Space Group Cmcm Research Articles

EMM-25: The Structure of Two-Dimensional 11 × 10 Medium-Pore Borosilicate Zeolite Unraveled Using 3D Electron Diffraction

The structure of the novel medium-pore borosilicate zeolite EMM-25 has been determined by continuous rotation electron diffraction (cRED). EMM-25 crystallizes in the space group Cmcm with unit cell parameters a = 11.055, b = 22.912, and c = 24.914 Å and a composition of |C4H8(C11H25N)2|2[Si112.5B3.5O232]. The EMM-25 framework possesses a two-dimensional channel system composed of 10-ring channels connected via 11-ring windows. Its channel system is analogous to that of the medium-pore zeolite NU-87 framework but with 11- rather than 12-ring windows, suggesting a different shape selectivity. EMM-25 was first obtained using 1,4-bis(N-methyl-N,N-dihexylammonium)butane as an organic structure directing agent (OSDA). Based on a molecular docking study of the OSDA within the pores of the determined framework structure, a new ammonium dication OSDA with an improved fit was devised. By using this new OSDA, the synthesis time was reduced 80%, from 52 to just 10 days. Furthermore, cRED data revealed a structural disorder of the EMM-25 framework present as swinging zigzag chains. The introduction of the disorder, which is a consequence of geometry relaxation, was crucial for an accurate structure refinement. Lastly, the cRED data from as-made EMM-25 showed residual potential consistent with the location of the OSDA position determined from the Rietveld refinement, concluding a complete refinement of the as-made structure based on the cRED data.

Mössbauer spectroscopic and XRD studies of two η-Fe2Al5 intermetallics

Two intermetallic FeAl compounds with Al content of 70.68 and 72.17 at% were studied using Mössbauer spectroscopy (5–296 K) and X-ray diffraction (15–300 K). The compounds were found to crystallize in the orthorhombic Cmcm space group (η-phase). The collected data revealed that dynamics of the Fe atoms (harmonic in entire temperature range) is significantly different that Al atoms. For the latter strong anharmonicity was evidenced. According to X-ray diffraction, the partial filling of the different Al sites leads to occurrence of low- and high-symmetry coordination of Fe atoms, which provides explanation of two doublets evidenced in collected Mössbauer spectra. All spectral parameters of the doublets as well as the Debye temperature, force constant, kinetic and potential energies of vibrations were determined. Those results revealed significant differences between both alloys, likely originating from approaching the stability boundary of the η-phase for Fe–Al 72.17 at% alloy.

Flux crystal growth of cesium bismuth silicates Cs3BiSi8O19 and Cs4Bi2Si8O21: Structure modification via Eu doping to yield Cs4Bi1.72Eu0.28Si8O21 and alkali metal ion exchange to yield Cs0.79K2.21BiSi8O19

Two new alkali bismuth silicates were prepared via high temperature flux crystal growth and their structures characterized by single crystal X-ray diffraction (SXRD). Cs3BiSi8O19 and Cs4Bi2Si8O21, crystallize in the orthorhombic space groups Pnma (a = 11.5903, b = 7.0346, c = 26.7393) and Pnn2 (a = 14.2674, b = 33.8270, c = 7.24260) respectively. Cs3BiSi8O19 was modified via ion exchange (K for Cs) and Cs4Bi2Si8O21 via Eu doping in a flux environment yielding Cs0.79K2.21BiSi8O19 and Cs4Bi1.72Eu0.28Si8O21, respectively. The two phases crystallize in the orthorhombic space group Cmcm and the monoclinic space group P21/n, respectively. Photoluminescence measurements demonstrated that the europium doped Cs4Bi1.72Eu0.28Si8O21 exhibited emission corresponding to the 5D0 → 7F2 (613 nm) red emission and 5D0 → 7F1 (590 nm) orange emission, characteristic of Eu3+ f-f transitions.

Phase equilibria in the Gd–Cr–Ge system at 1070 K

The isothermal section of the phase diagram of the Gd–Cr–Ge ternary system was constructed at 1070 K over the whole concentration range using X-ray diffractometry, metallography and electron microprobe (EPM) analysis. Three ternary compounds are realized in the Gd–Cr–Ge system at the temperature of annealing: Gd117Cr52Ge112 (Tb117Fe52Ge112 structure type, space group Fm-3m, Pearson symbol cF1124, a = 2.8971(6) nm), GdCr6Ge6 (SmMn6Sn6 structure type, space group P6/mmm, Pearson symbol hP16, a = 0.51797(2), c = 0.82901(4) nm) and GdCr1-хGe2 (CeNiSi2 structure type, space group Cmcm, Pearson symbol oS16, a = 0.41569(1)-0.41593(8), b = 1.60895(6)-1.60738(3), c = 0.40318(1)-0.40305(8) nm). For the GdCr1-xGe2 compound the homogeneity range was determined (x=0.73 – 0,69).

