Poly[bis([mu]-benzene-1,4-dicarboxyl­ato)bis[[mu]-6-(4-pyrid­yl)-5H-imidazolo[4,5-f][1,10]phenanthroline]dilead(II)]: an inter­penetrating [alpha]-Po net

The asymmetric unit of the title compound, [Pb₂(C₈H₄O₄)₂(C₁₈H₁₁N₅)₂]_n, contains two Pb^II atoms, two benzene-1,4-dicarboxyl­ate (1,4-bdc) dianions and two 6-(4-pyrid­yl)-5H-imidazolo­[4,5-f][1,10]phenanthroline (L) ligands. Each Pb^II atom is eight-coordinated by three N atoms from two different L ligands and five carboxyl­ate O atoms from three different 1,4-bdc dianions. The two 1,4-bdc dianions (1,4-bdc₁ and 1,4-bdc₂) show different coordination modes. Each 1,4-bdc₁ coordinates to two Pb^II atoms in a chelating bis-bidentate mode. Each carboxyl­ate group of the 1,4-bdc₂ anion connects two Pb^II atoms in a chelating-bridging tridentate mode to form a dinuclear unit. Neighbouring dinuclear units are connected together by the aromatic backbone of the 1,4-bdc dianions and the L ligands into a three-dimensional six-connected [alpha]-polonium framework. The most striking feature is that two identical three-dimensional single [alpha]-polonium nets are inter­locked with each other, thus leading directly to the formation of a twofold inter­penetrated three-dimensional [alpha]-polonium architecture. The framework is held together in part by strong N-H...O hydrogen bonds between the imidazole NH groups of the L ligands and the carboxyl­ate O atoms of 1,4-bdc dianions within different [alpha]-polonium nets.

S1. Comment

The design and synthesis of coordination polymers with infinite three-dimensional framework structures has been an area of rapid growth in recent years, owing to the potential of these polymers in various applications such as catalysis, electrical conductivity, host–guest chemistry and magnetism (Ockwig et al., 2005; O'Keeffe et al., 2008; Yang et al., 2008). In this regard, a great many coordination polymers with mineral topologies, including CdSO₄ (cds), NbO (nbo), Pt₃O₄ (pto), pyrite (pyr), quartz (qtz), rutile (rto), diamond (diaz) and sodalite (sod), have provided experimental examples of these theoretical topologies (Batten, 2001; Batten & Robson, 1998; Carlucci et al., 2003). As a result, the design and construction of diverse topological networks has received much attention (Eddaoudi et al., 2001). The topologies of coordination polymers can often be controlled and modified by the coordination geometry preferred by the metal ion and the chemical structure of the organic ligand (Long et al., 2002). It is well known that careful selection of a suitable organic ligand with certain features is helpful for constructing coordination polymers with desirable properties. So far, the combination of bridging carboxylates, 1,10-phenanthroline-like (phen-like) chelating ligands and metal ions has generated many interesting coordination architectures (Wang et al., 2008; Qiao et al., 2008; Kong et al., 2009). Unfortunately, owing to the termination effect of chelating phen-like ligands, such coordination polymers containing both polycarboxylates and phen-like ligands are usually only one- or two-dimensional (Wang et al., 2009, 2010; Qiao et al., 2009). High-dimensional complexes based on dicarboxylate and phen-like ligands have rarely been reported (Yang et al., 2007). Here, we have selected the benzene-1,4-dicarboxylate dianion (1,4-bdc) as an organic linker and 6-(pyridin-4-yl)-5H-cyclopenta[f][1,10]phenanthroline (L) as an N-donor ligand, generating a new two-fold interpenetrating coordination polymer with α-Po topology, [Pb₂(L)₂(1,4-bdc)₂]_n, (I).

The asymmetric unit of (I) contains two Pb^II atoms, two 1,4-bdc dianions and two L ligands (Fig. 1). Each Pb^II atom is eight-coordinated by three N atoms from two different L ligands and five carboxylate O atoms from three different 1,4-bdc dianions. The Pb—O distances (Table 1) are comparable with those observed for [Pb(eedb)(L')(DMF)] (eedb is 4,4'-ethylenedibenzoate, L' is pyrazino[2,3-f][1,10]phenanthroline and DMF is dimethylformamide) (Qiao et al., 2009). The two independent 1,4-bdc dianions show different coordination modes. For convenience, the 1,4-bdc anions containing atoms O1–O4 and O5–O8 are designated 1,4-bdc₁ and 1,4-bdc₂, respectively. Each 1,4-bdc₁ anion coordinates to two Pb^II atoms in a chelating bis-bidentate mode. Carboxylate atoms O1 and O2 chelate Pb1, while atoms O3 and O4 chelate Pb2^v [symmetry code: (v) x, y, z - 1]. Each carboxylate group of the 1,4-bdc₂ anion connects two Pb^II atoms in a chelating-bridging tridentate mode to form a dimer. Carboxylate atoms O5 and O6 chelate Pb1, while atom O5 bridges simultaneously to Pb2. The other O atoms, O7 and O8, chelate Pb2^vi, while atom O7 bridges simultaneously to Pb1^vi [symmetry code: (vi) 1 + x, y, z]. The distance between the Pb^II atoms in the dinuclear unit is 3.751 (3) Å.

Neighbouring dinuclear units are connected together by the aromatic backbone of both 1,4-bdc dianions and the L ligands. Each dinuclear Pb^II unit is surrounded by eight organic ligands: four bridging 1,4-bdc dianions and four bridging L ligands. Although each dinuclear Pb^II unit is ligated by eight bridging ligands, it is almost [Please check rephrasing] linked to six nearest neighbours, because two pairs of L ligands form two `double bridges' (Fig. 2). Each dinuclear unit therefore acts as a six-connecting node, and the overall three-dimensional framework topology is that of α-polonium (Fig. 2).

