Crystal Chemical Analysis Research Articles

Crystals of para-quaterphenyl and its trimethylsilyl derivative. I. Growth from solutions, structure and crystal chemical analysis by the Hirschfeld surface method

The results of crystal growth of para-quaterphenyl (4P) and its derivative – 4,4''-bis(trimethylsilyl)-para-quaterphenyl (TMS-4P-TMS) from solutions are presented. It has been established that TMS-4P-TMS crystals exhibit better growth characteristics compared to 4P. Parameters of phase transitions of 4P and TMS-4P-TMS in closed crucibles were refined using the method of differential scanning calorimetry. The crystal structure of TMS-4P-TMS in the triclinic space group P1 (Z = 2) has been decrypted for the first time using single-crystal X-ray diffraction and studied over a wide temperature range. Crystallographic analysis of the studied compounds in crystals was performed using the Hirshfeld surface method, and modeling of intermolecular interactions was conducted.

Crystals of para-Quaterphenyl and Its Trimethylsilyl Derivative. I: Growth from Solutions, Structure, and Crystal Chemical Analysis by the Hirschfeld Surface Method

Crystals of para-Quaterphenyl and Its Trimethylsilyl Derivative. I: Growth from Solutions, Structure, and Crystal Chemical Analysis by the Hirschfeld Surface Method

On the Polymorphism of Cu2V2O7: Synthesis and Crystal Structure of δ-Cu2V2O7, a New Polymorph

Single crystals of the new modification of copper pyrovanadate, δ-Cu2V2O7, were prepared using the chemical vapor transport reaction method. The crystal structure (monoclinic, P21/n, a = 5.0679(3), b = 11.4222(7), c = 9.4462(6) Å, β = 97.100(6)°, V = 542.61(6) Å3, Z = 4) was solved by direct methods and refined to R1 = 0.029 for 1818 independent observed reflections. The crystal structure contains two Cu sites: the Cu1 site in [4 + 2]-octahedral coordination and the Cu2 site in [4 + 1]-tetragonal pyramidal coordination. There are two V5+ sites, both tetrahedrally coordinated by O atoms. Two adjacent V1O4 and V2O4 tetrahedra share the O4 atom to form a V2O7 dimer. The crystal structure of δ-Cu2V2O7 can be described as based upon layers of V2O7 dimers of tetrahedra parallel to the (001) plane and interlined by chains of the edge-sharing Cu1O6 and Cu2O5 polyhedra running parallel to the a axis and arranged in the layers parallel to the (001) plane. The crystal chemical analysis of the three other known Cu2V2O7 polymorphs indicates that, by analogy with δ-Cu2V2O7, they are based upon layers of V2O7 groups interlinked by layers consisting of chains of CuOn coordination polyhedra (n = 5, 6). The crystal structures of the Cu2V2O7 polymorphs can be classified according to the mutual relations between the Cu-O chains, on the one hand, and the V2O7 groups, on the other hand. The analysis of the literature data and physical density values suggests that, at ambient pressure, α- and β-Cu2V2O7 are the low- and high-temperature polymorphs, respectively, with the phase transition point at 706–710 °C. The β-phase (ziesite) may form metastably under temperatures below 560 °C and, under heating, transform into the stable α-phase (blossite) at 605 °C. The δ- and γ-polymorphs have the highest densities and most probably are the high-pressure phases. The structural complexity relations among the polymorphs correspond to the sequence α = β < γ < δ; i.e., the δ phase described herein possesses the highest complexity, which supports the hypothesis about its stability under high-pressure conditions.

Refinement of the crystal structure of christofschäferite-(Ce) and the modular aspect of the chevkinite polysomatic series with the general formula of {A<sub>4</sub>B(T<sub>2</sub>O<sub>7</sub>)<sub>2</sub>}{C<sub>2</sub>D<sub>2</sub>O<sub>8</sub>}<sub>m</sub> (m = 1, 2)

