Showing papers by "Susumu Kitagawa published in 2000"

Microporous materials constructed from the interpenetrated coordination networks. Structures and methane adsorption properties

Abstract: Five new coordination compounds with 4,4‘-azopyridine (azpy), [Mn(azpy)(NO3)2(H2O)2]·2EtOH (1·2EtOH), [Co2(azpy)3(NO3)4]·Me2CO·3H2O (2·Me2CO·3H2O), [Co(azpy)2(NCS)2]·0.5EtOH (3·0.5EtOH), [Cd(azpy)2(NO3)2]·(azpy) (4·azpy), and [Cd2(azpy)3(NO3)4]·2Me2CO (5·2Me2CO), have been synthesized and structurally characterized. The reaction of Mn(NO3)2·6H2O with azpy in ethanol/acetone affords 1·2EtOH, whose network consists of one-dimensional chains of [Mn(azpy)(H2O)2]n. The chains are associated by hydrogen bonding to provide a logcabin-type three-dimensional structure, which creates about 8 × 8 A of channels, filled with ethanol molecules. The treatment of Co(NO3)2·6H2O and Co(NCS)2·4H2O with azpy produces 2·Me2CO·3H2O and 3·0.5EtOH, respectively, which have a brick-wall and a rhombus-type two-dimensional networks. The reaction of Cd(NO3)2·4H2O with azpy affords 4·azpy from the ethanol/H2O media, while the reaction in the ethanol/acetone media provides 5·2Me2CO. 4·azpy and 5·2Me2CO form a square-grid- and a herrin...

Molecular recognition of amines and amino esters by zinc porphyrin receptors: binding mechanisms and solvent effects.

Abstract: Zinc porphyrin receptors bearing 12 ester groups in the meso phenyl groups (1−3) were prepared, and binding of amines and α-amino esters was studied with emphasis on the binding mechanisms. The X-ray crystallographic analysis of 5,10,15,20-tetrakis(2,6-bis(carbomethoxymethoxy)-4-carbomethoxyphenyl)porphyrin (free base of 1) showed that the receptor has a binding pocket above the porphyrin plane. UV−visible titration experiments revealed that the zinc porphyrin receptors bound amines and α-amino esters with binding constants (Ka) ranging from 0.5 to 52 700 M-1 in CH2Cl2 at 25 °C. The ester functional groups of 1 assisted the binding of aromatic α-amino esters (Ka = 8 000−23 000 M-1 in CH2Cl2 at 25 °C) and inhibited the binding of bulky aliphatic α-amino esters (Ka = 460 M-1 for Leu-OMe in CH2Cl2 at 25 °C), indicating that CH−π type interactions and steric repulsions control the selectivity. The binding of amines and α-amino esters was tight both in a nonpolar solvent (CH2Cl2) and in a polar solvent (water)...

Novel layered structures constructed from metal(II)–chloranilate monomer compounds

Abstract: The new copper(II) and cobalt(II) assembled compounds {(G)2[M(CA)2(H2O)2]}n (M = Cu2+, Co2+; H2CA = chloranilic acid; G = 4-hydroxypyridinium cation (4-pyOH2+), 3-hydroxypyridinium cation (3-pyOH2+)) have been synthesized and characterized. In every compound two chloranilate dianions and two water molecules are coordinated to the metal ion making dianionic monomers, [M(CA)2(H2O)2]2−. The coordination environment around the metal ion is a distorted octahedron, where two water molecules sit in a trans position to each other. [M(CA)2(H2O)2]2− anions form anionic layer structures (1, 3) and an anionic chain structure (2) by using hydrogen bonding interactions. The cations are introduced between the {[M(CA)2(H2O)2]2−}l layers or chains, which are supported by both the hydrogen bonding interaction and the electrostatic interaction between the organic cations and the complexes. In compounds 1 and 3, the organic cations are stacked on each other to form a segregated columnar structure between the {[M(CA)2(H2O)2]2−}l layers. On the other hand, in compound 2, the cations are included in a cage as a dimer. The cage is constructed by the chlorine atoms of CA2− dianions of the chains and the organic cations are anchored to the chain by the hydrogen bonding interactions.

