The Family of MII3(TeIVO3)2(OH)2 (M = Mg, Mn, Co, Ni) Compounds—Prone to Inclusion of Foreign Components into Large Hexagonal Channels
Abstract
:1. Introduction
2. Materials and Methods
2.1. Synthesis
2.2. Diffraction Measurements and Crystal-Structure Refinements
2.3. Energy-Dispersive X-ray Spectrometry (EDS)
2.4. Raman Spectroscopy
3. Results and Discussion
3.1. Synthesis
3.2. Crystal Structures
3.3. EDS
3.4. Raman Spectroscopy
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Batch | Educts | Molar Ratios | Reaction Medium | Duration/d; Temperature/°C |
---|---|---|---|---|
1 * | CoSO4·7H2O, TeO2, KOH | 3:2:9 | water | 7; 210 |
2 * | Co(NO3)2·6H2O, TeO2, KOH | 3:2:9 | water | 7; 210 |
3 * | MnCO3, TeO2, KOH | 1:1:4 | water | 7; 210 |
4 | MnCO3, TeO2, NaOH | 1:1:4 | water | 7; 210 |
5 * | MnSO4·H2O, TeO2, KOH, K2CO3 | 1:1:4:2 | water | 7; 210 |
6 | MnSO4·H2O, TeO2, KOH | 1:1:4 | water | 7; 210 |
7 * | MnSO4·H2O, TeO2, NaOH | 1:1:4 | water | 7; 210 |
8 * | MnCl2·4H2O, TeO2, NaOH | 1:1:4 | water | 7; 210 |
9 * | MnBr2, TeO2, NaOH | 1:1:4 | water | 7; 210 |
10 * | MnSO4·H2O, TeO2 | 3:1 | ammonia | 5; 210 |
11 * | NiSO4·6H2O, TeO2 | 3:1 | ammonia | 5; 210 |
12 * | CoSeO4·5H2O, TeO2 | 3:1 | ammonia | 5; 210 |
13 * | NiO, Fe(NO3)3·9H2O, Mg(OH)2, TeO2 | 1:1:1:1 | water | 68; 200 |
Empirical Formula | H2Mn3O8Te2 | H1.70Mn3O8.30 S0.15Te2 | Br0.18H1.82Mn3 O7.82Te2 | H1.60Mg3O8.40 S0.20Te2 | Co3H1.64O8.36Se0.58 Te1.60 | H1.60Ni3O8.40S0.20Te2 |
---|---|---|---|---|---|---|
Structural Formula | Mn3(TeO3)2(OH)1.5{(OH)0.5} | Mn3(TeO3)2(OH)1.5{(SO4)0.15(OH)0.20} | Mn3(TeO3)2(OH)1.5{Br0.18(OH)0.32} | Mg3(TeO3)2(OH)1.5{(SO4)0.2(OH)0.1} | Co3(TeO3)1.6(SeO3)0.4-(OH)1.5{(SeO4)0.18(OH)0.14} | Ni3(TeO3)2(OH)1.5 {(SO4)0.2(OH)0.1} |
Obtained from batch | 5 | 7 | 9 | 13 | 12 | 11 |
Mr | 550.04 | 559.34 | 561.15 | 470.68 | 562.10 | 573.89 |
Temp./°C | −173 | 23 | 23 | 23 | 25 | −173 |
Cryst. dim./ mm3 | 0.09 × 0.04 × 0.03 | 0.11 × 0.02 × 0.02 | 0.12 × 0.02 × 0.02 | 0.30 × 0.01 × 0.01 | 0.09 × 0.01 × 0.01 | 0.05 × 0.01 × 0.01 |
Cryst. colour | light-yellow | light-yellow | light-yellow | colourless | blue | yellow |
Cryst. form | prism | prism | prism | prism | lath | lath |
Space group, No. | P63mc, 186 | P63mc, 186 | P63mc, 186 | P63mc, 186 | P63mc, 186 | P63mc, 186 |
Formula units Z | 4 | 4 | 4 | 4 | 4 | 4 |
a/Å | 13.410(4) | 13.4509(4) | 13.4389(2) | 13.0705(15) | 13.0390(7) | 12.9703(7) |
c/Å | 5.1393(17) | 5.1410(2) | 5.16780(10) | 5.0381(6) | 5.0199(4) | 4.9441(3) |
