Hydrogen-bonded three-dimensional network of a lanthanum(III) exocyclic complex with 5,10,15,20-tetra-4-pyridyl­porphyrin

In the complex diaqua­tetra­nitrato[5-(pyridinium-4-yl)-10,15,20-tri-4-pyridylporphyrin]lanthanum(III) 1,2-dichloro­benzene tri­solvate, [La(NO₃)₄(C₄₀H₂₇N₈)(H₂O)₂]·3C₆H₄Cl₂, the lan­thanum ion is coordinated to one of the peripheral pyridyl substituents of the porphyrin entity. Units of the complex are inter­linked to one another in three dimensions by a network of O—H...N, O—H...O and N—H...O hydrogen bonds between the water ligands, nitrate ions, and pyridyl and pyridinium groups of adjacent species. This is the first structural report of an exocyclic complex of the tetra­pyridylporphyrin ligand with any lanthanide ion and its self-assembly into a three-dimensional architecture sustained by hydrogen bonds.

S1. Comment

The tetrapyridylporphyrin (TPyP) and tetra(carboxyphenyl)porphyrin (TCPP) ligands have been utilized extensively as building blocks in the design of framework solids (Goldberg, 2008, 2005, 2000, and references therein). Of particular interest is the coordination polymerization of these scaffolds through the exocyclic nodes of the metal ions, which often results in the formation of open but robust architectures (Suslick et al., 2005). The use of lanthanide ions to this end is rather rare. Only recently have hybrid organic–inorganic networks composed of TCPPs and various lanthanide ions been reported (George et al., 2006; Lipstman et al., 2007; Muniappan et al., 2007). The metal ions are oxophilic and coordinate readily to the peripheral carboxyphenyl functions, an interaction which is facilitated by deprotonation of the latter and ion pairing between the component species. Although a few coordination polymers and complexes of some lanthanide ions with bipyridyls are known (Sharma & Rogers, 1999, and references therein), analogous compounds with the TPyP unit have not been obtained thus far. This can be attributed to the relatively low affinity of the lanthanides for coordination by neutral N-pyridyl groups and the need to incorporate additional counterions into the lattice. A number of double-decker-type compounds in which lanthanide ions are sandwiched between, and coordinated by, the central tetrapyrrole rings of two TPyPs (Ikeda et al., 2000; Magnera et al., 1997), or between one TPyP and one phthalocyanine ring (Bian et al., 2003; Sun et al., 2003), have also been described.

In the above context we report here on the first complex of the TPyP entity with a lanthanum ion, where the coordination takes place on the porphyrin periphery between the metal ion and one of the pyridyl substituents of TPyP. The reaction between TPyP and lanthanum trinitrate hexahydrate is associated with protonation of another pyridyl group (at N34) and formation of the TPyPH⁺–La(NO₃)₄(H₂O)₂^- complex, which crystallizes as the title o-dichlorobenzene trisolvate, (I). Similar behaviour of La^III ions complexed with four (rather than three) bidentate anions has been observed before (Sharma & Rogers, 1999).

The molecular structure of (I) is shown in Fig. 1. The lanthanum cation is 11-coordinate, where in addition to the nitrate ions it binds to one pyridyl and two water ligands (Table 1). A large excess of the lanthanum salt was used in the reaction mixture, anticipating simultaneous coordination of the metal ions to the four pyridyl corners of the porphyrin. Instead, such coordination occurred only at one out of the four sites. In the resulting complex, the H atoms of the two water ligands and the NH34 pyridylium group, along with the O atoms of the four nitrate ions, constitute complementary divergent molecular-recognition sites for supramolecular associations. All five of the potential H-atom donors are utitilized in intermolecular hydrogen bonding.

The supramolecular organization of (I) can be best described in a modular way. The La(NO₃)₄(H₂O)₂ ion is associated in four equatorial directions with four different TPyPs. This involves a direct La—N_py coordination, two O—H(water)···N_py hydrogen bonds from the two water ligands to porphyrin units, and an additional N_py—H⁺···O_water hydrogen bond in the fourth direction (Table 2). As a result, the molecular units assemble into undulating two-dimensional supramolecular square-grid-type layers (Fig. 2). The mean plane of the layers, which are stacked along the c axis, is parallel to (201). Additional hydrogen bonds operate between the La(NO₃)₄(H₂O)₂ connecting nodes of subsequent layers in the stack. The two water ligands donate their H atoms to the nitrate groups of the layer above, while two of the nitrate groups act as acceptors in hydrogen bonds with the water ligands from the layer below (Table 2). The crystal structure (Fig. 3) consists of alternating zones of the porphyrin moieties (centred at y = 0 and 1/2), and the La(NO₃)₄(H₂O)₂ connectors (centred at y = 1/4 and 3/4) aligned perpendicular to the b axis. Molecules of the o-dichlorobenzene solvent are enclathrated within the interstitial voids. They are positioned at the interface between porphyrin ligands of neighbouring layers, as well as between adjacent pillars of the metallic bridges in any given zone (Fig. 3). The supramolecular framework is held together by the inorganic pillars in a similar way to that observed in the coordination polymers of TCPP with solvated lanthanide ions (Lipstman et al., 2007; Muniappan et al., 2007).

In summary, this study confirms earlier observations (Sharma & Rogers, 1999) that lanthanide ions can be utilized in the formation of networked architectures involving not only coordination forces but also hydrogen bonds. It also indicates for the first time that, in addition to the TCPP building blocks, the TPyP moieties may also coordinate to lanthanides. In the former case, charge balance is achieved by deprotonation of the carboxylic acid groups. In structures with pyridyl porphyrins, the hydrogen-bonding sites of suitable counterions and water ligands located in the coordination environment of the metal centres provide additional/alternative means for supramolecular aggregation. This is well demonstrated by the three-dimensional supramolecular architecture of (I).

