Crystal structure of the lead-containing organic–inorganic hybrid: (C18H26N2)3[Pb4I14(DMSO)2]·2DMSO

Li, L.; Zhao, D.; Liu, Z.; Zhang, D.; Hu, Z.; Li, K.; Yang, J.

doi:10.1107/S2056989018016584

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ISSN: 2056-9890

Volume 74| Part 12| December 2018| Pages 1878-1880

https://doi.org/10.1107/S2056989018016584

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Crystal structure of the lead-containing organic–inorganic hybrid: (C₁₈H₂₆N₂)₃[Pb₄I₁₄(DMSO)₂]·2DMSO

Li Li,^a Dan Zhao,^a Zhi Liu,^a ^* Dingchao Zhang,^a Zhenhao Hu,^a Kunlun Li ^a and Jing Yang ^b

^aState Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, Shandong Province, People's Republic of China, and ^bSchool of Chemistry and Environmental Engineering, Shandong University of Science and Technology, Qingdao, People's Republic of China
^*Correspondence e-mail: lz@sdu.edu.cn

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 2 October 2018; accepted 21 November 2018; online 27 November 2018)

The title compound, tris(1,1′-dibutyl-4,4′-bipyridine-1,1′-diium) bis(dimethyl sulfoxide)di-μ₃-iodido-tetra-μ₂-iodido-octaiodidotetralead(II) dimethyl sulfoxide disolvate, (C₁₈H₂₆N₂)₃[Pb₄I₁₄(C₂H₆OS)₂]·2C₂H₆OS, belongs to a class of organic–inorganic hybrid materials with novel functionalities. In this compound, C—H⋯O and C—H⋯I hydrogen-bonding interactions, π–π interactions, other short contacts and Pb octahedral chains are present, extending the crystal structure into a three-dimensional supramolecular network.

Keywords: organic-inorganic hybrid; crystal structure; hydrogen-bonding interactions; π–π interactions.

CCDC reference: 1880239

1. Chemical context

Organic–inorganic hybrid materials have attracted more and more attention from researchers because of their interesting physical properties and novel functionalities, such as magnetism, ferroelectricity, electrical/optical properties and photochromism (Yao et al., 2017 ). The inorganic components provide rich structural possibilities, including discrete clusters, chains, layers and open frameworks, which dominate the significant electrical, optical and magnetic properties in hybrids (Sun et al., 2018 ). The organic moieties may exhibit unique molecular properties such as hyperpolarizability, photochromicity and polymerizability (Tang & Guloy, 1999 ). The title molecule was prepared by the reaction of viologens (N,N′-disubstituted-4,4′-bipyridinium) and a metal halide. Viologens show excellent redox and chemical stability. In addition, they can act as effective templates for the construction of various organic–inorganic hybrids, charge-transfer complexes and supramolecular systems (Liu et al., 2017 ). As lead is a heavy p-block metal in the IVA group, lead(II) halide-based organic–inorganic hybrids possess a large radius, a flexible coordination environment, and variable stereochemical activities of the lead center (Li et al., 2012 ).

2. Structural commentary

The title compound crystallizes in the triclinic system in space group Pī. The asymmetric unit consists of half a [(Pb₄I₁₄)]⁶⁻ trianion, one and a half BV²⁺ (BV²⁺ = 1,1′-dibutyl-4,4′- bipyridinium) dications and two DMSO molecules, as shown in Fig. 1. The BV²⁺ cation is located on a general position and adopts a non-planar structure, with a dihedral angle of 27.5 (3)° between the planes of the pyridinium rings. In the bipyridinium rings, C—N bond lengths vary from 1.335 (9) to 1.499 (10) Å and C—C bond lengths from 1.336 (17) to 1.636 (17) Å. C—N—C bond angles are in the range 118.6 (6)–121.1 (7)° and C—C—C bond angles in the range 107.9 (9)–122.1 (6)°. The inorganic anion can be considered as a set of mixed face-shared/edge-shared octahedra (Krautscheid et al., 2001 ). Pb1—I bond lengths range from 3.0765 (5) to 3.4315 (5) Å and Pb2—I bond lengths from 3.0802 (5) to 3.4010 (5) Å. I—Pb1—I bond angles are in the range 82.007 (13)–172.112 (13)° and O—Pb2—I bond angles in the range 82.78 (10)-174.71 (9)°. All the above angles deviate from the angles of an ideal octahedron (90 and 180°) due to the stereochemical activity of the Pb (6s²) lone pairs (Li et al., 2005 ).

Figure 1
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 25% probability level. The second lattice DMSO molecule and the third VB cation, generated by symmetry, are omitted for clarity. Symmetry code: (A) −x, −y, −z.

3. Supramolecular features

In the compound, the organic species interact with the inorganic [(Pb₄I₁₄)]⁶⁻ and DMSO via C—H⋯I and C—H⋯O hydrogen bonds (Table 1). The C⋯I distances are in the range 3.668 (8)–3.940 (10) Å while the C⋯O distances are 3.093 (9) and 3.517 (10) Å. The C—H⋯I angle values vary from 136 to 168°. Hydrogen bonds between the anionic entities [(Pb₄I₁₄)]⁶⁻ and organic species play an important role in stabilizing the crystal structure (Fig. 2). In addition, there are weak π–π interactions between adjacent free BV²⁺ cations with centroid-to-centroid distances between the pyridyl groups ranging from 4.249 (4) to 4.796 (4) Å (Table 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯I2ⁱ	0.93	2.94	3.668 (8)	136
C18—H18⋯O1ⁱⁱ	0.93	2.30	3.093 (9)	142
C21—H21⋯I7ⁱⁱⁱ	0.93	2.95	3.780 (7)	150
C22—H22⋯I2ⁱⁱ	0.93	2.86	3.776 (8)	168
C23—H23⋯I1^iv	0.93	2.85	3.753 (7)	165
C24—H24B⋯I5^v	0.97	2.99	3.940 (10)	166
C30—H30C⋯O2ⁱⁱ	0.96	2.57	3.517 (10)	169
Symmetry codes: (i) x+1, y+1, z-1; (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z+1; (iv) x+1, y+1, z; (v) x, y+1, z.

