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..


The crystal structures and microtwinning of two alkali amphiboles



: , ... : .., ..-.. ..., ..-.. : . ... 2014 . .. .. .. ..


1. 2. 3. . 4. , -. 4.1. 4.2. . 5. . 5.1. . . 15 17 18 24 24 27 28 3 5 8 12

2


. , , , , .. . . , .

, , , , [ ., 1981]. , , . . . , , . ( ), . , , , . 10-4 ­ 10-5 , [, 1981]. ( ) . . . 3












,



. , , : . [, 1974]. , . . .. , - .. , - .. , . , ..-.., . .. (, ) ..-.. .. ( , ).

4


1. . , [, , 2005], , - «» [, 1951]. - , , , [, 1983; ., 1992]. , 2 . , , , , , ().
G' 2 H,

(1)

H ­ . , . (1) 58 32 [ , 1983]. , , , n :
(n)

G

n H,

(2)

H ­ G. 153 [Wittke and Carrido, 1959]. (2), .. , , , , , . , . , , 5


, , . , .. : 1) (, ); 2) (, ). . , [ ., 1992]. , L L , , L L :
3



ai ''
j1

tij a j '

(3)

t

ij

­ T, .

, L L , . L L . «», «» «» [Friedel, 1933]. . , . [Friedel, 1926]: 1. (. 1); 2. (. 1); 3. () (. 1); 4. () (. 1). 6


, L L

. ,

, ,



, L L . , L L . , , .

()

()

()

()

. 1. : (), (), () (), () (). 7


, = . , , . , , , , , . L [International Tables, 1976]: n=

Vr = det(mij) VL

(4)

, . , . [Donnay and Donnay, 1974]: TLS (Twin Lattice Symmetry) ­ TLQS (Twin Lattise Quazi ­ Symmetry) ­ . , TLS ( ) ( ), TLQS ( ) ( ). , , , . 2. . n ­ . , , . «» , , 8


. , , H , : I( H ) = J1( H ) + (1-)J2( H ) (5) ­ , J1( H ) J2( H ) ­ H . I, J .

(5) . . , ( ). , , . . , , . , , , . 21 58 - , . 11 , . , . . 1. : I = J1. (6) (6), . , . , , 9 . (5) J1 = J2,


, . , . [Catti and Ferraris, 1976] I. , I, . 1. ,
1 2 / m , 2/ m m m m,mmm 1 2/ m mmm



3

3
m, 3 m /m , 4/m /m m m , 4 /m m m , 4 /m m m /m , 6 /m /m m m , 6 /m m m , 6/m m m

3 4 4 6 6

3 4/ 4/ 6/ 6/

m m mmm m mmm

m3 m 3 m, m 3 m

m3 m 3m

, , , , . (6) , . , ( = 0,5 0,5), . 2 37 . , . (6) , . . 2 , . , ( , 10


..) , , , 0.5. , 3 2/ m . , , . 2. = 0.5 2 , m , 2 /m 2 /m 2/ m 1 m m 2, m 2 m , 2 2 2 , mmm mmm 2/ mmm 0.5

m

3m , 32 , 3m 4 , 4 , 4 /m 4 22 , 4 m2 , 4 mm , 4 2m , 4 / mmm 4m m , 42 m , 42 2 , 4 / mm m 6 , 6 , 6 /m 6 2m , 6 m2 , 6 mm , 6 22 , 6 / m mm 6 2 m , 6m m , 62 2 , 6 / mm m 4 3m , 4 32 , m3m
,

3m 4/m

3m 4/ m

3 2/ m
mmm

4/mmm
4/ m m m

4 / mmm
4 / mmm

4/ m
3
3m

6/m 6/m mm
6/mm m
m 3m

6/ m 6 / mmm
6 / mmm
m3m


6/ m
m3









. ( TLS TLQS) . :

b

i

ri ri 2

1 2

ij

cij rj ,

(7)

