Zeolite Frameworks

14

Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on November 21, 2014 | http://pubs.acs.org Publication Date: August 1, 1974 | doi: 10.1021/ba-1971-0101.ch014

Zeolite Frameworks W. M. MEIER Institut für Kristallographie and Petrographie der ΕΤΗ, Zürich, Switzerland D. H. OLSON Mobil Research and Development Corp., Princeton, N. J. 08540 A collection of stereopairs showing the presently known framework structures of zeolites is presented. Only wellestablished structures have been incorporated in this survey which includes crystal data, information on channel geometry, and possible fault planes. "\Tost zeolite structures are fairly complex and cannot be visualized readily. For this reason, stereoscopic drawings of 27 well-established zeolite frameworks have been prepared as a general aid (Figures 1-27). These skeletal framework drawings are based on the T-atoms (Si,Al) only and T - O - T bridges are represented by straight lines. In general, the viewing direction has been chosen in such a way that the main channels are clearly visible. The idealized cell contents, crystal system, space group, and unit cell dimensions have been summarized in the figure captions. In many cases, the listed space group represents a pseudosymmetry which does not account for Si,Al ordering. The unit cell has been indicated in all cases where this appeared feasible. The present atlas of zeolite frameworks includes only reasonably well-established structures which have been at least partially refined. Mere proposals have been excluded since past experience has shown that all too frequently these have been incorrect. As a rule, the references in the captions have been limited to the first correct description of the framework structure and to its subsequent refinement. Zeolites do not represent an easily definable group of crystalline aluminosilicates. There are obvious borderline cases like some sodalitetype species which have been included in this survey. On the other hand, nepheline hydrate, the scapolites, osumilite (12), and buddingtonite, an ammonium feldspar with zeolitic water (17), have not been considered here. 155 In Molecular Sieve Zeolites-I; Flanigen, E., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1974.


156

MOLECULAR SIEVE ZEOLITES

Figure 1.

Analcime (29, 5 5 ) , Na Al Si O 16

32

16

g6

· 16 H 0, 2

1

viewed along [100]

cubic, Ia3d, a = 13.73 A Isotypes: wairakite (14), leucite (62), pollucite (40), viseite (31), kehoite (32)

Figure 2.

Laumontite

( 6 ) , Ca Al Si O u

8

16

h8

· 16 H 0 , viewed along 2

[100]

monoclinic, Am, a = 7.57, b = 14.75, c = 13.10, y = 112.0° CH: [100] 10 4.0 X 5.6* Isotype: leonhardite ( 13 ) G e n e r a l accounts of z e o l i t e structures a n d classification schemes c a n b e f o u n d i n several recent articles (20, 35, 50) Structure

a n d tables

(54).

Types

Species w h i c h are b a s e d o n t o p o l o g i c a l l y e q u i v a l e n t f r a m e w o r k s r e p resent the same structure t y p e i r r e s p e c t i v e of c o m p o s i t i o n , d i s t r i b u t i o n of the f r a m e w o r k atoms, c e l l d i m e n s i o n s , a n d s y m m e t r y . M a r k e d differences w i t h respect to these p r o p e r t i e s f r e q u e n t l y c a n b e o b s e r v e d f o r i s o t y p i c species. A n u m b e r of z e o l i t i c isotypes h a v e b e e n l i s t e d i n the figure c a p tions together w i t h a p p r o p r i a t e references, u s u a l l y to s t r u c t u r a l w o r k .

In Molecular Sieve Zeolites-I; Flanigen, E., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1974.


14.

MEIER AND OLSON

Figure

3.

Natrolite

Zeolite

Frameworks

(33, 42, 5 8 ) , Na Al Si O along [110] t6

16

u

80

• 16 H O 2

y

viewed

orthorhombic, Fdd2, a = 18.30, b = 18.63, c = 6.60 A CH: ± [001] H 2.6 X 3.9**

F?: (110). Isotype: scolecite (57)

Figure

4.