Table 2
Analysis of short ring–ring interactions (Å, °)

Cg(I)⋯Cg(J): ring centroid I,J (numbered as in Fig. 1); Cg⋯Cg: distance between ring centroids; α: dihedral angle between planes I and J; CgI_Perp: perpendicular distance of Cg(I) on ring J; CgJ_Perp: perpendicular distance of Cg(J) on ring I.

Cg(I)⋯Cg(J)	Cg⋯Cg	α	CgI_Perp	CgJ_Perp
Cg(2)⋯Cg(3)^vi	4.796 (4)	27.5 (3)	3.481 (3)	3.970 (3)
Cg(3)⋯Cg(2)^vi	4.795 (4)	27.5 (3)	3.970 (3)	3.480 (3)
Cg(3)⋯Cg(3)^vi	4.249 (4)	0.0 (4)	3.507 (3)	3.507 (3)
Symmetry code: (vi) 1 − x, 2 − y, 1 − z.

Figure 2
The crystal packing of the title compound with hydrogen bonds (Table 1

) shown as dashed lines.

4. Database survey

Lead(II) iodide complexes have been reported whose structures include chains of face-sharing ideal PbI₆ octahedra (Krautscheid et al., 2001; She et al., 2014 ) and chains of corner-sharing PbI₆ octahedra (Wang et al., 1995 ). The structure of 1,1′-dibutyl-4,4′-bipyridinium diiodide was reported by our research group (Zhao et al., 2012 ). Typical Pb–I-based hybrids templated with alkyl viologen cations include, for example, [(Pb₆I₂₂)(DMF)₂(DPB)₅] (Zhang et al., 2015 ), (C₂₁H₂₇N₃)[Pb₃I₉] (Hong-Xu et al., 2010 ), (C₁₄H₁₈N₂)[Pb₂I₆] (Pradeesh et al., 2010 ) and [IV][Pb₂I₆] (Kim et al., 2018 ).

5. Synthesis and crystallization

NaI (0.23 g, 1.5 mmol), PbI₂ (0.46 g, 1.0 mmol) and 10 ml of methanol were stirred under an argon atmosphere until dissolved. 1,1′-Dibutyl-4,4′-bipyridyl cation salt (0.52 g, 1.0 mmol) dissolved in methanol (5 ml) was added to the reaction mixture at room temperature. The resulting precipitate was dissolved in DMSO (3 ml) and placed in a sealed jar of anhydrous ether. Red crystals were produced two weeks later under an argon-protected atmosphere. After filtering and drying under vacuum, red needle-shaped crystals of 0.73 g (72.3%) with high quality were obtained. Analysis calculated for C₆₂H₁₀₂I₁₄N₆O₄Pb₄S₄: C 19.97, H 2.70, N 2.25%. Found: C 19.80, H 2.82, N 2.25%. IR (cm⁻¹): 3291 (w), 3108 (m), 3035 (s), 2931 (w), 2958 (w), 2857 (w), 944 (w), 1636 (m), 1634 (s), 1441 (m), 1060 (s), 833 (s).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and were included in the refinement in the riding-model approximation, with U_iso(H)= 1.2-1.5U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	(C₁₈H₂₆N₂)₃[Pb₄I₁₄(C₂H₆OS)₂]·2C₂H₆OS
M_r	1864.54
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	11.5011 (10), 14.2262 (13), 16.2969 (14)
α, β, γ (°)	80.305 (1), 78.449 (1), 81.753 (1)
V (Å³)	2558.5 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	10.90
Crystal size (mm)	0.55 × 0.50 × 0.09

Data collection
Diffractometer	Bruker APEX3 CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2017 )
T_min, T_max	0.065, 0.440
No. of measured, independent and observed [I > 2σ(I)] reflections	24466, 8975, 8219
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.099, 1.07
No. of reflections	8975
No. of parameters	432
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.47, −1.72
Computer programs: APEX3 and SAINT (Bruker, 2017), SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1880239

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018016584/ex2016sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018016584/ex2016Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Tris(1,1'-dibutyl-4,4'-bipyridine-1,1'-diium) bis(dimethyl sulfoxide)di-µ₃-iodido-tetra-µ₂-iodido-octaiodidotetralead(II) dimethyl sulfoxide disolvate top

Crystal data top

(C₁₈H₂₆N₂)₃[Pb₄I₁₄(C₂H₆OS)₂]·2C₂H₆OS	Z = 2
M_r = 1864.54	F(000) = 1682
Triclinic, P1	D_x = 2.419 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.5011 (10) Å	Cell parameters from 29882 reflections
b = 14.2262 (13) Å	θ = 1.8–25°
c = 16.2969 (14) Å	µ = 10.90 mm⁻¹
α = 80.305 (1)°	T = 296 K
β = 78.449 (1)°	Needle, red
γ = 81.753 (1)°	0.55 × 0.50 × 0.09 mm
V = 2558.5 (4) Å³

