The Crystallography of Silver Sulfide, Ag2s by ALFRED J

Zeitschrift fiir Kristallographie, Bd.ll0, S.136-144 (1958)

The Crystallography of Silver Sulfide, Ag2S By ALFRED J. FRUEH, JR.

With 5 figures

(Received October 25, 1957)

A uszug An einem Kristall von Akanthit (f3-Ag2S) von Freiberg i. Sa. wurde die Raumgruppe P21/n bestimmt; die Gitterkonstanten sind a = 4,23 A, b = 6,91 A, c = 7,87 A, f3 = 99° 35'. Die Elementarzelle enthiiJt 4 Ag2S. AIle Atome nehmen allgemeine Punktlagen ein mit Ag(I) in x = 0,758, Y = 0,015, z = 0,305; Ag(II) in x = 0,285, Y = 0,320, z = 0,435 und S in x = 0,359, Y = 0,239, z = 0,134. Akanthit hat wie auch der Argentit (a-Ag2S) ein raumzentriertes Gitter; die Atomanordnung ist jedoch bei beiden ganz verschieden. Das durch Abkiihlen aus a-Ag2S entstehende f3-Ag2S setzt sich aus kleinen Bereichen zusammen, in denen eine der Richtungen [103]*, [121]* und [121]* eines Bereichs parallel einer der beiden anderen Richtungen benachbarter Bereiche verliiuft.

Abstract The space group of a single crystal of naturally occurring acanthite (f3-Ag2S) from Freiberg, Saxony, was found to be monoclinic P21/n; the cell constants were determined as a = 4.23 A, b = 6.91 A, c = 7.87 A, 13 = 99° 35'. There are 4 (Ag2S) per unit cell and all atoms lie on the following fourfold general positions. Ag(I): x = 0.758, Y = 0.015, z = 0.305; Ag(II): x = 0.285, Y = 0.320, z = 0.435; and S at x = 0.359, Y = 0.239, z = 0.134. Acanthite has, in common with argentite (a-Ag2S), a body-centered cubic arrangement of the sulfur atoms, although the arrangement of the silver atoms in the two polymorphs is quite different. When crystals are cooled from a to 13, the crystals of 13contain many small domains related to each other in orientation by having the directions [103]*, [121]* and [121]* in one domain parallel to other combinations of these directions in the other domains.

Introduction At room temperature silver sulfide forms monoclinic crystals known to mineralogists as acanthite. The crystallography of this phase has The Crystallography of Silver Sulfide, Ag2S 137

been much discussed in the literature, the most recent and comprehen- sive study being that of RAMSDELLl. However, no complete structure determination has been attempted. Above 173 0 C the stable phase of silver sulfide (iX-Ag2S) is body- centered cubic. The mineralogists have labeled as argentite those crystals having cubic morphology, although the cubic structure is never retained at room temperature, and these specimens are actually acanthite pseudomorphic after argentite. The,structure of the IX phase was determined by RAHLFS2 from four lines on a powder photograph taken at 250 ° C. It was described as a structttre in which the sulfur atoms occupy the corners and center (0 0 0; ~..~..~) of a 4.88 A cubic cell, and in which the silver atoms are statistically distributed in the following 42 positions: (0 0 0; .~ ~ l) + (j (b) ~.0 0 Olo o 0 ~. 12 (d) ~.01 T~0 o } ~ ~ 0 it ~j10 o } ~ 24 (h) u u 0 uuo uuO uuO uOu uOu uOu uOu o U ~t Ouu Ouu Ouu where u = 5/8. The structure of acanthite RAMSDELLdetermined the cell constants as follows 1: a = 9.47 A, b = 6.92 A, c = 8.28 A, {3= 124°. The space group symmetry was determined as B 21/c (C~h)' With the density of 7.22 the cell contains 8 Ag2S. Although this orientation of the cell may have certain advantages, especially in describing the twinning, the adoption of a primitive cell related to RAMSDELL'S cell by

~ 0 ~/O1 01~ 0 ~is to be preferred. The cell constants for this new orientation were redetermined from a sample of acanthite from Freiberg, Saxony (Harvard University Museum No. 81814) by the BUERGER precession technique using MoK IX = 0.710 A as follows: a = 4.23 A, b = 6.91, c = 7.87, {3= 99°35'. 1 L. S. RAMSDELL, The crystallography of acanthite, Ag2S. Amer. Mineralo- gist 28 (1943) 401-425. 2 P. RAHLFS, Uber die kubischen Hochtemperaturmodifikationen der Sulfide, Selenide und Telluride des Silbers und des einwertigen Kupfers. Z. physik. Chern. B 31 (1936) 157-194.