The most striking feature of (I) is that two identical three-dimensional single α-polonium nets are interlocked with each other, thus leading directly to the formation of a twofold interpenetrated three-dimensional α-Po architecture (Fig. 3).

There are strong N—H···O hydrogen bonds between the N atoms of the L ligands and the carboxylate O atoms of the 1,4-bdc ligands within different α-Po nets (Table 2). Each α-Po net is hydrogen-bonded to its neighbour through these hydrogen bonds, which further consolidates the twofold interpenetrated framework.

To date, although a number of α-Po frameworks have been reported, we are not aware of any other example of a Pb^II coordination polymer with this motif (O'Keeffe et al., 2008; Wang et al., 2010). As far as we know, only one α-Po framework based on a 1,10-phen-like ligand, [Cd(1,4-ndc)(L'')]_n (L'' is pyrazino[2,3-f][1,10]phenanthroline and 1,4-ndc is naphthalene-1,4-dicarboxylate), has been reported so far (Qiao et al., 2008). In that structure, four Cd^II atoms are bridged by the carboxylate groups of the 1,4-ndc ligands to form tetranuclear cadmium carboxylate clusters. These tetranuclear cadmium carboxylate clusters are further connected together by the aromatic backbone of the dicarboxylate ligands to generate a three-dimensional non-interpenetrating α-Po net.

Notably, although the very recently reported compound {[Pb(L)(1,4-bdc)].2H₂O}_n (Wang et al., 2010) is constructed from the same mixed organic ligands and Pb^II atoms, its structure is entirely different from that of (I). In that compound, each carboxylate group of the 1,4-bdc anion chelates one Pb^II atom in a bidentate mode. All 1,4-bdc anions assume one kind of coordination mode, namely bridging bis(bidentate). Adjacent Pb^II atoms are bridged by 1,4-bdc dianions to form a one-dimensional zigzag chain. The L ligands are attached on both sides of the chains in chelating modes. Clearly, the topological difference between (I) and the previously reported compound is mainly attributed to the different coordination modes of the 1,4-bdc dianions and the L ligands. The water molecules are not coordinated to any of the metal atoms, and are in the voids between the chains. It should be pointed out that the previously reported compound was synthesized at 443 K, while (I) was prepared at 468 K in the presence of Pb^II, 1,4-bdc and L. Thus, the synthesis of the two structures can apparently be controlled through variation of the reaction temperature.

Related literature

For related literature, see: Batten (2001); Batten & Robson (1998); Carlucci et al. (2003); Eddaoudi et al. (2001); Kong et al. (2009); Long et al. (2002); O'Keeffe et al. (2008); Ockwig et al. (2005); Qiao et al. (2008, 2009); Wang et al. (2008, 2009, 2010); Yang et al. (2007, 2008).

S2. Experimental

A mixture of Pb(NO₃)₂ (0.5 mmol), 1,4-H₂bdc (0.5 mmol) and L (1 mmol) was dissolved in distilled water (12 ml). The resulting solution was stirred for about 2 h at room temperature, sealed in a 23 ml Teflon-lined stainless steel autoclave and heated at 468 K for 7 d under autogenous pressure. Afterwards, the reaction system was slowly cooled to room temperature. Pale-yellow block crystals of (I) suitable for single-crystal X-ray diffraction analysis were collected from the final reaction system by filtration, washed several times with distilled water and dried in air at ambient temperature (yield 35% based on Pb^II).

S3. Refinement

All H atoms were positioned geometrically, with N—H = 0.86 Å and C—H = 0.93 Å, and refined as riding, with U_iso(H) = 1.2U_eq(carrier).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. A view of the local coordination of the Pb^II atoms in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) x, y - 1, z; (ii) x - 1, y, z; (iii) x, y, 1 + z; (iv) x, 1 + y, z.]
	Fig. 2. A view of the three-dimensional α-polonium net of (I). Large balls represent the six-connected nodes.
	Fig. 3. A view of the twofold interpenetrated α-polonium structure of (I). Hydrogen-bonding interactions between the nets are shown as dashed lines.

Poly[bis(µ-benzene-1,4-dicarboxylato)bis[µ-6-(4-pyridyl)-5H- imidazolo[4,5-f][1,10]phenanthroline]dilead(II)]

Crystal data

[Pb2(C8H4O4)2(C18H11N5)2]	Z = 2
Mr = 1337.24	F(000) = 1280
Triclinic, P1	Dx = 1.932 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.9066 (7) Å	Cell parameters from 7984 reflections
b = 15.0537 (10) Å	θ = 1.4–25.0°
c = 15.0663 (10) Å	µ = 7.38 mm^−1
α = 75.890 (1)°	T = 293 K
β = 74.199 (1)°	Block, pale yellow
γ = 81.399 (1)°	0.27 × 0.22 × 0.16 mm
V = 2299.2 (3) Å^3

Data collection

Bruker APEX diffractometer	7984 independent reflections
Radiation source: fine-focus sealed tube	6315 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→11
Tmin = 0.56, Tmax = 0.77	k = −17→17
12743 measured reflections	l = −17→10

