Crystal and molecular structure of tetra-n-butylammoniumbis(stilbenedithiolato)-nickelate(III)

The crystal and molecular structure of the title compound, C₄₄H₅₆NS₄Ni, are reported. Crystals are triclinic, space groupP¯1 (No. 2) withZ=2 in a unit cell of dimensionsa=8.874(2) Å,b=9.549(5) Å,c=26.025(7) Å,=97.22(3)°,=95.06(2)°, and=98.75(3)°. The structure was solved by Patterson and Fourier methods and refined by full-matrix least squares toR=0.062 for 2910 unique diffractometer data. The metal atom of the anion has an approximate square-planar configuration and the nitrogen atom of the cation an approximate tetrahedral configuration. The anions as well as the cations are well separated, the closest NiNi and NN approaches being the lattice repeat of 8.874(2) Å.     

4- and 5-nitroindane

Mononitration of indane produces a mixture of 4- and 5- nitroindanes. Crystallization from mixtures occurs after distillation improves composition of a major component to above 80%. 4-Nitroindane: triclinic, space group (#2),a=7.332(4) Å,b=8.304(4) Å,c=8.358(4) Å, =61.43(4)°, =67.60(4)°, =70.15(4)°,V=405.4(4) ų,Z=2. Non-H-atoms are nearly planar, aliphatic H's are eclipsed. 5-Nitroindane: monoclinic, space groupP2₁/c (#14),a=10.946(8) Å,b=15.643(10) Å,c=9.415(6) Å, =92.34(5)°,V=1611(2) ų,Z=8. Non-H-atoms in the two molecules differ in torsion of the nitro group with respect to indane and fold of the nonbenzylic methylene group. Semiempirical calculations (PM3) suggest that distorsion from planarity may be associated with the two lowest energy vibrational modes. Uv, ir, ms, proton, and¹³C-nmr spectra are correlated with the solid state structures.     

A comparison of the coordination preferences of Zn, Co, and Cd(II) with the heteroscorpionate ligand (2-hydroxy-3-t-butyl-methylphenyl)bis (3,5-dimethylpyrazolyl)methane

Reaction of the Zn, Cd, or Co nitrate salts with the deprotonated ligand (2-hydroxy-3-t-butyl-methylphenyl)bis(3,5-dimethylpyrazolyl)methane (L1O^–) in methanol produced the following complexes: [(L1OH)Zn(NO₃)₂] in two isomorphs, a = 40.983(8) Å, b = 9.571(2) Å, c = 15.667(8) Å, = 90, = 106.38(1), = 90, C2/c, and a = 13.027(3) Å, b = 14.781(4) Å, c = 16.107(3) Å, = 90, = 105.30(1), = 90, P2₁/n; [(L1OH)Cd(pz)(NO₃)₂] a = 14.7476(2) Å, b = 13.5411(2) Å, c = 16.7223(2) Å, = 90, = 110.3840(10), = 90, P2₁/c; and [(L1O)Co(pz)(NO₃)] a = 11.4240(2) Å, b = 13.4498(2) Å, c = 13.8056(2) Å, = 105.2080(10), = 105.8130(10), = 112.7470(10), P . The Zn adopts a pseudotetrahedral four-coordinate geometry where the potentially tridentate ligand is actually bidentate with a protonated and uncoordinated phenoxy arm. The Co complex is pseudooctahedral six-coordinate where the phenoxy arm is deprotonated and coordinated. Finally the Cd complex is seven-coordinate but the metal is not coordinated through the phenoxy group that is again protonated.     

Crystal structure and conformation of N-(t-butoxycarbonyl)-L-isoleucyl-L-alanine benzylester

C₂₂N₂O₅H₃₂,M _r =404.5, monoclinic,C2,a=21.781(5),b=5.065(1),c=22.333(4)Å,=112.81(2)°,V=2271.1(9)ų,D _calc=1.148 g cm³, (CuK )=1.5418 Å,=5.89 cm^–1,F(000)=848, room temperature,R=0.058 for 2178 unique reflections [I2.5(I)]. The peptide linkage is in thetrans conformation. The molecule adopts the-sheet structure. The crystal structure is stabilized by a three-dimensional network of N-HO and C-HO hydrogen bonds.DCB Contribution No. 813.     

