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)°.     

Complexation with diol host compounds. Part 3. Molecular inclusion of 4-methylcyclohexanone and 2-methylcyclohexanone by the host,trans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene

The structures of the 12 molecular complexes oftrans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with 4-methylcyclohexanone (1) and with 2-methylcyclohexanone (2) have been determined by X-ray crystallography. The crystal data are as follows: Compound (1):P2₂/c,a=8.838(2) Å,b=8.92(1) Å,c=20.879(8)=Å,=98.67(2)°,V=1627(2) ų,Z=2 andR=0.062 for 2201 unique MoK reflections; Compound (2):P¯1,a=8.917(3) Å,b=9.900(2) Å,c=11.250(4) Å,a=68.72(2)°,=64.39(3)°, =74.86(2)°,V=828.1(5) ų,Z=1 andR=0.098 for 2563 unique reflections. Both inclusion compounds exhibit O-HO=C hydrogen bonding interactions. The thermal properties of these compounds have been characterized by DTA and TGA thermograms.     

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)°.     

Synthesis and crystal structure of 1-vinyl-cis-2,3-diphenylaziridine

1-Vinyl-cis-2,3-diphenylaziridine, C₁₆H₁₅N, has been synthesized and characterized by spectroscopic methods and single crystal X-ray analysis. The structure was studied at room temperature (2a) (18°C) and at low temperature (2b) (–70°C). The title compound crystallizes in the space group Cm with Z=2 showing no phase transformation between the two temperatures. The cell parameters area=8.258(3),b=15.880(3),c=5.827(2)Å, =122.32(2)° for (2a) anda=8.188(2),b=15.762(3),c=5.724(1)Å, =121.57(2)° for (2b). Both the studies show nearly the same conformation. With the exception of the vinyl group, the molecule hasm symmetry, so, the asymmetric unit is half a molecule. The mirror plane of the space group cuts the aziridine ring through the N atom. The vinyl group is distributed on two symmetrical positions by means of the same mirror plane. In this way, the crystal is built with the two diastereoisomers of the title compound.     

Crystal structure of 751-1751-1751-1751-2751-2751-2

The title compound crystallizes in the centrosymmetric triclinic space group (No. 2) witha=10.818(1)Å,b=10.876(1)Å,c=11.072(2)Å, =98.74(1)°, =98.83(1)°, =96.61(1)°,V=125906(3)ų andZ=2. Interatomic distances include Fe–P=2.243(2)Å, Fe–CO=1.771(6)–1.781(5)Å, Fe–C(C₅H₅)=2.074(6)–2.103(5)Å and P–F=1.511(6)–1.571(4)Å.     

An X-ray study of some 2,3-diphenyltetrazolium salts

An X-ray diffraction study is reported for three molecules of salts containing a cation with a positive charged 2,3-diphenyltetrazolium ring. The results confirm aromatic structure of the tetrazole ring and the delocalization of charge on the whole molecules of the cations. The molecular geometry obtained is compared with that for free mesoionic 2,3-diphenyltetrazoles which have already been studied and the ring parameters do not reveal significant differences. But is shows that the geometry of the (NNO)^– exocyclic group is changed as a result of alkylation. Compound I C₁₃H₁₂N₅Cl, P2₁/a,a=16.934(4),b=6.575(1),c=26.121(4) Å, =108.15(2)°, II C₁₄H₁₃N₆OI, P3₁2,a=10.774(3),c=12.821(4) Å, IV C₂₆H₂₀N₈Cl₂, C2/c,a=22.316(4),b=6.6903(7),c=20.437(3) Å, =92.51(1)°.     

Crystal structure of DMAP-C-HMTCAQ,C30H20N6O2, N,N-dimethylaminophenyl-carbamate-2′-hydroxymethyl-11,11,12,12-tetracyano-anthraquinodimethan

C₃₀H₂₀N₆O₂,M _r =496.53, triclinic, P¯1,a=8.748(4) Å,b=10.989(3) Å,c=13.541(8) Å,=90.67(4)°,=99.15(4)°, =98.62(4)°,V=1269.8 ų,Z=2,D _c =1.30 g cm^–3, (Mo K)=0.71069 Å,=1.02 cm^–1,F(000)=516.0,T=295(3) K,R=0.127% for 1839 observed reflections, 363 parameters. The molecule has an extended, rather than a folded geometry. The HMTCAQ moiety has mm symmetry, and is shaped like a hawk about to land. The anthraquinone ring system is folded, with a dihedral angle of 37.3°; the two propanedinitrile groups have a mutual dihedral angle of 80.2°. The dihedral angle between the central ring of the TCAQ moiety and the phenyl ring is 37.2°. The phenyl rings stack over each other with a perpendicular distance of 3.36 Å. The dipole moment of the molecule is 6.254 Debyes; the crystal Madelung energy isE _M=–8.989 kJ/mol; the dispersion energy isE _d =–318.370 kJ/mol; the repulsion energy isE _r =130.139 kJ/mol.On leave at Department of Chemistry, University of Alabama, Tuscaloosa, Ala. 35487-9671.     

