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The structural and microstructural responses of a model metal–organic framework material, Ni(3-methyl-4,4′-bipyridine)[Ni(CN)4] (Ni-BpyMe or PICNIC-21), to CO2 adsorption and desorption are reported for in situ small-angle X-ray scattering and X-ray diffraction measurements under different gas pressure conditions for two technologically important cases. These conditions are single or dual gas flow (CO2 with N2, CH4 or H2 at sub-critical CO2 partial pressures and ambient temperatures) and supercritical CO2 (with static pressures and temperatures adjusted to explore the gas, liquid and supercritical fluid regimes on the CO2 phase diagram). The experimental results are compared with density functional theory calculations that seek to predict where CO2 and other gas molecules are accommodated within the sorbent structure as a function of gas pressure conditions, and hence the degree of swelling and contraction in the associated structure spacings and void spaces. These predictions illustrate the insights that can be gained concerning how such sorbents can be designed or modified to optimize the desired gas sorption properties relevant to enhanced gas recovery or to addressing carbon dioxide reduction through carbon mitigation, or even direct air capture of CO2.

We report on the structure and electrical transport of single-crystal Eu2Ga11Sn35, the sole example of a very low cation concentration clathrate-I composition with atypical transport directly attributable to the structure and stoichiometry.

The structure, powder diffraction patterns and bandgap measurements of a series of manganese- and tungsten-containing alkaline-earth double perovskites (CaxSr2−x)MnWO6 (x = 0.25, 0.5, 0.75, 1.5, 1.75) have been investigated. Powder X-ray diffraction patterns of this series of compounds measured at room temperature have been submitted to be included in the Powder Diffraction File (PDF). These compounds crystallize in monoclinic space group P21/n (No.14). From (Ca1.75 Sr0.25)MnWO6 to (Ca0.25Sr1.75)MnWO6, lattice parameters a range from 5.6729(2) Å to 5.6774(4) Å, b from 5.5160(2) Å to 5.6638(4) Å, c from 7.8741(3) Å to 8.0051(4) Å, V from 240.39(2) Å3 to 257.410(12) Å3, and Z = 2. These compounds are pseudo-tetragonal. They all consist of distorted MnO6 and WO6 octahedra with rotational mismatch angles and tilt angles with respect to each other. For (CaxSr2−x)MnWO6, as x increases, the mismatch angles for MnO6 octahedra increase from 7.96 (6)° to 13.12(8)° and from 9.28(7)° to 14.87(9)° for WO6 octahedra. Correspondingly, the tilt angles range from 11.60(15)° to 14.20(3)° for MnO6, and from 13.34(2)° to 16.35(3)° for WO6. Bandgap measurements suggest that these compounds to be direct-allowed semiconductors with bandgaps ranging from 1.5 to 2.5 eV, indicating that members of (CaxSr2−x)MnWO6 are potential photocatalysts and photovoltaic materials that absorb visible light of the solar spectrum.

Single crystals of the quaternary chalcogenide BaCuGdTe3 were obtained by direct reaction of elements allowing for a complete investigation of the intrinsic electrical and thermal properties of this previously uninvestigated material.

Polarization and strain tuning of the Rashba spin-texture in quasi-one-dimensional organic–inorganic hybrid perovskites (MV)AI3Cl2 can be applied in spin field-effect-transistors and photovoltaic cells.

Solid solutions in the Ba(Pb1−xSrx)O3−z system were prepared by aliovalent substitution of Pb4+ by Sr2+ ions to investigate the effect of cation stoichiometry on thermal and electrical properties as x was varied between 0 and 0.4, in the temperature range 300–523 K. The starting compound, barium plumbate (BaPbO3), has a perovskite structure and is known to exhibit metallic conductivity due to an overlap of the O2p nonbonding and the Pb–O spσ antibonding band, which is partially filled by the available electrons. The large difference in the ionic radii between the Pb4+ and Sr2+ ions introduces significant strain into the (Pb/Sr)O6 octahedra of the perovskite structure. Additionally, charged defects are created on account of the different oxidation states of the Pb4+ and Sr2+ ions. Evidence of a metal to insulator transition (MIT) of the Mott–Hubbard type has been observed at a critical concentration of Sr2+ ions.

