Mineral-like Synthetic Compounds Stabilized under Hydrothermal Conditions: X-ray Diffraction Study and Comparative Crystal Chemistry
Abstract
:1. Introduction
2. Materials and Methods
2.1. Hydrothermal Synthesis
2.2. X-ray Spectral Analysis
2.3. Single-Crytsal X-ray Diffraction
3. Results and Discussion
3.1. Chemical Composition
3.2. Crystal Structure Solution
3.3. Na2CoSiO4, a Structural Analog of the Mineral Liberite
3.3.1. The Structural Description and Analysis of Interatomic Distances
3.3.2. Na2CoSiO4 and the Liberite Structural Family of Ionic Conductors
3.4. Na2Cu3O(Cu0.8Na0.2)(PO4)2Cl with Oxo-Centered Pyroxene-like Chains
3.4.1. Analysis of Interatomic Distances and Description of the Crystal Structure
3.4.2. Na2Cu3O(Cu0.8Na0.2)(PO4)2Cl in the Series of Compounds with Oxo-Centered Pyroxene-like Chains
3.5. Mineralogically Probable Na3V(OH)(HPO4)(PO4)
3.5.1. Description of Crystal Structure and Analysis of Interatomic Distances
3.5.2. Magnetic Properties of Na3V(OH)(HPO4)(PO4)
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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(I) | (II) | (III) |
---|---|---|
Na2CoSiO4 | Na2(Cu+0.8Na0.2)Cl[Cu2+3O(PO4)2] | Na3V(OH)(HPO4)(PO4) |
T 450 °C, P 500 atm | T 450 °C, P 500 atm | T 270 °C, P 70 atm |
2 g CoCl2 (15.4 mmol) 1 g SiO2 (16.7 mmol) NaOH solution | 3 g CuCl2 (22.3 mmol) 1 g CuCl (10.1 mmol) 2 g (12.2 mmol) Na3PO4 HCl solution | 1 g V2O3 (6.6 mmol) 2 g Na3PO4 (12 mmol) 0.2 g Li2CO3 (3 mmol) H2O |
pH 12 | pH 1.5 | pH 3 |
Copper-lined chrome-nickel autoclave, V 14 mL Autoclave filling 50% | Copper-lined chrome-nickel autoclave, V 14 mL Autoclave filling 50% | Steel autoclave lined with fluoroplastic, V 7 mL Autoclave filling 72% |
Structural Formula | (I) | (II) | (III) |
---|---|---|---|
Na2CoSiO4 | Na2Cu3O(Cu0.8Na0.2)(PO4)2Cl | Na3V(OH)(HPO4)(PO4) | |
Mr | 197.00 | 531.00 | 327.87 |
Space group, Z | Pn, 2 | Cmcm, 4 | C2/m, 4 |
Temperature (K) | 170 | 150 | 293 |
Unit cell parameters a, b, c (Å) | 5.2271(5) | 13.6243(2) | 15.4157(10) |
5.4198(4) | 10.3531(2) | 7.3107(4) | |
7.0466(6) | 6.3586(1) | 7.0556(4) | |
β (°) | 90.011(7) | 90 | 96.702(6) |
V (Å3) | 199.63(3) | 896.90(3) | 789.73 (8) |
Radiation | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 4.69 | 9.56 | 1.86 |
Crystal size (mm) | 0.15 × 0.06 × 0.02 | 0.17 × 0.11 × 0.07 | 0.19 × 0.09 × 0.06 |
Diffractometer | Oxford Diffraction Gemini | Xcalibur Sapphire3 | |
Number of reflections: measured independently based on [I > 2σ(I)] | 1800, 909, 894 | 8798, 732, 727 | 1352, 1352, 1043 |
Rint | 0.016 | 0.016 | - |
(sin θ/λ)max (Å−1) | 0.703 | 0.703 | 0.594 |
R [F2 > 2σ(F2)], wR(F2), S | 0.025, 0.064, 1.03 | 0.018, 0.046, 1.29 | 0.043, 0.109, 1.03 |
Number of refined parameters | 74 | 57 | 91 |
Δρmax, Δρmin (e Å−3) | 0.46, −0.45 | 0.74, −0.91 | 0.64, −0.57 |
Flack parameter * | 0.01(3) * | - | - |
Co–Tetrahedron | Si–Tetrahedron | ||
Co–O2 | 1.928(6) | Si1–O4 | 1.618(8) |
–O3 | 1.944(5) | –O3 | 1.627(4) |
–O1 | 1.958(4) | –O1 | 1.631(7) |
–O4 | 1.969(5) | –O2 | 1.644(8) |
<Co–O> | 1.95 | <Si–O> | 1.63 |
Na1–Tetrahedron | Na2–Tetrahedron | ||
Na1–O2 | 2.245(10) | Na2–O2 | 2.325(6) |
–O3 | 2.272(10) | –O4 | 2.344(12) |
–O4 | 2.279(5) | –O1 | 2.364(11) |
–O1 | 2.331(10) | –O3 | 2.407(10) |
<Na1–O> | 2.28 | <Na2–O> | 2.36 |
Na1 | Na2 | Co | Si | Σ | |
---|---|---|---|---|---|
O1 | 0.203, 0.052 | 0.189 | 0.487 | 0.981 | 1.91 |
