Synthesis and characterization of Co(II), Ni(II), and Cu(II) complexes containing an eight-membered disulfanenitrile chelating ring

Article abstract of DOI:10.1016/j.ica.2008.01.036

New types of λ⁶-sulfanenitrile-transition metal complexes, [MCl₂(ndsdsd)] (1) and [M(ndsdsd)₂]Cl₂ (2) (M = Co(II), Ni(II), Cu(II)), were obtained by reacting MCl₂ with bis[(nitrilo(diphenyl)-λ⁶

Full text of DOI:10.1016/j.ica.2008.01.036

Available online at www.sciencedirect.com
Inorganica Chimica Acta 361 (2008) 2540–2546
www.elsevier.com/locate/ica
Synthesis and characterization of Co(II), Ni(II), and Cu(II)
complexes containing an eight-membered disulfanenitrile chelating ring
a,
a
a
b
*
Takayoshi Fujii , Mihoko Kanno , Mitsuo Hirata , Tsukasa Nakahodo ,
Takatsugu Wakahara b, Takeshi Akasaka b
a Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Izumi-cho, Narashino, Chiba 275-8575, Japan
b Center for Tsukuba Advanced Research Alliance, University of Tsukuba, Tsukuba, Ibaraki 305-8577, Japan
Received 28 August 2007; received in revised form 25 January 2008; accepted 30 January 2008
Available online 7 February 2008
Abstract
New types of k6-sulfanenitrile–transition metal complexes, [MCl2(ndsdsd)] (1) and [M(ndsdsd)2]Cl2 (2) (M = Co(II), Ni(II), Cu(II)),
were obtained by reacting MCl2 with bis[(nitrilo(diphenyl)-k6-sulfanyl)](diphenyl)-k6-sulfanediimide Ph2S(@N–(Ph2)S„N)2 (ndsdsd).
The crystal structures of these complexes have been elucidated by X-ray crystallographic analysis. The results revealed that, in complexes
1 and 2, the two terminal nitrogen atoms chelate to the metal center to form an eight-membered sulfur–nitrogen ring.
Ó 2008 Elsevier B.V. All rights reserved.
Keywords: k6-Sulfanenitrile; Sulfur–nitrogen ligand; Sulfur–nitrogen multiple bonds; Transition–metal complexes; X-ray structures
1. Introduction
the multifunctional ligand coordinates exclusively through
the nitrogen atom of the SN triple bond and the alternating
double-single-triple bond in the SNSN backbone of the
ligand is maintained in the complexes. Very recently, we
have succeeded in synthesizing a new type of k6-sulfanenit-
rile with an SN triple bond at both ends, bis[(nitrilo(diphe-
nyl)-k6-sulfanyl)](diphenyl)-k6-sulfanediimide Ph2S(@N–
(Ph2)S„N)2 (ndsdsd) [3]. This compound was prepared
in an excellent yield from the one-pot synthesis of
diphenylsulfimide (Ph2SNH) with fluoro(diphenyl)-k6-sul-
fanenitrile (Ph2FS„N) [4] in the presence of 1,8-diazabicy-
clo[5.4.0]undec-7-ene (DBU), and its molecular structure
has been elucidated by X-ray crystallographic analysis.
Moreover, the nucleophilic character of both end terminal
nitrogen atoms in ndsdsd can be recognized in alkylation
and sulfonation to yield the corresponding bis-iminosulfo-
nium salts [3]. The aryl substituted k6-sulfanenitriles such
as Ph2RS„N [R = e.g. Ph, Me, Ph2(X)S@N– (X = LP,
HN@, O@), Ph2(HN@)S@C–] are much more stable even
under acidic or alkaline conditions and have a much higher
basicity of thiazyl nitrogen (SVI„N) than the above fluoro
derivatives [5]. In particular, Ph3S„N reacted with several
electrophiles and CuCl2 to give the corresponding
The coordination chemistry of sulfur–nitrogen ligands
has been extensively studied and has shown a unique variety
of structures with a range of bonding modes [1,2]. The most
commonly used starting material for the preparation of
metal sulfur–nitrogen complexes is S4N4, which reacts with
a wide range of transition metal species. (Me3SiNSN)2S has
also been used to generate palladium complexes of the
[S2N3]À anion [1c].
Glemser and Mews have reported that F3S„N and
F2RS„N (R = e.g. Me2N–, F2(O@)S@N–) can easily be
introduced into transition metal complexes by SO2 dis-
placement reactions [2]. Among these ligands, F2(O@)S@
N–(F2)S„N has attracted special attention because of
the structural properties of the complexes prepared with
metal cations [2d,2f]. The X-ray structures of cobalt(II)
and copper(II) complexes which were obtained from the
reaction with [M(SO2)n][AsF6]2 (M = Co, Cu) show that
*
Corresponding author. Fax: +81 47 474 2579.
E-mail address: t5fujii@cit.nihon-u.ac.jp (T. Fujii).
