Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013678/bt6076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013678/bt6076Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (Pb-F) = 0.001 Å
- R factor = 0.041
- wR factor = 0.098
- Data-to-parameter ratio = 16.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
RINTA_01 Alert C The value of Rint is greater than 0.10 Rint given 0.107 PLAT_030 Alert C Refined Extinction parameter within range .... 2.67 Sigma PLAT_731 Alert C Bond Calc 4.2374(10), Rep 4.2374(3) .... 3.33 s.u-Ratio PB -PB 1.555 1.655 PLAT_731 Alert C Bond Calc 4.2374(10), Rep 4.2374(3) .... 3.33 s.u-Ratio PB -PB 1.555 1.455 PLAT_731 Alert C Bond Calc 4.2374(10), Rep 4.2374(3) .... 3.33 s.u-Ratio PB -PB 1.555 1.565 PLAT_731 Alert C Bond Calc 4.2374(10), Rep 4.2374(3) .... 3.33 s.u-Ratio PB -PB 1.555 1.545 PLAT_731 Alert C Bond Calc 4.9523(11), Rep 4.9523(4) .... 2.75 s.u-Ratio PB -F 1.555 9.555 PLAT_731 Alert C Bond Calc 4.9523(11), Rep 4.9523(4) .... 2.75 s.u-Ratio PB -F 1.555 1.445 PLAT_731 Alert C Bond Calc 4.2374(10), Rep 4.2374(3) .... 3.33 s.u-Ratio I -I 1.555 1.565 PLAT_731 Alert C Bond Calc 4.2374(10), Rep 4.2374(3) .... 3.33 s.u-Ratio I -I 1.555 1.655 PLAT_731 Alert C Bond Calc 4.2374(10), Rep 4.2374(3) .... 3.33 s.u-Ratio I -I 1.555 1.455 PLAT_731 Alert C Bond Calc 4.2374(10), Rep 4.2374(3) .... 3.33 s.u-Ratio I -I 1.555 1.545 PLAT_731 Alert C Bond Calc 4.9523(11), Rep 4.9523(4) .... 2.75 s.u-Ratio F -PB 1.555 9.555 PLAT_731 Alert C Bond Calc 4.9523(11), Rep 4.9523(4) .... 2.75 s.u-Ratio F -PB 1.555 1.665 PLAT_731 Alert C Bond Calc 4.9523(11), Rep 4.9523(4) .... 2.75 s.u-Ratio F -PB 1.555 1.545 PLAT_731 Alert C Bond Calc 4.9523(11), Rep 4.9523(4) .... 2.75 s.u-Ratio F -PB 1.555 9.765 General Notes
ABSTM_02 The ratio of expected to reported Tmax/Tmin(RR) is > 2.00 Tmin and Tmax reported: 0.023 0.611 Tmin and Tmax expected: 0.000 0.730 RR = 79.809 Please check that your absorption correction is appropriate.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
16 Alert Level C = Please check
Single crystals of PbFI were synthesized under hydrothermal conditions, starting from stoichiometric amounts of PbI2 (Riedel-de Haën, pure) and PbF2 (Aldrich, 99+%). The materials were homogenized by grinding and filled in a 5 ml teflon inlay which was two-thirds filled with demineralized water. The teflon inlay then was closed, placed in a steel autoclave and heated in a laboratory furnace. The heating rate was 298 → 523 K [2 h], 523 K [10 d], 523 → 298 K [10 h]. Very thin crystals with plate-like habit and light yellow colour of the title compound were obtained. Microcrystalline samples of PbFI were prepared by reaction of PbI2 and PbF2 in sealed and evacuated silica ampoules at 653 K for one week.
Data collection: PW1100 Operation Software (Philips, 1980); cell refinement: PW1100 Operation Software; data reduction: PW1100 Operation Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS for Windows (Dowty, 1998); software used to prepare material for publication: SHELX97 (Sheldrick, 1997).
