Crystal system: trigonal
| a: | 8.9817 (±0.0013) Å |
| b: | 8.9817 (±0.0013) Å |
| c: | 11.006 (±0.002) Å |
| α: | 90° |
| β: | 90° |
| γ: | 120° |
Starting materials: HC(NH2)2I, PbI2,distilled HI (57% aqueous) (99.95%), H3PO2 (50% aqueous)
Product: Black FAPbI3 Crystals (alpha phase)
Description: Charge 100 ml 2-necked round bottom flask with a mixture of aqueous HI (6.8 ml, 7.58M) and aqueous H3PO2 (1.7 ml, 9.14M). The liquid was degassed by passing a stream of nitrogen through it for 1 min and keeping it under a nitrogen atmosphere throughout the experiment. Dissolve PbI2 (462 mg, 1 mmol) in the mixture upon heating the flask to 120 °C using an oil bath, under constant magnetic stirring, forming a bright yellow solution. Add solid HC(NH2)2I (172 mg, 1 mmol). Evaporate solution to approximately half its original volume by heating at 120 °C. Stop stirring and leave the solution to evaporate at 100 °C. Black hexagonal (8 faces) or trigonal (5 faces) crystals of the title compound were precipitated and grown at this temperature. After standing for 2-3 h at 100 °C, under a nitrogen atmosphere, set the temperature to 80 °C for a further 2-3 h. Repeat the previous step for two more times to reach 60 °C and 40 °C at which point the solution was left to come to room temperature by powering off the hotplate. The crystals were collected by filtration and washed with anhydrous EtOH.
Method: Single crystal X-ray diffraction
Description: Single-crystal X-ray diffraction experiments were performed using either an STOE IPDS II or IPDS 2T diffractometer using Mo Kα radiation (λ = 0.71073 Å) and operating at 50 kV and 40 mA. Integration and numerical absorption corrections were performed using the X-AREA, X-RED, and X-SHAPE programs. Refer to page 9025 Table 1.
Comment: This compound was assigned the trigonal space group P3m1 in the original publication (doi: 10.1021/ic401215x) and this assignment is therefore retained here. However, the literature consensus for the alpha phase of formamidinium, including a later report by some of the same authors (https://doi.org/10.1002/anie.201609538), is that the compound crystallizes in the cubic space group Pm-3m. Those later reports are considered more accurate.
Crystal system: trigonal
| a: | 17.7914 (±0.0008) Å |
| b: | 17.7914 (±0.0008) Å |
| c: | 10.9016 (±0.0006) Å |
| α: | 90° |
| β: | 90° |
| γ: | 120° |
Starting materials: HC(NH2)2I, PbI2, distilled HI 57% aqueous (99.95%), H3PO2 (50% aqueous)
Product: Black FAPbI3 Crystals (alpha phase)
Description: Charge 100 ml 2-necked round bottom flask with a mixture of aqueous HI (6.8 ml, 7.58M) and aqueous H3PO2 (1.7 ml, 9.14M). The liquid was degassed by passing a stream of nitrogen through it for 1 min and keeping it under a nitrogen atmosphere throughout the experiment. Dissolve PbI2 (462 mg, 1 mmol) in the mixture upon heating the flask to 120 °C using an oil bath, under constant magnetic stirring, forming a bright yellow solution. Add solid HC(NH2)2I (172 mg, 1 mmol). Evaporate solution to approximately half its original volume by heating at 120 °C. Stop stirring and leave solution to evaporate at 100 °C. Black hexagonal (8 faces) or trigonal (5 faces) crystals of the title compound were precipitated and grown at this temperature. After standing for 2-3 h at 100 °C, under a nitrogen atmosphere, set temperature to 80 °C for a further 2-3 h. Repeat the previous step for two more times to reach 60 °C and 40 °C at which point the solution was left to come to room temperature by powering off the hotplate. The crystals were collected by filtration and washed with anhydrous EtOH.
Method: Single crystal X-ray diffraction
Description: Single-crystal X-ray diffraction experiments were performed using either a STOE IPDS II or IPDS 2T diffractometer using Mo Kα radiation (λ = 0.71073 Å) and operating at 50 kV and 40 mA. Integration and numerical absorption corrections were performed using the X-AREA, X-RED, and X-SHAPE programs. Refer to Page 9025 Table 2.
Crystal system: hexagonal
| a: | 8.6603 (±0.0014) Å |
| b: | 8.6603 (±0.0014) Å |
| c: | 7.9022 (±0.0006) Å |
| α: | 90° |
| β: | 90° |
| γ: | 120° |
Starting materials: HC(NH2)2I, PbI2, distilled HI 57% (99.95%), H3PO2 50%
Product: Yellow FAPbI3 Crystals (delta phase)
Description: Charge 100 ml 2-necked round bottom flask with a mixture of aqueous HI (6.8 ml, 7.58M) and aqueous H3PO2 (1.7 ml, 9.14M). The liquid was degassed by passing a stream of nitrogen through it for 1 min and keeping it under a nitrogen atmosphere throughout the experiment. Dissolve PbI2 (462 mg, 1 mmol) in the mixture upon heating the flask to 120 °C using an oil bath, under constant magnetic stirring, forming a bright yellow solution. Add solid HC(NH2)2I (172 mg, 1 mmol). Evaporate solution to approximately half its original volume by heating at 120 °C. Stop stirring and leave solution to evaporate at 100 °C. Black hexagonal (8 faces) or trigonal (5 faces) crystals of the title compound were precipitated and grown at this temperature. Discontinue heating and cool the mixture to room temperature. After 4-5 h the black crystals fully convert to yellow ones of essentially the same shape. Collect yellow crystals by filtration and wash copiously with anhydrous EtOH. Yield 50-60%. The crystals are insensitive on exposure to the atmosphere but spontaneously hydrolyse to yellow PbI2 upon wetting in H2O.
