The three-dimensional coordination polymer poly[[aqua­[μ₄-2,2′-(diazene-1,2-di­yl)dibenzoato]lead(II)] 1,2-bis­(pyridin-4-yl)ethyl­ene hemisolvate]

A novel three-dimensional coordination polymer, {[Pb(C₁₄H₈N₂O₄)(H₂O)]·0.5C₁₂H₁₀N₂}_n, has been synthesized by hydro­thermal reaction of Pb(OAc)₂·3H₂O (OAc is acetate), 2,2′-(diazene-1,2-di­yl)di­benzoic acid (H₂L) and 1,2-bis­(pyridin-4-yl)ethyl­ene (bpe). The asymmetric unit contains a crystallographically independent Pb^II cation, one L²⁻ ligand, an aqua ligand and half a bpe mol­ecule. Each Pb^II centre is seven-coordinated by six O atoms of bridging–chelating carboxylate groups from L²⁻ ligands and by one O atom from a coordinated water mol­ecule. The Pb^II cations are bridged by L²⁻ ligands, forming [PbO₂]_n chains along the a axis. These chains are further connected by L²⁻ ligands along the b and c axes to give a three-dimensional framework with a 4¹²6³ topology. The channel voids are occupied by bpe mol­ecules.

S1. Introduction

The rational design and synthesis of novel coordination polymers have received much attention in the field of crystal engineering, mostly motivated by their unique structural motifs and potential applications in catalysis, gas adsorption, magnetism, nonlinear optics and molecular sensing (Kitagawa et al., 2003; Nugent et al., 2013; Sumida et al., 2012; Lee et al., 2009; Chen et al., 2010; Cook et al., 2013). The self-assembly of organic ligands and metal ions is currently the most efficient approach towards the design of one-, two- and three-dimensional coordination polymeric frameworks. Because the metal ions or clusters have certain preferred coordination geometries, connection of these moieties with organic ligands of predetermined shapes can lead to the construction of coordination polymers with predi­cta­ble structures (Das et al., 2011). Therefore, the selection of appropriate ligands is a key factor for the construction of new coordination polymers.

It is known that, compared with rigid organic ligands, flexible counterparts show more conformations to match the coordination requirements of the metal centre and give a richer variety of structures (Tanaka et al., 2008; Xie et al., 2010). Among them, azo­benzene–di­carb­oxy­lic acids have attracted much inter­est (Cairns et al., 2008; Bhattacharya et al., 2011; Liu et al., 2014; Yu et al., 2014), because the diazenediyl groups can increase the flexibility and length of the ligands. 2,2-(Diazene-1,2-diyl)di­benzoic acid (H₂L) is an example of such a flexible di­carboxyl­ate ligand and has the potential to construct novel functional coordination polymesr. Herein, we utilized H₂L as a bridging ligand and obtained a new three-dimensional coordination polymer, namely {[PbL(H₂O)]·0.5bpe}_n [bpe is 1,2-bis­(pyridin-4-yl)ethyl­ene], (I).

S2. Experimental

S2.1. Synthesis and crystallization

H₂L was synthesized according to the method of Reid & Pritchett (1953). All other chemicals used for the syntheses were commercially available reagents of analytical grade and were used without further purification. A mixture of Pb(OAc)₂·3H₂O (19 mg, 0.05 mmol), H₂L (7 mg, 0.025 mmol), bpe (5 mg, 0.025 mmol) and MeOH–H₂O (1:1 v/v, 4 ml) was sealed in a Teflon-lined autoclave and heated at 393 K for 48 h, then cooled to room temperature. Orange block-shaped crystals were collected and washed thoroughly with H₂O and dried in air (yield 48%, based on H₂L). Elemental analysis calculated for C₂₀H₁₅PbN₃O₅: C 41.09, H 2.58, N 7.19%; found: C 41.12, H 2.52, N 7.11%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were placed in geometrically idealized positions, with C—H = 0.93 Å for phenyl and pyridine groups, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C). Water H atoms were evident from a difference electron-density map and were restrained to reasonable distances.

S3. Results and discussion

Compound (I) crystallizes in the triclinic space group P1 and the asymmetric unit consists of a crystallographically independent Pb^II cation, one L^2- ligand, an aqua ligand and half an uncoordinated bpe molecule. The coordination environment of Pb^II is shown in Fig. 1. Each Pb^II centre is six-coordinated by five O atoms of bridging–chelating carboxyl­ate groups from the surrounding L^2- ligands and one O atom from a coordinated water molecule. In addition, there is a weak Pb1···O3 inter­action [2.768 (2) Å; dotted bond in Fig. 1]. Selected bond lengths and angles for (I) are listed in Table 2.

