Acta Cryst. (2012). E68, m19 [ doi:10.1107/S1600536811051853 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-iodido]]The title complex, {(C16H12FN2)[PbI3]}n, consists of 1-[(2-fluorobenzylidene)amino]quinolinium cations and a polymeric PbI3- anion formed by face-sharing PbI6 octahedra. These octahedra form straight and regular infinite chains along the b axis. In the asymmetric unit, one cation and one anionic [PbI3]- fragment are observed in general positions. Polymeric chains are produced by the glide plane perpendicular to the a axis.
A mixture of PbI2 (461.3 mg, 1.0 mmol) and 1-(2-fluorobenzylideneamino)-quinolinium iodide (377.9 mg, 1.0 mmol) in a 1:1 molar ratio in DMF was slowly evaporated to produce orange-red needle-shaped crystals. The yield of the compound (1) was 67%.
H atoms were placed to the bonded parent atoms in geometrically idealized positions and refined as riding atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./im2337fig1thm.gif)
| Fig. 1. Molecular structure of the cation showing displacement ellipsoids at the 30% probability level. |
![[Figure 2]](./im2337fig2thm.gif)
| Fig. 2. Cut-out of the polymeric polyanion consisting of face-sharing PbI6 octahedra showing displacement ellipsoids at the 30% probability level. |
| (C16H12FN2)[PbI3] | Z = 8 |
| Mr = 839.17 | F(000) = 2976 |
| Orthorhombic, Pbca | Dx = 2.677 Mg m−3 |
| Hall symbol: -P 2ac 2ab | Mo Kα radiation, λ = 0.71073 Å |
| a = 20.888 (4) Å | µ = 12.56 mm−1 |
| b = 7.9112 (15) Å | T = 296 K |
| c = 25.197 (5) Å | Neddle, orange-red |
| V = 4163.8 (14) Å3 | 0.04 × 0.02 × 0.01 mm |
| Siemens SMART CCD area-detector diffractometer | 4090 independent reflections |
| Radiation source: fine-focus sealed tube | 1770 reflections with I > 2σ(I) |
| graphite | Rint = 0.156 |
| phi and ω scans | θmax = 26.0°, θmin = 1.6° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −25→25 |
| Tmin = 0.747, Tmax = 0.882 | k = −9→9 |
| 30847 measured reflections | l = −31→31 |
| 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.082 | H-atom parameters constrained |
| S = 0.96 | w = 1/[σ2(Fo2) + (0.0158P)2] where P = (Fo2 + 2Fc2)/3 |
| 4090 reflections | (Δ/σ)max = 0.001 |
| 208 parameters | Δρmax = 0.96 e Å−3 |
| 0 restraints | Δρmin = −0.95 e Å−3 |
| (C16H12FN2)[PbI3] | V = 4163.8 (14) Å3 |
| Mr = 839.17 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 20.888 (4) Å | µ = 12.56 mm−1 |
| b = 7.9112 (15) Å | T = 296 K |
| c = 25.197 (5) Å | 0.04 × 0.02 × 0.01 mm |
| Siemens SMART CCD area-detector diffractometer | 4090 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 1770 reflections with I > 2σ(I) |
| Tmin = 0.747, Tmax = 0.882 | Rint = 0.156 |
| 30847 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
