‘The Costa Structure of Choestert Aniline Ball, Koreon Chom. Soe, Vol. 11, No. 5. 1990. 427 The Crystal Structure of Cholesteryl Aniline ‘Young Ja Park", Sangsoo Kim’, 14 Seung Bun Lee Department of Chemistry, Sook Myung Women's University, Seoul, Korea 140-742 "Lucky Central Research Institde, Taejon 305-343. Received May 24, 1990 CCholeseery aniline (Cassy) is monoctin 2-2, De~ 1.06 glem? and Dm ~ 1.04 glem?, A diffraction dataset was collected with Mo-Ke radiation ( space group P2s, with « = 9.020(3), b= 6.000(1), ¢= 27.130(9A, = 98.2212)*, mo7 Aone ‘iractometer witha grapite monochromator toa maximum 2@ valve of50°, by theo~20 scan techniqe. The coordinates ofthe non-hydogen atoms and their anstropic temperate factor were refined by fll-matrix est-quares metho 0 final of 0.058. Incolestrl group. bond distances were normal exeptin tal part where hgh thermal vibration eed in aparentshortering ofthe C-C diatances, The crystal strict consists of iayer f tikes d= 27.13 A. i ech of ‘hich there i the tail totai arrangement of melecles aligned in the ni cell with their long axes approximately parallel the 104] axis. The to haves ofthe double Iyer are related to each athe by the Screw as. Introduction ‘The crystal structure analysis of the cholesteryl aniline hhas been undertaken as one ofa series of X-ray crystal struc- ture determinations of cholesterol derivatives. Examination of the unit cell parameters ofthe cholesterol derivatives sug- ‘gests that the majority of derivatives may have one of three ‘common crystal packing arrangements, s0 called monolayers of type I and type I, and bilayers type.’ However, the crystal data of cholesteryl aniline we obtained indicate that the cholesteryl aniline belongs to none of three crystal structure types. Therefore the primary aim in this study is to obtain structural informations concerning the conformation and the ‘mode of the molecular interactions Experimental Cholestery1. aniline. from Sigma Chemical Company Ltd. was recrystallized by slow evaporation of a mixture of acetone, ethanol and ether solution at 5°C. The resulting ‘monoclinic, colorless, plate-like single crystals melted at 919°C. Preliminary X-ray Weissenberg photographies showed that the crystal system is monoclinic with space group P2, Subsequent X-ray data were collected using a Nonius CAD- 4 diffractometer with Mo-K. graphite-monochromated ra diation (A= 0.7107 A), And the accurate crystal lattice para meters were obtained by a least-squares fit of 23 reflections ble 1. Summary of Crystal Data, Intensity Collection and Least-Squares Refinements Statistics formula CattgNHCaHs Mi a6 space grou Pay ad 9.020) aa 6.000 (0) ok 27.1209) 8. eg 98.22 (2) i 2 v8 Hst.19 MMe Ke) eo! 066 density. glem’ tee) Lnstmeasred by’ Notation in 8 aa KI soltion) radiation -Mo-Klgraphite monochromator Ae ugir’s bax04x0. crystal size om cell constant determination 28 reflections (20°<20<28") feflection measured hime 7. wt 20 range. deg. 2st scan type ou scam range. dem 7+ 0:8 tan No.of observed reflection 288 |Hv|> 20( Fol) Kk 958 ke wot " ea) + APP) dlifeacometer raNonius CAD~4 with 20°<20< 28%. X-ray intensities were collected by 9-24 scan technique over a scan width of (0.7 + 0.35 tan @)° in w. Three standard reflections (5,1.2), @.2. monitored for intensity and orientation check every 135 reflections. There was no significant loss of intensities throughout data collection. The 3002 independent reflections measured, range of Ail; 05h 10, 0 2o|F,| were used in structure determination. Data were Cor- for Lorentz and polarization effects, but the absorp-428 Balt. Korean Chem. Soe, Vol 11, No. 8, 1990 Table 2. Fractional Atomic Coordinates (<1) and Eysivalent bo tropic ‘Thermal Parameters for Non-hydrogen Atoms of Cholestery! Aniline. arin parentheses. Veg. = U3 EE Uinta, (2109 o ‘Atom = ’ Ven cay BONS) 111) ——B8ONT) 58) a) s7a7) sora) 5842) cay) suas) 866) saztt) Sa cy 63644) 29817) 358K) 5412) cis) 7363) 258016) sama) TLE). is) 705-342) TSI). ci Teed) 31388) HK) ci) 954K) ats) 584) cs) 9a) 26106) awn) 450) cli) 8840) 10006) 5A 470) ca 1098265) s2m8) ORK 542) ci) 1i7eas) 587) 2aH) 8 cu ri2m4) 486) 225K) cus