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Article

Synthesis and Structure Determination of the Quaternary Zinc Nitride Halides Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1)

Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry and JARA-FIT, RWTH Aachen University, Aachen D-52056, Germany
*
Author to whom correspondence should be addressed.
Inorganics 2016, 4(4), 29; https://doi.org/10.3390/inorganics4040029
Submission received: 30 August 2016 / Revised: 22 September 2016 / Accepted: 23 September 2016 / Published: 29 September 2016
(This article belongs to the Special Issue Novel Solid-State Nitride Materials)

Abstract

:
The quaternary series Zn2NCl1−yBry and Zn2NBr1−yIy were synthesized from solid-liquid reactions between zinc nitride and the respective zinc halides in closed ampoules, and the evolution of their crystal structures was investigated by single-crystal and powder X-ray diffraction. Zn2NX1−yX′y (X, X′ = Cl, Br, I) adopts the anti-β-NaFeO2 motif in which each nitride ion is tetrahedrally coordinated by four zinc cations, and the halide anions are located in the voids of the skeleton formed by corner-sharing [NZn4] tetrahedra. While Zn2NCl1−yBry crystallizes in the acentric orthorhombic space group Pna21 (No. 33), isotypic to Zn2NX (X = Cl, Br), the structure of Zn2NBr1−yIy is a function of the iodide concentration, namely, Zn2NBr (Pna21) for low iodine content and Zn2NI (Pnma) for higher (y ≥ 0.38).

Graphical Abstract

1. Introduction

In recent years, there is a growing interest in mixed-anions solids such as metal nitride halides. For these, the literature covers alkali and alkaline-earth metal nitride halides [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16], rare-earth metal nitride halides [17,18,19,20], transition-metal nitride halides [21,22,23,24] and Millon’s base [25,26,27,28,29]. The zinc nitride halides Zn2NX (X = Cl, Br and I) [30,31] were synthesized from solid-liquid reactions of zinc nitride with the zinc halides, and their structures belong to the anti-β-NaFeO2 type [32]. In addition, it has been suggested that not only the ternary alkaline-earth metal nitride halides M2NX (X = F, Cl, Br and I), but also the quaternary variants M2NX1−yX′y (X, X′ = Cl, Br and I) are more complicated in terms of crystal structure. In particular, the variation of the mixed halides may change both structure and other properties [7]. After the successful synthesis of Zn2NX (X = Cl, Br and I) [30], we became interested in such quaternary nitride halides simply because of a potential change in crystallographic symmetry. While Zn2NX (X = Cl, Br) crystallizes in the acentric orthorhombic space group Pna21 (No. 33), Zn2NI adopts the centrosymmetric space group Pnma (No. 62). This paper presents the synthesis and structure determination of the mixed zinc nitride halides Zn2NX1−yX′y (X, X′ = Cl, Br, I) for which a change in symmetry is to be expected at some specific stoichiometry.

2. Result and Discussion

2.1. Crystal Structure

2.1.1. Crystal Structure of Zn2NCl0.47Br0.53

The crystal structure of Zn2NCl0.47Br0.53 as depicted in Figure 1a corresponds to the one of Zn2NX (X = Cl, Br) in Pna21, the anti-β-NaFeO2 type. While there are two crystallographically independent zinc atoms, the halide anions (Cl and Br) share the same site, and there is no indication for an ordered arrangement. Zn1 is at the center of a distorted tetrahedron with its N and Cl/Br neighbors and bond lengths of Zn1–N = 1.921(5) and 1.928(5) Å while Zn1–Cl/Br amounts to 2.606(2) and 2.823(2) Å. Zn2 also constitutes a distorted tetrahedron, the bond lengths being Zn2–N = 1.870(6) and 1.888(6) Å as well as Zn2–Cl/Br = 2.829 (2) and 2.926(2) Å.
Likewise, the N3− ion is coordinated by four zinc atoms (2 × Zn1 and 2 × Zn2), with an average Zn–N distance of 1.902 Å and Zn–N–Zn angles between 103° and 116°, in good accordance with what is known from Zn2NX (X = Cl, Br) [30]. For further comparison, the Zn–N distance varies between 2.13 and 2.16 Å in Zn3N2 [33], so it is significantly larger in the binary phase than in the ternary which most probably goes back to the more ionic bonding character in the latter. This, however, is an admittedly crude guess. Also, the Zn–Cl distance is between 2.28 and 2.33 Å in ZnCl2 while the mean Zn–Br distance is 2.42 Å in ZnBr2 [34,35].