We report the development of a high-temperature Seebeck coefficient Standard Reference Material (SRM) for use in instrument validation and interlaboratory data comparison in the temperature range of 295–900 K to support the research, development, and production of materials and devices related to thermoelectric-based energy conversion applications. We describe the synthesis, anneal–quench procedure, and physical characterization of a p-type boron-doped polycrystalline silicon–germanium alloy with a nominal composition of Si80Ge20. For the certification measurements, we describe the measurement protocols, statistical analysis, the certified Seebeck coefficient values, comprehensive uncertainty budgets, and metrological traceability. Our extensive efforts to identify, reduce, and quantify measurement uncertainties will be emphasized. This new SRM complements SRM 3451 Low-Temperature Seebeck Coefficient Standard (10–390 K) to provide certified reference materials traceable to the International System of Units (SI) for Seebeck coefficient measurements within the temperature range 10–900 K.

Layered perovskite Ca2.91Na0.09Ti2-xRhxO7 (x = 0.00, 0.02, 0.04, 0.06) were synthesized by a conventional solid-state reaction. Room temperature ferroelectricity has been confirmed. The remanent polarization increases with an increase of Rh content, which is due to a larger oxygen octahedral distortion by Rh doping. The coercive field increases with Rh doping as the pinning effect of oxygen vacancies reduce the mobility of domain wall. Remanent polarization and coercive field are caused by different mechanisms, so it is possible to modulate them independently to meet the requirement of application in ferroelectric field. The concentration of oxygen vacancy increased with Rh doping, leading to the significant increase of leakage current density. The bandgap of samples doped with Rh drastically decrease and the visible light response of the sample was improved by Rh doping due to the formation of impurity energy levels within the band gap.

Clathrates have been reported to form in a variety of different structure types; however, inorganic clathrate-I materials with a low-cation concentration have yet to be investigated. Furthermore, tin-based compositions have been much less investigated as compared to silicon or germanium analogs. We report the temperature-dependent structural and thermal properties of single-crystal Eu2Ga11Sn35 revealing the effect of structure and composition on the thermal properties of this low-cation clathrate-I material. Specifically, low-temperature heat capacity, thermal conductivity, and synchrotron single-crystal x-ray diffraction reveal a departure from Debye-like behavior, a glass-like phonon mean-free path for this crystalline material, and a relatively large Grüneisen parameter due to the dominance of low-frequency Einstein modes. Our analyses indicate thermal properties that are a direct result of the structure and composition of this clathrate-I material.

Hybrid improper ferroelectric Ca3Ti2O7 and Ca3Ti19Ru0.1O7 ceramics were successfully synthesized by conventional solid-state reaction method. Two strongest diffraction peaks located around 2θ = 33° shifted towards the lower angle region with Ru substitution, reflecting structure variation. Grain growth and higher oxygen vacancy concentration after doping resulted in a reduction in the coercive field about 20 kV/cm. Optical bandgap estimated by UV-vis diffuse reflectance (DR) spectrum and X-ray photoelectron spectroscopy (XPS) valence band spectra showed a decreasing trend due to the existence of impurity energy level upon Ru doping, which was consistent with the results of first-principles calculations. The origin of the unexpected induced magnetic moments in Ru-dope Ca3Ti2O7 is also discussed.

We envision an autonomous sorbent materials foundry (SMF) for rapidly evaluating materials for direct air capture of carbon dioxide (CO2), specifically targeting novel metal organic framework materials. Our proposed SMF is hierarchical, simultaneously addressing the most critical gaps in the inter-related space of sorbent material synthesis, processing, properties, and performance. The ability to collect these critical data streams in an agile, coordinated, and automated fashion will enable efficient end-to-end sorbent materials design through machine learning driven research framework.