Crystal structure of bis-(rhodanine)copper(I) iodide,C6H6CuIN2O2S4

The structure of the polymeric rhodanine compound, C₆H₆CuIN₂O₂S₄, was determined by X-rays.M _r =456.8, monoclinic, space groupP2₁/c,a=4.1947(7),b=17.6999(12),c=17.1048(8) Å,=96.15(1)°,V _c =1262.6 ų,Z=4,D _c =2.40Mg m^–3, CuK radiation (graphite crystal monochromator, =1.54056 Å),(CuK)=278.9 cm^s-1,F(000)=872,T=290 K. Final conventionalR-factor=0.029, andR _w =0.044 for 2384 unique reflections and 153 variables. The structure was solved using Patterson methods andDirdif, and refined by full-matrix least-squares methods. The compound forms zigzag chains alonga. The copper atom is in trigonal pyramidal coordination, with two sulfur atoms of the thiocarbonyl group and two bridging iodine atoms. The copper-sulfur distances are 2.278(1) and 2.299(1) Å, and the copper-iodine distances are 2.657(1) and 2.814(1) Å.     

Studies of systemic acylanilide fungicides. Part IV. Crystal structure and molecular conformation ofN-(2-methoxyacetyl)-N-(2,6-xylyl)-α-amino-γ-butyrolactone

The crystal structure of the title compound (C₁₅H₁₉NO₄, MW 277.3 amu) was determined by three-dimensional X-ray analysis from diffractometer data. Crystal data are: monoclinic,P2₁/n,a=9.600(3) Å,b=11.964(6) Å,c=12.802(4) Å,=101.25(3)°,V=1442.1(16) ų,Z=4;D _x =1.277 Mg m^–3;(MoK)=0.10 mm^–1. FinalR=0.055 for 1686 observed reflections having 2 (MoK)<50° andI>2.5 (I). The compound is isostructural withN-(2-methoxyacetyl)-N-(2,6-xylyl)-3-amino-1,3-oxazolidin-2-one. The dimethylphenyl ring is almost perpendicular to the amidic plane of the molecule (dihedral angle 81.9°); the butyrolactone ring is in the typical envelope conformation.     

Crystal structure,physical and photophysical properties of a platinum(II) complex coordinated to the biphenyl dianion and cyclooctadiene

The complex, Pt(bph)(COD), where bph is the biphenyl dianion and COD is 1,5-cyclooctadiene, crystallizes in the orthorhombic space groupPbca witha=12.178(4) Å,b=9.693(3) Å andc=25.344(9) Å andZ=8. The Pt–C distances to the olefinic carbon atoms that result from the electron donation of the COD ligand are in the range 2.20(3)–2.27(3) Å and the Pt–C distances to the bonded bph ligand are shorter at 2.01(3)–2.03(2) Å. The lowest energy absorption of the complex is at 383 nm (=1.2×10³). The emission spectrum is structured in fluid solution at room temperature with the emission energy maximum at 537 nm, _cm, and =1.93 s. Temperature dependent emission lifetime measurements result in ak _o value of 2.69×10⁴, a preexponential factor of 2.47×10⁶ and a E₁ value of 324 cm^–1.     

Crystal structure of (diphenyl)(morpholino)phosphiniminocyclotrithiazene

The title compound (C₆H₅)₂(OC₄H₈N)P=N–S₃N₃ crystallizes in the space group with unit cell parametersa=9.3900(2),b=9.4747(1),c=11.3850(3) Å, =95.73(4), =96.85(6), =104.26(2)^o, and Z=2. The tricoordinated sulfur of the cyclotrithiazene ring deviates from the mean plane of other skeletal atoms by 0.683(4) Å. The angle at this atom is the smallest in the ring and is enclosed by the longest S–N bonds observed in the ring.     

Structure oftrans-difluorobis(1,3-propanediamine)chromium(III) perchlorate,trans-[Cr(N2C3H10)2F2](C104)

The title compound is monoclinic,M _r =337.8,P2₁/c-C _2h ⁵ (No. 14),a=5.508(2),b=13.944(6),c=18.238(5) Å,=95.99(3)°,V=1393.1(9) ų,Z=4,D _x =1.61 g cm^–3, (MoK)=0.71073 Å,F(000)=660.0,=10.3 cm^–1, finalR=0.051 for 2122 observed [I>3(I)] reflections. The two six-membered rings resulting from the coordination of the 1,3-propanediamine ligands to the chromium atom are in the chair conformation. The Cr-N and Cr-F distances average 2.085(4) and 1.876(3) Å, respectively.     

