834
K. V. Dom asevitch et al. ■Diphenyltellurium (IV) Nitrosocarbamylcyanmethanides
Table III. Selected bond lengths (A) for
Ph6Te30 2{AC0}2*CH3CN.
Refinement was terminated with all non-hydrogen pa-
rameter shifts < 0.33a. Convergence was obtained at
R - 0.040 and \\R2 = 0.111, G. O. F. on F2 = 1.04. based
on 6383 independent reflections with I > 2cr(I) (557 re-
fined parameters, the data/parameters ratio is 11.5; largest
peak in the final difference map = 0.68 e/A3). Judging by
the values of the U parameter of the acetonitrile of crys-
tallization atoms C(43), C(44), N(7) [U > 0.20 Ä2], this
group is disordered, but all attempts to divide the os-
cillatory movement between two positions with partial
occupancies of 50 % were not successful.
Crystal data for C42H34N60 6Te3*CH3CN: FW =
1142.6, triclinic, space group PI with a = 12.382(2).
b = 13.100(2), c = 14.944(3) Ä, a = 87.74(1), ß =
85.04(2), 7 = 66.29(1)°, V = 2211.0(7) Ä3, Z = 2, Dv
= 1.72 g * cm“3, /i = 20.2 cm-1, F(000) = 1108.
Te( 1)-0(5)
Te(l)-C(13)
Te(l)-C(7)
Te(l)-0(1)
Te(2)-0(6)
Te(2)-0(5)
Te(2)-C(19)
Te(2)-C(25)
Te(3)-0(6)
Te(3)-C(31)
Te(3)-C(37)
Te(3)-0(3)
0(2)-C(3)
1.940(4)
2.115(8)
2.101(7)
2.358(5)
2.074(4)
2.095(4)
2.118(5)
2.12(1)
1.953(4)
2.104(7)
2.124(7)
2.326(4)
1.223(9)
1.320(7)
1.230(8)
0(1)-N(1)
N( 1)—C( 1)
N(2)-C(2)
N(3)-C(3)
N(4)-C(4)
N(5)-C(5)
N(6)-C(6)
C( 1)-C(2)
C( 1)-C(3)
C(4)-C(5)
C(4)-C(6)
1.328(8)
1.304(9)
1.14(1)
1.33(1)
1.305(8)
1.151(9)
1.32(1)
1.43(1)
1.47(1)
1.42(1)
1.474(9)
0.96(9)
0.73(9)
0.91(9)
0.78(10)
N(3)-H(N3.1)
N(3)-H(N3.2)
N(6)-H(N6.1)
N(6)-H(N6.2)
0(3)-N(4)
0(4)-C(6)
Selected bond distances and angles are listed in Tables
III and IV. Full crystallographic data have been deposited
at the Cambridge Crystallographic Data Centre [13].
Table IV. Selected angles (°) for
Ph6Te30 2{AC0}2*CH3CN.
0(5)-Te(l)-C(13) 91.6(2) C(37)-Te(3)-0(3) 83.9(2)
0(5)-Te(l)-C(7) 90.3(2) N(l)-0(1)-Te(l) 105.2(4)
C(13)-Te(l)-C(7) 96.2(3) N(4)-0(3)-Te(3) 104.1(3)
0(5)-Te(l)-0(l) 171.6(2) Te(l)-0(5)-Te(2) 124.2(2)
C(13)-Te(l)-0( 1) 86.6(3) Te(3)-0(6)-Te(2) 124.2(2)
Results and Discussion
The analytical data listed in Table I proved the
stoichiometric composition of the complexes. Due
to the hydrolysis of diphenyltellurium(IV) in aque-
ous acetonitrile both the complexes 2 and 3 contain
oxo ligands.
The IR data are also consistent with the forma-
tion of oxo tellurium derivatives. In 2, peaks at 635
and 445 cm-1 may be assigned to uasym and usym
of the Te-O-Te bridges by comparison with oxo-
bis(nitratodiphenyltellurium) (i'asym 607, usym 426
cm-1) [3]. The features of the spectra of 3 in this
region are the same (^asym 595, z/sym 445 cm-1,
Te-O-Te) (Table II). Unlike these species the com-
plex 1, prepared from anhydrous acetonitrile, do
not exhibit bands in this region. The vibrational fre-
C(7)-Te(l)-0(1) 81.7(2) C( 1)-N( 1)-0( 1)
0(6)-Te(2)-0(5) 167.4(2) C(4)-N(4)-0(3)
0(6)-Te(2)-C(19) 83.9(2) N(l)-C(l)-C(2)
0(5)-Te(2)-C(19) 84.2(2) N(l)-C(l)-C(3)
0(6)-Te(2)-C(25) 90.3(4) C(2)-C(l)-C(3)
0(5)-Te(2)-C(25) 87.3(4) N(2)-C(2)-C(l)
115.9(7)
114.8(5)
120.8(7)
120.1(7)
119.1(7)
177(1)
C(19)-Te(2)-C(25) 98.1(4) 0(2)-C(3)-N(3) 123.1(8)
0(6)-Te(3)-C(31) 90.2(2) N(4)-C(4)-C(6)
0(6)-Te(3)-C(37) 90.6(2) C(5)-C(4)-C(6)
119.3(6)
118.2(6)
C(31)-Te(3)-C(37) 96.6(3) N(5)-C(5)-C(4) 179.3(8)
0(6)-Te(3)-0(3) 170.9(2) 0(4)-C(6)-N(6) 124.0(7)
C(31)-Te(3)-Q(3) 83.3(2) N(7)-C(43)-C(44) 172(4)
parameters and the orientation matrix for data collec-
tion were obtained from least-squares refinement, using
the setting angles of 24 reflections in the range 13 < quencies of the Te-C stretching are the same for all
6 < 15°. Intensity data of 7253 reflections were col-
lected at 293(2) K in the range 1.37 < 6 < 23.97°
using graphite monochromated MoKQ radiation (u;/20
scans, A = 0.71073 A, hk\ range 0 < h < 14, -13
< k < 14, -17 < / < 17). Corrections for Lorentz
and polarization effects were applied. The structure was
solved by direct methods and refined by full-matrix
least-squares techniques in the anisotropic approxima-
tion using SHELXL-93 [11, 12]. In the refinement 6899
independent reflections (/?int = 0.019) were used. The
NH2 hydrogen atoms were located from the difference-
Fourier syntheses and refined isotropically. The phenyl
hydrogen atoms were placed at calculated positions
compounds.
The IR spectra reveal substantially lower val-
ues of U(no) in the tellurium compounds as com-
pared with those of the ionic nitrosocarbamylcyan-
methanide in its Cs+ salt (Table II). A similar de-
crease of i'(NO) was also observed for number of
organotin [7] and organoantimony nitrosocarbamyl-
cyanmethanides [8] (for example Ph4 Sb{ACO}).
reflecting the coordination of the {ACO} group to
the central atom via the nitroso oxygen atom. It is in-
teresting to note that the ^(no> vibrational frequency
of the PhbTejACO}2 complex is lower than for the
with their isotropic U values set invariant at 0.06 A2. oxo compounds 2 and 3 (Table II). This suggests
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