Synthesis, characterization and crystal structures of homo- and hetero-substituents containing trans six-coordinate tin(IV) complexes of H 2tmtaa (5,14-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11] tetraazacyclotetradecine), and the solid state NMR spectra study of 119Sn

Article abstract of DOI:10.1016/j.ica.2004.05.011

The reaction of Sn(tmtaa)Cl₂ (H₂tmtaa=5,14-dihydro-6, 8,15,17-tetramethyldi-benzo[b,i][1,4,8,11]tetraazacyclotetradecine) and ammonium thiocyanate or sodium azide under a mild condition resulted in trans six-coordinate tmtaa tin(IV) complexes, Sn(tmtaa)X₂ (X=NCS, 1; X=N₃, 2). However, the treatment of Sn(tmtaa)Cl₂ and sodium picrate produced Sn(tmtaa)(Cl)(OC₆H₂ (2,4,6-3NO₂)) (3). Only one chloro atom of Sn(tmtaa)Cl₂ was substituted because of low nucleophilicity of the 2,4,6-trinitrophenolic anion in 3. Furthermore, because of the steric hindrance between the 2,4,6-trinitrophenolic group and the tmtaa ligand, which has a non-planar, saddle-shaped conformation, two chloro atoms cannot be substituted by two 2,4,6-trinitrophenolic groups simultaneously. All complexes were characterized by IR spectra, UV spectra, mass spectra, NMR spectra and elemental analyses, as well as DSC measurements. X-ray crystal structures of 1 and 3 reveal that the complexes retain the characteristic saddle-shaped configuration of H ₂tmtaa but have adopted the trans geometry. Solid state ¹¹⁹Sn NMR spectroscopy was used to study the bonding environment in the series of six-coordinate trans Sn(IV) tmtaa complexes. It can be found that the ¹¹⁹Sn chemical shifts of the Sn(IV) tmtaa complexes are almost not influenced by the substituents.

Full text of DOI:10.1016/j.ica.2004.05.011

Inorganica Chimica Acta 357 (2004) 3510–3516
www.elsevier.com/locate/ica
Synthesis, characterization and crystal structures of homo-
and hetero-substituents containing trans six-coordinate
tin(IV) complexes of H2tmtaa (5,14-dihydro-6,8,15,17-
tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine),
q
119
and the solid state NMR spectra study of Sn
*
*
Xuan Shen , Akio Nakashima, Kazunori Sakata , Mamoru Hashimoto
Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology, 1-1 Sensui-cho, Tobata-ku, Kitakyushu 804-8550, Japan
Received 4 January 2004; accepted 1 May 2004
Available online 9 June 2004
Abstract
The reaction of Sn(tmtaa)Cl2 (H2tmtaa ¼ 5,14-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine) and
ammonium thiocyanate or sodium azide under a mild condition resulted in trans six-coordinate tmtaa tin(IV) complexes,
Sn(tmtaa)X2 (X ¼ NCS, 1; X ¼ N3, 2). However, the treatment of Sn(tmtaa)Cl2 and sodium picrate produced Sn(tmtaa)(Cl)(OC6H2
(2,4,6-3NO2)) (3). Only one chloro atom of Sn(tmtaa)Cl2 was substituted because of low nucleophilicity of the 2,4,6-trinitrophenolic
anion in 3. Furthermore, because of the steric hindrance between the 2,4,6-trinitrophenolic group and the tmtaa ligand, which has a
non-planar, saddle-shaped conformation, two chloro atoms cannot be substituted by two 2,4,6-trinitrophenolic groups simulta-
neously. All complexes were characterized by IR spectra, UV spectra, mass spectra, NMR spectra and elemental analyses, as well as
DSC measurements. X-ray crystal structures of 1 and 3 reveal that the complexes retain the characteristic saddle-shaped configu-
ration of H2tmtaa but have adopted the trans geometry. Solid state 119Sn NMR spectroscopy was used to study the bonding en-
vironment in the series of six-coordinate trans Sn(IV) tmtaa complexes. It can be found that the 119Sn chemical shifts of the Sn(IV)
tmtaa complexes are almost not influenced by the substituents.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Homo- and hetero-substituents; Trans six-coordinate complexes; Tin(IV) tmtaa complexes; Crystal structures; Solid state 119Sn NMR
spectra
1. Introduction
portant differences from porphyrins and phthalocya-
nines such as a smaller N4 coordination cavity ‘hole
size’ and typically possesses a non-planar, saddle-
shaped conformation. The similarity of H2tmtaa to the
porphyrins and phthalocyanines means that these syn-
thetic macrocycles are of bioinorganic relevance, while
their distinctive individual characteristics make them
interesting ligands in their own right. Syntheses, prop-
erties and structures of transition and main group
metals tmtaa complexes were compiled by Cotton and
Czuchajowska [1] and Mountford [2]. In the last de-
cade, tmtaa complexes of Group 14 elements, especially
germanium and tin, have enjoyed a resurgence of in-
terest [3–9]. We have also reported the preparation,
5,14-Dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,
11]tetraazacyclotetradecine, abbreviated as H2tmtaa
(Fig. 1), is a macrocyclic compound of a 14-membered
ring and has a structure and properties similar to
porphyrins and phthalocyanines. It also features im-
q Supplementary data associated with this article can be found, in the
online version, at doi:10.1016/j.ica.2004.05.011.
