Structural and spectral studies of N-trans-cinnamylidene-m-toluidine and N-trans-cinnamylidene-m-chloroaniline

N-trans-cinnamylidene-m-toluidine (1) C₁₆H₁₅N, and N-trans-cinnamylidene-m-chloroaniline (2) C₁₅H₁₂NCl form isomorphous crystals which are monoclinic, space group P2_l/c, with unit cell dimensionsa=5.967(2),b=13.793(3),c=15.048(5) Å, =91.97(3)° anda=5.868(2),b=13.788(4),c=15.191(4) Å, =91.87(3)°, respectively. The single-crystal X-ray structure determinations of the title compounds revealtrans structures. Ring (A) C_10–15 and ring (B) C_1–6, are practically planar in both structures with dihedral angels of 61.3(3) and 63.6(2)°, respectively.¹H nmr, u.v. and i.r. spectra are also reported.     

Structure and spectroscopic properties of the solid complex of 2-ethylpyridine with 2,6-dichloro-4-nitrophenol

The structure of the complex of 2-ethylpyridine with 2,6-dichloro-4-nitrophenol has been determined by X-ray diffraction. The crystals are monoclinic, space group P2₁/c,a=11.134(2),b=7.558(1),c=17.586(2) Å, =104.94(2)° andZ=4. The N⁺-H...O^– bridge of 2.613(2) Å with 相似文献   

Cage-annulated thiacrown ethers and thiacryptands

A series of cage-annulated sulfur-containing crown ethers and cryptands have been synthesized as possible specific metal host systems. The synthesis and structures of seven compounds are described, including a thiacryptand complex with Hg(II). The trishomocubane cage is essentially spherical except for a methylene group, which imparts no steric restrictions, and two disordered superimposed orientations occur in most structures. This superposition of four- and five-membered rings usually cannot be resolved into separate entities, resulting in distorted distances, angles, and thermal parameters for the cage. (3) I4₁ cd, a = 13.207(3) Å, b = 13.207(3) Å, c = 35.876(12) Å; (10) C2, a = 14.551(2) Å, b = 10.028(1) Å, c = 10.491(1) Å, = 107.108(2)°; (14) P2₁/n, a = 10.6277(8) Å, b = 9.8488(7) Å, c = 21.822(2) Å, = 97.945(2)°; (19) P2₁/c, a = 15.381(3) Å, b = 6.667(1) Å, c = 18.158(3) Å, = 94.838(4)°; (25) C2/c, a = 34.386(4) Å, b = 11.318(1) Å, c = 13.409(2) Å, = 110.044(2)°; (28) , a = 10.4487(8) Å, b = 11.5677(9) Å, c = 13.354(1) Å, = 71.042(1)°, = 87.344(1)°, = 65.839(1)°; (29) P2₁/c, a = 10.8138(5) Å, b = 16.4949(8) Å, c = 22.054(1) Å, = 96.087(1)°.     

Molecular structures of two conjugated ene-ynes derived from thiophene

The crystal structures of two conjugated ene-yne derivatives of thiophene are described, 2,5-di-(trimethylsilylethynyl)-3,4-dibromothiophene (1), is triclinic P witha=6.3281(4)Å,b=9.7421(6)Å,c=16.3669(9)Å; =80.516(5)°, =84.810(5)°, =74.072(5)°,Z=2,R=0.054; 2,3,4,5-tetra(trimethylsilylethynyl)thiophene (2), is monoclinic, P2₁/c with a=20.928(2)Å b=5.852(1)Å,c=23.907(2)Å; =100.245(6)°,Z=4,R=0.049. The ethynylic C atoms of both compounds lie near the thiophene plane, with deviations in the range 0.010(3)–0.455(4)Å. The phenyl groups of2 form a dihedral angle of 13.0(4)°.     

