Chiral Compound $[C_{24}H_{22}N_4O_4S]_2HCl$로 확인한 결정학적 단위포 변환시의 한 조언

Suh, Il-Hwan,Kim, Jin-Gyu,Park, Ji-Cheol,Park, Young-Soo,Park, Kyung-Lae Korea Crystallographic Association 2000 韓國結晶學會誌 Vol.11 No.2

A crystallographic unit cell can be transformed into another one by a 3×3 transformantion matrix. If the determinant of the transformation matrix has a negative value, the newly transformed unit cell becomes a left-handed cell. The best way of transforming the left-handed cell to the right-handed one is to multiply each element of the transformation matrix by-1, and its corresponding transformation matrix must be applied tot he atomic coordinates of a noncentrosymmetric crystal so as to maintain the absolute configuration unchanged. The behaviour of absolute configuration caused by transforming the crystallographic unit cell was examined theoretically and experimentally on the compound (S)-(+)-4-phenyl-1-[4-aminobenzoyl) indoline-5-sulfonyl]-4,5-dihydro-2-imidazolone hydrochloride.

Synthesis and Crystal Structure of Syn-Anti Carboxylate-Bridged Dinuclear Copper(II) Complex

최기영,Choi, Ki-Young Korea Crystallographic Association 2006 韓國結晶學會誌 Vol.17 No.2

이핵 구리 착물(錯物) {[Cu(pmea)Cl][Cu$(H_2O)_3]}Cl_2\cdot H_2O$ (1) (Hpmea=bis(2-pyridylmethyl)amino-2-ethanoic acid)을 합성(合成)하고 구조(構造)를 규명(糾明)하였다. 이 착물(錯物)은 단사정계(單斜晶系), 공간군(空間群) $P2_1/c$, a=9.0008(6) ${\AA}$, b=28.0171(19) ${\AA}$, c=8.5590(6) ${\AA}$, $\beta$=104.2280(10)$^{\circ}$, V=2092.2(2) ${\AA}^3$, Z=4로 결정화(決定化) 되었다. 착물(錯物) 1의 결정구조(結晶構造)는 대칭(對稱)-반대칭(反對稱) carboxylate 다리로 연결(連結)된 이핵 착물(錯物)로서, 각각(各各) 구리원자의 배위환경(配位環境)은 고천(若千) 일그러진 사각뿔구조(構造)와 고천(若干) 일그러진 사각평면구조(構造)를 갖는다. The dinuclear copper(II) complex {[Cu(pmea)Cl][Cu$(H_2O)_3]}Cl_2{\cdot} H_2O$ (1) (Hpmea=bis(2-pyridvlmethyl)amino-2-ethanoic acid) has been synthesized and characterized. It crystallizes in the monoclinic system $P2_1/c$, a=9.0008(6) ${\AA}$, b=28.0171(19) ${\AA}$, c=8.5590(6) ${\AA}$, $\beta$=104.2280(10)$^{\circ}$, V=2092.2(2) ${\AA}^3$, Z=4. Crystal structure of 1 reveals a syn-anti carboxylate-bridged dinuclear complex, in which the coordination environment around each copper atom exhibits a distorted square-pyramid and a distorted square plane, respectively.

$[Ni(L)](ClO_4)_2$(L: 2,13-bis(2-pyridylmethyl)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,$0^{1.18},0^{7.12}$docosane) 착물의 결정구조

Park, Ki-Young,Suh, Il-Hwan,Kim, Jing-Gyu,Park, Young-Soo Korea Crystallographic Association 1999 韓國結晶學會誌 Vol.10 No.1

The complex [Ni(L)](ClO4)2 (1) (L=2,13-bis(2-pyridylmethyl)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.1807.12]docosane) has been synthesized and characterized by X-ray crystallography. (1) crystallizes in the triclinic, space group P, with a=10.948(2), b=10.948(2), c=14.911(4) , α=93.73(2), β=93.77(2), γ=99.29(2)o, V=1754.8(7) 3, Z=2, R1(wR2) for 5217 observed reflections of [I>2σ(I)] was 0.048(0.099). The coordination environment around nickel(II) ion shows a distorted octahedron with four secondary and tertially amines of the macrocycle and two nitrogen atoms of pyridylmethyl groups.