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.070	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0361P)^2] where P = (Fo^2 + 2Fc^2)/3
7984 reflections	(Δ/σ)max = 0.001
649 parameters	Δρmax = 1.27 e Å^−3
0 restraints	Δρmin = −0.60 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	−0.0251 (5)	−0.5031 (4)	0.1199 (5)	0.056 (2)
H1	−0.1107	−0.4984	0.1189	0.068*
C2	0.0497 (6)	−0.5853 (4)	0.1164 (5)	0.0542 (19)
H2	0.0117	−0.6354	0.1133	0.065*
C3	0.5529 (5)	−0.6300 (4)	0.1037 (5)	0.0421 (15)
H3	0.5981	−0.6856	0.0936	0.051*
C4	0.6187 (6)	−0.5625 (4)	0.1133 (5)	0.0496 (17)
H4	0.7055	−0.5740	0.1114	0.060*
C5	0.3520 (5)	−0.3785 (4)	0.1311 (4)	0.0326 (13)
C6	0.5561 (5)	−0.4790 (4)	0.1255 (4)	0.0405 (15)
H6	0.5992	−0.4329	0.1319	0.049*
C7	0.4255 (5)	−0.4646 (4)	0.1280 (4)	0.0303 (12)
C8	0.3639 (5)	−0.5372 (3)	0.1207 (4)	0.0326 (13)
C9	0.2264 (5)	−0.5242 (4)	0.1224 (4)	0.0354 (14)
C10	0.0289 (5)	−0.4286 (4)	0.1251 (5)	0.0509 (18)
H10	−0.0197	−0.3725	0.1270	0.061*
C11	0.1565 (5)	−0.4374 (4)	0.1275 (4)	0.0358 (14)
C12	0.2814 (5)	−0.2343 (4)	0.1295 (4)	0.0354 (14)
C13	0.2237 (5)	−0.3646 (4)	0.1315 (4)	0.0361 (14)
C14	0.1904 (6)	0.0174 (5)	0.1066 (7)	0.081 (3)
H14	0.1188	0.0580	0.0995	0.097*
C15	0.1827 (6)	−0.0745 (4)	0.1131 (6)	0.071 (3)
H15	0.1078	−0.0944	0.1094	0.085*
C16	0.2843 (5)	−0.1363 (4)	0.1251 (4)	0.0364 (14)
C17	0.3904 (6)	−0.1014 (4)	0.1298 (6)	0.064 (2)
H17	0.4625	−0.1408	0.1384	0.077*
C18	0.3913 (7)	−0.0089 (4)	0.1219 (6)	0.066 (2)
H18	0.4653	0.0124	0.1253	0.080*
C19	0.4661 (6)	0.3605 (4)	0.3762 (6)	0.063 (2)
H19	0.5056	0.3015	0.3743	0.075*
C20	0.5390 (6)	0.4270 (4)	0.3804 (5)	0.056 (2)
H20	0.6244	0.4122	0.3819	0.068*
C21	0.4835 (6)	0.5143 (4)	0.3824 (5)	0.0501 (17)
H21	0.5309	0.5600	0.3842	0.060*
C22	0.3544 (5)	0.5340 (4)	0.3816 (4)	0.0359 (14)
C23	0.2859 (5)	0.4631 (4)	0.3776 (4)	0.0341 (13)
C24	0.1508 (5)	0.4784 (4)	0.3774 (4)	0.0332 (13)
C25	−0.0320 (6)	0.4220 (4)	0.3747 (4)	0.0462 (16)
H25	−0.0734	0.3732	0.3723	0.055*
C26	−0.1034 (6)	0.5060 (4)	0.3787 (5)	0.0462 (16)
H26	−0.1895	0.5128	0.3786	0.055*
C27	−0.0450 (5)	0.5784 (4)	0.3829 (4)	0.0430 (15)
H27	−0.0908	0.6354	0.3857	0.052*
C28	0.0842 (5)	0.5657 (4)	0.3830 (4)	0.0351 (14)
C29	0.1567 (5)	0.6355 (4)	0.3881 (4)	0.0331 (13)
C30	0.2842 (5)	0.6228 (4)	0.3857 (4)	0.0339 (13)
C31	0.2258 (5)	0.7624 (4)	0.3964 (4)	0.0350 (14)
C32	0.2231 (5)	0.8591 (4)	0.3999 (4)	0.0352 (13)
C33	0.1126 (6)	0.9170 (4)	0.4012 (5)	0.0473 (17)
H33	0.0375	0.8946	0.4015	0.057*
C34	0.3305 (6)	0.8973 (4)	0.4005 (5)	0.0496 (18)
H34	0.4076	0.8611	0.3999	0.060*
C35	0.1139 (6)	1.0081 (4)	0.4020 (5)	0.0473 (16)
H35	0.0381	1.0459	0.4027	0.057*
C36	0.3231 (6)	0.9892 (4)	0.4019 (5)	0.0496 (17)
H36	0.3963	1.0132	0.4030	0.060*
C37	0.2574 (5)	0.2445 (4)	−0.0805 (4)	0.0342 (13)
C38	0.2548 (5)	0.2308 (4)	−0.1743 (4)	0.0326 (13)
C39	0.1502 (5)	0.1949 (4)	−0.1841 (4)	0.0455 (16)
H39	0.0821	0.1800	−0.1320	0.055*
C40	0.1469 (6)	0.1813 (4)	−0.2709 (4)	0.0467 (16)
H40	0.0764	0.1576	−0.2770	0.056*
C41	0.2485 (5)	0.2030 (4)	−0.3489 (4)	0.0312 (13)
C42	0.2449 (6)	0.1920 (4)	−0.4448 (4)	0.0371 (14)
C43	0.3515 (5)	0.2412 (4)	−0.3402 (4)	0.0408 (15)
H43	0.4186	0.2579	−0.3926	0.049*
C44	0.3536 (5)	0.2544 (4)	−0.2528 (4)	0.0406 (15)
H44	0.4230	0.2797	−0.2469	0.049*