Temperature dependent crystal structure re‐determination and electronic properties of UI3

AbstractIn this work, we have re‐investigated the structural and physical properties of UI3 by means of temperature dependent powder neutron diffraction, heat capacity and magnetic measurements. We confirm that UI3 crystallizes in the PuBr3 structure type, space group Cmcm. We did not observe any temperature dependent structural phase transition in the temperature range from 10 to 300 K. We further report the first quantum chemical calculations of UI3 by density functional theory (DFT). The calculated structural and electronic properties demonstrate the pronounced two‐dimensional anisotropic effects present in UI3 due to its layered structure.

Coloring variants of the Re3B type

Abstract The Re3B type, space group Cmcm, has boron-centered trigonal prisms as central building units and is one of the basic structure types with numerous binary and ternary representatives. The coloring of different atoms on the two crystallographically independent rhenium sites leads to a manifold of compounds with different bonding peculiarities that are rather isopointal than isotypic with the prototype. Typical compounds are the S-phase precipitate MgCuAl2, the silicide ScPt2Si or the iodide Th0.5Pb0.5I3 (PuBr3 type). Differences in size or composition might force symmetry reductions. This is discussed for YZn3 (space group Pnma) and the different coloring variants ScRhSi2 and TaNi2P which show different twists of the trigonal prisms. Striking singular representatives with lower symmetry structures are BaThBr6 (Pmma) and NbCo2B (P21/c) which allow different ordering/distortion patterns for the prisms. All these crystal chemical details are discussed on the basis of group subgroup schemes (Bärnighausen trees).

Regularities of the property changes in the compounds EuLnCuS3 (Ln = La-Lu)

This work contains the results of complex experimental research of the compounds EuLnCuS3 (Ln = La-Lu) enhanced by the DFT calculations. It is aimed at the data replenishment with particular attention to the revelation of regularities in the property changes, in order to extend the potential applicability of the materials of the selected chemical class. The ab initio calculations of the fundamental vibrational modes of the crystal structures were in good agreement with experimental results. The wavenumbers and types of the modes were determined, and the degree of the ion participation in the modes was also estimated. The elastic properties of the compounds were calculated. The compounds were found out to be IR-transparent in the range of 4000–400 cm–1. The estimated microhardness of the compounds is in the range of 2.68–3.60 GPa. According to the DSC data, the reversible polymorphous transitions were manifested in the compounds EuLnCuS3 (Ln = Sm, Gd-Lu): for EuSmCuS3 Tα↔β = 1437 K, ΔНα↔β = 7.0 kJ·mol-1, Tβ↔γ = 1453 K, ΔНβ↔γ = 2.6 kJ·mol-1; for EuTbCuS3 Tα↔β = 1478 K, ΔНα↔β = 1.6 kJ·mol-1, Tβ↔γ = 1516 K, ΔНβ↔γ = 0.9 kJ·mol-1, Tγ↔δ = 1548 K, ΔНγ↔δ = 1.6 kJ·mol-1; for EuTmCuS3 Tα↔β = 1543 K, Tβ↔γ = 1593 K, Tγ↔δ = 1620 K; for EuYbCuS3 Tα↔β = 1513 K, Tβ↔γ = 1564 K, Tγ↔δ = 1594 K; for EuLuCuS3 Tα↔β = 1549 K, Tβ↔γ = 1601 K, Tγ↔δ = 1628 K. In the EuLnCuS3 series, the transition into either ferro- or ferrimagnetic states occurred in the narrow temperature range from 2 to 5 K. The tetrad effect in the changes of incongruent melting temperature and microhardness conditioned on rLn3+ as well as influencing of phenomenon of crystallochemical contraction were observed. For delimiting between space groups Cmcm and Pnma in the compounds ALnCuS3, the use of the tolerance factor t’ = IR(A)·IR(C) + a×IR(B)2 was verified.

