Solid-gas reactions and in situ powder X-ray diffraction investigations of trinuclear silver complexes {[3,4,5-(CF3)(3)Pz]Ag}(3) and {[4-Br-3,5-(CF3)(2)Pz]Ag}(3) supported by highly fluorinated pyrazolates reveal that they undergo intricate ethylene-triggered structural transformations in the solid-state producing dinuclear silver-ethylene adducts. Despite the complexity, the chemistry is reversible producing precursor trimers with the loss of ethylene. Less reactive {[3,5-(CF3)(2)Pz]Ag}(3) under ethylene pressure and low-temperature conditions stops at an unusual silver-ethylene complex in the trinuclear state, which could serve as a model for intermediates likely present in more common trimer-dimer reorganizations described above. Complete structural data of three novel silver-ethylene complexes are presented together with a thorough computational analysis of the mechanism.

A Mn(II) salt and A+CN- under anaerobic conditions react to form 2-D and 3-D extended structured compounds of AmMnIIn(CN)m+2n stoichiometry. Here, the creation and characterization of this large family of compounds, for example AMnII3(CN)7, A2MnII3(CN)8, A2MnII5(CN)12, A3MnII5(CN)13, and A2MnII[MnII(CN)6], where A represents alkali and tetraalkylammonium cations, is reviewed. Cs2MnII[MnII(CN)6] has the typical Prussian blue face centered cubic unit cell. However, the other alkali salts are monoclinic or rhombohedral. This is in accord with smaller alkali cation radii creating void space that is minimized by increasing the van der Waals stabilization energy by reducing angle Mn-N equivalent to C, which, strengthens the magnetic coupling and increases the magnetic ordering temperatures. This is attributed to the non-rigidity of the framework structure due the significant ionic character associated with the high-spin MnII sites. For larger tetraalkylammonium cations, the high-spin Mn sites lack sufficient electrostatic A+& sdot;& sdot;& sdot;NC stabilization and form unexpected 4- and 5-coordinated Mn sites within a flexible, extended framework around the cation; hence, the size, shape, and charge of the cation dictate the unprecedented stoichio-metry and unpredictable cation adaptive structures. Antiferromagnetic coupling between adjacent MnII sites leads to ferrimagnetic ordering, but in some cases antiferromagnetic coupling of ferrimagnetic layers are compensated and synthetic antiferromagnets are observed. The magnetic ordering temperatures for ferrimagnetic A2MnII[MnII(CN)6] with both octahedral high- and low-spin MnII sites increase with decreasing angle Mn-N equivalent to C. The crystal structures for all of the extended structured materials were obtained by powder diffraction. New extended structure types and unprecedented stoichiometries form from ionic MnII and ionic cyanides as a consequence of the shape of the cyanide cation that have applications as molecule-based magnets and batteries.image

Polar and magnetic Mn2MnMoO6 with a Ni3TeO6-type structure (R3) was synthesized at 1673 K under 8 GPa. Mn2MnMoO6 shows a large spontaneous polarization of 65.76 mu C.cm(-2), two magnetic transitions at 19 and 47 K, and a strong magnetic frustration factor (f) of 18.4. The polarization reversal barrier is estimated to be 232 meV. X-ray absorption spectroscopy established Mn22+Mn2+Mo6+O6 formal oxidation states. Theoretical calculations indicate an antiferromagnetic ground state of up-down-up-down-up-down spin alignment for Mn ions and a semiconductor characteristic with a band gap around 1.06 eV. Magnetism-dependent dielectric responses show no magnetodielectric and electric coupling, which is attributed to the high polarization reversal barrier and grain boundary effects.

The crystal structure of baricitinib has been solved and refined using synchrotron X-ray powder diffraction data and optimized using density functional techniques. Baricitinib crystallizes in space group I 2/ a (#15) with a = 11.81128(11), b = 7.06724(6), c = 42.5293(3) Å, β = 91.9280(4)°, V = 3548.05(5) Å 3 , and Z = 8. The crystal structure is characterized by hydrogen-bonded double layers parallel to the ab -planes. The dimers form a graph set R2,2(8). The sulfone ends of the molecules reside in the interlayer regions. The powder pattern has been submitted to ICDD for inclusion in the Powder Diffraction File™ (PDF ® ).

