Monoclinic Space Research Articles

The rich crystal chemistry of the AMM'(PO4)2 morphotropic series: NaZnAl(PO4)2, the first Na representative with a new structure type.

A novel phosphate, sodium zinc aluminium bis(phosphate), NaZnAl(PO4)2, was obtained under mild-temperature hydrothermal conditions at 553 K. The crystal structure has been studied using single-crystal X-ray experimental data. The pseudo-hexagonal phase NaZnAl(PO4)2 crystallizes in the monoclinic space group P21/c. Its unique crystal structure is based on a three-dimensional (3D) framework built by Zn-, Al- and P-centred tetrahedra sharing vertices. Channels parallel to the [101] and [-101] directions are limited by six- and eight-membered windows, and incorporate Na atoms. The new compound is discussed as a member of the morphotropic series AMM'PO4, where A = Na, K, Rb or NH4, M= Cu, Ni, Co, Fe, Zn or Mg and M' = Fe, Al or Ga. The title compound is the first Na representative within the series and is characterized by a 3D architecture of tetrahedra populated in an ordered manner by Zn2+, Al3+ and P5+ ions.

Incommensurate structures of the [CH3NH3][Co(COOH)3] compound.

The present article is devoted to the characterization of the structural phase transitions of the [CH3NH3][Co(COOH)3] (1) perovskite-like metal-organic compound through variable-temperature single-crystal neutron diffraction. At room temperature, compound 1 crystallizes in the orthorhombic space group Pnma (phase I). A decrease in temperature gives rise to a first phase transition from the space group Pnma to an incommensurate phase (phase II) at approximately 128 K. At about 96 K, this incommensurate phase evolves into a second phase with a sharp change in the modulation vector (phase III). At lower temperatures (ca 78 K), the crystal structure again becomes commensurate and can be described in the monoclinic space group P21/n (phase IV). Although phases I and IV have been reported previously [Boča et al. (2004). Acta Cryst. C60, m631-m633; Gómez-Aguirre et al. (2016). J. Am. Chem. Soc. 138, 1122-1125; Mazzuca et al. (2018). Chem. Eur. J. 24, 388-399], phases III and IV corresponding to the Pnma(00γ)0s0 space group have not yet been described. These phase transitions involve not only the occurrence of small distortions in the three-dimensional anionic [Co(HCOO)3]- framework, but also the reorganization of the [CH3NH3]+ counter-ions in the cavities of the structure, which gives rise to an alteration of the hydrogen-bonded network, modifying the electrical properties of compound 1.

Crystal structure of 5,15-dihexyl-5,15-di-hydro-benzo[2,1-b:4,3-c']dicarbazole hexane 0.375-solvate.

The title compound, C38H40N2·0.375C6H14, crystallizes in the monoclinic space group P21/c and has a host-guest structure with the helicene molecules forming a porous structure and mol-ecules of hexane inserted into the holes. The dihedral angles between the two carbazole sections of the right- and left-handed helicenes are 27.44 (3) and 25.63 (3)°, respectively. There are no classical π-π inter-actions or hydrogen-bonding inter-actions present between adjacent mol-ecules in the crystal structure. The hexane solvent mol-ecule shows positional disorder.

N-Valine-2-(3,5-dimethy-1,1-dioxido-2H-1,2,6-thiadiazin-4-yl)Benzamide: Synthesis, X-ray Structure and Hirshfeld Surface Analysis

Here we report the synthesis and crystal structure of the title compound N-valine-2-(3,5-dimethy-1,1-dioxido-2H-1,2,6-thiadiazin-4-yl)benzamide, C18H23N3O5S. The structure was determined by the single crystal X-ray diffraction method. The compound crystallized in a monoclinic Sohncke space C2 space group with cell values of a = 18.3096 (11) A, b = 7.4858 (5) A, c = 14.1452 (10) A, β = 90.176 (2)° and with Z = 4. Crystal structure analysis showed that the molecule is not planar and the thiadiazine ring is essentially orthogonal to the plane passing through the aromatic ring. The dihedral angle between the thiadiazine ring and the aromatic ring is 93.72°. The carbonyl of the amide bond deviates from co-planarity of the aromatic ring by 60.03° which is perhaps due to the steric hindrance of the carbonyl group towards the thiadiazine ring. The sulfur atom deviates from the mean plane of the ring by 0.102 A. The synthesis of the title compound, N-valine-2-(3,5-dimethy-1,1-dioxido-2H-1,2,6-thiadiazin-4-yl)benzamide, and its structural characterization by means of single crystal X-ray diffraction and Hirshfeld surface analysis are reported.