Observation of novel charge ordering and spin reorientation in perovskite oxide PbFeO3

PbMO3 (M = 3d transition metals) family shows systematic variations in charge distribution and intriguing physical properties due to its delicate energy balance between Pb 6s and transition metal 3d orbitals. However, the detailed structure and physical properties of PbFeO3 remain unclear. Herein, we reveal that PbFeO3 crystallizes into an unusual 2ap × 6ap × 2ap orthorhombic perovskite super unit cell with space group Cmcm. The distinctive crystal construction and valence distribution of Pb2+0.5Pb4+0.5FeO3 lead to a long range charge ordering of the -A-B-B- type of the layers with two different oxidation states of Pb (Pb2+ and Pb4+) in them. A weak ferromagnetic transition with canted antiferromagnetic spins along the a-axis is found to occur at 600 K. In addition, decreasing the temperature causes a spin reorientation transition towards a collinear antiferromagnetic structure with spin moments along the b-axis near 418 K. Our theoretical investigations reveal that the peculiar charge ordering of Pb generates two Fe3+ magnetic sublattices with competing anisotropic energies, giving rise to the spin reorientation at such a high critical temperature.

Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb23BiIII x SbIII 7-x SbV 2Cl54 (0 ≤ x ≤ 7).

Mixed-valent metal-halides containing ns2 lone pairs may exhibit intense visible absorption, while zero-dimensional (0D) ns2-based metal-chlorides are generally colorless but have demonstrated promising optoelectronic properties suitable for thermometry and radiation detection. Here, we report solvothermally synthesized mixed-valent 0D metal-halides Rb23BiIIIxSbIII7–xSbV2Cl54 (0 ≤ x ≤ 7). Rb23SbIII7SbV2Cl54 crystallizes in an orthorhombic space group (Cmcm) with a unique, layered 0D structure driven by the arrangement of the 5s2 lone pairs of the SbIIICl6 octahedra. This red material is likely the true structure of a previously reported monoclinic “Rb2.67SbCl6” phase, the structure of which was not determined. Partially or fully substituting SbIII with isoelectronic BiIII yields the series Rb23BiIIIxSbIII7–xSbV2Cl54 (0 < x ≤ 7), which exhibits a similar layered 0D structure but with additional disorder that yields a trigonal crystal system with an enantiomorphic space group (R32). Second harmonic generation of 532 nm light from a 1064 nm laser using Rb23BiIII7SbV2Cl54 powder confirms the noncentrosymmetry of this space group. As with the prototypical mixed-valent pnictogen halides, the visible absorption bands of the Rb23BiIIIxSbIII7–xSbV2Cl54 family are the result of intervalent SbIII–SbV and mixed-valent BiIII–SbV charge transfer bands (CTB), with a blueshift of the absorption edge as BiIII substitution increases. No PL is observed from this family of semiconductors, but a crystal of Rb23BiIII7SbV2Cl54 exhibits a high resistivity of 1.0 × 1010 Ω·cm and X-ray photoconductivity with a promising μτ product of 8.0 × 10–5 cm2 s–1 V–1. The unique 0D layered structures of the Rb23BiIIIxSbIII7–xSbV2Cl54 family highlight the versatility of the ns2 lone pair in semiconducting metal-halides, pointing the way toward new functional 0D metal-halide compounds.

Synthesis, structure, melting and optical properties of three complex orthorhombic sulfides BaDyCuS3, BaHoCuS3 and BaYbCuS3

Complex sulfides BaDyCuS3, BaHoCuS3 and BaYbCuS3 were synthesized in a flow of sulfiding gases (CS2, H2S) at 900оC from standard solutions of lanthanide and copper nitrates, as well as from the same standard Ba(OH)2 solution. The crystal structures of BaDyCuS3, BaHoCuS3 and BaYbCuS3 were obtained by the Rietveld refinement method. All three compounds crystallize in the Cmcm space group (KZrCuS3 structural type) as predicted by the tolerance factor analysis. Their micromorphological, thermal and spectroscopic properties are evaluated. BaDyCuS3 and BaHoCuS3 melt congruently at 1376.5 °C and 1363.8 °C. BaYbCuS3 melts incongruently at 1353.3 °C. The optical band gap is 2.45 eV for BaDyCuS3, 2.37 eV for BaHoCuS3 and 1.82 eV for BaYbCuS3. The low bandgap of BaYbCuS3 is explained by the charge transfer band of Yb at the bottom of conduction band. The vibrational parameters of BaDyCuS3, BaHoCuS3 and BaYbCuS3 crystals were determined with the use of Raman and Infrared spectroscopies.