0020-1693/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2008.01.036

T. Fujii et al. / Inorganica Chimica Acta 361 (2008) 2540–2546
2541
iminosulfonium salts ([Ph3S@N–R][X]: R = alkyl, tosyl,
acyl, NO2) and complexes ([CuCl2(l-NSPh3)]2 and
[CuCl2(Ph3SN)2]) [6]. The ndsdsd ligand has very interest-
ing properties in metal complexes because of the electron-
donating nature of the terminal thiazyl nitrogens, therefore
reactions of ndsdsd with transition metal salts such as
CoCl2, NiCl2, and CuCl2 were performed to prepare their
metal complexes. Here, we report the synthesis and the
structural and spectroscopic characterizations of ndsdsd–
Co(II), –Ni(II), and –Cu(II) complexes with eight-mem-
bered sulfur–nitrogen chelate rings.
Anal. Calc. for C36H32Cl2N4NiOS3: C, 56.71; H, 4.23; N,
7.35; Found: C, 56.66; H, 3.88; N, 7.37%.
2.2.1.3. Data for 1c. Dark yellow; Yield 95%, relative to
ndsdsd Á 2H2O; 208–210 °C (decomp., monohydrate); IR
(KBr) 3443, 1271, 1246, 1076, 1030, 984 cmÀ1; UV–Vis
(MeOH, kmax, nm (e, MÀ1 cmÀ1)) 208 (5.18 Â 104), 396
(sh) (7.70 Â 102); Anal. Calc. for C36H32Cl2CuN4OS3: C,
56.35; H, 4.20; N, 7.30; Found: C, 56.36; H, 3.88, N, 7.21%.
2.2.2. Preparation of [M(ndsdsd)2]Cl2 (M = Co(II) (a),
Ni(II) (b), Cu(II) (c)) (2)
2. Experimental
A solution of MCl2 (0.1 mmol) in methanol (1.0 ml) was
slowly added to a solution of ndsdsd Á 2H2O (325 mg,
0.5 mmol) in the same solvent (1.0 ml) at ambient temper-
ature. After stirring for 3 h, the solution was precipitated
with ether. The precipitate was then filtered, washed with
methanol and dried under vacuum at 100 °C for 24 h, but
appeared to be hygroscopic. X-ray quality crystals were
obtained by the slow diffusion of ether into methanol solu-
tions of 2a–c.
2.1. Material and general methods
All reagents and solvents were obtained commercially
and were further purified by general methods when neces-
sary. All NMR spectra were obtained with a Bruker
Avance-400S with TMS as the internal standard. IR spec-
tra were recorded on a Shimadzu FTIR-8400S spectrome-
ter. UV–vis spectra were recorded on a Jasco V-550
spectrometer. Melting points were measured on a Yanaco
Mp-J3 melting point apparatus. Elemental analyses were
carried out at the Chemical Analysis Center of the College
of Science and Technology, Nihon University.
2.2.2.1. Data for 2a. Dark blue; Yield 97%, relative to
CoCl2; 165–166 °C (decomp., dihydrate); IR (KBr) 3404,
1261, 1074, 1034, 984 cmÀ1; UV–Vis (MeOH, kmax, nm
(e, MÀ1 cmÀ1)) 208 (1.37 Â 105), 670 (9.00 Â 102); Anal.
Calc. for C72H64Cl2CoN8O2S6: C, 61.97; H, 4.62; N, 8.03;
Found: C, 61.89, H, 4.44, N, 8.00%.
2.2. Syntheses
The ligand, Ph2S(@N–(Ph2)S„N)2 (ndsdsd) was synthe-
sized as previously described [3].
2.2.2.2. Data for 2b. Dark blue; Yield 98%, relative to
NiCl2Á6H2O; 165–167 °C (decomp., dihydrate); IR (KBr)
nm (e, MÀ1 cmÀ1)) 207 (1.09 Â 105), 694 (2.10 Â 102); Anal.
Calc. for C72H64Cl2N8NiO2S6: C, 61.98; H, 4.62; N, 8.03;
Found: C, 62.18, H, 4.43, N, 8.04%.
3382, 1261, 1074, 1031, 984 cmÀ1; UV–Vis (MeOH, kmax
,
2.2.1. Preparation of [MCl2(ndsdsd)] (M = Co(II) (a),
Ni(II) (b), Cu(II) (c)) (1)
A solution of ndsdsd Á 2H2O (65 mg, 0.1 mmol) in meth-
anol (1.0 ml) was slowly added to a solution of MCl2
(0.5 mmol) in the same solvent (0.5 ml) at ambient temper-
ature, which started to precipitate a solid within 1 min (the
solution of 2a was precipitated with ether). The precipitate
was then filtered, washed with methanol and dried under
vacuum at 100 °C for 24 h, but appeared to be hygroscopic.
Crystals suitable for X-ray analysis were obtained from sat-
urated methanol (1a), methanol–ether (1b), and dichloro-
methane–methanol–ether (1c).
2.2.2.3. Data for 2c. Dark green; Yield 98%, relative to
CuCl2; 162–164 °C (decomp., dihydrate); IR (KBr) 3406,
1283, 1236, 1078, 1037, 986 cmÀ1; UV–Vis (MeOH, kmax
,
nm (e, MÀ1 cmÀ1)) 208 (1.13 Â 105), 383 (6.75 Â 103); Anal.
