ɀ ɍ Ɋ ɇ Ⱥ Ʌ ɋ Ɍ Ɋ ɍ... ɇɨɹɛɪɶ – ɞɟɤɚɛɪɶ ɋ. 1189 – 1194 2006. Ɍɨɦ 47, ʋ 6

ɀɍɊɇȺɅ ɋɌɊɍɄɌɍɊɇɈɃ ɏɂɆɂɂ
2006. Ɍɨɦ 47, ʋ 6
ɇɨɹɛɪɶ – ɞɟɤɚɛɪɶ
ɋ. 1189 – 1194
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
ɍȾɄ 548.736+541.49
ɋɂɇɌȿɁ, ɄɊɂɋɌȺɅɅɂɑȿɋɄȺə ɂ ɆɈɅȿɄɍɅəɊɇȺə ɋɌɊɍɄɌɍɊȺ ɊȺɁɇɈɅɂȽȺɇȾɇɈȽɈ
ɄɈɈɊȾɂɇȺɐɂɈɇɇɈȽɈ ɋɈȿȾɂɇȿɇɂə ZnPhen(n-C4H9OCS2)2
” 2006 Ɋ . Ɏ . Ʉ ɥ ɟ ɜ ɰ ɨ ɜ ɚ * , Ɍ . Ƚ . Ʌ ɟ ɨ ɧ ɨ ɜ ɚ , Ʌ . Ⱥ . Ƚ ɥ ɢ ɧ ɫ ɤ ɚ ɹ , ɋ . ȼ . Ʌ ɚ ɪ ɢ ɨ ɧ ɨ ɜ
ɂɧɫɬɢɬɭɬ ɧɟɨɪɝɚɧɢɱɟɫɤɨɣ ɯɢɦɢɢ ɢɦ. Ⱥ.ȼ. ɇɢɤɨɥɚɟɜɚ ɋɈ ɊȺɇ, ɇɨɜɨɫɢɛɢɪɫɤ
ɋɬɚɬɶɹ ɩɨɫɬɭɩɢɥɚ 16 ɹɧɜɚɪɹ 2006 ɝ.
ɋɢɧɬɟɡɢɪɨɜɚɧ ɪɚɡɧɨɥɢɝɚɧɞɧɵɣ ɤɨɦɩɥɟɤɫ ZnPhen(n-BuOCS2)2. ɉɨ ɞɢɮɪɚɤɰɢɨɧɧɵɦ ɪɟɧɬɝɟɧɨɜɫɤɢɦ ɞɚɧɧɵɦ (ɞɢɮɪɚɤɬɨɦɟɬɪ X8 APEX, MoKD-ɢɡɥɭɱɟɧɢɟ, 4254 Fhkl, R = 0,0448)
ɪɚɫɲɢɮɪɨɜɚɧɚ ɟɝɨ ɫɬɪɭɤɬɭɪɚ. Ʉɪɢɫɬɚɥɥɵ ɤɨɦɩɥɟɤɫɚ — ɬɪɢɤɥɢɧɧɵɟ ɫ ɩɚɪɚɦɟɬɪɚɦɢ:
a = 9,4464(3),
b = 11,0279(4),
c = 13,6528(6) Å;
D = 106,940(1),
E = 98,382(1),
J = 106,347(1)q; V = 1264,72(8) Å3; Z = 2, ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ P 1 . Ɉɫɧɨɜɭ ɫɬɪɭɤɬɭɪɵ ɫɨɫɬɚɜɥɹɸɬ ɞɢɫɤɪɟɬɧɵɟ ɨɞɧɨɹɞɟɪɧɵɟ ɦɨɥɟɤɭɥɵ. ɉɨɥɢɷɞɪ ɚɬɨɦɚ Zn — ɬɪɢɝɨɧɚɥɶɧɚɹ
ɛɢɩɢɪɚɦɢɞɚ N2S3, ɨɛɪɚɡɨɜɚɧɧɚɹ ɡɚ ɫɱɟɬ ɤɨɨɪɞɢɧɚɰɢɢ ɚɬɨɦɨɜ N ɛɢɞɟɧɬɚɬɧɵɯ ɦɨɥɟɤɭɥ
Phen ɢ ɚɬɨɦɨɜ ɫɟɪɵ ɦɨɧɨɞɟɧɬɚɬɧɨɝɨ ɢ ɛɢɞɟɧɬɚɬɧɨ-ɰɢɤɥɢɱɟɫɤɨɝɨ ɤɫɚɧɬɨɝɟɧɚɬɧɵɯ ɥɢɝɚɧɞɨɜ. ȼ ɫɬɪɭɤɬɭɪɟ ɨɛɪɚɡɭɸɬɫɹ ɞɢɦɟɪɧɵɟ ɚɧɫɚɦɛɥɢ ɜɫɥɟɞɫɬɜɢɟ S—S-ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɦɨɥɟɤɭɥ Phen.
Ʉ ɥ ɸ ɱ ɟ ɜ ɵ ɟ ɫ ɥ ɨ ɜ ɚ : ɪɚɡɧɨɥɢɝɚɧɞɧɵɣ ɤɨɦɩɥɟɤɫ, ɰɢɧɤ(II), 1,10-ɮɟɧɚɧɬɪɨɥɢɧ, nɛɭɬɢɥɤɫɚɧɬɨɝɟɧɚɬ-ɢɨɧ, ɤɪɢɫɬɚɥɥɢɱɟɫɤɚɹ ɫɬɪɭɤɬɭɪɚ, S—S-ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ.
Ⱥɥɤɢɥɤɫɚɧɬɨɝɟɧɚɬɵ ɰɢɧɤɚ(II), ɚ ɬɚɤɠɟ ɪɚɡɧɨɥɢɝɚɧɞɧɵɟ ɤɨɦɩɥɟɤɫɧɵɟ ɫɨɟɞɢɧɟɧɢɹ ɧɚ ɨɫɧɨɜɟ
ɷɬɢɯ ɯɟɥɚɬɨɜ ɢ 1,10-ɮɟɧɚɧɬɪɨɥɢɧɚ (Phen), 2,2c-ɛɢɩɢɪɢɞɢɧɚ (2,2c-Bipy) ɨɬɧɨɫɹɬɫɹ ɤ ɩɟɪɫɩɟɤɬɢɜɧɵɦ ɦɨɥɟɤɭɥɹɪɧɵɦ ɩɪɟɞɲɟɫɬɜɟɧɧɢɤɚɦ ZnS [ 1, 2 ]. ɉɨɷɬɨɦɭ ɩɨɥɟɡɧɨ ɩɨɥɭɱɟɧɢɟ ɞɚɧɧɵɯ ɨ
ɫɬɪɨɟɧɢɢ ɩɪɟɞɫɬɚɜɢɬɟɥɟɣ ɷɬɨɣ ɢɧɬɟɪɟɫɧɨɣ ɝɪɭɩɩɵ ɫɨɟɞɢɧɟɧɢɣ ɫ ɩɨɦɨɳɶɸ ɦɟɬɨɞɚ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɚɧɚɥɢɡɚ (ɊɋȺ).