Research subject. The crystal structure of christofschäferite-(Ce) was previously refined in terms of the P21/m low-symmetrical space group, which allowed the local features of cationic arrangements to be determined. In this work, we set out to refine the crystal structure of christofschäferite-(Ce) in terms of the P21/a high-symmetrical space group based on the previously collected diffraction data. A topology-symmetrical analysis of the members of the chevkinite group with the general formula of A4BC2D2(Si2O7)2O8 was conducted. Materials and methods. A magmatic rock sample with christofschäferite-(Ce) inclusions was found in the vicinity of the Laacher See volcano, near Mendig, Eifel Mountains, Rhineland-Palatinate (Rheinland-Pfalz), Germany. The crystal structure was studied using single-crystal X-ray analysis. Results. Despite an increase in the symmetry to the P21/a space group (in comparison with the previous data with the P21/m space group), the main patterns of cation distribution between the octahedral and tetrahedral sites are preserved. However, due to the lover number of cationic sites, this distribution becomes more disordered. Based on a crystal chemical analysis of the crystal structures of natural and synthetic members of the chevkinite group in the framework of the OD theory, it is possible to combine them into a united OD family with the same OD groupoid. Conclusions. According to the OD theory, there are two structural OD-subgroups of the chevkinite group (chevkinite and perrierite). The crystal structure and symmetry of possible MDO-polytypes are predicted.

A General Concept for the Electronic and Steric Modification of 1-Metallacyclobuta-2,3-dienes: A Case Study of Group 4 Metallocene Complexes.

The synthesis of group 4 metal 1-metallacyclobuta-2,3-dienes as organometallic analogues of elusive 1,2-cyclobutadiene has so far been limited to SiMe3 substituted examples. We present the synthesis of two Ph substituted dilithiated ligand precursors for the preparation of four new 1-metallacyclobuta-2,3-dienes [rac-(ebthi)M] (M=Ti, Zr; ebthi=1,2-ethylene-1,10-bis(η5-tetrahydroindenyl)). The organolithium compounds [Li2(RC3Ph)] (1 b: R=Ph, 1 c: R=SiMe3) as well as the metallacycles of the general formula [rac-(ebthi)M(R1C3R2)] (2 b: M=Ti, R1=R2=Ph, 2 c: M=Ti, R1=Ph, R2=SiMe3; 3 b: M=Zr, R1=R2=Ph; 3 c: M=Zr, R1=Ph, R2=SiMe3) were fully characterised. Single crystal X-ray diffraction and quantum chemical bond analysis of the Ti and Zr complexes reveal ligand influence on the biradicaloid character of the titanocene complexes. X-band EPR spectroscopy of structurally similar Ti complexes [rac-(ebthi)Ti(Me3SiC3SiMe3)] (2 a), 2 b, and 2 c was carried out to evaluate the accessibility of an EPR active triplet state. Cyclic voltammetry shows that introduction of Ph groups renders the complexes easier to reduce. 13C CPMAS NMR analysis provides insights into the cause of the low field shift of the resonances of metal-bonded carbon atoms and provides evidence of the absence of the β-C-Ti interaction.

Crystal chemistry, Raman and FTIR spectroscopy, optical absorption, and luminescence study of Fe-dominant sogdianite

Abstract Fe-dominant sogdianite, a cyclosilicate compound with the chemical formula (Fe3+ 0.74Zr0.64Ti0.46 Al0.15)(□1.02Na0.98)K[Li3Si12O30], was studied. The investigation involved a comprehensive analysis of the mineral sample, including crystal-chemical analysis, Raman and FTIR spectroscopy, optical absorption, and luminescence study. Crystallographic site populations were determined through single crystal structure refinement and electron probe microanalysis. The thermoelastic behavior of a powder was studied using in situ high-temperature X-ray diffraction (30–750 °C). Notably, no phase transition was detected; sogdianite exhibited anisotropic thermal expansion. The first time study of vibrational spectra and spectral bands assigning were performed. The electronic transitions in d 5-ion impurities of sogdianite were studied using optical absorption and luminescence spectroscopy. The origin of pink color and luminescence of sogdianite was clarified. The broad spectral bands in the visible UV spectral region are responsible for the pink color exhibited by sogdianite and could be attributed to d–d transitions occurring in Fe3+ ions.

Non-ambient crystal chemistry of stillwellite-like BaBPO<SUB>5</SUB> from single crystal XRD data

Stillwellite-(Ce) and some its synthetic analogues tend to undergo phase transition from polar (ferroelectric) to nonpolar (paraelectric) modification on heating. However, the reasons for the transition and phase stability remain the subject of scientific debate. Here we present detail studies (scanning electron microscopy, energy-dispersive X-ray spectroscopy, Raman spectroscopy and single-crystal X-ray diffraction (SCXRD)) of hydrothermally grown BaBPO5 isostructural with stillwellite-(Ce). Its thermal behavior was studied by an in situ low- (from –173 to +25 °C) and high-temperature (HT; 25–800 °C) SCXRD. Fully ordered crystal structure of BaBPO5 (at T = 25 °C: trigonal, P3221, a = 7.1166(1) Å, c = 7.0011(1) Å, V = 307.07(1) Å3, R1 = 1.42 %) does not exhibit any change of symmetry upon cooling / heating unlike natural stillwellite-(Ce). Thermal expansion of BaBPO5 is almost isotropic (αmin = 8.4, αmax = 8.7⋅10-6 °C-1) despite the chain nature of borophosphate anion. The comparative crystal chemical analysis of HT behavior of cationic polyhedra in the stillwellite-family members is presented.

