Crystal and molecular structure of an ion-pair complex based on [Ni(mnt)<Subscript>2</Subscript>]<Superscript>2−</Superscript> anion and imidazolium derivative cations

A new ion-pair complex, 1-methyl-3-benzylimidazolium bis(maleonitrile-dithiolato) nickelate(II), has been synthesized and characterized by IR spectroscopy, UV-visible spectroscopy and X-ray crystallography. The crystallographic data for the complex: triclinic , a = 8.415(1) Å, b = 9.924(1) Å, c = 11.333(2) Å, = 114.11(1), = 102.46(1), = 100.88(1), V = 801.8(2) ų, Z = 1. The molecular packing pattern showed a completely separated column stacking for cations and anions of the complex along with the b-axis. The anion is not completely planar. The five-membered nickel-containing rings are slightly puckered. The cation, [BzIm]⁺, adopts a conformation where the benzene ring and imidazole ring twisted with the reference plane C10–C11–N3.     

The crystal structure of 2-nitroresorcinol

2-Nitroresorcinol is triclinic, space group P; at –100°Ca=7.083(2),b=7.696(2),c=6.607(2) Å, =74.61(2), =77.81(2), =68.64(2)°,V=320.8(2) ų,D _x=1.606(1) g cm^–3,Z=2. The two hydroxyl groups form symmetric intramolecular hydrogen bonds to the nitro group. The molecules pack in stacks held together by - interaction with adjacent molecules in a head-to-tail arrangement.     

Crystal and molecular structure of 1R,3S,5S,7R,10R-3,6,6,10,14-Pentamethyltricyclo[10.3.0.05,7]pentadeca-11,14-diene-1, 10-dihydroxy-2,13-dione (Japodagrol), C20H28O4

A new cytotoxic macrocyclic diterpenoid named Japodagrol, C₂₀H₂₈O₄, has been isolated from the ornamental plantJatropha podagrica, family Euphorbiaceae, grown in Nigeria. The structure of the title compound, C₂₀H₂₈O₄, was solved by X-ray analysis.M _r =332.44, monoclinic space groupC2,a=23.285(4),b=6.5105(12),c=12.505(3) Å,=98.504(17),V=1874.8 ų,Z=4,D _c =1.178 Mg/m³. CuK radiation (graphite crystal monochromator, =1.54184 A), (CuK)=6.13 cm^–1,F(000)=720,T=290 K. Final conventionalR factor=0.035,R _w =0.038 for 3349 observed reflections. The structure was solved with the programDirdif. The 5-membered ring is closed to a half-chair form. The compound contains inter- and intramolecular hydrogen bonds.     

Crystal and molecular structure ofN-methylphenazinium bis(benzene-1,2-dithiolato)nickelate(III). Structure of (C13H11N2)[Ni(S2C6H4)2]

The crystal and molecular structure of the title compound, (C₁₃H₁₁N₂)[Ni(S₂C₆H₄)₂], is reported. Crystals are triclinic, space groupP¯1(No.2) withZ=2 in a unit cell of dimensionsa=9.363(1),b=10.148(1),c=13.623(1) Å,=85.64(1),=107.33(1), and =113.10(1)°. The structure was solved by the heavy-atom method and refined by the method of full-matrix least squares toR=0.036 for 2874 unique reflections. The metal atom of the anion has an approximate square-planar configuration. The metal atoms occupy the origins and A-face centers of the lattice. The anions with the metal atoms in the origins stack along thec-axis, the interplanar separation being thec-axis lattice repeat of 13.623(1) Å. The anions with the metal atoms in theA-face centers and the cations form a mixed stack along the short diagonal of theab-plane. The short interplanar distances (C–A=A–C=3.43 Å and C-C=3.91 Å) in the mixed stack (CAC-CAC) show the possibility of unusual electrical behavior. There is no evidence of direct or indirect metal-metal interaction.This work was supported by the Department of Science and Technology, Government of India, New Delhi, for which we are grateful. One of the authors (PK) also expresses his thanks to the U.G.C., New Delhi and Pachaiyappas College, Madras, for the award of FIP Fellowship.     

