Synthesis and characterization of 9-(4-nitrophenyl)3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione and its methoxyphenyl derivative

9-(4-Nitrophenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione (NTHA) crystallizes in orthorhombic space group P2₁2₁2₁ with a = 5.9716(1) Å, b = 18.0476(3) Å, c = 19.2445(2) Å, V = 2074.04(5) ų, Z = 4, D_cal = 1.263 Mg m^?3 and R = 0.0521 (wR = 0.1326) for 4078 observed reflections. 9-(4-Nitrophenyl)-10-(4-methoxyphenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione NMTHA, crystallizes in monoclinic space group P2₁/c with a = 15.669(5) Å, b = 10.652(4) Å, c = 18.337(6) Å, β = 108.25(1)^°, V = 2906.66(2) ų, Z = 4, D_cal = 1.245 Mg m^?3 and R = 0.0725 (wR = 0.1847) for 5105 observed reflections. The experimental values are compared with the theoretical values calculated based on the semiemperical methods. The structures are stabilized by N–H?sO and C–H?sO types of intermolecular interactions in addition to van der Waals forces.     

Synthesis and crystal structures of 2-amino-3-cyano-4-(2-chlorophenyl)-1,4-dihydro-2H-pyrano[3, 2-h]quinoline and 2-amino-3-cyano-4-(2-chlorophenyl)-8-(2-chlorobenzylidene)-1,4,5,6,7,8-hexahydrobenzo[b]pyran

The title compounds 2-amino-3-cyano-4-(2-chlorophenyl)-1,4-dihydro-2H-pyrano[3, 2-h]quinoline 1 (C₁₉H₁₂ClN₃O, M _r = 333.77) and 2-amino-3-cyano-4-(2-chlorophenyl)-8-(2-chlorobenzylidene)-1,4,5,6,7,8-hexahydrobenzo[b]pyran 2 were synthesized and crystallized. The crystals of compound 1 are triclinic, space group P-1, a = 7.488(2), b = 9.127(3), c = 12.252(3) Å, = 73.58(2), = 78.38(2)°, = 75.39(2), Z = 2, V = 769.5(4) ų; The compound 2 crystallizes in space group P2₁/n, with cell parameters a = 13.582(2), b = 8.974(1), c = 16.960(2) Å, = 103.34(1)° and D _calc = 1.352 g/cm^–3 for Z = 4. X-ray analysis reveals that atoms C(1)—C(5) and O form a pyran ring in compound 1, which adopts half-chair conformation. In compound 2 the atoms C(12)—C(16) and O form a pyran ring which adopts boat conformation, another six-membered ring (C(8)—C(13)) adopts a half-chair conformation. In addition, there are intermolecular hydrogen bonds in the crystal structures 1 and 2.     

Crystal structures of 2,4,9-trimethyl-(3ar,4c,9c,9ac)-3a,4,9,9a-tetrahydro-benzo[?] isoindole-1,3-dione(endo), C15H17NO2 (1), and 2-methyl-(3ac,9ac)-3a,4,9,9a-tetrahydro-4r,9c-ethano-benzo[?]isoindole-1, 3-dione(endo), C15H15NO2 (2)

The title compounds crystallize in the space group P-1 (compound 1), with a = 7.198(2) Å, b = 7.965(2) Å, c = 12.707(2) Å, α = 72.05(1)^∘, β = 87.65(2)^∘, γ = 65.18(2)^∘ and Pbca (compound 2), with a = 8.156(3) Å, b = 13.177(3) Å, c = 22.742(4) Å. The chiral centers in both compounds C3a, C4, C9, C9a are either R, S, R, S or S, R, S, R (compound 1) and either R, R, S, S or S, S, R, R (compound 2) because of the centric space group.     