The new heteropolyoxometalate compound (C6H8N)5[HAs2Mo6O26(H2O)]·3H2O: crystal structure and Hirshfeld surface analysis.

A detailed description of the crystal structure and a Hirshfeld surface analysis of the new heteropolyoxometalate compound (C6H8N)5[HAs2Mo6O26(H2O)]·3H2O are reported. The title compound was synthesized using solution methods and its structure was characterized by single-crystal X-ray diffraction. The investigated compound contains a new [HAs2Mo6O26(H2O)]5- polyanion and crystallizes in the monoclinic space group P21/c. The crystallographic analysis provided an understanding of the architecture and structural features of the complex crystal lattice and the Hirshfeld surface analysis shed more light on the intermolecular interactions occurring in the crystal.

Di-μ-chlorido-bis[chlorido(dimethylformamide-κN)(3,5-diphenyl-1H-pyrazole-κN2)copper(II)

The title compound, [Cu2Cl4(C15H12N2)2(C3H7NO)2], Cu2(μ-Cl)2Cl2(3,5-diphenyl-1H-pyrazole)2(DMF)2, where DMF isN,N-dimethylformamide, crystallizes in the monoclinic space groupP21/n. The five-coordinate CuIIions have a distorted square-pyramidal geometry and are joinedviatwo μ-Cl anions. The coordination environment of each CuIIion is completed by a terminal chloride anion, a nitrogen-coordinated 3,5-diphenyl-1H-pyrazole molecule, and a DMF molecule. Two intramolecular hydrogen bonds exist in the molecule as the H atom of the protonated N atom of the 3,5-diphenyl-1H-pyrazole bonds to a terminal chloride anion of the adjacent CuIIcation. In addition, molecules are linked into a two-dimensional sheetviaweak C—H...Cl intermolecular hydrogen bonds. Each dimer hydrogen bonds to four neighboring molecules as the H atom of the C atom in the fourth position of the pyrazole ring bonds to a μ-Cl on a neighboring molecule.

Structural and IR-spectroscopic characterization of pyridinium acesulfamate, a monoclinic twin

AbstractThe crystal structure of pyridinium 6-methyl-1,2,3,-oxathiazine-4(3H)-one-2,2-dioxide [(C5NH6)(C4H4NO4S)], for short, pyH(ace), was determined by X-ray diffraction methods. It crystallizes as a twin in the monoclinic space groupP21/cwitha=6.9878(9),b=7.2211(7),c=21.740(2) Å,β=91.67(1)° andZ=4 molecules per unit cell. The structure was determined employing 1599 reflections withI>2σ(I) from one of the twin domains and refined employing 2092 reflections from both crystal domains to an agreement R1 factor of 0.0466. Besides electrostatic attractions, intermolecular pyH···O=C(ace) hydrogen bonds stabilize the acesulfamate anion and the pyridinium cation into planar discrete units parallel to the (100) crystal plane. The units form stacks of alternating ace−and pyH+ions along theaaxis that favors inter-ring π–π interactions. The Fourier transform-infrared (FT-IR) spectrum of the compound was recorded and is briefly discussed. Some comparisons with related pyridinium saccharinate salts are also made.

Synthesis, crystal structure and catalytic activity in reductive amination of di-chlorido-(η6-p-cymene)(2'-di-cyclo-hexyl-phosphanyl-2,6-di-meth-oxy-biphen-yl-κP)ruthenium(II).

