ɀ ɍ Ɋ ɇ Ⱥ Ʌ ɋ Ɍ Ɋ ɍ... Ɇɚɣ – ɢɸɧɶ ɋ. 590 – 593 2006. Ɍɨɦ 47, ʋ 3

ɀɍɊɇȺɅ ɋɌɊɍɄɌɍɊɇɈɃ ɏɂɆɂɂ
2006. Ɍɨɦ 47, ʋ 3
Ɇɚɣ – ɢɸɧɶ
ɋ. 590 – 593
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
ɍȾɄ 548.736
ɄɊɂɋɌȺɅɅɂɑȿɋɄȺə ɋɌɊɍɄɌɍɊȺ ȾɂȽɂȾɊȺɌȺ ȾɂȽɂȾɊɈɗɌɂɅȿɇȾɂȺɆɂɇɌȿɌɊȺȺɐȿɌȺɌȺ(2–)
ɄȺɅɖɐɂə Ca(H2Edta)·2H2O
” 2006 Ɇ . ɐ ɚ ɛ ɟ ɥ ɶ 1 * , Ⱥ . Ʌ . ɉ ɨ ɡ ɧ ɹ ɤ 2 , ȼ . ɂ . ɉ ɚ ɜ ɥ ɨ ɜ ɫ ɤ ɢ ɣ 2
1
ɂɧɫɬɢɬɭɬ ɧɟɨɪɝɚɧɢɱɟɫɤɨɣ ɯɢɦɢɢ ɭɧɢɜɟɪɫɢɬɟɬɚ Ɋɟɝɟɧɫɛɭɪɝɚ, Ƚɟɪɦɚɧɢɹ
ɂɧɫɬɢɬɭɬ ɦɨɥɟɤɭɥɹɪɧɨɣ ɢ ɚɬɨɦɧɨɣ ɮɢɡɢɤɢ ɇȺɇ Ȼɟɥɚɪɭɫɢ, Ɇɢɧɫɤ
2
ɋɬɚɬɶɹ ɩɨɫɬɭɩɢɥɚ 11 ɨɤɬɹɛɪɹ 2005 ɝ.
Ʉɪɢɫɬɚɥɥɵ Ca(H2Edta)˜2H2O (ɪɨɦɛɢɱɟɫɤɚɹ ɫɢɧɝɨɧɢɹ, a = 8,5919(7), b = 17,807(2),
c = 18,941(2) Å; Z = 8, ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ Pbca) ɜɵɩɚɞɚɸɬ ɢɡ ɪɚɫɬɜɨɪɨɜ
Na2H2Edta˜2H2O ɢ CaCl2. Ⱥɬɨɦ Ca ɨɤɪɭɠɟɧ ɩɨ ɜɟɪɲɢɧɚɦ ɢɫɤɚɠɟɧɧɨɝɨ ɨɤɬɚɷɞɪɚ ɚɬɨɦɚɦɢ
ɤɢɫɥɨɪɨɞɚ ɦɨɥɟɤɭɥɵ ɜɨɞɵ ɢ ɤɚɪɛɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ ɩɹɬɢ ɫɨɫɟɞɧɢɯ ɚɧɢɨɧɨɜ H2Edta2– ɫ
ɩɪɨɬɨɧɢɪɨɜɚɧɧɵɦɢ ɚɬɨɦɚɦɢ ɚɡɨɬɚ. ȼ ɪɟɡɭɥɶɬɚɬɟ ɨɛɪɚɡɭɟɬɫɹ ɬɪɟɯɦɟɪɧɵɣ ɤɚɪɤɚɫ
[Ca(H2O)H2Edta)], ɜ ɤɨɬɨɪɵɣ ɜɫɬɪɨɟɧɵ ɦɨɥɟɤɭɥɵ ɤɪɢɫɬɚɥɥɢɡɚɰɢɨɧɧɨɣ ɜɨɞɵ.
Ʉ ɥ ɸ ɱ ɟ ɜ ɵ ɟ ɫ ɥ ɨ ɜ ɚ : ɤɪɢɫɬɚɥɥɢɱɟɫɤɚɹ ɫɬɪɭɤɬɭɪɚ, ɞɢɝɢɞɪɨɷɬɢɥɟɧɞɢɚɦɢɧɬɟɬɪɚɚɰɟɬɚɬ
ɤɚɥɶɰɢɹ.