Data collection top

Bruker APEX3 CCD area-detector diffractometer	8975 independent reflections
Radiation source: fine-focus sealed tube	8219 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −13→13
T_min = 0.065, T_max = 0.440	k = −16→16
24466 measured reflections	l = −19→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0562P)² + 3.2208P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.059
8975 reflections	Δρ_max = 2.47 e Å⁻³
432 parameters	Δρ_min = −1.72 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Bruker, 2017), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00081 (6)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Pb1	−0.019011 (19)	0.115698 (16)	0.614407 (14)	0.02456 (9)
Pb2	0.056844 (19)	0.234124 (16)	0.300143 (15)	0.02475 (9)
I3	−0.12457 (3)	0.27930 (3)	0.48471 (3)	0.02923 (11)
I4	−0.07737 (4)	0.39067 (3)	0.18256 (3)	0.04282 (14)
I5	0.27864 (4)	0.19949 (4)	0.16274 (3)	0.04566 (14)
I6	0.15180 (4)	0.24586 (3)	0.65461 (3)	0.04339 (14)
I7	−0.22112 (4)	0.16826 (4)	0.75974 (3)	0.04122 (13)
C7	0.9915 (6)	0.9485 (5)	0.0111 (4)	0.0338 (15)
N2	0.4596 (5)	0.6917 (4)	0.7240 (4)	0.0363 (13)
C1	0.5880 (9)	0.6807 (9)	0.1101 (8)	0.087 (3)
H1A	0.5779	0.7078	0.0535	0.130*
H1B	0.5298	0.7132	0.1499	0.130*
H1C	0.5775	0.6137	0.1193	0.130*
C2	0.7139 (8)	0.6923 (7)	0.1220 (7)	0.068 (3)
H2A	0.7239	0.7601	0.1120	0.082*
H2B	0.7218	0.6681	0.1801	0.082*
C3	0.8105 (7)	0.6412 (5)	0.0644 (5)	0.050 (2)
H3A	0.8006	0.6641	0.0064	0.060*
H3B	0.8012	0.5733	0.0756	0.060*
C4	0.9363 (7)	0.6536 (5)	0.0728 (5)	0.0496 (19)
H4A	0.9479	0.6299	0.1303	0.059*
H4B	0.9935	0.6161	0.0352	0.059*
N1	0.9583 (5)	0.7570 (4)	0.0515 (4)	0.0368 (13)
C5	0.9825 (8)	0.8037 (6)	0.1095 (5)	0.055 (2)
H5	0.9881	0.7715	0.1635	0.066*
C6	0.9992 (8)	0.8996 (6)	0.0897 (5)	0.055 (2)
H6	1.0160	0.9314	0.1306	0.067*
C9	0.9507 (8)	0.8038 (7)	−0.0262 (5)	0.060 (2)
H9	0.9343	0.7710	−0.0666	0.072*
C8	0.9665 (9)	0.8976 (7)	−0.0468 (5)	0.063 (3)
H8	0.9604	0.9284	−0.1011	0.076*
C10	0.2978 (9)	0.6823 (9)	1.0341 (6)	0.084 (3)
H10A	0.2572	0.6397	1.0793	0.127*
H10B	0.2407	0.7316	1.0127	0.127*
H10C	0.3547	0.7110	1.0548	0.127*
C11	0.3623 (9)	0.6262 (7)	0.9635 (6)	0.067 (3)
H11A	0.3150	0.5765	0.9594	0.081*
H11B	0.4382	0.5951	0.9771	0.081*
C12	0.3845 (7)	0.6903 (6)	0.8783 (5)	0.0481 (19)
H12A	0.3091	0.7237	0.8656	0.058*
H12B	0.4353	0.7380	0.8812	0.058*
C13	0.4431 (7)	0.6323 (5)	0.8086 (5)	0.0446 (18)
H13A	0.5203	0.6018	0.8201	0.054*
H13B	0.3944	0.5821	0.8083	0.054*
C14	0.3627 (6)	0.7293 (5)	0.6908 (5)	0.0381 (16)
H14	0.2872	0.7185	0.7213	0.046*
C15	0.3738 (5)	0.7837 (5)	0.6123 (5)	0.0393 (17)
H15	0.3059	0.8096	0.5899	0.047*
C16	0.4857 (5)	0.8001 (5)	0.5664 (5)	0.0310 (15)
C19	0.4996 (5)	0.8580 (5)	0.4816 (5)	0.0330 (16)
C23	0.5989 (6)	0.9090 (5)	0.4521 (5)	0.0392 (16)
H23	0.6563	0.9058	0.4856	0.047*
C22	0.6111 (6)	0.9628 (6)	0.3748 (5)	0.0468 (19)
H22	0.6775	0.9962	0.3555	0.056*
N3	0.5285 (5)	0.9690 (4)	0.3252 (4)	0.0419 (15)
C24	0.5471 (8)	1.0264 (7)	0.2402 (6)	0.064 (3)
H24A	0.6019	1.0729	0.2383	0.077*
H24B	0.4717	1.0613	0.2290	0.077*
C25	0.5966 (9)	0.9636 (9)	0.1732 (6)	0.076 (3)
H25A	0.5386	0.9216	0.1703	0.091*
H25B	0.6685	0.9242	0.1864	0.091*
C26	0.6271 (12)	1.0332 (11)	0.0828 (8)	0.112 (5)
H26A	0.5573	1.0779	0.0735	0.134*
H26B	0.6913	1.0699	0.0842	0.134*
C27	0.6594 (15)	0.9805 (13)	0.0197 (10)	0.140 (6)
H27A	0.7293	0.9371	0.0286	0.209*
H27B	0.6767	1.0219	−0.0331	0.209*
H27C	0.5955	0.9445	0.0183	0.209*
C21	0.4319 (6)	0.9209 (5)	0.3527 (5)	0.0430 (19)
H21	0.3755	0.9253	0.3181	0.052*
C20	0.4156 (5)	0.8659 (5)	0.4301 (5)	0.0363 (16)
H20	0.3480	0.8338	0.4483	0.044*
C17	0.5853 (5)	0.7597 (5)	0.6030 (5)	0.0378 (16)
H17	0.6619	0.7693	0.5740	0.045*
C18	0.5692 (6)	0.7060 (5)	0.6819 (5)	0.0372 (16)
H18	0.6353	0.6794	0.7062	0.045*
S1	0.09717 (14)	0.45421 (12)	0.35969 (11)	0.0341 (4)
O1	0.1616 (4)	0.3631 (3)	0.3269 (3)	0.0348 (11)
C30	0.1581 (7)	0.4585 (6)	0.4499 (5)	0.058 (2)
H30A	0.1352	0.4060	0.4928	0.087*
H30B	0.1285	0.5181	0.4710	0.087*