Structure of a platinum(II) complex containing a benzothiazole derivative: [NEt4][Pt(3,4-dsb)Br3]

Tetraethylammoniumtribromo[2-(3.4-dimethoxy)styrylbenzothiazole]platinate(II), [(C₂H₅)₄N]-[PtBr₃(C₁₇H₁₅NO₂S)], monoclinic,P2₁/c,a=13.454(7),b=11.991(3),c=19.004(5) Å, = 108.92(3)°,V=2900(4) ų,Z=4,D _r=1.975 g cm^–3, (MoK)=0.71073 Å, =95.59 cm^–1,F(000)=1656,T=303 K, finalR=0.051 for 2262 unique observed reflections. The structure was solved by heavy atom and Fourier methods. The molecule is nearly planar, with a dihedral angle of only 3.57(7)° between the benzothiazole and phenyl rings. The C–S–C angle in the thiazole ring is 91(1)°.     

Crystal structures of 1-(2-hydroxyphenyl)-3-phenyl-1,3-propanedione and 1-(1,3-benzodioxol-5-yl)-3-(2,4-dimethoxyphenyl)-1,3-propanedione

1-(2-Hydroxyphenyl)-3-phenyl-1,3-propanedione crystallizes in the triclinic space group (a=5.4233(5),b=13.910(1),c=17.036(1) Å, =68.311(6), =80.854(7), =78.760(8)°) as two independent enolic tautomers in which the hydroxyl and phenolic protons are hydrogen bonded to the ketonic oxygen atom. The structure was refined toR=0.039 for 2085I3(I) reflections. 1-(1,3-Benzodioxol-5-yl)-3-(2,4-dimethoxyphenyl)-1,3-propanedione, which belongs to the triclinic space group (a=7.3990(7),b=8.1239(5),c=14.004(1) Å, =86.673(6). =88.574(7), =64.885(7)°) also exists in the enolic form. The structure was refined toR=0.040 for 1564I3(I) reflections.     

Complexation with diol host compounds. Part 3. Molecular inclusion of 4-methylcyclohexanone and 2-methylcyclohexanone by the host,trans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene

The structures of the 12 molecular complexes oftrans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with 4-methylcyclohexanone (1) and with 2-methylcyclohexanone (2) have been determined by X-ray crystallography. The crystal data are as follows: Compound (1):P2₂/c,a=8.838(2) Å,b=8.92(1) Å,c=20.879(8)=Å,=98.67(2)°,V=1627(2) ų,Z=2 andR=0.062 for 2201 unique MoK reflections; Compound (2):P¯1,a=8.917(3) Å,b=9.900(2) Å,c=11.250(4) Å,a=68.72(2)°,=64.39(3)°, =74.86(2)°,V=828.1(5) ų,Z=1 andR=0.098 for 2563 unique reflections. Both inclusion compounds exhibit O-HO=C hydrogen bonding interactions. The thermal properties of these compounds have been characterized by DTA and TGA thermograms.     

Schiff bases and their complexes with metal ions. Part II. Structures of N-n-butyl-2-hydroxy-1-naphthaldimine and bis[N-n-pentyl-2-hydroxy-1-naphthaldiminato]nickel(II)