ȼ ɫɨɟɞɢɧɟɧɢɹɯ ɷɬɢɥɟɧɞɢɚɦɢɧɬɟɬɪɚɭɤɫɭɫɧɨɣ ɤɢɫɥɨɬɵ H4Edta ɫ ɧɟɤɨɬɨɪɵɦɢ ɦɟɬɚɥɥɚɦɢ ɦɨɝɭɬ ɩɪɢɫɭɬɫɬɜɨɜɚɬɶ ɢɨɧɵ H2Edta2–, ɜ ɤɨɬɨɪɵɯ ɚɬɨɦɵ ɚɡɨɬɚ ɩɪɨɬɨɧɢɪɨɜɚɧɵ. ɇɚ ɷɬɨ ɭɤɚɡɵɜɚɸɬ, ɜ
ɱɚɫɬɧɨɫɬɢ, ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɵɟ ɢɫɫɥɟɞɨɜɚɧɢɹ ɪɹɞɚ ɫɨɟɞɢɧɟɧɢɣ: Ɇ2(H2Edta)˜2H2O, ɝɞɟ Ɇ = Na
(IIa), K (IIb), Rb (IIc) [ 1 — 3 ], ɚ ɬɚɤɠɟ Mg(H2Edta)˜6H2O (III) [ 4 ]. Ɇɵ ɩɪɢɝɨɬɨɜɢɥɢ ɤɪɢɫɬɚɥɥɵ
ɧɨɜɨɝɨ ɫɨɟɞɢɧɟɧɢɹ ɷɬɨɝɨ ɪɹɞɚ, ɚ ɢɦɟɧɧɨ Ca(H2Edta)˜2H2O (I), ɢ ɜɵɩɨɥɧɢɥɢ ɢɯ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɵɣ ɚɧɚɥɢɡ.
ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɚɹ ɱɚɫɬɶ. Ʉɪɢɫɬɚɥɥɵ I ɨɛɪɚɡɭɸɬɫɹ ɩɪɢ ɦɟɞɥɟɧɧɨɦ ɨɯɥɚɠɞɟɧɢɢ ɝɨɪɹɱɟɝɨ
(90 qɋ) ɪɚɫɬɜɨɪɚ Na2H2Edta˜2H2O ɢ CaCl2, ɜɡɹɬɵɯ ɜ ɫɨɨɬɧɨɲɟɧɢɢ 2:1.
ɉɚɪɚɦɟɬɪɵ ɷɥɟɦɟɧɬɚɪɧɨɣ ɹɱɟɣɤɢ ɢ ɬɪɟɯɦɟɪɧɵɣ ɧɚɛɨɪ ɢɧɬɟɧɫɢɜɧɨɫɬɟɣ ɨɬɪɚɠɟɧɢɣ ɩɨɥɭɱɟɧɵ ɞɥɹ ɦɨɧɨɤɪɢɫɬɚɥɥɚ ɪɚɡɦɟɪɨɦ 0,66u0,52u0,50 ɦɦ ɧɚ ɞɢɮɪɚɤɬɨɦɟɬɪɟ STOE-IPDS (ɢɡɥɭɱɟɧɢɟ
MoKD, ɝɪɚɮɢɬɨɜɵɣ ɦɨɧɨɯɪɨɦɚɬɨɪ) ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ 173(1) K (ɨɯɥɚɠɞɚɸɳɚɹ ɩɪɢɫɬɚɜɤɚ Oxford
Cryosystems). Ʉɪɢɫɬɚɥɥɵ C10H18CaN2O10 (M = 366,64) ɪɨɦɛɢɱɟɫɤɢɟ: a = 8,5919(7), b = 17,807(2),
c = 18,941(2) Å; V = 2897,4(4) Å3, Z = 8, Uɜɵɱ = 1,679 ɝ/ɫɦ3, PMo = 0,492 ɦɦ–1, F(000) = 1536, ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ Pbca. ȼɫɟɝɨ ɡɚɪɟɝɢɫɬɪɢɪɨɜɚɧɨ 37025 ɪɟɮɥɟɤɫɨɜ (T = 2,15—26,91º, ɢɧɬɟɪɜɚɥ ɢɧɞɟɤɫɨɜ –10 d h d 10, –22 d k d 22, –23 d l d 23), ɢɡ ɧɢɯ 3120 ɧɟɡɚɜɢɫɢɦɵɯ ɪɟɮɥɟɤɫɨɜ
(Rint = 0,0344). ɉɨɩɪɚɜɤɚ ɧɚ ɩɨɝɥɨɳɟɧɢɟ ɭɱɢɬɵɜɚɥɚɫɶ ɱɢɫɥɟɧɧɵɦ ɦɟɬɨɞɨɦ ɩɨ ɮɨɪɦɟ ɤɪɢɫɬɚɥɥɚ
(Tmin = 0,7470, Tmax = 0,8116).
