Structure, properties and cytostatic activity of triorganotin (aminoaryl)carboxylates

Article abstract of DOI:10.1002/1099-0682(200212)2002:12<3214::AID-EJIC3214>3.0.CO;2-K

The properties of vinyltin and phenyltin complexes [Sn(CH=CH₂)₃{μ-OOCC₆H₃ (NH₂)₂-3,4}]_n (1), [Sn(C₆H₅)₃- {OOCC₆H₃(NH₂)₂-3,4}] (2), [Sn(C₆H₅)₃{OOC-2-C₆H₄ N= NC₆H₄N(CH₃)₂-4})] (3) and [Sn(CH=CH₂)₃{OOC-2-C₆H₄N= NC₆H₄N(CH₃)₂-4}] (4) have been investigated. The structures of complexes 1, 2, and 3, have been determined by X-ray crystallography, Compound 1 is a distorted trigonal-bipyramidal complex and compounds 2 and 3 adopt a distorted tetrahedral structure. Complex 1 is a single-strand polymer with a bridging 3,4-diaminobenzoato ligand coordinating via the O(1) atom of the carboxylato group and the nitrogen atom of the para-amino group. The oxygen and nitrogen atoms occupy the axial coordination sites. The Sn(1)-N(2A) bond is weak. In complexes 2 and 3 the carboxylato hgands are strongly coordinated to the central atom via one oxygen atom, and the Sn(1)-O(2) distances are considerably longer. Weak interactions of the central atom with the amino group in complex 1, and with the O(2) atoms in complexes 2 and 3, as well as the hydrogen bonds, stabilize the crystal structure. The complexes are effective cytostatic agents. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.

Full text of DOI:10.1002/1099-0682(200212)2002:12<3214::AID-EJIC3214>3.0.CO;2-K

FULL PAPER
Structure, Properties and Cytostatic Activity of Triorganotin
(Aminoaryl)carboxylates
[a]
[a]
[a]
[b]
´
Florian P. Pruchnik,* Małgorzata Banbuła, Zbigniew Ciunik, Henryk Chojnacki,
Małgorzata Latocha,[c] Barbara Skop,[c] Tadeusz Wilczok,[c] Adam Opolski,[d]
Joanna Wietrzyk,[d] and Anna Nasulewicz[d]
Keywords: Tin / Cytostatic agents / Antitumor activity / O ligands
The properties of vinyltin and phenyltin complexes
[Sn(CH=CH2)3{µ-OOCC6H3(NH2)2-3,4}]n (1), [Sn(C6H5)3-
of the para-amino group. The oxygen and nitrogen atoms oc-
cupy the axial coordination sites. The Sn(1)−N(2A) bond is
weak. In complexes 2 and 3 the carboxylato ligands are
strongly coordinated to the central atom via one oxygen
atom, and the Sn(1)−O(2) distances are considerably longer.
{OOCC6H3(NH2)2-3,4}]
(2),
[Sn(C6H5)3{OOC-2-C6H4N=
NC6H4N(CH3)2-4}] (3) and [Sn(CH=CH2)3{OOC-2-C6H4N=
NC6H4N(CH3)2-4}] (4) have been investigated. The struc-
tures of complexes 1, 2, and 3, have been determined by X- Weak interactions of the central atom with the amino group
ray crystallography. Compound 1 is a distorted trigonal-bi- in complex 1, and with the O(2) atoms in complexes 2 and 3,
pyramidal complex and compounds 2 and 3 adopt a distorted as well as the hydrogen bonds, stabilize the crystal structure.
tetrahedral structure. Complex 1 is a single-strand polymer The complexes are effective cytostatic agents.
with a bridging 3,4-diaminobenzoato ligand coordinating via ( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany,
the O(1) atom of the carboxylato group and the nitrogen atom
2002)
prise pyridinocarboxylato and aminosalicylato organotin
compounds.[5] Here, we report on the synthesis, properties,
structure, and in vitro cytostatic activity of trivinyltin and
triphenyltin complexes with 3,4-diaminobenzoate and 2-[4-
(dimethylamino)phenylazo]benzoate.
Introduction
Coordination and organometallic compounds belong to
the very important group of antitumor agents.[1,2] Many
platinum complexes and other transition metal compounds,
as well as organometallic compounds of the main group
metals show high cytostatic activity. A number of organotin
compounds have been shown to be active against various
types of cancers. A series of organotin dipeptide com-
pounds and a number of diorganotin halides containing
amino ligands [SnR2X2L2] have displayed modest anti-
tumor activity.[3,4] Many di-n-butyl-, tri-n-butyl-, and tri-
phenyltin hydroxycarboxylates, oxycarboxylates, and
Results and Discussion
The complexes [Sn(CHϭCH2)3{µ-OOCC6H3(NH2)2-
3,4}]n (1), [Sn(C6H5)3{OOCC6H3(NH2)2-3,4}] (2), [Sn-
(C6H5)3{OOC-2-C6H4NϭNC6H4N(CH3)2-4}] (3) and
[Sn(CHϭCH2)3{OOC-2-C6H4NϭNC6H4N(CH3)2-4}] (4)
are soluble in ethanol, methanol, acetone, chloroform,
dichloromethane, and in other polar organic solvents, and
are slightly soluble in aqueous ethanol (50%). The vinyl
complexes 1 and 4 have been obtained by the reactions of
SnO(CHϭCH2)2 and the appropriate acid in ethanol, while
complexes 2 and 3 have been prepared by the reactions of
SnO(C6H5)2 or {Sn(C6H5)3}2O with the acids. Thus, in the
reactions of SnO(CHϭCH2)2 and SnO(C6H5)2 with the ac-
ids, the vinyl or phenyl groups are transferred. Other prod-
ucts obtained were SnO(R)(OOCRЈ), Sn(OH)2R(OOCRЈ)
and similar monoorganotin() compounds, however, these
compounds were not pure enough.
