The Short Series of the Oxygen-Poor Lanthanide Oxide Selenides M10OSe14 with M = La–Nd
1. Introduction
2. Results and Discussion
2.1. Structure Description
Atom | x/a | y/b | z/c | Atom | x/a | y/b | z/c | ||
---|---|---|---|---|---|---|---|---|---|
La10OSe14 | Pr10OSe14 | ||||||||
La1 | 32g | 0.13003(4) | 0.02695(4) | 0.04721(2) | Pr1 | 32g | 0.12991(3) | 0.02686(3) | 0.04742(2) |
La2 | 32g | 0.37036(4) | 0.25434(4) | 0.05965(2) | Pr2 | 32g | 0.37071(3) | 0.25436(3) | 0.05951(2) |
La3 | 16f | 0.13330(4) | x + 1/4 | 1/8 | Pr3 | 16f | 0.13364(4) | x + 1/4 | 1/8 |
O | 8a | 0 | 1/4 | 3/8 | O | 8a | 0 | 1/4 | 3/8 |
Se1 | 32g | 0.02192(6) | 0.38134(7) | 0.00124(4) | Se1 | 32g | 0.02218(5) | 0.38111(5) | 0.00199(4) |
Se2 | 32g | 0.34224(7) | 0.07046(7) | 0.09270(4) | Se2 | 32g | 0.34290(5) | 0.07081(5) | 0.09262(4) |
Se3 | 32g | 0.03914(6) | 0.07100(7) | 0.17174(4) | Se3 | 32g | 0.03885(5) | 0.07057(5) | 0.17167(4) |
Se4 | 16e | 0.35523(9) | 0 | 1/4 | Se4 | 16e | 0.35463(7) | 0 | 1/4 |
Ce10OSe14 | Nd10OSe14 | ||||||||
Ce1 | 32g | 0.13000(3) | 0.02686(3) | 0.04741(2) | Nd1 | 32g | 0.12963(3) | 0.02694(3) | 0.04743(2) |
Ce2 | 32g | 0.37049(3) | 0.25428(3) | 0.05949(2) | Nd2 | 32g | 0.37075(3) | 0.25459(3) | 0.05933(2) |
Ce3 | 16f | 0.13347(3) | x + 1/4 | 1/8 | Nd3 | 16f | 0.13381(3) | x + 1/4 | 1/8 |
O | 8a | 0 | 1/4 | 3/8 | O | 8a | 0 | 1/4 | 3/8 |
Se1 | 32g | 0.02201(4) | 0.38106(5) | 0.00168(3) | Se1 | 32g | 0.02249(5) | 0.38122(5) | 0.00236(4) |
Se2 | 32g | 0.34256(5) | 0.07063(5) | 0.09262(3) | Se2 | 32g | 0.34298(5) | 0.07106(5) | 0.09269(4) |
Se3 | 32g | 0.03891(5) | 0.07076(5) | 0.17178(3) | Se3 | 32g | 0.03876(5) | 0.07060(5) | 0.17159(4) |
Se4 | 16e | 0.35487(6) | 0 | 1/4 | Se4 | 16e | 0.35395(7) | 0 | 1/4 |
M10OSe14 | M = La | M = Ce | M = Pr | M = Nd | ||
---|---|---|---|---|---|---|
M1 | –Se1 | (1×) | 298.7(1) | 296.4(1) | 294.4(1) | 292.4(1) |
–Se4 | (1×) | 301.1(1) | 298.2(1) | 296.2(1) | 294.1(1) | |
–Se2 | (1×) | 306.0(1) | 303.4(1) | 301.5(1) | 300.2(1) | |
–Se1' | (1×) | 306.2(1) | 304.2(1) | 302.2(1) | 300.2(1) | |
–Se3 | (1×) | 307.7(1) | 304.7(1) | 302.5(1) | 300.6(1) | |
–Se2' | (1×) | 309.8(1) | 307.1(1) | 305.4(1) | 303.8(1) | |
–Se3' | (1×) | 310.0(1) | 307.9(1) | 306.1(1) | 304.6(1) | |
–Se2'' | (1×) | 357.9(1) | 355.4(1) | 353.8(1) | 352.4(1) | |
M2 | –O | (1×) | 248.2(1) | 246.1(1) | 244.2(1) | 243.0(1) |
–Se1 | (1×) | 294.5(1) | 291.9(1) | 289.9(1) | 288.0(1) | |
–Se2 | (1×) | 304.2(1) | 301.4(1) | 299.2(1) | 297.6(1) | |
–Se3 | (1×) | 308.8(1) | 305.6(1) | 304.1(1) | 302.4(1) | |
–Se3' | (1×) | 314.9(1) | 312.0(1) | 310.1(1) | 308.6(1) | |
–Se4 | (1×) | 320.1(1) | 317.9(1) | 316.3(1) | 314.9(1) | |
– Se2' | (1×) | 329.1(1) | 326.2(1) | 323.6(1) | 321.6(1) | |
–Se1' | (1×) | 348.3(1) | 345.3(1) | 343.3(1) | 342.2(1) | |
M3 | –Se3 | (2×) | 300.6(1) | 298.1(1) | 296.2(1) | 294.5(1) |
–Se2 | (2×) | 308.1(1) | 305.6(1) | 303.4(1) | 301.8(1) | |
– Se1 | (2×) | 315.3(1) | 311.8(1) | 309.3(1) | 306.9(1) | |
