Diaquabis(dimethyl sulfoxide)bis(3,5-dinitrobenzoato)zinc(II) and the synthesis of the Cu, Ni and Co analogs

Article abstract of DOI:10.1107/S0108270103003779

In order to model processes of chemisorption in organic salts formed between dinitrobenzoic acids (DNBH) and secondary amines (R₂NH), a series of compounds of composition [M^II(3,5-DNB)₂(DMSO)₂(H₂O)₂ J (where M^II is Zn, Cu, Ni or Co, 3,5-DNB is the 3,5-dinitrobenzoate ion, and DMSO is dimethyl sulfoxide) have been prepared. In diaquabis-(dimethyl sulfoxide)bis(3,5-DNB)zinc(II), [Zn(C₇H₃N₂O₆)₂-(C₂ H₆OS)₂(H₂O)₂], the 3,5-DNB ions and molecules of DMSO are monodentate ligands that are coordinated to the Zn atom through their O atoms. These ligands, together with two molecules of water, form a slightly distorted octahedral coordination environment for the Zn atom, which lies on a center of symmetry.

Full text of DOI:10.1107/S0108270103003779

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
(Tahir et al., 1996), where 3,5-DNB ions are involved in the
coordination sphere of the Co atom in trans positions. The
benzoate ions act as bidentate ligands in complexes such as
bipyridinebis(p-nitrobenzoato)copper(II) (Usubaliev et al.,
1981) and tetrakis(benzoato)bis(pyridine)dicopper(II) (Speier
ISSN 0108-2701
È È
& Fulop, 1989), where Cu atoms are octahedrally coordinated
Diaquabis(dimethyl sulfoxide)bis(3,5-
dinitrobenzoato)zinc(II) and the
synthesis of the Cu, Ni and Co analogs
by four O atoms from two carboxyl groups and two N atoms
from the two pyridines in a trans con®guration. The [Cu3-
(3,5-DNB)6(CH3OH)2]n complex is a linear polymeric chain,
È
in which the 3,5-DNB ions form all of the bridges (Hokelek et
al., 1998). The DMSO molecule can have different modes of
coordination or can pack in the crystals as crystalline solvent
molecules. The reaction of benzylamine with palladium
chloride in the presence of DMSO gives [PdCl2(C7H9N)2]Á-
2Me2SO (Decken et al., 2000). In the crystal structure, these
molecules are packed in such way that each DMSO molecule
bridges two palladium complex molecules through long-range
intermolecular interactions (HÁ Á ÁCl and HÁ Á ÁO), thus forming
in®nite chains. In complexes of platinum with 2-methoxy-
pyridine, of composition [PtCl2(C6H7NO)(C2H6OS)] (Arva-
nitis et al., 2000), and in [RuCl2(C7H7NO)(C2H6OS)2] (Pal &
Pal, 2002), DMSO is coordinated to the metal atoms through
Elguja B. Miminoshvili,a Alexandre N. Sobolev,b*
Tamara N. Sakvarelidze,a Ketevan E. Miminoshvilia and
Elguja R. Kuteliaa
aRepublican Centre of Structural Studies, Georgia Technical University, 77 Kostava
Avenue, Tbilisi 380075, Georgia, and bChemistry Section, School of Biomedical and
Chemical Sciences, University of Western Australia, 35 Stirling Highway, Crawley,
6009 WA, Australia
Correspondence e-mail: ans@crystal.uwa.edu.au
Received 18 November 2002
Accepted 18 February 2003
Online 11 March 2003
In order to model processes of chemisorption in organic salts
formed between dinitrobenzoic acids (DNBH) and secondary
amines (R2NH), a series of compounds of composition
[MII(3,5-DNB)2(DMSO)2(H2O)2] (where MII is Zn, Cu, Ni
or Co, 3,5-DNB is the 3,5-dinitrobenzoate ion, and DMSO is
dimethyl sulfoxide) have been prepared. In diaquabis-
(dimethyl sulfoxide)bis(3,5-DNB)zinc(II), [Zn(C7H3N2O6)2-
(C2H6OS)2(H2O)2], the 3,5-DNB ions and molecules of
DMSO are monodentate ligands that are coordinated to the
Zn atom through their O atoms. These ligands, together with
two molecules of water, form a slightly distorted octahedral
coordination environment for the Zn atom, which lies on a
center of symmetry.
the S atom. The same type of coordination is observed in
heteroligand complexes of ruthenium(II) (Coe et al., 1993)
and vanadium(III) (Magill et al., 1993). In the trinuclear [Ni3-
(C17H16N2O2)2(C2H3O2)2(C2H6OS)2] complex with salicyl-
È
È
idene-1,3-propanediaminate ligands (Ulku et al., 1997), the
coordination octahedron of the terminal Ni atoms comprises
Comment
The complexes of Co, Ni, Cu and Zn obtained by the reaction
of dialkylammonium 3,5-dinitrobenzoates with hydrated
metal sulfates in dimethyl sulfoxide (DMSO) have the same
stoichiometry, with two molecules each of water and DMSO
accompanying each metal bis(3,5-dinitrobenzoate) moiety.
Both the 3,5-dinitrobenzoate ion (3,5-DNB) and the DMSO
ligands are known to be versatile reagents that, in complexes
of such ligands with metals, can interact with the metal cation
or remain as counter-anions (Hundal et al., 1996) or lattice
`solvents', and thus play signi®cant roles in the hydrogen
bonding in the crystal structures. When involved in coordi-
nation processes, benzoates exhibit a wide range of coordi-
nation modes. The carboxylate group can coordinate the metal
ions in a monodentate, bidentate or bridging fashion. A typical
example of monodentate coordination of 3,5-DNB is in the
structure of tetraaquabis(3,5-DNB)cobalt(II) tetrahydrate
Figure 1
The molecular structure of (I), showing the atom-numbering scheme and
displacement ellipsoids at the 50% probability level.
m118 # 2003 International Union of Crystallography
DOI: 10.1107/S0108270103003779
Acta Cryst. (2003). C59, m118±m120