Crystal and molecular structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate complex and of two pyrimidine thiones

The crystal structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate (I)a=9.032(2),b=12.458(2),c=18.067(3)Å,=103.25(3)°,Z=4;P2₁/c,R=0.049; 1-phenyl-4,6-dimethylpyrimidine-2-thione (II)a=12.005(3),b=10.090(2),c=9.649(2)Å,=104.4(1)°,Z=4;P2₁/n,R=0.038; and 4,6-dimethylpyrimidine-2-thione (III)a=15.485(3),b=13.255(3),c=7.127(2)Å,=104.3(1)°,Z=8,C2/c,R=0.041 are reported. In (I) the coordination around the cobalt(II) is distorted octahedral involving one ligand moleculevia sulphur and nitrogen atoms and four water molecules. It is relevant that the parameters in the complexed ligand are not different from those found in the uncomplexed one (II), excepting the distances on the nitrogen atom directly involved in the coordination. Bond distances and angles in compound (III) agree with those found in (II).     

The structure of N,N′-bis(2-hydroxyphenyl)butanediamide

The structure of N,N-bis(2-hydroxyphenyl)butanediamide has been determined. The molecule consists of two 2-hydroxyphenyl moieties which are attached (at the 2 position) to the two nitrogens of the butanediamide. The compound C₁₆H₁₆N₂O₄ crystallizes in the monoclinic space group P2₁/c witha=5.576(1),b=4.8853(6),c=25.397(6) Å and =90.58(1)°.     

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 and properties of potential nonlinear optical materials

The synthesis, structure and properties of four ferrocene derivatives of 2-amino-1,2,3-triazole are reported. Solvatochromism is used as a screening process to assess the potential nonlinear optical behavior of these compounds. In general, this technique involves a number of assumptions, which may not be valid for organometallic complexes. Compound 3 crystallizes in space group P-1 with cell dimensions a = 5.771(2), b = 19.048(5), c = 19.343(5) Å and = 61.104(4), = 88.410(5), = 89.858(5)°; compound 5 crystallizes in space group P2₁/c with cell dimensions a = 12.545(2), b = 13.308(2), c = 20.513(4) Å and = 104.035(3)°; compound 9 crystallizes in space group P2₁/n with cell dimensions a = 12.599(4), b = 14.734(4), c = 13.619(5) Å, and = 107.63(2); compound 11 crystallizes in space group P-1 with cell dimensions a = 7.638(3), b = 9.619(4), c = 12.692(5) Å and = 77.588(7), = 78.416(7), = 71.357(7).     

Synthesis and structure of the molecular complex between N-(N′, N′-dimethylaminopropyl)phenothiazine hydrochloride and 7,7,8,8-tetracyano-p-quinodimethane (DAPP-TCNQ)

Synthesis, spectroscopic, and X-ray structural analysis of the molecular complex between the N-(N, N-dimethylaminopropyl)phenothiazine hydrochloride, monohydrate, (DAPP) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ), has been carried out. Crystals of C₂₉H₂₇N₆OSCl are monoclinic, P2₁/c,a=12.190(2),b=7.695(2),c=28.928(3)Å, =91.68(1)°. The molecular complex consists of DAPP as donor binding to TCNQ as acceptor by the thiazine central ring and one of the aromatic rings stacking in parallel planes along thec-axis with an interplanar separation of 3.24Å and 3.16Å, respectively. The electronic and epr spectra of the complex are discussed.     

Crystal and molecular structures of two polymorphic forms of dimethyl-N-(2-ethylphenyl)-phosphoramidate (I) and dimethyl-N-(2,6-dimethylphenyl)-phosphoramidate (II)

The crystal structures of the phosphoric amides dimethyl-N-(2-ethylphenyl)-phosphoramidate (I) and dimethyl-N-(2,6-dimethylphenyl)-phosphoramidate (II) have been determined by direct methods and refined by full-matrix least squares. Compound (I) crystallizes in two polymorphic forms, both monoclinicP2₁/c, but with different cell parameters. Parameters for compound (I) are: FormA:a=10.878(5),b=8.890(4),c=25.11(1) Å,=92.18(2)°; FormB:a=7.071(4),b=17.059(9),c=10.221(5) Å,=97.07(2)°. Compound (II) is also monoclinicP2₁/c witha=8.453(4),b=14.231(7),c=10.283(5) Å,=108.95(2)°. Compound (I) exists as a hydrogen-bonded dimer, whereas compound (II) exists as a hydrogen-bonded polymeric species.     