* Corresponding authors. Tel.: +81-93-884-3307/3331; fax: +81-93-
884-3300.
E-mail addresses: chinsenjp@yahoo.co.jp (X. Shen), sakata@che.
kyutech.ac.jp (K. Sakata).
0020-1693/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.05.011

X. Shen et al. / Inorganica Chimica Acta 357 (2004) 3510–3516
3511
enced to the 119Sn resonance of tetramethyltin (SnMe4) at
0 ppm and potassium stannate trihydrate (K2SnO3 ꢁ
3H2O), which shift appeared at )569 ppm, was used as
secondary references.
Suitable crystals of 1 and 3 were mounted on glass
fibers. All measurements were made on a Rigaku
AFC7R diffractometer with graphite monochromated
H3C
CH3
NH
N
N
HN
ꢀ
Mo Ka radiation (k ¼ 0:71069 A) and a rotating anode
generator. The structures of 1 and 3 were solved by
direct methods [12] and expanded using Fourier tech-
niques [13]. All non-hydrogen atoms were refined with
anisotropic thermal parameters. Most of the hydrogen
atoms were located in calculated positions and/or in
positions found from difference Fourier maps. Crystal
data and details associated with data collection are
summarized in Table 1.
H3C
CH3
Fig. 1. Suggested structure of H2tmtaa.
characterization and structures of tmtaa complexes of
germanium in the +IV oxidation state recently [10,11].
In those theses, chloro-bridged dinuclear tmtaa ger-
manium (IV) complex and trans six-coordinate tmtaa
germanium (IV) complexes with homo- and hetero-
substituents were reported. Herein, as extension of our
research, we further report the investigations into a
number of derivatives of other Group 14 element, tin,
in the +IV oxidation state, including homo- and hetero-
substituents trans six-coordinate tmtaa complexes. Ad-
ditionally, the properties of solid state 119Sn NMR
spectra in the tmtaa complexes are also investigated.
2.3. Synthesis of Sn(tmtaa)(NCS)2 (1)
A solution of ammonium thiocyanate (0.030 g,
0.394 mmol) in methanol (5 ml) was added dropwise
to a solution of Sn(tmtaa)Cl2 (0.100 g, 0.188 mmol) in
methanol (20 ml) under a nitrogen atmosphere. After
being refluxed for 12 h, a product precipitated as a
red microcystalline solid. The product was collected
by filtration and washed thoroughly with methanol,
and then was recrystallized from toluene/dichlorome-
thane (1:4 vol/vol) to give red crystals suitable for X-
ray diffraction. Yield: 0.095 g (88%). Anal. Calc. for
Sn(tmtaa)(NCS)2 (C24H22N6S2Sn): C, 49.93; H, 3.84;
N, 14.56. Found: C, 50.01; H, 3.80; N, 14.44%. m.p.:
395–396 °C (DSC). IR (KBr pellet, cmꢀ1): 2047
(CBN), 1511, 1456, 1391 (C@C, C@N). UV–Vis
(CHCl3, kmax/nm): 386 (s), 430 (m). FAB-MS: m=z ¼
518 (M ) NCS), 460 (M ) 2NCS). Solid state 119Sn
NMR: d )432.