C45	0.5348 (5)	0.1564 (4)	0.1885 (5)	0.0363 (14)
C46	0.6565 (5)	0.1580 (3)	0.2175 (4)	0.0304 (12)
C47	0.7718 (5)	0.1719 (4)	0.1486 (4)	0.0371 (14)
H47	0.7752	0.1725	0.0861	0.044*
C48	0.8801 (5)	0.1848 (4)	0.1727 (4)	0.0349 (13)
H48	0.9560	0.1946	0.1264	0.042*
C49	0.8762 (5)	0.1830 (3)	0.2657 (4)	0.0319 (13)
C50	0.7636 (5)	0.1664 (4)	0.3343 (4)	0.0384 (14)
H50	0.7609	0.1640	0.3971	0.046*
C51	0.6545 (5)	0.1534 (4)	0.3101 (4)	0.0405 (14)
H51	0.5796	0.1414	0.3568	0.049*
C52	0.9942 (5)	0.1986 (4)	0.2921 (4)	0.0351 (14)
N1	0.4282 (4)	−0.6191 (3)	0.1082 (4)	0.0374 (12)
N2	0.1725 (4)	−0.5971 (3)	0.1170 (4)	0.0414 (13)
N3	0.3858 (4)	−0.2950 (3)	0.1310 (3)	0.0357 (11)
H3A	0.4601	−0.2831	0.1318	0.043*
N4	0.1786 (4)	−0.2735 (3)	0.1305 (4)	0.0365 (12)
N9	0.2942 (5)	0.0511 (3)	0.1098 (4)	0.0500 (14)
N10	0.2168 (5)	1.0452 (3)	0.4017 (3)	0.0406 (12)
O1	0.3628 (4)	0.2633 (3)	−0.0702 (3)	0.0470 (11)
O2	0.1613 (4)	0.2351 (3)	−0.0135 (3)	0.0476 (11)
O3	0.1348 (3)	0.2068 (3)	−0.4647 (3)	0.0391 (10)
O4	0.3458 (4)	0.1743 (3)	−0.5021 (3)	0.0439 (10)
O5	0.4314 (4)	0.1563 (3)	0.2500 (3)	0.0502 (11)
O6	0.5416 (3)	0.1629 (3)	0.1023 (3)	0.0403 (10)
O7	1.0982 (4)	0.1948 (3)	0.2319 (3)	0.0588 (13)
O8	0.9841 (4)	0.2119 (3)	0.3734 (3)	0.0415 (10)
N5	0.0910 (4)	0.4067 (3)	0.3739 (3)	0.0366 (11)
N6	0.3432 (4)	0.3761 (3)	0.3748 (4)	0.0455 (13)
N7	0.3281 (4)	0.7025 (3)	0.3900 (3)	0.0371 (12)
N8	0.1199 (4)	0.7250 (3)	0.3949 (3)	0.0361 (12)
H8A	0.0444	0.7525	0.3976	0.043*
Pb1	0.306872 (18)	0.228293 (14)	0.106810 (15)	0.03121 (7)
Pb2	0.216110 (19)	0.227339 (14)	0.365684 (15)	0.03315 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.026 (3)	0.050 (4)	0.104 (6)	−0.008 (3)	−0.021 (4)	−0.028 (4)
C2	0.036 (4)	0.039 (4)	0.100 (6)	−0.007 (3)	−0.022 (4)	−0.029 (4)
C3	0.033 (3)	0.026 (3)	0.066 (4)	−0.002 (3)	−0.017 (3)	−0.003 (3)
C4	0.028 (3)	0.049 (4)	0.075 (5)	−0.003 (3)	−0.019 (3)	−0.011 (4)
C5	0.034 (3)	0.025 (3)	0.042 (4)	−0.009 (2)	−0.008 (3)	−0.011 (3)
C6	0.035 (3)	0.033 (3)	0.057 (4)	−0.011 (3)	−0.017 (3)	−0.004 (3)
C7	0.031 (3)	0.027 (3)	0.037 (3)	−0.008 (2)	−0.010 (3)	−0.008 (3)
C8	0.035 (3)	0.019 (3)	0.045 (4)	−0.006 (2)	−0.012 (3)	−0.005 (3)
C9	0.038 (3)	0.027 (3)	0.044 (4)	−0.005 (3)	−0.014 (3)	−0.007 (3)
C10	0.034 (3)	0.039 (4)	0.085 (5)	−0.002 (3)	−0.013 (3)	−0.026 (4)
C11	0.034 (3)	0.026 (3)	0.048 (4)	−0.005 (2)	−0.009 (3)	−0.010 (3)
C12	0.035 (3)	0.027 (3)	0.047 (4)	−0.008 (3)	−0.008 (3)	−0.012 (3)
C13	0.032 (3)	0.029 (3)	0.046 (4)	−0.006 (2)	−0.001 (3)	−0.015 (3)
C14	0.041 (4)	0.033 (4)	0.173 (9)	0.004 (3)	−0.024 (5)	−0.036 (5)
C15	0.039 (4)	0.036 (4)	0.149 (8)	−0.007 (3)	−0.027 (5)	−0.033 (5)
C16	0.037 (3)	0.023 (3)	0.050 (4)	−0.006 (3)	−0.004 (3)	−0.014 (3)
C17	0.056 (4)	0.029 (4)	0.126 (7)	−0.002 (3)	−0.047 (5)	−0.028 (4)
C18	0.059 (5)	0.037 (4)	0.122 (7)	−0.004 (3)	−0.041 (5)	−0.034 (4)
C19	0.041 (4)	0.037 (4)	0.115 (7)	0.007 (3)	−0.017 (4)	−0.034 (4)
C20	0.033 (3)	0.037 (4)	0.101 (6)	0.004 (3)	−0.016 (4)	−0.024 (4)
C21	0.036 (3)	0.040 (4)	0.076 (5)	−0.009 (3)	−0.009 (3)	−0.018 (4)
C22	0.033 (3)	0.031 (3)	0.044 (4)	−0.004 (3)	−0.002 (3)	−0.016 (3)
C23	0.039 (3)	0.029 (3)	0.035 (3)	−0.008 (3)	−0.004 (3)	−0.013 (3)
C24	0.038 (3)	0.029 (3)	0.035 (3)	−0.004 (3)	−0.006 (3)	−0.014 (3)