11




ij

- , ,

. TLS, , . , , . TLQS . , . , , . , TLS, . , TLS , , , . , (14). , TLQS . , . , , , . 3. . «», (1801.), «amphibolos» ­ , , . . , ­ . , ( ) [, 1981]. 12


220,
2+

A1B2C5[T4O11]2W2 [Hawthorne et al., 2012], A = Li, K, Na; B = Ca, Na, Mg, Fe , Mn; C = Mg, Fe3+, Fe2+, Al, Mn, Ti, (Cr, V, Ni); T = Si, Al, (Ti) W = OH, O, Cl, F. . [(Si,Al)4O11]6
-

5,3 ( ),

, , (. 2). 1, 2 3 . B-. , , , Na+, K+ Li+. 1 2 . , 1 , 2 ­ . 2/m; P2/. : Pnma Pnmn. . . . [Thompson, 1970].

. 2. .

13


. 1, 2 3 0,57 0,91 (Mg, Al, Fe2+, Fe3+, Mn, Ti). 1 3 , , 3 -. 1, ­ 3. 1 3 [Hawthorne, 1981]. 2 , . 2 . , 4. ­ . , Na, K, Ca, - 2.7-3.4 [Hawthorne and Grundy, 1973; Robinson et al., 1970]. - 3. . . Ca, Na, Li, Mn, Fe2+, Mg, . B ­ . B- Mg, Fe2+, Mn- Ca-, Na- [Robinson et al., 1971; Ross and Papike, 1969; Ross et al., 1968]. , B , .. B- . , , B, . Ca, Na, Fe2+, 2/m. B Mg Mn, P21/m, B Pnma. 1, 2 3 , [, 1973]. , , , , . 14


, , , . , , . , , , . , - . , . 2013 [Hawthorne et al., 2012]. 4. ,

-. ALi2(LiC
A B 2+ 2

C3+2)[Si8O22](OH,F,Cl)2, :

(Na+K+2Ca) > 0.5 ; Li = 2 ; Li > 0.5 .

C

, (. 3): --, --, , -, , . 2013 ( ) . .. . , , 150 , . . , -, , , . , 15


0.1 5 . - (. 3), . .

. 3. .. , 22 (Z=2): (Na0.55K0.02) (Li
1.85

Na0.11Ca0.04) (Al1.86Fe2+
+

1.02

Mg0.9Li

0 .6 7

Fe3+0.44Mn

0.07

) [Si

7.73

Al0.27O22]

(OH)1.35F0.65. Fe2

/ Fe3

+



, . , Fe2+ 46.3 + 22.4 = 68.7%, Fe3+ 25.5 + 5.8 = 31.3%. , [Hawthorne et al., 2012], , . , , -, Fe2+ > Mg. 3. 16


-- -- - - -- --- -

NaLi2(Mg2Al2Li)[Si8O22](OH)2 NaLi2(Fe2+2Fe3+2Li)[Si8O22](OH)2 NaLi2(Fe2+2Al2Li)[Si8O22]F2 NaLi2(Mg2Al2Li)[Si8O22]F2 NaLi2(Mg2Fe3+2Li)[Si8O22](OH)2 NaLi2(Mg2Fe3+2Li)[Si8O22]F2 NaLi2(Fe2+2Fe3+2Li)[Si8O22]F2 NaLi2(Fe2+2Al2Li)[Si8O22](OH)2

: «» . , . 4.1. , Xcalibur Oxford Diffraction c CCD (. 4). : a = 9.3716(4), b = 17.649(1), c = 5.2800(6) å, = 102.22(1) °. . 4.

. 4. Xcalibur Oxford Diffraction, CCD- ( ).

17














.

.

P2/m,

..

(~10%), C-. , Ri
nt

~ 12.5%

R ~ 9% . h0l CrysAlis [Oxford Diffraction, 2009] , [1 0 0 / 0 -1 0 / -0.24 0 -1] (. 5). , "charge flipping" [Palatinus and Chapuis, 2007] . . 2/m R = 3.9 4843 I > 2(I). 0.681(3) / 0.319(3). ­ , ­ R-. Jana2006 [Petricek et al., 2006]. . 5, . 6, ­ . 7.