fluorocarboxylates
display
interesting
antitumor
activities.[5Ϫ15] However, only few tin carboxylates with am-
ino groups have been investigated. These complexes com-
[a]
Faculty of Chemistry, University of Wrocław,
ul. Joliot-Curie 14, 50-383 Wrocław, Poland
[b]
Institute of Physical and Theoretical Chemistry, Wrocław
University of Technology,
´
Wyb. Wyspianskiego 27, 50-370 Wrocław, Poland
[c]
Department of Molecular Biology, Biochemistry and
Biopharmacy, Medical University of Silesia,
´
41-200 Sosnowiec, ul. Narcyzow 1, Poland
[d]
Institute of Immunology and Experimental Therapy, Polish
Academy of Sciences,
Wrocław, Poland
3214  2002 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/02/1212Ϫ3214 $ 20.00ϩ.50/0 Eur. J. Inorg. Chem. 2002, 3214Ϫ3221

Structure, Properties and Cytostatic Activity of Triorganotin (Aminoaryl)carboxylates
Table 3. Bond lengths [A] and angles [°] for complex 3
FULL PAPER
˚
Sn(1)ϪO(1)
Sn(1)ϪO(2)
Sn(1)ϪC(311)
Sn(1)ϪC(111)
Sn(1)ϪC(211)
O(1)ϪC(1)
2.054(2)
2.827(2)
2.117(4)
2.121(4)
2.126(4)
1.314(4)
1.219(4)
O(1)ϪSn(1)ϪC(311)
O(1)ϪSn(1)ϪC(111)
C(311)ϪSn(1)ϪC(111)
O(1)ϪSn(1)ϪC(211)
C(311)ϪSn(1)ϪC(211)
C(111)ϪSn(1)ϪC(211)
C(1)ϪO(1)ϪSn(1)
108.23(12)
109.32(12)
118.20(15)
95.81(12)
112.61(14)
110.29(14)
110.1(2)
O(2)ϪC(1)
Figure 1. [Sn(CHϭCH2)3{µ-OOCC6H3(NH2)2-3,4}]n
˚
Table 4. Lengths [A] and angles [°] of the hydrogen bonds in solid
compound 1
DϪH···A[a]
DϪH H···A D···A
DϪH···A
N(2)ϪH(4N)···O(2)i
N(2)ϪH(3N)···C(2)ii
0.90(4) 2.06(4) 2.956(3) 170(3)
0.84(3) 3.08(3) 3.712(4) 134(3)
N(1)ϪH(1N)···X1A (C1/C2)iii 0.88(4) 2.63
N(1)ϪH(2N)···X1B (C3/C4)iv 0.89(4) 2.94
3.50
3.53
170
125
Figure 2. [Sn(C6H5)3{OOCC6H3(NH2)2-3,4}]
[a]
Symmetry transformations used to generate equivalent atoms: i:
Ϫx ϩ 1/2, y Ϫ 1/2, Ϫz ϩ 1/2; ii: Ϫx, y Ϫ 1, Ϫz ϩ 1/2; iii: x, Ϫy,
z Ϫ 1/2; iv: Ϫx, y, Ϫz ϩ 1/2.
˚
Table 5. Lengths [A] and angles [°] of the hydrogen bonds in solid
compound 2
DϪH···A[a]
DϪH
H···A
D···A
DϪH···A
N(1)ϪH(2N)···N(2)ii
N(2)ϪH(3N)···O(2)iii
0.87
0.92
2.40
2.08
3.181(5)
2.979(4)
150.5
165.7
[a]
Figure 3. [Sn(C6H5)3{OOC-2-C6H4NϭNO6H4N(CH3)2-4}]
Symmetry transformations used to generate equivalent atoms: i:
Ϫx, Ϫy Ϫ 1,Ϫz; ii: Ϫx, Ϫy, Ϫz; iii: Ϫx, y Ϫ 1/2, Ϫz ϩ 1/2.
˚
Table 1. Bond lengths [A] and angles [°] for complex 1
˚
Table 6. Lengths [A] and angles [°] of weak CϪH···π hydrogen
bonds in solid complex 3
Sn(1)ϪC(3)
Sn(1)ϪC(5)
Sn(1)ϪC(1)
Sn(1)ϪO(1)
Sn(1)ϪO(2)
Sn(1)ϪN(2i)
O(1)ϪC(7)
O(2)ϪC(7)
2.118(3)
2.120(3)
2.135(3)
C(3)ϪSn(1)ϪC(1)
C(5)ϪSn(1)ϪC(1)
C(3)ϪSn(1)ϪO(1)
113.18(12)
112.63(12)
96.01(10)
98.73(10)
92.61(10)
CϪH···Ph[a]
H···Ph
Offset
CϪH···Ph
2.1353(19) C(5)ϪSn(1)ϪO(1)
C(13)ϪH(13)···Ph5
C(3)ϪH(3)···Ph4i
3.07
2.54
3.07
2.63
0.91
0
1.04
0.32
134
155
144
168
2.955(3)
2.685(3)
1.310(3)
1.240(4)
C(1)ϪSn(1)ϪO(1)
C(3)ϪSn(1)ϪN(2i) 84.69(10)
C(5)ϪSn(1)ϪN(2i) 80.05(10)
C(1)ϪSn(1)ϪN(2i) 88.04(10)
C(213)ϪH(213)···Ph3ii
C(315)ϪH(315)···Ph1iii
C(3)ϪSn(1)ϪC(5) 130.87(12) O(1)ϪSn(1)ϪN(2i) 178.76(7)
[a]
Ph1 is defined by C(2), C(3), C(4), C(5), C(6), and C(7) atoms;
Ph3 by C(111), C(112), ..., C(116) atoms; Ph4 by C(211), C(212),
..., C(216) atoms; Ph5 by C(311), C(312), ..., C(316) atoms. Sym-
metry code superscript: (none) x, y, z; (i) x ϩ 1, y, z; (ii) x Ϫ1, y,
z; (iii) x, y Ϫ1, z.
˚
Table 2. Bond lengths [A] and angles [°] for complex 2
Sn(1)ϪO(1)
Sn(1)ϪC(11)
Sn(1)ϪC(21)
Sn(1)ϪC(31)
Sn(1)ϪO(2)
O(1)ϪC(1)
2.069(2)
2.121(3)
2.128(3)
2.146(3)
2.680(3)
1.320(4)
1.241(4)
O(1)ϪSn(1)ϪC(11)
O(1)ϪSn(1)ϪC(21)
C(11)ϪSn(1)ϪC(21)
O(1)ϪSn(1)ϪC(31)
C(11)ϪSn(1)ϪC(31)
C(21)ϪSn(1)ϪC(31)
O(2)ϪSn(1)ϪC(31)
112.05(12)
109.64(12)
119.14(13)
95.72(11)
108.51(13)
109.21(13)
149.18(13)
6, and the crystallographic data in Table 8. Compound
[Sn(CHϭCH2)3{OOCC6H3(NH2)2-3,4}] (1) is a distorted
trigonal-bipyramidal complex, it consists of three vinyl li-
gands and a bridging 3,4-diaminobenzoato ligand, which is
coordinated via one oxygen atom and the nitrogen atom of
the para-amino group. The monodentate coordination of
the carboxylate group is reflected in the short Sn(1)ϪO(1)
O(2)ϪC(1)
˚
bond [2.1353(19) A] and the different C(7)Ϫ(O1) and
˚
The structures of complexes 1, 2 and 3 are shown in Fig- C(7)ϪO(2) distances of 1.310(3) and 1.240(4) A, respect-
ures 1, 2, and 3, and selected bond lengths and angles are ively. The SnϪO(2) bond [2.955(3) A] is much longer than
given in Tables 1, 2, and 3, the lengths and angles of the the SnϪO(1) bond [2.1353(19) A], thus the interaction of
˚
˚
hydrogen bonds in the solid compounds in Tables 4, 5, and the O(2) atom with the central atom is very weak. The fifth
Eur. J. Inorg. Chem. 2002, 3214Ϫ3221
3215

