Synthesis and Characterization of Aplysinopsin Analogs

Abstract  Three aplysinopsin analogs were synthesized by reacting 5-bromo-5-fluoro- and 6-bromoindole-3-carboxaldehyde with either creatinine or 2-imino-1,3-dimethyl-imidazolidin-4-one or 2-imino-1-methyl-3-ethylimidazolidin-4-one Single crystal structures on 5-bromo-4′-de-N-methylaplysinopsin DMF solvate [from creatinine, space group P2₁/n, lattice parameters a = 13.117(3) ?, b = 8.6663(15) ?, c = 14.743(3) ?, β = 99.538(10)° at 173 K], 5-fluoroaplysinopsin DMF solvate [from 2-imino-1,3-dimethyl-imidazolidin-4-one, space group P2₁/c, lattice parameters a = 11.114(3) ?, b = 19.118(2) ?, c = 8.503(2) ?, β = 112.290(7)°], and 6-bromoindole-3-carboxaldehyde (space group P2₁/n, lattice parameters a = 7.657(2) ?, b = 7.933(2) ?, c = 13.521(3) ?, β = 99.046(13)°) have been determined. Characterizations include spectrometric identifications employing IR, UV, HRMS, and ¹H and ¹³C NMR. 5-Bromo-4′-de-N-methylaplysinopsin and 5-fluoroaplysinopsin exist in the E configuration. Index Abstract  Single crystal X-ray structural analyses were carried out on 5-bromo-4′-de-N-methylaplysinopsin, 5-fluoroaplysinopsin, and 6-bromoindole-3-carboxaldehyde.      

Hydrothermal Synthesis, Structural Characterization and Luminescent Property of a New 1-D Chain-like [Er(NC6H4O2)3(H2O)2]n

Abstract  

Erbium (III) coordination compound with the formula [Er(IN)₃(H₂O)₂]_n 1 (HIN = isonicotinic acid) was synthesized by mixing Er₂O₃ with isonicotinic acid under hydrothermal condition. The structure of the title compound was determined by single crystal X-ray diffraction analysis, which reveals that the 1-D chain-like structure is formed by the erbium polyhedra through the carboxyl groups of IN. It crystallizes in the monoclinic system, possesses space group C2/c, with lattice parameters: a = 20.229(10) ?, b = 11.594(6) ?, c = 9.871(5) ?, α = γ=90°, β = 115.509(6)°, V = 2089.3(18) ?³, and D _calc = 1.811 mg/cm³ for Z = 4, F(000) = 1108, GOF = 1.109, R1 = 0.0675. Compound 1 has been characterized by IR absorption spectroscopy, ultraviolet excitation and emission spectrum.     

N–H···π Interactions in Two Isomers of an Amino Group Containing <Emphasis Type="Italic">bis</Emphasis>-Phenol

Abstract  

Crystal structures of two bis-phenols namely bis-(3,5-dimethyl-2-hydroxyphenyl)(3-amino phenyl)methane 1 and bis-(3,5-dimethyl-4-hydroxyphenyl)(3-aminophenyl) methane 2 are determined. The compound 1 crystallises in monoclinic P2₁/c with a = 12.2579(16) ?, b = 16.0906(19) ?, c = 10.6664(13) ?, β = 115.417(7)°, V = 1900.2(4) ?³ whereas 2 crystallizes in monoclinic C2/c, a = 9.2538(2) ?, b = 18.6579(4) ?, c = 23.2725(5) ?, β = 98.796(2)°, V = 3970.89(15) ?³. The crystal lattice of both the compounds shows presence of N–H···π interactions but no O–H···π interactions.     

