Synthesis and Structure Determination of the Quaternary Zinc Nitride Halides Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1)
Abstract
:1. Introduction
2. Result and Discussion
2.1. Crystal Structure
2.1.1. Crystal Structure of Zn2NCl0.47Br0.53
2.1.2. Crystal Structure of Zn2NBr0.62I0.38
2.2. Structure Discussion of Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1)
3. Experimental
3.1. Synthesis of Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1)
3.2. X-ray Crystallography
4. Conclusions
Supplementary Materials
Author Contributions
Conflicts of Interest
References
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Formula | Zn2NCl0.47Br0.53 | Zn2NBr0.62I0.38 |
---|---|---|
Formula weight (g/mol) | 203.87 | 242.55 |
Color and form | colorless block | colorless block |
Temperature (K) | 293(2) | 293(2) |
Crystal system | orthorhombic | orthorhombic |
Space group; Z | Pna21 (No. 33); 4 | Pnma (No. 62); 4 |
a (Å) | 6.168(2) | 6.249(4) |
b (Å) | 7.538(3) | 6.164(4) |
c (Å) | 6.026(2) | 7.824(5) |
Cell volume (Å3) | 280.17(18) | 301.4(3) |
Calculated density (g/cm3) | 4.833 | 5.345 |
Crystal size (mm3) | 0.03 × 0.03 × 0.01 | 0.05 × 0.04 × 0.01 |
θ range (deg) | 5.45–32.83 | 5.21–33.36 |
Index ranges | −8 ≤ h ≤ 9 | −7 ≤ h ≤ 9 |
−8 ≤ k ≤ 11 | −9 ≤ k ≤ 9 | |
−8 ≤ l ≤ 9 | −12 ≤ l ≤ 6 | |
Reflections collected | 2455 | 2215 |
Indep. reflections, Rint | 824, 0.0366 | 585, 0.0326 |
Restraints; parameters | 1; 38 | 0; 27 |
Goodness-of-fit | 1.097 | 1.177 |
R1[I > 2σ(I)], wR(I) | 0.0371, 0.0867 | 0.0428, 0.1147 |
largest diff. peak; hole (e/Å3) | 1.136; −1.147 | 2.896; −2.869 |
Lattice Parameter | Zn2NCl [30] | Zn2NCl0.47Br0.53 | Zn2NBr [30] | Zn2NBr0.62I0.38 | Zn2NI [30] |
---|---|---|---|---|---|
a | 6.1241(9) | 6.168(2) | 6.2149(9) | 6.249(4) | 6.3590(13) |
b | 7.3885(11) | 7.538(3) | 7.6529(11) | 6.164(4) | 6.2592(12) |
c | 5.9362(9) | 6.026(2) | 6.0859(8) | 7.824(5) | 7.9549(16) |
V | 268.60(7) | 280.17(18) | 289.46(7) | 301.4(3) | 316.30(11) |
Atom | Wyckoff Site | x | y | z | Ueq (Å2) | Occ (X, X′) |
---|---|---|---|---|---|---|
Zn2NCl0.47Br0.53 | ||||||
Zn1 | 4a | 0.87415(12) | 0.82228(12) | 0.64994(16) | 0.0204(2) | |
Zn2 | 4a | 0.97750(14) | 0.46071(15) | 0.47667(16) | 0.0244(2) | |
N | 4a | 0.9284(7) | 0.3733(7) | 0.1907(10) | 0.0112(8) | |
Cl | 4a | 0.8107(13) | 0.12201(12) | 0.68891(14) | 0.0157(3) | 0.467(8) |
Br | 4a | - | - | - | - | 0.533(8) |
Zn2NBr0.62I0.38 | ||||||
Zn1 | 4c | 0.13822(12) | 3/4 | 0.31289(12) | 0.0222(3) | |
Zn2 | 4a | 0 | 0 | 0 | 0.0318(4) | |
N | 4c | 0.0644(8) | 1/4 | 0.8716(7) | 0.0108(9) | |