S2. Experimental

All reactants and solvents were obtained commercially and used without any further purification. TPyP (0.015 mmol) and lanthanum(III) nitrate hexahydrate (0.100 mmol) were dissolved in a 1:1 mixture of o-dichlorobenzene and ethanol (15 ml). The resulting solution was refluxed for 2 h. After filtration, the solute was allowed to evaporate slowly. X-ray quality red crystals of (I) were obtained after five weeks.

S3. Refinement

H atoms bound to C atoms were located in calculated positions and constrained to ride on their parent atoms, with C—H = 0.95 Å and with U_iso(H) = 1.2U_eq(C). Inspection of the contoured representation of the difference electron density indicated that the two N(pyrrole)-bound H atoms were disordered between the four pyrrole sites. They were then also located in calculated positions and constrained to ride on their parent atoms, with N—H = 0.88 Å and with U_iso(H) = 1.2U_eq(N). The H atoms of the two water ligands where either located in a difference Fourier map (atom O49) or in calculated positions to optimize the hydrogen bonding (atom O50). All O—H bond lengths were constrained at 0.83 Å but not refined, with U_iso(H) = 1.5U_eq(O). Finally, the H atom on the pyridyl group at N34 was located in a difference Fourier map as the highest residual peak. Its atomic coordinates were included in the final refinement with U_iso(H) = 1.2U_eq(N). One of the o-dichlorobenzene solvent species could not be modelled reliably by discrete atoms, though it was clearly identified in the difference Fourier map. Its contribution was subtracted from the diffraction pattern by the Squeeze method, using the PLATON software (Spek, 2003). In the unit cell, the sites accessible by these solvent species are centred at (0, 0, 0) and (0, 1/2, 0), each of the created voids being characterized by a volume of 444 ų with residual electron density of 165 e. The other two o-dichlorobenzene molecules of the asymmetric unit included in the structural model appear to be characterized by partial orientational disorder as well.

Computing details

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: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level at ca 110 K. H atoms have been omitted. The porphyrin ring exhibits a slightly saddled conformation.
	Fig. 2. The two-dimensional square-grid network motif observed in (I). Note that every La(NO3)4(H2O)2 connecting node is associated with four neighbouring porphyrin units, either via coordination or hydrogen bonds (denoted by dashed lines). H atoms have been omitted. The La and water O atoms are shown as small spheres.
	Fig. 3. The crystal packing of (I), showing (edge-on) the stacked arrangement of the undulating layers depicted in Fig. 2. Note the interlayer hydrogen-bonding interactions (dashed lines) from the water ligands of one layer to the nitrate anions of adjacent layers. Asterisks (*) indicate the approximate locations of the o-dichlorobenzene solvent molecules. H atoms have been omitted, and the La and water O atoms are shown as small spheres.

diaquatetranitrato[5-(pyridinium-4-yl)-10,15,20-tri-4- pyridylporphyrin]lanthanum(III) 1,2-dichlorobenzene trisolvate

Crystal data

[La(NO3)4(C40H27N8)(H2O)2]·3C6H4Cl2	F(000) = 2984
Mr = 1483.65	Dx = 1.616 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.1527 (3) Å	Cell parameters from 10292 reflections
b = 28.5415 (6) Å	θ = 1.4–25.0°
c = 13.5331 (2) Å	µ = 1.04 mm^−1
β = 112.984 (1)°	T = 110 K
V = 6099.34 (19) Å^3	Prism, red
Z = 4	0.25 × 0.20 × 0.10 mm

