Hydrogen-bonded dimer of N,N′-(5-n-butyl-5-oxodibenzo[b,d]phosphole-3,7-diyl)bis(benzamide) dimethylformamide solvate

The structure of a large wing-span phosphine, in the oxide form, N,N-(5-n-butyl-5-oxodibenzo[b,d]phosphole-3,7-diyl)bis(benzamide), C₃₀H₂₇N₂O₃P, cocrystallized with dimethylformamide (DMF), C₃H₇NO, is reported. The title compound is crystallized in a triclinic system with cell dimensions of a = 10.295(8) b = 12.743(5) c = 13.239(6) Å, = 108.14(3), = 108.16(5), = 101.20(4)°, and V=1484.4(5) ų, and forms a hydrogen-bonded dimer via two hydrogen bond linkages of the P—O ··· H—N type involving one of the two amide groups.     

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.     

Conformations of barbiturates related to pentobarbitone. II. Crystal structure oftrans-5-ethyl-5-(1′,3′-dimethylbut-1′-enyl) barbituric acid

Crystals oftrans-5-ethyl-5-(1,3-dimethylbut-1-enyl) barbituric acid (13M1TB), mp 183° C, are triclinic witha = 7.677(2),b = 10.393(3),c = 9.176(3) Å, = 104.331(1), = 106.919(1), = 96.494(1)°, space group P, with two molecules in the unit cell. The structure was solved by direct methods and refined by least-squares procedures toR = 0.050 for 2809 observed diffraction maxima. The 5-ethyl group is oriented under the barbiturate ring with the orientation of the but-1-enyl group directed away from the ring. This orientation is determined by the 1-methyl substituent. The molecules are linked together by N-H ... O=C hydrogen bonds across inversion centers, thus forming single ribbons alongb. Adjacent ribbons are held together in theac plane by van der Waals interactions between alternating ethyl and l,3-dimethylbut-l-enyl groups.     

Crystal and molecular structure of bis-(1-<Emphasis Type="Italic">tert-</Emphasis>butyl-1,2-dibenzoylhydrazine)-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-sulfide

The structure of the title compound bis-(1-tert-butyl-1,2-dibenzoylhydrazine)-N,N- sulfide was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic, space group P2(1)/c with the following crystallographic parameters: a = 14.681(7) Å, b = 14.501(7) Å, c = 16.535(8) Å, = 90°, = 109.173(9)°, = 90°, V = 3325(3) Å ³, z = 4, Dx = 1.244 mg/m³, F(000) = 1320, T = 293(2) K, 1.47° 25.00°, the final R factor: R₁ = 0.0584, wR₂ = 0.1111. The bond distances and angles in the tert-butyl groups are different, that can interpret its ¹H NMR spectra, which are very unusual for the absorption of –CMe₃ being multiple.     

Crystal structure of 2-N,N-diethylamino-1-carbomethoxy-2a,8a-dihydro-2a-methoxycyclobuta [b]naphthalene-3,8-dione,C19H21NO5

Crystals of the title compound, C₁₉H₂₁NO₅, are monoclinic, space groupP2₁/c,a = 7·706,b = 14·470,c = 16·836 Å, = 106·45°,Z = 4. The structure was determined with CuK diffractometer data by symbolic addition procedures and Fourier syntheses, and was refined by full-matrix least-squares methods toR = 0·079 for 2192 observed reflexions. All non-methyl hydrogen atom positions were determined. The non-aromatic six-membered ring has aboat conformation. The four-membered ring, which iscis-fused to the six-membered ring, is slightly folded, and the planar amino and carboxyl groups lie almost in the four-membered ring plane. This geometry, and the detailed bond distances suggest electron delocalization, which may make the compound a useful intermediate in the synthesis of a stable cyclobutadiene system.We thank Dr M. E. Kuehne for suggesting the problem and for crystals, the National Research Council of Canada for financial support, and the University of British Columbia Computing Centre for assistance.     

