Reversible CO2 fixation by intramolecularly coordinated diorganotin(IV) oxides

Article abstract of DOI:10.1016/j.jorganchem.2011.11.006

The intramolecularly coordinated organotin(IV) oxides [L(Ph)Sn(μ-O)] ₂ (1) and [L(Bu)Sn(μ-O)]₂ (2) readily absorb CO ₂ yielding molecular organotin(IV) carbonates L(Ph)SnCO₃ (3) and L(Bu)SnCO₃ (4) with terminally bonded the carbonate moiety. The easy desorption and reversible CO₂ fixation was achieved.

Full text of DOI:10.1016/j.jorganchem.2011.11.006

Journal of Organometallic Chemistry 699 (2012) 1e4
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Communication
Reversible CO2 fixation by intramolecularly coordinated diorganotin(IV) oxides
a
a
a
a,
ꢀb
*
ꢀ ꢁꢀ ꢀ
Barbora Mairychová , Libor Dostál , Ales Ruzicka , Ludvík Benes , Roman Jambor
a Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, CZ-532 10, Pardubice, Czech Republic
b Joint Laboratory of Solid State Chemistry, Institute of Macromolecular Chemistry of Academy of Sciences, v.v.i., Czech Republic
a r t i c l e i n f o
a b s t r a c t
Article history:
The intramolecularly coordinated organotin(IV) oxides [L(Ph)Sn(m-O)]2 (1) and [L(Bu)Sn(m-O)]2 (2)
Received 7 September 2011
Received in revised form
26 October 2011
readily absorb CO2 yielding molecular organotin(IV) carbonates L(Ph)SnCO3 (3) and L(Bu)SnCO3 (4) with
terminally bonded the carbonate moiety. The easy desorption and reversible CO2 fixation was achieved.
Ó 2011 Elsevier B.V. All rights reserved.
Accepted 3 November 2011
Keywords:
Organotin(IV)
CO2 fixation
Carbonate
1. Introduction
We have found out that a solution of intramolecularly coordi-
nated oxides, [L(Ph)Sn(m-O)]2 (1) or [L(Bu)Sn(m-O)]2 (2) (see
The increasing emission of carbon dioxide into the atmosphere
forced chemists to seek efficient solutions for the recovery of CO2
[1]. What else, CO2 being an inexpensive, nontoxic commodity,
holds considerable potential as a C1 feedstock for the preparation of
key intermediates, such as urea and dimethyl carbonate (DMC) [2].
For this reason, the fixation of CO2 is of current interest. The
possible solution is the CO2 fixation by organometallic species that
play an important role for the activation of the CeO bonds in CO2.
Organometallic compounds with MeX bonds are able to react with
CO2 providing new MeOeC(O)X fragments as the result of the CO2
insertion [3]. Interestingly, recent theoretical calculations sug-
gested that the coordination of CO2 to the metal atom is not the
driving force and that the insertion of CO2 is initiated by nucleo-
philic attack of X at the carbon atom of CO2 with assistance of the
metal center acting as a Lewis acid [4].
Scheme 1), readily absorbs gaseous CO2 at room temperature to
produce the unprecedented molecular organotin(IV) carbonates
L(Ph)SnCO3 (3) and L(Bu)SnCO3 (4) as air-stable crystalline mate-
rials. Compounds 3 and 4 are obtained when an excess of CO2 is
bubbled through the toluene solution of 1 or 2. The final products 3
and 4 were also detected when CH2Cl2 solution of 1 or 2 was
exposed for several days to air.
2. Result and discussion
The intramolecularly coordinated organotin(IV) oxides,
[LPhSn(m-O)]2 (1) and [L(Bu)Sn(m-O)]2 (2) were prepared by reac-
tion of the organotin(IV) chlorides L(Ph)SnCl2 and L(Bu)SnCl2 with
KOH (Scheme 1) [8].
In contrast to the variety of transition-metal compounds
that are able to form complexes with CO2, examples of main
group organometallic species known to bind CO2 are rare [1,5].
