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.      

Low Temperature X-ray Structures of Two Crystalline Forms (I) and (II) of the Pyrimidine Derivative and Sodium Channel Blocker BW1003C87: 5-(2,3,5-Trichlorophenyl)-2,4-diaminopyrimidine

Abstract The X-ray crystal structures of two crystalline forms of 5-(2,3,5-trichlorophenyl)-2,4-diaminopyrimidine, C₁₀H₇Cl₃N₄ (code name BW1003C87) (I) and (II), have been carried out at liquid nitrogen temperature. A detailed comparison of the two structures is given. Both are centrosymmetric, with structure (I) in the triclinic space group P unit cell a = 6.4870(10), b = 9.216(2), c = 12.016(2) ?, α = 75.78(3)°, β = 89.95(3)°, γ = 83.45(3)°, V = 691.5(2) ?³, Z = 2 and density (calculated) = 1.544 Mg/m3; and (II) in the monoclinic space group P2₁/c, unit cell a = 12.000(2), b = 7.518(2), c = 13.450(3) ?, β = 97.87(3)°, V = 1202.0(5) ?³, Z = 4, Density (calculated) = 1.600 Mg/m3. Structure (I) includes a solvated CH₃OH in the lattice. Final R indices [I > 2sigma(I)] are R1 = 0.0427, wR2 = 0.1075 for (I) and R1 = 0.0487, wR2 = 0.1222 for (II). R indices (all data) are R1 = 0.0470, wR2 = 0.1118 for (I) and R1 = 0.0623, wR2 = 0.1299 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. Both lamotrigine and 5-(2,3,5-trichlorophenyl)-2,4-diaminopyrimidine (code name BW1003C87), the subject of the present study, are anticonvulsant as well as neuroprotective in models of brain ischaemia and in a model of white matter ischaemia. BW1003C87 is a sodium channel blocker which also reduces the release of the neurotransmitter glutamate. The three dimensional structures reported here form part of a newly developed data base for the detailed investigation of members of this drug family and their biological activities. Index Abstract Rex A. Palmer, Brian S. Potter, Michael J Leach and Babur Z. Chowdhry 5-(2,3,5-trichlorophenyl)-2,4-diaminopyrimidine occurs in two crystalline forms whose X-ray structures are described here. The molecular conformations in (I) and (II) are quite distinct as illustrated, the ring linkage torsion angle differing by 23.5 deg. (I) has a methanol solvate molecule in the lattice.      

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.      

Structure of 3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine isethionate solvate (lamotrigine isethionate)

The crystal and molecular structure of lamotrigine isethionate, C₉H₈Cl₂N₅ ⁺ .HOC₂H₄SO₃ ^– has been determined by direct methods. The compound crystallizes in the tetragonal space group I4₁/a. The isethionate moiety forms multiple hydrogen bonds to the lamotrigine nucleus, three from one isethionate, two from a symmetry related isethionate and a further two from two different symmetry related molecules. Protonation of N(2) in the triazine ring, not observed in the native lamotrigine structure is presumably associated with the interaction of the isethionate moiety. Both rings in the lamotrigine moiety are essentially planar, with a dihedral angle of 66.08(7)° compared to 80.70° in native lamotrigine. The connecting bond length C(1)—C(6) = 1.493(3) Å also correlates well with values in related compounds (1.480(3) Å) in the native structures.     

Crystal structures of 3-[1-Benzenesulfonyl-3-phenylsulfanyl-1H-indol-2-yl]-1-[4-(methyl (I)/methoxy (II) phenyl)]-2-phenyl-propane-1-one

The compounds 3-(1-Benzenesulfonyl-3-phenylsulfanyl-1H-indol-2-yl)-1-[4-methyl (I)/methoxy (II)phenyl)]-2-phenyl-propane-1-one crystallize in triclinic space group P . The details are: compound I a = 11.941(6) ?, b = 12.154(7) ?, c = 13.006(7) ?, α = 63.124(8)°, β = 84.464(9)°, γ = 64.810(8)°, V = 1519.7(14) ?³, Z = 2, D _cal = 1.284 Mg m⁻³, and R = 0.0382 (wR = 0.0978); compound II a = 11.897(6) ?, b = 12.268(6) ?, c = 13.001(7) ?, α = 61.919(8)°, β = 83.480(8)°, γ = 64.676(7)°, V = 1504.0(14) ?³, Z = 2, D _cal = 1.333 Mg m⁻³, and R = 0.0422 (wR = 0.1049). The indole ring system in both the molecules I and II are not strictly planar and the dihedral angles formed by the pyrrole and benzo planes are 4.0(7)° and 3.5(8)°, respectively. The C–HO, C–Hπ and ππ types of interactions stabilize the molecules in the unit cell in addition to van der Waal's forces in I and II.     

