The Crystal Structure of Thiourea of Derivatives(I)

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DAEHN HWAHAK HWOEJEE

(Journal of the Korean Chemical Society) Vol. 21, No. 5, 1977

Printed in Republic of Korea

Thiourea Derivatives °| 결정과 분자구조 (제 1 ^보)

朴英子•徐廷善* •具廷會**

*Department of Chemical Engineering, College of Myungjee, Seoul, Korea

**Department of Chemistry, Seoul National University, Seoul, Korea 숙명여자대학교 이과대학 화학과

(1977. 2. 16 접수)

The Crystal Structure of Thiourea Derivatives (I)

Young Ja Park, Chung Sun Suh* and Chung Hoe Koo**

Department of Chemistry, Sook Myung Womens University, Seoul, Korea

(Received Feb. 16, 1977)

요 으E Thiourea derivative ^인N- (a-dimethyl /3-hydroxy) ethyl JV'-cyclochexyl thiourea, G1H22N2OS 의 결정 및 분자구조를 X-선 회 절 법 으로 해 명 하였다. 이 화합물의 결정 은 공간군 Pbca 에 속하는 orthorhombic 형으로"=10.33 (3), 6=11.82(3), c=22. 57(4) A 이고 Z=8 이다.

Weissenberg 사진촬영으로 얻은 회절반점의 총수는 1414개이며 중원자법을 적용하여 구조해명을 한 후 최소자승법으로 정밀화하였으며 최종 & 값은 0.13 이다.

Cyclohexane ring 은 normal 산iair conformation thiourea 부분은 평면을 이 루고 있다. 일차 알 코올의 hydroxyl group은 N⑵ 원자와 분자내 수소결합을 이뤄서 전체분자를 안정화 시키고 있다.

분자들은 결정내에서 수소결합과 van derWaals힘으로 서로 결합되어 있다. 분자내 수소결합 N⑵一H・・・O 는 강한 수소결합으로 N…。길이는 2.71A이고, 분자간 수소결합。…H…S 의

O… S 길이는 3. 02 A 으로 축에 나란하다.

ABSTRACT. The crystal structure of N- (a-dimethyl /3-hydroxy) ethyl TV7-cyclohexyl thiourea, C11H22N2OS, has been determined by X-ray diffraction method. The compound crystallizes in the orthorhombic space group Pbca with a—10. 33(3),^力=1L82(3), c=22. 57(4) A and Z=8. A total of 1414 observed reflections collected by the Weissenberg photographs and was solved by heavy atom method and refined by block diagonal least-squares methods to the R value of 0.13.

The cyclohexane ring has a normal chair conformation and the thiourea unit is planar. The primary alcoholic group 0—H bonded to C(l) makes an intramolecular hydrogen bond with N (2), which leads to stablize the molecule.

There are two independent hydrogen bonds in the structure. One of them is of the type N——intramolecular hydrogen bond with the length 2.71 A, another is of the type O一 interm시ec니ar hydrogen bond with the length 3.21A parallel to the b axis. Apart from the hydrogen bonding system the molecules are held together by van der Waals forces in the crystal.

-307 —

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朴英子，徐廷善•具廷會 308

INTRODUCTION

Crystallographic studies on the structures of the biological compounds have provided valuable information which has led to a better under

standing of the properties of the compounds as well as to their function in life processes.

These studies result in complete intramolecular and intermolecular stereo^산icmical information.

This includes configuration, conformation, bond lengths, valence angles and the system of hy

drogen bond. The data required for the crystal structure can be obtained by X-ray, neutron or electron diffraction metbods.

To an increasing extent, the structure deter

minations of a series of related compounds have been planned and completed. The results of these studies are much more meaningful than an isolated crystal structure investigation, and enable us to predict the conformation of the structures which have not yet been studied.

For the thiourea, an appreciable number of compounds have been studied, either as the free molecule1^3, or as components of more complex molecules4.

The structure determination of ^j^V- (a-dimethyl ^-hydroxy) ethyl N'-cyclohexyl thiourea has been planned and completed using single crystal X-ray diffraction method. The detailed crystal structure of the compound is presented.

It has long been o£ interest to study the con

formation of thiourea unit of the molecule, N—C—N, due to their planarity and the

S

II

partial double bond character for C一N and C=S bonds.

The structure determination was also under

taken in order to establish the conformation of cyclohexane ring which was expected to be chair form, and to examine the orientation

of the hydroxyl group which might be involved in intramolecular hydrogen bond.

EXPERIMEMTAL

The compound N- (a-dimethyl /3-hydroxy) ethyl IV'-cyclohexyl thiourea was kindly pro

vided professor Y. S. Chough of College of Pharmacy, Seoul National University. The compound was recrystallized from an acetone s시ution at room temperature. The crystals were welll-shaped colorless hexagonal prisms, elongated along the b axis. They were examined by oscillation and Weissenberg photographs and indicated 나le orthorhombic space group PAcfl.

Unit cell parameters were measured on hQl and 0 诳 Weissenberg photogaphs calibrated with superimposed aluminum foil as standard using CuKa radiation. The crystal density was measured by the flotation method in a mixture of benzene and carbontetrachloride. The crystal data are 요iven in Table 1.

Intensity data were collected from equi

inclination Weissenberg photographs taken with CuKa radiation by use of the m니tiple film method. The layers from hOl to h8l for the b axis and from Qkl to 2kl for the a axis were recorded. 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 con

stants were calculated from common equivalent reflections and the structure amplitudes were placed approximately on an absolute scale following the Wilson method. The final number of observed independent reflections was 1414. All calculations were performed on an IBM 360 version of a series of crystallographic program by Shiono5.

Journal of the Korean Chemical Society

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Thiourea Derivatives 의 결 정 과 분자구조 (제 1 보) 309 Table 1. The crystal data of N-(a-dimethyl ^-hydroyy)

ethyl N'-cyclohexyl thiourea.

平

! l-NH-C-NH-C-CH2 -OH

7 s ch

3

CnH^N/JS M. w. =230. 38 Unit cell parameters:

a =10. 33(3) A 3=11. 82(4) c=22. 57(5) Z —8

Space group: Pbca

from systematic absences Okl 乃=2就+1 hQl Z = 2n+1 hkO A—2«+l Density:

calculated value 1. 10 g. cm~3 measured value 1. 09

STRUCTURE DETERMINATION AND REFINEMENT

After the structure factors were converted into the normalized structure factor, E, a three- dimensional sharpened E2-l Patterson synthesis was computed. The position of the sulfur atom was obtained from the Harker sections and Harker lines of the Patterson map, but no other atoms could be found. A Fourier synthesis based on the sulfur atom showed the thiourea moiety of the molecule. Additional Fourier synthesis based on the 4 atoms, S, N(l), N(2), C(5) of a thiourea part gave the position of remaining other atoms of a stereochemically reasonable model for the molecule.

Refinement was performed by several cycles of isotropic and two cycles of anisotropic structure factor calculations usin용 the block

diagonal least-squares program for the IBM

Table 2. Fractional atomic coordinates and anisotropic thermal parameters in N-(a-dimethyl /3-hydroxy) ethyl N'-cyclohexyl thiourea.