The promising main group species are organotin(IV) oxides,
(R3Sn)2O, hydroxides, R3SnOH, or di- and triorganotin alkoxides,
RnSn(OR0)4ꢀn (R, R0 ¼ organic group, n ¼ 2, 3), which react with
gaseous CO2 providing polymeric triorganotin(IV) carbonates,
(R3Sn)2CO3 [6] or di- and triorganotin(IV) (alkoxy) carbonates,
R3Sn(O2COR0) and R2Sn(OR0)(O2COR0) [7].
The molecular structures of 1 (Fig. 1) and 2 (Figure S1, see
supporting information) [9] are similar and display an almost
planar Sn2O2 core with the L ligands placed in mutually trans
positions with the regard to Sn2O2 ring. The NeSn bond lengths
(range of 2.627(5)e2.819(6) Å for 2 and 2.742(2)e2.755(2) Å for 3)
suggest the presence of N / Sn coordination in both compounds.
The structures of 1 and 2 are retained in C6D6 solution. The 119Sn
NMR spectrum of 1 showed a singlet resonance at
d
ꢀ191.0
(d
ꢀ131.7 for 2). The 1H NMR spectrum of 1 revealed an AX-type
resonance at dA 2.96 and dx 4.70 for the diastereotopic
CH2N protons in accordance with structure (dA 2.75 and dx 4.78
for 2).
* Corresponding author.
E-mail address: roman.jambor@upce.cz (R. Jambor).
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.11.006

2
B. Mairychová et al. / Journal of Organometallic Chemistry 699 (2012) 1e4
Scheme 1. Synthesis of the intramolecularly coordinated organotin(IV) oxides 1 and 2.
The bubbling of an excess of CO2 through the toluene solution of
1 and 2 provided organotin(IV) carbonates L(Ph)SnCO3 (3) and
L(Bu)SnCO3 (4), respectively (see Scheme 2).
The molecular structures of 3 and 4 (Fig. 2) [10] display an
almost planar SnO2C core with a coordination of the carbonate
moiety as a terminal ligand in a chelating fashion. This binding
mode of the carbonate is very rare for main group metal com-
pounds and to our knowledge there are few examples with
terminally bonded carbonate group reported up to now [5b,11].
Structurally characterized main group carbonates usually possess
the carbonate entity in a bridging position [12].
The carbonate CO3 moiety is bonded to the tin atom by two
oxygen atoms as a terminal ligand providing a four-membered
SnCO2 ring. The Sn(1)eO(1) and Sn(1)eO(2) bond lengths are
similar (2.099(3) and 2.107(3) Å for 3; 2.110(2) and 2.125(2) z for 4)
proving nearly symmetrical coordination of the carbonate in 3
and 4. The geometry of the tin atom can be described as a strongly
distorted octahedron, where both carbon atoms are situated in the
axial positions and two nitrogen atoms and two oxygen atoms
define the equatorial plane. The distortion seems to originate from
the chelating coordination mode of the carbonate.
Fig. 1. ORTEP view of 1. The thermal ellipsoids are drawn with 50% probability.
Hydrogen atoms are omitted for clarity. Selected bond distances (Å) and angles (ꢁ):
Sn(1)eO(1) 2.016(4), Sn(1)eO(1a) 2.023(4), Sn(1)eN(1) 2.819(6), Sn(1)eN(2)
2.627(5).
The structures of 3 and 4 are retained in CDCl3 solution. The
119Sn NMR spectrum of 3 revealed a signal at
d
ꢀ379.2 ( ꢀ314.0
d
for 4) that is consistent with the hexacoordinate tin atom. The
presence of the carbonate moiety is evident from the 13C NMR
spectrum of 3, where a signal at
The intramolecular N / Sn coordination in compound 3 is retained
d 163.5 was found (d 163.9 for 4).
Scheme 2. Synthesis of organotin(IV) carbonates 3 and 4.
