The Crystal and Molecular Structure of Thiosinamine

신현소,구정회,이순원,Shin, Hyun-So,Koo, Chung-Hoe,Lee, Soon-Won Korean Chemical Society 1984 대한화학회지 Vol.28 No.4

Thiosinamine, $H_2NCSNHCH_2CHCH_2$의 결정 및 분자구조를 X-선 회절법으로 규명하였다. 이 결정은 공간군 $P2_1/a$의 단사정계에 속하며 단위세포상수는 a = 9.819(3), b = 8.553(3), c = 9.170(2)${\AA}$, ${\beta}$ = 127.3(1)$^{\circ}$이고 z = 4이다. 814개의 회절 반점에 대한 강도 data는 Rigaku-Denki 자동 4축 회절기를 써서 얻었다. 구조는 직접법과 Fourier법으로 규명하였으며 좌표의 정밀화는 Full Matrix 최소 자승법에 의하여 행하였고 최종의 R값은 0.046이다. Thiourea moiety는 평면이며, 결합길이와 결합각은 thiourea unit를 포함하는 화합물에서 얻어진 값들과 잘 일치하고 있다. 분자들은 결정내에서 b축을 따라 두 종류의 N-H${\cdots}$S수소결합에 의하여 상호 결합하고 있다. The crystal and molecular structure of thiosinamine, $H_2NCSNHCH_2CHCH_2$, has been determined by X-ray diffraction method. The crystals are monoclinic, space group $P2_1/a$ with four molecules in a unit cell of dimensions, a = 9.819(3), b = 8.553(3), c = 9.170(2)${\AA}$, ${\beta}$ = 127.3(1)$^{\circ}$, and z = 4. Intensity data for 814 reflections were collected with a Rigaku-Denki automatic four circle diffractometer. The structure was solved by direct and Fourier methods. Refinements were carried out by full matrix least-squares method to a final R value of 0.046. The thiourea unit is planar, and the bond lengths and angles in that unit agree well with those in the compounds which contain a thiourea moiety. The molecules are linked together by the two patterns of N-H${\cdots}$S hydrogen bonds along the b-axis.

The Crystal and Molecular Structure of Sulfadiazine

신현소,인권식,금훈섭,구정회,Shin Hyun So,Ihn Gwon Shik,Kim Hoon Sup,Koo Chung Hoe Korean Chemical Society 1974 대한화학회지 Vol.18 No.5

