Catena-Poly[[(di-2-pyridylamine)-silver(I)]-μ-nicotinato] and catenapoly[[(di-2-pyridylamine)silver(I)]-μ-2,6-dihydroxybenzoato]

Article abstract of DOI:10.1107/S0108270104026502

The structures of in catena-poly[[(di-2-pyridylamine-κ²N, N′)silver(I)]-μ-nicotinato-κ²N:O], [Ag(C ₆H₄NO₂)(C₁₀H₉N ₃)]_n was discussed. It was found that the Ag atom is tetracoordinated by two N atoms from the di-2-pyridylamine (BPA) ligand. A polymeric chain structure was generated, which extends along [100] by bridging nicotinate N and O atoms. The results show that the ribbons were linked between inversion-related pairs of 2,6-dihydroxybenzoate ligands to generate a three-dimensional network.

Full text of DOI:10.1107/S0108270104026502

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
compounds containing
a pyridine ring, nicotinic acid
(3-pyridinecarboxylic acid, niacin or vitamin B; henceforth
NA) plays important roles in metabolism. Dihydroxybenzoic
acids are known to be strong antioxidants (Maoka et al., 1997).
As one example, 2,6-dihydroxybenzoic acid (2,6-DHB) is
known to have a cytotoxic effect on tumor cells at low pH
values when mixed with acetylsalicylic acid (Kreutz, 1998).
Moreover 2,6-DHB always shows versatile coordination
modes in its complexes. We report here the structures of two
AgI complexes, viz. compound (I) with NA and the bidentate
pyridine-based ligand 2,20-bipyridylamine (BPA), viz. [Ag-
(NA)(BPA)]n, and compound (II) with 2,6-DHB and BPA,
viz. [Ag(2,6-DHB)(BPA)]n.
ISSN 0108-2701
catena-Poly[[(di-2-pyridylamine)-
silver(I)]-l-nicotinato] and catena-
poly[[(di-2-pyridylamine)silver(I)]-
l-2,6-dihydroxybenzoato]
Yue Wanga and Nobuo Okabeb*
aLaboratory of Inorganic Chemistry, China Pharmaceutical University, Nanjing
210009, People's Republic of China, and bFaculty of Pharmaceutical Sciences,
Kinki University, Kowakae 3-4-1, Higashiosaka, Osaka 577-8502, Japan
Correspondence e-mail: okabe@phar.kindai.ac.jp
Received 12 October 2004
Accepted 19 October 2004
Online 11 November 2004
In catena-poly[[(di-2-pyridylamine-ꢀ2N,N0)silver(I)]-ꢁ-nico-
tinato-ꢀ2N:O], [Ag(C6H4NO2)(C10H9N3)]n, the AgI atom is
tetracoordinated by two N atoms from the di-2-pyridylamine
Ê
(BPA) ligand [AgÐN = 2.3785 (18) and 2.3298 (18) A] and by
one N atom and one carboxylate O atom from nicotinate
Compound (I) comprises a one-dimensional polymer chain
(Fig. 1), with each AgI atom coordinated to two N atoms from
a BPA ligand, one N atom from a nicotinate ligand and one
carboxylate O atom from another nicotinate ligand [at (1 + x,
y, z)], as shown in Fig. 1; geometric details are given in Table 1.
The coordination geometry of the AgI ion is best described as
distorted tetrahedral. The carboxyl atom that is not bonded to
the Ag atom (O1) takes part in an intrachain CÐHÁ Á ÁO
hydrogen bond, further stabilizing the chain (Table 2).
Ê
Ê
ligands [AgÐN = 2.2827 (15) A and AgÐO = 2.3636 (14) A].
Bridging by nicotinate N and O atoms generates a polymeric
chain structure, which extends along [100]. The carboxyl O
atom not bonded to the Ag atom takes part in an intrachain
CÐHÁ Á ÁO hydrogen bond, further stabilizing the chain. Pairs
of chains are linked by NÐHÁ Á ÁO hydrogen bonds to generate
ribbons. There are no ꢂ±ꢂ interactions in this complex.