ɋɬɪɭɤɬɭɪɚ ɪɚɫɲɢɮɪɨɜɚɧɚ ɩɪɹɦɵɦ ɦɟɬɨɞɨɦ (SIR-97 [ 5 ] ) ɢ ɭɬɨɱɧɟɧɚ ɩɨɥɧɨɦɚɬɪɢɱɧɵɦ ɚɧɢɡɨɬɪɨɩɧɵɦ ɦɟɬɨɞɨɦ ɧɚɢɦɟɧɶɲɢɯ ɤɜɚɞɪɚɬɨɜ (SHELX-97 [ 6 ] ). Ⱥɬɨɦɵ H ɦɟɬɢɥɟɧɨɜɵɯ ɝɪɭɩɩ ɩɨɦɟɳɟɧɵ ɜ ɫɨɨɬɜɟɬɫɬɜɢɢ ɫ ɝɟɨɦɟɬɪɢɟɣ ɢ ɭɬɨɱɧɟɧɵ ɩɨ ɦɨɞɟɥɢ sɧɚɟɡɞɧɢɤɚs, ɨɫɬɚɥɶɧɵɟ — ɢɡ ɪɚɡɧɨɫɬɧɵɯ ɫɢɧɬɟɡɨɜ [ 6 ]. Ɉɤɨɧɱɚɬɟɥɶɧɵɟ ɩɚɪɚɦɟɬɪɵ ɭɬɨɱɧɟɧɢɹ: R1 = 0,0270, wR2 = 0,0715 ɞɥɹ
2884 ɨɬɪɚɠɟɧɢɣ ɫ I > 2V(I ), R1 = 0,0293, wR2 = 0,0729 ɞɥɹ ɜɫɟɯ ɨɬɪɚɠɟɧɢɣ (262 ɭɬɨɱɧɹɟɦɵɯ ɩɚɪɚɦɟɬɪɚ), GOOF = 1,049. Ɇɚɤɫɢɦɚɥɶɧɚɹ ɢ ɦɢɧɢɦɚɥɶɧɚɹ ɨɫɬɚɬɨɱɧɚɹ ɷɥɟɤɬɪɨɧɧɵɟ ɩɥɨɬɧɨɫɬɢ ɫɨɫɬɚɜɥɹɸɬ 0,334 ɢ –0,282 e·Å–3 ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ. Ʉɨɨɪɞɢɧɚɬɵ ɢ ɬɟɩɥɨɜɵɟ ɩɚɪɚɦɟɬɪɵ ɚɬɨɦɨɜ ɩɪɢɜɟɞɟɧɵ ɜ ɬɚɛɥ. 1, ɞɥɢɧɵ ɫɜɹɡɟɣ ɢ ɜɚɥɟɧɬɧɵɟ ɭɝɥɵ — ɜ ɬɚɛɥ. 2.
