Tetrakis­[(9-oxo-10-thia­xanthen-2-yl­oxy­ethyl)­ammonium] decaiodotriplumbate(II)

Maxcy, K.R.; Willett, R.D.; Mitzi, D.B.; Afzali, A.

doi:10.1107/S1600536803007414

Tetrakis[(9-oxo-10-thiaxanthen-2-yloxyethyl)ammonium] decaiodotriplumbate(II)

K. R. Maxcy, R. D. Willett, D. B. Mitzi and A. Afzali

The structure of the title compound, (AETO)₄[Pb₃I₁₀] or (C₁₅H₁₄NO₂S)₄[Pb₃I₁₀], contains chains of octahedrally coordinated PbI₆ species along with two crystallographically independent AETO cations that hydrogen bond to these chains. Individual (Pb₃I₁₀)_n^4n- chains are linked into layers via hydrogen bonds. The cations sheath each layer of chains, forming cation-chain-cation triple layers. Cations on adjacent triple layers interdigitate, forming stacks running parallel to [110]. There is a range of hydrogen bonding interactions between each cation and the (Pb₃I₁₀)_n^4n- chains.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007414/ac6035sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007414/ac6035Isup2.hkl Contains datablock I

CCDC reference: 214790

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.012 Å
R factor = 0.035
wR factor = 0.092
Data-to-parameter ratio = 16.4

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No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



THETM_01  Alert C The value of sine(theta_max)/wavelength is less than 0.590
          Calculated sin(theta_max)/wavelength =    0.5882

PLAT_420  Alert C D-H Without Acceptor       N(2)   -   H(2D)             ?


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

Comment top

The title structure, (I), consists of (Pb₃I₁₀)_n^4n- chains running parallel to (010) and stacks of the AETO cations running parallel to (110). The chains, illustrated in Fig. 1, can be viewed as centrosymmetric trimers of face-sharing octahedra joined together into chains via edge-sharing between terminal octahedra on adjacent trimers. The extended inorganic anion may thus be viewed as a mixed face-shared/edge-shared chain, with a repeat pattern (f₂e)_n, where f denotes the face-sharing of adjacent octahedra and e denotes edge-sharing. Similar chains are observed in several other lead(II) and tin(II) halide salts, both as (f₂e)_n (Krautscheid & Vielsack, 1997; Corradi et al., 1999; Corradi et al., 2001; Gröger et al., 2002; Lode & Krautscheid, 2001) and (fe)_n chains (Krautscheid et al., 2001). A longer face-sharing sequence is found in (C₆H₉N₂)Ni₅Cl₁₄(CH₃CN)₂ (Bond & Willett, 1993), where an (f₄e)_n repeat pattern is observed. These structures represent a variation of the parent hexagonal CsNiCl₃ structure type that contains chains of face-shared octahedra (Gmelin, 1966). The replacement of selected face-sharing linkages by edge-sharing units is one structural motif whereby a halide ion (or other ligand) can be incorporated into that parent structure.

The coordination of the central lead(II) ion (Pb1) within the trimeric unit is relatively symmetrical [Pb—I distances of 3.1683 (9), 3.2479 (14) and 3.2649 (11) Å, and bond angles ranging from 83.57 (2) to 94.05 (3)°]. The terminal lead(II) (Pb2) ions are much more distorted, with Pb—I distances ranging from 3.0700 (14) to 3.4471 (7) Å and angles from 77.22 (2) to 101.32 (2)°. This distortion is likely due to the asymmetric nature of the environment of the iodide ions coordinated to Pb2. Average values for octahedrally coordinated Pb^III₆ species from the Cambridge Structural Database (Version 5.24; Allen, 2002), are Pb—I ca 3.10–3.34 Å and angles in the range 77.69–97.25°.

The compound contains two crystallographicly independent cations (labeled cat1 for the cation containing N1 and cat2 for the cation containing N2). Fig. 2 illustrates cat2. In both cations, the ethoxyammonium arm has a gauche configuration. The cations forms stacks parallel to the (110) direction, as shown in Fig. 3. The sequence in these stacks is (cat1, cat1, cat2, cat2, ···). The (cat1, cat1) and (cat2, cat2) pairs are related by centers of inversion, so within each pair the keto C═O groups lie on opposite sides of the stacks. In contrast, for the (cat1, cat2) pairs, the keto C═O groups lie on the same sides of the stacks.