Synthesis and X-ray structural investigations of 2-amino-7-methyl-4-(1-naphthyl)-5-oxo4H,5H-pyrano[4,3-b]pyran-3-carbonitrile and 2-amino-4-(1-naphthyl)-5-oxo-4H,5Hpyrano[3,2-c]chromene-3-carbonitrile

Synthesis and X-ray structural investigations have been carried out for the two title compounds C₂₀H₁₄N₂O₃ (4) and C₂₃H₁₄N₂O₃⋅C₂H₃N (5). Compound 4 crystallizes in the monoclinic space group P2₁/n, with a = 7.0542(5), b = 8.822(1), c = 24.833(2) ?, β = 94.30(4)^∘, V = 1541.0(4) ?³, and Z = 4. Compound 5 crystallizes with an acetonitrile solvent molecule in the monoclinic space group P2₁/n, with a = 11.075(1), b = 7.854(1), c = 22.703(2) ?, β = 90.67(1)^∘, V = 1974.5(3) ?³, and Z = 4. In both molecules, the 4H-pyran ring adopts a flattened-boat conformation. The naphthalene substituent occupies a pseudo-axial position and the dihedral angle with the flat part of the pyran ring is equal to 94.6(3) in 4 and 76.8(3)^∘ in 5. The mutual orientation of these fragments and the flatness of the heterocyclic rings lead to H⋅sH intramolecular steric interactions: H4A⋅sH18A 1.98 ? in 4 and 2.11 ? in 5. In the crystal of 4, intermolecular hydrogen bonds N–H⋅sO and C–H⋅sN link molecules into infinite tapes along the b axis. In the crystals of 5, intermolecular hydrogen bonds N–H⋅sO and C–H⋅sN link molecules into infinite layers parallel to the bc plane. In each case, the C–H⋅sN interaction can be considered to be a weak hydrogen bond. The acetonitrile molecules link via intermolecular weak C–H⋅sN hydrogen bonds to form infinite chains along the b axes.     

Crystal structure oftrans-tetrachlorobis[2-(2-1H-imidazolyl)-1H-imidazolium]cadmium(II), [Cd(H3biim)2Cl4]

The reaction between cadmium(II) chloride and 2,2'-bi-1H-imidazole (H₂biim) in an acidic solution affords [Cd(H₃biim)₂Cl₄] (H₃biim=2-(2-1H-imidazolyl)-1H-imidazolium) in 63% yield. The compound crystallizes in the triclinic space groupP1, wherea=8.072(2),b=8.100(2),c=8.593(2) Å, =75.89(2), =62.94(2), =63.29(1)°,V=446.4(2) ų, andZ=1. The central Cd atom exhibits an octahedral geometry composed of a Cl₄N₂ core. The Cd-N bond distance is 2.392(2) Å. Cd–Cl distances are 2.5919(9) and 2.671(1) Å.     

Structure of 2-{2-[3-methyl-3-(2,4,6-trimethylphenyl) cyclobutyl]-2-oxoethyl}isoindole-1,3-dione

2-{2-[3-Methyl-3-(2,4,6-trimethylphenyl)cyclobutyl]-2-oxoethyl}isoindole-1,3-dione (C₂₄ H₂₅NO₃) was synthesized, and its crystal structure was determined by X-ray crystallographic techniques. The compound crystallizes in the triclinic space group P-1, with unit cell parameters: a = 14.109(9) Å, b = 14.130(8) Å, c = 12.152(6) Å, = 105.62(5)°, = 113.75(4)°, = 98.78(5)°, V = 2039.8(19) ų, D _c= 1.223 g/cm³, and Z = 4. The crystal structure has two crystallographically independent molecules, I and II. These molecules are held together by weak intermolecular C—H···O interactions, forming a continuous chain. The dihedral angles between the N-substituted phthalimide moiety and cyclobutane ring in molecules I and II are 60.37(14) and 68.18(18)°, respectively.     

