A new monoclinic crystal phase of [Bu4N][Ni(dmit)2]

The crystal structure of the title compound, tetrabutylammonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickelate(III), [N(C₄H₉)₄][Ni(C₃S₅)₂], is the fourth known phase of this polymorphous compound. It is monoclinic space group P2₁/c, with a = 20.040(2) Å, b = 13.1151(17) Å, c = 12.1093(15) Å, = 105.456(15)°, and V = 3067.5(6) ų with Z = 4, for D _calc = 1.503 g cm^–3. The [Ni(dmit)₂] anion packing arrangement consists of arrays of side-on touching anions and these arrays are connected via head-to-tail close S S contacts.     

Synthesis and structural studies of <Emphasis Type="Italic">tris</Emphasis>-2-chlorobenzylamine and <Emphasis Type="Italic">tris</Emphasis>-2-bromobenzylamine

The tris-2-chloro and 2-bromotribenzylamines are prepared from aqueous ammonia and 2-chlorobenzyl chloride and 2-bromobenzyl bromide, respectively, in ethanol. Recrystallization yielded colorless cubes of each product. The crystal structures are each solved in space group P , and are isostructural. The tris-2-chloro compound, 1, has a = 7.4226(5) Å, b = 9.0825(7) Å, c = 14.529(1) Å, = 78.279(1), = 82.389(1), = 84.661(1), and V = 948.41(12) ų with Z = 2, and d_calc = 1.368 Mg/m³. The tris-2-bromo analog, 2, has a = 7.6569(11) Å, b = 9.0922(13) Å, c = 14.614(2) Å, = 79.286(2), = 81.777(2), = 85.401(2), and V = 987.9(2) ų with Z = 2, and d_calc = 1.762 Mg/m³. Lithium–halogen exchange experiments conducted in tetrahydrofuran at –78C using n-butyl lithium revealed that no exchange occurred for the tris-2-chloro compound, but did occur for the tris-2-bromo analog to yield tribenzylamine upon quench and work-up.     

Structure and properties of potential nonlinear optical materials

The synthesis, structure and properties of four ferrocene derivatives of 2-amino-1,2,3-triazole are reported. Solvatochromism is used as a screening process to assess the potential nonlinear optical behavior of these compounds. In general, this technique involves a number of assumptions, which may not be valid for organometallic complexes. Compound 3 crystallizes in space group P-1 with cell dimensions a = 5.771(2), b = 19.048(5), c = 19.343(5) Å and = 61.104(4), = 88.410(5), = 89.858(5)°; compound 5 crystallizes in space group P2₁/c with cell dimensions a = 12.545(2), b = 13.308(2), c = 20.513(4) Å and = 104.035(3)°; compound 9 crystallizes in space group P2₁/n with cell dimensions a = 12.599(4), b = 14.734(4), c = 13.619(5) Å, and = 107.63(2); compound 11 crystallizes in space group P-1 with cell dimensions a = 7.638(3), b = 9.619(4), c = 12.692(5) Å and = 77.588(7), = 78.416(7), = 71.357(7).     

Cage-annulated thiacrown ethers and thiacryptands

A series of cage-annulated sulfur-containing crown ethers and cryptands have been synthesized as possible specific metal host systems. The synthesis and structures of seven compounds are described, including a thiacryptand complex with Hg(II). The trishomocubane cage is essentially spherical except for a methylene group, which imparts no steric restrictions, and two disordered superimposed orientations occur in most structures. This superposition of four- and five-membered rings usually cannot be resolved into separate entities, resulting in distorted distances, angles, and thermal parameters for the cage. (3) I4₁ cd, a = 13.207(3) Å, b = 13.207(3) Å, c = 35.876(12) Å; (10) C2, a = 14.551(2) Å, b = 10.028(1) Å, c = 10.491(1) Å, = 107.108(2)°; (14) P2₁/n, a = 10.6277(8) Å, b = 9.8488(7) Å, c = 21.822(2) Å, = 97.945(2)°; (19) P2₁/c, a = 15.381(3) Å, b = 6.667(1) Å, c = 18.158(3) Å, = 94.838(4)°; (25) C2/c, a = 34.386(4) Å, b = 11.318(1) Å, c = 13.409(2) Å, = 110.044(2)°; (28) , a = 10.4487(8) Å, b = 11.5677(9) Å, c = 13.354(1) Å, = 71.042(1)°, = 87.344(1)°, = 65.839(1)°; (29) P2₁/c, a = 10.8138(5) Å, b = 16.4949(8) Å, c = 22.054(1) Å, = 96.087(1)°.     

