First example of cocrystals of polymorphic maleic hydrazide

The first cocrystals of polymorphic maleic hydrazide with 3-methyluracil have been studied by X-ray diffraction methods. They crystallize in the orthorhombic system, space group Pmcn, a = 6.440 (1) Å, b = 6.974 (1) Å, c = 22.829 (11) Å, V = 1025.3 (5) ų, Z = 4. The asymmetric unit contains one molecule of each compound. Planar ribbons of the (1:1) molecular complex are obtained through the formation of O–H···O and O–H···N intermolecular hydrogen bonds, just forming a well-known R² ₂(8) supramolecular synthon. Supramolecular assemblies are then formed by weak C–H···O and C–H···N hydrogen bonds through adjacent antiparallel ribbons.     

Crystal and molecular structures of three trimethylamine-boron halide adducts: (CH3)3NBCl3, (CH3)3NBBr3, and (CH3)3NBI3

X-ray diffraction data from single crystals of the trimethylamine complexes of the three boron halides, BCl₃, BBr₃, and BI₃, lead to aP2₁/m monoclinic cell containing two molecules for each complex. The unit cell dimensions area = 6·68(1),b = 10·247(3),c = 6·502(6) Å, =116·2(1)° (chloro);a = 6·86(1),b = 10·612(4),c = 6·737(6) Å, = 115·8(1)° (bromo);a = 6·92(2),b = 10·86(1),c = 7·147(6) Å, = 93·9(1)° (iodo). The structures were solved by three-dimensional sharpened Patterson functions and show only the chloro and bromo compounds to be isomorphous. Refinement of 662,718 and 954 observed reflexions for the chloro, bromo and iodo complexes, respectively, using anisotropic thermal parameters yielded conventionalR factors of 0·045, 0·087 and 0·054.The molecules are shown to possess a B—N dative bond, a staggered conformation, and effective 3m (C _3v) symmetry. Average C—N bond lengths are 1·52(1) Å for all three complexes. Boronhalogen bond lengths average 1·864(4), 2·04(2) and 2·28(2) Å, while B—N bond distances are 1·609(6), 1·60(2) and 1·58(3) Å, respectively, for the chloro through iodo compounds. Bond angles are approximately tetrahedral with the C—N—C angle decreasing by several degrees in the Cl Br I series.Based in part on a dissertation submitted by Patty H. Clippard to the Rackham School of Graduate Studies of the University of Michigan, January 1969 in partial fulfillment of the requirements of the Ph.D. Degree.     

Synthesis and structure of (±)-4-O-methanesulfonyl-myo-inositol 1,3,5-orthoformate

Racemic 4-O-methanesulfonyl-myo-inositol 1,3,5-orthoformate was prepared by methanolysis of racemic 2,4-di-O-benzoyl-4-O-methanesulfonyl-myo-inositol 1,3,5-orthoformate, in the presence of triethylamine. The diol crystallizes in space group P2₁2₁2₁ with cell dimensions a = 6.094(1), b = 6.502(2), c = 25.947(3) Å, V = 1028.1(4) Å, Z = 4. The molecular crystals show both intra- and intermolecular O—H···O short contacts. The methine and the methyl hydrogens are involved in several C—H···O interactions.     

Anticooperative C—C—H···O···H—O hydrogen bonding in 5β-Hydroxy-5α-ethynyl-10β-methyl-Δ1(9)-octalin-2-one

In the x-ray crystal structure of the alkynol 5-hydroxy-5-ethynyl-10-methyl-¹⁽⁹⁾-octalin-2-one [C₁₃H₁₆O₂, Pbca, a = 10.244(7), b = 12.734(2), c = 17.125(2) Å, Z = 8], the hydroxyl and ethynyl groups are involved in a hydrogen bond arrangement C—C—H···O···H—O, which is supposed to be anticooperative, i.e., weaker than the sum of two isolated hydrogen bonds.     