Hydrogen bonding from the ammonium ion on cat1 forms N—H···I bonds bridging pairs of chains. This ties the chains of (Pb₃I₁₀)_n^4n- ions together into sheets parallel to (110), as seen in Fig. 3. In contrast, the N—H···I hydrogen bonds from cat2 involve iodide ions on a single chain. This hydrogen-bonding geometry is presented in Table 1. N1—H1C forms a bifurcated hydrogen bond between I2ⁱⁱ and I5ⁱⁱ. There is also an intramolecular hydrogen bond between N1 and O1. The other cation forms hydrogen bonds to the same chain with a bifurcated hydrogen bond N2—H2D to both I2 and I4. In addition, there is both inter- and intramolecular hydrogen bonding between N2 and O2/O3.

Experimental top

Under ambient conditions, stoichiometric amounts of (AETO)I (6.72 × 10⁻⁵ mol) and PbI₂ (5.04 × 10⁻⁵ mol) were sealed in a large test tube. Under flowing N₂ gas, 5 ml of concentrated hydroiodic acid and 5 ml of 2-propanol were added. The reaction was sealed and heated to 343 K, resulting in a yellow solution. The solution was cooled to 263 K over 24 h. Yellow needle-like crystals were collected and one was selected for structural investigation.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: XS in SHELXTL (Sheldrick, 1998); program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.

Figures top

	Fig. 1. (a) Illustration of the (Pb₃I₁₀)_n^4n- chain. Displacement ellipsoids shown at 50% probability. (b) Polyhedral representation of the chain.
	Fig. 2. Illustration of cation 2.
	Fig. 3. Packing diagram, illustrating the stacking of the cations parallel to (110). H atoms have been omitted for clarity.

Tetrakis[(9-oxo-10-thiaxanthen-2-yloxyethyl)ammonium] decaiodidotriplumbate(II) top

Crystal data top

(C₁₅H₁₄NO₂S)₄[Pb₃I₁₀]	Z = 1
M_r = 2979.90	F(000) = 1348
Triclinic, P1	D_x = 2.543 Mg m⁻³
a = 9.793 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.704 (2) Å	Cell parameters from 8192 reflections
c = 18.061 (4) Å	θ = 1.9–24.7°
α = 71.72 (3)°	µ = 10.60 mm⁻¹
β = 89.45 (3)°	T = 293 K
γ = 82.09 (3)°	Needle, yellow
V = 1945.7 (8) Å³	0.16 × 0.10 × 0.08 mm

Data collection top

SMART 1000 diffractometer	6618 independent reflections
Radiation source: normal-focus sealed tube	5205 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.084
Detector resolution: 8.3 pixels mm^-1	θ_max = 24.7°, θ_min = 1.9°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	k = −13→13
T_min = 0.249, T_max = 0.428	l = −21→21
18436 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0469P)²] where P = (F_o² + 2F_c²)/3
6618 reflections	(Δ/σ)_max = 0.001
403 parameters	Δρ_max = 1.93 e Å⁻³
228 restraints	Δρ_min = −1.73 e Å⁻³

Crystal data top

(C₁₅H₁₄NO₂S)₄[Pb₃I₁₀]	γ = 82.09 (3)°
M_r = 2979.90	V = 1945.7 (8) Å³
Triclinic, P1	Z = 1
a = 9.793 (2) Å	Mo Kα radiation
b = 11.704 (2) Å	µ = 10.60 mm⁻¹
c = 18.061 (4) Å	T = 293 K
α = 71.72 (3)°	0.16 × 0.10 × 0.08 mm
β = 89.45 (3)°