The title compound, [RuCl2(C10H14)(C26H35O2P)] (I), crystallizes in the monoclinic space group P21/c with two crystallographically independent mol-ecules (A and B) in the asymmetric unit. The geometries of both mol-ecules are very similar and distinguished only by the twist angles of the two benzene rings in the phosphine substituents [89.54 (14) and 78.36 (14)° for mol-ecules A and B, respectively]. The Ru atoms have classical pseudo-tetra-hedral piano-stool coordination environments. The conformation of each mol-ecule is stabilized by intra-molecular C-H⋯O and C-H⋯Cl hydrogen bonds and C-H⋯π inter-actions. The two mol-ecules are linked by a C-H⋯Cl hydrogen bond. In the crystal, the mol-ecules are further linked by C-H⋯ π inter-actions, forming -A-B-A-B- chains propagating along the a-axis direction. Complex I is an active catalyst for reductive amination reaction. The catalytic activity of this complex can be explained by the lability of the p-cymene ligand, which can be replaced by two-electron ligands such as CO or amine.

Supramolecular heterosynthon assemblies of ortho-phenylenediamine with substituted aromatic carboxylic acids

Co-crystallization experiments conducted between ortho-phenylenediamine (OPDA) and five substituted aromatic acids (phthalic acid, salicylic acid, 4-hydroxybenzoic acid, 4-nitrobenzoic acid and 3,5-dinitrobenzoic acid) reveal the formation of supramolecular networks constructed from acid–base heterosynthons of ortho-phenylenediammonium cations with respective aromatic anions. All of these coformers are generally regarded as safe (GRAS) molecules. The five reported crystal structures are sustained predominantly by intermolecular N+−H...O−, N—H...O− and N—H...O hydrogen-bonding interactions; in addition intramolecular O—H...O and intermolecular O—H...O, O—H...O− and C—H...O interactions contribute to the formation of various networks. Five 1:1 salts [NH2C6H4NH3]+·[COOHC6H4COO]− (1); [NH2C6H4NH3]+·[OHC6H4COO]− (2); [{NH2C6H4NH2}2·{OHC6H4COOH}2·{NH2C6H4NH3}+ 2·{OHC6H4COO}− 2] (OPDPHB) (3); [NH2C6H4NH3]+·[NO2C6H4COO]− (4) and [NH2C6H4NH3]+·[(NO2)2C6H4COO]− (5) were isolated as single crystals by the slow evaporation method and were characterized using spectroscopic and X-ray crystallographic techniques. X-ray diffraction studies confirmed the formation of salts. The pK a difference between the amine and respective acid favours the transfer of a proton from the acid to the amine, which leads to the formation of the anion and the cation. The interactions between these ions resulted in a stable heterosynthon in each case. The asymmetric units of salts (1), (2), (4) and (5) contain one anion and one cation each, but salt (3) consists of two anions, two cations and two neutral species in its asymmetric unit. A polymorph of salt (3) was also isolated from the crystallization of the ground material from liquid-assisted grinding [{NH2C6H4NH2}·{NH2C6H4NH3}+·{OHC6H4COO}−] (OPDPHB 3P). The polymorph crystallized in the monoclinic non-centrosymmetric space group P21. The liquid-assisted grinding experiments using a 1:1 ratio also revealed the formation of the expected salts, except salt (3), where this product matches with polymorph (OPDPHB 3P).

Assembly of ZnII and CdII coordination polymers with different dimensionalities based on the semi-flexible 3-(1H-benzimidazol-2-yl)propanoic acid ligand.

Two new coordination polymers, namely, poly[[μ3-3-(1H-benzimidazol-2-yl)propionato]zinc(II)], [Zn(C10H8N2O2)] n , (1), and poly[bis-[μ2-3-(1H-benzimid-azol-2-yl)propionato]cadmium(II)], [Cd(C10H8N2O2)2] n , (2) have been synthesized from 3-(1H-benzoimidazol-2-yl)propanoic acid ligands through a mixed-ligand synthetic strategy under a solvothermal environment, and studied by single-crystal X-ray diffraction. Complex 1 crystallizes in the ortho-rhom-bic space group Pbca and features a two-dimensional structure formed by a binuclear Zn2O4 core. Complex 2, however, crystallizes in the monoclinic space group P21/c and forms a one-dimensional chain structure. The ZnII and CdII ions have different coordination numbers and the 3-(1H-benzoimidazol-2-yl)propano-ate ligands display different coordination modes. The structures reported here show the importance of the selection of metal ions and suitable ligands.