Non-Hygroscopic, Self-Absorption Free, and Efficient 1D CsCu2I3 Perovskite Single Crystal for Radiation Detection.

A novel all-inorganic CsCu2I3 single-crystalline perovskite as a nonhygroscopic and efficient X-ray and γ-ray scintillator is described herein. It is featured by a one-dimensional (1D) perovskite structure with an orthorhombic system and a space group of Cmcm. The CsCu2I3 crystal emits yellow light peaking at 570 nm originated from strongly localized 1D exciton emission. It appears self-absorption free because of the large Stokes shift of 1.54 eV. The photophysics process of the self-trapped exciton was studied using temperature dependent photoluminescene spectra and decay kinetics measurements. The CsCu2I3 crystal exhibits an extremely low afterglow level of 0.008% at 10 ms under X-ray excitation. Under 137Cs γ-ray irradiation, its light yield is 16 000 photons/MeV with an energy resolution of 7.8% at 662 keV.

Investigation of structural, morphology, optical properties and electrical transport conduction of Li0.25Na0.75CdVO4 compound

Polycrystalline Li0.25Na0.75CdVO4 was synthesized via a solid-state technique under air atmosphere. It is found that X-ray diffraction peaks are listed as orthorhombic Na2CrO4 structure belonging to the space group Cmcm. Composition of elements was examined by energy dispersive X-ray analysis (EDX or EDS). Grains size and morphology of the present material were investigated by scanning electron microscopy (MEB) and atomic force microscopy (AFM). Electrical measurements were performed using complex impedance spectroscopy. Impedance curves confirm the presence of two contributions and an equivalent circuit was suggested. An electrical transport in the material as a thermally activated process has been achieved using DC conductivity. While; AC conductivity is analyzed by the non-overlapping small polar on tunneling (NSPT) conduction mechanism. Refractive index, extinction coefficient, and band gap energy were determined from ellipsometric measurements.

Interaction of Components in the Lu-Ag-Si System at 500 ºC

Isothermal section of the Lu-Ag-Si system at 500ºC was studied by means of X-ray powder diffraction, microstructure and EDX-analyses in the whole concentration range. The existence of earlier reported binary compounds LuAg4, LuAg2, LuAg and LuSi2, LuSi, Lu5Si3, Lu5Si4 was confirmed. New binary compound Lu3Si5 (own str. type) was found. Almost none of the binary silicides dissolve more than 5 at.% of third component. The exception is the existence of the substitution type solid solutions based on LuAg2 (MoSi2-type structure), which dissolves up to 20 at.% Si, as well as on Lu5Si3 (Mn5Si3-type structure), which dissolves up to 15 at.% Ag. The crystal structure of the LuSi compound was redetermined by X-ray single crystal diffraction (TlI-type, space group Cmcm, a = 4.1493(3), b = 10.2641(7), c = 3.7518(2) Å, R = 0.0173, wR = 0.0415 for 173 independent reflections). No ternary compound is observed in the Lu-Ag-Si system.

Quaternary Chalcohalides CdSnSX2 (X = Cl or Br) with Neutral Layers: Syntheses, Structures, and Photocatalytic Properties.

Inorganic chalcohalides are attracting a tremendous amount of attention because of their remarkable structural variety and desirable physical properties. Although great advances have been made in recent years, functional inorganic chalcohalides with two-dimensional neutral layers are still rare. Herein, two novel chalcohalides CdSnSX2 (X = Cl or Br) with high yields were obtained by reacting CdX2 with SnS using a traditional solid-state method at 823 K. Both of these chalcohalides adopt orthorhombic space group Cmcm (No. 63) with the following structural values: a = 4.014(4)-4.064(2) Å, b = 12.996(2)-13.746(3) Å, c = 9.471(2)-9.621(2) Å, V = 494.1(8)-537.5(2) Å3, and Z = 4. The prominent architectural feature is the unique two-dimensional [CdSnSX2] neutral layer consisting of composite [CdX2] and [SnS] sublattices that are connected alternately through the Cd-S-Sn bonds along the ac plane. The [CdX2] sublattice consists of a single octahedral chain of Cd-centered [CdX4S2] groups sharing cis-X edges, while the [SnS] sublattice consists of a bend-shaped chain of unusual [SnS2X2] units sharing vertices of S atoms. Significantly, each CdSnSX2 form (X = Cl or Br) shows high visible-light-induced photocatalytic activity for rhodamine B degradation, which is ∼7.0 times higher than that of nitrogen-doped TiO2 (TiO2-xNx) under the same experimental conditions. This discovery enriches the categories of inorganic chalcohalides and provides more choices of candidate materials for photocatalytic applications.