H30C	0.2436	0.4537	0.4349	0.087*
C31	0.1638 (9)	0.5487 (6)	0.2894 (7)	0.078 (3)
H31A	0.2470	0.5437	0.2926	0.117*
H31B	0.1248	0.6092	0.3047	0.117*
H31C	0.1559	0.5445	0.2326	0.117*
S2	0.44397 (18)	0.46100 (15)	0.66133 (14)	0.0493 (5)
O2	0.5347 (5)	0.5287 (4)	0.6236 (4)	0.0671 (18)
C28	0.3245 (8)	0.4909 (6)	0.6066 (6)	0.062 (2)
H28A	0.2831	0.5519	0.6188	0.092*
H28B	0.2707	0.4426	0.6240	0.092*
H28C	0.3543	0.4945	0.5469	0.092*
C29	0.4998 (9)	0.3496 (7)	0.6250 (9)	0.091 (4)
H29A	0.4961	0.3549	0.5660	0.136*
H29B	0.4523	0.3008	0.6566	0.136*
H29C	0.5812	0.3327	0.6327	0.136*
I2	0.10647 (3)	−0.07348 (3)	0.72885 (3)	0.02993 (12)
I1	−0.16306 (3)	−0.05420 (3)	0.56721 (3)	0.02845 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.02601 (14)	0.02141 (14)	0.02844 (15)	−0.00252 (10)	−0.00949 (10)	−0.00442 (10)
Pb2	0.02510 (14)	0.02060 (14)	0.03053 (15)	−0.00131 (10)	−0.00997 (10)	−0.00449 (10)
I3	0.0275 (2)	0.0228 (2)	0.0371 (2)	−0.00003 (16)	−0.00946 (17)	−0.00164 (18)
I4	0.0412 (3)	0.0305 (3)	0.0544 (3)	−0.0011 (2)	−0.0192 (2)	0.0108 (2)
I5	0.0392 (3)	0.0600 (3)	0.0366 (3)	0.0084 (2)	−0.0076 (2)	−0.0147 (2)
I6	0.0441 (3)	0.0374 (3)	0.0561 (3)	−0.0159 (2)	−0.0173 (2)	−0.0080 (2)
I7	0.0369 (2)	0.0492 (3)	0.0397 (3)	−0.0072 (2)	−0.00319 (19)	−0.0148 (2)
C7	0.029 (3)	0.044 (4)	0.032 (4)	−0.002 (3)	−0.010 (3)	−0.011 (3)
N2	0.032 (3)	0.036 (3)	0.043 (3)	0.002 (2)	−0.005 (2)	−0.021 (3)
C1	0.061 (6)	0.100 (9)	0.100 (9)	−0.029 (6)	−0.022 (6)	0.008 (7)
C2	0.058 (5)	0.063 (6)	0.086 (7)	−0.017 (5)	−0.012 (5)	−0.009 (5)
C3	0.072 (5)	0.026 (4)	0.056 (5)	−0.014 (4)	−0.031 (4)	0.009 (3)
C4	0.063 (5)	0.037 (4)	0.053 (5)	−0.004 (4)	−0.027 (4)	0.001 (4)
N1	0.043 (3)	0.032 (3)	0.040 (3)	−0.003 (3)	−0.016 (3)	−0.008 (3)
C5	0.088 (6)	0.041 (5)	0.039 (4)	0.013 (4)	−0.037 (4)	0.000 (4)
C6	0.093 (6)	0.043 (5)	0.045 (5)	0.006 (4)	−0.046 (4)	−0.018 (4)
C9	0.091 (7)	0.071 (6)	0.031 (4)	−0.046 (5)	−0.013 (4)	−0.008 (4)
C8	0.106 (7)	0.069 (6)	0.028 (4)	−0.053 (6)	−0.019 (4)	0.001 (4)
C10	0.072 (7)	0.132 (11)	0.045 (5)	−0.002 (6)	−0.003 (5)	−0.018 (6)
C11	0.074 (6)	0.071 (7)	0.055 (6)	−0.006 (5)	−0.013 (5)	−0.007 (5)
C12	0.036 (4)	0.059 (5)	0.051 (5)	−0.002 (4)	−0.005 (3)	−0.020 (4)
C13	0.049 (4)	0.040 (4)	0.047 (5)	0.004 (3)	−0.012 (3)	−0.014 (4)
C14	0.029 (3)	0.040 (4)	0.046 (4)	−0.003 (3)	−0.002 (3)	−0.015 (3)
C15	0.018 (3)	0.046 (4)	0.058 (5)	0.001 (3)	−0.007 (3)	−0.024 (4)
C16	0.025 (3)	0.029 (3)	0.043 (4)	0.000 (3)	−0.007 (3)	−0.019 (3)
C19	0.020 (3)	0.033 (4)	0.050 (4)	0.002 (3)	−0.004 (3)	−0.024 (3)
C23	0.026 (3)	0.047 (4)	0.047 (4)	−0.010 (3)	−0.010 (3)	−0.007 (4)
C22	0.027 (3)	0.049 (5)	0.067 (5)	−0.006 (3)	−0.008 (3)	−0.014 (4)
N3	0.029 (3)	0.044 (4)	0.048 (4)	0.008 (3)	−0.005 (3)	−0.008 (3)
C24	0.040 (4)	0.082 (7)	0.063 (6)	0.016 (4)	−0.015 (4)	−0.002 (5)
C25	0.072 (6)	0.108 (9)	0.049 (6)	−0.012 (6)	−0.015 (5)	−0.011 (6)
C26	0.108 (10)	0.143 (12)	0.092 (9)	0.056 (9)	−0.055 (8)	−0.052 (9)
C27	0.136 (13)	0.164 (16)	0.130 (14)	0.020 (11)	−0.042 (11)	−0.062 (12)
C21	0.020 (3)	0.043 (4)	0.072 (6)	0.007 (3)	−0.017 (3)	−0.023 (4)
C20	0.023 (3)	0.040 (4)	0.050 (4)	−0.001 (3)	−0.008 (3)	−0.017 (4)
C17	0.021 (3)	0.038 (4)	0.058 (5)	0.000 (3)	−0.011 (3)	−0.015 (4)
C18	0.029 (3)	0.033 (4)	0.055 (5)	0.004 (3)	−0.014 (3)	−0.020 (3)
S1	0.0289 (8)	0.0265 (8)	0.0481 (10)	−0.0021 (6)	−0.0051 (7)	−0.0117 (7)
O1	0.026 (2)	0.031 (2)	0.052 (3)	−0.0029 (18)	−0.007 (2)	−0.021 (2)
C30	0.056 (5)	0.064 (6)	0.065 (6)	−0.002 (4)	−0.013 (4)	−0.040 (5)
C31	0.065 (6)	0.039 (5)	0.123 (9)	−0.012 (4)	−0.009 (6)	0.006 (5)
S2	0.0485 (11)	0.0429 (11)	0.0629 (13)	−0.0001 (9)	−0.0184 (9)	−0.0197 (10)
O2	0.049 (3)	0.050 (4)	0.113 (5)	−0.012 (3)	−0.015 (3)	−0.037 (4)
C28	0.066 (5)	0.037 (5)	0.088 (7)	−0.012 (4)	−0.040 (5)	0.009 (4)
C29	0.060 (6)	0.050 (6)	0.168 (12)	0.004 (5)	−0.011 (7)	−0.049 (7)
I2	0.0277 (2)	0.0258 (2)	0.0380 (2)	−0.00431 (17)	−0.00994 (17)	−0.00347 (18)
I1	0.0271 (2)	0.0254 (2)	0.0363 (2)	−0.00027 (16)	−0.01434 (17)	−0.00608 (18)