. 5. h0l. 4.2. . :
M2


A




B







(Na0.55K0.02)

(Li

1.85

Na0.11Ca0.04)

C M1

[ (Fe1.03Mg0.9Mn0.07)

(Al

1.86

Fe0.14)

M3

(Li

0 .6 7

Fe0.33)] T[Si

7.73

Al0.27O22] W[(OH)1.35F0.65].

18


- (. 6), - , -. , , , , -. - .

()

()

. 6. - () - (100) (). - (. 7) , 1 (<1-O> = 2.095 å) Fe2+ (1.03 ) Mg (0.9 ) Mn (0.07 ). M2 1.924 å, (0.14 ). 3- (<3-O> = 2.115 å) Li (0.67 ) Fe (0.33 ). , , M2 Fe3+, M3 ­ Fe2+. M1 . , <-O> = 2.271 å. (0.11 ) (0.04 ). - (0.55 ) (0.02 ). , - ­ 19


, Fe2+ Mg. (100), P2/m. . . C2/m .

20


4. , (-1) . . a (å) b (å) c (å) (.) V (å3) Z () ; (å) (K) F(000) (.) h, k, l / R (Iobs > 2(I)) S R- min / max NaLi2[Fe2Al2Li][Si8O22](OH)2 2.211 C2/m 9.3716(4) 17.649(1) 5.2800(6) 102.22(1) 853.5(1) 2 0.15 x 0.18 x 0.20 X Calibur Oxford Diffraction MoK; 0.7107 293 791 4.12 - 56.2 -21 < h < 21 -39 < k < 41 -12 < l < 11 23602 5541 / 5.84 4843 F : w=1/(2F+0.002025F2) 1.03 R1=3.91; wR2=6.77 -0.92 / 1.92

21


A B M1 M2 M3 T1 T2 O1 O2 O3 O4 O5 O6 X

5. (xyz), (Q), (Ueq) - x y z Q Ueq 0.0748(4) 0 0.1499(7) 4 0.030(1) 0.5 0.2580(2) 0.5 4 0.030(1) 0.5 0.0899(1) 0.5 4 0.0091(1) 0.5 0.1799(1) 0 4 0.0064(1) 0.5 0 0 2 0.0043(1) 0.7847(1) 0.0879(1) 0.2783(1) 8 0.0055(1) 0.2025(1) 0.1737(1) 0.2084(1) 8 0.0056(1) 0.8462(1) 0.1234(1) 0.5624(1) 8 0.0121(1) 0.8581(1) 0.1291(1) 0.0650(1) 8 0.0110(1) 0.8363(1) 0 0.2874(2) 4 0.0115(2) 0.6089(1) 0.0945(1) 0.1978(1) 8 0.0072(1) 0.3801(1) 0.1753(1) 0.2580(1) 8 0.0078(1) 0.6224(1) 0.2468(1) 0.2096(1) 8 0.0098(1) 0.3830(1) 0 0.3028(2) 4 0.0110(2)

Composition Na0.55K0.02 Li1.85Na0.11Ca0.04 Fe1.03Mg0.9Mn0.07 Al1.86Fe0.14 Li0.67Fe0.33 Si3.73Al0.27 Si4.00

(OH)1.35F0.