Data collection

Nonius KappaCCD area-detector diffractometer	10767 independent reflections
Radiation source: fine-focus sealed tube	6137 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.091
Detector resolution: 12.8 pixels mm^-1	θmax = 25.0°, θmin = 2.2°
1° ϕ and ω scans	h = −20→18
Absorption correction: multi-scan (Blessing, 1995)	k = −33→0
Tmin = 0.798, Tmax = 0.911	l = 0→16
36533 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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0704P)^2] where P = (Fo^2 + 2Fc^2)/3
10767 reflections	(Δ/σ)max = 0.001
748 parameters	Δρmax = 0.83 e Å^−3
0 restraints	Δρmin = −0.77 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 asymmetric unit contains an additional molecule of the dichlorobenzene solvent. It is severely disordered, about the center of inversion at 0,0,0, and couldn't be modeled by discrete atoms. Its contribution was thus subtracted from the diffraction data by the Squeeze method, using the PLATON software (Spek, 2003). Correspondingly the analyzed crystal diffracted poorly at τ > 25°. Final structure factor calculations contain only 2 molecules of the solvent. The other two molecules of the dichlorobenzene solvate also reveal wide-amplitude ADP's.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
La1	0.96484 (2)	0.756793 (13)	0.32933 (3)	0.02382 (13)
C1	0.6931 (4)	0.9992 (2)	−0.2023 (5)	0.0315 (17)
C2	0.7806 (4)	0.9892 (2)	−0.1356 (5)	0.0302 (16)
H2	0.8282	1.0083	−0.1266	0.036*
C3	0.7811 (4)	0.9475 (2)	−0.0887 (5)	0.0318 (16)
H3	0.8294	0.9311	−0.0412	0.038*
C4	0.6927 (4)	0.9325 (2)	−0.1251 (5)	0.0263 (15)
C5	0.6669 (4)	0.8901 (2)	−0.0909 (5)	0.0304 (16)
C6	0.5843 (4)	0.8735 (2)	−0.1270 (5)	0.0274 (15)
C7	0.5562 (4)	0.8323 (2)	−0.0911 (5)	0.0290 (16)
H7	0.5913	0.8105	−0.0400	0.035*
C8	0.4699 (4)	0.8295 (2)	−0.1427 (5)	0.0311 (16)
H8	0.4349	0.8052	−0.1349	0.037*
C9	0.4420 (4)	0.8699 (2)	−0.2109 (5)	0.0269 (16)
C10	0.3577 (4)	0.8822 (2)	−0.2744 (5)	0.0263 (15)
C11	0.3310 (4)	0.9235 (2)	−0.3345 (5)	0.0298 (16)
C12	0.2440 (4)	0.9352 (2)	−0.3940 (5)	0.0332 (17)
H12	0.1959	0.9171	−0.3997	0.040*
C13	0.2437 (4)	0.9773 (2)	−0.4408 (5)	0.0358 (18)
H13	0.1954	0.9947	−0.4847	0.043*
C14	0.3310 (4)	0.9905 (2)	−0.4107 (5)	0.0305 (16)
C15	0.3563 (4)	1.0312 (2)	−0.4475 (5)	0.0278 (16)
C16	0.4414 (4)	1.0450 (2)	−0.4221 (5)	0.0283 (16)
C17	0.4694 (5)	1.0875 (2)	−0.4535 (6)	0.0403 (18)
H17	0.4339	1.1105	−0.5005	0.048*
C18	0.5541 (5)	1.0898 (2)	−0.4057 (5)	0.0368 (18)
H18	0.5890	1.1141	−0.4137	0.044*
C19	0.5827 (4)	1.0485 (2)	−0.3400 (5)	0.0310 (16)
C20	0.6649 (4)	1.0385 (2)	−0.2702 (5)	0.0249 (15)
N21	0.6414 (3)	0.96361 (18)	−0.1954 (4)	0.0272 (13)
H21	0.5861	0.9616	−0.2297	0.033*	0.50
N22	0.5131 (3)	0.89485 (18)	−0.2010 (4)	0.0257 (12)
H22	0.5133	0.9207	−0.2364	0.031*	0.50
N23	0.3832 (3)	0.95724 (18)	−0.3455 (4)	0.0283 (13)
H23	0.4389	0.9575	−0.3167	0.034*	0.50
N24	0.5112 (3)	1.02204 (18)	−0.3552 (4)	0.0251 (13)
H24	0.5111	0.9945	−0.3259	0.030*	0.50
C25	0.7346 (4)	0.8620 (2)	−0.0057 (5)	0.0245 (15)
C26	0.7812 (4)	0.8812 (2)	0.0936 (5)	0.0312 (16)
H26	0.7719	0.9128	0.1084	0.037*
