Structural study of nitrovinylindoles: (I) 2-methyl-3-(2′-methyl-2′-nitrovinyl)indole and (II) 3-(2′-nitrovinyl)indole

Compound (I) is 2-methyl-3-(2-methyl-2-nitrovinyl)indole, C₁₂H₁₂N₂O₂,M _r=216.24, monoclinic,P2₁/n,a=16.710(1),b=7.627(1),c=17.646(1) Å,=104.8(1)°,V=2174.7(1) ų,Z=8.D _x=1.321 g cm^–3, MoK, =0.71073 Å,=0.858 cm^–1,F(OOO)=912, room temperature,R=0.061 for 1956 observed reflections. Compound (II) is 3-(2-nitrovinyl)indole, C₁₀H₈N₂O₂,M _r=188.18, monoclinic,P2₁/n,a=10.178(1),b=10.608(1),c=8.411(1) Å,=105.5(2)°,V=875.0(1) ų,Z=4,D _x=1.4284 g cm^–3, CuK, =1.5418 Å,=8.068 cm^–1,F(000)=392, room temperature,R=0.040 for 1330 observed reflections. Compounds (I) and (II) have a similar geometry, the only significant difference lying in the rotation of the nitrovinyl chain. This feature could be responsible for the difference in biological activity. In both compounds, the molecules are associated, forming charge-transfer complexes.     

Crystal and molecular structures of 1,4-dihydro-6-methyl-5-N,N-diethylcarbamoyl-4-phenyl-2(3H)-pyrimidinethione (1) and 1,4-dihydro-6-methyl-5-N-methyl carbamoyl-4-(2′-nitrophenyl)-2(3H)-pyrimidinethione hemihydrate (2)

The crystal structure of 1,4-dihydro-6-methyl-5-N,N-diethylcarbamoyl-4-phenyl-2(3H)-pyrimidinethione, C₁₆ H ₂₁ N ₃OS (1), is monoclinic, space group P2₁/n, a = 6.818(1), b = 13.211(2), c = 18.807(3) Å, = 99.53(1)°, V = 1670.6(4) ų, Z = 4 and d _cal = 1.206 Mg/m³, R = 0.042 (wR = 0.119) for 190 parameters and 2560 observations with I 2(I) and 1,4-dihydro-6-methyl-5-N-methyl carbamoyl-4-(2-nitrophenyl)-2(3H)-pyrimidinethione hemihydrate, C₁₃ H ₁₄N₄O₃S 0.5H₂O, (2), is triclinic, space group P1, a = 7.513(1), b = 14.381(2), c = 15.506(2)Å, = 114.95(2), = 98.11(1), = 93.55(1)°, V = 1490.0(3) ų, Z = 4 and d _cal = 1.406 Mg/m³, R = 0.062 (wR = 0.165) for 388 parameters and 3094 observations with I 2(I).The compound 2 crystallized having two molecules in the asymmetric unit, which can be regarded as monohydrated dimers, and forming a hydrate. The conformation of the central heterocyclic ring (1,4-dihydropyrimidine) in both compounds was found to be close to a half-chair conformation. The 2-nitrophenyl substituent in 2 is in the axial synperiplanar orientation. In both compounds, the conformation of the 3-substituted carbamoyl group appears to be influenced by hydrogen bonding with anticlinal orientation observed for carbonyl groups serving as hydrogen bonding acceptors.     

Synthesis and structural analysis of (μ-SCH2CH2CH2S-μ)Fe2(CO)5(2-C5H4NPPh2)

Treatment of (μ-SCH₂CH₂CH₂S-μ)Fe₂(CO)₆ with equimolar 2-C₅H₄NPPh₂ in the presence of Me₃NO·2H₂O in CH₂Cl₂/MeCN solutions gave the title complex (μ-SCH₂CH₂CH₂S-μ)Fe₂(CO)₅(2-C₅H₄NPPh₂) in 76% yield. The title complex was characterized by spectroscopy as well as by single crystal X-ray diffraction analysis. The molecular structure consists of a butterfly [Fe₂S₂] cluster with propane, five carbonyls, and 2-C₅H₄NPPh₂. In the crystal packing diagram, intermolecular C–H···O hydrogen bonds between phenyl and carbonyl groups stabilize the solid state.     