Synthesis, structure, and properties of EuScCuS3 and SrScCuS3

The crystal structures of the first-synthesized compound EuScCuS3 and previously known SrScCuS3 are refined by Rietveld analysis of X-ray powder diffraction data. The structures are found to belong to orthorhombic crystal system, space group Cmcm, structural type KZrCuS3, with a ​= ​3.83413(3) Å, b ​= ​12.8625(1) Å, c ​= ​9.72654(8) Å (SrScCuS3) and a ​= ​3.83066(8) Å, b ​= ​12.7721(3) Å, c ​= ​9.7297(2) Å (EuScCuS3). The temperatures and enthalpies of incongruent melting are the following: Тm ​= ​1524.5 К, ΔHm ​= ​21.6 ​kJ•mol−1 (SrScCuS3), and Тm ​= ​1531.6 К, ΔHm ​= ​26.1 ​kJ•mol−1 (EuScCuS3). Ab initio calculations of the crystal structure and phonon spectrum of the compounds were performed. The types and wavenumbers of fundamental modes were determined and the involvement of ions participating in the IR and Raman modes was assessed. The experimental IR and Raman spectra were interpreted. EuScCuS3 manifests a ferromagnetic transition at 6.4 ​K. The SrScCuS3 compound is diamagnetic. The optical band gaps were found to be 1.63 ​eV (EuScCuS3) and 2.24 ​eV (SrScCuS3) from the diffuse reflectance spectra. The latter value is in good agreement with that calculated by the DFT method. The narrower band gap of EuScCuS3 is explained by the presence of 4f-5d transition in Eu2+ ion that indicates a possibility to control the band gap of the chalcogenides by the inclusion of Eu. The activation energy of crystal structure defects, being the source of additional absorption in the NIR spectral range, was found to be 0.29 ​eV.

Na2GaS2Cl: a new sodium-rich chalcohalide with two-dimensional [GaS2]∞ layers and wide interlayer space.

By introducing halogens to the A/Ga/Q (A = Na, K; Q = S, Se) system, one new chalcohalide namely Na2GaS2Cl was successfully obtained. It crystallizes in the orthorhombic space group Cmcm (63). Na2GaS2Cl has a layered structure consisting of two dimensional [GaS2]∞ layers which are stacked in "face to face" and "back to back" arrays and separated by Na+ and Cl- ions. Interestingly, supertetrahedral building units [Ga4S10] (T2) which are rarely found in metal chalcogenides and metal chalcohalides are formed in this structure. Moreover, the distances of two adjacent layers are around four times larger than the ionic radius of the Na+ ion, which is very likely to provide a perfect environment for the storage and migration of Na+ ions. In particular, the volume concentration of the Na+ cations in this compound is as high as 1.54 × 1022 cm-3. The UV-vis-NIR spectroscopy measurement reveals that the optical band gap of this title compound is 3.06 eV. The electronic structural calculations on Na2GaS2Cl show that the band gap is mainly determined by the [GaS4] groups and Na-Cl ionic bonding.

Electronic properties of orthorhombic InI and TlI crystals taking into account the quasiparticle corrections and spin-orbit interaction

The electronic properties of InI and TlI crystals of an orthorhombic structure with a space group Cmcm are studied. Calculations of electron properties are performed on the basis of the projector augmented waves by means of the ABINIT program. Total and partial densities of electronic states are calculated. Electron energy spectra are found with the exchange-correlation functional GGA, without and taking into account the spin-orbital interaction. It was found that the bandgap of the InI, obtained without spin-orbital interaction, is less than the experimental value by 38%, and by 42%, taking into account the latter. For the TlI crystal, the corresponding values are 27% and 39%. The bandgap found from the quasiparticle equation in the GW approximation exhibits an excellent agreement with the experimental values for both crystals.