F. P. Pruchnik et al.
FULL PAPER
coordination site is occupied by the N(2A) atom of a
Infrared spectra of all investigated complexes are consist-
neighboring molecule (Figure 1). Thus, complex 1 is a ent with X-ray data for compounds 1, 2, and 3. The pres-
single-strand polymer in the solid state. The Sn(1)ϪN(2A) ence of νas(COO) and νs(COO) in the ranges 1600Ϫ1614
distance is 2.685(3) A and the O(1)ϪSn(1)ϪN(2A) angle is cmϪ1, and 1334Ϫ1368 cmϪ1, respectively, and therefore the
˚
as
178.76(7)°. The angles C(1)ϪSn(1)ϪC(3) [113.18(12)°] and large ∆ν ϭ ν
Ϫ νsCOO values are consistent with the
COO
C(1)ϪSn(1)ϪC(5) [112.63(12)°] are considerably smaller, presence of the asymmetrically coordinated carboxylato
and the C(3)ϪSn(1)ϪC(5) angle [130.87(12)°] is substan- group in complexes 1, 2, 3, and 4. The ν(SnC) bands for
tially larger than those expected for a regular trigonal bipyr- the vinyl compounds (1 and 4) are observed in the range
amid. A relatively strong Sn(1)ϪN(2A) bonding interaction 496Ϫ542 cmϪ1, and are similar to the values in other
is important for the stabilization of the crystal structure of vinylϪSnIV compounds.[19] The substituent-sensitive r-
complex 1. The crystal structure is also stabilized by the modes for the phenyl groups were observed at 620 cmϪ1
relatively strong hydrogen bond N(2)ϪH(4N)···O(2)(i) and and 588 cmϪ1 for complex 2, and 636 cmϪ1, 610 cmϪ1, and
the weaker hydrogen bonds N(2)ϪH(3N)···C(2)(ii), 590 cmϪ1 for compound 3, and the y-modes at 452 cmϪ1
N(1)ϪH(1N)···X1A(C1/C2)(iii), and N(1)ϪH(2N)···X1B- and 442 cmϪ1 for 2, and 457 cmϪ1 and 444 cmϪ1 for 3.
(C3/C4)(iv) (Table 4). In complex 2, the central atom has a These values agree well with the data for Sn(C6H5)4.[19]
1
distorted tetrahedral geometry, with the Sn(1)ϪO(1) bond
The H chemical shift ranges for the trivinyl, triphenyl
˚
length of 2.069(2) A, the Sn(1)ϪC bond lengths of moieties and the carboxylato ligands were deduced from
2.121(3)Ϫ2.146(3) A, and the considerably longer resonance intensities and nJ(1H-1H) coupling constants.
˚
˚
Sn(1)ϪO(2) distance of 2.680(3) A. The C(11)ϪSn(1)Ϫ Both chemical shifts and coupling constants for complexes
C(31) and C(21)ϪSn(1)ϪC(31) angles are 108.51(13) and 1Ϫ4 agree well with the data found for [Sn(C6H5)3-
109.21(13)°, respectively, and the C(11)ϪSn(1)ϪC(21) angle (OOCC6H5)],[7] [Sn(C6H5)3(OOCC6H4NH2)], and other tri-
is 119.14(13)°. The interaction of the oxygen atom O(2) phenyltin() compounds,[20,21] [Sn(CHϭCH2)2X2] and
with the central atom Sn(1) is relatively strong in compar- [Sn(CHϭCH2)3X],[22Ϫ24] and with the spectra of 3,4-diami-
ison with analogous interactions in complex 1. The nobenzoic and 2-[(4-dimethylamino)phenylazo]benzoic acid
O(2)ϪSn(1)ϪC(31) angle is 149.18(13)°, while the and their metal salts. The first-order spectra of the vinyl
O(2)ϪSn(1)ϪC(11) and O(2)ϪSn(1)ϪC(21) angles are ligands of the [Sn(CHϭCH2)3(OOCR)] complexes 1 and 4
84.67(13) and 86.38(13)°, respectively. The structure of consist of three quadruplets with 119/117Sn satellites. The
complex 2 is similar to that of [Sn(C6H5)3(OOCC6H5)], in chemical shifts of H7, H8, and H9 and the 3J(H7H9),
[7,16]
2
The crystal 3J(H7H8), and J(H8H9) coupling constants in chloroform
˚
which the O(2)ϪSn distance is 2.674(3) A.
