Crystal Chemistry of 1:1 Molecular Complexes of Carbamate Salts Formed by Slow Aerial Carbonation of Amines

Abstract  Amines do have rare tendency to undergo aerial carbonation to form carbamic acid. Four different 1:1 molecular complex of carbamate salts reported herein obtained by the aerial carbonation of cyclic amines. X-ray crystal structures show a systematic change in the molecular structure did bring some gradual supramolecular change from one structural motif to another. Index Abstract  Amines do have rare tendency to undergo aerial carbonation to form carbamic acid. Four different 1:1 molecular complexes of carbamate salts reported herein obtained by the aerial carbonation of cyclic amines. X-ray crystal structures show a systematic change in the molecular structure did bring some gradual supramolecular change from one structural motif to another.      

Crystal Structure of<Emphasis Type="SmallCaps"> D</Emphasis>(−)-amino-(4-hydroxyphenyl)acetate,the Zwitter Ionic Form of Biologically Active<Emphasis Type="SmallCaps"> D</Emphasis>(−)-4-hydroxyphenylglycine

Abstract  Crystals of D(−)-amino-(4-hydroxyphenyl)acetate were analyzed by single crystal X-ray diffraction. The compound crystallizes in the chiral space group, P2₁ (No. 4) with one molecule in the asymmetric unit and a = 5.0994(10) ?, b = 9.3169(19) ?, c = 8.6960(17) ?, β = 91.50(3)°. The intermolecular interactions in the crystal have been visualised by plotting the Hirshfeld surface of the molecule. Graphical Abstract  The extensive hydrogen bonding network in D(−)-amino-(4-hydroxyphenyl)acetate has been described and visualised by plotting its Hirshfeld surface.      

Crystal Structure of the Radical-Cation Salt (<Emphasis Type="Italic">o</Emphasis>-Me<Subscript>2</Subscript>TTF)I<Subscript>3</Subscript> with Close Intermolecular Sulfur Contacts

Abstract  The synthesis and crystal structure of the organic radical-cation salt (o-Me₂TTF)I₃ is described. The salt crystallizes in the monoclinic space group P2 ₁ /n with a = 10.927(2) ?, b = 11.904(2) ?, c = 12.660(2) ?, β = 115.174(5)°. The bond length of the central C=C bond in o-Me₂TTF is 1.401(1) ?, indicating an approximate oxidation state of +1 for the o-Me₂TTF radical cation. Graphical Abstract  The X-ray crystallographic structure of the radical cation salt (o-Me₂TTF)I₃ has been determined and its structural properties and synthetic preparation are discussed.      

The First Coordination Compound with 5-methylisoxazole-3-carboxylate: Synthesis and Structural Characterization of [Cu(L<Subscript>2</Subscript>)(H<Subscript>2</Subscript>O)] · H<Subscript>2</Subscript>O

Abstract  The title compound, aquabis(5-methylisoazole-3-carboxylato-O,N)copper(II) monohydrate, [Cu(L₂)(H₂O)] · H₂O is synthesized and characterized by X-ray diffraction, elementary analysis, and IR. The ligand coordinates to the copper center in a bidentate O,N fashion through the carboxylic acid moiety and the heteroaromatic nitrogen atom. The complex crystallizes in the triclinic space group with unit cell parameters a = 8.4080(12)?, b = 8.810(3), c = 10.318(2)?, α = 110.08(3)°, β = 104.81(2)°, γ = 103.149(16)°, V = 650.9(3)?³, Z = 2. In addition, the synthesis of the free acid 5-methylisoazole-3-carboxylic acid and pyridine containing complex bis(5-methylisoazole-3-carboxylato)bispyridinecopper(II) monohydrate is described. Index Abstract  Synthesis and crystal structure of aquabis(5-methylisoazole-3-carboxylato-O,N)copper(II)monohydrate. The first coordination compound of 5-methylisoxazole-3-carboxylic acid.      

