Octahedral nickel(II) hexamethyleneimine-dithiocarbamato complexes involving bidentate N,N-donor ligands

Article abstract of DOI:10.1016/j.ica.2011.03.010

The nickel(II) complexes of the compositions [Ni(hmidtc)(bpy) ₂]ClO₄ (I), [Ni(hmidtc)(phen)₂]ClO₄ (II), [Ni(hmidtc)(phen)₂]SCN (III), [Ni(hmidtc)(phen) ₂]PF₆ (IV), [Ni(hmidtc)(phen)₂]BPh₄ (V), [Ni(hmidtc)(phen)₂]AcO·2H₂O (VI) and [Ni(hmidtc)(phen)₂]Br·H₂O (VII), involving a combination of one hexamethyleneimine-dithiocarbamate anion (hmidtc) and two bidentate N,N-donor ligands (2,2′-bipyridine (bpy) for I or 1,10-phenanthroline (phen) for II-VII), have been prepared. The compounds were characterized by elemental analysis, molar conductivity measurements, UV-Vis and IR spectroscopy, magnetochemical measurements and thermal analysis. A single-crystal X-ray analysis of the complex I revealed a distorted octahedral geometry with the nickel(II) ion coordinated by four nitrogen atoms (from two bidentate-coordinated bpy molecules) and two sulfur atoms (from one bidentate-coordinated hmidtc anion), together giving an NiN₄S ₂ donor set.

Full text of DOI:10.1016/j.ica.2011.03.010

Inorganica Chimica Acta 373 (2011) 286–290
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Note
Octahedral nickel(II) hexamethyleneimine-dithiocarbamato complexes
involving bidentate N,N-donor ligands
a
b,
⇑
Richard Pastorek , Zdenek Trávnícek , Pavel Štarha b
ˇ
ˇ
a
´
Department of Inorganic Chemistry, Faculty of Science, Palacky University, 17. listopadu 12, CZ-771 46 Olomouc, Czech Republic
b Regional Centre of Advanced Technologies and Materials, Department of Inorganic Chemistry, Faculty of Science, Palacky´ University, 17. listopadu 12,
CZ-771 46 Olomouc, Czech Republic
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 8 October 2010
Received in revised form 22 February 2011
Accepted 3 March 2011
Available online 13 March 2011
The nickel(II) complexes of the compositions [Ni(hmidtc)(bpy)2]ClO4 (I), [Ni(hmidtc)(phen)2]ClO4 (II),
[Ni(hmidtc)(phen)2]SCN (III), [Ni(hmidtc)(phen)2]PF6 (IV), [Ni(hmidtc)(phen)2]BPh4 (V), [Ni(hmidtc)
(phen)2]AcOꢀ2H2O (VI) and [Ni(hmidtc)(phen)2]BrꢀH2O (VII), involving a combination of one hexameth-
yleneimine-dithiocarbamate anion (hmidtc) and two bidentate N,N-donor ligands (2,20-bipyridine
(bpy) for I or 1,10-phenanthroline (phen) for II–VII), have been prepared. The compounds were
characterized by elemental analysis, molar conductivity measurements, UV–Vis and IR spectroscopy,
magnetochemical measurements and thermal analysis. A single-crystal X-ray analysis of the complex I
revealed a distorted octahedral geometry with the nickel(II) ion coordinated by four nitrogen atoms
(from two bidentate-coordinated bpy molecules) and two sulfur atoms (from one bidentate-coordinated
hmidtc anion), together giving an NiN4S2 donor set.