Synthesis and crystal structure of [WI(CO)(cis-dppen) η2-MeC2Me)2]I·CH2Cl2 {cis-dppen = bis(diphenylphosphino)ethene}

The complex [WI(CO)(cis-dppen)(²-MeC₂Me)₂]I·CH₂Cl₂(1) is prepared as a by-product from the reaction of equimolar quantities of [WI₂(CO)(NCMe)(²-MeC₂Me)₂] and cisdppen {dppen = bis(diphenylphosphino)ethene}. Complex 1, [WI(CO)(cis-dppen)(²-MeC₂Me)₂]I·CH₂Cl₂ crystallizes in the triclinic space group with a = 11.189(13), b = 12.331(14), c = 15.395(17) Å, = 83.61(1), = 86.06(1), = 64.48(1)°, U = 1904 ų, and Z = 2. The metal environment in the cation can best be considered as a distorted octahedron with the two but-2-yne groups taking up individual sites trans to phosphorus atoms of the dppen ligand. The coordination sphere is completed by mutually trans-carbonyl and iodide groups.     

Meisenheimer complex from picric acid and diisopropylcarbodiimide

Reaction of picric acid with diisopropylcarbodiimide produces a pale yellow 1:1 adduct N-(2,4,6-trinitrophenyl)-N,N-di(isopropyl)urea (5) and a 1:2 adduct fluorescent red zwitterionic Meisenheimer complex (6) as approximately N,N,N-tri(isopropyl)-4-oxo-6-(isopropyliminio)-2-s-(2H)triazinespiro-1-2,4,6-trinitro cyclohexadienylide. Crystals of (5) are triclinic, P-1 (#2), with a = 10.444(13) Å, b = 15.47(2) Å, c = 17.74(2) Å, = 110.43(9)°, = 99.85(10)°, = 92.78(10)°, V = 2629(6) ų for Z = 6 (three molecules per asymmetric unit). Crystals of (6) are orthorhombic, Pna2₁ (#33), with a = 24.12(4), b = 9.011(19) Å, c = 10.87(2) Å, V = 2362(8) ų for Z = 4. Nitro groups in the Meisenheimer complex are twisted 2–8° from the mean formerly aryl ring plane; in (5), nitro groups are twisted out of the aryl plane by 11–62°. In the Meisenheimer complex, cationic charge is distributed over an iminium/guanidinium group; anion charge is distributed over the cyclohexadienide ring and attached nitro groups.     

Chemical preparation and crystal structure of 6′-butoxy-2,6-diamino-3,3′azo-dipyridine monohydrate

Chemical preparation, X-ray single crystal, and calorimetric studies of C₁₄H₁₈N₆O·H₂O are described. The compound crystallizes in the triclinic space group, P with unit cell dimensions: a = 6.2640(3), b = 10.9840(4), c = 12.2220(3) Å, = 105.03(2), = 96.96(2), = 101.6(2)°, V = 712.10(5) ų, and Z = 2. The 6-butoxy-2,6-diamino-3,3-azo-dipyridine monohydrate structure is built up from organic layers parallel to the (120) plane linked via O—H···N bond.     

A novel class of naturally occurring halogenated pyrroles, 1,1′-dimethyl-3,3′,4,4′,5,5′-hexabromo-2,2′-bipyrrole, 5,5′-dichloro-1,1′-dimethyl-3,3′,4,4′-tetrabromo-2,2′-bipyrrole, and 1,1′-dimethyl-3,3′,4,4′,5,5′-hexachloro-2,2′-bipyrrole

Crystal structure determinations of the three title hexahalogenated bipyrroles, (I) C₁₀H₆Br₆N₂, (II) C₁₀H₆Br₄Cl₂N₂, and (III) C₁₀H₆Cl₆N₂, reveal essentially planar pyrrole rings having dihedral angles of 64.7, 65.1, and 64.2° between the least-squares planes, favoring in each case a closer methyl–halogen conformation. All three complexes crystallize in the orthorhombic space group Pbcn with the following cell dimensions: (I) a = 12.654(3) Å, b = 8.853(2) Å, c = 13.753(3) Å, = = = 90°, Z = 4; (II) a = 12.438(6) Å, b = 8.753(6) Å, c = 13.696(3) Å, = = = 90°, Z = 4; (III) a = 12.088(6) Å, b = 8.566(4) Å, c = 13.486(8) Å, = = = 90°, Z = 4.     

