Synthesis and Characterization of [(1-benzylpyrazole) [<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-bis(2-aminoethyl)-1,2-ethanediamine]copper(II)] Diperchlorate,a Structure with a Sterically Strained,Distorted-Trigonal-Bipyramidal Cation

Abstract  The synthesis, characterization, and molecular structure of the title compound, [(1-benzylpyrazole)[N,N-bis(2-aminoethyl)-1,2-ethanediamine]copper(II)] diperchlorate, [(nbp)(tren)Cu(II)](ClO₄)₂, 2  · 2ClO₄, is reported. The salt crystallized in the monoclinic space group P2₁/n with a = 10.1453(5) ?, b = 17.5250(8) ?, c = 13.6021(6) ?, β = 100.737(19)° and V = 2376.06(19) ?³ with Z = 4. The structure contains copper(II) (nbp)(tren) cations, each with a distorted-trigonal-bipyramidal CuN₅ coordination geometry, separated by perchlorate anions. The cations exhibit steric strain associated primarily with close contacts between the methylene protons of the nbp ligand and one of the amine groups of the tren ligand. The strain has a noticeable effect on the coordination geometry and certain physical properties of the complex. Graphical Abstract  In the title structure, steric strain in the (nbp)(tren)Cu(II) cations, associated with close contacts between protons of the nbp ligand and two of the amine groups of the tren ligand (dashed lines in the figure below) affects certain physical properties of the cation and is consistent with an anomalously long Cu(II)–N(pyrazole) distance (Cu–N41) and an unusually large axial–equatorial angle, N41–Cu–N12.      

Crystal Structure of bis(18-Crown-6)-bis(formato-O) dicaesium dihydrate

Abstract  The crystal structure of the title compound, [2Cs⁺(C₁₂H₂₄O₆)₂(CHO₂ ⁻)₂(H₂O)₂], was determined by an X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P2₁ /n with cell parameters a = 10.4278(7) ?, b = 10.0183(5) ?, c = 18.2383(12) ?, β = 93.723(5)°, V = 1910.3(2) ?³ and Z = 2. The Cs cations are bonded to each of the six O atoms of a crown ether ring, two water molecules, and one O atom of a formato anion. As a result of that, a centrosymmetric dimeric dinuclear complex is formed. The two halves of the dimer are connected by a ring of formato anions and water molecules which are linked by O–H···O hydrogen bonds. Index Abstract  The title compound, bis(18-crown-6)-bis(formato-O), caesium dihydrate, features a centrosymmetric dimeric dinuclear complex where two Cs cations are coordinated by six O atoms of a crown ether ring. The two halves of this complex are held together by a ring of formato anions and water molecules which are linked by hydrogen bonds.      

Isostructural Series of (2,2′-Bipyridinium)tetrabromometallate(II); Intermolecular Interactions in the Structures of (bpyH<Subscript>2</Subscript>)[MBr<Subscript>4</Subscript>]; M = Zn,Hg and Co

Abstract  A single crystal structure determination of the complexes (2,2′-bipyridinium)[MBr₄], M = Zn, Hg and Co, have been carried out. It crystallizes in the monoclinic space group P2₁ /c. The structures consist of alternating stacks of anions and cations. They demonstrate a supramolecularity represented by the inter anion···cation, N–H···Br and C–H···Br interactions. The N–H···Br hydrogen bonding interactions, ca. 3.306(3)–3.213(7) ? and with angles spanning the range 154–156°, tying the MBr₄ anions to the cations. Intra- and interstack anion···anion interactions represented by Br···Br interactions, also exist. All these interactions lead to a 3D-network. Index Abstract        

Crystal Structure of Meso-tetrakis[4-(pentyloxy)phenyl]porphyrin

Abstract  The crystal structure of the title compound, C₆₄H₇₀N₄O₄, has been determined by single crystal X-ray diffraction methods. The title compound crystallizes in the monoclinic space group P2(1)/c with cell dimensions a = 13.8946(3) ?, b = 16.1069(3) ?, c = 12.1974(2) ?, β = 93.4050(10)°, Z = 2. The porphyrin core to be composed of four pyrrole rings linked through methane carbon bridges. Each molecule lies across a crystallographic inversion center. The porphyrin core is planar, which facilitates π-electron delocalization. The inner nitrogen H atoms are found localized on opposite pyrrole rings and these rings differ structurally from the other two pyrrole rings. The imino H atoms form bifurcated intramolecular hydrogen bonds with the adjacent unprotonated N atoms due to the contract porphyrin core. Graphical Abstract  The crystal structure of meso-tetrakis[4-(pentyloxy)phenyl]porphyrin is reported in this paper.      

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.      

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.      