I | 4c | 0.92075(8) | 3/4 | 0.61964(7) | 0.0173(3) | 0.380(12) |
Br | 4c | - | - | - | - | 0.620(12) |
Atom | U11 | U22 | U33 | U12 | U13 | U23 |
---|---|---|---|---|---|---|
Zn2NCl0.47Br0.53 | ||||||
Zn1 | 0.0123(3) | 0.0198(4) | 0.0291(4) | 0.0049(3) | 0.0010(3) | 0.0006(3) |
Zn2 | 0.0234(4) | 0.0287(5) | 0.0211(4) | 0.0012(4) | −0.0058(3) | −0.0120(4) |
N | 0.0077(16) | 0.015(2) | 0.0108(19) | −0.0010(16) | 0.0012(16) | 0.0016(19) |
Cl | 0.0152(4) | 0.0158(4) | 0.0162(4) | −0.0004(3) | 0.0004(3) | −0.0002(3) |
Br | 0.0152(4) | 0.0158(4) | 0.0162(4) | −0.0004(3) | 0.0004(3) | −0.0002(3) |
Zn2NBr0.62I0.38 | ||||||
Zn1 | 0.0113(5) | 0.0327(5) | 0.0226(5) | 0 | −0.0053(3) | 0 |
Zn2 | 0.0284(5) | 0.0290(5) | 0.0380(6) | −0.0137(4) | −0.0087(4) | 0.0218(4) |
N | 0.0078(17) | 0.012(2) | 0.013(2) | 0 | 0.0002(15) | 0 |
I | 0.0148(4) | 0.0170(4) | 0.0200(4) | 0 | 0.00094(17) | 0 |
Br | 0.0148(4) | 0.0170(4) | 0.0200(4) | 0 | 0.00094(17) | 0 |
Zn2NCl0.47Br0.53 | Distance/Angle | Zn2NBr0.62I0.38 | Distance/Angle |
---|---|---|---|
Zn1–N | 1.921(5) | Zn1–N | 1.914(5) |
Zn1–N | 1.928(5) | Zn1–N | 1.920(5) |
Zn1–Cl/Br | 2.6055(15) | Zn1–Br/I | 2.7579(17) |
Zn1–Cl/Br | 2.8230(17) | Zn1–Br/I | 3.1487(19) |
Zn2–N | 1.870(6) | Zn2–N | 1.883(3) |
Zn2–N | 1.888(6) | Zn2–N | 1.883(3) |
Zn2–Cl/Br | 2.8292(15) | Zn2–Br/I | 3.1881(15) |
Zn2–Cl/Br | 2.9261(17) | Zn2–Br/I | 3.1881(15) |
N–Zn1–N | 138.6(2) | N–Zn1–N | 145.14(16) |
N–Zn2–N | 155.9(2) | N–Zn2–N | 180 |
Zn2–N–Zn2 | 110.2(3) | Zn2–N–Zn2 | 109.8(3) |
Zn2–N–Zn1 | 110.2(3) | Zn2–N–Zn1 | 109.60(17) |
Zn2–N–Zn1 | 110.1(3) | Zn2–N–Zn1 | 109.60(17) |
Zn2–N–Zn1 | 106.5(3) | Zn2–N–Zn1 | 105.08(17) |
Zn2–N–Zn1 | 103.0(3) | Zn2–N–Zn1 | 105.08(17) |
Zn1–N–Zn1 | 116.4(3) | Zn1–N–Zn1 | 117.4(3) |
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Li, Y.; Liu, X.; Dronskowski, R. Synthesis and Structure Determination of the Quaternary Zinc Nitride Halides Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1). Inorganics 2016, 4, 29. https://doi.org/10.3390/inorganics4040029
Li Y, Liu X, Dronskowski R. Synthesis and Structure Determination of the Quaternary Zinc Nitride Halides Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1). Inorganics. 2016; 4(4):29. https://doi.org/10.3390/inorganics4040029
Chicago/Turabian StyleLi, Yanqing, Xiaohui Liu, and Richard Dronskowski. 2016. "Synthesis and Structure Determination of the Quaternary Zinc Nitride Halides Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1)" Inorganics 4, no. 4: 29. https://doi.org/10.3390/inorganics4040029