2.1.2. Crystal Structure of Zn2NBr0.62I0.38

The compounds Zn2NBr0.62I0.38, see Figure 1b, and Zn2NI [30] are isostructural. Zn2NBr0.62I0.38 adopts the orthorhombic space group Pnma in which the N3− ion is coordinated by four zinc atoms, whereas the halide anions occupy the tetrahedral voids in the framework.
There are two crystallographically independent zinc atoms. Zn1 forms a distorted tetrahedron with its nitrogen, bromide, and iodide neighbors, with bond lengths of Zn1–N = 1.914(5) Å and 1.920(5) Å while Zn1–Br/I = 2.758(2) Å and Zn1–Br/I = 3.149(2) Å. Zn2 is at the center of a distorted tetrahedron with Zn2–N = 1.883(3) Å (twice) and Zn2–Br/I = 3.188 (2) Å (also twice). The N3− ions are tetrahedrally coordinated by four zinc atoms with an average Zn–N = 1.90 Å; the Zn−N−Zn angles vary between 105° and 117°. For comparison, the average Zn–N distance is 1.90 Å for Zn2NBr and 1.92 Å for Zn2NI. Also, the Zn–N–Zn angles are 104°–116° in Zn2NBr and 105°–117° in Zn2NI. We also note that the Zn–I distance is 2.58–2.68 Å in ZnI2 [36].
Owing to the increasing halide radius, the Zn–X distances enlarge in going from Cl to I. The halide anions are located in the voids resulting from the corner-sharing [NZn4] tetrahedral framework. The voids occupied by Cl/Br (N–Zn2–N is not linear) are smaller than those occupied by Br/I (N–Zn2–N strictly linear). Hence, the crystal packing of Zn2NBr1−yIy exhibits a higher symmetry than the one of Zn2NCl1−yBry for y ≥ 0.38 or even slightly lower.

2.2. Structure Discussion of Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1)

PXRD patterns of the quaternary zinc nitride halides are presented in Figure 2. There is an obvious shift of peaks to lower 2θ with increasing halide radii, as expected. One also witnesses tiny amounts of ZnO either resulting from the starting material Zn3N2 or from the quartz tube. Within the Zn2NBr1−yIy system, see Figure 2b, space group Pna21 (the one of Zn2NBr) and Pnma (the one of Zn2NI) cannot be distinguished for trivial crystallographic reasons.
Figure 3 displays the course of the lattice parameters and the unit cell volume (all taken from the powder, not the single-crystal data) against the bromide and iodide content in the Zn2NX1−yX′y system. For Zn2NCl1−yBry, a, b, c, and V increase linearly with the bromide content, see Figure 3a. For Zn2NBr1−yIy, the behavior is different, as shown in Figure 3b: b and c increase linearly with the iodide content but a first increases slightly for small iodide contents, followed by a sharper increase for larger iodine contents. This effect mirrors the structural change of the Zn2NBr1−yIy system in going from the acentric Pna21 to the centric Pnma space group which, according to the single-crystal data, sets in at about y = 0.38, possibly even slightly earlier than that.

