Citation for published version:
Ndoye, D, Diop, L, Molloy, KC & Kociok-Kohn, G 2013, 'X-ray crystal structures of [(Cy
2
NH
2
)]
3
[C
6
H
3
(CO
3
)]
_
4H
2
O and [i-Bu
2
NH
2
][(Me
3
SnO
2
C)2C6H
3
CO
2
]', Main Group Metal Chemistry, vol. 36, no. 5-6,
pp. 215-219. https://doi.org/10.1515/mgmc-2013-0019
DOI:
10.1515/mgmc-2013-0019
Publication date:
2013
Document Version
Publisher's PDF, also known as Version of record
Link to publication
University of Bath
Alternative formats
If you require this document in an alternative format, please contact:
openaccess@bath.ac.uk
General rights
Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners
and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.
Take down policy
If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately
and investigate your claim.
Download date: 10. Aug. 2022
DOI 10.1515/mgmc-2013-0019
Main Group Met. Chem. 2013; 36(5-6): 215–219
Daouda Ndoye*, Libasse Diop, Kieran C. Molloy and Gabriele Kociok-Köhn
X-ray crystal structures of
[(Cy
2
NH
2
)]
3
[C
6
H
3
(CO
2
)
3
]·4H
2
O and [i-Bu
2
NH
2
][(Me
3
SnO
2
C)
2
C
6
H
3
CO
2
]
Abstract: Two new benzene tricarboxylato derivatives
[(Cy
2
NH
2
)]
3
[C
6
H
3
(CO
2
)
3
]·4H
2
O (1) and [i-Bu
2
NH
2
][(Me
3
SnO
2
C)
2
C
6
H
3
CO
2
] (2) have been synthesized and characterized by
X-ray crystallography. In the solid state, compound 1 shows
a three-dimensional structure involving intra- and inter-
molecular hydrogen bonds, whereas the X-ray structure of
2 consists of pentacoordinated Sn centers bonded to three
methyl groups and two O atoms in a trans-O
2
SnC
3
environ-
ment, bridged by oxyanions leading to a layered structure;
the cation is involved in intramolecular hydrogen bonds.
Keywords: hydrogen bonds; organotin; 3D and layered
structures; tricarboxylate.
*Corresponding author: Daouda Ndoye, Laboratoire de Chimie
Minérale et Analytique, Département de Chimie, Faculté des
Sciences et Techniques, Université Cheikh Anta Diop, Dakar,
Sénégal, e-mail: ndoyedeve@yahoo.fr
Libasse Diop: Laboratoire de Chimie Minérale et Analytique,
Département de Chimie, Faculté des Sciences et Techniques,
Université Cheikh Anta Diop, Dakar, Sénégal
Kieran C. Molloy and Gabriele Kociok-Köhn: Department of
Chemistry, University of Bath, Bath BA2 7AY, UK
Introduction
The multifunctional ligand derived by deprotonation of
benzene-1,3,5-tricarboxylic acid has been widely used
for the manufacture of microporous materials (Yaghi
etal., 1996; Cheng etal., 2004). Thus, some solvated and
nonsolvated benzene-1,3,5-tricarboxylato metal deriva-
tives have been reported, for example, [(µ
4
-benzene-
1,3,5-tricarboxylato)-bis(methanol)-tris(trimethyltin(IV))]
and [(µ
3
-benzene-1,3,5-tricarboxylato)-tris(methanol-
trimethyltin(IV))] (Ma et al., 2005), [(µ
3
-benzene-1,3,5-
tricarboxylato)-tris(dimethylsulfoxide-trimethyltin(IV))]
dimethylsulfoxide solvate (Dakternieks etal., 2002), [(µ
3
-
benzene-1,3,5-tricarboxylato)-tris(tribenzyltin(IV))] and
[(µ
3
-benzene-1,3,5-tricarboxylato)-tris(triphenyltin(IV))]
ethanol solvate dihydrate (Ma et al., 2005), [(µ
3
-
benzene-1,3,5-tricarboxylato)-tris(triphenyltin(IV))]
dichloromethane diethylether solvate (Ma et al.,
2005) and catena [(µ
3
-benzene-1,3,5-tricarboxylato)-
bis(trimethyltin(IV))] monohydrate (Ma etal., 2005).