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.     

Crystal structures of five policyclic compounds related to the natural product forskolin

(3(Z),4,6a,9a,9b)-(±)-3a,4,6a,7,8,9,9a,9b-octahydro-4,7,7, 9b-tetramethyl-3a-[3-(methoxymethyloxy)-3-methyl-1-butenyl]-5H-naphto[1,8-de]-1,3-dioxin-6-one (I), C₂₂H₃₆O₅,M _r=378.51, monoclinic,P2₁/n,a=6.330(1),b=14.576(2),c=22.837(2)Å,=93.04(1)°,V=2104.1(2)ų,Z=4,D _c=1.19 Mg/m³, (MoK)=0.71069Å,=0.8 cm^–1,F(000)=832,T=298 K,R=0.054 for 1971 observed reflections; (7a,10a,10b,12)-(±)-7a,9, 10,10a,10b,11,12,12a-octahydro-2,2,10,10,10b,12a-hexamethyl-2H,8H-1-benzopyrano[4a,5,6,-de][1,3,2]-benzodioxin-11-one (II), C₂₀H₂₉O₄,M _r=334.5, triclinic,P-1,a=10.595(2),b=12.152(1),c=8.073(1)Å,=106.53(1),=105.65(1), =66.29(1)°,V=897.9(2)ų,Z=2,D _c=1.24 Mg/m³, (MoK)=0.71069Å,=0.8 cm^–1,F(000)=362,T=298 K,R=0.046 for 2848 observed reflections; (7a,10a,10b,12, 12a)-(±)-7a,9,10,10a,10b,11,12,12a-octahydro-2,2,10,10,10b,12a-hexamethyl-2H,8H-1-benzopyrano[4a,5,6-de][1,3,2]-benzodioxin-11, 12-diol (III), C₂₀H₃₂O₅ (two molecules in the asymmetric unit),M _r=352.2, triclinic,P-1,a=12.948(3),b=13.615(3),c=12.197(4)Å,=101.16(2),=111.88(2), =69.48(2)°,V=1863.8(9)ų,Z=2,D _C=1.26 Mg/m³,(MoK)=0.71069 Å,=0.8 cm^–1,F(000)=768,T=298 K,R=0.060 for 4570 observed reflections; 4-acetoxy-4-[[(4a,5,8a)-(±)-hexahydro-4a,6,6-trimethyl-4H-1,3-benzodioxin-4-one]-5-yl]butan-2-one (IV), C₁₇H₂₆O₆,M _r=326.4, monoclinic,P2₁/c,a=10.495(2),b=12.050(2),c=14.216(2)Å,=108.51(1)°,V=1704.8(5)ų,Z=4,D _c=1.27 Mg/m³,(MoK)=0.71069 Å,=0.9 cm^–1,F(000)=704,T=298 K,R=0.049 for2455 observed reflections; (3a,4,5,6,6a,9a,9b)-(±)-4,5-epoxy-decahydro-3, 3a-dihydroxy-2-ethoxy-4,7,7,9b-tetramethyl-naphto-[1,8-bc]-pyran-6-ol-acetate (V), C₂₀H₃₂O₇,M _r=383.5, monoclinic,C2/c,a=10.353(2),b=17.975(3),c=21.188(3)Å,=91.29(1)°,V=3942(1)ų,Z=8,D _c=1.29 Mg/m³,(MoK)=0.71069 Å,=0.8 cm^–1,F(000)=1664,T=298 K,R=0.051 for 2120 observed reflections. We report here the complete structures of four decalin derivatives (compoundsI, II, III, V) and one related compound (compoundIV) synthetized in order to find an efficient synthetic approach for the natural productforskolin.     