Geometric parameters (Å, º) top

Pb1—I7	3.0765 (5)	C14—H14	0.9300
Pb1—I6	3.1121 (5)	C15—C16	1.383 (9)
Pb1—I3	3.1493 (5)	C15—H15	0.9300
Pb1—I2	3.3282 (5)	C16—C17	1.403 (9)
Pb1—I1	3.3858 (5)	C16—C19	1.476 (10)
Pb2—O1	2.473 (4)	C19—C20	1.384 (9)
Pb2—I5	3.0802 (5)	C19—C23	1.400 (9)
Pb2—I4	3.1266 (5)	C23—C22	1.351 (11)
Pb2—I2ⁱ	3.3053 (5)	C23—H23	0.9300
Pb2—I1ⁱ	3.3187 (5)	C22—N3	1.350 (10)
Pb2—I3	3.4010 (5)	C22—H22	0.9300
C7—C6	1.364 (10)	N3—C21	1.348 (9)
C7—C8	1.378 (10)	N3—C24	1.479 (11)
C7—C7ⁱⁱ	1.481 (14)	C24—C25	1.499 (13)
N2—C18	1.335 (9)	C24—H24A	0.9700
N2—C14	1.340 (9)	C24—H24B	0.9700
N2—C13	1.483 (10)	C25—C26	1.636 (17)
C1—C2	1.534 (13)	C25—H25A	0.9700
C1—H1A	0.9600	C25—H25B	0.9700
C1—H1B	0.9600	C26—C27	1.336 (17)
C1—H1C	0.9600	C26—H26A	0.9700
C2—C3	1.491 (12)	C26—H26B	0.9700
C2—H2A	0.9700	C27—H27A	0.9600
C2—H2B	0.9700	C27—H27B	0.9600
C3—C4	1.518 (11)	C27—H27C	0.9600
C3—H3A	0.9700	C21—C20	1.361 (11)
C3—H3B	0.9700	C21—H21	0.9300
C4—N1	1.499 (9)	C20—H20	0.9300
C4—H4A	0.9700	C17—C18	1.373 (10)
C4—H4B	0.9700	C17—H17	0.9300
N1—C5	1.336 (9)	C18—H18	0.9300
N1—C9	1.341 (10)	S1—O1	1.522 (4)
C5—C6	1.380 (11)	S1—C30	1.763 (8)
C5—H5	0.9300	S1—C31	1.770 (9)
C6—H6	0.9300	C30—H30A	0.9600
C9—C8	1.349 (12)	C30—H30B	0.9600
C9—H9	0.9300	C30—H30C	0.9600
C8—H8	0.9300	C31—H31A	0.9600
C10—C11	1.520 (13)	C31—H31B	0.9600
C10—H10A	0.9600	C31—H31C	0.9600
C10—H10B	0.9600	S2—O2	1.492 (6)
C10—H10C	0.9600	S2—C28	1.749 (8)
C11—C12	1.524 (12)	S2—C29	1.774 (9)
C11—H11A	0.9700	C28—H28A	0.9600
C11—H11B	0.9700	C28—H28B	0.9600
C12—C13	1.508 (10)	C28—H28C	0.9600
C12—H12A	0.9700	C29—H29A	0.9600
C12—H12B	0.9700	C29—H29B	0.9600
C13—H13A	0.9700	C29—H29C	0.9600
C13—H13B	0.9700	I2—Pb2ⁱ	3.3053 (5)
C14—C15	1.371 (10)	I1—Pb2ⁱ	3.3187 (5)