The hydrogen bonding in 2-amino-3-cyano-4-(3-nitrophenyl)-4,6-dihydro-5H-pyrano[3,2-c]quinolin-5-one N,N-dimethylformamide solvate monohydrate

The crystal structure of 2-amino-3-cyano-4,6-dihydro-4-(3-nitrophenyl)-5H-pyrano[3,2-c]quinolin-5-one N,N-dimethylformamide solvate monohydrate is determined by room temperature X-ray diffraction. The title compound 1, C₂₂H₂₁N₅O₆, is triclinic, space group P-1, a=9.109(2) ?, b=11.340(2) ?, c=12.485(2) ?, α=70.02(1)°, β=69.36(1)°, γ=67.32(1)°, Z=2, V=1081.4(4) ?³. It is interesting that a bridge-like hydrogen bond O–H···O is formed between the title compound and solvent molecules of water with molecular ratio of 2:2 building a bi-layer framework. In addition, there are two other types of classical hydrogen bonds N–H···N and N–H···O in the crystal structure.Supplementary material Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-275001. Copies of available material can be obtained, free of charge, on application to the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, (fax: +44-(0) 1223–336033 or e-mail: deposit@ccdc.cam.ac.uk).     

The Crystal and Molecular Structure of 9-(3-Pentyl)-3,4,6,7,9,10-hexahydro-1,8(2H,5H) -acridine-dione

The crystal structure of the title compound is described. The structure has two molecules in the asymmetric unit and it crystallizes in the orthorhombic space group Pca21 with Z = 8. The unit cell dimensions are a = 14.574(2), b = 8.924(1) and c = 24.704(10) Å, V = 3212.7(14) ų, D_calc = 1.188 gcm^-3. All the rings of the molecule A adopt sofa conformation. One of the outer rings of molecule B adopts distorted sofa while the other two rings adopt sofa conformation.     

Synthesis and structural characterization of fac-BrMn(CO)3{PH(C6H5)2}2

In attempts to find appropriated methods for preparation of unstable sulfinyl and sulfonylphosphane complexes we have synthesized the diphenylphosphine complexes of Mn(I), BrMn(CO)₄PHPh₂, (1) and BrMn(CO)₃(PHPh₂)₂ (2). Both should undergo electrophilic substitution in the presence of an adequated base. Parallel to the reactions of stabilization of phosphanes we have studied by means of x-ray analysis the structure of fac-BrMn(CO)₃(PHPh₂)₂ (2). The compound crystallizes in the triclinic space group P, a = 9.840(2), b = 11.207(2), c = 13.083(3) Å, = 72.00(3), = 69.59(3), = 81.41(3)°, U = 1284.7(4) ų, and Z = 2. In this complex the manganese atom shows an octahedral coordination geometry, with three carbonyl ligands in a fac arrangement, and one bromide and two diphenylphosphine ligands cis to each other.     

Structure of 4-(2-chloro-4,5-dimethoxybenzylidene)-2-methyl-5-oxazolone. X-ray and NMR study

The azlactone of 6-chloroveratraldehyde 3 (4-(2-chloro-4,5-dimethoxybenzylidene)-2-methyl-5-oxazolone) was synthesized from 6-chloroveratraldehyde 2 and its structure investigated using X-ray crystallographic and nuclear magnetic resonance methods. Compound 3 crystallized in the P2₁/c (#14) space group (Z = 4) with cell dimensions a = 9.148(2), b = 22.938(2), c = 6.707(1) Å, and = 111.50(2)°. The X-ray study shows that azlactone 3 exists as the Z-isomer and crystallizes as a planar structure, i.e., both the phenyl and azlactone ring systems, as well as the functional groups attached to them, lie in the same plane. The ¹H and ¹³C NMR spectral values also support the formation of the Z-isomer only, during the synthesis of 4-(2-chloro-4,5-dimethoxybenzylidene)-2-methyl-5-oxazolone.     

9-(2-Methylphenyl)-3,4,5,6,9,10-hexa- hydroxanthene-1,8(2H,7H)-dione

Several 9-(2-R phenyl)xanthenediones have been synthesized and the x-ray diffraction structure for the 2-methylphenyl derivative (4b) has been determined. This compound crystallizes in the monoclinic system, space group P2₁/n, with a = 11.729 (3), b = 9.674 (3), c = 14.628 (4) Å, and = 106.30°. It presents a partially hydrogenated xanthene system in distorted boat conformation for the heterocyclic central ring, and an almost ideal envelope conformation for the outer rings. The aromatic substituent at the ninth position is at 84° in angle with the xanthene system.     