To identify the genesis of the differing magnetic behaviors for the ferro- (FO) and metamagnetic (MM) polymorphs of [FeCp*2][TCNQ] (Cp* = pentamethylcyclopentadienide; TCNQ = 7,7,8,8-tetracyano-p-quinodimethane) the low temperature (18 ± 1 K) structures of each polymorph were determined from high-resolution synchrotron powder diffraction data. Each polymorph possesses chains of alternating S = 1/2 [FeCp*2]˙+ cations and S = 1/2 [TCNQ]˙+, but with differing relative orientations. These as well as an additional paramagnetic polymorph do not thermally interconvert. In addition, the room and low (<70 ± 10 K) temperature structures of the MM polymorph, MMRT and MMLT, respectively, differ from that previously reported at 167 K (-106 °C) MM structure, and no evidence of either phase transition was previously noted even from the magnetic data. This transition temperature and enthalpy of this phase transition for MMRT⇌MM was determined to be 226.5 ± 0.4 K (-46.7 ± 0.4 °C) and 0.68 ± 0.04 kJ mol-1 upon warming, respectively, from differential calorimetry studies (DSC). All three MM phases are triclinic (P1[combining macron]) with the room temperature phase having a doubled unit cell relative to the other two. The lower temperature phase transition involves a small rearrangement of the molecular ions and shift in lattice parameters. These three MM and FO polymorphs have been characterized and form extended 1-D chains with alternating S = 1/2 [FeCp*2]˙+ cations, and S = 1/2 [TCNQ]˙- anions, whereas the fifth, paramagnetic (P) polymorph possesses S = 0 π-[TCNQ]22- dimers. At 18 ± 1 K the intrachain FeFe separations are 10.738(2) and 10.439(3) Å for the FO and MMLT polymorphs, respectively. The key structural differences between FO and MMLT at 18 ± 1 K are the 10% shorter interchain NN and the 2.8% shorter intrachain FeFe separation present for MMLT. Computational analysis of all nearest-neighbor spin couplings for the 18 K structures of FO and MMLT indicates that the intrachain [FeCp*2]˙+[TCNQ]˙- spin couplings (H = -2Si·Sj) are the strongest (4.95 and 6.5 cm-1 for FO and MMLT, respectively), as previously hypothesized, and are ferromagnetic due to their S = 1/2 spins residing in orthogonal orbitals. The change in relative [TCNQ]˙-[TCNQ]˙- orientations leads to a computed change from the ferromagnetic interaction (0.2 cm-1) for FO to an antiferromagnetic interaction (-0.1 cm-1) for MMLT in accord with its observed antiferromagnetic ground state. Hence, the magnetic ground state cannot be solely described by the dominant magnetic interactions.

Purification of C2H4 from an C2H4 /C2H6 mixture is one of the most challenging separation processes, which is achieved mainly through energy-intensive, cryogenic distillation in industry. Sustainable, non-distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF3)(2)Bp]Cu}(3) has features very desirable in an olefin-paraffin separation material. It binds ethylene exclusively over ethane generating [(CF3)(2)Bp]Cu(C2H4). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C2H4 /C2H6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In-situ PXRD provides a "live" picture of the reversible conversion between [(CF3)(2)Bp]Cu(C2H4) and the ethylene-free sorbent in the solid-state, driven by the presence or removal of C2H4. Molecular structures of trinuclear {[(CF3)(2)Bp]Cu}(3) and mononuclear [(CF3)(2)Bp]Cu(C2H4) are also presented.