Helical chirality of 1-phenacyl-1,10-phenanthrolinium bromides

Evidence for non-coplanarity of the pyridine and pyridinium rings in a series of 1-phenacyl-1,10-phenanthrolinium bromides was gleaned from ¹H-NMR data recorded in DMSO-d ₆ solution. The X-ray structure of 1-(4-chlorophenacyl)-1,10-phenanthrolinium bromide, as representative of this series, was determined in order to establish whether such a molecular distortion occurs in the solid state. The title compound crystallizes in the space group C2/c as a sesquihydrate of formula C₂₀H₁₄BrClN₂O·1.5H₂O with a = 35.7348(3) Å, b = 5.3468(1) Å, c = 21.7312(2) Å, = 116.4076(4)° and Z = 8. In the crystal, the helical chirality is manifested as a pronounced twist in the phenanthrolinium moiety, with the pyridine and pyridinium rings inclined at 6.8(2)°. This distortion is attributed to intramolecular hydrogen bonding of type C–H···N involving the methylene group and the uncharged nitrogen atom of the phenanthrolinium moiety. In the crystal, the cations surround an intricate array of water molecules and bromide ions held together by O–H···Br^– hydrogen bonds and comprising infinite chains ···Br^–···H–O–H···Br^–···, cross-linked by water molecules.     

Conformation and structure of 1,3-bis(2-hydroxy-5-bromosalicylideneamine)propan-2-ol

The Schiff base, 1,3-bis(2-hydroxy-5-bromosalicylideneamine)propan-2-ol, has been studied by AM1 semiempirical quantum mechanical method and X-ray analysis. It crystallizes in the orthorhombic space group Pca2₁ with a = 8.458(3), b = 6.139(2), c = 32.957(4) Å, D_calc = 1.770 g cm^-3, V = 1711(1) ų, Z = 4 and (MoK) = 0.476. The structure was solved by direct methods and refined to R = 0.041 for 1715 independent reflections [I > 2 (I)]. The title compound is not planar. Intramolecular hydrogen bonds are found between the hydroxyl and the amine nitrogen with O—H···N distances of 2.601(6) and 2.629(4) Å. There is also an intermolecular O—H···N hydrogen bond [3.176(6) Å] linking the neighbouring molecules. Minimum energy conformations from AM1 were calculated as a function of eight torsion angles varied every 5°. The optimized geometry of the crystal structure corresponding to the nonplanar conformation is the most stable conformation in all calculations. The results strongly indicate that the minimum energy conformation is primarily determined by nonbonded hydrogen—hydrogen repulsions.     

Crystal structure of [Mn2(III)(salpa)2Cl2(H2O)2] (H2salpa = 1-(salicylaldeneamino)-3-hydroxypropane)

The manganese complex, (Mn₂(III)(salpa)₂Cl₂(H₂O)₂], has been prepared and its structure determined using x-ray crystallography. The dimer is a di-₂-alkoxo complex which is a six-coordinate manganese dimer with unsupported alkoxide bridges and a rare example of a chloride- and water-containing manganese dimer. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.315(5), b = 11.130(4), c = 11.637(5) Å, = 104.33(3)°, V = 1169.0(9) ų, and Z = 2. The structure comprises discrete binuclear clusters in which the metal atoms are bridged by two alkoxo oxygens of the salpa^2– ligands. The Mn—O and Mn—N distances are in good agreement with those found for other manganese(III) Schiff base complexes. The Mn—Cl and Mn—O3 distances are 2.585(2) and 2.371(2) Å, respectively, and the Mn ··· Mn distance is 3.001(1) Å. In the crystal, there are two types of hydrogen bonding between the H₂O molecule and the Cl atom with Cl ··· H(H₂O) distance of 2.33(6) (intramolecule: –1 + x, y, –1 + z) and 2.68(6) Å (intermolecule: –1 + x, 0.5–y, –0.5 + z).     