The Structure and Fluorescence Property of a 3D Supramolecular Network [Cd2(2-mBIM)2Cl2(C4H4O4)(H2O)2(H2O)]n

Abstract  

A cadmium(II) coordination polymer [Cd₂(2-mBIM)₂Cl₂(C₄H₄O₄)(H₂O)₂(H₂O)] _n (1) (wherein 2-mBIM = bis(2-methylimidazo-1-yl) methane, C₄H₄O₄ = succinate anion) has been synthesized and characterized by X-ray diffraction. Complex 1 crystallizes in the monoclinic space group C2/c with a = 23.5265(15) ?, b = 7.3558(5) ?, c = 17.4771(11) ?, β = 90.3560(10)°, V = 3024.5(3) ?³, Z = 4. Each Cd(II) atom is octahedrally coordinated and connected with two adjacent Cd(II) atoms by two individual 2-mBIM ligands in a trans-configuration to form one-dimensional (1D) helical structure. Such 1D helical chain structures were connected to each other via the succinate anion ligands and result in the formation of a two-dimensional (2D) framework. Meanwhile, an overall three-dimensional (3D) supramolecular network was formed via the weak hydrogen bond interactions between metal-coordination and free water molecules.     

Synthesis and Crystal Structures of the Coordination Polymers Pb(PYTAC)<Subscript>2</Subscript> and Pb<Subscript>2</Subscript>(PYTAC)<Subscript>3</Subscript>(NO<Subscript>3</Subscript>) (PYTAC = 2-(pyridin-4-yl)thiazole-5-carboxylate)

Abstract  

Two lead coordination compounds, Pb(PYTAC)₂ (1), and Pb(PYTAC)₂(NO₃) (2), were grown as single crystals via hydrothermal synthesis (PYTAC = 2-(4-pyridyl) thiazole-4-carboxylate). Both compounds have been identified via single crystal X-ray diffraction. Coordination polymer 1 crystallizes in a triclinic space group P-1 (a = 5.5097(4) ?, b = 7.2822(5) ?, c = 11.3134(8) ?, α = 103.5580(10)°, β = 99.4330(10)°, γ = 97.1050(10)°), and forms 2-D layers parallel to the crystallographic (ac) plane. Coordination polymer 2 crystallizes in a triclinic space group P-1 (a = 9.8102(5) ?, b = 10.5972(6) ?, c = 14.8076(8) ?, α = 91.9350(10)°, β = 100.8050(10)°, γ = 103.1350(10)°), and forms an infinite 1-D chains along the a axis.     

Synthesis and Crystal Structure of [1,2,4]-Triazolo-annulated 3-Aza-A-homocholestane Derivative: A Novel Pentaheterocyclic Ring System

Abstract  

A novel pentaheterocyclic ring system derived from (5α)-cholestan-3-one, i.e. [1R-[1α(R*),3aβ,3bα,5aβ,12aα,12bβ,14aα]]-1-(1,5-dimethylhexyl)-1,2,3,3a,3b,4,5,11,12,12a,12b,13,14,14a-tetradecahydro-8,12a,14a-trimethyl-9-(2,4,6-trichlorophenyl)-cyclopenta[5,6]naphtho[2,1-d][1,2,4]triazolo[1,5-a]azepinium hexachloroantimonate (6) has been synthesized via the reverse-electron-demand 1,3-dipolar cycloaddition of the 1-aza-2-azoniaallene cation 4 to the triple bond of acetonitrile followed by ring enlargement. The structure of 6 was determined by NMR, IR and high-resolution mass spectra, and unequivocally confirmed by X-ray crystallographic analysis. The title compound crystallizes in monoclinic class under the space group P2-1 with a = 8.163(3) ?, b = 11.214(4) ?, c = 24.191(9) ?, α = 90°, β = 97.740(5)°, and γ = 90°. The five-membered triazole ring is essentially planar and aromatic, while the seven-membered azepine ring is not planar, but adopts a chair-like conformation.     