Key to the atomic numberin응 is 음iven in Fig. 1. The temperature factor expression used was exp (— (灼5ii + &%22 + Z%33+아的院 +가偽_3七初位3)〕,

The estimated standard deviations in parentheses refer to the last decimal positions of the corresponding parameters.

X z & j ^，33 312 彻₃

s -0.0271(5) 0- 4892(4) 0.4066(2) 0.0092(4) 0.0072(4) 0.0015(1) T). 0027(4) —0.0005(2) 0.0002(2) o 0. 287(2) 0.160(1) 0.416(1) 0.029(3) o.m ⑴₁ _0.004(1) _0.008(2) _-0.004(1) _-0.001(1) n（i） 0.158(1) 0.380(1) 0.467 ⑴ _0.008(1) _0.007(1) 0.001(1) 0.001(1) -0.000(1) -0.000(1) N(2) 0.142(1) 0.327(1) 0.369(1) 0.013(2) 0.009(1), 0.001(1) 0.002(1) ~0.000(1) -0.001(1) C(l) 0- 279(3) 0.197(2) 0.476(1) 0.0019(4) 0.012(2) 0.002(1) 0.006(2) 0.000(1) 0.001(1) c⑵ _0.285(2) _0.328(1) _0.480(1) _0.009(2) _o.ou⑵ _0.000⑴ _0.002(1) 0.000(1) 0.000(1) C(3) 0.312(2) 0. 310(2) 0.549(1) 0.016(3) 0.023(3) i 0.001(1) 0.008(2) 0.001(1) 0.000(1) C⑷ 0.398(2) 0. 384(2) 0.444(1) 0.008(3) 0.017(3) j 0.002(1) 0.001(2) 0.001(1) 0.000(1) C(5) 0.099(1) 0. 392(1) 0.413(1) 0.006(1) 0.009 ⑴ _0.001(1) _0.000(1) 0.000(1) 0.000(1) C(6) 0.096(2) 0.341(1) 0.306(1) 0.015(2) 0.008(1) 0.001(10) 0.000(1) -0. 001(1) -0.001(1) C(7) 0.189(2) 0.429(2) 0. 275(1) 0.017(3) 0.014(2)； _0.001(1) _-0.002(2) _0.000(1) _0.000(1) C(8) 0.151(3) 0.442(3) 0.207(1) 0.030(5) 0.019(3) ! 0.001(1) 0.002(3) 0.000(1) 0.001(1) C(9) 0-159(3) 0. 317(2) 0.178(1) 0.023(4) 0.023(3) 0.001(1) 0.008(3) 0.001(1) 0.003(1) C(10) 0.075(3) 0. 234(2) 0. 208(1) 0.019(4) 0.015(3) 0.004(1) 0.000(3) 0.000(1) 0.000(1) C(ll) 0.108(3) 0. 224(2) _{0. 278(1)} _0.027(4) ^{0.011(2) j} 0.002(1) 0.003(2) 0. 002(1) 0.003(1)

Vol. 21, No. 5, 1977

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310 朴英子-徐廷善•具廷會

Table 3. Observed and calculated structure factors: Columns are： Index, |Fobs |, |Fcai|.

h==0 k=Q 14 12- 36 16.30 8 6.80 8.00 25 9.56 12.42 i 18 26.74 25.70 17 17.22 22.51 4 55.74 46.60 16 27.15 35.03 12 6.30 9.62 .27 17- 67 19.71 25 18.04 12.09 20 33-64 29.37 6 119.42 113.90 20 10.18 14.77 16 4.78 9- 02 兀=4 k~l h=7 k=l 21 13.10 10.59 8 103.48 87.62 24 5.97 24. 27 h=l 0 53.27 59.24 1 23.56 22.26 22 25.29 21.75 10 123.17 104. 78 26 9.97 15.78 2 27.35 33.40 1 79.14 72.38 2 11.37 14.77 26 14.25 11.19 12 29.29 23.91 h=5 k=0 3 40.95 37.97 2 18.38 19.82 3 6.63 11.37 28 7.17 7.14 16 71.06 69.79 2 56.60 52.59 5 124.41 121.44 3 55.28 52.02 4 14.95 17.08 A=1 久=2 18 33.39 39.85 4 36.54 38.32 6 23.48 19.96 4 32.59 23.20 5 11.74 13.14 1 89.27 91.51 22 40.95 43.26 6 23.77 38-26 7 36.50 42.51 5 56.07 69.22 8 13.26 17.03 2 47.58 52.50 26 20.14 31-39 8 28.75 39.57 9 72.09 68.60 6 8.65 9.45 10 26.45 29.10 3 54.67 52.57 28 17.26 24-03 10 16.73 17.48 10 16.85 25.47 7 8. 20 12.03 14 13.18 8.58 4 36.62 40.82 h=l k=Q 12 7.99 2.53 11 82.31 76.40 8 11.45 12.47 15 7.58 9.74 5 22.45 26.43 2 122-14 109- 24 14 20.43 20.97 13 18.46 16.26 9 9.76 14.13 16 12.92 12.12 6 5.52 2.08 4 126- 92 116.86 18 16.27 21.26 15 49.39 45.32 10 26.24 28.56 A=8 ^=1 7 6.06 10.93 6 35.43 45.29 20 19.28 22.81 17 50. 22 49.52 11 6.14 8.60 0 15.98 19.19 8 6.59 4.79 10 95.12 37.03 24 6-10 8.63 19 11.82 16.64 12 6.39 2.60 1 11.33 17.13 9 7.13 4- 66 12 5.93 7.80 h~6 ^=0 20 16.11 18.85 13 6.63 5.73 2 19.69 25.83 10 34.52 34.59 14 46.63 48.33 0 37.16 28.43 21 31.80 32.66 14 6.88 8.66 3 32.30 30.42 11 67.97 64. 29 16 24.18 38.77 2 11.62 10.73 23 15.41 15-12 15 7.17 8.61 6 12.77 14.80 12 19.86 21.62 18 18.25 28.59 4 9.10 18.45 27 14.17 14.18 16 7.33 6.77 7 43.71 41.51 13 22.62 22.88 20 9.06 9.02 8 15.37 19.91 k=l 17 25.95 29.72 9 49.85 44.62 14 18.00 17.87 h=2 h=0 14 19.61 22.53 0 142.74 144.18 18 9.31 8.78 10 15.20 15.26 16 19.81 27.85 0 59,36 58.04 16 18.91 19.31 1 78.11 91.67 19 15.20 15.13 13 31.56 29.16 h=2 k=2 2 77.20 64.76 22 11.08 14.88 2 140. 97 150.19 21 10.42 13.23 15 14.50 18.25 0 111. 56 117. 78 4 125.11 122.63 A-7 D 3 24.68 21.91 25 7.95 13. 29 19 20.10 20.41 2 146.18 126.47 6 98.62 89.61 2 63.28 62.84 5 10.05 10.76 A=5 如=1 h=9 k=l 3 98.54 87.59 8 16,23 13.98 4 34.93 40.13 6 36.79 27.21 1 25.54 25.03 4 13.14 16.34 4 80.37 67.82 10 69.29 72.87 8 39.46 60.78 7 38.35 35- 56 2 22.45 25.87 8 13.14 16.39 5 37.98 31.11 12 32.71 42.44 10 30.98 34.65 10 36.13 37.66 5 43.96 35.22 A=10 为=고 6 52.94 55.23 14 6.06 7.01 12 12.48 16.35 11 30.73 28.63 7 32.91 27.65 1 13.06 15.40 7 8.32 14.45 16 25- 91 24.37 14 10.92 15.67 12 40.54 31.94 8 9.43 9.82 3 20.56 23.18 8 12.19 11.09 18 7.04 9.79 18 13.18 17.43 13 고4. 75 16.03 9 19.49 21.23 7 12.69 12.55 9 50.67 45- 73 20 33.74 41.35 20 17.69 15.76 14 10.01 8.03 12 24.55 31.67 9 12.32 14.13 10 60.92 48.15 22 18.66 26.19 22 6.84 9.30 18 14.79 15.82 13 7- 04 9.71 13 16.54 17. 11 11 26.90 27.83 26 9.15 5.27 24 15.16 18.57 20 12.03 19.50 14 22.86 27.28 16 9.76 2.74 12 56. 27 55.43 28 8.12 6- 78 4=8 D 21 10.92 15.41 15 25.62 25.63 h=0 知=2 14 28.30 31.21 0 6.84 3.43 22 8.32 13.88 16 18.41 26.36 0 60.19 47.52 16 36.62 36.20 2 7.09 3.25 4 15.53 17.95 23 H. 37 10.03 17 1가. 75 9. 26 1 113. 76 142.40 18 24.47 25- 75 6 6.06 1.33 10 8.90 6.43 A=3 k=l 18 10.73 14.09 2 33.70 36.27 19 20.60 19.32 8 25.79 21.73 A=9 k=0 1 48- 49 48.30 A=6 i=l 3 3.34 8.21 20 16.93 12.89 10 12.81 14.02 2 26. 25 22.87 2 4- 57 9.36 0 76.91 64.42 4 88.45 90.55 22 23.32 18.91 12 25.42 41.66 4 12.56 10.14 3 22.70 18.12 1 26.12 24.47 5 13. 26 3.92 26 18.91 21.32 14 41.90 76.74 8 32.05 35.55 5 51.25 49.99 2 21.13 27.22 6 116.54 126.24 20 14.09 14-38 16 14.83 18.56 10 17.44 17.14 7 53.84 46.00 3 40. 22 40. 25 7 48.90 45.29 h=3 k~2 18 5.07 6.82 12 18.79 20.98 10 54.58 46.23 5 6.14 5.24 8 9.10 4.92 1 69.41 70.11