Gas-solid structure differences in the donor-acceptor complex (CH3)2HN−SO2

The crystal structure of the donor — acceptor adduct (CH₃)₂HN–SO₂ is reported. Crystals of the compound are clear prisms, space group Pna2₁; at –96°C,a=9.894(1),b=6.051(2),c=16.478(3) Å,D=1.469 g/cm³,V=786.6(5) Å,Z=8. The unit cell contains two crystallographically independent adducts, with N–S bond lengths of 2.015(3) Å and 1.991(3) Å. The average value, 2.00(1) Å is 0.33(4) Å shorter than the 2.34(3) Å value previously determined from microwave spectroscopy of the gas phase species, revealing a large medium effect on the length of the donor — acceptor bond. The structural results are compared with published data for the trimethylamine — SO₂ adduct, and discussed in terms of existing experimental and theoretical results for other donor — acceptor systems.     

Crystal structure of bis 4-benzyl piperidinium monohydrogenmonophosphate pentahydrate, [C6H5CH2CHCH2CH2NH2CH2CH2]2HPO4·5H2O

The salt bis 4-benzyl piperidinium monohydrogenmonophosphate pentahydrate is orthorhombic with the following unit cell dimensions: a = 11.235(2) Å, b = 27.924(6) Å, c = 9.321(4) Å space group Pca2₁ with Z = 4. The structure was solved by the Patterson method and refined to final R value of 0.049 for 1802 independent reflections. The flack parameter is 0.14 with an e.s.d. of 0.23. The structure consists of infinite parallel two-dimensional [110] planes built of mutually connected ions and water molecules by strong O—H,...,O and N—H,...,O hydrogen bonding. There are no contacts other than normal van der Waals interactions between the layers.     

Di-hydroxy malonic acid as a building block of hydrogen-bonded 3-dimensional architectures

An examination of the crystal structures of di-hydroxy malonic acid 1 (P2₁/na = 5.384(2), b = 6.268(2), c = 14.354(8) Å, = 103.57(3)°) and N-ethylbenzylammonium di-hydroxy hydrogenmalonate 2 (P2₁2₁2₁ a = 13.373(2), b = 15.342(4), c = 18.741(4) Å,) has highlighted the influence of directional O–H···O interactions in the assembly of hydroxy-substituted dicarboxylic acids. The complementarity of carboxylic and hydroxy groups in 1 creates a very dense 3-D structure (D _c = 1.919 g cm^–3) through four O–H···O hydrogen bonds. In 2, the anions form infinite, spiraling chains created by head-to-tail O–H···O hydrogen bonds. Neighbouring chains are crosslinked into a complex 3-D anionic network with channels parallel to a and b. The cations are positioned within these channels and held in place via two N–H···O interactions.     

Intramolecular hydrogen bonding and tautomerism in N-(3-pyridil)-2-oxo-1-naphthylidenemethylamine

N-(3-pyridil)-2-oxo-1-naphthylidenemethylamine (C₁₆H₁₂N₂O) was studied by elemental analysis, IR, ¹H NMR, and UV–visible techniques and X-ray diffraction methods. The UV–visible spectrum of the compound was investigated in solutions effect polarity. The polarity of the some solvents was modifierly the additional (CF₃COOH) and [(C₂H₅)₃N]. The compound is in tautomeric equilibrium (phenol-imine O–H···N and keto-amine O···H–N forms) in polar and nonpolar solvents. The keto-amine form is observed in basic solutions of DMSO, ethanol, chloroform, benzene, cyclohexane, and in acidic solutions of chloroform and benzene, but not in acidic solutions of DMSO and ethanol. The compound crystallizes in the monoclinic, space group P2₁/a with a = 7.010(5) Å, b = 13.669(4) Å, c = 12.764(4) Å, = 101.23(4)°, V = 1199.6(10) ų, Z = 4, D _c = 1.375 g/cm³, (Mo K) = 0.088 mm^–1, R = 0.045 for 1658 reflections [I > 2(I)]. The title compound is not planar two Schiff base moieties A [C1–C11, O1] and B [N1, C12, C13, N2, C14, C15, C16] are inclined at an angle of 27.4(1)° reflecting mainly the twist about C12–N1 [C11–C12–N1–C13, 29.7(2)°]. There is a strong intramolecular hydrogen bond (O–H···N) of 2.529(2) Å.     