PbFI | Dx = 7.422 Mg m−3 |
Mr = 353.09 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P4/nmm | Cell parameters from 21 reflections |
a = 4.2374 (3) Å | θ = 6.8–21.8° |
c = 8.800 (2) Å | µ = 62.89 mm−1 |
V = 158.00 (4) Å3 | T = 293 K |
Z = 2 | Plate, light yellow |
F(000) = 288 | 0.17 × 0.15 × 0.01 mm |
Philips PW1100 diffractometer | 143 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.107 |
Graphite monochromator | θmax = 29.5°, θmin = 4.6° |
θ/2θ scans | h = −5→5 |
Absorption correction: numerical (SHELXTL; Siemens, 1995) | k = −5→5 |
Tmin = 0.023, Tmax = 0.611 | l = −12→12 |
1724 measured reflections | 3 standard reflections every 120 min |
162 independent reflections | intensity decay: none |
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)] = 0.041 | w = 1/[σ2(Fo2) + (0.0613P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.098 | (Δ/σ)max < 0.001 |
S = 1.13 | Δρmax = 5.98 e Å−3 |
162 reflections | Δρmin = −2.37 e Å−3 |
10 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.008 (3) |
PbFI | Z = 2 |
Mr = 353.09 | Mo Kα radiation |
Tetragonal, P4/nmm | µ = 62.89 mm−1 |
a = 4.2374 (3) Å | T = 293 K |
c = 8.800 (2) Å | 0.17 × 0.15 × 0.01 mm |
V = 158.00 (4) Å3 |
Philips PW1100 diffractometer | 143 reflections with I > 2σ(I) |
Absorption correction: numerical (SHELXTL; Siemens, 1995) | Rint = 0.107 |
Tmin = 0.023, Tmax = 0.611 | 3 standard reflections every 120 min |
1724 measured reflections | intensity decay: none |
162 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 10 parameters |
wR(F2) = 0.098 | 0 restraints |
S = 1.13 | Δρmax = 5.98 e Å−3 |
162 reflections | Δρmin = −2.37 e Å−3 |
Experimental. the measured distances of indexed crystal faces have been used for numerical absorption correction using the program SHELXTL (Siemens, 1995). |
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 | ||
Pb | 0.2500 | 0.2500 | 0.16392 (9) | 0.0225 (5) | |
I | 0.2500 | 0.2500 | 0.66297 (13) | 0.0177 (5) | |
F | 0.7500 | 0.2500 | 0.0000 | 0.022 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pb | 0.0178 (5) | 0.0178 (5) | 0.0318 (7) | 0.000 | 0.000 | 0.000 |
I | 0.0147 (5) | 0.0147 (5) | 0.0237 (8) | 0.000 | 0.000 | 0.000 |
F | 0.017 (3) | 0.017 (3) | 0.032 (6) | 0.000 | 0.000 | 0.000 |
Pb—Fi | 2.5631 (5) | I—Fxv | 3.6448 (11) |
Pb—Fii | 2.5631 (5) | I—Fvii | 3.6448 (11) |
Pb—Fiii | 2.5631 (5) | I—Fxvi | 3.6448 (11) |
Pb—F | 2.5631 (5) | I—Iv | 4.1478 (17) |
Pb—Iiv | 3.3613 (7) | I—Ivi | 4.1478 (17) |
Pb—Iv | 3.3613 (7) | I—Ivii | 4.1478 (17) |
Pb—Ivi | 3.3613 (7) | I—Iiv | 4.1478 (17) |
Pb—Ivii | 3.3613 (7) | I—Ixi | 4.2374 (3) |
Pb—Pbviii | 4.1594 (12) | I—Ix | 4.2374 (3) |
Pb—Pbix | 4.1594 (12) | I—Iii | 4.2374 (3) |
Pb—Pbi | 4.1594 (12) | I—Ixii | 4.2374 (3) |