Z. Kristallogr. BrI. 110, 2 10 138 ALFRED J. FRUEH, JR.

The space group in the new orientation is P 21/n, and with a cell volume of 226.8 A3 the cell contains 4 Ag2S. To obtain a single crystal for the purposes of determining intensities, it was necessary to fracture a small twinned Freiberg crystal at liquid-nitrogen temperature. The best tiny fragment chosen had but a trace of an unoriented crystal on it and was highly irregular in shape. This gave rise to strong anisotropic absorption for which no correction could be easily made. Intensity data for the a axis, zero, first, second and third levels were gathered by an equi-inclination GEIGER-counter spectrometer using CUKiX radiation. The data were corrected for LORENTZand polarization factors by the accepted method 3.

Fig. 1. PATTERSON projections of acanthite on (010), (100) and (001)

3 M. J. BUERGER and G. KLEIN, Correction of X-ray diffraction intensities for LORENTZ and polarization factors. J. Appl. Physics 16 (1945) 406-418. The Crystallography of Silver Sulfide, Ag2S 139

The silver atoms were located from PATTERSON projections on the three cell faces (Fig. 1) with the aidofa 0.483, 0.133M(xz) BUERGER minimum map 4 (Fig. 2) and HARKER-PATTERSON sections P(xyO) and P(xYl)' From the parameters of the silver atoms the signs of over 80 %of the reflections could be determined. Using only these reflections, electron- density projections were plotted on the (001), (010), and (100) faces. From these projections the silver positions could be confirmed but the sulfur positions could not be distinguished from the false detail about the silver peaks. To distinguish between the sulfur peaks and the false detail a second set of electron-density projections was constructed on the same planes using the same terms as used for the above projections except that the F values were calculated from THOMAS-FERMI scattering factors of the silver positions alone. The sulfur peaks could be identified as those peaks present on the original projections but not present on the second set. All positions were further refined by successive electron-density maps using all observed terms, and finally by least-squares refinement using the LB.lVI. 704 computer as set up by the Service Bureau Corporation of New York. The final electrondensity projections on the three cell faces are shown in Fig. 3. All atoms are located on the fourfold general positions x, Y, z; -x, -Y, -z; x +L ~--y, z +~; and ~-x, Y +}, ~-z. The final parameters are listed in Table 1. In Table 2 the intensities for all spots of non-zero intensity, as calculated from these parameters, are c

Table 1. Parameters of acanthite

x y Z Fig. 2. 0.483, 0.113 M(xz) Ag1 0.758 0.015 0.305 BUERGER minimum Agn 0.285 0.320 0.435 map of acanthite S 0.359 0.239 0.134

--- t M. J. BUERGER, A new approach to crystal-structure analysis. Acta Crystallogr. 4 (1951) 531-544.

10* 140 ALFRED J. FRUEH, .JR. compared with those observed. The standard discrepancy factor R is 0.27, and the final isotropic temperature factors are BAg1 = 1.01; BAgn = 1.16; Bs = 0.93.

a b a ~Ir~ ~~,~ Fig. 3. Electron-density projections of acanthite on (010), (100) and (001)

The structure The structure of acanthite is ilJustrated in Fig. 4a and 4b. The sulfur atoms are arranged in a slightly distorted body-centered cubic array with one of the twofold axes of the cube parallel to [010], the 21 axis of the monoclinic space group. The faces ofthe cube lie in the (103), (121), and (121) planes. The average length ofthe cell edge of this sulfur cube is 4.86 A. There is an almost planar distribution of the sulfur atoms perpendicular to the b axis. One of the Ag atoms lies either a little above or a little below the plane, and is triangularly coordinated to The Crystallography of Silver Sulfide, Ag2S 141

three sulfurs at 2.50 A, 2.61 A and 2.69 A respectively. The other Ag atom lies half way between the planes, and links them together by having one close sulfur In the plane above and one in the plane below at 2.49 Aand 2.52 A. Table 3 presents a list of the interatomic distances.