In catena-poly[[(di-2-pyridylamine-ꢀ2N,N0)silver(I)]-ꢁ-2,6-di-
hydroxybenzoato-ꢀ2O1:O2], [Ag(C7H5O4)(C10H9N3)]n, the
AgI atom has a distorted tetrahedral coordination, with three
strong bonds to two pyridine N atoms from the BPA ligand
Ê
[AgÐN = 2.286 (5) and 2.320 (5) A] and to one carboxylate O
atom from the 2,6-dihydroxybenzoate ligand [AgÐO =
Ê
2.222 (4) A]; the fourth, weaker, Ag-atom coordination is to
Ê
one of the phenol O atoms [AgÁ Á ÁO = 2.703 (4) A] of an
adjacent moiety, and this interaction generates a polymeric
chain along [100]. Pairs of chains are linked about inversion
centers by NÐHÁ Á ÁO hydrogen bonds to form ribbons, within
which there are ꢂ±ꢂ interactions. The ribbons are linked about
inversion centers by pairs of CÐHÁ Á ÁO hydrogen bonds and
additional ꢂ±ꢂ interactions between inversion-related pairs of
2,6-dihydroxybenzoate ligands to generate a three-dimen-
sional network.
Comment
Silver(I) complexes with AgÐN bonds have been found to
show effective antimicrobial activity (Spadaro et al., 1974;
Nomiya et al., 1997), and silver compounds with pyridine or
its derivatives have attracted attention recently (Zhu et al.,
2001, 2003; Bi et al., 2002; Kristiansson, 2000). Among the
Figure 1
An ORTEP-3 (Farrugia, 1997) drawing of part of the polymeric chain in
(I), with the atomic numbering scheme. Displacement ellipsoids for non-
H atoms are drawn at the 30% probability level. [Symmetry codes: (A)
x
1, y, z; (B) 1 + x, y, z.]
Acta Cryst. (2004). C60, m605±m608
DOI: 10.1107/S0108270104026502
# 2004 International Union of Crystallography m605

metal-organic compounds
The coordination mode of (I) can be compared with
some previous ®ndings for silver(I)±nicotinic acid systems.
In catena-(pyridine-3-carboxylato-O,O0)silver(I) (Smith &
Reddy, 1994), the AgI ion has a trigonal coordination
geometry, being connected to three nicotinate residues, two
via carboxylate O atoms and the third through the pyridine N
six-membered Ag1/N11/C12/N3/C22/N21 ring has a slightly
deformed envelope conformation, with atom Ag1 as the ¯ap.
In the crystal structure (Fig. 2), pairs of inversion-related
chains are linked by NÐHÁ Á ÁO hydrogen bonds (Table 2) to
generate ribbons extending along [100]. Calculations with
PLATON (Spek, 2003) show that there are only van der Waals
interactions between the ribbons.
Ê
atom [AgÐO = 2.258 (8) and 2.280 (8) A, and AgÐN =
Ê
2.362 (10) A]; in ammonium bis(pyridine-3-carboxylato-
O,N,N0)silver(I) monohydrate (Smith & Reddy, 1994), the AgI
ion again has three-coordinate distorted trigonal±planar
geometry and is bonded to two pyridine N atoms and one
carboxylate O atom from three independent nicotinate ligands
Ê
= 2.248 (3) and 2.269 (3) A, and AgÐO =
[AgÐN
I
Ê
2.342 (2) A]. The Ag coordination mode in (I) is also
different from that reported in catena-bis(pyridine-3-
carboxylato-N,N )silver(I) (Kall et al., 2001), where the Ag
I
0
È
ion has distorted octahedral coordination geometry, lies on an
inversion center with the N atoms in axial positions (AgÐN =
ꢀ
Ê
2.234 A and NÐAgÐN = 180 ) and is bonded weakly to four
carboxylate O atoms from four independent nicotinate mol-
Ê
ecules (AgÐO = 2.803 and 2.821 A). The AgÐN distances in
(I) are slightly longer than those in silver complexes of other
pyridine derivatives, such as bis(3-amino-2-chloropyridine-
Ê
ꢀN)silver(I) perchlorate [2.197 (4)±2.199 (4) A; Li et al., 2002],
bis(2-aminopyridine-ꢀN1)(benzoato-ꢀO)silver(I) [2.205 (4)±
0
Ê
2.230 (3) A; Zhu et al., 2003] and catena-poly[[silver(I)-ꢁ-4,4 -
Ê
bipyridine] nitrate] [2.211 (4) A; Bi et al., 2002].