As shown in Fig. 2, the Pb^II cations are bridged to each other by O atoms from L^2- ligands, forming [PbO₂]_n chains along the a axis. The Pb···Pb···Pb angle is 155.24(?)° and the Pb···Pb distances between adjacent Pb^II centres are 4.2024 (9) and 4.2649 (9) Å. The chains are further connected by L^2- ligands along the b and c axes to give a three-dimensional framework, and the 1,2-bis­(pyridin-4-yl)ethyl­ene (bpe) molecules are located in the channel voids as noncoordinating guests (Fig. 3). The overall structure of (I) can be specified by a Schläfli symbol of 4¹²6³.

In the crystal packing of (I), there are extensive inter­molecular inter­actions. The coordinated water molecule (O1W), acting as a donor, is hydrogen bonded to atom O3 of the L^2- ligand (O1W—H1WA ···O3ⁱⁱ; Table 3) and atom N3 of the bpe molecule (O1W—H1WB···N3; Table 3). Moreover, there are π—π stacking inter­actions between the benzene ring (atoms C2–C7) and its symmetry-related partner at (-x, -y+2, -z+1) along the [PbO₂]_n chain, with an inter­planar distance of 3.755 (2) Å. The dihedral angle defined by the planes of the stacked rings is 0° and the slippage angles are both 21.40°, indicting that these rings are parallel to each other. These moderate inter­molecular inter­actions have further enhanced the stability of compound (I).

In conclusion, a new three-dimensional coordination polymer, {[PbL(H₂O)]·0.5bpe}_n, displays a 4¹²6³ topology network in which bpe molecules act as noncoordinating guests. Inter­molecular hydrogen bonds and π–π stacking inter­actions further strengthen the three-dimensional framework.

Related literature

For related literature, see: Bhattacharya et al. (2011); Cairns et al. (2008); Chen et al. (2010); Cook et al. (2013); Das et al. (2011); Kitagawa et al. (2003); Lee et al. (2009); Liu et al. (2014); Nugent et al. (2013); Reid & Pritchett (1953); Sumida et al. (2012); Tanaka et al. (2008); Xie et al. (2010); Yu et al. (2014).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. A view of the coordination environment around the Pb^II centre, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and all H atoms have been omitted for clarity. The weak Pb1···O3 interaction is shown as a dotted line. [Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+1.]
	Fig. 2. A view of the [PbO2]n chain in (I).
	Fig. 3. A view of the three-dimensional framework of (I). All H atoms have been omitted for clarity. Bpe molecules were shown in bright green.
	Fig. 4. The intermolecular interactions in (I), with pink dashed lines indicating π–π stacking interactions and turquoise dashed lines indicating hydrogen bonds. The planes of the stacked rings were shown in bright green.

Poly[[aqua[µ₄-2,2'-(diazene-1,2-diyl)dibenzoato]lead(II)] 1,2-bis(pyridin-4-yl)ethylene hemisolvate]

Crystal data

[Pb(C14H8N2O4)(H2O)]·0.5C12H10N2	Z = 2
Mr = 584.54	F(000) = 556
Triclinic, P1	Dx = 2.093 Mg m^−3
a = 8.2704 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.927 (2) Å	Cell parameters from 6381 reflections
c = 11.729 (2) Å	θ = 2.5–28.5°
α = 95.99 (3)°	µ = 9.14 mm^−1
β = 101.66 (3)°	T = 296 K
γ = 97.16 (3)°	Block, red
V = 927.3 (3) Å^3	0.20 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer	3181 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
φ and ω scans	θmax = 25.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
Tmin = 0.169, Tmax = 0.187	k = −8→11
6886 measured reflections	l = −14→13
3331 independent 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)] = 0.017	Hydrogen site location: mixed
wR(F^2) = 0.041	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0166P)^2 + 0.7401P] where P = (Fo^2 + 2Fc^2)/3
3331 reflections	(Δ/σ)max = 0.001
270 parameters	Δρmax = 0.68 e Å^−3
2 restraints	Δρmin = −0.83 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. ISOR, SIMU and DELU instructions were used to make the geometrical configurations and displacement parameters reasonable