Crystal Structure of 1,7-Bis(4-chlorophenyl)-4-(1,3-dithiolan-2-ylidene)-1,6-heptadiene-3,5-dione

Abstract  The synthesis and crystal structure of 1,7-bis(4-chlorophenyl)-4-(1,3-dithiolan-2-ylidene)-1,6-heptadiene-3,5-dione is described. This compound is a curcuminoid analogue, configurationally symmetric about the C4–C5 atoms and also retains the two fold axis in the crystal phase. This compound crystallizes in the space group C2/c with unit cell parameters a = 19.203(1) ?, b = 13.147(1) ?, c = 8.801(1) ?, β = 112.99(1)°, with half a molecule in the asymmetric unit. The ketenedithioacetal functionality present between the carbonyl groups prevents the possibility of keto-enol tautomerization in this compound. The push-pull nature of the ketenedithioacetal functionality organizes the cinnamoyl groups parallel to each other. Index Abstract  The details regarding synthesis and crystal structure of the title compound which is a curcuminoid analogue is reported in this paper.      

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.      

Crystal Structure of N-(tert-Butyl)-1-(3,5-dioxo-2-phenyltetrahydro-4-isoxazolyl)cyclohexane Carboxamide

Abstract  The crystal structure of N-(tert-butyl)-1-(3,5-dioxo-2-phenyltetrahydro-4-isoxazolyl)-cyclohexane-carboxamide 1 has been determined. The title compound crystallized in the orthorhombic space group pbca with cell parameters, a = 10.6556(6) ?, b = 18.0132(11) ?, c = 19.5513(12) ?, v = 3752.7(4) ?³, Z = 8, D _cal = 1.269 Mg/m³ at T = 120 K. The structure refined by full-matrix least-squares procedures to find R ₁ = 0.0463 and wR ₂ = 0.0937 for 3059 reflections. The soxazole ring isn’t coplanar with the phenyl ring. Index Abstract  The crystal structure of N-(tert-butyl)-1-(3,5-dioxo-2-phenyltetrahydro-4-isoxazolyl)-cyclohexane-carboxamide 1 has been studied.      

Crystal Structure and Magnetic Properties of a Novel Octa-coordinated Manganese(II) Complex

Abstract  The self-assembly and structural characterization of the new manganese(II) [MnL ₂](ClO₄)₂(CH₃OH)_0.5 (1) complex has been achieved. The crystallographic data for the complex 1: Orthorhombic Pbca , a = 16.287(2) ?, b = 21.293(2)?, c = 32.718(3) ?, V = 11,347(2) ?³, Z = 8. The two polydentate ligands strand intertwined each other and around the manganese(II) ions forming a mononuclear complex. The Mn(II) ion is eight-coordinated with the eight donor nitrogen atoms of two ligands to form a distorted square antiprismatic coordination geometry. The magnetic properties investigation indicates that there is a weak antiferromagnetic exchange coupling between the Mn(II) ions of the complex. Index Abstract  An octa-coordinated Mn(II) complex which exhibits a distorted square antiprismatic coordination geometry has been achieved by using a bisbidentate Schiff-base ligand.      

Synthesis and Structural Characterization of Bis(μ2-Iodo)-Bis(Diethyl Ether)-(N-N′-(Bis(2,6-Diisopropylphenyl)Pentane-2,4-Diketiminato)-Lithium-Chromium, a Cr(II) (β-Diketiminato) Complex with a Coordinated LiI Salt

Abstract  Addition of CrI₂ to the lithium salt of N-N′-bis(2,6-diisopropylphenyl)-2,4-diketiminate in diethylether yields a Cr(II) iodide complex with a coordinated, solvated LiI salt. This complex is the intermediate in the synthesis of a bridging iodide complex that is itself a precursor to a side-on bridging dinitrogen complex. This complex crystallizes in the P2₁/n space group with the crystal cell parameters a = 12.3160(19) ?, b = 21.067(3) ?, c = 15.837(3)?, β = 96.767°, V = 4080.6(11) ?³ and Z = 4. Graphical Abstract  Addition CrI2 to the lithium salt of N-N′-bis(2,6- diisopropylphenyl)-2,4-diketiminate in diethylether yields a Cr(II) iodide complex with a coordinated, solvated LiI salt. Herein we report the spectroscopic and structural characterization. An erratum to this article can be found at     

The Solid-state Structure of a 4,13-Diaza-18-crown-6 NaI Complex: A Unique Chain-link Assembly