Synthesis and Crystal Structure of 13-Membered Tetraaza Macrocyclic Cobalt(III) Complex with Azido Ligand

최기영,Choi, Ki-Young Korea Crystallographic Association 2006 韓國結晶學會誌 Vol.17 No.2

[ $cis-[Co(13-aneN_4)(N_3)_2]Cl{\cdot}H_2O$ ] (1) (13-ane$N_4$ = 1,4,7,10-tetraazacyclotridecane) 착물(錯物)을 합성(合成)하고 구조(構造)를 규명(糾明)하였다. 이 착물(錯物)은 단사정계(單斜晶系), 공간군(空間群) Pbca, a = 7.8282(4) ${\AA}$, b = 14.3197(7) ${\AA}$, c = 29.9021(15) ${\AA}$, V= 3351.9(3) ${\AA}^3$, Z = 8로 결정화(決定化) 되었다. 착물(錯物) 1의 코발트(III)이온은 거대(巨大)고리 리간드의 4개(個)의 질소원자(窒素原子)와 시스 위치에 2개(個)의 azide 리간드가 결합(結合)한 고천(若干) 일그러진 팔면체(八面體) 구조(構造)를 갖는데, 착물(錯物)의 양이온, 염소(鹽素) 음이온 및 물분자(分子)를 통하여 1차원의 수소결합(水素結合)을 형성(形成)한다. The complex $cis-[Co(13-aneN_4)(N_3)_2]Cl\cdot H_2O$ (1) (13-ane$N_4$ = 1,4,7,10-tetraazacyclotridecane) has been synthesized and structurally characterized by X-ray crystalloaraphy. It crystallizes in the orthorhombic system Pbca, a = 7.8282(4) ${\AA}$, b = 14.3197(7) ${\AA}$, c = 29.9021(15) ${\AA}$, V = 3351.9(3) ${\AA}^3$, Z = 8. The cobalt(III) ion in 1 is coordinated to four nitrogen atoms from the macrocycle and two azide ligands of cis position in a distorted octahedral environment, which forms the 1D polymer through hydrogen bonding contacts involving the cation, chloride anion and solvent water molecules.

InterplanarA: A Computer Program for the Calculation of the Crystallographic Interplanar Angles

서태원,강상욱,서일환,Suh, Tae-Weon,Kang, Sang-Ook,Suh, Il-Hwan Korea Crystallographic Association 2009 韓國結晶學會誌 Vol.20 No.1

실격자(real lattice)에서 이차원적인 (hkl)면의 총 집합이 역격자(reciprocal lattice)에서 한 개의점(點)으로 나타내어지며 원점에서 이 역격자점을 이은 vector의 방향은 (hkl)면의 방향이다. 따라서 두 역격자 vectors간의 각도가 결정학적 두 면간의 각도이므로 이들 각도들을 계산해보면 역격자의 개념을 이해하는데 도움이 된다. 이 논문에서는 6개의 실격자 상수 a, b, c, $\alpha$, $\beta$, $\gamma$를 사용하여 두 결정학적 면 ($h_1k_1l_1$)과 ($h_2k_2l_2$)간의 각도를 계산하는 한 computer program 'InterplanarA'를 소개하였다.

Synthesis and Structure of $[Ni(dppe)_2] (dppe=Ph_2PCH_2CH_2PPh_2)$

Kim, Wan -Sung,Lee, Ji-Hwa,Lee, Soon W. Korea Crystallographic Association 2000 韓國結晶學會誌 Vol.11 No.2

Compound [Ni(P(OEt)3)4] (1) reacted with bis(diphenylphosphino)ethane (Ph2PCH2CH2Ph2, dppe) to give bis(bis(diphenylphosphine)ethane)nickel(0), [Ni(dppe)2] (2). Compound 2 was characterized by spectroscopy (1H-and 31P{1H}-NMR) and X-ray crystallography. Crystallographic data for 2: monoclinic space group P21/n, a=9.826(1)Å, b=21.167(2)Å, c=21.425(2)Å, β=91.957(9)°, Z=4, R(wR2)=0.0377(0.0882).