The synthesis and structural characterization of silyl-substituted fluorenes

Three silyl-substituted fluorenes have been prepared by direct synthetic methods and structurally characterized by X-ray diffraction. The three silyl-substituted fluorenes studied were 9-trimethylsilylfluorene (1), 9-(tert-butyldimethyl)silylfluorene (2), and 2,7-di-tert-butyl-9-trimethylsilylfluorene (3). Complex 1 is orthorhombic, P2₁2₁2₁, a = 6.2681(14) Å, b = 14.329(3) Å, c = 15.231(4) Å, Z = 4. Complex 2 is monoclinic, P2₁/c, a = 12.1953(10) Å, b = 6.9977(6) Å, c = 19.6536(17) Å, = 93.818(2), Z = 4. Complex 3 is monoclinic, P2₁/c, a = 11.9954(9) Å, b = 9.8978(7) Å, c = 18.5464(13) Å, = 92.456(2), Z = 4. The long carbon–silicon bonds effectively remove any significant intramolecular interactions as little distortion is exhibited around the sp ³-carbon atom and the fluorenyl backbone demonstrates near planarity. The bulky silicon substituents also prevent intermolecular interactions, as only a few close contacts less than 4.0 Å exist in all three solid state structures.     

Hydrogen-bonded coordination network in crystal structures of [Cu(3-PM)4Cl2] and [Cu(4-PM)4Cl]Cl, (PM = pyridylmethanol)

The crystal and molecular structures of [Cu(3-PM)₄Cl₂] (1) and [Cu(4-PM)₄Cl]Cl (2) have been determinated by X-ray crystallography. Complex 1 crystallizes in the triclinic system, space group P–1, with lattice parameters a = 7.972(2) Å, b = 8.293(2) Å, c = 10.707(2) Å, = 105.73(3)°, = 90.04(3)°, = 110.38(3)°, and Z = 1 at 100 K. The coordination geometry of each Cu atom is approximately octahedral formed by four nitrogen atoms of pyridine rings of 3-pyridylmethanol molecules in the equatorial plane and two chlorine atoms occupying the axial positions. The O—HsO, C—HsCl, and O—HsCl intermolecular hydrogen bonds and s stacking link the molecules in 3-D hydrogen-bonded coordination network. Complex 2 crystallizes in the tetragonal system, space group P4/n, with lattice parameters a = 10.464(1) Å, c = 11.339(2) Å, and Z = 2 at 217 K and a = 10.352(1) Å, c = 11.201(2) Å, and Z = 2 at 293 K. The coordination geometry of Cu atom in the [Cu(4-PM)₄Cl]⁺ ion is approximately square pyramidal formed by four nitrogen atoms of pyridine rings of 4-pyridylmethanol molecules in equatorial plane and one chlorine atom in axial position. The O—HsCl and C—HsCl intermolecular hydrogen bonds link the molecules in 2-D hydrogen-bonded coordination network.     

Synthesis,characterization and crystal structure of oxovanadium(IV) complex with tridentate o-van-gly and bidentate phenanthroline

A novel oxovanadium(IV) complex with tridentate schiff base and bidentate phenanthroline ligands, VO(o-van)(phen) 2H₂O[o-van-gly: o-vanillin-glycine; phen: phenanthroline], was synthesized and characterized by elemental analysis, IR and UV-vis spectra. The crystal structure was determined by X-ray single crystal diffraction analysis. The crystal of title complex (C₂₂H₂₁N₃O₇V, M_w = 490.36) belongs to triclinic, space group P-1 with the following crystallographic parameters: a = 9.247(3) Å, b = 10.125(4) Å, c = 13.100(5) Å, = 106.343(6), = 96.042(7), = 101.726(7), V = 1135.0(7) ų, Z = 2, D_c = 1.435 Mg m^–3, (MoK = 0.485 mm^–1, F(000) = 506, and final R₁ = 0.0779, wR₂ = 0.1598 for observed reflections 1606 (I > 2(I)). V(IV) is six-coordinate with three oxygen atoms and three nitrogen atoms in a distorted octahedral geometry. The complex forms a 3-D network via – stacking and hydrogen bonds.     