Calc. for C72H64Cl2N8CuO2S6: C, 61.76; H, 4.61; N, 8.00;
Found: C, 61.83; H, 4.45; N, 7.96%.
2.3. X-ray crystallography
2.2.1.1. Data for 1a. Dark blue; Yield 94%, relative to
ndsdsd Á 2H2O; mp 232–233 °C (decomp., monohydrate);
IR (KBr) 3443, 1285, 1076, 1032, 984 cmÀ1; UV–Vis
(MeOH, kmax, nm (e, MÀ1 cmÀ1)) 207 (5.37 Â 104), 670
(3.90 Â 102); Anal. Calc. for C36H32Cl2CoN4OS3: C,
56.69; H, 4.23; N, 7.35; Found: C, 56.53; H, 3.88; N, 7.36%.
Diffraction data were collected with a Rigaku RAXIS
RAPID imaging plate using graphite-monochromated
Mo Ka radiation (k = 0.71075 A). The data were corrected
˚
for Lorentz and polarization effects, and an empirical
absorption correction was applied which resulted in trans-
mission factors (see Tables 1 and 2). Structures 1a–c and
2a–c were solved by the direct method using SHELXS-97
and were refined using SHELXL-97 [7]. Crystal data for
[CoCl2(ndsdsd)] (1a), [NiCl2(ndsdsd)] (1b), [CuCl2(ndsdsd)]
(1c), [Co(ndsdsd)2]Cl2 (2a), [Ni(ndsdsd)2]Cl2 (2b), and
[Cu(ndsdsd)2]Cl2 (2c) are given in Tables 1 and 2.
2.2.1.2. Data for 1b. Dark blue; Yield 98%, relative to
ndsdsd Á 2H2O; 237–239 °C (decomp., monohydrate); IR
(KBr) 3383, 1277, 1076, 1031, 984 cmÀ1; UV–Vis (MeOH,
k
max, nm (e, MÀ1 cmÀ1)) 206 (6.19 Â 104), 694 (0.92 Â 102);

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T. Fujii et al. / Inorganica Chimica Acta 361 (2008) 2540–2546
Table 1
Crystallographic data for compounds 1a–c
1a
1b
1c
Formula
Fw
C36H30Cl2CoN4S3
744.65
C36H30Cl2N4NiS3
744.43
C36H30Cl2CuN4S3
749.26
Crystal size (mm)
Temperature (K)
0.40 Â 0.09 Â 0.06
0.48 Â 0.38 Â 0.36
0.51 Â 0.43 Â 0.14
123(2)
123(2)
123(2)
˚
k (A)
0.71075
0.71075
0.71075
Crystal system
Space group
orthorhombic
Pbca
orthorhombic
Pbca
orthorhombic
Pbca
˚
a (A)
16.696(3)
17.612(3)
22.944(3)
90.00
90.00
90.00
6746.9(17)
8
1.466
0.886
3064
16.5832(18)
17.568(3)
22.977(4)
90.00
90.00
90.00
6694.1(17)
8
1.477
0.960
3072
16.315(2)
17.785(3)
22.955(3)
90.00
90.00
90.00
6660.6(18)
8
1.494
1.038
3080
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
3
˚
V (A )
Z
qc (Mg/m3)
l (mmÀ1
F(000)
)
Tmin/Tmax
h Range (°)
Reflections collected
Independent reflections
Rint
0.7182/0.9488
3.02–27.48
61237
7714
0.095
0.6558/0.7238
3.03–27.48
60522
7640
0.026
0.6196/0.8683
3.06–27.48
60478
7625
0.042
Data/restrains/parameters
R1, wR2 (I > 2r[I])
R1, wR2 (all data)
Goodness-of-fit on F2
7714/0/415
0.0396, 0.0752
0.0643, 0.0827
1.026
7640/0/415
0.0309, 0.0796
0.0345, 0.0816
1.073
7625/0/536
0.0269, 0.0665
0.0320, 0.0691
1.043
Table 2
Crystallographic data for compounds 2a–c
2a Á 2MeOH Á 10.5H2O
2b
2c Á 4H2O
Formula
C
O
74H89Cl2CoN8
12.5S6
C72H60Cl2N8
NiS6
C72H68Cl2Cu
N8O4S6
Fw
1612.72
0.61 Â 0.60 Â 0.33
90(2)
0.71075
monoclinic
P21/a
1359.25
0.34 Â 0.19 Â 0.15
90(2)
0.71075
monoclinic
P21/c
1436.14
Crystal size (mm)
Temperature (K)
0.23 Â 0.20 Â 0.17
123(2)
˚
k (A)
0.71075
monoclinic
P21/c
Crystal system
Space group
˚
a (A)
17.544(3)
23.162(4)
21.496(4)
90.00
10.146(2)
17.284(4)
17.518(4)
90.00
10.470(3)
18.848(4)
17.112(6)
90.00
˚
b (A)
˚
c (A)
a (°)
b (°)
111.023(6)
90.00
8154(3)
93.260(9)
90.00
3067.1(12)
2
1.472
0.661
91.751(12)
90.00
3375.1(16)
2
1.405
0.645
c (°)
V (A3)
Z
4
qc (Mg/m3)
1.314
0.492
l (mmÀ1
)
h Range (°)
F(000)
2.98–23.26
3384
2.99–27.48
1412
3.03–27.49
1478
Tmin/Tmax
0.7535/0.8545
46760
11655
0.8064/0.9073
29012
7004
0.8659/0.8983
13082
7692
Reflections collected
Independent reflections
Rint
0.0456
0.0270
0.0359
Data/restrains/parameters
R1, wR2 (I > 2r[I])
R1, wR2 (all data)
Goodness-of-fit on F2
11655/0/1000
0.0649, 0.1671
0.0763, 0.1746
1.042
7004/0/524
0.0313, 0.0897
0.0362, 0.0918
1.141
7692/0/551
0.0571, 0.1286
0.0890, 0.1449
1.041

T. Fujii et al. / Inorganica Chimica Acta 361 (2008) 2540–2546
2543
[MCl2(ndsdsd)] (1)
Cl(1)
Ph
S
Ph
S
Ph
S
C(1)
N
N
N
N
Ph
Ph
Ph
Cl(2)
ndsdsd
N(1)
S(1)
[M(ndsdsd)2]Cl2 (2)
Co(1)
M = Co(II) (a), Ni(II) (b), Cu(II) (c)
N(2)
Scheme 1. Synthesis of 1 and 2.