Table 2. Calculated and observed intensit'ies for non-zero reflections

Index Fca1c Bin& Index Index l'lob' Fcale IFloba calc IFlab!! Fca1c IFIobs " 040 .446 .;.119 .224 215 .;.167 '94 ''-1 . 62 1')6 .815 . 84 53 .579 37 060 .670 -+121, m .296 -195 '74" "7 .7':>8 -64 79 225 .61' . 40 080 .89) . '" .486 -106 m .782 . 68 245 .722 -50'4 46 .149 . " ",'" .590 - 8' '" .821 . 40" 29 255 .796 +134 90 OJ,'" .:3"34 _168 161 .6g6 28 b6 '" .872 206 .753 24 " '58" - "7 . '8 - .457 79 .803 bO 86 107 690 96 53 .648 .96 04' - '08 . - " 20' "95 .')67 . 48 53 '" .314 -114 117 .699 98 84 226 .685 -137 '" '" '32 - '06 061 .677 - 79 .308 . 60 13'1 .767 . 237 .805 -154 95 071 .737 29 46 .445 20 147 .iJ22 76 208 .620 +151 - " '37 7 - " 92 _106 " 128 " 002 .199 - 26 ,,,142 SB 79 .875 - "37 .228 . "6; 77 .629 90 128 -79" 66 .<.:;66 29 022 - 8'8 - '7 .299 -166 128 '62 .730 . "4 22 '"370 .598 - 46 OJ2 .389 .BY} 26 200 .370 -215 224 .711 26 . '72 - "0 . " 04? . ~88 - 98 "9 112 .27? +1')6 " 2'0 .386 . 88 .868 " " " '" 220 "0 - '0 C').? .')92 - 59 122 .333 . .432 - " .580 79" 062 .69.3 , j1 240 .57:;1 .5:;10 - - " 132 .416 59 - 69 92 '" -76 88 ,,. - " " ", " '" " 0'2 .306 . 96 142 .:'10 - 84 m 250 .668 . .621 - :)1 ~.;1g +140 152 .610 +123 260 .764 .66:;1 '0 12'g; '87 -105 " '" . " .373 +106 162 .713 .414 02' -22 64 2" 2 '" '" .731 -4J" "48 o ~3 .He . b6 68 lOJ .;76 -143 221 .457 . 21 20" '" .804 . 27 J7 70 70 .;92 . 92 .520 +115 66 ,61 .885 49 48 .'In - , '" '" - 05; .6;3 97 12J'" .437 "9 2612" .778 J9 22 + iJ5 29 . 311 .558 - 25 06) .1"33 . \1 9'j 1')3 .672 . 211 .383 - 6 "9 321 .591 . 99 97 .>3;6 163 .767 '0 221 on . 84 - 77 .42') . 45 62 341 .706 . 94 17) '0'" .9j '30 004 .398 - "2' 42 .866 25' .496 .630 . 64 .413 +109 103 . ~24 +290 224 241 .577 _102 .658 39 " 'J6 '"m - " 024 .4')6 . 60 70 113 .30 48 271 .861 m .704 . 20" 0)4 .')20 6J 57 123 .395 202 .448 9 J42 .763 67 24 - - jj " . " J\1 82 133 .4f,5 .17 24 m .462 .570 82 84 - " - " 31'2 - 46 143 .5')1 . 64 84 m .')00 . 64" 322 .600 . 12 22 .';;10 .644 .j7 57 252 .559 8' 22 .650 J4 -132 '08 1')' 332 . . 78 77 163 .743 . 85 90 242 .632 . 82 66 .788 80 90 .')4') 3')2 - " 03', .'000 - 46 26 171 .844 57 272 .S9'3 4J 44 362 870 . 51 04() - _162 -7') 46 .479 . 60 70 202 .390 ." 303 .585 " '61 -101 '" .573 +158 ,,. 212 .405 +102 31) .59') 68 8' n. " . 44 06) . 41 144 32) .'1\4 68 .64') - ?9 222 .449 +149 'J6 .626 . 9 JOb ,,, .726 51 .673 47 48'8 .5'37 " 242 .')92 . 3'3 - 016 92 114 .425 79 59 252 .680 52 H3 .735 41 J7 " - " - " - 026 .637 + 79 64 124 .467 - 26 262 .774 .5' "15 363 .888 - 046 .74) j7 134 .')29 205 272 .86 64 J4 + ',') -223" .872 .743 - " " oj? .77) 144 .605 '3 BB . 21' .524 94 '14 '14''" .637 . 60 20 08B 174 .881 J' - -10 15 - 59 "48 24\ .b19 . '24 .665 . 42 46 .,)')'J 7J 97 .757 78'8 51 334 .710 +145 '0' - - gg " .211 . 20 .570 52 213 86 344 .769 '"77 "0 - '5 '" .H':J - - 120 .289 +125'9 106 '" 72 77 22) 97 .804 - .48') +101 . " .;82 22 105'" .')01 +100 99 23) 84 '"305 .681 67 62 '30 - 'j .')49 -9j - " .4:.12 115 .62; " '<0 - gg59 .513 - \1 24'3" -64 57 315 .690 .74 68 160 12~ .548 J2 42 77 .717 46 .6':n ."" - " 2?'3" .707 - '8 325 . .91U 69 b4 n~ .602 4J \1 27) 22 316 .7?3 '80 . - .''893 - '8 jj - " '01 .224 . 62 1?5 .749 . 42 204 .')87 326 .777 .61" 62 .8)5 - " .2')U +114 '08" 165 . 6J" 70 214 .')97 -71" 40 336 .816 -77 . ~1b +167 1n "6 .66 ~-87 7J 224 .627 . 346 .868 - 81 " '" .402 146 .7[on 46 2)4 .67') . 307 .815 +118 'J',,, - ." 5'" " " .4'}'] . 62" "92 '56 .859 - 76 29 204 .496 + 43 " 317 .823 _. " .600 67 121 116 .60') +123 75 214 .881 '0 '\1 - .')09 . " 337 '8 " 68 b4 74 '51 .70S . "6 "6 .6)':. - 64 224 .')44 - "84 " 318 .899 . 48" .91) +~4 j? \46 .743 89 88 254 .746 '81 + -103 "0"