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

	x	y	z	Uiso*/Ueq
Pb1	0.23785 (2)	0.46880 (2)	0.46715 (2)	0.02555 (5)
C1	0.1999 (4)	0.7452 (3)	0.5320 (3)	0.0272 (7)
C2	0.2003 (4)	0.8928 (3)	0.5745 (3)	0.0263 (7)
C3	0.0836 (4)	0.9273 (4)	0.6383 (3)	0.0358 (8)
H3	0.0067	0.8583	0.6533	0.043*
C4	0.0795 (5)	1.0616 (4)	0.6800 (3)	0.0410 (9)
H4	0.0001	1.0827	0.7223	0.049*
C5	0.1936 (5)	1.1646 (4)	0.6589 (3)	0.0395 (8)
H5	0.1907	1.2554	0.6867	0.047*
C6	0.3113 (4)	1.1336 (3)	0.5969 (3)	0.0338 (8)
H6	0.3888	1.2032	0.5837	0.041*
C7	0.3150 (4)	0.9985 (3)	0.5540 (3)	0.0270 (7)
C8	0.4562 (4)	0.5465 (3)	0.7101 (3)	0.0262 (7)
C9	0.5791 (4)	0.6397 (3)	0.8070 (3)	0.0282 (7)
C10	0.6739 (5)	0.7525 (4)	0.7783 (3)	0.0384 (8)
H10	0.6582	0.7698	0.7007	0.046*
C11	0.7904 (5)	0.8382 (4)	0.8642 (4)	0.0473 (10)
H11	0.8534	0.9130	0.8445	0.057*
C12	0.8142 (6)	0.8135 (4)	0.9796 (4)	0.0520 (11)
H12	0.8938	0.8713	1.0372	0.062*
C13	0.7208 (5)	0.7038 (4)	1.0098 (3)	0.0420 (9)
H13	0.7377	0.6874	1.0876	0.050*
C14	0.6012 (4)	0.6174 (4)	0.9241 (3)	0.0304 (7)
C15	0.2794 (5)	0.7547 (4)	0.1945 (3)	0.0429 (9)
H15	0.2982	0.7574	0.2757	0.052*
C16	0.3708 (5)	0.8532 (4)	0.1491 (3)	0.0437 (9)
H16	0.4470	0.9216	0.1992	0.052*
C17	0.3489 (4)	0.8500 (4)	0.0283 (3)	0.0331 (8)
C18	0.2329 (5)	0.7461 (4)	−0.0404 (3)	0.0390 (8)
H18	0.2137	0.7390	−0.1219	0.047*
C19	0.1453 (5)	0.6526 (4)	0.0127 (3)	0.0447 (10)
H19	0.0677	0.5833	−0.0352	0.054*
C20	0.4417 (5)	0.9495 (4)	−0.0278 (3)	0.0383 (8)
H20	0.4161	0.9405	−0.1094	0.046*
N1	0.4273 (3)	0.9706 (3)	0.4789 (2)	0.0295 (6)
N2	0.5031 (4)	0.4990 (3)	0.9471 (2)	0.0331 (6)
N3	0.1654 (4)	0.6559 (3)	0.1278 (3)	0.0409 (7)
O1	0.0737 (3)	0.6594 (2)	0.5277 (2)	0.0403 (6)
O2	0.3281 (3)	0.7089 (2)	0.5024 (2)	0.0342 (5)
O3	0.3041 (3)	0.5285 (3)	0.7094 (2)	0.0398 (6)
O4	0.5143 (3)	0.4936 (3)	0.6266 (2)	0.0351 (5)
O1W	0.0449 (4)	0.4912 (4)	0.2751 (3)	0.0509 (8)
H1WA	−0.053 (4)	0.507 (6)	0.278 (5)	0.076 (18)*
H1WB	0.069 (6)	0.543 (5)	0.227 (4)	0.073 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.02501 (8)	0.02474 (8)	0.02567 (7)	−0.00138 (5)	0.00674 (5)	0.00148 (5)