Reactivity of 1,2,4,5-tetracarboxylatebenzene with cobalt(II)

The complexes [Co(H₂O)₆][Co(BTCA)(H₂O)₄]⋅7.2H₂O (1) and [Na₂Co(H₂O)₄(μ-H₂O)₂ (μ-BTCA)] (2) (BTCA = 1,2,4,5-tetracarboxylatebenzene) have been synthesized and characterized by single crystal X-ray diffraction. Compound (1) crystallizes in the triclinic space group P-1 with a = 6.8591(9) Å, b = 9.9691(13) Å, c = 10.9231(11) Å, α = 93.021(2)^∘, β = 104.883(2)^∘, and γ = 103.702^∘ with Z = 1. This compound exhibits a 1-dimensional structure of two alternating layers. A chain of cobalt ions and BTCA constitute one layer. Cobalt complex ions and solvent water molecules occupy the other. Compound (2) crystallizes in the monoclinic space group C 2/m with a = 8.8647(6) Å, b = 10.5247(7) Å, c = 21.2265(14) Å, and β = 92.525(2)^∘, with Z = 2. This compound consists of a 3-dimensional network of cobalt and sodium ions linked by BTCA. The sodium complex moiety is disordered around a center of inversion.     

The Synthesis and Crystal Structure of 5-(4-Bromophenylamino)-2-methylsulfanylmethyl-2<Emphasis Type="Italic">H</Emphasis>-1,2,3-triazol-4-carboxylic Acid Ethyl Ester

Abstract  The 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester 6 was synthesized from p-bromoaniline. The yielded product 6 was investigated with X-ray crystallographic, NMR, MS, and IR techniques. Compound 6, C₁₃H₁₅BrN₄O₂S, Mr = 371.26, crystallizes in the monoclinic space group P2₁/n with unit cell parameters a = 5.5220(1), b = 26.996(5), c = 10.596(2) ?, β = 103.83(3). V = 1533.8(5) ?³, Z = 4, Dx = 1.608 mg m⁻³. The final R ₁ was 0.0844; wR ₂ was 0.1560. H-bond is discussed. Index Abstract  The structure of 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester from 5-amino-1-(4-bromophenyl)-1,2,3-triazol-4-carboxylic acid ethyl ester is studied. H-bond is discussed.      

Crystal structure of 5-(p-methoxyphenylamino)indane and AM1 calculations on N-arylamines derivatives, precursors of phenothiazine drugs

The structural determination by X-ray crystallography of the titled N-arylamine 4a, as well as AM₁ calculations on a series of derivatives (4b–c, 5a–c), are reported. The compound 4a is monoclinic P2₁/c with a = 7.656(3), b = 23.655(5), c = 7.686(9) Å, = 112.59(6)°, V = 1285.2(2) ų and Z = 4. This structure has been used as a template for the building of some others derivatives used for AM₁ calculations. The results show that the cyclization position on the aromatic rings, which can lead to two regioisomers, depends on the nature of the benzylic substituants.     

The structure of 2-amino-3-cyano-4-(4-methylphenyl)-6-methoxyl-1,4,9,10-tetrahydrobenzo[<Emphasis Type="Italic">f</Emphasis>]chromene

The X-ray crystal structure of 2-amino-3-cyano-4-(4-methylphenyl)-6-methoxyl-1,4,9,10-tetrahydrobenzo [f]chromene 1, C₂₂H₂₀N₂O₂, is determined. The crystals of compound 1 are triclinic, space group P-1, a = 10.120(1), b = 13.127(1), c = 15.203(2) Å, = 67.841(9), = 80.81(1), = 77.58(1), Z = 4, V = 1819.7(4) ų. It is interesting that all the atoms of the pyran ring are coplanar, which is different from other similar compounds. The structure is stabilized by intermolecular hydrogen bonds.     