Data collection top

SMART 1000 diffractometer	6618 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	5205 reflections with I > 2σ(I)
T_min = 0.249, T_max = 0.428	R_int = 0.084
18436 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	228 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 0.97	Δρ_max = 1.93 e Å⁻³
6618 reflections	Δρ_min = −1.73 e Å⁻³
403 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pb1	0.0000	0.5000	0.0000	0.04785 (12)
Pb2	−0.11247 (3)	0.87148 (2)	−0.036604 (17)	0.04846 (10)
I1	0.16212 (5)	0.66942 (5)	0.06260 (3)	0.05194 (14)
I2	−0.26605 (5)	0.62643 (5)	0.07053 (3)	0.05325 (15)
I3	−0.12019 (6)	0.97463 (4)	0.11289 (3)	0.05237 (14)
I4	0.07412 (6)	0.27621 (5)	0.16057 (3)	0.05907 (16)
I5	−0.36409 (7)	1.04956 (6)	−0.12162 (4)	0.0804 (2)
S1	0.7585 (3)	0.01220 (19)	0.54453 (12)	0.0612 (6)
N1	0.5658 (7)	0.1995 (6)	0.0524 (4)	0.0614 (18)
H1A	0.6243	0.1384	0.0832	0.092*
H1B	0.5966	0.2207	0.0042	0.092*
H1C	0.4832	0.1760	0.0521	0.092*
O1	0.5916 (6)	0.1811 (5)	0.2119 (3)	0.0572 (14)
O2	0.9460 (7)	0.2980 (6)	0.3677 (3)	0.0719 (17)
C1	0.5546 (9)	0.3058 (7)	0.0825 (5)	0.057 (2)
H1E	0.4596	0.3267	0.0948	0.069*
H1D	0.5814	0.3755	0.0425	0.069*
C2	0.6461 (9)	0.2761 (7)	0.1544 (4)	0.054 (2)
H2A	0.7405	0.2494	0.1441	0.065*
H2B	0.6445	0.3467	0.1718	0.065*
C3	0.6408 (8)	0.1514 (7)	0.2880 (4)	0.0470 (18)
C4	0.5739 (9)	0.0633 (7)	0.3404 (5)	0.0541 (19)
H4A	0.5025	0.0323	0.3230	0.065*
C5	0.6140 (9)	0.0233 (7)	0.4172 (5)	0.055 (2)
H5A	0.5708	−0.0367	0.4518	0.067*
C6	0.7186 (8)	0.0705 (6)	0.4451 (4)	0.0487 (18)
C7	0.7847 (8)	0.1609 (6)	0.3925 (4)	0.0463 (18)
C8	0.7418 (8)	0.1984 (6)	0.3133 (4)	0.0457 (17)
H8A	0.7846	0.2574	0.2775	0.055*
C9	0.8940 (9)	0.2178 (7)	0.4157 (5)	0.0513 (19)
C10	0.9459 (8)	0.1763 (7)	0.4982 (5)	0.053 (2)
C11	0.8933 (8)	0.0875 (8)	0.5577 (5)	0.056 (2)
C12	1.0541 (9)	0.2314 (9)	0.5170 (5)	0.063 (2)
H12A	1.0883	0.2929	0.4784	0.076*
C13	1.1098 (10)	0.1953 (10)	0.5918 (6)	0.078 (3)
H13A	1.1823	0.2312	0.6035	0.094*
C14	1.0571 (12)	0.1055 (11)	0.6494 (6)	0.082 (3)
H14A	1.0951	0.0811	0.6999	0.099*
C15	0.9502 (11)	0.0518 (9)	0.6337 (5)	0.070 (3)
H15A	0.9155	−0.0081	0.6733	0.083*
S2	0.5594 (2)	0.71198 (18)	0.52361 (13)	0.0567 (5)