V/Å3 | 800.3(6) | 805.53(6) | 808.28(3) | 745.39(19) | 739.12(10) | 720.31(9) |
μ/mm−1 | 11.815 | 11.784 | 12.571 | 8.156 | 15.704 | 15.778 |
X-ray density/g·cm−3 | 4.565 | 4.612 | 4.611 | 4.194 | 5.051 | 5.292 |
θmin–θmax/° | 3.509–32.066 | 3.029–34.991 | 1.750–33.182 | 1.799–32.518 | 3.125–25.429 | 3.141–30.986 |
h range | −20–20 | −20–21 | −16–19 | −19–19 | −14–15 | −17–18 |
k range | −20–20 | −21–13 | −20–20 | −19–19 | −15–15 | −18–18 |
l range | −7–7 | −8–8 | −7–7 | −7–7 | −6–6 | −7–7 |
Measured refl. | 14,498 | 19,118 | 10,425 | 13,504 | 5006 | 6453 |
Independent refl. | 1041 | 1300 | 1131 | 1006 | 516 | 858 |
Observed refl. (I > 2σ(I)) | 992 | 1245 | 1059 | 856 | 455 | 794 |
Rint | 0.0553 | 0.0443 | 0.0621 | 0.0978 | 0.0972 | 0.0809 |
Tmin; Tmax | 0.5435; 0.7463 | 0.2816; 0.3604 | 0.5354; 0.7862 | 0.5652; 0.7464 | 0.4717; 0.7452 | 0.5554; 0.7462 |
No. of parameters | 51 | 57 | 54 | 54 | 42 | 53 |
Flack parameter [24,25] | 0.00(3) using 430 quotients | −0.01(2) using 547 quotients | −0.13(9) using 462 quotients | 0.02(4) using 344 quotients | 0.07(11) | 0.01(5) using 330 quotients |
R1 (F2 > 2σ(F2)) | 0.0201 | 0.0149 | 0.0317 | 0.0364 | 0.0337 | 0.0328 |
wR2(F2 all) | 0.0472 | 0.0351 | 0.0784 | 0.0855 | 0.0807 | 0.0707 |
GOF | 1.118 | 1.044 | 1.072 | 1.066 | 1.055 | 1.059 |
CSD-deposition code | 2,203,365 | 2,203,363 | 2,203,360 | 2,203,368 | 2,203,369 | 2,203,367 |
Mn3(TeO3)2(OH)1.5(OH)0.5 | Mn3(TeO3)2(OH)1.5-{(SO4)0.15(OH)0.20} | Mn3(TeO3)2(OH)1.5-{Br0.18(OH)0.32} | |
M1—O2 | 2.113(4) | 2.122(3) | 2.137(7) |
M1—O1 | 2.119(3) | 2.137(2) | 2.142(5) |
M1—O3 | 2.169(4) | 2.171(3) | 2.175(7) |
M1—O2 | 2.201(4) | 2.217(2) | 2.227(6) |
M1—O4 | 2.219(4) | 2.218(3) | 2.231(6) |
M1—O4 | 2.347(4) | 2.339(3) | 2.333(6) |
Te1—O2 (2×) | 1.877(4) | 1.874(2) | 1.871(6) |
Te1—O1 | 1.910(5) | 1.883(4) | 1.898(9) |
Te2—O3 (3×) | 1.854(6) | 1.852(4) | 1.851(9) |
O4—H1 | 0.87(3) | 0.97(3) | 1.0(3) |
H1—O4 · O3 | 3.111(10) | 3.124(9) | 3.122(11) |
Mg3(TeO3)2(OH)1.5-{(SO4)0.2(OH)0.1} | Co3(TeO3)1.6(SeO3)0.4-(OH)1.5{(SeO4)0.18(OH)0.14} | Ni3(TeO3)2(OH)1.5-{(SO4)0.2(OH)0.1} | |
M1—O2 | 2.031(8) | 2.035(11) | 2.014(8) |
M1—O1 | 2.060(6) | 2.097(9) | 2.065(5) |
M1—O3 | 2.049(9) | 2.097(11) | 2.040(8) |
M1—O2 | 2.090(7) | 2.085(10) | 2.032(7) |
M1—O4 | 2.130(9) | 2.157(12) | 2.124(7) |
M1—O4 | 2.240(9) | 2.220(12) | 2.172(8) |
Te1—O2 (2×) | 1.880(6) | 1.851(10) | 1.885(7) |
Te1—O1 | 1.866(10) | 1.862(17) | 1.912(11) |
