Sept., 1945
X-RAYCRYSTALLOGRAPHIC STUDIES OF ORGANIC SULFONATES
Recovery'of Anthracene from Anthracene-T. N. F. Complex Chromatographic Separation.-A benzene solution of 0.6014 g. mthracene-T. S. F. complex was passed over a short column of activated alumina. The T. N. F. formed a dark ring at t h e top of the column vhich moved slowly down t h e column while t h e anthracene was readily eluted with benzi:ne. The movement of t h e anthracene was foll o ~ e dby its fluorescence in ultraviolet light. SVhen all !.he anthracene was eluted, the T. S. F. was 4 1 1 on the column. X quantitative recovery of anthracene was obrained by evaporation of the percolate. Reduction with Tin and Hydrochloric Acid.-To a solution of 0.378 g . clf aiithraccne-T. N.F. comp!es in 20 cc. id there was added 1 g , of tin and 3 cc. of conceritrai.ed hy:irochloric acid. The iiiixture was refluxed twcnty minutes, during 7r;hich time all the tin went into solution and t h e niixtute turnctl from a tlecp red to a rcry light red. The hot mixture was pourctl onto ice and :he precipitate filtered 311d dried. 1-he precipitate was rlissolved iri benzeiie, treated ivith norite, filtered arid the filtrate coiicentr;~tcd. There was recovcrctl 0.1 12 g. of ;iiithracene, i n . 11. 21:3-2lt5'. Catalytic Reduction.-In a preliminary experinicnt 78 8 mg. of pure T. S .1;. \vas reduced in ethanol solution with .Adatus p!;ttinuni oxide catalyst at room conditions. At
[COSTRIRIITION FROX
T E I E UEPARTMESTS OF
1729
the end of forty-eight minutes, 9 moles of hydrogcn per mole of T. S. F. was absorbed, and the compound continued to take up hydrogen slowly. -4n ethanol-benzene solution of 0.6128 g. of anthracene-T. S.F. complex was hydrogenated under similar conditions. At the end of 132 minutes, 8.2 moles of hydrogen per mole of compound i m s absorbed, at which point the reduction was interrupted. The reaction mixture was extracted with dilute hydrochloric acid and the organic layer separated, washed with water and dried. After treatment with norite, the colution gave, on concentration, 0.1590 g. of anthraceiie, n1. p. 212-215".
Summary The molecular complexes between 2,1,T-trixitrofluorenone and twenty-nine aromatic polynuclcar compounds are described. The hydrocarbmi p r tion of these complexes can be readily recovered. The advantages of using the molecular complexes of 2,4,7-trinitrofluorenone for the charactcri7atiori and purification of polynuclear aromatic compounds are indicated. PITTSBURGII, PENSA.
CHEMISTRY OF
THE USIVERSITY OF SIOSART COLLEGE]
RECEIWDA P R I L 17, 1946
WASHINGTON ASD
OF
EMMANUEL 111s-
X-Ray Crystallographic Studies of Organic Sulfonates. 11. The Hemihydrates of Certain Sodium 1-Alkane-sulfonates1 BY L, €1. J E K S E N ' ~ AND E. C. LINGIFELTER
In the first paper of this serieslb we reported the unit cells and space groups of the quarterhydrates of so8:Iium 1-octane-, 1-decane-, l-tetradecane-, 1-hexadecane- and l-octadecanesulfonate. \Ye haw! now prepared satisfactory single crystals of the heniihydrates of sodium l-dodec:me-, I-tetradecane-, 1-hexadecane- and l-octadecanesulfonate. Sodium 1-octanesulfonate and 1-decanesulfonate have not formed hemihydrates under the conditions so far investigated.
Experimental The compounds used were of the same batch as in the previous work.1b The crystals were grown by slow evaporation from mixtures of carbon tetrachloride arid water a t temperatures between cu. 30 and 50'. Sodium l-dodecanesulfonate and 1-tetradecanesulfonate hemihydrates were also obtained from water alone. The crys: tals of all four substances are thin tabular parallel to { 001 ] and elongated parallel to the a axis. 'The tablet is cutlined by { 0101 and { 122) in most cases, rarely by ( O l O } , (ill] and { 122) or by (0101 and {111). il index could not be obtained because of the extreirle thinness of the crystals.) The degree ' ~ hydration i was measured by the weight loss in a vacuum drying experiment as tlr(11 Presriitcvl . i t t h e Y < > r t l i w e \ lI < c % i i i n ; i l Slectiri!:, hcdtlle \Va\hi n g t i i n , October 2 0 I i 4 i ( l a ) A t I:rnm.inriel A l i , \ i < i i i ; x y C o l I w c , llerricti Sfirinxs. Michi-
gan. ( 1 6 ) Jenseu ;arid I . i n g x f e l t ? r , ' r t l i h J O U R X A I . , 66, I ' J l f j (l!J44).
