24- and 26-membered macrocyclic diorganotin(IV) bis-dithiocarbamate complexes with N,N′-disubstituted 1,3- and 1,4-bis(aminomethyl)benzene and 1,1′-bis(aminomethyl)ferrocene as spacer groups

Article abstract of DOI:10.1021/ic801464s

The potassium bis-dithiocarbamate (bis-dtc) salts of 1,3- bis(benzylaminomethyl)benzene (1,3-Bn-ambdtc), 1,3-bis(iso-butylaminomethyl) benzene (1,3-ⁱBu-ambdtc), 1,4-bis(benzylaminomethyl)benzene (1,4-Bn-ambdtc), and 1,4-bis(iso-butylaminomethyl

Full text of DOI:10.1021/ic801464s

Inorg. Chem. 2008, 47, 9804-9812
24- and 26-Membered Macrocyclic Diorganotin(IV) Bis-Dithiocarbamate
Complexes with N,N′-Disubstituted 1,3- and
1,4-Bis(aminomethyl)benzene and 1,1′-Bis(aminomethyl)ferrocene as
Spacer Groups
Ericka Santacruz-Jua´rez, Jorge Cruz-Huerta, Ira´n Fernando Herna´ndez-Ahuactzi,
Reyna Reyes-Mart´ınez, Hugo Tlahuext, Hugo Morales-Rojas, and Herbert Ho¨pfl*
Centro de InVestigaciones Qu´ımicas, UniVersidad Auto´noma del Estado de Morelos, AV.
UniVersidad 1001, C.P. 62209 CuernaVaca, Me´xico
Received April 14, 2008
The potassium bis-dithiocarbamate (bis-dtc) salts of 1,3-bis(benzylaminomethyl)benzene (1,3-Bn-ambdtc), 1,3-
bis(iso-butylaminomethyl)benzene (1,3-iBu-ambdtc), 1,4-bis(benzylaminomethyl)benzene (1,4-Bn-ambdtc), and 1,4-
bis(iso-butylaminomethyl)benzene (1,4-iBu-ambdtc) were reacted with three different diorganotin dichlorides (R2SnCl2
with R ) Me, nBu, and Ph) in 1:1 stoichiometric ratios to give the corresponding diorganotin bis-dithiocarbamates.
Additionally, the dimethyltin bis-dithiocarbamate of 1,1′-bis(benzylaminomethyl)ferrocene (1,1′-Bn-amfdtc) was
prepared. The resulting complexes have been characterized as far as possible by elemental analysis, FAB+ mass
spectrometry, IR and NMR (1H, 13C, and 119Sn) spectroscopy, and single-crystal X-ray diffraction, showing that the
tin complexes are dinuclear 24- and 26-membered macrocyclic species of composition [{R2Sn(bis-dtc)}2]. As shown
by 119Sn NMR spectroscopy, the tin centers are hexa-coordinated in all cases; however, two different coordination
environments are possible, as detected by single-crystal X-ray diffraction. In the dimethyltin derivatives of 1,3-Bn-
ambdtc, 1,3-iBu-ambdtc, 1,4-Bn-ambdtc, and 1,1′-Bn-amfdtc and the di-n-butyltin derivative of 1,3-iBu-ambdtc, the
metal atoms are embedded in skewed-trapezoidal-bipyramidal coordination polyhedra with asymmetrically coordinating
trans-oriented dtc groups. In contrast, in the diphenyltin derivative 1,3-iBu-ambdtc, the metal centers have distorted
octahedral coordination with symmetrically coordinating cis-oriented dtc functions. Thus, for the complexes derived
from 1,3-Bn/iBu-ambdtc, two different macrocyclic structures were observed. In the dimethyl- and di-n-butyltin
derivatives, the bridging bis-dtc ligands adopt U-shaped conformations, while in the case of the diphenyltin derivative,
the conformation is L-shaped. Furthermore, two different macrocyclic ring conformations can occurr, which differ in
the spatial orientation of the substituents attached to the nitrogen atoms (Bn or iBu). The dimethyltin derivatives of
1,4-Bn-ambdtc and 1,1′-Bn-amfdtc have cavities, in which aromatic rings are accomodated in the solid state.
1. Introduction
creation of a large number of metallosupramolecular archi-
tectures having either macrocyclic, cagelike or polymeric
structures.1 A series of different applications such as selective
molecular and ion recognition, separation, storage, transport,
and catalysis are envisioned for these systems, and one of
the main targets is the generation of discrete or infinite
systems having cavities, channels, or pores.2 The evolution
of this chemistry is now getting to a point, at which the cavity
The past two decades have shown that the combination
of metal ions with di- or oligofunctional ligands allows the
* Author to whom correspondence should be addressed. Fax: (+52) 777
329 79 97. E-mail: hhopfl@ciq.uaem.mx.
(1) For recent reviews, see: (a) Rao, C. N. R.; Natarajan, S.; Vaidhy-
anathan, R. Angew. Chem., Int. Ed. 2004, 43, 1466. (b) Ferey, C.;
Mellot-Draznieks, C; Serre, C.; Millange, F. Acc. Chem. Res. 2005,
38, 217. (c) Hosseini, M. W. Acc. Chem. Res. 2005, 38, 313. (d)
Nitschke, J. R. Acc. Chem. Res. 2007, 40, 103. (e) Pitt, M. A.; Johnson,
D. W. Chem. Soc. ReV. 2007, 36, 1441. (f) Thomas, J. A. Chem. Soc.
ReV. 2007, 36, 856. (g) Ariga, K.; Hill, J. P.; Lee, M. V.; Vinu, A.;
Charvet, R.; Acharya, S. Sci. Technol. AdV. Mater. 2008, 9, 014109
(96 pp).
(2) For recent reviews, see: (a) Rowsell, J. L. C.; Yaghi, O. M. Angew.
Chem., Int. Ed. 2005, 44, 4670. (b) Sanchez, C.; Julia´n, B.; Belleville,
P.; Popall, M. J. Mater. Chem. 2005, 15, 3559. (c) Mueller, U.;
Schubert, M.; Teich, F.; Puetter, H.; Schierle-Arndt, K.; Pastre´, J. J.
Mater. Chem. 2006, 16, 626.
9804 Inorganic Chemistry, Vol. 47, No. 21, 2008
10.1021/ic801464s CCC: $40.75  2008 American Chemical Society
Published on Web 10/01/2008

Diorganotin(IV) Bis-Dithiocarbamate Complexes
propertiesssize, shape, and functionalityscan be tuned.3
Possible sites for modifications in this respect are the metal
centers, the metal-coordinating functions, the spacer groups
between the coordinating donor atoms, and additional
substituents located in the interior or at the periphery of the
cavity. To reduce the synthetic effort required for this purpose
to a minimum, it is important to develop metal-ligand
assemblies, in which as many as possible of the above-
mentioned parameters can be easily modified.
The vast majority of metallosupramolecular assemblies are
constructed from ligands having nitrogen or oxygen as metal-
coordinating donors.1 Recently, the research groups of
Tiekink and Beer have shown that architectures based on
sulphur-containing ligands, in particular bis- and tris-
dithiocarbamate ligands, are an excellent alternative choice
for this purpose that merit further exploration.4 Important
differences from conventional oxygen- and nitrogen-contain-
ing ligands, such as amines, carboxylates, sulfonates, and
phosphonates, arise from the formation of frequently strong,
but less polar metal-sulfur bonds, which enhances the
solubulity of the resulting metal complexes in organic
solvents and provides them with lipophilic cavities. Further-
more, using secondary amine precursors, it is possible to
introduce a variety of additional substituents in dithiocarba-
mates.
So far, little is known about assemblies derived from
organometallic building blocks, albeit they have the advan-
tage that the organic substituents provide a further, easily
accessible site for modifications of the molecular properties.