metal-organic compounds
two O and two N atoms of the aromatic ligand in the equa-
torial plane and O atoms of acetate and DMSO molecules in
axial positions. It has been reported that [Ru(tpy)(b-
py)(DMSO)](CF3SO3)2 (tpy is terpyridine and bpy is bipyr-
idine) demonstrates intermolecular phototriggered linkage
isomerism in the solid state (Rack et al., 2001).
In the title compound, (I), Zn is shown to lie on a crystal-
lographic center of symmetry, with the ligands bonded to Zn in
an all-trans fashion (Fig. 1). The coordination polyhedron
around the Zn atom is a slightly distorted octahedron
(Table 1) that involves the O atoms of the DMSO groups in
axial positions. The OÐZnÐO angles around the Zn atom are
in the range 86.53 (3)±93.47 (3)ꢀ (Table 1). The ZnÐO11 bond
is slightly longer than other examples in the literature [e.g.
orientation of the DMSO fragment in the molecule can be
described by the angle between planes O1/Zn/O11 and Zn/
O11/S1 [14.7 (1)ꢀ], where one of the methyl groups (atom
C11) lies almost in the Zn/O11/S1 plane. The C11ÐS1Ð
O11ÐZn torsion angle is 176.49 (5)ꢀ and C12ÐS1ÐO11ÐZn
is 80.86 (6)ꢀ. The crystal packing of (I) consists of columns
parallel to the b axis (Fig. 2), where molecules in neighboring
columns are linked by weak hydrogen bonds (Table 2) that
comprise the shortest intermolecular interaction.
The 3,5-DNB ion and DMSO are monodentate ligands that
are coordinated to the metal through their O atoms. This
conformation re¯ects the chemisorption processes and
con®rms that dinitrobenzoates may act as corrosion inhibitors.
The monodentate carboxylate O-atom binding implies that
the rest of the ligand should project from the metal surface,
thus inhibiting the approach of further molecules to the metal.
Ê
ZnÐODMSO = 2.122 A (Lalioti et al., 1998) or 2.10 (1) and
Ê
2.12 (1) A (Persson, 1982)]. The ZnÐO71 distance falls within
the range for typical ZnÐOcarboxylate bonds [2.047 (1)±
Ê
2.180 (2) A], and the ZnÐO1 distance is also comparable to
Ê
literature values [ZnÐOwater = 2.052 (1)±2.195 (3) A; Arranz-
Experimental
Mascaros et al., 2000; Lalioti et al., 1998; Nefedov et al., 1991;
Persson, 1982; Sequeira et al., 1992; Tahir et al., 1997]. The
other ligand geometries correspond to normal values and are
in good agreement with literature data (Shvelashvili et al.,
2001). The conformation of the molecule is described by the
dihedral and torsion angles. The angle between the plane of
the carboxylate groups and the equatorial plane formed by
water atom O1, the Zn atom and carboxyl atom O71 is
13.7 (1)ꢀ; the angle between the equatorial plane and the
plane of the benzene ring is 23.2 (1)ꢀ. The nitro and
carboxylate groups of the 3,5-DNB molecules are planar and
are approximately coplanar with the benzene ring; the angles
between the benzene ring and planes O71/C7/O72, O31/N3/
O32 and O51/N5/O52 are 10.1 (1), 5.1 (2) and 8.2 (1)ꢀ,
respectively. The coordinated water molecules are bonded to
the uncoordinated carboxylate O atoms with particularly
strong intramolecular hydrogen bonds [O1Á Á ÁO72i =
Solutions of ZnSO4Á7H2O (1.43 g, 0.005 mol) in DMSO (15 ml) and
piperidinium 3,5-dinitrobenzoate (2.86 g, 0.010 mol) in DMSO
(15 ml) were mixed and ®ltered. The ®ltrate was allowed to stand at
room temperature for 24 h over which time colorless crystals
deposited slowly. The crystals were collected, washed with diethyl
ether and dried at room temperature (Table 3). The same technique
was used for the synthesis of analogous compounds with Cu, Ni and
Co. All the complexes obtained in this way showed low solubility in
water. 2,4-Dinitrobenzoates could be obtained with similar ease.
Crystal data
3
[Zn(C7H3N2O6)2(C2H6OS)2(H2O)2]
Mr = 679.89
Dx = 1.795 Mg m
Mo Kꢁ radiation
Cell parameters from 8192
re¯ections
Monoclinic, P21=n
Ê
a = 10.479 (2) A
ꢂ = 16.4±37.5ꢀ
ꢃ = 1.23 mm
T = 153 (2) K
Ê
b = 5.296 (1) A
1
Ê
c = 22.686 (5) A
ꢀ = 91.96 (3)ꢀ
V = 1258.3 (4) A
Z = 2
3
Ê
Prism, colorless
0.20 Â 0.20 Â 0.14 mm
Ê
2.6292 (11) A; symmetry code: (i) 1 x, y, 1 z]. The
Data collection
Bruker SMART CCD
diffractometer
! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.791, Tmax = 0.847
24 698 measured re¯ections
6588 independent re¯ections
5319 re¯ections with I > 2ꢄ(I)
Rint = 0.031
ꢂmax = 37.6ꢀ
h = 17 ! 17
k = 9 ! 8
l = 38 ! 38
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
ZnÐO1
ZnÐO11
ZnÐO71
2.0857 (7)
2.1475 (8)
2.0747 (7)
S1ÐO11
S1ÐC11
S1ÐC12
1.5245 (8)
1.7875 (10)
1.7846 (11)
O1ÐZnÐO11
O1iÐZnÐO11
O11ÐZnÐO71
O11ÐZnÐO71i
O71ÐZnÐO1
O71ÐZnÐO1i
86.53 (3)
93.47 (3)
85.81 (3)
94.19 (3)
88.61 (3)
91.39 (3)
O11ÐS1ÐC11
O11ÐS1ÐC12
C12ÐS1ÐC11
S1ÐO11ÐZn
C7ÐO71ÐZn
103.63 (5)
105.92 (5)
98.05 (5)
128.21 (4)
127.75 (6)
Figure 2
Perspective packing diagram in the [101] projection, showing the
intermolecular hydrogen bonds (dashed lines).
Symmetry code: (i) 1 x; y; 1 z.
ꢁ
Acta Cryst. (2003). C59, m118±m120
Elguja B. Miminoshvili et al.
[Zn(C7H3N2O6)2(C2H6OS)2(H2O)2] m119