Keywords:
Nickel(II) complexes
Hexamethyleneimine
Dithiocarbamate
X-ray structure
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
of such complexes have been determined and deposited within the
Cambridge Structural Database (CSD ver. 5.31, May 2010 update
A large number of nickel complexes involving various dithiocar-
bamate anions as ligands in the inner coordination sphere have
been described in the literature to date. Focusing on the hexameth-
yleneimine-dithiocarbamato (hmidtc) complexes of nickel, the
following substances have been reported: [Ni(X)(hmidtc)(Y)],
[8]) to date, namely [Ni(bzppzdtc)(phen)2]ClO4ꢀCHCl3 [6] and [Ni(-
pe2dtc)(phen)2]ClO4 [7]. Thus, only the third X-ray structure of a
nickel(II) complex of the above-mentioned [Ni(dtc)(N–N)2]+ type
is described herein, together with a series of the complexes I–VII
involving a dithiocarbamato ligand (hmidtc anion) different from
the mentioned complexes in combination with the bidentate N-do-
nor ligands (bpy in the case of I and phen in the case of II–VII) coor-
dinated to the metal center. The outer coordination sphere contains
where X = Clꢁ, Brꢁ, Iꢁ or NCSꢁ and Y = PPh3 or PBu3 [1]; [Ni(
l-SR)
(hmidtc)]2, where SR = thiophenol, 4-methylthiophenol, 2-thio-
naphthol, thiosalicylic acid, 1-hexanethiol or 1-butanethiol [2];
dppf = 1,10-bis(diphenylphos-
various anions, concretely ClO4 (I, II), SCNꢁ (III), PF6 (IV), BPh4
ꢁ
ꢁ
ꢁ
[Ni(hmidtc)(dppf)]ClO4,
phino)ferrocene [3]; [Ni2(
where
-dpph)(hmidtc)2X2], where dpph = 1,6-
l
(V), AcOꢁ (VI) and Brꢁ (VII).
bis(diphenylphosphino)hexane and X = Clꢁ, Brꢁ, Iꢁ or NCSꢁ [4];
[Ni(hmidtc)2X] and [Ni(hmidtc)2X2], where X = SbI3 or AsI3 [5]. As
for the octahedral nickel(II) complexes involving a different dithio-
carbamato ligand from hmidtc, we have to mention the [Ni(ndtc)
(phen)2]X and [Ni(ndtc)(bpy)2]ClO4 complexes [ndtc = N,N0-ben-
zyl-methyldithiocarbamate (bzmedtc), N,N0-dipentyldithiocarba-
mate (pe2dtc) and 4-benzylpiperazinedithiocarbamate anions
(bzppzdtc); X ¼ ClO4ꢁ or SCNꢁ] [6,7]. These complexes are structur-
ally analogical to the nickel(II) complexes I–VII reported herein, i.e.
the central Ni(II) ion is hexacoordinated by two bidentate N-donor
ligand and by one bidentate dithiocarbamate-based S-donor ligand
forming the [Ni(dtc)(N–N)2]+ type of complex. Two X-ray structures
2. Experimental
2.1. Starting materials
Chemicals and solvents employed in this work were purchased
from commercial sources (Sigma–Aldrich Co., Lachema Co., and
Fluka Co.). [Ni(hmidtc)2] was prepared according to a previously
described procedure [9].
2.2. Syntheses of nickel(II) complexes I–VII
The ethanolic (30 mL) suspension of powdered [Ni(hmidtc)2]
(1 mmol) was mixed with 4 molar equivalents of 2,20-bipyridyl
(I) or 1,10-phenanthroline (II) dissolved in 20 mL of ethanol. The
⇑
Corresponding author. Tel.: +420 585 634 352; fax: +420 585 634 954.
ˇ
E-mail address: zdenek.travnicek@upol.cz (Z. Trávnícek).
0020-1693/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.03.010

R. Pastorek et al. / Inorganica Chimica Acta 373 (2011) 286–290
287
mixture was stirred for 10 min at laboratory temperature. After
that, pulverized NiCl2ꢀ6H2O (1 mmol) and LiClO4ꢀ3H2O (2 mmol)
were poured into the reaction mixture which was afterwards re-
fluxed for 10 h. In the case of I, the clear red solution was cooled
down, filtered, and the filtrate was left to crystallize at laboratory
temperature. The product, which formed in 5 days, was filtered
off, washed with diethyl ether and dried at 40 °C under an infrared
lamp. Some of the obtained crystals were suitable for a single crys-
tal X-ray analysis. As for II, the hot solution was filtered and the
powder product formed while the solution was cooling down. It
was filtered off, washed with hot distilled water, ethanol and
diethyl ether and dried at 40 °C under an infrared lamp. The syn-
theses of III–VII are similar to that of II, but KSCN (for III), K[PF6]
(for IV) or Na[BPh4] (for V) was used instead of LiClO4ꢀ3H2O.