| wR(F2) = 0.082 | Δρmax = 0.96 e Å−3 |
| S = 0.96 | Δρmin = −0.95 e Å−3 |
| 4090 reflections | Absolute structure: ? |
| 208 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| C12 | −0.1124 (8) | 0.409 (2) | 0.2967 (6) | 0.073 (5) | |
| Pb1 | 0.24868 (3) | 0.30676 (6) | 0.394853 (19) | 0.04686 (15) | |
| I1 | 0.31600 (4) | 0.05236 (13) | 0.48094 (3) | 0.0538 (3) | |
| I2 | 0.12891 (4) | 0.05643 (12) | 0.40030 (4) | 0.0583 (3) | |
| I3 | 0.31533 (4) | 0.05436 (13) | 0.30998 (3) | 0.0596 (3) | |
| F1 | −0.1508 (4) | 0.4781 (12) | 0.2589 (4) | 0.111 (4) | |
| N1 | 0.0224 (5) | 0.2690 (14) | 0.1530 (4) | 0.049 (3) | |
| N2 | 0.0119 (5) | 0.2585 (14) | 0.2088 (4) | 0.058 (3) | |
| C1 | −0.0187 (7) | 0.2012 (17) | 0.1191 (5) | 0.060 (4) | |
| H1 | −0.0562 | 0.1525 | 0.1318 | 0.073* | |
| C2 | −0.0062 (7) | 0.2018 (18) | 0.0630 (6) | 0.071 (5) | |
| H2 | −0.0359 | 0.1579 | 0.0392 | 0.086* | |
| C3 | 0.0503 (7) | 0.2683 (18) | 0.0453 (6) | 0.064 (4) | |
| H3 | 0.0597 | 0.2675 | 0.0093 | 0.077* | |
| C4 | 0.0927 (7) | 0.336 (2) | 0.0803 (7) | 0.070 (5) | |
| C5 | 0.1517 (7) | 0.408 (2) | 0.0643 (6) | 0.090 (6) | |
| H5 | 0.1622 | 0.4115 | 0.0284 | 0.108* | |
| C6 | 0.1922 (7) | 0.471 (2) | 0.0994 (6) | 0.112 (7) | |
| H6 | 0.2299 | 0.5216 | 0.0877 | 0.134* | |
| C7 | 0.1793 (7) | 0.464 (2) | 0.1555 (6) | 0.097 (6) | |
| H7 | 0.2087 | 0.5072 | 0.1796 | 0.117* | |
| C8 | 0.1249 (7) | 0.394 (2) | 0.1730 (6) | 0.080 (5) | |
| H8 | 0.1170 | 0.3871 | 0.2092 | 0.096* | |
| C9 | 0.0800 (7) | 0.3326 (18) | 0.1367 (6) | 0.055 (4) | |
| C10 | −0.0397 (6) | 0.3288 (15) | 0.2223 (5) | 0.043 (3) | |
| H10 | −0.0665 | 0.3773 | 0.1971 | 0.052* | |
| C11 | −0.0565 (7) | 0.3323 (17) | 0.2785 (5) | 0.051 (4) | |
| C13 | −0.1289 (7) | 0.421 (2) | 0.3469 (6) | 0.080 (5) | |
| H13 | −0.1660 | 0.4788 | 0.3563 | 0.096* | |
| C14 | −0.0916 (9) | 0.350 (2) | 0.3848 (7) | 0.096 (6) | |
| H14 | −0.1040 | 0.3526 | 0.4202 | 0.115* | |
| C15 | −0.0353 (8) | 0.274 (2) | 0.3700 (6) | 0.083 (6) | |
| H15 | −0.0097 | 0.2252 | 0.3959 | 0.099* | |
| C16 | −0.0158 (7) | 0.2680 (18) | 0.3182 (6) | 0.065 (4) | |
| H16 | 0.0238 | 0.2220 | 0.3093 | 0.078* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C12 | 0.076 (12) | 0.102 (14) | 0.042 (10) | 0.015 (11) | −0.003 (9) | −0.037 (10) |
| Pb1 | 0.0469 (3) | 0.0437 (3) | 0.0499 (3) | −0.0005 (2) | −0.0006 (4) | −0.0024 (3) |
| I1 | 0.0494 (6) | 0.0675 (6) | 0.0444 (5) | −0.0033 (6) | −0.0076 (4) | −0.0005 (5) |
| I2 | 0.0422 (5) | 0.0616 (6) | 0.0710 (6) | −0.0023 (5) | −0.0070 (5) | −0.0082 (6) |
| I3 | 0.0676 (6) | 0.0681 (6) | 0.0432 (5) | −0.0080 (6) | 0.0125 (5) | −0.0060 (6) |
| F1 | 0.067 (7) | 0.161 (10) | 0.104 (8) | 0.055 (6) | 0.000 (6) | −0.021 (7) |