Ɋɚɧɟɟ ɦɵ ɨɩɪɟɞɟɥɢɥɢ ɫɬɪɭɤɬɭɪɵ ɪɹɞɚ ɫɨɟɞɢɧɟɧɢɣ ZnPhen(ROCS2)2, ɝɞɟ R=Et, i-Pr, i-Bu
[ 3 — 5 ]. Ɉɤɚɡɚɥɨɫɶ, ɱɬɨ ɜ ɷɬɢɯ ɫɨɟɞɢɧɟɧɢɹɯ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɟ ɱɢɫɥɨ (Ʉɑ) ɢɨɧɚ Zn2+ ɪɚɜɧɨ 5
(R=Et), 5 ɢ 6 (R=i-Pr), ɢ 6 (R=i-Bu). ɉɨɫɤɨɥɶɤɭ ɜ ɪɹɞɭ ɚɥɤɢɥɶɧɵɯ ɝɪɭɩɩ Et, i-Pr, i-Bu ɢɡɦɟɧɹɟɬɫɹ
ɧɟ ɬɨɥɶɤɨ ɱɢɫɥɨ ɚɬɨɦɨɜ ɭɝɥɟɪɨɞɚ, ɧɨ ɢ ɫɬɪɨɟɧɢɟ ɝɪɭɩɩ, ɞɥɹ ɨɩɪɟɞɟɥɟɧɢɹ ɜɡɚɢɦɨɫɜɹɡɢ Ʉɑ ɢ ɩɪɢɪɨɞɵ R ɢɡɜɟɫɬɧɵɯ ɞɚɧɧɵɯ ɧɟɞɨɫɬɚɬɨɱɧɨ. ȼ ɫɜɹɡɢ ɫ ɷɬɢɦ ɧɟɨɛɯɨɞɢɦɨ ɩɨɥɭɱɢɬɶ ɢɧɮɨɪɦɚɰɢɸ ɨ
ɫɬɪɨɟɧɢɢ ɫɨɟɞɢɧɟɧɢɣ ZnPhen(ROCS2)2, ɤɨɝɞɚ R ɢɦɟɟɬ ɧɨɪɦɚɥɶɧɨɟ ɫɬɪɨɟɧɢɟ ɰɟɩɢ (n-Pr, n-Bu).
ɐɟɥɶɸ ɞɚɧɧɨɣ ɪɚɛɨɬɵ ɹɜɥɹɟɬɫɹ ɫɢɧɬɟɡ ɧɨɜɨɝɨ ɪɚɡɧɨɥɢɝɚɧɞɧɨɝɨ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ ZnPhen(n-BuOCS2)2, ɨɩɪɟɞɟɥɟɧɢɟ ɟɝɨ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ ɢ ɦɨɥɟɤɭɥɹɪɧɨɣ ɫɬɪɭɤɬɭɪɵ, ɚ
ɬɚɤɠɟ ɢɡɭɱɟɧɢɟ ɦɟɠɦɨɥɟɤɭɥɹɪɧɵɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ.
ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɚɹ ɱɚɫɬɶ. ȼ ɫɢɧɬɟɡɟ ɢɫɩɨɥɶɡɨɜɚɥɢ ɝɟɤɫɚɧ, CH2Cl2, n-C4H9OCS2K ɤɜɚɥɢɮɢɤɚɰɢɢ sɱs; Zn(CH3COO)2˜4H2O, Phen˜H2O ɤɜɚɥɢɮɢɤɚɰɢɢ sɨɫ.ɱ.s
ɋɢɧɬɟɡ ZnPhen(n-C4H9OCS2)2 (I). Ʉ ɪɚɫɬɜɨɪɭ 0,55 ɝ (2,5 ɦɦɨɥɹ) Zn(CH3COO)2˜4H2O ɢ 1,0 ɝ
(5 ɦɦɨɥɟɣ) Phen˜H2O ɜ 10 ɦɥ H2O ɱɟɪɟɡ ɛɭɦɚɠɧɵɣ ɮɢɥɶɬɪ ɞɨɛɚɜɥɹɥɢ ɪɚɫɬɜɨɪ 0,94 ɝ (5 ɦɦɨɥɟɣ)
n-C4H9OCS2K ɜ 10 ɦɥ H2O. ɋɦɟɫɶ ɩɟɪɟɦɟɲɢɜɚɥɢ ɜ ɬɟɱɟɧɢɟ 30 ɦɢɧ. Ɉɛɪɚɡɨɜɚɜɲɢɣɫɹ ɛɟɥɵɣ ɨɫɚɞɨɤ ɨɬɮɢɥɶɬɪɨɜɵɜɚɥɢ, ɩɪɨɦɵɜɚɥɢ ɜɨɞɨɣ, ɫɭɲɢɥɢ ɧɚ ɜɨɡɞɭɯɟ. ɉɪɨɞɭɤɬ ɩɟɪɟɨɫɚɠɞɚɥɢ ɩɭɬɟɦ
ɪɚɫɬɜɨɪɟɧɢɹ ɜ 30 ɦɥ CH2Cl2 ɢ ɞɨɛɚɜɥɟɧɢɹ 90 ɦɥ ɝɟɤɫɚɧɚ. ɋɜɟɬɥɨ-ɠɟɥɬɵɣ ɨɫɚɞɨɤ ɨɬɮɢɥɶɬɪɨɜɵɜɚɥɢ ɫ ɨɬɫɚɫɵɜɚɧɢɟɦ, ɩɪɨɦɵɜɚɥɢ ɷɬɚɧɨɥɨɦ, ɫɭɲɢɥɢ ɧɚ ɜɨɡɞɭɯɟ, ɡɚɬɟɦ ɜ ɜɚɤɭɭɦɟ. ȼɵɯɨɞ 0,44 ɝ
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1190
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
Ɍɚɛɥɢɰɚ 1
Ʉɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ, ɞɟɬɚɥɢ ɷɤɫɩɟɪɢɦɟɧɬɚ ɢ ɭɬɨɱɧɟɧɢɹ ɫɬɪɭɤɬɭɪɵ
ɞɥɹ ɪɚɡɧɨɥɢɝɚɧɞɧɨɝɨ ɤɨɦɩɥɟɤɫɚ ZnPhen(n-BuOCS2)2 (I)
ɗɦɩɢɪɢɱɟɫɤɚɹ ɮɨɪɦɭɥɚ
Ɇɨɥɟɤɭɥɹɪɧɵɣ ɜɟɫ
Ɍɟɦɩɟɪɚɬɭɪɚ, K
Ⱦɢɮɪɚɤɬɨɦɟɬɪ
Ⱦɥɢɧɚ ɜɨɥɧɵ, Å
Ɇɨɧɨɯɪɨɦɚɬɨɪ
Ɇɟɬɨɞ ɫɴɟɦɤɢ
ɋɢɧɝɨɧɢɹ
ɉɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ
ɉɚɪɚɦɟɬɪɵ ɷɥɟɦɟɧɬɚɪɧɨɣ
ɹɱɟɣɤɢ, Å, ɝɪɚɞ.
Ɉɛɴɟɦ, Å3
Z; d ɜɵɱ, ɝ/ɫɦ3
Ʉɨɷɮ. ɩɨɝɥ., ɫɦ–1
F(000)
Ⱦɢɚɩɚɡɨɧ T, ɝɪɚɞ.