* E-mail: manfred.zabel@chemie.uni-regensburg.de
591
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
Ɍɚɛɥɢɰɚ 1
4
2
3
Ʉɨɨɪɞɢɧɚɬɵ ɚɬɨɦɨɜ (u10 ) ɢ ɬɟɩɥɨɜɵɟ ɩɚɪɚɦɟɬɪɵ (Å u10 )
Ⱥɬɨɦ
x
y
z
Ueq*
Ⱥɬɨɦ
x
y
z
Ueq*
Ca(1)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(1w)
N(1)
N(2)
C(1)
7760(1)
9403(1)
8652(1)
9991(1)
10698(1)
9932(1)
9289(1)
10284(1)
8825(1)
6735(2)
7943(1)
7938(1)
7752(2)
835(1)
2157(1)
3069(1)
4214(1)
3427(1)
1729(1)
1034(1)
29(1)
–539(1)
–292(1)
2760(1)
1020(1)
3139(1)
6430(1)
2774(1)
2027(1)
4869(1)
4004(1)
4489(1)
5432(1)
3216(1)
2395(1)
5993(1)
3913(1)
3601(1)
3208(1)
15(1)
23(1)
21(1)
33(1)
23(1)
22(1)
24(1)
20(1)
26(1)
43(1)
15(1)
16(1)
18(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
O(2w)
H(1N)
H(2N)
8693(1)
8145(2)
9750(1)
6658(1)
6553(1)
8225(2)
9231(1)
7651(2)
9051(1)
7273(1)
8785(19)
8788(19)
2748(1)
3320(1)
3691(1)
2216(1)
1552(1)
681(1)
1199(1)
441(1)
–66(1)
–1786(1)
2516(9)
1287(9)
2628(1)
4495(1)
4446(1)
4090(1)
3589(1)
4322(1)
4787(1)
3037(1)
2872(1)
6240(1)
3908(8)
3467(8)
18(1)
18(1)
18(1)
18(1)
17(1)
18(1)
18(1)
19(1)
17(1)
41(1)
18
19
* Ueq ɨɩɪɟɞɟɥɟɧɵ ɤɚɤ ɨɞɧɚ ɬɪɟɬɶ ɫɥɟɞɚ ɨɪɬɨɝɨɧɚɥɢɡɨɜɚɧɧɨɝɨ ɬɟɧɡɨɪɚ Uij.
Ɍɚɛɥɢɰɚ 2
Ⱦɥɢɧɵ ɫɜɹɡɟɣ d, Å
ɋɜɹɡɶ
d
ɋɜɹɡɶ
d
ɋɜɹɡɶ
d
Ca(1)—O(6)
Ca(1)—O(1w)
Ca(1)—O(8)#1
Ca(1)—O(4)#2
Ca(1)—O(7)#3
Ca(1)—O(2)#4
O(1)—C(2)
O(2)—C(2)
O(3)—C(4)
2,3298(9)
2,3442(12)
2,3391(10)
2,3546(10)
2,3748(9)
2,3811(9)
1,2469(15)
1,2737(14)
1,2443(16)
O(4)—C(4)
O(5)—C(8)
O(6)—C(8)
O(7)—C(10)
O(8)—C(10)
N(1)—C(1)
N(1)—C(5)
N(1)—C(3)
N(2)—C(6)
1,2596(15)
1,2529(15)
1,2577(14)
1,2548(15)
1,2507(14)
1,5062(15)
1,5067(16)
1,4954(16)
1,5207(16)
N(2)—C(7)
N(2)—C(9)
N(1)—H(1N)
N(2)—H(2N)
C(1)—C(2)
C(3)—C(4)
C(5)—C(6)
C(7)—C(8)
C(9)—C(10)
1,5123(15)
1,5057(16)
0,845(16)
0,908(16)
1,5321(17)
1,5320(18)
1,5195(17)
1,5406(17)
1,5358(17)
ɉ ɪ ɢ ɦ ɟ ɱ ɚ ɧ ɢ ɟ. Ɉɩɟɪɚɰɢɢ ɫɢɦɦɟɬɪɢɢ: #1 3/2–x, –y, 1/2+z; #2 x–1/2, 1/2–y, 1—z; #3 2–x, –y,
1–z; #4 x, 1/2–y, 1/2+z.
Ɇɨɥɟɤɭɥɹɪɧɚɹ ɝɪɚɮɢɤɚ ɜɵɩɨɥɧɟɧɚ ɫ ɩɨɦɨɳɶɸ ɩɪɨɝɪɚɦɦɵ PLATON [ 7 ].