Fig. 2. ORTEP view of 3 (A) and 4 (B). The thermal ellipsoids are drawn with 50% probability. Hydrogen atoms are omitted for clarity. Selected bond distances (Å) and angles (ꢁ): for
3: Sn(1)eO(1) 2.099(3), Sn(1)eO(2) 2.107(3), C(19)eO(1) 1.331(6), C(19)eO(2) 1.322(6), C(19)eO(3) 1.221(5), Sn(1)eN(1) 2.456(5), Sn(1)eN(2) 2.538(4), O(1)eSn(1)eO(2) 62.47(14),
C(1)eSn(1)eC(13) 145.83(17), N(1)eSn(1)eN(2) 133.20(14). For 4: Sn(1)eO(1) 2.110(2), Sn(1)eO(2) 2.125(2), C(17)eO(1) 1.333(4), C(17)eO(2) 1.325(4), C(17)eO(3) 1.223(4), Sn(1)e
N(1) 2.453(3), Sn(1)eN(2) 2.513(3), O(1)eSn(1)eO(2) 62.55(8), C(1)eSn(1)eC(13) 148.98(14), N(1)eSn(1)eN(2) 131.07(9).

B. Mairychová et al. / Journal of Organometallic Chemistry 699 (2012) 1e4
3
4. Experimental
4.1. General methods
The starting compounds [2,6-(Me2NCH2)2C6H3](Ph)SnCl2, [2,6-
(Me2NCH2)2C6H3](Bu)SnCl2 were prepared according to the litera-
ture [8]. Solvent was used as received without any drying. The
1H, 13C, 119Sn NMR spectra were recorded on a Bruker Avance500
spectrometer at 300 K in C6D6 or CDCl3. The 1H, 13C, 119Sn NMR
chemical shifts
d are given in ppm and referenced to external
Me4Sn (119Sn), Me4Si (13C, 1H). Elemental analyses were performed
on an LECO-CHNS-932 analyzer. The thermogravimetric analysis
was done using a homemade apparatus constructed of a computer-
controlled oven and a Sartorius BP210S balance. The measurements
were carꢀri1ed out in air between 30 and 450 ꢁC at a heating rate of
5 ꢁC min
.
4.2. Synthesis of [{2,6-(Me2NCH2)2C6H3}(Ph)Sn(m-O)]2 (1)
A solution of KOH (0.4 g, 6.7 mmol) in H2O (15 mL) was added to
a suspension of [2,6-(Me2NCH2)2C6H3](Ph)SnCl2 (0.3 g, 0.7 mmol)
in toluene (15 mL) at room temperature. The resulting mixture was
stirred for further 2 h at room temperature. After separation of the
mixture toluene-water, the toluene phase was evaporated in vacuo
to leave a solid residue. The solid was recrystallized from hexane to
give 1 as a white powder. Yield: 0.1 g (40%). Mp. 216e218 ꢁC. Anal.
calcd for C36H48N4O2Sn2 (805.40 g molꢀ1): C, 53.64; H, 6.00. Found:
Fig. 3. The reversible CO2 absorption process monitored by the 1H NMR spectroscopy
of compounds 1 and 3.
C, 54.03; H, 6.22. 1H NMR (C6D6, 500.13 MHz):
2.96 (AX system, 2H, CH2), 4.70 (AX system, 2H, CH2), 7.11e7.40
d 2.21 (s, 12H, CH3),
(m, 6H, ArH), 7.55 (d, 2H, ArH). 13C NMR (C6D6, 125.77 MHz):
d 44.7
(CH3), 64.2 (CH2), 125.9 (C (3,5)), 127.0 (C0(3,5)Ph), 127.3 (C0(4)Ph),
127.9 (C(4)), 135.2 (C0(2,6)Ph), 144.4 (C0(1)Ph), 146.2 (C(2,6)), 147.9
in solution resulting in an AX-type 1H NMR resonance at dA 3.33 and
dx 4.17 for the diastereotopic CH2N protons and two resonances at
(C(1)). 119Sn NMR (C6D6, 186.49 MHz):
d
ꢀ191.0.
d
2.19 and
2.70 for 4).
