Molecular and crystal structures of 1R,4R-cis-2-(4-hydroxybenzylidene)-p-menthan-3-one

The molecular and crystal structures of chiral 1R, 4R-cis-2-(4-hydroxybenzylidene)-p-menthan-3-one (I) are determined by X-ray diffraction analysis. Single crystals of I are orthorhombic, a = 8.997(2) Å, b = 11.314(2) Å, c = 14.847(3) Å, V = 1511.3(5) ų, Z = 4, and space group P2₁2₁2₁. The cyclohexanone ring in molecules of compound I has a chair-type conformation with the axial methyl and equatorial isopropyl groups. The enone and benzylidene groupings are nonplanar. The considerable distortion of bond angles at the sp ² carbon atoms of the benzylidene grouping and the puckering parameters of the cyclohexanone ring in the structure of I are close to those observed for the previously studied compound with the p-methoxy substituent. In the crystal, molecules I are linked by very short intermolecular hydrogen bonds .     

Crystal structures of double vanadates, Ca9 R(VO4)7 ⋅ III. R = Nd, Sm, Gd, or Ce

The crystal structures of Ca₉ R(VO₄)₇ (R = Nd (I), Sm (II), or Gd (III)) were studied by the Rietveld method. The compounds are isostructural to Ca₃(VO₄)₂ and are crystallized in the trigonal system (sp. gr. R3c, Z = 6). The unit-cell parameters are as follows: for I, a = 10.8720(5) Å, c = 38.121(1) Å; for II, a = 10.8652(5) Å, c = 38.098(1) Å; and for III, a = 10.8631(5) Å, c = 38.072(1) Å. In the structures of I and II, the M(1), M(2), and M(3) positions are statistically occupied by the rare-earth cations and calcium anions. In the structure of III, the Gd³⁺ cations occupy the _M(1) and _M(2) positions. The distributions of the R ³⁺ cations over the positions are characteristic of each structure. The composition of the cerium-ontaining compound Ca_9.81Ce_0.42(VO₄)₇ (a = 10.8552(5) Å, c = 38.037(1) Å) was refined and its crystal structure was solved from the X-ray powder data. In this compound, cerium atoms are in the oxidation states +3 and +4.     

Molecular and crystal structures of 8,9-dimethoxy-5′,5′-dimethyl-1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinoline-1-spiro-2′-cyclohexane-3,1′,3′-trione

The crystal and molecular structures of 8,9-dimethoxy-5′,5′-dimethyl-1,2,3,5,6,10b-hexahydropyr-rolo[2,1-a]isoquinoline-1-spiro-2′-cyclohexane-3,1′,3′-trione are studied by X-ray diffraction. The unit cell parameters are a = 9.478(2) Å, b = 9.844(3) Å, c = 11.663(3) Å, α = 111.17(2)°, β = 99.56(2)°, γ = 105.82(2)°, Z = 2, and space group P1ˉ. The structure is solved by the direct method and refined to R = 0.0411 [I > 4σ(I)]. Conformational and geometric characteristics of the compound studied and the molecular packing in the crystal are discussed. __________ Translated from Kristallografiya, Vol. 45, No. 2, 2000, pp. 286–288. Original Russian Text Copyright ? 2000 by Lyakhov, Ivashkevich, Govorova, Mikhal’chuk.     

Molecular and crystal structures of 3-methyl-3-[1,7-dicarba-closo-dodecaborane(12)-1-oyl-peroxy]-but-1-yne

The crystal and molecular structures of 3-methyl-3-[1,7-dicarba-closo-dodecaborane(12)-1-oylperoxy]-but-1-yne (I) are determined by X-ray diffraction analysis (Nicolet R3m automated diffractometer, MoK _α radiation, θ/2θ scan mode). It is found that the compound crystallizes in the orthorhombic crystal system, space group P2₁2₁2₁. The unit cell parameters are as follows: a = 7.355(2) Å, b = 9.773(3) Å, c = 21.938(7) Å, and Z = 4. The structure is solved by the direct method and refined to R = 0.0658. The structural features of the molecule and the C-H?O contacts in the structure are discussed.     

Crystal structure and spectral characteristics of 2,4,7-trinitro-9-fluorenone

The crystal structure of 2,4,7-trinitro-9-fluorenone C₁₃H₅N₃O₇ is determined by X-ray diffraction analysis. The crystals are monoclinic, a = 4.024(1) Å, b = 16.763(3) Å, c = 18.250(4) Å, β = 96.32(3)°, V = 1223.6(5) ų, Z = 4, space group P2₁/c, and R = 0.0640 for 605 reflections with I > 2σ(I). The crystal is built of planar isolated molecules. The compound is characterized using IR and electronic absorption spectroscopy.     