The chemistry of organotin (IV) derivatives is still
the subject of many studies linked to various applica-
tions in the areas of medicine, industry, and agricul-
ture (Ayrey and Poller, 1980; Owen, 1980; Blunden
et al., 1984; Gielen, 1985; Crowe, 1994; Gielen et al.,
1995). With this aim, several supramolecular organotin
compounds have been synthesized and characterized
(Chandrasekhar etal., 2003; Kapoor etal., 2005; Herntrich
and Merzweiler, 2006). In our laboratory, some of them
containing SnMe
3
and SnPh
3
residues have been recently
published (Diop etal., 2011, 2012; Sow etal., 2012a,b). In
this context, we have recently published a supramolecu-
lar trimethyltin(IV) triscarboxylate [Cy
2
NH
2
]
2
[1-Me
3
(H
2
O)
SnOCO-3,5-(OOC)
2
C
6
H
3
]·EtOH (Ndoye etal., 2012). Thus, in
a continuation of these works, we have initiated here the
study of the interactions between both 1,3,5-(HOOC)
3
C
6
H
3
and Cy
2
NH and between [i-Bu
2
NH
2
]
3
[1,3,5-(OOC)
3
C
6
H
3
] and
SnMe
3
Cl, which have yielded the title derivatives for which
X-ray structures have been determined.
Results and discussion
The structure of 1 consists of a three-dimensional (3D)
network involving intra- and intermolecular hydrogen
bonds (Figure 1). Every tricarboxylate anion is surrounded
by three dicyclohexyl ammonium cations involving N
1
, N
2
and N
3
. The N
1
- and N
3
-containing cations are involved in
eight-membered ring formation, whereas that based on the
N
2
-containing cation forms a 12-membered ring. A fourth
12-membered ring involving two water molecules (con-
taining O
8
and O
9
) and two carboxylic acid groups (con-
taining C
7
and C
8
) and a fifth 14-membered ring involving
three water molecules (containing O
7
, O
8
and O
9
) and two
carboxylic acids (containing C
8
and C
9
) complete the hydro-
gen bond network. Two cations (containing N
1
and N
2
) are
hydrogen-bonded to a carboxylic acid and a water molecule
while the cation (containing N
3
) hydrogen bonds to two car-
boxylic acid groups. The water molecules are also involved
Authenticated | ndoyedeve@yahoo.fr author's copy
Download Date | 1/3/14 12:11 PM
216
D. Ndoye etal.: Structure of benzene tricarboxylato organotin complexes
in a diverse network of hydrogen bonds, with only the water
molecule (containing O
7
) not forming the maximum of
three such interactions. Thus, the water molecule (contain-
ing O
7
) only hydrogen bonds to one other water molecule
(containing O
8
) and one carboxylic acid moiety (containing
C
9
), and not at all as H-bond receptor. The O
8
atom links to
two water molecules and one carboxylic acid moiety, while
Figure 1The asymmetric unit of compound 1.
Selected bond distances (Å): O(1)-C(7): 1.2482(18); O(2)-C(7):
1.2635(18); O(3)-C(8): 1.2647(18); O(4)-C(8): 1.2543(19); O(5)-C(9):
1.2307(19); O(6)-C(9): 1.273(2); angles (°): O(1)-C(7)-O(2): 123.98(14);
O(4)-C(8)-O(3): 123.73(14); O(5)-C(9)-O(6): 124.54(14). Symmetry
operations: (′) 1-x, 1/2+y, 3/2-z; (″) 3/2-x, 2-y, 1/2+z; (′″) -x, y-1/2,
3/2-z.
Figure 23D structure of compound 1.
Table 1Hydrogen-bond geometry (Å, °).
