 (3)	O31—Dy1—O36	104.29 (11)
C9—C10—C19	116.8 (4)	N16—Dy1—O36	70.23 (11)
C1—N11—C4	110.4 (3)	O27—Dy1—O36	159.49 (9)
C1—N11—H11	127.3	O25—Dy1—N38	110.38 (12)
C4—N11—H11	122.1	O39—Dy1—N38	26.61 (11)
C9—N12—C6	105.6 (3)	O28—Dy1—N38	73.28 (11)
C18—C13—C14	117.4 (4)	O40—Dy1—N38	26.54 (11)
C18—C13—C5	120.3 (4)	O32—Dy1—N38	157.26 (11)
C14—C13—C5	122.3 (4)	O35—Dy1—N38	100.54 (11)
C15—C14—C13	119.1 (4)	O31—Dy1—N38	149.15 (10)
C15—C14—H14	120.5	N16—Dy1—N38	81.79 (11)
C13—C14—H14	120.5	O27—Dy1—N38	90.41 (11)
N16—C15—C14	123.6 (4)	O36—Dy1—N38	90.00 (12)
N16—C15—H15	118.2	O25—Dy1—N30	76.23 (11)
C14—C15—H15	118.2	O39—Dy1—N30	158.31 (11)
C17—N16—C15	116.7 (3)	O28—Dy1—N30	100.69 (10)
C17—N16—Dy1	121.5 (3)	O40—Dy1—N30	147.97 (12)
C15—N16—Dy1	121.1 (3)	O32—Dy1—N30	26.19 (9)
N16—C17—C18	123.4 (4)	O35—Dy1—N30	72.60 (10)
N16—C17—H17	118.3	O31—Dy1—N30	26.05 (10)
C18—C17—H17	118.3	N16—Dy1—N30	104.24 (10)
C17—C18—C13	119.7 (4)	O27—Dy1—N30	89.08 (11)
C17—C18—H18	120.1	O36—Dy1—N30	87.85 (11)
C13—C18—H18	120.1	N38—Dy1—N30	172.46 (10)
C20—C19—C24	118.8 (4)	Dy1—O25—H25A	120.4
C20—C19—C10	119.5 (4)	Dy1—O25—H25B	120.0
C24—C19—C10	121.7 (4)	H25A—O25—H25B	104.3
C21—C20—C19	119.7 (5)	O29—N26—O28	122.4 (3)
C21—C20—H20	120.2	O29—N26—O27	122.0 (4)
C19—C20—H20	120.2	O28—N26—O27	115.6 (3)
N22—C21—C20	119.6 (5)	O29—N26—Dy1	169.4 (3)
N22—C21—H21	120.2	O28—N26—Dy1	54.83 (18)
C20—C21—H21	120.2	O27—N26—Dy1	61.6 (2)
C21—N22—C23	123.6 (4)	N26—O27—Dy1	92.3 (2)
C21—N22—H22	118.2	N26—O28—Dy1	100.1 (2)
C23—N22—H22	118.2	O33—N30—O31	121.0 (3)
N22—C23—C24	118.2 (5)	O33—N30—O32	122.1 (4)
N22—C23—H23	120.9	O31—N30—O32	116.9 (4)
C24—C23—H23	120.9	O33—N30—Dy1	179.7 (3)
C23—C24—C19	120.2 (5)	O31—N30—Dy1	58.7 (2)
C23—C24—H24	119.9	O32—N30—Dy1	58.2 (2)
C19—C24—H24	119.9	N30—O31—Dy1	95.3 (2)
O25—Dy1—O39	84.46 (11)	N30—O32—Dy1	95.6 (2)
O25—Dy1—O28	116.89 (10)	O37—N34—O36	123.9 (4)
O39—Dy1—O28	79.18 (11)	O37—N34—O35	120.1 (3)
O25—Dy1—O40	135.09 (11)	O36—N34—O35	116.0 (4)
O39—Dy1—O40	53.09 (11)	N34—O35—Dy1	100.0 (2)
O28—Dy1—O40	73.14 (10)	N34—O36—Dy1	93.8 (3)
O25—Dy1—O32	75.02 (11)	O41—N38—O40	123.1 (4)
O39—Dy1—O32	153.41 (10)	O41—N38—O39	121.5 (5)
O28—Dy1—O32	125.15 (10)	O40—N38—O39	115.4 (4)
O40—Dy1—O32	137.92 (11)	O41—N38—Dy1	175.5 (3)
O25—Dy1—O35	148.64 (10)	O40—N38—Dy1	58.5 (2)
O39—Dy1—O35	125.43 (10)	O39—N38—Dy1	57.1 (2)
O28—Dy1—O35	66.71 (10)	N38—O39—Dy1	96.3 (3)
O40—Dy1—O35	76.26 (10)	N38—O40—Dy1	95.0 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N22—H22···O35^ii	0.88	2.26	2.926 (5)	132
O25—H25A···O27^iii	0.95	1.86	2.784 (4)	164
O25—H25B···O33^iv	0.95	1.83	2.762 (4)	168

Symmetry codes: (ii) −x+1, −y+1, −z; (iii) −x−1, −y+1, −z; (iv) −x, −y+1, −z.

