• Bulletin of the Korean Chemical Society
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• v.20 no.3
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• pp.345-351
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• 1999

The structures, the energetics, and the spectra of K+(H2O)3 have been studied at HF and MP2 levels with the basis set of triple-zeta plus two sets of polarization functions (TZ2P) for water molecules. Two structures considered are 3+0 (D3), and 2+1 (C2v). The 2+1 (C2v) has two hydrogen bonds between the primary hydration and the secondary hydration shell water molecules. They have similar binding energy and enthalpy. The most stable conformation of K+(H2O)3 is entropy driven as shown in Na+(H2O)5 and in Na+(H2O)6 cases. The 3+0 (D3) conformation is the most stable at 298 K and at 1 atm, based on Gibbs free energy changes (ΔGr). The thermal contributions to the enthalpy and the Gibbs free energy are corrected for the low frequency modes. The corrected ΔGr is in good agreement with the experimental value. Vibrational frequencies of two conformations are revealed as their characteristics.

• Korean Journal of Crystallography
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• v.8 no.2
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• pp.144-148
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• 1997

the molecular and crystal 3-dimensional structure of bentazone, C10H12N2O3S, has been determined from single crystal x-ray diffraction study. Crystal system is monoclinic: a=8.7817(9)Å, b=9.6059(9) Å, c=13.574(9) Å, β=97.269(1)', V=1136.1(6)Å, space group : P21/c, z=4. The molecular structure model was solved by direct method and refined by full matrix least squares. The final reliable factor, R, is 0.045 for 1396 independent reflections(Fo2>4σFo2). A molecule has a staggered conformation with thiocarbazin ring and isopropyl functional group and the molecules by hydrogen bonds are cross stacked along the c-axis.

• Korean Journal of Crystallography
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• v.10 no.1
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• pp.1-8
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• 1999

Two conformational isomers of p-tert-butylcalix[4]arene hexanoate were prepared from the reaction of-p-tert-butylcalix[4]arene and hexanoly chloride in the presence of AlCl3 in CH2Cl2 and their structures were determined by NMR spectra and X-ray diffraction as a cone and a 1,3-alternate conformer, respectively. The crystal of cone conformer (C68H96O8·(CH3)2CO) is triclinic, P, a=15.066(1) , b=16.063(1) , c=16.365(1) , α=79.75(2)o, β=109.95(2)o, γ=80.32(0)o, V=3602.7(4) 3, Z=2. The intensity data were collected on Simens SMART diffractometer/CCD area detector. The structure was solved by direct method and refined by least-squares calculations to a final R value of 0.144 for 4638 observed reflections. The molecular conformation is distorted symmetric cone with the flattening A and D phenyl rings. The crystal of 1,3-alternate conformer (C68H96O8·2CHCl3) is orthorhombic, Pca21, a=34.586(5) , b=10.207(3) , c=20.394(4) , V=7199(3) 3, Z=4. The intensity data were collected on an Enraf-Noninus CAD-4 Diffractometer with a graphite monochromated Mo-K radiation. The structure was solved by direct method and refined by least-squares calculations to a final R value of 0.152 for 2241 observed reflections. The molecule has a pseudo mirror symmetric 1,3-alternate conformation.

• Bulletin of the Korean Chemical Society
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• v.28 no.10
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• pp.1871-1873
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• 2007

• Korean Journal of Crystallography
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• v.8 no.2
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• pp.111-118
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• 1997

The structrue of hydroxy-bisbenzoyloxy-allyloxycalix[4]arene (C45H36O6) has been determined by X-ray crystallography. The crystals are monoclinic, space group P21, unit cell constants a=11.045(3), b=33.545(2) c=10.319(4)Å, β=113.86(2)˚, Z=4, V=3496.0(1.8) Å3, DC=1.28 gcm-3. The intensity data were collected on an Enraf-Noninus CAD-4 Diffractometer with a graphite monochromated Mo-Kα radiation. The structure was solved by direct method and refined by full-matrix least-squares calculations to a final R value of 0.076 for 2945 observed reflections. Two independent enantiomeric molecules are crystallized in a 1:1 racemate mixture. They have the flattened cone conformation with the flattening hydroxy1 pheny1 rings. There is an intramolecular hydrogen bond in both molecules.

• Bulletin of the Korean Chemical Society
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• v.15 no.12
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• pp.1108-1112
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• 1994

25-Acetoxy-26,27,28-trimethoxycalix[4]arene was synthesized by the treatment of calix[4]arene trimethyl ether with acetyl chloride in the presence of NaH. The solution conformation was inferred as a partial cone conformation based on the $^1H$-and $^{13}C$ NMR spectra. The crystal structure has been determined by X-ray diffraction method. The crystals are monoclinic, space group $P2_1$/n, a=8.186 (1), b=17.137 (2), c=19.878 (3) ${\AA}$, ${\beta}$=95.67 (1)$^{\circ}$, Z=4, V=2774.90 ${\AA}^3$, $D_c$= 1.22 g $cm^{-3}$, $D_m$=1.23 g $cm^{-3}$. The intensity data were collected on an Enraf-Noninus CAD-4 Diffractometer with a graphite monochromated $Cu-K{\alpha}$ radiation. The structure was solved by direct method and refined by full-matrix least-squares methods to a final R value of 0.054 for 3675 observed reflections. The molecule possesses a partial cone conformation with one flattened phenyl unit, in which one anisol ring, distal to the ester ring, is inverted. The acetoxyphenyl ring is flattened.