Low Temperature Crystal Structures of Two Rhodanine Derivatives, 3-Amino Rhodanine and 3-Methyl Rhodanine: Geometry of the Rhodanine Ring

Abstract  Rhodanines (2-thio-4-oxothiazolidines) are synthetic small molecular weight organic molecules with diverse applications in biochemistry, medicinal chemistry, photochemistry, coordination chemistry and industry. The X-ray crystal structure determination of two rhodanine derivatives, namely (I), 3-aminorhodanine [3-amino-2-thio-4-oxothiazolidine], C₃H₄N₂OS_2, and (II) 3-methylrhodanine [3-methyl-2-thio-4-oxothiazolidine], C₄H₅NOS₂, have been conducted at 100 K. I crystallizes in the monoclinic space group P2₁/n with unit cell parameters a = 9.662(2), b = 9.234(2), c = 13.384(2) ?, β = 105.425(3)°, V = 1151.1(3) ?³, Z = 8 (2 independent molecules per asymmetric unit), density (calculated) = 1.710 mg/m³, absorption coefficient = 0.815 mm⁻¹. II crystallizes in the orthorhombic space group Iba2 with unit cell a = 20.117(4), b = 23.449(5), c = 7.852(2) ?, V = 3703.9(12) ?³, Z = 24 (three independent molecules per asymmetric unit), density (calculated) = 1.584 mg/m³, absorption coefficient 0.755 mm⁻¹. For I in the final refinement cycle the data/restraints /parameter ratios were 2639/0/161, goodness-of-fit on F² = 0.934, final R indices [I > 2sigma(I)] were R1 = 0.0299, wR2 = 0.0545 and R indices (all data) R1 = 0.0399, wR2 = 0.0568. The largest difference peak and hole were 0.402 and −0.259 e ?⁻³. For II in the final refinement cycle the data/restraints/parameter ratios were 3372/1/221, goodness-of-fit on F² = 0.950, final R indices [I > 2sigma(I)] were R1 = 0.0407, wR2 = 0.1048 and R indices (all data) R1 = 0.0450, wR2 = 0.1088. The absolute structure parameter = 0.19(9) and largest difference peak and hole 0.934 and −0.301 e ?⁻³. Details of the geometry of the five molecules (two for I and three for II) and the crystal structures are fully discussed. Corresponding features of the molecular geometry are highly consistent and firmly establish the geometry of the rhodanine ring. Index Abstract  Low temperature X-ray structures of (I) 3-aminorhodanine [3-amino-2-thio-4-oxothiazolidine] and (II) 3-methylrhodanine3-methyl-2-thio-4-oxothiazolidine are presented. Crystals of I are monoclinic and occupy space group P2₁/n with eight molecules (2 per asymmetric unit cell) and (II) is orthorhombic in space group Iba2 with 24 molecules (3 per asymmetric unit). This study has provided five highly consistent copies of the rhodanine ring at high resolution thus enabling its geometry to be established with confidence. The two independent molecules in the asymmetric unit of 3-aminorhodanine (left) and the three independent molecules in the asymmetric unit of 3-methylrhodanine (right) showing space filling and van der Waals contacts (drawn with MERCURY [Bruno et al. Acta Cryst B58:389, 2002]).     

