DAEHAN HWAHAK HWOE j EE
(Jeurnal of the Korean Chemical Socieiy) Vol. 20, No. 1, 1976
Printed in Republic o£ Korea
Sodium Sulfisoxazole Hexahydrate 의 결정 및 분자구조와 수소결합에 관한 연구
朴英子•具廷會*
숙명 여 자대 학교 문리 과대 학 화학과 (1975. 11. 13 접수)
The Crystal and Molecular Structure of Sodium Sulfisoxazole Hexahydrate
Young Ja Park and Chung Hoe Koo
Department of Chemistry, Sookmyung Women s University, Seoul, Korea (Received Nov. 13, 1975)
요
약. Sodium sulfisoxazole hexahydrate, CnH^NsOsSNa - 6HQ 의 결정 및 분자구조를 X- 선 화 절법으로 해명하였다. 이 화합물의 결정은 공간군 F2 i / g 에 속하는 단사형으로 4=15.68(3) 5-7. 70
(2), c- 17. 94(4) A, 6=118(2) 。 Z=4 이다.
Weissenberg 사진 촬영으로 얻은 회절반점의 총수는 1717 개이며 중원자법을 적용하여 구조해
명을 한 후 최소 자승법으로 정밀화하였으며 최종 R 값은 0.14 이다.
Benzene ring 과 isoxazole ring 은 평민구조를 가지며 서로 60° 의 각을 이루고 있 匸 +. 나트륨 원자는 다섯개의 물의 산소 원자들과 N(l) 으로 만들어진 찌끄러진 팔면체로 배위되어 있다.
분자들은 결정내에서 14 개의 서로 다른 종류의 수소결합으로 결합되여 있다. 여섯종류의。一日…
O—H, 세 종류의 O — H … O, 두종류의 O—H…N 및 각각 한종류의 N —H… O, O — H…N, N — H … 。■一 H 수소결 합들이 며 그 길 이 는 2. 71 에 서 3. 04 A 까지 이 다.
ABSTRACT. The crystal structure of sodium sulfisozazole hexaliydrate, CuH^NQaSNa - 6 玦 Q has been determined by X-ray diffraction method. The compound crystallizes in the monocEnic space group P2i/c with <2=15. 68(3), 5=7.70(2), c=17. 94(4) A, y3=118(2)° and Z=4. A total of 1717 observed reflections were collected by the Weissenberg method with CuKa radiation. Structure was solved by heavy atom method and refined by block-diagonal least-squares methods to the R value of 0.14.
The conformational angle formed by the S 一 C(l) bond with that of N(2)—C ( 7) , when the projec
tion in taken along the S 一 N(2), is 73°. The benzene ring is planar and makes an angle of 60°
with the plane of the isoxazole ring, which is also planar.
The sodium atom has a distorted octahedral coordination of N(l) and five oxygen atoms from hydrate molecules. Sodium sulfisoxazole hexahydrate shows fourteen different hydrogen bodings in the crystal. These are six -- --- bonds, three -- --- bonds, two O 一 N…N, one N- H…O, O— —N — —— — bond, with the distances in the range of 2. 71 to 3. 04 A.
♦Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul, Korea
—19 —
20 朴英子•具延會
INTRODUCTION
Though the crystal structure of sulfisoxazole1 (Nf-(3, 4~dimethyl-5-isoxazolyl) sulfanilamide, 3, 4-dimethyl - 5 - sulfanilamidoisoxazole) was solved the structure of a sulfisoxazole salt has not yet been reported. In the framework of a study of the electronic structure and chemical bonding of sulfur-containing compounds 1 ^ 7 it seemed interesting to study sodium sulfisoxazole hexahydrate, because of the many different types of bonds present in this compound including anticipated hydrogen bonds.
It is also o£ interest to study the aromatic character of isoxazole ring which was expected to be approximately planar, and to establish the
□de of six hydrate molecules in the crystalline state, and to examine the coordination geometry of sodium atom.
EXPERIMENTAL
Sodium sulfisoxazole hexahydrate was prepared by so slowly evaporating a solution of equi- molecular quantities of sulfisoxazole and sodium hydroxide. After several days clean transparent crystals with prismatic habit were formed, which could grow to rather considerable sizes.
Oscillation and Weissenberg photographs indi cated the monoclinic space group P2\/c. Unit cell parameters were measured on the hOl and hkO Weissenberg photographs calibrated with superimposed NaCl powder as standard using Cu- Ka radiation. The crystal density was measured by the flotation method in a mixture of benzene and chloroform. The crystal data are given in
^Table 1.
Intensity data were collected from equi-inclin- ation Weissenberg photographs taken with CuKa radiation by use of the multiple-film method.
The layers from AO/ to h6l for the b axis and from hkQ to hk\ for the c axis were recorded.
Table 1. The crystal data of sodium sulfisoxazole hexahydrate.
Sodium sulfisoxazole hexahydrate:
& — SO2Na. 6H 2O
H3C ch 3
C11H12N3O3S Na. 6H 2O M. W. -397. 37 Unite cell parameters:
fl = 15. 68(3) A 3 = 7. 70(2) c=17. 94(4) 0 = 118(2) 。 Z=4
Space group : P2i/c,
from systematic absences 0^0 for A—2«+l hOl for Z=2n + 1
Density： calculated value 1. 39 g. cm"3 measured value 1. 40
The approximate sizes of the crystals used for the data collections for the b and c axes were 0. 2 X 0. 2 X 0. 3 and 0. 2X0. 3X0. 5 mm respecti
vely.
The relative intensities were visually estimated by comparison with a calibrated film strip.
The intensities were corrected for spot-shape, Lorentz and polarization effects, and reduced to structure amplitudes. Interlayer scaling constants were calculated from common equivalent reflec tions and the structure amplitudes were placed approximately on an absolute scale following the Wilson method. A total of 1717 independent reflections was observed. All calculations were performed on an IBM 1130 computer with a series of programs by Shiono 8 .
STRUCTURE DETERMINATION and REFINEMENT
After the structure factors were converted into the normalized structure factor, E, a three-
Journal of the Korean Chemical Society
Sodium Sulflsoxazole Hexahydrate 의 결정 및 분자구조와 수소결합에 관한 연구 21
dimensional sharpened Patterson synthesis was computed using 1015 reflections with E value>
0. 55. A Patterson synthesis showed the position of the sulfur atom, but no other atoms could be found. A Fourier synthesis based on the position of sulfur atom showed the remaining non-hydrogen atoms of a sulfisoxazole. Addi tional Fourier synthesis based on the 16 atoms of a sulflsoxazole molecule gave the positions of sodium atom and six oxygen atoms of hydrate molecules consistent with a reasonable molecular packing in the crystal.
Refinement was performed by several cycles of isotropic structure factor calculations using the block-diagonal least-squares program for the IBM 1130, and gave a final lvalue of 0.14 for all the 1717 observed reflections with Hughes9 weighting scheme. No allowance was made for the hydrogen 乙 toms. The atomic scattering factor used were those from the International Table for X-Ray Crystallography. 10 The final positional and thermal parameters are given in Table 2 with their estimated standard deviations.
The observed and calculated structure factors are listed in Table 3.
Table 2. Fractional atomic coordinates and isotropic thermal parameters for sodium sulflsoxazole hexahyd
rate. The key to the atomic numbering is given in Fig 1. The estimated standard deviations given in parentheses refer to the last decimal positions of the corresponding parameters.
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