A=4 为₌₀ 14 25.62 26.78 11 59.65 60.35 6 9.89 3.00 9 12.85 7.39 2 33.99 29.92 0 53.66 49.36 20 8.03 11.09 12 37.49 37.00 7 28.59 29.20 10 43.83 42.34 3 6.55 11.32 2 59.32 72.37 A=10 i=0 14 20.80 25.22 9 28-10 27.46 11 57.18 45.53 4 8.85 4.77 4 20.89 22.64 0 8.01 11.45 15 16.81 18. 22 10 9. 72 10. 85 12 54.62 50.37 5 33.49 32.05 6 37.45 39- 61 A=ll k=Q 16 10.05 9.56 11 17.30 18.63 13 6.34 12-01 6 22.95 26.87 8 15.37 27.61 2 9.35 10.79 17 17.46 15.58 13 33.00 37.50 14 13.68 8.03 7 32.96 32.40 10 32.75 32.88 4 12.65 10.73 19 20.80 24.22 15 23.98 23.97 15 6.96 9.09 8 44.37 47.02 12 56.81 60.02 6 8.98 9.71 21 23.77 24.13 18 14.95 16.41 16 52.89 53.36 9 21.79 22.86

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Thiourea Derivatives의 결정과 분자구조 （제 1보） 311

11 12.77 15.63 16 22.08 22-18 14 20.23 21.58 I 3 4.37 4.80 7 22.86 23.24 14 10.42 4.34 20 고0.92 9.11 15 45.19 49.34 4 38.39 38.68 8 10.96 16.48 15 10.83 14.10 22 9.60 2.87 16 8.77 9.21 5 6.55 7.88 11 27.93 31.17 16 11.25 11.86 A-7 <6=2 17 11.95 12.02 7 35. 51 38.03 15 12.52 12.01 18 12.98 16.02 1 9.27 9.98 18 8.69 10.68 9 40.25 36.83 21 7.70 10.34 19 10.71 14.58 2 34.48 32.57 19 16.19 19.96 11 10.38 12.85 A=8 k—3 20 13.10 15.32 3 14.83 16.92 20 17.88 18.66 12 17.10 18.46 1 15.61 18.30 24 10.22 11.20 4 38.15 36.51 21 23.52 21-40 13 28.67 32.19 3 39.71 35- 25 A=4 k=2 5 16.60 19.14 23 11.86 15.80 15 20.52 28- 31 4 13-68 13- 91 0 61.30 64.17 6 20.05 21.24 25 13.55 18.98 16 20- 43 21- 79 6 7.99 10.46 1 64.51 60.14 7 15.61 15.02 27 14.42 13. 16 19 11.49 13.56 7 13.97 13.68 2 22.00 28- 03 8 29.70 33.06 h=2 i=3 23 9.35 9.77 10 11.53 14.39 3 59.49 57.08 10 20.10 20.46 0 110.67 6.29 A=5 &=3 11 8.94 10.59 4 61.13 55.67 11 31.10 27.95 1 65.99 72.27 1 43-42 39.83 12 19.53 16.81 5 21.92 22.63 12 26.04 19.27 2 18.46 20.88 2 6.63 6.81 13 24.84 21.55 6 45.97 43.64 14 23.93 23.10 3 102.02 94.97 3 12.94 18.99 15 10.88 10.69 7 21.59 25- 03 18 22.20 20.83 4 14.46 8.91 4 11.58 11.52 17 8.40 8.77 9 7.95 10- 26 20 15.45 12.19 5 19.86 23.74 5 4.61 10.61 19 8- 32 9.12 10 40.66 37.27 22 9.10 4.76 6 9.10 7.82 6 27.60 26.80 21 6.63 6.15 12 17.51 16.29 A=8 k=2 7 4.49 1- 79 7 7.95 11.06 h=9 知=3 13 11.53 11.78 2 10.18 6.48 8 11.00 12.46 8 9.23 13.20 3 11.53 8.45 14 10.92 12.43 3 12.52 11.94 9 11.78 16.50 9 19.03 17.53 4 8.94 5- 56 16 16.40 16.81 10 10.71 8.94 10 18.29 16.37 10 23.11 24.58 6 8.94 8.98 17 10.59 15.40 A=9 k=2 11 9.10 8.40 11 31.43 32.93 7 8.99 5.72 18 10- 71 4.40 2 31.56 29.05 12 6.59 6.80 12 12.44 14.31 10 9.43 4.64 20 11.82 10.68 4 16.93 18.13 13 22.78 28.99 13 5.73 6.40 11 9.27 7.04 21 11.53 10.74 6 13.14 10.03 15 9.80 14- 30 15 12.40 11.96 16 8.28 7.23 22 26.65 27.68 7 15.15 15.91 16 16.22 22.44 16 13.10 14.18 A=10 为₌₃ 26 9.47 7.25 8 29.25 27.74 17 10.46 14.11 17 14.62 13.87 1 13-39 11.73