raszwey) 1392) = 21104) 50) us) assay - 30029) 88) cay L1732%5) 196519) 14290) TKe) cam 12408) He) 17540) 5a) cas 293ue) 222719) 542) ca9 seem) 25518) 7402) 2) cz) 410148) 31a) 172341) 3) cee) 4876) ovat) 2082) KG) cz 1432245) 73412) 11842) 8) 623) 138505) 665115) 109012) 10044) C24) eI) USKIY SI) 025) 1773718) SIMs) 422) 1285) ces) 1774413) 9752) 10H) 4 com 18722113) BAO) ToS) aL ce 394343) 56) 43851) cay sams) 200774 Co ee eo) cis rsa) ate) A748 93) ca) Bart) $7900) 49621) BACH) cay 32a) 81818) 7K HCD =1736) 1964) x 492819) tions were ignored. All ofthe erystal data are summerized in Table 1 Structure Determination and Refinement The phase problem was solved by direct method using the program SHELXS-86.! The direct method were applied to 589 reflections with ||>1.3. All the carbon and nitrogen atoms were located on the E map. The refinement was car ried out with full-matrix least-square method, using the pro gram SHELX-76 * Four cycles of isotropic full-matrix least squares refinements decreased I value to U.I4. And then anisotropic thermal parameters were introduced forthe car bon and nitrogen atoms. After four cycles of anisotropic re finement, K reduced to 0.11, At this stage the i hydrogen atoms were found on the difference Fourier map and remain- Young Je Parke al Table 3. Hond Distances (A) fr Cholestery] Aniline. The es.d's ace in parentheses cue) 15246) CU-CALO) 155700) cere) 1.5086) 43)-Cuy 1.5206) CON 149) Gua)-C45) 1.50648) cwrce 1320) 5)-CA) 151548) cwrer, 14958) 7-08) 1.54085) ce 1586) (g-ct14) 1.50540) cry-cx10) 1592) @(U-cKLI) 15476) cuo-ciy 13876) CaO) 114) cucu) 1.3485) casper) cus-or sam) cuscc18) CUI 1.8355) GS)-CUU6) CIT) E5846) CT-CRO ceo-cen 150317) CBO CY cece) 15276) CBC 488) Cesc) 109) eRsKCR ——LA7THI2) crescent) zac” 1.39665) C2808) 115) CEN 1.37348) Ceca 14006) eBOLCIS 1.38107) conc) 1.3786) CRC) 38916) Table 4. Hond Angles (*) for Cholestery Aniline. The es.’ are in parentheses C-c2-Ca) — 114.4 CU-CUO-C) 108.213) CUr-CAoRCt — 108.46) CL-CLO-CU) 109.813) ceMaD-CUD — 1184) 2-CB-C) 110.26 COrCH} 1392) CB-CHCH) 1181) CONCH) 12479) CU-CI-N 108.863) CUHCGHCH 1983) C-CEHCH 116402 COHCHHC — 124.73) CSHCAM-C) TLR) CHHCIO-CY 108.18) CHWKEGHCOy» 128.718) Cl6-CT-CB—— 112.32) CATCIB-CW) 108.813) CHHCB-CUY 11.62) CBCW-CUM 112.319) cH-CH-CU—THLIG)—CBCU-CO) 4B) Cw-COM-CD 118.714) CHREB-CUA) 109.509) cen-coo-COy) 111.49) EwRENL-Ca2) 115.209) CHOMcIMCID 11332 CUM-cAZ-CAy 1115) CHAHCH-Co4) 105.8) CUAHCH-CU7) 117.008) Cha-CUs-C18) 110.702) CUIHCLLA)-CI5) 104.413) CUSKCUT-CHE) 104.36) CUBKCAT-CaW 118.813) cuM-cus-crn 10.82) CUA-CHS-CH8) 111.619) CU14)-C19-CU 104.2) CIS-CG-CAT 107.18) CUB-C7-C2 L7G) CATHCHISKCUN) 110.40) CU7-C20-C2)— 13.43) GAT-Cea0}-C22) 109.4) c20-022)-02) 114.214) CB1-CRV-C22) Lal) CL2-0RD-C2) 114510) 02B-CEA-C2S) 117.36) C24)-C25)-C2H) 10.96) C24)-CRB-C27) 113.319) c26-025)-C27 113.012) N-CRB-COM 122.5) N-Ci28-CR) 118.43) C2B-CRB-CBO) 118.6) CeB-CRS)-Ci32) 120.118) Cl29-CRA)-CEs) 18.90) C29-CRO-CI31) 120. C0-C81)-C482) 120.018) CBHCE-CAB 120.53) ing. hydrogen atomic positions were calculated from the car ‘bon framework assuming standard geometry (C-H = 1.08 A, it 108°). The function Eu(\F|-[F,)? was mini‘The Costal Structure of Cholesterst Aniline Figure 1. Molecular conformation with atomic numbering in Cho- lester aniline mized in the refinements, where iris the weight ofthe reflec Sion, defined by = 1.00[#4F) + 0.0084). ln the inal re finement, the positional parameters ofall atoms, anisotro pically for the carbon and nitrogen atoms. isotropic thermal parameters for the hydrogen atoms were refined. The final and Re values were 0.058 and 0.074, respectively forthe 2296 observed reflections. "The final atomic coordinates and thermal parameters of the non-hydrogen atoms are given in Table 2. Results and Discussion The molecular conformation is depicted in Figure 1. The bond! distances in the tail show the apparent shortening Which is characteristic of cholesteryl compounds, and is ‘caused by the high thermal vibrations in this region. tn this cease, itis especially pronounced in the C(25-CU27) bond of 1.418 A. In the cholesterol rings, the C-C bond distances from 1.495 (4) to 1.557 (5) A and the C13) = C16) dist 324 (4) A. In aniline group. the C-C bond distances range from 1.378 (8) to 1.415 (4) A, respectively. ‘The inte molecular distance C(3)...CU16) whieh is useful for comparing the length of the tetracyclic system has a value of 8:81 Which is close to the limits of range of 8.810 9.11 A observ e of the twist ofthe ring. nn by the CUSHCO0). cd in related molecules.! A measur systems about its long axis, i Bul, Korvon Chem. Soe. Vol. 11, No. 5. 