(II) 5,10,15,20-tetrakis(pyridin-1-ium-4-yl)porphyrin pentaaquadinitratodysprosate(III) pentanitrate diethanol solvate dihydrate

Crystal data

(C40H30N8)[Dy(NO3)2(H2O)5](NO3)5·2C2H6O·2H2O	Z = 2
Mr = 1437.54	F(000) = 1462
Triclinic, P1	Dx = 1.698 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.8961 (2) Å	Cell parameters from 12265 reflections
b = 12.9222 (2) Å	θ = 1.4–27.9°
c = 18.5978 (3) Å	µ = 1.44 mm^−1
α = 71.6843 (7)°	T = 110 K
β = 80.9684 (8)°	Needle, purple
γ = 73.3707 (7)°	0.55 × 0.10 × 0.05 mm
V = 2811.52 (8) Å^3

Data collection

Nonius KappaCCD diffractometer	13315 independent reflections
Radiation source: fine-focus sealed tube	11865 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 12.8 pixels mm^-1	θmax = 27.9°, θmin = 2.3°
1 deg. ϕ & ω scans	h = 0→16
Absorption correction: multi-scan (Blessing, 1995)	k = −15→16
Tmin = 0.512, Tmax = 0.932	l = −23→24
47169 measured reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0428P)^2 + 2.844P] where P = (Fo^2 + 2Fc^2)/3
13315 reflections	(Δ/σ)max = 0.002
813 parameters	Δρmax = 2.00 e Å^−3
0 restraints	Δρmin = −1.62 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	0.18608 (19)	0.0746 (2)	0.32693 (13)	0.0131 (5)
C2	0.09301 (19)	0.1310 (2)	0.28390 (14)	0.0149 (5)
H2	0.0892	0.1369	0.2321	0.018*
C3	0.0111 (2)	0.1748 (2)	0.32993 (14)	0.0161 (5)
H3	−0.0597	0.2177	0.3159	0.019*
C4	0.05066 (18)	0.1444 (2)	0.40363 (13)	0.0126 (5)
C5	−0.00806 (19)	0.1697 (2)	0.46869 (13)	0.0126 (5)
C6	0.02624 (19)	0.1258 (2)	0.54305 (13)	0.0127 (5)
C7	−0.03958 (19)	0.1515 (2)	0.60912 (14)	0.0149 (5)
H7	−0.1115	0.1979	0.6099	0.018*
C8	0.0210 (2)	0.0969 (2)	0.66893 (14)	0.0159 (5)
H8	−0.0005	0.0955	0.7204	0.019*
C9	0.12571 (19)	0.0404 (2)	0.63936 (13)	0.0125 (5)
C10	0.21373 (19)	−0.0217 (2)	0.68418 (13)	0.0124 (5)
C11	0.31577 (19)	−0.0774 (2)	0.65869 (13)	0.0125 (5)
C12	0.40846 (19)	−0.1375 (2)	0.70220 (14)	0.0149 (5)
H12	0.4122	−0.1454	0.7543	0.018*
C13	0.4899 (2)	−0.1810 (2)	0.65582 (14)	0.0150 (5)
H13	0.5601	−0.2256	0.6700	0.018*
C14	0.45118 (19)	−0.1478 (2)	0.58175 (13)	0.0126 (5)
C15	0.51018 (18)	−0.1702 (2)	0.51642 (14)	0.0128 (5)
C16	0.47678 (19)	−0.1247 (2)	0.44197 (13)	0.0130 (5)
C17	0.5443 (2)	−0.1461 (2)	0.37505 (14)	0.0151 (5)
H17	0.6170	−0.1903	0.3738	0.018*
C18	0.48353 (19)	−0.0910 (2)	0.31525 (14)	0.0148 (5)
H18	0.5056	−0.0871	0.2635	0.018*
C19	0.37760 (19)	−0.0389 (2)	0.34571 (13)	0.0121 (4)
C20	0.28906 (19)	0.0208 (2)	0.30118 (13)	0.0129 (5)
N21	0.15586 (16)	0.08257 (17)	0.39959 (11)	0.0120 (4)
H21	0.1978	0.0524	0.4377	0.014*	0.50
N22	0.12636 (16)	0.05713 (17)	0.56269 (11)	0.0118 (4)
H22	0.1796	0.0297	0.5326	0.014*	0.50
N23	0.34595 (16)	−0.08433 (17)	0.58566 (11)	0.0121 (4)
H23	0.3043	−0.0530	0.5474	0.015*	0.50
N24	0.37580 (16)	−0.05861 (17)	0.42265 (11)	0.0128 (4)
H24	0.3214	−0.0341	0.4531	0.015*	0.50
C25	−0.11340 (19)	0.2568 (2)	0.45620 (13)	0.0127 (5)
C26	−0.1140 (2)	0.3659 (2)	0.41069 (14)	0.0171 (5)
H26	−0.0483	0.3831	0.3857	0.021*
C27	−0.2099 (2)	0.4481 (2)	0.40207 (15)	0.0190 (5)
H27	−0.2106	0.5225	0.3713	0.023*
N28	−0.30283 (17)	0.42321 (19)	0.43727 (12)	0.0182 (4)
H28	−0.3644	0.4821	0.4229	0.022*
C29	−0.3059 (2)	0.3191 (2)	0.47957 (15)	0.0184 (5)
H29	−0.3732	0.3039	0.5025	0.022*
C30	−0.21189 (19)	0.2335 (2)	0.49012 (14)	0.0153 (5)
H30	−0.2141	0.1595	0.5202	0.018*
C31	0.19750 (19)	−0.0302 (2)	0.76687 (14)	0.0142 (5)
C32	0.1699 (2)	0.0650 (2)	0.79307 (14)	0.0169 (5)