VI and VII were prepared by the reactions of [Ni(hmidtc)2]
(1 mmol), 1,10-phenanthroline (4 mmol) and Ni(CH3COO)2ꢀ4H2O
(1 mmol; VI) or NiBr2ꢀ3H2O (1 mmol; VII) which were suspended
in 30 mL of ethanol and the suspension was refluxed for 4 h.
I: Red crystals. Yield: 77%. Anal. Calc. for C27H28N5ClO4S2Ni
(Mr = 644.8): C, 50.3; H, 4.4; N, 10.8; Cl, 5.5; Ni, 9.1. Found: C,
50.1; H, 4.6; N, 11.1; Cl, 5.8; Ni, 9.0%. II: Light brown powder. Yield:
77%. Anal. Calc. for C31H28N5O4S2ClNi (Mr = 692.9): C, 53.7; H, 4.1;
N, 10.1; Cl, 5.1; Ni, 8.5. Found: C, 53.4; H, 4.2; N, 9.8; Cl, 4.8; Ni,
9.1%. III: Red crystals. Yield: 85%. Anal. Calc. for C32H28N6S3Ni
(Mr = 651.5): C, 59.0; H, 4.3; N, 12.6; Ni, 9.0. Found: C, 58.6; H,
4.7; N, 12.9; Ni, 8.8%. IV: Red-brown powder. Yield: 68%. Anal. Calc.
for C31H28N5F6PS2Ni (Mr = 738.4): C, 50.4; H, 3.8; N, 9.5; Ni, 7.9.
Found: C, 50.0; H, 3.7; N, 9.3; Ni, 7.7%. V: Orange-brown powder.
Yield: 73%. Anal. Calc. for C55H48N5BS2Ni (Mr = 912.6): C, 72.4; H,
5.3; N, 7.7; Ni, 6.4. Found: C, 72.1; H, 4.9; N, 7.3; Ni, 6.6%. VI: Brown
and bromine contents were determined using the Schöniger meth-
od. The nickel content was determined by the chelatometric titra-
tion with murexide as an indicator. The measurements of the room
temperature magnetic susceptibilities were performed using the
Faraday method with a laboratory designed instrument with a Sar-
torius 4434 MP-8 microbalance; Co[Hg(NCS)4] was used as a cali-
brant and the correction for diamagnetism was performed using
Pascal constants [10]. The molar conductivity of the 10ꢁ3 M nitro-
methane solutions was measured by an LF 330/SET conductometer
(WTW GmbH) at 25 °C. Electronic absorption spectra (10ꢁ3 M DMF
solutions) and diffuse-reflectance spectra were recorded on a Spe-
cord M40 device (nujol technique). IR spectra (450–4000 cmꢁ1 re-
gion; KBr pellets) were recorded on a Perkin-Elmer Spectrum one
FT-IR spectrometer. Thermogravimetric (TG) and differential ther-
mal (DTA) analyses were performed simultaneously by an Exstar
TG/DTA 6200 (Seiko Instruments Inc.) in a dynamic air atmosphere
(100 mL minꢁ1
)
from laboratory temperature to 1050 °C
(2.5 °C minꢁ1 gradient).
X-ray data of the selected crystal of [Ni(hmidtc)(bpy)2](ClO4) (I)
was collected on an Xcalibur™2 diffractometer (Oxford Diffraction
Ltd.) with a Sapphire2 CCD detector, and with Mo K
a radiation
(Monochromator Enhance, Oxford Diffraction Ltd.). Data collection
and reduction were performed using the CrysAlis software [11].