Synthesis and structure of p-chlorophenylhydrazone of 3-(methylthio)-5-propanoyl-1,2,4-triazine

The reaction of 3-(methylthio)-5-propanoyl-1,2,4-triazine with p-chlorophenylhydrazine hydrochloride is completed within 5 min at room temperature in ethanol leading to p-chlorophenylhydrazone of 3-(methylthio)-5-propanoyl-1,2,4-triazine 1 in good yield. Title compound, 1 (R = C₂H₅, R₁ = Cl, Z = SCH₃), C₁₃H₁₄N₅SCl, crystallizes in the monoclinic system, space group P2₁/n, with cell constants a = 12.5206(6) Å, b = 9.3122(8) Å, c = 12.8524(9) Å, and = 98.822(5)°, Z = 4, T = 293 K, D_cal = 1.381 g cm^–3. The structure was solved by direct methods and refined to R value of 0.0671 for 1,679 reflections. The molecule as a whole has an almost planar conformation and possesses (E) configuration with respect to the C=N double bond. The crystal structure is stabilized by a weak N(13)–H(13)···N(2) intermolecular hydrogen bond and significant stacking, characteristic for -electron systems.     

2-(1-Methyl-1H-indol-3-ylmethylene)-1-aza-bicyclo[2.2.2] octan-3-one: Acid-catalyzed isomerization of the Z isomer to the E isomer

Crystals of (Z)-2-(1-methyl-1H-indol-3-ylmethylene)-1-aza-bicyclo[2.2.2]octan-3-one (I) were obtained from a condensation reaction of 1-methyl-1H-indole-3-carboxaldehyde with 1-aza-bicyclo[2.2.2]octan-3-one and subsequent crystallization of the product from methanol. The isomeric (E)-2-(1-methyl-1H-indol-3-ylmethylene)-1-aza-bicyclo[2.2.2] octan-3-one hydrochloride (II) was obtained by treating a methanolic solution of I with a 1M solution of hydrogen chloride diethyl ether, followed by crystallization of resultant product from methanol. Crystal data: I, is monoclinic, P2₁, a = 5.7440(10), b = 11.102(2), c = 10.708(2) Å, = 91.751(10)°, and V = 682.5(2) ų with Z = 2, for D _cal= 1.296 mg/m³ and II, is monoclinic, P2₁/c, a = 8.8510(2), b = 17.4990(5), c = 20.4300(5) Å, = 101.3620(12)°, V = 3102.26(14) with Z = 8, for D _cal= 1.316 mg/m³.     

Structure of 2-(1-phenylimidiazolidin-2-ylidene)- malononitrile and 2-(hexahydropyrimidinyl-2-ylidene)- malononitrile

The crystal structure of 2-(1-phenylimidazolidin-2-ylidene)-malononitrile, I, and 2-(hexahydropyrimidin-2-ylidene)-malononitrile, II, were determined with crystal data (I: Monoclinic, P2₁/n, a=8.116(3) ?, b=7.650(3) ?, c=17.399(7) ?, β=93.065(6)°, R _all=0.0980; II: Monoclinic, P2₁/n, a=9.169(2) ?, b=8.103(2) ?, c=10.337(3) ?, β=99.853(4)°, R _all=0.0877). N−H···N hydrogen bonds were responsible for the formation of centrosymmetric dimers of I and one-dimensional zigzag molecular chains of II.     

Synthesis and X-ray diffraction study of (Cs0.5Ba0.25)[UO2(CH3COO)3] and Ba0.5[UO2(CH3COO)3]

Uranyl triacetate complexes (Cs_0.5Ba_0.25)[UO₂(CH₃COO)₃] (I) and Ba_0.5[UO₂(CH₃COO)₃] (II) are synthesized for the first time and their structures are determined by X-ray diffraction. Both compounds crystallize in the cubic crystal system. The crystal data are as follows: a = 17.3289(7) ?, V = 5203.7(4) ?³, space group I2₁3 and Z = 16 (I); a = 17.0515(8)?, V = 4957.8(4) ?³, space group I $ \bar 4 $ \bar 4 3d, and Z = 16 (II). In I and II, as in all uranyl triacetates studied earlier, the coordination polyhedron of the uranium atom is a hexagonal bipyramid whose vertices are occupied by the oxygen atoms of the uranyl and three acetate groups. The uranium-containing group belongs to the AB ₃⁰¹ (A = UO₂²⁺, B ⁰¹ = CH₃COO⁻) crystal chemical group of uranyl complexes. It was found that compound II is isostructural to the (Rb_0.50Ba_0.25)[UO₂(CH₃COO)₃] studied earlier.     

