The one-dimensional organic–inorganic hybrid: catena-poly[bis­[1-(3-ammonio­prop­yl)-1H-imidazolium] [[iodidoplumbate(II)]-tri-μ-iodido-plumbate(II)-tri-μ-iodido-[iodidoplumbate(II)]-di-μ-iodido]]

A Trigui; H Boughzala; A Driss; Y Abid

doi:10.1107/S160053681100941X

. 2011 Mar 15;67(Pt 4):m458–m459. doi: 10.1107/S160053681100941X

The one-dimensional organic–inorganic hybrid: catena-poly[bis[1-(3-ammoniopropyl)-1H-imidazolium] [[iodidoplumbate(II)]-tri-μ-iodido-plumbate(II)-tri-μ-iodido-[iodidoplumbate(II)]-di-μ-iodido]]

A Trigui ^a, H Boughzala ^b,^*, A Driss ^b, Y Abid ^a

PMCID: PMC3099864 PMID: 21753976

Abstract

The organic–inorganic hybrid, {(C₆H₁₃N₃)₂[Pb₃I₁₀]}_n, was obtained by the reaction of 1-(3-ammoniopropyl)imidazolium triiodide and PbI₂ at room temperature. The structure contains one-dimensional {[Pb₃I₁₀]⁴⁻}_n polymeric anions spreading parallel to [001], resulting from face–face–edge association of PbI₆ distorted octahedra. One of the Pb^II cations is imposed at an inversion centre, whereas the second occupies a general position. N—H⋯I hydrogen bonds connect the organic cations and inorganic anions.

Related literature

For organic–inorganic hybrid materials, see: Billing & Lemmerer (2004 ▶); Dammak et al. (2009 ▶); Elleuch et al. (2007 ▶, 2010 ▶); Gebauer & Schmid (1999 ▶); Ishihara et al. (1990 ▶); Krautscheid et al. (2001 ▶). For the structures of lead iodide-based complexes, see: Maxcy et al. (2003 ▶); Mitzi et al. (2001 ▶); Mousdis et al. (1998 ▶); Papavassiliou et al. (1999 ▶); Samet Kallel et al. (2008 ▶).

Experimental

Crystal data

(C₆H₁₃N₃)₂[Pb₃I₁₀]
M _r = 2144.99
Triclinic,
a = 8.652 (3) Å
b = 11.728 (5) Å
c = 11.972 (6) Å
α = 117.21 (3)°
β = 98.05 (2)°
γ = 107.17 (3)°
V = 976.7 (9) Å³
Z = 1
Mo Kα radiation
μ = 20.81 mm⁻¹
T = 293 K
0.40 × 0.20 × 0.02 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.139, T _max = 0.624
4950 measured reflections
3796 independent reflections
2749 reflections with I > 2σ(I)
R _int = 0.024
2 standard reflections every 120 min intensity decay: 6%

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.110
S = 1.02
3796 reflections
143 parameters
H-atom parameters constrained
Δρ_max = 2.17 e Å⁻³
Δρ_min = −2.09 e Å⁻³

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100941X/yk2002sup1.cif

e-67-0m458-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100941X/yk2002Isup2.hkl

e-67-0m458-Isup2.hkl^{(186.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Pb1—I5	3.155 (2)
Pb1—I1	3.1757 (13)
Pb1—I3	3.2264 (14)
Pb1—I1ⁱ	3.2652 (13)
Pb1—I2	3.3039 (14)
Pb1—I4	3.309 (2)
Pb2—I4	3.2105 (15)
Pb2—I3	3.2388 (14)
Pb2—I2	3.263 (2)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9A⋯I5	0.89	2.84	3.67 (2)	156
N9—H9B⋯I2ⁱⁱⁱ	0.89	2.90	3.68 (2)	147
N9—H9C⋯I5^iv	0.89	2.89	3.64 (2)	143

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Symmetry codes: (iii) Inline graphic ; (iv) .

supplementary crystallographic information

Comment

Recently, self-assembling organic–inorganic hybrid compounds have been the focus of a great number of investigations owing to their unique structural, magnetic, optical nonlinear and optoelectronic functionality (Papavassiliou et al., 1999; Ishihara et al., 1990; Mitzi et al., 2001). In particular, the lead iodide-based hybrid materials have been extensively studied (Gebauer & Schmid, 1999; Dammak et al., 2009; Elleuch et al., 2010) since they show strong room temperature excitonic optical features with large exciton binding energy and oscillator strengths. These low dimensional complexes include zero dimensional (0D), one dimensional (1D), and two dimensional (2D) lead iodide networks with organic groups as spacers. Among them, 1D-hybrids are more attractive in nanoscaled applications since they form a variety of crystalline structures, which differ in the inorganic chain where the [PbI₆] octahedra can be connected in different ways: face sharing (Elleuch et al., 2007), edge sharing (Samet Kallel et al., 2008), corner sharing (Mousdis et al., 1998) or through several combinations of these various types of sharing (Maxcy et al., 2003; Billing & Lemmerer, 2004; Krautscheid et al., 2001), as in the case of our compound. We present here the structure of the organic–inorganic one dimensional hybrid compound (C₆H₁₃N₃)₂Pb₃I₁₀.

The crystal structure of the title compound consists of (Pb₃I₁₀)_n^4n- chains extending along [001] with the 1-(3-ammoniopropyl)-imidazolium cations as counter-ions (Fig. 1). The inorganic anion, shown in Fig. 1, can be considered as a set of mixed face-shared/edge-shared octahedra. In fact, the unit cell contains three octahedra with two crystallographically independent Pb atoms: Pb1 and Pb2. The central Pb2 octahedron is connected to the Pb1 octahedra by shared faces, while the Pb1 octahedra are linked via edge-sharing at both ends of Pb₃I₁₀^4- to adjacent units.

The coordination octahedron of the central lead ion Pb2 is only slightly distorted since it is located on an inversion centre and is bound to three unique I atoms: I2, I3 and I4, which participate in the face-sharing between the Pb2 and Pb1 octahedra. The bond lengths around Pb2 are very similar (3.2105 (15), 3.2388 (14), 3.263 (2) Å), the bond angles I—Pb2—I deviate slightly from ideal octahedral values, ranging from 83° to 94°. In contrast, Pb1 has a more distorted environement with Pb—I distances ranging from 3.155 (2) to 3.309 (2) Å and with all cis and trans angles different (see Table 1). This Pb atom is bonded to five unique I atoms, where two I1 atoms are responsible for the edge sharing between the neighbouring units to form one-dimensional infinite chains. Atom I5 is the only halide not involved in any bonding with adjacent octahedra and has the shortest Pb—I distance [3.155 (2) Å].

Cations fill channels between the anionic chains (Fig.2). Each terminal ammonium group forms three N—H···I hydrogen bonds to I atoms of three different chains (see Table 2).

Experimental

Single crystals of (C₆H₁₃N₃)₂Pb₃I₁₀ were grown by the slow evaporation at room temperature of a solution containing PbI₂ and C₆H₁₃N₃I₃ salts. An aqueous solution of HI was added to the aminopropylimidazole to synthesize C₆H₁₃N₃I₃ precursor. Under ambient conditions, stoechiometric amounts of C₆H₁₃N₃I₃ and PbI₂ with excess HI were sailed in DMF. This mixture was stirred and remained clear without any precipitate. Pale-yellow flatted crystals were obtained few weeks later. Supplementary data for this paper are available from the IUCr electronic archives (Reference: CCDC 782074).