Crystal structure of 5,5-dimethyl-2-p-bromophenylimino-Δ3-1,3,4-oxadiazoline

Oxidation of acetone-4-p-bromophenylsemicarbazone with lead tetraacetate yields only one isomer of 5,5-dimethyl-2-p-bromophenylimino-³-1,3,4-oxadiazoline, C₁₀H₁₀BrN₃O. Crystals of this compound are triclinic, space groupP¯1,a = 5·91(1),b = 9·52(1),c = 11·59(2) Å, =114·1(1) °, = 93·5(1) ° and = 108·8(1) °;z = 2 and the chemical composition is C₁₀H₁₀BrN₃O. Of 2306 independent reflexions examined, 877 were strong enough to be measured with integrated precession photographs using MoK radiation. The structure was refined using a full-matrix least-squares program to a finalR value of 0·064. The structure consists of planar phenyl and oxadiazoline rings, with a van der Waals interaction between a phenyl hydrogen atom and oxygen atom of the five member ring preventing the two rings from being co-planar; the H(13)-O(1) separation is 2·47 Å. TheZ-configuration of the product suggests a specific mechanism for the ring closure involving an organolead intermediate.     

Bis(2,6-(2′,6′-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II)

Bis(2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II) was prepared by the reaction of 2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenol with nickel chloride. The title complex crystallized in P2₁/c, with cell dimensions a = 9.962(2) Å, b = 12.087(3) Å, c = 24.445(6) Å, and = 97.032(5), giving a volume of 2921.4(13) ų. The bis(2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II) adapts an ideal parallelogram, in which the Ni atom is coordinated with two phenolic oxygen atoms [O(1), O(1A)] and two imino nitrogen atoms [N(1), N(1A)].     

Pentacoordination in dibromo-N-2-methylthiophenyl-2′-pyridylmethyleneiminezinc

The crystal structure of dibromo-N-2-methylthiophenyl-2-pyridylmethyleneiminezinc has been determined and refined by Fourier and least-squares methods toR = 0·058 using three-dimensional X-ray data collected at room-temperature on a single-crystal automated diffractometer. The crystals are triclinic (space groupP¯i), with two molecules in the unit cell of dimensions:a = 9·384(6),b = 11·587(7),c = 7·962(7) Å, = 113·3(1), = 104·3(1), = 92·7(1) °. The zinc atom is five-coordinated through two bromine atoms (Zn-Br=2.366, 2.398 Å), one sulphur atom (Zn-S=2.645 Å) and two nitrogen atoms (Zn-N=2.121, 2.150 Å) from the organic molecule, which behaves as a tridentate ligand. Packing is determined by normal van der Waals interactions.     

Crystal structure of triethylentetraammonium bis monohydrogenmonophosphate dihydrate, [NH3(CH2)2NH2(CH2)2NH2(CH2)2NH3](HPO4)2 · 2H2O

The salt triethylentetraammonium bis monohydrogenmonophosphate dihydrate is monoclinic with the following unit cell dimensions: a = 8.462(1), b = 10.500(1), c = 9.520 Å, = 99.297(1)°, space group P2₁/n with Z = 2. The structure was solved by the Patterson method and refined to final R value of 0.043 for 1590 independent reflections. The structure consists of infinite parallel two-dimensional [ 01] planes built of mutually connected ions and water molecules by strong O—H···O and N—H···O hydrogen bonding.     