Ɋɟɡɭɥɶɬɚɬɵ ɢ ɢɯ ɨɛɫɭɠɞɟɧɢɟ. Ʉɪɢɫɬɚɥɥɵ I ɫɨɫɬɨɹɬ ɢɡ ɢɨɧɨɜ ɤɚɥɶɰɢɹ ɢ H2Edta2–, ɚ ɬɚɤɠɟ
ɦɨɥɟɤɭɥ ɜɨɞɵ. ȼ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɣ ɫɮɟɪɟ ɋɚ (ɢɫɤɚɠɟɧɧɵɣ ɨɤɬɚɷɞɪ) ɧɚɯɨɞɢɬɫɹ ɚɬɨɦ O(1w) ɦɨɥɟɤɭɥɵ ɜɨɞɵ ɢ ɩɹɬɶ ɚɬɨɦɨɜ ɤɢɫɥɨɪɨɞɚ ɤɚɪɛɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ ɩɹɬɢ ɫɨɫɟɞɧɢɯ ɢɨɧɨɜ H2Edta2–
(ɪɢɫ. 1, ɬɚɛɥ. 2). ȼ ɫɜɨɸ ɨɱɟɪɟɞɶ, ɜ ɫɨɝɥɚɫɢɢ ɫɨ ɫɬɟɯɢɨɦɟɬɪɢɟɣ ɫɨɟɞɢɧɟɧɢɹ, ɤɚɠɞɵɣ ɚɧɢɨɧ
H2Edta2– ɫɜɹɡɚɧ ɫ ɩɹɬɶɸ ɚɬɨɦɚɦɢ ɋɚ, ɜ ɪɟɡɭɥɶɬɚɬɟ ɱɟɝɨ ɢɡ ɷɬɢɯ ɫɨɫɬɚɜɥɹɸɳɢɯ ɨɛɪɚɡɭɟɬɫɹ ɬɪɟɯɦɟɪɧɚɹ ɫɟɬɱɚɬɚɹ ɫɬɪɭɤɬɭɪɚ (ɪɢɫ. 2). Ɏɨɪɦɢɪɨɜɚɧɢɟ ɟɟ ɦɨɠɧɨ ɩɪɟɞɫɬɚɜɢɬɶ ɫɥɟɞɭɸɳɢɦ ɨɛɪɚɡɨɦ.
Ⱦɜɚ ɚɬɨɦɚ ɋɚ ɢ ɞɜɚ ɚɧɢɨɧɚ H2Edta2–, ɫɨɨɬɧɨɫɹɳɢɟɫɹ ɫ ɰɟɧɬɪɨɦ ɫɢɦɦɟɬɪɢɢ, ɨɛɴɟɞɢɧɹɸɬɫɹ ɜ ɞɢɦɟɪ. ȼ ɨɫɧɨɜɟ ɞɢɦɟɪɚ 16-ɱɥɟɧɧɵɣ ɰɢɤɥ (ɫɦ. ɪɢɫ. 1), ɩɨɫɤɨɥɶɤɭ ɞɜɚ ɚɬɨɦɚ ɋɚ ɜ ɧɟɦ ɫɜɹɡɚɧɵ ɦɟɠɞɭ ɫɨɛɨɣ ɚɰɟɬɚɬɧɵɦɢ ɝɪɭɩɩɚɦɢ, ɩɪɢɧɚɞɥɟɠɚɳɢɦɢ ɨɞɧɨɦɭ ɚɬɨɦɭ ɚɡɨɬɚ ɚɧɢɨɧɚ H2Edta2–, ɫ ɭɱɚɫɬɢɟɦ ɚɬɨɦɨɜ Ɉ(6) ɢ Ɉ(7). ȿɫɥɢ ɩɪɢɧɹɬɶ ɜɨ ɜɧɢɦɚɧɢɟ ɬɨɥɶɤɨ ɚɬɨɦɵ Ɉ(7) ɢ Ɉ(8), ɩɪɢɧɚɞɥɟɠɚɳɢɟ
ɨɞɧɨɣ ɤɚɪɛɨɤɫɢɥɶɧɨɣ ɝɪɭɩɩɟ, ɬɨ ɚɬɨɦɵ ɋɚ ɨɤɚɠɭɬɫɹ ɜ ɰɟɩɨɱɤɟ —ɋɚ—Ɉ(7)—ɋ—Ɉ(8)—ɋɚ—
Ɉ(7)—ɋ—Ɉ(8)—ɋɚ— ɜɞɨɥɶ ɨɫɢ x, ɜ ɤɨɬɨɪɨɣ ɤɚɠɞɵɣ ɢɡ ɚɬɨɦɨɜ ɭɝɥɟɪɨɞɚ ɩɪɢɧɚɞɥɟɠɢɬ
ɪɚɡɥɢɱɧɵɦ ɢɨɧɚɦ H2Edta2–. ɋ ɞɨɛɚɜɥɟɧɢɟɦ ɚɬɨɦɚ Ɉ(6) ɤɚɠɞɵɣ ɢɡ ɚɬɨɦɨɜ ɋɚ ɷɬɨɣ ɰɟɩɨɱɤɢ ɨɤɚ-
592
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
Ɋɢɫ. 1. Ⱦɢɦɟɪ [Ca(H2O)(H2Edta)]2 ɜ ɫɬɪɭɤɬɭɪɟ I.