Nhkl ɢɡɦɟɪ. / Nhkl ɧɟɡɚɜ.
Ɇɟɬɨɞ ɭɬɨɱɧɟɧɢɹ
Nhkl / Npar
GOOF ɞɥɹ F 2
R-ɮɚɤɬɨɪ, I ! 2V(I )
R-ɮɚɤɬɨɪ (ɩɨ ɜɫɟɦ Ihkl)
C22 H26 N2 O2 S4 Zn
544,06
293(2)
X8 APEX
0,71073
Ƚɪɚɮɢɬ
M-ɋɤɚɧɢɪɨɜɚɧɢɟ ɫ ɢɧɬɟɪɜɚɥɨɦ 0,5q
Ɍɪɢɤɥɢɧɧɚɹ
P1
ɚ = 9,4464(3); D = 106,940(1)
b = 11,0279(4); E = 98,382(1)
c = 13,6528(6); J = 106,347(1)
1264,72(8)
2; 1,429
13,22
564
1,61–25,99
8695 / 4855
[R(int) = 0,0156]
ɆɇɄ ɩɨɥɧɨɦɚɬɪ. ɩɨ F 2
4855 / 300
1,101
R1 = 0,0444; wR2 = 0,1302
Nhkl = 4254
R1 = 0,0506; wR2 = 0,1349
(45 %). ɇɚɣɞɟɧɨ: C 48,6, H 5,1, N 5,2, S 23,2, Zn 12,2. Ⱦɥɹ C22H26O2N2S4Zn ɜɵɱɢɫɥɟɧɨ, %: C 48,6,
H 4,8, N 5,2, S 23,5, Zn 12,0.
Ɇɨɧɨɤɪɢɫɬɚɥɥɵ ɤɨɦɩɥɟɤɫɚ I ɜɵɪɚɫɬɢɥɢ ɩɪɢ ɦɟɞɥɟɧɧɨɦ ɢɫɩɚɪɟɧɢɢ ɪɚɫɬɜɨɪɚ ɫɨɟɞɢɧɟɧɢɹ ɜ
ɫɦɟɫɢ CH2Cl2—ɝɟɤɫɚɧ (1:1) ɜ ɯɨɥɨɞɢɥɶɧɢɤɟ. Ⱦɥɹ ɊɋȺ ɨɬɨɛɪɚɥɢ ɩɪɨɡɪɚɱɧɵɣ ɫɜɟɬɥɨ-ɠɟɥɬɵɣ
ɤɪɢɫɬɚɥɥ ɜ ɮɨɪɦɟ ɢɡɨɦɟɬɪɢɱɧɨɝɨ ɨɛɥɨɦɤɚ. ɇɚɛɨɪ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɨɬɪɚɠɟɧɢɣ ɩɨɥɭɱɢɥɢ ɧɚ
ɚɜɬɨɞɢɮɪɚɤɬɨɦɟɬɪɟ X8 APEX ɩɭɬɟɦ M-ɫɤɚɧɢɪɨɜɚɧɢɹ ɫ ɢɧɬɟɪɜɚɥɨɦ 0,5q. Ʉɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ
ɩɚɪɚɦɟɬɪɵ ɢ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɷɤɫɩɟɪɢɦɟɧɬɚ ɩɪɢɜɟɞɟɧɵ ɜ ɬɚɛɥ. 1. Ʉɪɢɫɬɚɥɥɵ ɤɨɦɩɥɟɤɫɚ ɨɬɧɟɫɟɧɵ ɤ ɬɪɢɤɥɢɧɧɨɣ ɫɢɧɝɨɧɢɢ, ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ P 1 .
ɋɬɪɭɤɬɭɪɚ I ɪɚɫɲɢɮɪɨɜɚɧɚ ɩɪɹɦɵɦ ɦɟɬɨɞɨɦ ɢ ɭɬɨɱɧɟɧɚ ɩɨɥɧɨɦɚɬɪɢɱɧɵɦ ɆɇɄ ɜ ɚɧɢɡɨɬɪɨɩɧɨɦ ɞɥɹ ɧɟɜɨɞɨɪɨɞɧɵɯ ɚɬɨɦɨɜ ɩɪɢɛɥɢɠɟɧɢɢ ɩɨ ɤɨɦɩɥɟɤɫɭ ɩɪɨɝɪɚɦɦ SHELX-97 [ 6 ]. ɉɨɡɢɰɢɢ ɜɫɟɯ ɚɬɨɦɨɜ H ɪɚɫɫɱɢɬɚɧɵ ɢ ɭɬɨɱɧɟɧɵ ɜ ɩɪɢɛɥɢɠɟɧɢɢ ɠɟɫɬɤɨɝɨ ɬɟɥɚ, ɢɡɨɬɪɨɩɧɵɟ ɬɟɩɥɨɜɵɟ ɩɚɪɚɦɟɬɪɵ ɱɚɫɬɢ ɚɬɨɦɨɜ ɇ ɩɪɢɪɚɜɧɟɧɵ ɤ Uɷɤɜ ɫɜɹɡɚɧɧɵɯ ɫ ɧɢɦɢ ɧɟɜɨɞɨɪɨɞɧɵɯ ɚɬɨɦɨɜ.
Ɉɤɨɧɱɚɬɟɥɶɧɵɟ ɡɧɚɱɟɧɢɹ ɩɨɡɢɰɢɨɧɧɵɯ ɢ ɷɤɜɢɜɚɥɟɧɬɧɵɯ ɢɡɨɬɪɨɩɧɵɯ ɬɟɩɥɨɜɵɯ ɩɚɪɚɦɟɬɪɨɜ ɛɚɡɢɫɧɵɯ ɚɬɨɦɨɜ ɩɪɢɜɟɞɟɧɵ ɜ ɬɚɛɥ. 2, ɚ ɨɫɧɨɜɧɵɟ ɦɟɠɚɬɨɦɧɵɟ ɪɚɫɫɬɨɹɧɢɹ ɢ ɜɚɥɟɧɬɧɵɟ ɭɝɥɵ — ɜ
ɬɚɛɥ. 3. Ɍɚɛɥɢɰɵ ɤɨɨɪɞɢɧɚɬ ɚɬɨɦɨɜ H ɢ ɚɧɢɡɨɬɪɨɩɧɵɯ ɬɟɩɥɨɜɵɯ ɩɚɪɚɦɟɬɪɨɜ, ɚ ɬɚɤɠɟ ɬɚɛɥɢɰɵ
ɡɧɚɱɟɧɢɣ ɫɬɪɭɤɬɭɪɧɵɯ ɮɚɤɬɨɪɨɜ ɦɨɠɧɨ ɩɨɥɭɱɢɬɶ ɭ ɚɜɬɨɪɨɜ.