| N1 | 0.046 (8) | 0.065 (9) | 0.035 (8) | 0.004 (7) | −0.006 (6) | −0.009 (6) |
| N2 | 0.050 (8) | 0.080 (9) | 0.043 (8) | 0.009 (6) | 0.010 (6) | −0.005 (6) |
| C1 | 0.052 (10) | 0.071 (11) | 0.059 (11) | 0.007 (8) | −0.001 (8) | −0.019 (8) |
| C2 | 0.037 (10) | 0.117 (15) | 0.060 (11) | 0.014 (10) | −0.023 (8) | −0.021 (10) |
| C3 | 0.044 (10) | 0.088 (12) | 0.061 (11) | −0.013 (9) | −0.002 (8) | −0.015 (9) |
| C4 | 0.039 (10) | 0.085 (13) | 0.087 (13) | 0.008 (9) | 0.016 (9) | −0.004 (10) |
| C5 | 0.034 (9) | 0.190 (19) | 0.046 (9) | −0.021 (11) | 0.002 (7) | −0.037 (11) |
| C6 | 0.059 (11) | 0.21 (2) | 0.062 (11) | −0.040 (12) | 0.019 (10) | −0.037 (13) |
| C7 | 0.023 (8) | 0.20 (2) | 0.066 (11) | −0.017 (11) | 0.003 (7) | −0.045 (12) |
| C8 | 0.052 (11) | 0.124 (16) | 0.064 (11) | −0.005 (10) | 0.008 (9) | −0.012 (10) |
| C9 | 0.043 (10) | 0.067 (11) | 0.057 (11) | −0.004 (8) | 0.013 (8) | −0.013 (9) |
| C10 | 0.057 (10) | 0.046 (9) | 0.027 (8) | 0.006 (7) | −0.014 (7) | 0.000 (6) |
| C11 | 0.044 (9) | 0.065 (10) | 0.042 (9) | 0.001 (8) | 0.007 (7) | −0.005 (7) |
| C13 | 0.035 (9) | 0.134 (15) | 0.072 (12) | 0.023 (11) | 0.016 (8) | −0.017 (12) |
| C14 | 0.089 (15) | 0.123 (16) | 0.077 (15) | 0.019 (12) | 0.020 (12) | −0.018 (12) |
| C15 | 0.071 (14) | 0.109 (15) | 0.068 (13) | 0.014 (11) | −0.011 (10) | 0.010 (11) |
| C16 | 0.065 (12) | 0.095 (13) | 0.036 (9) | 0.017 (9) | 0.005 (9) | −0.004 (9) |
| C12—C13 | 1.313 (17) | C3—H3 | 0.9300 |
| C12—F1 | 1.359 (16) | C4—C5 | 1.418 (18) |
| C12—C11 | 1.397 (17) | C4—C9 | 1.446 (18) |
| Pb1—I3i | 3.1935 (12) | C5—C6 | 1.323 (17) |
| Pb1—I2 | 3.1938 (11) | C5—H5 | 0.9300 |
| Pb1—I1i | 3.2102 (11) | C6—C7 | 1.440 (18) |
| Pb1—I2i | 3.2339 (11) | C6—H6 | 0.9300 |
| Pb1—I3 | 3.2402 (11) | C7—C8 | 1.335 (18) |
| Pb1—I1 | 3.2761 (11) | C7—H7 | 0.9300 |
| I1—Pb1ii | 3.2102 (11) | C8—C9 | 1.399 (18) |
| I2—Pb1ii | 3.2339 (11) | C8—H8 | 0.9300 |
| I3—Pb1ii | 3.1935 (11) | C10—C11 | 1.457 (16) |
| N1—C1 | 1.324 (14) | C10—H10 | 0.9300 |
| N1—C9 | 1.366 (15) | C11—C16 | 1.407 (17) |
| N1—N2 | 1.427 (13) | C13—C14 | 1.355 (19) |
| N2—C10 | 1.260 (14) | C13—H13 | 0.9300 |
| C1—C2 | 1.437 (17) | C14—C15 | 1.373 (19) |
| C1—H1 | 0.9300 | C14—H14 | 0.9300 |
| C2—C3 | 1.366 (17) | C15—C16 | 1.368 (17) |
| C2—H2 | 0.9300 | C15—H15 | 0.9300 |
| C3—C4 | 1.358 (18) | C16—H16 | 0.9300 |
| C13—C12—F1 | 119.5 (15) | C3—C4—C9 | 120.7 (15) |
| C13—C12—C11 | 124.6 (16) | C5—C4—C9 | 116.5 (15) |
| F1—C12—C11 | 115.9 (13) | C6—C5—C4 | 121.3 (15) |
| I3i—Pb1—I2 | 94.65 (3) | C6—C5—H5 | 119.4 |
| I3i—Pb1—I1i | 84.55 (3) | C4—C5—H5 | 119.4 |
| I2—Pb1—I1i | 90.95 (3) | C5—C6—C7 | 121.4 (15) |
| I3i—Pb1—I2i | 89.13 (3) | C5—C6—H6 | 119.3 |
| I2—Pb1—I2i | 175.06 (4) | C7—C6—H6 | 119.3 |