A New Self-Assembled Porphyrin-Silver(I) Network

Abstract: A new self-assembled porphyrin compound, [Ag(H2TPyP)]·PF6 (H2TPyP = 5,10,15,20-tetrakis(4-pyridyl)porphyrin) (1), was synthesized and structurally characterized. Among four pyridyl groups of the H2TPyP molecule, the two groups in the trans positions are coordinated to the silver atom, resulting in the formation of a linear one-dimensional network, in which the other two pyridyl moieties remain metal-free. Each of the chain is associated by a weak π–π interaction to afford a slipped-stack structure.

Triple hydrogen bond directed crystal engineering of metal assembled complexes: the effect of a bifunctional ligand on supramolecular structure

Abstract: The crystal structures of compounds [Hmel]2[M(tdpd)2(OH2)2]·2H2O (M = Ni2+, Co2+; Hmel+ = melaminium cation; H2tdpd = 1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile) are reported; the metal complex supramolecular structures can be rationally designed via hydrogen bonding interactions.

Gas storable organic metallic complex and its production and gas storage device

Abstract: PROBLEM TO BE SOLVED: To increase gas adsorptivity per volume by using an org. metallic complex having a three-dimensional structure constituted from a bivalent metal ion, an org. ligand having an atom capable of coordinating to the metal ion and capable of bidentate coordination and a halogenated bivalent metal anion for gas storage. SOLUTION: The org. metallic complex having the three-dimensional structure and capable of storing gas is constituted from the bivalent metal ion, the org. ligand having the atom capable of coordinating to the metal ion and capable of bidentate coordination and the halogenated bivalent metal anion. Here, the org. ligand capable of bidentate coordination is at least one kind selected from a group consisting of pyrazine, 4,4'-bipyridyl, trans-1,2-bis(4-pyridyl)ethylene, 4,4'-bipyridylethane, 4,4'-bispyridylphenylene and N-(4-pyridyl)isonicotinamide.

Hydrogen-Bond Network of Dimeric Copper Complex of Vanillic Acid (HVA), [Cu(VA)2(H2O)]2

Abstract: The crystal structure of the title complex was first determined, showing a dimeric copper form with the four carboxylate groups. The Cu···Cu distance is short, associated with the hydrogen bond link of the apically coordinated water molecules with the nearest neighbor vanillic hydroxyl group. The hydrogen bond links afford an infinite 3-D network.

Synthesis and crystal structure of [Cu(N-salicylidene-3-aminopyridine)(2)](n) constructed from unsymmetric bridging ligand with two dissimilar metal-binding sites

Abstract: Synthesis and characterization of novel coordination polymer, [Cu(salapy)2] n (Hsalapy = N-salicylidene-3-aminopyridine), having the 2-D thick layer structure is reported.

Iron-chloranilate intercalation compounds: synthesis, crystal structures, and thermal properties

Abstract: Hydrogen bond supported new iron-chloranilate assemblies, {(Hpy)[Fe(CA)2(H2O)2](H2O)}n (py = pyridine, H2CA = chloranilic acid, C6H2O4Cl2) (1), and [(phz)2[Fe(CA)2(H2O)2](H2O)2]n (phz = phenazine, ...

Crystal structure of diisonicotinatotetraaquamanganese(II), [Mn(C5H4NCOO)2(H2O)4]