C25	0.054 (4)	0.035 (4)	0.056 (4)	−0.016 (3)	−0.016 (3)	−0.012 (3)
C26	0.035 (3)	0.044 (4)	0.068 (5)	−0.004 (3)	−0.018 (3)	−0.021 (3)
C27	0.041 (3)	0.030 (3)	0.064 (4)	0.001 (3)	−0.022 (3)	−0.015 (3)
C28	0.036 (3)	0.035 (3)	0.037 (3)	−0.007 (3)	−0.002 (3)	−0.017 (3)
C29	0.032 (3)	0.027 (3)	0.039 (3)	−0.009 (2)	−0.004 (3)	−0.009 (3)
C30	0.038 (3)	0.028 (3)	0.038 (3)	−0.008 (3)	−0.006 (3)	−0.013 (3)
C31	0.039 (3)	0.024 (3)	0.044 (4)	−0.009 (3)	−0.003 (3)	−0.013 (3)
C32	0.044 (3)	0.029 (3)	0.033 (3)	−0.007 (3)	−0.004 (3)	−0.010 (3)
C33	0.044 (4)	0.029 (3)	0.073 (5)	−0.014 (3)	−0.014 (3)	−0.011 (3)
C34	0.033 (3)	0.028 (3)	0.089 (5)	−0.003 (3)	−0.011 (3)	−0.019 (3)
C35	0.045 (4)	0.028 (3)	0.067 (5)	−0.004 (3)	−0.010 (3)	−0.010 (3)
C36	0.044 (4)	0.039 (4)	0.071 (5)	−0.016 (3)	−0.007 (3)	−0.022 (3)
C37	0.030 (3)	0.032 (3)	0.041 (4)	−0.005 (2)	−0.010 (3)	−0.007 (3)
C38	0.030 (3)	0.037 (3)	0.037 (3)	−0.006 (2)	−0.014 (3)	−0.012 (3)
C39	0.029 (3)	0.071 (5)	0.037 (4)	−0.017 (3)	−0.001 (3)	−0.012 (3)
C40	0.039 (3)	0.072 (5)	0.039 (4)	−0.021 (3)	−0.014 (3)	−0.016 (3)
C41	0.031 (3)	0.028 (3)	0.039 (3)	0.001 (2)	−0.014 (3)	−0.009 (3)
C42	0.040 (4)	0.030 (3)	0.047 (4)	−0.008 (3)	−0.017 (3)	−0.009 (3)
C43	0.033 (3)	0.049 (4)	0.038 (4)	−0.005 (3)	−0.005 (3)	−0.008 (3)
C44	0.035 (3)	0.052 (4)	0.041 (4)	−0.012 (3)	−0.011 (3)	−0.014 (3)
C45	0.035 (3)	0.024 (3)	0.051 (4)	−0.005 (2)	−0.014 (3)	−0.005 (3)
C46	0.028 (3)	0.026 (3)	0.039 (3)	−0.003 (2)	−0.013 (3)	−0.005 (3)
C47	0.038 (3)	0.043 (4)	0.034 (3)	0.001 (3)	−0.012 (3)	−0.013 (3)
C48	0.024 (3)	0.040 (3)	0.038 (3)	−0.006 (2)	−0.001 (3)	−0.007 (3)
C49	0.030 (3)	0.025 (3)	0.040 (3)	−0.005 (2)	−0.012 (3)	−0.002 (3)
C50	0.040 (3)	0.044 (4)	0.031 (3)	−0.003 (3)	−0.009 (3)	−0.009 (3)
C51	0.030 (3)	0.048 (4)	0.042 (4)	−0.014 (3)	−0.004 (3)	−0.006 (3)
C52	0.036 (3)	0.027 (3)	0.045 (4)	−0.003 (2)	−0.016 (3)	−0.005 (3)
N1	0.036 (3)	0.027 (3)	0.053 (3)	−0.006 (2)	−0.016 (2)	−0.008 (2)
N2	0.037 (3)	0.026 (3)	0.068 (4)	−0.003 (2)	−0.020 (3)	−0.014 (3)
N3	0.034 (3)	0.033 (3)	0.045 (3)	−0.013 (2)	−0.008 (2)	−0.013 (2)
N4	0.032 (3)	0.024 (2)	0.056 (3)	−0.004 (2)	−0.007 (2)	−0.017 (2)
N9	0.047 (3)	0.031 (3)	0.079 (4)	−0.009 (2)	−0.015 (3)	−0.023 (3)
N10	0.045 (3)	0.029 (3)	0.044 (3)	−0.008 (2)	−0.003 (2)	−0.007 (2)
O1	0.039 (2)	0.068 (3)	0.044 (3)	−0.018 (2)	−0.011 (2)	−0.021 (2)
O2	0.034 (2)	0.077 (3)	0.037 (2)	−0.015 (2)	−0.004 (2)	−0.021 (2)
O3	0.033 (2)	0.051 (3)	0.038 (2)	−0.0044 (19)	−0.0090 (19)	−0.019 (2)
O4	0.035 (2)	0.058 (3)	0.040 (3)	0.000 (2)	−0.005 (2)	−0.023 (2)
O5	0.028 (2)	0.070 (3)	0.050 (3)	−0.006 (2)	−0.007 (2)	−0.008 (2)
O6	0.036 (2)	0.042 (2)	0.050 (3)	−0.0034 (18)	−0.017 (2)	−0.017 (2)
O7	0.037 (3)	0.094 (4)	0.047 (3)	−0.019 (2)	−0.007 (2)	−0.014 (3)
O8	0.040 (2)	0.043 (2)	0.048 (3)	−0.0073 (19)	−0.016 (2)	−0.015 (2)
N5	0.037 (3)	0.029 (3)	0.049 (3)	−0.008 (2)	−0.013 (2)	−0.011 (2)
N6	0.034 (3)	0.027 (3)	0.077 (4)	−0.001 (2)	−0.010 (3)	−0.019 (3)
N7	0.034 (3)	0.028 (3)	0.050 (3)	−0.006 (2)	−0.005 (2)	−0.014 (2)
N8	0.036 (3)	0.024 (2)	0.051 (3)	−0.003 (2)	−0.010 (2)	−0.015 (2)
Pb1	0.03078 (12)	0.03135 (13)	0.03598 (14)	−0.00628 (9)	−0.01026 (10)	−0.01111 (10)
Pb2	0.03446 (13)	0.03374 (13)	0.03622 (14)	−0.00678 (10)	−0.01022 (10)	−0.01278 (10)