The reactions of Mn-II(O2CCH3)(2)with NEt(3)Me(+)CN(-)and NEt(2)Me(2)(+)CN(-)form (NEt3Me)(2)Mn-5(II)(CN)(12)(1) and (NEt2Me2)(2)Mn-5(II)(CN)(12)(2), respectively. Structure model-building and Rietveld refinement of high-resolution synchrotron powder diffraction data revealed a cubic [a=24.0093 angstrom (1), 23.8804 angstrom (2)] 3D extended structural motif with adjacent tetrahedral and octahedral Mn(II)sites in a 3:2 ratio. Each tetrahedral Mn(II)site is surrounded by four low-spin octahedral Mn(II)sites, and each octahedral Mn(II)site is surrounded by six high-spin tetrahedral Mn(II)sites; adjacent sites are antiferromagnetically coupled in 3D. Compensation does not occur, and magnetic ordering as a ferrimagnet is observed atT(c)=13 K for2based on the temperature at which remnant magnetization,M-r(T)-> 0. The hysteresis has an unusual constricted shape with inflection points around 50 and 1.2 kOe with a 5 K coercivity of 16 Oe and remnant magnetization,M-r, of 2050 emuOe mol(-1). The unusual structure and stoichiometry are attributed to the very ionic nature of the high-spin N-bonded Mn(II)ion, which enables the maximization of the attractive van der Waals interactions through minimization of void space via a reduced angle MnNC. This results in an additional example of the A(x)Mn(y)(II)(CN)(x+2y)(x=0,y=1;x=1,y=3;x=2,y=1;x=2,y=2;x=2,y=3;x=3,y=5; andx=4,y=1) family of compounds possessing an unprecedented stoichiometry and lattice motif that are cation adaptive structured materials.

Understanding the electric dipole switching in multiferroic materials requires deep insight of the atomic-scale local structure evolution to reveal the ferroelectric mechanism, which remains unclear and lacks a solid experimental indicator in high-pressure prepared LiNbO3-type polar magnets. Here, we report the discovery of Zn-ion splitting in LiNbO3-type Zn2FeNbO6 established by multiple diffraction techniques. The coexistence of a high-temperature paraelectric-like phase in the polar Zn2FeNbO6 lattice motivated us to revisit other high-pressure prepared LiNbO3-type A(2)BB'O-6 compounds. The A-site atomic splitting (similar to 1.0-1.2 angstrom between the split-atom pair) in B/B'-mixed Zn2FeTaO6 and O/N-mixed ZnTaO2N is verified by both powder X-ray diffraction structural refinements and high angle annular dark field scanning transmission electron microscopy images, but is absent in single-B-site ZnSnO3. Theoretical calculations are in good agreement with experimental results and suggest that this kind of A-site splitting also exists in the B-site mixed Mn-analogues, Mn2FeMO6 (M = Nb, Ta) and anion-mixed MnTaO2N, where the smaller A-site splitting (similar to 0.2 angstrom atomic displacement) is attributed to magnetic interactions and bonding between A and B cations. These findings reveal universal A-site splitting in LiNbO3-type structures with mixed multivalent B/B', or anionic sites, and the splitting-atomic displacement can be strongly suppressed by magnetic interactions and/or hybridization of valence bands between d electrons of the A- and B-site cations.

The reaction of Mn-II(O2CMe)(2) and NaCN or LiCN in water forms a light green insoluble material. Structural solution and Rietveld refinement of high-resolution synchrotron powder diffraction data for this unprecedented, complicated compound of previously unknown composition revealed a new alkali-free ordered structural motif with [Mn-4(II)((3)-OH)(4)](4+) cubes and octahedral [Mn-II(CN)(6)](4-) ions interconnected in 3D by Mn-II-NC-Mn-II linkages. The composition is {[Mn-II(OH2)(3)][Mn-II(OH2)](3)}((3)-OH)(4)][Mn-II(-CN)(2)(CN)(4)]H2O=[Mn-4(II)((3)-OH)(4)(OH2)(6)][Mn-II(-CN)(2)(CN)(4)]center dot H2O, which is further simplified to [Mn-4(OH)(4)][Mn(CN)(6)](OH2)(7) (1). 1 has four high-spin (S=5/2) Mn-II sites that are antiferromagnetically coupled within the cube and are antiferromagnetically coupled to six low-spin (S=1/2) octahedral [Mn-II(CN)(6)](4-) ions. Above 40K the magnetic susceptibility, chi(T), can be fitted to the Curie-Weiss expression, chi proportional to (T-theta)(-1), with theta = -13.4K, indicative of significant antiferromagnetic coupling and 1 orders as an antiferromagnet at T-c=7.8K.