D—H···A D—H H···A D···A D—H···A
O—HA···O
i
. () . () . () ()
O—HB···O . () . () . () ()
O—HA···O . () . () . () ()
O—HB···O . () . () . () ()
O—HB···O . () . () . () ()
O—HA···O
ii
. () . () . () ()
O—HA···O . () . () . () ()
O—HB···O
iii
. () . () . () ()
N—HA···O
ii
. () . () . () . ()
N—HB···O . () . () . () . ()
N—HA···O . () . () . () . ()
N—HB···O . () . () . () . ()
N—HA···O . () . () . () . ()
N—HB···O
iii
. () . () . () . ()
Symmetry codes: (i) -x+, y+/, -z+/; (ii) -x+, y-/, -z+/; (iii)
-x+/, -y+, z+/.
Figure 3The asymmetric unit of compound 2; only the major com-
ponent of the disordered cation is shown for clarity.
Selected bond distances (Å): Sn(1)-O(1): 2.2322(15); Sn(1)-O(5′):
2.2975(15), Sn(2)-O(3) 2.1670(16), Sn(2)-O(2″) 2.4046(16), O(1)-C(7):
1.273(3); O(2)-C(7): 1.242(3); O(3)-C(9): 1.280(3): O(4)-C(9): 1.242(3);
O(5)-C(8): 1.266(3); O(6)-C(8): 1.249(3); angles (°): C(11)-Sn(1)-C(12)
125.20(14), C(11)-Sn(1)-C(10) 115.75(18), C(12)-Sn(1)-C(10), 118.87(19),
C(11)-Sn(1)-O(1) 96.64(9), C(12)-Sn(1)-O(1): 90.70(9), C(10)-Sn(1)-
O(1) 86.52(10), C(11)-Sn(1)-O(5′) 91.25(8), C(12)-Sn(1)-O(5′) 88.58(9),
C(10)-Sn(1)-O(5′) 85.82(10), O(1)-Sn(1)-O(5′) 170.82(6), C(14)-Sn(2)-
C(15) 117.14(15), C(14)-Sn(2)-C(13) 116.75(15), C(15)-Sn(2)-C(13)
125.09(12), C(14)-Sn(2)-O(3) 87.13(9), C(15)-Sn(2)-O(3) 97.65(9),
C(13)-Sn(2)-O(3) 94.68(9), C(14)-Sn(2)-O(2″) 85.13(9), C(15)-Sn(2)-
O(2″) 86.16(9), C(13)-Sn(2)-O(2″) 88.56(9), O(3)-Sn(2)-O(2″)
172.26(6). Symmetry operations: (′) x-1, y, z; (″) -x+1/2, y-1/2, (′″)
1+x, y, z.
Authenticated | ndoyedeve@yahoo.fr author's copy
Download Date | 1/3/14 12:11 PM
D. Ndoye etal.: Structure of benzene tricarboxylato organotin complexes
217
the water molecule (containing O
9
) H-bonds to two carbox-
ylic acids (containing C
7
and C
8
) and one water molecule
(containing O
8
). The water molecule (containing O
10
) links
with two carboxylic acid groups (containing C
8
and C
9
) and
one cation (containing N
2
). The overall network is a reticu-
lar grid (Figure2); the relevant geometric data relating to
these hydrogen bonds are given in Table 1.