The Schiff base ligand (1), [C₁₅H₁₇NO] crystallizes in the monoclinic space group P2₁/c witha=10.054(3),b=10.313(3), c=13.173(4)Å, =107.42(4)°,V=1303.2(7)ų,Z=4,Dx=1.159 g cm^–3, and (MoK)=0.674 cm^–1. The C2-O[1.23(1)Å] and C3–C4 [1.33(2)Å] bond lengths are short, due to its quinoidal structure. In the Schiff base nickel complex (2), [Ni(C₁₆H₁₈NO)₂] the asymmetric unit is comprised of two half-complexes. It crystallizes in the triclinic space group witha=5.124(3),b=16.227(3),c=16.886(4)Å, =95.47(8), =96.00(1), =90.71(4)°,V=1389.6(9) ų,Z=2,Dx=1.289 g cm^–3, and (MoK) =12.1 cm^–1. The coordination of the Ni(II) ions are square planar with bond angles between 87.9(1) and 92.1(1)°. The Ni–O and Ni–N distances are 1.819(2), 1.922(2) and 1.823(2), 1.914(3)Å in these two complexes.     

Synthesis and structure of (η5-C5H5)2Hf(η1-NC4H4)2

The crystal structure of (⁵-C₅H₅)₂Hf(¹-NC₄H₄)₂ has been determined from X-ray data measured by counter methods. The title compound is isostructural with (⁵-C₅H₅)₂Zr(¹-NC₄H₄)₂, and crystallizes in the monoclinic space groupP2₁/c (C _2h ⁵ , No. 14) with unit cell constantsa=9.605(3),b=8.174(3),c=19.487(4) Å, =90.85(3)°, andZ=4 forD _c=1.91 gcm^–3. Full-matrix least-squares refinement gave a finalR value of 0.068 for 2154 independent observed reflections. The two cyclopentadienyl rings are ⁵-coordinated to the hafnium atom at an average Hf-C(⁵–) distance of 2.51(1) Å. The Hf-N-centroid (-pyrrolyl) angles average 166°.     

Crystal structure of 4,6-dinitro-1-(5-tetrazolyl)-1H-indazole trihydrate

The title compound, C₈H₄N₈O₄·3H₂O, crystallizes in space groupP¯1 with cell constantsa=7.022(1),b=9.507(2),c=10.906(2) Å,=84.99(1),=71.89(1),=72.56(1)°,Z=2, andV _c =660.2 ų. The structure was solved by direct methods using diffractometer data and was refined by full-matrix least-squares methods to anR value of 0.060 for 2112 observed reflections. The molecule, consisting of a phenyl ring fused to a pyrazole ring with a tetrazole ring connected to it equatorially, is planar except for the N(7) nitro-group oxygen atoms. The structure is stabilized by a three-dimensional network of O-HO, O-HN, and N-HO hydrogen bonds through the water molecules.     

Structural investigation on hexasubstituted benzene derivatives. Part 1. The structure of ortho-dinitrotetramethylbenzene

C₁₀H₁₂N₂O₄ (M _r =224.2) crystallizes in the triclinic system, space groupP¯1 witha=8.327(3),b=8.734(3),c=8.453(3) Å;a=63.6(1),=97.0(1), =100.4(1)°;V=541.0(6) ų,Z=2,D _c =1.38 g cm^–3,(Cu-K)=8.7 cm^–1, =1.5418 Å, F(000)=236. Deviation from theoretic geometry of the benzene ring and from planarity is observed in accordance with the-electron-withdrawing character of the NO₂ groups and the high steric hindrance of the substituents.     

Crystal and molecular structure of 1,6-dimethyl-3,6-dimethoxy-3-[(N-methylindol-3-yl)methyl] piperazine-2,5-dione,C18H23N3O4

The structure of the title compound, C₁₈H₂₃N₃O₄, was determined by X-rays.M _r =344.40, triclinic, space groupP¯1,a=8.163(4),b=9.230(2),c=13.297(2) Å,=102.70(2),=103.58(3)°,=102.50(3)°,V=911.3 ų,Z=2,D _c =1.26 Mg m^–3. CuK radiation (graphite crystal monochromator,=1.54178 Å),(CuK)=7.50 cm^–1,T=290 K. Final conventionalR-factor=0.068,R _w =0.079 for 1912 unique reflections and 295 variables. The structure was solved usingMultan andDirdif. The title compound is the first example of a 3,6-tetrasubstituted dioxopiperazine adopting a folded conformation, owing to a direct interaction between the dioxopiperazine ring and the aromatic side chain.     