C1	0.0291 (17)	0.0281 (17)	0.0231 (15)	−0.0020 (14)	0.0064 (13)	0.0042 (13)
C2	0.0254 (16)	0.0260 (16)	0.0258 (16)	−0.0005 (13)	0.0046 (13)	0.0023 (13)
C3	0.0347 (19)	0.040 (2)	0.0352 (19)	0.0019 (15)	0.0156 (15)	0.0051 (15)
C4	0.045 (2)	0.045 (2)	0.037 (2)	0.0099 (17)	0.0182 (17)	0.0003 (16)
C5	0.049 (2)	0.0331 (19)	0.0355 (19)	0.0101 (17)	0.0067 (17)	−0.0019 (15)
C6	0.0361 (19)	0.0278 (18)	0.0345 (18)	−0.0006 (15)	0.0048 (15)	0.0025 (14)
C7	0.0256 (16)	0.0274 (16)	0.0249 (16)	−0.0005 (13)	0.0021 (12)	0.0012 (13)
C8	0.0282 (17)	0.0323 (17)	0.0200 (15)	0.0059 (13)	0.0066 (13)	0.0082 (13)
C9	0.0292 (17)	0.0316 (18)	0.0254 (16)	0.0071 (14)	0.0091 (13)	0.0023 (13)
C10	0.046 (2)	0.037 (2)	0.0348 (19)	0.0011 (16)	0.0188 (16)	0.0057 (15)
C11	0.051 (2)	0.039 (2)	0.051 (2)	−0.0085 (18)	0.0225 (19)	−0.0024 (18)
C12	0.050 (3)	0.047 (2)	0.050 (2)	−0.005 (2)	0.0057 (19)	−0.0112 (19)
C13	0.046 (2)	0.046 (2)	0.0282 (19)	0.0007 (18)	0.0027 (16)	−0.0022 (16)
C14	0.0343 (18)	0.0328 (18)	0.0255 (16)	0.0087 (14)	0.0084 (14)	0.0022 (13)
C15	0.049 (2)	0.048 (2)	0.0309 (19)	−0.0017 (18)	0.0087 (16)	0.0118 (17)
C16	0.046 (2)	0.043 (2)	0.036 (2)	−0.0093 (18)	0.0034 (17)	0.0096 (16)
C17	0.0303 (18)	0.0335 (19)	0.0375 (19)	0.0030 (14)	0.0097 (15)	0.0114 (15)
C18	0.044 (2)	0.040 (2)	0.0319 (19)	−0.0039 (17)	0.0114 (16)	0.0062 (15)
C19	0.048 (2)	0.041 (2)	0.041 (2)	−0.0126 (18)	0.0119 (18)	0.0046 (17)
C20	0.039 (2)	0.040 (2)	0.0348 (19)	−0.0045 (15)	0.0112 (16)	0.0102 (15)
N1	0.0309 (14)	0.0251 (14)	0.0320 (15)	−0.0035 (11)	0.0099 (12)	0.0042 (11)
N2	0.0413 (17)	0.0368 (16)	0.0210 (12)	0.0065 (13)	0.0053 (12)	0.0058 (11)
N3	0.0402 (18)	0.0425 (18)	0.0416 (18)	−0.0024 (14)	0.0138 (14)	0.0136 (14)
O1	0.0313 (13)	0.0275 (13)	0.0620 (17)	−0.0056 (10)	0.0167 (12)	0.0051 (11)
O2	0.0327 (13)	0.0274 (12)	0.0449 (14)	−0.0010 (10)	0.0192 (11)	0.0014 (10)
O3	0.0302 (14)	0.0555 (16)	0.0340 (13)	0.0005 (11)	0.0137 (10)	0.0020 (11)
O4	0.0317 (13)	0.0485 (15)	0.0242 (11)	0.0026 (11)	0.0107 (10)	−0.0037 (10)
O1W	0.0372 (17)	0.080 (2)	0.0369 (15)	−0.0020 (15)	0.0102 (12)	0.0242 (15)