Structure of 4,6-dimethylisothiazolo[5,4-b]pyridin-3(2H)-one and its 2-[4-(2-methylphenyl) piperazin-1-ylmethyl] derivative

The crystal and molecular structures of 4,6-dimethylisothiazolo[5,4-b]pyridin-3(2H)-one, C₈H₈N₂OS, 1, and its 2-[4-(2-methylphenyl)piperazin-1-ylmethyl] derivative, C₂₀H₂₄N₄OS, 2c, are described. These compounds crystallize in the monoclinic system in the space group P2 ₁/c. The cell constants for compound 1 are a = 5.049(1), b = 14.897(1), c = 11.330(1) Å, = 98.07(1)°, Z = 4, T = 293 K, and D _cal = 1.419 g cm^–3, and for compound 2c are a = 15.525(1), b = 12.021(1), c = 10.911(1) Å, = 106.42(1)°, Z = 4, T = 293 K, and D _cal = 1.253 g cm^–3 The structures were solved by direct methods and refined to R values of 0.0411 and 0.0380 for 1640 and 3504 reflections for 1 and 2c, respectively. The analysis of the geometry and difference electron density map reveal that the dimethylisothiazolopyridine 1 exists in the amino tautomeric form in the crystalline state. The conformation of the o-methylphenylpiperazine part of the molecule 2c strongly depends on the substituents effect in the phenyl ring and is very similar to those observed in crystals for other investigated arylopiperazine derivatives of the isothiazolopyridine.     

Crystal and molecular structure of 2-(p-tolyl)-2-dehydrosparteine

The formula of the title compound is C₂₂H₃₀N₂,M _T =322.5; monoclinic:P2₁,a=7.569(3),b=9.381(1),c=13.684(4) Å,=105.81(2)°,Z=2,V _c =933.7 ų,D _x =1.15 g cm^–3,(CuK)=5.1 cm^–1. The sparteine skeleton (bis-quinolizidine system) has atrans-trans configuration. RingA has an intermediate form between the sofa and half-chair conformations, ringsB andD-chair, and ringC-boat conformations, respectively. The double bond C(2)=C(3) is equal to 1.343(9) Å. The phenyl ring is planar and makes an angle with a plane through N(1), C(2), C(3), and C(4) atoms equal to 43.9°.     

Molecular structures of M(tfac)3 (M=Al, Co) and Cu(H2O)(fod)2: Examples of unusual supramolecular architecture

The molecular structures of Al(tfac)₃ (1), Co(tfac)₃ (2) (H-tfac = 1,1,1-trifluoroacetylacetone) and Cu(H₂O)(fod)₂ (3) (H-fod = 1,1,1,2,2,3,3-hepta-fluoro-7,7-dimethyloctane-4,6-dione) have been determined. The metal coordination spheres in compounds 1 and 2 are essentially the same as the respective M(acac)₃ derivatives. Despite the isomorphous nature of the structures of compounds 1 and 2, the identity of the nearest intermolecular van der Waals contacts are altered by minor changes in the metal coordination sphere. The geometry about copper in compound 3 is close to that of an ideal square bipyramid with the -diketonate ligands occupying the basal plane. The water ligand in each molecule of compound 3 is hydrogen bonded to an oxygen of a -diketonate ligand on an adjacent molecule resulting in the formation of dimers, which form rods along the y-axis due to weak C–F···Cu interactions. Crystal data: (1) orthorhombic, Pca2₁, a = 14.949(3), b = 19.806(4), c = 13.624(3) Å, V = 4033(1) ų, and Z = 8, and (2) orthorhombic, Pca2₁, a = 14.930(3), b = 19.620(4), c = 13.540(3) Å, V = 3966(1) ų, and Z = 8,; (3) monoclinic, P2₁/c, a = 12.447(3), b = 10.486(2) c = 21.980(4) Å, = 102.65(3)°, V = 2799(1) ų, and Z = 4.     