Ɉɩɟɪɚɰɢɢ ɫɢɦɦɟɬɪɢɢ x, 0,5–y, 0,5+z; x–0,5, 0,5–y, 1–z ɢ 1,5–x, –y, 0,5+z ɞɥɹ ɚɬɨɦɨɜ O(2c), O(4c) ɢ O(8c) ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ.
Ⱥɬɨɦɵ ɜɨɞɨɪɨɞɚ ɧɟ ɩɨɤɚɡɚɧɵ, ɡɚ ɢɫɤɥɸɱɟɧɢɟɦ H(N). ɒɬɪɢɯɨɜɵɟ ɥɢɧɢɢ — ɜɨɞɨɪɨɞɧɵɟ ɫɜɹɡɢ N—H…O
ɠɟɬɫɹ ɜ ɫɨɫɬɚɜɟ ɭɩɨɦɹɧɭɬɨɝɨ ɜɵɲɟ ɞɢɦɟɪɚ. ɉɨɫɤɨɥɶɤɭ ɞɪɭɝɢɟ ɚɬɨɦɵ ɋɚ ɞɢɦɟɪɨɜ ɬɚɤɠɟ ɜɯɨɞɹɬ
ɜ ɫɨɫɬɚɜ ɞɪɭɝɢɯ ɰɟɩɨɱɟɤ, ɬɨ ɦɵ ɩɪɢɯɨɞɢɦ ɤ ɡɚɤɥɸɱɟɧɢɸ, ɱɬɨ ɫ ɭɱɚɫɬɢɟɦ ɧɚɡɜɚɧɧɵɯ ɬɪɟɯ ɚɬɨɦɨɜ
ɤɢɫɥɨɪɨɞɚ ɨɞɧɨɣ ɩɨɥɨɜɢɧɵ ɢɨɧɚ H2Edta2– ɮɨɪɦɢɪɭɸɬɫɹ ɫɥɨɢ, ɩɚɪɚɥɥɟɥɶɧɵɟ ɩɥɨɫɤɨɫɬɢ xz. ɋɜɹɡɢ ɋɚ—Ɉ(2) ɢ ɋɚ—Ɉ(4) ɫ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɞɪɭɝɨɣ ɩɨɥɨɜɢɧɵ ɢɨɧɚ H2Edta2– sɫɲɢɜɚɸɬs ɫɥɨɢ ɜ
ɬɪɟɯɦɟɪɧɵɣ ɤɚɪɤɚɫ (ɫɦ. ɪɢɫ. 2).
ȼ ɢɨɧɟ H2Edta2–, ɤɚɤ ɨɛɵɱɧɨ, ɚɬɨɦɵ N, ɤɨɝɞɚ ɨɧɢ ɧɟ ɫɜɹɡɚɧɵ ɫ ɢɨɧɨɦ ɦɟɬɚɥɥɚ, ɨɤɚɡɵɜɚɸɬɫɹ
ɩɪɨɬɨɧɢɪɨɜɚɧɧɵɦɢ ɢ ɭɱɚɫɬɜɭɸɬ ɜɨ ɜɧɭɬɪɢɦɨɥɟɤɭɥɹɪɧɵɯ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɹɯ [ 8, 9 ] (ɫɦ. ɪɢɫ. 1,
ɬɚɛɥ. 3). ȼ ɫɬɪɭɤɬɭɪɟ I ɢɦɟɸɬɫɹ ɬɚɤɠɟ ɜɨɞɨɪɨɞɧɵɟ ɫɜɹɡɢ ɫ ɭɱɚɫɬɢɟɦ ɦɨɥɟɤɭɥɵ H2O(2w). Ʉɨɧɮɢɝɭɪɚɰɢɹ ɢɨɧɚ H2Edta2–, ɤɨɬɨɪɚɹ ɨɩɪɟɞɟɥɹɟɬɫɹ, ɜ ɱɚɫɬɧɨɫɬɢ, ɬɨɪɫɢɨɧɧɵɦ ɭɝɥɨɦ N—C—C—N ɜ
ɷɬɢɥɟɧɞɢɚɦɢɧɨɜɨɦ ɮɪɚɝɦɟɧɬɟ, ɦɟɧɹɟɬɫɹ ɨɬ ɫɨɟɞɢɧɟɧɢɹ ɤ ɫɨɟɞɢɧɟɧɢɸ. Ⱦɥɹ IIa ɢ III ɷɬɨɬ ɭɝɨɥ
ɪɚɜɟɧ 180° (ɪɚɡɜɟɪɧɭɬɚɹ ɮɨɪɦɚ) ɩɨ
ɬɪɟɛɨɜɚɧɢɸ
ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɨɣ
ɫɢɦɦɟɬɪɢɢ, ɚ ɞɥɹ IIb ɢ IIc — 78,6° ɢ