Geometric parameters (Å, º)

Pb1—O2	2.374 (2)	C10—H10	0.9300
Pb1—O4^i	2.521 (2)	C11—C12	1.380 (6)
Pb1—O1W	2.532 (3)	C11—H11	0.9300
Pb1—O1	2.585 (3)	C12—C13	1.374 (6)
Pb1—O4	2.612 (3)	C12—H12	0.9300
Pb1—O1^ii	2.743 (2)	C13—C14	1.390 (5)
Pb1—C1	2.842 (3)	C13—H13	0.9300
Pb1—O3	2.768 (2)	C14—N2	1.425 (4)
C1—O1	1.251 (4)	C15—N3	1.332 (5)
C1—O2	1.262 (4)	C15—C16	1.377 (5)
C1—C2	1.497 (5)	C15—H15	0.9300
C2—C3	1.390 (5)	C16—C17	1.388 (5)
C2—C7	1.398 (4)	C16—H16	0.9300
C3—C4	1.378 (5)	C17—C18	1.378 (5)
C3—H3	0.9300	C17—C20	1.467 (5)
C4—C5	1.381 (5)	C18—C19	1.382 (5)
C4—H4	0.9300	C18—H18	0.9300
C5—C6	1.373 (5)	C19—N3	1.322 (5)
C5—H5	0.9300	C19—H19	0.9300
C6—C7	1.389 (5)	C20—C20^iii	1.314 (7)
C6—H6	0.9300	C20—H20	0.9300
C7—N1	1.434 (4)	N1—N1^iv	1.247 (5)
C8—O3	1.246 (4)	N2—N2^v	1.250 (5)
C8—O4	1.270 (4)	O1—Pb1^ii	2.743 (2)
C8—C9	1.504 (5)	O4—Pb1^i	2.521 (2)
C9—C14	1.393 (5)	O1W—H1WA	0.85 (2)
C9—C10	1.396 (5)	O1W—H1WB	0.83 (2)
C10—C11	1.376 (6)
O2—Pb1—O4^i	74.75 (8)	C14—C9—C8	122.3 (3)
O2—Pb1—O1W	91.11 (11)	C10—C9—C8	118.7 (3)
O4^i—Pb1—O1W	89.99 (9)	C11—C10—C9	120.3 (3)
O2—Pb1—O1	52.14 (8)	C11—C10—H10	119.9
O4^i—Pb1—O1	124.44 (8)	C9—C10—H10	119.9
O1W—Pb1—O1	77.30 (11)	C10—C11—C12	120.2 (4)
O2—Pb1—O4	76.80 (9)	C10—C11—H11	119.9
O4^i—Pb1—O4	70.11 (8)	C12—C11—H11	119.9
O1W—Pb1—O4	158.74 (9)	C13—C12—C11	120.3 (4)
O1—Pb1—O4	107.32 (9)	C13—C12—H12	119.8
O2—Pb1—O1^ii	125.74 (8)	C11—C12—H12	119.8
O4^i—Pb1—O1^ii	152.30 (8)	C12—C13—C14	120.1 (4)
O1W—Pb1—O1^ii	72.77 (9)	C12—C13—H13	120.0
O1—Pb1—O1^ii	73.67 (8)	C14—C13—H13	120.0
O4—Pb1—O1^ii	128.48 (8)	C13—C14—C9	120.0 (3)
O2—Pb1—C1	26.07 (8)	C13—C14—N2	123.7 (3)
O4^i—Pb1—C1	99.97 (9)	C9—C14—N2	116.2 (3)
O1W—Pb1—C1	84.58 (11)	N3—C15—C16	123.2 (4)
O1—Pb1—C1	26.11 (8)	N3—C15—H15	118.4
O4—Pb1—C1	91.38 (9)	C16—C15—H15	118.4
O1^ii—Pb1—C1	99.78 (9)	C15—C16—C17	119.8 (4)
O1—C1—O2	121.0 (3)	C15—C16—H16	120.1
O1—C1—C2	119.6 (3)	C17—C16—H16	120.1
O2—C1—C2	119.3 (3)	C18—C17—C16	116.8 (3)
O1—C1—Pb1	65.37 (18)	C18—C17—C20	119.6 (3)
O2—C1—Pb1	55.78 (16)	C16—C17—C20	123.6 (3)
C2—C1—Pb1	173.4 (2)	C17—C18—C19	119.4 (4)
C3—C2—C7	118.1 (3)	C17—C18—H18	120.3
C3—C2—C1	119.1 (3)	C19—C18—H18	120.3
C7—C2—C1	122.8 (3)	N3—C19—C18	123.9 (4)
