Inclusion property of (R,R)-(-)-trans-2,3,-bis(hydroxydiphenylmethyl)-1,4-dioxaspiro[4,4]nonane for aromatic components

An optically active host molecule, (R,R)-(-)-trans-2,3-bis(hydroxydiphenylmethyl)-1,4- dioxaspiro[4,4]nonane (1), is able to form inclusion complexes with nonpolar aromatic components such as benzene, toluene, p-xylene, mesitylene, and ethylbenzene. The host 1 crystallizes in the monoclinic space group C2 with a = 15.694(2), b = 9.326(2), c = 18.457(1) Å, = 10.34(1)°, and Z = 4. An inclusion complex (1-B) of 1 with benzene crystallizes in the orthorhombic space group P2₁2₁2 with a = 17.007(4), b = 19.670(5), c = 8.634(4) Å, and Z = 4. An inclusion complex (1-X) involving both 1 and p-xylene has the monoclinic space group P2₁ with a = 17.211(3), b = 20.143(3), c = 8.603(3) Å, = 92.64(2)°, and Z = 2. In the inclusion complexes, molecules of 1 are dimerized by intramolecular and intermolecular hydrogen bonds forming eight-membered (OH)₄ rings. The benzene and p-xylene molecules fit into the voids of the crystal packing of 1. In addition, the inclusion complexes are stabilized by van der Waals contacts between the hydrophobic sites. Thermal analysis of the inclusion complexes indicated that the number and the size of the alkyl group of the aromatic components affects the stability of the inclusion complexes.     

Synthesis and Characterisation of Scandium (III)-, Yttrium (III)-, and Lanthanum (III) Violurate Complexes

Sc³⁺-, Y³⁺ -and La³⁺ violurate complexes were prepared. The isolated complexes are freely soluble in water, dilute mineral acids, MeOH, Me₂CO, DMF, DMS, partially soluble in AcOH and insoluble in EtOH, CHCl₃ and CCl₄. Molecular compositions of the complexes were formulated on the basis of elemental analysis, molar conductivity and infrared spectra. The IR spectra of violuric acid and its metal complexes reveal that bonding takes place through coordination bond between the central metal ion and the oxygen atom of the oxygen atom of the oximino (C N = O) group and convalenet bond between the central metal ion and oxygen atom of the phenolic (ketonic, C O H) group in the case of 1:2 and 1:3 complexes, and through coordination bond between the central metal ion and C O H and N H groups in the case of 2:3 complexes. All the isomorphous complexes detected by the X-ray powder patterns [the (2:3) Sc³⁺-VA and (2:3) Y³⁺-VA complexes, (1:2) Sc³⁺-VA, (1:2) Y³⁺-VA and (1:2) La³⁺-VA complexes, and the (1:3) Y³⁺-VA and (1:3) La³⁺-VA complexes] have similar X-ray, eletronic and IR spetrograms and chemical formulae. The electronic spectra in DMF and in nujol mulls characterise the octahedral stereochemistry for the investigated complexes.     

Synthesis,spectral, X-ray diffraction and DFT studies on 1-(2-methyl-2-propenyl)-3-(2,3,4,5,6-pentamethylbenzyl)benzimidazolium chloride hydrate

A new benzimidazole based N-heterocyclic carbene (NHC) salt (1) was synthesized by the reaction of benzimidazole precursor with alkyl halide. The structure of 1 was determined by elemental analysis, FT-IR, ¹H NMR and ¹³C NMR spectroscopy tecniques and X-ray crystallography. The compound crystallized in the triclinic space group P-1 with two molecules in the unit cell. The optimization of 1 was firstly performed at B3LYP/6-311G++(d,p) level, then the theoretical spectral studies performed and compared with the experimental values. Besides the frontier molecular orbital energies and chemical reactivity analysis of 1, together with the electrostatic potential and molecular electrostatic potential analyses were performed at the same level of theory.     

