Twinning, Superstructure and Chemical Ordering in Spryite, Ag8(As3+0.50As5+0.50)S6, at Ultra-Low Temperature: An X-Ray Single-Crystal Study
Abstract
:1. Introduction
2. X-ray Crystallography
3. Description of the Low-Temperature Structure and Discussion
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Spryite | |
---|---|
Temperature | 30(2) K |
Wavelength | 0.71073 Å |
Crystal system | Orthorhombic |
Space group | Pna21 |
Unit cell dimensions | a = 14.866(2) Å |
b = 22.240(4) Å | |
c = 10.3940(10) Å | |
Volume | 3436.5(8) Å3 |
Z | 4 |
Density (calculated) | 6.549 Mg/mm3 |
Crystal size | 0.040 × 0.030 × 0.020 mm3 |
Theta range for data collection | 4.78 to 30.00° |
h,k,l ranges | −20 ≤ h ≤ 20, −31 ≤ k ≤ 31, −14 ≤ l ≤ 14 |
Reflections collected | 38705 |
Independent reflections | 4705 [Rint = 0.0355] |
Data/restraints/parameters | 4705/1/408 |
Goodness of fit on F2 | 1.052 |
Final R indices [Fo > 4σ(Fo)] | R1 = 0.0329, wR2 = 0.0670 |
R indices (all data) | R1 = 0.0346, wR2 = 0.0678 |
Extinction coefficient | 0.000301(17) |
Largest diff. peak and hole | 1.90 and −1.67 e.Å-3 |
Twin matrices (referred to the orthorhombic cell) | |
Twin fractions | 0.28(3), 0.20(2), 0.16(2), 0.14(2), 0.12(2), 0.10(2) |
Site | x/a | y/b | z/c | Ueq |
---|---|---|---|---|
Ag1A | 0.1257(3) | 0.07361(17) | 0.3742(5) | 0.0383(5) |
Ag1B | 0.1269(2) | 0.40562(13) | 0.3764(4) | 0.0359(4) |
Ag1C | 0.1269(4) | 0.7341(3) | 0.3739(6) | 0.0393(6) |
Ag2A | 0.06183(4) | 0.07485(2) | 0.83671(6) | 0.02599(11) |
Ag2B | 0.05993(4) | 0.40511(2) | 0.83817(6) | 0.02494(11) |
Ag2C | 0.06321(3) | 0.73552(2) | 0.83630(6) | 0.02402(11) |
Ag3A | 0.43197(5) | 0.02050(3) | 0.01921(7) | 0.03304(14) |
Ag3B | 0.43246(4) | 0.35041(3) | 0.01990(7) | 0.02850(13) |
Ag3C | 0.43262(5) | 0.68067(4) | 0.01956(9) | 0.03866(17) |
Ag4A | 0.2768(4) | 0.1662(3) | 0.0834(8) | 0.0290(10) |
Ag4B | 0.27687(4) | 0.50675(14) | 0.08245(6) | 0.0286(4) |
Ag4C | 0.2770(5) | 0.8364(4) | 0.0819(9) | 0.0391(16) |
Ag5A | 0.41845(5) | 0.03021(3) | 0.69619(9) | 0.03584(14) |
Ag5B | 0.41848(4) | 0.36017(3) | 0.69717(8) | 0.03396(13) |
Ag5C | 0.41868(4) | 0.70034(3) | 0.69693(7) | 0.02805(12) |
Ag6A | 0.27281(4) | 0.12823(3) | 0.68399(7) | 0.02865(12) |
Ag6B | 0.27274(5) | 0.46785(3) | 0.68435(9) | 0.03504(13) |
Ag6C | 0.27304(4) | 0.79812(3) | 0.68428(7) | 0.02883(12) |
Ag7A | 0.01698(4) | 0.0045(6) | 0.60282(8) | 0.0387(10) |
Ag7B | 0.0175(4) | 0.3339(3) | 0.6021(6) | 0.0249(9) |
Ag7C | 0.0168(5) | 0.6639(3) | 0.6036(8) | 0.0351(15) |
Ag8A | 0.25877(4) | 0.04283(3) | 0.90577(8) | 0.03030(13) |
