Acta Cryst. (2007). E63, i189 [ doi:10.1107/S1600536807050581 ]
Single crystals of ammonium lead iodide, NH4PbI3, have been obtained by solid-state reactions. Each PbII ion is coordinated by six I- ions in a distorted octahedral environment. PbI6 octahedra are connected by common edges, forming a one-dimensional anion chain. All atoms except one H atom in a general position have site symmetry m.
A mixture of PbI2 (92 mg, 0.2 mmol) and Bu4NI (74 mg, 0.2 mmol) was pressed into a pellet, which was then sealed into an evacuated quartz tube. The quartz tube was heated at 473 K for 2 days, and then cooled slowly to room temperature. Prism-shaped yellow crystals of suitable for X-ray analysis were obtained.
The N—H distances were restrained to 0.80 (2) Å. The displacement parameters of H atoms were set at 1.5 times Ueq of the N atom. The highest peak is located 1.17 Å from I1 and the deepest hole is located 0.74 Å from Pb1.
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).
![[Figure 1]](./pk2055fig1thm.gif)
| Fig. 1. The asymmetric uni of (I), together with additional I atoms to complete the coordination of Pb atom. Displacement ellipsoids are plotted at the 50% probability level. [Symmetry code: (A) x, 1 + y, z; (B) 1 – x, 1 – y, 1 – z, (C) x, – 0.5 – y, z] Fig. 2. Packing Diagram of (I) looking down b axis. |
| NH4Pb1I3 | F000 = 1008 |
| Mr = 605.94 | Dx = 4.766 Mg m−3 |
| Orthorhombic, Pnma | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 2002 reflections |
| a = 10.3029 (14) Å | θ = 3.1–27.5º |
| b = 4.7411 (5) Å | µ = 30.84 mm−1 |
| c = 17.288 (2) Å | T = 293 (2) K |
| V = 844.48 (18) Å3 | Prism, yellow |
| Z = 4 | 0.10 × 0.08 × 0.05 mm |
| Rigaku Mercury CCD diffractometer | 1080 independent reflections |
| Radiation source: Sealed Tube | 1012 reflections with I > 2σ(I) |
| Monochromator: Graphite Monochromator | Rint = 0.045 |
| T = 293(2) K | θmax = 27.5º |
| ω scans | θmin = 3.1º |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | h = −12→13 |
| Tmin = 0.064, Tmax = 0.214 | k = −6→6 |
| 6247 measured reflections | l = −22→17 |
| 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)] = 0.033 | Only H-atom coordinates refined |
| wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0484P)2 + 2.6931P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 1080 reflections | Δρmax = 1.11 e Å−3 |
| 39 parameters | Δρmin = −1.78 e Å−3 |
| 9 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| NH4Pb1I3 | V = 844.48 (18) Å3 |
| Mr = 605.94 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα |
| a = 10.3029 (14) Å | µ = 30.84 mm−1 |
| b = 4.7411 (5) Å | T = 293 (2) K |
| c = 17.288 (2) Å | 0.10 × 0.08 × 0.05 mm |
| Rigaku Mercury CCD diffractometer | 1080 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | 1012 reflections with I > 2σ(I) |
| Tmin = 0.064, Tmax = 0.214 | Rint = 0.045 |
| 6247 measured reflections |
| R[F2 > 2σ(F2)] = 0.033 | 9 restraints |
| wR(F2) = 0.083 | Only H-atom coordinates refined |
| S = 1.02 | Δρmax = 1.11 e Å−3 |
| 1080 reflections | Δρmin = −1.78 e Å−3 |
| 39 parameters |
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 > 2σ(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. |
| x | y | z | Uiso*/Ueq | ||
| Pb1 | 0.66816 (4) | 0.7500 | 0.44155 (2) | 0.02949 (16) | |
| I1 | 0.47613 (7) | 0.2500 | 0.38364 (4) | 0.0303 (2) | |
| I2 | 0.80933 (8) | 0.7500 | 0.28586 (5) | 0.0401 (2) | |
| I3 | 0.84262 (7) | 0.2500 | 0.51297 (5) | 0.0374 (2) | |
| N1 | 0.9132 (13) | −0.2500 | 0.6757 (6) | 0.053 (4) | |
| H1 | 0.952 (12) | −0.2500 | 0.715 (5) | 0.080* | |
