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42, 5

2001

535.37:543.422.25
.. , .. , .. , .. , ..




NH4TiF5 (I) (; = 14,683(1), b = 6,392(1),
= 20,821(2) , = 110,538(2); .. P21/n, Z = 4). I
TiF6, [ 101 ] , , . I. 19F 1H NH4TiF5 270 530 K.
.


IV , , (IV) c , (I) [ 1 4 ].
NH4TiF5 (I),
,
, .
I 270 530 K.

NH4TiF5 (I)
(NH4)2TiF6 (II) . , I
[ 5 ]. , , NH4TiOF3.
NH4TiF5 [ 6 ],
(NH4)2TiF6
. NH4TiF5,
, ,
NH4TiF5 573 623 K
. NH4TiF5 , . 295 K 19F 1H, (
3 4 %), 1,19 1,14
.. , . . , . . ., 2001

922

.. , .. , .. .

, 1,25.
,

I
555 K.

-
NH4TiF5

640,74

293(2) K

K (0,71073 )


P21/n
0,100,200,03
,
14,683(1)
a,

6,392(1)
b,

20,821(2)
c,

110,538(2)
,

1829,9(3)
V, 3
Z
16
d,, /3
2,326
1,870
, -1
.
F(000)
1236

0,1 0,2 0,03


2,96 30,18

SMART
20 h 18, 8 k 8,
1000
CCD

12 l 29
Bruker


12090
K-
5248 (Rint = 0,0381)
. , 2635
I > 2(I )




2
F

267

S
0,847
R1 = 0,0367, wR2 = 0,0875
R- I > 2(I)

R-
R1 = 0,0825, wR2 = 0,1003

[ 7 ].


0,00065(13)

0,562/0,613

(/), e/3
( Ti)

[ 8 ].
, .
, . 1.

923

2
3

(10 ) (10 )
NH4TiF5

Ti(1)
Ti(2)
Ti(3)
Ti(4)
F(1)
F(2)
F(3)
F(4)
F(5)
F(6)
F(7)
F(8)
F(9)
F(10)

8608(1)
8921(1)
6086(1)
6388(1)
8754(2)
7369(1)
9035(2)
8349(2)
9988(1)
8577(1)
10169(1)
8910(1)
8681(2)
9090(1)

3177(1) 2129(1)
2336(1) 361(1)
2481(1) 353(1)
3055(1) 2138(1)
3360(3) 3012(1)
4005(3) 1810(1)
5894(3) 2116(1)
443(3) 2048(1)
2398(3) 2366(1)
3125(3) 1167(1)
2803(3) 842(1)
352(3) 664(1)
5045(3) 117(1)
1502(3) 405(1)

23(1)
22(1)
22(1)
24(1)
51(1)
52(1)
45(1)
62(1)
45(1)
43(1)
48(1)
42(1)
53(1)
46(1)

F(11)
F(12)
F(13)
F(14)
F(15)
F(16)
F(17)
F(18)
F(19)
F(20)
N(1)
N(2)
N(3)
N(4)

7499(1)
6225(2)
4827(1)
6461(1)
5945(2)
6045(2)
6051(2)
6492(2)
7618(1)
6580(2)
7727(4)
5435(3)
4597(3)
7222(3)

1855(3)
2017(4)
3092(3)
5202(3)
286(3)
2870(4)
5815(3)
279(3)
3547(3)
3384(5)
7845(6)
7941(7)
7042(8)
7820(7)

115(1)
519(1)
629(1)
240(1)
571(1)
1304(1)
2119(1)
2105(1)
1604(1)
2921(1)
9052(2)
6541(2)
8443(2)
946(2)

36(1)
55(1)
48(1)
52(1)
49(1)
51(1)
53(1)
80(1)
55(1)
79(1)
40(1)
40(1)
40(1)
41(1)

, ()
(U), . 2.
19
F, 1H ( )
SWL 3-100 (84,66 ) 270 530 K 2. S2 B ( ) 10 2 % .
() : = 154,7 /,
, ( )
[ 9 ].

(NH4TiF5)
TiF6, [ 101 ] -, ,
(. 1). TiF6 .
. 3. 2,85 2,98 .
S2 . 2.
S2 (~19 2) (270 390 K), 19F (. . 2)
- 104
. S2(F)
, (NH4)2TiF6 (II)

.. , .. , .. .

