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.     

X-ray mapping in heterocyclic design: VIII. Synthesis and X-ray diffraction study of dimethyl 3-(p-chlorobenzoyl)-5-chloroindolizine-1,2-dicarboxylate and the product of its cyclization 1,2-bis(carbomethoxy)-6-chloro-3H-isoquinolino[1,2,3-d,c]indolizine-3-one

Dimethyl 3-(p-chlorobenzoyl)-5-chloroindolizine-1,2-dicarboxylate, C₁₉H₁₃Cl₂NO₅, (2) and the product of its cyclization 1,2-bis(carbomethoxy)-6-chloro-3H-isoquinolino[1,2,3-d,c]indolizine-3-one, C₁₉H₁₂ClNO₅, (3) are synthesized, and their molecular and crystal structures are determined by the single-crystal X-ray diffraction technique. Crystals 2 are monoclinic, a = 9.627(3) Å, b = 6.646(2) Å, c = 28.500(9) Å, β = 98.72(2)°, Z = 4, and space group P2₁/c. Crystals 3 are monoclinic, a = 7.048(4) Å, b = 10.582(4) Å, c = 21.760(7) Å, β = 97.23(4)°, Z = 4, and space group P2₁/c. The structures are solved by the direct method and refined in the anisotropic approximation by the full-matrix least-squares procedure to R = 0.0504 and 0.0510 for 2 and 3, respectively. In both structures, the intramolecular and intermolecular contacts involving the C, H, and O atoms are observed.     

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 .     

X-ray mapping in heterocyclic design: IX. X-ray structure investigation of conjugated aminodienes

The single-crystal structures of two aminodienes containing an oxazole fragment, namely, 1-pip-eridyl-4-[5-(4-nitrophenyl)-oxazol-2-yl]-buta-1,3-diene C 18 H 19 N 3 O 3 (IIa) and 1-hexamethyleneimine-4-[5-(4-nitrophenyl)-oxazol-2-yl]-buta-1,3-diene C₁₉H₂₁N₃O₃ (IIb), are studied by X-ray diffraction. Structures IIa [a = 16.181(6) Å, b = 5.939(3) Å, c = 17.337(9) Å, β = 96.13(2)°, Z = 4, and space group P2₁] and IIb [a = 7.4704(11) Å, b = 10.9904(19) Å, c = 43.434(6) Å, β = 91.24(1)°, Z = 8, and space group P2₁/_c] are solved by the direct method and refined to R = 0.060 and 0.238, respectively. Although the ring sizes of the cyclic amines in compounds IIa and IIb are different, the designs of two structures are identical. Each structure contains two topologically identical but crystallographically independent molecules. In structure IIa, the intramolecular hydrogen bonds between the N atoms of the oxazole fragments and the H atoms of the diene fragments are formed. In structure IIb, similar bonds are absent.     

X-ray mapping in heterocyclic design: XI. X-ray diffraction study of 1-benzoyl-3-(pyridin-2-yl)-thiocarbamide and the product of its reaction with oxidants

The structures of 1-benzoyl-3-(pyridin-2-yl)-thiocarbamide C₁₃H₁₁N₃O₁S₁ (I) and 2-benzoylimino-1,2,4-thiadiazole[2,3-a]pyridine C₁₃H₉N₃O₁S₁ (II) are studied by X-ray diffraction. Structures I [a = 5.342(4) Å, b = 20.428(5) Å, c = 11.784(4) Å, β = 90.55(2)°, Z = 4, space group P2₁/n) and II [a = 6.258(6) Å, b = 18.068(14) Å, c = 10.185(10) tA, β = 95.45(8)°, Z = 4, space group P2₁/n) are determined by direct methods and refined to R ₁ = 0.0673 and 0.0802, respectively. In structure I, both intramolecular (involving the O atom) and intermolecular (involving the N and S atoms) hydrogen bonds are observed. The latter bonds are responsible for the formation of centrosymmetric molecular dimers. In structure II, a short intramolecular contact (2.168 Å) is observed between the S and O atoms.     

Crystal structures of benzo-18-crown-6 complexes with oxonium hexafluorotantalate and oxonium hexafluoroniobate

The crystal structures of [(benzo-18-crown-6) · H₃O]TaF₆ and [(benzo-18-crown-6) · H₃O]NbF₆ complex compounds are determined by X-ray diffraction. It is revealed that the tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and orthorhombic (II) modifications. The unit cell parameters of these compounds are as follows: a = 14.784(2) Å, b = 8.390(4) Å, c = 18.005(6) Å, β = 95.78(2)°, Z = 4, and space group P2₁/n for modification I; and a = 8.456(2) Å, b = 21.967(5) Å, c = 24.122(5) Å, Z = 8, and space group Pbca for modification II. The orthorhombic niobium complex [(benzo-18-crown-6) · H₃O]NbF₆ with the unit cell parameters a = 8.454(1) Å, b = 21.943(3) Å, c = 24.127(4) Å, Z = 8, and space group Pbca (III) is isostructural with tantalum complex II. The oxonium cation in complexes I–III is encapsulated by the crown ether and thus forms one ordinary and two bifurcate hydrogen bonds with the oxygen atoms of the crown ether. This macrocyclic cation is bound to the anions through the C-H ...F contacts (H...F, 2.48–2.58 Å).     