• Textile Coloration and Finishing
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• v.6 no.1
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• pp.62-70
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• 1994

Silk fibroin was dissolved in 9.3 M LiBr aqueous solution at 4$0^{\circ}C$ for 1 hour. The dissolved silk fibroin was regenerated by casting the dialyzed solution into the membrane. The freshly prepared silk fibroin membrane was soluble in water and was. mainly consisted of random coil conformation. By the treatments in saturated water vapor at 3$0^{\circ}C$ and in 75% ethanolic aqueous solution (V/V), the insoluble membranes were obtained and the structure and morphology of those were investigated for the structure by means of X-ray diffraction analysis, infrared spectroscopy, thermal analysis. Rheovibron and scanning electron micrograph. Silk II type crystals were obtained by treating amorphous silk fibroin membrane in the random coil conformtion with 75% ethanol solution(V/V). Crystallization to silk II type crystals occured even after a few minutes, and a large number of silk II type crystals were formed after 30 mins. On the other and, the membrane treated in saturated water vapor was composed of the mixtures of silk I and silk II type crystals. A large number of silk I and silk II type crystals were formed after 24 hours. The micro brownian motion in the amorphous regions of silk fibroin membrane started at about 175~185$^{\circ}C$. $\alpha$ dispersion appeared at about 20$0^{\circ}C$ in the amorphous membrane, and at about 22$0^{\circ}C$ in the crystalline membrane. The crystallization of random coil conformation to silkII type crystals occured at about 215$^{\circ}C$. The surface, bottom and cross-section of the membranes were observed by scanning electrom microscope. Fine forms alike spherulites appeared at the surface of crystalline membrane.

• Korean Journal of Crystallography
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• v.13 no.3_4
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• pp.158-164
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• 2002

Tetrahomodioxa p-phenylcalix(4)arene dihexylether(C/sub66/H/sub68/O/sub6/) has been synthesized and structurally characterized by X-ray diffraction. Reaction of tetrahomodioxa p-phenylcalix(4)arene with hexyl halide and NaH in DMF leads to the dihexyl derivatives, 7,13,21,27-tetraphenyl-29,31-dihexyloxy- 2,3,16,17-tetrahomo-3,17-dioxacalit(4)arenes. The crystal is orthorhombic, P2₁2₁2₁, a= 9.764(2), b=16.167(2), c=32.994(3) Å, V=5208(1) Å, Z= 4, Dc = 1.221 gcm/sup -3/. The structure was solved by direct methods and refined by full-matrix least squares. Refinement converged at R = 0.070 for 2009 observed reflections. This molecule has a C-1,2-alternate conformation with pseudo-centrosymmetry and has two pairs of opposite phenyl rings, which are approximately parallel to each other. The benzene rings A and B are up, and the rings C and D rings are down with respect to the plane of the macrocyclic ring.

• Korean Journal of Crystallography
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• v.7 no.2
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• pp.105-112
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• 1996

The structure of the tetra-tert-butyl-dipropionyloxy-dihydroxycalis[4]arene (C50H64O6) has been determined by X-ray diffraction methods. The crystal is monoclinic, space group C2/c, unit cell constant a=16.067(2), b=26.391(17), c=10.335(1)Å, β=94.26(1)°, Z=4, V=4370.2(29)Å3, Dc=1.16, Dm=1.2 gcm-3. The intensity data were collected on an Enraf-Nonius CAD-4 Diffractometer with a graphite monochromated Cu-Kα radiation (λ=1.5418Å). The structure was solved by direct methods and refined by least-squares methods. The final R value was 0.07 for 2354 observed reflections. The molecule has the 1, 3-alternate conformation with own two-fold symmetry axis, : two propionyloxy phenyl groups are up and the other two hydroxy phenyl groups are down.

• Korean Journal of Crystallography
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• v.4 no.1
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• pp.25-35
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• 1993

Tetra-tert-butyl-tetrapropionycalix (4) arena (C56H7208) is Triclinic, space group Pl, with a=13.664(5), b=17.585(5), c=12.863(2)A, a=109.33(2), B=111.97(2), γ=76.45(3) ˚, Z=2, V=2684.08A3, D, =1.152g/cm3, Dm=1.15g/cm3. The intensity data were collected on an Enraf-Nonius CAD-4 Diffractometer with a graphite monochromated Mo-Ka radiation. The structure was solved by direct methods and refined by leastsquares methods. The final R factor was 0.084 for 2561 observed reflections. The configuration of the molecule from the X-ray crystallographic investigation has the partial cone conformation, three tort-butylphenyls are down and a tort-butylphenyl is up. Three propionyloxy groups direct toward the exterior of the macrocycle cavity.