H32	0.1628	0.1378	0.7580	0.020*
C33	0.1530 (2)	0.0531 (2)	0.87011 (15)	0.0191 (5)
H33	0.1328	0.1177	0.8882	0.023*
N34	0.16514 (17)	−0.0500 (2)	0.91918 (12)	0.0187 (5)
H34	0.1452	−0.0517	0.9675	0.022*
C35	0.1928 (2)	−0.1437 (2)	0.89666 (15)	0.0196 (5)
H35	0.2006	−0.2154	0.9333	0.024*
C36	0.2097 (2)	−0.1362 (2)	0.82055 (14)	0.0179 (5)
H36	0.2297	−0.2025	0.8044	0.022*
C37	0.61640 (19)	−0.2563 (2)	0.52762 (13)	0.0130 (5)
C38	0.6176 (2)	−0.3676 (2)	0.56697 (14)	0.0174 (5)
H38	0.5517	−0.3876	0.5882	0.021*
C39	0.7145 (2)	−0.4486 (2)	0.57502 (14)	0.0174 (5)
H39	0.7157	−0.5246	0.6021	0.021*
N40	0.80711 (16)	−0.41985 (18)	0.54462 (12)	0.0167 (4)
H40	0.8657	−0.4701	0.5563	0.020*
C41	0.8094 (2)	−0.3135 (2)	0.50728 (15)	0.0180 (5)
H41	0.8768	−0.2960	0.4873	0.022*
C42	0.7146 (2)	−0.2292 (2)	0.49769 (14)	0.0166 (5)
H42	0.7161	−0.1537	0.4711	0.020*
C43	0.30547 (18)	0.0287 (2)	0.21861 (13)	0.0133 (5)
C44	0.3304 (2)	−0.0677 (2)	0.19423 (14)	0.0163 (5)
H44	0.3362	−0.1396	0.2302	0.020*
C45	0.3467 (2)	−0.0580 (2)	0.11733 (14)	0.0176 (5)
H45	0.3648	−0.1233	0.1001	0.021*
N46	0.33671 (17)	0.04407 (19)	0.06738 (12)	0.0165 (4)
H46	0.3542	0.0450	0.0151	0.020*
C47	0.3120 (2)	0.1388 (2)	0.08856 (14)	0.0173 (5)
H47	0.3052	0.2097	0.0512	0.021*
C48	0.2964 (2)	0.1331 (2)	0.16457 (14)	0.0161 (5)
H48	0.2795	0.1999	0.1800	0.019*
Dy1	0.702253 (9)	−0.533180 (10)	0.860983 (6)	0.01390 (4)
O49	0.79708 (15)	−0.69702 (15)	0.81793 (10)	0.0199 (4)
H49A	0.8172	−0.7634	0.8445	0.024*
H49B	0.8423	−0.6869	0.7747	0.024*
O50	0.53003 (14)	−0.40517 (16)	0.85230 (11)	0.0192 (4)
H50A	0.4649	−0.4177	0.8488	0.023*
H50B	0.4989	−0.3514	0.8703	0.023*
O51	0.60420 (15)	−0.66595 (16)	0.92000 (10)	0.0207 (4)
H51A	0.5587	−0.6801	0.8992	0.025*
H51B	0.5921	−0.6989	0.9706	0.025*
O52	0.61767 (15)	−0.53740 (16)	0.75738 (10)	0.0199 (4)
H52A	0.6314	−0.5968	0.7424	0.024*
H52B	0.5453	−0.4813	0.7409	0.024*
O53	0.84279 (15)	−0.63785 (17)	0.94207 (11)	0.0235 (4)
H53A	0.9035	−0.6593	0.9206	0.028*
H53B	0.8528	−0.6200	0.9806	0.028*
N54	0.81617 (19)	−0.4013 (2)	0.73552 (13)	0.0204 (5)
O55	0.71768 (15)	−0.36119 (17)	0.75410 (11)	0.0249 (4)
O56	0.86375 (16)	−0.49236 (17)	0.78242 (12)	0.0263 (4)
O57	0.86330 (19)	−0.3566 (2)	0.67666 (12)	0.0337 (5)
N58	0.67758 (18)	−0.43113 (19)	0.98290 (12)	0.0195 (5)
O59	0.64632 (15)	−0.51949 (16)	0.99439 (11)	0.0211 (4)
O60	0.71819 (16)	−0.39194 (16)	0.91558 (10)	0.0211 (4)
O61	0.67073 (18)	−0.38445 (17)	1.03207 (11)	0.0274 (4)
N62	0.44367 (17)	−0.14617 (19)	−0.07865 (12)	0.0174 (4)
O63	0.44498 (17)	−0.24763 (16)	−0.07121 (11)	0.0247 (4)
O64	0.44997 (18)	−0.11915 (18)	−0.02132 (11)	0.0268 (4)
O65	0.43644 (17)	−0.07576 (17)	−0.14238 (11)	0.0251 (4)
N66	0.33915 (17)	−0.38738 (19)	0.73972 (12)	0.0179 (4)
O67	0.25350 (15)	−0.32683 (18)	0.71152 (12)	0.0275 (4)
O68	0.42315 (15)	−0.41293 (16)	0.69836 (11)	0.0212 (4)
O69	0.34212 (15)	−0.42492 (18)	0.81182 (11)	0.0240 (4)
N70	−0.50681 (18)	0.63320 (18)	0.35290 (12)	0.0177 (4)
O71	−0.42356 (16)	0.64165 (17)	0.30935 (11)	0.0242 (4)
O72	−0.59990 (15)	0.67572 (16)	0.32957 (11)	0.0232 (4)
O73	−0.49684 (15)	0.58102 (17)	0.42244 (10)	0.0239 (4)
N74	0.09616 (18)	−0.0024 (2)	1.08898 (12)	0.0199 (5)
O75	0.13928 (17)	−0.09653 (17)	1.07435 (11)	0.0255 (4)
O76	0.07883 (19)	0.08400 (18)	1.03513 (12)	0.0338 (5)
O77	0.07380 (17)	−0.0008 (2)	1.15574 (11)	0.0302 (5)
N78	0.98078 (18)	−0.62369 (19)	0.65074 (13)	0.0212 (5)