structure of the complex 2 is stabilized not only by the solution are slightly higher than those found for [Sn(CHϭ
1
Sn(1)ϪO(2) interaction, but also by intermolecular hydro- CH2)3X] (X ϭ Cl, Br, I). It has been found that the H
gen
bonds,
namely,
N(1)ϪH(2N)···N(2)(ii)
and chemical shifts and the nJ(1H-1H) coupling constants of the
N(2)ϪH(3N)···O(2)(iii) (Table 5). Complex 3 has a molecu- vinyltin halides depend on the electronegativity of the hal-
lar structure similar to that of compound 2, with the ide.[22] Thus, deshielding of H1, H2, and H3 and a slight
n
Sn(1)ϪO(1) bond length of 2.054(2) A, Sn(1)ϪC bond increase in the J(1H-1H) coupling constants are caused by
˚
˚
lengths of 2.117(4)Ϫ2.126(4) A and Sn(1)ϪO(2) bond the higher electronegativity of the RCOO ligand in compar-
length of 2.827(3) A. Thus, in this compound the interac- ison with that of the ligands Cl, Br, and I. The chemical
˚
tion between the Sn(1) and O(2) atoms is weaker than in shift differences [δ(H7) Ϫ δ(H8)] for complexes 1 and 4 are
complex 2. However, the crystal structure of compound 3 also greater because of the higher electronegativity of the
is also stabilized by weak CϪH···Ph intermolecular and in- carboxylato ligand. These differences increase in more polar
tramolecular hydrogen bonds (Table 6), as well as by inter- solvents. They are equal to δ ϭ 0.24 ppm in CDCl3 and
molecular stacking interactions between parallel C(2)ϪC(7) 0.36 ppm in (CD3)2CO and (CD3)2SO. The 119Sn chemical
and C(8)(i)ϪC(13)(i) phenyl rings of the two neighboring shifts are higher for four-coordinate compounds than for
molecules. The distance between these rings is 2.49 A and the five-coordinate complexes. The values of δ(119Sn) in the
˚
the offset is 1.42 A. There are three intermolecular and one latter are shifted upfield over a wide range.[20Ϫ22,24] The
˚
intramolecular C(13)ϪH(13)···Ph5 (C311,C312, ..., C316 119Sn chemical shifts for compounds 1 and 4 in acetone are
ring) hydrogen bonds (Table 6). Two bonds with short dis- δ ϭ Ϫ167.9 and Ϫ168.9 ppm, respectively. They are lower
tances between the hydrogen donor atom and the phenyl than the chemical shift for Sn(CHϭCH2)4 (δ
ϭ
centroid (Ph1 and Ph4) have a short offset, which is defined Ϫ157.4 ppm),[24] and greater than for [Sn(CHϭCH2)2-
as the distance from the ring centroid to the projection of (OOCPh)2] in CDCl3 (δ ϭ Ϫ317.7 ppm).[23] The value of
the H-atom position on the plane of the ring.[17] These the 1J(119/117Sn-13C7) coupling constant for complex 4 in
bonds are also more linear than long hydrogen bonds. In- chloroform is 600.2/574.9 Hz and is similar to that found
termolecular hydrogen bonds link all the molecules located for complex [Sn(CHϭCH2)3Cl] in CDCl3 (594.7/568.2 Hz).
1
along the [100] and [010] directions in the crystal. Short Thus, the H, 13C, and 119Sn NMR spectra indicate that
lattice vectors a and b, relative to c, suggest that analyzed complexes 1 and 4 in chloroform solution are tetrahedral
weak hydrogen bonds control the growth of the crystals. molecules, and that the coordination of acetone, methanol
The same was observed earlier in the case of other com- or dimethyl sulfoxide with tin compounds is rather weak.
pounds.[18]
The formation of weak adducts of complexes 2 and 3 with
3216
Eur. J. Inorg. Chem. 2002, 3214Ϫ3221

Structure, Properties and Cytostatic Activity of Triorganotin (Aminoaryl)carboxylates
FULL PAPER
polar solvents is also confirmed by the 13C and 119Sn NMR
The geometry optimization in the first case was per-
1
spectra. The J(119Sn-13C) coupling constants for tetrahed- formed at the PM3 level and in the second case within the
ral SnPh3X (X ϭ Cl, RCOO, etc.) complexes in chloroform 3-21G basis set and MP2 formalism. The evaluated SnϪO1
˚
solution are in the range 550Ϫ650 Hz, while for five-coord- bond length with PM3 is found to be 2.019 A and the
˚
inate complexes, they are often in the range 770Ϫ850 Hz. Sn···O2 distance 2.685 A. The respective ab initio results are
2
The J(119Sn-13C) coupling constants do not depend on the 2.071 A and 2.609 A, whereas the relevant crystallographic
˚
˚
˚
˚
coordination number of tin and have values of values are 2.1353(19) A and 2.955(2) A, respectively. This
47.6Ϫ50.0 Hz, and the 3J(119Sn-13C) and 4J(119Sn-13C) discrepancy results from the formation of the weak
coupling constants are slightly greater for five-coordinate Sn(1)ϪN(2A) bond and the distorted trigonal-bipyramidal
compounds than for four-coordinate complexes and are in coordination of the tin atom in the solid state. In complex
the range 63Ϫ73 Hz and 12.7Ϫ14.6 Hz, respective- 2, in which the SnϪN bond in the solid state is not formed,
ly.[20Ϫ22,24] Small differences between five-coordinate and the Sn(1)ϪO(1) bond [2.069(2) A] and the Sn(1)ϪO(2)
˚
˚
four-coordinate triphenyltin() compounds were found in bond [2.680(3) A] are very similar to those calculated with
the values of the chemical shifts δ(13Ci) of the carbon atoms semiempirical and ab initio methods. Thus, these methods
in the ipso-positions of the phenyl groups. The values of the can most likely be applied for the calculations of the inter-
δ(13Ci) for the five-coordinate complexes are shifted down- actions of SnIV compounds with nucleotides and other mo-
field from those of four-coordinate tin compounds by sev- lecules important for the explanation of the biological activ-
eral ppm.[20] The 13C chemical shifts and nJ(119Sn-13C) ity of tin compounds. The theoretical dipole moment is
coupling constants for complexes 2 and 3 in chloroform 1.543 D, the ionization energy is 8.572 eV, and the heat of
are in the range characteristic of tetrahedral triphenyltin formations is estimated to be 9.98 kJ/mol.
compounds since δ(13Ci) ϭ 138.88 ppm and 1J(119/117Sn-
Complexes 1, 2, 3, and 4 belong to the efficient cytostatic
13Ci) ϭ 651.0/621.8 Hz for the ipso-carbon atoms of com- agents (Table 7). Compound 2 is very active against
1
plex 2, and δ(13Ci) ϭ 138.48 ppm and J(119/117Sn-13Ci) ϭ HCV29T cells (ID50 ϭ 0.0072 µmol/dm3). The activity of
644.6/618.5 Hz for those of compound 3. The chemical shift the compounds against the HCV29T cell line decreases in
δ(13Ci) is slightly higher in more polar solvents, thus for the order 2 Ͼ 1 Ͼ 3 Ͼ 4. It is worth noting that the com-
complex 2 in (CD3)2CO a value of δ ϭ 140.69 ppm is ob- plexes are also very active in ethanol solution. Cytostatic
served and for compound 3 in CD3OD, a value of δ ϭ activity of complexes 1 and 2 against the A549 and CACO-
140.12 ppm is observed. The values of δ(119Sn) in CDCl3 2 lines is relatively high, although lower than that against
for 2 and 3 are δ ϭ Ϫ118.9 and Ϫ108.6 ppm, and are sim- HCV29T cells. Thus, these compounds are promising cyto-
ilar to those found for complexes [SnPh3(OOCC6H4NH2- static agents against some tumor lines in vitro.