X-선 회절법을 이용하여 sulfadiazine, $C_{10}H_{10}N_4O_2S$, 의 결정 및 분자 구조를 규명하였다. Acetone 과 ethanol의 혼합용액으로 부터 얻은 결정은 일사축계에 속하며, 단위세포에는 4분자가 있고, 공간군은 P21/c이다. 단위세포 상수는 $a=13.71{\pm}0.04,\;b=5.84{\pm}0.03,\;c=15.11{\pm}0.05{\AA},\;{\beta}=115.0{\pm}0.3^{\circ}$이다. 결정구조는 3차원적인 와이센버그사진으로 부터 얻어진 실험치를 이용하여 패터슨합성과 프리에합성을 하고 이를 해석하여 밝혀냈다. 수소원자를 제외한 원자들의 좌표치는 최소자승법으로 정밀화 하였으며, 최종 R값은 관측된 1517개의 독립반사에 대하여 0.15이다. 벤젠고리와 피리미딘고리의 두 평면이 이루는 각은 $76^{\circ}$이고, S-N(1)결합을 중심으로 한 N(1)-C(1) 결합과 S-C(5)결합이 이루는 conformational angle은 $77^{\circ}$로서 gauche형을 하고 있다. 이미노기의 질소원자, N(1)은 대칭중심에 의하여 옮겨지는 다른 분자의 피리미딘고리의 질소원자, N(3)와 $N-H{\cdots}N$형의 수소결합을 이루고 있으며, 아미노기의 질소원자, N(4)는 b축의 거리만큼 떨어져 있는 다른분자의 산소원자, O(1) 및 O(2)와 두개의 $N-H{\cdots}O$형 수소결합을 이루고 있다. 이들 수소결합의 2차원적 그물은 (100)면에 평행한 무한한 분자층을 형성하며 인접분자층 사이에는 van der Waals의 힘에 의하여 결합되어 있다 Sulfadiazine, $C_{10}H_{10}N_4O_2S$, forms monoclinic crystals of space group $P21}c$ from a mixture of acetone and ethanol with $a=13.71{\pm}0.04,\;b=5.84{\pm}0.03,\;c=15.11{\pm}0.05{\AA},\;{\beta}=115.0{\pm}0.3^{\circ}$, and four molecules per cell. Three dimensional photographic data were collected with $CuK\alpha$ radiation. The structure was determined using Patterson and Fourier synthesis methods and refined by block diagonal least-squares methods with isotropic thermal parameter for all non-hydrogen atoms. The final R value was 0.15 for the 1517 observed independent reflections. The dihedral angle between the planes through the benzene ring and the pyrimidine ring is $76^{\circ}$. The conformational angle formed by the projection of the S-C(5) bond with that of N(1)-C(1) where the projection is taken along the S-N(1) bond is $77^{\circ}$. The imino nitrogen atom, N(1), and pyrimidine nitrogen atom, N(3), form intermolecular $N-H{\cdots}N$ hydrogen bond between the molecules related by center of symmetry. Amino nitrogen atom, N(4), forms two intermolecular $N-H{\cdots}O$ hydrogen bonds, with O(1) and O(2) atoms of different molecules separated by b. A two dimensional network of hydrogen bonds form infinite molecular sheets parallel to the (100) plane. Adjacent sheets are bound together by van der Waals forces.

(dl)-2-Benzyl-4-ethylester-5-(p-methylphenyl)-3H,5H,6H-1,2,6-thiadiazine-1,1-dioxide, $C_{20}H_{22}N_2O_4S$의 結晶 및 分子構造

신현소,김의성,송현,이채호,Shin, Hyun-So,Kim, Euisung,Song, Hyun,Lee, Chai-Ho 대한화학회 1995 대한화학회지 Vol.39 No.5

(d I)-2-Benzyl-4-ethyl-ester-5-(p-methylphenyl)-3H,5H,6H-1,2,6-thiadiazine-1,1-dioxide의 결정 및 분자구조를 단결정 X-선 회절법을 이용하여 해석하였다. 결정은 단사정계에 해당하고 공간군은 $P2_1$이며, 단위세포 상수는 $a=8.756(8)\AA$, $b=25.757(2)\AA$, $c=8.628(1)\AA$, $\beta=99.15(4)^{\circ}$이었다. 기타 다른 변수값은 V= 1,921(2) ${\AA}^3$, $T=298^{\circ}K$, $D_C=1.336\;g/cm^3$, ${\mu}=1.54\;cm^{-1}$ 및 Z=4이다. $3{\sigma}(Fο)$ 이상인 2049개의 독립회절반점에 대한 최종 신뢰도 R값은 0.051이었다. 단위세포내에는 결정학적으로 비대칭성인 2개의 독립된 분자가 존재한다. 슬폰기의 배열은 다소 왜곡된 정사면체 구조를 나타내며, N(6)와 N(6')는 각각의 thiadiazine 고리의 최소 자승면으로부터 상당히 이탈된 사실을 알 수 있다. 결정내에서 분자들간에는 2개의 N-H---O형 분자간 수소결합과 van der Waals 힘으로 결합되어 있다. The crystal and molecular structure of the title compound has been determined from 2568 reflections collected on an automatic CAD4 diffractometer using graphite-monochromated $Mo-K\alpha$ radiation. The crystal is monoclinic system, space group $P2_1$ with unit cell dimensions $a=8.756(8)\AA$, $b=25.757(2)\AA$, $c=8.628(1)\AA$, $\beta=99.15(4)^{\circ}$, V= 1,921(2) ${\AA}^3$, Z=4, $D_C=1.336\;g/cm^3$, ${\mu}=1.54\;cm^{-1}\;and\;T=298^{\circ}K$. The final R factor was 0.051 for 2049 reflections over $3{\sigma}(Fο).$ The crystal has two asymmetric molecules in the unit cell. The arrangement of sulfon group was shown a distorted tetrahedron structure and N(6), N(6') atoms were deviated from the least-squares planes of the thiadiazine rings, respectively. The molecular packings in the unit cell are linked by the two intermolecular hydrogen bonds of N-H---O type and van der Waals forces.