Crystal structure of complexes of bivalent Co,Ni, and Cd with anions of benzoic and 2-(acetylamino)-5-nitrobenzoic acids

The structure of three complexes of bivalent metals (cobalt, nickel, and cadmium) with anions of benzoic (HL ¹) and 2-(acetylamino)-5-nitrobenzoic (HL ²) acids, namely, [Co₂¹ (H₂O)₂(μ-C₄H₄N₂)] _n (I), [NiL²(H₂O)₅]L² · 2H₂O (II), and [Cd(μ-L ²)₂(H₂O)₂] _n · 2nH₂O (III), is determined. In chainlike structure I, cobalt atoms are connected by bridging pyrazine molecules; structure II contains isolated complexes. In structure III, centrosymmetric (CdOCO)₂ cycles and polymeric ribbons are formed due to the coordination of the carboxylate group of the L ² ligand to two cadmium atoms.     

Structure of 2-[(Phenyl)-(3,5-Dimethyl-Pyrazol-1-yl)-Methyl]-Malonic Acid Diethyl Ester

Abstract  

The titled new functionalized ligand of type 2-[(phenyl)-(3,5-dimethyl-pyrazol-1-yl)-methyl]-malonic acid diethyl ester (4) is prepared in good yield through condensation of 3,5-dimethyl-pyrazole, with 2-arylidene-malonic acid diethyl esters 3. The structure of 4 was determined by spectral (IR, ¹H and ¹³C NMR), elemental analyses and X-ray diffraction data. The title compound (4) crystallizes in the monoclinic space group P2₁/a, with a = 7.9253 (2), b = 17.1299 (5), c = 13.4522 (4) ?, β = 90.220 (2)°, V = 1,826.25 (9) ?³, Z = 4 and with R _int = 0.021. The molecular conformation shows two possible pockets ready to coordinate two metal atoms. The crystal structure of (4) is stabilized by inter-molecular C–H⋯O and C–H⋯N hydrogen bonding.     

Synthesis and Crystal Structures of 3,3,6,6-tetramethyl-9-(2,4-dichlorophenyl)-3,4,6,7,9,10-hexahydro-2H,5H-acridine-1,8-dione and 3,3,6,6-tetramethyl-9,10-di(4-methoxyphenyl)-3,4,6,7,9,10-hexahydro-2H,5H-acridine-1,8-dione

The title compounds 3,3,6,6-tetramethyl-9-(2,4-dichlorophenyl)-3,4,6,7,9,10-hexahydro-2H,5H-acridine-1,8-dione 1 (C₂₃H₂₅Cl₂NO₂, Mr = 418.34) and 3,3,6,6-tetramethyl-9,10-di(4-methoxy-phenyl)-3,4,6,7,9,10-hexahydro-2H,5H-acridine-1,8-dione 2 (C₃₁H₃₅NO₄, Mr = 485.60) were synthesized and crystallized. The crystals of compound 1 are monoclinic, space group P2₁/c, a = 9.826(3), b = 19.866(5), c = 11.471(3) ?, β = 111.929(4)°, Z = 4, V = 2077(1) ?³; The compound 2 crystallizes in space group P2₁/c, with cell parameters a = 12.089(2), b = 11.447(2), c = 19.742(3) ?, β = 101.00(1)°, V = 2681.8(8) ?³ and D _calc = 1.203 g/cm³ for Z = 4. X-ray analysis reveals that atoms C(1), C(6), C(7), C(8), C(13) and N(1) form a 1,4-dihydropyridine ring in compound 1, which adopts half-chair conformation. In compound 2 the atoms C(1), C(6), C(7), C(8), C(13) and N form a 1,4-dihydropyridine ring which adopts boat conformation. In addition, the two outer six-membered rings display half-chair conformations in the crystal structures 1 and 2.     