4)] and [SnPh3(OOCC6H4NH2-2)] (δ ϭ Ϫ122.6 and
Ϫ116.8 ppm).[20] The δ(119Sn) values for complex 2 in acet-
one (δ ϭ Ϫ123.1 ppm) is ca. 4 ppm greater than that in
chloroform. These data also confirm the formation of weak
adducts of compounds 2 and 3 with polar solvents.
Conclusion
Investigations of the structures of the complexes [Sn-
The molecular and electronic structures of a single mole- (CHϭCH2)3{µ-OOCC6H3(NH2)2-3,4}]n (1), [Sn(C6H5)3-
cule of [Sn(CHϭCH2)3(OOCC6H3(NH2)2-3,4)] with C1 {OOCC6H3(NH2)2-3,4}] (2), and [Sn(C6H5)3{OOC-2-
symmetry has been studied by both semiempirical and non- C6H4NϭNC6H4N(CH3)2-4}] (3) reveal that the coordina-
empirical ab initio methods. The quantum chemical calcula- tion of the central atom in complex 1 is distorted trigonal-
tions were performed using the PM3 of the MOPAC2000 bipyramidal, and in complexes 2 and 3 distorted tetrahed-
package,[25] and the GAUSSIAN-98 computer program.[26] ral. Complex 1 is a regular single-strand polymer. The vinyl
Table 7. Inhibition doses ID50 of complexes 1Ϫ4
Compound
Cancer
A549
HCV29T
CACO
ID50
Solvent
ID50
Solvent
ID50
Solvent
[µmol/dm3]
[µmol/dm3]
[µmol/dm3]
1
2
1.36
0.0072
0.058
3.40
0.53
7.05
1.28
20.16
84.29
i.
MeOH
MeOH
EtOH
DMSO
EtOH
DMSO
EtOH
DMSO
EtOH
EtOH
20.0
0.90
EtOH
EtOH
12.0
i.
EtOH
EtOH
3
n. d.[a]
n. d.
n. d.
i.
4
n. d.
HOOCC6H4NϭNC6H4NMe2-4
i.
i.
H2O
EtOH
H2O
HOOCC6H3(NH2)2-3,4
EtOH
i.
[a]
n.d.: activity was not determined; i.: inactive.
Eur. J. Inorg. Chem. 2002, 3214Ϫ3221
3217

F. P. Pruchnik et al.
FULL PAPER
(νCH), 2940 w (νCH), 1614 vs (νCOO), 1599 s (νCϭC), 1590 s, 1584 s,
1570 s, 1556 vs (νCOO), 1520 s, 1442 m, 1396 s, 1362 vs (νCOO),
1332 vs(νCOO),1304 vs, 1248 vs, 1152 m, 1096 w, 1004 s, 956 s, 904
w, 820 m, 784 s, 648 m, 588 m, 542 m (νSnC), 498 m (νSnC), 451 m,
389 m. 1H NMR (CDCl3, ppm): δ ϭ 7.50 [dd, 3J(H5H6) ϭ 8.1,
4J(H2H6) ϭ 1.8 Hz, H6], 7.43 (d, H2), 6.65 [d, H5], 6.59 [dd,
3J(H7H8) ϭ 13.5, 3J(H7H9) ϭ 20.4, 2J(119/117SnH7) ϭ 125.9/
ligands are coordinated in the equatorial positions and the
bridging 3,4-diaminobenzoato ligands occupy the axial co-
ordination sites, and form a strong SnϪO bond and a weak
SnϪN bond with the para-amino group, the Sn(1)ϪO(1)
˚
and Sn(1)ϪN(2A) distances are 2.1353(19) and 2.685(3) A,
respectively. In complexes 2 and 3, the carboxylato ligand
is strongly coordinated to the central atom via one oxygen
atom and the Sn(1)ϪO(2) distances are considerably longer.
However, these weak interactions, as well as the NϪH···O,
2
3
120.4 Hz, H7], 6.32 [dd, J(H8H9) ϭ 2.6, J(119/117SnH8) ϭ 236.2/
226.0 Hz, H8], 5.96 [dd, 3J(119/117SnH9) ϭ 115.9/110.9 Hz, H9],
1
3.47, 3.69 (2s, H3, H4). H NMR [(CD3)2CO, ppm]: δ ϭ 7.60 [dd,
NϪH···C, NϪH···N hydrogen bonds, and in the case of 3J(H5H6) ϭ 8.3, 4J(H2H6) ϭ 1.9 Hz, H6], 7.20 (d, H2), 6.74 (d, H5),
6.62 [dd, 3J(H7H8) ϭ 13.6, 3J(H7H9) ϭ 20.4, 2J(119/117SnH7) ϭ
complex 3 the CϪH···Ph hydrogen bonds, stabilize the crys-
tal structure of these complexes. The crystal structure of
129.0/122.9 Hz, H7], 6.26 [dd, 2J(H8H9) ϭ 2.9, 3J(119/117SnH8) ϭ
239.5/228.2 Hz, H8], 6.01 [dd, 3J(119/117SnH9) ϭ 114.9/109.9 Hz,
complex 3 is additionally stabilized by the intermolecular
H9], 3.47, 3.69 (H3, H4). 119Sn NMR [(CD3)2CO, ppm]: δ ϭ
stacking interaction between parallel C(2)ϪC(7) and
C(8)(i)ϪC(13)(i) phenyl rings of the 2-[4-(dimethylamino)-
Ϫ167.9.
phenylazo]benzoato ligand of two neighboring molecules.
The IR and NMR spectra reveal that the structure of com-
plex 4 is analogous to that of the complexes 2 and 3. The
molecular and electronic structure of a single molecule of
complex 1 [Sn(CHϭCH2)3(OOCC6H3(NH2)2-3,4)], calcu-
lated both with semiempirical and ab initio methods, reveal
that coordination about the tin atom is similar to that in
complex 2. Thus, the relatively long Sn(1)ϪO(1) bond in
complex 1, relative to that in compounds 2 and 3, results
from the weak interaction between the Sn atom and the N
atom of the para-amino group of the 3,4-diaminobenzoato
ligand. The complexes are effective cytostatic agents against
HCV29T, A549 and CACO-2 tumor lines.
[Sn(C6H5)3{OOCC6H3(NH2)2-3,4}]·0.5C6H5CH3
(2).
Method
a: mixture of Sn(C6H5)2O (0.58 g, 2.01 mmol) and
A
HOOCC6H3(NH2)2 (0.31 g, 2.03 mmol) in toluene/ethanol (3:1) (10
mL) was refluxed with stirring for 4 h. The light brown solid was
filtered. The yellow filtrate was slowly concentrated giving yellow
crystals of complex 2. The solid was washed with cold ethanol and
dried in vacuo. Yield 0.32 g (56%). C28,5H26N2O2Sn (547.24): C
62.55, H 4.79, N 5.12, Sn 21.69; found C 62.50, H 4.85, N 5.40,
Sn 22.02. Single crystals for X-ray investigations were prepared by
slow concentration of a toluene/ethanol solution of the complex.