2. Experimental
2.1. Materials
All analytical grade chemicals were purchased com-
mercially and used without further purification. All
solvents were distilled under a nitrogen atmosphere.
Sn(tmtaa)Cl2 is prepared according to the literature
method [6].
2.4. Synthesis of Sn(tmtaa)(N3)2 (2)
2.2. Physical measurements
After Sn(tmtaa)Cl2 (0.100 g, 0.188 mmol) was dis-
solved in methanol (20 ml) completely under a nitrogen
atmosphere, a methanol solution (5 ml) of sodium azide
(0.025 g, 0.385 mmol) was added dropwise. The solution
was refluxed for 12 h and then was cooled to room
temperature. After being filtered, the solution was re-
duced to half by evaporating. The product precipitated
when the solution was cooled to room temperature
again. The product was collected by filtration and wa-
shed thoroughly with methanol, and then was recrys-
tallized from acetonitrile to give red microcrystalline
Elemental analyses were performed on a Yanaco
CHN corder MT-3. IR spectra (4000–400 cmꢀ1) were
recorded on a JASCO FT/IR-400 spectrophotometer in
KBr pellets at room temperature. Ultraviolet and visible
spectra were recorded on a Shimadzu UV-200S double
beam spectrophotometer in chloroform at room tem-
perature. DSC data were obtained using a Shimadzu
DSC-50 differential calorimeter. 1H NMR measurements
were taken on a BRUKER AVANCE-400 in chloro-
form-d (CDCl3), and chemical shifts were given in ppm
relative to tetramethylsilane as an internal reference
standard. Cross polarization magic angle spinning
(CPMAS) NMR spectra were recorded on a BRUKER
MSL300 spectrometer at Larmor frequencies l0=2p of
111.9 MHz for 119Sn. 119Sn chemical shielding is refer-
solid. Yield: 0.078
g
(76%). Anal. Calc. for
Sn(tmtaa)(N3)2 (C22H22N10Sn): C, 48.47; H, 4.07; N,
25.69. Found: C, 48.21; H, 4.16; N, 25.86%. m.p.: 366–
368 °C (DSC). IR (KBr pellet, cmꢀ1): 2075 (NNN),
1523, 1465, 1388 (C@C, C@N). UV–Vis (CHCl3, kmax
/

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X. Shen et al. / Inorganica Chimica Acta 357 (2004) 3510–3516
Table 1
Crystal data, data collection and refinement parameters for complexes 1 and 3
Complex
1
3
Empirical formula
Formula weight
C24H22N6S2Sn1
577.29
C28H24Cl1N7O7Sn1 ꢁ CH3CN
765.74
red, chunk
Crystal color, habit
Crystal dimensions
Crystal system
red, block
0.10 ꢂ 0.10 ꢂ 0.10 mm
monoclinic
0.20 ꢂ 0.30 ꢂ 0.40 mm
triclinic
ꢁ
Space group
P21=nð#14Þ
25 (20.2 27.4°)
P1ð#2Þ
Number of reflections used for unit cell
determination (2h range)
Lattice parameters
25 (21.3 31.0°)
ꢀ
a (A)
13.055(2)
12.587(2)
14.687(2)
98.938(10)
92.20(1)
89.65(2)
2411.8(6)
4
10.416(2)
16.417(3)
9.3955(9)
ꢀ
b (A)
ꢀ
c (A)
a (°)
b (°)
c (°)
92.98(1)
3
ꢀ
V (A )
1585.0(5)
2
Z value
F ð000Þ
1160.00
1.590
772.00
1.604
Dcalc (g/cm3)
Radiation
ꢀ
ꢀ
Mo Ka (k ¼ 0:71069 A) graphite
Mo Ka (k ¼ 0:71069 A) graphite
monochromated
20.0
monochromated
20.0
Temperature (°C)
Scan type
x ꢀ 2h
x ꢀ 2h
2hmax
Number of reflections measured
56.0°
56.0°
Total
Unique
6356
8068
5830 (Rint ¼ 0:067)
0.119; 0.163
0.056
8064 (Rint ¼ 0:022)
0.128; 0.229
0.070
Residuals: R; Rw
Residuals: R1
Goodness-of-fit indicator
1.24
0.000
1.56
0.000
Maximum shift/error in final cycle
nm): 385 (s), 425 (m). FAB-MS: m=z ¼ 502 (M ) N3),
460 (M ) 2N3). Solid state 119Sn NMR: d )436.