Ɋɟɡɭɥɶɬɚɬɵ ɢ ɢɯ ɨɛɫɭɠɞɟɧɢɟ. Ɉɫɧɨɜɭ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ ɫɬɪɭɤɬɭɪɵ ɤɨɦɩɥɟɤɫɚ I ɫɨɫɬɚɜɥɹɸɬ ɞɢɫɤɪɟɬɧɵɟ ɨɞɧɨɹɞɟɪɧɵɟ ɦɨɥɟɤɭɥɵ, ɜɫɟ ɚɬɨɦɵ ɤɨɬɨɪɵɯ ɪɚɫɩɨɥɨɠɟɧɵ ɜ ɨɛɳɢɯ ɩɨɡɢɰɢɹɯ
(ɪɢɫ. 1, a). ȼ ɛɥɢɠɚɣɲɭɸ ɤɨɨɪɞɢɧɚɰɢɨɧɧɭɸ ɫɮɟɪɭ ɰɟɧɬɪɚɥɶɧɨɝɨ ɚɬɨɦɚ Zn ɜɯɨɞɹɬ ɞɜɚ ɚɬɨɦɚ N
1191
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
Ɍɚɛɥɢɰɚ 2
4
Ʉɨɨɪɞɢɧɚɬɵ ɛɚɡɢɫɧɵɯ ɚɬɨɦɨɜ (u10 ) ɢ ɢɯ ɷɤɜɢɜɚɥɟɧɬɧɵɟ ɢɡɨɬɪɨɩɧɵɟ ɬɟɩɥɨɜɵɟ ɩɚɪɚɦɟɬɪɵ (Å2u103,
Uɷɤɜ = 1/3(U11 + U22 + U33)) ɜ ɫɬɪɭɤɬɭɪɟ ɤɨɦɩɥɟɤɫɚ ZnPhen(n-BuOCS2)2
Ⱥɬɨɦ
x
Zn(1)
S(1)
S(2)
S(3)
S(4)
C(1)
O(1)
C(11)
C(21)
C(31)
C(41)
C(2)
O(2)
C(12)
C(22)
C(32)
2767(1)
1070(1)
2794(1)
1465(1)
2308(1)
1493(4)
786(3)
–401(6)
–1079(6)
–2(7)
–633(9)
2671(4)
3922(3)
5088(9)
5165(13)
6256(13)
y
z
1768(1) 2536(1)
854(1)
3511(1)
3752(1) 4093(1)
2094(1) 1113(1)
3996(1)
–7(1)
2484(3) 4268(2)
2856(2) 5019(2)
1835(4) 5190(4)
2584(5) 5997(4)
3283(6) 7069(4)
4197(7) 7829(5)
3505(3) 1007(3)
4098(3) 1795(2)
5282(8) 1816(7)
6473(10) 2690(18)
7792(13) 3249(9)
Uɷɤɜ
Ⱥɬɨɦ
46(1)
C(42)
62(1)
N(1f)
67(1)
N(2f)
54(1)
C(1f)
80(1)
C(2f)
52(1)
C(3f)
64(1)
C(4f)
83(1)
C(5f)
90(1)
C(6f)
94(1)
C(7f)
110(2) C(8f)
54(1)
C(9f)
87(1) C(10f)
167(4) C(11f)
296(11) C(12f)
312(10)
x
y
z
Uɷɤɜ
5519(11)
2890(3)
5114(3)
1768(4)
2014(5)
3462(5)
4674(4)
4320(3)
5513(3)
7030(4)
8154(4)
7740(4)
6211(4)
6235(5)
7346(4)
8633(11)
–160(2)
2165(2)
–1305(3)
–2387(3)
–2277(3)
–1090(3)
–48(3)
1190(3)
1362(3)
2600(4)
3549(4)
3299(4)
–860(4)
295(4)
3823(10)
1596(2)
2790(2)
1015(3)
323(3)
233(3)
823(3)
1504(2)
2145(2)
2093(3)
2761(4)
3432(3)
3420(3)
785(3)
1380(3)
194(5)
46(1)
47(1)
57(1)
67(1)
66(1)
52(1)
42(1)
43(1)
54(1)
70(1)
70(1)
60(1)
68(1)
67(1)
Ɋɢɫ. 1. ɋɬɪɨɟɧɢɟ ɦɨɥɟɤɭɥɵ ɤɨɦɩɥɟɤɫɚ ZnPhen(n-BuOCS2)2 ɫ ɧɭɦɟɪɚɰɢɟɣ ɧɟɜɨɞɨɪɨɞɧɵɯ ɚɬɨɦɨɜ — a,
ɭɩɚɤɨɜɤɚ ɦɨɥɟɤɭɥ ɤɨɦɩɥɟɤɫɚ ɜ ɩɪɨɟɤɰɢɢ ɧɚ ɩɥɨɫɤɨɫɬɶ (100) — ɛ
ɛɢɞɟɧɬɚɬɧɨ-ɰɢɤɥɢɱɟɫɤɨɝɨ ɥɢɝɚɧɞɚ Phen ɧɚ ɪɚɫɫɬɨɹɧɢɹɯ Zn—N, ɪɚɜɧɵɯ 2,089(2) ɢ 2,185(2) Å, ɞɜɚ
ɚɬɨɦɚ S(1) ɢ S(2) ɛɢɞɟɧɬɚɬɧɨ-ɰɢɤɥɢɱɟɫɤɨɝɨ ɥɢɝɚɧɞɚ n-BuOCS 2 , ɚ ɬɚɤɠɟ ɨɞɢɧ ɚɬɨɦ S(3) ɜɬɨɪɨɝɨ
ɤɫɚɧɬɨɝɟɧɚɬɧɨɝɨ ɢɨɧɚ ɧɚ ɪɚɫɫɬɨɹɧɢɹɯ Zn—S, ɪɚɜɧɵɯ 2,3185(9), 2,4194(9), 2,5594(9) Å. Ⱥɬɨɦ
S(4), ɧɚɯɨɞɹɳɢɣɫɹ ɧɚ ɪɚɫɫɬɨɹɧɢɢ 4,8384(9) Å, ɜ ɤɨɨɪɞɢɧɚɰɢɨɧɧɭɸ ɫɮɟɪɭ ɚɬɨɦɚ Zn(1) ɧɟ ɜɨɲɟɥ.
Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɦɨɥɟɤɭɥɚ ɤɨɦɩɥɟɤɫɚ I ɯɚɪɚɤɬɟɪɢɡɭɟɬɫɹ ɧɚɥɢɱɢɟɦ ɞɜɭɯ ɥɢɝɚɧɞɨɜ n-BuOCS 2 ɫ
ɱɟɬɤɨ ɜɵɪɚɠɟɧɧɵɦɢ ɪɚɡɥɢɱɢɹɦɢ ɢɯ ɮɭɧɤɰɢɣ — ɛɢɞɟɧɬɚɬɧɨ-ɰɢɤɥɢɱɟɫɤɨɣ ɢ ɦɨɧɨɞɟɧɬɚɬɧɨɣ.