High Temperature Ionic Liquids: Thermal Properties and Dimorphism in [1-(Methoxycarbonyl) Ethyl] Triphenylphosphonium <Emphasis Type="Italic">p</Emphasis>-Toluenesulfonate

Abstract  Investigation of the thermal properties of triphenylphosphonium p-toluenesulfonates, which are high temperature ionic liquids, reveals that they solidify to a noncrystalline material on fast cooling from the melt. During the study, a second crystalline form of [1-(methoxycarbonyl) ethyl] triphenylphosphonium p-toluenesulfonate (form II) has been obtained. Form II is monoclinic P2₁/c, with a = 11.002(5)?, b = 12.793(5)?, c = 18.805(5)?, and β = 102.498(5)°. Comparison with form I reveals the existence of a common robust structural feature involving interactions between cations and anions. Graphical Abstract  Investigation of thermal properties of ionic liquids has revealed a second crystalline form of [1-(methoxycarbonyl) ethyl] triphenylphosphonium p-toluenesulfonate.      

Using of Taguchi Method for Experimental Design of Crystallization Processes of an Oxidant: Tetraethylammonium Chlorochromate (VI)

Abstract  Crystallization of tetraethylammonium chlorochromate (C₂H₅)₄N[CrO₃Cl], TEACC, with desirable particle size as a performance characteristic was used to illustrate the design procedure. Taguchi design of experiments (DOE) method has been used for to plan a minimum number of experiments and optimization of crystallization processes. Four factors, which influence the crystal size, crystal growth and nucleation, were chosen. These factors are concentration, temperature, type of solvent and method of crystallization. After optimization the results show that concentration is most effective factor that has largest percent of contribution 53.26% and type of solvent is least effective factor that has smallest percent of contribution 4.33%. The optimum conditions are vapor diffusion as method, 0.043 g/15 mL for concentration, 0 °C for temperature and acetonitrile as solvent. These conditions must be produced suitable crystals for single crystal X-ray diffraction experiment. These results confirmed by experimental data and the crystals of the optimum conditions found to have suitable properties for single crystal X-ray diffraction. These crystals had sent for single crystal X-ray diffraction and diffraction data gathered successfully. A red block crystal was mounted on a glass fiber. The X-ray data determined monoclinic system, space group C2(#5), with a = 12.023(3), b = 7.998(2), c = 14.527(4) ?, β = 114.187(4)°, V = 1274.4(6) ?³ and Z = 4. Index Abstract  The Taguchi design of experiments (DOE) method has been used for to plan a minimum number of experiments and optimization of crystallization processes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis and Crystal Structure of a New Binuclear Samarium Complex with Salicylate

Index Abstract  In the dinuclear compound (HPhen)₂[Sm₂(Hsal)₈(H₂O)₂] · 2H₂O (Hsal = o-HOC₆H₄CO₂ ⁻, Phen = 1,10-phenanthroline), intermolecular hydrogen bonds and π–π stacking interactions between parallel aromatic rings result in the formation of a two-dimensional supramolecular network.      

A Unusual Bridging Mode of Diphenylhydantoin in Pentaaquabis[(5,5-Diphenylhydantoinato)Potassium]

Abstract  A new complex of diphenylhydantoin, pentaaquabis[(5,5-diphenylhydantoinato)potassium], has been synthesized and the structure has been solved by X-ray diffraction. The crystals are monoclinic, space group C2/c, with a = 34.959(5) ?, b = 8.273(4) ?, c = 11.692(2) ?, β = 109.069(13)°, M _r = 670.80, V = 3196.0(17) ?³, Z = 4 and R = 0.050. The potassium cations are assembled in dimers bridged through the carbonyl O atoms of the anions. The metal atom is in a distorted octahedral coordination environment. Index Abstract  In pentaaquabis[(5,5-diphenylhydantoinato)potassium] the potassium cations are coupled in dimers through the carbonyl O atoms of the anions.      