The reversibility of the absorption process is required, prefer-
d 2.41 for the NCH3 protons (dA 3.26 and dx 4.17; d 2.13 and
d
4.3. Synthesis of [{2,6-(Me2NCH2)2C6H3}(Bu)Sn(
m-O)]2 (2)
ably at a low temperature, to be suitable organometallic species for
the fixation and recovery of CO2 [1]. A thermogravimetric analysis
(TGA) of 3 and 4 showed mass loss between 140 and 195 ꢁC (10.8%
found, 9.8% calculated) in the first step of TGA for 3 and mass lost
between 100 and 150 ꢁC (8.0% found, 10.3% calculated) in the first
step of TGA for 4 associated with the liberation of CO2 (see
Supporting information).
A solution of KOH (1.0 g, 18 mmol) in H2O (15 mL) was added to
a suspension of [2,6-(Me2NCH2)2C6H3](Bu)SnCl2 (0.8 g, 1.8 mmol)
in toluene (15 mL) at room temperature. The consequent mixture
was stirred for further 2 h at room temperature. After separation of
the mixture tolueneewater, the toluene phase was evaporated
in vacuo to leave a solid residue. The solid was recrystallized from
hexane to give 2 as a white powder. Yield: 0.3 g (40%). Mp.
242e244 ꢁC. Anal. calcd for C34H56N4O2Sn2 (765.38 g molꢀ1):
C, 46.46; H, 6.93. Found: C, 46.03; H, 6.52. 1H NMR (C6D6,
The heating of 200 mg of 3 and 4 at 150 ꢁC for 2 h under argon
atmosphere resulted to the released of CO2 and the residual
material was identified by the 1H and 119Sn NMR spectroscopy as
the starting organotin(IV) oxides 1 and 2, respectively (for 1 see
Fig. 3). The residual organotin(IV) oxides 1 and 2 were dissolved in
toluene and used for the reabsorption of CO2. The 1H and 119Sn NMR
spectra of the crude products indicated the renewed quantitative
formation of 3 and 4, respectively (for 3 Fig. 3). This procedure was
repeated for 3 times without any loss of mass of the starting
material.
500.13 MHz):
d 0.73e1.35 (m, 9H, Bu), 2.21 (s, 12H, CH3), 2.75
(AX system, 2H, CH2), 4.78 (AX system, 2H, CH2), 6.70e7.20 (m, 3H,
ArH). 13C NMR (C6D6, 125.77 MHz):
d
13.8 (C0(4)Bu), 19.7 (C0(1)Bu),
23.0 (C0(1)Bu), 27.7 (C0(3)Bu), 27.8 (C0(3)Bu), 29.9 (C0(2)Bu), 31.2
(C0(2)Bu), 44.4 (CH3), 64.2 (CH2), 125.9 (C(3,5)), 129.0 (C(4)), 137.5
(C(1)), 145.9 (C(2,6)).119Sn NMR (C6D6, 186.49 MHz):
d
ꢀ131.7.
4.3. Synthesis of [2,6-(Me2NCH2)2C6H3](Ph)SnCO3 (3)
3. Conclusion
Carbon dioxide was bubbled through toluene solution (20 mL)
of 1 (0.2 g, 0.45 mmol) for 1 h at room temperature [Alternatively,
the toluene solution (20 mL) of 1 (0.2 g, 0.45 mmol) and dry ice was
stirred in an autoclave under the pressure 2 bar for 2 h]. After the
solid was precipitated from the solution, the solvent was decanted
and solid residue was washed with hexane to give 3 as a white
powder. Yield: 0.2 g (72%). Mp. 280e283 ꢁC. Anal. calcd for
C19H23N2O3Sn (447.01 g molꢀ1): C, 51.00; H, 5.40. Found: C, 50.73;
We have shown that the intramolecularly coordinated organo-
tin(IV) oxide [L(Ph)Sn(m-O)]2 (1) and [L(Bu)Sn(m-O)]2 (2) readily
absorb CO2 producing air-stable molecular organotin(IV) carbon-
ates L(Ph)SnCO3 (3) and L(Bu)SnCO3 (4), respectively. Compounds
3 and 4 contain planar SnO2C core due to an unusual coordination
of the carbonate moiety. The easy desorption of CO2 from com-
pounds 3 and 4 gave the starting organotin(IV) oxides 1 and 2. This
desorption process was achieved at rather low temperatures,
following by successful reabsorption of CO2.