I7—Pb1—I6	93.528 (15)	C12—C13—H13B	109.1
I7—Pb1—I3	91.655 (15)	H13A—C13—H13B	107.8
I6—Pb1—I3	93.038 (15)	N2—C14—C15	120.7 (6)
I7—Pb1—I2	95.153 (14)	N2—C14—H14	119.7
I6—Pb1—I2	90.519 (14)	C15—C14—H14	119.7
I3—Pb1—I2	172.112 (13)	C14—C15—C16	120.2 (7)
I7—Pb1—I1	93.512 (14)	C14—C15—H15	119.9
I6—Pb1—I1	170.159 (14)	C16—C15—H15	119.9
I3—Pb1—I1	93.622 (13)	C15—C16—C17	117.8 (7)
I2—Pb1—I1	82.007 (13)	C15—C16—C19	121.0 (6)
O1—Pb2—I5	84.47 (10)	C17—C16—C19	121.2 (6)
O1—Pb2—I4	87.45 (11)	C20—C19—C23	118.0 (7)
I5—Pb2—I4	94.693 (16)	C20—C19—C16	122.1 (6)
O1—Pb2—I2ⁱ	174.71 (9)	C23—C19—C16	119.9 (6)
I5—Pb2—I2ⁱ	100.234 (14)	C22—C23—C19	119.9 (7)
I4—Pb2—I2ⁱ	89.734 (15)	C22—C23—H23	120.0
O1—Pb2—I1ⁱ	99.08 (11)	C19—C23—H23	120.0
I5—Pb2—I1ⁱ	90.803 (14)	N3—C22—C23	121.1 (7)
I4—Pb2—I1ⁱ	171.859 (14)	N3—C22—H22	119.5
I2ⁱ—Pb2—I1ⁱ	83.372 (13)	C23—C22—H22	119.5
O1—Pb2—I3	82.78 (10)	C21—N3—C22	119.9 (7)
I5—Pb2—I3	162.883 (14)	C21—N3—C24	120.8 (7)
I4—Pb2—I3	96.095 (14)	C22—N3—C24	119.3 (7)
I2ⁱ—Pb2—I3	93.076 (12)	N3—C24—C25	111.0 (8)
I1ⁱ—Pb2—I3	80.016 (12)	N3—C24—H24A	109.4
Pb1—I3—Pb2	100.953 (13)	C25—C24—H24A	109.4
C6—C7—C8	116.9 (7)	N3—C24—H24B	109.4
C6—C7—C7ⁱⁱ	121.8 (7)	C25—C24—H24B	109.4
C8—C7—C7ⁱⁱ	121.3 (8)	H24A—C24—H24B	108.0
C18—N2—C14	121.1 (7)	C24—C25—C26	107.9 (9)
C18—N2—C13	120.3 (6)	C24—C25—H25A	110.1
C14—N2—C13	118.6 (6)	C26—C25—H25A	110.1
C2—C1—H1A	109.5	C24—C25—H25B	110.1
C2—C1—H1B	109.5	C26—C25—H25B	110.1
H1A—C1—H1B	109.5	H25A—C25—H25B	108.4
C2—C1—H1C	109.5	C27—C26—C25	110.1 (14)
H1A—C1—H1C	109.5	C27—C26—H26A	109.6
H1B—C1—H1C	109.5	C25—C26—H26A	109.6
C3—C2—C1	113.3 (9)	C27—C26—H26B	109.7
C3—C2—H2A	108.9	C25—C26—H26B	109.6
C1—C2—H2A	108.9	H26A—C26—H26B	108.1
C3—C2—H2B	108.9	C26—C27—H27A	109.5
C1—C2—H2B	108.9	C26—C27—H27B	109.5
H2A—C2—H2B	107.7	H27A—C27—H27B	109.5
C2—C3—C4	114.6 (7)	C26—C27—H27C	109.5
C2—C3—H3A	108.6	H27A—C27—H27C	109.5
C4—C3—H3A	108.6	H27B—C27—H27C	109.5
C2—C3—H3B	108.6	N3—C21—C20	121.1 (6)
C4—C3—H3B	108.6	N3—C21—H21	119.4
H3A—C3—H3B	107.6	C20—C21—H21	119.4
N1—C4—C3	111.1 (6)	C21—C20—C19	119.9 (6)
N1—C4—H4A	109.4	C21—C20—H20	120.1
C3—C4—H4A	109.4	C19—C20—H20	120.1
N1—C4—H4B	109.4	C18—C17—C16	119.7 (6)
C3—C4—H4B	109.4	C18—C17—H17	120.1
H4A—C4—H4B	108.0	C16—C17—H17	120.1
C5—N1—C9	119.6 (7)	N2—C18—C17	120.6 (6)
C5—N1—C4	120.8 (6)	N2—C18—H18	119.7
C9—N1—C4	119.6 (6)	C17—C18—H18	119.7
N1—C5—C6	120.2 (7)	O1—S1—C30	104.1 (3)
N1—C5—H5	119.9	O1—S1—C31	104.7 (4)
C6—C5—H5	119.9	C30—S1—C31	99.9 (5)
C7—C6—C5	121.0 (7)	S1—O1—Pb2	123.4 (2)
C7—C6—H6	119.5	S1—C30—H30A	109.5
C5—C6—H6	119.5	S1—C30—H30B	109.5
N1—C9—C8	121.2 (7)	H30A—C30—H30B	109.5
N1—C9—H9	119.4	S1—C30—H30C	109.5
C8—C9—H9	119.4	H30A—C30—H30C	109.5
C9—C8—C7	121.1 (8)	H30B—C30—H30C	109.5
C9—C8—H8	119.4	S1—C31—H31A	109.5
C7—C8—H8	119.5	S1—C31—H31B	109.5
C11—C10—H10A	109.5	H31A—C31—H31B	109.5
C11—C10—H10B	109.5	S1—C31—H31C	109.5
H10A—C10—H10B	109.5	H31A—C31—H31C	109.5
C11—C10—H10C	109.5	H31B—C31—H31C	109.5
H10A—C10—H10C	109.5	O2—S2—C28	108.1 (4)
H10B—C10—H10C	109.5	O2—S2—C29	107.1 (4)
C10—C11—C12	112.1 (8)	C28—S2—C29	98.0 (5)
C10—C11—H11A	109.2	S2—C28—H28A	109.5
C12—C11—H11A	109.2	S2—C28—H28B	109.5
C10—C11—H11B	109.2	H28A—C28—H28B	109.5
C12—C11—H11B	109.2	S2—C28—H28C	109.5
H11A—C11—H11B	107.9	H28A—C28—H28C	109.5
C13—C12—C11	111.1 (7)	H28B—C28—H28C	109.5
C13—C12—H12A	109.4	S2—C29—H29A	109.5
C11—C12—H12A	109.4	S2—C29—H29B	109.5
C13—C12—H12B	109.4	H29A—C29—H29B	109.5
C11—C12—H12B	109.4	S2—C29—H29C	109.5
H12A—C12—H12B	108.0	H29A—C29—H29C	109.5
N2—C13—C12	112.5 (6)	H29B—C29—H29C	109.5
N2—C13—H13A	109.1	Pb2ⁱ—I2—Pb1	97.673 (13)
C12—C13—H13A	109.1	Pb2ⁱ—I1—Pb1	96.290 (13)
N2—C13—H13B	109.1