Method b: A mixture of {Sn(C6H5)3}2O (0.716 g, 1.0 mmol) and
HOOCC6H3(NH2)2 (0.31 g, 2.03 mmol) in ethanol (15 mL) was re-
fluxed with stirring for 0.3 h. The red-brown solution was filtered.
The filtrate was concentrated, giving a yellow polycrystalline pre-
cipitate of complex 2. The solid was recrystallized from toluene and
washed with cold ethanol and dried in vacuo. Yield 0.652 g (65%).
IR (KBr, cmϪ1): ν˜ ϭ 3408 s (νNH2), 3320 s (νNH2), 3295 w (νNH2),
3250 w (νNH2), 3200 w (νNH2), 3075 w (νCH), 3070 w (νCH), 3064
w (νCH), 1632 s (δ NH2), 1600 vs (νCOO), 1572 vs, (νCOO), 1518 s,
1480 s, 1446 w 1430 vs, 1368 vs (νCOO), 1334 vs (νCOO),1300 vs,
1246 vs, 1192 w, 1152 s, 1112 w, 1076 s, 1060 w, 1024 w, 956 vw,
898 w, 836 m, 778 s, 732 vs, 700 vs, 658 s, 620 w (r-mode SnC), 588
w (r-mode SnC), 512 m, 468 w, 452 m (y-mode SnC), 442 s (y-
mode SnC), 402 m. C28,5H26N2O2Sn (547.24): C 62.55, H 4.79, N
Experimental Section
Materials and Methods
Compounds: 3,4-diaminobezoic acid was obtained from Aldrich, 2-
[4-(dimethylamino)phenylazo]benzoic acid from POCH (Poland),
diphenyltin dichloride and divinyltin dichloride from Strem and
used without further purification. Diphenyltin oxide, triphenyltin
oxide, and divinyltin oxide were prepared from diphenyltin dichlor-
ide, triphenyltin chloride, and divinyltin dichloride with sodium hy-
droxide in aqueous ethanol solution. Syntheses were carried out
under nitrogen. Infrared spectra (KBr pellets) were recorded with
a Bruker IFS 113v, and 1H NMR spectra were recorded with a
Bruker AMX 300 and a Bruker Avance 500. C,H,N analyses were
performed with a PerkinϪElmer 2400 CHN analyzer, and Sn was
determined using ICP-AES with an ARL 3410.
Synthesis of Complexes
1
5.12, Sn 21.69; found C 62.40, H 4.65, N 5.30, Sn 21.92. H NMR
3
[Sn(CH؍CH2)3{OOCC6H3(NH2)2-3,4}] (1):
A
suspension of
(CDCl3, ppm): δ ϭ 7.78Ϫ7.84 [m, J(1H-119/117Sn) ϭ 63.6 Hz, Ho],
Sn(CHϭCH2)2O (0.75 g, 3.95 mmol) and HOOCC6H3(NH2)2 7.60 [dd, 3J(H5H6) ϭ 8.1, 4J(H2H6) ϭ 1.8 Hz, H6], 7.50 (d, H2),
(0.60 g, 3.95 mmol) in ethanol (10 mL) was refluxed with stirring 7.43Ϫ7.49 (m, Hm,p), 7.29 [Hm(toluene)], 7.19 [Ho,p(toluene)], 6.63
for 5 h. The dark-brown solid was filtered and the filtrate was con-
centrated to dryness. The dry residue was extracted with chloro-
form. The light beige solid was filtered. The filtrate was concen-
trated and the obtained solid was crystallized from hot toluene.
The light brown product [Sn(CHϭCH2)3{OOCC6H3(NH2)2-3,4}]
(1) was filtered and washed with cold toluene. Yield 0.32 g (46%).
C13H16N2O2Sn (350.95): C 44.49, H 4.59, N 7.98, Sn 33.82; found:
C 44.06, H 4.50, N 7.65, Sn 33.43. Single crystals were grown by
concentration of a toluene solution of the compound. IR (KBr,
(d, H5), 3.38, 3.69 (2s, H3,4), 2.37 [s, CH3(toluene)]. 13C NMR
(CDCl3, ppm): δ ϭ 173.34 (COO), 140.39 (C4) 138.88 , [1J(13C-119/
117Sn) ϭ 651.0/621.8 Hz, Ci], 136.88 [2J(13C-119/117Sn) ϭ 48.0 Hz,
Co], 133.20 (C3), 129.93 [4J(13C-119/117Sn) ϭ 13.0 Hz, Cp], 128.78
[3J(13C-119/117Sn) ϭ 62.7 Hz, Cm], 124.49 (C6), 120.91 (C1), 119.46
(C2), 114.73 (C5); toluene: 137.82 (Ci), 128.99 (Co), 128.19 (Cm),
125.26 (Cp), 21.41 (CH3). 13C NMR [(CD3)2CO, ppm]: δ ϭ 172.14
(COO), 141.79 (C4), 140.69 (Ci), 137.65 [2J(13C-119/117Sn) ϭ
47.5 Hz, Co], 134.61 (C3), 130.61 [4J(13C-119/117Sn) ϭ 13.2 Hz, Cp],
cmϪ1): ν˜ ϭ 3412 s (νNH2), 3348 s (νNH2), 3048 w (νCH), 2984 w 129.50 [3J(13C-119/117Sn) ϭ 64.4 Hz,Cm], 123.57 (C6), 119.71 (C1),
3218 Eur. J. Inorg. Chem. 2002, 3214Ϫ3221

Structure, Properties and Cytostatic Activity of Triorganotin (Aminoaryl)carboxylates
FULL PAPER
118.43 (C2), 114.24 (C5); toluene: 129.73 (Co), 129.01 (Cm) 126.09 4 h. The red solid was filtered. The red filtrate was concentrated,
(Cp), 21.43 (CH3). 119Sn NMR (CDCl3, ppm): δ ϭ Ϫ118.9, giving a red solid that was crystallized from a hot dioxane/toluene
[(CD3)2CO, ppm]: δ ϭ Ϫ123.1.
mixture (1:4, v/v). Red needles of complex 4 were separated and
washed with diethyl ether and dried in vacuo. Yield 0.22 g (47%).