Thomsonite

( 5 7 ) , Na,Ca Al Si O [100] 8

20

20

80

· 24 H 0, 2

orthorhombic, Pnn2, a = 13.07, b = 13.08, c = C H : ± [001] 8 2.6 X 3.9** F F : (I00j, (ΟΙΟ;

viewed i3.I8 A


along


158

MOLECULAR SIEVE ZEOLITES 1

Figure

5.

( 5 6 ) , Ba Al.Si O [110]

Edingtonite

2

6

20

' 8 HO 2

f

viewed

along

orthorhombic, P2i2i2, a = 9.54, b = 9.65, c = 6.50 A CH: ± [001] 8 3.5 X 3.9**

FP: (110)

Figure 6.

Sodalite

(30, 43), Na Al Si O 6

6

6

u

• 2 NaCl, viewed along

[100]

cubic, P43n, a = 8.87 A FP:(111) Isotypes: sodalite hydrate or Zhdanov G (48, 49), TMA-sodalite (2), tugtupite ( 15 ) S y n t h e t i c zeolite N a P l

( o r L i n d e B ) is a p p a r e n t l y a n i s o t y p e of

g i s m o n d i n e ( F i g u r e 14) a c c o r d i n g to a recent s t u d y b y B a e r l o c h e r a n d M e i e r (4).

T h e c u b i c structure w h i c h w a s p r o p o s e d earlier has b e e n

r u l e d o u t i n t h i s w o r k . T h e s y m m e t r y of t h e N a P l f r a m e w o r k is n o n c u b i c ( d e s p i t e t h e fact that t h e u n i t c e l l is c o m p a t i b l e w i t h c u b i c s y m m e t r y ) , a n d t h e phase appears to consist of m i m e t i c t w i n s .



14.

MEIER

Figure

7.

Zeolite

A N D OLSON

Cancrinite

Frameworks

(24, 4 2 ) , Na Al Si O along [001] 6

6

6

u

159

· CaCO

· 2 H 0,

s

2

viewed

hexagonal P 6 , a = 12.75, c = 5.14 A CH: [001] 1 2 6.2* FP: (001). Isotype: cancrinite hydrate ( 61 ) 3

Figure

8.

Gmelinite

( 1 9 ) , (Na ,Ca) Al Si 0 [001] 2

u

s

16

}t8

· 24 H O, s

viewed

along

hexagonal, P63/mmc, a = Hi.3, c = JO.O A CH: [001] 1 2 7.0* -L [001] 8 3.6 X 3.9** FP.fOOI)

Channel

Geometry

T h e figure captions i n c l u d e i n f o r m a t i o n o n t h e channels ( C H ) . A s h o r t h a n d n o t a t i o n has b e e n u s e d f o r the d e s c r i p t i o n of t h e channels i n the v a r i o u s f r a m e w o r k s .

E a c h system of e q u i v a l e n t channels has b e e n

c h a r a c t e r i z e d b y t h e c h a n n e l d i r e c t i o n , t h e n u m b e r of t e t r a h e d r a f o r m i n g the smallest rings of t h e channels, a n d t h e c r y s t a l l o g r a p h i c free diameters



160

Figure


9.

(16, 5 1 ) , Ca Al Si 0

Chabazite

6

12

2i

1

• 40 H 0, viewed along [001]

72

2

hexagonal, R3m, a = 13.17, c = 15.06 A CH: _L [001] 8 3.6 X 3.7***

FP:(001)

Figure

10.

EHonite

( 5 2 ) , (Na ,Ca, etc.) Al Si 0 along [001] 2

k

5

9

27

72

· 27 H 0, 2

viewed

hexagonal, P6 /mmc, a = 13.26, c = 15.12 A 3

CH: JL [001] 8 3.6 X 5.2*** FP:(00i;

of t h e channels.

T h e free d i a m e t e r values a r e b a s e d o n 1.35 A f o r t h e

o x y g e n r a d i u s , a n d b o t h m i n i m u m a n d m a x i m u m values are g i v e n f o r n o n c i r c u l a r apertures.