C27	0.8415 (4)	0.8545 (2)	0.1713 (5)	0.0306 (16)
H27	0.8741	0.8690	0.2379	0.037*
N28	0.8567 (3)	0.80923 (18)	0.1582 (4)	0.0229 (12)
C29	0.8109 (4)	0.7906 (2)	0.0612 (5)	0.0257 (15)
H29	0.8207	0.7587	0.0492	0.031*
C30	0.7503 (4)	0.8151 (2)	−0.0220 (5)	0.0292 (16)
H30	0.7200	0.8002	−0.0890	0.035*
C31	0.2919 (4)	0.8492 (2)	−0.2720 (5)	0.0298 (16)
C32	0.2894 (4)	0.8034 (2)	−0.3048 (5)	0.0330 (17)
H32	0.3301	0.7923	−0.3307	0.040*
C33	0.2273 (4)	0.7732 (2)	−0.2999 (5)	0.0328 (17)
H33	0.2274	0.7412	−0.3189	0.039*
N34	0.1678 (4)	0.7892 (2)	−0.2685 (4)	0.0337 (14)
H34	0.124 (4)	0.769 (2)	−0.265 (5)	0.040*
C35	0.1678 (4)	0.8342 (3)	−0.2368 (5)	0.0390 (18)
H35	0.1240	0.8449	−0.2161	0.047*
C36	0.2308 (4)	0.8643 (3)	−0.2345 (5)	0.0349 (17)
H36	0.2329	0.8952	−0.2076	0.042*
C37	0.2895 (4)	1.0649 (2)	−0.5100 (5)	0.0276 (15)
C38	0.2398 (4)	1.0856 (2)	−0.4621 (5)	0.0395 (19)
H38	0.2482	1.0782	−0.3903	0.047*
C39	0.1777 (5)	1.1173 (3)	−0.5209 (6)	0.045 (2)
H39	0.1426	1.1302	−0.4882	0.054*
N40	0.1641 (3)	1.13114 (19)	−0.6231 (4)	0.0343 (14)
C41	0.2127 (5)	1.1116 (3)	−0.6668 (5)	0.0403 (19)
H41	0.2044	1.1203	−0.7379	0.048*
C42	0.2747 (5)	1.0794 (2)	−0.6147 (6)	0.0393 (18)
H42	0.3080	1.0667	−0.6502	0.047*
C43	0.7291 (4)	1.0756 (2)	−0.2613 (5)	0.0277 (15)
C44	0.7486 (4)	1.0882 (2)	−0.3487 (5)	0.0387 (19)
H44	0.7217	1.0728	−0.4157	0.046*
C45	0.8079 (5)	1.1235 (3)	−0.3372 (6)	0.047 (2)
H45	0.8204	1.1316	−0.3976	0.057*
N46	0.8480 (3)	1.14660 (18)	−0.2450 (4)	0.0330 (14)
C47	0.8298 (4)	1.1342 (2)	−0.1615 (5)	0.0318 (17)
H47	0.8577	1.1503	−0.0956	0.038*
C48	0.7730 (4)	1.0995 (2)	−0.1648 (5)	0.0309 (16)
H48	0.7637	1.0917	−0.1021	0.037*
O49	0.9432 (3)	0.70262 (14)	0.1751 (3)	0.0306 (11)
H49A	0.9211	0.6782	0.1833	0.046*
H49B	0.9601	0.7028	0.1259	0.046*
O50	1.0480 (3)	0.78081 (14)	0.2141 (3)	0.0258 (10)
H50A	1.0224	0.7826	0.1486	0.039*
H50B	1.0798	0.8035	0.2241	0.039*
N51	1.1563 (4)	0.7302 (2)	0.4536 (4)	0.0349 (15)
O52	1.1402 (3)	0.77285 (19)	0.4364 (4)	0.0444 (13)
O53	1.0945 (3)	0.70162 (17)	0.4164 (4)	0.0397 (12)
O54	1.2283 (3)	0.71593 (18)	0.5071 (4)	0.0482 (13)
N55	0.9465 (3)	0.6708 (2)	0.4579 (4)	0.0302 (13)
O56	0.9616 (3)	0.71280 (15)	0.4953 (3)	0.0289 (10)
O57	0.9306 (3)	0.66620 (15)	0.3602 (3)	0.0325 (11)
O58	0.9498 (3)	0.63734 (16)	0.5159 (4)	0.0363 (12)
N59	0.7864 (4)	0.7722 (2)	0.3193 (5)	0.0384 (15)
O60	0.8031 (3)	0.73672 (16)	0.2765 (4)	0.0347 (11)
O61	0.8476 (3)	0.79993 (17)	0.3710 (3)	0.0384 (12)
O62	0.7142 (3)	0.78075 (19)	0.3121 (5)	0.0586 (15)
N63	1.0287 (4)	0.8411 (2)	0.4778 (5)	0.0372 (15)
O64	1.0108 (3)	0.84371 (16)	0.3791 (3)	0.0338 (11)
O65	1.0160 (3)	0.80242 (16)	0.5148 (3)	0.0356 (12)
O66	1.0573 (3)	0.87437 (19)	0.5371 (4)	0.0550 (15)
Cl1	0.42251 (15)	0.70342 (8)	−0.22617 (16)	0.0626 (6)
Cl2	0.35825 (13)	0.71216 (8)	−0.03930 (17)	0.0607 (6)
C67	0.4937 (5)	0.7063 (2)	−0.0949 (6)	0.0441 (19)
C68	0.5817 (6)	0.7047 (3)	−0.0686 (10)	0.069 (3)
H68	0.6029	0.7031	−0.1237	0.082*
C69	0.6377 (6)	0.7054 (3)	0.0394 (10)	0.077 (3)
H69	0.6971	0.7045	0.0579	0.092*
C70	0.6070 (7)	0.7076 (3)	0.1164 (9)	0.078 (3)
H70	0.6462	0.7074	0.1891	0.093*