Solid State Structure of 6,7-Dihydro-1,4-Di(2′-Pyridyl)-5<Emphasis Type="Italic">H</Emphasis>-Cyclopenta[d]Pyridazine

Abstract  The X-ray structure of 6,7-dihydro-1,4-di(2′-pyridyl)-5H-cyclopenta[d]pyridazine ligand (5-dppn) shows the existence of a trans/trans conformation. The 5-dppn crystallizes in a triclinic space group P-1 with a = 7.1048(15) ?; b = 9.008(2) ?; c = 10.986(3) ?; α = 88.279(16)°; β = 85.454(15)°; γ = 69.104(12)°; V = 654.7(3) ?³ and Z = 2. The analysis of 5-dppn crystal structure demonstrates the presence of edge-edge Ar–H···N and face-face Aliph-H···N centrosymmetric dimer interactions. The unit cell packing arrangement confirmed the presence of two molecules opposite to each other. Index Abstract  The X-ray structure of 6,7-dihydro-1,4-di(2′-pyridyl)-5H-cyclopenta[d]pyridazine ligand (5-dppn) shows the existence of a trans/trans conformation.      

Intermolecular Hydrogen Bonds and the Supramolecular Structure of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-Bis(<Emphasis Type="Italic">p</Emphasis>-tolylsulfonyl)diethylenetriamine

Abstract  The title compound N,N′-bis(p-tolylsulfonyl)diethylenetriamine (1) was synthesized and its crystal structure determined by X-ray diffraction. Adjacent molecules of 1, symmetrically related through a c-glide, are linked by alternating hydrogen bonds that form molecular chains along [0 0 1]. Two molecular chains occur in each unit cell and pack to form alternating layers in a three-dimensional supramolecular structure. The compound crystallizes in the Pca2₁ space group stabilized by the inclusion of solvent dichloromethane molecules in structural voids between molecules of 1. The dichloromethane molecules are related through a twofold screw rotation axis and are not disordered. Index Abstract  Intermolecular hydrogen bonds involving sulfonamide moieties of title compound afford a supramoleular structure that accommodates the inclusion of dichloromethane in alternating layers.      

Classification of Structural Motifs in Porphyrinic Coordination Polymers Assembled from Porphyrin Building Units, 5,10,15,20-Tetrapyridylporphyrin and Its Derivatives

Abstract  In this review, we classify 1D, 2D, and 3D structural motifs found in porphyrinic coordination polymers assembled from 5,10,15,20-tetrapyridylporphyrin (TPyP) and its derivatives. The classifications are based on dimensionality, metal-to-porphyrin linkage, porphyrin type, and metal-to-porphyrin ratio. 1D porphyrin polymers often share the same connectivity (or structural motifs) with analogous 2D and 3D polymers. We identify interrelationships among 1D, 2D, and 3D coordination polymers and examine the connectivity of such interrelated structures. We also discuss the broad similarities and differences of the synthetic methods of all structures presented here. Graphical Abstract  We classify 1D, 2D, and 3D structural motifs found in porphyrinic coordination polymers assembled from 5,10,15,20-tetrapyridylporphyrin (TPyP) and its derivatives. The classifications are based on dimensionality, metal-to-porphyrin linkage, porphyrin type, and metal-to-porphyrin ratio. We identify interrelationships among 1D, 2D, and 3D coordination polymers and examine the connectivity of such interrelated structures.      

Synthesis and Crystal Structure of Heptyl 3-(3,4-dihydroxyphenyl)-2-propenoate

Abstract  The title compound, C₁₆H₂₂O₄, synthesized by modified Knoevenagel condensation of protocatechualdehyde with monoheptyl-malonate and recrystallized from benzene, was confirmed by single-crystal X-ray diffraction (CCDC 272827). The compound crystallizes in triclinic space group Pī with cell parameters a = 5.296(3) ?, b = 10.711(13) ?, c = 13.870(4) ?, α = 98.84(7)°, β = 90.97(4)°, γ = 96.77(7)° and Z = 2. The structure is the E isomer and its packing is stabilized by intermolecular O–H···O and C–H···O hydrogen bonds. Index Abstract  The title compound, C₁₆H₂₂O₄, synthesized by modified Knoevenagel condensation, was confirmed by single-crystal X-ray diffraction showing its structure is in E isomer and its packing is stabilized by hydrogen bonds.      