Methyl 4-((E)-2-{3-[(3-{ (E)-2-[4-(methoxycarbonyl)phenyl]- 1-diazenyl}-5,5-dimethylhexahydro-1-pyrimidinyl)methyl]-5,5-dimethylhexahydro-1-pyrimidinyl-1-diazenyl) benzoate. X-ray crystal structure

Methyl 4-((E)-2-{3-[(3-{(E)-2-[4-(methoxycarbonyl)phenyl]-1-diazenyl}-5, 5-dimethyl hexahydro-1-pyrimidinyl)methyl]-5, 5- dimethylhexahydro-1- pyrimidinyl}-1- diazenyl) benzoate (1) has been synthesized by reaction of a mixture of formaldehyde and 2,2-dimethyl-1,3-propanediamine with p-methoxycarbonylbenzenediazonium chloride. The crystal structure of 1 has been determined by single crystal X-ray diffraction analysis. The crystals of 1 displayed problems of disorder; the asymmetric unit is built up by two independent molecules, which display disorder within a methoxycarbonyl group. The two independent molecules in the asymmetric unit are very similar, differing only slightly about the mutual orientation of the aryltriazenyl groups. With respect to the N–C–N bridge between the hexahydropyrimidinyl rings, the two equivalent fragments containing the triazene moieties are in a cis orientation. The N–N single bonds, in the range 1.319(4)–1.348(4) Å, and the N=N double bonds, in the range 1.255(5)–1.275(4) Å, indicate significant conjugations within the triazene moieties. All the hexahydropyrimidine six-membered rings adopt a chair conformation as shown by their puckering parameters. The crystal packing is determined only by simple van der Waals interactions. The crystal structure of 1 is compared with the previously reported structure of the unbranched hexahydropyrimidine analogue 2. Crystal data: 1 C29H40N8O4, triclinic, space group P-1, a = 13.9652(2), b = 14.2908(3), c = 16.6129(4) Å, = 97.279(1), = 90.872(1), = 107.385(1), V = 3133.6(1) ų, for Z = 4.     

Identification of Seven-coordinate LnIII Ions in a LnIII[15-MCFeIIIN(shi)-5](OAc)2Cl Species Crystallized from Methanol and Pyridine

The title metallacrown (MC) complexes Ln^III[15-MC_Fe^III_N(shi)-5](OAc)₂Cl(C₅H₅N)₆ (Ln1), where OAc^– is acetate, shi^3? is salicylhydroximate, and Ln?=?Gd and Dy, were synthesized via a self-assembly reaction in methanol and pyridine. Single crystals were grown using slow evaporation and characterized using X-ray diffraction. Seven-coordinate capped octahedron geometries were observed for the lanthanide ion in both complexes, which is uncommon for trivalent lanthanide species. The 15-MC-5 is a ruffled metallacrown archetype similar to previously reported mixed-valent manganese metallacrowns.

Graphic Abstract

The title metallacrown (MC) complexes Ln^III[15-MC_Fe^III_N(shi)-5](OAc)₂Cl(C₅H₅N)₆ (Ln1), where OAc^– is acetate, shi^3? is salicylhydroximate, and Ln?=?Gd and Dy, contains seven-coordinate capped octahedron geometries for the lanthanide ion in both complexes, which is uncommon for trivalent lanthanide species.

     

Synthesis,crystal structure,HF and DFT calculations of 1-(2-chlorobenzyl)-N-(1-(2-chlorobenzyl)-4,5-dihydro-1H-imidazol-2-yl)-1H-benzimidazol-2-amine

The titled compound (1), has been synthesized and characterized by IR and ¹H-NMR spectroscopy, and single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P-1. The crystal structure is stabilized by C-H…π and aromatic π-π interactions. There are also intramolecular N-H…N and C-H…N hydrogen bonds in the molecule. The use of quantum chemical calculations to characterise and optimise the choice of material is illustrated by ab initio treatments. Vibrational frequencies and LUMO-HOMO energy difference of 1 have also been investigated by Density functional theory (DFT) and Hartree-Fock (HF) calculations. Calculated frequencies are in good agreement with the corresponding experimental data.     