C71	0.5237 (6)	0.7100 (3)	0.0968 (7)	0.066 (3)
H71	0.5047	0.7117	0.1539	0.079*
C72	0.4654 (5)	0.7098 (3)	−0.0120 (7)	0.048 (2)
Cl3	0.36970 (14)	0.84834 (9)	0.03135 (17)	0.0676 (7)
Cl4	0.35418 (17)	0.95703 (9)	−0.00892 (19)	0.0787 (8)
C73	0.4599 (6)	0.8831 (4)	0.0853 (6)	0.057 (2)
C74	0.5388 (7)	0.8645 (4)	0.1437 (7)	0.078 (3)
H74	0.5447	0.8315	0.1527	0.094*
C75	0.6076 (6)	0.8918 (5)	0.1880 (6)	0.088 (4)
H75	0.6606	0.8781	0.2304	0.105*
C76	0.6010 (6)	0.9427 (4)	0.1711 (7)	0.068 (3)
H76	0.6490	0.9627	0.1996	0.081*
C77	0.5230 (7)	0.9595 (4)	0.1131 (7)	0.073 (3)
H77	0.5169	0.9924	0.1019	0.087*
C78	0.4517 (5)	0.9322 (4)	0.0690 (6)	0.067 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La1	0.0243 (2)	0.0265 (2)	0.02030 (19)	−0.00187 (19)	0.00833 (16)	−0.00041 (18)
C1	0.040 (5)	0.024 (4)	0.039 (4)	−0.005 (3)	0.024 (4)	−0.006 (3)
C2	0.015 (4)	0.041 (5)	0.028 (4)	−0.007 (3)	0.002 (3)	0.001 (3)
C3	0.026 (4)	0.033 (4)	0.034 (4)	−0.007 (3)	0.010 (3)	0.000 (3)
C4	0.025 (4)	0.024 (4)	0.027 (4)	−0.002 (3)	0.006 (3)	−0.002 (3)
C5	0.028 (4)	0.031 (4)	0.027 (4)	−0.003 (3)	0.006 (3)	−0.001 (3)
C6	0.025 (4)	0.024 (4)	0.031 (4)	−0.003 (3)	0.008 (3)	−0.005 (3)
C7	0.028 (4)	0.024 (4)	0.034 (4)	0.000 (3)	0.011 (3)	0.005 (3)
C8	0.035 (4)	0.018 (4)	0.033 (4)	−0.005 (3)	0.005 (4)	0.006 (3)
C9	0.022 (4)	0.029 (4)	0.025 (3)	−0.007 (3)	0.005 (3)	0.003 (3)
C10	0.025 (4)	0.023 (4)	0.027 (4)	0.002 (3)	0.006 (3)	0.002 (3)
C11	0.023 (4)	0.035 (4)	0.031 (4)	−0.007 (3)	0.009 (3)	0.001 (3)
C12	0.026 (4)	0.043 (5)	0.027 (4)	0.008 (3)	0.007 (3)	0.009 (3)
C13	0.032 (4)	0.040 (5)	0.036 (4)	0.008 (4)	0.014 (4)	0.004 (3)
C14	0.033 (4)	0.032 (4)	0.025 (4)	−0.007 (3)	0.010 (3)	0.003 (3)
C15	0.031 (4)	0.022 (4)	0.027 (4)	0.004 (3)	0.008 (3)	−0.001 (3)
C16	0.029 (4)	0.022 (4)	0.029 (4)	−0.006 (3)	0.007 (3)	−0.001 (3)
C17	0.035 (5)	0.028 (5)	0.046 (4)	0.000 (4)	0.003 (4)	0.005 (3)
C18	0.046 (5)	0.021 (4)	0.039 (4)	−0.005 (3)	0.012 (4)	0.007 (3)
C19	0.033 (4)	0.024 (4)	0.036 (4)	−0.011 (3)	0.013 (4)	−0.005 (3)
C20	0.022 (4)	0.019 (4)	0.032 (4)	−0.006 (3)	0.009 (3)	−0.003 (3)
N21	0.019 (3)	0.027 (3)	0.030 (3)	−0.003 (3)	0.004 (3)	0.006 (3)
N22	0.016 (3)	0.029 (3)	0.023 (3)	−0.001 (3)	−0.002 (2)	0.009 (2)
N23	0.024 (3)	0.028 (3)	0.026 (3)	0.003 (3)	0.003 (3)	0.006 (3)
N24	0.023 (3)	0.024 (3)	0.024 (3)	−0.001 (3)	0.004 (3)	−0.001 (2)
C25	0.027 (4)	0.022 (4)	0.025 (4)	−0.008 (3)	0.011 (3)	0.001 (3)
C26	0.025 (4)	0.024 (4)	0.043 (4)	0.006 (3)	0.011 (4)	−0.004 (3)
C27	0.031 (4)	0.027 (4)	0.031 (4)	0.001 (3)	0.009 (3)	0.002 (3)
N28	0.019 (3)	0.022 (3)	0.025 (3)	0.002 (2)	0.006 (3)	0.004 (2)
C29	0.020 (4)	0.028 (4)	0.027 (4)	0.001 (3)	0.007 (3)	−0.002 (3)
C30	0.027 (4)	0.031 (4)	0.032 (4)	−0.003 (3)	0.013 (3)	−0.003 (3)
C31	0.021 (4)	0.033 (5)	0.024 (4)	0.002 (3)	−0.003 (3)	0.010 (3)
C32	0.031 (4)	0.029 (4)	0.034 (4)	−0.013 (3)	0.008 (3)	0.000 (3)
C33	0.026 (4)	0.034 (4)	0.028 (4)	−0.004 (3)	−0.001 (3)	−0.001 (3)
N34	0.035 (4)	0.038 (4)	0.027 (3)	−0.010 (3)	0.012 (3)	0.005 (3)
C35	0.035 (5)	0.046 (5)	0.038 (4)	0.004 (4)	0.016 (4)	0.003 (4)
C36	0.033 (4)	0.033 (4)	0.033 (4)	−0.006 (4)	0.007 (4)	0.007 (3)