Crystal and Molecular Structure of Diterpenoid Alkaloid 3-Acetylaconitine

Abstract  3-Acetylaconitine (1), C₃₆H₄₉NO₁₂, was isolated from the ammonium hydroxide wetted root of A. szechenyianum Gay. X-ray diffraction analysis demonstrated that it consists of four-six-membered rings A, B, C, D and two-five-membered rings E, F. The fused-ring system A, B, C and D are in chair, chair, chair and boat conformations, respectively; ring E is in a half-chair; and ring F is in an envelope confirmation. The crystal of 3-acetylaconitine is in orthorhombic crystal system with space group P2₁2₁2₁, lattice constants: a = 9.2002(8) ?, b = 11.06454(9) ?, and c = 33.072(3) ?, V = 3543.3(5) ?³, Z = 4. Index Abstract  3-Acetylaconitine, C₃₆H₄₉NO₁₂, was isolated from the ammonium hydroxide wetted root of A. szechenyianum Gay, and its crystal and molecular structure was determined by X-ray diffraction analysis.      

Synthesis and Crystal Structure of Benzoyloxymethyl (4α,8β,13β)-13-methyl-16-oxo-17-norkauran-18-carbonate Ester

Abstract  Isosteviol derivative: benzoyloxymethyl (4α,8β,13β)-13-methyl-16-oxo-17-norkauran-18-carbonate ester was synthesized by esterification of isosteviol with chloromethyl benzoate and its crystal structure was determined by X-ray diffraction method. The compound crystallizes in the triclinic space group P1 with unit cell parameters: a = 8.784(3) ?, b = 9.079(3) ?, c = 15.950(6) ?, α = 79.343(6)°, β = 79.061(5)°, γ = 89.849(5)°, Z= 2. The conformation of rings A and B is chair, whereas the conformation of ring C is unsymmetrical twist chair. The carbonyl group at the C20 is coplanar with the benzene ring. The fragment of the ester group occupying the pseudoaxial site of C1 position adopts a zigzag conformation. Index Abstract  Isosteviol derivative: benzoyloxymethyl (4α,8β,13β)-13-methyl-16-oxo-17-norkauran -18-carbonate ester was synthesized and its crystal structure was determined by X-ray diffraction method.      

Synthesis,Characterization and Crystal Structure of Bis(isothiocyanato)-bis(pyridine) Zinc(II) Crystal

Abstract  Bis(isothiocyanato)-bis(pyridine) zinc(II) crystal has been prepared at room temperature and characterized by elemental analysis, IR spectrum and X-ray single crystal determination. The complex crystallizes in monoclinic space group P2₁/m with unit cell parameters: a = 5.5786(3), b = 11.0587(5), c = 12.1616(6) ?, β = 96.776(3)°, V = 745.03(6) ?³, Z = 2, D _x  = 1.514 g cm⁻³. The X-ray structure determination has revealed that the crystal is centered-symmetrical and the crystallographic symmetry face runs the two isothiocyanate ligands and the Zn(II) cation. Index Abstract  The title compound, bis(isothiocyanato)-bis(pyridine) zinc(II), was synthesized by zinc compound, KSCN and C₅H₅N (pyridine) and its crystal structure was determined. Single crystal X-ray structure determination reveals that the crystal is centered-symmetrical, and the crystallographic symmetry face runs the two isothiocyanate ligands and the Zn(II) cation.      

3-Methyl-3a,4-Dihydro-3H-Thiochromeno[4,3-c]isoxazol

Abstract  The crystal structure of the title compound, C₁₁H₁₁NOS, was determined by an X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P2₁/c with cell parameters a = 10.533(2) ?, b = 12.7826(19) ?, c = 7.6491(17) ?, β = 107.997(17)^°, V = 979.5(3) ?³ and Z = 4. The S containing heterocycle adopts a sofa conformation, whereas the 5-membered ring adopts an envelope conformation. The crystal packing is characterized by weak C–H···N contacts and π-stacking interactions. Graphical Abstract  The title compound, 3-methyl-3a,4-dihydro-3H-thiochromeno[4,3-c]isoxazol was synthesized by an 1,3 dipolar cycloaddition reaction and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that the aromatic 6-membered ring is planar, whereas the ring containing the S atom adopts a sofa conformation and the 5-membered ring an envelope conformation. The methyl group is in an equatorial position.      