Pb—Pbiii | 4.1594 (12) | I—Pbxv | 4.4082 (18) |
Pb—Pbx | 4.2374 (3) | I—Fxvii | 5.5893 (8) |
Pb—Pbii | 4.2374 (3) | I—Fxviii | 5.5893 (8) |
Pb—Pbxi | 4.2374 (3) | F—Pbi | 2.5631 (5) |
Pb—Pbxii | 4.2374 (3) | F—Pbx | 2.5631 (5) |
Pb—I | 4.3915 (18) | F—Pbiii | 2.5631 (5) |
Pb—Ixiii | 4.4082 (18) | F—Iiv | 3.6448 (11) |
Pb—Fviii | 4.9523 (4) | F—Ixiii | 3.6448 (11) |
Pb—Fxiv | 4.9523 (4) | F—Ivii | 3.6448 (11) |
I—Pbiv | 3.3613 (7) | F—Ixix | 3.6448 (11) |
I—Pbv | 3.3613 (7) | F—Pbviii | 4.9523 (4) |
I—Pbvi | 3.3613 (7) | F—Pbxx | 4.9523 (4) |
I—Pbvii | 3.3613 (7) | F—Pbxii | 4.9523 (4) |
I—Fiv | 3.6448 (11) | F—Pbxxi | 4.9523 (4) |
Fi—Pb—Fii | 71.535 (15) | Fxv—I—Iv | 149.271 (15) |
Fi—Pb—Fiii | 111.50 (3) | Fvii—I—Iv | 105.411 (17) |
Fii—Pb—Fiii | 71.535 (15) | Fxvi—I—Iv | 105.411 (17) |
Fi—Pb—F | 71.535 (15) | Pbiv—I—Ivi | 108.263 (10) |
Fii—Pb—F | 111.50 (3) | Pbv—I—Ivi | 108.263 (10) |
Fiii—Pb—F | 71.535 (15) | Pbvi—I—Ivi | 70.697 (19) |
Fi—Pb—Iiv | 140.903 (8) | Pbvii—I—Ivi | 163.20 (4) |
Fii—Pb—Iiv | 140.903 (8) | Fiv—I—Ivi | 105.411 (18) |
Fiii—Pb—Iiv | 74.574 (17) | Fxv—I—Ivi | 149.271 (15) |
F—Pb—Iiv | 74.574 (17) | Fvii—I—Ivi | 149.271 (15) |
Fi—Pb—Iv | 74.574 (18) | Fxvi—I—Ivi | 105.411 (17) |
Fii—Pb—Iv | 74.574 (18) | Iv—I—Ivi | 61.43 (3) |
Fiii—Pb—Iv | 140.903 (8) | Pbiv—I—Ivii | 108.263 (10) |
F—Pb—Iv | 140.903 (8) | Pbv—I—Ivii | 108.263 (10) |
Iiv—Pb—Iv | 126.10 (4) | Pbvi—I—Ivii | 163.20 (4) |
Fi—Pb—Ivi | 140.903 (8) | Pbvii—I—Ivii | 70.697 (19) |
Fii—Pb—Ivi | 74.574 (18) | Fiv—I—Ivii | 149.271 (15) |
Fiii—Pb—Ivi | 74.574 (18) | Fxv—I—Ivii | 105.411 (18) |
F—Pb—Ivi | 140.903 (8) | Fvii—I—Ivii | 105.411 (18) |
Iiv—Pb—Ivi | 78.149 (18) | Fxvi—I—Ivii | 149.271 (15) |
Iv—Pb—Ivi | 78.149 (18) | Iv—I—Ivii | 61.43 (3) |
Fi—Pb—Ivii | 74.574 (18) | Ivi—I—Ivii | 92.50 (5) |
Fii—Pb—Ivii | 140.903 (8) | Pbiv—I—Iiv | 70.697 (19) |
Fiii—Pb—Ivii | 140.903 (8) | Pbv—I—Iiv | 163.20 (4) |
F—Pb—Ivii | 74.574 (18) | Pbvi—I—Iiv | 108.263 (10) |
Iiv—Pb—Ivii | 78.149 (18) | Pbvii—I—Iiv | 108.263 (10) |
Iv—Pb—Ivii | 78.149 (18) | Fiv—I—Iiv | 105.411 (18) |
Ivi—Pb—Ivii | 126.10 (4) | Fxv—I—Iiv | 105.411 (18) |
Fi—Pb—Pbviii | 35.768 (8) | Fvii—I—Iiv | 149.271 (15) |
Fii—Pb—Pbviii | 35.768 (8) | Fxvi—I—Iiv | 149.271 (15) |
Fiii—Pb—Pbviii | 91.76 (3) | Iv—I—Iiv | 92.50 (5) |
F—Pb—Pbviii | 91.76 (3) | Ivi—I—Iiv | 61.43 (3) |
Iiv—Pb—Pbviii | 163.03 (3) | Ivii—I—Iiv | 61.43 (3) |
Iv—Pb—Pbviii | 70.86 (2) | Pbiv—I—Ixi | 50.926 (9) |
Ivi—Pb—Pbviii | 108.320 (13) | Pbv—I—Ixi | 129.074 (9) |
Ivii—Pb—Pbviii | 108.320 (13) | Pbvi—I—Ixi | 50.926 (9) |
Fi—Pb—Pbix | 91.76 (3) | Pbvii—I—Ixi | 129.074 (9) |
Fii—Pb—Pbix | 35.768 (8) | Fiv—I—Ixi | 54.458 (13) |