Synthesis and structural characterization of five new coordination polymer chain structures using a new,Z-shaped ligand, 2,2′-bis-(4-pyridylethynyl)tolane

Using the new ligand, 2,2-bis-(4-pyridylethynyl)tolane we have synthesized five new coordination polymers: HgBr₂[2,2-bis-(4-pyridylethynyl)tolane] (1), HgI₂[2,2-bis-(4-pyridylethynyl)tolane] (2), Ni(acetylacetonate)₂[2,2-bis-(4-pyridylethynyl)tolane] (3), Zn(acetylacetonate)₂[2,2-bis-(4-pyridylethynyl)tolane] (4), and Cu(hexafluoro acetylacetonate)₂[2,2-bis-(4-pyridylethynyl)tolane]CHCl₃ (5). 2,2-Bis-(4-pyridyl ethynyl)tolane is a rigid ligand with a Z-shape that promotes the formation of zig-zag chains. Compounds 1– 5 were characterized by single crystal X-ray diffraction; and compounds 1– 3 were additionally characterized by IR, elemental analysis, and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic space group C2/c with a = 29.761(3) Å, b = 5.0531(5) Å, c = 16.7823(15) Å, = 104.090(2), V = 2447.9(4) ų, Z = 4. Each mercury is bound to two tolane ligands and two bromine anions, resulting in a tetrahedral coordination environment. Compound 2 crystallizes in the monoclinic space group P2/c, with a = 20.3061(17) Å, b = 5.6303(5) Å, c = 24.5459(19) Å, = 110.338(2), V = 2631.4(4) ų, Z = 4. Here also, each mercury is bound to two tolane ligands and two iodine anions in a tetrahedral coordination environment. The ligand orientation differs in compounds 1 and 2 being trans oriented in 1 and cis oriented in 2. Compound 3 crystallizes in the monoclinic space group P2₁/c with a = 14.5947(14) Å, b = 6.3082(6) Å, c = 18.3939(18) Å, = 112.112(2), V = 1568.9(3) ų, Z = 2. Each nickel is bound to two tolane ligands and two bidentate AcAc anions, resulting in an octahedral coordination environment. Compound 4, which is isostructural with 3, also crystallizes in the monoclinic space group P2₁/c with a = 14.6990(9) Å, b = 6.2724(4) Å, c = 18.6433(11) Å, = 112.8610(10), V = 1583.86(17) ų, Z = 2. Compound 5 crystallizes in the triclinic space group P-1 with a = 6.5487(4) Å, b = 11.6471(7) Å, c = 14.3225(9) Å, = 70.1360(10), = 89.3990(10), = 88.7680(10), V = 1027.18(11) ų, Z = 1. Each copper in 5 is bound to two tolane ligands and two bidentate hfAcAc anions, resulting in an octahedral coordination environment identical to that found in 3 and 4.     

A structural study on gallium and indium β-diketonates

In an attempt to prepare pentacoordinate chlorobis(-diketonato) gallium(III) and indium(III) complexes only the corresponding tris-products, Ga(PhCOCHCOPh)₃ (1), Ga(^tBuCOCHCO^tBu)₃ (1a), and In(PhCOCHCOPh)₃ (2), could be isolated. The crystal and molecular structures of 1 and 2 were determined. Both the complexes were found to have triclinc crystal system, with P1 space group. Cell parameters: 1 – a = 9.913(3) Å, b = 10.534(6) Å, c = 18.05(2) Å, = 93.86(5)°, = 94.40(4)°, = 106.58(4)°, V = 1805(2) ų, z = 2; 2 – a = 10.507(3) Å, b = 11.448(3) Å, c = 16.322(4) Å, = 107.38(2)°, = 97.38(2)°, = 102.23(2)°, V = 1792(1) ų, z = 2.     