Geometric parameters (Å, º)

C1—C10	1.369 (7)	C31—C32	1.465 (7)
C1—C2	1.381 (8)	C32—C33	1.376 (8)
C1—H1	0.9300	C32—C34	1.383 (8)
C2—N2	1.326 (7)	C33—C35	1.377 (8)
C2—H2	0.9300	C33—H33	0.9300
C3—N1	1.330 (7)	C34—C36	1.379 (8)
C3—C4	1.383 (8)	C34—H34	0.9300
C3—H3	0.9300	C35—N10	1.324 (7)
C4—C6	1.367 (8)	C35—H35	0.9300
C4—H4	0.9300	C36—N10	1.328 (7)
C5—N3	1.362 (6)	C36—H36	0.9300
C5—C13	1.381 (7)	C37—O2	1.240 (7)
C5—C7	1.422 (7)	C37—O1	1.281 (6)
C6—C7	1.399 (7)	C37—C38	1.485 (8)
C6—H6	0.9300	C38—C44	1.379 (8)
C7—C8	1.407 (7)	C38—C39	1.388 (7)
C8—N1	1.354 (7)	C39—C40	1.383 (8)
C8—C9	1.477 (7)	C39—H39	0.9300
C9—N2	1.350 (6)	C40—C41	1.389 (8)
C9—C11	1.418 (7)	C40—H40	0.9300
C10—C11	1.388 (7)	C41—C43	1.385 (7)
C10—H10	0.9300	C41—C42	1.505 (8)
C11—C13	1.428 (7)	C42—O4	1.239 (7)
C12—N4	1.338 (6)	C42—O3	1.290 (6)
C12—N3	1.351 (6)	C42—Pb2^i	2.870 (6)
C12—C16	1.466 (7)	C43—C44	1.385 (8)
C13—N4	1.384 (7)	C43—H43	0.9300
C14—N9	1.325 (8)	C44—H44	0.9300
C14—C15	1.377 (8)	C45—O5	1.249 (7)
C14—H14	0.9300	C45—O6	1.261 (7)
C15—C16	1.358 (8)	C45—C46	1.511 (7)
C15—H15	0.9300	C46—C51	1.374 (8)
C16—C17	1.365 (8)	C46—C47	1.401 (8)
C17—C18	1.369 (8)	C47—C48	1.379 (7)
C17—H17	0.9300	C47—H47	0.9300
C18—N9	1.308 (8)	C48—C49	1.384 (7)
C18—H18	0.9300	C48—H48	0.9300
C19—N6	1.331 (7)	C49—C50	1.383 (8)
C19—C20	1.391 (8)	C49—C52	1.511 (7)
C19—H19	0.9300	C50—C51	1.389 (7)
C20—C21	1.367 (8)	C50—H50	0.9300
C20—H20	0.9300	C51—H51	0.9300
C21—C22	1.398 (8)	C52—O7	1.249 (7)
C21—H21	0.9300	C52—O8	1.260 (7)
C22—C23	1.411 (7)	N3—H3A	0.8600
C22—C30	1.444 (7)	Pb1—O1	2.508 (4)
C23—N6	1.370 (7)	Pb1—O2	2.691 (4)
C23—C24	1.458 (7)	Pb1—O5	2.772 (4)
C24—N5	1.360 (6)	Pb1—O6	2.591 (4)
C24—C28	1.413 (7)	Pb1—O7^ii	2.555 (4)
C25—N5	1.324 (7)	Pb1—N1^iii	2.824 (4)
C25—C26	1.387 (8)	Pb1—N2^iii	2.829 (4)
C25—H25	0.9300	Pb1—N9	2.681 (5)
C26—C27	1.363 (7)	Pb2—O3^iv	2.424 (4)
C26—H26	0.9300	Pb2—O4^iv	2.651 (4)
C27—C28	1.394 (7)	Pb2—O5	2.761 (4)
C27—H27	0.9300	Pb2—O7^ii	2.836 (4)
C28—C29	1.433 (7)	Pb2—O8^ii	2.545 (4)
C29—N8	1.367 (6)	Pb2—N5	2.853 (4)
C29—C30	1.367 (7)	Pb2—N6	2.852 (4)
C30—N7	1.378 (6)	Pb2—N10^v	2.662 (5)
C31—N7	1.323 (7)	N8—H8A	0.8600
C31—N8	1.367 (6)
C10—C1—C2	118.9 (5)	C41—C42—Pb2^i	163.3 (4)
C10—C1—H1	120.6	C44—C43—C41	119.4 (6)
C2—C1—H1	120.6	C44—C43—H43	120.3
N2—C2—C1	124.0 (5)	C41—C43—H43	120.3
N2—C2—H2	118.0	C38—C44—C43	121.3 (5)
C1—C2—H2	118.0	C38—C44—H44	119.3
N1—C3—C4	123.2 (5)	C43—C44—H44	119.3
N1—C3—H3	118.4	O5—C45—O6	123.2 (5)
C4—C3—H3	118.4	O5—C45—C46	118.2 (5)
C6—C4—C3	119.9 (5)	O6—C45—C46	118.3 (5)
C6—C4—H4	120.0	C51—C46—C47	118.9 (5)
C3—C4—H4	120.0	C51—C46—C45	120.9 (5)