Fiii—Pb—Pbix | 35.768 (8) | Fxv—I—Ixi | 90.0 |
F—Pb—Pbix | 91.76 (3) | Fvii—I—Ixi | 125.542 (13) |
Iiv—Pb—Pbix | 108.320 (13) | Fxvi—I—Ixi | 90.0 |
Iv—Pb—Pbix | 108.320 (13) | Iv—I—Ixi | 120.717 (14) |
Ivi—Pb—Pbix | 70.86 (2) | Ivi—I—Ixi | 59.283 (14) |
Ivii—Pb—Pbix | 163.03 (3) | Ivii—I—Ixi | 120.717 (14) |
Pbviii—Pb—Pbix | 61.244 (19) | Iiv—I—Ixi | 59.283 (14) |
Fi—Pb—Pbi | 35.768 (8) | Pbiv—I—Ix | 50.926 (9) |
Fii—Pb—Pbi | 91.76 (3) | Pbv—I—Ix | 129.074 (9) |
Fiii—Pb—Pbi | 91.76 (3) | Pbvi—I—Ix | 129.074 (9) |
F—Pb—Pbi | 35.768 (8) | Pbvii—I—Ix | 50.926 (9) |
Iiv—Pb—Pbi | 108.320 (13) | Fiv—I—Ix | 90.0 |
Iv—Pb—Pbi | 108.320 (13) | Fxv—I—Ix | 54.458 (13) |
Ivi—Pb—Pbi | 163.03 (3) | Fvii—I—Ix | 90.0 |
Ivii—Pb—Pbi | 70.86 (2) | Fxvi—I—Ix | 125.542 (13) |
Pbviii—Pb—Pbi | 61.244 (19) | Iv—I—Ix | 120.717 (14) |
Pbix—Pb—Pbi | 92.17 (3) | Ivi—I—Ix | 120.717 (14) |
Fi—Pb—Pbiii | 91.76 (3) | Ivii—I—Ix | 59.283 (14) |
Fii—Pb—Pbiii | 91.76 (3) | Iiv—I—Ix | 59.283 (14) |
Fiii—Pb—Pbiii | 35.768 (8) | Ixi—I—Ix | 90.0 |
F—Pb—Pbiii | 35.768 (8) | Pbiv—I—Iii | 129.074 (9) |
Iiv—Pb—Pbiii | 70.86 (2) | Pbv—I—Iii | 50.926 (9) |
Iv—Pb—Pbiii | 163.03 (3) | Pbvi—I—Iii | 50.926 (9) |
Ivi—Pb—Pbiii | 108.320 (13) | Pbvii—I—Iii | 129.074 (9) |
Ivii—Pb—Pbiii | 108.320 (13) | Fiv—I—Iii | 90.0 |
Pbviii—Pb—Pbiii | 92.17 (3) | Fxv—I—Iii | 125.542 (13) |
Pbix—Pb—Pbiii | 61.244 (19) | Fvii—I—Iii | 90.0 |
Pbi—Pb—Pbiii | 61.244 (19) | Fxvi—I—Iii | 54.458 (13) |
Fi—Pb—Pbx | 90.0 | Iv—I—Iii | 59.283 (14) |
Fii—Pb—Pbx | 145.752 (16) | Ivi—I—Iii | 59.283 (14) |
Fiii—Pb—Pbx | 90.0 | Ivii—I—Iii | 120.717 (14) |
F—Pb—Pbx | 34.248 (16) | Iiv—I—Iii | 120.717 (14) |
Iiv—Pb—Pbx | 50.926 (9) | Ixi—I—Iii | 90.0 |
Iv—Pb—Pbx | 129.074 (9) | Ix—I—Iii | 180.00 (6) |
Ivi—Pb—Pbx | 129.074 (9) | Pbiv—I—Ixii | 129.074 (9) |
Ivii—Pb—Pbx | 50.926 (9) | Pbv—I—Ixii | 50.926 (9) |
Pbviii—Pb—Pbx | 120.622 (10) | Pbvi—I—Ixii | 129.074 (9) |
Pbix—Pb—Pbx | 120.622 (10) | Pbvii—I—Ixii | 50.926 (9) |
Pbi—Pb—Pbx | 59.378 (10) | Fiv—I—Ixii | 125.542 (13) |
Pbiii—Pb—Pbx | 59.378 (10) | Fxv—I—Ixii | 90.0 |
Fi—Pb—Pbii | 90.0 | Fvii—I—Ixii | 54.458 (13) |
Fii—Pb—Pbii | 34.248 (16) | Fxvi—I—Ixii | 90.0 |
Fiii—Pb—Pbii | 90.0 | Iv—I—Ixii | 59.283 (14) |
F—Pb—Pbii | 145.752 (16) | Ivi—I—Ixii | 120.717 (14) |
Iiv—Pb—Pbii | 129.074 (9) | Ivii—I—Ixii | 59.283 (14) |
Iv—Pb—Pbii | 50.926 (9) | Iiv—I—Ixii | 120.717 (14) |
Ivi—Pb—Pbii | 50.926 (9) | Ixi—I—Ixii | 180.00 (6) |
Ivii—Pb—Pbii | 129.074 (9) | Ix—I—Ixii | 90.0 |
Pbviii—Pb—Pbii | 59.378 (10) | Iii—I—Ixii | 90.0 |
Pbix—Pb—Pbii | 59.378 (10) | Pbiv—I—Pb | 116.95 (2) |
Pbi—Pb—Pbii | 120.622 (10) | Pbv—I—Pb | 116.95 (2) |
Pbiii—Pb—Pbii | 120.622 (10) | Pbvi—I—Pb | 116.95 (2) |
Pbx—Pb—Pbii | 180.00 (4) | Pbvii—I—Pb | 116.95 (2) |