scribed in the previous paper.Ib The weight loss corresponded to the hemihydrate. Data were obtained from oscillation and equiinclination Weissenberg photographs using unfiltered copper radiation from a hot-cathode X-ray tube. The constants of the monoclinic unit cells are given in Table I. In Table I1 the ratio ao/bois compared with the value obtained by measurement of the angle between the zone axes 1210) and (%io), using a microscope with n rotating stage. TABLE I CONSTANTS OF TIIE Us11 CEi.1. Substance
no, k X . bo,
C1~H2SS03Na.1/2H20,A X(i ii 8.i C14H29SOan'a. l/pH?O C16H&03Na~1/pH20 i i . 8 i i C,8H37S03Na.1# 2H.O ii,S(i 'r.knLc. C O N P A R I S O X (?FX - R A Y A S U
kS.
cn,
6
kS
1.5.40 2 9 . 4 0 1 5 . X 32.74 15.35 36 3 i l5.3ii 3 1 , 7:;
PR '30' $lO"36' R4c23'
91 's(j'
II GO.
Substance
an/bo. X - r a y
Cl&jSO?A-a. *,'?€I20 ClrF!lJSCi, Sa,': zI-T,O ci tiH:.91/~k = 18.98 kX.2 ’The angle of tiltzamay be estimated if we assume this angle and the packing cd the ends of the chains to be the same for all four heniihydrates. With these assumptions, the angle of tilt is the angle whose cosine is the ratio of’ the average do01 increment in the hemihydrates to the average GO increment in the quarterhydrates. Thus cos (tilt) = 3.51/5.10 = 0.688, whence the angle of tilt is cu. 46’30’. Using this value f a - the tilt, the effective cross-section of the molecule perpendicular to the chain axis may be calculated. The value obtained is 18.12 kX2, which i.s slightly smaller than the value of 18.24 found ior long paraffin-chain hydrocarbons3 and considerably smaller than the cross-sections found for the corresponding sodium 1-alkanesulfonate quarter-hydrates.lb (2) .411 dirneil :i,ms in the previous paper are given in kX anits, rather than i n ~i L? 1;ibelled. (2a) This a n g l e is defined as the angle between t h e chain direction a n d the normal t o the 1001) plane. (3) Buruu, i I U J L J . 1‘:rdday Soc., 35, 482 (1939).
Vol. 68
While no attempt has been made as yet to establish the complete details of the structure, due to the large number of parameters involved, the general features may be inferred from the evidence as to habit, size and symmetry of the unit cell, and size and shape of the paraffin chain ions. The habits of all alkanesulfonate crystals which have been grown in this laboratory are similar in the extreme thinness of the crystals in the tdirection. This would indicate weak crystal forces along the c axis, caused probably by a “head-to-head and tail-to-tail” arrangement, with the cations and water molecules in a layer between the heads. A similar arrangement has been suggested for the ions in the soap micelles existing in aqueous solutions a t moderate to high concent r a t i o n ~and , ~ has been discussed by Buerger6 for sodium palmitate and stearate. This arrangement is corroborated by the fact that co is always an even multiple of the single chain length, occasionally decreased somewhat by tilt. The cross section of a straight paraffin chain is about 4.5by 4.0 kX. Since the unit cell is two chains long in the c-direction, the i O O l ) plane must contain four chains. The tilt of 46’30‘ would increase the 4.5 to 4.5/0.688 = 6.5 kX, while (4) (4.0) = 16 kX, thus accounting satisfactorily for the values of uoand bo. The positions of the eight paraffin chain ions may be fixed approximately if we assume that all of the sodium ions and water molecules lie in a plane parallel to the { 001 1 plane, with a plane of “heads” (;.e., -SO3groups) on either side. The space group P21/a contains a pair of glide planes { 0101 with glide component 4 2 , separated by a distance b0/2. Because of the size of the paraffin chains, no chain can lie in a glide plane. Adjacent chains in the { 001 ] plane will therefore be separated by b0/4 4 2 , leading to a close packed arrangement. The presence of the 2fold screw axis will cause all chains to be tilted in the same direction.
+
Summary 1. Single crystals of the hemihydrates of sodium l-dodecane-, l-tetradecane-, l-hexadecaneand 1-octadecanesulfonate have been grown. 2 . The substances all have the same structure. The monoclinic unit cell contains 4 molecules of 2RSO3Na*H20. The space group is Czh5(P&/u). 3. The general features of the structure are discussed. ’
SEATTLE, WASHINGTON
RECEIVED MAY10, 1946
(1) Hdrkiils, M a t t o u n and Corrin, THISJorrnS.4~,6 8 , 22(1 (1946). ( 5 ) Buerger, A m . Mineral., 30, 5.51 (1945).