C(2)
C(4)
N(4)
C(3)
3. Results and discussion
S(2)
S(3)
3.1. Syntheses and general characterizations
N(3)
C(6)
Bis[(nitrilo(diphenyl)-k6-sulfanyl)](diphenyl)-k6-sulfane-
diimide Ph2S(@N–(Ph2)S„N)2 (ndsdsd) was prepared by
the reaction of Ph2SNH with Ph2FS„N in the presence of
DBU in an excellent yield [3]. The reaction of ndsdsd with
MCl2 (M = Co(II), Ni(II), Cu(II)) in the ratio 1:5 at ambient
temperature gave the corresponding [MCl2(ndsdsd)] (1),
while an excess amount of ndsdsd (5 equivalents) resulted
in the formation of the corresponding [M(ndsdsd)2]Cl2 (2)
almost quantitatively (Scheme 1). The complexes obtained
were crystalline and stable in air but hygroscopic.
C(5)
Fig. 1. ORTEP drawing of 1a (50% probability thermal ellipsoids; H and
C atoms (apart from the Ca atoms of the phenyl rings) have been omitted
for clarity).
Elemental analyses show that their compositions are
mono- and di-hydrated complexes, [MCl2(ndsdsd)] Á H2O
and [M(ndsdsd)2]Cl2 Á 2H2O, respectively. The electronic
absorption spectra of compounds 1 and 2 in methanol solu-
tion appear to be mainly of intraligand character. These
intense bands at ca. 207 nm can be attributed to the p–p*
transitions on the phenyl groups of the ligand, since the
uncoordinated ndsdsd reveals strong absorption at
208 nm. Other transitions in the 350–800 nm range are also
observed. The d–d spectrum of Co(II) and Ni(II) com-
plexes is observed at 670 (1a and 2a), 689 (1b), and 694
nm (2b) [8a]. The Cu(II) complexes 1c and 2c show the
charge-transfer transition [8b]. In the IR spectrum of all
of the complexes, the IR band is observed between 1285
and 1261 cmÀ1 which is attributed to the terminal S–N
stretching vibrations. The S„N stretching band
(1313 cmÀ1) of the free ndsdsd is shifted to a slightly lower
frequency upon complexation and a similar observation
was previously found in the mononuclear copper(II) com-
plex (mSN = 1225 cmÀ1 in [CuCl2(Ph3SN)2]) [6b] of
Ph3S„N (mSN = 1267 cmÀ1) [5a], suggesting that the two
terminal nitrogen atoms of ndsdsd are coordinated to the
metal ion.
N(2)
S(1)
N(1)
S(2)
N(3)
N(5)
Co(1)
N(4)
S(3)
S(4)
S(6)
N(7)
N(8)
N(6)
S(5)
Fig. 2. ORTEP drawing of 2a (50% probability thermal ellipsoids; H, C
atoms (apart from the Ca atoms of the phenyl rings), two chloride anions,
two methanol, and uncoordinated water molecules have been omitted for
clarity).
N(3)
S(2)
S(3)
Ni(1)
N(1)*
N(4)*
N(4)
N(1)
N(2)
S(1)
3.2. Description of the crystal structures
In order to confirm the identity of [MCl2(ndsdsd)]
(M = Co(II) (a), Ni(II) (b), Cu(II) (c)) (1) and
[M(ndsdsd)2]Cl2 (M = Co(II) (a), Ni(II) (b), Cu(II) (c))
(2), single crystal X-ray structure determinations were car-
ried out. ORTEP drawings of 1a and 2b are depicted in
Figs. 1 and 3 (as a representative) while 2a is shown
in Fig. 2. ORTEP drawings of 1b–c and 2c are depicted
Fig. 3. ORTEP drawing of 2b (50% probability thermal ellipsoids; H, C
atoms (apart from the Ca atoms of the phenyl rings), and two chloride
anions have been omitted for clarity).