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 and properties of isomers of 3,5-dinitro-(4-acetylphenyl)aminobenzoyl (p-bromophenyl)amide

The para and ortho isomers of 3,5-dinitro-(4-acetylphenyl)aminobenzoyl (p-bromophenyl)amide (I and II, respectively) are synthesized, and their physicochemical properties and structure are investigated. The para isomer I has a higher melting temperature and is less soluble in organic solvents as compared to the ortho isomer II. The electronic absorption spectra indicate that absorption for molecule I occurs at longer wavelengths than for molecule II. A correlation between the physicochemical properties and the crystal structures of compounds I and II is revealed. Crystals I · 0.5C₆H₆ are triclinic; the unit cell parameters are a = 11.760(2) Å, b = 13.958(3) Å, c = 15.012(3) Å, α = 108.01(2)°, β = 103.95(1)°, γ = 92.00(2)°, V = 2258.3(8) ų, space group $P\bar 1$ , and Z = 4. Crystals II are monoclinic; the unit cell parameters are a = 9.302(2) Å, b = 16.380(3) Å, c = 13.480(3) Å, β = 100.09(3)°, V = 2022.1(7) ų, space group P2₁/c, and Z = 4. Structures I · 0.5C₆H₆ and II are characterized by intramolecular and intermolecular hydrogen bonds.     

X-ray diffraction investigation of trans-2,8-dihydroxy-2,8-diphenyl-4,4′,6,6′,10,10′, 12,12′-octamethylcyclohexasiloxane and trans-2,8-dihydroxy-2,4,4′,6,6′,8,10,10′, 12,12′-decamethyl-5-carbahexacyclosiloxane

The crystal structures of two organosilicon compounds are studied by X-ray diffraction. Crystals of trans-2,8-dihydroxy-2,8-diphenyl-4,4′,6,6′,10,10′,12,12′-octamethylcyclohexasiloxane, C₂₀H₃₆O₈Si₆, (I) are triclinic; at 110 K, a = 11.476(1) Å, b = 12.106(1) Å, c = 13.636(1) Å, α = 94.337(1)°, β = 112.669(1)°, γ = 112.216(1)°, space group $P\bar 1$ , Z = 2, and R = 0.057 for 5069 reflections with F > 4σ(F). Crystals of trans-2,8-dihydroxy-2,4,4′,6,6′,8,10,10′,12,12′-decamethyl-5-carbahexacyclosiloxane, C₁₁H₃₄O₇ Si₆, (II) are tetragonal; at 293 K, a = b = 15.487(3) Å, c = 11.364(3) Å, space group P4₂/n, Z = 4, and R = 0.055 for 955 reflections with F > 4σ (F). It is found that the structure of compound I, in which the substituents at the Si(1) atom differ in volume and inductive effect, contains two crystallographically independent molecules with different conformations of the hexasiloxane ring. In structure II, the oxygen atom and the methylene group are statistically disordered as a result of the location of the molecule at the center of symmetry. Although the SiCSi angle [122.1(1)°] differs noticeably from the tetrahedral angle, its value is characteristic of cyclohexasiloxanes and is not related to the disorder.     

N-isopropyl-2-(isopropylamino)troponiminate complexes of lithium and calcium

The synthesis and structures of [(i-Pr)₂ATI]Li₂(thf)(I)(1) and [(i-Pr)₂ATI]Ca(thf)₂(I)₂Li₂(thf)₂-[(i-Pr)₂ATI] (2) (where [(i-Pr)₂ATI]=N-isopropyl-2-(isopropylamino)troponiminate) have been described. The lithium atoms in compounds1 and2 occupy positions above and below the plane of the aminotroponiminate ligand. The calcium atom in2 adopts a pseudo-octahedral geometry with two tetrahydrofurans occupying thetrans-positions. Compound1 crystallizes as dimeric units. Crystal data with MoKα at 193 K:1, C₁₇H₂₇ILi₂N₂O,a=13.217(2)Å,b=9.875(2)Å,c=16.410(4)Å, B=111.41(1)^o,V=1993.4(6)ų, a monoclinic space groupP2₁/n,Z=4,R=0.029;2, C₄₂H₇₀CaI₂Li₂N₄O₄,a=911.390(2)Å,b=30.880(4)Å,c=13,465(2)Å, B=93.85(1)^o,V=4724(1)ų, monoclinic space groupC2/c,Z=4,R=0.027.     