N2	−0.0421 (10)	0.5220 (7)	0.2557 (5)	0.093 (3)
H2C	0.0431	0.4884	0.2740	0.140*
H2D	−0.0565	0.5107	0.2101	0.140*
H2E	−0.1028	0.4876	0.2895	0.140*
O3	0.1156 (7)	0.6054 (6)	0.3471 (4)	0.0743 (18)
O4	0.2705 (7)	0.4457 (6)	0.6220 (4)	0.0779 (19)
C16	−0.0579 (11)	0.6477 (8)	0.2456 (5)	0.070 (3)
H16A	−0.1313	0.6697	0.2772	0.084*
H16B	−0.0793	0.6947	0.1914	0.084*
C17	0.0875 (12)	0.6711 (9)	0.2733 (6)	0.083 (3)
H17A	0.1594	0.6492	0.2409	0.100*
H17B	0.0845	0.7566	0.2675	0.100*
C18	0.2217 (8)	0.6325 (7)	0.3861 (5)	0.0507 (19)
C19	0.2368 (8)	0.5704 (7)	0.4650 (5)	0.053 (2)
H19A	0.1778	0.5145	0.4882	0.064*
C20	0.3396 (7)	0.5909 (6)	0.5103 (4)	0.0455 (17)
C21	0.4282 (8)	0.6756 (6)	0.4750 (4)	0.0474 (18)
C22	0.4134 (9)	0.7360 (7)	0.3946 (5)	0.059 (2)
H22A	0.4735	0.7905	0.3708	0.070*
C23	0.3109 (9)	0.7159 (7)	0.3501 (5)	0.057 (2)
H23A	0.3011	0.7573	0.2969	0.069*
C24	0.3481 (9)	0.5218 (7)	0.5936 (5)	0.0517 (19)
C25	0.4530 (8)	0.5411 (7)	0.6454 (5)	0.0517 (19)
C26	0.5477 (8)	0.6258 (7)	0.6195 (5)	0.0495 (19)
C27	0.6390 (9)	0.6425 (8)	0.6738 (5)	0.059 (2)
H27A	0.6995	0.6995	0.6576	0.071*
C28	0.6381 (10)	0.5737 (9)	0.7513 (6)	0.070 (2)
H28A	0.6980	0.5850	0.7872	0.084*
C29	0.5511 (9)	0.4898 (9)	0.7759 (5)	0.070 (3)
H29A	0.5533	0.4431	0.8282	0.084*
C30	0.4597 (8)	0.4728 (8)	0.7245 (5)	0.061 (2)
H30A	0.4010	0.4147	0.7426	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.0542 (3)	0.0432 (2)	0.0467 (2)	−0.01079 (18)	−0.00005 (19)	−0.01338 (18)
Pb2	0.05522 (19)	0.04371 (17)	0.04744 (18)	−0.01225 (13)	−0.00110 (13)	−0.01349 (13)
I1	0.0546 (3)	0.0553 (3)	0.0465 (3)	−0.0184 (2)	−0.0043 (2)	−0.0122 (2)
I2	0.0460 (3)	0.0642 (3)	0.0470 (3)	−0.0115 (2)	−0.0003 (2)	−0.0124 (2)
I3	0.0679 (3)	0.0430 (3)	0.0458 (3)	−0.0114 (2)	0.0056 (2)	−0.0120 (2)
I4	0.0820 (4)	0.0560 (3)	0.0435 (3)	−0.0194 (3)	−0.0009 (3)	−0.0176 (2)
I5	0.0706 (4)	0.0631 (4)	0.0936 (5)	−0.0114 (3)	−0.0195 (4)	−0.0033 (3)
S1	0.0790 (16)	0.0519 (12)	0.0448 (12)	−0.0005 (11)	0.0096 (10)	−0.0080 (9)
N1	0.059 (4)	0.059 (4)	0.057 (4)	−0.015 (3)	−0.010 (3)	−0.003 (3)
O1	0.060 (3)	0.061 (3)	0.049 (3)	−0.024 (3)	−0.004 (3)	−0.010 (3)
O2	0.086 (5)	0.071 (4)	0.061 (4)	−0.036 (3)	−0.001 (3)	−0.013 (3)
C1	0.058 (5)	0.053 (5)	0.055 (5)	0.002 (4)	−0.007 (4)	−0.013 (4)