C37	0.024 (4)	0.025 (4)	0.025 (4)	−0.003 (3)	0.000 (3)	−0.004 (3)
C38	0.043 (5)	0.044 (5)	0.024 (4)	0.020 (4)	0.006 (4)	0.001 (3)
C39	0.053 (5)	0.043 (5)	0.040 (5)	0.008 (4)	0.019 (4)	−0.005 (4)
N40	0.036 (4)	0.032 (4)	0.029 (3)	0.008 (3)	0.006 (3)	−0.001 (3)
C41	0.049 (5)	0.041 (5)	0.028 (4)	0.014 (4)	0.012 (4)	0.001 (3)
C42	0.048 (5)	0.030 (4)	0.043 (4)	0.008 (4)	0.021 (4)	−0.007 (4)
C43	0.027 (4)	0.024 (4)	0.030 (4)	0.002 (3)	0.008 (3)	0.005 (3)
C44	0.044 (5)	0.043 (5)	0.030 (4)	−0.021 (4)	0.017 (4)	−0.010 (3)
C45	0.054 (5)	0.059 (6)	0.037 (4)	−0.015 (4)	0.027 (4)	−0.005 (4)
N46	0.038 (4)	0.024 (3)	0.037 (3)	−0.008 (3)	0.015 (3)	0.000 (3)
C47	0.031 (4)	0.028 (4)	0.031 (4)	−0.006 (3)	0.007 (3)	−0.007 (3)
C48	0.030 (4)	0.036 (4)	0.026 (4)	0.001 (3)	0.010 (3)	−0.001 (3)
O49	0.046 (3)	0.026 (3)	0.029 (2)	−0.009 (2)	0.024 (2)	0.000 (2)
O50	0.033 (3)	0.024 (3)	0.022 (2)	−0.005 (2)	0.013 (2)	0.0026 (19)
N51	0.035 (4)	0.051 (5)	0.022 (3)	0.004 (4)	0.014 (3)	−0.003 (3)
O52	0.043 (3)	0.040 (3)	0.040 (3)	0.007 (3)	0.004 (3)	0.002 (2)
O53	0.032 (3)	0.041 (3)	0.042 (3)	−0.002 (3)	0.011 (2)	0.001 (2)
O54	0.030 (3)	0.056 (4)	0.052 (3)	0.008 (3)	0.009 (3)	0.003 (3)
N55	0.027 (3)	0.032 (4)	0.035 (4)	−0.001 (3)	0.017 (3)	0.002 (3)
O56	0.035 (3)	0.019 (3)	0.033 (3)	−0.007 (2)	0.014 (2)	−0.003 (2)
O57	0.038 (3)	0.034 (3)	0.021 (3)	−0.006 (2)	0.007 (2)	−0.002 (2)
O58	0.048 (3)	0.029 (3)	0.039 (3)	0.002 (2)	0.023 (3)	0.010 (2)
N59	0.030 (4)	0.051 (5)	0.036 (4)	−0.004 (3)	0.015 (3)	0.004 (3)
O60	0.030 (3)	0.031 (3)	0.045 (3)	−0.005 (2)	0.016 (2)	−0.005 (2)
O61	0.032 (3)	0.050 (3)	0.031 (3)	−0.004 (3)	0.010 (2)	−0.004 (2)
O62	0.036 (3)	0.062 (4)	0.085 (4)	0.002 (3)	0.032 (3)	−0.004 (3)
N63	0.032 (4)	0.036 (4)	0.035 (4)	−0.017 (3)	0.003 (3)	−0.006 (3)
O64	0.040 (3)	0.038 (3)	0.018 (2)	−0.002 (2)	0.005 (2)	0.003 (2)
O65	0.049 (3)	0.034 (3)	0.028 (3)	−0.013 (2)	0.019 (2)	0.000 (2)
O66	0.069 (4)	0.044 (4)	0.035 (3)	−0.018 (3)	0.001 (3)	−0.001 (3)
Cl1	0.0807 (16)	0.0606 (15)	0.0488 (12)	0.0157 (12)	0.0278 (12)	0.0055 (11)
Cl2	0.0495 (13)	0.0745 (16)	0.0646 (14)	0.0119 (12)	0.0293 (12)	0.0017 (12)
C67	0.048 (5)	0.027 (4)	0.057 (5)	0.000 (4)	0.021 (4)	0.008 (4)
C68	0.075 (7)	0.019 (5)	0.142 (10)	0.001 (5)	0.075 (7)	0.012 (5)
C69	0.027 (5)	0.042 (6)	0.122 (9)	−0.007 (4)	−0.012 (6)	0.007 (6)
C70	0.049 (7)	0.070 (8)	0.089 (8)	−0.005 (5)	0.000 (6)	−0.014 (6)
C71	0.080 (8)	0.049 (6)	0.053 (6)	0.000 (5)	0.009 (5)	−0.012 (4)
C72	0.056 (5)	0.031 (5)	0.062 (5)	0.001 (4)	0.028 (5)	−0.005 (4)
Cl3	0.0657 (15)	0.0862 (18)	0.0505 (13)	−0.0324 (13)	0.0221 (12)	−0.0113 (12)
Cl4	0.0864 (19)	0.092 (2)	0.0657 (15)	−0.0231 (15)	0.0380 (15)	−0.0161 (14)
C73	0.061 (7)	0.076 (7)	0.033 (5)	−0.032 (5)	0.017 (5)	−0.007 (5)
C74	0.083 (8)	0.115 (9)	0.036 (5)	−0.055 (7)	0.024 (6)	−0.019 (5)
C75	0.056 (7)	0.180 (13)	0.032 (5)	−0.045 (8)	0.023 (5)	−0.028 (7)
C76	0.064 (7)	0.107 (9)	0.030 (5)	−0.023 (6)	0.015 (5)	−0.029 (5)
C77	0.079 (8)	0.108 (9)	0.039 (5)	−0.041 (7)	0.031 (6)	−0.022 (5)
C78	0.046 (6)	0.129 (10)	0.021 (4)	−0.025 (6)	0.007 (4)	−0.015 (5)

