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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Crystal Structures of 5,6,5′,6′-Tetramethoxy-1,1′-spirobisindane-3,3′-dione and two of its Fluorene Adducts

Abstract  

The structures of three spirobisindanes 1, 2a and 2b are reported. Each compound is a precursor to a Polymers of Intrinsic Microporosity (PIM) and is the component that provides the necessary site of contortion within the polymer. Of particular importance are the angles formed between the aromatic units around the spiro-centre as it may have direct relevance to the inefficiency of packing in the solid state packing, we think, induces microporosity in the final polymer. Compound 1 crystallized in the monoclinic P21/c space group with unit cell parameters a = 9.8000(5) Ǻ, b = 17.8710(9) Ǻ, c = 10.4100(5) Ǻ, β = 106.6280(10)°, V = 1746.92(15) A³, Z = 4, D = 1.401 Mg/m³. Compound 2a crystallized in the monoclinic P21/c space group with unit cell parameters a = 9.7460(13) Ǻ, b = 30.291(4) Ǻ, c = 8.6740(12) Ǻ, β = 97.111(3)°, 2541.0(6) A³, Z = 4, D = 1.319 Mg/m³. Compound 2b crystallized in the monoclinic P21/n space group with unit cell parameters a = 13.5670(9) Ǻ, b = 12.7930(8) Ǻ, c = 22.1960(14) Ǻ, β = 96.6630(10)°, V = 3826.4(4) A³, Z = 4, D = 1.265 Mg/m³.     

The Synthesis and Crystal Structure of 5-Methyl-1-(1-naphthyl)-1,2,3-triazol-4-carboxyl Acid

Abstract  5-Methyl-1-(1-naphthyl)-1,2,3-triazol-4-carboxyl acid 3 was synthesized from 1-aminonaphthalene. The yielded product 3 was investigated with X-ray crystallographic, NMR, MS and IR techniques. Compound 3, C₁₄H₁₁N₃O₂, Mr = 253.26, crystallizes in the orthorhombic space group Pbca with unit cell parameters a = 10.068(2), b = 12.353(2), c = 20.102(4) ?, V = 2500.1(8) ?³, Z = 8, Dx = 1.346 Mgm^-3. The final R was 0.0474. The molecular packing is stabilized by intermolecular O–H···N interactions. Index Abstract  5-Methyl-1-(1-naphthyl)-1,2,3-triazol-4-carboxyl acid 3 was synthesized from 1-aminonaphthalene. The yielded product 3 was investigated with X-ray crystallographic, NMR, MS and IR techniques. Compound 3, C₁₄H₁₁N₃O₂, Mr = 253.26, crystallizes in the orthorhombic space group Pbca with unit cell parameters a = 10.068(2), b = 12.353(2), c = 20.102(4) ?, α = β = γ = 90.00o. V = 2,500.1(8) ?³, Z = 8, Dx = 1.346 Mgm⁻³. The final R was 0.0474. The molecular packing is stabilized by intermolecular O–H···N interactions.      

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.     

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.      

Molecular Structure of an Unexpected Binuclear Salicylaldimine Semicarbazone Palladium(II) Complex

Abstract  

Reaction of a salicylaldehyde semicarbazone ligand with PdCl₂(PPh₃)₂ yields an unexpected binuclear Pd(II) complex, 2. The complex crystallizes in a triclinic system with a P-1 space group, with unit cell parameters a = 14.0283(3) ?, b = 15.2603(3) ?, c = 18.7142(3) ?, α = 66.662(10)°, β = 86.162(10)°, γ = 76.265(10)°, Z = 2. The semicarbazone ligand acts as a tridentate chelating donor to one palladium metal centre, forming a five- and six- membered ring, and a monodentate donor to the second palladium centre. There are four molecules of solvent per complex molecule in the asymmetric unit. Each metal centre is contained within a slightly distorted square-planar environment.     