C2	0.060 (5)	0.055 (5)	0.044 (4)	−0.017 (4)	0.002 (4)	−0.006 (4)
C3	0.049 (4)	0.049 (4)	0.043 (4)	−0.005 (3)	0.001 (3)	−0.015 (3)
C4	0.061 (5)	0.049 (4)	0.057 (5)	−0.023 (4)	0.012 (4)	−0.017 (4)
C5	0.060 (5)	0.043 (4)	0.062 (5)	−0.014 (4)	0.023 (4)	−0.013 (4)
C6	0.057 (5)	0.038 (4)	0.048 (4)	0.000 (3)	0.011 (4)	−0.011 (3)
C7	0.052 (4)	0.037 (4)	0.047 (4)	0.002 (3)	0.005 (3)	−0.011 (3)
C8	0.055 (5)	0.039 (4)	0.043 (4)	−0.014 (3)	0.009 (3)	−0.011 (3)
C9	0.058 (5)	0.044 (4)	0.055 (5)	0.000 (4)	0.002 (4)	−0.023 (4)
C10	0.054 (5)	0.063 (5)	0.045 (4)	0.006 (4)	0.000 (4)	−0.026 (4)
C11	0.053 (5)	0.064 (5)	0.050 (5)	0.021 (4)	−0.003 (4)	−0.028 (4)
C12	0.057 (5)	0.078 (6)	0.065 (5)	−0.002 (4)	0.003 (4)	−0.042 (5)
C13	0.066 (6)	0.110 (8)	0.069 (6)	0.015 (6)	−0.005 (5)	−0.054 (6)
C14	0.082 (7)	0.109 (8)	0.061 (6)	0.032 (6)	−0.016 (5)	−0.053 (6)
C15	0.083 (7)	0.070 (6)	0.048 (5)	0.014 (5)	0.002 (5)	−0.018 (4)
S2	0.0539 (12)	0.0461 (11)	0.0674 (13)	−0.0127 (9)	−0.0007 (10)	−0.0117 (10)
N2	0.118 (8)	0.061 (5)	0.085 (6)	−0.010 (5)	0.001 (5)	−0.001 (4)
O3	0.080 (4)	0.076 (4)	0.062 (4)	0.009 (3)	−0.015 (3)	−0.023 (3)
O4	0.076 (4)	0.092 (5)	0.063 (4)	−0.040 (4)	0.003 (3)	−0.008 (3)
C16	0.110 (8)	0.054 (5)	0.045 (5)	−0.013 (5)	0.011 (5)	−0.014 (4)
C17	0.117 (9)	0.065 (6)	0.079 (7)	−0.025 (6)	0.025 (6)	−0.035 (5)
C18	0.045 (4)	0.052 (4)	0.061 (5)	−0.001 (3)	−0.001 (4)	−0.029 (4)
C19	0.048 (5)	0.046 (4)	0.063 (5)	−0.005 (3)	0.003 (4)	−0.015 (4)
C20	0.039 (4)	0.043 (4)	0.053 (4)	0.001 (3)	0.005 (3)	−0.015 (3)
C21	0.047 (4)	0.041 (4)	0.054 (5)	0.001 (3)	0.007 (4)	−0.016 (4)
C22	0.059 (5)	0.051 (5)	0.064 (5)	−0.004 (4)	0.007 (4)	−0.016 (4)
C23	0.063 (5)	0.051 (5)	0.058 (5)	0.000 (4)	0.003 (4)	−0.021 (4)
C24	0.057 (5)	0.047 (4)	0.053 (5)	−0.010 (4)	0.008 (4)	−0.018 (4)
C25	0.039 (4)	0.050 (4)	0.066 (5)	0.002 (3)	0.005 (4)	−0.021 (4)
C26	0.041 (4)	0.043 (4)	0.063 (5)	0.004 (3)	0.003 (4)	−0.018 (4)
C27	0.050 (5)	0.059 (5)	0.072 (6)	−0.004 (4)	−0.005 (4)	−0.026 (4)
C28	0.058 (6)	0.086 (6)	0.070 (6)	0.006 (5)	−0.009 (5)	−0.037 (5)
C29	0.053 (5)	0.090 (7)	0.058 (5)	−0.001 (5)	−0.005 (4)	−0.014 (5)
C30	0.046 (5)	0.080 (6)	0.052 (5)	−0.007 (4)	0.009 (4)	−0.017 (4)