Polymorphism and twinning When Ag2S crystallizes above 173 0 argentite crystals with cubic symmetry and morphology are formed. Upon cooling, a single crystal of argentite rapidly inverts to a polycrystalline body of acanthite 142 ALFRED J. FRUEH, JR. while retaining the cubic morphology. After the transformation one twofold axis of the cube is retained as the twofold screw or b axis ofthe monoclinice acanthite. As there are six twofold axes to a cube there are also six possible orientations the acanthite can take with respect to the argentite morphology. The usual case is to have several, if not all, of these orientations as small intergrowing domains.

x o

5/J o ()

526 o

?'65 ~,

Fig. 4. The structure of acanthitc, dark circles represent sulfur atoms, light circles silver atoms. (a) Orthogonal projection pcrpendicular to the b axis; (b) Projection inclined 200 to b axis. y co-ordinates in A

Table 3. Some interatomic distances in acanthite

Atom Neighbor Distance

Ag[ Agr 3.41; :~.56; 3.57 Agll 3.04; 3.12; 3.14; 3.19 S 2.49; 2.52; 3.07 AgJI Agn 3.15; 3.73 S 2.50; 2.61; 2.69 S S 4.08; 4.09; 4.15; 4.19

Fig. 5 will serve to illustrate the domain structure of a small cube of "argentite" from Freiberg, Saxony (Harvard University Museum No. 93079). Fig. 5a shows the zero-level, a axis BUERGER precession photograph of argentite taken above 2000 C. Fig. 5 b is a picture taken The Crystallography of Silver Sulfide, Ag2S 143 at the same setting ofthe same crystal at room temperature. Fig. 5c is a zero-level, [103]* direction, precession picture of a single crystal of acanthite. It can be seen that if Fig. 5 c were rotated 900 about the precession axis, [103]*, and superimposed upon itself it would produce Fig. 5b. The pictures taken by precessing about the other morphologi- cal cube axes are identical to that of Fig. 5b. Attempts to find a statistical arrangement of the silver atoms for the high-temperature form based upon the silver positions in the low form did not yield calculated intensities as close to the observed intensities as those determined by RAHLFS for the parameters men- tioned in the introduction of this paper.

Fig. 5. BUERGER precession photo- graphs of Ag2S (Mo Ka).

(a) Zero level a axis of argentite abovc 2000 C.

(b) Same setting as (a) at room temperature.

5b 5c 144 ALFRED .J. FRUEH, .JR.

Acknowledgements This work is part of a research program on the crystal chemistry of the sulfides, made possible, in part, by a grant from the National Science Foundation. The author wishes to express his appreciation to Prof. CLIFFORD FRONDEL, Prof. LEWIS RAMSDELL, Dr. GEORGE SWITZER and ALBERT FORSLEV for supplying the crystals investigated. The technical assistance of Mr. DAVID NORTHROP is gratefully acknowl- edged.

University of Chicago, Chicago 37, Illinois