123%
Voi. A4
NOTES
Choppin and Padgitt3 the boiling point-composition curve has been determined.
about three hours for each determination. Temperatures were measured with calibrated thermometers graduated in 0.05' with a precision of *0.05O. The liquid and vapor phases were analyzed by means of refractive index using the values reported by Amis, Choppin and Padgitt.3 The results are tabulated in the table and represented graphically in the figure. CONTRIBUTION FROM THE CHARLES EDWARD COATESCHEMICAL LABORATORY LOUISIANA STATE UNIVERSITY BATONROUGE,LA. RECEIVED JULY29, 1941 ~____
Addition Compounds of Tetrahydrothiopyran BY HARRYJ, WORTH AND HELMUT M. HAENDLER
100
60 40 20 Weight % MeOH. Fig. l.-~-.Vaporphase, 0; liquid phase, 0
go
Two addition compounds of tetrahydrothiopyran (pentamethylene sulfide) and inorganic metal salts have been reported : HgC12-(CH2)& 'The methyl alcohol arid dioxane were purified by Grischkewitsch-Trochimowski and xHgIz. as previously described3; the apparatus used (CH2)&3 by Bost and Corm.* This sulfide forms was that of 0thnier.l Equilibrium between the addition compounds with other metal halides, ,~ vapor and liquid phases was established after offering comparison with d i t h i a ~ ~ edioxane, and m~rpholine.~Tetrahydrothiopyran exhibTABLE I ited less tendency to form addition compounds BOILINGPOINT-COMPOSITION DATA FOR THE METHYL than did dithiane or dioxane, but greater tendency ALCOHOL-DIOXANE SYSTEM AT ONEATMOSPHERE than morpholine. B. P., Wt., % MeOH vapor OC. liquid The compounds are crystalline, somewhat sew 64.60 1i)o 100 sitive to water, and are white, except for the 64.72 116.5 98. I yellow gold(II1) chloride, tin(1V) bromide, and 91.9 94.2 64.90 platinum(I1) iodide, the red-brown gold(II1) 86.7 91.9 64.96 bromide, and the orange-red palladium(I1) chlo65.10 82.9 89.4 ride compounds. There was some indication of re78.0 86.3 65.27 65.34 io.7 85.2 action with silver iodide, silver bromide, and tin65.55 09.7 81.7 (IV) iodide, but no compounds could be isolated. 65.78 61.7 77.9 The following compounds gave no results: copper54.6 75.7 66.50 (11) fluoride, cadmium halides, zinc chloride, iron 48.4 72.6 66.94 (111) chloride, arsenic(II1) iodide, antimony67.10 38.8 72.2 70.2 67.60 29.8 (111) iodide and chloride, germanium(1V) chlo67.89 29.0 67.9 ride, and silicon(1V) chloride. 20.0 66.1 68.20 The thiopyran was prepared by a modification 17.0 63.9 68.50 of the methods of von Braune and Clarke,' using 62.5 69.30 15.4 100 g. of benzoylpiperidine and 110 g. of phos70.40 !4,7 59.0 6.0 52.7 73.20 phorus pentachloride. The benzonitrile was hy78.20 3.9 44.1 drolyzed by warming under reflux, the dichloro82.80 8 .7 30.8 pentane steam distilled, and converted to tetra2.4 19. I 89.20 I)
-r
93.50 96.04 100.38 100.54 101.05
1.6 0,7
.a .3 .0
11.1
S.7 1.9 1.8 0. 0
(3) Amis, Choppin and Padgitt, THIS JOURNAL, 64, 1207 (1842). (4) Othmer I n d . Eni.. ChPm.. 20, 743 (1928).
(1) Grischkewitsch-Trochimowski, Chem. Z e n f r . , 87, I , 1503 (1923). (2) Bost and Conn, I n d . Eng. Chew&.,13, 93 (1931). (3) Bouknight and Smith, THIS JOURNAL, 61, 28 (1939). 14) Rheinboldt, Luyken and Schmittmann, J . puekf. C h e w . , 119, 30 (1937). ( 5 ) Haendler and Smith, THIS ]OURNAL, 68, 1164 11941 ) , (6) von Braun, Bey., 37,2915 (1904). ' 7 ) C l a r k e , J C h e w . Soc., 101, 1783 (1912).