3. Results and discussion
3.1. Synthesis and characterization
2.5. Synthesis of Sn(tmtaa)(Cl)(OC6H2(2,4,6-3NO2)) ꢁ
CH3CN (3)
The reaction of free base H2tmtaa with SnCl4 under
mild condition resulted in Sn(tmtaa)Cl2 [6]. Because of
+IV oxidation state of the central metal and a trans six-
coordinate geometry, Sn(tmtaa)Cl2 shows great reac-
tivity at the axial position. The substituting reaction of a
methanol solution of Sn(tmtaa)Cl2 with two equivalents
of ammonium thiocyanate or two equivalents of sodium
azide in methanol under mild condition (in a nitrogen
atmosphere, refluxing) yielded new trans six-coordinate
tin(IV) tmtaa complexes, Sn(tmtaa)(NCS)2 (1) or
Sn(tmtaa)(N3)2 (2). 1 and 2 were characterized by IR
spectra, UV spectra, mass spectra, NMR spectra and
elemental analyses, as well as DSC measurements. In the
IR spectrum of 1, the CBN stretching band of NCS
group was observed at 2047 cmꢀ1, while the NNN
stretching band of the azido group in 2 appeared at 2075
cmꢀ1 in its IR spectrum. The X-ray crystal structure of 1
shows an approximately octahedral coordination ge-
ometry with trans configuration. Analysis of the struc-
ture shows that it is nitrogen atom that coordinates to
A solution of sodium picrate (0.113 g, 0.450 mmol) in
methanol (5 ml) was added dropwise to a solution of
Sn(tmtaa)Cl2 (0.100 g, 0.188 mmol) in methanol (20 ml)
under a nitrogen atmosphere. After being refluxed for 12
h, the solution was cooled to room temperature and was
filtrated. Evaporating the filtrate resulted in red powder.
Red crystals containing one molecule of acetonitrile,
which were suitable for X-ray diffraction, were obtained
by recrystallizating the powder from acetonitrile. Yield:
0.123 g (90%). Anal. Calc. for Sn(tmtaa)(Cl)(OC6H2
(2,4,6-3NO2))ꢁCH3CN (C28H24ClN7O7Sn ꢁ CH3CN): C,
47.05; H, 3.55; N, 14.63. Found: C, 47.16; H, 3.45; N,
14.78%. m.p.: 345-346 °C (DSC). IR (KBr pellet, cmꢀ1):
1582, 1488, 1457, 1397 (C@C, C@N). UV–Vis (CHCl3,
k
max/nm): 390 (s), 420 (sh). FAB-MS: m=z ¼ 495
(M ) OC6H2(NO2)3), 460 (M ) Cl–OC6H2(NO2)3). So-
lid state 119Sn NMR: d )415.

X. Shen et al. / Inorganica Chimica Acta 357 (2004) 3510–3516
1
3513
the central metal, while it is not sulfur atom. The spectra
data of 2 are similar to those of 1, so that the structure
of 2 should be analogous to that of 1.
3.3. H NMR Spectra
1
Complexes 1–3 give well-resolved H NMR spectra.
1H NMR data for Sn(tmtaa)Cl2 and 1–3 are listed in
Table 2. The aromatic protons, which appear as a broad
singlet at d 6.98 ppm in the 1H NMR spectrum of
H2tmtaa in CDCl3 solution [20], separate into two
multiplets in all the spectra. The signals of methine and
methyl groups are all singlets. However, comparing with
starting compound, the signals of 1–3 shift a little to
upfield or downfield. This seems to indicate that the
interactions between substituted groups and tmtaa units
are different. For example, in the spectrum of
Sn(tmtaa)Cl2, the signals of methine and methyl groups
appeared at d 5.13 and 2.48 ppm, respectively. However,
in the spectrum of 1, the signals of methine and methyl
groups appeared at d 5.15 and 2.49 ppm, respectively,
shifting a little to downfield. This may suggest that the
interaction between NCS groups and tmtaa in 1 is
stronger than the interaction between Cl groups and
tmtaa in Sn(tmtaa)Cl2. If stronger interaction appears
between tmtaa and substituted groups, the protons
electron cloud of tmtaa is attracted by substituted
groups and the density of electron cloud becomes lower
and lower. Thus, the proton signals shift to downfield in
1H NMR spectra. This can also be observed in other
complexes. Besides proton signals of tmtaa are ob-
served, aromatic protons of substituted groups in 3 ap-
pear as singlet at d 8.70 ppm.