Synthesis and Crystal Structures of (E)-1-Phenyl-3-[(2,4,6-Trimethylphenyl)]prop-2-En-1-One and (E)-1-Phenyl-3-[(4-Trifluoromethylphenyl)]prop-2-En-1-One

Two chalcone compounds, namely (E)-1-phenyl-3-[(2,4,6-trimethylphenyl)]prop-2-en-1-one (1) and (E)-1-phenyl-3-[(4-trifluoromethylphenyl)]prop-2-en-1-one (2), have been synthesized and structurally characterized by elemental analysis, ¹H NMR spectrum, and single-crystal X-ray diffraction analysis. The chalcone molecules in (1) and (2) have the common skeleton of 1,3-diaryl-2-propen-1-one and adopt an (E)-configuration about the C = C double bonds. In addition, X-ray analysis reveals that the π···π stacking interactions are well observed in the crystal structure of (1) and (2).     

X-ray Crystallographic Structures of Two Lamotrigine Analogues: (I) 3,5-Diamino-6-(2-chlorophenyl)-1,2,4-triazine Water Solvate and (II) 3,5-Diamino-6-(3,6-dichlorophenyl)-1,2,4-triazine Methanol Solvate

Abstract The X-ray crystal structures of two lamotrigine derivatives (I) 3,5-diamino-6-(2-chlorophenyl)-1,2,4-triazine, C₉H₈ClN₅, (465BL) as a hydrate, and (II) 3,5-diamino-6-(3,6-dichlorophenyl)-1,2,4-triazine, C₉H₇Cl₂N₅, (469BR) as a methanol solvate, have been carried out at liquid nitrogen temperature and room temperature, respectively. A detailed comparison of the two structures is given. Both are centrosymmetric with (I) in the orthorhombic space group Pbca, a = 12.2507(3), b = 15.7160(6), c = 21.71496(9) ?, Z = 16, and (II) in the monoclinic space group C2/c, a = 38.553(3), b = 4.9586(2), c = 14.546(2) ?, β = 111.59(1)°, Z = 8. Final R indices [I > 2sigma(I)] for (I) are R1 = 0.0670, wR2 = 0.1515 and for (II) R1 = 0.0434, wR2 = 0.1185. Structure (I) has water of crystallization in the lattice and (II) includes a solvated CH₃OH. Structure (I) is characterized by having two crystallographically independent molecules, A and B, of 465BL, per asymmetric unit. Molecule B has a very unusual feature in that the 2-chlorophenyl ring is statistically disordered, occupying site (1) in 87.5% of the structure and site (2) in 12.5% of the structure. Sites (1) and (2) are related by an exact 180° pivot of the phenyl ring about the ring linkage bond. The presence of two independent molecules per asymmetric unit provides an ideal opportunity for the conformational flexibility of the molecule 465BL to be studied. Structure (I) also includes a further unusual feature in that the lattice contains one fully occupied water molecule and an additional solvated water which is only 33% occupied. Index Abstract Rex A. Palmer, Brian S. Potter, Michael J Leach and Babur Z. Chowdhry The crystal structures of two lamotrigine analogues: (I) 3, 5-diamino-6-(2-chlorophenyl)-1, 2, 4-triazine, water solvate and (II) 3, 5-diamino-6-(3,6-dichlorophenyl)-1, 2, 4-triazine methanol solvate are presented. Structure (I) includes two molecules per asymmetric unit labeled A and B where molecule B is unusually disordered having Cl in either position 2 (87.5% occupied) or position 6 of the phenyl ring (12.5% occupied), the two sites being related by 180deg rotation about the ring linkage bond. Molecule I(A) on the other hand shows no disorder. The relative orientations of the two rings in I(A and B) and in II is shown to be different. 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. BW 1003C87 has also been shown to reduce the release of glutamate evoked by veratrine in brain tissue, providing a therapeutic approach in both cerebral ischemia and epilepsy [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.]. This is one of a series of papers on the structures of lamotrigine analogues.      