Crystal structure of hydrazine 5-amino-1-benzyl-1,2,3-triazole-4-carboxylate hexafluorosilicate trihydrate

Hydrazine 5-amino-1-benzyl-1,2,3-triazole-4-carboxylate hexafluorosilicate trihydrate (I) is synthesized. The crystal structure of the compound synthesized is determined. Crystals I are monoclinic, a = 13.353(1) Å, b = 21.094(2) Å, c = 20.233(2) Å, β = 94.05(3)°, space group P2₁/c, and R = 0.0584 for 16 601 reflections with I > 2σ(I). In the asymmetric part of the unit cell, four organic cations protonated at the terminal hydrazine nitrogen atoms, two hexafluorosilicate anions, and six water molecules are linked into a three-dimensional framework through hydrogen bonds of the N-H?F, N-H?O, and O-H?F types.     

Crystal structure of <Emphasis Type="Italic">p</Emphasis>-carboxyphenylhydrazone benzoylacetone

The crystal structure of p-carboxyphenylhydrazone benzoylacetone is determined. The crystals are monoclinic, a = 13.614(4) Å, b = 11.388(2) Å, c = 20.029(6) Å, β = 104.82(2)°, V = 2339(9) ų, Z = 8, space group C2/c, and R = 0.038 for 1622 reflections with I > 2σ(I). The crystal is built of C₁₇H₁₄N₂O₄ neutral molecules that are linked by O-H?O hydrogen bonds between the carboxyl groups into centrosymmetric pseudodimers. The effect of carboxylation of the phenylhydrazone fragment and the position of the carboxyl group on the molecular packing in the crystal is determined. The N(1)-H(1N)?O(1) intramolecular hydrogen bond (N-H, 0.94 Å; H?O, 1.87 Å; N?O, 2.59 Å; and the N-H?O angle, 133°) is formed in the molecule.     

Molecular and crystal structures of 1R,4S-2-(4-carbomethoxy)benzylidene-n-menthan-3-one

The molecular and crystal structures of chiral 1R,4S-2-(4-carbomethoxy)benzylidene-n-menthan-3-one (I) are determined by X-ray diffraction analysis. Crystals I are orthorhombic; at 20°C: a = 11.961(3) Å, b = 26.453(8) Å, c = 5.400(2) Å, space group P2₁2₁2₁, and Z = 4 (C₁₉H₂₅O₃). In molecule I, the cyclohexanone ring with the axial methyl and isopropyl substituents adopts a chair conformation. It is found that the enone and arylidene fragments of compound I have a substantially nonplanar structure. The shortened intramolecular contacts between atoms of the arylidene grouping and the α fragment of the cyclohexanone ring and their associated distortions of bond angles at the sp ² carbon atoms are the common structural features of 2-arylidene-n-menthan-3-ones irrespective of the stereochemical configuration of the C(4) chiral center.     

Synthesis and the crystal and molecular structure of two modifications of bis(1,10-phenanthroline)trinitratoerbium(III) Er(NO3)3(Phen)2

Two crystalline modifications (I and II) of the phenanthroline complex of erbium nitrate with the same chemical composition, Er(NO₃)₃(Phen)₂, are synthesized by a procedure similar to that used for preparing the phenanthroline complexes of europium nitrate. The crystal structures of these modifications are determined using X-ray diffraction. Crystals of compound I belong to the isostructural family Ln(NO₃)₃(Phen)₂ (Ln = La-Lu). Crystals of compound II are isostructural to those of modification II (new phase) of the Eu(NO₃)₃(Phen)₂ compound. Crystals of I and II are monoclinic, space group C2/c, and Z = 4. The unit cell parameters are as follows: a = 11.126 Å, b = 17.815 Å, c = 12.976 Å, β = 100.45°, and V = 2529 ų for modification I and a = 9.459 Å, b = 15.463 Å, c = 17.076 Å, β = 93.52°, and V = 2493 ų for modification II. The molecular complexes in the structures of compounds I and II are nearly identical. The mean lengths of the Er-N and Er-O bonds are equal to 2.500 and 2.466 Å in compound I and 2.508 and 2.457 Å in compound II, respectively. The difference between the structures of compounds I and II is associated with the difference between intermolecular interactions in the unit cell.     