Crystal chemical indicators of oxo-centered tetrahedra establishment in divalent lead minerals

A complex crystal-chemical analysis of 1567 oxygen positions in 216 crystal structures of lead- containing minerals belonging to the classes of silicates, phosphates, oxides, oxohalides, and a number of others has been carried out. It was shown that the combined application of the bond valence method and the analysis of the geometric characteristics of Voronoi-Dirichlet polyhedra make it possible to confidently distinguish between oxygen positions related to cation structure blocks and oxygen positions for which a description based on an anion-centered approach is more justified. Numerical indicators for such a separation of oxygen positions are substantiated, which can be used to analyze large arrays of structural data using the machine learning approaches.

Crystal-chemical origins of the ultrahigh conductivity of metallic delafossites

Despite their highly anisotropic complex-oxidic nature, certain delafossite compounds (e.g., PdCoO2, PtCoO2) are the most conductive oxides known, for reasons that remain poorly understood. Their room-temperature conductivity can exceed that of Au, while their low-temperature electronic mean-free-paths reach an astonishing 20 μm. It is widely accepted that these materials must be ultrapure to achieve this, although the methods for their growth (which produce only small crystals) are not typically capable of such. Here, we report a different approach to PdCoO2 crystal growth, using chemical vapor transport methods to achieve order-of-magnitude gains in size, the highest structural qualities yet reported, and record residual resistivity ratios ( > 440). Nevertheless, detailed mass spectrometry measurements on these materials reveal that they are not ultrapure in a general sense, typically harboring 100s-of-parts-per-million impurity levels. Through quantitative crystal-chemical analyses, we resolve this apparent dichotomy, showing that the vast majority of impurities are forced to reside in the Co-O octahedral layers, leaving the conductive Pd sheets highly pure (∼1 ppm impurity concentrations). These purities are shown to be in quantitative agreement with measured residual resistivities. We thus conclude that a sublattice purification mechanism is essential to the ultrahigh low-temperature conductivity and mean-free-path of metallic delafossites.

Crystal growth, structural, optical, mechanical characterization and quantum chemical analysis by DFT of an organic nonlinear optical single crystal 4-Hydroxy pyridinium succinate for photonic and optoelectronic devices

A new organic nonlinear optical single crystal 4-Hydroxypyridinium Succinate was synthesized and grown successfully by slow evaporation method using methanol as solvent at ambient temperature. Single crystal X –ray diffraction studies on the grown crystal reveals that 4HPS crystallizes into orthorhombic structure with the non-centrosymmetric space group (Pna21). In structural point of view, the 4-Hydroxypyridinium cation is bonded to the hydrogen succinate anion by direct electron conjugation through nitrogen atom. In addition, the UV visible transmittance spectrum implies that the crystal has high transparency domain in the entire UV visible region with a lower cut-off wavelength of 286 nm. The various functional groups present in the crystal and their frequency assignments are derived from FTIR spectral analysis. The Photoluminescence spectrum brings forth that the grown crystal has violet emission property. The microhardness measurements testify that the crystal belongs to soft material category with reasonable hardness parameters. The compound was found to be thermally stable up to 188 °C without any weight loss from the TGA and DTG traces. The detailed quantum chemical calculation done by density functional theory (DFT) indicates the Homo –Lumo energy gap of the molecule is 3. 956 eV and 4. 289 eV for α and β wave functions respectively. The Laser induced damage threshold of the crystal investigated using Nd: YAG laser of 1064 nm radiation was found to be 21. 93 Gw/cm2. The second harmonic generation efficiency of the 4HPS crystal was confirmed by the emission of green light under Kurtz and Perry powder test.