The number of feasible candidates for such an application
is quite reduced, first, because the building blocks should
have metal-carbon bonds of reasonable stability from a
kinetic and thermodynamic point of view and, second,
because the organometallic entities should have a metal
center large enough for combination with chelating ligand
functions, since these provide stronger metal-ligand interac-
tions.5 Organotin moieties fullfill both requirements and are
therefore ideal candidates.
assemblies obtained from R4-nSn(IV) groups and di- or
oligofunctional organic ligands are rare so far and deal
principally with ligands containing carboxylate functions.6,7
With diorganotin moieties, macrocycles with sulphur-
containing ligands have been explored previously mainly by
the research groups of Lockhart, Gielen, and Ma.8,9 Although
the chemistry of organotin dithiocarbamate complexes has
been widely explored,10 for macrocyclic organotin bis(dithio-
carbamates), there are only three reports.9 Two date from
1986 and describe the molecular structures of [R2Sn(endtc)]9a
and [R′2Sn(1,3-pdtc)]9b [with endtc ) 1,2-ethylenebis(dithio-
carbamate); 1,3-pdtc ) 1,3-phenylenebis(dithiocarbamate);
t
n
R ) Bu, Ph, and R′ ) Me, Cy, Bu]. The third dates from
2008 and describes the 26-membered macrocycles [R2Sn(1,6-
Bn-hmdtc)]9c (with 1,6-Bn-hmdtc ) N,N′-dibenzyl-1,6-
9c
n
hexamethylenebis(dithiocarbamate); R ) Me, Bu).
Herein, we report on the preparation and structural
characterization of a further 13 diorganotin(IV) bis(dithio-
carbamates) with 24- and 26-membered macrocyclic struc-
tures, which have been obtained from 1,3- and 1,4-
bis(aminomethyl)benzene and 1,1′-bis(aminomethyl)ferrocene
as spacer groups.
2. Experimental Section
Instrumental. NMR studies were carried out with Varian Gemini
200 and Varian Inova 400 instruments. Standard references were
used: TMS (δ1H ) 0 and δ13C ) 0) and SnMe4 (δ119Sn ) 0). IR
spectra have been recorded on a Bruker Vector 22 FT spectropho-
tometer. Mass spectra were obtained on a Jeol JMS 700 instrument.
Elemental analyses have been carried out on Perkin Elmer Series
(6) (a) Pettinari, C.; Marchetti, F.; Pettinari, R.; Martini, D.; Drozdov,
A.; Troyanov, S. J. Chem. Soc., Dalton Trans. 2001, 1790. (b) Beltran,
H.I.; Zamudio-Rivera, L.S.; Mancilla, T.; Santillan, R.; Farfan, N
Chem.sEur. J. 2003, 9, 2291. (c) Prabusankar, G.; Murugavel, R.
Organometallics 2004, 23, 5644. (d) Baul, T. S. B.; Singh, K. S.;
Lycka, A.; Holcapek, M.; Linden, A. J. Organomet. Chem. 2005, 690,
1581. (e) Baul, T. S. B.; Masharing, C.; Willem, R.; Biesemans, M.;
Holcapek, M.; Jirasko, R.; Linden, A. J. Organomet. Chem. 2005,
690, 3080. (f) Baul, T. S. B.; Singh, K. S.; Holcapek, M.; Jirasko, R.;
Rivarola, E.; Linden, A. J. Organomet.Chem. 2005, 690, 4232. (g)
Ma, C.; Li, J.; Zhang, R.; Wang, D. Inorg. Chim. Acta 2005, 358,
4575. (h) Bowen, R. J.; Caddy, J.; Fernandes, M. A.; Layh, M.; Mamo,
M. A.; Meijboom, R. J. Organomet. Chem. 2006, 691, 717. (i)
Chandrasekhar, V.; Thirumoorthi, R. Organometallics 2007, 26, 5415.
(7) (a) Garcia-Zarracino, R.; Ramos-Quin˜ones, J.; Ho¨pfl, H. Inorg. Chem.
2003, 42, 3835. (b) Garcia-Zarracino, R.; Ho¨pfl, H. Angew. Chem.,
Int. Ed. 2004, 43, 1507. (c) Zamudio-Rivera, L. S.; George-Tellez,
R.; Lopez-Mendoza, G.; Morales-Pacheco, A.; Flores, E.; Ho¨pfl, H.;
Barba, V.; Fernandez, F. J.; Cabirol, N.; Beltran, H. I. Inorg. Chem.
2005, 44, 5370. (d) Garcia-Zarracino, R.; Ho¨pfl, H. J. Am. Chem. Soc.
2005, 127, 3120. (e) Hernandez-Ahuactzi, I. F.; Cruz-Huerta, J.; Barba,
V.; Ho¨pfl, H.; Zamudio-Rivera, L. S.; Beltran, H. I. Eur. J. Inorg.
Chem. 2008, 1200.
Although there are several reports on macrocyclic or
cagelike organotin systems with monofunctional ligands such
as carboxylates, phosphates, phosphonates, and so forth,5b,d-f
(3) (a) Eddahoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O’Keeffe,
M.; Yaghi, O. M. Science 2002, 295, 469. (b) Li, C.-J.; Hu, S.; Li,
W.; Lam, C.-K.; Zheng, Y.-Z.; Tong, M.-L. Eur. J. Inorg. Chem. 2006,
1931. (c) Sudik, A. C.; Cote, A. P.; Wong-Foy, A. G.; O′Keeffe, M.;
Yaghi, O. M. Angew. Chem., Int. Ed. 2006, 45, 2529.
(4) For reviews, see: (a) Tiekink, E. R. T. CrystEngComm 2003, 5, 101.
(b) Cookson, J.; Beer, P. D. Dalton Trans. 2007, 1459. (c) Tiekink,
E. R. T. Appl. Organomet. Chem. 2008, 22, 533.
(5) For reviews on macrocyclic and supramolecular assemblies based on
organometallic species of main group elements, see: (a) Uhl, W. Chem.
Soc. ReV. 2000, 29, 259. (b) Haiduc, I.; Edelmann, F. T. Supramo-
lecular Organometallic Chemistry; Wiley-VCH: Weinheim, Germany,
2000. (c) Ho¨pfl, H. Structure and Bonding; Roesky, H. W., Atwood,
D. A., Eds.; Springer Verlag: Berlin, 2002; Vol. 103, pp 1-56. (d)
Chandrasekhar, V.; Nagendran, S.; Baskar, V. Coord. Chem. ReV.
2002, 235, 1. (e) Chandrasekhar, V.; Gopal, K.; Thilagar, P. Acc.
Chem. Res. 2007, 40, 420. (f) Ho¨pfl, H. In Tin Chemistry: Funda-
mentals, Frontiers and Applications; Davies, A. G., Gielen, M., Panell,
K. H., Tiekink, E. R. T., Eds.; Wiley: Chichester, UK, 2008; pp
117–137. (g) Chandrasekhar, V.; Singh, P.; Gopal, K. In Tin
Chemistry: Fundamentals, Frontiers and Applications; Davies, A. G.,
Gielen, M., Panell, K. H., Tiekink, E. R. T., Eds.; Wiley: Chichester,
UK, 2008; pp 93–116.
(8) (a) Lockhart, T. P. Organometallics 1988, 7, 1438. (b) Meunier-Piret,
J.; Boualam, M.; Willem, R.; Gielen, M. Main Group Met. Chem.
1993, 16, 329. (c) Ma, C.; Jiang, Q.; Zhang, R. J. Organomet. Chem.
2003, 678, 148. (d) Ma, C.; Han, Y.; Zhang, R.; Wang, D. Dalton
Trans. 2004, 1832. (e) Ma, C.; Jiang, Q.; Zhang, R. Can. J. Chem.
2004, 82, 608. (f) Ma, C.; Zhang, Q.; Zhang, R.; Wang, D.
Chem.sEur. J. 2006, 12, 420.
(9) (a) Jung, O.-S.; Sohn, Y. S.; Ibers, J. A. Inorg. Chem. 1986, 25, 2273.
(b) Lee, W. H.; Jung, O.-S.; Sohn, Y. S.; Kim, P. Bull. Korean Chem.
Soc. 1986, 7, 421. (c) Reyes-Mart´ınez, R.; Mejia-Huicochea, R.;
Guerrero-Alvarez, A. A.; Ho¨pfl, H.; Tlahuext, H. ArkiVoc 2008, V,
19.
(10) Heard, P. J. Main Group Dithiocarbamate Complexes. In Progress in
Inorganic Chemistry; John Wiley & Sons, New Jersey, 2005; Vol.
53, pp 1-70.
Inorganic Chemistry, Vol. 47, No. 21, 2008 9805

Santacruz-Jua´rez et al.
II 2400 and Elementar Vario ELIII instruments, using samples that
have been dried previously at 65 °C for 2 h in an Abderhalden
instrument.