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.     

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.     

Carbon–hydrogen and carbon–phosphorus bond cleavage in a triruthenium cluster complex containing dppm: The crystal and molecular structures of Ru3(CO)6{μ 3-OPPh2 C2H(C6H4)PPhCH2PPh}(μ 3-OPPh2)Ph and Ru3(CO)6 {μ-OPPh2C2H(C6H4)PPhO}(μ-PPh2)(μ-PPh2O)

The crystal and molecular structures of Ru₃(CO)₆{μ ₃-OPPh₂C₂H(C₆H₄)PPhCH₂PPh}-(μ ₃-OPPh₂)Ph (1) and Ru₃(CO)₆{μ-OPPh₂C₂H(C₆H₄)PPhO}(μ-PPh₂)(μ-PPh₂O) (2) have been determined by single crystal X-ray diffraction. Both complexes contain oxygen atoms oxidatively inserted into phosphorus–ruthenium bonds, and unique σ/π multidentate ligands formed from C $---{\text{H}}$ H and C $--$ P bond cleavage in bis(diphenylphosphino)acetylene and bis(diphenylphosphino)methane. Complex 1 crystallized in the triclinic space group ${\bar 1}$ , with lattice parameters a = 11.642(4) Å, b = 15.018(5) Å, c =16.587(5) Å, α = 2.48(3)°, β = 76.47(2)°, γ = 70.35(3)°, V = 2651.1(15) ų, Z = 2. Complex 2 crystallized in the centered monoclinic space group, C2/c, with lattice parameters a = 34.467(4) Å, b = 14.274(2) Å, c = 23.258(3) Å, β = 5.29(1)°, V = 11394(3) ų, Z = 8.     

Crystal structure analysis of (Morpholino)(Phenyl)(Dicyclohexylamino) phosphiniminocyclotrithiazene

The title compound (C₆H₅)(C₄H₈NO)[N(C₆H₁₁)₂]P=N-S₃N₃ crystallizes in a triclinic crystal system with unit cell parameters a = 9.8884(4) Å, b = 10.6075(1) Å, c = 14.2276(2) Å, α = 78.14(3)°, β = 79.31(1)°, λ = 65.42(2)°, V = 1319.44(6) ų, Z = 2, and space group $P\bar 1$ . The cyclotrithiazene ring adopts a “distorted chair” conformation with a deviation of 0.682(7) Å for the tricoordinated sulfur atom. Remarkably, a short exocyclic S-N bond length 1.489(4) Å along with a large P-N-S angle 136.2(3)° are observed with the iminophosphorus moiety.     

The structures of N-(t-butoxycarbonyl)-3-methylbenz[f]indole and N-benzenesulfonyl-4-bromo-3-methylbenz[f]indole

N-(t-butoxycarbonyl)-3-methylbenz[f]indole,1, C₁₈H₁₉NO₂, crystallizes in orthorhombic space groupPna2₁ witha=6.0338(2),b=24.839(4),c=10.2481(7) Å,V=1535.9(3) ų,Z=4. The structure was refined toR=0.051 for 2007 observed reflections. The benz[f]indole ring system is nearly planar, exhibiting mean deviation of 0.048 Å. The ester plane of thet-butoxycarbonyl substituent is nearly coplanar with the benz[f]indole ring system, forming a C?N?C=O torsion angle with magnitude 10.6(5)⁰.N-benzenesulfonyl-4-bromo-3-methyl-benz[f]indole,2, C₁₉H₁₄BrNO₂S crystallizes in triclinic space groupP?1 witha=8.1400(5),b=10.0587(8),c=10.8863(7) Å, α=89.927(7), β=110.495(5), γ=96.846(6)⁰,V=828.2(3) ų,Z=2. The structure was refined toR=0.050 for 2653 observed reflections. The benz[f]indole ring system is nearly planar, with mean deviation 0.016 Å, and forms a dihedral angle of 80.93(9)⁰ with the phenyl plane.     