Structure ofcatena-(2-amino-1,3,4-thiadiazolium, 2-amino-1,3,4-thiadiazole bis(μ-iodo)-di-iodo-bismuth(III)

[(C₂H₄N₃S) (C₂H₃N₃S) BiI₄]; [(HL) (L) BiI₄] (L=2-amino-1,3,4-thiadiazole),M _r=919.86. monoclinic, P 1 2₁/a 1,a=7.622(1),b=18.977(2),c=12.821(1) Å, =102.77(1)°, finalR=0.033. The crystals consist of HL⁺ cations, neutral L molecules and polymeric [BiI₄] ^– anions built up of edge-sharing [BiI₆]^3– octahedra, with Bi–I(bridging) distances in the range 3.320(1)–3.057(1) Å and Bi–I(terminal) distances in the range 2.917(1)–2.929(1) Å. The¹H and¹³C spectra in DMSO-d₆ solution are used in conjunction with the X-ray structural results to establish the preferred protonation site of the thiadiazole ring.     

Synthesis and crystal structure of iodo-1-(2′-aminophenyl)-2,6-diaza-6-methyl-9-amino-1-noneno copper(II) iodide

Reaction of equimolar amounts of 2-aminobenzaldehyde and 3,3-diamino-N-methyldipropyl-amine in methanol affords a novel 11 condensation product, abaMedpt, which has been isolated as the copper(II) complex, [Cu(abaMedpt)I]I. The crystal structure of the complex has been determined from single crystal diffractometer data and refined to a finalR factor of 0.0353 with 2492 unique observations and 206 variables. The complex crystallizes in the monoclinic space group P2₁/c (N° 14) witha=9.263(2),b=18.189(3),c=11.740(3) Å,=92.97(4)°,Z=4,D _c =1.902 g cm^–3. The structure involves a five-coordinate square-pyramid CuN₄I chromophore and an uncoordinated iodide anion. Nitrogen atoms constitute the basal plane, while the bonded iodine occupies the apical position. The structure contrasts with the more usual distorted trigonal-bipyramidal stereochemistries of CuN₄I chromophores reported so far.     

Crystal Structure?4-(2,4-Dihydroxybenzylideneamino)-5-methyl-2H-1,2,4-triazol-3(4H)-one

Abstract  

The title compound (I), 4-(2,4-dihydroxybenzlideneamino)-5-methyl-2H-1,2,4-triazol-3(4H)-one was characterized by single crystal X-ray diffraction. This crystal is monoclinic, space group P2₁/c with a = 10.1447(7) ?, b = 7.0972(3) ?, c = 14.6726(10) ?, β = 98107(5)°, V = 1045.85(11) ?³, Z = 4, D _c = 1.487 g/cm³, F ₀₀ = 488, R = 0.039 and wR = 0.1025, S = 1.003, T = 293 (2) K. The title molecule is planar: the angle between the triazole ring and benzene ring is 179.1(1)°. The crystal structure contains two intramolecular (O–H···N and C–H···O) and three intermolecular interaction (O–H···N, N–H···O, and C–H···O). In addition, there is also π–π interactions.     

Supramolecular structure of tetrakis-μ-(4-chloro-3-nitrobenzoato)-bis(methanol)dicopper(II)

The title compound, [Cu₂(II)(4-Cl-3-NO₂–C₆H₃CO₂)₄(CH₃OH)₂] or [Cu₂(4-chloro-3-nitrobenzoate)₄(MeOH)₂] has been prepared and its structure determined using X-ray crystallography. The complex crystallizes in the triclinic space group P-1 with a = 9.6887(9)Å, b = 10.6448(9)Å, c = 11.4194(10)Å, = 108.094(2), = 110.682(2), = 105.055(2), V = 952.691(15)ų, and Z = 1. The structure consists of centrosymmetric dimers in which the Cu(II) atoms display a square pyramidal CuO₅ coordination, with four carboxylate O atoms in the basal plane [CuO 1.951(2)–1.968(2)Å] and the methanol O atoms in the apical position [CuO 2.170(2)Å]. The Cu atoms are 2.614(1)Å apart and are bridged by four benzoate groups. The discrete dimers are extended into 1D chains that result from hydrogen bonding between the coordinated methanol on one Cu(II) dimer and the nitro substituent on an adjacent Cu(II) dimer. The chains are interdigited and held by – stacking interactions forming 3D supramolecular array.     