One Dimensional Hydrogen Bonded Arrangement in New Schiff-Base Compound (<Emphasis Type="Italic">E</Emphasis>)-2-(2,5-dimethoxybenzylideneamino)phenol (1): Synthesis,Characterization, Crystal Structure and Conformational Studies

Abstract  

New Schiff-base compound (E)-2-(2,5-dimethoxybenzylideneamino)phenol (1) was synthesized and characterized by elemental analyses, FT-IR and ¹H-NMR spectroscopy and single crystal X-ray diffraction. Molecular orbital calculation has been carried out for 1 by using HF method at 6-31G basis set. The title compound 1 crystallizes in monoclinic system, space group C2/c, with a = 19.4581(13) ?, b = 9.5805(5) Ǻ, c = 13.8431(7) Ǻ, β = 93.471(2)°, V = 2575.9(3) Ǻ³ and Z = 8. In the crystal structure two molecules are stabilized by a pair of intermolecular O1–H1···N1ⁱ hydrogen bonds. The dimeric units are further linked via C6–H6···O3ⁱⁱ hydrogen bond.     

Syntheses,characterization and crystal structures of two structurally similar Schiff bases isonicotinic acid [1-(3-methoxy-2-hydroxyphenyl)methylidene]hydrazide and isonicotinic acid [1-(4-dimethylaminophenyl)methylidene]hydrazide monohydrate

The Schiff base compounds, isonicotinic acid [1-(3-methoxy-2-hydroxyphenyl) methylidene]hydrazide (C₁₄H₁₃N₃O₃, 1) and isonicotinic acid [1-(4-dimethylaminophenyl) methylidene]hydrazide monohydrate (C₁₅H₁₆N₄O·H₂O, 2) have been synthesized by the condensation of equimolar 3-methoxysalicylaldehyde or 4-dimethylaminobenzaldehyde with isonicotinic acid hydrazide in MeOH or EtOH. The compounds were characterized by elemental analysis, IR, ¹HNMR spectra, and single crystal X-ray diffractions. Compound 1 crystallizes in the monoclinic space group P-1 with unit cell dimensions a = 7.662(1) ?, b = 16.249(2) , c = 10.874(2) ?, β = 110.426(3)°, V = 1268.7(3) ′³, Z = 4, R ₁ = 0.0644, and wR ₂ = 0.1283. Compound 2 crystallizes in the orthorhombic space group P2₁2₁2₁ with unit cell dimensions a = 7.388(1) ?, b = 11.812(1) ?, c = 17.197(2) ?, V = 1500.7(2) ′³, Z = 4, R ₁ = 0.0585, and wR ₂ = 0.1143. X-ray structure determinations revealed that the molecules of both compounds display trans configurations with respect to the C=N double bonds. In the crystal structure of 1, molecules are linked through N–H···N intermolecular hydrogen bonds, forming layers parallel to the bc plane, while in the crystal structure of 2, molecules are linked through N–H···O, O–H···O, and O–H···N intermolecular hydrogen bonds, forming a network. Supplementary material CCDC-615072 and 620235 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at http://www.ccdccam. ac.uk/const/retrieving.html or from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223–336033 or e-mail: deposit@ccdc.cam.ac.uk.     