X-ray reference powder patterns and structures have been determined for a series of cobalt- and tungsten-containing cubic alkaline-earth perovskites, (BaxSr1–x)2CoWO6 (x = 0.1, 0.2, 0.3, 0.5, 0.7, and 0.9). The structure of the end members of the series, Sr2CoWO6 and Ba2CoWO6, were tetragonal and cubic, respectively, agreeing with the literature data. From Rietveld refinements, it was found that when x = 0.1 and 0.2, the structure was tetragonal I4/m (a = 5.60481(6) and 5.62305(11) Å and c = 7.97989(12) and 7.9847(2) Å, respectively; Z = 2). When x > 0.2, the structure was cubic (Fm$\bar{3}$m, No. 225; Z = 4) (from x = 0.3 to 0.9, a increases from 7.98399(13) to 8.08871(10) Å). This tetragonal series of compounds exhibit the characteristics of a distorted double-perovskite structure. The bond valence sum values for the alkaline-earth (Ba, Sr) sites in all (BaxSr1−x)2CoWO6 members are greater than the ideal value of 2.0, indicating over-bonding situation, whereas for the W sites, as x increases, a change from under-bonding to slightly over-bonding situation was observed. Density functional theory calculations revealed that while Sr2CoWO6 is a semiconductor, Ba2CoWO6 and SrBaCoWO6 are half-metals. Powder X-ray diffraction patterns of this series of compounds (BaxSr1−x)2CoWO6, with x = 0.1, 0.2, 0.3, 0.5, 0.7, and 0.9, have been submitted to be included in the Powder Diffraction File.

Many ferroelectric (FE) organic-inorganic hybrid perovskites (OIHPs) show great promise in the fields of photovoltaic cells and information memory devices. We systematically investigated the FE, optical, and electric properties of quasi-one-dimensional OIHPs $(\mathrm{MV})A{\mathrm{I}}_{3}{\mathrm{Cl}}_{2}$ ($\mathrm{MV}=\mathrm{methylviologen}, A=\mathrm{Bi},\mathrm{Sb}$) using density functional theory calculations. The FE polarization mechanism of $(\mathrm{MV})A{\mathrm{I}}_{3}{\mathrm{Cl}}_{2}$ mainly originates from octahedral distortion along the direction of octahedral chains with the $p\text{\ensuremath{-}}p$ coupling of ${A}^{3+}$ cations and ${\mathrm{I}}^{\ensuremath{-}}$ anions. Due to the loosely coupled FE chains, $(\mathrm{MV})\mathrm{Bi}{\mathrm{I}}_{3}{\mathrm{Cl}}_{2}$ and $(\mathrm{MV})\mathrm{Sb}{\mathrm{I}}_{3}{\mathrm{Cl}}_{2}$ possess a relatively low energy barrier of polarization switching at the 180\ifmmode^\circ\else\textdegree\fi{} reversal of the FE polarization. The estimated upper limit memory densities of 14.9 and $15.0\phantom{\rule{0.16em}{0ex}}\mathrm{Tb}/\mathrm{c}{\mathrm{m}}^{2}$ for $(\mathrm{MV})\mathrm{Bi}{\mathrm{I}}_{3}{\mathrm{Cl}}_{2}$ and $(\mathrm{MV})\mathrm{Sb}{\mathrm{I}}_{3}{\mathrm{Cl}}_{2}$, respectively, hold promise to be applied to high-density FE memory devices. The strong anisotropic optical absorption of $(\mathrm{MV})A{\mathrm{I}}_{3}{\mathrm{Cl}}_{2}$ is in the visible light region, and its estimated maximum power conversion efficiencies are g23%. The high anisotropic carrier mobility in $(\mathrm{MV})A{\mathrm{I}}_{3}{\mathrm{Cl}}_{2}$ enhances the separation of electron-hole pairs. Both $(\mathrm{MV})\mathrm{Bi}{\mathrm{I}}_{3}{\mathrm{Cl}}_{2}$ and $(\mathrm{MV})\mathrm{Sb}{\mathrm{I}}_{3}{\mathrm{Cl}}_{2}$ possess positive piezoelectric effect; therefore, strain design is an effective approach to enhance power conversion efficiency and carrier mobility of $(\mathrm{MV})A{\mathrm{I}}_{3}{\mathrm{Cl}}_{2}$, leading to experimental design of FE photovoltaic cell.