In 2, each of the two tin atoms is five-coordinated by
two carboxylate oxygen atoms derived from the triscar-
boxylate ligand, which are in apical positions, and to
three methyl groups occupying the equatorial positions
of a trigonal bipyramid (Figure 3). There are two types of
carboxylate groups in the structure: one which is biden-
tate involving C
7
and two monodentate carboxylates
based on C
8
and C
9
. There are two types of tin centers
with a trigonal bipyramidal environment in the mol-
ecule, although they have similar geometries but differ-
ent O-Sn-O angles – O
1
-Sn
1
-O
5′
[170.82°(6)] and O
3
-Sn
2
-O
2″
[172.26°(6)] angles show that the O-Sn-O frameworks
deviate from linearity. The almost planar SnMe
3
skeletons
[ΣC-Sn
1
-C angles: 359.82, 358.98° ] are bridged by the car-
boxylate O atoms, leading to a layered structure. Thus,
the layered structure is composed of tetranuclear rings
in which the noncoordinated carboxylate O atoms (O
4
and O
6
) are involved in hydrogen bonds with NH
2
groups
of i-Bu
2
NH
2
+
cations, which lie within these macrocy-
cles [H
1A
…O
6
, 1.784 Å; H
1B
…O
4
, 1.862 Å], offset from their
centers to allow bonding to the two carboylate groups at
one corner (Figure 4). The Sn-O bond lengths between
the bridging ligand and the tin centers [2.2322(15),
2.2975(15), 2.4046(16), and 2.1670(16) Å, respectively, for
Sn
1
-O
1
, Sn
1
-O
5′
, Sn
2
-O
2
, and Sn
2
-O
3″
] are in the range of
reported Sn-O distances (Diassé-Sarr etal., 2004; Alvarez
Boo etal., 2006). The structure of [(Me
3
SnO
2
C)
2
C
6
H
3
CO
2
]
[i-Bu
2
NH
2
] (2) can be compared with the related species
(Me
3
SnO
2
C)
2
C
6
H
3
CO
2
H·H
2
O (Ma etal., 2005). Although the
framework formed by the [1,3-(Me
3
SnO
2
C)
2
-6-(OOC)C
6
H
3
]
-
anion is similar in both cases, the remaining counter-
cations [i-Bu
2
NH
2
]
+
or [H
3
O]
+
impart quite different lattice
structures. Thus, while [i-Bu
2
NH
2
]
+
hydrogen bonds to
two carboxylate groups within the same plane, generat-
ing layers independent of each other, the [H
3
O]
+
species
forms hydrogen bonds between layers, generating a 3D
structure.
Figure 4Lattice structure of compound 2.
The isobutyl groups on nitrogen have been omitted for clarity.
Authenticated | ndoyedeve@yahoo.fr author's copy
Download Date | 1/3/14 12:11 PM
218
D. Ndoye etal.: Structure of benzene tricarboxylato organotin complexes
Crystal data and structure refinement
Details of the crystallographic data are given in Table 2.
In both cases, data were collected at 150(2) K using Mo-k
α
radiation (λ = 0.71073 Å). Refinement was full-matrix
least-squares based on F
2
; the absorption correction was
semiempirical from equivalents. In the final cycles of
least-squares refinement, all nonhydrogen atoms were
allowed to vibrate anisotropically. Specific details for the
two structures are as follows. 1: Water molecule hydrogen
atoms have been located in the difference Fourier map and
were refined freely with idealized bond lengths. 2: Hydro-
gen atoms when included at calculated positions were rel-
evant, save for those of the NH
2
group, which were located
in the difference map and refined. Disorder in the cation
in the ratio 65:35 required the C
21A
-C
23A
bond length to be
constrained. The structure has been solved by SHELXS
and refined by SHELXL (Sheldrick etal., 1986, 1997).
Experimental
All chemicals were purchased from Aldrich (Germany) and used with-
out any further purication. The following abbreviations are used: vs
(very strong), s (strong), m (medium), sh (shoulder), br (broad).
Synthesis of [(Cy
2
NH
2
)
3
C
6
H
3
(CO
2
)
3
·4H
2
O]
[(Cy
2
NH
2
)
3
C
6
H
3
(CO
2
)
3
‧4H
2
O] was obtained on neutralizing an aqueous
solution of benzene-1,3,5-tricarboxylic acid with Cy
2
NH in a 1:3 ratio;
aer a water evaporation at 60°C, crystals (m.p., 205°C) were col-
lected (yield, 92%). Elemental analysis: found (calc. for C
45
H
83
N
3
O
10
):
C: 65.60 (65.42), H: 9.97 (10.13), N: 5.04 (5.09)%. Infrared data (cm
-1
):
3442s (br) ν(OH); 2936 vs ν(NH
2
); 1637 vs, 1600 vs ν(COO)as; 1355 vs
ν(COO)s.