Unusual thermolysis of aza-cyclic allene under microwave conditions: crystal structure of (3RS,3aSR,8RS,8aRS)-methyl 5,6-dimeth-oxy-3a,10-dimethyl-1-phenyl-3,3a,8,8a-tetra-hydro-3,8-(epimino-methano)-cyclo-penta-[a]indene-2-carboxyl-ate from synchrotron X-ray diffraction.

The title compound, C25H27NO4 (I), the product of the unusual thermolysis of aza-cyclic allene methyl 10,11-dimeth-oxy-3,8-dimethyl-6-phenyl-3-aza-benzo[d]cyclo-deca-4,6,7-triene-5-carboxyl-ate, represents a bicyclic heterosystem and crystallizes in the monoclinic space group P21/c with three crystallographically independent mol-ecules in the unit cell. These independent mol-ecules adopt very similar geometries and differ only in the conformations of the two meth-oxy substituents on the benzene ring. In two of the three independent mol-ecules, both meth-oxy groups are almost coplanar with the benzene ring [the C-C-O-Me torsion angles are 10.8 (2), 12.3 (2), 9.1 (2) and 13.6 (3)°], whereas in the third mol-ecule, one of the meth-oxy groups is practically coplanar to and the other meth-oxy group is roughly perpendicular to the benzene ring, the C-C-O-Me torsion angles being 14.1 (2) and 76.5 (2)°. The mol-ecule of (I) comprises a fused tetra-cyclic system containing two five-membered rings (cyclo-pentenes) and two six-membered rings (piperidine and benzene). The five-membered rings have the usual envelope conformation, with the methyl-subsituted C atom as the flap in each molecule, and the six-membered piperidine ring has a chair conformation. The methyl substituent at the N atom occupies the sterically favourable equatorial position. The carboxyl-ate group lies almost within the basal plane of the parent cyclo-pentene ring [making dihedral angle of 11.68 (8), 18.94 (9) and 15.16 (9)° in the three independent mol-ecules], while the phenyl substituent is twisted by 48.26 (6), 42.04 (6) and 41.28 (6)° (for the three independent mol-ecules) relative to this plane. In the crystal, mol-ecules of (I) form stacks along the b-axis direction. The mol-ecules are arranged at van der Waals distances.

Microstructural Evolution of Intermetallic Compound Formed in Boron Steel Hot-Dipped in Al–7%Ni Alloy

The microstructural evolution of the intermetallic compound (IMC) layer formed on and in boron steel that was hot dipped in an Al–7Ni (wt %) bath at 690 °C for 30–180 s was investigated, and the growth mechanism of the IMC was identified. Except for the solidification structure of Al, the reaction layer consisted of one layer on the steel surface and two layers in the steel interior. The reaction phase formed on the original surface of the steel was the Al9FeNi (T) phase, which has a monoclinic (space group: P21/c) crystal structure. The reaction phase formed from the T phase was the Fe2Al5 (η) phase, which is orthorhombic (space group: Cmcm). The variation in thickness of the η phase increased linearly with increasing dipping time, which is in accordance with the diffusion growth, a growth mechanism of the η phase in Al-coated pure Fe and low-carbon steels. The Fe3AlC (κ) phase (which had a band shape with a width of 100 nm) and a cubic system were formed along the interface between the Fe2Al5 (η) phase and the steel.

Superposition of M5X5 superstructures and X-ray diffraction in TiO1.0 titanium monoxide

The interpretation of diffraction spectra of ordered high-temperature phases of solid solutions and strongly nonstoichiometric compounds is discussed. It has been shown that variations of the intensities of superstructure reflections, which cannot be explained within simple ordering models, can be due to the superposition of superstructures with different symmetries in the matrix of the basis crystal structure. Using an example of atom–vacancy ordering in TiO1.0 titanium monoxide, a model of the order–order transition state formed by the superposition of low-temperature monoclinic (space group A2/m (C2/m)) and high-temperature cubic (space group Pm3m) M5X5 superstructures has been proposed. It has been shown that the transition state is thermodynamically equilibrium and should be implemented instead of the M5X5 cubic superstructure. The transition state model can be considered as an M(5–i)X(5–i) superstructure (i = 1, 14/18, 11/18) with the monoclinic symmetry (space group P1m1).