h=5 k=2 14 18.04 15.63 18 14.79 20.96 21 18.50 19.37 2 20.14 19.22 1 44.04 47.02 18 16.11 14.89 19 30.44 27.44 h=6 k=3 7 22.37 21-17 2 31.84 31.42 20 11.21 10.28 20 8.49 6.26 0 7.50 0.05 9 16.31 16.34 3 24.72 23.30 A~10 k=2 21 20.10 25.41 1 6.34 14.70 13 10.05 9.87 4 37.94 41.60 9 12.15 9.43 A=3 4=3 2 8.12 9.17 16 8.65 3.48 5 22.78 21.87 h=ll k=2 1 85.44 84.13 3 42.39 43.18 17 5.73 6.33 8 23.07 18.73 2 18.04 15.16 3 10.54 24.12 4 15.00 18.06 h=ll 4=3 10 24.72 25.93 4 10.63 9.66 4 31.06 24.87 5 23.19 24.25 11 13-84 11.25 11 22.86 26.45 8 18- 70 13.57 5 100.06 96.15 6 9.15 11.13 A=12 &=3 12 30.48 33.08 12 14- 25 12.12 6 30.03 31.42 7 31.56 29.65 1 6.47 6.12 14 36.13 37.85 14 18.46 12.64 7 18.74 22-13 9 38.68 40.92 3 7.74 10.08 17 10.71 12.62 k=3 8 40.56 35.04 10 12.56 14.64 7 6.88 9.59 18 10.71 10.57 1 40.78 47.70 9 42.88 51.59 11 7. 70 12.52 9 17.30 12.45 19 10.55 9.57 2 41.69 43.06 10 17.76 17.41 13 22.62 20.13 A=0 『4 20 13-64 15.05 3 16.07 18.38 11 37.82 32.56 15 7.29 8.48 0 54.25 44.70 24 13-68 12.73 4 19- 36 22.88 15 19- 83 17.47 16 8.16 8.76 1 56.60 49.30 A=6 &=2 5 75.96 71.05 16 6.92 7.02 17 25.01 24.98 2 75.35 83.91 0 47.21 44.04 6 6.88 9.24 17 37.98 48.46 18 7.91 11. 71 3 13.68 15.68 1 12.36 7.33 7 48.36 44.07 20 8.90 9.42 19 20.56 19.86 4 37.86 31.67 2 10.96 4.19 8 14.95 15.62 21 19.20 70.24 23 6.07 11. 23 5 129.52 104.40 3 11.86 13- 42 9 9- 52 13.55 23 12.28 11- 42 24 6.22 7.07 6 54.58 46.18 6 24- 22 20.31 10 5.77 9.31 27 10.71 14.11 h=7 A=3 7 47.46 40.35 9 26.04 23.27 11 47- 95 48- 55 A=4 k—3 3 11.21 15.05 8 40.37 42- 69 10 28.34 27.38 12 31.10 28.15 0 ； 68.18 64.53 4 6.55 7.55 9 50.42 44- 42 11 11.16 12.79 13 14.75 23.74 2 10-88 14.42 5 16.89 16.79 1 아 81.36 79.92

12 37.03 37.46 15 47.13 48.85 16 36.05 36.80 17 43.30 42.05 19 8.03 11.99 20 15-65 14.79 22 12.77 13.89 26 16.23 12.71

1 17.95 14.53 2 71.97 71.38 3 16.48 12.24 4 45.93 61.95 5 4.17 4.60 6 17.14 20.26 7 35.47 37.52 8 14.75 17.03 1고 13.84 12.26 12 18.62 10.76 13 20.43 22.04 14 9.97 10.67 15 22.08 20.70 16 20.10 24.94 18 7.13 6.52 20 11.82 16.93 27 8.40 13.70

h=2 农₌₄ 0 127. 71 125. 73 1 7- 70 9.50 2 45.27 41.80 3 5.36 5.34 4 31.76 31.76 5 30.03 30.02 6 74.65 74.65 7 10.42 10-42 10 41.11 35.64 12 20.60 22.24 13 11.95 15.38 14 9. 76 14.61 16 45.52 41.01 18 9.76 8.95 20 14.46 12- 73 22 21.38 21.61 26 16.81 16.08

兀=3

1 17.34 21.64 2 70-16 62.23 3 36- 87 28.86 4 30- 65 24.73 6 9.56 14.33 7 12.23 11.77 8 20.52 23.32 9 7.74 10.32 10 18.33 22.42