– Se4 | (2×) | 322.8(1) | 319.7(1) | 317.5(1) | 315.8(1) |
Distances/angles/examples | La10OSe14 | Ce10OSe14 | Pr10OSe14 | Nd10OSe14 | |
---|---|---|---|---|---|
d(Se2––M3+) | 295–358 | 292–355 | 290–354 | 288–352 | |
example 1 | C-La2Se3 [15] | C-Ce2Se3 [16] | C-Pr2Se3 [15] | C-Nd2Se3 [17] | |
304–323 | 302–320 | 299–318 | 297–317 | ||
example 2 | La5NSe6 [18] | Ce3ONSe2 [19] | Pr2OSe2 [1] | Nd3ONSe2 [19] | |
289–355 | 293–355 | 293–331 | 289–347 | ||
d(O2––M3+) | (4×) | 248.2 | 246.1 | 244.2 | 243.0 |
example | La10OS14 [8] | Ce10OS14 [8] | Pr10OS14 [8] | Nd10OS14 [8] | |
245.4 | 243.0 | 242.1 | 240.8 | ||
∢M2-O-M2 | (4×) | 107.9 | 108.0 | 108.0 | 108.1 |
∢M2-O-M2' | (2×) | 112.6 | 112.5 | 112.4 | 112.2 |
example | La10OS14 [8] | Ce10OS14 [8] | Pr10OS14 [8] | Nd10OS14 [8] | |
∢M2-O-M2 | (4×) | 108.1 | 108.2 | 108.2 | 108.3 |
∢M2-O-M2' | (2×) | 112.3 | 112.1 | 112.1 | 111.9 |
2.2. Optical Band Gaps
General formula | Reference | M = La | M = Ce | M = Pr | M = Nd |
---|---|---|---|---|---|
M10OSe14 | this work | 2.04 eV | 1.97 eV | 1.89 eV | 1.98 eV |
M4O4Se[Se2] | [7] | 1.89 eV | 1.69 eV | 1.87 eV | 1.87 eV |
M2Se3 | [21] | 2.3 eV | 1.85 eV | 2.0 eV | 2.0 eV |
3. Experimental Section
M10OSe14 | M = La | M = Ce | M = Pr | M = Nd |
---|---|---|---|---|
Colour | red | ruby red | ruby red | ruby red |
Crystal system | tetragonal | tetragonal | tetragonal | tetragonal |
Space group/Formula units | I41/acd/Z = 8 | I41/acd/Z = 8 | I41/acd/Z = 8 | I41/acd/Z = 8 |
a (pm) | 1592.04(9) | 1578.96(9) | 1568.74(8) | 1559.83(8) |
c (pm) | 2106.48(14) | 2086.59(14) | 2073.42(13) | 2062.91(12) |
c/a | 1.323 | 1.321 | 1.322 | 1.322 |
Vm (cm3/mol)/Dx (g/cm3) | 401.91/6.247 | 391.60/6.442 | 384.11/6.588 | 377.83/6.786 |
F(000)/ θmax | 8432/30.2 | 8512/31.6 | 8592/30.4 | 8672/31.6 |
±h/±k/±l | 22/22/29 | 23/23/30 | 22/22/29 | 22/22/30 |
Reflections (all/independent) | 36621/1999 | 52742/2178 | 43025/1926 | 39083/2117 |
μ/mm–1 | 34.70 | 36.69 | 38.66 | 40.58 |
Rint/Rσ | 0.118/0.051 | 0.127/0.047 | 0.101/0.034 | 0.087/0.026 |
R1/wR2 | 0.069/0.078 | 0.066/0.057 | 0.052/0.067 | 0.059/0.096 |
GooF | 0.986 | 0.973 | 0.986 | 1.037 |
4. Conclusions
Acknowledgments
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Weber, F.A.; Schurz, C.M.; Frunder, S.; Kuhn, C.F.; Schleid, T. The Short Series of the Oxygen-Poor Lanthanide Oxide Selenides M10OSe14 with M = La–Nd. Crystals 2012, 2, 1136-1145. https://doi.org/10.3390/cryst2031136
Weber FA, Schurz CM, Frunder S, Kuhn CF, Schleid T. The Short Series of the Oxygen-Poor Lanthanide Oxide Selenides M10OSe14 with M = La–Nd. Crystals. 2012; 2(3):1136-1145. https://doi.org/10.3390/cryst2031136
Chicago/Turabian StyleWeber, Frank A., Christian M. Schurz, Susanne Frunder, Charlotte F. Kuhn, and Thomas Schleid. 2012. "The Short Series of the Oxygen-Poor Lanthanide Oxide Selenides M10OSe14 with M = La–Nd" Crystals 2, no. 3: 1136-1145. https://doi.org/10.3390/cryst2031136