Synthesis and Crystal Structure of 1,3-Bis[2-(pyrrol-2-carbonyloxy)ethoxy]Benzene

Abstract  

A new compound, 1,3-bis[2-(pyrrol-2-carbonyloxy)ethoxy]benzene (1), was synthesized and characterized by X-ray diffraction. The crystal is monoclinic, space group P2₁/c with a = 6.3571(7), b = 11.0416(11), c = 28.156(3) ?, b = 92.821(2), V = 1974.0(4) ?³, Z = 4, Dc = 1.293 g/cm³, F(000) = 808, μ = 0.097 mm⁻¹. The final R = 0.0395 and wR = 0.0927 for 3478 observed reflections with I > 2 σ(I), and R = 0.0660 and wR = 0.1058 for all reflections. The title compound assembles into 2-D structure through a catemer type N–H⋯O hydrogen bonding motif and further forms 3-D structure through C–H···O hydrogen bonds.     

Crystal Structure of <Emphasis Type="Italic">N</Emphasis>-(2-Pyridylmethylene)benzene-1,4-diamine

Abstract  

The crystal structure of amino containing Schiff base, N-(2-pyridylmethylene)benzene-1,4-diamine, was determined via X-ray diffraction analysis. The title compound crystallizes in orthorhombic system, space group Pc2 ₁ n, with unit cell dimensions a = 5.8945(6), b = 11.9233 (10), c = 14.5356 (16) ?, V = 1021.59 (18) ?³, Z = 4. The molecules are linked by intermolecular N–H···N hydrogen bonds to form supramolecular sheets along with the bc crystallographic plane. The crystal structure is further stabilized by C–H···π stacking interactions.     

Synthesis, Structural Characterization and Spectroscopic Properties of 1,2-Bis[4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-oxobutyl]benzene

Abstract  

The crystal structure of the title compound C₂₂H₃₀N₄O₂·H₂O (L), has been determined using X-ray diffraction at 293 K. The crystal of 1,2-bis[4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-oxobutyl]benzene is in triclinic crystal system with space group P(−1) (Z = 2), lattice parameters a = 8.225(6) ?, b = 10.967(6) ?, c = 12.903(6) ?, V = 1119.1(11) ?³. Analyses of single crystals of L, crystallized from dichloromethane/diethyl ether (1:1), revealed that the molecules are arranged in couples, which adopt a pseudo chair conformation, by means of intermolecular O–H···N hydrogen bonding interactions. Moreover, the extended structure revealed a 1D chain caused by several C–H···N intermolecular interactions.     

Synthesis and Crystal Structure Analysis of Substituted Diethyl Malonate

Abstract  

As intermediates of light stabilizer malonate, diethyl 3,5-di-t-butyl-4-hydroxybenzyl phenyl malonates (F.W. 454.58) was synthesized, characterized by ¹H NMR, element analysis and confirmed by X-ray crystal structure analysis. This compound crystallizes in monoclinic class under the space group P21/c with cell parameters, a = 9.8218(4) ?, b = 13.5571(5) ?, c = 19.7233(8) ?; β = 102.3530(10)°, and Z = 4. The structure exhibits inter-molecular hydrogen bonds of the type O–H–O, leading to the formation of one dimensional chains.     

Kinetics of Desolvation and Structure of Bulky Xanthenol Inclusion Compounds

Abstract  The inclusion compounds of 14-hydroxy-14-toluenyldibenzo[a:j]xanthene (H) with the guests acetone (H·ACE), pyridine (H·PYR) and N,N-dimethylformamide (H·DMF) were all successfully solved in the triclinic spacegroup P-1 with unit cell dimensions for H·ACE: a = 9.415(2) ?, b = 9.730(2) ?, c = 12.994(3) ?, α = 82.65(3), β = 76.69(3), γ = 88.67(3), Z = 2; for H·PYR: a = 9.482(2) ?, b = 10.169(2) ?, c = 13.089(3) ?, α = 106.59(3), β = 95.91(3), γ = 90.35(3), Z = 2 and for H·DMF: a = 9.537(19) ?, b = 10.055(2) ?, c = 13.129(3) ?, α = 79.18(3), β = 74.42(3), γ = 86.46(3), Z = 2. The thermal stabilities for all compounds were investigated and in particular the kinetics of desolvation for the DMF compound was determined using both isothermal and non-isothermal methods. Index Abstract  The host compound 14-hydroxy-14-toluenyldibenzo[a:j]xanthene forms inclusion compounds with the guests acetone, pyridine and N,N-dimethylformamide. The crystal structures were determined and their thermal stabilities investigated. The kinetics of desolvation for the DMF compound was determined using both isothermal and non-isothermal methods.      

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.