Crystal and molecular structure of 3-dimethylaminobenzoic acid

The title compound C₉H₁₁NO₂ is triclinic, space group P¯1, with the cell dimensionsa=7.022(1),b=7.476(2),c=8.957 (1) Å,=87.02(2),=110.88(1),=99.10(1)°,V=433.8(4) ų,Z=2,M _r =165.2,Do=1.27,Dx=1.26 mg/m³,F(000)=176,T=293 K,R=0.057 for 939 observed reflections. The molecules are packed as centrosymmetric hydrogen bonded dimers with an O-HO distance of 2.626(3) Å. The COOH group is rotated by 1.7(1)° about the exocyclic C(1)-C(7) bond out of the benzene ring plane. The molecules lie on (0 2-1) plane for which thed value is found to be 3.378 Å which is very close to the mean separation between the parallel packed benezene rings [3.347(4) Å]. The entire molecule is planar except for the two methyl groups attached to the nitrogen atom. The N atom is free from any binding of either type C-HN or O-HN.N. C. L. Communication No. 4699.     

Structure of bis(2-amino-5-methylpyridinium) tetrachlorozincate at 298 and 150 K

Reaction of 2-amino-5-methylpyridine with zinc chloride and HCl in aqueous solution yields bis(2-amino-5-methylpyridinium) tetrachlorozincate. The complex crystallizes in the monoclinic space group P2₁/c, with minimal tetrahedral distortion of the ZnCl₄ ^2– ion at both 298 and 150 K; at 298 K, a = 8.090(2) Å, b = 14.795(6) Å, c = 15.850(4) Å, = 101.93 (2); at 150 K, a = 8.0986(2) Å, b = 14.7190(5) Å, c = 15.7684(7) Å, = 102.862(2). The anisotropic cell contraction results in significant changes in nonbonding Cl Cl contacts.     

Crystal structures of bis-11-aminoundecanoic chlorocuprate and bis-11-aminoundecanoic-Cu(II) sulfate trihydrate

Bis-11-aminoundecanoic chlorocuprate: (I),M _r =609.5, triclinic,P¯1 (No. 2),a=7.237(1),b=7.536(1),c=27.605(2) Å, =97.98(8),=92.45(8), =90.02(8)°,V _c =1492 ų,Z=2,D _x =1.357 g cm^–3,D _m =1.35(1) g cm^–3 (flotation), =43.85 cm^–1, CuK radiation=1.5418 Å,F(000)=642,T=23 °C,R=0.065 for 4121 observed reflections. Bis-11-aminoun-decanoic sulfate Cu(II) trihydrate: (II),M _r =616.4, triclinic,P¯1,a=7.745(2),b=9.553(4),c=20.343(5) Å, =80.91(3),=79.28(2), =87.58(3)°,V _c =1460 ų,Z=2,D _x =1.40(1) g cm^–3,D _m =1.38(2) g cm^–3 (flotation),=8.16 cm^–1, MoK radiation=0.71069 Å,F(000)=658,T=23°C,R=0.064 for 3384 observed reflections. In (I) the two copper ions are in special positions 0, 0, 0 and 1/2, 1/2, 0 octahedrally coordinated to Cl^–. The CuCl ₂ ^2– ions make square planes with the short bonds of mean values 2.289 and 2.295 Å. The carbonyls are hydrogen bonded, and the conformation of the amino acid chains ist for whole chain except at C(11) of chainA and N of chainB where it isg. In (II) Cu²⁺ shows a very distorted octahedral coordination with a mean value of 1.959 Å for the short bonds Cu-O and 2.512 Å for the long bonds. TheB amino acid chain presents a similar conformation change at C(11) as in theA chain of complex (I).     

Conformational study on aryl ketones: The structure of 2,6-dimethyl-1,5-di-(2-methyl)-propanoylnaphthalene

C₂₀H₂₄O₂ (M _r =296.4) crystallizes in the monoclinic system, space groupC2/c witha=24.154(4),b=8.001(2),c=12.751(3) Å;=136.8(1)°;V=1686.9 ų,Z=4,D _c =1.17 g cm^–3,(Cu-)=5.4 cm^–1,=1.5418 Å,F(000)=640. The molecule in the solid state adopts a centrosymmetric geometry with the molecular center of symmetry coincident with a crystallographic center of symmetry. This fact forces the molecule to themeso conformation.     