Modern machine learning and autonomous experimentation schemes in materials science rely on accurate analysis of the data ingested by these models. Unfortunately, accurate analysis of the underlying data can be difficult, even for domain experts, complicating the training of the models intended to drive experiments. This is especially true when the goal is to identify the presence of weak signatures in diffraction or spectroscopic datasets. In this work, we examine a set of as-obtained diffraction data that track the phase transition from monoclinic to tetragonal in a Nb-doped VO2 film as a function of temperature and dopant concentration. We then task a set of domain experts and a set of machine learning experts with identifying which phase is present in each diffraction pattern manually and algorithmically, respectively; in both cases, the labels can vary dramatically, especially at the phase boundaries. We use the mode of the labels and the Shannon entropy as a method to capture, preserve and propagate consensus labels and their variance. Further we use the expert labels as a benchmark and demonstrate the use of Shannon entropy weighted scoring to test the performance of machine learning generated labels. Finally, we propose a material data challenge centered around generating improved labeling algorithms. This real-world dataset curated with expert labels can act as test bed for new algorithms. The raw data, annotations and code used in this study are all available online at data.gov and the interested reader is encouraged to replicate and improve the existing models

Porphyrinic compounds are of increasing interest to the materials science community, yet little attention has been paid to crystallographically controlled voids and channels in these materials. We have conducted an initial survey of the voids and channels in a random subset of 1000 porphyrinic compounds with known crystal structures. From calculations using a rolling-probe subroutine, we have found that about 5% of these compounds have line-of-sight channels, which differ in their topology depending on the crystallography. A small but significant number of porphyrinic compounds have calculated void contents of >25 volume %. We discuss in detail the void and channel characteristics, including pore-size distribution, of four representative compounds, with technological implications.

Structure and optical properties have been successfully determined for a series of niobium- and tantalum-containing layered alkaline-earth silicate compounds, Ba3(Nb6−xTax)Si4O26 (x = 0.6, 1.8, 3.0, 4.2, 5.4). The structure of this solid solution was found to be hexagonal P-62m (No. 189), with Z = 1. With x increases from 0.6 to 5.4, the lattice parameter a increases from 8.98804(8) to 9.00565(9) Å and c decreases from 7.83721(10) to 7.75212(12) Å. As a result, the volume decreases from 548.304(11) to 544.479(14) Å3. The (Nb/Ta)O6 distorted octahedra form continuous chains along the c-axis. These (Nb/Ta)O6 chains are in turn linked with the Si2O7 groups to form distorted pentagonal channels in which Ba ions were found. These Ba2+ ions have full occupancy and a 13-fold coordination environment with neighboring oxygen sites. Another salient feature of the structure is the linear Si–O–Si chains. When x in Ba3(Nb6−xTax)Si4O26 increases, the bond valence sum (BVS) values of the Ba sites increase slightly (2.09–2.20), indicating the size of the cage becoming progressively smaller (over-bonding). While SiO cages are also slightly smaller than ideal (BVS range from 4.16 to 4.19), the (Nb/Ta)O6 octahedral cages are slightly larger than ideal (BVS range from 4.87 to 4.90), giving rise to an under-bonding situation. The bandgaps of the solid solution members were measured between 3.39 and 3.59 eV, and the x = 3.0 member was modeled by density functional theory techniques to be 3.07 eV. The bandgaps of these materials indicate that they are potential candidates for ultraviolet photocatalyst.

Sr2Nb10O27 and Sr2Ta10−xO27−y exhibit the tripled tetragonal-tungsten-bronze (TTTB)-related superstructures. In contrast to Sr2Ta10−xO27−y, where an extended solid solution was found, Sr2Nb10O27 only forms a narrow range of solid solution, Sr1−xNb10O27−z (0 ≤ x ≤ 0.04). Serial X-ray and neutron diffraction studies show that both compounds can be modelled in the orthorhombic Pba2 space group. Lattice parameters obtained from powder X-ray refinements are a = 12.3887(14) A, b = 37.103(4) A, c = 3.866(2) A, for Sr2Ta10−xO27−y, and a = 12.3888(2) A, b = 36.9839(5) A, and c = 3.94027(3) A for Sr2Nb10O27. Neutron Rietveld refinements of both structures revealed the possible reason for the differing solid solution behavior. For Sr2Nb10O27, all Nb sites are fully occupied, whereas in Sr2Ta10−xO27−y, three out of the nine crystallographically unique Ta sites were shown to be partially occupied. Charge adjustment is therefore possible by increasing the Sr concentration, leading to a solid solution series and smaller Ta/Sr ratio as compared to Sr2Nb10O27. In the TTTB-related structures, Nb and Ta ions both occupy octahedral and pentagonal bipyramidal coordination sites. Layers of interconnected corner-shared octahedra were found parallel to the ab plane, with 3-, 4- and 5-fold tunnels found in the structure running parallel to the c-axis. Sr ions partially fill the 4- and 5-fold tunnels.