metal-organic compounds
Re®nement
SHELXTL (Bruker, 1998); software used to prepare material for
publication: SHELXL97.
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.027
wR(F2) = 0.071
S = 1.01
6588 re¯ections
195 parameters
w = 1/[ꢄ2(F2o) + (0.04P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max = 0.002
The authors thank Professor Allan H. White and Associate
Professor Jack M. Harrow®eld for experimental assistance and
helpful discussion.
3
Ê
Áꢅmax = 0.61 e A
3
Ê
0.31 e A
Áꢅmin
=
H atoms treated by a mixture of
independent and constrained
re®nement
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: TA1404). Services for accessing these data are
described at the back of the journal.
Table 2
Hydrogen-bonding geometry (A, ).
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ꢀ
Ê
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DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O1ÐH11Á Á ÁO11ii
O1ÐH12Á Á ÁO72i
C11ÐH111Á Á ÁO31iii
C11ÐH112Á Á ÁO52iv
C11ÐH113Á Á ÁO1ii
C12ÐH121Á Á ÁO52v
0.844 (10)
0.840 (10)
0.98
0.98
0.98
2.128 (11)
1.835 (11)
2.49
2.51
2.50
2.8851 (11)
2.6292 (11)
3.2968 (14)
3.2376 (14)
3.3214 (15)
3.2389 (14)
149.1 (13)
156.2 (14)
140
131
141
0.98
2.42
141
1
2
3
2
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;
y; 12 ‡ z; (iv)
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(I)
[Zn(C7H3N2O6)2(C2H6SO)2(H2O)2] 10.01
(Colorless) (9.61)
(II) [Cu(C7H3N2O6)2(C2H6SO)2(H2O)2] 8.48
32.48
(31.80) (3.26) (8.24)
32.25 3.43 9.17
(31.88) (3.27) (8.26)
32.78 3.19 8.88
(32.11) (3.29) (8.32)
32.75 3.05 8.43
(32.10) (3.29) (8.32)
3.00
8.75
(Light green)
(III) [Ni(C7H3N2O6)2(C2H6SO)2(H2O)2] 8.41
(Green)
(IV) [Co(C7H3N2O6)2(C2H6SO)2(H2O)2] 9.21
(9.37)
(8.72)
(Pale pink)
(8.75)
È
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Ê
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Ê
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È
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ꢁ
m120 Elguja B. Miminoshvili et al.
[Zn(C7H3N2O6)2(C2H6OS)2(H2O)2]
Acta Cryst. (2003). C59, m118±m120