Until now, investigations into the interaction of
tmtaa units and axial substituents containing aromatic
groups in Group 14 elements tmtaa complexes have not
been extensively developed. However, several titanium,
zirconium, ruthenium and iron tmtaa complexes con-
taining aromatic rings in the axial positions, which show
very interesting configurations, have been reported [14–
19]. In our work, though we changed the molar rate of
Sn(tmtaa)Cl2 and sodium picrate from 1:2 to 1:5, only
one kind of tin tmtaa complexes, Sn(tmtaa)(Cl)(OC6H2-
(2,4,6-3NO2)) (3), in which only one chloro atom was
substituted, was obtained. This may be due to low nu-
cleophilicity of the 2,4,6-trinitrophenolic anion. Fur-
thermore, because of the steric hindrance between the
2,4,6-trinitrophenolic group and the tmtaa ligand, which
has a non-planar, saddle-shaped conformation, two
chloro atoms cannot be substituted by two 2,4,6-trini-
trophenolic groups simultaneously. The X-ray crystal
structure of 3 shows that the complex keeps the trans
configuration and a chloro atom and a 2,4,6-trinitro-
phenolic group are in two sides of tmtaa ligand. Because
of the interaction of 2,4,6-trinitrophenolic group and
tmtaa unit, the aromatic ring in 2,4,6-trinitrophenolic
group is not vertical to the N4 plane of tmtaa.
3.2. Mass spectra
In the FABþ mass spectra of starting compound,
Sn(tmtaa)Cl2, no molecular ion peaks were observed,
but only the peaks of major fragments correspond-
ing to [M ) Cl]þ and [M ) 2Cl]þ were observed [6].
This was also observed in our work. FABþ mass
spectra of all complexes show the peaks of major
fragments corresponding to molecule minus one and
two substituents. This suggests that the substituents
in trans positions may be easily cleaved in FABþ
mass measurements.
3.4. Solid state NMR spectra of tin(IV)
The use of 119Sn NMR spectroscopy has proven to be
an invaluable structural probe in all areas of tin chem-
istry [21]. A large body of data is now available [22]
which demonstrates that 119Sn NMR studies provide
accurate, relatively easily obtainable information on the
bonding to the tin atom. In many cases, the most im-
portant spectroscopic parameter available from these
studies is the value of the chemical shift (d). While much
Table 2
1H NMR (400 MHz)a and 119Sn solid state NMR (111.9 MHz)b spectroscopic data for Sn(tmtaa)Cl2 and complexes 1–3
1H NMR
Solid state 119Sn NMR
Complex
Macrocyclic skeleton
C6H4 (m, m, 4 H, 4 H)
Others
CH (s, 2 H)
CH3 (s, 12 H)
Aromatic ring
Sn(tmtaa)Cl2
7.20, 7.07
7.22, 7.10
7.10, 7.20
7.20, 7.12
5.13
5.15
5.07
5.05
2.48
2.49
2.51
2.49
)432
)432
)436
)415
1
2
3
8.70 (s, 2H)
a Chemical shifts are given in ppm for TMS. Measured in CDCl3. Multiplicity of a proton signal is given in parentheses after d value: s, singlet; m,
multiplet.
b Chemical shielding is referenced to the 119Sn resonance of tetramethyltin (SnMe4) at 0 ppm and potassium stannate trihydrate (K2SnO3 ꢁ 3H2O) is
used as the secondary reference, which chemical shielding appeared at )569 ppm.

3514
X. Shen et al. / Inorganica Chimica Acta 357 (2004) 3510–3516
of the chemical shift data concerns isotropic 119Sn shift
values measured in solution. Nevertheless, the com-
plexes studied in our works do not have good solubility
in non-polar or low polar solvents. Furthermore, in
polar or high polar solvents, the axial substituents of
these complexes will be substituted by solvent molecule
and the coordination property of tin and ligands will
perhaps change. Thus, the 119Sn NMR spectroscopy was
studied in solid state in our works. In the last few years,
solid state 119Sn NMR spectroscopy of various or-
ganotin complexes or other organometallic complexes
containing tin has been studied [23–33]. Unfortunately,
there are no studies available for tmtaa compound class.