O79	0.88620 (15)	−0.63361 (17)	0.67191 (11)	0.0231 (4)
O80	1.05422 (18)	−0.66565 (19)	0.69486 (13)	0.0339 (5)
O81	1.00108 (15)	−0.56880 (17)	0.58273 (11)	0.0251 (4)
O82	1.03608 (16)	−0.69470 (18)	0.86309 (12)	0.0277 (4)
H82	1.0212	−0.6644	0.8129	0.033*
C83	1.1105 (3)	−0.6398 (3)	0.8749 (2)	0.0410 (8)
H83A	1.1611	−0.6937	0.9126	0.049*
H83B	1.0699	−0.5769	0.8960	0.049*
C84	1.1733 (3)	−0.5954 (4)	0.8043 (2)	0.0482 (9)
H84A	1.1235	−0.5423	0.7666	0.072*
H84B	1.2164	−0.6578	0.7844	0.072*
H84C	1.2218	−0.5566	0.8147	0.072*
O85	0.15098 (16)	−0.38868 (18)	0.91730 (12)	0.0278 (5)
H85	0.2198	−0.3971	0.8844	0.033*
C86	0.0596 (3)	−0.3396 (3)	0.8703 (2)	0.0396 (8)
H86A	0.0640	−0.3847	0.8352	0.048*
H86B	0.0617	−0.2621	0.8396	0.048*
C87	−0.0442 (3)	−0.3365 (4)	0.9190 (2)	0.0474 (9)
H87A	−0.0508	−0.2874	0.9512	0.071*
H87B	−0.0446	−0.4128	0.9511	0.071*
H87C	−0.1053	−0.3074	0.8867	0.071*
O88	0.35170 (16)	0.12419 (17)	−0.08839 (11)	0.0243 (4)
H88A	0.3952	0.0699	−0.1105	0.029*
H88B	0.3799	0.1796	−0.1038	0.029*
O89	0.44753 (16)	−0.69169 (17)	0.84548 (11)	0.0251 (4)
H89A	0.3922	−0.6344	0.8569	0.030*
H89B	0.4507	−0.6734	0.7911	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0152 (11)	0.0133 (12)	0.0108 (11)	−0.0024 (9)	−0.0010 (9)	−0.0042 (9)
C2	0.0156 (11)	0.0181 (12)	0.0099 (11)	−0.0009 (9)	−0.0026 (9)	−0.0049 (9)
C3	0.0136 (11)	0.0187 (13)	0.0119 (11)	0.0010 (9)	−0.0022 (9)	−0.0029 (9)
C4	0.0108 (10)	0.0143 (12)	0.0111 (11)	−0.0009 (9)	−0.0007 (9)	−0.0036 (9)
C5	0.0116 (11)	0.0129 (11)	0.0123 (11)	−0.0013 (9)	−0.0005 (9)	−0.0041 (9)
C6	0.0144 (11)	0.0120 (11)	0.0110 (11)	−0.0025 (9)	0.0000 (9)	−0.0034 (9)
C7	0.0122 (11)	0.0185 (13)	0.0130 (11)	−0.0014 (9)	0.0010 (9)	−0.0064 (10)
C8	0.0148 (11)	0.0204 (13)	0.0114 (11)	−0.0017 (9)	0.0009 (9)	−0.0066 (10)
C9	0.0140 (11)	0.0115 (11)	0.0109 (11)	−0.0022 (9)	0.0005 (9)	−0.0031 (9)
C10	0.0158 (11)	0.0118 (11)	0.0087 (10)	−0.0025 (9)	0.0004 (9)	−0.0031 (9)
C11	0.0143 (11)	0.0121 (11)	0.0104 (11)	−0.0025 (9)	0.0002 (9)	−0.0037 (9)
C12	0.0157 (11)	0.0164 (12)	0.0116 (11)	−0.0012 (9)	−0.0036 (9)	−0.0039 (9)
C13	0.0146 (11)	0.0154 (12)	0.0127 (11)	0.0007 (9)	−0.0046 (9)	−0.0033 (9)
C14	0.0115 (10)	0.0131 (12)	0.0127 (11)	−0.0023 (9)	−0.0017 (9)	−0.0033 (9)
C15	0.0110 (10)	0.0126 (11)	0.0135 (11)	−0.0010 (9)	−0.0004 (9)	−0.0041 (9)
C16	0.0113 (11)	0.0135 (12)	0.0129 (11)	−0.0010 (9)	0.0006 (9)	−0.0045 (9)
C17	0.0146 (11)	0.0153 (12)	0.0135 (11)	−0.0001 (9)	0.0009 (9)	−0.0057 (9)
C18	0.0134 (11)	0.0174 (12)	0.0119 (11)	−0.0026 (9)	0.0021 (9)	−0.0043 (9)
C19	0.0126 (11)	0.0130 (11)	0.0101 (11)	−0.0021 (9)	0.0003 (9)	−0.0042 (9)
C20	0.0151 (11)	0.0120 (11)	0.0103 (11)	−0.0018 (9)	−0.0012 (9)	−0.0024 (9)
N21	0.0107 (9)	0.0141 (10)	0.0089 (9)	−0.0001 (7)	0.0006 (7)	−0.0034 (8)
N22	0.0103 (9)	0.0142 (10)	0.0091 (9)	−0.0002 (7)	0.0004 (7)	−0.0038 (8)
N23	0.0104 (9)	0.0143 (10)	0.0101 (9)	−0.0005 (7)	−0.0007 (7)	−0.0038 (8)
N24	0.0121 (9)	0.0139 (10)	0.0102 (9)	−0.0003 (8)	−0.0003 (7)	−0.0035 (8)
C25	0.0125 (11)	0.0155 (12)	0.0108 (11)	−0.0009 (9)	−0.0017 (9)	−0.0065 (9)
C26	0.0155 (12)	0.0189 (13)	0.0145 (12)	−0.0016 (10)	0.0004 (9)	−0.0044 (10)
C27	0.0208 (13)	0.0175 (13)	0.0153 (12)	−0.0009 (10)	−0.0021 (10)	−0.0035 (10)
N28	0.0156 (10)	0.0195 (11)	0.0167 (10)	0.0051 (8)	−0.0046 (8)	−0.0083 (9)
C29	0.0123 (11)	0.0249 (14)	0.0185 (12)	−0.0021 (10)	0.0003 (9)	−0.0100 (11)
C30	0.0131 (11)	0.0174 (12)	0.0147 (11)	−0.0031 (9)	−0.0011 (9)	−0.0041 (10)