A Unique Example of a Co-crystal of [Co(AMTTO)2(H2O)2](NO3)2 and [Co(AMTTO)2(CH3CN)2](NO3)2 (AMTTO = 4-amino-5-methyl-1,2,4-triazol-3(2H)-thione)

A co-crystal of cobalt(II) complexes, Co(AMTTO)₂(CH₃CN)₂]²⁺(NO₃)₂. [Co(AMTTO)₂(H₂O)₂]²⁺(NO₃)₂, compound (1) was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine (AMTTO) in acetonitrile as solvent. Isolated crystals were characterized by elemental analyses, IR spectroscopy as well as X-ray diffraction studies. Crystal data for 1 at 95 K revealed a monoclinic space group P2₁/n, a?=?11.7903(5), b?=?12.1279(5), c?=?14.1443(6) Å, β?=?99.244(4)°, Z?=?2, R₁?=?0.0339. Compound 1 consists of two co-crystallized Co(II) complexes [Co(AMTTO)₂(CH₃CN)₂]²⁺ and [Co(AMTTO)₂(H₂O)₂]²⁺ and four nitrate counter anions In both complexes, cobalt(II) ions are in an octahedral arrangement. Two S, N bidentate AMTTO ligands are coordinated to both Co(II) ions. The coordination sphere of Co1 is completed by two acetonitrile molecules, and these positions are occupied by water molecules for Co2.

Graphic Abstract

A co-crystal of cobalt(II) compound was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine in acetonitrile as solvent.

     

Synthesis and characterization of copper(II) tetraaza macrocyclic complex with 2- benzimidazolepropionate ligand

A mononuclear complex [Cu(L)(bip)₂] (1) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,0^1.18, 0^7.12]docosane; bip = 2-benzimidazolepropionate) has been synthesized and structurally characterized by X-ray crystal structure analysis. The crystals are monoclinic P2 ₁/n with a = 10.2990(2), b = 15.9400(3), c = 11.991(14) Å, = 101.92(7)°, V = 1926(2) ų, Z = 2. The copper(II) coordination geometry exhibits an axially elongated octahedron with four nitrogen atoms from the macrocycle and two oxygen atoms from the bip ligands. The cyclic voltammogram of 1gives 2 one-electron waves corresponding to Cu^II/Cu^III and Cu^II/Cu^I processes.     

Crystal structure of R[UO2(CH3COO)3] (R = NH 4+ , K+, or Cs+)

The single crystal structure of NH₄[UO₂(CH₃COO)₃] (I), K[UO₂(CH₃COO)₃] (II), and Cs[UO₂(CH₃COO)₃] (III) is studied by X-ray diffraction. I and II crystallize in the tetragonal crystal system. The crystal data are as follows: a = 13.6985(3) and c = 27.5678(14) ?, V = 5173.1(3) ?³, space group I4₁/a, Z = 16, and R = 0.023 for I; a = 13.8890(5) and c = 26.0839(18) ?, V = 5031.7(4) ?³, space group I4₁/a, Z = 16, and R = 0.037 for II. Crystals III are orthorhombic, a = 18.176(2), b = 13.119(2), and c = 22.088(4) ?, V = 5267(1)?³, space group Pbca, Z = 16, and R = 0.0424. In structures I–III, the uranium-containing structural units are represented by discrete mononuclear [UO₂(CH₃COO)₃]⁻ groups, which belong to the AB ₃⁰¹ (A = UO₂²⁺, B ⁰¹=CH₃COO⁻) crystal chemical group of uranyl complexes.     

3-(benzo[d]thiazol-2-YL)phenol and 4-(benzo[d]thiazol-2-YL)phenol: Crystal Structure Determination,DFT Calculations and Visualizing Intermolecular Interactions Using Hirshfeld Surface Analysis

This article describes the synthesis and X-ray crystal structure analysis of 3-(benzo[d]thiazol-2-yl) phenol (I) and 4-(benzo[d]thiazol-2-yl)phenol (II), crystallized in centrosymmetric triclinic and orthorhombic space groups respectively. The packing in the unit cell of these two positional isomers are different resulting difference in various types of intermolecular interactions (C-H…S, O-H…O_w and O-H…N) connect the molecules into 2D frameworks. Due to presence of lattice water in compound (I), H-bonding interactions are strong and melting point of (I) is comparatively higher than (II). The DFT optimized molecular geometries in (I) and (II) agree closely with those obtained from crystallographic studies.     