ɉɪɢ ɤɨɨɪɞɢɧɚɰɢɢ ɛɢɞɟɧɬɚɬɧɨ-ɰɢɤɥɢɱɟɫɤɨɝɨ ɥɢɝɚɧɞɚ n-BuOCS 2 ɡɚɦɵɤɚɟɬɫɹ ɯɟɥɚɬɧɵɣ ɰɢɤɥ
1192
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
Ɍɚɛɥɢɰɚ 3
Ɉɫɧɨɜɧɵɟ ɦɟɠɚɬɨɦɧɵɟ ɪɚɫɫɬɨɹɧɢɹ d, Å ɢ ɜɚɥɟɧɬɧɵɟ ɭɝɥɵ Z, ɝɪɚɞ. ɜ ɫɬɪɭɤɬɭɪɟ ɤɨɦɩɥɟɤɫɚ
ZnPhen(n-BuOCS2)2
ɋɜɹɡɶ
Zn(1)—N(2f)
Zn(1)—N(1f)
Zn(1)—S(3)
Zn(1)—S(1)
Zn(1)—S(2)
Zn(1)—S(4)
S(1)—C(1)
S(2)—C(1)
S(3)—C(2)
S(4)—C(2)
C(1)—O(1)
O(1)—C(11)
C(11)—C(21)
C(21)—C(31)
C(31)—C(41)
C(2)—O(2)
O(2)—C(12)
C(12)—C(22)
d
2,089(2)
2,185(2)
2,3185(9)
2,4194(9)
2,5594(9)
4,8384(9)
1,688(3)
1,684(3)
1,709(3)
1,652(4)
1,332(4)
1,449(4)
1,510(6)
1,496(7)
1,536(7)
1,329(5)
1,442(6)
1,47(2)
ɋɜɹɡɶ
C(22)—C(32)
C(32)—C(42)
N(1f)—C(1f)
N(1f)—C(5f)
N(2f)—C(10f)
N(2f)—C(6f)
C(1f)—C(2f)
C(2f)—C(3f)
C(3f)—C(4f)
C(4f)—C(5f)
C(4f)—C(11f)
C(5f)—C(6f)
C(6f)—C(7f)
C(7f)—C(8f)
C(7f)—C(12f)
C(8f)—C(9f)
C(9f)—C(10f)
C(11f)—C(12f)
d
1,429(5)
1,435(5)
1,328(4)
1,350(4)
1,327(4)
1,360(4)
1,390(5)
1,366(6)
1,395(5)
1,407(4)
1,436(5)
1,431(4)
1,406(4)
1,414(5)
1,427(5)
1,365(6)
1,388(5)
1,334(6)
ɍɝɨɥ
Z
ɍɝɨɥ
Z
N(2f)—Zn(1)—N(1f)
N(2f)—Zn(1)—S(3)
N(1f)—Zn(1)—S(3)
N(2f)—Zn(1)—S(1)
N(1f)—Zn(1)—S(1)
S(3)—Zn(1)—S(1)
N(2f)—Zn(1)—S(2)
N(1f)—Zn(1)—S(2)
S(3)—Zn(1)—S(2)
S(1)—Zn(1)—S(2)
C(1)—S(1)—Zn(1)
C(1)—S(2)—Zn(1)
C(2)—S(3)—Zn(1)
O(1)—C(1)—S(2)
77,61(9)
119,88(7)
94,86(7)
128,18(8)
95,99(7)
111,85(4)
98,58(7)
162,40(7)
101,80(4)
72,65(3)
84,6(1)
80,3(1)
105,5(1)
115,5(2)
O(1)—C(1)—S(1)
S(2)—C(1)—S(1)
C(1)—O(1)—C(11)
O(2)—C(2)—S(4)
O(2)—C(2)—S(3)
S(4)—C(2)—S(3)
C(2)—O(2)—C(12)
C(1f)—N(1f)—C(5f)
C(1f)—N(1f)—Zn(1)
C(5f)—N(1f)—Zn(1)
C(10f)—N(2f)—C(6f)
C(10f)—N(2f)—Zn(1)
C(6f)—N(2f)—Zn(1)
122,3(2)
122,1(2)
119,2(3)
125,4(3)
112,4(3)
122,1(2)
119,9(4)
118,4(3)
129,3(2)
111,5(2)
118,2(3)
127,0(2)
114,3(2)
ZnS2C. Ⱥɬɨɦɵ N ɢ S ɨɛɪɚɡɭɸɬ ɜɨɤɪɭɝ ɚɬɨɦɚ Zn(1) (Ʉɑ 5) ɬɪɢɝɨɧɚɥɶɧɭɸ ɛɢɩɢɪɚɦɢɞɭ ɫ ɷɤɜɚɬɨɪɢɚɥɶɧɨɣ ɩɥɨɫɤɨɫɬɶɸ S(1)S(3)N(2F)Zn(1) (ɫɪɟɞɧɟɟ ɨɬɤɥɨɧɟɧɢɟ ɚɬɨɦɨɜ ɨɬ ɩɥɨɫɤɨɫɬɢ ɪɚɜɧɨ
0,014 Å), ɚɩɢɤɚɥɶɧɵɟ ɩɨɡɢɰɢɢ ɡɚɧɢɦɚɸɬ ɚɬɨɦɵ N(1f) ɢ S(2), ɩɪɢ ɷɬɨɦ ɜɟɤɬɨɪɵ Zn(1)—N(1f) ɢ
Zn(1)—S(2) ɫɨɫɬɚɜɥɹɸɬ ɫ ɷɤɜɚɬɨɪɢɚɥɶɧɨɣ ɩɥɨɫɤɨɫɬɶɸ ɭɝɥɵ 78,7 ɢ 71,2q ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ (ɭɡɟɥ
ZnN2S3). Ⱥɧɚɥɨɝɢɱɧɨɟ ɫɬɪɨɟɧɢɟ ɭɡɥɚ ɢɦɟɟɬ ɦɟɫɬɨ ɜ ɫɬɪɭɤɬɭɪɟ ɤɨɦɩɥɟɤɫɚ ZnPhen(EtOCS2)2 [ 3 ] ɢ
ɜ ɨɞɧɨɣ ɢɡ ɦɨɞɢɮɢɤɚɰɢɣ (ɦ-1) ɤɨɦɩɥɟɤɫɚ ZnPhen(i-PrOCS2)2 [ 4 ]. Ⱦɥɢɧɵ ɫɜɹɡɟɣ ɢ ɜɟɥɢɱɢɧɵ ɜɚɥɟɧɬɧɵɯ ɭɝɥɨɜ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɝɨ ɭɡɥɚ ZnN2S3 ɫɨɨɬɜɟɬɫɬɜɭɸɬ ɚɧɚɥɨɝɢɱɧɵɦ ɡɧɚɱɟɧɢɹɦ ɜ ɫɬɪɭɤɬɭɪɚɯ ɪɚɡɧɨɥɢɝɚɧɞɧɵɯ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɚɥɤɢɥɤɫɚɧɬɨɝɟɧɚɬɨɜ Zn(II) [ 3 ].