O2 | 0.242 | 0.205 | 0.528 | 0.947 | 1.92 |
O3 | 0.229 | 0.173, 0.061 | 0.506 | 0.992 | 1.96 |
O4 | 0.226 | 0.197 | 0.473 | 1.016 | 1.91 |
Σ | 0.95 | 0.83 | 1.99 | 3.94 |
Cu1 Octahedron | Cu2 Tetragonal Pyramid | Cu3 * Trigonal Bipyramid | |||
Cu1–O3 × 2 | 1.852(1) | Cu2–O3 | 1.911(2) | Cu3–O2 × 2 | 2.032(2) |
–O4 × 4 | 2.254(2) | –O1 | 1.921(2) | –Cl | 2.394(5) |
–O4 × 2 | 2.022(2) | –Cl × 2 | 3.1875(1) | ||
<Cu1–O> | 2.12 | –Cl1 | 2.5789(8) | ||
<Cu2–O> | 1.97 | <Cu3–O> | 2.03 | ||
Na Octahedron | P Tetrahedron | ||||
Na–O2 × 2 | 2.309(2) | P–O2 | 1.532(2) | ||
–O1 × 2 | 2.460(2) | –O1 | 1.544(2) | ||
–O4 × 2 –Cl × 2 | 2.884(2) 3.270(2) | –O4 × 2 | 1.544(2) | ||
<Na–O> | 2.55 | <P–O> | 1.54 |
Cu1 | Cu2 | Cu3 ** | P | Na | ∑ | |
---|---|---|---|---|---|---|
O1 | 0.520 | 1.212 | 0.155 ×2↓ ×2→ | 2.04 | ||
O2 | 0.182 ×2↓ | 1.251 | 0.212 ×2↓ ×2→ | 1.98 | ||
O3 | 0.626 ×2↓ ×2→ | 0.534 ×2→ | 2.32 | |||
O4 | 0.212 ×4↓ | 0.395 ×2↓ | 1.213 ×2↓ | 0.064×2↓ | 1.88 | |
Cl | 0.209 ×2→ | 0.144 0.02 ×2↓ ×2→ | 0.073 ×2↓ ×4→ | 1.04 | ||
∑ | 2.10 | 2.05 | 0.95 | 4.89 | 1.01 |
D–H···A | D–H, Å | H···A, Å | D···A, Å | D–H···A, ° |
---|---|---|---|---|
O1–H1···O6 | 0.82(1) | 1.80(2) | 2.616(7) | 172(9) |
O2–H2···O1 | 0.82(1) | 2.53(3) | 3.319(7) | 164(8) |
V-Centered Octahedron | P1–Tetrahedron | P2–Tetrahedron | |||
V–O3 –O3 –O4 –O4 –O2 –O2 <V–O> | 1.966(3) 1.966(3) 2.020(3) 2.020(3) 2.039(2) 2.039(2) 2.008 | P1–O6 –O4 –O4 –O1 <P1–O> | 1.526(5) 1.538(3) 1.538(3) 1.582(5) 1.544 | P2–O5 –O7 –O3 –O3 <P2–O> | 1.508(5) 1.510(5) 1.558(3) 1.558(3) 1.534 |
Na1–Octahedron | Na2–Polyhedron | Na3–Octahedron | |||
Na1–O5 –O5 –O4 –O4 –O1 –O1 <Na1–O> | 2.259(3) 2.259(3) 2.448(3) 2.448(3) 2.747(4) 2.747(4) 2.485 | Na2–O7 –O5 –O2 –O4 –O4 <Na2–O> | 2.175(6) 2.238(6) 2.435(5) 2.550(3) 2.550(3) 2.390 | Na2–O3 –O3 –O6 –O6 –O7 –O7 <Na3–O> | 2.427(3) 2.427(3) 2.460(4) 2.460(4) 2.482(4) 2.482(4) 2.456 |
Na1 | Na2 | Na3 | V | P1 | P2 | H1 | H2 | Σ | |
---|---|---|---|---|---|---|---|---|---|
O1 | 0.086 ×2↓ ×2→ | 1.093 | 0.71 | 0.06 | 2.04 | ||||
O2 | 0.163 | 0.449 ×2↓ ×2→ | 0.94 | 2.00 | |||||
O3 | 0.166 ×2↓ | 0.547 ×2↓ | 1.167 ×2↓ | 1.88 | |||||
O4 | 0.159 ×2↓ | 0.129 ×2↓ | 0.473 ×2↓ | 1.231 ×2↓ | 1.99 | ||||
O5 | 0.235 ×2↓ ×2→ | 0.246 | 1.335 | 2.05 | |||||
O6 | 0.155 ×2↓ ×2→ | 1.272 | 0.29 | 1.87 | |||||
O7 | 0.28 | 0.148 ×2↓ ×2→ | 1.328 | 1.90 | |||||
Σ | 0.96 | 0.95 | 0.94 | 2.94 | 4.83 | 5.00 | 1 | 1 |
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Share and Cite
Kiriukhina, G.; Yakubovich, O.; Verchenko, P.; Volkov, A.; Shvanskaya, L.; Dimitrova, O.; Simonov, S. Mineral-like Synthetic Compounds Stabilized under Hydrothermal Conditions: X-ray Diffraction Study and Comparative Crystal Chemistry. Minerals 2024, 14, 46. https://doi.org/10.3390/min14010046
Kiriukhina G, Yakubovich O, Verchenko P, Volkov A, Shvanskaya L, Dimitrova O, Simonov S. Mineral-like Synthetic Compounds Stabilized under Hydrothermal Conditions: X-ray Diffraction Study and Comparative Crystal Chemistry. Minerals. 2024; 14(1):46. https://doi.org/10.3390/min14010046
Chicago/Turabian StyleKiriukhina, Galina, Olga Yakubovich, Polina Verchenko, Anatoly Volkov, Larisa Shvanskaya, Olga Dimitrova, and Sergey Simonov. 2024. "Mineral-like Synthetic Compounds Stabilized under Hydrothermal Conditions: X-ray Diffraction Study and Comparative Crystal Chemistry" Minerals 14, no. 1: 46. https://doi.org/10.3390/min14010046