H, 5.22. 1H NMR (CDCl3, 500.13 MHz):
d 2.19 (s, 6H, CH3), 2.41 (s, 6H,
CH3), 3.33 (AX system, 2H, CH2), 4.17 (AX system, 2H, CH2),
7.15e7.50 (m, 6H, ArH), 7.79 (d, 2H, ArH). 13C NMR (CDCl3, 125.77

4
B. Mairychová et al. / Journal of Organometallic Chemistry 699 (2012) 1e4
(c) A.-A.G. Shaikh, S. Sivaram, Chem. Rev. 96 (1996) 951e976;
MHz):
d
45.2 (CH3), 62.1 (CH2), 126.9 (C (3,5)), 128.9 (C0(3,5)Ph),
(d) X. Yin, J.R. Moss, Coord. Chem. Rev. 181 (1999) 27e59;
(e) D.B. Dell0Amico, F. Calderazzo, L. Labella, F. Marchetti, G. Pampaloni, Chem.
Rev. 103 (2003) 3857e3898;
130.5 (C0(4)Ph), 131.4 (C(4)), 133.5 (C0(1)Ph), 135.2 (C0(2,6)Ph),
136.7(C(1)), 143.3 (C(2,6)), 163.5 (CO). 119Sn NMR (CDCl3,
(f) Ch. Song, Catal. Today 115 (2006) 2e32;
(g) I. Omae, Catal. Today 115 (2006) 33e52.
186.49 MHz):
d
ꢀ379.2.
[2] For latest see (a) M. Honda, A. Suzuki, B. Noorjahan, K.-I. Fujimoto, K. Suzuki,
K. Tomishige, Chem. Commun. (2009) 4596e4598;
4.4. Synthesis of [2,6-(Me2NCH2)2C6H3](Bu)SnCO3 (4)
(b) M. Aresta, A. Dibenedetto, C. Pastore, C. Cuocci, B. Aresta, S. Cometa, E. De
Giglio, Catal. Today 137 (2008) 125e131;
(c) J. Bian, M. Xiao, S. Wang, Y. Lu, Y.Z. Meng, Catal. Commun. 10 (2009)
1142e1145;
(d) K. Alumusaiteer, Catal Commun. 10 (2009) 1127e1131;
(e) B.B. Fan, H.Y. Li, W.B. Fan, J.L. Zhang, R.F. Li, Appl. Catal. A 372 (2010)
94e102.
Carbon dioxide was bubbled through toluene solution (20 mL)
of 2 (0.3 g, 0.7 mmol) for 1 h at room temperature [Alternatively,
the toluene solution (20 mL) of 2 (0.3 g, 0.7 mmol) and dry ice was
stirred in an autoclave under the pressure 2 bar for 2 h]. After the
solid was precipitated from solution, the solvent was decanted and
solid residue was washed with hexane to give 4 as a white powder.
Yield: 0.2 g (61%). Mp. 238e240 ꢁC. Anal. calcd for C17H28N2O3Sn
(427.012 g molꢀ1): C, 41.9; H, 5.8. Found: C, 41.53; H, 5.42. 1H NMR
[3] (a) D.H. Gibson, in: J.A. McCleverty, T.J. Meyer (Eds.), Comprehensive Coordi-
nation Chemistry II, vol. 1, Elsevier, Oxford, 2004, pp. 595e602 ch. 30;
(b) D. Ballivet-Tkatchenko, H. Chermette, L. Plasseraud, O. Walter, Dalton
Trans. (2006) 5167e5175.