High temperature phase diagram of pseudo binary Ba(Zr0.2Ti0.8)O3-(Ba0.7Ca0.3)TiO3 ceramic system: In situ X-ray diffraction and dielectric studies

ABSTRACTLead free perovskite Ba(Zr0.2Ti0.8)O3-(Ba0.7Ca0.3)TiO3 is considered to be one of the most studied system for piezoelectric and energy harvesting applications. Present work reports the temperature dependent X-ray diffraction and dielectric properties of perovskite (1-x)Ba(Zr0.2Ti0.8)O3–x(Ba0.7Ca0.3)TiO3 ceramic system prepared using a standard high-temperature solid-state reaction method. Dielectric studies showed two dielectric relaxations. The lower phase transition ranged between −10°C (x = 0) to 85°C (x = 1) whiles the high temperature phase transitions, diffusive in character occur from 575°C (x = 0) to 620°C (x = 1), which places the present ceramic system in the list of potential candidate for high temperature applications. The high temperature phase transitions in the system were well supported by in situ X-ray diffraction studies. X-ray diffraction analyses indicated that the present system have a perovskite-type monoclinic (space group: P2/m) at high temperatures. Phase transition behaviour has been illustrated in the form of a temperature-composition phase diagram of BZT-xBCT system.

Formamidinium iodide: crystal structure and phase transitions.

At a temperature of 100 K, CH5N2+·I- (I), crystallizes in the monoclinic space group P21/c. The formamidinium cation adopts a planar symmetrical structure [the r.m.s. deviation is 0.002 Å, and the C-N bond lengths are 1.301 (7) and 1.309 (8) Å]. The iodide anion does not lie within the cation plane, but deviates from it by 0.643 (10) Å. The cation and anion of I form a tight ionic pair by a strong N-H⋯I hydrogen bond. In the crystal of I, the tight ionic pairs form hydrogen-bonded zigzag-like chains propagating toward [20-1] via strong N-H⋯I hydrogen bonds. The hydrogen-bonded chains are further packed in stacks along [100]. The thermal behaviour of I was studied by different physicochemical methods (thermogravimetry, differential scanning calorimetry and powder diffraction). Differential scanning calorimetry revealed three narrow endothermic peaks at 346, 387 and 525 K, and one broad endothermic peak at ∼605 K. The first and second peaks are related to solid-solid phase transitions, while the third and fourth peaks are attributed to the melting and decomposition of I. The enthalpies of the phase transitions at 346 and 387 K are estimated as 2.60 and 2.75 kJ mol-1, respectively. The X-ray powder diffraction data collected at different temperatures indicate the existence of I as the monoclinic (100-346 K), ortho-rhom-bic (346-387 K) and cubic (387-525 K) polymorphic modifications.

Crystal structures of N2,N3,N5,N6-tetra-kis-(pyridin-2-ylmeth-yl)pyrazine-2,3,5,6-tetra-carboxamide and N2,N3,N5,N6-tetra-kis-(pyridin-4-ylmeth-yl)pyrazine-2,3,5,6-tetra-carboxamide.