Crystal structures of 2,6- and 3,5-dichlorobenzoic acids: nonbonded Cl ⋅ ⋅ ⋅ Cl contacts

The crystal structures of 2,6-dichlorobenzoic acid (1) and 3,5-dichlorobenzoic acid (2) were obtained by single-crystal X-ray diffraction. Crystallization of 1 occurred in the centrosymmetric triclinic space group P1 (No. 2) with a = 7.2678(9), b = 9.8543(8), and c = 11.8290(11) Å = 95.000(7), = 104.262(10), and = 102.128(8); and Z = 4. Crystallization of 2 occurred in the monoclinic centrosymmetric space group P2₁/n (No. 14) with a = 3.7812(3), b = 13.996(2), and c = 14.514(2) Å = 95.183(8); and Z = 4. Chlorine substituents of four dimeric molecules of 2 formed square channels, ca. 3.54 Å on a side, which run parallel to the crystallographic a axis. Monomers of 1 and 2 formed centrosymmetric dimers via near-linear hydrogen bonds. Details of the structures and spectroscopic results are presented and discussed.     

Synthesis and crystal structure of N-<Emphasis Type="Italic">tert-</Emphasis>butyl-N′-thio [O-(1-methylthioethylimino)-N″-methylcarbamic acid]-N,N′-dibenzoylhydrazine

The novel compound N-tert-butyl-N-thio[O-(1-methylthioethylimino)-N-methyl carbamic acid]- N,N-dibenzoylhydrazine has been synthesized by the reaction of N-tert-butyl-N,N-dibenzoylhydrazine with N-sulfenyl chloride of O-(1-methylthio ethylimino) -N-methylcarbamic acid. Its structure was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic, space group P2₍₁₎/n with the following crystallographic parameters: a = 7.569(3) Å, b = 20.585(7) Å, c = 16.347(5) Å, = 90, = 92.606(6), = 90, V = 2544.4(14) ų, z = 4, Dx = 1.276 mg/m³, F(000) = 1032, T = 293(2) K, 2.34 25.01, the final R factor: R₁ = 0.0475, wR₂ = 0.0907. The N–N bond adopts a gauche conformation with a dihedral angle() of 98.8 for C(17)=N(1)=N(2)=C(7), whereas its parent compound N-tert-butyl-N,N-dibenzoyl hydrazine has the dihedral angle of –71.8.     

The coordination of 2-(hydroxymethyl)pyridine to oxorhenium(V). Synthesis and crystal structure of [ReOCl(C<Subscript>5</Subscript>H<Subscript>4</Subscript>N–CH<Subscript>2</Subscript>O)<Subscript>2</Subscript>]

The title compound was prepared from the reaction of (n-Bu₄N)[ReOCl₄] with a twofold molar excess of 2-(hydroxymethyl)pyridine in benzene. It has a distorted octahedral coordination geometry, and it crystallizes in the monoclinic space group P2₁/n, with cell dimensions a = 14.4545(4), b = 7.0168(2), c = 14.5269(4) Å, = 116.995(1), V = 1312.85(7) ų, and Z = 4.     

Synthesis and crystal structure of macrocyclic nickel(II) complex bridged by chromate

A novel compound catena-(-CrO₄-O,O)[Ni(L¹)Ni(L²)] 3H₂O (1) (L¹ = 3,5,10,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane and L² = 2,5,9,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been synthesized for the first time and structurally characterized. 1 crystallizes in the triclinic space group P with a = 9.623(1), b = 10.084(1), c = 12.723 (3) Å, = 66.74(2), = 75.20(1), = 72.02(1)°, V = 1066.2(3) ų, and Z = 2. The coordination environment around the Ni(II) ions is an axially elongated octahedron with the secondary amines of the isomeric ligands and two oxygen atoms of [CrO₄]^2–.     

Molecular structures of two conjugated ene-ynes derived from thiophene

The crystal structures of two conjugated ene-yne derivatives of thiophene are described, 2,5-di-(trimethylsilylethynyl)-3,4-dibromothiophene (1), is triclinic P witha=6.3281(4)Å,b=9.7421(6)Å,c=16.3669(9)Å; =80.516(5)°, =84.810(5)°, =74.072(5)°,Z=2,R=0.054; 2,3,4,5-tetra(trimethylsilylethynyl)thiophene (2), is monoclinic, P2₁/c with a=20.928(2)Å b=5.852(1)Å,c=23.907(2)Å; =100.245(6)°,Z=4,R=0.049. The ethynylic C atoms of both compounds lie near the thiophene plane, with deviations in the range 0.010(3)–0.455(4)Å. The phenyl groups of2 form a dihedral angle of 13.0(4)°.     