3. Experimental

3.1. Synthesis of Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1)

Because the starting materials are air and moisture sensitive, all manipulations were carried out under a continuously purified and monitored argon atmosphere in a glove-box (H2O and O2 below 1 ppm) or under vacuum. The quaternary zinc nitride halides were prepared from solid–liquid reactions. The starting materials, dark gray Zn3N2 (Alfa, Karlsruhe, Germany, 99%) and white ZnCl2 (Alfa, 99.99%; m.p.: 283 °C), ZnBr2 (Alfa, 99.999%; m.p.: 394 °C), or ZnI2 (Alfa, 99.995%; m.p.: 446 °C) were thoroughly mixed using a 1:(1 − y):y molar ratio. For X = Cl, X′ = Br or X = Br, X′ = I, the ratio of y was varied from 0 to 1 in increments of 0.25. The mixture was loaded in a quartz tube which was then sealed under vacuum. The ampoule was heated and kept at a temperature of 550 °C for 20 h. The reaction follows the simple equation:
Zn3N2(s) + (1 − y) ZnX2(l) + y ZnX′2(l) → 2 Zn2NX1−yX′y(s)
Pale white powders of Zn2NCl1−yBry and Zn2NBr1−yIy were obtained and checked by X-ray powder diffraction (XRPD). Colorless single crystals of Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38 were also obtained by the reaction of Zn3N2 with the respective ZnX2 at temperatures from 550 to 600 °C for about three days. However, any attempts to synthesize Zn2NCl1−yIy were unsuccessful.
Quaternary zinc nitride halides are stable in dry air for several hours, thereby resembling the ternary zinc nitride halides.

3.2. X-ray Crystallography

Single crystals of Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38 were fixed on a glass fiber in air. The single-crystal data were collected at 293(2) K with a Bruker SMART APEX CCD diffractometer (Bruker AXS Inc., Madison, WI, USA) using monochromatic Mo-Kα radiation. The collection and reduction of the data were implemented with the Bruker Suite software package [37,38]. An empirical absorption correction was carried out with SADABS.
The structures of Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38 were solved by analogy with the ternary phases and refined by full-matrix least-squares techniques on the basis of intensities with SHELXL [37,38]. Undoubtedly, Zn2NCl0.47Br0.53 crystallizes in the acentric space group Pna21 (No. 33) and is isotypic with Zn2NX (X = Cl, Br). Zn2NBr0.62I0.38, however, crystallizes in the centrosymmetric space group Pnma (No. 62) and is isotypic with Zn2NI. The halide contents result from the single-crystal refinements which are more reliable in terms of stoichiometry.
The powder X-ray diffraction data of Zn2NX1−yX′y (X, X′ = Cl, Br, I) were recorded at room temperature by means of a calibrated Huber Image Plate (G 670) powder diffractometer (Rimsting, Germany) (Cu-Kα1 radiation, 6°–100° in 2θ) with a flat-sample holder. The background was manually subtracted by linear interpolation, and the FULLPROF program package [39] was used for Rietveld refinements using a pseudo-Voigt profile function. The final structural models of Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38 derived from single-crystal XRD were fully confirmed from the Rietveld data, as depicted in Figure 4.
Details of the crystallographic data collection and structure refinement are given in Table 1. Lattice parameters, refined atomic coordinates, equivalent isotropic displacement parameters, and anisotropic displacement parameters are listed in Table 2, Table 3 and Table 4. Selected bond distances and angles are presented in Table 5. Further information in the form of CIF data has been deposited at Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany, and may be obtained from there using the depository CSD numbers 431875 (Zn2NCl0.47Br0.53) and 431876 (Zn2NBr0.62I0.38), respectively.

4. Conclusions

The quaternary series Zn2NCl1−yBry and Zn2NBr1−yIy were synthesized and their crystal structures were investigated by single-crystal and powder X-ray diffraction. Zn2NX1−yX′y (X, X′ = Cl, Br, I) follow the anti-β-NaFeO2 motif. Each N3− is tetrahedrally coordinated by four zinc atoms, and the X anions are located in the voids of the skeleton formed by corner-sharing [NZn4] tetrahedra. While Zn2NCl1−yBry is isotypic with Zn2NX (X = Cl, Br) and crystallizes in the acentric orthorhombic space group Pna21, the Zn2NBr1−yIy series changes its space groups as a function of the iodide content, that is, Pna21 for low I content and Pnma for higher, namely y ≥ 0.38 or even slightly lower according to single-crystal data.

Supplementary Materials

Supplementary materials can be found at https://www.mdpi.com/2304-6740/4/4/29/s1.