X-ray crystal structure of (1-methylthyminato)triethylphosphinegold(I)

The crystal structure of the title compound reveals that the gold atom exists in a linear geometry defined by a P atom [Au-P 2.223(6) Å] and the N(3) atom of the 1-methylthyminate nucleobase [Au-N(3) 2.06(2) Å] with a P-Au-N angle of 178.4(5)°. The crystal lattice is characterized by significant hydrogen bonding contacts involving both the carbonyl oxygen atoms and the solvent water molecule of crystallization. The crystals are monoclinic, space groupP2₁ with unit cell dimensionsa 8.037(1),b=11.329(2),c09.501(1) Å,=104.08(1)°,Z=2. The structure was refined to finalR=0.047 for 2069 reflections which satisfiedI3.0(itI).     

Complexation with diol host compounds. Part 2. Structures of 1,1,2,2-tetraphenylethane-1,2-diol and its 1∶2 molecular inclusion complex with dimethylsulphoxide

The structures of 1,1,2,2-tetraphenylethane-1,2-diol and its 12 molecular inclusion complex with dmso have been elucidated by X-ray crystallography from single crystal diffraction data. Crystals of the host, compound I, are monoclinic, space groupP2₁/n, witha=17.669(6) Å,b=6.144(6) Å,c=17.873(6) Å,=92.67(3)°,z=4. Crystals of the clathrate, compound II, are triclinic,P¯1, witha=9.138(5) Å,b=18.384(6) Å,c=18.496(3) Å,=61.16(2)°,=83.22(3)°, =88.06(3)°,Z=4. Both structures were solved by direct methods and refined to finalR values of 0.072 and 0.107, respectively. Compound I is partially disordered and its packing is governed by strong intermolecular hydrogen bonds. Compound II is characterized by crossing channels which accommodate the guest dmso molecules. The thermal properties of the latter compound have been characterized by DTA and TGA thermograms.     

Refinements of the crystal structures of 1,4-diphenylbutadiyne and its complex with two moles of Co2(CO)6

1,4-diphenylbutadiyne, C₁₆H₁₀, crystallizes in monoclinic space group P2₁/n witha=6.6152(6),b=6.0768(7),c=14.634(1) Å, =100.981(8)⁰,V=577.5(2) ų,Z=2. The structure was refined toR=0.077 andR _w=0.069 for 1007 observed reflections with CuK radiation. The molecule lies on an inversion center. Our determination represents and increase in precision of a factor of approximately three over the original determination. The 21 cobalt complex, C₁₆H₁₀[Co₂(CO)₆]₂, also crystallizes in monoclinic space group P2₁/n witha=8.9568(12),b=17.7057(10),c=18.5671(12) Å, =90.606(12)^o,V=2944.3(5) ų,Z=4. The structure was refined toR=0.032 andR _w=0.031 for 4312 observed reflections. The diphenylbutadiyne triple bonds elongate to 1.346(3) Å and the angles at the diyne C atoms decrease to 134.1(3)–144.9(3)^o upon complexation. The Co-Co distance is 2.4580(4)Å. Our data represent an increase in precision by a factor of 2–3 over the original determination.     

Crystal structure of lanthanum(III) oxalate decahydrate

La₂(C₂O₄)₃·10H₂O crystallizes in space groupP2¹/c (No. 14) witha=11.382(6),b=9.624(5),c=10.502(8) Å,=114.52(4)°, andZ=2. The structure (R=0.029 for 3190 MoK data) is composed of two-dimensional networks of edge-sharing 153 coordination polyhedra matching the (020) set of planes, each La(III) atom being surrounded by three ⁴ chelating oxalate groups and three aqua ligands with La-O distances in the range 2.518(4)–2.622(4) Å. The remaining water molecules are disordered over seven principal sites in the intervening space.     

Structure of 6β-acetoxyprogesterone,C23H32O4

The X-ray crystal structure of 6-acetoxyprogesterone, C₂₃H₃₂O₄, has been determined. This compound crystallizes in space groupP2₁2₁2₁ witha=13.195(3),b=15.035(4),c=10.705(3) Å,V=2139.8(9) ų,M _r=372.5,Z=4,D _x=1.156g cm^–3; MoK radiation (=0.7107 Å),=0.72 cm^–1,F(000)=808;R=0.069, andR _w=0.052 for 1292 reflections. RingA adopts a normal 1,2-half-chair conformation. The side chain is typical for a 20-ketosteroid conformation.