Abstract  Reported within is the crystal structure of 4,13-diaza-18-crown-6 and NaI (P21/c; a = 7.0732(5) ?, b = 15.4058(10) ?, c = 9.9605(6) ?, b = 96.7950(10)°, V = 1077.75(12) ?³, Z = 2). The structure was obtained serendipitously from a crystallization attempt of these two components in the presence of indole. There are two non-equivalent sodium cations, one encapsulated within the diazacrown, and a second cation linking two adjacent diazacrowns and coordinating to both. The sodium cations are also linked through a water bridge. This leads to the formation of infinite 1–D chains in which iodide counterions occupy the space between the chains. This is the first reported example of an unsubstituted 4,13-diaza-18-crown-6 encapsulating Na⁺. The first structure of 4,13-diaza-18-crown-6 and NaI containing two symmetrically inequivalent Na⁺ ions, only one of which is encapsulated by the diazacrown, is reported. Index Abstract  The first structure of 4,13-diaza-18-crown-6 and NaI containing two symmetrically inequivalent Na+ ions, only one of which is encapsulated by the diazacrown, is reported

Synthesis and Crystal Structure of a Polymorph of the DMF Solvate of the Dicoppertetracarboxylate Paddlewheel Complex Cu<Subscript>2</Subscript>(p-aminobenzoate)<Subscript>4</Subscript>(DMF)<Subscript>2</Subscript>

Abstract  Reaction between p-aminobenzoic acid (HpABA) and Cu(NO₃)₂ · 2.5H₂O in basic MeOH/DMF affords green crystals of the dicopper paddlewheel complex, Cu₂(pABA)₄(DMF)₂ · 2DMF, 1, identified by single crystal X-ray crystallography: triclinic P-1, with a = 10.3728(2) ?, b = 10.617(2) ?, c = 11.128(2) ?, α = 81.705(3)°, β = 79.984(2)°, γ = 65.965(2)° and Z = 2. The crystal structure of 1 reveals that it is the second polymorph of Cu₂(pABA)₄(DMF)₂ · 2DMF and experiments on the stability of 1 indicate that it can be converted to Form I through desolvation followed by exposure to DMF. Graphical Abstract  Crystal structure of a polymorphic discrete dicoppertetracarboxylate is investigated for the conversion between the two forms influenced by hydrogen bonds.      

Synthesis and Crystal Structure of a New Coordination Polymer from Cadmium and V-Shape Ligand Bis(imidazol-1-yl) methane

Abstract  The new coordination polymer, [Cd(BIM)₂(NO₃)₂]_n, has been prepared from the reaction of bis(imidazol-1-yl) methane (BIM) with Cd(NO₃)₂ in methanol and water. The compound were characterized by single crystal X-ray diffraction and IR spectroscopy, it crystallizes in the monoclinic space group C2/m with a = 14.400(3) ?, b = 9.3894(18) ?, c = 8.6926(17) ?, β = 123.499(2)°, V = 980.1(3) ?³, Z = 2. The Cd atoms are coordinated to four nitrogen atoms from four different BIM ligands and two nitrates to form a slightly distorted octahedral geometry. Further, the BIM ligands act as a bridged ligand to form 1D infinite cationic double chain with a 16-membered macrometallacyclic tetragonal box structure. Graphical Abstract   Synthesis and Crystal Structure of a New Coordination Polymer from Cadmium and V-Shape Ligand Bis(imidazol-1-yl) methane Chuan-Ming Jin*, Ling-Yan Wu, Zhen-Xing Zhong A new coordination polymer with 1D infinite cationic double chain with a 16-membered macrometallacyclic tetragonal box structure has been prepared from the reaction of bis(imidazol-1-yl) methane (BIM) and Cd(NO₃)₂.      

Synthesis and Crystal Structure of a Mixed-Ligand Cobalt(II) Complex with 2-Aminobenzimidazole

Abstract  The cobalt(II) complex, [Co(abz)₂(SCN)₂] 1, has been synthesized by the reaction of cobalt(II) nitrate with ammonium thiocyanate and abz ligands (abz = 2-aminobenzimidazole), and was fully structurally characterized by elemental analysis, IR spectra, X-ray diffraction and thermogravimetric experiments. It crystallizes in the triclinic P-1 space group with a = 8.6316(10), b = 9.3426(10), c = 13.254(2) ?, α = 95.793(2), β = 95.870(2), γ = 115.7380(10), V = 945.1(2) ?³, and Z = 2. The central cobalt(II) atom is four-coordinated to nitrogen donors from two neutral abz ligands and two isothiocyanate anions respectively, adopting a slightly distorted tetrahedral geometry. In addition, the intermolecular N–H···N and N–H···S hydrogen bonds interactions link the discrete mononuclear units into infinite three-dimensional networks. Index Abstract  The essence sentence of the paper: In the mixed-ligand mononuclear complex, [Co(abz)₂(SCN)₂], the four coordinated cobalt(II) atom exhibits a slightly distort tetrahedron, which is further assembled into 3D infinite network by intermolecular hydrogen interactions.      