1,3,5-trichlorotricyanobenzene complexes with mesitylene (1/1) and benzene (1/3)

Trichlorotricyanobenzene-mesitylene (1/1) is monoclinic, space group P2₁/n; at ?88°Ca=10.509(3),b=14.863(7),c=11.518(3) Å, β=99.38(2)⁰,V=1775(2) ų,D _x =1.409(2) g cm^?3,Z=4. Trichlorotricyanobenzene-benzene (1/3) is hexagonal, space group $P\bar 6$ ; at ?99°Ca=17.3914(3),c=7.2673(1) Å,V=1903.6(1) ų,D _x =1.2844(1) g cm^?3,Z=3. In both complexes there are stacks of alternating trichlorotricyanobenzene and hydrocarbon molecules. In both complexes there are sheets of molecules perpendicular to the stacks. In the mesitylene complex these sheets contain equal numbers of both kinds of molecules with the trichlorotricyanobenzene molecules arranged in tapes. In the benzene complex the sheets contain only one kind of molecule or the other. The sheets containing the trichlorotricyanobenzene molecules have approximately linear C?N...Cl?C intermolecular interactions with N...Cl distances about 3.02 å.     

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, Crystal Structure and Conformational Studies of Schiff-Base Compound 2-{[4-(Phenyldiazenyl)Phenyl]Iminomethyl}-5-Bromophenol

Abstract  

Schiff-base compound 2-{[4-(Phenyldiazenyl)phenyl]iminomethyl}-5-bromo phenol (1), containing an azo group was synthesized from the reaction of p-aminoazobenzene with 5-bromosalicylaldehyde and characterized by elemental analyses, FT-IR spectroscopy and X-ray single-crystal diffraction analysis. Molecular orbital calculation has been carried out using density functional method (B3LYP) at 6-31G basis set. Compound 1 crystallizes in the orthorhombic system, space group Pca2₁, with a = 12.1781(2) ?, b = 4.4894(10) ?, c = 27.7841(5) ?, V = 1519.02(5) ?³, and Z = 4. Compound 1 displays a trans configuration with respect to the C=N and N=N double bonds.     

Crystal structure of N,N ′-bis(cyclohexyl)-1-(N,N-dihexylamino)perylene-3,4:9,10-bis(dicarboximide)

An asymmetric dialkylamino-substituted perylene bisimide (1), N,N′-bis(cyclohexyl)-1-(N,N-dihexylamino)perylene-3,4:9,10-bis(dicarboximide), was synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P–1, with a = 9.8924(6), b = 14.6338(10), c = 15.6221(10) Å, α= 105.098(3)°, β = 103.386(2)°, γ = 107.772(3)°, and Z = 2. The central perylene core of 1 is twisted with dihedral angles of 14.9(3)° and 11.6(3)°; this twist configuration induces the axial chirality in this family of perylene bisimide dyes. In the crystal structure, the intermolecular C–H···O interaction links a pair of molecules into a cyclic centrosymmetric dimer that is connected to one another via the intermolecular π–π stacking, so linking the molecules into a continuous one-dimensional framework along the [100] direction.     

Supramolecular Organization in Tetra Aqua (μ-8-Hydroxyquinoline-5-sulfonate) Barium (II) and Ag···I Interactions in a Pseudopolymorphic Form of (7-Iodo-8-hydroxyquinoline-5-sulfonate) Silver (I) Monohydrate

Abstract  

The complexes, Ba (HQS) (H₂O)₄ (HQS = 8-hydroxyquinoline-5-sulfonic acid) (1) and Ag (HIQS) (H₂O) (Ferron = 7-iodo-8-hydroxyquinoline-5-sulfonic acid) (2) have been synthesized and characterized by X-ray diffraction analysis and spectroscopic studies. In compound 1, Ba²⁺ ion has a nine-coordinate monocapped antiprismatic geometry. In compound 2, Ag⁺ has distorted tetrahedral coordination and Ag···I interactions generate the supramolecular architectures. The complexes have been characterized by FT-IR and UV–Visible measurements. In both the structures, the inversion-related organic ligands are stacked over one another leading to three-dimensional networks.     