C31	0.0123 (11)	0.0159 (12)	0.0124 (11)	−0.0004 (9)	−0.0015 (9)	−0.0038 (9)
C32	0.0175 (12)	0.0157 (12)	0.0155 (12)	−0.0007 (9)	−0.0020 (9)	−0.0044 (10)
C33	0.0180 (12)	0.0222 (14)	0.0178 (12)	−0.0010 (10)	−0.0027 (10)	−0.0099 (10)
N34	0.0191 (11)	0.0265 (12)	0.0102 (10)	−0.0027 (9)	0.0002 (8)	−0.0081 (9)
C35	0.0202 (12)	0.0212 (14)	0.0149 (12)	−0.0042 (10)	0.0000 (10)	−0.0033 (10)
C36	0.0198 (12)	0.0176 (13)	0.0146 (12)	−0.0010 (10)	−0.0006 (10)	−0.0056 (10)
C37	0.0123 (11)	0.0147 (12)	0.0115 (11)	0.0009 (9)	−0.0005 (9)	−0.0070 (9)
C38	0.0131 (11)	0.0193 (13)	0.0164 (12)	−0.0020 (9)	0.0007 (9)	−0.0030 (10)
C39	0.0177 (12)	0.0157 (12)	0.0158 (12)	−0.0010 (10)	−0.0015 (10)	−0.0033 (10)
N40	0.0121 (10)	0.0158 (11)	0.0189 (11)	0.0029 (8)	−0.0022 (8)	−0.0057 (9)
C41	0.0139 (11)	0.0205 (13)	0.0183 (12)	−0.0035 (10)	0.0015 (10)	−0.0056 (10)
C42	0.0153 (11)	0.0158 (12)	0.0176 (12)	−0.0037 (9)	0.0000 (9)	−0.0039 (10)
C43	0.0100 (10)	0.0169 (12)	0.0107 (11)	−0.0004 (9)	−0.0007 (8)	−0.0037 (9)
C44	0.0173 (12)	0.0151 (12)	0.0133 (12)	−0.0010 (9)	0.0007 (9)	−0.0032 (9)
C45	0.0189 (12)	0.0192 (13)	0.0152 (12)	−0.0028 (10)	0.0015 (10)	−0.0088 (10)
N46	0.0174 (10)	0.0210 (11)	0.0118 (10)	−0.0035 (8)	0.0010 (8)	−0.0079 (8)
C47	0.0189 (12)	0.0164 (13)	0.0142 (12)	−0.0039 (10)	−0.0007 (10)	−0.0016 (10)
C48	0.0175 (12)	0.0165 (12)	0.0132 (11)	−0.0017 (9)	−0.0006 (9)	−0.0053 (10)
Dy1	0.01412 (6)	0.01434 (7)	0.01207 (6)	−0.00234 (4)	0.00030 (4)	−0.00387 (4)
O49	0.0221 (9)	0.0155 (9)	0.0159 (9)	−0.0007 (7)	0.0036 (7)	−0.0020 (7)
O50	0.0136 (8)	0.0206 (10)	0.0253 (10)	0.0001 (7)	−0.0003 (7)	−0.0137 (8)
O51	0.0248 (10)	0.0225 (10)	0.0162 (9)	−0.0124 (8)	0.0009 (7)	−0.0027 (7)
O52	0.0219 (9)	0.0204 (10)	0.0177 (9)	0.0007 (7)	−0.0043 (7)	−0.0100 (7)
O53	0.0186 (9)	0.0282 (11)	0.0210 (10)	0.0018 (8)	−0.0043 (7)	−0.0090 (8)
N54	0.0259 (12)	0.0226 (12)	0.0164 (11)	−0.0129 (9)	0.0046 (9)	−0.0073 (9)
O55	0.0179 (9)	0.0277 (11)	0.0239 (10)	−0.0056 (8)	−0.0021 (8)	0.0000 (8)
O56	0.0210 (10)	0.0190 (10)	0.0304 (11)	−0.0025 (8)	0.0076 (8)	−0.0024 (8)
O57	0.0442 (13)	0.0374 (13)	0.0234 (11)	−0.0255 (11)	0.0154 (10)	−0.0088 (9)
N58	0.0226 (11)	0.0197 (12)	0.0149 (10)	−0.0026 (9)	−0.0013 (9)	−0.0057 (9)
O59	0.0244 (10)	0.0215 (10)	0.0190 (9)	−0.0096 (8)	0.0011 (8)	−0.0058 (8)
O60	0.0305 (10)	0.0198 (10)	0.0130 (9)	−0.0098 (8)	0.0016 (7)	−0.0032 (7)
O61	0.0415 (12)	0.0266 (11)	0.0149 (9)	−0.0056 (9)	−0.0002 (8)	−0.0106 (8)
N62	0.0186 (10)	0.0222 (12)	0.0130 (10)	−0.0068 (9)	0.0020 (8)	−0.0071 (9)
O63	0.0351 (11)	0.0194 (10)	0.0223 (10)	−0.0063 (8)	0.0021 (8)	−0.0120 (8)
O64	0.0429 (12)	0.0286 (11)	0.0147 (9)	−0.0149 (9)	0.0019 (8)	−0.0107 (8)
O65	0.0334 (11)	0.0277 (11)	0.0136 (9)	−0.0096 (9)	−0.0015 (8)	−0.0038 (8)
N66	0.0174 (10)	0.0181 (11)	0.0193 (11)	−0.0040 (8)	−0.0020 (9)	−0.0072 (9)
O67	0.0175 (9)	0.0305 (11)	0.0313 (11)	0.0032 (8)	−0.0090 (8)	−0.0095 (9)
O68	0.0177 (9)	0.0236 (10)	0.0204 (9)	−0.0013 (7)	0.0018 (7)	−0.0089 (8)
O69	0.0206 (9)	0.0340 (12)	0.0177 (9)	−0.0064 (8)	−0.0009 (7)	−0.0083 (8)
N70	0.0211 (11)	0.0133 (11)	0.0176 (11)	−0.0011 (8)	−0.0025 (9)	−0.0054 (8)
O71	0.0253 (10)	0.0247 (11)	0.0214 (10)	−0.0066 (8)	0.0056 (8)	−0.0083 (8)
O72	0.0218 (9)	0.0195 (10)	0.0269 (10)	0.0022 (8)	−0.0104 (8)	−0.0073 (8)
O73	0.0239 (10)	0.0246 (10)	0.0134 (9)	0.0065 (8)	−0.0011 (7)	−0.0035 (8)