2544
T. Fujii et al. / Inorganica Chimica Acta 361 (2008) 2540–2546
Table 3
Table 4
˚
˚
Selected bond lengths (A) and angles (°) for compounds 1a–c
Selected bond lengths (A) and angles (°) for compounds 2a–c
Compound 2a
1a (M = Co)
2a (M = Ni)
3a (M = Cu)
Co(1)–N(1)
Co(1)–N(4)
Co(1)–N(5)
Co(1)–N(8)
S(1)–N(1)
S(1)–N(2)
S(2)–N(2)
S(2)–N(3)
N(1)–Co(1)–N(4)
N(1)–Co(1)–N(5)
N(1)–Co(1)–N(8)
N(4)–Co(1)–N(5)
N(4)–Co(1)–N(8)
1.995(4)
1.994(4)
1.990(4)
1.965(4)
1.481(4)
1.672(4)
1.570(4)
1.564(4)
103.29(15)
107.44(15)
113.90(15)
117.55(15)
109.11(16)
S(3)–N(3)
S(3)–N(4)
S(4)–N(5)
S(4)–N(6)
S(5)–N(6)
S(5)–N(7)
S(6)–N(7)
S(6)–N(8)
N(5)–Co(1)–N(8)
Co(1)–N(1)–S(1)
Co(1)–N(4)–S(3)
Co(1)–N(5)–S(4)
Co(1)–N(8)–S(6)
1.667(4)
1.474(4)
1.470(4)
1.663(4)
1.567(4)
1.554(4)
1.676(4)
1.467(4)
105.84(15)
131.2(2)
124.8 (2)
136.4(2)
140.0(2)
M(1)–Cl(1)
M(1)–Cl(2)
M(1)–N(1)
M(1)–N(4)
S(1)–N(1)
S(1)–N(2)
S(1)–C(1)
S(1)–C(2)
S(2)–N(2)
S(2)–N(3)
S(2)–C(3)
S(2)–C(4)
S(3)–N(3)
S(3)–N(4)
S(3)–C(5)
S(3)–C(6)
Cl(1)–M–Cl(2)
Cl(1)–M–N(1)
Cl(1)–M–N(4)
Cl(2)–M–N(1)
Cl(2)–M–N(4)
N(1)–M–N(4)
N(1)–S(1)–N(2)
N(1)–S(1)–C(1)
N(1)–S(1)–C(2)
N(2)–S(1)–C(1)
N(2)–S(1)–C(2)
C(1)–S(1)–C(2)
N(2)–S(2)–N(3)
N(2)–S(2)–C(3)
N(2)–S(2)–C(4)
N(3)–S(2)–C(3)
N(3)–S(2)–C(4)
C(3)–S(2)–C(4)
N(3)–S(3)–N(4)
N(3)–S(3)–C(5)
N(3)–S(3)–C(6)
N(4)–S(3)–C(5)
N(4)–S(3)–C(6)
C(5)–S(3)–C(6)
M(1)–N(1)–S(1)
S(1)–N(2)–S(2)
S(2)–N(3)–S(3)
M(1)–N(4)–S(3)
2.2810(7)
2.2776(7)
2.003(2)
1.982(2)
1.468(2)
1.667(2)
1.785(2)
1.793(2)
1.554(2)
1.5581(19)
1.769(2)
1.777(3)
1.675(2)
1.468(2)
2.2687(5)
2.2659(5)
1.9736(14)
1.9586(14)
1.4702(14)
1.6606(14)
1.7834(16)
1.7899(16)
1.5570(14)
1.5561(13)
1.7717(15)
1.7719(16)
1.6758(13)
1.4719(13)
1.7852(16)
1.7959(16)
117.019(19)
108.50(4)
111.58(4)
113.99(4)
106.26(4)
97.81(6)
2.2677(5)
2.2756(5)
1.9503(13)
1.9387(13)
1.4716(13)
1.6539(14)
1.7810(16)
1.7893(16)
1.5604(13)
1.556(13)
1.7697(15)
1.7712(16)
1.6758(13)
1.4700(13)
1.7854(16)
1.7893(15)
104.954(18)
104.96(4)
125.98(4)
125.96(4)
101.06(4)
96.25(6)
Compound 2b
Ni(1)–N(1)
Ni(1)–N(4)
S(1)–N(1)
S(1)–N(2)
N(1)–Ni(1)–N(4)
N(1)–Ni(1)–N(1)*
N(1)–Ni(1)–N(4)*
1.783(2)
1.799(2)
1.9201(14)
1.9165(14)
1.4792(14)
1.6676(14)
92.20(6)
S(2)–N(2)
S(2)–N(3)
S(3)–N(3)
S(3)–N(4)
N(4)–Ni(1)–N(4)*
Ni(1)–N(1)–S(1)
Ni(1)–N(4)–S(3)
1.5520(14)
1.5566(14)
1.6564(14)
1.4717(14)
180.00(3)
124.24(9)
130.65(9)
111.60(3)
112.09(6)
112.27(6)
112.64(6)
108.46(6)
99.13(8)
180.00(8)
87.80(6)
Compound 2c
Cu(1)–N(1)
Cu(1)–N(4)
S(1)–N(1)
S(1)–N(2)
N(1)–Cu(1)–N(4)
N(1)–Cu(1)–N(1)*
N(1)–Cu(1)–N(4)*
121.37(11)
115.34(12)
111.62(11)
98.60(11)
105.57(11)
101.94(11)
120.89(11)
105.59(11)
109.76(11)
111.67(11)
102.66(11)
105.31(12)
124.26(10)
101.82(11)
96.16(11)
109.63(12)
117.44(12)
104.96(11)
124.68(12)
118.95(12)
118.78(12)
128.19(13)
121.23(7)
116.42(8)
111.07(8)
98.16(7)
120.70(7)
116.92(8)
110.57(7)
98.83(7)
1.984(3)
1.984(3)
1.471(3)
1.665(3)
91.68(11)