(m), 993 νas(CSS) (m), 879 (w), 790 (m), 700 (w), 608 (w), 556
1
(w) cm-1. H NMR (200 MHz, CDCl3, TMS, 20 °C): δ 0.94 (d,
2
24H, CH-CH3), 1.63 (s, 12H, JSn-H ) 84 Hz, Sn-CH3), 2.35 (m,
i
Preparative Part. Benzylamine, iso-butylamine, isophthalde-
hyde, terephthaldehyde, 1,1′-ferrocenedicarboxaldehyde, Me2Sn-
4H, CH-CH3), 3.59 (br, s, 8H, CH2 Pr), 5.10 (br, s, 8H, NCH2C6H4),
7.08 (m, 6H, 2-H, 4-H, 6-H), 7.33 (t, 2H, 5-H). 13C NMR (50 MHz,
n
Cl2, Bu2SnCl2, and Ph2SnCl2 were commercially available and
CDCl3, TMS, 20 °C): δ 16.1 (Sn-CH3), 20.6 (CH-CH3), 27.4 (CH-
i
have been used without further purification. The dialdehydes
were reacted in one-pot syntheses with benzylamine/iso-butyl-
amine and sodium borohydride to give the N,N′-disubstituted
1,3-bis(aminomethyl)benzene, 1,4-bis(aminomethyl)benzene, and
1,1′-bis(aminomethyl)ferrocene ligands in quantitative yields. For
the preparation of the diorganotin compounds 1-13, the same
synthetic procedure has been used, which is therefore given in
detail only for compound 1.
CH3), 57.7 (CH2 Pr), 60.3 (NCH2C6H4), 123.5 (C-2), 127.2 (C-4,
C-6), 129.0 (C-5), 136.4 (C-1, C-3), 202.4 (CSS). 119Sn NMR (149
MHz, CDCl3, SnMe4, 20 °C): δ -339.3. MS (FAB+): m/z (%) 1095
([M + H]+, 5), 1079 ([M - CH3]+, 6). Anal. calcd for
C40H62N4S8Sn2 (1094.90): C, 43.88; H, 5.89; N, 5.12. Found: C,
43.63; H, 5.78; N, 5.15.
[{nBu2Sn(1,3-iBu-ambdtc)}2] (5). Yield: 78%. Mp: 157-159 °C.
IR (KBr): ν˜ 2958 (m), 2921 (m), 2865 (w), 1609 (w), 1467 ν(N-
CSS) (s), 1416 (m), 1347 (w), 1281 (w), 1230 (m), 1179 (m), 1117
[{Me2Sn(1,3-Bn-ambdtc)}2] (1). 1,3-Bis(benzylaminomethyl)
benzene (0.100 g, 0.32 mmol), triethylamine (0.09 mL, 0.64 mmol),
and carbon disulfide (0.95 mL, 15.8 mmol) were dissolved in
methanol (25 mL) and stirred for 2 h, whereupon dimethyltin
dichloride (0.070 g, 0.32 mmol) dissolved in 10 mL of methanol
was added. The mixture was stirred for 2 h. A white powder
precipitated that was filtered and recrystallized from a mixture of
dichloromethane and benzene. Yield: 0.133 g (70%). Mp: 177-179
°C. IR (KBr): ν˜ 3027 (w), 2917 (w), 1604 (w), 1463 ν(N-CSS)
(m), 1412 (m), 1352 (w), 1215 (m), 1154 (w), 1085 (w), 994
νas(CSS) (w), 787 (w), 741 (w), 692 (w), 623 (w), 558 (w), 521
1
(m), 994 νas(CSS) (w), 875 (w), 693 (w), 608 (w) ppm. H NMR
(200 MHz, CDCl3, TMS, 20 °C): δ 0.93 (m, 36H, CH-CH3, δ-H),
1.45 (m, 8H, γ-H), 1.96 (m, 8H, ꢀ-H), 2.12 (m, 8H, R-H), 2.34
i
(m, 4H, CH-CH3), 3.63 (d, 8H, CH2 Pr), 5.20 (s, 8H, NCH2C6H4),
7.07-7.20 (m, 6H, 2-H, 4-H, 6-H), 7.32 (t, 2H, 5-H). 13C NMR
(50 MHz, CDCl3, TMS, 20 °C): δ 14.2 (C-δ), 20.4 (CH-CH3), 26.6,
i
26.7 (CH-CH3, C-γ), 29.0 (C-ꢀ), 34.7 (C-R), 57.6 (CH2 Pr), 60.5
(NCH2C6H4), 123.2 (C-2), 126.5, 127.2 (C-4, C-6), 129.3 (C-5),
136.1, 136.5 (C-1, C-3), 203.1 (CSS). 119Sn NMR (74.5 MHz,
CDCl3, SnMe4, 20 °C): δ -340.6. MS (FAB+): m/z (%) 1263 ([M
1
n
(w) cm-1. H NMR (400 MHz, CDCl3, TMS, 20 °C): δ 1.77 (s,
+ H]+, 1), 1205 ([M - Bu]+, 2). Anal. calcd for C52H88N2S8Sn2
2
12H, JSn-H ) 79 Hz, Sn-CH3), 5.01 (m, 16 H, NCH2), 7.02 (dd,
(1263.22): C, 49.44; H, 7.02; N, 4.44. Found: C, 49.32; H, 7.58;
4H, 4-H, 6-H), 7.26-7.39 (m, 24H, 2-H, 5-H, C6H5). 13C NMR
(100 MHz, CDCl3, TMS, 20 °C): δ 16.6 (Sn-CH3), 55.7, 56.0
(NCH2), 123.7 (C-2), 127.6 (C-p), 127.9 (C-m), 128.1 (C-4, C-6),
129.0 (C-o), 129.1 (C-5), 135.2, 136.2 (C-1, C-3, C-i), 203.1 (CSS).
119Sn NMR (74.5 MHz, CDCl3, SnMe4, 20 °C): δ -335.7. MS
(FAB+): m/z (%) 1231 ([M + H]+, 10), 1215 ([M - CH3]+, 13).
Anal. Calcd for C52H56N4S8Sn2 ·2C6H6 (1387.19): C, 55.41; H, 4.94;
N, 4.04. Found: C, 55.02; H, 4.95; N, 4.31.
N, 4.29.
[{Ph2Sn(1,3-iBu-ambdtc)}2] (6). Yield: 82%. Mp: 144-147 °C.
IR (KBr): ν˜ 3051 (w), 2957 (m), 2611 (w), 2494 (w), 1623 (w),
1479 ν(N-CSS) (s), 1422 (m), 1348 (w), 1233 (m), 1176 (m), 1114
(m), 983 νas(CSS) (m), 730 (m), 693 (m), 611 (w), 451 (w) cm-1
.
1H NMR (200 MHz, CDCl3, TMS, 20 °C): δ 0.92 (d, 24H, CH-
i
CH3), 2.25 (m, 4H, CH-CH3), 3.50 (d, 8H, CH2 Pr), 5.01 (s, 8H,
NCH2C6H4), 7.10-7.35 (m, 20H, 2-H, 4-H, 5-H, 6-H, m-H, p-H),
[{nBu2Sn(1,3-Bn-ambdtc)}2] (2). Yield: 75%. Mp: 152-154 °C.
IR (KBr): ν˜ 3028 (w), 2921 (m), 2859 (w), 1620 (w), 1462 ν(N-
CSS) (s), 1408 (m), 1352 (w), 1273 (w), 1212 (m), 1150 (m), 986
νas(CSS) (m), 879 (w), 694 (m), 629 (w), 562 (w) cm-1. 1H NMR
(400 MHz, CDCl3, TMS, 20 °C): δ 1.02 (t, 12H, δ-H), 1.52-1.60
(m, 8H, γ-H), 2.05-2.09 (m, 8H, ꢀ-H), 2.22-2.28 (m, 8H, R-H),
5.08 (br, s, 16H, NCH2), 7.23-7.37 (m, 28H, aromatic hydrogens).
119Sn NMR (74.5 MHz, CDCl3, SnMe4, 20 °C): δ -338.2. MS
7.88 (m, 8H, JSn-H ) 77 Hz, o-H). 13C NMR (50 MHz, CDCl3,
3
i
TMS, 20 °C): δ 20.4 (CH-CH3), 27.3 (CH-CH3), 58.7 (CH2 Pr),
61.8 (NCH2C6H4), 121.8 (C-2), 125.9 (C4, C-6), 126.9 (C-p), 128.2
(C-m), 129.5 (C-5), 134.2 (C-o), 135.5 (C-1, C-3), 151.6 (C-i), 201.9
(CSS). 119Sn NMR (74.5 MHz, CDCl3, SnMe4, 20 °C): δ -499.6.
