Doklady Chemistry, Vol. 390, Nos. 4–6, 2003, pp. 162–167. Translated from Doklady Akademii Nauk, Vol. 390, No. 6, 2003, pp. 777–782.
Original Russian Text Copyright © 2003 by Ivanov, Ivakhnenko, Forsling, Gerasimenko.
CHEMISTRY
Single-Crystal X-ray Diffraction and CP/MAS 13C and 15N NMR
Study of Zinc N,N-Di-iso-butyldithiocarbamate Complex:
A Unique Structural Organization
A. V. Ivanov*, E. V. Ivakhnenko*, W. Forsling**, and A. V. Gerasimenko***
Presented by Academician V.I. Serginko November 25, 2002
Received December 12, 2002
Most zinc dithiocarbamate complexes have binu- iso-butyldithiocarbamato-S,s')zinc(II)], [Zn2{S2CN(iso-
clear molecular structures: [Zn2(S2CNR2)4] (R = CH3 C4H9)2}4], and mononuclear molecules of bis(N,N-di-
[1], C2H5 [2], C3H7 [3], iso-C3H7 [4], C4H9 [5]; or R2 = iso-butyldithiocarbamato-S,S')zinc(II), [Zn{S2CN(iso-
(CH2)4 [6]; R2 = (CH2)6 [7]; R2 = (CH3, C2H5), (CH3,
C3H7), (CH3, iso-C3H7), (CH3, C4H9) [8]; R2 = (C2H5,
cyclo-C6H11) [9]). In these compounds, pairs of ligands
have different structural functions: bidentate chelating
and bridging. The former ligands are involved in planar
four-membered metallacycles ZnS2C, whereas the
other two ligands act as bridges that link neighboring
zinc atoms into a dimer, which results in the formation
of an extended nonplanar eight-membered Zn2S4C2
metallacycle (a chair [2–10] or boat [1, 5] conforma-
tion). Therefore, each zinc atom has a distorted tetrahe-
dral or trigonal-bipyramidal environment of four
or five sulfur atoms. The only exception is the
mononuclear dicyclohexyldithiocarbamate complex
[Zn{S2CN(cyclo-C6H11)2}2], with a tetrahedral struc-
ture [9]. The presence of two bulky cyclic alkyl substit-
uents in the ligand renders the formation of the binu-
clear molecular structure sterically impossible.
C4H9)2}2], was prepared by reacting aqueous solutions
1
of ZnCl2 and Na{S2CN(iso-C4H9)2} · 3H2O. The
resulting solid was recrystallized from absolute etha-
nol. 13C and 15N NMR spectra were recorded on a Che-
magnetics Infinity CMX-360 spectrometer operating at
90.52 and 36.48 MHz, respectively, with a supercon-
ducting magnet (Ç0 = 8.46 T) and Fourier transform.
Proton cross polarization was used for recording the
spectra. To suppress 13C–1H and 15N–1H dipole–dipole
interactions, CW decoupling at the proton resonance
frequency was used [10]. Samples of the complexes
under study (~350 mg) were placed in a zirconia rotor
7.5 mm in diameter. In MAS 13C/15N NMR experi-
ments, the spinning frequency was 5000/3000(1) Hz;
the number of scans was 3000/20600; the proton π/2
pulse width was 5.0/5.0 µs; the 1H–13C/1H–15N contact
time was 3.0/2.0 ms; and the repetition time was 2.0/2.0 s.
Isotropic 13C NMR chemical shifts were measured
from tetramethylsilane. Isotropic 15N NMR chemical
shifts were measured from the signal of crystalline
NH4Cl (0 ppm; –341 ppm on the absolute scale [11]).
The homogeneity of the magnetic field was monitored
by measuring the width of the reference signal of crystal-
line adamantine with δ(13C) = 38.56 ppm, which was
In this work, we pioneered the synthesis of a zinc
dithiocarbamate complex with a unique structural orga-
nization. The latter was characterized by X-ray single-
crystal diffraction and CP/MAS 13C and 15N NMR data.
The unit cell of this complex concurrently contains
mono- and binuclear molecular species in a 1 : 1 ratio.
In both types of molecules, all six dithiocarbamate
ligands are structurally and NMR nonequivalent.
13
2.4 Hz. The ë/15N chemical shifts were corrected for
the magnetic field drift in the course of the experiments,
which constituted 0.098/0.032 Hz/h on the frequency
scale. To refine the chemical shifts and integrated inten-
sity ratios for overlapping signals in the 13C NMR spec-
tra, spectra were simulated piecewise with allowance for
the line position and width, as well as for the Lorentzian
and Gaussian contributions to the line shape.
The complex with the composition Zn3S12N6C54H108
(compound I), composed of binuclear molecules of
bis[µ-(N,N-di-iso-butyldithiocarbamato-S,S')(N,N-di-
* Amur Institute of Integrated Research, Amur Scientific
Center, Far East, Division, Russian Academy of Sciences,
Relochnyi per. 1, Blagoveshchensk, 675000 Russia
Unit cell parameters were determined and intensi-
ties of 28977 reflections (of them, 10284 unique reflec-
tions and 4547 reflections with I > 2σ(I)) were collected
** Luleå University of Technology, S-971 87 Luleå, Sweden
1
*** Institute of Chemistry, Far East Division,
Russian Academy of Sciences,
Sodium di-iso-butyldithiocarbamate was obtained by reacting
carbon disulfide with di-iso-butylamine in an alkaline medium.
pr. Stoletiya Vladivostoka 159, Vladivostok,
690022 Russia
Thermal analysis shows that the solid is a crystal hydrate. The
13
compound was additionally characterized by C NMR (Table 1).
0012-5008/03/0006-0162$25.00 © 2003 åÄIä “Nauka /Interperiodica”
Ivanov