Geometric parameters (Å, º) top

Pb1—I1ⁱ	3.1683 (9)	C12—H12A	0.9300
Pb1—I1	3.1683 (9)	C13—C14	1.380 (15)
Pb1—I4	3.2479 (14)	C13—H13A	0.9300
Pb1—I4ⁱ	3.2479 (14)	C14—C15	1.368 (15)
Pb1—I2ⁱ	3.2649 (11)	C14—H14A	0.9300
Pb1—I2	3.2649 (11)	C15—H15A	0.9300
Pb2—I5	3.0700 (14)	S2—C26	1.721 (8)
Pb2—I3ⁱⁱ	3.1379 (12)	S2—C21	1.735 (8)
Pb2—I4ⁱ	3.2211 (10)	N2—C16	1.411 (11)
Pb2—I3	3.2818 (9)	N2—H2C	0.8900
Pb2—I1	3.4231 (15)	N2—H2D	0.8900
Pb2—I2	3.4471 (7)	N2—H2E	0.8900
S1—C6	1.736 (8)	O3—C17	1.323 (11)
S1—C11	1.741 (10)	O3—C18	1.386 (10)
N1—C1	1.497 (10)	O4—C24	1.235 (10)
N1—H1A	0.8900	C16—C17	1.600 (14)
N1—H1B	0.8900	C16—H16A	0.9700
N1—H1C	0.8900	C16—H16B	0.9700
O1—C3	1.382 (8)	C17—H17A	0.9700
O1—C2	1.423 (9)	C17—H17B	0.9700
O2—C9	1.226 (9)	C18—C19	1.380 (11)
C1—C2	1.506 (10)	C18—C23	1.402 (12)
C1—H1E	0.9700	C19—C20	1.394 (11)
C1—H1D	0.9700	C19—H19A	0.9300
C2—H2A	0.9700	C20—C21	1.405 (10)
C2—H2B	0.9700	C20—C24	1.466 (11)
C3—C8	1.344 (10)	C21—C22	1.400 (11)
C3—C4	1.396 (10)	C22—C23	1.381 (12)
C4—C5	1.359 (11)	C22—H22A	0.9300
C4—H4A	0.9300	C23—H23A	0.9300
C5—C6	1.396 (11)	C24—C25	1.482 (11)
C5—H5A	0.9300	C25—C30	1.398 (11)
C6—C7	1.409 (10)	C25—C26	1.420 (11)
C7—C8	1.408 (10)	C26—C27	1.409 (11)
C7—C9	1.464 (11)	C27—C28	1.379 (12)
C8—H8A	0.9300	C27—H27A	0.9300
C9—C10	1.486 (10)	C28—C29	1.355 (13)
C10—C11	1.391 (12)	C28—H28A	0.9300
C10—C12	1.409 (12)	C29—C30	1.372 (12)
C11—C15	1.400 (11)	C29—H29A	0.9300
C12—C13	1.376 (12)	C30—H30A	0.9300