The size of the organic cation dictates both the composition and the extended 3-D structure for hybrid organic/inorganic Prussian blue analogues (PBAs) of A aMnII b(CN) a+2 b (A = cation) stoichiometry. Alkali PBAs are typically cubic with both MC6 and M'N6 octahedral coordination sites and the alkali cation content depends on the M and M' oxidation states. The reaction of MnII(O2CCH3)2 and A+CN- (A = NMe4, NEtMe3) forms a hydrated material of A3MnII5(CN)13 composition. A3MnII5(CN)13 forms a complex, 3-D extended structural motif with octahedral and rarely observed square pyramidal and trigonal bipyramidal MnII sites with a single layer motif of three pentagonal and one triangular fused rings. A complex pattern of MnIICN chains bridge the layers. (NMe4)3MnII5(CN)13 possesses one low-spin octahedral and four high-spin pentacoordinate MnII sites and orders as an antiferromagnet at 11 K due to the layers being bridged and antiferromagnetically coupled by the nonmagnetic cyanides. These are rare examples of intrinsic, chemically prepared and controlled artificial antiferromagnets and have the advantage of having controlled uniform spacing between the layers as they are not physically prepared via deposition methods. A3Mn5(CN)13 (A = NMe4, NEtMe3) along with [NEt4]2MnII3(CN)8, [NEt4]MnII3(CN)7, and Mn(CN)2 form stoichiometrically related A aMnII b(CN) a+2 b ( a = 0, b = 1; a = 2, b = 3; a = 1, b = 3; and a = 3, b = 5) series possessing unprecedented stoichiometries and lattice motifs. These unusual structures and stoichiometries are attributed to the very ionic nature of the high-spin N-bonded MnII ion that enables the maximization of the attractive van der Waals interactions via minimization of void space via a reduced ∠MnNC. This A aMnII b(CN) a+2 b family of compounds are referred to as being cation adaptive in which size and shape dictate both the stoichiometry and structure.

We report a new polymorph of acridine, C 13 H 9 N, denoted form IX, obtained as thin needles by slow evaporation of a toluene solution. The structure was solved and refined from powder X-ray data. The structures of five unsolvated forms were previously known, but this is only the second with one molecule in the asymmetric unit. The melting point [differential scanning calorimetry (DSC) onset] and heat of fusion are 108.8 (3) °C and 19.2 (4) kJ mol −1 , respectively.

Polycrystalline samples of Cs1.17In0.81Cl3 were prepared by annealing a mixture of CsCl, InCl, and InCl3, stoichiometric for the targeted CsInCl3. Synchrotron powder X-ray diffraction refinement and chemical analysis by energy dispersive X-ray indicated that Cs1.17In0.81Cl3, a tetragonal distorted perovskite derivative (I4/m), is the thermodynamically stable product. The refined unit cell parameters and space group were confirmed by electron diffraction. In the tetragonal structure, In+ and In3+ are located in four different crystallographic sites, consistent with their corresponding bond lengths. In1, In2, and In3 are octahedrally coordinated, whereas In4 is at the center of a pentagonal bipyramid of Cl because of the noncooperative octahedral tilting of In4Cl6. The charged-ordered In+ and In3+ were also confirmed by X-ray absorption and Raman spectroscopy. Cs1.17In0.81Cl3 is the first example of an inorganic halide double perovskite derivative with charged-ordered In+ and In3+. Band structure and optical conductivity calculations were carried out with both generalized gradient approximation (GGA) and modified Becke-Johnson (mBJ) approach; the GGA calculations estimated the band gap and optical band gap to be 2.27 eV and 2.4 eV, respectively. The large and indirect band gap suggests that Cs1.17In0.81Cl3 is not a good candidate for photovoltaic application.

The simple planar molecule acridine is polymorphically promiscuous, with, at latest count, eight distinct unsolvated forms, and one hydrate. This makes it a compelling model system to study its polymorphism, as this represents a challenge to our understanding of crystallization.