Powder X-ray diffraction patterns for three forms of MIL-53(Al), a metal organic framework (MOF) compound with breathing characteristics, were investigated using the Rietveld refinement method. These three samples are referred to as the MIL-53(Al)as-syn (the as synthesized sample), orthorhombic, Pnma, a = 17.064(2) Å, b = 6.6069(9) Å, c = 12.1636(13) Å, V = 1371.3(2) Å3, Z = 4), MIL-53(Al)LT-H (low-temperature hydrated phase, monoclinic P21/c, a = 19.4993(8) Å, b = 15.2347(6) Å, c = 6.5687(3) Å, β = 104.219(4) °, V = 1891.55(10) Å3, Z = 8), and MIL-53(Al)HT-D (high-temperature dehydrated phase, Imma, a = 6.6324(5) Å, b = 16.736(2) Å, c = 12.840(2), V = 1425.2(2) Å3, Z = 4). The crystal structures of the “as-syn” sample and the HT-D sample are confirmed to be the commonly adopted ones. However, the structure of the MIL-53(Al)LT-H phase is confirmed to be monoclinic with a space group of P21/c instead of the commonly accepted space group Cc, resulting in a cell volume double in size. The structure has two slightly different types of channel. The pore volumes and pore surface area were estimated to be 0.11766 (8) cm3/g and 1461.3(10) m2/g for MIL-53(Al)HT-D (high-temperature dehydrated phase), and 0.08628 (5) cm3/g and 1401.6 (10) m2/g for MIL-53(Al)as-syn phases, respectively. The powder patterns for the MIL-53(Al)as-syn and MIL-53(Al)HT-D phases are reported in this paper.

Structural characterization and X-ray reference powder pattern determination have been conducted for the Co- and Zn-containing tridymite derivatives Ba(Co1−xZnx)SiO4 (x = 0.2, 0.4, 0.6, 0.8). The bright blue series of Ba(Co1−xZnx)SiO4 crystallized in the hexagonal P63 space group (No. 173), with Z = 6. While the lattice parameter “a” decreases from 9.126 (2) Å to 9.10374(6) Å from x = 0.2 to 0.8, the lattice parameter “c” increases from 8.69477(12) Å to 8.72200(10) Å, respectively. Apparently, despite the similarity of ionic sizes of Zn2+ and Co2+, these opposing trends are due to the framework tetrahedral tilting of (ZnCo)O4. The lattice volume, V, remains comparable between 626.27 Å3 and 626.017 (7) Å3 from x = 0 to x = 0.8. UV-visible absorption spectrum measurements indicate the band gap of these two materials to be ≈3.3 and ≈3.5 eV, respectively, therefore potential UV photocatalytic materials. Reference powder X-ray diffraction patterns of these compounds have been submitted to be included in the Powder Diffraction File (PDF).

Based on the experimentally determined framework structure of porous MnO2 octahedral molecular sieve (OMS)-5, we used density functional theory-based calculations to evaluate the effect of Na+ cation on pore dimensionality and structural stability, and the interaction between CO2 and OMS-5. We quantified the formation energy of one CO2/unit tunnel and two CO2/unit tunnel, and projected the electronic density of states on the OMS-5 framework, CO2 molecules, and Na+ cations to reveal their individual contributions and bonding nature. Partial charge densities were also calculated to investigate CO2 adsorption behavior in the OMS-5. Our studies predict the initial stage and driving force for the adsorption of CO2 in the OMS-5, guiding the OMS material design for carbon capture and storage applications.