C21H23N3O2Sn [Sn(CHϭCH2)3{OOC-2-C6H4NϭNC6H4N(CH3)2-
4}] (468.15): C 53.88, H 4.95, N 8.98, Sn 25.36; found C 53.40, H
4.65, N 9.05, Sn 24.69. IR (KBr, cmϪ1): ν˜ ϭ 3070 vw (νCH), 3065
vw (νCH), 3040 vw (νCH), 2980 w (νCH), 2936 w (νCH), 2860 vw
as
(νCH), 2800 vw (νCH), 1602 vs (ν
), 1560 ms, 1546 ms, 1526 s,
COO
1482 m 1465 w, 1452 vw, 1442 wm, 1420 ms, 1400 s, 1366 vs (ν
s
COO), 1338 w, 1312 s,1276 ms, 1248 w, 1230 m1196 vw, 1148 vs,
1112 ms, 1092 m, 1060 w, 1040 vw, 998 m, 944 ms, 880 vw, 860 vw,
830 w, 820 s, 790 vw, 766 ms, 747 vw, 730 w, 688 w672 wm, 636
wm, 618 vw, 580 w, 544 s, 520 wm (νSnC), 496 m (νSnC), 426 vw,
416 w, 390 w, 385 w. 1H NMR (CDCl3, ppm): δ ϭ 7.81 [d,
3J(H2ЈH3Ј) ϭ 8.9 Hz, H2Ј ϩ H6Ј], 7.27Ϫ7.67 (m, H3 ϩ H4 ϩ H5 ϩ
[Sn(C6H5)3{OOC-2-C6H4N؍NC6H4N(CH3)2-4}] (3). Method a: A
mixture of Sn(C6H5)2O (0.58 g, 2.01 mmol) and 2-[4-(dimethylami-
no)phenylazo]benzoic acid [HOOCC6H4NϭNC6H4N(CH3)2-4]
(0.58 g, 2.01 mmol) in ethanol (15 mL) was refluxed with stirring
for 4 h. The red solid was filtered. The red filtrate was slowly con-
centrated, giving red crystals of complex 3. The solid was washed
with cold hexane and dried in vacuo. Yield 0.32 g (50%).
C33H29N3O2Sn [Sn(C6H5)3{OOC-2-C6H4NϭNC6H4N(CH3)2-4}]
(618.33): C 64.10, H 4.73, N 6.80, Sn 19.20; found C 64.80, H 4.95,
N 7.15, Sn 18.85. Method b: A mixture of {Sn(C6H5)3}2O (0.716 g,
1.0 mmol) and) and 2-[(4-dimethylamino)phenylazo]benzoic acid
[HOOCC6H4NϭNC6H4N(CH3)2-4] (0.54 g, 2.01 mmol) in ethanol
(15 mL) was refluxed with stirring for 0.3 h. The red solution was
filtered. The red filtrate was slowly concentrated, giving a red prod-
uct. The solid was washed with cold hexane and dried in vacuo.
Yield 0.841 g (68%). C33H29N3O2Sn [Sn(C6H5)3{OOCϪ2-C6H4Nϭ
NC6H4N(CH3)2-4}] (618.33): C 64.10, H 4.73, N 6.80, Sn 19.20;
3
3
H6), 6.73 (d, H3Ј ϩ H5Ј), 6.56 [dd, J(H7H8) ϭ 13.5, J(H7H9) ϭ
2
2
20.2, J(119/117SnH7) ϭ 128.2/125.6 Hz, H7], 6.32 [dd, J(H8H9) ϭ
2.5, 3J(119/117SnH8) 236.6/225.2 Hz, H8], 5.95 [dd, 3J-
ϭ
(
119/117SnH9) ϭ 114.2/109.2 Hz, H9], 3.14 (s, CH3). 1H NMR
[(CD3)2CO, ppm]: δ ϭ 7.83 [d, 3J(H2ЈH3Ј) ϭ 8.9 Hz, H2Ј ϩ H6Ј],
7.35Ϫ7.65 (m, H3 ϩ H4 ϩ H5 ϩ H6), 6.83 (d, H3Ј ϩ H5Ј), 6.59 [dd,
3J(H7H8) ϭ 13.6, J(H7H9) ϭ 20.4 Hz, H7], 6.23 [dd, J(H8H9) ϭ
3
2
3.0 Hz, H8], 5.99 (dd, H9), 3.11 (s, CH3). 1H NMR [(CD3)2SO,
ppm]: δ ϭ 7.73 [d, J(H2ЈH3Ј) ϭ 8.9 Hz,H2Ј ϩ H6Ј], 7.33Ϫ7.50 (m,
3
H3 ϩ H4 ϩ H5 ϩ H6), 6.79 (d, H3Ј ϩ H5Ј), 6.50 [dd, J(H7H8) ϭ
3
3
2
13.3, J(H7H9) ϭ 20.2, J(119/117SnH7) ϭ 132.1/127.4 Hz, H7], 6.14
[dd, 2J(H8H9) ϭ 3.1 Hz, 3J(119/117SnH8) ϭ 244.5/234.2 Hz, H8],
5.92 [dd, J(119/117SnH9) ϭ 122.2/116.0 Hz, H9], 3.05 (s, CH3). 13C
3
found C 64.40, H 4.85, N 7.04, Sn 18.94. IR (KBr, cmϪ1): ν˜ ϭ
NMR (CDCl3, ppm): δ ϭ 173.53 (COO), 152.38 (C2), 151.28 (C4Ј),
as
3068 w (νCH), 3048 w, 3020 vw, 1640 m, 1600 vs (ν
), 1560 w,
COOH
143.95 (C1Ј), 137.79 (C8), 135.95 [1J(13C-119/117Sn)
ϭ 600.2/
1520 s, 1480 m, 1442 w, 1432 m, 1416 w, 1406 m, 1366 vs (νCs OOH),
1340 s (νCs OOH), 1312 m, 1276 w, 1250 w, 1232 w, 1190 vw, 1144 vs,
1088 w, 1076 w, 1020 vw, 996 wm, 944 m, 860,w, 820 ms, 784 w,
760 m, 746 w, 736 s, 726 s, 696 s, 676 w 636 w (r-mode SnC), 610
vw (r-mode SnC), 590 vw (r-mode SnC), 570 vw, 546 m, 510 wvw,
494 vw, 464 w, 457 m (y-mode SnC), 444 m (y-mode SnC), 390 w.