65

6. U11 A 0.042(2) B 0.020(1) M1 0.0102(1) M2 0.0065(1) M3 0.0060(1) T1 0.0065(1) T2 0.0062(1) O1 0.0097(2) O2 0.0080(2) O3 0.0109(2) O4 0.0060(1) O5 0.0064(1) O6 0.0105(2) X 0.0108(2)

- U22 U33 U12 U13 0.019(1) 0.038(2) 0 0.027(1) 0.053(2) 0.018(1) 0 0.007(1) 0.0089(1) 0.0089(1) 0 0.0036(1) 0.0061(1) 0.0068(1) 0 0.0018(1) 0.0021(1) 0.0046(1) 0 0.0007(1) 0.0046(1) 0.0056(1) -0.0000(1) 0.0019(1) 0.0053(1) 0.0057(1) 0.0007(1) 0.0019(1) 0.0172(2) 0.0091(2) 0.0014(2) 0.0015(1) 0.0154(2) 0.0100(2) 0.0001(1) 0.0026(1) 0.0044(2) 0.0192(3) 0 0.0029(2) 0.0076(1) 0.0082(2) 0.0000(1) 0.0018(1) 0.0090(2) 0.0082(2) 0.0002(1) 0.0022(1) 0.0075(2) 0.0110(2) -0.0035(1) 0.0016(1) 0.0091(2) 0.0130(3) 0 0.0020(2)

U23 0 0 0 0 0 -0.0001(1) 0.0001(1) -0.0063(2) 0.0065(2) 0 0.0001(1) -0.0006(1) 0.0004(1) 0

22


7. -. A O3 O3 O1 O2 X O3 O2 A O5 O6 O1 O4 X O5 O6 O5 O4 O4 O4 X 2.492(4) 2.615(4) 2.669(2) 2.678(2) 2.829(4) 2.911(4) 3.021(3) <2.758> 1.879(5) 2.102(3) 2.110(1) 2.602(3) <2.271> 2.070(1) 2.079(1) 2.135(1) <2.095> 1.843(1) 1.942(1) 1.988(1) <1.924> 2.112(1) 2.112(1) 2.122(1) <2.115> T1 x2 x2 T2 x2 O2 O1 O4 O3 O6 O5 O2 O1 1.613(1) 1.615(1) 1.616(1) 1.623(1) <1.617> 1.591(1) 1.629(1) 1.637(1) 1.642(1) <1.625>

A B

x2 x2 x2 x2 x2 x2 x2 x2 x2 x2 x2 x2

M1

M2

M3

23


5. . Si/Al ~ 6/2, , , . ACa2(C
2+







,
3

C3+Ti)[Al2Si6O22]O2.



:
A Z

(Na+K+2Ca) > 0.5 ; O > 1.0 . :

Ti > 0.5 ;

W



NaCa2(Mg3AlTi)(Al2Si6O22)O2, - NaCa2(Fe2+3AlTi)(Al2Si6O22)O2 NaCa2(Mg3Fe3+Ti)(Al2Si6O22)O2. . , 16 , (Na0.7K0.3)Ca2.0(Mg3.4Fe1.0Ti0.6)(Si5.95Al2.05O22)F1.1O0.9. [Hawthorne and Grundy, 1973], X- , OH- , - 3000­4000 ­
1

( .. ).
2+

: OH- , , F + O = 4 Fe : Fe3+ . , , [ ., 2008]. 5.1. , Xcalibur Oxford Diffraction c CCD (. 4). : a = 9.8637(2), b = 18.0353(4), c = 5.3087(2) å, = 105.551(2) °. . 9. . . C2/m. , , 3468I > (I), - (. 7). h0l 24


(001) ( [-1 0 -1 / 0 -1 0 / 0 0 1]), , 781 , 2687I > (I) C-. [Padilla and Yeates, 2003.] . , , , -, , [, 2012]. - . . . , , . . 1 [, , 2012]. .

. 7. hkl, l = 1 , (hkl: h+k=2n).

25


9. , (-1) a (å) b (å) c (å) (.) V (å3) () ; (å) (K) (.) h, k, l Iobs > 2(I)) NaCa2(Mg3FeTi)(Al2Si4O22)OF 2.5 9.8637(2) 18.0353(4) 5.3087(2) 105.551(2) 909.82(4) 0.65 â 0.15 â 0.15 X Calibur Oxford Diffraction MoK; 0.7107 293 4.13 - 54.97 -22 < h < 21 -39 < k < 39 -10 < l < 12 76123 38568

26


. - ­ , Fe2+ Mg. (100), P2/m. . . C2/m . , . -. . , , , .