Crystal and molecular structure oftrans-1-benzylidene-1,2,3,4-tetrahydronaphthalene

The compound C₁₇H₁₆ crystallizes in the triclinic space groupP¯1 witha=6.719(1),b=11.598(2),c=8.757(2) Å, =108.54(2),=97.58(1), =97.40(1)°,Z=2. The structure was determined by direct methods and refined by full-matrix least squares toR=0.045 for 1012 reflections. The molecule adopts thetrans configuration. The cyclohexenylidene ring has the half-chair conformation.     

X-ray crystal structure of the 1∶2 triethyleneglycol dimethyl ether (triglyme): Dichloropicric acid adduct

The anhydrous 12 triglyme:Dichloropicric acid adduct is triclinic, space group ; at 24°Ca=8.703(5),b=10.381(4), c=10.404(3) Å, =114.42(3), =99.69(5), =106.40(6)°,D _x=1.656 g cm^–3, V = 776(2)ų,Z=1. Bond lengths and angles are normal except that one C–C–O–C torsion angle in the triglyme is approximately 90° rather than the expected 60 or 180°. Each phenolic OH group hydrogen bonds with a terminal OCH₃ of the polyether. The O...O distance, 2.557(3) Å, is in fair agreement with the 2.52 Å estimated from the single observed IRv (OH) stretch at 1714 cm^–1.     

Influence of the spectator cation on the structure of anionic pyridine-2,6-dicarboxylato complexes of cobalt(II), nickel(II), and copper(II)

The structures of anionic pyridine-2,6-dicarboxylato (pdc^2–) complexes of cobalt, nickel, and copper have been studied. The stoichiometries and structures are very much dependent on whether KOH, Et₄NOH, or NaOH is used in the synthesis to deprotonate the H₂pdc ligand. Crystallographic results are: (1) K₂[Co(pdc)₂] · 7H₂O, orthorhombic, Pnna, Z = 4, a = 20.637(2)Å, b = 13.480(1)Å, c = 8.200(1)Å (2) K₂[Ni(pdc)₂] · 7H₂O, orthorhombic, Pnna, Z = 4, a = 20.648(1)Å, b = 13.375(1)Å, c = 8.2393(8)Å (3) [Co₂(H₂O)₅(pdc)₂] · 2H₂O, monoclinic, P2₁/c, Z = 4, a = 8.3880(6)Å, b = 27.384(2)Å, c = 9.6110(8)Å, = 98.271(6)° (4) [Ni(Hpdc)₂] · 3H₂O, monoclinic, P2₁/c, Z = 4, a = 13.679(1)Å, b = 10.0450(9)Å, c = 13.767(2)Å, = 115.184(7)° (5) Na₆[Co(H₂O)₆][Co(pdc)₂]₄ · 28H₂O, monoclinic, P2₁/n, Z = 2, a = 13.363(1)Å, b = 8.437(1)Å, c = 40.689(3)Å, = 91.288(5)° (6) Na[Ni(Hpdc)(pdc)] · 11.5H₂O, monoclinic, C2/m, Z = 4, a = 15.200(2)Å, b = 22.299(2)Å, c = 8.3596(7)Å, = 118.894(7)° (7) Na[Cu(Hpdc)(pdc)] · 3H₂O, monoclinic, P2₁/n, Z = 4, a = 9.516(4)Å, b = 14.917(6)Å, c = 12.247(5)Å, = 92.00(5)°. The potassium and sodium complexes have extensive K⁺—H₂O and Na⁺—H₂O networks. The fact the Et₄N⁺ ion does not appear in any of the complexes is likely due to the fact that it is incapable of forming the intricate cation—water and hydrogen-bonding networks observed in all of the other structures.     

Studies of systemic acylanilide fungicides. Part I. Crystal structure and molecular conformation ofdl-methyl-N-(2,6-dimethylphenyl)-N-(2-methoxyacetyl) alaninate

The crystal structure of metalaxyl (C₁₅H₂₁NO₄) was determined by three-dimensional X-ray analysis from diffractometer data. The crystals are monoclinic,P2₁/c,a=7.851(3) Å,b=13.119(10) Å,c=15.107(7) Å,=101.71(6)°,Z=4,D _x=1.218 g cm^–3, (MoKa)=0.095 mm^–1. FinalR=0.079 for 1203 observed reflections. The dimethylphenyl ring is almost perpendicular to the amidic plane of the molecule.     