Chloride Metathesis and Dimethylamide Transfer in the Reaction of TaCl(NMe2)4 with ZnMe2 and MeMgCl: Spectroscopic Studies and X-ray Diffraction Structures of TaCl(Me)(NMe2)3 and ZnCl2(NHMe2)2

Abstract  

Treatment of TaCl(NMe₂)₄ with ZnMe₂ in pentane furnishes a mixture of TaCl(Me)(NMe₂)₃, TaMe(NMe₂)₄, and Ta(NMe₂)₅ as the principal reaction products based on ¹H NMR spectroscopy. Depending upon the work-up conditions employed, the compounds TaCl(Me)(NMe₂)₃ and ZnCl₂(NHMe₂)₂ have been isolated and their molecular structures established by X-ray crystallography. TaCl(Me)(NMe₂)₃ crystallizes in the orthorhombic space group Pna2₁, a = 13.644(4) ?, b = 12.934(4) ?, c = 6.992(2) ?, V = 1233.9(7) ?³, Z = 4, and d _calc = 1.958 Mg/m³; R = 0.0316 and wR ₂ = 0.0707 for 2630 reflections with I > 2σ(I). The molecular structure of TaCl(Me)(NMe₂)₃ consists of a trigonal bipyramidal core and contains axial and equatorial chlorine and methyl groups, respectively. ZnCl₂(NHMe₂)₂ crystallizes in the orthorhombic space group P2₁2₁2₁, a = 5.759(1) ?, b = 10.810(2) ?, c = 15.174(3) ?, V = 944.1(3) ?³, Z = 4, d _calc = 1.593 Mg/m³; R = 0.0213 and wR ₂ = 0.0494 for 1872 reflections with I > 2σ(I). ZnCl₂(NHMe₂)₂ exhibits a tetrahedral motif and represents the first reported four-coordinate zinc(II) compound containing acyclic monodentate secondary amine groups. The reaction between TaCl(NMe₂)₄ and MeMgCl afforded a mixture of tantalum products, of which TaCl(Me)(NMe₂)₃ and Ta(NMe₂)₅ were found as the major products by ¹H NMR spectroscopy.     

Synthesis, Crystal Structures and Molecular Packing of a Series of Pyrazolo-Benzothiazine Hybrid Derivatives

Abstract  

The crystal structures of four derivatives of pyrazolo[4,3-c][1,2]benzothiazine-2,4-dihydro-3,4-dimethyl-,5,5-dioxide containing benzothiazine dioxide and pyrazolo fused rings that have been synthesized were determined. (C₁₁ H₁₁ N₃ O₂ S): Mr = 249.29, monoclinic, P2₁/c, a = 8.3070(3), b = 13.6331(5), c = 10.1661(3) ?, β = 106.924(2)°, V = 1101.45(7) ?^3, Z = 4. (C₁₂ H₁₃ N₃ O₂ S): Mr = 263.31, monoclinic, P2₁/n, a = 9.729(3), b = 11.224(4), c = 11.436(3) ?, β = 98.85(2)°, V = 1233.9(7) ?³, Z = 4. (C₁₄ H₁₅ N₃ O₄ S): Mr = 321.35, monoclinic, P2₁/c, a = 9.2534(3), b = 19.3920(7), c = 7.9489(2) ?, β = 95.323(2)°, V = 1420.21(8) ?^3, Z = 4. (C₁₄ H₁₅ N₃ O₃ S): Mr = 305.35, monoclinic, P2₁ /c, a = 13.816(7), b = 7.464(3), c = 14.674(8) ?, β = 109.05(3)°, V = 1430.3(12) ?³, Z = 4. The heterocyclic thiazine rings adopt half-chair conformations, and the mean-planes of the phenyl and pyrazolo rings lie between 10.43(11) and 15.93(16)° with respect to each other. In each case, the geometry about thiazine N-atom is trigonal pyramidal and only the first compound containing a donor N-atom shows classical hydrogen bonds. However, non-classical H-bonding of the type C–H···O is observed in all 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.      