MS (FAB+): m/z (%) 1343 ([M + H]+, 1), 1265 ([M - Ph]+, 2).
Anal. calcd for C60H72N2S8Sn2 (1343.18): C, 53.65; H, 5.40; N,
4.17. Found: C, 53.69; H, 5.73; N, 4.41.
n
(FAB+): m/z (%) 1399 ([M + H]+, 18), 1341 ([M - Bu]+, 60).
[{Me2Sn(1,4-Bn-ambdtc)}2] (7). Yield: 75%. Mp: 128-130 °C
(dec.). IR (KBr): ν˜ 3028 (w), 2917 (w), 1606 (w), 1512 (w), 1494
(w), 1470 ν(N-CSS) (s), 1452 (m), 1408 (s), 1354 (m), 1270 (w),
1217 (s), 1151 (m), 1078 (w), 976 νas(CSS) (m), 937 (w), 790 (m),
Anal. calcd for C64H80N4S8Sn2 (1399.29): C, 54.93; H, 5.76; N,
4.00. Found: C, 55.35; H, 5.70; N, 4.22.
[{Ph2Sn(1,3-Bn-ambdtc)}2] (3). Yield: 70%. Mp: 107-109 °C.
IR (KBr): ν˜ 3028 (w), 2915 (w), 1711 (w), 1605 (w), 1493 (w),
1469 ν(N-CSS) (m), 1451 (m), 1411 (m), 1355 (m), 1215 (s),
1150 (m), 1078 (w), 977 νas(CSS) (m), 789 (m), 734 (w), 699 (m),
626 (w), 555 (w), 516 (w) cm-1. 1H NMR (200 MHz, CDCl3, TMS,
20 °C): δ 4.96 (s, 16H, NCH2), 6.92-7.26 (m, 40H, aromatic
hydrogens), 7.90 (d, 8H, o-H). 13C NMR (50 MHz, CDCl3, TMS,
20 °C): δ 56.9, 57.5 (NCH2), 127.5, 127.9, 128.2, 128.4, 129.0,
129.1 (C-2, C-4, C-5, C-6, C-o, C-m, C-p, CSn-m, CSn-p), 134.4,
134.6, 135.6 (C-1, C-3, C-i, CSn-o), 150.9 (CSn-i), 202.3 (CSS).
119Sn NMR (74.5 MHz, CDCl3, SnMe4, 20 °C): δ -491.0. MS
(FAB+): m/z (%) 1402 ([M - Ph]+, 1), 1047 (21), 663 ([M -
2Ph]2+, 72). Anal. calcd for C72H64N4S8Sn2 (1479.25): C, 58.46;
H, 4.36; N, 3.79. Found: C, 58.72; H, 4.71; N, 4.04.
733 (w), 698 (m), 606 (w), 554 (w) cm-1. H NMR (200 MHz,
1
2
CDCl3, 20 °C, TMS): δ 1.60 (s, 12H, JSn-H ) 81 Hz, Sn-CH3),
5.00 (br, s, 16H, NCH2), 7.19-7.35 (m, 28H, aromatic hydrogens).
119Sn NMR (74.5 MHz, CDCl3, SnMe4, 20 °C): δ -338.4. MS
(FAB+): m/z (%) 1231 ([M + H]+, 5), 1215 ([M - CH3]+, 6). Anal.
calcd for C52H56N4S8Sn2 (1230.97): C, 50.74; H, 4.59; N, 4.55.
Found: C, 50.57; H, 5.10; N, 4.96.
[{nBu2Sn(1,4-Bn-ambdtc)}2] (8). Yield: 75%. Mp: 158-159 °C.
IR (KBr): ν˜ 3029 (w), 2955 (m), 2922 (m), 2854 (w), 1638 (w),
1512 (w), 1494 (w), 1468 ν(N-CSS) (s), 1408 (s), 1353 (m), 1216
(s), 1150 (m), 1078 (w), 976 νas(N-CSS) (m), 876 (w), 732 (m),
697 (s), 605 (m) 554 (m) cm-1. 1H NMR (400 MHz, CDCl3, TMS,
20 °C): δ 0.94 (t, 12H, δ-H), 1.47 (m, 8H, γ-H), 1.99 (m, 8H,
ꢀ-H), 2.15 (m, 8H, R-H), 5.01 (s, 16H, NCH2), 7.20-7.26 (m, 28H,
aromatic hydrogens). 13C NMR (50 MHz, CDCl3, TMS, 20 °C): δ
14.2 (C-δ), 26.7 (C-γ), 29.0 (C-ꢀ), 35.0 (C-R), 55.6, 56.0 (NCH2),
[{Me2Sn(1,3-iBu-ambdtc)}2] (4). Yield: 83%. Mp: 232-234 °C.
IR (KBr): ν˜ 2959 (m), 2926 (m), 2870 (w), 1611 (w), 1470 ν(N-
CSS) (s), 1416 (m), 1350 (w), 1280 (w), 1228 (m), 1179 (m), 1116
9806 Inorganic Chemistry, Vol. 47, No. 21, 2008

Diorganotin(IV) Bis-Dithiocarbamate Complexes
127.8 (C-p), 128.0, 128.2, 128.9 (C-2, C-3, C-5, C-6, C-o, C-m),
135.2, 135.3 (C-1, C-4, C-i), 203.6 (SCS). 119Sn NMR (74.5 MHz,
CDCl3, SnMe4, 20 °C): δ -339.0. MS (FAB+): m/z (%) 1399 ([M
1471 ν(N-CSS) (s), 1418 (m), 1352 (m), 1267 (m), 1234 (m), 1198
(s), 1136 (m), 1076 (w), 1032 (m), 989 νas(CSS) (w), 923 (w), 875
(w), 790 (m), 732 (m), 691 (m), 628 (w), 579 (w), 519 (w), 487
1
(m) cm-1. H NMR (200 MHz, CDCl3, TMS, 20 °C): δ 1.57 (s,
n
+ H]+, 2), 1341 ([M - Bu]+, 5). Anal. calcd for C64H80N4S8Sn2
12H, 2JSn-H ) 84 Hz, Sn-CH3), 4.06 (dd, 8H, 3-H, H-4), 4.49 (dd,
8H, 2-H, 5-H), 4.66 (s, 8H, NCH2Cp), 5.11 (s, 8H, NCH2Ph),
7.26-7.39 (m, 20H, C6H5). 119Sn NMR (74.5 MHz, CDCl3, SnMe4,
20 °C): δ -350.0. MS (FAB+): m/z (%) 1447 ([M]+, 0.5), 1038
([C34H38FeN3S8Sn2]+, 100). Anal. calcd for C60H64Fe2N4S8Sn2
(1446.81): C, 49.81; H, 4.46; N, 3.87. Found: C, 50.69; H, 4.48;
N, 3.95.
(1399.29): C, 54.93; H, 5.76; N, 4.00. Found: C, 54.37; H, 5.93;
N, 4.31.
[{Ph2Sn(1,4-Bn-ambdtc)}2] (9). Yield: 76%. Mp: 196-198 °C.
IR (KBr): ν˜ 3059 (w), 2960 (m), 2928 (w), 2870 (w), 1637 (w),
1478 ν(N-CSS) (m), 1428 (w), 1414 (w), 1388 (w), 1353 (w), 1271
(w), 1230 (w), 1174 (w), 1115 (w), 1065 (w), 1019 (w), 981
1
νas(CSS) (w), 729 (w), 694 (w) 608 (w), 450 (w) cm-1. H NMR
X-Ray Crystallography. X-ray diffraction studies were per-
formed on a Bruker-APEX diffractometer with a CCD area detector
(λΜꢁΚR ) 0.71073 Å; monochromator, graphite). Frames were
collected at T ) 293 K (compounds 1, 6, and 7), T ) 200 K
(compound 13), and T ) 100 K (compounds 4 and 5) via ω/φ
rotation at 10 s per frame (SMART).11a The measured intensities
were reduced to F2 and corrected for absorption with SADABS
(SAINT-NT).11b Corrections were made for Lorentz and polariza-
tion effects. Structure solution, refinement, and data output were
carried out with the SHELXTL-NT program package.11c,d Non-
hydrogen atoms were refined anisotropically, while hydrogen atoms
were placed in geometrically calculated positions using a riding
model.