Crystal structure of 2-{(R)-1-hydroxy-1-[(2S)-1-tritylaziridin-2-yl] methyl}acrylate and spectroscopic properties of the (R,S) and (S,S) stereoisomers

The crystal and molecular structure of 2-{(R)-1-Hydroxy-1-[(2S)-1-tritylaziridin-2-y1] methy1}acrylate is described. Crystal data: C₂₆H₂₅NO₃, orthorhombic, space group P2₁2₁2₁, a = 9.6954(5), b = 13.1458(5), c = 16.7885(7) Å, V = 2139.8(2) ų, Z = 4. The (R,S) diastereomer shows an intramolecular hydrogen bonding N···H—O under formation of a five-membered ring with N···O distance of 2.664 Å. IR, ¹H NMR and ¹³C NMR data are discussed. The ¹H NMR of the (R,S) diastereomer shows a singlet- whereas the (S,S) diastereomer exhibits a doublet-pattern for the hydroxyl proton.     

syn,E-1-cyclopentano-4-ethyl-3-thiosemicarbazone and syn,E-1-cyclopentano-4-phenyl-3-thiosemicarbazone

The structures of two thiosemicarbazones are described: syn,E-1-cyclopentano-4-ethyl-3-thiosemicarbazone (1) and syn,E-1-cyclopentano-4-phenyl-3-thiosemicarbazone (2). Crystal data: for 1: tetragonal, P4₃ (#78), a = b = 8.922(7) Å, c = 12.899(13) Å, and Z = 4; for 2: monoclinic a = 15.163(18) Å, b = 7.482(5) Å, c = 12.467(15) Å, = 119.04(7)°, and Z = 4. In 1, molecules are linked by hydrogen-bonding into infinite chains with non-planar 9-ring subunits in which thioamides interact with the H—N—C—N—N groups of neighbors. Thioamide groups in 2 form dimers linked by N—B···HS hydrogen-bonds with a planar 8-ring as in solid state structures of carboxylic acids. The semicarbazide syn conformation fosters formation of N—H···N intramolecular hydrogen-bonding in each structure. The solid state structures are consistent with their infrared and proton nuclear magnetic resonance spectra.     

Very strong hydrogen bonds in hydrated 1:1 adducts of an olefinic double betaine with perchloric and nitric acids: L·HClO4·H2O and L·HNO3·H2O [L=cis-(p-Me2N+C5H4N)2C2(COO−)2]

The hydrated 1:1 adducts of an olefinic double betaine with perchloric and nitric acids, L·HClO₄·H₂O I and L·HNO₃·N₂O2 [L=cis-(p-Me₂N⁺C₅H₄N)₂C₂(COO^–)₂], have been shown to be nearly isostructural by X-ray crystallography and infrared spectroscopy. The common cationic unit HL⁺ of both compounds exhibits significant semi-quinonoid character and possesses symmetrym, ist two coplanar carboxylate groups being linked by a very strong, nearly linear intramolecular O–H–O hydrogen bond [O...O 2.397(9)Å and O–H–O 167.1° for1; 2.388(7)Å and 167.4° for2]. The HL⁺ units are further connected by intermolecular O–H...O hydrogen bonds between the exocyclic carboxyl oxygen atoms and the water molecules to generate polymeric zigzag chains running parallel to thec axis, and the disordered ClO₄ or NO ₃ ^– anions occupy channels running parallel to thea axis in the resulting host lattice.     

Crystal structure of the cytotoxic marine alkaloid 2-bromoleptoclinidinone

2-Bromoleptoclinidinone methanol solvate, C₁₈H₈BrN₃O·CH₄O, crystallizes in the orthorhombic space group Pbca with a = 15.7013(2), b = 7.3308(1), and c = 26.9326(1) Å. The molecule is essentially planar, with the largest deviations occurring at bromine (–0.21 Å), carbonyl oxygen O(l) (+0.19 Å) and in ring-A (C(9) –0.15 Å, C(10) –0.15 Å). Methanol occupies the 1,10-phenanthroline-like metal binding site of the title compound.     