Solid-State Intermolecular Contacts Involving the Nitrile Group in p-Cyano-N-(p-cyanobenzylidene)aniline and 4,4′-(azinodimethylidyne)bis-benzonitrile

Abstract  

As part of an investigation of the solid-state intermolecular contacts in which the nitrile group participates, the crystal structures of p-cyano-N-(p-cyanobenzylideneaniline), C₁₅H₉N₃ (CN/CN) and 4,4′-(azinodimethylidyne)bis-benzonitrile, C₁₆H₁₀N₄ (CN//CN) have been determined at −100 °C. Cell parameters for CN/CN: a = 4.7270(9) ?, b = 10.443(2) ?, c = 11.943(2) ?; α = 90°, β = 98.70(3)°, γ = 90°; monoclinic, space group P2₁/c. Cell parameters for CN//CN: a = 3.8008(8) ?, b = 7.9627(16) ?, c = 11.181(2) ?; α = 70.23(3)°, β = 84.66(3)°, γ = 81.93(3)°; triclinic, space group P[`1] P\overline{1} . Both molecules occupy crystallographic inversion centers, which requires that (CN/CN) be disordered. Both molecules assume nearly planar conformations in the solid state. Neither (CN/CN) nor (CN//CN) is isostructural with its halogen-nitrile substituted analogues, although (CN/CN) is found to be isostructural with the corresponding stilbene. Both (CN/CN) and (CN//CN) engage in centrosymmetric H-bonding interactions that define an R ₂²(10) motif. This motif is also observed in many related structures, although noteworthy exceptions can be found.     

Synthesis,Crystal Structure and Fluorescent Study of Bis(2-(2-hydroxyphenyl)benzimidazolate)zinc with Ethanol Solvate

Abstract  The zinc(II) complex with 2-(2-hydroxyphenyl)benzimidazole, namely [Zn(2-(2-hydroxyphenyl)benzimidazolate)₂]·C₂H₅OH (1 · C₂H₅OH) has been synthesized and characterized by X-ray crystallography and photoluminescent analysis. The complex crystallizes in monoclinic space group P2₁/c with cell parameters a = 10.156(1) ?, b = 25.771(3) ?, c = 9.674(1) ?, α = 90°, β = 103.641(2)°, γ = 90°, Z = 4, V = 2460.4(4) ?³. The central Zn(II) is four-coordinate and has a tetrahedral geometry. The steady-state and time-resolved photoluminescent spectra for the title compound have also been studied. The emission property can be ascribed to ligand-centered charge-transfer transition (LCCT) with π → π* property. Index Abstract   A new co-crystal of Zn(II) complex of 2-(2-hydroxylphenyl)benzimidazole with ethanol solvate has been prepared, characterized by X-ray crystallography and fluorescent studies.      

Inclusion of Caffeine by a Diol Host

Abstract  

The host compound 9,9′-(ethyne-1,2-diyl)-bis(fluoren-9-ol), H, forms inclusion compounds with caffeine (H·CAF) and methanol (H·MeOH). The host and guest ratios were 1:2 and 1:1, respectively. Both of these structures were successfully solved in P-1 with unit cell dimensions for H·CAF: a = 7.2121(14) ?, b = 9.2782(19) ?, c = 15.206(3) ?, α = 73.23(3)°, β = 84.20(3)°, γ = 73.39(3)°, Z = 2 and for H·MeOH : a = 9.7592(10) ?, b = 11.2584(11) ?, c = 20.7854(19) ?, α = 97.161(2)°, β = 99.263(2)°, γ = 95.257(2) ?, Z = 2. These crystal structures were studied together with that of a mixed clathrate, H·CAF·MeOH with stoichiometry 2:1:1.5. For H·CAF·MeOH which was solved in P2₁/c : a = 12.2051(5) ?, b = 46.8023(19) ?, c = 9.0121(4) ?, β = 91.9650(10)°, Z = 4. The kinetics of desolvation of the methanol solvate (H·MeOH) yielded an activation energy of 69.6–83.9 kJ mol⁻¹.     