For compound 4, the asymmetric unit contains two independent
molecule halves. Solvent molecules were present in the crystal
lattices of compounds 1 (benzene), 7 (dichloromethane), and 13
(benzene and dichloromethane), of which the dichloromethane
molecules in the crystal lattice of compound 7 were disordered over
three positions. For compounds 5 and 6, the crystals were of lower
quality (Rint ) 0.084 and 0.105, respectively); however, the data
were of sufficient quality to determine the molecular and crystal
structures. In compound 6, one of the four iso-butyl groups is
disordered over two positions. In the final electron density map of
compound 6, there are two peaks with residual electron densities
of ∆F ) 2.27 and 2.18, which, however, are located in the proximity
of one of the tin atoms. There was no further peak with a residual
electron density larger than ∆F ) 0.76.
(200 MHz, CDCl3, TMS, 20 °C): δ 4.79, 4.85 (s, 16H, NCH2),
6.95-7.34 (m, 40H, aromatic hydrogens), 7.98 (m, 8H, o-H). 119Sn
NMR (74.5 MHz, CDCl3, SnMe4, 20 °C): δ -495.8. MS (FAB+):
m/z (%) 1265 (5). Anal. calcd for C72H64N4S8Sn2 (1479.25): C,
58.46; H, 4.36; N, 3.79. Found: C, 58.76; H, 4.71; N, 4.51.
[{Me2Sn(1,4-iBu-ambdtc)}2] (10). Yield: 70%. Mp: 114-116
°C. IR (KBr): ν˜ 2959 (w), 1628 (w), 1471 ν(N-CSS) (s), 1414 (m),
1350 (w), 1277 (w), 1231 (m), 1176 (m), 1116 (w), 985 νas(CSS)
(m), 790 (m), 611 (w), 553 (w) cm-1. 1H NMR (200 MHz, CDCl3,
TMS, 20 °C): δ 0.95 (d, 24H, CH-CH3), 1.58 (br, s, 12H, 2JSn-H
)
82 Hz, Sn-CH3), 2.34 (m, 4H, CH-CH3), 3.59 (d, 8H, J ) 7.0 Hz,
i
CH2 Pr), 5.18 (s, 8H, NCH2C6H4) 7.24 (s, 8H, 2-H, 3-H, 5-H, 6-H).
13C NMR (50 MHz, CDCl3, TMS, 20 °C): δ 16.4 (Sn-CH3), 20.5
i
(CH-CH3), 27.4 (CH-CH3), 57.5 (CH2 Pr), 60.6 (NCH2C6H4), 127.9
(C-2, C-3, C-5, C-6), 134.9 (C-1, C-4), 202.3 (CSS). 119Sn NMR
(74.5 MHz, CDCl3, SnMe4, 20 °C): δ -339.3. MS (FAB+): m/z
(%) 1095 ([M + H]+, 12), 1079 ([M - CH3]+, 18). High resolution
MS (FAB+) for C40H63N4S8Sn2 ([M+H]+): m/z (%) 1095.0681 (20).
Error: -16.6 ppm. Anal. calcd for C40H62N4S8Sn2 (1094.90): C,
43.88; H, 5.89; N, 5.12. Found: C, 43.63; H, 5.78; N, 5.15.
[{nBu2Sn(1,4-iBu-ambdtc)}2] (11). Yield: 75%. Mp: 214-216
°C. IR (KBr): ν˜ 2957 (m), 2921 (m), 2866 (w), 1628 (w), 1468
ν(N-CSS) (s), 1412 (m), 1348 (w), 1277 (w), 1229 (m), 1176 (m),
1
1114 (m), 984 νas(CSS) (w), 876 (w), 687 (w), 609 (w) cm-1. H
NMR (200 MHz, CDCl3, TMS, 20 °C): δ 0.96 (d, 24H, CH-CH3,
δ-H), 1.47 (m, 8H, γ-H), 1.95 (br, m, 8H, ꢀ-H), 2.09 (br, m, 8H,
i
R-H), 2.34 (m, 4H, CH-CH3), 3.62 (d, 8H, CH2 Pr), 5.21 (s, 8H,
NCH2C6H4), 7.23 (s, 8H, 2-H, 3-H, 5-H, 6-H). 13C NMR (50 MHz,
CDCl3, TMS, 20 °C): δ 14.2 (C-δ), 20.4 (CH-CH3), 26.6 (C-γ),
Crystallographic data for the structures reported in this paper
have been deposited with the Cambridge Crystallographic Data
Centre as supplementary publications, nos. CCDC-682738-682740
and 697178-697180. Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road, Cambridge CB2
1EZ, U.K. (fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk;
www: http://www.ccdc.cam.ac.uk).
i
27.3 (CH-CH3), 28.8 (C-ꢀ), 34.7 (C-R), 57.3 (CH2 Pr), 60.4
(NCH2C6H4), 127.8 (C-2, C-3, C-5, C-6), 135.0 (C-1, C-4), 203.1
(CSS). 119Sn NMR (74.5 MHz, CDCl3, SnMe4, 20 °C): δ -340.1.
MS (FAB+): m/z (%) 1263 ([M + H]+, 2), 1205 ([M - nBu]+, 5).
Anal. calcd for C52H88N2S8Sn2 (1263.22): C, 49.44; H, 7.02; N,
4.44. Found: C, 49.34; H, 7.32; N, 4.29.
[{Ph2Sn(1,4-iBu-ambdtc)}2] (12). Yield: 83%. Mp: 215-217
°C. IR (KBr): ν˜ 3055 (m), 2960 (m), 2923 (m), 2867 (m), 1572
(w), 1480 ν(N-CSS) (s), 1418 (s), 1346 (m), 1274 (w), 1230 (s),
1174 (s), 1113 (s), 1061 (m), 1019 (w), 976 νas(CSS) (w), 949 (m),
808 (w), 755 (m), 728 (s), 692 (m), 608 (m), 544 (w), 446 (m)
3. Results and Discussion
3.1. Preparation and Spectroscopic Characterization.
Since it is well-known that dithiocarbamates obtained from
secondary amines give more stable metal complexes,10 the
1
cm-1. H NMR (200 MHz, CDCl3, TMS, 20 °C): δ 0.92 (d, 24H,
i
CH-CH3), 2.28 (m, 4H, CH-CH3), 3.51 (d, 8H, CH2 Pr), 5.05 (br,
(11) (a) SMART, versions 5.057, 5.618; Bruker Analytical X-ray Systems:
Madison, WI, 1997, 2000. (b) SAINT + NT, versions 6.01, 6.04; Bruker
Analytical X-ray Systems: Madison, WI, 1999, 2001. (c) Sheldrick,
G. M. SHELX-86; University of Go¨ttingen: Go¨ttingen, Germany, 1986.
(d) SHELXTL-NT, versions 5.10, 6.10; Bruker Analytical X-ray
Systems: Madison, WI, 1999, 2000.
(12) Isophthaldehyde, terephthaldehyde, and 1,1′-ferrocenedicarboxaldehyde
were reacted in one-pot syntheses with benzylamine/iso-butylamine
and sodium borohydride to give 1,3-bis(benzylaminomethyl)benzene
(1,3-Bn-amb), 1,3-bis(iso-butylaminomethyl)benzene (1,3-iBu-amb),
1,4-bis(benzylaminomethyl)benzene (1,4-Bn-amb), 1,4-bis(iso-buty-
laminomethyl)benzene (1,4-iBu-amb), and 1,1′-bis(benzylaminometh-
yl)ferrocene (1,1′-Bn-amf) in quantitative yields. The spectroscopic
data of these ligands will be reported in a forthcoming article.
s, 8H, NCH2C6H4), 7.06-7.34 (m, 20H, 2-H, 3-H, 5-H, 6-H, m-H,
3
p-H), 7.91 (d, 8H, JSn-H ) 84 Hz, o-H). 13C NMR (200 MHz,
i
CDCl3): δ 20.4 (CH-CH3), 27.4 (CH-CH3), 58.6 (CH2 Pr), 61.6
(NCH2C6H4), 127.9 (C-2, C-3, C-5, C-6, C-p), 128.3 (C-m), 134.2
(C-o), 151.4 (C-i), 201.7 (CSS). 119Sn NMR (74.5 MHz, CDCl3,
SnMe4, 20 °C): δ -494.6. MS (FAB+): m/z (%) 1265 ([M - Ph]+,
1). Anal. calcd for C60H72N2S8Sn2 (1343.18): C, 53.65; H, 5.40;
N, 4.17. Found: C, 53.46; H, 5.88; N, 4.43.