Abstract: Ci2Hi6MnN208 , triclinic, PI (No. 2), a = 6.3973(6) Ä, b = 6.941(1) Ä, с = 9.336(1) Ä, α = 95.527(6)°, β = 104.386(2)°, γ = 112.518(2)°, V= 362.4 Ä 3 , Z = 1, Rgt(F) = 0.041, wRp(F) = 0.063, 7 = 273 K. Source of material An aqueous solution (1 ml) of sodium isonicotinate (0.2 mmol) was transferred to a test tube, then an methanolic solution (1 ml) of manganese(II) chloride (0.1 mmol) was poured into the tube without mixing the two solutions. Large colourless crystals were obtained after one week. Table 3. Atomic coordinates and displacement parameters (in Ä). Discussion The reaction of sodium isonicotinate with manganese chloride affords a mononuclear complex [Mn(H20)4(CsH4NC00)2]. The manganese centres are coordinated by four oxygen and two nitrogen atoms in a slightly distorted octahedral manner. Interestingly the isonicotinate ligand is only coordinating via the pyridyl nitrogen atoms and not via the carboxylate group. The [Mn(H20)4(C5H4NCOO)2] molecule has a crystallographically imposed centre of inversion. The Μη—О bond lengths are 2.170( 1) Ä and 2.211 (2) Ä, respectively, whereas the Μη—N distance is 2.273(2) Ä. The acute O M n O angles are 86.18(8)° and 93.82(8)°, whereas the O M n N angles range from 87.08(6)° to 92.92(6)°. The organic ligand has its expected geometry. Table 1. Data collection and handling. Crystal: colourless column, size 0 .20x0 .21 χ 0.36 mm Wavelength: Mo Ka radiation (0.7107 A) μ: 9.50 cm\" 1 Diffractometer, scan mode: Rigaku CCD, ω 20max: 55.2° N(hkl)measured, N(hkl)unique: 1398, 1398 Criterion for Fobs. N(hkl)gl: U s > 3 a ( W , 1329 N(param) refined: 106 Programs: teXsan [1], SIR92 [2] Table 2. Atomic coordinates and displacement parameters (in A\"). Atom Site X У ζ ί / i so H( l ) 2i 0.7645 0.2878 0.4145 0.0230 H(2) 2 i 1.0007 0.3980 0.6689 0.0258 H(3) 2 i 0.4400 0.2936 0.8063 0.0286 H(4) 2i 0.1869 0.1711 0.5580 0.0249 H(5) 2 i 1.1701 0.7503 0.8000 0.0382 H(6) 2 i 1.3646 0.8647 0.9696 0.0382 H(7) 2 i 1.1053 0.1924 0.8595 0.0286 H(8) 2 i 1.2955 0.2889 1.0316 0.0286 Atom Site X У ζ U π ί/22 Ui3 U η Un £/23 Mn(l ) 1 с 1.0 1/2 1.0 0.0180(3) 0.0282(3) 0.0118(3) 0.0106(2) 0.0027(2) 0.0025(2) 0 (1 ) 2 i 0.3967(3) 0.2028(3) 0.1977(2) 0.0285(8) 0.059(1) 0.0182(9) 0.0229(8) 0.0058(7) 0.0108(7) 0 ( 2 ) 2 i 0.0731(3) 0.0792(3) 0.2711(2) 0.0209(7) 0.041(1) 0.024(1) 0.0088(7) -0.0007(7) 0.0036(7) * Correspondence author (e-mail: ki taga@sbchem.kyoto-u.ac. jn) 172 Diisonicotinatotetraaquamanganese(II) Table 3. Continued. Atom Site X У г Un ί/22 г / э з Ul2 U[3 U23 0(3) 2i 1.2216(3) 0.7537(3) 0.9058(2) 0.0270(8) 0.0392(9) 0.036(1) 0.0130(7) 0.0145(7) 0.0136(7) 0(4) 2 i 1.1642(3) 0.2886(3) 0.9556(2) 0.0259(7) 0.0343(9) 0.0185(8) 0.0170(6) 0.0037(6) 0.0020(6) N(l) 2 i 0.7436(3) 0.3569(3) 0.7609(2) 0.0212(8) 0.0287(9) 0.0132(9) 0.0102(7) 0.0022(7) 0.0028(6) C(l) 2 i 0.2938(4) 0.1631(3) 0.2964(2) 0.024(1) 0.024(1) 0.017(1) 0.0123(8) 0.0022(8) 0.0024(7) C(2) 2 i 0.4503(3) 0.2259(3) 0.4597(2) 0.0196(9) 0.0172(9) 0.015(1) 0.0084(7) 0.0023(8) 0.0026(7) C(3) 2 i 0.6954(4) 0.2900(3) 0.4961(2) 0.020(1) 0.027(1) 0.016(1) 0.0083(8) 0.0061(8) 0.0052(7) C(4) 2i 0.8331(4) 0.3531(4) 0.6459(2) 0.0181(9) 0.032(1) 0.019(1) 0.0102(8) 0.0054(8) 0.0045(8) C(5) 2 i 0.5061(4) 0.2898(4) 0.7252(3) 0.024(1) 0.036(1) 0.019(1) 0.0106(9) 0.0087(9) 0.0033(8) Acknowledgment. This work was supported by a Grant-in-Aid for Scientific Research from the Japanese Ministry of Education, Science and Culture. References 1. Molecular Structure Corporation, Rigaku Corporation. teXsan. Single Crystal Structure Analysis Software. Version 1.10. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA. Rigaku, 3-9-12 Akishima, Tokyo, Japan 1999. 2. Altomare, G.; Cascarano, G.; Giaccovazzo, C.; Guagliardi, Α.; Burla, Μ. С.; Polidori, G.: SIR92 a program for automatic solution of crystal structures by direct methodes. J. Appl. Crystallogr. 27 (1994) 435.