C4—C3—C2	121.3 (3)	N3—C19—H19	118.1
C4—C3—H3	119.3	C18—C19—H19	118.1
C2—C3—H3	119.3	C20^iii—C20—C17	125.4 (4)
C3—C4—C5	119.8 (3)	C20^iii—C20—H20	117.3
C3—C4—H4	120.1	C17—C20—H20	117.3
C5—C4—H4	120.1	N1^iv—N1—C7	112.5 (3)
C6—C5—C4	120.2 (3)	N2^v—N2—C14	113.3 (4)
C6—C5—H5	119.9	C19—N3—C15	116.9 (3)
C4—C5—H5	119.9	C1—O1—Pb1	88.5 (2)
C5—C6—C7	120.2 (3)	C1—O1—Pb1^ii	165.1 (2)
C5—C6—H6	119.9	Pb1—O1—Pb1^ii	106.33 (8)
C7—C6—H6	119.9	C1—O2—Pb1	98.16 (19)
C6—C7—C2	120.4 (3)	C8—O4—Pb1^i	140.5 (2)
C6—C7—N1	118.8 (3)	C8—O4—Pb1	95.67 (19)
C2—C7—N1	120.5 (3)	Pb1^i—O4—Pb1	109.89 (8)
O3—C8—O4	122.1 (3)	Pb1—O1W—H1WA	117 (4)
O3—C8—C9	121.3 (3)	Pb1—O1W—H1WB	124 (4)
O4—C8—C9	116.5 (3)	H1WA—O1W—H1WB	101 (5)
C14—C9—C10	119.1 (3)
O1—C1—C2—C3	17.9 (5)	C10—C9—C14—N2	−178.7 (3)
O2—C1—C2—C3	−161.3 (3)	C8—C9—C14—N2	1.4 (5)
O1—C1—C2—C7	−163.0 (3)	N3—C15—C16—C17	−1.7 (7)
O2—C1—C2—C7	17.8 (5)	C15—C16—C17—C18	0.5 (6)
C7—C2—C3—C4	0.4 (5)	C15—C16—C17—C20	−179.4 (4)
C1—C2—C3—C4	179.5 (3)	C16—C17—C18—C19	0.3 (6)
C2—C3—C4—C5	−0.3 (6)	C20—C17—C18—C19	−179.9 (4)
C3—C4—C5—C6	−0.3 (6)	C17—C18—C19—N3	0.0 (7)
C4—C5—C6—C7	0.8 (6)	C18—C17—C20—C20^iii	−178.0 (5)
C5—C6—C7—C2	−0.7 (5)	C16—C17—C20—C20^iii	1.8 (8)
C5—C6—C7—N1	173.3 (3)	C6—C7—N1—N1^iv	50.3 (5)
C3—C2—C7—C6	0.1 (5)	C2—C7—N1—N1^iv	−135.7 (4)
C1—C2—C7—C6	−179.0 (3)	C13—C14—N2—N2^v	20.1 (6)
C3—C2—C7—N1	−173.8 (3)	C9—C14—N2—N2^v	−163.8 (4)
C1—C2—C7—N1	7.1 (5)	C18—C19—N3—C15	−1.1 (6)
O3—C8—C9—C14	60.2 (5)	C16—C15—N3—C19	2.0 (6)
O4—C8—C9—C14	−123.5 (3)	O2—C1—O1—Pb1	4.0 (3)
O3—C8—C9—C10	−119.7 (4)	C2—C1—O1—Pb1	−175.1 (3)
O4—C8—C9—C10	56.6 (4)	O2—C1—O1—Pb1^ii	−173.6 (7)
C14—C9—C10—C11	1.7 (5)	C2—C1—O1—Pb1^ii	7.2 (11)
C8—C9—C10—C11	−178.5 (3)	Pb1—C1—O1—Pb1^ii	−177.7 (9)
C9—C10—C11—C12	−0.2 (6)	O1—C1—O2—Pb1	−4.4 (3)
C10—C11—C12—C13	−0.5 (7)	C2—C1—O2—Pb1	174.7 (2)
C11—C12—C13—C14	−0.3 (7)	O3—C8—O4—Pb1^i	155.3 (3)
C12—C13—C14—C9	1.8 (6)	C9—C8—O4—Pb1^i	−21.0 (5)
C12—C13—C14—N2	177.8 (4)	O3—C8—O4—Pb1	24.2 (3)
C10—C9—C14—C13	−2.5 (5)	C9—C8—O4—Pb1	−152.1 (2)
C8—C9—C14—C13	177.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···N3	0.83 (2)	1.92 (2)	2.744 (4)	170 (5)
O1W—H1WA···O3^ii	0.85 (2)	2.10 (3)	2.912 (4)	159 (5)

Symmetry code: (ii) −x, −y+1, −z+1.