Two-dimensional Cu Coordination Polymer: [$Cu_2Cl_2$(4,4'-dipyen)]

허현수,이순원,Huh, Hyun-Sue,Lee, Soon-W. Korea Crystallographic Association 2007 韓國結晶學會誌 Vol.18 No.1

수열 반응 조건 하에서, [$Cu(OAc)_2]{\cdot}H_2O$, 4,4-dipyen, 그리고 KCl로부터 2차원 구리 배위 고분자 [$Cu_2Cl_2$(4,4'-dipyen)] (1)이 합성되었다. 고분자 1 내에서, 구리 원자들이 4,4-dipyen 리간드들로 대략 b-축 방향으로 연결되고, 또한 Cl 리간드들로 대략 a-축 방향으로 연결되어 직사각형 그물 망 형태의 2차원 층이 형성된다. Under hydrothermal conditions, a 2-dimensional copper(I) coordination polymer [$Cu_2Cl_2$(4,4'-dipyen)] (1) was prepared from [$Cu(OAc)_2]{\cdot}H_2O$, 4,4'-dipyen, and KCl. In polymer 1, copper atoms are linked by the 4,4'-dipyen ligands approximately along the b-axis and are also linked by the chloro ligands approximately along the a-axis to form a 2-D layer, a network of rectangles.

Structure of [$CoL_2(MeOH)(NO_3)_2$] [L = N1-(1-(pyridin-4-yl)ethylidene)naphthalene-1,5-diamine)]

김성훈,허현수,이순원,Kim, Sung-Hoon,Huh, Hyun-Sue,Lee, Soon-W. Korea Crystallographic Association 2007 韓國結晶學會誌 Vol.18 No.1

Dipyridyl 리간드 L'(N,N'-bis-(1-pyridin-4-yl-ethylidene)-naphthalene-1,5-diamine)을 함유한 $CH_2Cl_2$ 용액을 $Co(NO_3)_2{\cdot}6H_2O$을 함유한 MeOH 용액 위에 깔았을 때, 배위 고분자가 아닌, 분자성 코발트 화합물 [$CoL_2(MeOH)(NO_3)_2$] (1)이 형성되었다. 화합물 1의 X-ray 구조 분석 결과, 이 화합물은 pyridyl-amine 리간드 L(N1-(4-Imino-1-methyl-but-2-enylidene)-naphthalene-1,5-diamine)을 함유하고 있었다. 반응 중에 리간드 L'이 리간드 L로 가수분해되었다는 것을 화합물 1의 구조가 강하게 암시하고 있다. When a $CH_2Cl_2$ solution of the dipyridyl species L' (N,N'-bis-(1-pyridin-4-yl-ethylidene)-naphthalene-1,5-diamine) was layered onto the top of a MeOH solution of $Co(NO_3)_2{\cdot}6H_2O$, a molecular cobalt compound [$CoL_2(MeOH)(NO_3)_2$] (1), not a coordination polymer, was formed. X-ray structural analysis of compound 1 revealed that it contains the pyridyl-amine ligand L (N1-(4-imino-1-methyl-but-2-enylidene)-naphthalene-1,5-diamine), instead of L'. Structure of compound 1 strongly suggests that the original ligand L' has been hydrolyzed to ligand L during the reaction.

Preparation and Structure of [1,2-Bis(diphenylphosphino)ethane](nitrato)(trifluoromethylsulfonato)platinum(II): [Pt(dppe)($NO_3$)($CF_3SO_3$)]

허현수,이순원,Huh, Hyun-Sue,Lee, Soon-W. Korea Crystallographic Association 2008 韓國結晶學會誌 Vol.19 No.1

[[Pt(dppe)$Cl_2]$]와 1 당량 $AgNO_3$ 및 1 당량 AgOTf (OTf=$CF_3SO_3$)의 순차적 반응으로 표제 착물 [Pt(dppe)($NO_3$)($CF_3SO_3$)] (dppe=1,2-bis(diphenylphosphino)ethane, $Ph_2PCH_2CH_2PH_2$)이 합성되었다. Pt 금속은 dppe 리간드의 두 P 원자, nitrato ($NO^-_3$) 리간드의 O 원자, 그리고 triflato (trifluoromethylsulfonato, $OTf^-$) 리간드의 O 원자로 배위되어 있다. Pt 금속의 배위권은 일그러진 평면 사각형으로 기술될 수 있다. The title complex [Pt(dppe)($NO_3$)($CF_3SO_3$)] (dppe=1,2-bis(diphenylphosphino)ethane, $Ph_2PCH_2CH_2PH_2$) was prepared by sequentially treating [Pt(dppe)$Cl_2$] with 1 equiv of $AgNO_3$ and 1 equiv AgOTf (OTf=$CF_3SO_3$). The Pt metal is coordinated by two phosphorous atoms of the dppe ligand, one oxygen atom of the nitrato ($NO^-_3$) ligand, and one oxygen atom of the triflato(trifluoromethylsulfonato, $OTf^-$) ligand. The coordination sphere of Pt metal can be described as a distorted square plane.