Synthesis and Crystal Structure of MnII(OAc)2[15-MC MnIII(N)shi-5](Im)3(EtOH)3 (shi3??=?salicylhydroximate, ?OAc?=?acetate, Im?=?imidazole, and EtOH?=?ethanol)

Abstract  

The metallacrown complex Mn^II(OAc)₂[15-MC_Mn^III _(N)shi-5](Im)₃(EtOH)₃ has been synthesized and characterized by single-crystal X-ray diffraction and infrared spectroscopy. The compound crystallizes in the monoclinic space group P2₁/c with a = 24.3326(15) ?, b = 24.0354(15) ?, c = 27.0531(17) ?, α = 90.00°, β = 100.3883(11)°, γ = 90.00°, V = 15562.5(17) ?³, Z = 4, and Z′ = 2. Four of the five manganese(III) ions of the metallacrown ring adopt a distorted octahedral coordination geometry, and the fifth manganese(III) ion is five coordinate and exhibits a distorted square pyramidal environment. The configuration of the manganese(III) ions about the ring follows a pattern of ΔΛΔPP, with P representing planar. In addition, the imidazole units are bound to three separate ring manganese(III) ions, and the imidazole units are directed to the outside of the molecule. A manganese(II) ion is encapsulated in the central core of the molecule, and the central ion is seven coordinate with a face-capped trigonal prismatic geometry.     

Structural determination by X-Ray diffraction and 183W NMR spectroscopy of mono substituted hexatungstates [(n-C4H9)4N]3MW5O19 (M = Nb, V)

The tetrabutylammonium salt of mononiobotungstate [(n-C₄H₉)₄N]₃NbW₅O₁₉ (1) and the tetrabutylammonium salt of monovanadotungstate [(n-C₄H₉)₄N]₃VW₅O₁₉ (2) are isotypes; both crystallize in the monoclinic system, space group C2/c (N° 15) with Z=8. The cell parameters for 1 are a=30.4038(8) ?, b=18.5948(8) ?, c=27.3330(3) ?, β=112.4555(6)°, V=14281.1(7) ?³ and the final reliability factors are R=0.043 and R _w=0.047 for 5801 reflections. The cell parameters for 2 are a=30.096(8) ?, b=18.373(3) ?, c= 27.201(6) ?, β=112.402(14)°, V=13906(5) ?³ and the final reliability factors are R=0.048 and R _w=0.054 for 6122 reflections. Both anions, [NbW₅O_19] ³⁻ and [VW₅O_19] ³⁻ exhibit the Lindqvist structure of the parent hexatungstate anion. The six metal positions are disordered and for each metal site the occupation factor is close to 1/6 M (M=Nb, V) and 5/6 W. Furthermore the two compounds were characterized by IR in the solid state, and ¹⁸³W solution NMR. The ¹⁸³W spectrum of [NbW₅O_19] ³⁻ presents two resonances with relative intensities 4:1 in agreement with the C_4v symmetry of the anion.     

Synthesis and Crystal Structure of New Heterocyclic Compounds Containing 1,2,3-Triazole Moiety

Abstract  

A series of new heterocyclic compounds bearing 1,2,3-triazole moiety were synthesized using 4-acetyl-2-phenyl-1,2,3-triazole 1 as the starting material. The target compounds were prepared and the structures were characterized by IR, ¹H NMR, MS and elemental analysis. Meanwhile, the crystal structures of the synthesized compounds were also furthered confirmed by X-ray diffraction analysis. Compound 3b crystallized in the monoclinic P2(1)/c space group with unit cell parameters a = 10.6974(17) ?, b = 20.356(3) ?, c = 7.8049(12) ?, α = 90°, β = 102.840(3)°, γ = 90o, V = 1657.1(5) ?³, Z = 4, T = 293(2) K. Compound 7c crystallized in the Triclinic P-1 space group with unit cell parameters a = 7.364(2) ?, b = 7.366(2) ?, c = 26.089(8)?, α = 87.114(7)°, β = 87.040(7) (3)°, γ = 82.337(7)°, V = 1399.2(7) ?³, Z = 2, T = 293(2) K. Compound 10c crystallized in the Triclinic P-1 space group with unit cell parameters a = 9.8152(10) ?, b = 10.0806(13) ?, c = 11.1267(14) ?, α = 100.344(3)°, β = 111.975(3)°, γ = 107.852(3)°, V = 916.18(19) ?³, Z = 2, T = 293(2) K.     