Te2—O3 (3×) | 1.832(11) | 1.750(15) | 1.886(10) |
O4—H1 | — | — | — |
H1—O4 · O3 | — | — | — |
Batch | M | Possible Inclusions | Measurement | T/°C | a/Å | c/Å | V/Å3 |
---|---|---|---|---|---|---|---|
1 | Co | SO42−, OH− | powder | 25 | 13.1146(7) | 5.0475(3) | 751.8 |
single-crystal | −173 | 13.1102(7) | 5.0179(4) | 746.9 | |||
1 * | powder | 25 | 13.1186(7) | 5.0335(3) | 750.2 | ||
2 | Co | NO3−, OH− | powder | 25 | 13.1126(7) | 5.0452(3) | 751.3 |
single-crystal | −173 | 13.0907(4) | 5.02810(10) | 746.2 | |||
2 * | powder | 25 | 13.1127(8) | 5.0394(3) | 750.4 | ||
3 | Mn | CO32−, OH− | powder | 25 | 13.42771(15) | 5.16593(7) | 806.7 |
single-crystal | −173 | 13.3999(4) | 5.1359(2) | 798.6 | |||
4 | Mn | CO32−, OH− | powder | 25 | 13.4171(3) | 5.16516(11) | 805.3 |
5 | Mn | SO42−, CO32−, OH− | powder | 25 | 13.4271(3) | 5.16877(10) | 807.0 |
single-crystal | −173 | 13.4082(5) | 5.1371(3) | 799.8 | |||
single-crystal | −173 | 13.410(4) | 5.1393(17) | 800.5 | |||
6 | Mn | SO42−, OH− | powder | 25 | 13.4779(2) | 5.16844(10) | 813.1 |
7 | Mn | SO42−, OH− | powder | 25 | 13.4902(5) | 5.1673(2) | 814.4 |
single-crystal | −173 | 13.4216(7) | 5.1712(4) | 806.7 | |||
8 | Mn | Cl−, OH− | powder | 25 | 13.4206(2) | 5.17517(8) | 807.2 |
single-crystal | 25 | 13.4364(4) | 5.1738(3) | 808.9 | |||
9 | Mn | Br−, OH− | powder | 25 | 13.4383(2) | 5.17202(8) | 808.9 |
single-crystal | 25 | 13.4389(2) | 5.16780(10) | 808.3 | |||
Co3(TeO3)2(OH)2 [23] | OH− | single-crystal | 25 | 13.034(6) | 5.016(3) | 738.0 | |
Co3(TeO3)2(OH)2-·~0.45H2O [28] | OH−, H2O | single-crystal | 25 | 13.164(1) | 5.0321(6) | 755.2 |
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Eder, F.; Weil, M.; Missen, O.P.; Kolitsch, U.; Libowitzky, E. The Family of MII3(TeIVO3)2(OH)2 (M = Mg, Mn, Co, Ni) Compounds—Prone to Inclusion of Foreign Components into Large Hexagonal Channels. Crystals 2022, 12, 1380. https://doi.org/10.3390/cryst12101380
Eder F, Weil M, Missen OP, Kolitsch U, Libowitzky E. The Family of MII3(TeIVO3)2(OH)2 (M = Mg, Mn, Co, Ni) Compounds—Prone to Inclusion of Foreign Components into Large Hexagonal Channels. Crystals. 2022; 12(10):1380. https://doi.org/10.3390/cryst12101380
Chicago/Turabian StyleEder, Felix, Matthias Weil, Owen P. Missen, Uwe Kolitsch, and Eugen Libowitzky. 2022. "The Family of MII3(TeIVO3)2(OH)2 (M = Mg, Mn, Co, Ni) Compounds—Prone to Inclusion of Foreign Components into Large Hexagonal Channels" Crystals 12, no. 10: 1380. https://doi.org/10.3390/cryst12101380