準重原子를 포함하는 結晶의 새로운 構造解析法

김직태,신현소,구정회,Kim, Jik-Tae,Shin, Hyun-So,Koo, Chung-Hoe 대한화학회 1972 대한화학회지 Vol.16 No.1

A method is described to obtain the refined atomic coordinates from two dimensional electron density projections containing partially or completely overlapped semiheavy atoms. Benzidine perchlorate and hydrazonium diphosphate were used in this work as examples. The results show that the suggested method gives an excellent guide.

X-線 廻折法을 利用한 벤지딘過鹽素酸鹽의 結晶構造에 關한 硏究 (II)結晶構造의 解析

구정회,신현소,강만형,Koo, Chung-Hoe,Shin, Hyun-So,Kang, Man-Hyong 대한화학회 1970 대한화학회지 Vol.14 No.1

The approximate crystal structure of benzidine monoperchlorate has been determined by single crystal X-Ray diffraction technique and patterson method. As the molecule has a center of symmetry in it and location of perchlorate ion is symmetrically on the mirror plane in the unit cell, perchlorate ion is forming hydrogen bond with two -$NH_2$ groups in the different molecule. Thus, one molecule of benzidine and perchloric acid combines 1:1 by mole ratio.

The Crystal and Molecular Structure of Theophylline Hydrochloride

구정회,신현소,오선숙,Chung Hoe Koo,Hyun So Shin,Sun Suk Oh Korean Chemical Society 1978 대한화학회지 Vol.22 No.2

Theophylline 鹽酸鹽의 結晶 및 分子 構造를 3次元的인 X-線 回折 data로부터 Patterson法에 의하여 決定하였고, Block-diagonal least square와 Fourier法으로서座標를 精密化하였다. 이化合物은 a = 14.01, b = 11.49, c = 6.77${\AA}$의 單位格子를 가지는 斜方晶系에 屬하는 結晶 이며 空間群은 $P_{na21}$ 이다. 743개의 觀測된 data에 대한 최종 R값은 12.2%이다. Theophylline 分子內 原子間 距離는 유사化合物에서 얻은 값과 거의 일치한다. 이들 原子는 同一平面을 이루고 있으며 HCl의 鹽素原子는 theophylline의 N(1) 原子와 3.06${\AA}$ 距離의 Cl${\cdot}{\cdot}{\cdot}$N(1), 水素結合을 이루고 있다. 모든 分子 는 대략 (001)과 (002)面上에 배열되어 있고 各分子間은 van derWaals force에 의해 三次元的 構造를 이루고 있다. The crystal and molecular structure of theophylline hydrochloride has been determined from X-ray data by Patterson techniques. The structure has been refined by block-diagonal least-squares and Fourier synthesis on three dimensional data. The unit cell is orthorhombic, space group $P_{na21}$, with a = 14.01, b = 11.49, c = 6.77${\AA}$, and contains four molecules. The final R value based on 743 observed reflexions is 12.2%. The intramolecular distances are similar to those in other compounds containing a purine or pyrimidine group. The molecules are nearly planar and are stacked in layers parallel to the (001)plane. The chlorine atom is coordinated to N(1) atom at a distance of 3.06${\AA}$. The structure is stabilized mainly by van der Waals interactions; however, a short N${\cdot}{\cdot}{\cdot}$Cl contact of length $3.06\AA$, which is slightly less than the expected van der Waals separation, suggest that weak charge transfer interaction may be present. The relationship between this structure and the known structures of theophylline monohydrate and caffeine monohydrate are discussed.