Geometric parameters (Å, º)

La1—O49	2.506 (4)	C32—H32	0.9500
La1—O50	2.583 (4)	C33—N34	1.330 (8)
La1—O56	2.593 (4)	C33—H33	0.9500
La1—O61	2.601 (4)	N34—C35	1.352 (9)
La1—O53	2.602 (5)	N34—H34	0.96 (7)
La1—O64	2.611 (4)	C35—C36	1.373 (9)
La1—O60	2.643 (4)	C35—H35	0.9500
La1—O65	2.654 (4)	C36—H36	0.9500
La1—O57	2.720 (4)	C37—C38	1.388 (9)
La1—N28	2.773 (5)	C37—C42	1.400 (9)
La1—O52	2.820 (5)	C38—C39	1.387 (9)
La1—N59	3.043 (6)	C38—H38	0.9500
C1—N21	1.375 (8)	C39—N40	1.367 (8)
C1—C20	1.411 (9)	C39—H39	0.9500
C1—C2	1.446 (9)	N40—C41	1.319 (8)
C2—C3	1.345 (9)	C41—C42	1.375 (9)
C2—H2	0.9500	C41—H41	0.9500
C3—C4	1.464 (9)	C42—H42	0.9500
C3—H3	0.9500	C43—C44	1.396 (8)
C4—N21	1.348 (8)	C43—C48	1.402 (9)
C4—C5	1.426 (9)	C44—C45	1.397 (9)
C5—C6	1.389 (8)	C44—H44	0.9500
C5—C25	1.508 (9)	C45—N46	1.339 (8)
C6—N22	1.382 (8)	C45—H45	0.9500
C6—C7	1.427 (9)	N46—C47	1.333 (8)
C7—C8	1.370 (9)	C47—C48	1.377 (9)
C7—H7	0.9500	C47—H47	0.9500
C8—C9	1.436 (9)	C48—H48	0.9500
C8—H8	0.9500	O49—H49A	0.8213
C9—N22	1.373 (7)	O49—H49B	0.8232
C9—C10	1.409 (8)	O50—H50A	0.8230
C10—C11	1.402 (9)	O50—H50B	0.8225
C10—C31	1.480 (9)	N51—O54	1.232 (7)
C11—N23	1.363 (8)	N51—O52	1.250 (7)
C11—C12	1.432 (9)	N51—O53	1.274 (7)
C12—C13	1.356 (9)	N55—O58	1.223 (6)
C12—H12	0.9500	N55—O57	1.248 (6)
C13—C14	1.440 (9)	N55—O56	1.288 (6)
C13—H13	0.9500	N59—O62	1.228 (7)
C14—N23	1.365 (8)	N59—O60	1.256 (7)
C14—C15	1.398 (9)	N59—O61	1.282 (7)
C15—C16	1.419 (9)	N63—O66	1.216 (7)
C15—C37	1.482 (9)	N63—O64	1.251 (6)
C16—N24	1.355 (8)	N63—O65	1.266 (7)
C16—C17	1.429 (9)	Cl1—C67	1.720 (8)
C17—C18	1.341 (9)	Cl2—C72	1.729 (8)
C17—H17	0.9500	C67—C72	1.389 (10)
C18—C19	1.440 (9)	C67—C68	1.411 (11)
C18—H18	0.9500	C68—C69	1.401 (13)
C19—C20	1.386 (9)	C68—H68	0.9500
C19—N24	1.386 (8)	C69—C70	1.340 (13)
C20—C43	1.499 (8)	C69—H69	0.9500
N21—H21	0.8800	C70—C71	1.349 (12)
N22—H22	0.8800	C70—H70	0.9500
N23—H23	0.8800	C71—C72	1.421 (11)
N24—H24	0.8800	C71—H71	0.9500
C25—C26	1.381 (8)	Cl3—C73	1.740 (9)
C25—C30	1.401 (9)	Cl4—C78	1.743 (10)
C26—C27	1.380 (9)	C73—C74	1.380 (13)
C26—H26	0.9500	C73—C78	1.415 (13)
C27—N28	1.344 (8)	C74—C75	1.343 (12)
C27—H27	0.9500	C74—H74	0.9500
N28—C29	1.348 (7)	C75—C76	1.469 (14)
C29—C30	1.386 (8)	C75—H75	0.9500
C29—H29	0.9500	C76—C77	1.347 (12)
C30—H30	0.9500	C76—H76	0.9500
C31—C32	1.377 (9)	C77—C78	1.375 (11)
C31—C36	1.399 (9)	C77—H77	0.9500
C32—C33	1.390 (9)
O49—La1—O50	66.29 (13)	C19—N24—H24	125.2
O49—La1—O56	112.12 (13)	C26—C25—C30	117.3 (6)
O50—La1—O56	148.77 (13)	C26—C25—C5	120.9 (6)
O49—La1—O61	126.68 (14)	C30—C25—C5	121.7 (6)
O50—La1—O61	131.39 (13)	C27—C26—C25	119.9 (6)
O56—La1—O61	76.20 (13)	C27—C26—H26	120.0
O49—La1—O53	79.97 (14)	C25—C26—H26	120.0
O50—La1—O53	81.84 (13)	N28—C27—C26	123.8 (6)
O56—La1—O53	67.56 (13)	N28—C27—H27	118.1
O61—La1—O53	141.73 (13)	C26—C27—H27	118.1
O49—La1—O64	137.12 (13)	C27—N28—C29	116.0 (5)
O50—La1—O64	73.81 (13)	C27—N28—La1	120.7 (4)
O56—La1—O64	110.07 (13)	C29—N28—La1	123.1 (4)
O61—La1—O64	71.06 (14)	N28—C29—C30	124.0 (6)
O53—La1—O64	109.85 (15)	N28—C29—H29	118.0
O49—La1—O60	80.95 (14)	C30—C29—H29	118.0
O50—La1—O60	131.51 (13)	C29—C30—C25	118.9 (6)
O56—La1—O60	75.77 (13)	C29—C30—H30	120.5
O61—La1—O60	48.90 (14)	C25—C30—H30	120.5
O53—La1—O60	127.79 (15)	C32—C31—C36	118.4 (6)
O64—La1—O60	117.08 (14)	C32—C31—C10	121.8 (6)
O49—La1—O65	167.68 (14)	C36—C31—C10	119.8 (6)
O50—La1—O65	112.57 (13)	C31—C32—C33	120.1 (6)
O56—La1—O65	61.93 (13)	C31—C32—H32	120.0
O61—La1—O65	63.96 (14)	C33—C32—H32	120.0
O53—La1—O65	87.72 (15)	N34—C33—C32	120.1 (7)
O64—La1—O65	48.29 (13)	N34—C33—H33	120.0
O60—La1—O65	106.67 (14)	C32—C33—H33	120.0
O49—La1—O57	64.58 (12)	C33—N34—C35	121.4 (6)
O50—La1—O57	123.25 (12)	C33—N34—H34	121 (4)
O56—La1—O57	47.74 (12)	C35—N34—H34	117 (4)
O61—La1—O57	100.67 (14)	N34—C35—C36	120.3 (6)
O53—La1—O57	63.42 (14)	N34—C35—H35	119.9
O64—La1—O57	157.72 (13)	C36—C35—H35	119.9
O60—La1—O57	64.46 (14)	C35—C36—C31	119.6 (7)
O65—La1—O57	109.43 (13)	C35—C36—H36	120.2
O49—La1—N28	78.71 (14)	C31—C36—H36	120.2
O50—La1—N28	72.51 (13)	C38—C37—C42	116.4 (6)
O56—La1—N28	138.71 (13)	C38—C37—C15	119.3 (6)
O61—La1—N28	66.67 (13)	C42—C37—C15	124.3 (6)
O53—La1—N28	151.60 (13)	C39—C38—C37	118.9 (6)
O64—La1—N28	74.86 (14)	C39—C38—H38	120.5