Crystal and molecular structure of bis(acetylacetonato) nickel(II)diethanol

The title compound, Ni(C₅H₇O₂)₂· (C₂H₅OH)₂, crystallizes in the triclinic system with unit cell dimensionsa = 8·923,b = 5·283,c = 9·522 Å, = 81·4, = 106·1 and = 103·3 °;Z= 1, space groupP¯1. The structure was solved by Fourier methods, and the 1557 three-dimensional counter diffraction intensity data (CuK) were used in a least-squares refinement to a conventional unweightedR of 0·053. The nickel atom is surrounded by the four oxygen atoms of the two acetylacetone ligands and the two oxygen atoms of the ethanol molecules, forming a tetragonally-distorted octahedron with acetylacetone oxygen atoms at 1·997 and 2·026 Å and ethanol oxygen atoms at 2·140 Å. Parallel molecules are linked into columns along theb-axis by hydrogen bonds between the ethanol oxygen atom of one molecule and an acetylacetone oxygen atom of a neighboring molecule.Presented at the Amer. Cryst. Ass'n. Summer Meeting, Ames, Iowa, Aug. 1971.Taken in part from the M.S. Thesis in Physics of T. S. Burke, Syracuse University, 1971.     

Crystal structure of a (25R)-2α,3α-epoxy-5α-spirostan-6, 23-dione hemi-ethyl acetate solvate

The compound (25R)-2,3-epoxy-5-spirostan-6,23-dione, crystallizes as a hemi-ethyl acetate solvate, having two host molecules of similar conformation per molecule of ethyl acetate, in the asymmetric unit. The O atom of the epoxy group is -oriented. The presence of the epoxy group disturbs the chair conformation in the ring A of the steroidal nucleus. Ring A has a C5,C10 half-chair conformation. The six-membered rings B, C, and F have chair conformation as expected. The D ring adopts a C14-envelope conformation and the E ring is midway between a C22,O3 half-chair and a C22-envelope conformations. The A/B, B/C, and C/D ring junctions are trans. Crystal data: C₂₇H₃₈O₅·1/2C₄H₈O₂, Monoclinic, space group P2₁, a = 7.7363(18) b = 28.769(12) c = 12.038(6) Å, = 90.88(5), V = 2679.0(10) ų, Z = 4. The packing of the molecules is assumed to be dictated by van der Waals interactions and by intermolecular C—H ··· O hydrogen bonds.     

Crystal and molecular structure of 1,N6-ethenoadenosine hydrochloride

The X-ray structure of 1,N ⁶-ethenoadenosine hydrochloride, C₁₂H₁₄N₅O₄Cl, has been determined from three-dimensional diffractometer data and refined by full-matrix least-squares techniques. The crystals are monoclinic:P2₁ No. 14,a=6.1540(5),b=18.511(1),c=6.7412(4) Å,=112.602(5)°,andZ=2; finalR=0.045 for 2662 observed reflections. The crystal and molecular structure of Ado·HC1 is very similar to that of Ado·HC1. On the other hand, the dimensions and conformation of the Ado·H⁺ cation are drastically different from those of Et Ado·H⁺. The adenosine·H⁺ moiety is not planar but has an S shape. The ribose is 2-endo-3-exo puckered, with ag ⁺ side chain; the glycosidic torsion angle is in theanti region. The structure contains a three-dimensional network of H bonds in which also C-HA interactions seem to play an important role. There is no base stacking in the structure.     

X-ray structure of [(μ-H)Os3(CO)10(μ-1,8-η2-C9H6N)]

Decacarbonyl--hydrido--1,8-²-quinoline-triosmium crystallizes in the triclinic space group P with a = 7.8551(6), b = 9.1283(8), c = 16.7915(8) Å, = 74.788(2), = 88.086(2), = 66.392(3)°, V = 1062.22(13)° ų, T = 150 K, and Z = 2. The molecule consists of an Os₃ triangle with the hydride and the heterocyclic ligand bridging the same Os—Os edge. The heterocyclic ligand is coordinated through the C(8) carbon and nitrogen atoms in a new -1,8-²-bonding mode. The Os—Os distances lie in the close range 2.8837(4)–2.9034(4) Å with an average value of 2.892(7) Å.     