[{Me2Sn(1,1′-Bn-amfdtc)}2] (13). Yield: 64%. Mp: 180-182
°C (dec.). IR (KBr): ν˜ 3085 (w), 3028 (w), 2916 (w), 1630 (w),
Inorganic Chemistry, Vol. 47, No. 21, 2008 9807

Santacruz-Jua´rez et al.
Scheme 1. Reaction Sequence for the Preparation of Compounds 1-13
Table 1. Selected NMR Spectroscopic Data for Compounds 1-13 (in CDCl3, ppm)
δ1H
δ1H
N-CH2-R′
δ1H
δ13C
N-CH2-spacer
δ13C
N-CH2-R′
δ13C
Sn-C
δ13C
CSS
compound
N-CH2-spacer
Sn-CH, (2JSn-H
)
δ
119Sn
1,3-Bn-amb
1
3.77
5.01
5.08
4.96
3.72
5.10
5.20
5.01
3.88a
5.00
5.01
4.85
3.74
5.18
5.21
5.05
3.42
4.66
3.77
5.01
5.08
4.96
2.40
3.59
3.63
3.50
3.91a
5.00
5.01
4.85
2.41
3.59
3.62
3.51
3.76
5.11
53.1a
55.7a
b
53.3a
56.0a
b
1.77 (79)
2.26
7.90
16.6
b
150.9
203.1
b
202.3
-335.7
-338.2
-491.0
2
3
56.9a
57.1
60.3
60.5
61.8
52.8a
b
57.5a
53.7
57.7
57.6
58.7
53.0a
b
1,3-iBu-amb
4
5
6
1.63 (84)
2.12
7.88 (77)
16.1
34.7
151.6
202.4
203.1
201.9
-339.3
-340.6
-499.6
1,4-Bn-amb
7
1.60 (81)
2.15
7.98
b
35.0
b
b
203.6
b
-338.4
-339.0
-495.8
8
9
55.6a
b
56.0a
b
1,4-iBu-amb
57.5
60.6
60.4
61.6
48.1
b
53.9
57.5
57.3
58.6
53.4
b
10
11
12
1.58 (82)
2.09
7.91 (84)
16.4
34.7
151.4
202.3
203.1
201.7
-339.3
-340.1
-494.6
1,1′-Bn-amf
13
1.57 (84)
b
b
-350.0
a Signals might be interchanged. b Low solubility.
N,N′-dibenzyl and N,N′-di-iso-butyl derivatives of 1,3-
bis(aminomethyl)benzene and 1,4-bis(aminomethyl)benzene
were prepared12 and then combined in methanol with carbon
disulfide, triethylamine, and the corresponding diorganotin
The formation of dithiocarbamate complexes could be
evidenced by the IR spectra, which showed strong bands in
the region of 1462-1480 and 976-994 cm-1, resulting from
the ν(N-CSS) and νas(CSS) vibrations of metal-coordinated
dithiocarbamate functions.13
A comparison of the 1H NMR spectra between the starting
N,N′-disubstituted diamines and the resulting products (Table
1) showed significant shift displacements to lower fields for
the N-CH2 methylene hydrogen atoms (∆δ ) 0.97-1.48 for
the N-CH2-spacer methylene group and ∆δ ) 0.97-1.35
n
dichloride R2SnCl2 (R ) Me, Bu, and Ph) to give com-
pounds 1-12 in yields varying from 70 to 83%. Additionally,
using the same methodology, the dimethyltin bis-dithiocar-
bamate of 1,1′-bis(aminomethyl)ferrocene was synthesized
in 64% yield (Scheme 1). All products have been character-
ized as far as possible by elemental analysis, FAB+ mass
spectrometry, IR and NMR (1H, 13C, 119Sn) spectroscopy,
and single-crystal X-ray diffraction (compounds 1, 4, 5, 6,
7, and 13).
(13) (a) Durgaprasad, G.; Sathyanarayana, D. N.; Patel, C. C. Can. J. Chem.
1969, 47, 631. (b) Brown, D. A.; Glass, W. K.; Burke, M. A.
Spectrochim. Acta 1976, 32A, 137. (c) Chandra, S.; Magee, R. J.;
James, B. D. Main Group Met. Chem. 1988, 11, 57.
9808 Inorganic Chemistry, Vol. 47, No. 21, 2008

Diorganotin(IV) Bis-Dithiocarbamate Complexes
Table 2. Crystallographic Data for Compounds 1, 4, 5, 6, 7, and 13
crystal dataa
1
4
5
6
7
13
formula
MW (g mol-1
space group
temp (K)
a (Å)
b (Å)
c (Å)
R (deg)
ꢀ deg)
C
52H56N4S8Sn2 · 2C6H6
C
40H64N4S8Sn2
C
52H88N4S8Sn2
C
60H72N4S8Sn2
C
52H56N4S8Sn2 · 2CH2Cl2
C
60H64Fe2N4S8Sn2 · 2CH2Cl2 · 4C6H6
)
1387.08
1094.81
1263.12
P21/c
100
12.3452(12)
13.4135(14)
18.2726(18)
90
98.842(2)
90
2989.8(5)
2
1.151
1.403
0.078
1343.08
Pca21
293
24.8002(16)
14.7940(9)
17.2450(11)
90
90
90
6327.1(7)
4
1.093
1400.72
1929.00
P21/c
200
10.7077(6)
23.1803(14)
17.9389(11)
90
95.917(1)
90
4428.9(5)
2
1.233
1.447
0.058
j
j
j
P1
P1
P1
293
100
293
8.8321(7)
12.5154(10)
15.5870(13)
70.199(1)
82.954(1)
81.590(1)
1598.7(2)
1
1.084
1.441
0.045
0.121
10.2879(8)
13.5669(12)
19.2408(16)
104.915(1)
103.964(2)
96.073(2)
2477.7(4)
2
1.377
1.467
0.056
0.119
10.674(6)
10.774(6)
14.854(8)
101.994(9)
109.034(8)
90.062(9)
1575.1(14)
1
1.265
1.477
0.048
0.139
γ (deg)
V (Å3)
Z
µ (mm-1
)
Fcalcd (g cm-3
)
1.410
0.081
0.171
Rb c
,
d e
,
Rw
0.146
0.125
a
λMoKR ) 0.71073 Å. b I > 2σ(I). c R ) ∑(Fo - Fc )/∑Fo . d All data. e Rw ) [∑w(Fo - Fc )2/∑w(Fo )2]1/2
.