Molecular Structure of PCP Pincer Complexes: Poisoning Catalyst on the Dehydrogenation of Alkanes

이지현,전상진,권기혁,이도원,Lee Ji Hyun,Chun Sang Jin,Kwon Ki Hyeok,Lee Do Weon Korea Crystallographic Association 2005 韓國結晶學會誌 Vol.16 No.1

알칸화합물(alkanes)에서 탄소-수소결합을 활성화시켜서 더욱 값이 비싸고 더 유용한 알켄화합물(alkenes)로 만들 수 있는 촉매를 만들고자 지난 수 십 년간 많은 화학자들이 연구해왔다 이러한 목적의 하나로서 두개의 수소를 가지는 이리디움 P-C-P핀서(pincer) 착물 $(IrH_2{C_6H_3-2,6-(CH_2PBu_2^t)_2})$을 성공적으로 합성하였다. 이 착물은 알칸의 탈수소화반응(dehyrogenation)에 아주 효과적인 촉매로 알려졌다 알칸의 탈수소화반응에 촉매독으로 작용하는 질소, 물, 이산화탄소 및 일산화탄소와 같은 작은 화합물들과 직접 반응시켜서 어떻게 촉매독으로 작용하는지를 알아봤다. 촉매독으로 작용할 수 있는 화합물들을 합성하여 핵자기공명분광법(NMR)과 적외선분광법(IR)으로 확인하였고 분자구조를 알아보기 위해서 단결정X-ray 회절법을 통하여 확인하였다. 본 논문에서는 촉매 및 촉매독물질의 합성과 분자구조와 각각의 화합물의 반응성과 특이성을 알아보았다. The dihydrido P-C-P pincer complex, $IrH_2{C_6H_3-2,6-(CH_2PBu_2^t)_2}$ (1), was successfully prepared from the reaction of the hydrochloride complex, $IrClH (C_6H_3-2,6-(CH_2PBu_2^t)_2}$, and super acid $(LiBEt_3H)$ under 1 atm of hydrogen in pentane solution at room temperature and followed by Heating at $130^{\circ}C$ in vacuo. Jensen recently found that the dihydrido P-C-P pincer complex 1 is a highly active homogeneous catalyst for the transfer dehydrogenation of alkanes with unusual longterm stability at temperatures as high as $200^{\circ}C$. The treatment of dihydrido complex 1 with nitrogen, water, carbon dioxide, and carbon monoxide in presence of tert-butylethylene (the) at room temperature in an appropriate solution gave the dinitrogen complex, $[Ir{C-6H_3-2,6-(CH_2PBu_2^t)_2}]_2({\mu}-N_2)$ (2), the hydrido hydroxyl complex, $IrH(OH){C_6H_3-2,6-(CH_2PBu_2^t)_2}$ (3), the carbon dioxide complex, $Ir({\eta}^2-CO_2) {C_6H_3-2,6-(CH_2PBu_2^t)_2}$ (including the bicarbonate complex, $IrH({\kappa}^2-O_2COH){C_6H_3-2,6-(CH_2PBu_2^t)_2}\;(4))$, and the carbonyl complex, $Ir(CO) {C_6H_3-2,6-(CH_2PBu_2^t)_2}\;(5)$ (including the carboxyl complex, $IrH(C(O)OH) {C_6H_3-2,6-(CH_2PBu_2^t)_2}\;(6))$, in good yield, respectively. These P-C-P iridium complexes were isolated and characterized by $^1H,\;^{13}C,\;^{31}P\; NMR$, and IR spectroscopy. In addition, the complexes (1-6) were characterized by a single crystal X-ray crystallography. These complexes account for these small molecules' inhibition of dehydrogenation of alkanes catalyzed by the dihydrido complex 1.