Synthesis and structure of (H2O)(12-crown-4)-Co(II)(Co(II)Cl3)(μ-Cl) isolated from a liquid clathrate medium

The crystal structure of (H₂O)(12-crown-4)Co(II)(Co(II)Cl₃)(μ-Cl)1 is reported. Crystal data for1: monoclinic, space groupP2 ₁/m, a=7.958(8) Å,b=12.006(1) Å,c=69.017(9) Å, β=107.896(2)⁰, D_c=1.84 g cm^?3,Z=2,R1=0.025,wR2=0.059. The crown ether acts as a tetradentate ligand and partially completes the binding sphere of the Co(II) ion which also includes one water oxygen atom and a bridging chloride ligand, the latter of which may be regarded to originate from a [CoCl₄]^2? ion.     

Reaction of ethyl diazoacetate with Co3(CO)9(μ3-CCl): Isolation and X-ray structures of Co3(CO)9(μ3-CCO2Et), Co3(CO)9(μ3-CCH2CO2Et), and [Co3(CO)9(μ3-CCHCO2Et)]2

The reaction between the tricobalt cluster Co₃(CO)₉(₃-CCl) (1) and AlCl₃, followed by treatment with ethyl diazoacetate, N₂CHCO₂Et, affords a complex mixture of products in low yields. Column chromatography has allowed the isolation of the four cluster compounds Co₃(CO)₉(₃-CH) (2), Co₃(CO)₉(₃-CCO₂Et) (3), Co₃(CO)₉(₃-CCH₂CO₂Et) (4), and [Co₃(CO)₉(₃-CCHCO₂Et)]₂ (5). Clusters 4 and 5 are new and have been fully characterized in solution by IR and ¹H NMR spectroscopy. The molecular structures of clusters 3–5 have also been determined by single-crystal X-ray diffraction analysis. Co₃(CO)₉(₃-CCO₂Et) crystallizes in the triclinic space group P , a = 8.8393(5), b = 14.727(1), c = 15.272(1) Å, = 93.361(6), = 105.509(5)°, = 100.336(6)°, V = 1872.6(2) ų, Z = 4, and d _calc = 1.823 g/cm³. Co₃(CO)₉(₃-CCH₂CO₂Et) crystallizes in the monoclinic space group P2₁/n, a = 9.3806(7), b = 9.2617(8), c = 22.455(2) Å, = 94.483(7)°, V = 1944.9(3) ų, Z = 4, and d _calc = 1.803 g/cm³. [Co₃(CO)₉(₃-CCHCO₂Et)]₂ crystallizes in the monoclinic space group C2/c, a = 21.585(2), b = 8.7977(7), c = 20.784(1) Å, = 104.807(6)°, V = 3815.8(5) ų, Z = 4, and d _calc = 1.835 g/cm³. Plausible pathways leading to the formation of clusters 2, 4, and 5 are discussed.     

Synthesis and crystal structure of 1-(1′,3′-dimethyl-5′-chloropyrazol-4′-carbonyl′-3-(2′-chlorophenyl)-5-amino-4-cyanopyrazole

The title compound 1-(1,3-dimethyl-5-chloropyrazol-4-carbonyl)-3-(2-chlorophenyl)-5-amino-4-cyanopyrazole (C₁₆H₁₂Cl₂N₆O) has been synthesized and characterized by X-ray diffraction: Triclinic, space group P1, with a = 8.6712(8) Å, b = 9.5091(10) Å, c = 11.2170(11) Å = 71.531(2)°, = 84.683(2)°, = 74.099(2)° Z = 2; V = 843.7(14) ų. C(10), O(1), C(11), and N(2) atoms are coplanar with the average deviation of 0.0071 Å, which form 11.03° and 43.93° dihedral angles with pyrazole planes (I) and (II), respectively.     