Structure and titanium distribution of feiite characterized using synchrotron single-crystal X-ray diffraction techniques

Abstract A solid solution of the mineral feiite (Fe3TiO5) was recently discovered in a shock-induced melt pocket of the Shergotty martian shergottite. It is particularly interesting for its potential as an indicator of pressure-temperature (P-T) and oxygen fugacity in martian crustal and mantle material. To date, complete crystallographic analysis of feiite has not been conducted, as the mineral was previously analyzed by electron backscatter diffraction on micrometer-size grains (Ma et al. 2021). Here we report a convergent crystal-structure model for feiite based on synchrotron single-crystal X-ray diffraction data collected on three grains of feiite synthesized at 12 GPa and 1200 °C. Feiite adopts the CaFe3O5 structure type (Cmcm, Z = 4), which is composed of two octahedral M1 and M2 sites and one trigonal prismatic M3 site (M = metal) in a ratio of 1:2:1. The three feiite grains with composition Ti0.46–0.60Fe3.54–3.40O5 were best modeled by substituting Ti4+ into only the octahedral M2 site, accounting for 30% of this site. Comparisons of the measured average bond lengths in the coordination polyhedra with the optimized Ti4+–O, Fe2+–O, and Fe3+–O bond lengths suggest that ferrous iron occupies the trigonal M3 site, while iron is mixed valence in the octahedral M1 and M2 sites. The Ti4+ and Fe3+ content constrained by our crystal-chemical analyses suggests that at least ~30% of the available iron must be ferric (i.e., Fe3+/Fetotal = 0.3) for the sample synthesized at 12 GPa and 1200 °C and higher P-T conditions may be needed to form the end-member feiite (Fe32+TiO5).

Enantiomorph conversion in single crystals of the Weyl semimetal CoSi

Chiral intermetallic phases may show unusual chemical and physical properties with nontrivial structure-property relationship. It is therefore of particular interest to study the structural conversion between domains of different handedness. Here, the atomic decoration of the enantiomorph exchange area within single crystal of the Weyl semimetal CoSi is determined by a combination of atomic-resolution scanning transmission electron microscopy imaging, single crystal X-ray diffraction and quantum chemical analysis of atomic interactions. Two-atomic [CoSi] units are shown to be the bonding base for the FeSi-type structure and may be considered as ‘pseudo-molecules’, thinking of molecular organic crystals. Tiny reorganisation of atomic interactions within these units results in the appearance of sequence ‘faults’ in the structure pattern i.e. in a different structural motif in the enantiomorph exchange area, which – contrary to the A and B enantiomorphs of CoSi – contains an inversion centre and allows a local enantiomorph ‘conversion’. Due to the special features of atomic interactions, the reorganisation of multi-atomic bonds leads to slightly higher total energy. This appears within one and the same grain which is prepared by the short distance chemical vapor transport.

Synthesis and crystal structure of silicon pernitride SiN2 at 140 GPa.

Silicon pernitride, SiN2, was synthesized from the elements at 140 GPa in a laser-heated diamond anvil cell. Its crystal structure was solved and refined by means of synchrotron-based single-crystal X-ray diffraction data. The title compound crystallizes in the pyrite structure type (space group Pa , No. 205). The Si atom occupies a site with multiplicity 4 (Wyckoff letter b, site symmetry ..), while the N atom is located on a site with multiplicity 8 (Wyckoff letter c, site symmetry .3.). The crystal structure of SiN2 is comprised of slightly distorted [SiN6] octa-hedra inter-connected with each other by sharing vertices. Crystal chemical analysis of bond lengths suggests that Si has a formal oxidation state of +IV, while nitro-gen forms pernitride anions (N-N)4-.

Sample size dependence of high-temperature thermal stability of Ti2AlN MAX phase

The thermal stability of Titanium Aluminum Nitride (Ti2AlN) microcrystalline powder in vacuum has been studied by in-situ high-temperature X-ray diffraction. The limit of thermal stability for Ti2AlN phase is T < 850 °C. The process of thermal decomposition consists of the Al atoms sublimation and the formation of a new TiNx phase on the sample surface. An increase in sample size leads to an increase in thermal stability limit (850 °C for microcrystals and 1550 °C for dense bulk sample). Based on crystal chemical analysis and quantum chemical calculations, a mechanism of thermal dissociation was proposed. Kinetics of thermal dissociation of the Ti2AlN phase was modeled using the Avrami equation. Avrami exponent parameters (n = 1.09; 1.28) indicate that the process of germs formation occurs at a subgrain boundaries of the sample. The observed temperature dependence of the parameter n can be associated with a probability change of crosslinking formation during the growth of a new phase. The size dependence of Ti2AlN thermal stability was explained by the ratios of Al diffusion coefficients in the crystallite bulk and along the subgrain boundaries.