Fi—Pb—Pbxi | 145.752 (16) | Fiv—I—Pb | 144.458 (13) |
Fii—Pb—Pbxi | 90.0 | Fxv—I—Pb | 144.458 (13) |
Fiii—Pb—Pbxi | 34.248 (16) | Fvii—I—Pb | 144.458 (13) |
F—Pb—Pbxi | 90.0 | Fxvi—I—Pb | 144.458 (13) |
Iiv—Pb—Pbxi | 50.926 (9) | Iv—I—Pb | 46.25 (2) |
Iv—Pb—Pbxi | 129.074 (9) | Ivi—I—Pb | 46.25 (2) |
Ivi—Pb—Pbxi | 50.926 (9) | Ivii—I—Pb | 46.25 (2) |
Ivii—Pb—Pbxi | 129.074 (9) | Iiv—I—Pb | 46.25 (2) |
Pbviii—Pb—Pbxi | 120.622 (10) | Ixi—I—Pb | 90.0 |
Pbix—Pb—Pbxi | 59.378 (10) | Ix—I—Pb | 90.0 |
Pbi—Pb—Pbxi | 120.622 (10) | Iii—I—Pb | 90.0 |
Pbiii—Pb—Pbxi | 59.378 (10) | Ixii—I—Pb | 90.0 |
Pbx—Pb—Pbxi | 90.0 | Pbiv—I—Pbxv | 63.05 (2) |
Pbii—Pb—Pbxi | 90.0 | Pbv—I—Pbxv | 63.05 (2) |
Fi—Pb—Pbxii | 34.248 (16) | Pbvi—I—Pbxv | 63.05 (2) |
Fii—Pb—Pbxii | 90.0 | Pbvii—I—Pbxv | 63.05 (2) |
Fiii—Pb—Pbxii | 145.752 (16) | Fiv—I—Pbxv | 35.542 (13) |
F—Pb—Pbxii | 90.0 | Fxv—I—Pbxv | 35.542 (13) |
Iiv—Pb—Pbxii | 129.074 (9) | Fvii—I—Pbxv | 35.542 (13) |
Iv—Pb—Pbxii | 50.926 (9) | Fxvi—I—Pbxv | 35.542 (13) |
Ivi—Pb—Pbxii | 129.074 (9) | Iv—I—Pbxv | 133.75 (2) |
Ivii—Pb—Pbxii | 50.926 (9) | Ivi—I—Pbxv | 133.75 (2) |
Pbviii—Pb—Pbxii | 59.378 (10) | Ivii—I—Pbxv | 133.75 (2) |
Pbix—Pb—Pbxii | 120.622 (10) | Iiv—I—Pbxv | 133.75 (2) |
Pbi—Pb—Pbxii | 59.378 (10) | Ixi—I—Pbxv | 90.0 |
Pbiii—Pb—Pbxii | 120.622 (10) | Ix—I—Pbxv | 90.0 |
Pbx—Pb—Pbxii | 90.0 | Iii—I—Pbxv | 90.0 |
Pbii—Pb—Pbxii | 90.0 | Ixii—I—Pbxv | 90.0 |
Pbxi—Pb—Pbxii | 180.00 (4) | Pb—I—Pbxv | 180.0 |
Fi—Pb—I | 124.248 (16) | Pbiv—I—Fxvii | 16.810 (6) |
Fii—Pb—I | 124.248 (16) | Pbv—I—Fxvii | 118.45 (3) |
Fiii—Pb—I | 124.248 (16) | Pbvi—I—Fxvii | 89.912 (18) |
F—Pb—I | 124.248 (16) | Pbvii—I—Fxvii | 61.354 (11) |
Iiv—Pb—I | 63.05 (2) | Fiv—I—Fxvii | 49.300 (9) |
Iv—Pb—I | 63.05 (2) | Fxv—I—Fxvii | 29.255 (2) |
Ivi—Pb—I | 63.05 (2) | Fvii—I—Fxvii | 77.795 (18) |
Ivii—Pb—I | 63.05 (2) | Fxvi—I—Fxvii | 90.51 (2) |
Pbviii—Pb—I | 133.915 (17) | Iv—I—Fxvii | 161.40 (2) |
Pbix—Pb—I | 133.915 (17) | Ivi—I—Fxvii | 124.093 (6) |
Pbi—Pb—I | 133.915 (17) | Ivii—I—Fxvii | 99.979 (11) |
Pbiii—Pb—I | 133.915 (17) | Iiv—I—Fxvii | 77.646 (19) |
Pbx—Pb—I | 90.0 | Ixi—I—Fxvii | 67.724 (3) |
Pbii—Pb—I | 90.0 | Ix—I—Fxvii | 40.700 (9) |
Pbxi—Pb—I | 90.0 | Iii—I—Fxvii | 139.300 (9) |
Pbxii—Pb—I | 90.0 | Ixii—I—Fxvii | 112.276 (3) |
Fi—Pb—Ixiii | 55.752 (16) | Pb—I—Fxvii | 122.047 (12) |
Fii—Pb—Ixiii | 55.752 (16) | Pbxv—I—Fxvii | 57.953 (12) |
Fiii—Pb—Ixiii | 55.752 (16) | Pbiv—I—Fxviii | 16.810 (6) |
F—Pb—Ixiii | 55.752 (16) | Pbv—I—Fxviii | 118.45 (3) |
Iiv—Pb—Ixiii | 116.95 (2) | Pbvi—I—Fxviii | 61.354 (11) |
Iv—Pb—Ixiii | 116.95 (2) | Pbvii—I—Fxviii | 89.912 (18) |
Ivi—Pb—Ixiii | 116.95 (2) | Fiv—I—Fxviii | 29.255 (2) |