Synthesis and structure of oxovanadium(IV) complexes [VO(<Emphasis Type="Italic">Acac</Emphasis>)<Subscript>2</Subscript>] and [VO(<Emphasis Type="Italic">Sal</Emphasis>: <Emphasis Type="Italic">L</Emphasis>-alanine)(H<Subscript>2</Subscript>O)]

Bis(acetylacetonato)oxovanadium C₁₀H₁₄O₅V (I) and (S)-[2-(N-salicylidene)aminopropionate]oxovanadium monohydrate C₁₀H₉NO₅V (II) are synthesized. The crystal structures of compounds I and II are determined using single-crystal X-ray diffraction. Crystals of compound I are triclinic, a = 7.4997(19) Å, b = 8.2015(15) Å, c = 11.339(3) Å, α = 91.37(2)°, β = 110.36(2)°, γ = 113.33(2)°, Z = 2, and space group \(P\bar 1\). Crystals of compound II are monoclinic, a = 8.5106(16) Å, b = 7.373(2) Å, c = 9.1941(16) Å, β = 101.88(1)°, Z = 2, and space group P2₁. The structures of compounds I and II are solved by direct methods and refined to R₁ = 0.0382 and 0.0386, respectively. The oxovanadium complexes synthesized are investigated by vibrational spectroscopy.     

Synthesis and structure of two crystalline modifications of Bis(1,10-Phenanthroline)trinitratoeuropium(III) Eu(NO3)3(Phen)2

Two crystalline modifications (I and II) of the phenanthroline complex of europium nitrate with the same chemical composition, Eu(NO₃)₃(Phen)₂, are synthesized under different conditions by varying the solvents, temperatures, and crystallization rates. The crystal structures of these modifications are determined using X-ray diffraction. Crystalline modifications I and II differ in the unit cell parameters and the positions of the complexes in the unit cell. The geometric characteristics of the complexes in the structures of compounds I and II differ insignificantly. Crystals of compound I belong to the isostructural family Ln(NO₃)₃(Phen)₂ (Ln = La-Lu). Crystals of compound II (new phase) are studied for the first time. Crystals of I and II are monoclinic, space group C2/c, and Z = 4. The unit cell parameters are as follows: a = 11.1555(10) Å, b = 17.9698(10) Å, c = 13.0569(10) Å, β = 100.507(10)°, and V = 2572.1(3) ų for modification I and a = 9.5153(10) Å, b = 15.4546(10) Å, c = 17.1763(10) Å, β = 93.451(10)°, and V = 2521.3(3) ų for modification II. The difference between the molecular complexes in the structures of compounds I and II is revealed by the superposition method. Complexes II are arranged along the C ₂ axis and are statistically disordered with respect to this axis.     

Molecular and crystal structures of 1R,4R-cis-2-(4-phenylbenzylidene)-n-menthan-3-one

The molecular and crystal structures of chiral 1R,4R-cis-2-(4-phenylbenzylidene)-n-menthan-3-one (I) have been determined by X-ray diffraction analysis. Crystals I are monoclinic, a = 6.755(3) Å, b = 9.860(3) Å, c = 14.103(6) Å, β = 98.95(1)°, space group P2₁, Z = 2, and R = 0.035 for 1031 reflections. A chair conformation of the cyclohexanone ring in the molecule is substantially distorted toward a “half-chair” conformation. The enone and benzylidene groupings are virtually planar (the torsion angles are equal to 13.0° and 4.9°, respectively). The benzene rings of the biphenyl fragment are rotated with respect to each other through an angle of 40°–43°. Among the compounds under consideration, the distortion of bond angles at the sp ² carbon atoms of the benzylidene grouping as a criterion for the steric stress of molecules is maximum in structure I.     

Crystal structures of molecular complexes of 18-crown-6 with 2-aminobenzoic and 5-amino-1-benzyl-1,2,3-triazole-4-carboxylic acid hydrazides

The crystal structures of two host-guest molecular complexes of 18-crown-6 with 2-aminobenzoic acid hydrazide monohydrate (the ratio host: guest: H₂O = 1: 2: 2) (complex I) and 5-amino-1-benzyl-1,2,3-triazole-4-carboxylic acid hydrazide (the host: guest ratio = 1: 2) (complex II) are determined by X-ray diffraction analysis. Crystals I are monoclinic, a = 8.468(2) Å, b = 17.378(3) Å, c = 10.517(2) Å, β = 96.88(3)°, space group P2₁/n, and R = 0.0393 for 6692 reflections. Crystals II are orthorhombic, a = 18.489(1) Å, b = 10.192(3) Å, c = 20.412(2) Å, space group Pbca, and R = 0.0540 for 3513 reflections. In both complexes, the centrosymmetric 18-crown-6 and guest molecules are joined together through the NH?O (crown) hydrogen bonds, which involve all the hydrogen atoms of the hydrazine group. The NH?O=C intramolecular hydrogen bond is observed in the guest molecule. In structure I, the water molecule serves as a bridge between the guest molecules related by the glide-reflection plane and combines the guest-host-guest complexes into layers. In structure II, the guest molecules are linked into chains through hydrogen bonds of the NH?O=C type; in turn, the chains composed of guest molecules and the crown ether molecules bonded to these chains form a layered structure.     