GeCn Coordination Polyhedra in the Crystal Structures

A crystal-chemical analysis has been performed for germanium compounds whose structure includes GeCn coordination polyhedra using the intersecting sectors method and Voronoi–Dirichlet polyhedra. In the structures of organogermanium compounds, the germanium atoms have coordination numbers of 2–6 and 10 with respect to the carbon atoms. The influence of the coordination number and oxidation state of germanium atoms on the main characteristics of their Voronoi–Dirichlet polyhedra (VDP) was considered. The existence of a single linear dependence of the solid angles of VDP faces corresponding to valence and nonvalence Ge–C and Ge⋅⋅⋅C contacts on the corresponding internuclear distances was established. A stereo effect of the lone pair of electrons of Ge(II) atoms in the GeCn complexes (n = 2–6 or 10) found; it manifests itself as a displacement of the nuclei of Ge(II) atoms from the centers of gravity of their VDPs (0.15–0.58 Å) and as asymmetry of the coordination sphere. The deviation of the GeC3 complexes from planar geometry in the crystal structures was shown to be directly proportional to the displacement of the nuclei of Ge atoms from the centers of gravity of their VDP.

TO A QUESTION OF SULFUR SITES IN CRYSTAL STRUCTURES OF TETRAHEDRITE GROUP MINERALS: RELATIONSHIPS BETWEEN OCCUPANCY, EFFECTIVE ION SIZES, AND UNIT CELL PARAMETERS

In this work, a crystal chemical analysis of the known experimentally deciphered crystal structures of tetrahedrite group minerals was carried out in order to reveal the relationships between the occupancies of anion crystallographic sites in the structures, their effective sizes and unit cell parameters. To achieve this aim, we analyzed the effective sizes of the 24g and 2a anion sites in 68 deciphered crystal structures of tetrahedrite group minerals according to the published data. The analysis was carried out using the TOPOSPro software package by partitioning the space into Voronoi–Dirichlet polyhedra (VDP). It has been shown theoretically for the first time that the content of a large sulfur ion and its deficiency affect the unit cell parameter. A linear correlation between the VDP volume of the anionic site of S2– (24g) and the unit cell parameter in minerals of the tetrahedrite group was established, which shows that the anionic substructure dictates the structural motif in this class of compounds. It was found that the change in the VDP volumes of sulfur anions is associated with different occupancies of anionic sites. It is found that the formula (unit cell) of the compound contains fewer than 13 sulfur ions in almost all deciphered crystal structures of tetrahedrite group minerals. It was concluded that the calculated VDP volume of the 24g anionic position less than 22 Å3 indicates a significant deficit in the anionic substructure. It was shown that, using information about the VDP volumes of all anionic and cationic sites in the structure, it is possible to predict the unit cell parameters of minerals of the tetrahedrite group with an accuracy of 0.01 Å

Structural peculiarities? Aperiodic crystals, modulated phases, composite structures

Abstract According to a general understanding, a crystal structure is defined by a lattice and the content of the unit cell of this lattice. As consequence a crystal exhibits three-dimensional periodicity with respect to the atoms. However, an increasing number of known crystal structures does not follow this idea of periodicity, but shows an aperiodic arrangement of its atoms. This group of so-called “aperiodic crystals” contains quasicrystals, modulated phases and composite structures. The latter two can be properly described within the higher-dimensional superspace approach to enable an accurate crystal-chemical analysis. Here the superspace is a mathematical tool, in which periodicity can be recovered in a higher-dimensional space. In the first part of this review the basic concept of periodic and aperiodic crystals is presented and similarities and differences of modulated phases, composite structures and quasicrystals are discussed. In a second part the higher-dimensional superspace approach is introduced in reciprocal and in direct space and the implementation of symmetry in superspace is reviewed. In the last part representative examples and the origin of aperiodicity in the crystal structures are discussed.