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312 朴英子•徐廷善•具廷會

12 20.31 21-40 8 22.00 22.17 25 10.05 6.10 10 18.25 12.73 9 14.05 16-30 7 34.56 35.91 18 17.71 18.54 10 8.24 7.39 27 13.02 17.64 12 12.11 12.26 10 10.96 11.56 9 24.96 27.79 20 14.34 16.25 11 8.32 6.92 A—2 k=5 13 21.13 24.76 11 8.77 8.23 10 40.91 39.34 26 8.94 10.27 12 13.38 19.18 1 23.48 18.43 15 17.51 19- 09 13 4.49 5.77 11 10.88 11.89 A=4 方=4 14 28.22 26.41 2 12.15 20.35 16 8.73 10.84 16 6.55 8.24 12 28.38 28.88 0 86.92 73.13 18 13.43 13.93 4 52.85 45.27 19 14.50 14.84 17 5.15 4.74 14 24.43 26.57 1 16.40 17.76 20 & 03 9.85 5 51.12 44.66 20 6.63 8.71 18 3.87 1.59 15 5.23 10.73 2 46.18 47.45 物=응 k=4 6 31.68 28.58 21 5.81 7.20 19 3.63 4.47 16 6.59 7.46 3 23- 40 26.01 1 9.95 9.17 7 15.32 14.15 22 4- 86 4.42 21 5- 60 6.47 18 23.73 30.36 4 45.89 38.25 14 8.90 10-64 8 2.76 5.73 23 6.71 5.58 A=8 20 13.55 9.40 5 22.53 19.14 h=9 『4 9 12.40 14.49 25 10.30 11.83 0 26.41 26. 20 22 18.87 15.97 6 32- 42 31.94 1 9.36 8.17 11 10.22 13.34 A=5 &=5 1 10.26 8.95 23 10.75 12.48 8 7.54 9.27 2 21.34 19.53 13 15.24 15.01 1 28- 67 27.28 2 15.32 17.90 25 7.99 9.42 10 27.11 24.32 4 20.47 18.04 14 17.05 17- 31 2 25.13 23.50 3 23.81 27.27 26 16.11 20.83 12 10.34 14.71 5 11.82 14.13 15 32.71 36.22 3 2.97 5.29 4 4.45 4.11 A=1 k=6 14 17.96 17.83 8 10.62 12.23 16 8.61 10.96 4 5.81 12.16 5 13.39 15.18 1 49.68 49.46 15 12.11 15- 42 9 8.16 9.43 17 18.33 22.26 5 48.57 45.70 6 6.96 7.87 2 14.79 22 39 16 21- 38 24.80 12 10.22 10.50 18 21.13 24- 35 7 22.37 21.97 7 4.49 3.80 3 17.80 20.32 18 18.70 20.89 14 13.43 12 69 19 10.46 16.06 8 17.05 18.47 8 4.47 3.82 4 3.91 5.02 20 16.73 17.58 17 7.25 4.97 21 6.71 4.34 9 16.19 19.48 9 6.96 7.55 5 20.93 20.85 22 17.43 16.09 18 13.59 10.55 22 3.71 5.70 11 39.34 37.33 11 5.23 4.16 6 4.53 4.36 26 9. 35 10. 27 A=10 必=4 h=3 k=5 12 17.67 20.32 13 13.31 13.39 7 13.02 16.00 h=5 『4 6 9.64 10.20 1 48.20 42.13 13 11.21 14.43 16 9.27 9.13 8 9- 52 12.83 1 9.15 7.45 8 & 53 9.43 2 23.32 23.40 14 6-88 12.30 17 11.78 12.47 10 8.16 12- 29 2 31.76 31.96 10 8.12 3.86 4 17.55 16.34 15 16.81 20.31 19 14.46 15.44 12 12.40 15.83 4 13.88 17.47 12 8.24 7.16 5 19. 28 15.23 16 14.21 16.04 h=9 知=5 13 14.17 13.78 6 7.83 8.88 14 7.29 4.57 6 3.83 3.63 17 23- 65 23.93 4 7.50 3.85 14 13.80 13.56 7 12.77 16.17 A ==11 知=4 7 29.78 31.18 21 12- 40 11.13 8 7.04 10.36 15 9.80 9.52 8 53.06 48,62 2 17.26 15.05 8 9.19 8.92 23 8.96 10.49 10 9.27 9.44 16 27.23 29.42 10 24.71 24.94 4 12.23 11.96 9 22.00 23.03 h=6 4=5 13 7.37 7.79 17 15.90 15.32 11 19.20 23.08 8 19.32 18.64 10 8.40 8.51 0 15-28 15.66 A=10 4=5 18 4.86 7.24 12 9.52 11- 59 11 11- 78 2.94 11 36.17 39.63 1 18.99 21- 91 1 5.07 7.13 h=2 k=6 14 22- 33 22.67 12 8.07 6.48 12 6.59 5.92 2 5.27 7.65 3 12.85 13.40 0 5.68 7.79 15 18.54 18- 80 A=1 13 6.18 7.73 3 24- 06 25.81 6 6.88 7.26 1 5.93 8.61 18 15.49 15.67 1 42.80 54.74 14 13-10 19.12 4 3.83 9.60 7 15-16 14.99 2 16.40 14.70 24 15.08 14.04 2 6.18 5.70 15 44.16 41.21 6 11.86 11.98 9 17.71 15.00 3 20.27 21.82 A=6 A=4 3 15.45 17.53 16 4.41 8.83 7 21.13 21.14 i 13 15.32 16.16 4 30.03 28.79 0 10.50 17.12 4 44.24 38.30 17 21.05 25.78 9 12.65 15.80 i 16 7.58 4.07 6 39.79 37.32 2 8.24 8.31 5 69.13 66.02 18 14.91 17.66 10 6.67 9.50 A=ll i=5 10 28.63 31.85 3 10.71 12.30 6 25.66 21.42 20 12.44 12.72 12 11.41 12.93 5 6.76 7.67 11 8.73 7.26 4 30.61 28.82 7 17.67 21.12 21 14.71 15.94 13 11.86 12.50 8 5.03 5.08 12 14.78 17.67 6 36.09 34.72 8 20-31 20.69 23 8.12 9.49 15 4.90 2.21 9 4.82 4.09 13 21.46 26.46 8 7.50 9.69 9 19.90 18.58 25 8.40 11.83 16 5.60 5.99 10 4.53 3.80 14 14.79 10.13 10 26- 57 29.14 10 IL 워6 13.44 26 4.40 7.86 17 5.15 4.95 11 4.16 4.47 16 22.90 22.78 11 6- 92 6.63 11 31.02 31.76 A=4 A=5 19 6.22 7.95 A=12 ^=5 19 10. 42 9.03 12 30-24 28-18 12 3.83 4- 45 0 36.17 33.65 20 5- 85 5. 77 1 8.03 7.77 20 16.40 20.35 20 11.53 12.58 14 40.29 36.88 1 24.02 25.28 23 12- 73 13-23 3 12.44 11.41 22 16.19 17.94 22 8.82 6.83 15 15.94 11.34 2 10.26 10.00 A—7 k=5 A=0 R=6 26 4.12 2.62 A=7 k=i 16 13.43 15.94 3 37.36 32.90 1 6.39 9.27 0 103.32 93.57 方=3 &=6 1 7.46 10-17 17 12.07 14.72 5 5.85 9.87 2 9.43 10.92 1 5.64 0.68 1 33.49 31.31 2 11.25 13.55 19 9.06 10.36 6 ,24. 55 27. 05 3 7.21 8.89 2 80.87 60.22 2 19.36 20.69 4 12.07 9.89 21 20.56 25.29 7 44.0앙 40.61 4 6.51 12. 24 '4 78.15 73.06 3 8.03 6.82 5 17- 26 18.76 23 3.61 5.96 8 4.82 9.21 5 20.68 23.28 1 5 ,36. 75 27.43 4 64- 80 59.20 6 17.06 17.93 24 10.38 11.24 9 41.57 42.69 8 4.41 6.48 1 6 7.83 13.01 1 5 18- 83 17.25

Journal of the Korean Chem ical Society

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Thiourea Derivatives의 결정과 분자구조 （제 1 보） 313

6 7.66 9.23 13 4.86 7.97 7 27.68 27.86 23 6.47 5.62 10 9.47 9.81 4 20- 31 17.82 7 32.13 33.85 16 10.13 12.03 8 12.40 15.63 A=4 农₌₇ 11 12.32 11.32 5 14.21 12- 69 8 17.34 15.63 20 5.44 5.37 9 22.82 22.83 0 1.81 5.55 13 18.46 17.78 6 49.43 46.88 10 11.37 10.09 22 10.83 13.39 10 3.54 4.58 2 15.82 16.61 15 13.59 18.17 7 4.00 0.10 11 14.83 14.63 h—7 k=6 11 32.83 33.46 3 44.41 44.59 18 4.98 6.41 8 1813 15.16 12 7. 79 12. 2S 1 13.47 13.63 12 5.23 4.16 4 23- 89 23.68 19 9.31 9.23 9 2.92 3.13 14 43.58 42.32 2 24.43 23.40 13 4.61 0.70 6 18.74 19.33 h=7 k=7 10 18.66 11.33 17 11.58 12.21 3 5.31 4.85 14 12.85 10.81 7 13.51 16.07 1 18.41 20.46 11 22.90 23.94 20 5.36 3.52 4 5.36 7.13 15 13.68 16.00 9 14.05 9.46 2 6.55 4.15 12 15.78 20.83 21 8.90 6.59 5 9.35 9.02 17 27.35 26.48 10 15.12 15-15 4 5.73 5.56 13 5-36 5.13 24 8.36 7.81 8 14.17 15.28 18 6.18 5.41 11 9.23 12.64 6 10- 55 9.84 14 15.90 11.45 方=4 k=6 10 4.86 4.26 21 20.72 19.61 12 9.85 11.03 9 7.58 6.51 15 8.36 12.07 0 55.78 52.08 12 16.52 17.90 22 7.99 7.12 13 12.77 13.80 14 5.48 3.76 16 29.83 28.72 1 17.10 16.35 14 9.39 12.09 23 3.79 7.62 14 6.71 6.64 15 6.84 9.28 18 10. 42 5. 61 2 37. 28 35.99 15 9.15 9.50 24 5.81 6.50 16 4- 78 4.56 16 7.70 8.28 20 22.16 22.44 3 33.04 27.59 17 9.72 6.72 h=2 k=7 17 5.77 10.53 17 6.14 7.22 22 12.94 14.73 5 21.26 25.81 18 10.71 9.65 0 20.80 17.13 19 16.64 15- 50 18 6.55 6.18 23 9.97 9.35 6 49.68 46.16 20 10.30 9. 70 1 7.66 7.48 20 3.83 4.64 A—8 k=7 24 4- 74 4.34