We were therefore anxious to record the solid state
spectra of Sn(IV) in some tmtaa complexes with the
expectation that such a study would reveal large aniso-
tropies in their chemical shift tensors which would help
elucidate the nature of the bonding in these complexes.
High resolution solid state 119Sn cross polarization
magic angle spinning (CPMAS) NMR spectroscopy is
an effective tool for detecting subtle details of structural
and electronic properties of tin compounds [34,35].In
our works, CPMAS NMR spectra were recorded at
Larmor frequencies x0=2p of 111.9 MHz for 119Sn.
119Sn chemical shielding is referenced to the 119Sn reso-
nance of tetramethyltin (SnMe4) at 0 ppm and potas-
sium stannate trihydrate (K2SnO3 ꢁ 3H2O) is used as the
secondary reference.
Fig. 2. 1H NMR data (part of methine, vertical axis) and the solid state
119Sn NMR data (horizontal axis) of Sn(tmtaa)Cl2 and complexes 1–3.
of the weak electron donative ability of the substituents
to the central metal. Furthermore, being different from
Sn(tmtaa)Cl2, 1 and 2, which have two homo-substitu-
ents, 3 has two hetero-substituents. The electron dona-
tive ability of two hetero-substitutes to tin atom in 3 is
lower than those in Sn(tmtaa)Cl2, 1 and 2. Thus, the
119Sn signal of 3 shifts a little downfield.
3.5. Crystal structures
The structural representation of 1 is shown in Fig. 3.
Selected bond lengths and bond angles are given in
Table 3. Notable features of the structural chemistry of
tmtaa complexes are non-planar, saddle-shaped con-
formation and smaller N4 coordination cavity ‘hole size’
than that of porphyrins and phthalocyanines. The
structure determination of 1 reveals that it adopts trans
six-coordinate configuration. The saddle shapes of the
macrocyclic ligands are almost retained. The tin atom is
The data of Sn(tmtaa)Cl2 and complexes 1–3, ob-
tained from solid state NMR experiments, are also given
in Table 2. The singlet sharp signal of K2SnO3 ꢁ 3H2O
appeared at )569 ppm and broad peak of Sn(tmtaa)Cl2
was observed at )432 ppm. Because of the analogous
structures comparing with Sn(tmtaa)Cl2, signals of 1
and 2 have similar shapes and appear at )432 and )436
ppm, respectively. 119Sn chemical shift of 3 appears at
)415 ppm, which is a little lower than those of
Sn(tmtaa)Cl2, 1 and 2. Combining the discussion of the
1H NMR spectra, we concluded the 1H NMR data (part
of methine) and the solid state 119Sn NMR data in
Fig. 2. It can be found that 1H chemical shifts of
Sn(tmtaa)Cl2 and 1–3 appear at different positions. This
may be due to the anisotropy effect of the triple bonds
(CBN) existing in the substituents of 1 and the NNN
bonds existing in the substituents of 2, and the ring
current effect of aromatic ring existing in the substituent
of 3. Because of the different interactions between sub-
1
stituents and tmtaa unit, the H chemical shifts of 1–3
shift to upfield or downfield comparing with
Sn(tmtaa)Cl2. However, 119Sn chemical shifts of
Sn(tmtaa)Cl2, 1 and 2 appear at similar positions. This
may be due to the electron donative ability of tmtaa
group to the central metal which is greater than that of
substituents to the central metal. Thus, though the
substituents are different, 119Sn chemical shifts of
Sn(tmtaa)Cl2, 1 and 2 are similar to each other because
Fig. 3. ORTEP view of complex 1 with thermal ellipsoids shown at the
50% probability level. Hydrogen atoms have been omitted for clarity.