The disordered structure of (p-tolythiomethyl)triphenylgermanium

The disordered crystal structure of Ph₃GeCH₂SC₆H₄Me has been determined in space groupC2/c with cell dimensionsa=16.916(8),b=11.110(8),c=24.217(16)Å, and -98.86(2)°. The structure can be represented by two overlapping images which are only partially resolved. The germanium atom is in a distorted tetrahedral environment and refinement converged atR=0.049. The crystal structure of a similar organogermanium compound, Ph₃GeCH₂SO₂C₆H₅, which crystallizes in space group Cmca witha=11.037(2),b=17.077(3), andc=23.016(6)Å, is also shown to be highly disordered.     

The crystal and molecular structures of highly substituted cubanes: 1,2,4,7-tetra(carboxymethyl)cubane and 1,2,3,5,7-penta(carboxymethyl)cubane

The structures of the title compounds, 1,2,4,7-tetra(carboxymethyl)cubane 1 and 1,2,3,5,7-penta(carboxymethyl)cubane2, have been determined.1 crystallized in the space group with cell dimensionsa=6.098(2),b=10.686(2),c=13.459(2) Å, =69.82(1), =77.01(1), =74.00(1)°, while2 crystallized in the monoclinic space group P2₁/c with cell dimensionsa=15.139(2),b=12.775(1),c=9.849(2) Å, =107.01(1)°. These molecules were derived from their parent carboxylic acids by esterification with methanol. They are unusual for several reasons. The first is that they both contain substituents on adjacent carbon atoms in the cubane framework. There are only a few reports in the literature of this type of cubane structure. The second molecule is unique in that it has five substituents attached to a cubane moiety. This is the one of the few cubane derivatives with more than four substituents to be structurally characterized and results in a cubane molecule in which there are three faces with three substituents and three faces with only two substituents.     

Structure of (Z)-1-p-methoxyphenyltelluro-1,4-diphenyl but-1-en-3-yne

C₂₃H₁₈TeO,M _r=437.97, ,a=9.940(2),b=13.664(3),c=7.895(2) Å, =80.60(1), =69.71(2), =75.95(1)°,V=972.0(4) ų,Z=2,R=0.041 for 2668 observed reflections. The Te–C bond distances are 2.109(5)Å and the C–Te–C angle is 96.0(2)°. The phenyl rings are planar to within experimental accuracy, making dihedral angles of 64.6(2), 65.3(2) and 31.1(3)°.     

Molecular and crystal structures of a tricyclic γ-lactam ketone and its Mannich base

A tricyclic -lactam ketone, 1,10a-Dihydropyrrolo[1,2]isoquinoline-3,10(2H,5H)-dione, and its corresponding Mannich base, 10a-(Dimethylaminomethyl)-1,10a-dihydropyrrolo[1,2b]isoquinoline-3,10(2H,5H)-dione hydrochloride, have been synthesized. The molecular and crystal structures of both compounds were studied by NMR-spectroscopy and X-ray crystallography. Unit cell parameters are:a=8.799(7),b=7.137(6),c=16.156(8)Å,=76.28(5)°, space groupP2₁/c forthe first compound, anda=15.343(9),b=7.490(6),c=13.465(8) Å,=110.98(3)°, space groupP2₁/c for the second. The structures were refined to discrepancy factorsR=0.068 for 1261 andR=0.047 for 2138 observed CuK data, respectively. The conversion of the tricyclic -lactam ketone to its corresponding Mannich base does not affect thecis configuration between the fused tetrahydropyridine and -lactam rings, but does result in conformational changes in both rings.     

Structures of Z-(nitrostilbene)chromium tricarbonyl complexes: The effect of metal coordination on the nonplanarity of the stilbene system

The structures of the nitrostilbene complexes Z-(4-R–C₆H₄–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃ (R=Me₂N,1; H,2; F₃C,3), are reported. The copounds were prepared as part of a study of the synthesis of organometallic complexes with potential nonlinear optics applications. For Z-(4-Me₂N–C₆H₄–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃,1, triclinic, ,a=7.214 (3) Å,b=7.340 (3) Å,c=17.238 (9)Å, =88.23 (5)°, =88.76 (4)°, =87.66 (3) °,Z=2. For Z-(C₆H₅–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃,2, monoclinic, P2₁/C,a=12.255 (3) Å,b=9.415 (1) Å,c=13.579 (4) Å, =105.60 (2)°,Z=4. For Z-(4-F₃C–C₆H₄–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃,3, triclinic, ,a=7.094 (2) Å,b=8.057 (5) Å,c=17.295 (9) Å, =87.95 (5)° =85.94 (4)°, =64.24 (5)°,Z=2. The structural data show that the Z isomers exhibit bond lengths and angles similar to those observed in the E isomers, but the stilbene fragment is considerably more nonplanar. As a consequence, these molecules are unlikely to behave as NLO materials.     