I1ⁱ—Pb1—I1	180.000 (16)	C12—C10—C9	117.7 (8)
I1ⁱ—Pb1—I4	88.84 (3)	C10—C11—C15	120.2 (9)
I1—Pb1—I4	91.16 (3)	C10—C11—S1	124.2 (6)
I1ⁱ—Pb1—I4ⁱ	91.16 (3)	C15—C11—S1	115.5 (8)
I1—Pb1—I4ⁱ	88.84 (3)	C13—C12—C10	120.9 (10)
I4—Pb1—I4ⁱ	180.000 (15)	C13—C12—H12A	119.6
I1ⁱ—Pb1—I2ⁱ	83.57 (2)	C10—C12—H12A	119.6
I1—Pb1—I2ⁱ	96.43 (2)	C12—C13—C14	119.5 (11)
I4—Pb1—I2ⁱ	85.95 (3)	C12—C13—H13A	120.3
I4ⁱ—Pb1—I2ⁱ	94.05 (3)	C14—C13—H13A	120.3
I1ⁱ—Pb1—I2	96.43 (2)	C15—C14—C13	121.3 (9)
I1—Pb1—I2	83.57 (2)	C15—C14—H14A	119.4
I4—Pb1—I2	94.05 (3)	C13—C14—H14A	119.4
I4ⁱ—Pb1—I2	85.95 (3)	C14—C15—C11	119.7 (10)
I2ⁱ—Pb1—I2	180.0	C14—C15—H15A	120.2
I5—Pb2—I3ⁱⁱ	98.79 (3)	C11—C15—H15A	120.2
I5—Pb2—I4ⁱ	95.69 (3)	C26—S2—C21	104.3 (4)
I3ⁱⁱ—Pb2—I4ⁱ	91.09 (3)	C16—N2—H2C	109.5
I5—Pb2—I3	94.29 (3)	C16—N2—H2D	109.5
I3ⁱⁱ—Pb2—I3	91.64 (3)	H2C—N2—H2D	109.5
I4ⁱ—Pb2—I3	169.130 (17)	C16—N2—H2E	109.5
I3ⁱⁱ—Pb2—I1	82.71 (3)	H2C—N2—H2E	109.5
I4ⁱ—Pb2—I1	84.99 (3)	H2D—N2—H2E	109.5
I3—Pb2—I1	84.92 (3)	C17—O3—C18	118.1 (8)
I5—Pb2—I2	101.320 (19)	N2—C16—C17	105.0 (8)
I3ⁱⁱ—Pb2—I2	159.574 (17)	N2—C16—H16A	110.7
I4ⁱ—Pb2—I2	83.429 (16)	C17—C16—H16A	110.7
I3—Pb2—I2	90.400 (16)	N2—C16—H16B	110.7
I1—Pb2—I2	77.219 (15)	C17—C16—H16B	110.7
Pb1—I1—Pb2	78.54 (2)	H16A—C16—H16B	108.8
Pb1—I2—Pb2	76.91 (2)	O3—C17—C16	109.9 (8)
Pb2ⁱⁱ—I3—Pb2	88.36 (3)	O3—C17—H17A	109.7
Pb2ⁱ—I4—Pb1	80.43 (2)	C16—C17—H17A	109.7
C6—S1—C11	104.0 (4)	O3—C17—H17B	109.7
C1—N1—H1A	109.5	C16—C17—H17B	109.7
C1—N1—H1B	109.5	H17A—C17—H17B	108.2
H1A—N1—H1B	109.5	C19—C18—O3	115.6 (8)
C1—N1—H1C	109.5	C19—C18—C23	120.4 (8)
H1A—N1—H1C	109.5	O3—C18—C23	124.0 (8)
H1B—N1—H1C	109.5	C18—C19—C20	120.6 (8)
C3—O1—C2	117.6 (6)	C18—C19—H19A	119.7
N1—C1—C2	110.4 (6)	C20—C19—H19A	119.7
N1—C1—H1E	109.6	C19—C20—C21	119.5 (7)
C2—C1—H1E	109.6	C19—C20—C24	117.2 (7)
N1—C1—H1D	109.6	C21—C20—C24	123.4 (7)
C2—C1—H1D	109.6	C22—C21—C20	119.3 (7)
H1E—C1—H1D	108.1	C22—C21—S2	115.9 (6)
O1—C2—C1	105.7 (7)	C20—C21—S2	124.8 (6)
O1—C2—H2A	110.6	C23—C22—C21	121.0 (8)
C1—C2—H2A	110.6	C23—C22—H22A	119.5
O1—C2—H2B	110.6	C21—C22—H22A	119.5
C1—C2—H2B	110.6	C22—C23—C18	119.3 (8)
H2A—C2—H2B	108.7	C22—C23—H23A	120.4
C8—C3—O1	126.6 (7)	C18—C23—H23A	120.4
C8—C3—C4	120.4 (7)	O4—C24—C20	121.3 (8)
O1—C3—C4	113.1 (7)	O4—C24—C25	118.7 (7)
C5—C4—C3	119.4 (8)	C20—C24—C25	120.0 (7)
C5—C4—H4A	120.3	C30—C25—C26	117.6 (8)
C3—C4—H4A	120.3	C30—C25—C24	118.7 (7)
C4—C5—C6	121.4 (7)	C26—C25—C24	123.8 (7)
C4—C5—H5A	119.3	C27—C26—C25	119.7 (8)
C6—C5—H5A	119.3	C27—C26—S2	116.5 (6)
C5—C6—C7	119.3 (7)	C25—C26—S2	123.8 (6)
C5—C6—S1	116.6 (6)	C28—C27—C26	119.6 (9)
C7—C6—S1	124.1 (6)	C28—C27—H27A	120.2
C8—C7—C6	117.6 (7)	C26—C27—H27A	120.2
C8—C7—C9	118.6 (7)	C29—C28—C27	120.9 (9)
C6—C7—C9	123.8 (7)	C29—C28—H28A	119.5
C3—C8—C7	121.9 (7)	C27—C28—H28A	119.5
C3—C8—H8A	119.0	C28—C29—C30	120.8 (9)
C7—C8—H8A	119.0	C28—C29—H29A	119.6
O2—C9—C7	121.1 (7)	C30—C29—H29A	119.6
O2—C9—C10	119.0 (8)	C29—C30—C25	121.4 (9)
C7—C9—C10	119.9 (8)	C29—C30—H30A	119.3
C11—C10—C12	118.4 (8)	C25—C30—H30A	119.3
C11—C10—C9	123.9 (8)