Synthesis and Crystal Structure of New Salicylate-Bridged Coordination Polymer, [Cu2(sal)2(pyz)(MeOH)2]n

Abstract: The title compound, {[Cu2(sal)2(pyz)]·2MeOH}n (H2sal = salicylic acid, pyz = pyrazine) (1), has been synthesized, and structurally characterized Each sal ligand connects the three copper centers to afford a novel 2-D network structure The CuII-sal framework forms a rhombus type two-dimensional coordination framework The pyz molecules, which fill the voids of the network, bind to the Cu site to afford zigzag chain

Gas storing organometallic complex, its production and gas storing device

Abstract: PROBLEM TO BE SOLVED: To obtain an organometallic complex useful as a gas occluding material by mixing a solution of an organic ligand capable of coordinating to a specific metal ion with a solution of the said metal salt SOLUTION: An organometallic complex having a three dimensional structure constituted of a two valent metal ion and an organic ligand having a bidentate amide bond containing atoms capable of coordinating to the said metal ion in the molecule, eg a complex expressed by the formula [Cd(pcia)2 (NO3)2]n [pcia is N-(4-picoryl)-isonicotinamide], is obtained by mixing a solution of a bidentate organic ligand capable of coordinating to be bidentate to a two valent metal (eg magnesium, etc), eg a ligand expressed by the formula (R and R' are each an alkylene, alkenyl or an arylene) with a solution of the bivalent metal salt The crystal of the organometallic complex is obtained by standing the obtained mixture solution for, eg at normal temperature -60 degC for several hours to several days, filtering the precipitated solid by suction and drying at 100 degC for 5 hours in vacuum

Crystal Structure and Magnetic Property of Cobalt(II) Assembled Compound, {[Co(CA)(bipym)](H2O)2}n (H2CA = chloranilic acid, bipym = 2,2′-bipyrimidine)

Abstract: Cobalt(II) assembled complex compound, ([Co(CA)(bipym)](H 2 O) 2 } n (H 2 CA = chloranilic acid, bipym = 2.2'-bipyrimidine) (1) has been synthesized and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystalizes in the monoclinic, space group C2/c(#15), with a = 16.652(4) A, b = 11.163(3) A, c = 10.081(3) A, β = 116.12(2), V = 1682.4(7) A 3 , Z = 4. The bipym ligands bridge the cobalt centers in bis-bidentate fashion and make zigzag chains. The chains form layer structures by stacking interaction and hydrogen bonding interaction with the help of interstitial water molecules. The temperature dependence of the magnetic susceptibility of 1 shows intramolecular antiferromagnetic interaction with θ = - 39.7 K.

Chiral Recognition of α-Amino Esters on the Chiral Helical Surface of Zinc Bilinone

Abstract: Chiral recognition of α-amino esters was examined using the homochiral helical dimer of the zinc complex of linear tetrapyrrole (zinc bilinone) as a host. 1H NMR and thermodynamic studies indicated that favorable (Phe–Ome and Leu–Ome) or unfavorable (Asp–(Ome)2) interactions of the side chain of α-amino esters with zinc bilinone lead to enantioselectivity.

Synthesis and Molecular Structure of the Amido-Bridged Dinuclear Rhodium Complex [Cp*Rh{μ2-(NH)2C10H6-2,3}(μ2-Cl)RhCp*][PF6] (Cp* = η5-C5Me5)

Abstract: Reaction of [Cp*RhCl2]2 (1) with (LiNH)2C10H6-2,3 gives the mononuclear species Cp*Rh(NH)2C10H6-2,3 (3), which is selectively converted to the amido-bridged dinuclear Rh(III) complex [Cp*Rh{μ2-(NH)...