Crystal and molecular structure of indolizine derivative C22H12O2NBr

The crystal structure of indolizine derivative C₂₂H₁₂O₂NBr (1) is studied using X-ray diffraction. The crystals are monoclinic, a = 12.888(3), b = 8.6250(2), c = 15.479(3)Å, β = 101.6(3)°, V = 1685.5(6) ų, Z = 4, space group P2₁/c and R = 0.0722 for 1292 reflections with I > 2σ(I). Single-crystal X-ray diffraction analysis reveals that the molecule 1 is monomeric and contains four six-membered rings and one five-membered ring. The fused four rings are in the same plane, giving rise to conjugative effect. Hydrogen bonds link the monomers into double chain. Short ring interactions with intrañhain π-π stacking are observed (distance between ring centroids is 3.85 Å, and the dihedral angle between their planes is ?8.7°). The data of IR spectroscopy confirm the formation of the structure.     

Copper(II) bis [2-((E)-2-(pyrid-2-yl)ethylimino)methyl)-6-bromo-4-chlorophenolate]

A new complex CuL ₂ [HL = 2-((E)-(2-(pyridin-2-yl)ethylimino)methyl)-6-bromo-4-chlorophenol] was synthesized, and its structure (C₂₈H₂₂Br₂Cl₂CuN₄O₂, Mr = 740.76) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the triclinic system, space group $P\bar 1$ , with a = 5.157(6), b = 12.090(1), c =12.310(1) Å, α = 113.962(2)°, β = 96.7910(10)°, γ = 90.0300(10)°, V = 695.4(8) ų, Z = 1, R = 0.0481. The complex molecules are linked via the weak C-H...N hydrogen bonds, leading to the formation of one dimension (1D) chains along the a axis.     

Structure of a new crystalline modification of 4-amino-5-ethoxymethyl-1,2-dimethylpyrimidinium iodide

The structure of a new crystalline modification (II) of 4-amino-5-ethoxymethyl-1,2-dimethylpyrimidinium iodide, C₉H₁₆IN₃O, the major product of methylation of 4-amino-5-ethoxymethyl-2-methylpyrimidine has been determined. The lattice parameters are a = 6.528(4) Å, b = 15.325(7) Å, c = 12.653(6) Å, γ = 97.57(50)°, sp. gr. P2₁/b, Z = 4, R = 0.0348 (over 1480 independent reflections). The molecule is planar. Its pyrimidine ring has the 2,5-diene structure and shows a weak tendency to adopt the C(2)-sofa conformation. Molecules in the crystal structure are linked into centrosymmetric dimers by N(8)-H?N(3) hydrogen bonds. These dimers, in turn, are linked into a three-dimensional framework by I^?-ions. The structure of modification II is compared with the structures of other 4-aminopyrimidines.     

X-Ray diffraction and IR-spectroscopic studies of UO2(n-C3H7COO)2(H2O)2 and Mg(H2O)6[UO2(n-C3H7COO)3]2

Single crystals of UO₂(n-C₃H₇COO)₂(H₂O)₂ (I) and Mg(H₂O)₆[UO₂(n-C₃H₇COO)₃]₂ (II) are synthesized. Their IR-spectroscopic and X-ray diffraction studies are performed. Crystals I are monoclinic, a = 9.8124(7) Å, b = 19.2394(14) Å, c = 12.9251(11) Å, β = 122.423(1)°, space group P2₁/c, Z = 6, and R = 0.0268. Crystals II are cubic, a = 15.6935(6) Å, space group $Pa\bar 3$ , Z = 4, and R = 0.0173. The main structural units of I and II are [UO₂(C₃H₇COO)₂(H₂O)₂] molecules and [UO₂(C₃H₇COO)₃]^? anionic complexes, respectively, which belong to AB ₂ ⁰¹ M ₂ ¹ (I) and AB ₃ ⁰¹ (II) crystal chemical groups of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₇COO^?, and M ¹ = H₂O). A crystal chemical analysis of UO₂ L ₂ · nH₂O compounds, where L is a carboxylate ion, is performed.     

Effect of the acid-base interactions in a solution on the composition of the coordination sphere of aluminum and gallium complexonates

Hydroxocomplexonate K₂[GaEdta(OH)] · 6H₂O (I) and nitronium salts BH⁺GaEdta · 4H₂O (II) and BH⁺AlEdta · 4H₂O (IV) are synthesized from aqueous solutions at pH 8, 6, and 7, respectively. AlHEdta(H₂O) (III) is isolated from an acid solution (pH 1.5). Structures I, II, and IV are determined by single-crystal X-ray diffraction. The X-ray powder diffraction analysis of III has revealed that its crystals are not isostructural with those of similar complexes of other metals. Crystals I–IV are monoclinic. The unit cell parameters are a = 10.482(1), 15.735(4), 5.768(4), and 15.756(4) Å; b = 10.442(2), 12.511(2), 14.884(11), and 12.453(3) Å; c = 19.590(4), 17.330(5), 19.113(12), and 17.328(6) Å; β = 101.30(2)°, 104.54(2)°, 90.74(5)°, and 104.75(2)° for I–IV, respectively.