Influences of cooperative hydrogen bonding economy on protein-nucleic acid complexation: Structure of unidecahydrated Inosine C5′-monophosphate and L-glutamine (2C10H13N4O8P · C5H10N2O3 · 11H2O) cocrystal at atomic resolution

The crystal structure of a unidecahydrated co-complex between two Inosine 5-monophosphate (IMP) and one L-glutamine has been determined at atomic resolution by X-ray crystallographic methods. The crystal belongs to the monoclinic space group P2₁ with cell dimensions a = 8.690(2), b = 21.900(3), c = 12.370(1) Å, and = 110.59(3)°. This structure reveals the recognition mechanism of glutamine to the nucleotide through direct and water-mediated hydrogen bonds. The phosphate oxygen (O23) seems to prefer the nonspecific interaction with the functional sites of glutamine (NA···O23 = 2.672, OH···O23 = 3.063, OE···O23 = 3.104 Å), whereas the bases prefer specific (N23···O = 2.874 Å) bindings. But here no specific interaction has been observed at N17 and N27, which were observed in serine—IMP complex. However, the solvent mediated N17···OW3···N27 hydrogen bonds for stabilization of the stacked purine bases have been observed as in other aminoacid-nucleotide cocrystals. The striking habit of glutamine to occupy the nearly same region of the nucleotide cocrystal as was found in the serine—IMP complex through substantial replacement of free and bound water molecules, shows certainly the cooperative hydrogen bonding economy of water molecules.     

Synthesis and crystal structure of the two-dimensional coordination polymer catena(bis(μ3-iodo)-(μ 2-pyrazine)-di-copper(I))

The two-dimensional coordination polymer [Cu₂ i ₂(pyz)]_n (where pyz = pyrazine) has been synthesized hydrothermally and structurally characterized by single crystal X-ray diffraction analysis. [Cu₂ i ₂(pyz)]_n crystallizes in the space group P with a = 4.1759(4) Å, b = 7.1281(7) Å, c = 8.1279(8) Å, = 109.607(2), = 101.769(2), = 96.676(2), and Z = 1. The sheet-like polymer is characterized by infinite stair step [Cu₂ i ₂]_n double chains connected in two dimensions through bridging pyrazine ligands. The coordination environment about each copper is approximately tetrahedral having three Cu–I bonds and a single Cu–N bond.     

Hydrogen-bonded networks formed by substituted 2,6-diarylpyrazines

The X-ray crystal structure of 2,6-bis(4-hydroxyphenyl)pyrazine and 2,6-bis(4carboxyphenyl)pyrazine are reported. The structure of the 2,6-bis(4-carboxyphenyl) pyrazine dimethylsulfoxide complex (C₁₈H₁₂N₂O₄)(C₂H₆OS) is triclinic, P-1, with a = 7.9933(8), b = 10.7165(10), c = 12.1337(12) Å, = 66.385(2), = 84.070(2), = 77.219(2). The structure comprises stacked two-dimensional sheets of the hydrogen bonded complex. The two-dimensional sheets comprise hydrogen-bonded ribbons of the (carboxyphenyl)pyrazine that are connected by bridging hydrogen bonds to the dimethylsulfoxide. The structure of 2,6-bis(4-hydroxyphenyl)pyrazine, C₁₆H₁₂N₂O₂, is monoclinic, P2₁/c, with a = 10.6107(13) Å, b = 14.6743(18) Å, c = 8.3772(10) Å and = 104.982(2). The structure reveals that two-dimensional hydrogen-bonded sheets are formed with pyrazine–phenol and phenol–phenol hydrogen bonds.