Two-dimensional crown ether complex. Synthesis and crystal structure of [Na(N15C5)]<Subscript>2</Subscript>[Cu(mnt)<Subscript>2</Subscript>]

A novel crown ether complex [Na(N15C5)]₂[Cu(mnt)₂] (1) (where N15C5 = 2,3-naphtho-15-crown-5 and mnt = maleonitriledithiolate, [C₂S₂(CN)₂]^2–) was synthesized and characterized by elemental analysis, FT-IR spectra, UV-visible spectra and single crystal X-ray diffraction. Structural analysis reveals that the complex 1 consists of two [Na(N15C5)]⁺ complex cations and one [Cu(mnt)₂]^2– complex anion and the complex molecules are assembled into a novel 2D network by Na–N interactions. In the network, there are 34-member macrocycles formed by four sodium ions of complex cations and four complex anions through Na–N bonds. In each macrocycle, – stacking interactions occurred between two parallel naphthylene moieties of N15C5. It is interesting that the 2D network displays an open-capped wave-like sheet viewed along the crystallographic a axis.     

Central Nervous System Drugs: Low Temperature X-ray Structures of (I) the Base 5-(2,3-Dichlorophenyl)-2,4-diamino-6-fluoromethyl-pyrimidine (4030W92) and (II) 5-(2,6-Dichlorophenyl)-1-H-2,4-diamino-6-methyl-pyrimidine methanesulphonic acid salt (227C89)

Abstract  The X-ray crystal structures of (I), the base 4030W92, 5-(2,3-dichlorophenyl)-2,4-diamino-6-fluoromethyl-pyrimidine, C₁₁H₉Cl₂FN₄, and (II) 227C89, the methanesulphonic acid salt of 5-(2,6-dichlorophenyl)-1-H-2,4-diamino-6-methyl-pyrimidine, C₁₁H₁₁Cl₂N₄ · CH₃O₃S, have been carried out at low temperature. A detailed comparison of the two structures is given. Structure (I) is non-centrosymmetric, crystallizing in space group P2₁ with unit cell a = 10.821(3), b = 8.290(3), c = 13.819(4) ?, β = 105.980(6)°, V = 1191.8(6) ?³, Z = 4 (two molecules per asymmetric unit) and density (calculated) = 1.600 mg/m³. Structure (II) crystallizes in the triclinic space group with unit cell a = 7.686(2), b = 8.233(2), c = 12.234(2) ?, α = 78.379(4), β = 87.195(4), γ = 86.811(4)°, V = 756.6(2) ?³, Z = 2, density (calculated) = 1.603 mg/m³. Final R indices [I > 2sigma(I)] are R1 = 0.0572, wR2 = 0.1003 for (I) and R1 = 0.0558, wR2 = 0.0982 for (II). R indices (all data) are R1 = 0.0983, wR2 = 0.1116 for (I) and R1 = 0.1009, wR2 = 0.1117 for (II). 5-Phenyl-2,4 diaminopyrimidine and 6-phenyl-1,2,4 triazine derivatives, which include lamotrigine (3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine), have been investigated for some time for their effects on the central nervous system. The three dimensional structures reported here form part of a newly developed data base for the detailed investigation of members of this structural series and their biological activities. Index Abstract  Low temperature X-ray structures of (I): the base 5-(2,3-dichlorophenyl)-2,4-diamino-6-fluoromethyl-pyrimidine (4030W92); and (II): 5-(2,6-dichlorophenyl)-1-H-2,4-diamino-6-methyl-pyrimidine methanesulphonic acid salt (227C89) are presented. Both drugs act on the central nervous system. (I) crystallizes in non-centrosymmetric space group P2₁ with two molecules A and B per asymmetric unit cell and (II) is triclinic in space group . The absolute configuration of (I) is determined.      