The phase equilibrium diagram of the CaO-½Ho2O3-CoOz system was determined at 885 °C in air. This diagram offers compatibility relationships in the ternary oxide system that are essential for processing and for the understanding of properties of several thermoelectric phases in the system. Four three-phase regions and three solid solution tie-line regions were determined in the CaO-½Ho2O3-CoOz system. In the CaO-Ho2O3 system, while a small solid solution region was identified for (Ho1-xCax)O(3-z)/2 (0 ≤x ≤ 0.14), Ho was not present in the Ca site of CaO. Neither the reported Ho2CoO4 phase in the Ho2O-CoOz system nor the Ca-doped (Ho1+xCa1-x)CoO4-z phase was present at 885 °C. No solid solution of the distorted perovskite, (Ho1-xCax)CoO3-z, was established at this temperature. The CaO-CoOz system consists of two calcium cobaltate thermoelectric compounds. The 2D thermoelectric oxide, (Ca3-xHox)Co4O9-z (0 ≤x ≤ 0.5), has a misfit layered structure, and the 1D Ca3Co2O6 consists of chains of alternating CoO6 trigonal prisms and CoO6 octahedra. Ca3Co2O6 was found to be a stoichiometric compound. A comparison of the phase diagrams of the CaO-½R2O3-CoOz (R = La, Nd, Eu, and Ho) systems is given.

Ruddlesden-Popper layered Ca3Ti2O7 (CTO) and Ca2.85Na0.15Ti2O7 (CNTO) ceramics were successfully prepared by a conventional solid-state reaction process. The ferroelectric coercive field greatly decreased via Na doping. Interestingly, a diode-like electric transport effect was observed in the CNTO sample, which is most likely due to a newly formed p-n junction caused by the applied electric field. Optical characterization by UV–visible absorption showed a decrease of band gap from 3.55 to 3.41eV via Na doping. First-principles calculation showed a similar decreasing trend which confirmed the experimental results.

A series of double-perovskite oxides, Sr2RNbO6 (R = Sm, Gd, Dy, Ho, Y, Tm, and Lu) were prepared and their crystal structure and powder diffraction reference patterns were determined using the Rietveld analysis technique. The crystal structure of each of the Sr2RNbO6 phase is reported in this paper. The R = Gd, Ho, and Lu samples were studied using synchrotron radiation, while R = Sm, Dy, Y, and Tm samples were studied using laboratory X-ray diffraction. Members of Sr2RNbO6 are monoclinic with a space group of P21/n and are isostructural with each other. Following the trend of “lanthanide contraction”, from R = Sm to Lu, the lattice parameters “a” of these compounds decreases from 5.84672(10) to 5.78100(3) Å, b from 5.93192(13) to 5.80977(3) Å, c from 8.3142(2) to 8.18957(5) Å, and V decreases from 288.355(11) to 275.057(2) Å3. In this double-perovskite series, the R3+ and Nb5+ ions are structurally ordered. The average Nb–O bond length is nearly constant, while the average R–O bond length decreases with the decreasing ionic radius of R3+. Powder diffraction patterns for these compounds have been submitted to the Powder Diffraction File (PDF).

Single crystals of clathrate-I Ba8Cu16As30 have been synthesized and their structure and electronic properties determined using synchrotron-based X-ray diffraction and first-principles calculations. The structure is confirmed to be Pm3n (No. 223), with lattice parameter a = 10.4563(3) A, and defined by a tetrahedrally bonded network of As and Cu that forms two distinct coordination polyhedra, with Ba residing inside these polyhedra. All crystallographic positions are fully occupied with no vacancies or superstructure with the Cu atoms, while occupying all framework sites in the network, exhibiting a preference for the 6c site. Agreement between the experimental and theoretically predicted structures was achieved after accounting for spin–orbit coupling. Our calculated Fermi surface, electron localization, and charge transfer, as well as a comparison with the results for elemental As46, provide insight into the fundamental properties of this clathrate-I material.