Ag8B | 0.25881(4) | 0.37291(3) | 0.90561(8) | 0.03138(13) |
Ag8C | 0.25860(4) | 0.70268(3) | 0.90549(7) | 0.02573(12) |
As5+ | 0.37565(4) | 0.07852(3) | 0.34985(10) | 0.02252(13) |
Ge | 0.37583(4) | 0.40121(3) | 0.34959(10) | 0.01968(12) |
As3+ | 0.37990(3) | 0.78942(3) | 0.29965(11) | 0.02286(12) |
S1A | 0.1227(8) | 0.1644(5) | 0.9763(8) | 0.030(3) |
S1B | 0.12244(14) | 0.5046(18) | 0.9770(3) | 0.037(3) |
S1C | 0.1221(10) | 0.8341(6) | 0.9774(13) | 0.046(4) |
S2A | −0.00394(18) | 0.09037(11) | 0.2315(3) | 0.0388(5) |
S2B | −0.00418(18) | 0.42044(11) | 0.2316(3) | 0.0380(5) |
S2C | −0.00434(16) | 0.75029(10) | 0.2313(3) | 0.0358(5) |
S3A | 0.37300(17) | 0.15601(12) | 0.4794(3) | 0.0362(5) |
S3B | 0.37279(16) | 0.48499(10) | 0.4791(3) | 0.0379(5) |
S3C | 0.37272(16) | 0.81480(14) | 0.4788(3) | 0.0327(5) |
S4A | 0.25826(17) | 0.07751(13) | 0.2306(3) | 0.0380(5) |
S4B | 0.25859(18) | 0.40740(13) | 0.2300(3) | 0.0402(5) |
S4C | 0.25859(18) | 0.73719(13) | 0.2306(3) | 0.0407(5) |
S5A | 0.3861(7) | 0.1054(4) | 0.8663(12) | 0.0334(10) |
S5B | 0.3867(9) | 0.4357(5) | 0.8691(16) | 0.0322(11) |
S5C | 0.3855(13) | 0.7631(10) | 0.879(2) | 0.0398(19) |
S6A | 0.12309(13) | 0.08887(10) | 0.6117(3) | 0.0320(4) |
S6B | 0.12280(14) | 0.42869(10) | 0.6117(3) | 0.0351(5) |
S6C | 0.12278(14) | 0.75866(10) | 0.6112(3) | 0.0337(4) |
Atoms | Distance | Atoms | Distance |
---|---|---|---|
Ag1A-S2A | 2.460(6) | Ag6A-S6A | 2.507(2) |
Ag1A-S4A | 2.474(5) | Ag6A-S4C | 2.515(3) |
Ag1A-S6A | 2.492(6) | Ag6A-S5A | 2.586(12) |
<Ag1A-S> | 2.475 | Ag6A-S3A | 2.669(3) |
Ag1B-S4B | 2.480(5) | <Ag6A-S> | 2.569 |
Ag1B-S2B | 2.484(4) | Ag6B-S6B | 2.510(2) |
Ag1B-S6B | 2.499(5) | Ag6B-S4A | 2.528(3) |
<Ag1B-S> | 2.488 | Ag6B-S3B | 2.629(3) |
Ag1C-S4C | 2.461(6) | Ag6B-S5B | 2.659(16) |
Ag1C-S2C | 2.477(7) | <Ag6B-S> | 2.582 |
Ag1C-S6C | 2.527(6) | Ag6C-S6C | 2.517(2) |
Ag1C-S5A | 2.870(12) | Ag6C-S4B | 2.521(3) |
<Ag1C-S> | 2.584 | Ag6C-S3C | 2.626(3) |
Ag2A-S6A | 2.529(3) | Ag6C-S5C | 2.74(2) |
Ag2A-S1A | 2.624(11) | <Ag6C-S> | 2.601 |
Ag2A-S5B | 2.636(13) | Ag7A-S6A | 2.453(10) |
Ag2A-S3B | 2.670(3) | Ag7A-S2A | 2.506(12) |
<Ag2A-S> | 2.615 | Ag7A-S3B | 2.511(3) |
Ag2B-S6B | 2.587(3) | <Ag7A-S> | 2.490 |
Ag2B-S5A | 2.611(11) | Ag7B-S2C | 2.313(6) |
Ag2B-S3C | 2.678(3) | Ag7B-S3A | 2.509(6) |
Ag2B-S1B | 2.80(3) | Ag7B-S6B | 2.627(6) |
<Ag2B-S> | 2.699 | <Ag7B-S> | 2.483 |
Ag2C-S3A | 2.497(3) | Ag7C-S2B | 2.307(8) |
Ag2C-S6C | 2.554(3) | Ag7C-S3C | 2.548(8) |
Ag2C-S5C | 2.68(2) | Ag7C-S6C | 2.634(7) |