Ɏɟɧɚɧɬɪɨɥɢɧɨɜɵɟ ɤɨɥɶɰɚ ɦɨɥɟɤɭɥ Phen ɢɦɟɸɬ ɩɪɚɤɬɢɱɟɫɤɢ ɩɥɨɫɤɨɟ ɫɬɪɨɟɧɢɟ (ɫɪɟɞɧɟɟ ɨɬɤɥɨɧɟɧɢɟ ɚɬɨɦɨɜ ɨɬ ɩɥɨɫɤɨɫɬɢ ɪɚɜɧɨ 0,017 Å). ɉɪɢ ɪɚɫɱɟɬɟ ɩɥɨɫɤɨɫɬɟɣ, ɩɪɨɯɨɞɹɳɢɯ ɱɟɪɟɡ ɚɬɨ-
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
1193
Ɋɢɫ. 2. ɋɬɟɩɟɧɶ ɩɟɪɟɤɪɵɜɚɧɢɹ Phen-ɝɟɬɟɪɨɰɢɤɥɨɜ ɜ ɩɪɨɟɤɰɢɢ ɧɚ ɢɯ ɫɪɟɞɧɟɫɬɚɬɢɫɬɢɱɟɫɤɭɸ ɩɥɨɫɤɨɫɬɶ — ɞɢɦɟɪɧɵɣ ɚɧɫɚɦɛɥɶ ɜ ɫɬɪɭɤɬɭɪɟ I
ɦɵ ɯɟɥɚɬɧɨɝɨ ɰɢɤɥɚ ZnS2C, ɩɨɥɭɱɢɥɢ ɫɪɟɞɧɟɟ ɡɧɚɱɟɧɢɟ ɨɬɤɥɨɧɟɧɢɹ ɚɬɨɦɨɜ 0,027 Å, ɞɜɭɝɪɚɧɧɵɣ ɭɝɨɥ
ɦɟɠɞɭ ɩɥɨɫɤɨɫɬɹɦɢ SZnS ɢ SCS ɪɚɜɟɧ 5,9q, ɬ.ɟ. ɧɚɛɥɸɞɚɟɬɫɹ ɧɟɡɧɚɱɢɬɟɥɶɧɚɹ ɞɟɮɨɪɦɚɰɢɹ ɷɬɨɝɨ ɰɢɤɥɚ.
ȼ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ ɫɬɪɭɤɬɭɪɟ ɤɨɦɩɥɟɤɫɚ I ɜɫɟ
ɦɟɠɦɨɥɟɤɭɥɹɪɧɵɟ ɤɨɧɬɚɤɬɵ ɧɚɯɨɞɹɬɫɹ ɜ ɩɪɟɞɟɥɚɯ
ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɵɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ. ɇɚɢɛɨɥɟɟ ɤɨɪɨɬɤɢɟ ɢɡ ɧɢɯ ɨɬɦɟɱɟɧɵ ɦɟɠɞɭ ɚɬɨɦɚɦɢ ɋ ɦɨɥɟɤɭɥ
Phen, ɪɚɡɦɧɨɠɟɧɧɵɯ ɰɟɧɬɪɨɦ ɫɢɦɦɟɬɪɢɢ: C(3f)—
C(7f) 3,608(6); C(3f)—C(12f) 3,669(6), C(4f)—C(11f) 3,664(6); C(5f)—C(11f) 3,562(6) Å. ɋ ɭɱɟɬɨɦ
ɷɬɢɯ ɤɨɧɬɚɤɬɨɜ ɪɚɫɫɦɨɬɪɟɧɚ ɭɩɚɤɨɜɤɚ ɦɨɥɟɤɭɥ ɤɨɦɩɥɟɤɫɚ ɜ ɩɪɨɟɤɰɢɢ ɜɞɨɥɶ ɨɫɢ ɚ (ɫɦ. ɪɢɫ. 1, ɛ).
ɇɚ ɪɢɫɭɧɤɟ ɱɟɬɤɨ ɜɵɞɟɥɹɸɬɫɹ ɩɚɪɵ ɩɚɪɚɥɥɟɥɶɧɵɯ ɦɨɥɟɤɭɥ Phen, ɩɥɨɫɤɨɫɬɢ ɤɨɬɨɪɵɯ ɧɚɯɨɞɹɬɫɹ
ɧɚ ɪɚɫɫɬɨɹɧɢɢ d(hkl) = 3,55 Å, ɚ ɰɟɧɬɪɵ ɮɟɧɚɧɬɪɨɥɢɧɨɜɵɯ ɤɨɥɟɰ — ɧɚ ɪɚɫɫɬɨɹɧɢɢ r = 4,49 Å. ȼ
ɫɨɨɬɜɟɬɫɬɜɢɢ ɫ ɪɚɫɫɱɢɬɚɧɧɵɦɢ ɡɧɚɱɟɧɢɹɦɢ d(hkl) ɢ r ɫɞɜɢɝ ɰɟɧɬɪɨɜ ɤɨɥɟɰ Phen ɜ ɩɪɨɟɤɰɢɢ ɧɚ
ɩɪɨɟɤɬɢɪɭɟɦɭɸ ɩɥɨɫɤɨɫɬɶ 'r ɪɚɜɟɧ 2,75 Å. ɗɬɢ ɡɧɚɱɟɧɢɹ, ɫɨɝɥɚɫɧɨ [ 7, 8 ], ɭɤɚɡɵɜɚɸɬ ɧɚ ɜɨɡɧɢɤɧɨɜɟɧɢɟ S—S-ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɦɟɠɞɭ ɦɨɥɟɤɭɥɚɦɢ Phen ɞɜɭɯ ɫɨɫɟɞɧɢɯ ɤɨɦɩɥɟɤɫɨɜ, ɜ ɪɟɡɭɥɶɬɚɬɟ ɤɨɬɨɪɨɝɨ ɨɛɪɚɡɭɸɬɫɹ ɞɢɦɟɪɧɵɟ ɚɧɫɚɦɛɥɢ. ɇɚ ɪɢɫ. 2 ɩɪɟɞɫɬɚɜɥɟɧ ɨɞɢɧ ɢɡ ɷɬɢɯ ɚɧɫɚɦɛɥɟɣ ɜ ɩɪɨɟɤɰɢɢ ɧɚ ɟɝɨ ɫɪɟɞɧɟɫɬɚɬɢɫɬɢɱɟɫɤɭɸ ɩɥɨɫɤɨɫɬɶ. Ɉɛɪɚɡɨɜɚɧɢɟ ɞɢɦɟɪɧɵɯ ɦɨɥɟɤɭɥɹɪɧɵɯ
ɚɧɫɚɦɛɥɟɣ — ɯɚɪɚɤɬɟɪɧɚɹ ɱɟɪɬɚ ɧɟ ɬɨɥɶɤɨ ɢɡɭɱɟɧɧɵɯ ɪɚɡɧɨɥɢɝɚɧɞɧɵɯ ɤɨɦɩɥɟɤɫɨɜ ɚɥɤɢɥɤɫɚɧɬɨɝɟɧɚɬɨɜ Zn(II), ɧɨ ɬɚɤɠɟ ɤɨɦɩɥɟɤɫɨɜ ɞɢɚɥɤɢɥɞɢɬɢɨɤɚɪɛɚɦɚɬɨɜ ɢ ɞɢɢɡɨɛɭɬɢɥɞɢɬɢɨɮɨɫɮɢɧɚɬɨɜ
ɩɟɪɟɯɨɞɧɵɯ ɦɟɬɚɥɥɨɜ (Zn, Cd, Mn, Co, Ni) ɫ Phen ɢ 2,2c-Bipy [ 9, 10 ].