161,8° ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ. Ⱦɥɹ ɫɬɪɭɤɬɭɪɵ
I ɨɧ ɫɨɫɬɚɜɥɹɟɬ 65,4°, ɱɬɨ ɛɥɢɡɤɨ ɤ
ɡɧɚɱɟɧɢɹɦ 50°—60° ɭ ɪɚɡɥɢɱɧɵɯ ɤɨɦɩɥɟɤɫɨɜ, ɝɞɟ ɢɦɟɟɬɫɹ ɷɬɢɥɟɧɞɢɚɦɢɧɨɜɵɣ ɦɟɬɚɥɥɨɰɢɤɥ. Ȼɥɚɝɨɞɚɪɹ ɬɚɤɨɣ
sɫɜɟɪɧɭɬɨɣs ɮɨɪɦɟ H2Edta2– ɜ I, ɤɚɤ ɢ ɜ
IIb, ɫɬɚɧɨɜɹɬɫɹ ɜɨɡɦɨɠɧɵɦɢ ɜɧɭɬɪɢɦɨɥɟɤɭɥɹɪɧɵɟ ɜɨɞɨɪɨɞɧɵɟ ɫɜɹɡɢ (ȼɋ)
ɚɬɨɦɚ ɚɡɨɬɚ ɫ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɞɪɭɝɨɣ ɩɨɥɨɜɢɧɵ ɚɧɢɨɧɚ (ɩɨɡɢɰɢɢ 3 ɢ 4 ɜ
ɬɚɛɥ. 3). ȼ ɤɪɢɫɬɚɥɥɟ ɫɜɨɛɨɞɧɨɣ ɤɢɫɥɨɬɵ H4Edta, ɝɞɟ ɩɪɨɬɨɧɢɪɨɜɚɧɵ ɚɬɨɦɵ ɚɡɨɬɚ ɢ ɞɜɟ ɤɚɪɛɨɤɫɢɥɶɧɵɟ ɝɪɭɩɩɵ
Ɋɢɫ. 2. ɉɪɨɟɤɰɢɹ ɫɬɪɭɤɬɭɪɵ I ɜɞɨɥɶ ɨɫɢ x.
Ⱥɬɨɦɵ ɜɨɞɨɪɨɞɚ ɢ O(2w) ɧɟ ɩɨɤɚɡɚɧɵ
593
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
Ɍɚɛɥɢɰɚ 3
Ƚɟɨɦɟɬɪɢɱɟɫɤɢɟ ɩɚɪɚɦɟɬɪɵ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ ɜ ɫɬɪɭɤɬɭɪɟ I
ɋɜɹɡɶ A—H…B
N(1)–H(1N)...O(1)
N(1)–H(1N)...O(4)
N(1)–H(1N)...O(5)
N(2)–H(2N)...O(1)
N(2)–H(2N)...O(5)
O(1w)–H...O(2w)
O(1w)–H...O(3)#1
O(1w)–H...O(3)#2
O(2w)–H...O(2)#3
O(2w)–H...O(5)#4
Ɋɚɫɫɬɨɹɧɢɟ, Å
H…B
A—H
0,845(16)
0,845(16)
0,845(16)
0,908(16)
0,908(16)
0,82(3)
0,82(2)
0,82(2)
0,91(2)
0,90(3)
2,303(15)
2,316(16)
2,037(16)
2,099(16)
2,309(15)
1,95(2)
2,50(2)
1,95(2)
1,94(2)
1,93(2)
A…B
2,7172(14)
2,6534(14)
2,7360(14)
2,8531(14)
2,7121(14)
2,7399(17)
2,9320(17)
2,7403(18)
2,8421(16)
2,7719(15)
ɍɝɨɥ AHB, ɝɪɚɞ.