27


: .. , . . . ... . .-. . . 2012. .., .. , , . .: «», 2005. 512 . .. . .: , 1981. . 1. 384 . .., .., .. . .: , 1981. . 2. 359 . .. (, , ). : . , 1973. 125 . .. . .: , 1974. 248 . . . . .. . 3. . 3. .: , 1981. 398 . .. . .: , 1983. 295 . .., .. ­ (Na,Ca,K)2(Ca,Na)4(Mg,Fe)5(Mg,Fe,Ti)5[Si12Al4O44](F,O)4

// . 2012. . 57. . 430-435. .., .., .. // : . .: , 1992. . 165-181. .., .., .., . . «» // . 2008. . 43. . 72 .. . .; .: , 1951. 172 . Catti M., Ferraris G. Twinning by merohedry and X-ray crystal structure determination // Acta Cryst. 1976. A32. P. 163-165. Donnay G., Donnay J.D.H. Classification of triperiodic twins // Canad. Miner. 1974. V. 12. P. 422-425. Freidel G. Sur un nouveau type de macles // Bull. Soc. Fr. Miner. et Cristallogr. 1933 V. 56. P . 262-274. Friedel G. Lecons de cristallograpie. P.: Berger-Leverault, 1926. 316 p. Hawthorne F.C. Crystal chemistry of the amphiboles // Rev. Miner. 1981. V. 9A. P. 1-101. Hawthorne F.C., Grundy H.D. The crystal chemistry of amphiboles. II. Refinement of the crystal structure of oxykaersutite // Mineral. Mag. 1973. V. 39. P. 390-400. 28


Hawthorne F.C., Grundy H.D. The crystal chemistry of amphiboles. I. Refinement of the crystal structure of ferrotschermakite // Miner. Mag. 1973. V. 39. P. 36-48. Hawthorne F.C., Oberti R., Harlow G.E., et al. IMA Report. Nomenclature of the amphibole supergroup // American Mineralogist. 2012. V. 97. P. 2031­2048. International tables for X-ray crystallography. Birmingham: Kynoch press, 1959. V. 2. P. 224231. Oxford Diffraction. CrysAlisPro. Oxford Diffraction Ltd, Abingdon, Oxfordshire, UK 2009. Padilla J., Yeates T.O. A statistic for local intensity differences: robustness to anisotropy and pseudo-centering and utility for detecting twinning // Acta Cryst. 2003. D59. P. 11241130. Palatinus, L., Chapuis, G. SUPERFLIP ­ a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions // J. Appl. Cryst. 2007. V. 40. P. 786-790. Petricek, V., Dusek, M. & Palatinus, L. Jana2006. Structure determination software programs. Institute of Physics, Praha, Czech Republic. 2006. Robinson K., Gibbs G.V., Ribbe P.H. A refinement crystal structure of pargasite // Amer. Miner. 1970. V. 55. P. 307. Robinson K., Ross M., Jaffe H.W., Klein C. Orientation of exolution lamellal in clynopyroxenes and clinoamphyboles: Consideration of optimal phase boundaries // Amer. Miner. 1971. V. 56. P. 909-939. Ross M., Papike J.J. Exsolution textures in amphyboles as indicators of subsolidus thermal histories // Miner. Soc. Amer. Spec. Pap. 1969. V. 2. P. 275-299. Ross M., Papike J.J., Weblen P.W. Exsolution in clinoamphyboles // Science. 1968. V. 159. P. 1099-1102. Thompson J.B. Geometrical possibilities for amphibole structures: Model biopyriboles // Amer. Miner. 1970. V. 55. P. 292-293. Wittke O., Carrido J. Symmetrie des polyedres polychromatiques // Bull. Soc. Fr. Miner. et Cristallogr. 1959. V. 82. P. 223-230.

29