T h e n u m b e r of asterisks f o l l o w i n g these

figures

i n d i c a t e s w h e t h e r t h e c h a n n e l system is one-, t w o - , o r t h r e e - d i m e n s i o n a l . O n l y those apertures h a v e b e e n t a k e n i n t o a c c o u n t w h i c h are m o r e o p e n t h a n r e g u l a r s i x - m e m b e r e d r i n g s . I n m o s t cases, these smaller openings



14.

MEIER

Figure 11.

AND

OLSON

Zeolite

161

Frameworks

Offretite ( 8 ) , (Na ,Ca, 2

etc.) Al Si 0 [001] 2

h

u

· 14 H 0,

36

2

viewed

along

hexagonal, P6m2, a = 13.3, c — 7.6 A CH: [001] 1 2 6.4* ± [001] 8 3.6 X 5.2** FP:(001)

Figure 12.

Linde L ( 5 ) , K Na Al Si 0 6

3

9

27

72

• 21 H 0, 2

viewed along

[001]

hexagonal, P6/mmm, a = 18.4, c = 7.5 A CH: [001] 1 2 7.1* FP.(OOl)

f o r m s i m p l e w i n d o w s ( r a t h e r t h a n c h a n n e l s ) c o n n e c t i n g l a r g e r cavities. I n t e r c o n n e c t i n g c h a n n e l systems are separated b y a d o u b l e a r r o w ( ). A v e r t i c a l b a r ( | ) means t h a t there is no d i r e c t access f r o m one c h a n n e l system to the other. C r y s t a l l o g r a p h i c free diameters d e p e n d o n the state a n d the c o m p o s i t i o n of the zeolite.

T h e c h a n n e l d i m e n s i o n s of i s o t o y p i c species

differ a p p r e c i a b l y , p a r t i c u l a r l y i n the case of n o n r i g i d f r a m e w o r k s .


can


162


Figure 13.

Phillipsite ( 5 3 ) , (K,Na) Al Si O [100] 10

10

22

6i

· 20 H 0, 2

1

viewed along

orthorhombic, B2mb, a = 9.96, b = 14.25, c = 14.25 A CH: [100] 8 4.2 X 4.4* [010] 8 2.8 X 4.8* [001] 8 3.3* FP: (010). Isotype: harmotome (47)

Figure 14.

Gismondine ( 1 8 ) , Ca Al Si 0 i

8

8

32

viewed along [010]

· 16 H 0, 2

monoclinic, P 2 i / a , a = 9.84, b = 10.02, c = 10.62 A, y = 92.4° CH: {[100] 8 3.1 X 4.4 +-* [010] 8 2.8 X 4.9}*** FP:(101) (Oil) Isotypes: TMA-gismondite ( 3 ), Barrer PI or Linde Β ( 4 ) t

Figure 15.

Yugawaralite (27, 2 8 ) , C a ^ A / j S ^ O ^ · 8 H 0 , viewed along [001] 2

monoclinic, Pc, a = 6.73, b = 13.95, c = 10.03 Α, β = 111.5° CH: [100] 8 3.1 X 3.5* < - » [001] 8 3.2 X 3.3*



14.

M E I E R

AND

Figure 16.

CH:

OLSON

Heulandite

Zeolite

163

Frameworks

(37, 3 8 ) , Ca Al Si 0 [001] ll

s

28

72

· 24 H O, z

viewed

monoclinic, C m , a = J7.73, b = 17.82, c = 7.43 A,B = 116.3° [100]

Figure 17.

8 4.0 X 5.5*

{[001] 1 0 4.4 X 7.2* and 8 4.1 X F P : (010)

Stilbite ( 2 1 ) , Na Ca Al Si O 2

i

10

26

72

4.7}*

• 28 H 0 , viewed along 2

monoclinic, C 2 / m , a = 13.64, b = 18.24, c = 11.27 Α, β = C H : [100] 1 0 4.1 X 6.2*

Zeolite Frameworks

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