180.00(2)
88.32(11)
S(2)–N(2)
S(2)–N(3)
S(3)–S(3)
S(3)–N(4)
N(4)–Cu(1)–N(4)*
Cu(1)–N(1)–S(1)
Cu(1)–N(4)–S(3)
1.549(3)
1.551(3)
1.652(3)
1.468(3)
180.00(19)
125.36(17)
125.17(19)
105.88(7)
101.66(7)
120.94(7)
105.54(7)
109.66(8)
111.77(7)
102.71(8)
105.24(8)
124.56(7)
101.74(7)
96.24(7)
109.35(8)
117.58(8)
104.72(7)
125.69(8)
118.58(8)
118.23(8)
128.87(8)
106.16(7)
101.35(7)
121.01(7)
105.29(7)
109.12(7)
112.15(7)
102.54(7)
105.83(7)
125.01(7)
100.89(7)
96.99(7)
109.42(8)
116.40(8)
105.68(7)
125.78(8)
117.36(8)
119.08(8)
128.03(8)
The atom labeling scheme is shown in Figs. 2 and 3.
(99.13(8)°) and 2a (103.29(15)–105.84(15)°; mean 104.6°)
are smaller than the ideal tetrahedral angle, while the N–
Co–N angles in [Co(F2(O@)S@N– (F2)S„N)4][AsF6]2 are
108.0(2)–110.5(2)° (mean 109.5°) [2d]. These smaller angles
are probably attributed to the stereochemical requirement
of the chelate ring, because the Cl–Co(1)–Cl and Cl–
Co(1)–N bond angles (mean 111.4°) in 1a and other N–
Co(1)–N bond angles (mean 112.0°) in 2a are similar to a
regular tetrahedral angle. Similarly, the bite angles of N–
M–N of 1b (97.81(6)°) and 1c (96.25(6)°) in the distorted
tetrahedra with Ni(II) and Cu(II) centers are also consider-
ably less. The bond angles of Co(1)–N(1)–S(1) and Co(1)–
N(4)–S(3) are 124.68(12) and 128.19(13)° in 1a, which are
somewhat smaller than the corresponding bond angles in
2a (124.8(2)–140.0(2)°; mean 133.1°). The Co(1)–N bond
The atom labeling scheme is shown in Fig. 1.
in Figures S1–3, Supplementary materials. Selected bond
lengths and angles for complexes 1a–c and 2a–c are col-
lected in Tables 3 and 4. The structures of the complexes
of 2a–c consist of well-separated [M(ndsdsd)2]2+ (M =
Co(II), Ni(II), Cu(II)) cations and ClÀ anions. Crystals of
2a and 2c contain methanol as a lattice solvate and lattice
water molecules.
˚
˚
lengths in 1a (1.982(2)–2.003(2) A; mean 1.993 A) are close
to those of 2a (1.965(4)–1.995(4) A; mean1.986 A) and
[Co(F2(O@)S@N–(F2)S„N)4][AsF6]2 (mean 1.969 A)
˚
˚
˚
[2d,2f]. The distances between the cobalt and nitrogen
atoms (N(2) and N(3)) in 1a are 3.584(2) and 3.907(2) A,
indicating that the nitrogen atoms of the chelate ring are
not coordinated to the cobalt atom. These are also similar
to the corresponding distances in the other complexes.
Therefore, the structures in all of the present complexes
The cobalt atom in [CoCl2(ndsdsd)] (1a) and
[Co(ndsdsd)2]Cl2 (2a) is surrounded by two nitrogen and
two chlorine atoms or four nitrogen atoms originating
from two coordinated ndsdsd ligands, respectively. In
both, the geometries around the Co atoms are slightly
distorted tetrahedra. The bite angles of N–Co(1)–N in 1a
˚

T. Fujii et al. / Inorganica Chimica Acta 361 (2008) 2540–2546
2545
˚
show a rare example of an eight–membered cyclometalla-
thiazene1 [1b].
ated [Ph3S@N–Me][ClO4] (S–N: 1.514(3) A, C–N–S:
118.6(3)°) [6a].