Method: Single crystal X-ray diffraction
Description: Single-crystal X-ray diffraction experiments were performed using either a STOE IPDS II or IPDS 2T diffractometer using Mo Kα radiation (λ = 0.71073 Å) and operating at 50 kV and 40 mA. Integration and numerical absorption corrections were performed using the X-AREA, X-RED, and X-SHAPE programs. Refer to Page 9025 Table 3.
Crystal system: cubic
| a: | 6.362 (±0.0008) Å |
| b: | 6.362 (±0.0008) Å |
| c: | 6.362 (±0.0008) Å |
| α: | 90° |
| β: | 90° |
| γ: | 90° |
Starting materials: Lead acetate trihydrate, HI, H3PO2, formamidinium acetate
Product: FAPbI3 Crystals (alpha phase)
Description: 6.000g of lead acetate trihydrate added to flask with reflux condenser containing 12.4mL HI and 3.1 mL H3PO2. Then, 1.647g of formamidinium acetate was heated with solution to 100°C and left to cool, forming crystals. Crystals were then filtered and washed with dry diethyl ether and heated to 130°C for two hours.
Method: Powder X-ray diffraction (PXRD)
Description: Patterns collected on Siemens / Bruker D5000 diffractometer using Cu Ka radiation (λ = 0.15418 nm).
Comment: This compound was assigned the trigonal space group P3m1 in the original publication (doi: 10.1021/ic401215x) and this assignment is therefore retained here. However, the literature consensus for the alpha phase of formamidinium, including a later report by some of the same authors (https://doi.org/10.1002/anie.201609538), is that the compound crystallizes in the cubic space group Pm-3m. Those later reports are considered more accurate.
Crystal system: cubic
| a: | 6.357878 (±4e-06) Å |
| b: | 6.357878 (±4e-06) Å |
| c: | 6.357878 (±4e-06) Å |
| α: | 90° |
| β: | 90° |
| γ: | 90° |
Crystal system: cubic
| a: | 6.372556 (±4e-06) Å |
| b: | 6.372556 (±4e-06) Å |
| c: | 6.372556 (±4e-06) Å |
| α: | 90° |
| β: | 90° |
| γ: | 90° |
Crystal system: cubic
| a: | 6.384013 (±4e-06) Å |
| b: | 6.384013 (±4e-06) Å |
| c: | 6.384013 (±4e-06) Å |
| α: | 90° |
| β: | 90° |
| γ: | 90° |
Crystal system: cubic
| a: | 6.394969 (±4e-06) Å |
| b: | 6.394969 (±4e-06) Å |
| c: | 6.394969 (±4e-06) Å |
| α: | 90° |
| β: | 90° |
| γ: | 90° |
Crystal system: cubic
| a: | 6.40223 (±4e-06) Å |
| b: | 6.40223 (±4e-06) Å |
| c: | 6.40223 (±4e-06) Å |
| α: | 90° |
| β: | 90° |
| γ: | 90° |
Starting materials: PbO, concentrated aqueous HI (57 % w/w), (HC(NH2)2)(O2CCH3) [OR HC(NH2)2Cl], HCl (37 % w/w), HCl (37 % w/w)
Product: HC(NH2)2PbI3 Powder
Description: "3 4.46 g (20 mmol) of PbO was dissolved in 15 mL of concentrated aqueous HI (57 % w/w) and the solution temperature was raised and held to boiling (ca. 130 °C). In a separate beaker, 2.08 g (20 mmol) of (HC(NH2)2)(O2CCH3) or 1.61 g (20 mmol) of freshly prepared HC(NH2)2Cl (prepared from (HC(NH2)2)(O2CCH3) and concentrated HCl (37 % w/w), followed by copious washing with toluene to remove excess acetic acid)4 were dissolved in 5 mL of concentrated aqueous HI (57 % w/w). The latter step was found to be necessary since commercially available HC(NH2)2Cl is extremely hygroscopic and contains hydrolysis products. Addition of the HC(NH2)2I solution to the PbI2 solution resulted immediately in a fine black precipitate. The reaction was stopped after 5 min and the solution was filtered hot under vacuum to avoid co-precipitation of hydrated phases obtained for the cooled solution. During filtration, the black solid turns to yellow, completely converting over a period of 5 to 10 min. The yellow solid was transferred in a vacuum oven and heated at 120° C overnight, yielding a black solid that is stable for a period of 20 to 30 days before converting back to the yellow phase. Note that if the latter step is performed in an evacuated ampule under static vacuum, the black phase converts to the yellow one within 5 to 10 min. The obtained black material consists of the crystallographically pure α-phase of HC(NH2)2PbI3. Yield: 9 to 10 g (70 % to 80 %)."
Method: Powder X-ray diffraction (PXRD)
Description: "High resolution synchrotron X-ray powder diffraction data were collected using beamline 11-BM at the Advanced Photon Source (APS), Argonne National Laboratory at a wavelength of 0.459200 Å. 50 mg of ground, yellow HC(NH2)2PbI3 was packed and sealed into a 0.5 mm OD Kapton capillary."
Comment: This is the paper referenced in this comment from dataset 2514: "However, the literature consensus for the alpha phase of formamidinium, including a later report by some of the same authors (https://doi.org/10.1002/anie.201609538), is that the compound crystallizes in the cubic space group Pm-3m. Those later reports are considered more accurate."