Ligand-induced polyhedral opening in the mixed-metal cluster MeCCo2NiCp(CO)6 by 4,5-Bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): X-ray structure of Co2NiCp(CO)4[μ2,η2,η1-C(Me)C=C(PPh2)C(O)CH2C(O)](μ2-PPh2)

The mixed-metal cluster MeCCo₂NiCp(CO)₆ (1) reacts with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) in refluxing CH₂Cl₂ to afford the disubstituted cluster MeCCo₂NiCp(CO)₄(bpcd) (2), which exists as a 1:1 mixture of bridging and chelating bpcd isomers. VT ³¹P NMR spectroscopy confirms that the two bpcd isomers do not interconvert in solution over the temperature range of 182–298 K. Thermolysis of cluster 2 leads to bpcd/cluster activation and formation of the phosphido-bridged cluster Co₂NiCp(CO)₄[μ₂,η²,η¹-C(Me)C=C(PPh₂)C(O)CH₂C(O)](μ₂-PPh₂) (3). The ligand-induced polyhedral expansion that accompanies the formation of the title cluster was established by X-ray diffraction analysis. Co₂NiCp(CO)₄[μ₂,η²,η¹-C(Me)C=C(PPh₂)C(O)CH₂C(O)](μ₂-PPh₂) crystallizes in the triclinic space group P-1, a=9.679(2), b=11.691(2), c=16.653(3) ?, α=85.849(3)°, β=85.456(4)°, γ=66.453(3)°, V=1720.3(6) A³, Z=2, D _cacl=1.632 Mg/m³; R=0.0874, R _w=0.1998 for 7053 observed reflections with I > 2σ(I).     

Synthesis and crystal structures of two novel 3,4,5- trimethoxyphenyl derivatives from (Z)-1-[(2′,3′-dinitro-4′-methoxy)-phenyl]-2-[(3″,4″,5″-trimethoxy)-phenyl] ethene

The title compounds, (Z)-1-[(2′,4′-dimethoxy-3′-nitro)-phenyl]-2-[(3″,4″,5″-trimethoxy)-phenyl]ethene, C₁₉H₂₁O₇N (I), and 2-amino-4-methyl-6-(3,4,5-trimethoxy-phenyl)-pyrimidine, C₁₄H₁₇O₃N₃ (II), were obtained unexpectedly from a reaction involving (Z)-1-[(2′,3′-dinitro-4′-methoxy)-phenyl]-2-[(3″,4″,5″-trimethoxy)-phenyl]ethene (IV). The molecular structures of these compounds were obtained by single-crystal X-ray diffraction. Crystallization of I occurs in the centrosymmetric monoclinic space group P2₁/c (No. 14) with a=7.7311(5), b=19.9239(13), c=11.5725(8); and β=92.193(3) and Z=4. Crystallization of II occurs in the centrosymmetric monoclinic space group C2/c (No. 15) with a=21.296(2), b=6.8963(7), c=20.001(2); and β=114.121(6) and Z=8. Details of the synthesis and the structural characterization of the title compounds are presented and discussed.     

Palladium (II) compounds with diaminocarboxylic acids: Crystal structures of [Pd(H2Cdta)] · H2O, [Pd(H3Edtp)Cl] · 2H2O, and (H6Edtp)[PdCl4] · 4H2O

The crystal structures of three Pd(II) compounds with diamine tetracarboxylates in different protonation states are determined, namely, [Pd(H₂ Cdta)] · H₂O (I), [Pd(H₃ EdtpCl] · 2H₂O (II), and (H₆ Edtp)[PdCl₄] · 4H₂O (III) (R ₁ = 0.0230, 0.0313, and 0.0277 for 3040, 3377, and 3809 reflections with I > 2σ(I) for I–III, respectively). Crystals I and II are built of neutral complexes [Pd(H₂ Cdta)] and [Pd(H₃ Edtp)Cl], respectively, and crystallization water molecules. Crystal III consists of [PdCl₄]²⁻ anionic complexes, H₆ Edtp ²⁺ cations, and water molecules. In I, one of the protonated acetate groups of the H₂ Cdta ²⁻ ligand forms a very weak additional Pd-O bond [2.968(2) Å] over the 2N + 2O coordination square. In II and III, the protonated propionate groups of the H₃ Edtp ⁻ ligand and the H₆ Edtp ²⁺ cation are not involved in Pd coordination and the coordination squares consist of the 2N + O + Cl and 4Cl atoms, respectively. __________ Translated from Kristallografiya, Vol. 48, No. 2, 2003, pp. 278–282. Original Russian Text Copyright ? 2003 by Polyakova, Poznyak, Sergienko.