1H NMR (CD3OD, ppm): δ ϭ 7.78Ϫ7.86 [m, 3J(1H-119/117Sn) ϭ
63 Hz, Ho], 7.62 [d, 3J(H2ЈH3Ј) ϭ 9.1 Hz, H2Ј ϩ H6Ј], 7.48Ϫ7.59
(m, H3 ϩ H6), 7.30Ϫ7.46 (m, H4 ϩ H5 ϩ Hm ϩ Hp), 6.71 [d,
3J(H5ЈH6Ј) ϭ 9.1 Hz, H3Ј ϩ H5Ј], 3.08 (s, CH3). 13C NMR (CDCl3,
ppm): δ ϭ 174.47 (COO), 152.88 (C2), 152.43 (C4Ј), 143.89
574.9 Hz, C7], 133.58 (C1), 130.62 (C4), 129.22 (C6), 128.26 (C5),
125.60 (C2Ј, C6Ј), 116.68 (C3), 111.26 (C3Ј, C5Ј), 40.29 (NCH3).
119Sn NMR [(CD3)2CO, ppm]: δ ϭ Ϫ168.9.
(C1Ј), 138.48 [1J(13C-119/117Sn)
ϭ
644.6/618.5 Hz, Ci], 136.99
[2J(13C-119/117Sn) ϭ 48.0 Hz, Co], 131.50 (C1, C4), 130.31 (C6),
129.91 [4J(13C-119/117Sn) ϭ 13.0 Hz, Cp], 128.76 [3J(13C-119/117Sn) ϭ
63.5 Hz, Cm], 128.06 (C5), 125.48 (C2Ј, C6Ј), 118.36 (C3), 111.36
(C3Ј, C5Ј), 40.25 (NCH3). 13C NMR (CD3OD, ppm): δ ϭ 173.25
(COO), 154.45 (C2), 152.54 (C4Ј), 144.76 (C1Ј), 140.12 (Ci), 137.76
[2J(13C-119/117Sn) ϭ 48.1 Hz, Co], 132.57 (C1), 131.62 (C4), 130.36
(Cp), 130.05 (C6), 129.58 (Cm), 129.11 (C5), 126.62 (C2Ј, C6Ј), 118.23
(C3), 112.63 (C3Ј, C5Ј), 40.45 (NCH3). 119Sn NMR (CDCl3, ppm):
δ ϭ Ϫ108.6.
X-ray Crystallographic Study: All measurements were performed at
low temperature using an Oxford Cryosystem device with a Kuma
KM4CCD κ-axis diffractometer with graphite-monochromated
Mo-Kα radiation (Table 8). The crystal was positioned at 65 mm
from the CCD camera. 612 frames were measured at 0.75Θ inter-
vals with a counting time of 20 s. Accurate cell parameters were
determined and refined by least-squares fit of the strongest
reflections. The data were corrected for Lorentz and polarization
effects. No absorption correction was applied. Data reduction and
analysis were carried out with the Oxford Diffraction, Poland (for-
merly Kuma Diffraction Wrocław, Poland), programs. The struc-
ture was solved by direct methods (program SHELXS-97[27]) and
refined by the full-matrix least-squares method on all F2 data using
the SHELXL-97[28] programs. Non-hydrogen atoms were refined
with anisotropic vibrational parameters; hydrogen atoms were in-
cluded from the geometry of the molecules and ∆ρ maps and were
refined with isotropic vibrational parameters. CCDC-176692,
-176693, and -176694 contain the supplementary crystallographic
[Sn(CH؍CH2)3{OOC-2-C6H4N؍NC6H4N(CH3)2-4}] (4): A mix-
ture of Sn(CHϭCH2)2O (0,38 g, 2.0 mmol) and 2-[4-(dimethylami-
no)phenylazo]benzoic acid HOOCC6H4NϭNC6H4N(CH3)2-4 data for this paper. These data can be obtained free of charge at
(0.54 g, 2.0 mmol) in ethanol (15 mL) was refluxed with stirring for
www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge
Eur. J. Inorg. Chem. 2002, 3214Ϫ3221
3219

F. P. Pruchnik et al.
FULL PAPER
Table 8. Crystal data and structure refinement for complexes [Sn(CHϭCH2)3{OOCC6H3(NH2)2-3,4}] (1), [Sn(C6H5)3{OOCC6H3(NH2)2-
3,4}]·0.5C6H5CH3 (2·0.5C6H5CH3), and [Sn(C6H5)3{OOC-2-C6H4NϭNC6H4N(CH3)2-4}] (3)
1
2·0.5C6H5CH3
3
Empirical formula
Formula mass
T [K]
C13H16N2O2Sn
350.97
100(2)
C25H22N2O2Sn·0.5C6H5CH3
547.20
100(2)
C33H29N3O2Sn
618.28
100(2)
˚
λ [A]
0.71073
0.71073
0.71073
Crystal system
Space group
monoclinic
C2/c
20.137(3)
8.0714(15)
19.020(3)
90
117.04(3)
90
2753.4(8)
8
monoclinic
P21/c
15.4320(19)
9.3788(12)
17.510(2)
90
102.291(10)
90
2476.3(5)
4
triclinic
P1
7.958(2)
8.719(2)
21.162(4)
88.20(3)
87.58(3)
76.72(3)
1427.4(6)
2
¯
˚
a [A]
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
3
˚
V [A ]
Z
Dcalcd. [Mg·mϪ3
]
1.693
1.852
1392
1.468
1.059
1108
1.438
0.929
628
µ [mmϪ1
F(000)
]
Crystal size [mm]
Diffractometer
θ range [°]
Ranges of h,k,l
Reflections collected
Independent reflections (Rint
Data/parameters
GOF(F2)
0.15 ϫ 0.15 ϫ 0.12
Kuma KM4CCD
3.31Ϫ28.42
Ϫ26/26, Ϫ10/6, Ϫ25/25
8935
3151(0.0436)
3151/227
1.079
0.14 ϫ 0.12 ϫ 0.08
Kuma KM4CCD
3.47Ϫ28.41
Ϫ19/20, Ϫ12/12, Ϫ23/14
15971
5788(0.0268)
5788/355
0.15 ϫ 0.10 ϫ 0.10
Kuma KM4CCD
3.21Ϫ28.44
Ϫ10/6, Ϫ11/11, Ϫ28/28
9924
6270(0.0584)
6270/469
0.910
)
1.078
Final R1/wR2 ind.(I Ͼ 2σI)
Largest difference peak/hole [e· A
0.0313/0.0777
1.568/Ϫ1.412
0.0389/0.0981
1.982/Ϫ1.852
0.0453/0.0568
0.616/Ϫ0.585
Ϫ3
˚
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Eur. J. Inorg. Chem. 2002, 3214Ϫ3221

Structure, Properties and Cytostatic Activity of Triorganotin (Aminoaryl)carboxylates
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