1,3,5-trichlorotricyanobenzene complexes with mesitylene (1/1) and benzene (1/3)

Trichlorotricyanobenzene-mesitylene (1/1) is monoclinic, space group P2₁/n; at −88°Ca=10.509(3),b=14.863(7),c=11.518(3) ?, β=99.38(2)⁰,V=1775(2) ?³,D _x =1.409(2) g cm⁻³,Z=4. Trichlorotricyanobenzene-benzene (1/3) is hexagonal, space group ; at −99°Ca=17.3914(3),c=7.2673(1) ?,V=1903.6(1) ?³,D _x =1.2844(1) g cm⁻³,Z=3. In both complexes there are stacks of alternating trichlorotricyanobenzene and hydrocarbon molecules. In both complexes there are sheets of molecules perpendicular to the stacks. In the mesitylene complex these sheets contain equal numbers of both kinds of molecules with the trichlorotricyanobenzene molecules arranged in tapes. In the benzene complex the sheets contain only one kind of molecule or the other. The sheets containing the trichlorotricyanobenzene molecules have approximately linear C−N...Cl−C intermolecular interactions with N...Cl distances about 3.02 ?.     

Synthesis, Crystal Structures and Properties of Two Copper (II) Complexes with Pyridazine Derivative Ligand

Abstract  Two new complexes, [Cu(L)₂(CH₃OH)] · (ClO₄)₂ (1) and [Cu(L)₂(H₂O)] · (NO₃)₂ (2), have been synthesized and their crystal structures have been determined by X-ray analysis, where L = 3-(3,5-bimethylpyrazole-yl)-6-chloro-pyridazine]. The complex 1 crystallizes in the monoclinic, space group C2/c, and the coordination configuration of copper (II) is better described as trigonal pyramidal geometry with four N atoms from L and one O_methanol^. The coordination configuration of 2 is quite similar to that of 1 except O_water instead of O_methanol^. The intermolecular hydrogen bonds link the repeat units and extend the molecules to multinuclear structures in both compounds. The spectral properties of the title compounds have been studied and discussed. Furthermore, the antibacterial activities of the title compounds have been detected, the results indicate that the ligands and two copper(II) complexes exhibit certain fungicidal activities again several bacteria. Index Abstract  Two new complexes, [Cu(L)2(CH3OH)]·(ClO4)2 (1) and [Cu(L)2(H2O)]·(NO3)2 (2), have been synthesized and their crystal structures have been determined by X-ray analysis, where L= 3-(3,5-bimethylpyrazole-yl)-6-chloro-pyridazine. The intermolecular hydrogen bonds extend the molecules to multinuclear structures in both compounds.      

Crystal structures of ester derivatives of 2,6-bis(1-pyrrolidinylmethyl)-4-benzamidophenol antiarrhythmic agents

The N atoms in both of the pyrrolidine rings in the title compounds are protonated which prevents the formation of an intramolecular hydrogen bond between the phenol OH group and the ring N atom. This hydrogen bond is thought to be important for maintaining the active shape of these drugs. The positions of the pyrrolidine rings are determined by a chain of hydrogen bonds which link the N⁺–H through the Cl^– back to portions of the same molecule. In both molecules, the carbonyl bond of the ester substituent is aligned parallel to the carbonyl bond of the central amide. The benzanilide fragment is flattened relative to the common conformation found in tabulated structures. Extensive hydrogen bonding is observed due to the presence of solvent and chloride ions. Compound1, 2,6-bis(1-pyrrolidinylmethyl)-4-(4-carboethoxybenzamido)phenol, crystallizes as the dihydrochloride methanol hydrate in the monoclinic space group C2/c with 8 molecules per unit cell and cell constants:a=20.3013,b=11.296(2),c=24.901(5)Å, =93.19(1)°, 4945 unique reflections, 2946 observed,R=0.071. Compound2, 2,6-bis[1-pyrrolidinylmethyl-4-[4-(2-carboethoxyethyl)benzamido]phenol, crystallizes as the dihydrochloride salt in the monoclinic space group P2₁/c with 4 molecules per unit cell anda=12.903(3),b=16.430(4),c=13.731(2)Å, =103.64(2)°, 5712 unique reflections, 2449 observed,R=0.057.