2
2
2
2
2
2
Table 3. Selected Bond Lengths [Å], Bond Angles [deg], Intramolecular Distances [Å], and Cavity Dimensions [Å2] for Compounds 1, 4, 5, 6, 7, and
13
4d
1
molecule 1
molecule 2
5
6e
7
13
Bond Lengths
2.131(7)
Sn-C
2.112(5)
2.116(5)
2.5086(13)
2.5217(12)
2.8791(15)
3.1519(14)
1.741(4)
1.697(5)
1.744(5)
1.681(5)
1.323(6)
1.331(6)
2.109(6)
2.121(6)
2.5319(16)
2.5356(17)
2.8855(17)
2.966(2)
1.750(6)
1.694(7)
1.752(6)
1.695(7)
1.320(8)
1.329(7)
2.124(5)
2.126(6)
2.155(13)/2.154(10)
2.168(10)/2.163(12)
2.571(3)/2.571(3)
2.580(3)/2.575(3)
2.701(3)/2.662(3)
2.713(3)/2.708(3)
1.707(11)/1.700(12)
1.721(12)/1.702(12)
1.723(12)/1.704(12)
1.736(11)/1.707(12)
1.353(12)/1.339(14)
1.318(12)/1.373(14)
2.117(6)
2.123(5)
2.5320(17)
2.5364(17)
2.9078(19)
3.0496(19)
1.747(5)
1.701(6)
1.754(5)
1.697(5)
1.335(6)
1.338(7)
2.116(5)
2.129(5)
2.5147(15)
2.5205(13)
2.9667(14)
2.9977(15)
1.750(5)
1.697(5)
1.755(5)
1.697(5)
1.331(6)
1.335(6)
2.132(5)
Sn-Scov
Sn· · ·Scoord
C-S
2.5306(17)
2.5401(17)
2.949(2)
2.963(2)
1.739(7)
1.699(7)
1.762(6)
1.675(7)
1.340(7)
1.340(8)
2.5230(19)
2.524(2)
2.895(2)
2.994(2)
1.750(7)
1.683(8)
1.757(8)
1.703(8)
1.314(9)
1.336(10)
C-Ndtc
Bond Angles
C-Sn-C
Scov-Sn-Scov
S-Sn-S (chelate)
131.9(2)
81.60(4)
62.12(4)
65.89(4)
150.40(4)
118.0(3)
120.7(3)
139.9(2)
84.24(5)
64.60(5)
65.80(5)
145.31(5)
118.1(4)
118.6(4)
142.6(3)
83.07(5)
64.87(5)
65.01(5)
147.55(5)
119.3(4)
119.7(4)
141.9(3)
82.87(6)
64.48(6)
65.82(6)
147.04(6)
117.6(4)
119.8(5)
102.2(4)/102.3(4)
150.17(10)/148.25(11)
67.58(9)/67.19(10)
67.79(9)/68.43(9)
82.17(9)/81.83(10)
118.2(6)/116.8(6)
119.5(6)/118.3(7)
139.1(3)
84.19(5)
63.91(5)
65.67(5)
146.26(4)
118.9(3)
119.9(3)
137.9(2)
81.05(4)
64.49(4)
64.76(4)
149.85(4)
118.5(3)
118.7(3)
Scoord · · ·Sn· · ·Scoord
S-C-S
Others
Sn· · ·Sntransannular
5.72
5.40
13.67
5.63
5.07
12.97
5.74
5.01
12.46
5.86
5.18
12.76
11.02
6.34
9.09
9.70
7.56
9.09
3.09 × 4.56
11.53
a
N· · ·Nspacer
8.71
centroid· · ·centroidb
10.00f
cavity dimensionsc
3.44 × 3.65
a N· · ·N distance within the spacer. b Distances between the phenylene centroids. c Effective cavity size. d Two molecule halves in the asymmetric unit.
e Molecule with two independent tin atoms (molecule without crystallographic symmetry element). f Transannular Fe · · ·Fe interaction.
for the N-CH2-R′ methylene group). The dimethyltin moieties
gave signals at δ ) 1.77, 1.63, 1.60, 1.58, and 1.57 with
2JSn-H coupling constants of 79, 84, 81, 82, and 84 Hz for
1, 4, 7, 10, and 13, respectively, thus giving, according to
Lockhard’s equation,14 calculated C-Sn-C bond angles of
129.6, 136.1, 131.9, 133.4, and 136.1°. Because of the low
solubility of compounds 1-13, 13C NMR spectra could only
be measured for the more soluble compounds, 1, 3-6, 8,
and 10-12. As in the case of the 1H NMR data, the signals
for the NCH2 carbon atoms are low-field-shifted when
compared to the starting diamine (∆δ ) 2.6-4.7 for the
N-CH2-spacer methylene group and ∆δ ) 3.4-5.0 for the
N-CH2-R′ methylene group). The NCS2 groups gave signals
varying from δ ) 201.7 to 203.6 that are in the region
typically observed for diorganotin dithiocarbamates.15 In-
terestingly, in the H NMR spectra, the signals for the
1
N-methylene hydrogen atoms are broadened, indicating that
the complexes are involved in at least one dynamic process.
Both intra- and intermolecular ligand exchange reactions and
configurational or conformational equilibria are possible.7,16
The 119Sn NMR chemical shifts for the dimethyltin deriva-
tives 1, 4, 7, 10, and 13 vary from δ ) -335.7 to -350.0;
(15) (a) Smith, P. J.; Tupciauskas, A. P. Ann. Rep. NMR Spectrosc. 1978,
8, 291. (b) Wrackmeyer, B. Ann. Rep. NMR Spectrosc. 1985, 16, 73.
(c) Lockhart, T. P.; Manders, W. F.; Schlemper, E. O. J. Am. Chem.
Soc. 1985, 107, 7451. (d) Dakternieks, D.; Zhu, H.; Masi, D.; Mealli,
C. Inorg. Chem. 1992, 31, 3601. (e) Seth, N.; Gupta, V. D.; No¨th, H.;
Thomann, M. Chem. Ber. 1992, 125, 1523. (f) Sharma, J.; Singh, Y.;
Bohra, R.; Rai, A. K. Polyhedron 1996, 15, 1097.
(16) (a) Wengrovius, J. H.; Garbauskas, M. F. Organometallics 1992, 11,
1334. (b) Beckmann, J.; Jurkschat, K. Coord. Chem. ReV. 2001, 215,
267.
(14) Lockhart, T. P.; Manders, W. F. Inorg. Chem. 1986, 25, 892.
Inorganic Chemistry, Vol. 47, No. 21, 2008 9809

Santacruz-Jua´rez et al.
Figure 1. Perspective views of the molecular structures of (a) compound 1, (b) compound 4, (c) compound 5, and (d) compound 6. Ellipsoids are shown
at the 30 % (1 and 6) and 50 % (4 and 5) probability levels. For clarity, in compound 6, the iso-butyl groups are only represented by the corresponding
R-CH2 groups.
those for the di-n-butyltin derivatives 2, 5, 8, and 11 from δ
) -338.2 to -340.6; and those for the diphenyltin deriva-
tives 3, 6, 9, and 12 from δ ) -491.0 to -499.6 (Table 1).
These are typical ranges for diorganotin dithiocarbamates.15
For compounds 1, 4, 5, 6, 7, and 13, crystals suitable for
X-ray diffraction analysis could be grown, which revealed
dinuclear macrocyclic structures in all six cases. The
molecular structures are shown in Figures 1-3. The most
relevant crystallographic data and selected geometric pa-
rameters are summarized in Tables 2 and 3.
As shown in Figure 1, the diorganotin complexes of the
ligands derived from 1,3-bis(aminomethyl)benzene are 24-
membered dinuclear {C14N4S4Sn2} macrocyclic ring struc-
tures, however, with different tin-atom configurations as
well as ligand and ring conformations. In the molecular
structures of the dimethyl- and di-n-butyltin derivatives 1,
4, and 5 (Figures 1a-c), the tin atoms have skewed-
trapezoidal-bipyramidal coordination geometries, in which
both the organic and the dtc functions are trans-oriented. In
contrast, in diphenyltin compound 6 (Figure 1d), the
coordination polyhedra of the tin atoms are distorted
octahedral with cis-oriented dtc functions. This coordination
geometry has been already observed for other diphenyltin
dithiocarbamates17 but is unknown for dialkyltin derivatives.4c
For dimethyltin derivatives 1 and 4, the calculated and
experimental Me-Sn-Me bond angles agree very well
(129.6 versus 131.9(2) ° for 1, 136.1 versus 139.9(2) and
142.6(3)° for 4), thus indicating that the structures in solution
and the solid state are similar. The trapezoidal planes are
formed by the sulfur atoms of the chelating ligands, which
are coordinated in an anisobidentate manner (Sn-S )
2.5086(13)-2.5401(17) Å, Sn · · ·S ) 2.8791(14)-3.1519(14)
(17) (a) Alcock, N. W.; Culver, J. J. Chem. Soc., Dalton Trans 1992, 1477.
(b) Hook, J. M.; Linahan, B. M.; Taylor, R. L.; Tiekink, E. R. T.; van
Gorkom, L.; Webster, L. K. Main Group Met. Chem. 1994, 17, 293.
(c) Farina, Y.; Othman, A. H.; Razak, I. A.; Fun, H.-K.; Ng, S. W.;
Baba, I. Acta Crystallogr. 2001, E57, m46. (d) Menezes, D. C.; de
Lima, G. M.; Porto, A. O.; Donnici, C. L.; Ardisson, J. D.; Doriguetto,
A. C.; Ellena, J. Polyhedron 2004, 23, 2104.
9810 Inorganic Chemistry, Vol. 47, No. 21, 2008

Diorganotin(IV) Bis-Dithiocarbamate Complexes
Scheme 2. Graphical Illustration of (a) the Differences in the
Tin-Atom Configurations and Ligand Conformations and (b) the
Conformational Ring Isomerism Found in Compounds 1, 4, 5, and 6
Figure 3. Perspective view of the molecular structure of compound 13.
Ellipsoids are shown at the 30% probability level.