Syntheses and structural characterization of two novel α-diketone bisacylhydrazones

Benzil bis(3,4,5-trimethoxybenzohydrazone) (I) and 3,3-dimethoxybenzil bis(benzohydrazone) (II) were synthesized by condensation, acid catalyzed, of the proper -diketone and the corresponding hydrazide. Compound I crystallizes in the monoclinic system, space group P2₁/n, with a = 11.464(2), b = 21.098(4), c = 13.837(2) Å, = 109.50(1)° V = 3154.8(9) ų and D _c = 1.319 g/cm³ for Z = 4. Compound II crystallizes in the triclinic system, space group P , with a = 11.106(3), b = 11.728(10), c = 10.656(5) Å, = 91.86(2), = 92.68(3), = 110.00(2)° V = 1301.1(7) ų and D _c = 1.293 g/cm³ for Z = 2.     

Crystal structure of μ-adeninatobis (methylmercury (II)) perchlorate monohydrate

The title compound belongs to the triclinic space groupP¯1,a= 8.189 Å,b = 9.863 Å,c = 10.726 Å, = 69.93 °, = 68.62 °, = 73.66 °, andZ = 2. The structure was refined on 1337 observed reflections to anR factor of 0.042. The crystals contain [adeninato(CH₃Hg)₂]⁺ complex cations in which mercury is linearly bonded to N(7) and N(9) of a deprotonated adenine ring. Centrosymmetrically related complex cations are paired via two N(6)-H(6) N(l) hydrogen bonds. Those planar units are stacked in the crystal with a distance of 3.4 Å between rings. The water molecule and the ClO₄ ^-ion are involved in hydrogen bonding and HgO contacts. This structure identifies N(7) as the best residual coordination site after H(9) has been substituted by CH₃Hg.     

Syntheses and structures of N-phenylmaleimidetriazoles and by-products

The syntheses, properties, and structures of N-phenylmaleimidetriazole derivatives are described. Intermediates and by-products are also discussed. 1b. a = 43.997(7) Å, 5.7610(9) Å, 8.245(1) Å, = 99.339(4), C₂/c; 2a. a = 13.646(4) Å, b = 7.744(2) Å, c = 10.612(3) Å, = 91.979(6), P2₁/c. 3a. a = 22.245(1) Å, b = 22.245(1) Å, 10.010(1) Å, P42/n. 3a. a = 11.727(2) Å, b = 14.075(3) Å, c = 16.080(3) Å, = 105.859(3), = 105.331(3), = 98.187(3), P-1. 3b. a = 8.561(3) Å, b = 14.755(5) Å, c = 22.771(7) Å, = 97.006(5), P2₁/c. 3c. a = 10.500(2) Å, b = 12.189(2) Å, c = 13.040(2) Å, = 109.091(3), = 106.089(3), = 101.022(3), P-1. 8a. a = 16.389(8) Å, b = 5.749(3) Å, c = 19.316(3) Å, = 97.467(9), P2₁/n. 8b. a = 5.822(2) Å, b = 10.114(3) Å, c = 16.705(4) Å, = 84.681(5), = 82.840(5), = 75.769(4), P-1. 9b. a = 11.251(1) Å, 13.335(3) Å, 13.376(3) Å, = 102.456(4), P2₁/n. 9c. a = 15.836(3) Å, b = 8.236(2) Å, c = 5.447(3) Å, = 92.551(3), P2₁/c. 10a. a = 13.177(2) Å, b = 14.597(2) Å, c = 5.5505(8) Å, = 110.979(2), Cc. 11a. a = 14.720(2) Å, b = 13.995(2) Å, c = 38.245(6) Å, = 94.430(3), P2₁/n. 12b. a = 15.067(5) Å, b = 20.378(6) Å, c = 8.669(5) Å, = 99.16(4), = 99.32(3), = 105.23(3), P-1. 13b. a = 8.2824(6) Å, b = 10.5245(7) Å, c = 15.518(1) Å, = 92.305(1), = 100.473(1), = 100.124(1), P-1. 15a. a = 15.357(3) Å, b = 7.778(2) Å, c = 22.957(2) Å, Pbca. 16b. a = 18.0384(4) Å, b = 12.474(3) Å, c = 20.078(5) Å, Pbca.     