The same software was used for data correction for an absorption
effect by the empirical absorption correction using spherical har-
monics, implemented in SCALE3 ABSPACK scaling algorithm. The
structure was solved by direct methods using SHELXS-97 and refined
on F2 using the full-matrix least-squares procedure (SHELXL-97) [12].
Non-hydrogen atoms were refined anisotropically and hydrogen
atoms were located in a difference map and refined using the rid-
ing model with C–H = 0.95 and 0.99 Å, N–H = 0.88 Å and Uiso(-
H) = 1.2Ueq(CH, CH2, NH) or 1.5Ueq(CH3). The crystal data and
structure refinement are given in Table 1. The molecular graphics
as well as additional structural calculations were drawn and inter-
preted using DIAMOND [13].
powder. Yield: 81%. Anal.
Calc. for
C
33H31N5O2S2Niꢀ2H2O
(Mr = 688.5): C, 57.3; H, 5.1; N, 10.2; Ni, 8.5. Found: C, 57.6; H,
5.3; N, 10.1; Ni, 8.2%. VII: Light-brown powder. Yield: 76%. Anal.
Calc. for C31H28N5BrS2NiꢀH2O (Mr = 691.3): C, 53.9; H, 4.4; N,
10.1; Cl, 11.6; Ni, 8.5. Found: C, 53.5; H, 4.5; N, 10.2; Cl, 11.1; Ni,
8.5%. A schematic representation of the composition of the com-
plexes I–VII is depicted in Scheme 1.
3. Results and discussion
The values of molar conductivity of nitromethane solutions of I–
VII range from 79.6 to 93.4 S cm2 molꢁ1 (Table 2), which are typical
2.3. Methods
Elemental analyses (C, H, N) were performed on a Fisons
EA-1108 CHNS-O Elemental Analyzer (Thermo Scientific). Chlorine
Table 1
Crystal data and structure refinement for [Ni(hmidtc)(bpy)2]ClO4 (I).
Formula
Formula weight
C27H28N5ClO4S2Ni
644.82
T (K)
100(2)
k (Å)
0.71073
Crystal system, space group
monoclinic, C2/c
Unit cell dimensions
a (Å)
b (Å)
c (Å)
15.3888(3)
23.8055(5)
15.7739(3)
a
(°)
90.00
b (°)
103.630(2)
c
(°)
90.00
5615.9(2)
8, 1.525
0.978
V (Å3)
Z, Dcalc (g cmꢁ3
)
Absorption coefficient (mmꢁ1
Crystal size (mm)
)
0.30 ꢂ 0.20 ꢂ 0.20
F (0 0 0)
2672
h range for data collection (°)
Index ranges (h, k, l)
2.91 6 h 6 25.00
ꢁ18 6 h 6 18
ꢁ28 6 k 6 28
ꢁ15 6 l 6 18
26 391/4947 (0.0249)
4947/0/361
1.001
Reflections collected/unique (Rint
Data/restraints/parameters
Goodness-of-fit (GOF) on F2
)
Final R indices [I > 2
r
(I)]
R1 = 0.0266, wR2 = 0.0770
R1 = 0.0318, wR2 = 0.0786
0.855, ꢁ0.293
R indices (all data)
Largest peak and hole (e Åꢁ3
)
Scheme 1. Composition of the prepared nickel(II) complexes I–VII.

288
R. Pastorek et al. / Inorganica Chimica Acta 373 (2011) 286–290
Table 2
Magnetic, molar conductivity, UV–Vis and IR data for complexes I–VII.