[4] (a) F. Hutschka, A. Dedieu, M. Eichberger, R. Fornika, W. Leitner, J. Am. Chem.
Soc. 119 (1997) 4432e4443;
(CDCl3, 500.13 MHz): d 1.00 (t, 3H, Bu), 1.52 (m, 2H, Bu), 1.59 (m, 2H,
Bu), 1.95 (m, 2H, Bu), 2.13 (s, 6H, CH3), 2.70 (s, 6H, CH3), 3.26
(AX system, 2H, CH2), 4.17 (AX system, 2H, CH2), 7.12 (d, 2H, ArH),
(b) Y. Ohnishi, T. Matsunaga, Y. Nakao, H. Sato, S. Sakaki, J. Am. Chem. Soc. 127
(2005) 4021e4032;
(c) M.L. Man, K.C. Lam, W.N. Sit, S.M. Ng, Z. Zhou, Z. Lin, C.P. Lau, Chem. Eur. J.
12 (2006) 1004e1015;
7.36 (t, 1H, ArH). 13C NMR (CDCl3, 125.77 MHz):
d
13.8 (C0(4)Bu),
18.2 (C0(1)Bu), 26.7 (C0(3)Bu), 26.9 (C0(2)Bu), 43.5 (CH3), 46.6 (CH3),
63.0 (CH2), 126.6 (C(3,5)), 131.4 (C(4)), 135.3 (C(2,6)), 143.4 (C(1)),
(d) K. Wakamatsu, A. Orita, J. Otera, Organometallics 29 (2010) 1290e1295.
[5] (a) J. Beckmann, D. Dakternieks, A. Duthie, N.A. Lewcenko, C. Mitchell, Angew.
Chem. Int. Ed. 43 (2004) 6683e6685;
163.9 (CO). 119Sn NMR (CDCl3, 186.49 MHz):
d
ꢀ314.0.
(b) E. Simon-Manso, C.P. Kubiak, Angew. Chem. Int. Ed 44 (2005) 1125e1128.
[6] (a) A.J. Bloodworth, A.G. Davies, S.C. Vasishtha, J. Chem. Soc.
C (1967)
1309e1313;
4.5. X-ray structure determination
(b) S.J. Blunden, R. Hill, J.N.R. Ruddick, J. Organomet. Chem. 267 (1984) C5eC8;
(c) J. Kümmerlen, A. Sebald, H. Reuter, J. Organomet. Chem. 427 (1992)
309e323.
Compounds 1 and 2 were dissolved in hexane and slow diffu-
sion of prepared solutions gave X-ray quality material. Compound 3
and 4 were dissolved in CH2Cl2 and slow diffusion of prepared
solutions gave X-ray quality material. The X-ray data for colorless
crystals of 1e4 (see Table S1 in supporting information) were
obtained at 150 K using Oxford Cryostream low temperature device
[7] (a) J.-C. Choi, T. Sakakura, T. Sako, J. Am. Chem. Soc. 121 (1999) 3793e3794;
(b) T. Sakakura, J.-C. Choi, Y. Saito, T. Masuda, T. Sako, T. Oriyama, J. Org. Chem.
64 (1999) 4506e4508;
(c) D. Ballivet-Tkatchenko, O. Douteau, S. Stutzmann, Organometallics 19
(2000) 4563e4567;
(d) H. Yasuda, J.-C. Choi, S.-C. Lee, T. Sakakura, J. Organomet. Chem. 659 (2002)
133e141;
(e) D. Ballivet-Tkatchenko, T. Jerphagnon, R. Ligabue, L. Plasseraud, D. Poinsot,
Appl. Catal. A 255 (2003) 93e99;
on
a
Nonius KappaCCD diffractometer with MoKa radiation
and scan
(l
¼ 0.71073 Å), a graphite monochromator, and the
4
c
(f) H.C. Clark, R.G. Goel, J. Organometal. Chem. 7 (1967) 263e272.