Synthesis of [
i
Bu
2
NH
2
]
+
[C
6
H
3
(CO
2
)
3
(SnMe
3
)
2
]
-
[i-Bu
2
NH
2
]
2
[C
6
H
3
(CO
2
)
2
CO
2
H]·0.5H
2
O was obtained on neutralizing
benzene-1,3,5-tricarboxylic acid with i-Bu
2
NH in water in a 1:3 ratio; a
white powder is collected aer solvent evaporation at 60°C. When an
aqueous solution of [i-Bu
2
NH
2
]
2
[C
6
H
3
(CO
2
)
2
CO
2
H]·0.5H
2
O was mixed
with an ethanolic solution of SnMe
3
Cl in 1:2 molar ratio, a clear solu-
tion was obtained, which was stirred for 2 h. When this solution was
submitted to a slow solvent evaporation, crystals of [i-Bu
2
NH
2
][C
6
H
3
(CO
2
)
3
(SnMe
3
)
2
] (2) suitable for X-ray study were obtained (yield,
72%; m.p. 220°C). Elemental analysis: found (calc. for C
23
H
41
NO
6
Sn
2
):
C: 40.95 (41.54), H: 6.74 (6.21), N: 2.44 (2.11)%. Infrared data (cm
-1
):
3541m (br) ν(OH); 2962 vs ν(NH
2
); 1618 vs, 1568s ν(COO)as; 1351 vs,
1402 sh ν(COO)s.
Received March 30, 2013; accepted September 21, 2013
References
Alvarez Boo, P.; Casas, J. S.; Couce, M. D.; Farto, R.; Fernandez-
Moreira, V.; Freijanes, E.; Sordo, J.; Vazquez-Lopez, E.
Synthesis, characterization and antibacterial activity of some
new triphenyltin(IV) sulfanylcarboxylates: crystal structure
of [(SnPh
3
)
2
(p-mpspa)], [(SnPh
3
)
2
(cpa)] and [(SnPh
3
)
2
(tspa)
(DMSO)]. J. Organomet. Chem. 2006, 691, 45–52.
Ayrey, G.; Poller, R. C. In Developments in Polymers Stabilization,
2nd Edition. Scott, G., Ed. Applied Science: London, 1980.
Blunden, S. J.; Hobbs, L. A.; Smith, P. J. The environmental chemistry
of organotin compounds. In Environmental Chemistry, SPR 35.
1984; Vol. 3, pp. 49–77.
Chandrasekhar, V.; Boomishankar, R.; Steiner A.; Bickley, J. F. First
example of a hydrogen bonded three-dimensional pillared
structure involving an organotin motif: synthesis and X-ray
crystal structures of {
n
Bu
2
Sn(H
2
O)
3
(L)Sn(H
2
O)
n
Bu
2
]
2+
[L]
2-
}
2MeOH2H
2
O and {[Ph
3
Sn(L)Sn(H
2
O)Ph
3
]
n
}.THF
{L = 1,5-naphthalene disulfonate}. Organometallics 2003, 22,
3342–3344.
Cheng, D.; Khan, M. A.; Houser, R. P. Structural variability of cobalt
(II) coordination polymers: three polymorphs of Co
3
(TMA)
2
[TMA = trimesate, C
6
H
3
(COO)
3
3-
]. Cryst. Growth Des. 2004, 4,
599–604.
Table 2Crystallographic data for compounds 1 and 2.
Empirical formula C
H
N
O
C
H
NO
Sn
Formula mass . .
Crystal system Orthorhombic Monoclinic
a (Å) .() .()
b (Å) .() .()
c (Å) .() .()
β (°) .()
Unit cell volume (Å
) .() .()
Space group P
P
/n
No. of formula units per unit cell, Z
Absorption coefficient, μ (mm
-
) . .
No. of reflections measured , ,
No. of independent reflections ,
R
int
. .
Final R
values [I > σ(I)] . .
Final wR(F
) values [I > σ(I)] . .
Final R
values (all data) . .
Final wR(F
) values (all data) . .
Goodness of fit on F
. .
CCDC number
Authenticated | ndoyedeve@yahoo.fr author's copy
Download Date | 1/3/14 12:11 PM