X. Shen et al. / Inorganica Chimica Acta 357 (2004) 3510–3516
3515
Table 3
ꢀ
Selected bond lengths (A) and bond angles (°) for complex 1
Bond lengths
Sn(1)–N(1)
Sn(1)–N(2)
Sn(1)–N(3)
Sn(1)–N(4)
Sn(1)–N(5)
2.055(5)
2.057(6)
2.060(5)
2.062(5)
2.180(7)
Sn(1)–N(6)
N(5)–C(23)
N(6)–C(24)
C(23)–S(1)
C(24)–S(2)
2.207(6)
1.058(9)
1.096(8)
1.666(8)
1.620(8)
Sn(1)–N4 least
squares plane
0.041
Bond angles
N(5)–Sn(1)–N(6)
Sn(1)–N(5)–C(23)
Sn(1)–N(6)–C(24)
N(5)–C(23)–S(1)
N(6)–C(24)–S(2)
N(1)–Sn(1)–N(3)
N(2)–Sn(1)–N(4)
N(5)–Sn(1)–N(1)
N(5)–Sn(1)–N(2)
178.8(2)
162.7(7)
150.7(6)
177.1(7)
177.3(7)
177.5(2)
177.7(2)
91.5(2)
N(5)–Sn(1)–N(3)
N(5)–Sn(1)–N(4)
N(6)–Sn(1)–N(1)
N(6)–Sn(1)–N(2)
N(6)–Sn(1)–N(3)
N(6)–Sn(1)–N(4)
N(1)–Sn(1)–N(2)
N(2)–Sn(1)–N(3)
N(3)–Sn(1)–N(4)
N(4)–Sn(1)–N(1)
91.0(2)
90.3(2)
89.3(2)
89.1(2)
88.2(2)
88.9(2)
96.5(2)
83.2(2)
97.8(2)
82.3(2)
91.7(2)
Fig. 4. ORTEP view of complex 3 with thermal ellipsoids shown at the
50% probability level. Hydrogen atoms have been omitted for clarity.
displaced from the N4 plane towards the benzenoid face
ꢀ
of tmtaa by 0.041 A. In trans six-coordinate tmtaa
germanium(IV) complex, Ge(tmtaa)(NCS)2, the germa-
nium atom is displaced from the N4 plane towards the
ꢀ
benzenoid face of the ligand by only 0.03 A [11]. These
small displacements may be a steric consequence of the
trans geometry. The mean Sn–N bond distance in N4
ꢀ
plane is 2.059 A. It is a little longer than the mean Ge–N
Table 4
ꢀ
Selected bond lengths (A) and bond angles (°) for complex 3
Bond lengths
Sn(1)–N(1)
Sn(1)–N(2)
Sn(1)–N(3)
Sn(1)–N(4)
Sn(1)–Cl(1)
Sn(1)–O(1)
O(1)–C(23)
2.067(5)
2.076(6)
2.059(4)
2.070(7)
2.405(2)
2.229(4)
1.267(7)
N(5)–C(24)
N(5)–O(2)
N(5)–O(3)
N(6)–C(26)
N(6)–O(4)
N(6)–O(5)
N(7)–C(28)
N(7)–O(6)
N(7)–O(7)
1.467(8)
1.215(9)
1.230(8)
1.459(8)
1.232(7)
1.205(7)
1.472(7)
1.218(8)
1.220(8)
ꢀ
bond distance (1.926 A) in N4 plane in complex
Ge(tmtaa)(NCS)2 [11]. This may be due to the different
hole sizes of 1 and Ge(tmtaa)(NCS)2. In 1, each NCS
ligand adopts the most stereochemically favorable ori-
entation with respect to the saddle-shaped macrocycle.
ꢀ
The Sn(1)–N(5) distance (2.180 A) on the benzenoid face
Sn(1)–N4 least
squares plane
0.208
ꢀ
is also shorter than the Sn(1)–N(6) distance (2.207 A) on
the opposite face of the molecule. Nitrogen atoms of
NCS ligands and central metal are almost in the same
line. N(5)–Sn(1)–N(6) bond angle is 178.8°. Trans axial
nitrogen atoms are almost vertical to N4 planes of the
tmtaa ligands. NCS ligands keep their line character-
ization. N(5)–C(23)–S(1) and N(6)–C(24)–S(2) bond
angles are 177.1° and 177.3°, respectively, whereas the
Sn(1)–N(5)–C(23) and Sn(1)–N(6)–C(24) linkages are
lightly bent (162.7° and 150.7°, respectively). All of these
are similar to those of complex Ge(tmtaa)(NCS)2 [11].