Crystal and molecular structure of 1,1′-ferrocene-dicarbaldehyde

The crystal and molecular structure of 1,1-ferrocene-dicarbaldehyde 1 is reported. Crystal data for 1: monoclinic, space group P2₁/n, a = 5.876(1), b = 11.349(1), c = 29.460(3) Å, = 95.067(2)°, V = 1956.9(3) ų, and D _c = 1.64 g/cm³, for Z = 8. The complex crystallizes such that two molecules are located in the asymmetric unit in which the complexes display different degrees of twisting of the cyclopentadienyl (Cp) rings and formyl substituents about the Cp—Fe—Cp and Cp—COH axes, respectively. The molecule self-assembles in the solid state to form a 2D layered structure held together by - interactions and C—H···O hydrogen bonds.     

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.     

The structure of bis(trimethylammonium) undecachlorotriantimonate(III) [(CH3)3NH]2Sb3Cl11 containing a novel antimony(III) anion

The structure of [(CH₃)₃NH]₂Sb₃Cl₁₁ (space group P2₁/n; a = 10.374(2), b = 23.723(5), c = 11.884(2) Å, = 113.46(3)°; V = 2682.9(9) ų) consists of a structurally novel [Sb₃Cl^2– ₁₁] anion and two crystallographically nonequivalent trimethylammonium cations. The anion is composed of three deformed octahedra in the asymmetric part of the unit cell. The octahedra are connected with each other by edges and corners forming a characteristic polyanionic layer. Trimethylammonium cations, one ordered and one disordered, are connected to the inorganic sublattice by N—H···Cl hydrogen bonds.     

Structure of 2-{2-[3-methyl-3-(2,4,6-trimethylphenyl) cyclobutyl]-2-oxoethyl}isoindole-1,3-dione

2-{2-[3-Methyl-3-(2,4,6-trimethylphenyl)cyclobutyl]-2-oxoethyl}isoindole-1,3-dione (C₂₄ H₂₅NO₃) was synthesized, and its crystal structure was determined by X-ray crystallographic techniques. The compound crystallizes in the triclinic space group P-1, with unit cell parameters: a = 14.109(9) Å, b = 14.130(8) Å, c = 12.152(6) Å, = 105.62(5)°, = 113.75(4)°, = 98.78(5)°, V = 2039.8(19) ų, D _c= 1.223 g/cm³, and Z = 4. The crystal structure has two crystallographically independent molecules, I and II. These molecules are held together by weak intermolecular C—H···O interactions, forming a continuous chain. The dihedral angles between the N-substituted phthalimide moiety and cyclobutane ring in molecules I and II are 60.37(14) and 68.18(18)°, respectively.     

Crystal structure of a one-dimensional ladder-shape CoII complex through hydrogen bonds with an amino-acid-like ligand 1,5-diazacyclooctane-N,N′-diacetate acid

The crystal structure of a one-dimensional ladder-shape complex [CoL(H₂O)]·2H₂O, (L being 1,5-diazacyclooctane-N,N-diacetate acid), has been determined by X-ray diffraction analysis: monoclinic, space group P2₁/c with a = 14.406(4) Å, b = 7.380(2) Å, c = 14.594(5) Å, = 112.685(2)°, M _r = 341.23, V = 1431.5(8) ų, Z = 4. The Co^II center is penta-coordinated by two O atoms of the carboxylic pendant arms, two nitrogen donors of the 1,5-diazacyclooctane (DACO) moiety, and a water molecule. The coordination geometry of Co^II could be described as a distorted square pyramid and the DACO backbone adopts a normal boat/chair conformation. The complex forms a one-dimensional ladder-shape structure through inter- and intra-molecular O—H···O hydrogen bonds.