The geometries around the metal centers in 1b and 1c
are of distorted tetrahedral coordination, while 2b and 2c
adopt an essentially flat structure with square planar Ni(II)
and Cu(II) centers. The M–Cl bond lengths in 1b–c and the
M–N bond lengths in 1b–c and 2b–c have the values of
4. Conclusions
The reaction of ndsdsd with MCl2 (M = Co(II) (a),
Ni(II) (b), Cu(II) (c)) in the ratio 1:5 at ambient temperature
gives the corresponding [MCl2(ndsdsd)] (1), while an excess
of ndsdsd (5 equivalents) results in the formation of the cor-
responding [M(ndsdsd)2]Cl2 (2) almost quantitatively. The
products were characterized by X-ray crystallography, IR
spectroscopy, and elemental analysis. The X-ray structures
of 1 and 2 indicate the following characteristic properties.
The two terminal nitrogen atoms of ndsdsd exhibit similar
bidentate coordination mode when combined with Co(II),
Ni(II), and Cu(II) centers in the corresponding complexes
1 and 2. The eight-membered M(NSN)2S rings in 1 and 2
adopt a boat-twist conformation. The geometry around
the metal centers in 1 and 2a is a distorted tetrahedral coor-
dination with smaller N–M–N bite angles, while 2b and 2c
adopt an essentially flat structure with square planar Ni(II)
and Cu(II) centers. The s-character of the M–N bond
increases, which leads to S–N bond shortening. The coordi-
nated S–N bond lengths in 1 and 2 are similar to those of
the free ligand, and the internal S–N bond lengths lie
between those of single and double bonds. These results
indicate that the bond order in the N„S–N@S@N–S„N
backbone of ndsdsd has been maintained.
˚
˚
2.2659(5)–2.756(5) A and 1.9165(14)–1.984(14) A, respec-
tively, indicating the coordination character of the bonds.
The M(NSN)2S rings in 1b–c and 2b–c adopt a boat-twist
conformation. Among them, complex 1c is one of the rare
examples of a tetrahedral Cu(II) complex. The bond angles
around the Cu(II) ion with two nitrogen and two chlorine
atoms span the range 96.25(6)–125.98(4)°, substantially
deviating from the ideal tetrahedral angle. The dihedral
angle between the Cl(1)–Cu(1)–Cl(2) and N(1)–Cu(1)–
N(4) planes of 72.08° shows deviation from the ideal 90°
for a tetrahedral arrangement. These observed bond angles
in 1c are not significantly different from the corresponding
bond angles (96.9(3)–125.8(1)°) of [CuCl2(Ph3SN)2] [6b].
˚
The bond lengths of Cu(1)–Cl (2.2677(5)–2.2756(5) A;
˚
˚
˚
mean 2.261 A) and Cu(1)–N (1.9387(13)–1.9503(13) A;
mean 1.945 A) in 1c are also similar to those of
˚
[CuCl2(Ph3SN)2] (Cu–Cl; mean 2.249(2) A, Cu–N; mean
1.969(4) A) [6b].
˚
The coordinated and internal S–N bond lengths of com-
plexes 1 and 2 are very similar. The coordinated S–N bond
˚
lengths of 1.467(4)–1.481(4) A are close to the terminal S–
˚
N bond length of the free ligand (1.457(2) A) [3]. The inter-
˚
nal S–N bond lengths range from 1.5520(14) to 1.793(2) A.
Acknowledgments
Such bond lengths lie between those of single and double
bonds and are close to those of the free state (1.550(2)–
1.656(2) A). The mean values of the bond angles around
the sulfur atoms in the ligand are also close to those of
the free state. These results indicate that the bond order
in the N„S–N@S@N–S„N backbone of ndsdsd has been
maintained.
This work was partially supported by a Grants-in-Aid
for Scientific Research (No. 16750030 and 19550051) from
the Ministry of Education, Culture, Sports, Science and
Technology of Japan and supported by a Grant from High
Technology Research Center, College of Industrial Tech-
nology, Nihon University.
˚
Recently, Mews et al. have reported the X-ray structures
of the F2(O@)S@N–(F2)S„N–A system (A = Co, Cu,
AsF5, BF3, Me) [2f]. They concluded that the S–N bond
length decreases with increasing A–N–S angle. The results
obtained in this work may also be related to Mews finding.
The coordinated S–N bond lengths (mean 1.472 A) and M–
N–S bond angles (mean 128.5°) in 1 and 2 are significantly
shorter and larger, respectively, than those of N-methyl-
Appendix A. Supplementary material
ORTEP drawings of 1b–c and 2c (Figs. S1–S3) and
X-ray crystallographic files in CIF format for the structure
determination of 1 and 2. CCDC 648178, 648179, 648180,
648181, 648182 and 648183 contain the supplementary
crystallographic data for this 1a, 1b, 1c, 2a, 2b and 2c.
These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.
ac.uk/data_request/cif. Supplementary data associated
with this article can be found, in the online version, at
doi:10.1016/j.ica.2008.01.036.