Structure of bis(2-amino-5-methylpyridinium) tetrachlorozincate at 298 and 150 K

Reaction of 2-amino-5-methylpyridine with zinc chloride and HCl in aqueous solution yields bis(2-amino-5-methylpyridinium) tetrachlorozincate. The complex crystallizes in the monoclinic space group P2₁/c, with minimal tetrahedral distortion of the ZnCl₄ ^2– ion at both 298 and 150 K; at 298 K, a = 8.090(2) Å, b = 14.795(6) Å, c = 15.850(4) Å, = 101.93 (2); at 150 K, a = 8.0986(2) Å, b = 14.7190(5) Å, c = 15.7684(7) Å, = 102.862(2). The anisotropic cell contraction results in significant changes in nonbonding Cl Cl contacts.     

A comparison of the coordination preferences of Zn, Co, and Cd(II) with the heteroscorpionate ligand (2-hydroxy-3-t-butyl-methylphenyl)bis (3,5-dimethylpyrazolyl)methane

Reaction of the Zn, Cd, or Co nitrate salts with the deprotonated ligand (2-hydroxy-3-t-butyl-methylphenyl)bis(3,5-dimethylpyrazolyl)methane (L1O^–) in methanol produced the following complexes: [(L1OH)Zn(NO₃)₂] in two isomorphs, a = 40.983(8) Å, b = 9.571(2) Å, c = 15.667(8) Å, = 90, = 106.38(1), = 90, C2/c, and a = 13.027(3) Å, b = 14.781(4) Å, c = 16.107(3) Å, = 90, = 105.30(1), = 90, P2₁/n; [(L1OH)Cd(pz)(NO₃)₂] a = 14.7476(2) Å, b = 13.5411(2) Å, c = 16.7223(2) Å, = 90, = 110.3840(10), = 90, P2₁/c; and [(L1O)Co(pz)(NO₃)] a = 11.4240(2) Å, b = 13.4498(2) Å, c = 13.8056(2) Å, = 105.2080(10), = 105.8130(10), = 112.7470(10), P . The Zn adopts a pseudotetrahedral four-coordinate geometry where the potentially tridentate ligand is actually bidentate with a protonated and uncoordinated phenoxy arm. The Co complex is pseudooctahedral six-coordinate where the phenoxy arm is deprotonated and coordinated. Finally the Cd complex is seven-coordinate but the metal is not coordinated through the phenoxy group that is again protonated.     

Crystal structure of 1,5,8-trihydroxyl-3-methoxy xanthone from Swertia chirayita

In order to study the relationship between biological and pharmacological activities with their structures, a series of tri-, tetra-oxygenated xanthones including 1-hydroxyl-2,3,4,7-tetramethoxy xanthone 1, 1-hydroxyl-2,3,4,5-tetramethoxyl xanthone 2, 1-hydroxyl-3,5-dimethoxy xanthone 3, 1,8-dihydroxyl-3,5-dimethoxyl xanthone 4, 1,5,8-trihydroxyl-3-methoxy xanthone 5 has been isolated from Swertia chirayita. Their structures were established on the basis of spectral and chemical evidence. The crystal structure of 5 was also investigated by single crystal X-ray diffraction analysis. It crystallizes in the triclinic system, space group P , with a = 7.1540(10) Å, b = 7.520(2) Å, c = 10.671(2) Å, V = 562.7(2) ų, = 86.50(3), = 80.06(3), = 85.00(3), Z = 2, D_c = 1.618 g m^–3, R_int = 0.0230, wR(F²) = 0.1028, F(000) = 284. The molecular structure is nearly plane and four substituents are much closer to the plane of the molecule. Compound 5 also shows three intermolecular hydrogen bonds. A recent study shows that phenolic hydroxyls in xanthones are the main active groups capable of scavenging OH and O₂.