Synthesis and crystal structure of new double indium phosphates M 3 I In(PO4)2 (M I = K and Rb)

Double potassium indium and rubidium indium phosphates K₃In(PO₄)₂ (I) and Rb₃In(PO₄)₂ (II) are synthesized by solid-phase sintering at T = 900°C. The compounds prepared are characterized by X-ray powder diffraction (I and II), X-ray single-crystal diffraction (II), and laser-radiation second harmonic generation. Structure I is solved using the Patterson function and refined by the Rietveld method. Both compounds crystallize in the monoclinic crystal system. For crystals I, the unit cell parameters are as follows: a = 15.6411(1) Å, b = 11.1909(1) Å, c = 9.6981(1) Å, β = 90.119(1)°, space group C2/c, R _p = 4.02%, and R _wp = 5.25%. For crystals II, the unit cell parameters are as follows: a = 9.965(2) Å, b = 11.612(2) Å, c = 15.902(3) Å, β = 90.30(3)°, space group P2₁/n, R ₁ = 4.43%, and wR ₂ = 10.76%. Structures I and II exhibit a similar topology of the networks which are built up of { In[PO₄]₂} (I) and { In₂[PO₄]₄} (II) structural units.     

Synthesis and crystal structure of bis[2-[N-(2-chlorophenyl)formimidayl]-1-naphtholato]-(6Cl)copper(II)

The title compound, bis[2-[N-(2-chlorophenyl)formimidayl]-1-naphtholato]-(6Cl) copper(II), [Cu(C₁₇H₁₁NOCl)₂] (1) was synthesized and its crystal structure was determined. The Compound 1 is monoclinic, space group P2 ₁/c with a = 9.146(3) Å, b = 18.724(3) Å, c = 16.230(2) Å, β = 96.46(1)°, V = 2761.8(11) ų, Z = 4, D _c = 1.503 g cm^?3, μ(Mo Kα) = 1.020 mm^?1, R = 0.0606 for 2361 reflections [I > 2σ(I)]. In the title compound, the Cu atom is coordinated by an N₂O₂ donor set from the imine-phenol ligand in a slightly distorted square planar coordination geometry, with the two phenolate O atoms being deprotonated. The Cu–O bond lengths are 1.878(4) and 1.889(4) Å, the Cu–N bond lengths are 1.980(5) and 1.985(5) Å. The angles O1–Cu–N1 and O2–Cu–N2 are 90.96(19) and 90.72(19)°, respectively.     

Reaction of o-phenylenediamine with 2,3-dichloromaleic anhydride: synthesis of N-substituted maleimide derivatives and 2,3-dichloropyrrolo[1,2-a]benzimidazol-1-one. X-ray structures of 2,3-dichloro-N-o-C6H4(NH2)maleimide and N, N′-o-C6H4-bis(2,3-dichloromaleimide)

Refluxing equimolar amounts of 2,3-dichloromaleic anhydride and o-phenylenediamine in toluene affords the three compounds 2,3-dichloro-N-o-C₆H₄(NH₂)maleimide (1), N,N′-o-C₆H₄-bis(2,3-dichloromaleimide) (2), and 2,3-dichloropyrrolo[1,2-a]benzimidazol-1-one (3). Under these conditions the former compound is observed as the major product. Repeating the same reaction in the presence of added PTSA furnishes the heterocyclic compound 2,3-dichloropyrrolo[1,2-a]benzimidazol-1-one, as the major product. Treatment of compound 1 with PTSA, coupled with water removal, gives compound 3 in near quantitative yield and confirms the intermediacy of 1 en route to 3. The new compounds 1–3 have been isolated by column chromatography and characterized in solution by spectroscopic methods. The molecular structures of the maleimide-substituted compounds 1 and 2 were determined by X-ray crystallography. 2,3-Dichloro-N-o-C₆H₄(NH₂)maleimide crystallizes in the monoclinic space group P2₁/c, a = 20.693(8) Å, b = 5.712(2) Å, c = 8.787(4) Å, β = 92.819(7)°, V = 1037.3(7) ų, Z = 4, and d _calc = 1.646 Mg/m³; R = 0.0604, R _w = 0.1140 for 1354 reflections with I > 2 σ (I), with N,N′-o-C₆H₄-bis(2,3-dichloromaleimide) crystallizing in the triclinic space group P?1, a = 7.9509(4) Å, b = 10.2532(6) Å, c = 12.1126(7) Å, α = 82.637(1)°, β = 87.799(1)°, γ = 71.634(1)°, V = 929.42(9) ų, Z = 2, and d _calc = 1.651 Mg/m³; R = 0.0499, R _w = 0.1545 for 1977 reflections with I > 2σ (I).     