Crystal and molecular structure of the photocatalyst tris(2,2′-bipyrazine)ruthenium(II) hexafluorophosphate

The X-ray structure determination of the complex tris(2,2-bipyrazine)ruthenium(II) hexafluorophosphate, [Ru(C₈N₄H₆)₃](PF₆)₂, has shown that the compound crystallizes in the monoclinic space group P2₁/c witha=13.459(5),b=23.486(8),c=17.913(10) Å,=139.85(1)°, andZ=4. Each asymmetric unit also contains one dimethylformamide and one water molecule. Least-squares refinement led to an R factor of 0.074 based on 3463 reflections for which I>2(I). The [Ru(C₈N₄H₆)₃]²⁺ cation has no crystallographic symmetry, but the requirements for point symmetry 32 are nearly met. The six Ru-N bond lengths agree within experimental error and have an average length of 2.05(1) Å.     

X-ray study of two 1-substituted 3-acylamino-2-pyrazolines

The previously reported IR study on 21 different 1-substituted 3-acylamino-2-pyrazolines assumed thecis configuration for the amide groups. In order to establish the configuration, X-ray structure determinations of two model compounds (1-phenyl-3-benzoylaminopyrazoline, monoclinic,a = 5.218,b = 8.830,c = 14.372 Å, = 90.7 °,Z = 2, P2 ₁; 1-benzyl-3-acetaminopyrazoline, monoclinic,a = 9.529,b = 13.679,c = 18.112 Å, = 96.7 °,Z = 8,P2₁/n) were performed. Both structures were solved by direct methods, and refined to a finalR = 0.075 for 710 andR = 0.122 for 2140 observed reflections. The configurations of the amide groups were found to betrans.     

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 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.     

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 structures of two azo compounds, 2-methyl-2-(4-bromphenylazo)-1,3-indandione and 2-methyl-2-(4-ethoxyphenylazo)-1,3-indandione

In the two title compounds, the 2-methyl-1,3-dioxoindan-2-yl and 4-(brom; ethoxy) phenyl groups aretrans with respect to one another. The phenyl ring and the azo group are not coplanar in the two molecules. The five-membered rings of the two compounds adopt an envelope conformation. The crystallographic parameters are as follows: 2-Methyl-2-(4-bromphenylazo)-1,3-indandione (I): monoclinic, P2₁/a witha=8.098(2),b=14.442(2),c=12.554(1)Å, =100.55(2)^o, andD _calc=1.58 g cm^–3 forZ=4; 2-methyl-2-(4-ethoxyphenylazo)-1, 3-indandione (II): monoclinic, P2₁/a witha=8.258(2),b=14.449(1),c=13.559(2)Å, =101.19(1)^o, andD _calc=1.29 g cm^–3 forZ=4.     

Crystal and molecular structure of palladium(II), copper(II) and zinc(II) complexes of 1-methyl-3-(4-methyl)phenyltriazen-1-oxide

The structures of palladium(II), copper(II) and zinc(II) bis(chelates) of 1-methyl-3-(4-methyl)phenyltriazen-1-oxide have been determined by single-crystal X-ray methods. The crystals of [Pd(OMeN₃C₆H₄Me-4)₂] (I) are triclinic witha=7.410(3),b=7.806(3),c=8.371(2) Å, =65.80(2), =88.73(3), =81.04(3)°,Z=1, space group . The crystals of [Cu(OMeN₃C₆H₄Me-4)₂] (II) are monoclinic,a=14.934(5),b=10.111(4),c=11.762(3) Å, =96.00(2)°,Z=4, space group P2₁/c. The crystals of [Zn(OMeN₃C₆H₄Me-4)₂] (III) are triclinic witha=7.912(2),b=10.056(2),c=11.600(2) Å, =87.31(3), =74.96(3), =74.02(3)°,Z=2, space group . The structures of (I), (II), and (III) were solved to final values ofR=0.029, 0.043 and 0.034, respectively. A planar structure has been found for (I), (II) exhibits a tetrahedrally distorted square planar structure, whereas (III) is tetrahedral. The crystals of all three complexes are held by networks of stacking interactions.     

Crystal structure of two lipophilic antifolates: 2,4-diamino-5-(n-hexyl)-6-methylpyrimidine and 2,4-diamino-5-(n-heptyl)-6-methylpyrimidine ethanesulfonate

The 5-hexyl (I) and the 5-heptyl (II) analogs of 2,4-diamino-6-methylpyrimidine both crystallize in the space groupP2₁/c withZ=4. Unit cell parameters of I are C₁₁H₂₀N₄·H₂O,a=17.204(3),b=4.609(9),c=16.765(2)Å,= 91.53(2)°; those of II are C₁₂H₂₃N₄ ⁺·C₂H₅SO₃ ^–,a=12.489(1),b=16.702(2),c=8.9558(7)Å,=99.208(8)°. The molecular packing of I contains one water, while II forms a salt with ethanesulfonic acid. The alkyl chain of I adopts an alltrans conformation; in contrast, II has onegauche orientation between carbons 2 and 3 of heptyl. These are the first structural data on two alkyl lipophilic antifolates with antineoplastic activity.