7 4.24 4.91 A=8 2 27.19 26.10 21 3.91 5.75 1 13.80 14.03 h=l k=8

8 5.44 - 7.33 0 9.64 9.78 3 9.35 9.23 22 7.95 12.64 3 11.58 12.95 1 7.00 6.82 9 14.62 13.33 4 5.60 4.58 4 13.14 12.60 23 3.54 4.44 4 4.78 3.72 2 3.75 8.62 10 27.97 27.10 5 5.60 6.20 5 3.67 0.89 24 4.53 7.09 6 6.14 6.52 5 23.98 25.37 12 28.26 26.15 h=9 互=6 6 26.82 28.46 h=5 k=7 7 18.28 18.22 6 7.04 8.61 13 & 45 5.95 2 13.31 13.42 7 14.79 16.55 1 8.77 11.43 8 4.28 4.37 7 22.45 2L 36 14 3.87 7.43 4 9.56 9.68 8 7.79 3.40 2 5.31 6.59 9 29.70 26.26 8 3.34 3.70 15 9.64 14. 59 8 17. 26 17.32 9 8.82 7.47 3 3.50 3.68 13 12.19 10.67 9 3.01 4.63 16 32.59 35. 24 9 5.23 5- 45 10 15.24 14- 77 4 4.20 2.96 14 8.90 7.01 10 7.04 12.46 19 10.09 10.01 10 9.56 10.41 12 18.58 21.01 5 45.15 43-11 15 7.50 5.95 11 14.46 12.85 20 9.68 8.90 11 4- 98 6.78 13 14.91 16.26 6 16.31 18.82 16 5.44 4.76 12 3.67 4.23 22 8.77 6.73 12 18.58 15.28 15 7.37 4.54 7 8.77 7.43 17 5.07 5.09 13 11.33 9-80 A=5 k=6 14 15.61 13.60 16 30.98 33.89 8 20.97 19.01 h=9 k=7 15 11.12 11.97 1 7.79 6.30 15 7.54 7.01 18 10.63 10.59 9 5.73 6.45 3 5.97 5.36 16 5.07 5.11 2 27.68 25.91 17 4.45 5.12 23 4.49 4.81 10 9.47 9.64 4 4.61 4.69 17 4.12 3.21 3 10.46 9.34 A=10 必=6 A=3 k=7 11 23.93 22.47 6 5.23 5.73 18 4.57 4.96 4 12.89 16.86 1 6.84 7.13 1 32.50 26.91 12 4.74 4.75 7 6.01 5.66 19 4.00 2.94 5 19.49 25. 22 3 6.76 9.16 2 22.04 25.09 13 6.76 4.11 8 9.60 10.23 23 6.22 6.40 6 26.82 31.26 4 5.07 4.84 3 5.73 3- 96 14 14.34 12.30 U 12.73 12.68 24 5.73 5- 08 8 24.51 25.94 6 6.51 4.81 4 29.95 26. 20 15 10.83 11.39 A=10 『7 h=2 k=S 9 9.72 13.81 7 5.40 6.97 5 28.47 31.03 17 10.42 10.24 0 8.77 8.27 0 42.02 51.80 11 17.80 15.51 9 12.48 11- 59 6 21.01 24.65 18 6- 76 7.83 3 17.38 13.89 1 16.48 20.38 13 7.83 9.91 A=ll &=6 7 12.65 13.93 19 4.20 4.07 7 8.61 7.90 2 12.32 12.40 18 11.99 16.03 2 13.02 13.88 8 10.30 8.92 20 5.52 4.07 9 7- 99 8- 67 3 20.39 18.32 20 10.92 11.89 4 11.58 9.88 9 12.89 16.62 21 7.95 11.09 10 6.34 5.72 4 14.46 14.57 21 5.56 5.14 5 5.85 6.78 10 3.63 5.45 23 : 5.64 6.02 12 7.87 5.44 5 12.69 12.33 A=6 互=6 6 5.64 4.88 11 27.85 25.08 A=6 k=7 h = ll 4=7 6 30.03 26.74 0 20.80 21.35 7 5.77 5.94 12 20.72 21.84 0 32.34 33.23 1 5.36 3.82 7 17.96 15.92 1 8.94 14.67 8 15.12 13.69 13 6.88 9.83 1 15.12 15.49 2 7-50 8.46 8 2.97 5.39 2 4.82 4.76 14 28- 47 28.09 2 13.51 13.29 4 7.21 6.04 9 25.95 26.73 4 27- 39 29.50 1 33.00 40.67 15 24.43 24.86 3 14.71 15.33 6 8.16 6.71 10 34.15 33.00 6 20.52 22.97 2 13.84 20.11 17 8.03 7.12 4 11- 95 10.32 A=0 12 17.42 17.24 7 9.68 5.30 3 24.88 21.30 18 11.53 10.48 5 4.41 8.50 0 32.05 30.35 13 4.78 5.08 9 13.72 16.23 4 5-68 5.40 19 5.93 6.56 6 5-19 7.22 1 23.23 28.77 14 4.04 5.90 10 12.23 14.15 5 28.88 30.29 20 7.42 8.23 7 11.00 13.06 2 23.32 29.53 15 4.57 3.93 12 11- 53 13- 24 6 13.14 13.64 21 13.18 10.45 9 6.63 6.67 3 4.82 10.32 16 24.96 23.81

Vol. 21, No. 5, 1977

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17 12.36 9- 40 16 4.98 2.70 18 7- 58 9.18 17 4.45 2.45 19 14.27 13.81 19 5.15 5-15 20 7.00 3.83 20 9.31 9.53 21 4.94 4.50 21 3.46 1.02 22 10.01 9.26 22 10.26 12.48 23 3.95 3.57 h=5 k=8

A=3 k=8 1 18.58 15.68 1 11.95 13.23 2 17.01 16.99 2 7.00 7.20 3 9.56 9.87 3 17.86 15.32 4 15.45 13. 22 4 5.68 6.42 5 24.96 20.02 5 14.75 17.91 6 10.90 12.63 6 17.63 19.20 7 8.49 9.37 8 14- 21 17- 06 8 4.76 5.32 9 4.53 4.39 9 8.86 9.53 10 10.38 9.63 11 6.80 8.11 11 11.91 12.56 12 20.10 20.01 12 6-18 3.49 13 4.12 5.32 13 9.39 5- 82 14 18.82 19.71 14 5.03 4.97 15 4- 53 2.87 15 11.86 11.37 16 4.41 3.30 17 8.65 8.42 17 8.49 10.13 18 8.43 7.31 18 12.11 8.88 23 6.01 3.59 20 4.61 6.97 A=4 &=8 21 7.95 8.76