Crystal and molecular structure of CI Solvent Yellow 18, 4-(2′,4′-dimethyl phenyl hydrazono)-5-methyl-2-phenyl-3H-pyrazol-3-one

The crystal structure of CI Solvent Yellow 18, C₁₈H₁₈N₄O, has been determined by single crystal X-ray diffraction techniques. It crystallizes in the monoclinic system witha=7.480(2) Å,b=19.184(3) Å,c=11.260(1) Å,=98.00(3)°, space groupP2₁/n andZ=4. The structure has been solved by direct methods, and least-squares refinement has been completed on three-dimensional data (2310 reflections, CuK radiation). The hydrogen atoms have been found, but only their positional parameters refined. Final residual 0.085 (all positive intensity data). The molecule exists as the hydrazone tautomer and intramolecular hydrogen bonding keep the molecule approximately planar. The molecules are packed in layers parallel to the (¯202) plane and in columns parallel tob. Alternate molecules within the columns are in antiparallel. The molecules are linked by van der Waals' forces.     

Synthesis and crystal structure of N-(1-phenyl-3-methyl-4-benzal-pyrazolone-5)- N′-salicylidene hydrazine

A novel Schiff base compound, N-(1-phenyl-3-methyl-4-benzal-pyrazolone-5)-salicylidene hydrazine (PMBP-SAH), has been synthesized and characterized by X-ray diffraction: monoclinic, space group C2/c with a = 21.796(5) Å, b = 18.370(3) Å, c = 20.843(3) Å, = 95.440(10)°, V = 8308(3) ų, and Z = 16. The title compound contains two kinds of tautomers: the red compound is the keto form and the other is the enol form. Changes in color are due to the isomerization of the enol and keto forms by the intramolecular proton transfer.     

Crystal Structures and Properties of Bis(2-Aminopyrimidine-N-)-Bis(Thiocyanato-N)Zinc(II) and Catena-[2-Aminopyrimidine-N- (μ-Thiocynanto-S,N)(Thiocyanato-S)Cadmium(II)]

Abstract  

Complexes [Zn(NCS)₂(2-AMP)₂] (2-AMP = 2-aminopyrimidine) 1 and [Cd(SCN)₂(2-AMP)₂]_n 2 are prepared and characterized by X-ray crystallographic methods. 1 crystallizes in the monoclinic, space group C2/c, with a = 13.5761(14), b = 8.3330(10), c = 13.5962(15) ?, β = 99.5450(10)°, V = 1516.8(3) ?³, Z = 4. In 1, the zinc atom is coordinated by four N atoms from two AMP and two NCS⁻. 2 crystallizes in the monoclinic, space group C2/c, with a = 9.7259(11), b = 19.332(2), c = 8.2149(9) ?, β = 99.817(2)°, V = 1522.0(3) ?³, Z = 4. Complex 2 is made up of 1D chains along a-axis. Each Cd is attached to four NCS⁻ bridges and two pendant 2-AMP ligands.     

Synthesis and crystallographic characterization of [Cd(OH2)2 (μ-Br)4 (Cd(2-hydroxyethyl sulfide) (μ-Br))2]n

The reaction of equal millimolar quantities of CdBr₂ and 2-hydroxyethyl sulfide in 31 CH₃CNCH₃OH produced [Cd(OH₂)₂(Br)₄ (Cd(2-hydroxy ethyl sulfide) (-Br))₂]_n. The compound crystallizes as a bromide-bridged polymer with hydrogen bonding interactions between the polymeric chains. Each of the two unique metal centers has a distorted octahedral geometry. The thioether ligand is bidentate to one cadmium position with one alcoholic terminus uncoordinated. The uncoordinated portion of the molecule is disordered with each conformation participating in slightly different hydrogen bonding environments. The other unique cadmium center is coordinated to four bridging bromides and twotrans water molecules.     