N3—C5—C13	105.5 (5)	C47—C46—C45	120.0 (5)
N3—C5—C7	131.0 (5)	C48—C47—C46	120.6 (5)
C13—C5—C7	123.5 (5)	C48—C47—H47	119.7
C4—C6—C7	118.3 (5)	C46—C47—H47	119.7
C4—C6—H6	120.9	C47—C48—C49	120.1 (5)
C7—C6—H6	120.9	C47—C48—H48	119.9
C6—C7—C8	118.8 (5)	C49—C48—H48	119.9
C6—C7—C5	124.0 (5)	C50—C49—C48	119.5 (5)
C8—C7—C5	117.1 (5)	C50—C49—C52	120.3 (5)
N1—C8—C7	121.8 (5)	C48—C49—C52	120.3 (5)
N1—C8—C9	117.9 (5)	C49—C50—C51	120.4 (5)
C7—C8—C9	120.2 (5)	C49—C50—H50	119.8
N2—C9—C11	122.3 (5)	C51—C50—H50	119.8
N2—C9—C8	117.2 (5)	C46—C51—C50	120.5 (5)
C11—C9—C8	120.4 (5)	C46—C51—H51	119.8
C1—C10—C11	119.5 (6)	C50—C51—H51	119.8
C1—C10—H10	120.2	O7—C52—O8	123.5 (5)
C11—C10—H10	120.2	O7—C52—C49	117.1 (5)
C10—C11—C9	117.7 (5)	O8—C52—C49	119.3 (5)
C10—C11—C13	124.7 (5)	C3—N1—C8	118.0 (5)
C9—C11—C13	117.6 (5)	C2—N2—C9	117.5 (5)
N4—C12—N3	112.6 (4)	C12—N3—C5	107.6 (4)
N4—C12—C16	124.9 (5)	C12—N3—H3A	126.2
N3—C12—C16	122.5 (5)	C5—N3—H3A	126.2
C5—C13—N4	110.8 (5)	C12—N4—C13	103.6 (4)
C5—C13—C11	121.1 (5)	C18—N9—C14	116.0 (5)
N4—C13—C11	128.0 (5)	C18—N9—Pb1	119.9 (4)
N9—C14—C15	123.5 (6)	C14—N9—Pb1	123.9 (4)
N9—C14—H14	118.3	C35—N10—C36	116.6 (5)
C15—C14—H14	118.3	C35—N10—Pb2^iii	119.6 (4)
C16—C15—C14	120.1 (6)	C36—N10—Pb2^iii	122.5 (4)
C16—C15—H15	120.0	C37—O1—Pb1	97.5 (3)
C14—C15—H15	120.0	C37—O2—Pb1	89.9 (3)
C15—C16—C17	116.2 (5)	C42—O3—Pb2^i	96.4 (3)
C15—C16—C12	121.8 (5)	C42—O4—Pb2^i	87.2 (3)
C17—C16—C12	122.0 (5)	C45—O5—Pb2	157.8 (4)
C16—C17—C18	120.4 (6)	C45—O5—Pb1	88.6 (3)
C16—C17—H17	119.8	Pb2—O5—Pb1	85.34 (11)
C18—C17—H17	119.8	C45—O6—Pb1	96.8 (3)
N9—C18—C17	123.8 (6)	C52—O7—Pb1^vi	166.2 (4)
N9—C18—H18	118.1	C52—O8—Pb2^vi	100.9 (3)
C17—C18—H18	118.1	C25—N5—C24	117.5 (5)
N6—C19—C20	123.9 (6)	C25—N5—Pb2	119.0 (4)
N6—C19—H19	118.0	C24—N5—Pb2	123.5 (3)
C20—C19—H19	118.0	C19—N6—C23	117.6 (5)
C21—C20—C19	119.2 (6)	C19—N6—Pb2	118.2 (4)
C21—C20—H20	120.4	C23—N6—Pb2	124.2 (3)
C19—C20—H20	120.4	C31—N7—C30	104.4 (4)
C20—C21—C22	119.0 (5)	C29—N8—C31	107.1 (4)
C20—C21—H21	120.5	C29—N8—H8A	126.5
C22—C21—H21	120.5	C31—N8—H8A	126.5
C21—C22—C23	118.9 (5)	O1—Pb1—O7^ii	132.98 (13)
C21—C22—C30	124.3 (5)	O1—Pb1—O6	89.16 (13)
C23—C22—C30	116.9 (5)	O7^ii—Pb1—O6	131.70 (14)
N6—C23—C22	121.5 (5)	O1—Pb1—N9	90.13 (15)
N6—C23—C24	116.7 (5)	O7^ii—Pb1—N9	78.78 (16)
C22—C23—C24	121.9 (5)	O6—Pb1—N9	78.89 (14)
N5—C24—C28	121.5 (5)	O1—Pb1—O2	49.80 (12)
N5—C24—C23	118.6 (5)	O7^ii—Pb1—O2	83.23 (12)
C28—C24—C23	119.9 (5)	O6—Pb1—O2	130.95 (12)
N5—C25—C26	124.4 (5)	N9—Pb1—O2	76.17 (15)
N5—C25—H25	117.8	O1—Pb1—O5	137.61 (12)
C26—C25—H25	117.8	O7^ii—Pb1—O5	86.88 (12)