N74	0.0169 (10)	0.0281 (13)	0.0154 (11)	−0.0053 (9)	0.0026 (8)	−0.0091 (9)
O75	0.0371 (11)	0.0220 (10)	0.0155 (9)	−0.0031 (9)	−0.0020 (8)	−0.0066 (8)
O76	0.0453 (13)	0.0254 (11)	0.0205 (10)	0.0018 (10)	−0.0006 (9)	−0.0032 (9)
O77	0.0307 (11)	0.0476 (14)	0.0140 (9)	−0.0087 (10)	0.0047 (8)	−0.0153 (9)
N78	0.0214 (11)	0.0172 (11)	0.0206 (11)	0.0031 (9)	−0.0040 (9)	−0.0055 (9)
O79	0.0225 (10)	0.0226 (10)	0.0186 (9)	−0.0016 (8)	0.0016 (8)	−0.0034 (8)
O80	0.0308 (11)	0.0330 (12)	0.0330 (12)	0.0044 (9)	−0.0167 (9)	−0.0071 (10)
O81	0.0199 (9)	0.0238 (10)	0.0209 (10)	0.0024 (8)	0.0041 (8)	−0.0014 (8)
O82	0.0238 (10)	0.0277 (11)	0.0293 (11)	−0.0024 (8)	−0.0030 (8)	−0.0080 (9)
C83	0.0382 (18)	0.044 (2)	0.046 (2)	−0.0117 (15)	−0.0054 (16)	−0.0175 (17)
C84	0.045 (2)	0.062 (3)	0.049 (2)	−0.0258 (19)	0.0048 (17)	−0.025 (2)
O85	0.0192 (9)	0.0353 (12)	0.0294 (11)	−0.0007 (8)	−0.0069 (8)	−0.0131 (9)
C86	0.0320 (17)	0.046 (2)	0.0380 (19)	−0.0074 (15)	−0.0112 (14)	−0.0059 (16)
C87	0.0287 (17)	0.071 (3)	0.047 (2)	−0.0189 (17)	0.0013 (15)	−0.020 (2)
O88	0.0316 (11)	0.0239 (10)	0.0178 (9)	−0.0105 (8)	0.0024 (8)	−0.0056 (8)
O89	0.0308 (11)	0.0281 (11)	0.0192 (10)	−0.0111 (9)	0.0032 (8)	−0.0095 (8)

Geometric parameters (Å, º)

C1—N21	1.374 (3)	C41—H41	0.9500
C1—C20	1.399 (3)	C42—H42	0.9500
C1—C2	1.431 (3)	C43—C48	1.392 (3)
C2—C3	1.359 (3)	C43—C44	1.393 (4)
C2—H2	0.9500	C44—C45	1.383 (3)
C3—C4	1.435 (3)	C44—H44	0.9500
C3—H3	0.9500	C45—N46	1.338 (3)
C4—N21	1.367 (3)	C45—H45	0.9500
C4—C5	1.401 (3)	N46—C47	1.340 (3)
C5—C6	1.409 (3)	N46—H46	0.9600
C5—C25	1.492 (3)	C47—C48	1.378 (3)
C6—N22	1.370 (3)	C47—H47	0.9500
C6—C7	1.452 (3)	C48—H48	0.9500
C7—C8	1.345 (3)	Dy1—O51	2.3172 (18)
C7—H7	0.9500	Dy1—O50	2.3532 (17)
C8—C9	1.454 (3)	Dy1—O53	2.3582 (18)
C8—H8	0.9500	Dy1—O52	2.3802 (18)
C9—N22	1.372 (3)	Dy1—O60	2.4185 (19)
C9—C10	1.408 (3)	Dy1—O49	2.4280 (18)
C10—C11	1.397 (3)	Dy1—O56	2.4372 (19)
C10—C31	1.492 (3)	Dy1—O55	2.507 (2)
C11—N23	1.377 (3)	Dy1—O59	2.5196 (19)
C11—C12	1.437 (3)	Dy1—N54	2.892 (2)
C12—C13	1.359 (3)	Dy1—N58	2.897 (2)
C12—H12	0.9500	O49—H49A	0.8329
C13—C14	1.433 (3)	O49—H49B	0.9132
C13—H13	0.9500	O50—H50A	0.9151
C14—N23	1.374 (3)	O50—H50B	0.8368
C14—C15	1.394 (3)	O51—H51A	0.8394
C15—C16	1.407 (3)	O51—H51B	0.9118
C15—C37	1.494 (3)	O52—H52A	0.8598
C16—N24	1.368 (3)	O52—H52B	1.0263
C16—C17	1.456 (3)	O53—H53A	0.8346
C17—C18	1.347 (3)	O53—H53B	0.8564
C17—H17	0.9500	N54—O57	1.223 (3)
C18—C19	1.453 (3)	N54—O55	1.265 (3)
C18—H18	0.9500	N54—O56	1.277 (3)
C19—N24	1.370 (3)	N58—O61	1.224 (3)
C19—C20	1.406 (3)	N58—O59	1.263 (3)
C20—C43	1.492 (3)	N58—O60	1.283 (3)
N21—H21	0.8800	N62—O64	1.242 (3)
N22—H22	0.8800	N62—O65	1.245 (3)
N23—H23	0.8800	N62—O63	1.270 (3)
N24—H24	0.8800	N66—O67	1.240 (3)
C25—C26	1.396 (4)	N66—O68	1.252 (3)
C25—C30	1.396 (3)	N66—O69	1.277 (3)
C26—C27	1.374 (4)	N70—O71	1.249 (3)
C26—H26	0.9500	N70—O72	1.252 (3)
C27—N28	1.346 (3)	N70—O73	1.264 (3)
C27—H27	0.9500	N74—O76	1.235 (3)
N28—C29	1.336 (4)	N74—O77	1.235 (3)
N28—H28	0.9349	N74—O75	1.279 (3)
C29—C30	1.379 (3)	N78—O80	1.239 (3)
C29—H29	0.9500	N78—O79	1.251 (3)
C30—H30	0.9500	N78—O81	1.269 (3)
C31—C32	1.397 (4)	O82—C83	1.423 (4)
C31—C36	1.401 (4)	O82—H82	0.9192
C32—C33	1.381 (4)	C83—C84	1.472 (5)
C32—H32	0.9500	C83—H83A	0.9900
C33—N34	1.340 (4)	C83—H83B	0.9900
C33—H33	0.9500	C84—H84A	0.9800
N34—C35	1.339 (4)	C84—H84B	0.9800
N34—H34	0.8903	C84—H84C	0.9800
C35—C36	1.375 (4)	O85—C86	1.450 (4)
C35—H35	0.9500	O85—H85	0.9950