924


NH4TiF5

d,

d,

Ti(1)F(1)
Ti(1)F(4)
Ti(1)F(2)
Ti(1)F(3)
Ti(1)F(5)
Ti(1)F(6)
Ti(2)F(7)
Ti(2)F(10)
Ti(2)F(9)
Ti(2)F(8)
Ti(2)F(6)
Ti(2)F(11)
Ti(1)Ti(2)
Ti(2)Ti(3)
Ti(1)Ti(4)

1,7787(19)
1,784(2)
1,7850(19)
1,8493(18)
1,974(2)
1,9872(18)
1,778(2)
1,7811(19)
1,8045(18)
1,8322(18)
1,9797(17)
1,9955(19)
3,9033(1)
3,8994(1)
3,9046(1)

Ti(3)F(13)
Ti(3)F(12)
Ti(3)F(14)
Ti(3)F(15)
Ti(3)F(16)
Ti(3)F(11)
Ti(4)F(20)
Ti(4)F(18)
Ti(4)F(19)
Ti(4)F(17)
Ti(4)F(5)
Ti(4)F(16)

1,7766(19)
1,780(2)
1,8146(19)
1,8189(18)
1,9742(18)
1,9974(19)
1,762(2)
1,780(2)
1,785(2)
1,8376(19)
1,972(2)
1,9751(19)
1,972(2)
3,9113(1)

Ti(4)F(5)
Ti(3)Ti(4)

~14 2,
,
-

I,
,


(). , , ,

, 19F
[ 10 12 ]. , S2(F)
II 19F ,

. 1. (a)
(); .1, ,

925

. 2. 19F (I) 1H (II) NH4TiF5


19F (1 4), 1H (5 8)
270 (1, 5), 410 (2, 6),
480 (3, 7) 530 K (4, 8)

,
10 2 [ 13 ].

S2(F) K2TiF6, [ 10 ].

NH4TiF5 ,
F H . S2(F) , NH4TiF5 .
, - . c ,
. F H NH4TiF5.
NH4TiF5
- [ 9, 11 ]

5
n

319 r (F F ) 6 + 1,1 r (F Ti ) 6 + 319 r (F F ) 6

j
i
i
n
5
i j i

1
=
=
1
i
i

,
S 2 (F) = N i

m
k
i =1
l

6
6
6
+ 1,1 r (Fi Ti l ) + 2,2 r (Fi N m ) + 159 r (Fi H k )
i =1
i =1
i =1

(1)
Ni , r(FiFj),
r(FiFn), r(FiTi), r(FiTil), r(FiNm) r(FiHk) TiF6 , 4,5
. , . , (
7,0 2) , ( 0,2 2).
S2(F) 11,8 2 ( 19 2) F H.
400 K :
(. . 2, 2 4) S2 19F NH4TiF5.

926

.. , .. , .. .

.
~ 62 /. ,

(. . 1,).


. ,
TiF6 K2TiF6 [ 10 ] , S2
0,64 2,
: 0,62 0,03 2 653 K. 490 500 K, 0,25 2 530 K,
(~0,2 )
525 K (E 80,3 /).
NH4TiF5, 230 390 K 4,8 0,2 ,
(3,5 0,2 2),
S2(H),
NH +4 [ 2, 14, 15 ],
. S2(H) 400 475 K - . 480 K (. . 2, 7),
, , ,
. , 475 K
,
74,2 /. NH +4 I , (. . 2, 8).
, NH4TiF5
(480 530 K) ,
. ( .. NH4TiF5 545 555 K 5106 /.)
( 99-03-32672).

1.
2.
3.

.., .., .. // . . 1991. 17, 1.


. 35 43.
.., .., .., .. // . . .
1995. 40, 9. . 1463 1465.
.., .., .. // . . . 1995. 36, 4.
. 697 702.

4.
5.
6.
7.
8.
9.
10.

11.
12.
13.
14.
15.

927

.., .., .., .. // . 2000. 41, 4.


. 730 736.
.., .., .. . // . . . - .
.. . 1969. 60. . 107 110.
Menz D.H. // J.Therm. Anal. 1992. 38, N 2. P. 321 334.
Bruker. SMART and SAINT-Plus. Versions 5.0. Data Collection and Processing Software for
the SMART System. Bruker AXS Inc., Madison, Wisconsin, USA, 1988.
Sheldrick G.M. SHELXTL/PC. Versions 5.10. An Integrated System for Solving, Refining
and Displaying Crystal Structures From Diffraction Data. Bruker AXS Inc., Madison, Wisconsin, USA, 1988.
.., .. -. .: , 1986. 224 .
.., .., .., ..
, ,
. , 1988. 45 . (/
, . -, - ; 485).
.., .. . :
, 1986. 176 .
.. // . . . 1998. 39, 1. . 61 65.
Watton A., Koster E., Sandhu H.S., Petch H.E. // J. Chem. Phys. 1979. 70, N 11.
P. 5197 5202.
Albert S., Gutowsky H.S. // Ibid. 1973. 59, N 7. P. 3585 3594.
Watton A., Reynhardt E. C., Petch H.E. // Ibid. 1976. 65, N 11. P. 4370 4374.

,
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