Low Temperature X-ray Crystallographic Structures of Two Lamotrigine Analogues: (I) 2-Methyl,3-amino, 5-imino-6-(2,3-dichlorophenyl)-1,2,4-triazine Water Solvate and (II) 2-Methyl,3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine Isethionate,Hemi-hydrate

Abstract The X-ray crystal structures of two lamotrigine derivatives (I) 2-methyl, 3-amino, 5-imino-6-(2, 3-dichlorophenyl)-1,2,4-triazine, C₁₀H₉Cl₂N₅, as the hemi hydrate and (II) 2-methyl,3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine, C₁₀H₁₀Cl₂N₅, as the isethionate-water solvate, have been carried out at liquid nitrogen temperature. A detailed comparison of the two structures is given. Both are monoclinic and centrosymmetric, with (I) in space group C2/c, and (II) in space group P2₁/n. For (I) the unit cell dimensions are a = 19.5466(10), b = 7.5483(4), c = 15.7861(8) ?, β = 91.458(3)°, volume = 2328.4(2) ?³, Z = 8, density = 1.590 Mg/m³; for (II). For (II) the unit cell dimensions are a = 6.0566(2), b = 11.0084(4) c = 23.9973(9) ?, β = 92.587(3)°, volume = 1598.35(10) ?³, Z = 4, density = 1.597 Mg/m³. For (I) final R indices [I > 2sigma(I)] are R1 = 0.0356, wR2 = 0.0782 and R indices (all data) are R1 = 0.0424, wR2 = 0.0817. For (II) final R indices [I > 2sigma(I)] are R1 = 0.0380, wR2 = 0.0871 and R indices (all data) R1 = 0.0558, wR2 = 0.0949. Both structures have a molecule of water of crystallization and (II) also includes a solvated CH₃SO₃. Comparisons are made between the two structures. Structure (I) is very unusual in having a = NH group at position C5′ on the triazine ring. No other examples of this particular substitution, which is usually −NH₂, have been reported. Index Abstract Rex A. Palmer, Brian S. Potter, Michael J Leach and Babur Z. Chowdhry The crystal structures of (I) 2-methyl,3-amino, 5-imino-6-(2, 3-dichlorophenyl)-1, 2, 4-triazine, water solvate and (II) 2-methyl,3, 5-diamino-6-(2, 3-dichlorophenyl)-1, 2, 4-triazine isethionate water solvate are presented. The relative orientation of the two rings is shown to vary. Lamotrigine and analogues have been investigated for some time for their effects on the central nervous system. For example both lamotrigine and 5-(2,3,5-trichlorophenyl)-2,4-diaminopyrimidine (code name BW 1003C87) are voltage-gated sodium channel blockers as well as blocking the release of the neurotransmitter glutamate [D. R. Riddall, M. J. Leach, J. Garthwaite, Mol. Pharmacol. 2006, 69 (1), 278.3], BW10003C87 (like lamotrigine) has been shown to exhibit excitatory amino acid antagonist activity similar to that of three conventional antiepileptic drugs phenytoin, carbamazepine and phenobarbital [R. Lingamaneni, H. C. Hemmings Jr., Epilepsy Res. 1993, 15, 101.]. BW 1003C87 has also been shown [B. S. Meldrum, J. H. Swan, M. J. Leach, M. H. Millan, R. Gwinn, K. Kadota, S. H Graham, J. Chen, R. P. Simon , Brain Res., 1992, 593, 1.] to reduce the release of glutamate evoked by veratrine in brain tissue, providing a therapeutic approach in both cerebral ischemia and epilepsy. This is one of a series of papers on the structures of lamotrigine analogues.      

Synthesis and molecular structure of 4,4,5,5-tetramethyl-2-(1-(phenylsulfonyl)propan-2-yl)-1,3,2-dioxaborolane

The compound 4,4,5,5-tetramethyl-2-(1-(phenylsulfonyl)propan-2-yl)-1,3,2-dioxabo- rolane has been prepared by the rhodium catalyzed hydroboration of allyl phenyl sulfone and characterized by a single crystal X-ray diffraction study. The title compound crystallized in the monoclinic space group P2₁/c, with cell parameters a=16.0728(8) ?, b=9.8884(5) ?, and c=10.1926(5) ?, β=92.067(1)°, Z=4, and V=1618.90(14) ?³. The structure was solved by direct methods and refined to a final R=0.0449 for 3627 reflections with I>2σ(I). No significant intramolecular or intermolecular interaction is observed with the Lewis acidic boron atom.