C36—H36	0.9500	C86—C87	1.491 (5)
C37—C38	1.390 (4)	C86—H86A	0.9900
C37—C42	1.395 (3)	C86—H86B	0.9900
C38—C39	1.375 (3)	C87—H87A	0.9800
C38—H38	0.9500	C87—H87B	0.9800
C39—N40	1.339 (3)	C87—H87C	0.9800
C39—H39	0.9500	O88—H88A	0.9271
N40—C41	1.337 (3)	O88—H88B	0.8452
N40—H40	0.8496	O89—H89A	0.9226
C41—C42	1.377 (3)	O89—H89B	0.9605
N21—C1—C20	125.6 (2)	C47—N46—H46	121.5
N21—C1—C2	107.1 (2)	N46—C47—C48	119.8 (2)
C20—C1—C2	127.3 (2)	N46—C47—H47	120.1
C3—C2—C1	108.2 (2)	C48—C47—H47	120.1
C3—C2—H2	125.9	C47—C48—C43	119.5 (2)
C1—C2—H2	125.9	C47—C48—H48	120.3
C2—C3—C4	107.7 (2)	C43—C48—H48	120.3
C2—C3—H3	126.2	O51—Dy1—O50	83.77 (7)
C4—C3—H3	126.2	O51—Dy1—O53	89.82 (7)
N21—C4—C5	125.9 (2)	O50—Dy1—O53	144.32 (6)
N21—C4—C3	107.4 (2)	O51—Dy1—O52	78.20 (7)
C5—C4—C3	126.7 (2)	O50—Dy1—O52	70.58 (6)
C4—C5—C6	126.1 (2)	O53—Dy1—O52	142.08 (6)
C4—C5—C25	116.1 (2)	O51—Dy1—O60	123.86 (6)
C6—C5—C25	117.7 (2)	O50—Dy1—O60	75.63 (6)
N22—C6—C5	125.2 (2)	O53—Dy1—O60	79.16 (7)
N22—C6—C7	110.8 (2)	O52—Dy1—O60	137.02 (6)
C5—C6—C7	123.9 (2)	O51—Dy1—O49	75.13 (7)
C8—C7—C6	106.7 (2)	O50—Dy1—O49	137.69 (6)
C8—C7—H7	126.7	O53—Dy1—O49	72.73 (7)
C6—C7—H7	126.7	O52—Dy1—O49	69.45 (6)
C7—C8—C9	106.6 (2)	O60—Dy1—O49	146.16 (7)
C7—C8—H8	126.7	O51—Dy1—O56	147.01 (7)
C9—C8—H8	126.7	O50—Dy1—O56	123.87 (7)
N22—C9—C10	125.5 (2)	O53—Dy1—O56	77.20 (7)
N22—C9—C8	110.7 (2)	O52—Dy1—O56	93.52 (7)
C10—C9—C8	123.8 (2)	O60—Dy1—O56	83.76 (7)
C11—C10—C9	126.1 (2)	O49—Dy1—O56	72.09 (7)
C11—C10—C31	116.2 (2)	O51—Dy1—O55	147.18 (6)
C9—C10—C31	117.6 (2)	O50—Dy1—O55	72.45 (6)
N23—C11—C10	125.5 (2)	O53—Dy1—O55	122.64 (7)
N23—C11—C12	107.0 (2)	O52—Dy1—O55	72.80 (7)
C10—C11—C12	127.5 (2)	O60—Dy1—O55	72.23 (7)
C13—C12—C11	108.1 (2)	O49—Dy1—O55	107.76 (6)
C13—C12—H12	125.9	O56—Dy1—O55	51.53 (6)
C11—C12—H12	125.9	O51—Dy1—O59	72.78 (6)
C12—C13—C14	107.9 (2)	O50—Dy1—O59	75.60 (6)
C12—C13—H13	126.0	O53—Dy1—O59	68.99 (6)
C14—C13—H13	126.0	O52—Dy1—O59	137.25 (6)
N23—C14—C15	125.7 (2)	O60—Dy1—O59	51.76 (6)
N23—C14—C13	107.4 (2)	O49—Dy1—O59	129.27 (6)
C15—C14—C13	126.8 (2)	O56—Dy1—O59	127.42 (7)
C14—C15—C16	126.5 (2)	O55—Dy1—O59	120.51 (7)
C14—C15—C37	116.4 (2)	O51—Dy1—N54	155.91 (6)
C16—C15—C37	117.0 (2)	O50—Dy1—N54	98.26 (7)
N24—C16—C15	125.0 (2)	O53—Dy1—N54	101.53 (7)
N24—C16—C17	110.7 (2)	O52—Dy1—N54	79.88 (7)
C15—C16—C17	124.2 (2)	O60—Dy1—N54	79.50 (6)
C18—C17—C16	106.7 (2)	O49—Dy1—N54	87.93 (6)
C18—C17—H17	126.6	O56—Dy1—N54	25.98 (7)
C16—C17—H17	126.6	O55—Dy1—N54	25.85 (6)
C17—C18—C19	106.3 (2)	O59—Dy1—N54	131.09 (6)
C17—C18—H18	126.8	O51—Dy1—N58	98.26 (7)
C19—C18—H18	126.8	O50—Dy1—N58	74.15 (6)
N24—C19—C20	125.5 (2)	O53—Dy1—N58	72.13 (6)
N24—C19—C18	111.0 (2)	O52—Dy1—N58	144.72 (6)
C20—C19—C18	123.5 (2)	O60—Dy1—N58	25.98 (6)
C1—C20—C19	126.1 (2)	O49—Dy1—N58	144.23 (6)
C1—C20—C43	116.3 (2)	O56—Dy1—N58	106.10 (7)
C19—C20—C43	117.6 (2)	O55—Dy1—N58	96.62 (7)
C4—N21—C1	109.68 (19)	O59—Dy1—N58	25.77 (6)
C4—N21—H21	125.2	N54—Dy1—N58	105.40 (6)
C1—N21—H21	125.2	Dy1—O49—H49A	127.5
C6—N22—C9	105.12 (19)	Dy1—O49—H49B	118.2
C6—N22—H22	127.4	H49A—O49—H49B	108.6
C9—N22—H22	127.4	Dy1—O50—H50A	128.2
C14—N23—C11	109.53 (19)	Dy1—O50—H50B	134.8
C14—N23—H23	125.2	H50A—O50—H50B	91.3
C11—N23—H23	125.2	Dy1—O51—H51A	124.7
C16—N24—C19	105.17 (19)	Dy1—O51—H51B	128.8
C16—N24—H24	127.4	H51A—O51—H51B	104.7
C19—N24—H24	127.4	Dy1—O52—H52A	122.0
C26—C25—C30	118.6 (2)	Dy1—O52—H52B	121.0
C26—C25—C5	119.4 (2)	H52A—O52—H52B	113.5