Formation of a samarium alkoxide–aryloxide complex containing a novel butterfly framework: X-ray crystal structures of Sm4(μ3-O-i-Pr)3(μ2-O-i-Pr)4(O-i-Pr)2(O-2,6-i-Pr2C6H3)3(THF) and [Ti(O-i-Pr)2(O-2,6-i-Pr2C6H3) (μ-O-i-Pr)]2

Reaction of a 1:1 mixture of Sm[N(SiMe₃)₂]₃ and Ti(O-i-Pr)₄ with three equivalents of 2,6-di-iso-propylphenol, followed by crystallization from hexane/THF, leads to isolation of the tetranuclear samarium alkoxide Sm₄(₃-O-i-Pr)₃(₂-O-i-Pr)₄(O-i-Pr)₂(O-2,6-i-Pr₂C₆H₃)₃(THF) (1), in addition to the dimeric titanium alkoxide [Ti(O-i-Pr)₂(O-2,6-i-Pr₂C₆H₃)(-O-i-Pr)]₂ (2). 1 crystallizes in the space group while 2 crystallizes in space group P2₁/c. Cell parameters for 1: a = 15.928(6), b = 17.677(7), c = 18.99(1) Å, = 113.24(3), = 94.99(4), = 109.59(2)°, V = 4477(4) ų, D _calc = 1.350 Mg/m³, and Z = 2. Cell parameters for 2: a = 25.336(2), b = 12.082(1), c = 15.570(2) Å, = 96.510(8)°, V = 4735.4(8) ų, D _calc = 1.129 mg/m³, and Z = 4.     

Decarbonylation Reaction of [Os3(CO)10(μ-H)(μ-SN2C4H5)]: X-ray Structures of the Two Isomers of [Os3(CO)9(μ-H)(μ 3-η 2-SN2C4H5)]

Abstract  The thermal reaction of [Os₃(CO)₁₀(μ-H)(μ-SN₂C₄H₅)] (1) at 110 °C afforded the new compound [Os₃(CO)₉(μ-H)(μ ₃-η ²-SN₂C₄H₅)] (2) in 84% yield. Compound 2 exists as two isomers, which differ in the disposition of the bridging hydride ligand. Both of the isomers of 2 have been characterized by a combination of elemental analysis, infrared and ¹H NMR spectroscopic data together with single crystal X-ray crystallography. The isomers crystallize together in the triclinic space group P-1 with a = 10.4775(2), b = 13.3056(3), c = 15.0325(3) ?, α = 110.8890(10), β = 99.3880(10), γ = 96.1620(10)°, Z = 2 and V = 1900.31(7) ?³. Index Abstract  The synthesis and the molecular structures of the two isomers of [Os₃(CO)₉(μ-H)(μ ₃-η ²-SN₂C₄H₅)] are described. The isomers differ in the disposition of the hydride ligand.      

Synthesis,Crystal Structure and Biological Activity of N′-tert-butyl-N-(3-methoxylbenzoyl)-N-(4-methyl-1,2,3-thiadiazole-5-formylhydrazine

Abstract  

The title compound, N′-tert-butyl-N-(3-methoxylbenzoyl)-N-(4-methyl-1,2,3-thiadiazole-5-formylhydrazine (C₁₆H₂₀N₄O₃S) was prepared from the reaction of 4-methyl-1,2,3-thiadiazole-5-carbonyl chloride with N′-tert-Butyl-3-methoxylbenzohydrazine, and its structure was characterized by ¹Hydrogen Nuclear Magnetic Resonance, High-Resolution Mass Spectrometry, IR spectra, and single crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic system, space group P 21/c with cell parameters a = 17.986(2) ?, b = 8.0180(10) ?, c = 12.0190(14) ?, α = 90°, β = 91.160(5)°, γ = 90°, V = 1732.9(4) ?³, Z = 4, D _c  = 1.335 g/cm³, μ (Mo Ka) = 0.209 mm⁻¹, F (000) = 736, R = 0.0367 and wR = 0.0932. X-ray diffraction analysis indicates that all rings in the title compound are non-planar. The bioassay results indicated that, the title compound had good fungicide activity against Sclerotinia sclerotiorum, certain extent of insecticidal activity against Plutella xylostella L.     