Ivii—Pb—Ixiii | 116.95 (2) | Fxv—I—Fxviii | 49.300 (9) |
Pbviii—Pb—Ixiii | 46.085 (17) | Fvii—I—Fxviii | 90.51 (2) |
Pbix—Pb—Ixiii | 46.085 (17) | Fxvi—I—Fxviii | 77.795 (18) |
Pbi—Pb—Ixiii | 46.085 (17) | Iv—I—Fxviii | 161.40 (2) |
Pbiii—Pb—Ixiii | 46.085 (17) | Ivi—I—Fxviii | 99.979 (11) |
Pbx—Pb—Ixiii | 90.0 | Ivii—I—Fxviii | 124.093 (5) |
Pbii—Pb—Ixiii | 90.0 | Iiv—I—Fxviii | 77.646 (19) |
Pbxi—Pb—Ixiii | 90.0 | Ixi—I—Fxviii | 40.700 (9) |
Pbxii—Pb—Ixiii | 90.0 | Ix—I—Fxviii | 67.724 (3) |
I—Pb—Ixiii | 180.0 | Iii—I—Fxviii | 112.276 (3) |
Fi—Pb—Fviii | 58.831 (5) | Ixii—I—Fxviii | 139.300 (9) |
Fii—Pb—Fviii | 29.401 (2) | Pb—I—Fxviii | 122.047 (12) |
Fiii—Pb—Fviii | 100.936 (14) | Pbxv—I—Fxviii | 57.953 (12) |
F—Pb—Fviii | 122.91 (2) | Fxvii—I—Fxviii | 31.095 (4) |
Iiv—Pb—Fviii | 160.221 (12) | Pbi—F—Pbx | 108.465 (15) |
Iv—Pb—Fviii | 47.390 (19) | Pbi—F—Pbiii | 111.50 (3) |
Ivi—Pb—Fviii | 82.087 (8) | Pbx—F—Pbiii | 108.465 (15) |
Ivii—Pb—Fviii | 113.683 (4) | Pbi—F—Pb | 108.465 (15) |
Pbviii—Pb—Fviii | 31.153 (5) | Pbx—F—Pb | 111.50 (3) |
Pbix—Pb—Fviii | 65.169 (6) | Pbiii—F—Pb | 108.465 (15) |
Pbi—Pb—Fviii | 90.911 (14) | Pbi—F—Iiv | 159.790 (17) |
Pbiii—Pb—Fviii | 116.86 (3) | Pbx—F—Iiv | 62.746 (14) |
Pbx—Pb—Fviii | 148.831 (5) | Pbiii—F—Iiv | 88.71 (2) |
Pbii—Pb—Fviii | 31.169 (5) | Pb—F—Iiv | 62.746 (14) |
Pbxi—Pb—Fviii | 115.329 (1) | Pbi—F—Ixiii | 62.746 (14) |
Pbxii—Pb—Fviii | 64.671 (1) | Pbx—F—Ixiii | 159.790 (17) |
I—Pb—Fviii | 106.934 (9) | Pbiii—F—Ixiii | 62.746 (14) |
Ixiii—Pb—Fviii | 73.066 (9) | Pb—F—Ixiii | 88.71 (2) |
Fi—Pb—Fxiv | 29.401 (2) | Iiv—F—Ixiii | 131.460 (16) |
Fii—Pb—Fxiv | 58.831 (5) | Pbi—F—Ivii | 88.71 (2) |
Fiii—Pb—Fxiv | 122.91 (2) | Pbx—F—Ivii | 62.746 (14) |
F—Pb—Fxiv | 100.936 (14) | Pbiii—F—Ivii | 159.790 (17) |
Iiv—Pb—Fxiv | 160.221 (12) | Pb—F—Ivii | 62.746 (14) |
Iv—Pb—Fxiv | 47.390 (19) | Iiv—F—Ivii | 71.08 (3) |
Ivi—Pb—Fxiv | 113.683 (4) | Ixiii—F—Ivii | 131.460 (16) |
Ivii—Pb—Fxiv | 82.087 (8) | Pbi—F—Ixix | 62.746 (14) |
Pbviii—Pb—Fxiv | 31.153 (5) | Pbx—F—Ixix | 88.71 (2) |
Pbix—Pb—Fxiv | 90.911 (14) | Pbiii—F—Ixix | 62.746 (14) |
Pbi—Pb—Fxiv | 65.169 (6) | Pb—F—Ixix | 159.790 (17) |
Pbiii—Pb—Fxiv | 116.86 (3) | Iiv—F—Ixix | 131.460 (16) |
Pbx—Pb—Fxiv | 115.329 (1) | Ixiii—F—Ixix | 71.08 (3) |
Pbii—Pb—Fxiv | 64.671 (1) | Ivii—F—Ixix | 131.460 (16) |
Pbxi—Pb—Fxiv | 148.831 (5) | Pbi—F—Pbviii | 58.831 (5) |
Pbxii—Pb—Fxiv | 31.169 (5) | Pbx—F—Pbviii | 150.599 (1) |
I—Pb—Fxiv | 106.934 (9) | Pbiii—F—Pbviii | 100.936 (14) |
Ixiii—Pb—Fxiv | 73.066 (9) | Pb—F—Pbviii | 57.09 (2) |
Fviii—Pb—Fxiv | 35.218 (2) | Iiv—F—Pbviii | 119.058 (7) |
Pbiv—I—Pbv | 126.10 (4) | Ixiii—F—Pbviii | 42.744 (11) |
Pbiv—I—Pbvi | 78.149 (18) | Ivii—F—Pbviii | 89.331 (12) |