The title compounds, C32H28N10O4· unknown solvent, (I), and C32H28N10O4, (II), are pyrazine-2,3,5,6-tetra-carboxamide derivatives. In (I), the substituents are (pyridin-2-ylmeth-yl)carboxamide, while in (II), the substituents are (pyridin-4-ylmeth-yl)carboxamide. Both compounds crystallize in the monoclinic space group P21/n, with Z' = 1 for (I), and Z' = 0.5 for (II). The whole mol-ecule of (II) is generated by inversion symmetry, the pyrazine ring being situated about a center of inversion. In (I), the four pyridine rings are inclined to the pyrazine ring by 83.9 (2), 82.16 (18), 82.73 (19) and 17.65 (19)°. This last dihedral angle involves a pyridine ring that is linked to the adjacent carboxamide O atom by an intra-molecular C-H⋯O hydrogen bond. In compound (II), the unique pyridine rings are inclined to the pyrazine ring by 33.3 (3) and 81.71 (10)°. There are two symmetrical intra-molecular C-H⋯O hydrogen bonds present in (II). In the crystal of (I), mol-ecules are linked by N-H⋯O and N-H⋯N hydrogen bonds, forming layers parallel to (10-1). The layers are linked by C-H⋯O and C-H⋯N hydrogen bonds, forming a three-dimensional framework. In the crystal of (II), mol-ecules are linked by N-H⋯N hydrogen bonds, forming chains propagating along the [010] direction. The chains are linked by a weaker N-H⋯N hydrogen bond, forming layers parallel to the (101) plane, which are in turn linked by C-H⋯O hydrogen bonds, forming a three-dimensional structure. In the crystal of compound (I), a region of disordered electron density was treated with the SQUEEZE routine in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18]. Their contribution was not taken into account during refinement. In compound (II), one of the pyridine rings is positionally disordered, and the refined occupancy ratio for the disordered Car-Car-Npy atoms is 0.58 (3):0.42 (3).

Ethyl 4-(furan-2-yl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate: a triclinic polymorph

The title compound, C12H14N2O4, crystallizes in the triclinic space groupP-1. The previously reported polymorph occurs in the monoclinic space groupP21/c, and has two independent molecules in the asymmetric unit [Wang (2010).Acta Cryst.E66, o2822]. The dihydropyrimidine ring adopts a screw-boat conformation. The furan ring is positioned axially and makes a dihedral angle of 85.94 (7)° with the mean plane through the pyrimidine ring. In the crystal, molecules are linkedviapairs of N—H...O hydrogen bonds, forming inversion dimers with anR22(8) ring motif. The dimers are linked by N—H...O and C—H...O hydrogen bonds, forming chains propagating along thea-axis direction.

A second polymorph of 3H-1,2-benzodithiole-3-thione

The title compound, C7H4S3, is crystallizes in the monoclinic space groupP21/n; it is the second polymorph, the first having been reported recently in space groupC2/c[Boukebbouset al.(2016)IUCrData,1, x161688]. The molecule displays an almost planar geometry with two fused rings [S10—C3—C4—C9 torsion angle = 0.2 (5)°]. In the crystal, short S...S [3.555 (1) and 3.503 (1) Å] contacts and π–π aromatic stacking [shortest centroid–centroid separation = 4.006 (5) Å] sustain the three-dimensional molecular packing.

Synthesis and crystal structure of a new alluaudite-like iron phosphate Na2CaMnFe(PO4)3.

A new iron phosphate, disodium calcium manganese(II) iron(III) tris(phosphate), Na2CaMnFe(PO4)3, has been synthesized as single crystals by the flux technique. This compound crystallizes in the monoclinic space group C2/c. The structure belongs to the alluaudite structural type and thus, it obeys the X(2)X(1)M(1)M(2)2(PO4)3 general formula. Both the X(2) and X(1) sites are fully occupied by sodium, while M(1) is occupied by calcium and M(2) exhibits a statistical distribution of iron and manganese.

Crystal structure of 1,2-bis-(6-bromo-3,4-dihydro-2H-benz[e][1,3]oxazin-3-yl)ethane: a bromine-containing bis-benzoxazine.

The title benzoxazine molecule, C18H18Br2N2O2, was prepared by a Mannich-type reaction of 4-bromo-phenol with ethane-1,2-di-amine and formaldehyde. The title compound crystallizes in the monoclinic space group C2/c with a centre of inversion located at the mid-point of the C-C bond of the central CH2CH2 spacer. The oxazinic ring adopts a half-chair conformation. The structure is compared to those of other functionalized benzoxazines synthesized in our laboratory. In the crystal, weak C-H⋯Br and C-H⋯O hydrogen bonds stack the mol-ecules along the b-axis direction.