Figure 3
In the nicotinate ligand, the plane of the carboxyl group
(C3/C7/O1/O2) is rotated 10.7 (1)ꢀ around the exocyclic C3Ð
C7 bond out of the N1/C2±C7 plane. The two pyridine rings in
the BPA ligand form an interplanar angle of 9.7 (1)ꢀ, and the
An ORTEP-3 (Farrugia, 1997) drawing of part of the polymeric chain in
(II), with the atomic numbering scheme. Displacement ellipsoids for non-
H atoms are drawn at the 30% probability level. [Symmetry codes: (A)
x
1, y, z; (B) 1 + x, y, z.]
Figure 2
Figure 4
A view of a pair of inversion-related chains linked by NÐHÁ Á ÁO
hydrogen bonds to generate a ribbon extending in the a direction.
Hydrogen bonds are indicated by broken lines. [Symmetry codes: (#) x,
y, 1 z; (*) 1 + x, y, z.]
A view of a pair of inversion-related chains linked by NÐHÁ Á ÁO
hydrogen bonds to generate a ribbon extending in the a direction. The
weak AgÁ Á ÁO contact and hydrogen bonds are indicated by broken lines.
[Symmetry codes: (#) 1 x, 1 y, 1 z; (*) 1 + x, y, z; ($) x 1, y, z.]
ꢁ
m606 Wang and Okabe [Ag(C6H4NO2)(C10H9N3)] and [Ag(C7H5O4)(C10H9N3)]
Acta Cryst. (2004). C60, m605±m608

metal-organic compounds
Ê
the C1±C6 aromatic ring at (x, y, z) is 3.763 A from the
centroid of the same ring at (2 x, 2 y, z); the distance
Ê
between these parallel rings is 3.425 A and the shortest CÁ Á ÁC
Ê
contact is 3.413 (3) A, between atoms C2 and C6(2 x, 2 y,
z). The overall effect of all these interactions is to generate a
three-dimensional network.
Experimental
Thin colorless needle-shaped crystals of (I) were obtained by slow
evaporation of an aqueous solution (containing a small amount of
methanol) of a mixture of nicotinic acid, 2,20-bipyridineamine and
AgNO3 (molar ratio 1:1:1) at room temperature. Colorless prismatic
crystals of (II) were obtained by slow evaporation of a mixture of
2,6-dihydroxybenzoic acid, 2,20-bipyridineamine and AgNO3 (molar
ratio 4:4:1) in methanol/water (80%) at room temperature.
Figure 5
A stereoview along the a direction of part of the structure of (II), showing
ꢂ±ꢂ interactions between inversion-related pairs of BPA ligands and
between inversion-related pairs of 2,6-DHB ligands.
Compound (I)
In complex (II) (Fig. 3), the AgI atom has a distorted
tetrahedral coordination, with three strong bonds to two
pyridine N atoms from the BPA ligand and one carboxylate O
atom from the 2,6-DHB ligand; the fourth, weaker, Ag-atom
coordination is to one of the phenol O atoms (O61) of an
adjacent moiety (Table 3), thus generating a polymeric chain
along [100]. BPA atoms N11 and N12 together with carboxyl
atom O2 are the atoms that are strongly bonded to atom Ag1;
these atoms de®ne a trigonal plane, with atom Ag1 lying
Crystal data
3
[Ag(C6H4NO2)(C10H9N3)]
Mr = 401.17
Monoclinic, P21=n
a = 7.9623 (1) A
b = 8.9487 (1) A
Ê
c = 21.887 (1) A
ꢃ = 96.000 (1)ꢀ
V = 1550.95 (8) A
Z = 4
Dx = 1.718 Mg m
Mo Kꢄ radiation
Cell parameters from 12 577
re¯ections
Ê
Ê
ꢅ = 3.0±27.5ꢀ
ꢁ = 1.31 mm
T = 296 K
1
3
Ê
Needle, colorless
0.30 Â 0.10 Â 0.10 mm
Data collection
Ê
0.319 (2) A from the plane.