0 7.37 12.36 k=8

1 8.49 8.06 0 12.07 13.00 2 7.95 10-00 2 19.40 18.40 3 13.84 16.52 3 18.17 14.75 4 37.65 36.44 7 & 32 8.07 5 8.28 5.56 11 7.17 7.09 6 19.36 20.03 13 5.36 2.43 7 7.76 7.47 14 14.58 13.06 8 4.41 2.19 15 4- 33 3.17 9 7.21 5.80 16 11.58 13.52 10 23.56 22.37 18 4.00 5.90 12 13.55 11.45 19 3.30 0.17 13 21.71 20.41 20 3.75 5.93 15 8.73 5.86 h=7 k=8

1 5.40 6- 94 1 9 6.14 6.37 2 23.40 20.57 h=l k—9 3 12.81 8.62 ! 1 25.42 23.45 4 21.75 17.64 ? 2 12.03 17.14 6 4.61 6.06 3 7.62 7.50 7 8.55 8.00 4 12.15 14.60 8 31.14 26.04 5 25.99 27.92 9 8.20 7.82 7 13.68 12- 67 10 13.18 12.29 8 9.76 11.24 11 11.86 9.93 9 9. 85 12. 52 14 16-81 12- 72 11 27.27 29.64 15 7.46 6.82 12 9. 97 12.31 17 4.53 5.30 14 11.32 13.09 18 10.38 10.29 15 22.53 23.64 A—8 k~8 17 21.79 21.10 0 8.73 6.37 18 7.00 9.08 3 4.61 4.66 20 8.61 11.13 6 13.70 10.88 21 7.25 6.82 10 7.62 8.00 h=2 h=9 12 7.79 8.26 1 22.53 27.61 13 6.59 5.66 4 9.35 14.75 14 3.95 0.31 5 8-16 9.48 15 4.65 2.61 6 10.62 10.92 16 5.89 6.72 7 11.74 10.94 A=9 k=8 13 13.76 14.54 1 9.93 7.88 A=0 A=10 2 13.02 13.77 0 14.25 18.88 4 10.67 11.24 2 20.60 22.52 6 15.37 10.86 3 36.87 35.50 8 14.71 13.50 4 13.30 15.33 10 5.77 4.91 5 12.84 14.12 11 10.63 7.26 6 23.03 19.68 12 6.30 7.05 9 20.89 16.18 14 9.10 7.41 10 16.52 17.24 A=10 知느 8 12 16.15 14.81 1 4. 78 4.84

3 12.56 10.84 4 5.68 5.82 6 4.66 4. 42 7 10. 92 9.23

13 21.09 20.96 14 8. 40 12. 29 16 26.90 19. 22 17 8. 69 10.71 19 21. 75 20. 74

a=i i=io 5 9.27： _7.33 3 8.03 9.09 6 9.19 11.17 9 12.19 24.07 7 15. 26： 14.08 13 7.79 6.12 9 12.28 10.69 h=2 『10 10 14. 21 13. 27 0 22.16 24.89 12 11.08 9.87 2 9.68 9.03 13 12.48 11.90 3 10.88 14.29 15 10. 79 7. 72 4 21.22 21.79 17 5.93 3.84 6 28.96 27.21 A-2 &=12 7 10.96 12.59 3 9. 27 9.86 9 9.76 7.93 7 10.88 10.62 10 13- 76 15.64 9 10.42 8. 73 12 16.44 15.06 10 10.09 9. 51 13 12- 28 11.50 14 8.20 6. 27 15 8.69 8.70 15 6.10 6. 87 16 13-14 13.64 16 5. 97 7.32 h = [ k = ll 17 5.93 5.36 1 15.74 17.15 A = 1 为₌₁₃ 2 11.49 15.22 2 16.81 13.08 3 8.12 7.43 5 8.94 6.48 4 18.99 19.21 6 6.63 7.19 5 20.60 21.66 7 7.95 5.61 7 10- 59 9.79 9 12-11 3.74 8 14.83 16.16 11 6.10 9.23 9 8. 77 11- 97 12 6. 71 6. 47 10 8.61 5.61 15 5.93 0. 96 11 11.95 11.78 为₌₂ ₌₁₃ 12 11.62 9.58 6 10.38 5.40 14 16.68 16.80 14 5.23 0-20 15 9.15 9.70 =0 =14 17 7.37 5.86 2 6.39 2.24 18 14.34 11.67 4 11.41 2. 25 A=2 11 8 5.81 1.87 2 10.92 9.51 10 6.84 6.52 h=0 k=12 11 4.61 2.10 0 17.34 18.76 i=2 t =14

1 10.26 12. 11 5 8. 36 2. 37 3 25.83 21.49 9 6. 92 9.10 4 17.10 16.13 11 4. 94 0. 27

360, and gave a final R value of 0.13 for all reflections with Cruikshank6 weighting scheme.

No allowance was made for the hydrogen atoms.

The atomic scattering factor used were those from the International Table for X-Ray Crystallography7. The final positional and thermal parameters were given in Table 2 with their estimated standard deviations.

The observed and calculated structure factors are listed in Table 3.

MOLECULAR CONFORMATION The bond lengths and angles are given in Fig. 1 with atomic numbering and in Table 4.

The cyclohexane ring has the normal chair conformation8, i. e. conformation 4Ci9, with an equatorial substituent of thiourea part of the molecule. The atoms C(7) and C(10) deviate from the least-square plane of C(6), C(8), C(9) and C(ll), by 0.74 and 一0.67 A re

spectively (see Table 5)- The average confor-

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Thiourea Derivatives 의 결정과 분자구조 (제 1 보) 315

mation angle of the cyclohexane ring is 73° as found in /)-tercyclohexane-l10, free cyclohexane molecule11 and crystal structures12 in other six membered ring where the rings have the normal chair conformation.

The thiourea unit is planar within the accuracy of our measurements. The structures of thiourea and deuterated thioura at room and liqud nitrogen tempertures by X-ray1^3 and neutron diffraction data1, are also planar. The C = S bond length of 1.74 A. which is distinctly longer than the corresponding normal double bond length o£ 1. 59 A, is indicative of partial double bond character. The C(5)一N(l) and C(5)—N(2) bond leng나is of 1. 35 and 1. 36 A respectively are significantly shorter than a C .---bond length of 1.446 A. Thus these C—N bonds possess some double bond character.

The lengthening of the C=S bond and the shortening of the C一S bonds are a general

Fig. 1. Bond lengths (A) and angles (°) with atomic numbering of N- (a-dimethyl j3-hydroxy) ethyl N'-cy시ohexyl thiourea.

Vol. 21, No. 5, 1977

property of N—C—N group, which are in gsd S

agreement with the results of other crystal structures of salicylaldehyde-4-piperidinothio- semicarbazone13, o~chlorobenzaldehyde cyclohexyl thiosemicarbazone14 and thiourea1^3.

Table 4. Bond lengths and angles in N- (a-dimethyl

^-hydroxy) ethyl N'-cyclohexyl thiourea.