˚
1
The only example of the eight-membered MS3N4 ring system,
[Cp2Ti(S3N4)], was prepared by the reaction of [Cp2Ti(CO)2] with S4N4.
The seven-atom NSNSNSN sequence is an approximately planar in three
independent molecules. The bite angle of N–Ti–N is equivalent for the
three molecules with a mean of 94.6(2)°. The coordinated S–N bond
˚
lengths (1.482–1.500 A) and the internal S–N bond lengths (1.555–
˚
References
1.605 A) in [Cp2Ti(S3N4)] are similar to those observed in 1 and 2 (see:
C.G. Marellus, R.T. Oakley, W.T. Pennington, A.W. Cordes, Organom-
tallics 5 (1986) 1395). An cyclometallathiazene of MS4N3, [Pt(S4N3)Cl],
has been reported, but the S4N3 ligand is coordinated to platinum as a
tridentate via the terminal S atoms and central nitrogen atom (see: H.
Endres, E. Galantai, Angew. Chem., Int. Ed. Engl. 19 (1980), 653).
[1] (a) P.F. Kelly, J.D. Woollins, Polyhedron 5 (1986) 607;
(b) T. Chivers, F. Edelmann, Polyhedron 5 (1986) 1661;
(c) P.F. Kelly, A.M.Z. Slawin, A. Soriano-Rama, J. Chem. Soc.,
Dalton Trans. (1996) 53;

2546
T. Fujii et al. / Inorganica Chimica Acta 361 (2008) 2540–2546
(d) T. Chivers, A Guide to Chalcogen–Nitrogen Chemistry, World
Scientific Publishing Co. Pte. Ltd., Singapore, 2005, Chapter 7, p. 122
and references therein.
[5] (a) T. Yoshimura, K. Hamada, M. Imado, K. Hamata, K. Tomoda, T.
Fujii, H. Morita, C. Shimasaki, S. Ono, E. Tsukurimichi, N.
Furukawa, T. Kimura, J. Org. Chem. 62 (1997) 3802;
[2] (a) O. Glemser, R. Mews, Angew. Chem., Int. Ed. Engl. 19 (1980)
883;
(b) T. Yoshimura, T. Fujii, S. Murotani, S. Miyoshi, T. Fujimori, M.
Ohkubo, S. Ono, H. Morita, J. Organomet. Chem. 611 (2000) 272;
(c) T. Fujii, T. Fujimori, S. Miyoshi, S. Murotani, M. Ohkubo, T.
Yoshimura, Heteroat. Chem. 12 (2001) 263;
(b) U. Behrens, R. Hoppenheit, W. Isenberg, E. Lork, J. Petersen,
R. Mews, Z. Naturforsch. 49b (1994) 238;
(c) U. Behrens, E. Lork, J. Petersen, A. Waterfeld, R. Mews, Z.
Anorg. Allg. Chem. 623 (1997) 1518;
(d) T. Fujii, T. Suzuki, T. Sato, E. Horn, T. Yoshimura, Tetrahedron
Lett. 42 (2001) 6151;
(d) R. Hoppenheit, E. Lork, J. Petersen, R. Mews, Chem.
Commun. (1997) 1659;
(e) T. Fujii, T. Ikeda, T. Mikami, T. Suzuki, T. Yoshimura, Angew.
Chem., Int. Ed. 41 (2002) 2576.
(e) U. Behrens, J. Petersen, E. Lork, P.G. Watson, R. Mews,
Angew. Chem. Int. Ed. Engl. 36 (1997) 1878;
(f) R. Mews, T. Borrmann, R. Hoppenheit, E. Lork, S. Parsons, J.
Petersen, M. Schro¨ter, W.-D. Stohrer, A. Waterfeld, P.G. Watson,
J. Fluorine Chem. 125 (2004) 1649;
[6] (a) T. Yoshimura, T. Fujii, K. Hamata, M. Imado, H. Morita, S. Ono,
E. Horn, Chem. Lett. (1998) 1013;
(b) T. Yoshimura, T. Fujii, H. Dai, Chem. Lett. (2002) 1000.
[7] G.M. Sheldrick, SHELXS97 and SHELXL97. Program for Crystal Structure
Solution and Refinement, University of Gottingen, Germany, 1997.
[8] (a) B.N. Figgis, in: G. Wilkinson, R.D. Gillard, J.A. McCleverty
(Eds.), Comprehensive Coordination Chemistry, vol. 5, Pergamon
Press, Oxford, England, 1987, p. 213;
(g) R. Mews, E. Lork, P.G. Watson, B. Go¨rtler, Coord. Chem.
Rev. 197 (2000) 277.
[3] T. Fujii, M. Kanno, M. Hirata, T. Fujimori, T. Yoshimura, Inorg.
Chem. 44 (2005) 8653.
[4] T. Fujii, S. Asai, T. Okada, W. Hao, H. Morita, T. Yoshimura,
Tetrahedron Lett. 44 (2003) 6203.
(b) B.J. Hathaway, in: G. Wilkinson, R.D. Gillard, J.A. McCleverty
(Eds.), Comprehensive Coordination Chemistry, vol. 5, Pergamon
Press, Oxford, England, 1987, p. 533.