a
Complex
leff
lB
/
kM
UV–Vis (ꢂ 103 cmꢁ1
)
IR (cmꢁ1
)
Diffuse-reflectance
Solution
m(Cꢀ ꢀ ꢀS)
m(Cꢀ ꢀ ꢀN) Other
( )
eb
4ClO4ꢁ)], 1072s [(
m
3ClO4ꢁ)]
3ClO4ꢁ)]
mas(C„N)]
[Ni(hmidtc)(bpy)2]ClO4 (I)
[Ni(hmidtc)(phen)2]ClO4 (II)
[Ni(hmidtc)(phen)2]SCN (III)
[Ni(hmidtc)(phen)2]PF6 (IV)
[Ni(hmidtc)(phen)2]BPh4 (V)
[Ni(hmidtc)(phen)2]AcOꢀ2H2O
(VI)
3.07
3.10
3.07
3.02
3.13
3.02
93.4 11.7, 19.8, 27.8, 32.1
88.4 11.8, 19.4, 29.7, 34.1, 36.3, 42.1, 44.7
89.2 11.6, 19.6, 29.2, 32.4
90.1 11.9, 19.6, 28.7, 33.4, 40.4
79.6 11.6, 19.2, 26.9, 32.9, 40.0
88.3 11.5, 19.4, 25.9, 29.7, 35.3, 36.2, 37.0
11.6 (23.7) 984m
11.5 (26.5) 982m
12.6 (13.2) 964m
11.6 (19.2) 982m
11.6 (18.9) 982m
11.5 (15.2) 980m
1514m
1515m
1508m
1516m
1515s
623s [(
m
623s [
740w [
839s [(
m
4(ClO4–)], 1088s [(m
m
m
(C–S)], 2048 m [
PF6ꢁ)]
1515s
[Ni(hmidtc)(phen)2]BrꢀH2O (VII) 3.15
87.5 11.5, 19.3, 26.2, 30.4, 32.9, 34.9, 35.8,
39.9
11.5 (23.0) 982m
1514s
a
S cm2 molꢁ1
.
b
dm3 molꢁ1 cmꢁ1
.
ꢁ
values for the 1:1 electrolyte type in the solvent used [14]. The
magnetochemical measurements proved paramagnetic behavior
of III, and PF6 anion in the structure of IV was also detected by IR
spectroscopy (Table 2) [21–23].
of the complexes I–VII with two unpaired electrons (3.02–
3.15 leff/lB, see Table 2), thus indirectly showing on the presence
of a hexacoordinated nickel(II) ion and octahedral geometry
around the metal center [15].
Three maxima, characteristic for the d–d transitions of the
octahedral nickel(II) complexes, were detected in the diffuse-
reflectance UV–Vis spectra of the studied compounds at 11
The thermal analysis proved the complexes I–V to be non-sol-
vated and VI and VII solvated (see Appendix A Supplementary
material). The thermal decay of VI and VII started right after the
beginning of the analyses as a consequence of the water molecules
of crystallization elimination (two for VII and one for VI) from the
structure of the mentioned complexes.
The X-ray crystal structure of [Ni(hmidtc)(bpy)2](ClO4) (I) con-
tains the [Ni(hmidtc)(bpy)2]+ cations and perchlorate anions with
the shortest Ni1ꢀ ꢀ ꢀCl1 contact of 6.8902(5) Å (Fig. 1). The Ni(II)
atom is coordinated by three bidentate ligands, i.e. by one S-donor
hexamethyleneimine-dithiocarbamate anion (hmidtc) and two N-
donor 2,20-bipyridine molecules (bpyA containing N2 and N3 atoms
and bpyB containing N4 and N5 atoms), thus forming the distorted
octahedral arrangement in the vicinity of the metal center. The
bond lengths between the Ni(II) center and donor atoms S1, S2,
N2, N3, N4 and N5 (see Table 3) did not exceed the interval found
for nickel(II) complexes involving bidentate-coordinated dithiocar-
bamate (2.164–2.485 Å, an average value of 2.211 Å) and with the
2,20-bipyridine molecule coordinated through both nitrogen atoms
(1.963–2.153 Å, an average value of 2.083 Å), as it has been found
for the compounds deposited in the Cambridge Structural Database
(CSD ver. 5.31, May 2010 update) [8].