Probenecid, $C_{13}H_{19}NO_4S$의 結晶構造

김의성,신현소,Kim, Eui-Sung,Shin, Hyun-So Korean Chemical Society 1991 대한화학회지 Vol.35 No.6

Probenecid의 결정구조는 graphite-monochromated Mo-K${\alpha}$선을 사용하는 ENRAF-NONIUS CAD-4 자동 X-선 4축 회절기에서 수집된 2574개의 독립적 회절 반점들을 이용하여 결정되었다. 결정은 triclinic system에 속하고, 공간군은 P$\bar{1}$이며, 단위세포 상수는 a = 7.535(2)${\AA}$, b = 18.473 (5)${\AA}$, c = 5.317(9)${\AA}$, ${\alpha} = 92.00(5)^{\circ}$, ${\beta} = 99.02(5)^{\circ}$, ${\gamma} = 94.89(2)^{\circ}$, V = 727.4(2)${\AA}^3$이었다. 이 밖의 다른 parameters로서, Z = 2, $D_m$ = 1.310, $D_x = 1.302 gcm^{-3}$, ${\mu} = 1.88 cm^{-1}$, F(000) = 304, and T = 298 K이었다. 5${\sigma}(F_o)$ 이상인 1209개의 반점들에대한 최종 R및 $R_w$는 각각 0.0676과 0.0630이었다. 질소원자 N(13)의 공간배열에서, 결합각의 합은 350.9이며, 질소 주위의 세 원자가 이루는 평면에서 0.268(6)${\AA}$ 만큼 벗어나 있다. S(1)-C(4) 결합길이는 1.792(6)${\AA}$이며 C(4)-S(1)-N(13) 결합각은 $106.5(3)^{\circ}$이다. 분자의 전체적인 형태는 황에 대하여 접혀진 구조를 나타내고 있다. The crystal structure of Probenecid has been determined from 2574 independent reflections collected on an automatic ENRAF-NONIUS CAD-4 diffractometer using graphite-monochromated $Mo-K{\alpa}$ radiation. The crystal is triclinic, space group P$\bar{1}$ with unit cell dimensions a = 7.535(2)${\AA}$, b = 18.473 (5)${\AA}$, c = 5.317(9)${\AA}$, ${\alpha} = 92.00(5)^{\circ}$, ${\beta} = 99.02(5)^{\circ}$, ${\gamma} = 94.89(2)^{\circ}$, V = 727.4(2)${\AA}^3$, Z = 2, $D_m$ = 1.310, $D_x$ = $1.302 gcm^{-3}$, ${\mu}$ = $1.88 cm^{-1}$, F(000) = 304, and T = 298 K. Final R = 0.0676 and $R_w$ = O.0630 for 1209 reflections > 5${\sigma}(F_o)$. In the spacial arrangement about N(13), the sum of bond angles about nitrogen is 350.9° and the nitrogen lies only 0.268(6)${\AA}$ out of S(1)-C(14)-C(17) plane. The S(1)-C(4) distance is 1.792(6)${\AA}$ and the C(4)-S(1)-N(13) angle is $106.5(3)^{\circ}$. The overall conformation of the molecule is folded with respect to sulfur.

The Crytal and Molecular Structure of Morpholinothiosemicarbazide

구정회,김훈섭,신현소,이영자,Chung Hoe Koo,Hoon Sup Kim,Hyun So Shin,Yungja Lee Korean Chemical Society 1973 대한화학회지 Vol.17 No.2