I7—Pb1—I3—Pb2	−173.613 (13)	C17—C16—C19—C23	−28.4 (9)
I6—Pb1—I3—Pb2	92.765 (15)	C20—C19—C23—C22	−0.9 (10)
I2—Pb1—I3—Pb2	−23.93 (9)	C16—C19—C23—C22	−179.3 (6)
I1—Pb1—I3—Pb2	−79.987 (13)	C19—C23—C22—N3	0.4 (11)
O1—Pb2—I3—Pb1	−98.01 (11)	C23—C22—N3—C21	0.0 (11)
I5—Pb2—I3—Pb1	−55.87 (5)	C23—C22—N3—C24	−178.2 (7)
I4—Pb2—I3—Pb1	175.355 (13)	C21—N3—C24—C25	−79.3 (9)
I2ⁱ—Pb2—I3—Pb1	85.294 (14)	C22—N3—C24—C25	98.9 (9)
I1ⁱ—Pb2—I3—Pb1	2.580 (11)	N3—C24—C25—C26	−174.4 (8)
C1—C2—C3—C4	178.3 (8)	C24—C25—C26—C27	−173.3 (11)
C2—C3—C4—N1	−61.5 (9)	C22—N3—C21—C20	0.2 (10)
C3—C4—N1—C5	117.3 (8)	C24—N3—C21—C20	178.4 (7)
C3—C4—N1—C9	−61.1 (10)	N3—C21—C20—C19	−0.7 (10)
C9—N1—C5—C6	0.2 (12)	C23—C19—C20—C21	1.1 (9)
C4—N1—C5—C6	−178.2 (8)	C16—C19—C20—C21	179.4 (6)
C8—C7—C6—C5	−0.1 (13)	C15—C16—C17—C18	0.0 (9)
C7ⁱⁱ—C7—C6—C5	179.7 (8)	C19—C16—C17—C18	−179.8 (6)
N1—C5—C6—C7	0.0 (14)	C14—N2—C18—C17	−0.2 (9)
C5—N1—C9—C8	−0.4 (13)	C13—N2—C18—C17	179.1 (6)
C4—N1—C9—C8	178.1 (8)	C16—C17—C18—N2	0.2 (10)
N1—C9—C8—C7	0.3 (15)	C30—S1—O1—Pb2	126.1 (4)
C6—C7—C8—C9	−0.1 (14)	C31—S1—O1—Pb2	−129.5 (5)
C7ⁱⁱ—C7—C8—C9	−179.8 (9)	I5—Pb2—O1—S1	150.1 (3)
C10—C11—C12—C13	−177.2 (8)	I4—Pb2—O1—S1	55.2 (3)
C18—N2—C13—C12	112.7 (7)	I2ⁱ—Pb2—O1—S1	−2.7 (15)
C14—N2—C13—C12	−68.0 (8)	I1ⁱ—Pb2—O1—S1	−119.9 (3)
C11—C12—C13—N2	176.7 (7)	I3—Pb2—O1—S1	−41.3 (3)
C18—N2—C14—C15	0.1 (10)	I7—Pb1—I2—Pb2ⁱ	86.695 (15)
C13—N2—C14—C15	−179.2 (6)	I6—Pb1—I2—Pb2ⁱ	−179.716 (13)
N2—C14—C15—C16	0.1 (10)	I3—Pb1—I2—Pb2ⁱ	−62.87 (9)
C14—C15—C16—C17	−0.2 (9)	I1—Pb1—I2—Pb2ⁱ	−6.140 (11)
C14—C15—C16—C19	179.6 (6)	I7—Pb1—I1—Pb2ⁱ	−88.621 (15)
C15—C16—C19—C20	−26.5 (9)	I6—Pb1—I1—Pb2ⁱ	46.99 (9)
C17—C16—C19—C20	153.3 (6)	I3—Pb1—I1—Pb2ⁱ	179.495 (10)
C15—C16—C19—C23	151.8 (6)	I2—Pb1—I1—Pb2ⁱ	6.097 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···I2ⁱⁱⁱ	0.93	2.94	3.668 (8)	136
C18—H18···O1^iv	0.93	2.30	3.093 (9)	142
C21—H21···I7^v	0.93	2.95	3.780 (7)	150
C22—H22···I2^iv	0.93	2.86	3.776 (8)	168
C23—H23···I1^vi	0.93	2.85	3.753 (7)	165
C24—H24B···I5^vii	0.97	2.99	3.940 (10)	166
C30—H30C···O2^iv	0.96	2.57	3.517 (10)	169