Hydrogen Bonding and Sulfur–Sulfur Interactions in the Crystal Structure of the Radical-Cation Salt (BPDT-TTF)2[W6O19]

Abstract  The synthesis and crystal structure of the salt (BPDT-TTF)₂[W₆O₁₉] is described. The compound crystallizes in the triclinic space group P − 1 with a = 10.927(2) ?, b = 11.904(2) ?, c = 12.660(2) ?, α = 101.261(5)°, β = 115.174(5)°, and γ = 114.434(5)°. The bond length of the central C=C bond in BPDT-TTF is 1.384(17) ?, in accord with an oxidation state of +1 for the BPDT-TTF radical-cations and the observed stoichiometry between BPDT-TTF and [W₆O₁₉]²⁻ which is 2:1. Index Abstract  The X-ray crystallographic structure of the radical cation salt (BPDT-TTF)₂[W₆O₁₉] has been determined and its structural features, including examples of interatomic interactions, as well as its synthetic preparation are discussed.      

Synthesis of (2,4-Diamino-5-(3′,4′,5′-trimethoxybenzyl) Pyrimidine) Copper (II) Complex at 20–25 °C and its Structural Characterization

Abstract  The title copper (II) complex with Trimethoprim was prepared at 20–25 °C and its crystal structure was determined by single crystal X-ray diffraction. Compound (C₃₆H₅₀Cu₃N₈O₁₆) is triclinic, space group P-1 with a = 6.4642(5) ?, b = 12.5495(9) ?, c = 13.4911(10) ?, α = 77.518(1)°, β = 85.326(1)°, γ = 84.413(2)°, Z = 1. In this compound, three copper atoms are bonded to each other, two terminal coppers are bonded to three oxygen atoms and N₁ of pyrimidine ring of Trimethoprim and central copper is bonded to four oxygen atoms. The amino nitrogen atoms are not involved in the coordination to the metal. Graphical Abstract  To enhance the activity of trimethoprim, its derivative was prepared and there bacterial activity against several bacteria was analyzed.      

The Crystal Structure of <Emphasis Type="SmallCaps">dl</Emphasis>-Lomenfloxacin Hydrate

Abstract  The dl-lomenfloxacin hydrate is an innersalt, which crystallizes in space group C2/c with cell parameters a = 22.897(10), b = 8.682(1), c = 18.365(2) ?, β = 93.633(9)°, V = 3,705(3) ?³ and Z = 8. The piperazinyl ring adopts a chair conformation, and the quinolone ring is essentially planar. The plane defined by C atoms of the piperazinyl ring is not coplanar with the quinolone ring. The carboxylate group shows two disorder parts, and is not coplanar with the quinolone ring, the dihedral angle between them is 113.8°. The disorder carboxylate group is split into two parts, the planes of which are skewed at the dihedral angles of 24.5 and 21.6° with the plane of the quinolone ring, respectively. The IR of the title compound is measured and studied. Index abstract  The crystal structure of dl-lomenfloxacin hydrate is determined by X-ray diffraction. The IR is measured and shows great differences from previous studies.      

Synthesis,Characterization, and Crystal Structure of <Emphasis Type="Italic">N</Emphasis>-<Emphasis Type="Italic">p</Emphasis>-Bromophenyl-<Emphasis Type="Italic">N</Emphasis>′-Phenylacetylthiourea

Abstract   N-p-bromophenyl-N′-phenylacetylthiourea was characterized by elemental analysis, IR and ¹H NMR etc. Single crystal structure of the title compound was determined on X-ray diffraction instrument. The title compound crystallizes in monoclinic space group c2/c, with a = 21.442(5) ?, b = 12.208(2) ?, c = 11.955(2) ?, β = 109.375(4)°, and D _calc = 1.571 g/cm³ for Z = 8. An intermolecular hydrogen bond N–H···S which links two thiourea molecules as a dimer and an offset face-to-face π–π stacking interaction were observed in the title compound. The strong non-covalent interaction influences the conformation and property of thiourea derivatives. Index Abstract  The title compound, N-p-bromophenyl-N′-phenylacetylthiourea, was synthesized by the treatment of phenylacetyl chloride with 4-bromoaniline and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that hydrogen bonds and face-to-face π–π stacking interactions have strong influence on the conformation and molecular stacking of the title compound.