110,6(12)
104,3(13)
139,7(14)
139,9(14)
106,6(11)
164(3)
114,7(18)
162(2)
171(2)
156(2)
ɉ ɪ ɢ ɦ ɟ ɱ ɚ ɧ ɢ ɟ . Ɉɩɟɪɚɰɢɢ ɫɢɦɦɟɬɪɢɢ ɞɥɹ ɚɬɨɦɨɜ B: #1 x–1/2, 1/2–y, 1–z; #2 3/2–x, y–1/2, z;
#3 3/2–x, –y, 1/2+z; #4 2–x, –y, 1–z.
(ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɚɹ ɫɢɦɦɟɬɪɢɹ 2), ɭɝɨɥ N—C—C—N ɪɚɜɟɧ 67,1° ɢ ɬɚɦ ɬɚɤɠɟ ɜɨɡɦɨɠɧɵ
ɩɨɞɨɛɧɵɟ ȼɋ [ 10 ].
ɇɟɞɚɜɧɨ [ 11 ] ɨɩɭɛɥɢɤɨɜɚɧɚ ɫɬɪɭɤɬɭɪɚ ɫɨɟɞɢɧɟɧɢɹ ɢɨɧɚ ɋɚ2+ ɫ ɩɪɨɬɨɧɢɪɨɜɚɧɧɵɦ ɚɧɢɨɧɨɦ
ɢɦɢɧɨɞɢɚɰɟɬɚɬɚ H2N+(CH2CO 2 )2 (Hida–) ɫɨɫɬɚɜɚ Ca(Hida)2 (IV). ɂɨɧ Hida– ɦɨɠɧɨ ɪɚɫɫɦɚɬɪɢɜɚɬɶ ɤɚɤ ɩɨɥɨɜɢɧɭ H2Edta2– ɛɟɡ ɷɬɢɥɟɧɨɜɨɝɨ ɦɨɫɬɢɤɚ, ɨɞɧɚɤɨ ɫɬɪɭɤɬɭɪɚ IV ɢɦɟɟɬ ɦɚɥɨ ɨɛɳɟɝɨ ɫ
I. ɉɪɟɠɞɟ ɜɫɟɝɨ, ɨɧɚ ɫɥɨɢɫɬɚɹ, ɚɬɨɦɵ ɋɚ ɧɚɯɨɞɹɬɫɹ ɜ ɰɟɧɬɪɟ ɢɧɜɟɪɫɢɢ ɢ ɨɧɢ ɨɤɪɭɠɟɧɵ ɲɟɫɬɶɸ
ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ, ɩɪɢɧɚɞɥɟɠɚɳɢɦɢ ɲɟɫɬɢ ɫɨɫɟɞɧɢɦ ɢɨɧɚɦ Hida–, ɬɚɤ ɱɬɨ ɤɚɠɞɵɣ ɚɧɢɨɧ ɫɜɹɡɚɧ ɫ ɬɪɟɦɹ ɚɬɨɦɚɦɢ ɋɚ. ɉɪɢ ɷɬɨɦ ɢɡ ɞɜɭɯ ɚɬɨɦɨɜ ɋɚ ɢ ɞɜɭɯ ɤɚɪɛɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ ɪɚɡɥɢɱɧɵɯ
ɚɧɢɨɧɨɜ ɨɛɪɚɡɭɸɬɫɹ 8-ɱɥɟɧɧɵɟ ɰɢɤɥɵ ɋɚ(ɈɋɈ)2ɋɚ, ɚ ɜ I ɰɢɤɥɵ ɛɨɥɟɟ ɩɪɨɬɹɠɟɧɧɵɟ (ɦɢɧɢɦɭɦ
16-ɱɥɟɧɧɵɟ).
ɋɉɂɋɈɄ ɅɂɌȿɊȺɌɍɊɕ
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ɒɤɨɥɶɧɢɤɨɜɚ Ʌ.Ɇ., ɉɨɪɚɣ-Ʉɨɲɢɰ Ɇ.Ⱥ. // ɍɫɩ. ɯɢɦɢɢ. – 1990. – 59, ʋ 7. – ɋ. 1111 – 1143.
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ɉɨɥɹɤɨɜɚ ɂ.ɇ., ɉɨɡɧɹɤ Ⱥ.Ʌ., ɋɟɪɝɢɟɧɤɨ ȼ.ɋ. // ɀɭɪɧ. ɧɟɨɪɝɚɧ. ɯɢɦɢɢ. – 2003. – 48, ʋ 12. –
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