| I1i—Pb1—I2i | 86.24 (3) | C8—C7—C6 | 120.0 (14) |
| I3i—Pb1—I3 | 96.66 (3) | C8—C7—H7 | 120.0 |
| I2—Pb1—I3 | 89.01 (3) | C6—C7—H7 | 120.0 |
| I1i—Pb1—I3 | 178.79 (3) | C7—C8—C9 | 120.0 (14) |
| I2i—Pb1—I3 | 93.71 (3) | C7—C8—H8 | 120.0 |
| I3i—Pb1—I1 | 179.26 (3) | C9—C8—H8 | 120.0 |
| I2—Pb1—I1 | 85.80 (3) | N1—C9—C8 | 121.5 (14) |
| I1i—Pb1—I1 | 96.03 (3) | N1—C9—C4 | 117.6 (14) |
| I2i—Pb1—I1 | 90.45 (3) | C8—C9—C4 | 120.8 (15) |
| I3—Pb1—I1 | 82.76 (3) | N2—C10—C11 | 118.4 (12) |
| Pb1ii—I1—Pb1 | 75.16 (2) | N2—C10—H10 | 120.8 |
| Pb1—I2—Pb1ii | 75.97 (2) | C11—C10—H10 | 120.8 |
| Pb1ii—I3—Pb1 | 75.88 (2) | C16—C11—C12 | 115.4 (13) |
| C1—N1—C9 | 121.7 (13) | C16—C11—C10 | 122.6 (13) |
| C1—N1—N2 | 120.8 (12) | C12—C11—C10 | 121.9 (13) |
| C9—N1—N2 | 117.0 (12) | C12—C13—C14 | 119.9 (16) |
| C10—N2—N1 | 111.8 (11) | C12—C13—H13 | 120.1 |
| N1—C1—C2 | 121.0 (14) | C14—C13—H13 | 120.1 |
| N1—C1—H1 | 119.5 | C13—C14—C15 | 118.9 (17) |
| C2—C1—H1 | 119.5 | C13—C14—H14 | 120.6 |
| C3—C2—C1 | 118.6 (13) | C15—C14—H14 | 120.6 |
| C3—C2—H2 | 120.7 | C16—C15—C14 | 122.0 (16) |
| C1—C2—H2 | 120.7 | C16—C15—H15 | 119.0 |
| C4—C3—C2 | 120.2 (15) | C14—C15—H15 | 119.0 |
| C4—C3—H3 | 119.9 | C15—C16—C11 | 119.1 (14) |
| C2—C3—H3 | 119.9 | C15—C16—H16 | 120.5 |
| C3—C4—C5 | 122.9 (16) | C11—C16—H16 | 120.5 |
| Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) −x+1/2, y−1/2, z. |
The authors thank the Natural Science Foundation of China for financial support (grant No. 21002096).
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Inorganic-organic hybrid materials have attracted intense interest in recent years, owing to their technologically important physical properties from optics to electronics, such as second-order nonlinear optical (NLO) properties, (Guloy et al., 2001) pyroelectricity, ferroelectricity (Horiuchi et al., 2010) and triboluminescence (Chen et al., 2001).
Inorganic metal-halide building blocks exhibiting [MX6]4-/3- fragments (M = Sn2+, Pb2+, Bi3+, Sb3+; X = F-, Cl-, Br-, I-) have received special attention in the construction of inorganic-organic hybrid materials (Zhang et al., 2006; Bi et al., 2008). Herein we report the crystal structure of the title compound (I) (Figure 1).
The title compound crystallizes in the orthorhombic space group Pbca with an asymmetric unit containing one anionic PbI3 fragment together with one Schiff base cation. The polymeric anion [PbI3]nn- possesses slightly distorted PbI6 octahedra which are linked to polymeric chains by symmetry related atoms (symmetry code 1/2 - x, 1/2 + y, z). Bond lengths and angles are in good agreement with the other structurally characterized compounds with the same anion (Zhao et al., 2010; Duan et al., 2011)