4-Chloro-2,6-bis(hydroxymethyl)pyridinium Chloride and 4-Dimethylamino-2,6-bis(hydroxymethyl)pyridinium Chloride Hemihydrate

Abstract  Two substituted pyridinium chloride salts, namely 4-chloro-2,6-bis(hydroxymethyl)pyridinium chloride (triclinic, P-1, a = 6.0651(8) ?, b = 8.4393(8) ?, c = 8.6554(9) ?, α = 78.845(1)°, β = 83.156(1)°, γ = 89.047(1)°; V = 431.55(8) ?³; Z = 2) and 4-dimethylamino-2,6-bis(hydroxymethyl)pyridinium chloride hemihydrate (orthorhombic, Aba2, a = 17.2179(14) ?, b = 17.6332(15) ?, c = 7.2068(6) ?; V = 2188.0(3) ?³; Z = 4), have been structurally characterized. Hydrogen bonding and van der Waals contacts are evident in both structures. Furthermore, the 4-dimethylamino derivative features a trigonal planar dimethylamino group with some π interaction between the nitrogen atom and the pyridine ring. Graphical Abstract  Two compounds, namely 4-chloro-2,6-bis(hydroxymethyl)pyridinium chloride and 4-dimethylamino-2,6-bis(hydroxymethyl)pyridinium chloride hemihydrate, have been spectroscopically and structurally characterized.      

Supramolecular Aggregation in the 1:1 Co-crystal Formed Between Merocyanine Dye and 3-Nitrophenol,Characterized as a Hydrate

Abstract  The title organic salt comprises a (E)-4-[2-(4-hydroxyphenyl)vinyl]-1-methylpyridinium cation, a 3-nitro-phenoxide anion and a solvent water molecule of crystallisation. The anions and water molecules aggregate to form supramolecular chains facilitated by charge-assisted O–H···O hydrogen bonds and these form layers which are interspersed by layers of cations. Interactions between layers include O–H···O hydrogen bonding, as well as C–H···O and C–H···π contacts; π···π and C–H···O contacts are found within layers of cations. The compound crystallizes in the monoclinic space group P2₁/n with a = 15.018(7) ?, b = 7.328(2) ?, c = 17.571(7) ?, β = 112.342(15)°, and Z = 4. Index Abstract  A layer structure comprising alternating anions/water molecules and cations associated via charge-assisted O–H···O hydrogen bonding as well as C–H···O, C–H···π and π···π contacts is found in (II) .     

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.      

Crystallographic and Conformational Analysis of [(Z)-2-ethoxy-6-[(2-hydroxyphenylamino)methylene]cyclohexa-2,4-dienone]

Abstract  The single crystal X-ray diffraction analysis of the title compound, C₁₅H₁₅NO₃, shows that the structure is adopted to its NH tautomeric form and crystallizes in the orthorhombic space group P bcn with a = 21.2424(15) ?, b = 12.7696(9) ?, c = 9.3605(10) ?, Z = 8, V = 2539.1(4) ?³, D _c  = 1.346 g/cm³. The molecular conformation in the crystal is stabilized by an intramolecular H-bond and the crystal structure is stabilized by the bifurcated O–H···O type intermolecular H-bonds. In order to understand the effects on conformational flexibility of the title molecule, molecular energy profile was calculated as a function of the selected torsion angle by means of AM1 semi-empirical method. Index Abstract  Molecular and crystal structure of [(Z)-2-ethoxy-6-[(2-hydroxyphenylamino)methylene]cyclohexa-2,4-dienone], C₁₅H₁₅NO₃, have been determined by single crystal X-ray diffraction study, and conformational analysis of the title molecule with respect to the selected torsion angle has been achieved by AM1 semi-empirical calculations.      

catena-Bis(μ-chloro)-(κ-O, κ-N-{2-thenoylhydrazine})-cadmium(II), a Novel Cadmium Coordination Polymer

Abstract  The title compound, [CdCl₂(C₅H₆N₂OS)] _n , crystallizes in the polar space group R3c with the crystal cell parameters a = 23.363(3) ?, c = 9.5560(19) ?, V = 4,478.4(13) ?³ and Z = 18. Each cadmium is coordinated to four bridging chloro ligands, the carbonyl oxygen and the terminal nitrogen atom of a 2-thenoylhydrazine ligand. The chelating coordination by the latter moiety implies a distorted cis octahedral arrangement around the metal center. The resulting helical polymer chains in the direction of the crystallographic c axis are cross-linked by the N–H···O hydrogen bonds to a three-dimensional network. Index Abstract   catena-Bis(μ-chloro)-(κ-O, κ-N-{2-thenoylhydrazine})-cadmium(II) crystallizes in the polar space group R3c as a helical polymer which expands along the c axis.