High-temperature behavior of the UV-luminescent sodalite-type natural compound Na8(Al6Si6O24)(HS)2: Comparative study by in situ single-crystal X-ray diffraction and Raman spectroscopy

The in situ single-crystal X-ray diffraction and Raman spectroscopy were performed for a sapozhnikovite Na8(Al6Si6O24)(HS)2, a rare mineral with sodalite-type crystal structure. The crystal chemical analysis and calculation of thermal expansion coefficients based on the refinement of Na8(Al6Si6O24)(HS)2 crystal structures in the temperature range of 300–1273 K show that this sodalite-type compound undergoes: (1) reversible phase transition P4‾ 3n ↔ Pm3‾n at 1223 K, (2) drastic increase of linear expansion coefficient at 1173 K, (3) non-elastic behavior of sapozhnikovite framework after cooling. The temperature dependencies of the unit-cell parameters were divided into two parts and described by quadratic a = 8.911(12) – 0.000018(33)T + 0.000000138(22)T2 (from 300 to 1173 K) and linear a = 7.765(13) + 0.001130(11)T (from 1173 to 1273 K) polynomial functions. Raman spectroscopy data reveal the partial transformations of the extra-framework HS− anion by follows reactions: 6HS–→ S3•– + 3H2S (gas) and 2HS– – 2e → S22− + 2H+. These transformations may cause the observed discontinuity in the thermal expansion curve for sapozhnikovite at 1173 K with drastic increase of linear expansion coefficient and not fully elastic behavior of framework after removal of temperature exposure. After the heat treatment experiments (300–1273 K) the HS− anion restores in the β-cage of sapozhnikovite crystal structure. In the synthetic analogue of sapozhnikovite the heat treatment leads to the irreversible transformation according to the reactions: 2HS– + 2.5O2 (gas) → SO42− + 0.25S4 + H2O (gas) and 2HS– + 3.5O2 (gas) → SO42− + SO2 (gas) + H2O (gas). The orange luminescence of Na8(Al6Si6O24)(HS)2 is stable up to the 1073 K.

Crystallochemical Role of Benzoate and Phenylacetate Ions in Structures of Coordination 3d-Metal Compounds

A crystal chemical analysis of the 3d-metal benzoate- and phenylacetate-containing compounds is carried out in terms of the stereoatomic crystal structure model using characteristics of the Voronoi–Dirichlet polyhedra. Coordination types of benzoate and phenylacetate anions toward the transition metals from Ti to Zn are considered. The influence of the coordination type on the characteristics of M–O bonds in the crystal structures is revealed. The electron-donating ability of benzoate and phenylacetate anions toward 3d metals is quantitatively estimated using the 18-electron rule.

Dependence of antimicrobial properties on site-selective arrangement and concentration of bioactive Cu2+ ions in tricalcium phosphate

Cu-doped solid solutions Ca10.5–xCux(PO4)7 with β-Ca3(PO4)2 (β-TCP) structure were synthesized using high-temperature solid-state synthesis. Correctly characterizing the location of Cu2+ in the structure is important for a correct understanding of the biological properties formation. The limit of Ca10.5–xCux(PO4)7 solid solutions without impurity phases was found at x = 1.5. The crystal-chemical analysis reveals that the Cu2+ ions cannot be located in the M4 site of the β-TCP-type structure due to the very distorted environment. The Cu2+ ions preferably occupy the M5 site (x ≤ 1.00) and then located in the M3 and M2 sites (x > 1.00). The chemical composition, local environment, and structural features of Ca10.5–xCux(PO4)7 phosphates were investigated by a complex of methods. The antibacterial properties were studied on one fungus (C. albicans) and four bacteria (E. coli, E. faecalis S. aureus and P. aeruginosa). Biocompatibility tests were performed on human bone marrow mesenchymal stem cells (hMSCs). The biological response of the Cu2+ strongly depends on the occupied ion position and its concentration. The concentration-dependent behavior of the bacteria growth inhibition was observed, and the sample with x = 1.33 exhibits the highest activity between single-phase samples. Further increasing of bacteria growth inhibition is attributed to Ca3Cu3(PO4)4 impurity phase. Also, antimicrobial properties depend on the Cu2+ location in the β-TCP crystal structure in accordance with ion release behavior. The Cu2+ location in the large M3 polyhedra leads to a noticeable increase in ion release. Biocompatibility assays on hMSCs showed the absence of cytotoxicity in direct and indirect contact for single-phase samples. In the biphasic sample the presence of impurity Ca3Cu3(PO4)4 phosphate at 2 wt% causes a cytotoxicity effect. Thus, phase purity plays a critical role in understanding the regularities of bioactive properties formation. This work can be an initial basis for further investigations of the site-selective arrangement of bioactive ions, such as Cu2+ and other similar ions, in the β-TCP structure to enhance biological potential.