Crystal structure and resonance Raman spectroscopic study of {1,3-bis[3-(5-amino-1,2,4-triazolyl)]triazenido-N′4,N2,N″4}chloro palladium(II)-methanol (1/1)

The crystal and molecular structure of the complex [Pd(batt)Cl]·CH₃OH, in which Hbatt is 1,3-bis[3-(5-amino-1,2,4-triazolyl)]triazene, has been determined by X-ray diffraction methods. The crystals are triclinic, space group (a = 10.1883(9) Å, b = 10.5095(8)Å, c = 13.1760(11) Å, = 94.518(6)°, = 109.040(7)°, = 113.678(7)°; Z = 4). The deprotonated batt^– ligand exhibits terdentate chelate coordination with a new nitro-type ligation mode of the triazenido group and N⁴ coordination of the two outer triazolyl substituents. The asymmetric unit contains two crystallographically independent, almost parallel Pd(batt)Cl molecules with Pd–Pd contacts of 3.4584(7)Å and two independent methanol molecules. The complexes are packed in a layer structure with numerous intermolecular H-bond connections. Raman spectra have been recorded for various excitation wavelengths along the contour of the intense triazenido -* absorption band at 465 nm and resonance profiles measured for the most important Raman bands. A comparison is made with the analog [Cu(batt)Cl] complex. Structural and spectral differences between the two molecules are emphasized and related to differences in metal-ligand bonding.     

PhPMe2 ligand substitution in the tetracobalt cluster Co4(CO)10(μ4-PPh)2: X-ray diffraction structure of Co4(CO)8(PPhMe2)2(μ4-PPh)2

The thermal substitution chemistry of the tetracobalt cluster Co₄(CO)₁₀(₄-PPh)₂ with the phosphine ligand PhPMe₂ (2.5 equiv) has been explored and found to afford the bis(phosphine)-substituted cluster Co₄(CO)₈(PPhMe₂)₂(₄-PPh)₂ as the major reaction product. The regiochemistry and stereoselectivity exhibited by the two phosphine ligands in Co₄(CO)₈(PPhMe₂)₂(₄-PPh)₂ have been unambiguously established by X-diffraction analysis as having a 1,3-cis orientation. Co₄(CO)₈(PPhMe₂)₂(₄-PPh)₂ crystallizes in the monoclinic space group P2₁/n,a=10.314(1) Å,b=18.051(3) Å,c=21.313(2) Å, =90.10(1)°,V=3968.0(8) ų,Z=4,d _calc=1.590 g cm^–3;R=0.051,R _w=0.042 for 4987 observed reflections withI>3(I). Generalizations concerning the stereochemical disposition of two P-ligands about the Co₄(CO)₈P₂(₄-PPh)₂ (where P=phosphine or phosphite) polyhedron are discussed with respect to the cone angle of the P-ligand and its steric interactions with the capping phenylphosphinidene group.     

Synthesis and Structural Characterization of (2,4-Diamino-5-(3′,4′,5′-Trimethoxybenzyl)Pyrimidine Copper (II)) Complex

Abstract  The reaction of Cu(OOCCH₃)₂·H₂O with (2,4-diamino-5-(3′,4′,5′-trimethoxybenzyl) pyrimidine (trimethoprim) in ethanolic solution at 80 °C affords the title complex which has been characterized by elemental, IR, and NMR (¹H and ¹³C).The crystal structure has been determined by single crystal X-ray diffraction. Compound 1 (C₃₆H₄₈Cu₂N₈O₁₄) is triclinic, space group P-1 with a = 7.2676(4) ?, b = 11.6721(7) ?, c = 12.8279(8) ?, α = 95.839(1)°, β = 93.456(1)°, γ = 105.541(1)°, Z = 1. Two copper atoms are coordinated directly to each other as well as are held together by four bridging aceto groups. Each copper atom is also bonded opposite the Cu–Cu vector to a trimethoprim molecule through the N(1) atom of the pyrimidine ring. Trimethoprim acts as a monodentate ligand through the pyrimidine nitrogen N(1) atom. The complex was screened for the activity against several bacteria, showing more activity against bacteria as compared to trimethoprim. Graphical Abstract  To enhance the activity of trimethoprim, its derivative was prepared and there bacterial activity against several bacteria was analyzed.