ɋɪɚɜɧɟɧɢɟ ɢɫɫɥɟɞɨɜɚɧɧɵɯ ɪɚɧɟɟ ɢ ɜ ɧɚɫɬɨɹɳɟɣ ɫɬɚɬɶɟ ɤɪɢɫɬɚɥɥɢɱɟɫɤɢɯ ɫɬɪɭɤɬɭɪ ɪɚɡɧɨɥɢɝɚɧɞɧɵɯ ɤɨɦɩɥɟɤɫɨɜ Zn(II) ɫ Phen ɢ ɚɥɤɢɥɤɫɚɧɬɨɝɟɧɚɬ-ɢɨɧɚɦɢ ROCS 2 (R=Et, i-Pr, i-Bu, n-Bu)
ɩɨɤɚɡɚɥɨ, ɱɬɨ ɜɫɟ ɨɧɢ ɢɦɟɸɬ ɞɢɫɤɪɟɬɧɨɟ ɨɞɧɨɹɞɟɪɧɨɟ ɫɬɪɨɟɧɢɟ.
ȼ ɬɚɛɥ. 4 ɩɪɢɜɟɞɟɧɵ ɝɟɨɦɟɬɪɢɱɟɫɤɢɟ ɩɚɪɚɦɟɬɪɵ ɦɨɥɟɤɭɥ ɜ ɫɬɪɭɤɬɭɪɚɯ ɷɬɢɯ ɤɨɦɩɥɟɤɫɨɜ ɢ
ɩɚɪɚɦɟɬɪɵ ɦɟɠɦɨɥɟɤɭɥɹɪɧɵɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ. ȼɢɞɧɨ, ɱɬɨ ɜ ɪɚɫɫɦɚɬɪɢɜɚɟɦɵɯ ɫɨɟɞɢɧɟɧɢɹɯ Ʉɑ
ɢɨɧɚ Zn2+ ɡɚɜɢɫɢɬ ɨɬ ɩɪɢɪɨɞɵ R. ȿɫɥɢ R=Et, n-Bu, ɬɨ Ʉɑ 5, ɬɚɤ ɤɚɤ ɜ ɮɨɪɦɢɪɨɜɚɧɢɢ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɝɨ ɭɡɥɚ ZnN2S3 ɭɱɚɫɬɜɭɸɬ ɤɚɤ ɛɢɞɟɧɬɚɬɧɨ-ɰɢɤɥɢɱɟɫɤɢɣ, ɬɚɤ ɢ ɦɨɧɨɞɟɧɬɚɬɧɵɣ ɥɢɝɚɧɞɵ
EtOCS 2 ɢ n-BuOCS 2 [ 3 ]. Ⱦɥɹ ɫɨɟɞɢɧɟɧɢɹ, ɜ ɤɨɬɨɪɨɦ R = i-Pr, ɩɨɥɭɱɟɧɵ ɞɜɟ ɦɨɞɢɮɢɤɚɰɢɢ [ 4 ].
Ⱦɥɹ ɩɟɪɜɨɣ Ʉɑ 5 (ɭɡɟɥ ZnN2S3), ɬɚɤ ɤɚɤ ɮɭɧɤɰɢɢ ɥɢɝɚɧɞɨɜ i-PrOCS 2 ɚɧɚɥɨɝɢɱɧɵ ɬɚɤɨɜɵɦ ɩɪɢ
R=Et ɢ n-Bu. ɇɚɩɪɨɬɢɜ, ɞɥɹ ɜɬɨɪɨɣ ɦɨɞɢɮɢɤɚɰɢɢ Ʉɑ 6 (ɭɡɟɥ ZnN2S4), ɬɚɤ ɤɚɤ ɨɛɚ ɥɢɝɚɧɞɚ
i-PrOCS 2 ɹɜɥɹɸɬɫɹ ɛɢɞɟɧɬɚɬɧɨ-ɰɢɤɥɢɱɟɫɤɢɦɢ. ȼ ɫɥɭɱɚɟ, ɤɨɝɞɚ R = i-Bu, Ʉɑ ɬɚɤɠɟ ɪɚɜɧɨ 6
(ɭɡɟɥ ZnN2S4) [ 5 ].
ɋɪɚɜɧɟɧɢɟ ɪɟɡɭɥɶɬɚɬɨɜ ɢɫɫɥɟɞɨɜɚɧɢɹ ɫɬɪɭɤɬɭɪɵ ZnPhen(n-BuOCS2)2 ɢ ɤɨɦɩɥɟɤɫɨɜ
ZnPhen(ROCS2)2 (R=Et, i-Pr, i-Bu) ɩɨɡɜɨɥɹɟɬ ɫɞɟɥɚɬɶ ɜɵɜɨɞ ɨ ɜɡɚɢɦɨɫɜɹɡɢ Ʉɑ ɢ ɩɪɢɪɨɞɵ R.
Ɉɱɟɜɢɞɧɨ, ɱɬɨ ɩɪɢ ɧɚɥɢɱɢɢ ɧɟɪɚɡɜɟɬɜɥɟɧɧɵɯ ɚɥɤɢɥɶɧɵɯ ɝɪɭɩɩ Et ɢ n-Bu Ʉɑ 5 (ɭɡɟɥ ZnN2S3). ȼ
ɷɬɨɦ ɫɥɭɱɚɟ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɟ ɩɨɥɢɷɞɪɵ N2S3 ɢɦɟɸɬ ɮɨɪɦɭ ɞɟɮɨɪɦɢɪɨɜɚɧɧɵɯ 5-ɜɟɪɲɢɧɧɢɤɨɜ — ɬɟɬɪɚɝɨɧɚɥɶɧɨɣ ɩɢɪɚɦɢɞɵ ɢɥɢ ɬɪɢɝɨɧɚɥɶɧɨɣ ɛɢɩɢɪɚɦɢɞɵ. Ɋɚɡɜɟɬɜɥɟɧɢɟ ɝɪɭɩɩɵ R ɩɪɢɜɨɞɢɬ ɤ ɜɨɡɦɨɠɧɨɫɬɢ ɫɭɳɟɫɬɜɨɜɚɧɢɹ ɦɨɞɢɮɢɤɚɰɢɣ, ɢɦɟɸɳɢɯ Ʉɑ 5 ɢ 6 (R = i-Pr), ɚ ɩɪɢ ɩɟɪɟɯɨɞɟ ɤ R = i-Bu ɨɛɪɚɡɭɟɬɫɹ ɫɨɟɞɢɧɟɧɢɟ ɫ Ʉɑ 6 ɫ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɦ ɩɨɥɢɷɞɪɨɦ N2S4 ɜ ɮɨɪɦɟ ɢɫɤɚɠɟɧɧɨɝɨ ɨɤɬɚɷɞɪɚ.