| H2 | 0.963 (11) | −0.2500 | 0.641 (6) | 0.080* | |
| H3 | 0.871 (5) | −0.115 (12) | 0.674 (5) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Pb1 | 0.0328 (3) | 0.0274 (3) | 0.0283 (3) | 0.000 | 0.00360 (17) | 0.000 |
| I1 | 0.0298 (4) | 0.0360 (4) | 0.0250 (4) | 0.000 | −0.0016 (3) | 0.000 |
| I2 | 0.0453 (5) | 0.0413 (5) | 0.0336 (4) | 0.000 | 0.0133 (4) | 0.000 |
| I3 | 0.0326 (4) | 0.0293 (4) | 0.0503 (5) | 0.000 | −0.0092 (3) | 0.000 |
| N1 | 0.071 (9) | 0.053 (8) | 0.036 (6) | 0.000 | −0.001 (6) | 0.000 |
| Pb1—I2 | 3.0595 (9) | I1—Pb1iii | 3.2459 (6) |
| Pb1—I3i | 3.2210 (6) | I1—Pb1ii | 3.3679 (9) |
| Pb1—I3 | 3.2210 (6) | I3—Pb1iii | 3.2210 (6) |
| Pb1—I1 | 3.2459 (6) | N1—H1 | 0.79 (7) |
| Pb1—I1i | 3.2459 (6) | N1—H2 | 0.78 (7) |
| Pb1—I1ii | 3.3679 (9) | N1—H3 | 0.78 (6) |
| I2—Pb1—I3i | 94.12 (2) | I3i—Pb1—I1ii | 84.40 (2) |
| I2—Pb1—I3 | 94.12 (2) | I3—Pb1—I1ii | 84.40 (2) |
| I3i—Pb1—I3 | 94.78 (2) | I1—Pb1—I1ii | 90.443 (18) |
| I2—Pb1—I1 | 91.05 (2) | I1i—Pb1—I1ii | 90.443 (18) |
| I3i—Pb1—I1 | 174.78 (2) | Pb1—I1—Pb1iii | 93.83 (2) |
| I3—Pb1—I1 | 85.461 (16) | Pb1—I1—Pb1ii | 89.557 (18) |
| I2—Pb1—I1i | 91.05 (2) | Pb1iii—I1—Pb1ii | 89.557 (18) |
| I3i—Pb1—I1i | 85.461 (16) | Pb1iii—I3—Pb1 | 94.78 (2) |
| I3—Pb1—I1i | 174.78 (2) | H1—N1—H2 | 108 (5) |
| I1—Pb1—I1i | 93.83 (2) | H1—N1—H3 | 109 (3) |
| I2—Pb1—I1ii | 177.81 (3) | H2—N1—H3 | 110 (3) |
| I2—Pb1—I1—Pb1iii | 88.87 (2) | I1i—Pb1—I1—Pb1ii | −90.474 (19) |
| I3—Pb1—I1—Pb1iii | −5.18 (2) | I1ii—Pb1—I1—Pb1ii | 0.0 |
| I1i—Pb1—I1—Pb1iii | 180.0 | I2—Pb1—I3—Pb1iii | −85.50 (2) |
| I1ii—Pb1—I1—Pb1iii | −89.526 (19) | I3i—Pb1—I3—Pb1iii | 180.0 |
| I2—Pb1—I1—Pb1ii | 178.399 (19) | I1—Pb1—I3—Pb1iii | 5.23 (2) |
| I3—Pb1—I1—Pb1ii | 84.34 (2) | I1ii—Pb1—I3—Pb1iii | 96.12 (2) |
| Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z. |
This work was supported financially by the National Natural Science Foundation of China (No. 50572030, 50372022) and the Research Fund of Huaqiao University (No. 06BS216)
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Considerable current interests focus on fundamental as well as more applied studies of iodoplumbates related to their significant structural, electrical, non-linear optical, and other physical properties (Mitzi et al., 1995; Guloy et al., 2001; Fan et al., 2006). Lead(II) iodide and its low-dimensional derivatives represent a potential class of functional materials. We report here the crystal structure of the title lead(II) iodide complex, which has a one-dimensional anion chain.
There is one crystallographically independent PbII ion in the asymmetric unit (Fig. 1). PbII ion is six-coordinated in a distorted octahedral environment by six I− ions with Pb—I distances ranging from 3.0595 (9) to 3.3679 (9) Å and cis I—Pb—I angles from 84.40 (2) to 94.78 (2)° (Table 1). Adjacent octahedra are joined by a common edge (I1/I3) to form a chain; two neighboring chains are connected through a common edge (I1/I1) to form a one-dimensional anion chain [PbI3]nn– along the b axis (Fig. 2). As a consequence of the connectivity of PbI6 octahedra, the I− ions are acting as µ3 (I1) and µ bridge (I3) and as a terminal ligand (I2). The longest Pb—I bond length is observed for the triply bridging ligand I1 due to its higher connectivity and the trans influence of the terminal ligand I2 in trans position to I2 (Krautscheid, et al., 2001). At 473 K, the C—N bonds of [Bu4N]+ are broken, so the cation of [NH4]+ is formed. The anion chain has no significant hydrogen-bonding interactions with the cations.