Low-temperature study of the molecular and crystal structures of 2-(2′-tosylamino-5′-nitrophenyl)-4H-3,1-benzoxazin-4-one, an organic luminophore

The crystal structure of 2-(2′-tosylamino-5′-nitrophenyl)-4H-3,1-benzoxazin-4-one (I) is studied by X-ray diffraction at 100 K (C₂₁H₁₅N₃O₆S, a = 20.899(2) Å, b = 10.948(1) Å, c = 8.260(1) Å, V = 1889.3(1) ų, Z = 4, and space group Pbn2₁). The compound exhibits an anomalous Stokes shift. Upon cooling, the oxazineaminophenyl fragment of compound I acquires a quinoid structure and the linear parameters of the intramolecular N-H?N hydrogen bond increase (the distance between the heterocyclic nitrogen atom and the hydrogen atom of the tosylamino group becomes 1.92 Å). The complete optimization of the geometry of molecules in compound I and unsubstituted 2-(2′-tosylaminophenyl)-4H-3,1-benzoxazin-4-one in the ground singlet electronic state is performed by the semiempirical method with the MOPAC program. It is shown that the oxygen atoms in the sulfo group of molecule I are nonequivalent, because one of them is involved in the intermolecular C-H?O hydrogen bond.     

Molecular and crystal structure of the echinochrome complex with dioxane

The molecular and crystal structures of a complex of echinochrome (2,3,5,6,8-pentahydroxy-7-ethyl-1,4-naphthoquinone) with dioxane are determined. The molecular complex 2(C₁₂H₁₀O₇) · C₄H₈O₂ crystallizes in the form of dark red transparent thin plates. The crystal data of the compound are as follows: a = 4.563(1) Å, b = 6.382(1) Å, c = 22.812(4) Å, α = 91.955(5)°, β = 90.408(5)°, γ = 104.801(4)°, space group $P\overline 1 $ , and Z = 2. The crystal structure is solved by direct methods and refined to R ₁ = 0.0656 and wR ₂ = 0.1196.     

Crystal structure and nonlinear optical properties of the K2UO2(SO4)2 · 2H2O compound at 293 K

Single crystals of potassium uranyl sulfate are grown, and their atomic structure is determined using X-ray diffraction analysis. The compound crystallizes in the orthorhombic crystal system with space group Pna2₁ [a = 13.773(4) Å, b = 7.288(2) Å, c = 11.556(4) Å, R ₁ = 0.033, wR ₂ = 0.0892 for 2630 reflections with I > 2σ(I)]. The crystal structure of the K₂UO₂(SO₄)₂ · 2H₂O compound is built up of two-dimensional infinite, negatively charged layers of the composition [UO₂(SO₄)₂·H₂O] _2∞ ^δ? ], which are linked together through the K⁺ ions. The specific features of the atomic arrangement in the structure of this compound are analyzed, and the second harmonic generation of laser radiation is investigated.     

Crystal and molecular structures of 11,12-epoxydrim-8(9)-en-11β-ol-7-one

The crystal structure of 11,12-epoxydrim-8(9)-en-11β-ol-7-one is determined by X-ray diffraction. The crystal data for the C₁₅H₂₂O₃ composition are as follows: a = 6.646(1) Å, b = 7.242(1) Å, c = 7.635(2) Å, α = 84.34(3)°, β = 84.50(3)°, γ = 69.84(3)°, space group P1, and Z = 1. The structure is solved by the direct method and refined in the anisotropic approximation to R = 0.043 and R _w = 0.110. The stereochemical formula of the compound is determined. It is shown that the hydroxyl group at the C(11) atom is situated at the β position. In the crystal, the molecules related by the translation along the a-b direction of the unit cell are linked into infinite chains by intermolecular hydrogen bonds between the hydrohyl group and the carbonyl oxygen atom [O-H?O, 2.867(4) Å].