C27—C26—C25	118.8 (5)	O6—Pb1—O5	48.49 (12)
C27—C26—H26	120.6	N9—Pb1—O5	83.81 (15)
C25—C26—H26	120.6	O2—Pb1—O5	159.04 (13)
C26—C27—C28	119.1 (5)	O1—Pb1—N1^iii	91.40 (13)
C26—C27—H27	120.5	O7^ii—Pb1—N1^iii	117.17 (15)
C28—C27—H27	120.5	O6—Pb1—N1^iii	76.11 (12)
C27—C28—C24	118.7 (5)	N9—Pb1—N1^iii	154.93 (14)
C27—C28—C29	124.7 (5)	O2—Pb1—N1^iii	122.69 (13)
C24—C28—C29	116.5 (5)	O5—Pb1—N1^iii	78.27 (13)
N8—C29—C30	105.6 (5)	O1—Pb1—N2^iii	93.17 (14)
N8—C29—C28	130.3 (5)	O7^ii—Pb1—N2^iii	75.12 (15)
C30—C29—C28	124.1 (5)	O6—Pb1—N2^iii	133.84 (12)
C29—C30—N7	111.0 (5)	N9—Pb1—N2^iii	147.09 (14)
C29—C30—C22	120.6 (5)	O2—Pb1—N2^iii	81.14 (13)
N7—C30—C22	128.3 (5)	O5—Pb1—N2^iii	114.08 (13)
N7—C31—N8	111.9 (4)	N1^iii—Pb1—N2^iii	57.75 (13)
N7—C31—C32	125.8 (5)	O3^iv—Pb2—O8^ii	82.40 (13)
N8—C31—C32	122.2 (5)	O3^iv—Pb2—O4^iv	51.73 (12)
C33—C32—C34	116.7 (5)	O8^ii—Pb2—O4^iv	130.42 (13)
C33—C32—C31	121.0 (5)	O3^iv—Pb2—N10^v	83.64 (14)
C34—C32—C31	122.3 (5)	O8^ii—Pb2—N10^v	79.47 (14)
C32—C33—C35	119.7 (6)	O4^iv—Pb2—N10^v	77.92 (14)
C32—C33—H33	120.2	O3^iv—Pb2—O5	134.04 (12)
C35—C33—H33	120.2	O8^ii—Pb2—O5	126.98 (12)
C36—C34—C32	119.9 (6)	O4^iv—Pb2—O5	85.16 (12)
C36—C34—H34	120.1	N10^v—Pb2—O5	70.88 (14)
C32—C34—H34	120.1	O3^iv—Pb2—O7^ii	128.71 (12)
N10—C35—C33	123.8 (6)	O8^ii—Pb2—O7^ii	48.15 (12)
N10—C35—H35	118.1	O4^iv—Pb2—O7^ii	153.24 (13)
C33—C35—H35	118.1	N10^v—Pb2—O7^ii	75.75 (15)
N10—C36—C34	123.3 (5)	O5—Pb2—O7^ii	81.85 (12)
N10—C36—H36	118.3	O3^iv—Pb2—N6	86.80 (14)
C34—C36—H36	118.3	O8^ii—Pb2—N6	132.49 (13)
O2—C37—O1	121.1 (5)	O4^iv—Pb2—N6	69.75 (14)
O2—C37—C38	120.8 (5)	N10^v—Pb2—N6	144.92 (15)
O1—C37—C38	118.1 (5)	O5—Pb2—N6	92.72 (13)
C44—C38—C39	119.0 (5)	O7^ii—Pb2—N6	133.96 (15)
C44—C38—C37	121.3 (5)	O3^iv—Pb2—N5	80.93 (13)
C39—C38—C37	119.7 (5)	O8^ii—Pb2—N5	75.59 (12)
C40—C39—C38	120.3 (6)	O4^iv—Pb2—N5	109.41 (12)
C40—C39—H39	119.8	N10^v—Pb2—N5	152.12 (14)
C38—C39—H39	119.8	O5—Pb2—N5	135.25 (13)
C39—C40—C41	120.2 (5)	O7^ii—Pb2—N5	96.20 (13)
C39—C40—H40	119.9	N6—Pb2—N5	57.02 (13)
C41—C40—H40	119.9	O3^iv—Pb2—C42^iv	26.53 (14)
C43—C41—C40	119.7 (5)	O8^ii—Pb2—C42^iv	108.23 (15)
C43—C41—C42	119.0 (5)	O4^iv—Pb2—C42^iv	25.55 (13)
C40—C41—C42	121.1 (5)	N10^v—Pb2—C42^iv	82.83 (15)
O4—C42—O3	123.0 (5)	O5—Pb2—C42^iv	110.32 (15)
O4—C42—C41	119.8 (5)	O7^ii—Pb2—C42^iv	150.37 (14)
O3—C42—C41	117.0 (5)	N6—Pb2—C42^iv	73.97 (16)
O4—C42—Pb2^i	67.3 (3)	N5—Pb2—C42^iv	93.25 (15)
O3—C42—Pb2^i	57.1 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1^vii	0.86	1.93	2.720 (6)	151
N8—H8A···O3^viii	0.86	2.02	2.822 (6)	155

Symmetry codes: (vii) −x+1, −y, −z; (viii) −x, −y+1, −z.