Two-layer compounds in rare earth-{Fe, Co, Ni, Rh, Pd, Pt}-Te systems: crystal structure and magnetic properties

The partial isothermal sections of {Gd, Ho}-Ni-Te and Gd-Co-Te systems (~40–100 ​at. % of rare earth) have been investigated at 1070 ​K by X-ray and electron microprobe analysis. The Y5Ni2Te2-type {Tb, Dy, Ho}5Fe2Te2 and {Gd, Tb, Dy, Ho}5{Co, Ni}2Te2 (space group Cmcm, No. 63, oC36), Er7Ni2Te2-type Er7Co2Te2, {Y, Dy, Ho}7Ni2Te2, Ho7{Rh, Pd}2Te2 and {Y, Gd}7Pt2Te2 (space group Imm2, No. 44, oI22), Fe2P-type Ho6NiTe2 (space group P-62m, No. 189, hP9) and Sc6PdTe2-type Ho6{Rh, Pd}Te2 and {Y, Gd}6PtTe2 (space group Pnma, No. 62, oP36) compounds have been established using powder X-ray diffraction studies. Magnetization measurements show that the Y5Ni2Te2-type {Tb, Dy, Ho}5Fe2Te2, {Gd, Tb, Dy}5Co2Te2 and {Tb, Ho}5Ni2Te2 compounds exhibit a high-temperature ferromagnetic ordering with low-temperature spin-reorientation transition for Tb-, Dy- and Ho-containing compounds. Below Curie temperature, Tb5Fe2Te2, Tb5Co2Te2 and Ho5Ni2Te2 are soft ferromagnets, while they show hard magnetic properties below spin-reorientation transition. At 2 ​K, Tb5Co2Te2 and Tb5Fe2Te2 exhibit a coercive field of 35 ​kOe and ~30 ​kOe and the residual magnetization of 17.2 μB and 22.9 μB per formula unit, leading to theoretical maximum energy product of ~620 ​kJ/m3 and ~700 ​kJ/m3, respectively. Ho5Ni2Te2 reaches a maximum magnetic entropy change of −10.0 ​J/kg⋅K and −9.4 ​J/kg⋅K for a magnetic field change of 0–50 ​kOe ​at 45 ​K and 20 ​K, respectively.

Synthesis, crystal structure and luminescence properties of a new samarium borate phosphate, CsNa2Sm2(BO3)(PO4)2.

A new caesium sodium samarium borate phosphate, CsNa2Sm2(BO3)(PO4)2, has been obtained successfully by the high-temperature solution growth (HTSG) method and single-crystal X-ray diffraction analysis reveals that it crystallizes in the orthorhombic space group Cmcm. The structure contains BO3, PO4, NaO7 and SmO7 polyhedra which are interconnected via corner- or edge-sharing O atoms to form a three-dimensional [Na2Sm2(BO3)(PO4)2]∞ network. This network delimits large cavities where large Cs+ cations reside to form the total structure. Under 402 nm light excitation, CsNa2Sm2(BO3)(PO4)2 exhibits three emission bands due to the 4f→4f transitions of Sm3+. Furthermore, we introduced Gd3+ into Sm3+ sites to optimize the Sm3+ concentration and improve the luminescence intensity. The optimal concentration is Gd/Sm = 98/2. The luminescent lifetime of a series of CsNa2Gd2(1-x)Sm2x(BO3)(PO4)2 phosphors shows a gradual degradation of lifetime from 2.196 to 0.872 ms for x = 0.01-0.10. The Commission Internationale de l'Eclairage (CIE) 1931 calculation reveals that CsNa2Gd1.96Sm0.04(BO3)(PO4)2 can emit orange light under 402 nm excitation.

New Zr3MNx (M = Co, Ni) Subnitrides: Theoretical Analyses, Crystal Structure, and Hydrogen-Sorption Properties

The free energy and density of states are computed by the DFT method for the Zr3NiO and Zr3NiN compounds. Their formation was confirmed and numerous Zr3MNx (M = Co, Ni) compounds were synthesized for the first time. It is shown that all these compounds are insertion derivatives of the Re3B structural type (space group Cmcm). We study the process of gas-phase hydrogenation of the obtained subnitrides. It is shown that some specimens form single-phase hydrides (Zr3NiN0.5H5.64 and Zr3CoNH5.62) preserving the crystal structure of the original matrix with an increase in the volume of elementary cell by ∼ 16%. The process of hydrogen desorption in a vacuum was studied by the TDS method for various Zr3CoN(O)x hydrides. We compare the desorption properties of hydrides depending on the type of stabilizing element and the hydrogen content of hydride.