1990 429) Figure 2. Molecular packing in Cholesteryl aniline viewed down the a-axis, Atoms are shown as 20% probability elipsoi. C(13-CU8) pseudo torsion angle, which has a value of 14.8 3°, This torsion angle ranges between 7.9° and 18.0° in other related structures. Ring A and C assume the chair con: formations: for ring A,"= 3.94 and = 4.91: for ring C, = 6.64 and = 8.7. Ring B ass ‘mes a half chair and ring D the expected 138, 1 4¢-half chair vonformations. The torsion angles, C2-CG-N-COB) and (C)-CE)-N-C28) which are important for determining the overall structure of the molecule are vely : The CU7)...C(25) distance of 6.40 A is taken asa measure of the extension of tal, this structure is almost fully extend ed. The seven atoms, C7), C20), C22), C123). CC24). C2) ‘and C(25), are in a zigeag planar chain and C21) and C27) are out of the plane. The erystal structure is shown in Figures 2 and 3. ‘The “crystal structure consists of bilayers of thickness dygy# 27.13 Alin each of which there is the tail to tail arrangement of ‘molecules aligned in the unit cell with their Tong axes approx: imately parallel to the [104] axis. The to halves of the dou ble layer are related to each other by the screw axis sym- metry. Such bilayers are similar to those of sodium choles tery] sulfate dibydrate* 5° and — 161 respect: Ge: miror plane asymmety parameter BG=1E (rvs Vm Cp: two-fold asymmetry parameter OGLE h-¥ Vm) where ACim) is measure ofthe devitins from mirtor symmetry About a plane passing through atom and the cametrically opposed. atom , and (ro) fa measure ofthe deviations fem tof symmetry about an axis bisecting bond (-0). The symmetry related torsion angles are and y", and m isthe mumber of such pairs4830 Bul Korean Chom. Soc, Vol. 12, No. 5, 1990 Figure 8. The structure of Cholestery] aniline in projection down the b-axis. Atoms are shown as 30% probability elipoids. ‘The aniline groups, the rigid steroid skeleta and the bran- cched hydrocarbon side chains form three regions with dif ferent packing character within the bilayer. The lateral packing ofthe steroid skeleta i different from that found in other cholesteryl derivatives. In cholesteryl esters." the skeleta pack laterally in a double row arrange: ‘ment in which the projecting methyl groups face each other and can interdigitate due toa displacement of the steroid ske leta in the direction of their maximum extension. In c teryl aniline the skeleta packed in single rows only. ‘The ‘methyl groups project into the space between two skeleta of the adjacent row The aniline groups are aligned so that their rings are stacked parallel in columns in the a direction and packed with its screw axis related neighbor. The closest approach between these two groups is 3.712 A (Cl32)...N comtact) and the interplanar angle between two symmetry related benzene Fings is 52.02 ‘The packing of the bulky steroid and aniline groups pro vides the tail chain with umusually large space. This may ex plain the observed large thermal vibrations in the chain pack: ing region. Young Ja Pork et a ‘There are several intermolecular contacts legs than 4.0 A of which the shortest s C1) C129) of 654 A ‘Acknowledgement. This work ‘was supported by @ rh grant (901-1303-010"2) from the Korea Science and Engineering Founation, References 1. B. M. Craven, “The Physical Chemistry of Lipids”, “Handbook of Lipid Research’ Vol. 4, Chapter 6 Edit., D. M, Small, Plenum Press, New York (1986). 2. G, M. Sheldrick, SHELXS-86; Program for Crystal Structure Determination, Institute far Anorganische Chemie der Universitat Gottingen, FRG (1986). 3.G. M. 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