O60—La1—N28	66.54 (14)	C37—C38—H38	120.5
O65—La1—N28	113.04 (15)	N40—C39—C38	124.0 (6)
O57—La1—N28	121.83 (14)	N40—C39—H39	118.0
O49—La1—O52	108.02 (14)	C38—C39—H39	118.0
O50—La1—O52	62.45 (13)	C41—N40—C39	116.2 (6)
O56—La1—O52	90.74 (14)	N40—C41—C42	123.4 (6)
O61—La1—O52	124.86 (15)	N40—C41—H41	118.3
O53—La1—O52	46.68 (15)	C42—C41—H41	118.3
O64—La1—O52	63.82 (15)	C41—C42—C37	121.0 (6)
O60—La1—O52	166.03 (14)	C41—C42—H42	119.5
O65—La1—O52	62.73 (14)	C37—C42—H42	119.5
O57—La1—O52	109.05 (14)	C44—C43—C48	116.4 (6)
N28—La1—O52	124.94 (15)	C44—C43—C20	121.7 (6)
O49—La1—N59	103.50 (15)	C48—C43—C20	121.9 (5)
O50—La1—N59	135.86 (14)	C43—C44—C45	119.8 (6)
O56—La1—N59	75.36 (14)	C43—C44—H44	120.1
O61—La1—N59	24.70 (14)	C45—C44—H44	120.1
O53—La1—N59	140.82 (15)	N46—C45—C44	123.0 (6)
O64—La1—N59	94.08 (16)	N46—C45—H45	118.5
O60—La1—N59	24.22 (14)	C44—C45—H45	118.5
O65—La1—N59	85.79 (15)	C47—N46—C45	117.0 (6)
O57—La1—N59	82.58 (15)	N46—C47—C48	124.1 (6)
N28—La1—N59	63.35 (14)	N46—C47—H47	117.9
O52—La1—N59	148.42 (15)	C48—C47—H47	117.9
N21—C1—C20	124.5 (6)	C47—C48—C43	119.7 (6)
N21—C1—C2	110.5 (6)	C47—C48—H48	120.2
C20—C1—C2	124.9 (6)	C43—C48—H48	120.2
C3—C2—C1	106.5 (6)	La1—O49—H49A	109.7
C3—C2—H2	126.8	La1—O49—H49B	133.3
C1—C2—H2	126.8	H49A—O49—H49B	116.2
C2—C3—C4	106.6 (6)	La1—O50—H50A	118.6
C2—C3—H3	126.7	La1—O50—H50B	126.6
C4—C3—H3	126.7	H50A—O50—H50B	99.7
N21—C4—C5	126.0 (6)	O54—N51—O52	121.9 (6)
N21—C4—C3	110.4 (5)	O54—N51—O53	120.6 (6)
C5—C4—C3	123.5 (6)	O52—N51—O53	117.4 (6)
C6—C5—C4	125.3 (6)	N51—O52—La1	92.9 (4)
C6—C5—C25	117.5 (6)	N51—O53—La1	102.9 (4)
C4—C5—C25	117.1 (6)	O58—N55—O57	122.3 (6)
N22—C6—C5	126.6 (6)	O58—N55—O56	121.5 (5)
N22—C6—C7	106.8 (5)	O57—N55—O56	116.1 (5)
C5—C6—C7	126.5 (6)	N55—O56—La1	100.4 (3)
C8—C7—C6	108.4 (6)	N55—O57—La1	95.3 (3)
C8—C7—H7	125.8	O62—N59—O60	121.9 (6)
C6—C7—H7	125.8	O62—N59—O61	120.5 (6)
C7—C8—C9	107.7 (6)	O60—N59—O61	117.6 (5)
C7—C8—H8	126.1	O62—N59—La1	176.4 (5)
C9—C8—H8	126.1	O60—N59—La1	59.7 (3)
N22—C9—C10	126.2 (6)	O61—N59—La1	58.0 (3)
N22—C9—C8	107.0 (5)	N59—O60—La1	96.0 (4)
C10—C9—C8	126.8 (6)	N59—O61—La1	97.3 (4)
C11—C10—C9	126.1 (6)	O66—N63—O64	121.7 (6)
C11—C10—C31	117.9 (6)	O66—N63—O65	120.5 (6)
C9—C10—C31	115.9 (5)	O64—N63—O65	117.8 (5)
N23—C11—C10	125.3 (6)	O66—N63—La1	177.4 (5)
N23—C11—C12	111.0 (6)	O64—N63—La1	57.9 (3)
C10—C11—C12	123.7 (6)	O65—N63—La1	60.0 (3)
C13—C12—C11	106.4 (6)	N63—O64—La1	98.2 (4)
C13—C12—H12	126.8	N63—O65—La1	95.7 (3)
C11—C12—H12	126.8	C72—C67—C68	118.4 (8)
C12—C13—C14	106.6 (6)	C72—C67—Cl1	120.5 (6)
C12—C13—H13	126.7	C68—C67—Cl1	121.1 (7)
C14—C13—H13	126.7	C69—C68—C67	119.6 (9)
N23—C14—C15	126.2 (6)	C69—C68—H68	120.2
N23—C14—C13	110.4 (6)	C67—C68—H68	120.2
C15—C14—C13	123.3 (6)	C70—C69—C68	119.6 (9)
C14—C15—C16	125.3 (6)	C70—C69—H69	120.2
C14—C15—C37	117.7 (6)	C68—C69—H69	120.2
C16—C15—C37	116.7 (6)	C69—C70—C71	123.8 (10)
N24—C16—C15	125.7 (6)	C69—C70—H70	118.1
N24—C16—C17	107.3 (6)	C71—C70—H70	118.1
C15—C16—C17	126.7 (6)	C70—C71—C72	117.8 (9)
C18—C17—C16	108.9 (6)	C70—C71—H71	121.1
C18—C17—H17	125.6	C72—C71—H71	121.1
C16—C17—H17	125.6	C67—C72—C71	120.8 (8)
C17—C18—C19	107.6 (6)	C67—C72—Cl2	120.4 (6)
C17—C18—H18	126.2	C71—C72—Cl2	118.8 (7)
C19—C18—H18	126.2	C74—C73—C78	119.0 (8)
C20—C19—N24	126.5 (6)	C74—C73—Cl3	122.2 (8)
C20—C19—C18	126.8 (6)	C78—C73—Cl3	118.8 (8)
N24—C19—C18	106.6 (6)	C75—C74—C73	121.8 (12)
C19—C20—C1	127.3 (6)	C75—C74—H74	119.1
C19—C20—C43	115.4 (6)	C73—C74—H74	119.1
C1—C20—C43	117.1 (6)	C74—C75—C76	120.2 (11)
C4—N21—C1	105.9 (5)	C74—C75—H75	119.9
C4—N21—H21	127.0	C76—C75—H75	119.9
C1—N21—H21	127.0	C77—C76—C75	116.2 (10)
C9—N22—C6	110.0 (5)	C77—C76—H76	121.9
C9—N22—H22	125.0	C75—C76—H76	121.9
C6—N22—H22	125.0	C76—C77—C78	124.2 (11)
C11—N23—C14	105.6 (5)	C76—C77—H77	117.9
C11—N23—H23	127.2	C78—C77—H77	117.9
C14—N23—H23	127.2	C77—C78—C73	118.5 (9)
C16—N24—C19	109.5 (5)	C77—C78—Cl4	120.8 (10)
C16—N24—H24	125.2	C73—C78—Cl4	120.6 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N34—H34···O50^i	0.96 (7)	1.88 (7)	2.810 (7)	163 (6)
O49—H49A···N40^ii	0.82	1.92	2.652 (7)	148
O49—H49B···O65^iii	0.82	2.08	2.899 (5)	172
O50—H50A···O56^iii	0.82	1.93	2.751 (6)	179
O50—H50B···N46^iv	0.82	1.84	2.658 (6)	179

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