Bond lengths in A s —C (5) 1. 74(2) 0 -C(l) 1. 42(3') n（i） -C(2) 1. 48(3) N(l) -C(5) 1- 36(2)

N⑵ _-c⑸ _{1. 35(2)}

N⑵ -C(6) 1. 49(3) C⑴ -C(2) 1.55(3) C(2) -C(3) 1. 58(4) C(2) -C(4) 1. 57(4) C(6) -C(7) 1. 59(3) C(7) -C(8) 1. 59(4) C(8) -C(9) 1. 61(5) c⑼ 一 C (10) 1.48(5) C(10)-C(U) 1. 61(4) C (11) - C (16) 2. 53(3)

Bond angles is (°)

S -C(5) -n（i） 119⑴

S -C(5) -N(2) 113⑴

n（i） ~C(5) -N(2) 117(2)

0 -C(l) -C(2) 111(2)

c⑵ -N(l) -C(5) 129(2)

c⑸ -N(2) -C(6) 123(2)

C(l) 一 C(2) 一 C(3) 86(2)

c⑴ -C(2) -C(4) 115(2)

C(l) -C(2) -N(l) 111⑵

C(3) -C(2) -C(4) 116(2)

C(3) -C(2) -n（i） 114⑵

C⑷ _{-C(2) -N}⑴ 112(2)

C(7) — C(6) -N⑵ ₁₀₇₍₂₎

C (11) - C (6) -N(2) 108(2) C(7) — C(6) -C (11) 109(2)

c⑹ -C(7) -C(8) 110(2)

C(7) 一C(8) -C(9) 108(3)

C(8) -C(9) -C(io) ₁₁₃₍₃₎ C(9) -C (10) 一 C (11) 111⑶ C (10) 一 C (11) 一 C (6) 109⑵

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Table 5. Least-squares best planes in N- (a-dimethy /3-hydroxy) ethyl N'-cyclohexyl thiourea. (Equation for the plane： Ax-\-By-irCz=D, where x, y, z are in A)

Atoms in plane Atoms out of plane Distance from the best plane Constants

Thiourea S 0. 00 A A = 0. 656

N⑴ 0. 00 B=0. 712

N(2) 0.00 C = -0. 249

C(5) 0.01 D = L 640

Cyclohexane c⑹ -0. 01 A = 0. 973

C(8) 0.01 B = —0. 035

C⑼ 一 0. 01 C=0. 227

C(U) 0. 01 D=2. 397

C(7) 0. 74

C(10) -0. 67

(These resets are compared in Tab" 6 with this work.), These are also confirmed by the planarity and conjugation of N—C一N.

SII

The detailed conformational angles are given in Table 7. The conformation of the

-- C(6)—C(ll) is zzn^-clinar8 (torsion angle of 98°) with respect to the N(2)一C(6) bond and that of 산le C(4)-- ---C(5) is s：y^刀-시inar (torsion angle of—53°) with respect to the C(2)一N(l) bond. These conformations are favored to avoid van der Waals repulsion between S and C(ll), C(4) and N(2) atoms respectively.

However the conformation of the O一C (1) —C (2) —C (4) is 5^n-periplanar, eclipsed, (torsion angle of —29°) with respect to C(l)—C(2) bond. This can be easily explained by the formation of the intramolecular hydrogen bond between O and N(2). This hydrogen bond leads to stablize the molecule from the free rotation of primary alcoholic group around C(l) atom.

All - ---- bonds of the molec니e are single bonds of s伊-hybridized C atoms and these lengths vary from 1. 49 to 1. 61 A with a mean value of 1. 57 A over 9 values. Although the

deviation of 0. 03 A from the normal - ---- bond lenth of 1.54 A is rather significant, it is within 3(7 of the C——bond lengths and can be attributed to the fact that the intensities were measused by photographic method and were visually estimated. No other bond lengths and valence angles are not significnatly diff

erence from the normal values (see Table 4).

INTERMOLECULAR PACKING AND HYDROGEN BONDING

The amusement of the molecules in the crystal structure is shown in Fig. 2(a) and (b). The molecules are linked by hydrogen bonds whose description is given in Table 8.

There are two independent hydrogen bonds involving oxygen atom of the hydroxyl group, one as acceptor in the intramolecular and the other as donor in the intermolecular hydrogen bond. The intramolecular hydrogen bond be

tween N(2)——is strong bond with N…O distance of 2. 71 A. On the other hand, the oxygen atom also form a intermolecular hy

drogen bond to the sulfur atom of other molecule related by the b glide plane perpendicular to the a axis, with the distance of 3. 20 A.

Apart from the hydrogen bonds, the molecules

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Thiourea Derivatives의 결정과 분자구조 （제 1보） 317

Fig, 2 The hydrogen bonding and molecular packing in the crystal structure of N- (a-dimethyl /3-hydroxy) ethyl cyclohexyl thiourea. Solid lines 'indicate the molecule； dotted lines indicate the intramolecular and dashed lines indicate the intermoleoular hydrogen bonds with the arrows pointing in the donor direction. (헌) View down the b axis, (b) view down the a axis.

Vol. 21, No. 5, 1977

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Table 6. A comparison of the N ——---group conformation.

II

S

Compound S-C(5) C(5)—N ⑴ C(5) — N(2) S-C-N(l) S—C—N(2) N ⑴一C—N(2)

HT 29까 1. 709 A 1. 333 A 121. 67°

DT 29까 1. 701 1. 329 121. 35

HT 110, l1 1. 732 1. 334 121.40

DT 110, l1 1.707 1. 330 121.39

HT 110, 가 1. 733 1. 335 120. 88

DT 110, 21 1. 740 1. 326 120. 53

T. U. D. 1. 74 1.36 1.35 A 119 123 117

S. P. T. 13 1.66 1. 35 1. 35 124.1 121.8 114.1

C. C. T. M 1. 75 1.40 1.24 124 118 118

HT 293： thiourea at 293° K; DT 293： deuterated thiourea at 293°K; HT 110,1： thiourea at 11(尸K, molecule 1； T. U. D. : N- (a-dimethyl £-hydroxy) ethyl AT7-cyclohexyl thiourea; S. P. T. : salicylaldehyde-4- piperidinothioseniicarbazone; C. C. T, :chlorobenzaldehyde cyclohexyl thiosemicarbazone.

Table 7. Important conformation angles in degrees in the molecule.

O -C(l) -C(2) -N(l) +84

O -C(l) -C(2) -C(4) -29

C(l) -C(2) -N(l) -c(5) -79

C(3) -C(2) -N(l) -C(5) + 127 C(4) -C(2) -N(l) -C(5) 一 53

C(2) -N(l) -C(5) 一N(2) -100

S -N(l) - C (5) -N(2) + 127

N(l) -C(5) -N(2) -C(6) + 122

S -C(5) 一 N(2) -C(6) 一 128

C(5) 一 N(2) — C(6) -C(7) -58 C(5) -N(2) -C(6) - C (11) +98 C (11) - C (6) -C(7) -C(8) +87 C(6) -C(7) 一 C(8) -C(9) 一 45 C(7) -C(8) -C(9) - C (10) +87 C(8) -C(9) - C (10) - C (11) -60 C(9) - C (10) - C (11) - C (6) +95