500–11 900 cmꢁ1 for the electronic transition 3A2g ? 3T2g
(
m
1),
and 25 900–
3) [16–18]. The bands, whose
19 200–19 800 cmꢁ1 for 3A2g ? 3T1g (F)
29 700 cmꢁ1 for 3A2g ? 3T1g (P) (
(m2)
m
maxima exceeded 30 000 cmꢁ1, may be assigned to intraligand
charge-transfer transitions. Table 3 also shows the position of the
maxima observed in the electronic UV–Vis spectra of the 10ꢁ3
DMF solutions of I–VII together with the appropriate molar
absorption coefficient values. These bands are again assignable to
the above-described d–d transitions.
The bands of the vibrations characteristic for dithiocarbamtes,
i.e.
m
(Cꢀ ꢀ ꢀS) and (Cꢀ ꢀ ꢀN), were detected in the IR spectra of the pre-
m
pared nickel(II) complexes (Table 2) [19,20]. The presence of the
ClO4 anion in the structure of I and II, SCNꢁ anion in the structure
ꢁ
The dihedral angles formed by the planes created through the
selected atoms of the mentioned ligands and central atom (Ni1–
Table 3
Selected bond lengths (Å) and angles (°) of [Ni(hmidtc)(bpy)2]ClO4 (I).
Compound
I
Bond lengths
Ni1–S1
Ni1–S2
Ni1–N2
Ni1–N3
Ni1–N4
Ni1–N5
N2–C10
N2–C14
N3–C15
N3–C19
N4–C20
N4–C24
N5–C25
N5–C29
S1–C1
N3–Ni1–S1
N3–Ni1–S2
N4–Ni1–N5
N4–Ni1–S1
N4–Ni1–S2
N5–Ni1–S1
N5–Ni1–S2
S1–Ni1–S2
Ni1–N2–C10
Ni1–N2–C14
Ni1–N3–C15
Ni1–N3–C19
Ni1–N4–C20
Ni1–N4–C24
Ni1–N5–C25
Ni1–N5–C29
Ni1–S1–C1
93.39(4)
96.00(4)
78.20(6)
172.91(5)
102.97(4)
95.37(4)
89.10(4)
73.69(2)
126.52(13)
114.23(12)
114.64(12)
126.92(13)
126.40(13)
114.74(13)
114.47(12)
126.31(13)
85.74(6)
2.4022(5)
2.4625(5)
2.073(2)
2.069(2)
2.101(2)
2.094(2)
1.341(2)
1.349(2)
1.351(2)
1.344(2)
1.345(3)
1.343(3)
1.350(2)
1.345(2)
1.719(2)
1.725(2)
S2–C1
Bond angles
N2–Ni1–N3
N2–Ni1–N4
N2–Ni1–N5
N2–Ni1–S1
N2–Ni1–S2
N3–Ni1–N4
N3–Ni1–N5
Ni1–S2–C1
C10–N2–C14
C15–N3–C19
C20–N4–C24
C25–N5–C29
S1–C1–N1
83.73(6)
118.6(2)
118.2(2)
118.4(2)
79.50(6)
91.69(6)
97.41(6)
92.11(4)
164.93(4)
93.19(6)
170.83(6)
118.0(2)
121.13(14)
115.78(11)
123.09(14)
Fig. 1. The molecular structure of [Ni(hmidtc)(bpy)2]ClO4 (I) with non-hydrogen
atoms drawn as thermal ellipsoids at the 50% probability level, the hydrogen atoms
and perchlorate anion were omitted for clarity.