The ORTEP view of 3 is shown in Fig. 4. Selected
bond lengths and bond angles are given in Table 4. One
molecule of acetonitrile in the crystal lattice was ob-
served. Because of the low reactivity of 2,4,6-trinitro-
phenolic anion, only one chloro atom which is on the
opposite benzenoid face of the molecule was substituted
from Sn(tmtaa)Cl2. The chloro atom on the benzenoid
face was retained, while the Sn(1)–Cl(1) distance (2.405
Bond angles
Cl(1)–Sn(1)–O(1)
Sn(1)–O(1)–C(23)
N(1)–Sn(1)–N(3)
N(2)–Sn(1)–N(4)
Cl(1)–Sn(1)–N(1)
Cl(1)–Sn(1)–N(2)
Cl(1)–Sn(1)–N(3)
Cl(1)–Sn(1)–N(4)
O(1)–Sn(1)–N(1)
O(1)–Sn(1)–N(2)
O(1)–Sn(1)–N(3)
O(1)–Sn(1)–N(4)
N(1)–Sn(1)–N(2)
N(2)–Sn(1)–N(3)
N(3)–Sn(1)–N(4)
N(4)–Sn(1)–N(1)
177.8(1)
138.3(4)
168.1(2)
168.9(2)
96.8(2)
94.0(1)
95.2(1)
97.1(2)
85.3(2)
86.5(2)
82.7(2)
82.4(2)
96.5(2)
82.3(2)
96.3(2)
82.5(2)
O(2)–N(5)–O(3)
123.8(7)
118.0(6)
118.1(7)
122.6(6)
117.7(6)
119.7(5)
124.6(6)
117.8(6)
117.6(6)
122.5(6)
124.9(5)
112.6(5)
118.7(6)
117.1(5)
124.2(6)
119.4(5)
118.8(6)
121.8(6)
119.7(5)
115.8(5)
124.5(5)
O(2)–N(5)–C(24)
O(3)–N(5)–C(24)
O(4)–N(6)–O(5)
O(4)–N(6)–C(26)
O(5)–N(6)–C(26)
O(6)–N(7)–O(7)
O(6)–N(7)–C(28)
O(7)–N(7)–C(28)
O(1)–C(23)–C(24)
O(1)–C(23)–C(28)
C(24)–C(23)–C(28)
N(5)–C(24)–C(23)
N(5)–C(24)–C(25)
C(23)–C(24)–C(25)
N(6)–C(26)–C(25)
N(6)–C(26)–C(27)
C(25)–C(26)–C(27)
N(7)–C(28)–C(23)
N(7)–C(28)–C(27)
C(23)–C(28)–C(27)
ꢀ
ꢀ
A) became shorter than that in Sn(tmtaa)Cl2 (2.453 A)
[6]. Because of two different substitutions in two sides of

3516
X. Shen et al. / Inorganica Chimica Acta 357 (2004) 3510–3516
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the molecule, the tin atom is displaced from the N4
plane towards the benzenoid face of the ligand by 0.208
ꢀ
A. It is obviously longer than that in other tmtaa Sn(IV)
complexes (1 and Sn(tmtaa)Cl2[6]) containing two same
substitutions. The mean Sn–N bond distance in N4
ꢀ
plane is 2.068 A. Because of the interaction of 2,4,6-
trinitrophenolic group and tmtaa unit, the aromatic ring
in the 2,4,6-trinitrophenolic group is not vertical to the
N4 plane of tmtaa. The dihedral angle of N4 plane and
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ring, their dihedral angle being 8.7°. However, the
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dihedral angles are 38.0° and 31.2°, respectively. This
may be due to the interaction of these two nitro groups
and the methyl groups of the tmtaa unit.
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Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Center, CCDC Nos. 192195 and 192196 for crys-
tals of complexes 1 and 3. Copies of the data may be
obtained free of charge from The Director, CCDC, 12
Union Road. Cambridge, CB2 1EZ, UK (fax: +44-1223-
336-033; E-mail: deposit@ccdc.cam.ac.uk or www:
www.ccdc.cam.ac.uk).
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Acknowledgements
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We are grateful to the Center for Instrumental
Analysis, Kyushu Institute of Technology, Japan for
FAB mass spectra, H NMR spectra, solid state 119Sn
NMR spectra, elemental analyses and X-ray structure
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