mode. Data reductions were performed with DENZO-SMN [13]. The
absorption was corrected by integration methods [14]. Structures
were solved by direct methods (Sir92) [15] and refined by full
matrix least-square based on F2 (SHELXL97) [16]. Hydrogen atoms
were mostly localized on a difference Fourier map, however to
ensure uniformity of the treatment of the crystal, all hydrogen
atoms were recalculated into idealized positions (riding model) and
assigned temperature factors Hiso(H) ¼ 1.2 Ueq(pivot atom) or of
1.5 Ueq for the methyl moiety with CeH ¼ 0.96, 0.97, and 0.93 Å for
methyl, methylene and hydrogen atoms in aromatic rings moiety,
respectively.
ꢁꢀ ꢀ
ꢀ
ꢀ
[8] (a) A. Ruzicka, R. Jambor, J. Brus, I. Císarová, J. Holecek, Inorg. Chim. Acta. 323
(2001) 163e170;
ꢁꢀ ꢀ
ꢀ
ꢀ
(b) A. Ruzicka, R. Jambor, I. Císarová, J. Holecek, Chem. Eur. J. 9 (2003)
2411e2418.
[9] 1:
C36H48N4O2Sn2,
triclinic,
P
,
a ¼ 9.8670(6),
b ¼ 11.0989(6),
ꢀ1
c ¼ 18.7191(12),
a
¼ 77.892(5)ꢁ,
b
¼ 77.300(6)ꢁ,
g
¼ 65.238(4)ꢁ, V ¼ 1799.9(2)
Å3, Z ¼ 2, R1 (obsd data) ¼ 0.0554, wR2 (all data) ¼ 0.1112. CCDC
835082.2: C32H56N4O2Sn2, triclinic,
P
ꢀ1
,
a ¼ 9.8370(4), b ¼ 9.9380(3),
c ¼ 10.2931(4),
a
¼ 69.179(3)ꢁ,
b
¼ 65.041(3)ꢁ,
g
¼ 84.333(3)ꢁ, V ¼ 851.14(6)
Å3, Z ¼ 1, R1 (obsd data) ¼ 0.0220, wR2 (all data) ¼ 0.0532. CCDC 835514.
[10] 3: C19H24N2O3Sn, monoclinic, P21/c
,
a ¼ 9.2780(2), b ¼ 14.8611(11),
c ¼ 16.2460(13),
a
¼ 90.0ꢁ,
b
¼ 122.122(4)ꢁ,
g
¼ 90.0(4)ꢁ, V ¼ 1897.1(2) Å3,
Z ¼ 4, R1 (obsd data) ¼ 0.0424, wR2 (all data) ¼ 0.1217. CCDC 835515. 4: (2 ꢂ 4),
CH2Cl2: C35H52N4Cl2O6Sn, triclinic,
P
,
a ¼ 9.5980(11), b ¼ 12.1691(18),
ꢀ1
b
c ¼ 18.2560(10),
a
¼ 91.480(7)ꢁ,
¼ 101.821(8)ꢁ,
g
¼ 103.742(9)ꢁ,
V ¼ 2021.1(4) Å3, Z ¼ 2, R1 (obsd data) ¼ 0.0324, wR2 (all data) ¼ 0.0776. CCDC
Acknowledgment
835513.
[11] (a) M.H. Hsu, R.T. Chen, W.S. Sheu, M. Shieh, Inorg. Chem. 45 (2006)
The authors wish to thank the Grant Agency of the Czech
Republic (project no. P106/10/0443) and The Ministry of Education
of the Czech Republic (projects no. VZ0021627501) for financial
support.
6740e6747;
ꢀ
ꢁꢀ ꢀ
ꢀ
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Appendix. Supplementary material
Supplementary material associated with this article can
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11.006.
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