Ag2C-S1C | 2.780(13) | <Ag7C-S> | 2.496 |
<Ag2C-S> | 2.628 | Ag8A-S5A | 2.384(7) |
Ag3A-S6B | 2.399(3) | Ag8A-S3B | 2.462(3) |
Ag3A-S5A | 2.560(11) | <Ag8A-S> | 2.428 |
Ag3A-S2B | 2.739(3) | Ag8B-S5B | 2.389(10) |
Ag3A-S1B | 2.919(8) | Ag8B-S3C | 2.464(3) |
<Ag3A-S> | 2.654 | <Ag8B-S> | 2.427 |
Ag3B-S6C | 2.396(3) | Ag8C-S5C | 2.33(2) |
Ag3B-S5B | 2.553(14) | Ag8C-S3A | 2.344(3) |
Ag3B-S2A | 2.732(3) | <Ag8c-S> | 2.337 |
Ag3B-S1A | 2.882(12) | As5+-S1B | 2.11(3) |
<Ag3B-S> | 2.722 | As5+-S4A | 2.141(3) |
Ag3C-S6A | 2.402(3) | As5+-S2B | 2.168(3) |
Ag3C-S5C | 2.45(2) | As5+-S3A | 2.187(3) |
Ag3C-S2C | 2.843(3) | <As5+-S> | 2.152 |
Ag3C-S1C | 2.870(15) | S1B-As5+-S4A | 111.4(4) |
<Ag3C-S> | 2.641 | S1B-As5+-S2B | 110.6(3) |
Ag4A-S4A | 2.511(8) | S4A-As5+-S2B | 110.09(12) |
Ag4A-S1A | 2.548(14) | S1B-As5+-S3A | 103.2(7) |
Ag4A-S6C | 2.557(7) | S4A-As5+-S3A | 110.48(11) |
<Ag4A-S> | 2.539 | S2B-As5+-S3A | 110.81(10) |
Ag4B-S6A | 2.375(3) | Ge-S1C | 1.998(13) |
Ag4B-S1B | 2.544(2) | Ge-S4B | 2.145(3) |
Ag4B-S4B | 2.703(4) | Ge-S2A | 2.177(3) |
<Ag4B-S> | 2.541 | Ge-S3B | 2.299(3) |
Ag4C-S1C | 2.545(18) | <Ge-S> | 2.155 |
Ag4C-S6B | 2.556(8) | S1C-Ge-S4B | 116.5(4) |
Ag4C-S4C | 2.707(10) | S1C-Ge-S2A | 115.3(5) |
<Ag4C-S> | 2.551 | S4B-Ge-S2A | 109.55(13) |
Ag5A-S1B | 2.426(10) | S1C-Ge-S3B | 102.5(4) |
Ag5A-S5A | 2.481(12) | S4B-Ge-S3B | 105.74(10) |
Ag5A-S2B | 2.778(3) | S2A-Ge-S3B | 106.06(9) |
<Ag5A-S> | 2.562 | As3+-S3C | 1.949(3) |
Ag5B-S1C | 2.433(13) | As3+-S2C | 2.061(2) |
Ag5B-S5B | 2.498(15) | As3+-S4C | 2.262(3) |
Ag5B-S2C | 2.780(2) | As3+-S3C | 1.949(3) |
<Ag5B-S> | 2.570 | <As(3)-S> | 2.055 |
Ag5C-S5C | 2.40(2) | ||
Ag5C-S1A | 2.505(9) | ||
Ag5C-S2A | 2.778(3) | ||
<Ag5C-S> | 2.561 |
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Bindi, L.; Morana, M. Twinning, Superstructure and Chemical Ordering in Spryite, Ag8(As3+0.50As5+0.50)S6, at Ultra-Low Temperature: An X-Ray Single-Crystal Study. Minerals 2021, 11, 286. https://0-doi-org.brum.beds.ac.uk/10.3390/min11030286
Bindi L, Morana M. Twinning, Superstructure and Chemical Ordering in Spryite, Ag8(As3+0.50As5+0.50)S6, at Ultra-Low Temperature: An X-Ray Single-Crystal Study. Minerals. 2021; 11(3):286. https://0-doi-org.brum.beds.ac.uk/10.3390/min11030286
Chicago/Turabian StyleBindi, Luca, and Marta Morana. 2021. "Twinning, Superstructure and Chemical Ordering in Spryite, Ag8(As3+0.50As5+0.50)S6, at Ultra-Low Temperature: An X-Ray Single-Crystal Study" Minerals 11, no. 3: 286. https://0-doi-org.brum.beds.ac.uk/10.3390/min11030286