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

Analysis of short ring–ring interactions (Å, °) top

Cg(I)···Cg(J): ring centroid I,J (numbered as in Fig. 1); Cg···Cg: distance between ring centroids; α: dihedral angle between planes I andJ; CgI_Perp: perpendicular distance of Cg(I) on ring J; CgJ_Perp: perpendicular distance of Cg(J) on ring I.

Cg(I)···Cg(J)	Cg···Cg	α	CgI_Perp	CgJ_Perp
Cg(2)···Cg(3)^vi	4.796 (4)	27.5 (3)	3.481 (3)	3.970 (3)
Cg(3)···Cg(2)^vi	4.795 (4)	27.5 (3)	3.970 (3)	3.480 (3)
Cg(3)···Cg(3)^vi	4.249 (4)	0.0 (4)	3.507 (3)	3.507 (3)

Symmetry code: (vi) 1 - x, 2 - y, 1 - z.

The fractional coordinates of Cg(I) top

Cg(I)	x	y	z
Cg(1)	0.9749 (3)	0.8517 (2)	0.03147 (19)
Cg(2)	0.4727 (2)	0.7451 (2)	0.6464 (2)
Cg(3)	0.5142 (2)	0.9143 (2)	0.4028 (2)

Funding information

The research was supported by the Natural Science Foundation of Shandong Province (grant No. ZR2010EM017).

References

Bruker (2017). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hong-Xu, G., Xi-Zhong, L., Wen-Bing, W. & Wen, W. (2010). Chin. J. Struct. Chem. 29, 181–186. Google Scholar
Kim, K. J., Kim, G. H., Lampande, R., Ahn, D. H., Im, J. B., Moon, J. S., Lee, J. K., Lee, J. Y., Lee, J. Y. & Kwon, J. H. (2018). J. Mater. Chem. C. 6, 1343–1348. CrossRef Google Scholar
Krautscheid, H., Lode, C., Vielsack, F. & Vollmer, H. (2001). J. Chem. Soc. Dalton Trans. pp. 1099–1104. Web of Science CrossRef Google Scholar
Li, H.-H., Chen, Z.-R., Li, J.-Q., Huang, C.-C., Xiao, G.-C., Lian, Z.-X. & Hu, X.-L. (2005). Acta Chim. Sin. 63, 697–702. Google Scholar
Li, H.-H., Wang, Y.-J., Lian, Z.-X., Xu, Y.-F., Wang, M., Huang, S.-W. & Chen, Z.-R. (2012). J. Mol. Struct. 1016, 118–125. CrossRef CAS Google Scholar
Liu, G., Liu, J., Nie, L., Ban, R., Armatas, G. S., Tao, X. & Zhang, Q. (2017). Inorg. Chem. 56, 5498–5501. CrossRef Google Scholar
Pradeesh, K., Agarwal, M., Rao, K. K. & Prakash, G. V. (2010). Solid State Sci. 12, 95–98. CrossRef Google Scholar
She, Y.-J., Zhao, S.-P., Tian, Z.-F. & Ren, X.-M. (2014). Inorg. Chem. Commun. 46, 29–32. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, C., Du, M. X., Xu, J. G., Mao, F. F., Wang, M. S. & Guo, G. C. (2018). Dalton Trans. 47, 1023–1026. CrossRef Google Scholar
Tang, Z. & Guloy, A. M. (1999). J. Am. Chem. Soc. 121, 452–453. Web of Science CrossRef CAS Google Scholar
Wang, S., Mitzi, D. B., Feild, C. A. & Guloy, A. (1995). J. Am. Chem. Soc. 117, 5297–5302. CrossRef CAS Web of Science Google Scholar
Yao, Z.-Y., Zou, Y., Chen, X. & Ren, X.-M. (2017). Inorg. Chem. Commun. 81, 5–9. CrossRef Google Scholar
Zhang, W., Zhang, N., Shen, L., Wu, H., Li, X., Li, S., Yue, J. & Niu, Y. (2015). Synth. React. Inorg. Met.-Org. Nano-Met. Chem. 45, 1347–1351. CrossRef Google Scholar
Zhao, D., Liu, Z., Shi, L.-Q., Yu, W.-T., Cui, D.-L. & Tao, X.-T. (2012). Z. Kristallogr. New Cryst. Struct. 227, 245–246. Google Scholar

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