π-electron density within the CS2 groups is delocalized, as
can be seen from the relatively small differences between
the C-S bond lengths that range from 1.700(12) to 1.736(11)
Å. The C-Ndtc bonds vary from 1.318(12) to 1.373(14) Å
and are comparable to those found for the above-discussed
complexes.
Å for 1 and 4), as it is generally observed for diorganotin
dithiocarbamates.4c The bonding asymmetry of the ligands
is reflected in the C-S bonds, which are significantly
different from each other (1.681(5)-1.703(8) Å versus
1.739(7)-1.762(6) Å). Within the dithiocarbamate function,
the C-Ndtc bond lengths of 1.320(8)-1.340(8) Å indicate a
substantial delocalization of π-electron density in this bond.18
The coordination geometry in the di-n-butyltin complex 5
is very similar (Table 3).
According to the cis orientation of the organic substituents
and the dtc groups in compound 6, the C-Sn-C bond angles
are 102.2(4) and 102.3(4)°, while the three types of S-Sn-S
bond angles range from 67.19(10) to 68.43(9), 81.83(10) to
89.80(10), and 148.25(11) to 150.17(10)°. The coordination
of the dtc ligands approximates an isobidentate mode, since
the differences between the Sn-S bond lengths are smaller
than 0.2 Å (2.571(3)-2.713(3) Å). As a consequence, the
Due to the variation in the metal coordination environment,
the ligand conformation changes from syn-syn (compounds
1, 4, and 5) to syn-anti (compound 6), thus giving different
spatial distributions of the dtc functions. The CSS-N-
N′-CSS′ torsion angles for compounds 1, 4, 5, and 6 are
56.4, 48.5/46.3, 50.6, and -67.6/31.1°, respectively. The
conformational flexibility of the bis-dithiocarbamates can be
attributed to the rotational degree of freedom of the C6H4-
CH2-N methylene groups and is intermediate, when com-
pared to connectors that contain only rigid π-conjugated or
extended aliphatic spacer groups, which makes these ligands
ideal candidates for the self-assembly of metal-organic
macrocyclic structures. The impact of the flexibility provided
by the cis/trans tin coordination environment and the ligand
conformation on the macrocycle structure is illustrated in
Scheme 2a.
There are further variables in the conformation of the
macrocyclic rings. The first is in regard to the orientation of
i
the Bn and Bu substituents attached to the nitrogen atoms,
as can be seen from a comparison of the molecular structures
of dimethyltin derivatives 1 and 4 (Figure 1a and b). In
compound 1, the substituents of each ligand are trans-
oriented, while they are cis-oriented in compound 4. As
shown in Scheme 2b, the conformational isomers of 1 and
4 can be distinguished by the sequence of the substituent
orientations with respect to the macrocyclic ring plane. Since
both molecules possess crystallographic inversion centers,
this results in different orientations of the pseudo-C2 sym-
metry axes; however, it should be noticed that both molecules
are 1,3-alternated conformers when applying the nomencla-
ture used for the conformational isomerism of calixarenes.19
Figure 2. Perspective view of the molecular structure of compound 7.
Ellipsoids are shown at the 30% probability level.
(18) Wheeler, K. A.; Harrington, B.; Zapp, M.; Casey, E. CrystEngComm
2003, 5, 337.
Inorganic Chemistry, Vol. 47, No. 21, 2008 9811

Santacruz-Jua´rez et al.
Beer et al. have prepared related macrocycles using
transition metal ions such as Zn(II), Cu(II), Cu(III), Ni(II),
Pd(II), Pt(II), and Au(III) ions as metal nodes for the
macrocycle assembly process.4b,20 Their binding studies have
shown that dinuclear assemblies can selectively bind di-
amines and dicarboxylates within the macrocyclic cavities,
taking advantage of the Lewis-acidic metal sites. Related
experiments with organotin macrocycles have been carried
out by Jurkschat et al.21
As shown in Figure 4a, the macrocyclic voids of com-
pound 13 allow for the inclusion of two benzene molecules,
which in the solid-state structure are accomodated above and
below the molecule center. Similarly, in the crystal lattice
of compound 7, phenyl groups of neighboring molecules are
located within the cavity (Figure 4b). UV-vis and NMR
titrations were carried out to test the possibility of inclusion
of small aromatic molecules in solution. Thus, nitrobenzene
was added to chloroform solutions of 7 or 13 (15 mM for
1H NMR), covering a concentration range from 2 mM up to
30 mM; however, no significant changes in the signals
corresponding to the aromatic regions were observed under
these conditions.
Figure 4. Fragments of the crystal lattices of compounds 13 (a) and 7 (b),
showing the inclusion of aromatic rings within the macrocycle voids. For
clarity, the aromatic guest molecules are uniformly colored (dark yellow).
The conformations of di-n-butyl and diphenyltin complexes
5 and 6 are analogous to that of compound 4. Secondly, there
are differences in the orientation of the aromatic rings
forming part of the macrocycles. This can be evidenced by
the angles formed between the mean planes of the macro-
cycle and the phenylene groups. While the mutual orientation
of the macrocycle (mean planes calculated from the four
nitrogen atoms) and the phenylene rings is close to parallel
in compound 1 (21.1°), it approximates a perpendicular
disposition in compounds 4, 5, and 6 (35.5/55.0° for 4, 43.9°
for 5, and 41.9/44.8° for 6).
4. Conclusions
This report has shown that diorganotin moieties and bis-
dithiocarbamates can be easily assembled to dinuclear
macrocyclic rings, when the coordinating functional groups
are separated by an adequate spacer. The bis(aminomethyl)
benzene and -ferrocene connectors used herein are ligands
with intermediate flexibility when compared to other π-de-
localized and aliphatic connectors, thus giving rise to
conformational isomers of the macrocyles. The macrocyclic
structures described herein can be modified at the organic
substituents attached to the tin and nitrogen atoms for further
studies.
Compounds 7 and 13 have 26- and 24-membered
{C16N4S4Sn2} and {C12Fe2N4S4Sn2} macrocyclic structures.
In both cases, the tin atoms have skewed-trapezoidal-
bipyramidal coordination geometries, whose geometric pa-
rameters are very similar to that found for dimethyltin
complex 1 (Table 3). Also in this case, the calculated and
experimental Me-Sn-Me bond angles agree reasonably well
(131.9 versus 139.1(3)° for 7, 136.1 versus 137.9(2)° for 13).
Albeit the macrocycle of compound 13 contains a smaller
number of ring members than that of 7, the transannular
Sn · · ·Sn distances are significantly larger (9.70 Å for 7 versus
11.53 Å for 13). This can be attributed to the larger separation
of the N-CSS functions in the 1,1′-bis(aminomethyl)ferrocene
groups of compound 13 when compared to the 1,4-bis(ami-
nomethyl)benzene spacer of compound 7 (8.71 Å versus 7.56
Å for the N · · ·N distance within the spacer). However, since
in compound 7 the orientation of the phenylene rings is
almost perpendicular to the macrocyclic ring plane, the
effective cavity sizes of 7 and 13 are comparable: 3.09 ×
4.56 Å2 for 7 and 3.44 × 3.65 Å2 for 13. The Fe · · · Fe
distance in compound 13 is 10.00 Å.
Acknowledgment. The authors thank CONACyT for
financial support (Project number: 47347-Q).
IC801464S
(20) (a) Lai, S. W.; Drew, M. G. B.; Beer, P. D. J. Organomet. Chem.
2001, 637-639, 89. (b) Beer, P. D.; Berry, N.; Drew, M. G. B.; Fox,
O. D.; Padilla-Tosta, M. E.; Patell, S. Chem. Commun. 2001, 199. (c)
Wong, W. W. H.; Curiel, D.; Cowley, A. R.; Beer, P. D. Dalton Trans.
2005, 359. (d) Wong, W. W. H.; Cookson, J.; Evans, E. A. L.;
McInnes, E. J. L.; Wolowska, J.; Maher, J. P.; Bishop, P.; Beer, P. D.
Chem. Commun. 2005, 2214.
(21) (a) Jurkschat, K.; Uhlig, W.; Mu¨gge, C.; Tzschach, A. Z. Anorg. Allg.
Chem. 1988, 556, 161. (b) Altmann, R.; Gausset, O.; Horn, D.;
Jurkschat, K.; Schu¨rmann, M. Organometallics 2000, 19, 430.
(19) Vo¨gtle, F. Supramolekulare Chemie; Teubner Verlag: Stuttgart,
Germany, 1992.
9812 Inorganic Chemistry, Vol. 47, No. 21, 2008