May, 1942
NOTES
1233
TABLE I ADDITION COMPOUNDS OF TETRAHYDROTHIOPYRAN Inorg. salt
Solvent
Solubility
M. p.. OC.
Formula
Metal analyses, % Calcd. Found
Alcohol Alcohol Alc. HCI Alcohol Alc. KBr Alc. K I Ether Alcohol Ether Alcohol
S1. sol. hot aq. alc. 101-105 HgBrc (CHd.3 43.36 43.26 Ins. aq., org. solv. 154.5-157 Cu Cl. (CHz)&S 31.59 31.55 Same 154.5-160 CUCI.(CHZ)~S 31.59 31.50 Same 123-124 CuBr.(CHz)6S 25.88 25.85 Same 121.5-122.5 CuBr. (CH2)& 25.88 25.79 Same 164-165 d. CUI.(CHz)aS 21.73 21.85 SI. sol. alc., ins. eth. 120-122 d. AuCls.(CHz)sS 48.60 48.39 Ins. alc. eth. 179-182 d. AuCls (CHz)sS 58.89 58.66 SI. sol. alc. eth. 140-145 d. AuBw (CH&S 36.58 36.70 a S1. sol. hot alc. 173-179 d. AuBr. (CH&S 51.99 51.83 b Sol. chl., dec. aq. SnCL 149-151.5 SnClr,2(CH&S 25.53 25.57 Chlorof. Sol. chl., dec. aq. 149.5-151 SnBrc2(CH2) SnBrr 18.36 18.45 H~PtC1~-KIC Alcohol Ins. alc. 194.5-196 d. PtIz'2(CHz)sS 29.88 29.98 AcetoneHz0 SI. sol. acet., ins. aq. 146.5-148.5 d. P ~ C ~ Z . ~ ( C H ~27.93 )~S PdClr 28.07 a AuBra.(CH2)sSboiled with alcohol and excess thiopyran. Thiopyran and tin(1V) chloride mixed directly. Excess potassium iodide solution added to chloroplatinic acid in alcohol, precipitate dissolved by heating, and thiopyran added till no further precipitation. HgBrz cuc12 Cu2Clz CuBrz CuzBr2 c!u2Iz HAuClr HAuClr HAuBr4
hydrothiopyran by refluxing with excess sodium sulfide in ethanol. The addition compounds were formed by dissolving the metal salt in ethanol or ether, adding salt or acid if necessary, and adding slight excess of sulfide, sometimes dissolved in the solvent. The data on the complexes are given in Table I.
potassium and ammonium fluogermanates. The single needle-like specimen may or may not have been rubidium fluogermanate : the values of the lattice constants indicate that it may have been a different crystalline modification of closely related and only slightly more complicated structure than that to be discussed here. In any case we must correct our earlier statement a t least to the DEPARTMENT OF CHEMISTRY UNIVERSITY OF WASHINGTON extent of asserting that the usual and presumably SEATTLE, WASHINGTON RECEIVED FEBRUARY 2, 1942 the stable form a t room temperature of rubidium fluogermanate is fully isomorphous with the corStructures of Complex Fluorides. Rubidium responding ammonium and potassium salts. The X-ray data for Rb2GeFslead to a hexagonal Hexafluogermanate unit cell with a = 5.82, c = 4.79 A., space-group BY W. B. VINCENT AND J. L. HOARD D:d - C%m,containing one stoichiometric moleIn an earlier paper' we have reported the X-ray cule. The atomic coordinates2 are Ge in (a): determination of structure for the isomorphous 000; 2Rb in 2(d): l/s u; tZ with u = crystalline compounds potassium hexafluoger- 0.695; 6 F in 6(i): xxz, etc., with x = 0.144, z = manate and ammonium hexafluogermanate, 0.213. R2GeF6. Upon the basis of X-ray data obtained The methods used in establishing this structure from a single specimen of what we supposed was closely paralleled those previously described. rubidium fluogermanate, we stated at that time A comparison of calculated with observed rethat this substance crystallizes in a more com- flection amplitudes for over one hundred forms in plex structural type than do the corresponding rubidium fluogermanate led to generally excellent potassium and ammonium salts. This particular agreement. Having presented' the corresponding specimen occurred as a hexagonal prism, almost data in detail for potassium fluogermanate, and needle-like in shape, whereas we have since ob- ammonium hexafluogermanate, it seems untained only hexagonal tablets and plates by re- necessary to reproduce the rather extensive crystallizing rubidium fluogermanate from aque- tables3 for rubidium hexafluogermanate in this ous solution a t room temperature. X-Ray study note. In addition we find that a Fourier projecof a number of these tabular crystals shows that (2) "Internationale Tabellen zur Bestimmung von Kristallstrukthey crystallize in the same structural type as do turen," Gebriider-Borntraeger, Berlin, 1935, Vol. I, p. 258. (1) J. L. Hoard and W. B. Vincent, THISJOURNAL, 61, 2849 (1939)
(3) The amplitude data for rubidium hexafluogermanate are available in the Thesis of W. B. Vincent, "The Structures of Some Fluosilicates and Fluogermanates," Cornel1 University Library. 1940.