Crystal structure of tylophorine methiodide monohydrate,C25H30NO 4 + I−·H2O

The crystal structure of tylophorine (Chemical name 2,3,6,7 tetramethoxy phenanthro [9,10:6, 7] indolizidine. Contribution No. 0871.) methiodide monohydrate has been determined. C₂₅H₃₀NO ₄ ⁺ I^–·H₂0, triclinic, P,a=8.831(1)Å, b=10.842(2),c=13.902(2), =105.0(1)^o, =104.7(1), =97.3(1),V=1210.22ų, Z=2,D _x =1.428 g./cm^–3, (CuK)=1.54184Å, (CUK)=107.2 cm^–1, F(000)=544,T=295^oK,R=0.038,Rw=0.046, for 2331 observed reflections withI2(I). Apart from van der Waals forces, the structure is stabilized by two hydrogen bonds of the type Ow(H) ... O and Ow(H) ... I^– involving the water molecule as the donor and atom O4 of the methoxy group and I^– as acceptors.     

Synthesis and X-ray structural analysis of (2<Emphasis Type="Italic">Z</Emphasis>)-3(4-hydroxyphenyl)-2-pyridin-4-ylacrylonitrile and (2<Emphasis Type="Italic">Z</Emphasis>)-3-(3,5-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-4-hydroxyphenyl)2-pyridin-4-ylacrylonitrile

Synthesis and X-ray structural investigations have been carried out for the two title compounds C₁₄H₁₀N₂O (3a) and C₂₂H₂₆N₂O (3b). Compound 3a crystallizes in the monoclinic space group P2₁/c, with a = 3.843(1) Å, b = 24.618(5) Å, c = 11.318(2) Å, = 92.61(3), V = 1069.7(4) Å,³ and Z = 4. Compound 3b crystallizes in the triclinic space group P-1, with a = 9.004(2) Å, b = 9.447(2) Å, c = 11.713(2) Å, = 76.70(3), = 83.12(3), = 82.16(3), V = 956.5(3) Å,³ and Z = 2. Both stilbazole derivatives have Z-geometry about the ethylene bridge which links the heterocyclic and aromatic rings. The molecular skeleton of 3a is slightly non-planar: the dihedral angles between the acrylonitrile linkage and the pyridine ring, and between this linkage and the p-hydroxyphenyl ring are 7.2(2) and 4.1(2), respectively. The molecular skeleton of 3b is less planar: the values of similar dihedral angles are 17.0(2) and 20.8(2), respectively. In the crystal of 3a, the molecules are packed in stacks along the a axis with head-to-head orientation. Intermolecular hydrogen bonds O=H s N and C=H s N link molecules into sheets parallel to (100) plane. In the crystals of 3b, the molecules have a head-to-tail orientation and intermolecular hydrogen bonds O=H s N link the molecules into infinite chains along [01-1] direction.     

A novel vanadyl selenite templated by organic salt: [(VO)(H2O)2(SeO3)]2[(H2pipe)SO4]

The title compound [(VO)(H₂O)₂(SeO₃)]₂[(H₂pipe)SO₄] was synthesized under hydrothermal condition with VOSO₄, piperazidine (pipe), and SeO₂, and its crystal structure was established using single-crystal X-ray diffraction method. The title compound was characterized with IRFluorescence. The crystal data: P-1 (No. 2), a = 8.633(2) Å, b= 9.223(2) Å, c= 12.508(3) Å, =109.28(3)°, =90.42(3)°, = 107.79(3)°, Mr = 644.08, V=888.5(3) ų, Z=2, Dc = 2.407 g cm^–3, =5.350 mm^–1, F(000)=632. The structure of the title compound consists of an infinite neutral ladder chain, which is built up from VO₆ octahedral and SeO₃ pyramidal units sharing vertices, and organic salt. The biprotonized pipe (piperazidine) and SO₄ ^2– interact with one another and the inorganic chain through strong hydrogen bonds N–H···O or O–H···O to give a 3D structure. Hydrogen bonds play a role of stabilization structure.     