ɉɨɜɵɲɟɧɢɟ Ʉɑ ɩɪɢ ɤɨɨɪɞɢɧɚɰɢɢ ɚɥɤɢɥɤɫɚɧɬɨɝɟɧɚɬɧɵɯ ɥɢɝɚɧɞɨɜ, ɢɦɟɸɳɢɯ ɪɚɡɜɟɬɜɥɟɧɧɭɸ ɚɥɤɢɥɶɧɭɸ ɝɪɭɩɩɭ, ɦɨɠɧɨ ɨɛɴɹɫɧɢɬɶ ɬɟɦ, ɱɬɨ ɨɩɪɟɞɟɥɹɸɳɭɸ ɪɨɥɶ ɜ ɪɟɚɤɰɢɨɧɧɨɣ ɫɩɨɫɨɛɧɨɫɬɢ ɷɬɢɯ ɥɢɝɚɧɞɨɜ, ɩɨ-ɜɢɞɢɦɨɦɭ, ɢɝɪɚɟɬ ɢɧɞɭɤɰɢɨɧɧɵɣ ɷɮɮɟɤɬ ɚɥɤɢɥɶɧɵɯ ɡɚɦɟɫɬɢɬɟɥɟɣ, ɚ ɧɟ
ɫɬɟɪɢɱɟɫɤɢɣ ɷɮɮɟɤɬ. ɂɡɜɟɫɬɧɨ, ɱɬɨ ɞɥɹ ɚɥɤɢɥɶɧɵɯ ɝɪɭɩɩ ɩɪɢ ɢɯ ɪɚɡɜɟɬɜɥɟɧɢɢ ɡɧɚɱɟɧɢɹ ɢɧɞɭɤ-
1194
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
Ɍɚɛɥɢɰɚ 4
ɉɚɪɚɦɟɬɪɵ ɦɟɠɦɨɥɟɤɭɥɹɪɧɵɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ ɜ ɪɚɡɧɨɥɢɝɚɧɞɧɵɯ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɫɨɟɞɢɧɟɧɢɹɯ Zn
ɫ ɚɥɤɢɥɤɫɚɧɬɨɝɟɧɚɬ-ɢɨɧɚɦɢ ROCS 2 (R=Et, i-Pr, i-Bu, n-Bu) ɢ Phen
ɋɨɟɞɢɧɟɧɢɟ,
ɥɢɬɟɪɚɬɭɪɚ
ɉɪ. ɝɪ.,
V, Z
ZnPhen(EtOCS2)2
[3]
P21/c,
2125,0(7)
4
ɍɡɟɥ
Zn—N (Å)
Zn—S (Å)
Ɍɪɢɝɨɧɚɥɶɧɚɹ 2,049(4) 2,298(1); 4,767(2)
ɛɢɩɢɪɚɦɢɞɚ 2,132(4) 2,332(1); 2,873(2)
ZnN2S3
F
r, 'r
d(hkl)
10,9
4,50
3,01
3,35
(ɞ.ɚ.).
4,15
2,45
3,35
(ɞ.ɚ.)
6,62
3,03
4,11
2,14
3,51
(ɞ.ɚ.)
4,49
2,75
3,55
(ɞ.ɚ.)
ZnPhen(i-BuOCS2)2
[5]
P21/n, Ɍɟɬɪɚɝɨɧɚɥɶɧɚɹ 2,102(5) 2,527(2); 2,436(2)
ɩɢɪɚɦɢɞɚ
2347,6(8)
2,199(4) 2,321(2); 3,404(2)
2,0
ZnN2S3
4
Ɉɤɬɚɷɞɪ
2,149(3) 2,507(1); 2,528(1) F1=6,2
P21/n,
2311,3(8)
ZnN2S4
2,174(2) 2,697(1); 2,425(1) F2=1,5
4
Pcab
2,170(8) 2,497(5); 2,560(4) F1=1,1
Ɉɤɬɚɷɞɪ
5102,5(8)
2,155(9) 2,428(3); 2,672(5) F2=6,9
ZnN2S4
8
ZnPhen(n-BuOCS2)2
[ɇɚɫɬ. ɪɚɛɨɬɚ]
Ɍɪɢɝɨɧɚɥɶɧɚɹ 2,089(2) 2,4194(9);2,5594(9)
P1
1264,72(8) ɛɢɩɢɪɚɦɢɞɚ 2,185(2) 2,3185(9);4,8384(9)
ZnN2S3
2
ZnPhen(i-PrOCS2)2
[4] (ɦɨɞɢɮ.-1)
ZnPhen(i-PrOCS2)2
[4] (ɦɨɞɢɮ.-2)
5,9
ɉ ɪ ɢ ɦ ɟ ɱ ɚ ɧ ɢ ɟ. d(hkl) — ɪɚɫɫɬɨɹɧɢɟ ɦɟɠɞɭ ɩɚɪɚɥɥɟɥɶɧɵɦɢ ɩɥɨɫɤɨɫɬɹɦɢ ɦɨɥɟɤɭɥ Phen ɢɥɢ 2,2cBipy; r — ɪɚɫɫɬɨɹɧɢɟ ɦɟɠɞɭ ɰɟɧɬɪɚɦɢ ɬɹɠɟɫɬɢ ɦɨɥɟɤɭɥ Phen; 'r — ɫɞɜɢɝ ɰɟɧɬɪɨɜ ɬɹɠɟɫɬɢ ɦɨɥɟɤɭɥ Phen
ɨɬɧɨɫɢɬɟɥɶɧɨ ɞɪɭɝ ɞɪɭɝɚ; F — ɭɝɥɵ ɜ ɯɟɥɚɬɧɵɯ ɰɢɤɥɚɯ ɦɟɠɞɭ ɩɥɨɫɤɨɫɬɹɦɢ SZnS ɢ SCS; ɞ.ɚ. —
ɞɢɦɟɪɧɵɟ ɚɧɫɚɦɛɥɢ.
ɰɢɨɧɧɵɯ ɤɨɧɫɬɚɧɬ V* Ɍɚɮɬɚ ɡɧɚɱɢɬɟɥɶɧɨ ɭɛɵɜɚɸɬ, ɱɬɨ ɫɨɨɬɜɟɬɫɬɜɭɟɬ ɜɨɡɪɚɫɬɚɧɢɸ +I-ɷɮɮɟɤɬɚ
[ 11 ].
Ɋɚɛɨɬɚ ɜɵɩɨɥɧɟɧɚ ɩɪɢ ɮɢɧɚɧɫɨɜɨɣ ɩɨɞɞɟɪɠɤɟ ɊȺɇ (ɩɪɨɝɪɚɦɦɚ 9.5).
ɋɉɂɋɈɄ ɅɂɌȿɊȺɌɍɊɕ
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1999. – 7, ʋ 4. – ɋ. 451 – 461.
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5. Ƚɥɢɧɫɤɚɹ Ʌ.Ⱥ., Ʌɟɨɧɨɜɚ Ɍ.Ƚ., Ʉɢɪɢɱɟɧɤɨ ȼ.ɇ. ɢ ɞɪ. // Ɍɚɦ ɠɟ. – 1997. – 38, ʋ 1. – ɋ. 142 – 147.
6. Sheldrick G.M. SHELX-97, release 97-2. – Germany: University of Goettingen, 1998.
7. Hunter C.A., Sanders J.K.M. // J. Amer. Chem. Soc. – 1990. – 112. – P. 5525 – 5534.
8. Janiak C. // J. Chem. Soc., Dalton Trans. – 2000. – P. 3885 – 3896.
9. Klevtsova R.F., Glinskaya L.A., Zemskova S.M., Larionov S.V. // Polyhedron. – 1999. – 18, N 26. –
P. 3559 – 3565.
10. Ʉɥɟɜɰɨɜɚ Ɋ.Ɏ., Ƚɥɢɧɫɤɚɹ Ʌ.Ⱥ., Ʉɨɤɢɧɚ Ɍ.ȿ., Ʌɚɪɢɨɧɨɜ ɋ.ȼ. // ɀɭɪɧ. ɫɬɪɭɤɬɭɪ. ɯɢɦɢɢ. – 2005. – 46,
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