Author Contributions

Yanqing Li and Xiaohui Liu conceived and designed the experiments; Yanqing Li performed the experiments; Yanqing Li and Xiaohui Liu analyzed the data; Yanqing Li, Xiaohui Liu and Richard Dronskowski wrote the paper.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Polyhedral representation of [NZn4] tetrahedra and the local nitrogen coordination in Zn2NCl0.47Br0.53 (a) and Zn2NBr0.62I0.38 (b). The Cl/Br and the Br/I anions statistically occupy the tetrahedral voids in the framework.
Figure 1. Polyhedral representation of [NZn4] tetrahedra and the local nitrogen coordination in Zn2NCl0.47Br0.53 (a) and Zn2NBr0.62I0.38 (b). The Cl/Br and the Br/I anions statistically occupy the tetrahedral voids in the framework.
Inorganics 04 00029 g001
Figure 2. PXRD patterns of zinc nitride halides Zn2NCl1−yBry (a) and Zn2NBr1−yIy (b) with 0 ≤ y ≤ 1. Two samples Zn2NCl0.75Br0.25 and Zn2NCl within (a) contain small amount ZnO (asterisks).
Figure 2. PXRD patterns of zinc nitride halides Zn2NCl1−yBry (a) and Zn2NBr1−yIy (b) with 0 ≤ y ≤ 1. Two samples Zn2NCl0.75Br0.25 and Zn2NCl within (a) contain small amount ZnO (asterisks).
Inorganics 04 00029 g002
Figure 3. Course of the lattice parameters a, b, and c (left and blue) and volume V (right and red) based on XRPD data as a function of the bromide content for Zn2NCl1−yBry (a) and the iodide content for Zn2NBr1−yIy (b).
Figure 3. Course of the lattice parameters a, b, and c (left and blue) and volume V (right and red) based on XRPD data as a function of the bromide content for Zn2NCl1−yBry (a) and the iodide content for Zn2NBr1−yIy (b).
Inorganics 04 00029 g003
Figure 4. Rietveld refinement of the X-ray powder pattern of Zn2NCl0.47Br0.53 (a) and Zn2NBr0.62I0.38 (b) showing measured and fitted intensities (red/black), the position of the Bragg peaks (green) and the difference curve (blue).
Figure 4. Rietveld refinement of the X-ray powder pattern of Zn2NCl0.47Br0.53 (a) and Zn2NBr0.62I0.38 (b) showing measured and fitted intensities (red/black), the position of the Bragg peaks (green) and the difference curve (blue).
Inorganics 04 00029 g004
Table 1. Crystal data and details of the structural refinements of Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38.
Table 1. Crystal data and details of the structural refinements of Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38.
FormulaZn2NCl0.47Br0.53Zn2NBr0.62I0.38
Formula weight (g/mol)203.87242.55
Color and formcolorless blockcolorless block
Temperature (K)293(2)293(2)
Crystal systemorthorhombicorthorhombic
Space group; ZPna21 (No. 33); 4Pnma (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)4.8335.345
Crystal size (mm3)0.03 × 0.03 × 0.010.05 × 0.04 × 0.01
θ range (deg)5.45–32.835.21–33.36
Index ranges−8 ≤ h ≤ 9−7 ≤ h ≤ 9
−8 ≤ k ≤ 11−9 ≤ k ≤ 9
−8 ≤ l ≤ 9−12 ≤ l ≤ 6
Reflections collected24552215
Indep. reflections, Rint824, 0.0366585, 0.0326
Restraints; parameters1; 380; 27
Goodness-of-fit1.0971.177
R1[I > 2σ(I)], wR(I)0.0371, 0.08670.0428, 0.1147