S1–C1–S2
S2–C1–N1

R. Pastorek et al. / Inorganica Chimica Acta 373 (2011) 286–290
289
Fig. 2. Part of the crystal structure of the complex I showing selected non-covalent interactions of the C–Hꢀ ꢀ ꢀO, C–Hꢀ ꢀ ꢀS, C–Hꢀ ꢀ ꢀC and Cꢀ ꢀ ꢀC types (dashed green lines);
hydrogen atoms not involved in the depicted interactions were omitted for clarity. The d(D–H), d(Hꢀ ꢀ ꢀA), d(Dꢀ ꢀ ꢀA) and \(DHA) parameters are equaled to 0.990 Å, 2.876(2) Å,
3.726(3) Å and 144.40(14)° for C5–H5Aꢀ ꢀ ꢀC16i, 0.950 Å, 2.8316(4) Å, 3.557(2) Å and 133.92(12)° for C12–H12Aꢀ ꢀ ꢀS1ii, 0.950 Å, 2.6192(14) Å, 3.479(2) Å and 150.71(12)° for
C13–H13Aꢀ ꢀ ꢀO2iii, 0.950 Å, 2.6639(14) Å, 3.315(2) Å and 126.21(12)° for C13–H13Aꢀ ꢀ ꢀO4iii, 0.950 Å, 2.6016(13) Å, 3.547(2) Å and 173.07(12)° for C16–H16Aꢀ ꢀ ꢀO2iii, 0.950 Å,
2.8373(5) Å, 3.743(2) Å and 159.69(13)° for C26–H26Aꢀ ꢀ ꢀS2iv, 0.950 Å, 2.4490(14) Å, 3.224(3) Å and 138.76(13)° for C27–H27Aꢀ ꢀ ꢀO2iv and C21ꢀ ꢀ ꢀC21iv = 3.286(3) Å. Symmetry
codes: i = 0.5 ꢁ x, y ꢁ 0.5, 0.5 ꢁ z; ii = ꢁx, 1 ꢁ y, ꢁz; iii = 0.5 ꢁ x, y + 0.5, 0.5ꢁz; iv = 1 ꢁ x, y, 0.5 ꢁ z. (For interpretation of the references to color in this figure legend, the reader
is referred to the web version of this article.)
S1–C1–S2 for hmidtc, Ni1–N2–C14–C15–N3 for bpyA and Ni1–N4–
C24–C25–N5 for bpyB) equal 86.43(3)° (between hmidtc and bpyA),
85.34(4)° (between hmidtc and bpyB) and 86.77(5)° (between bpyA
and bpyB). The deviations of the donor atoms from the mentioned
planes were found to be ꢁ0.0082(5) Å (S1), ꢁ0.0080(5) Å (S2),
0.038(2) Å (N2), ꢁ0.001(2) Å (N3), 0.035(2) Å (N4) and 0.083(2) Å
(N5). Two rings of each bpy molecule formed the dihedral angles
of 11.88(5)° (for bpyA) and 15.83(6)° (for bpyB), which shows on
the substantial deformation of the bpy ligands.
The C–Hꢀ ꢀ ꢀO, C–Hꢀ ꢀ ꢀS, C–Hꢀ ꢀ ꢀC, Cꢀ ꢀ ꢀO and Cꢀ ꢀ ꢀC van der Waals
non-covalent contacts stabilize the secondary structure of the
complex I, a part of which is, together with the parameters of the
detected non-covalent contacts, given in Fig. 2.
In summary, a series of seven octahedral nickel(II) dithiocarb-
amato complexes involving a combination of the hexamethylenei-
mine-dithiocarbamate anion (hmidtc) and 2,20-bipyridine (I) or
1,10-phenanthroline (II–VII) were prepared and characterized by
various techniques including the single-crystal X-ray analysis of
the complex [Ni(hmidtc)(bpy)2]ClO4 (I). The molecular structure
of I represents a rare structural type among numerous nickel
dithiocarbamato complexes. Concretely, it is only the third exam-
ple of the complexes involving two bidentate-coordinated N-donor
Sports of the Czech Republic (a Grant No. MSM6198959218). The
authors also thank Mrs. Pavla Richterová for performing CHN ele-
ˇ
ˇ
mental analyses, and Assoc. Prof. Zdenek Šindelár for magnetic sus-
ceptibility measurements.
Appendix A. Supplementary material
CCDC 796091 for [Ni(hmidtc)(bpy)2](ClO4) (I) contains the sup-
plementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif. TG and DTA data
and curves of I–VII are given in Fig. S1. Supplementary data asso-
ciated with this article can be found, in the online version, at
doi:10.1016/j.ica.2011.03.010.
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