몰포리노치오세미카바자이드의 결정 구조가 X-선 해석에 의하여 결정되었다. 세포 상수는 a=4.19(2), b=6.56(2), c=26.67(4)$A^{\circ}$ 이고, 단위 세포는 4분자를 포함하며, 공간 군은 $P2_12_12_1$이다. 원자좌표치는 최소자승법으로 정밀화하였으며 R값은 651개의 관측 반사를 써서 계산한 결과 0.07이다. 아미노 질소 원자는 a-축에 평행한 2회의 나선 축에 의하여 옮겨지는 다른 분자의 황원자와 3.48 및 3.49$A^{\circ}$의 수소결합을 하고 있으며 아미노 질소 원자는 a-축에 평행한 2회의 나선 축에 의하여 옮겨지는 다른 분자의 아미노 질소 원자와 3.04${\AA}$의 수소결합을 하고 있다. 이들 3개의 수소결합은 분자들을 2회의 나선축 부근에 배열하게 한다. 수소결합 이외로 분자들을 연결하는 힘은 van der waals의 힘이다. The crystal structure of morpholinothiosemicarbazide has been determined by single crystal X-ray analysis. The lattice constants are a = 4.19(2), b = 6.56(2) and c = 26.67(4)${\AA}$. The unit cell contains 4 molecules and the space group is$P2_12_12_1$. The atomic parameters have been refined by least-squares method to a final R value of 0.07, based on the 651 observed reflexions. The amino nitrogen atom forms hydrogen bonds to the sulfur atoms of the other molecules related by the two-fold screw axis parallel to the a-axis, the distances of the hydrogen bonds being 3.48 and 3.49${\AA}$. On the other hand, the imino nitrogen atom forms a hydrogen bond to the amino nitrogen atom of the other molecule related by the two-fold screw axis parallel to the a-axis, the distance of the hydrogen bond being 3.04${\AA}$. These three hydrogen bonds arrange the molecules around the two-fold screw axis. Apart from the hydrogen bonding system the structure is held together by van der Waals forces.

Benzidine 鹽酸鹽의 結晶構造

구정회,김훈섭,신현소,Koo, Chung-Hoe,Kim, Hoon-Sup,Shin, Hyun-So 대한화학회 1972 대한화학회지 Vol.16 No.1

Benzidine dihydrochloride crystallizes in the triclinic system. The space group is $P_1$. The unit cell dimensions are; a = 4.38${\pm}$0.01, b = 5.76${\pm}$0.01, c = 12.82${\pm}$0.02${\AA}$, $\alpha$ = 101.5${\pm}$0.2, $\beta$ = 99.5${\pm}$0.2, $\gamma$ = 99.5${\pm}$0.2$^{\circ}$; with one molecule per unit cell. The crystal structure has been solved by two dimensional Patterson and by trial and error methods, and refined by means of two dimensional differential synthesis. The bond distances are C-C(*) = 1.40${\pm}$0.02, C-C = 1.52${\pm}$0.02, C-N = 1.51${\pm}$0.03 and N-H${\cdot}{\cdot}{\cdot}$Cl = 3.21${\pm}$0.03${\AA}$. The structure consists of hydrogen bonded molecular layers, extending to the (100) plane, and the hydrogen bonding scheme is similar to that of p-phenylenediamine dihydrochloride. The adhesion between hydrogen bonded molecular layers is due to van der Waals forces.

X-線 廻折法을 利用한 벤지딘過鹽素酸鹽의 結晶構造에 關한 硏究 (I) 空間群과 Diamine 鹽 結晶의 組成과 關係

구정회,사공열,강만형,신현소,Koo, Chung-Hoe,Sa Kong, Yul,Kang, Man-Hyong,Shin, Hyun-So 대한화학회 1970 대한화학회지 Vol.14 No.1

In those six kinds of diamine salt crystal of which their structures had already been determined up to date, commonly one molecule of diamine and two molecules of acid were combined; although the crystal of benzidine perchlorate, only one molecule each of benzidine and perchloric acid were combined. At the case of benzidine perchlorate, one molecule acts as the role of two molecules by coincidence of the center of symmetry point of both the lattice and molecule, and perchlorate ion is locating symmetrically between two -$NH_2$ groups of different benzidine molecule, therefore benzidine and acid could be combined together with 1:1 by mole ratio. When forming the salt with diamine and acid, the combining mole ratio would be determined in accordance with the relationship between the symmetry element that presented by the space group and the symmetry element of diamine salt melecule.