Pbv—I—Pbvi | 78.149 (18) | Ixix—F—Pbviii | 105.092 (17) |
Pbiv—I—Pbvii | 78.149 (18) | Pbi—F—Pbxx | 150.599 (1) |
Pbv—I—Pbvii | 78.149 (18) | Pbx—F—Pbxx | 58.831 (5) |
Pbvi—I—Pbvii | 126.10 (4) | Pbiii—F—Pbxx | 57.09 (2) |
Pbiv—I—Fiv | 42.679 (13) | Pb—F—Pbxx | 100.936 (14) |
Pbv—I—Fiv | 89.87 (3) | Iiv—F—Pbxx | 42.744 (11) |
Pbvi—I—Fiv | 42.680 (13) | Ixiii—F—Pbxx | 119.058 (7) |
Pbvii—I—Fiv | 89.87 (3) | Ivii—F—Pbxx | 105.092 (17) |
Pbiv—I—Fxv | 42.679 (13) | Ixix—F—Pbxx | 89.331 (12) |
Pbv—I—Fxv | 89.87 (3) | Pbviii—F—Pbxx | 144.782 (2) |
Pbvi—I—Fxv | 89.87 (3) | Pbi—F—Pbxii | 57.09 (2) |
Pbvii—I—Fxv | 42.679 (13) | Pbx—F—Pbxii | 100.936 (14) |
Fiv—I—Fxv | 48.540 (16) | Pbiii—F—Pbxii | 150.599 (2) |
Pbiv—I—Fvii | 89.87 (3) | Pb—F—Pbxii | 58.831 (5) |
Pbv—I—Fvii | 42.680 (13) | Iiv—F—Pbxii | 105.092 (17) |
Pbvi—I—Fvii | 89.87 (3) | Ixiii—F—Pbxii | 89.331 (12) |
Pbvii—I—Fvii | 42.679 (13) | Ivii—F—Pbxii | 42.744 (11) |
Fiv—I—Fvii | 71.08 (3) | Ixix—F—Pbxii | 119.058 (7) |
Fxv—I—Fvii | 48.540 (16) | Pbviii—F—Pbxii | 49.663 (12) |
Pbiv—I—Fxvi | 89.87 (3) | Pbxx—F—Pbxii | 146.131 (19) |
Pbv—I—Fxvi | 42.680 (13) | Pbi—F—Pbxxi | 100.936 (14) |
Pbvi—I—Fxvi | 42.679 (13) | Pbx—F—Pbxxi | 57.09 (2) |
Pbvii—I—Fxvi | 89.87 (3) | Pbiii—F—Pbxxi | 58.831 (5) |
Fiv—I—Fxvi | 48.540 (16) | Pb—F—Pbxxi | 150.599 (2) |
Fxv—I—Fxvi | 71.08 (3) | Iiv—F—Pbxxi | 89.331 (12) |
Fvii—I—Fxvi | 48.540 (16) | Ixiii—F—Pbxxi | 105.092 (17) |
Pbiv—I—Iv | 163.20 (4) | Ivii—F—Pbxxi | 119.058 (7) |
Pbv—I—Iv | 70.697 (19) | Ixix—F—Pbxxi | 42.744 (11) |
Pbvi—I—Iv | 108.263 (10) | Pbviii—F—Pbxxi | 146.131 (19) |
Pbvii—I—Iv | 108.263 (10) | Pbxx—F—Pbxxi | 49.663 (12) |
Fiv—I—Iv | 149.271 (15) | Pbxii—F—Pbxxi | 144.782 (2) |
Symmetry codes: (i) −x+1, −y, −z; (ii) x−1, y, z; (iii) −x+1, −y+1, −z; (iv) −x+1, −y+1, −z+1; (v) −x, −y, −z+1; (vi) −x, −y+1, −z+1; (vii) −x+1, −y, −z+1; (viii) −x, −y, −z; (ix) −x, −y+1, −z; (x) x+1, y, z; (xi) x, y+1, z; (xii) x, y−1, z; (xiii) x, y, z−1; (xiv) x−1, y−1, z; (xv) x, y, z+1; (xvi) x−1, y, z+1; (xvii) −x+2, −y+1, −z+1; (xviii) x, y+1, z+1; (xix) x+1, y, z−1; (xx) x+1, y+1, z; (xxi) −x+2, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | PbFI |
Mr | 353.09 |
Crystal system, space group | Tetragonal, P4/nmm |
Temperature (K) | 293 |
a, c (Å) | 4.2374 (3), 8.800 (2) |
V (Å3) | 158.00 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 62.89 |
Crystal size (mm) | 0.17 × 0.15 × 0.01 |
Data collection | |
Diffractometer | Philips PW1100 diffractometer |
Absorption correction | Numerical (SHELXTL; Siemens, 1995) |
Tmin, Tmax | 0.023, 0.611 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1724, 162, 143 |
Rint | 0.107 |