Crystal structure ofcis-diaqua bis(2,2′-bipyridyl)chromium(III) nitrate, [Cr(bipy)2(H2O)2] (NO3)3

cis-Diaquabis(2,2-bipyridyl)chromium(III) nitrate crystallizes in the mono-clinic system, space groupP2₁/c, witha=16.102(6),b=10.792(5),c=15.076(6) Å,=112.90(5)°, andZ=4. The saltlike structure was determined from X-ray crystallography and refined toR=7.5% for 3342 observed reflections. The Cr atom is octahedrally surrounded by twocis water molecules and by two chelated 2,2-bypiridyl ligands forming two nearly orthogonal planes. Selected bond distances are: Cr-O, 2.00(1) and 1.98(1) Å, Cr-N, 2.04 Å (mean).     

Crystal structures and energy refinement of some 2,2′-disubstituted biphenyl compounds

Synthesis and structural determination by X-ray crystallography of three substituted biphenyl structures are reported: (2) is monoclinic P2₁/n witha=10.805(4),b=8.079(3),c=16.232(6)Å, =100.96(5)°: (4) is monoclinic P2₁/n witha=9.966(3),b=10.007(3),c=13.053(4) Å, =96.74(5)°; (5) is triclinic witha=12.033(5),b=16.903(8),c=9.752(4)Å, =94.70(3)°, =112.56(3)° =76.12(3)°. In all compounds the biphenyl has two identical substituents in an ortho position to the center inter-ring bond and present variable inter-ring twist angles. In the process of investigating molecular geometry, we are interested in studying whether the calculated conformations of our molecules can fit the crystallographic structures.     

Crystal and molecular structure of dihydro-8b,8c-diphenyl-1H,3H,4H,5H,7H,8H,-2,6-dioxa-3a,4a,7a,8a-tetraazacyclopenta[def]fluorene-4,8-dithione

The title compound C₂₀H₁₈N₄O₂S₂ crystallizes in the monoclinic space group P2₁/n witha=8.4930(1) Å,b=11.4880(1) Å,c=20.0709(2) Å, =94.933(1)°,V=1951.01(3) ų,Z=4. The crystal structure has been solved by vector search methods and refined by fullmatrix least-squares toR=0.04 for 2888 reflections and 116 restraints. The title compound has a suitable geometry for synthesizing receptor molecules with a cleft for selective complexation.     

Molecular structure of [CpRu(PPh3)2(C6H11SH)]BF4·CH2Cl2

The structure of the [CpRu(PPh₃)₂(C₆H₁₁SH)]BF₄·CH₂Cl₂ complex was determined by X-ray diffraction techniques; triclinic space group ,a=12.567(1),b=13.409(1),c=14.733(1) Å, =95.380(7), =111.041(7), =96.454(8)°,V=2278.5(4) ų,Z=2,R=0.056,R _w=0.088. The Ru is attached to two triphenylphosphine ligands, a cyclopentadienyl and the S atom of the cyclohexylthiol. The Ru–S distance is 2.389(2) Å and the S–H distance is 1.23 Å.     

Structure of 1-ethyl-2-(2′-chloro-4′-nitrostyryl)benzimidazole

The title compound C₁₇H₁₄ClN₃O₂ (et-4-nsbiz) is monoclinic, witha=12.240(2),b=12.144(4),c=10.544(4)Å,=100.09(2)°,V=1543(1)ų,Z=4,D _x =1.411 g cm^–3, (MoK)=0.71073Å,=2.57 cm^–1,F(000)=680,M _r =327.77,T=298K. The structure was solved by heavy atom and Fourier methods and refined toR=0.049 for 1503 unique observed reflections in space groupP2₁/c. Except for the ethyl group, the molecule is almost planar, with a dihedral angle of 9.5(5)° between the benzimidazole and phenyl rings. The dihedral angle between the ethyl group and the benzimidazole ring to which it is attached is 91.5(2)°.