largest diff. peak; hole (e/Å3)1.136; −1.1472.896; −2.869
Table 2. Lattice parameter for Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1).
Table 2. Lattice parameter for Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1).
Lattice ParameterZn2NCl [30]Zn2NCl0.47Br0.53Zn2NBr [30]Zn2NBr0.62I0.38Zn2NI [30]
a6.1241(9)6.168(2)6.2149(9)6.249(4)6.3590(13)
b7.3885(11)7.538(3)7.6529(11)6.164(4)6.2592(12)
c5.9362(9)6.026(2)6.0859(8)7.824(5)7.9549(16)
V268.60(7)280.17(18)289.46(7)301.4(3)316.30(11)
Table 3. Refined atomic coordinates and equivalent isotropic displacement parameters for Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38.
Table 3. Refined atomic coordinates and equivalent isotropic displacement parameters for Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38.
AtomWyckoff SitexyzUeq2)Occ (X, X′)
Zn2NCl0.47Br0.53
Zn14a0.87415(12)0.82228(12)0.64994(16)0.0204(2)
Zn24a0.97750(14)0.46071(15)0.47667(16)0.0244(2)
N4a0.9284(7)0.3733(7)0.1907(10)0.0112(8)
Cl4a0.8107(13)0.12201(12)0.68891(14)0.0157(3)0.467(8)
Br4a----0.533(8)
Zn2NBr0.62I0.38
Zn14c0.13822(12)3/40.31289(12)0.0222(3)
Zn24a0000.0318(4)
N4c0.0644(8)1/40.8716(7)0.0108(9)
I4c0.92075(8)3/40.61964(7)0.0173(3)0.380(12)
Br4c----0.620(12)
Table 4. Anisotropic displacement parameters (Å2) for Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38.
Table 4. Anisotropic displacement parameters (Å2) for Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38.
AtomU11U22U33U12U13U23
Zn2NCl0.47Br0.53
Zn10.0123(3)0.0198(4)0.0291(4)0.0049(3)0.0010(3)0.0006(3)
Zn20.0234(4)0.0287(5)0.0211(4)0.0012(4)−0.0058(3)−0.0120(4)
N0.0077(16)0.015(2)0.0108(19)−0.0010(16)0.0012(16)0.0016(19)
Cl0.0152(4)0.0158(4)0.0162(4)−0.0004(3)0.0004(3)−0.0002(3)
Br0.0152(4)0.0158(4)0.0162(4)−0.0004(3)0.0004(3)−0.0002(3)
Zn2NBr0.62I0.38
Zn10.0113(5)0.0327(5)0.0226(5)0−0.0053(3)0
Zn20.0284(5)0.0290(5)0.0380(6)−0.0137(4)−0.0087(4)0.0218(4)
N0.0078(17)0.012(2)0.013(2)00.0002(15)0
I0.0148(4)0.0170(4)0.0200(4)00.00094(17)0
Br0.0148(4)0.0170(4)0.0200(4)00.00094(17)0
Table 5. Selected bond distances (Å) and angles (°) in Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38.
Table 5. Selected bond distances (Å) and angles (°) in Zn2NCl0.47Br0.53 and Zn2NBr0.62I0.38.
Zn2NCl0.47Br0.53Distance/AngleZn2NBr0.62I0.38Distance/Angle
Zn1–N1.921(5)Zn1–N1.914(5)
Zn1–N1.928(5)Zn1–N1.920(5)
Zn1–Cl/Br2.6055(15)Zn1–Br/I2.7579(17)
Zn1–Cl/Br2.8230(17)Zn1–Br/I3.1487(19)
Zn2–N1.870(6)Zn2–N1.883(3)
Zn2–N1.888(6)Zn2–N1.883(3)
Zn2–Cl/Br2.8292(15)Zn2–Br/I3.1881(15)
Zn2–Cl/Br2.9261(17)Zn2–Br/I3.1881(15)
N–Zn1–N138.6(2)N–Zn1–N145.14(16)
N–Zn2–N155.9(2)N–Zn2–N180
Zn2–N–Zn2110.2(3)Zn2–N–Zn2109.8(3)
Zn2–N–Zn1110.2(3)Zn2–N–Zn1109.60(17)
Zn2–N–Zn1110.1(3)Zn2–N–Zn1109.60(17)
Zn2–N–Zn1106.5(3)Zn2–N–Zn1105.08(17)
Zn2–N–Zn1103.0(3)Zn2–N–Zn1105.08(17)
Zn1–N–Zn1116.4(3)Zn1–N–Zn1117.4(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

AMA Style

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 Style

Li, 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

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