Synchrotron X-ray single crystal structure determination of two 2D Hofmann-related compounds, [Ni(p-Xylyenediamine)n-tetracyanonickelate] (abbreviated as Ni-pXdam) and [Ni(tetrafluoro-p-Xylyenediamine)n-tetracyanonickelate] (abbreviated as Ni-pXdamF4), have been conducted. Both the pXdam and pXdamF4 ligands contain two short chains of -CH2NH2 at the para-positions of a phenyl ring. These flexible chains link the 6-fold coordinated Ni2 sites throughout the network. In Ni-pXdam, the closed-2D network of [Ni-(CN-Ni1/4-)4]∞ is broken into 1D chains, leaving the C≡N groups at the trans-positions of the Ni(CN)4 moiety unbridged. The resulting 1D chains [(trans-)-NC-Ni(CN)2-CN-Ni-]∞ runs along the [010] direction of the unit cell. The pXdam ligands bridge in pair between the Ni atoms of the adjacent chains. The catenation structure of [Ni{(pXdam)}]∞ could be referred to as double -1D. In Ni-pXdamF4, the -CH2NH2 ligands connect the neighboring chains via the 6-fold Ni2 site. Surrounding the 4-fold Ni1 site, the two trans terminal C≡N groups were replaced by the Lewis base NH3 during the synthesis process, therefore preventing the propagation of the 2D net to form a 3D network. Computed pore volume of both compounds indicated that there is not sufficient space in the structure to accommodate gas molecules. In both compounds, hydrogen bonds were found, and solvent of crystallization was absent due to the limited free space in the structure.

The crystal structure and powder patterns were prepared for the distorted perovskite series R(Co3/4Ti1/4)O3 (R = La, Pr, Nd, Sm, Eu, Gd, Dy, Ho). The R(Co3/4Ti1/4)O3 members are isostructural with each other and are crystallized in the orthorhombic crystal system with space group Pnma, Z = 4. From R = La to Ho, the lattice parameters a range from 5.4614(3) to 5.5368(2) Å, b range from 7.7442(4) to 7.4859(2) Å, and c range from 5.5046(3) to 5.2170(2) Å. The unit-cell volumes, V which range from 232.81(2) to 216.237(11) Å3 follow the trend of “lanthanide contraction”. The structure distortion of these compounds is evidenced in the tilt angles θ, ϕ, and ω, which represent rotations of an octahedron about the pseudo-cubic perovskite [110]p, [001]p and [111]p axes. All three tilt angles increase across the lanthanide series (for R = La to R = Ho: θ increases from 8.34° to 17.00°, ϕ from 6.24° to 8.53°, and ω from 10.41° to 18.96°), indicating a greater octahedral distortion as the ionic radius of R3+ [r(R3+)] decreases. The bond valence sum values for the (Co/Ti) site and the R site of R(Co3/4Ti1/4)O3 reveal no significant bond strain in these compounds. X-ray diffraction patterns of the R(Co3/4Ti1/4)O3 samples were submitted to the Powder Diffraction File.

The crystal structures, solid solution limit, and powder X-ray reference diffraction patterns for two ‘natural superlattice’ series Bi1-xBaxCuOSe (x = 0.05, 0.075, 0.1, 0.2, and 0.3), and Bi1-xCaxCuOSe (x = 0, 0.05, 0.075, 0.1, 0.2 and 0.3) have been determined. The structure/property relationships of these thermoelectric materials are summarized. As the ionic radius of Ba2+ is greater than that of Bi3+, the unit cell volume, V, of Bi1-xBaxCuOSe increases progressively from x = 0 to x = 0.2 (from 137.868 (5) A3 to 141.194 (10) A3, respectively). However, even though the ionic radius of Ca2+ is smaller than that of Bi3+, the unit cell volumes, V, of Bi1-xCaxCuOSe also show an increasing trend as a function of x (137.868 (5) A3 to 139.295 (12) A3 from x = 0 to 0.3, respectively) due to the relatively large increase in c parameter. The structure of Bi1-xAxCuOSe (A = Ba and Ca) can be considered as built from [Bi2(1-x)A2xO2]2(1−x)+ layers normal to the c-axis alternating with fluorite-like [Cu2Se2]2(1−x)- layers in the c-direction. The substitutions of Ba and Ca on the Bi site of Bi1-xAxCuOSe lead to the weakening of the ‘bonding’ between the [Bi2(1-x)A2xO2]2(1−x)+ and the [Cu2Se2]2(1−x)- layers (a decrease of Columbic force), resulting in an increase of the c-axis parameter and V. Powder X-ray diffraction patterns of Bi1-xAxCuOSe were submitted for inclusion in the Powder Diffraction File (PDF).