(sin θ/λ)max (Å−1) | 0.692 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.098, 1.13 |
No. of reflections | 162 |
No. of parameters | 10 |
Δρmax, Δρmin (e Å−3) | 5.98, −2.37 |
Computer programs: PW1100 Operation Software (Philips, 1980), PW1100 Operation Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ATOMS for Windows (Dowty, 1998), SHELX97 (Sheldrick, 1997).
Pb—Fi | 2.5631 (5) | Pb—I | 4.3915 (18) |
Pb—Iii | 3.3613 (7) | Pb—Iiii | 4.4082 (18) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y+1, −z+1; (iii) x, y, z−1. |
Compounds of the matlockite (PbFCl) structure type are technologically interesting materials. For example, Sm2+– or Eu2+-doped BaFX (X = Cl, Br, I) crystals are well established optical luminophores (Takahashi et al., 1985) or can be used as X-ray phosphors in imaging plate systems (Tanaka et al., 1990; Sato et al., 1992). Many isotypic representatives MFX of divalent lead, the larger alkaline earth ions (M = Ca, Sr, Ba) and of stable divalent rare earth elements (M = Sm, Eu) have been synthesized in the past and their structures determined from single-crystal or powder data.
Focusing on the system PbFX, the structures of PbFCl (Nieuwenkamp & Bijvoet, 1932a) and PbFBr (Nieuwenkamp & Bijvoet, 1932b) were the first to be characterized by X-ray diffraction techniques within this structure family. Synthesis and lattice parameters of microcrystalline PbFI have already been described by Rulmont (1973) and Aurivillius (1976), but no structure parameters of this compound were published up to now, although high quality powder refinements had been previously performed (Haberkorn, 1988).
The crystal structure of PbFI consists of a lattice of alternating coplanar layers with a sequence I–Pb–F–Pb–I–(I–Pb–F–Pb–I)- -extending along [001] (Fig. 1). The coordination polyhedron around the Pb atom is a square antiprism with four short Pb—F bonds and four longer Pb—I bonds (Fig. 2). In contrast to the other lead halide fluorides, PbFCl and PbFBr, where an appreciable interaction between the metal atom and the neighbouring halide layers was observed (and which results in a [4 + 4+1] coordination with a monocapped square antiprism as corresponding coordination figure) only very weak interactions between the Pb atom and the more distant iodine layers [d(Pb—I) ca 4.4 Å] can be found. Between two adjacent iodine layers [distance layer-layer = 2.8681 Å, d(I—I) within a layer = 4.2374 (3) Å, d(I—I) between two I atoms of different layers = 4.1478 (17) Å] only van der Waals interactions stabilize the structure. This corresponds to the very easy cleavage of the crystals along [001].
The presented single-crystal results are in good agreement with the results obtained from powder data (Haberkorn, 1988).