Crystal Structures of N-(4-butyryl-3-hydroxyphenyl)acetamide Monohydrate and 4-(4-Chlorophenyl)-2-methyl-4-oxobutanoic Acid: Possibilities of Yang Photocyclization

Abstract  

N-(4-butyryl-3-hydroxyphenyl)acetamide monohydrate, (I), and 4-(4-chlorophenyl)-2-methyl-4-oxobutanoic acid, (II), are photochemically inert, which is a result of their conformation. The geometrical parameters describing the molecular conformation and possibilities of the Yang photocyclization in crystals have been calculated and discussed. Compound (I) forms double ribbons along the a axis, stabilized by hydrogen bonds and π⋯π interactions. Compound (II) forms dimers. (I): triclinic, space group \textP[`1] {\text{P}}\bar{1} , a = 6.9291(12) ?, b = 7.5736(16) ?, c = 13.0528(18) ?, α = 79.643(17)°, β = 85.818(15)°, γ = 63.97(2)°, Z = 2. (II): monoclinic, space group P2₁/c, a = 11.904(2) ?, b = 9.6508(12) ?, c = 10.666(2) ?, β = 110.64(2)°, Z = 4.     

The Crystal Structure and Conformational Studies of Acridinedione Derivatives

Abstract  

Two crystal structures of acridinediones namely, TMHAD and MPHAD were studied by X-ray crystallographic method in view of their occurrence in numerous commercial products including pharmaceuticals, fragrances and dyes. Crystal data of TMHAD are: C₁₇H₂₃NO₂, orthorhombic, Fdd2, with cell parameters a = 40.417(6) ?, b = 5.744(1) ?, c = 12.979(2) ?, V = 3013.1(7) ?³, Z = 8, D_cal = 1.205 Mg/m³, μ = 0.078 mm⁻¹. Crystal data of MPHAD are: C₂₀H₁₈NO₃; monoclinic, P2₁/c with cell parameters a = 10.182(9) ?, b = 17.105(14) ?, c = 10.895(9) ?, β = 117.857(1)°, V = 1678(2) ?³, Z = 4, D_cal = 1.268 Mg/m³, μ = 0.085 mm⁻¹. Both data were collected using λ (MoK_α) = 0.71073 ?. The central ring in the acridinedione moieties tends to be planar while the outer two rings adopt sofa conformations. Intermolecular interactions of C–H···O type of hydrogen bond help the molecules to stabilize into the crystal packing. Interestingly, a week forces of C–H···π interactions also helps the molecules for stabilization.     

Synthesis and Structural Characterization of Two New Layered Inorganic–Organic Hybrid Zinc Phosphites Templated by Cyclam: Zn(HPO3)2·0.5(C10H28N4) and Zn2(HPO3)3·0.5(C10H28N4)

Abstract  

Using 1,4,8,11-tetraazacyclotetradecane (cyclam) as a template, two new layered zincophosphites, Zn(HPO₃)₂·0.5(C₁₀H₂₈N₄) (1) and Zn₂(HPO₃)₃·0.5(C₁₀H₂₈N₄) (2), were synthesized and characterized by single crystal X-ray diffraction. The two new compounds crystallize in the triclinic system with the space group P − 1 and the cell parameters: a = 8.3130 ?, b = 8.7289 ?, c = 9.0055 ?, α = 106.90(1), β = 95.56(1), γ = 105.30(1), V = 592.31 ?³, Z = 2 for 1 and a = 9.0406 ?, b = 9.4234 ?, c = 9.4519 ?, α = 91.19(1), β = 100.73(1), γ = 106.85(1), V = 754.82 ?³, Z = 2 for 2. Both structures are described in terms of phosphometallic slabs hosting the cyclam cation.     