Treating deuterohemin, chloro(deuteroporphyrinato)iron(III), with a non-coordinating base in DMSO/methanol allows for the isolation of [(deuteroporphyrinato)iron(III)](2), deuterohematin anhydride (DHA), an analogue of malaria pigment, the natural product of heme detoxification by malaria. The structure of DHA obtained from this solvent system has been solved by X-ray powder diffraction analysis and displays many similarities, yet important structural differences, to malaria pigment. Most notably, a water molecule of solvation occupies a notch created by the propionate side chains and stabilizes a markedly bent propionate ligand coordinated with a long Fe-O bond, and a carboxylate cluster associated with water molecules is generated. Together, these features account for its increased solubility and more open structure, with an increased porphyrin-porphyrin separation. The IR spectroscopic signature associated with this structure also accounts for the strong IR band at 1587 cm(-1) seen for many amorphous preparations of synthetic malaria pigment, and it is proposed that stabilizing these structures may be a new objective for antimalarial drugs. The important role of the vinyl substituents in this biochemistry is further demonstrated by the structure of deuterohemin obtained by single-crystal X-ray diffraction analysis.

An entry from the Inorganic Crystal Structure Database, the world’s repository for inorganic crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the joint CCDC and FIZ Karlsruhe Access Structures service and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

It is well established that the structure of both natural and synthetic hemozoin (malaria pigment or hematin anhydride, HA) is a chain of proprionate-linked dimers of iron(III)(protoporphyrin-IX); this is true also of solvated crystals, and of the partially soluble mesoporphyrin analog in which the vinyl groups are hydrogenated.It is widely regarded, that the quinoline family of antimalarials inhibits of the formation of hemozoin, although the mechanism is still unclear.We have recently obtained the structure of another slightly soluble analog, iron(III)(deuteroporphyrin-IX), in which the vinyl groups are replaced by hydrogen atoms.As determined from powder diffraction data, the crystal is monoclinic, with Z = 4.The deuterohematin anhydride (DHA) structure also comprises proprionate-linked dimers, but the intra-dimer geometry and inter-dimer interactions are significantly different than hemozoin.Influencing precipitation in the direction of the DHA binding motif, in order to increase the solution concentration of heme, could be a new approach to seeking drug targets, complementary to currently pursued mechanisms based on binding to the facets of the growing hemozoin crystal in the parasite's digestive vacuole.Left: Structure of hematin anhydride.

Transition-metal-only perovskite oxides can introduce additional magnetic functionality with robust magnetoelectric properties but are rare. In this work we prepared a new transition-metal-only perovskite Mn-2(Fe0.8Mo0.2)MoO6 at high pressure and temperature. Uniquely, Mn-2(Fe0.8Mo0.2)MoO6 was discovered as a line phase upon composition modulation that was motivated from the above-room-temperature multiferroic Mn2FeMoO6 corundum phase. It exhibits ferrimagnetic Fe-Mo sublattice (Tc = 194 K) and Mn sublattice antiferromagnetic (T-m similar to 45 K) transitions. Below T-m the two sublattice orderings are coupled and give rise to canted components in both. A first-order field induced transition is also observed below 45 K. Mn-2(Fe0.8SMo0.2)MoO6 is a Mott variable range hopping semiconductor. These findings for the first time show that either an exotic perovskite or a corundum phase can be achieved by composition modulation besides the pressure effect.

Y2CoRuO6 was synthesized as a B-site ordered double perovskite with distorted monoclinic P2(1)/n symmetry and an average tilting of the CoO6 and RuO6 octahedra of (psi) over bar = 19.7 degrees. DC magnetization measurements show a ferrimagnetic transition at around 82 K. Although long-range ferrimagntic order is supported by neutron diffraction studies, aging phenomena in time-dependent isothermal magnetization, frequency dependence of AC susceptibility, and a smeared peak in the specific heat together reveal spin glass-like dynamics. The magnetic subtleties resemble chaotic behavior as previously observed in some ferro- or ferrimagnetic materials that exhibit spin glass-like dynamics. It is argued that the magnetic dynamics in Y2CoRuO6 mainly stem from competition between antiferromagnetic Co up arrow-O-(Ru)-O-Co down arrow/Ru up arrow-O-(Co)-O-Ru down arrow and antiferromagnetic Co up arrow-O-Ru down arrow interactions, besides a degree of Co:Ru antisite disorder. Herein, the B-site ordered Y2CoRuO6 offers a model to explore the intriguing dynamics in correlated 3d-4d transition metal double perovskites.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.