I4—Pb1—I1—Pb2	−142.52 (2)	C11—C10—C12—C13	2.3 (12)
I4ⁱ—Pb1—I1—Pb2	37.48 (3)	C9—C10—C12—C13	−178.3 (8)
I2ⁱ—Pb1—I1—Pb2	131.43 (2)	C10—C12—C13—C14	−1.2 (13)
I2—Pb1—I1—Pb2	−48.57 (2)	C12—C13—C14—C15	−0.2 (14)
I3ⁱⁱ—Pb2—I1—Pb1	−129.76 (2)	C13—C14—C15—C11	0.5 (14)
I4ⁱ—Pb2—I1—Pb1	−38.01 (2)	C10—C11—C15—C14	0.6 (12)
I3—Pb2—I1—Pb1	137.93 (2)	S1—C11—C15—C14	179.6 (7)
I5—Pb2—I3—Pb2ⁱⁱ	−98.94 (3)	C18—O3—C17—C16	−166.5 (7)
I3ⁱⁱ—Pb2—I3—Pb2ⁱⁱ	0.0	N2—C16—C17—O3	−59.8 (10)
I4ⁱ—Pb2—I3—Pb2ⁱⁱ	104.51 (9)	C17—O3—C18—C19	173.2 (8)
I1—Pb2—I3—Pb2ⁱⁱ	82.53 (3)	C17—O3—C18—C23	−7.2 (11)
I1ⁱ—Pb1—I4—Pb2ⁱ	39.994 (19)	O3—C18—C19—C20	−179.6 (7)
I1—Pb1—I4—Pb2ⁱ	−140.006 (19)	C23—C18—C19—C20	0.8 (11)
I2ⁱ—Pb1—I4—Pb2ⁱ	−43.64 (2)	C18—C19—C20—C21	0.1 (11)
I2—Pb1—I4—Pb2ⁱ	136.36 (2)	C18—C19—C20—C24	179.7 (7)
C3—O1—C2—C1	−168.5 (6)	C19—C20—C21—C22	−1.4 (10)
N1—C1—C2—O1	−64.6 (8)	C24—C20—C21—C22	179.1 (7)
C2—O1—C3—C8	−4.1 (11)	C19—C20—C21—S2	179.3 (6)
C2—O1—C3—C4	175.8 (7)	C24—C20—C21—S2	−0.3 (10)
C8—C3—C4—C5	−1.6 (12)	C26—S2—C21—C22	179.0 (6)
O1—C3—C4—C5	178.5 (7)	C26—S2—C21—C20	−1.6 (7)
C3—C4—C5—C6	1.5 (12)	C20—C21—C22—C23	1.8 (11)
C4—C5—C6—C7	−0.4 (12)	S2—C21—C22—C23	−178.8 (6)
C4—C5—C6—S1	179.4 (6)	C21—C22—C23—C18	−0.9 (12)
C11—S1—C6—C5	178.6 (6)	C19—C18—C23—C22	−0.4 (11)
C11—S1—C6—C7	−1.6 (7)	O3—C18—C23—C22	−180.0 (7)
C5—C6—C7—C8	−0.6 (10)	C19—C20—C24—O4	2.4 (11)
S1—C6—C7—C8	179.5 (6)	C21—C20—C24—O4	−178.0 (7)
C5—C6—C7—C9	179.0 (7)	C19—C20—C24—C25	−178.7 (7)
S1—C6—C7—C9	−0.9 (10)	C21—C20—C24—C25	0.9 (11)
O1—C3—C8—C7	−179.6 (7)	O4—C24—C25—C30	−0.3 (11)
C4—C3—C8—C7	0.5 (12)	C20—C24—C25—C30	−179.3 (7)
C6—C7—C8—C3	0.6 (11)	O4—C24—C25—C26	180.0 (8)
C9—C7—C8—C3	−179.1 (7)	C20—C24—C25—C26	1.0 (11)
C8—C7—C9—O2	1.2 (11)	C30—C25—C26—C27	−3.1 (11)
C6—C7—C9—O2	−178.5 (7)	C24—C25—C26—C27	176.6 (7)
C8—C7—C9—C10	−177.2 (6)	C30—C25—C26—S2	176.8 (6)
C6—C7—C9—C10	3.1 (11)	C24—C25—C26—S2	−3.5 (10)
O2—C9—C10—C11	179.0 (7)	C21—S2—C26—C27	−176.7 (6)
C7—C9—C10—C11	−2.6 (11)	C21—S2—C26—C25	3.4 (7)
O2—C9—C10—C12	−0.4 (11)	C25—C26—C27—C28	1.9 (11)
C7—C9—C10—C12	178.0 (7)	S2—C26—C27—C28	−178.0 (6)
C12—C10—C11—C15	−2.0 (11)	C26—C27—C28—C29	0.3 (13)
C9—C10—C11—C15	178.7 (7)	C27—C28—C29—C30	−1.3 (14)
C12—C10—C11—S1	179.1 (6)	C28—C29—C30—C25	−0.1 (14)
C9—C10—C11—S1	−0.3 (11)	C26—C25—C30—C29	2.2 (12)
C6—S1—C11—C10	2.1 (7)	C24—C25—C30—C29	−177.5 (8)
C6—S1—C11—C15	−176.9 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···I1ⁱⁱⁱ	0.89	2.92	3.576 (7)	132
N1—H1C···I2ⁱ	0.89	3.21	3.653 (6)	113
N1—H1A···I3^iv	0.89	2.88	3.689 (7)	152
N1—H1C···I5ⁱ	0.89	2.94	3.635 (7)	136
N1—H1A···O1	0.89	2.53	2.831 (8)	100
N2—H2D···I2	0.89	3.10	3.786 (9)	136
N2—H2D···I4	0.89	3.24	3.832 (9)	126
N2—H2E···O2^v	0.89	2.21	2.780 (10)	121
N2—H2C···O3	0.89	2.36	2.745 (11)	107

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

Experimental details

Crystal data
Chemical formula	(C₁₅H₁₄NO₂S)₄[Pb₃I₁₀]
M_r	2979.90
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.793 (2), 11.704 (2), 18.061 (4)
α, β, γ (°)	71.72 (3), 89.45 (3), 82.09 (3)
V (Å³)	1945.7 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	10.60
Crystal size (mm)	0.16 × 0.10 × 0.08

Data collection
Diffractometer	SMART 1000 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1999)
T_min, T_max	0.249, 0.428
No. of measured, independent and observed [I > 2σ(I)] reflections	18436, 6618, 5205
R_int	0.084
(sin θ/λ)_max (Å⁻¹)	0.588

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.092, 0.97
No. of reflections	6618
No. of parameters	403
No. of restraints	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.93, −1.73

Computer programs: SMART (Bruker, 1998), SMART, SAINT-Plus (Bruker, 1999), XS in SHELXTL (Sheldrick, 1998), XL in SHELXTL, XP in SHELXTL, XCIF in SHELXTL.