Orthorhombic Polymorphs of 1-Phenyl-3-(3-Hydroxyphenyl)-2-Propen-1-One

Abstract  

Chalcones, 1,3-diphenyl-2-propene-1-ones, exist naturally and synthetically, and are characterized by the linkage of two aromatic rings joining a three carbon α-β-unsaturated carbonyl entity. We report the observation of two new polymorphs of a hydroxy chalcone, C₆H₅–CO–CH=CH–C₆H₄ (m-OH), identified as a result of a Claisen–Schmidt synthesis and manual screening technique. One polymorph of this compound has been reported previously and exists in the monoclinic system, space group P2/n, with unit cell parameters a = 13.295(6) ?, b = 5.659(2) ?, c = 16.144(8) ?, β = 109.73(5)°, V = 1143.3(9) ?³, and Z = 4. Two crystalline forms (II and III) reported herein, are polymorphs of the reported monoclinic form (I). Form II exists in the orthorhombic system, space group Pca2₁, with unit cell constants a = 11.631 (2) ?, b = 13.163 (3) ?, c = 7.3977 (14) ?, V = 1132.6 (4) ?³, and Z = 4. Form III also crystallizes in the orthorhombic system, however in space group Pbca, with unit cell parameters a = 11.8100(8) ?, b = 7.4075(5) ?, c = 25.8729(19) ?, V = 2263.4(3) ?³, and Z = 8. Variations in the hydrogen bonding connectivity help to distinguish these two forms from the monoclinic, whereas crystal packing differentiates the two orthorhombic forms. The conformation of the C=C (C2–C3) is E for both orthorhombic forms.     

Crystal Forms of the Antiepileptic Lamotrigine: Molecular Salts and Solvates with Fluorobenzoic Acid,Nicotinic Acid, 2-Thiobarbituric Acid, 3-Picoline and Butyl Alcohol

Abstract  

The crystal structures of three salts and two solvated multicomponent crystals of lamotrigine with 4-fluorobenzoic acid, nicotinic acid, 2-thiobarbituric acid, 3-picoline and butyl alcohol are reported. Compound 1a crystallizes in monoclinc system, space group P2₁ with a = 13.3860(5) ?, b = 8.3420(3) ?, c = 15.5200(6) ?, β = 93.524(1)°, V = 1729.78(11) ?³, and Z = 2. Compound 1b crystallizes in monoclinic system, space group P2₁/c with a = 10.6625(7) ?, b = 16.2575(11) ?, c = 13.6346(9) ?, β = 100.904(1)°, V = 2320.8(3) ?³, and Z = 4. Compound 1c crystallizes in triclinic system, space group P[`1] \overline{1} , with a = 10.1309(7) ?, b = 12.0260(8) ?, c = 14.0826(10) ?, α = 71.783(1)°, β = 86.451(1)°, γ = 80.902(1)°, V = 1609.10(19) ?<sup>3</sup>, and Z = 1. Compound 1d crystallizes in monoclinic system, space group P2<sub>1</sub>/c with a = 14.9570(10) ?, b = 8.0230(6) ?, c = 13.8162(10) ?, β = 102.884(1)°, V = 1616.2(2) ?<sup>3</sup>, and Z = 4. Compound 1e crystallizes in triclinic system, space group P[`1] \overline{1} , with a = 7.5710(6) ?, b = 8.5721(7) ?, c = 13.5532(11) ?, α = 85.364(1)°, β = 79.632(1) (1)°, γ = 86.188(1)°, V = 861.19(12) ?³, and Z = 2. Characteristic R₂²(8) dimer is observed in all five structures. A complete hydrogen bonded motif analysis is described. Lamotrigine-lamotrigine base pair is observed in all the structures, except in (1b). In (1c), the R₂²(7) dimer is noticed while, in all other structures R₂²(8) dimer exist between the lamotrigine-lamotrigine base pair. In all the six structures, chlorine atoms of the lamotrigine molecules are not involved in any interactions.