Structure, thermal behavior, and IR investigations of (C6H9N2)H2PO4

Chemical preparation, X-ray single-crystal, thermal behavior, and IR spectroscopy studies of a new dihydrogenmonophosphate associated to an organic cation, the 3-(ammoniummethyl)pyridine dihydrogenmonophosphate (denoted as AMPP) are described. The AMPP crystallizes in the monoclinic system with P2₁/c space group. The unit cell dimensions are a = 5.8465(2) Å, b = 19.9776(9) Å, c = 7.3103(3) Å, = 90.848(3)° with V = 853.74(4) ų and Z = 4. The structure has been solved using direct method and refined to a reliability R factor of 0.0393. The structure of AMPP includes three types of hydrogen bonds. The first one, O H O, links the H₂PO₄ groups to form infinite inorganic chains [H₂PO₄]n ^n–, parallel to the c axis. The two other types, O H N and N H O assemble inorganic chains so as to build up a three-dimensional arrangement.     

The molecular structure of dibutylbis(2-pyridinethiolato-5-ethyl ester)tin(IV), [SnBu2(TNEE)2]

The crystal structure of [SnBu₂(TNEE)₂], (HTNEE=5-ethyl ester of 2-mercaptopyridine-5-carboxylic acid) has been determined by X-ray single crystal diffraction study. The crystal is triclinic, space groupP,a=10.042(1),b=18.421(2),c=7.979(1) Å, =98.7(1), =107.3(1), =87.7(1)^o,V=1393(1) ų, and Z=2 The tin center is coordinated to two butyl groups and to the nitrogen and the sulfur atoms of two ligand molecules in a very distorted trapezoidal bipyramid.     

Crystal structures of 4-amino-1,2,4-triazolidine-3,5-dione (urazine) (C2H4N4O2) and dichlorobis (4-amino-1,2,4-triazolidine-3,5-dione-N,O) copper (II) (C4H8Cl2CuN8O4)

Crystal structure analyses of urazine and of its adduct with CuCl₂ show that this ligand can exchange interactions of stacking that cannot be defined as simple - interactions. The copper atoms are octahedrally coordinated by two oxygen atoms and two aminic nitrogen from chelating uraxines and two chlorine atoms. The crystals of urazine are monoclinicP2₁ c:a=6.741(1),b=5.815(1),c=11.141(2) Å,/gb=92.13(1)°,V _c=436.4(1) ų,Z=4,R=0.0402 for 714 independent observed reflections; the crystals of [CuCl₂(urazine)₂] are triclinicP¯1:a=5.236(1),b=6.662(1),c=8.411(1) Å,=93.00(1),=104.87(1), =105.69(1)°,V _c=270.66(8) ų,Z=1,R=0.0380 for 875 independent observed reflections.     

Structure oftrans-difluorobis(1,3-propanediamine)chromium(III) perchlorate,trans-[Cr(N2C3H10)2F2](C104)

The title compound is monoclinic,M _r =337.8,P2₁/c-C _2h ⁵ (No. 14),a=5.508(2),b=13.944(6),c=18.238(5) Å,=95.99(3)°,V=1393.1(9) ų,Z=4,D _x =1.61 g cm^–3, (MoK)=0.71073 Å,F(000)=660.0,=10.3 cm^–1, finalR=0.051 for 2122 observed [I>3(I)] reflections. The two six-membered rings resulting from the coordination of the 1,3-propanediamine ligands to the chromium atom are in the chair conformation. The Cr-N and Cr-F distances average 2.085(4) and 1.876(3) Å, respectively.     

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

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