C30—C25—C5	122.0 (2)	Dy1—O53—H53A	115.8
C27—C26—C25	119.8 (2)	Dy1—O53—H53B	123.4
C27—C26—H26	120.1	H53A—O53—H53B	107.8
C25—C26—H26	120.1	O57—N54—O55	122.7 (2)
N28—C27—C26	119.9 (2)	O57—N54—O56	121.8 (2)
N28—C27—H27	120.0	O55—N54—O56	115.5 (2)
C26—C27—H27	120.0	O57—N54—Dy1	170.23 (19)
C29—N28—C27	122.0 (2)	O55—N54—Dy1	59.79 (12)
C29—N28—H28	124.1	O56—N54—Dy1	56.70 (12)
C27—N28—H28	113.2	N54—O55—Dy1	94.36 (15)
N28—C29—C30	120.4 (2)	N54—O56—Dy1	97.32 (14)
N28—C29—H29	119.8	O61—N58—O59	123.2 (2)
C30—C29—H29	119.8	O61—N58—O60	120.9 (2)
C29—C30—C25	119.3 (2)	O59—N58—O60	115.8 (2)
C29—C30—H30	120.4	O61—N58—Dy1	176.54 (19)
C25—C30—H30	120.4	O59—N58—Dy1	60.16 (12)
C32—C31—C36	118.3 (2)	O60—N58—Dy1	55.68 (12)
C32—C31—C10	121.9 (2)	N58—O59—Dy1	94.06 (14)
C36—C31—C10	119.8 (2)	N58—O60—Dy1	98.33 (15)
C33—C32—C31	119.8 (2)	O64—N62—O65	121.1 (2)
C33—C32—H32	120.1	O64—N62—O63	118.7 (2)
C31—C32—H32	120.1	O65—N62—O63	120.2 (2)
N34—C33—C32	119.6 (2)	O67—N66—O68	120.8 (2)
N34—C33—H33	120.2	O67—N66—O69	119.9 (2)
C32—C33—H33	120.2	O68—N66—O69	119.3 (2)
C35—N34—C33	122.6 (2)	O71—N70—O72	121.7 (2)
C35—N34—H34	121.7	O71—N70—O73	119.1 (2)
C33—N34—H34	115.2	O72—N70—O73	119.2 (2)
N34—C35—C36	120.0 (2)	O76—N74—O77	122.5 (2)
N34—C35—H35	120.0	O76—N74—O75	118.1 (2)
C36—C35—H35	120.0	O77—N74—O75	119.4 (2)
C35—C36—C31	119.7 (2)	O80—N78—O79	121.4 (2)
C35—C36—H36	120.1	O80—N78—O81	119.7 (2)
C31—C36—H36	120.1	O79—N78—O81	118.9 (2)
C38—C37—C42	118.8 (2)	C83—O82—H82	106.4
C38—C37—C15	119.2 (2)	O82—C83—C84	112.3 (3)
C42—C37—C15	121.9 (2)	O82—C83—H83A	109.1
C39—C38—C37	119.8 (2)	C84—C83—H83A	109.1
C39—C38—H38	120.1	O82—C83—H83B	109.1
C37—C38—H38	120.1	C84—C83—H83B	109.1
N40—C39—C38	119.8 (2)	H83A—C83—H83B	107.9
N40—C39—H39	120.1	C83—C84—H84A	109.5
C38—C39—H39	120.1	C83—C84—H84B	109.5
C41—N40—C39	122.1 (2)	H84A—C84—H84B	109.5
C41—N40—H40	120.4	C83—C84—H84C	109.5
C39—N40—H40	116.7	H84A—C84—H84C	109.5
N40—C41—C42	120.3 (2)	H84B—C84—H84C	109.5
N40—C41—H41	119.8	C86—O85—H85	109.6
C42—C41—H41	119.8	O85—C86—C87	110.0 (3)
C41—C42—C37	119.1 (2)	O85—C86—H86A	109.7
C41—C42—H42	120.4	C87—C86—H86A	109.7
C37—C42—H42	120.4	O85—C86—H86B	109.7
C48—C43—C44	118.9 (2)	C87—C86—H86B	109.7
C48—C43—C20	120.2 (2)	H86A—C86—H86B	108.2
C44—C43—C20	120.8 (2)	C86—C87—H87A	109.5
C45—C44—C43	119.6 (2)	C86—C87—H87B	109.5
C45—C44—H44	120.2	H87A—C87—H87B	109.5
C43—C44—H44	120.2	C86—C87—H87C	109.5
N46—C45—C44	119.5 (2)	H87A—C87—H87C	109.5
N46—C45—H45	120.3	H87B—C87—H87C	109.5
C44—C45—H45	120.3	H88A—O88—H88B	106.0
C45—N46—C47	122.7 (2)	H89A—O89—H89B	103.9
C45—N46—H46	115.6

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N28—H28···O73	0.93	1.82	2.727 (3)	164
N34—H34···O75	0.89	1.88	2.743 (3)	162
N40—H40···O81	0.85	1.88	2.722 (3)	174
N46—H46···O88	0.96	1.87	2.749 (3)	150
O49—H49A···O75^i	0.83	1.96	2.776 (3)	167
O49—H49B···O79	0.91	1.87	2.744 (3)	159
O50—H50A···O69	0.92	1.86	2.748 (3)	163
O50—H50B···O63^ii	0.84	1.90	2.724 (3)	168
O51—H51A···O89	0.84	1.93	2.769 (3)	173
O51—H51B···O63^iii	0.91	1.82	2.726 (3)	174
O52—H52A···O72^iv	0.86	2.06	2.834 (3)	149
O52—H52B···O68	1.03	1.74	2.744 (3)	164
O53—H53A···O82	0.83	1.89	2.719 (3)	174
O53—H53B···O85^i	0.86	1.93	2.759 (3)	163
O82—H82···O80	0.92	2.17	3.011 (3)	151
O85—H85···O69	1.00	1.94	2.923 (3)	170
O88—H88A···O65	0.93	2.05	2.924 (3)	156
O88—H88B···O89^v	0.85	2.00	2.840 (3)	172

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