Rigaku R-AXIS RAPID
diffractometer
! scans
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
Tmin = 0.649, Tmax = 0.877
15 058 measured re¯ections
3530 independent re¯ections
2779 re¯ections with I > 2ꢆ(I)
Rint = 0.017
In the 2,6-DHB ligand, the plane of the carboxyl group (C3/
C7/O1/O2) is rotated 2.4 (3)ꢀ around the exocyclic C1ÐC7
bond out of the C1±C7 plane. Both phenol OH groups form
intramolecular OÐHÁ Á ÁO hydrogen bonds (Table 4) with
adjacent carboxyl O atoms. The two pyridine rings in the BPA
ligand form an interplanar angle of 5.2 (2)ꢀ, and as in (I), the
six-membered Ag1/N11/C12/N3/C22/N21 ring has a slightly
deformed envelope conformation, with atom Ag1 as the ¯ap.
The participation of the BPA ligand means that the Ag
coordination environment in (II) is (as expected) completely
different from the dimer-bridged coordination mode reported
for the 2,6-DHB ligand in bis(ꢁ2-2,6-dihydroxybenzoato-
O,O0)disilver(I) (Smith et al., 1988).
In the crystal structure of (II), inversion-related chains are
linked [as in (I)] by NÐHÁ Á ÁO hydrogen bonds involving the
BPA N3ÐH3 group and carboxyl atom O1 of an adjacent
moiety (Table 1), thus generating ribbons extending along
[100], as shown in Fig. 4. Also present in these ribbons are ꢂ±ꢂ
interactions between inversion-related BPA ligands. The
distance between the ring centroids of the N11/C12±C16 and
N21/C22±C26 [at (1 x, 1 y, 1 z)] BPA pyridine rings is
ꢅmax = 27.6ꢀ
h = 10 ! 10
k = 11 ! 11
l = 28 ! 28
Re®nement
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.024
wR(F2) = 0.055
S = 0.90
3530 re¯ections
208 parameters
H-atom parameters constrained
w = 1/[ꢆ2(F2o) + (0.0291P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢆ)max = 0.001
3
Ê
Áꢇmax = 0.47 e A
3
Ê
0.27 e A
Áꢇmin
=
Table 1
Selected geometric parameters (A, ) for (I).
ꢀ
Ê
Ag1ÐN1
Ag1ÐN11
2.2827 (15)
2.3785 (18)
Ag1ÐN21
Ag1ÐO2i
2.3298 (18)
2.3636 (14)
N1ÐAg1ÐN21
N1ÐAg1ÐO2i
N21ÐAg1ÐO2i
125.12 (6)
128.08 (5)
99.28 (6)
N1ÐAg1ÐN11
N21ÐAg1ÐN11
O2iÐAg1ÐN11
105.36 (6)
77.97 (6)
109.43 (6)
Symmetry code: (i) 1 ‡ x; y; z.
Ê
Ê
3.616 A and the shortest atom±atom separation is 3.466 (9) A,
between atoms C12 and C22(1 x, 1 y, 1 z). This ring
overlap can be seen clearly in Fig. 5, which also shows that the
ribbons are linked by an inter-ribbon CÐHÁ Á ÁO hydrogen
bond involving the C25ÐH25 group and phenol atom O21(x,
Table 2
Hydrogen-bonding geometry (A, ) for (I).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N3ÐH3Á Á ÁO2ii
0.86
0.93
2.03
2.29
2.894 (2)
3.096 (2)
177
144
y
1, z), which is not involved in any Ag contact (see Table 4).
C6ÐH6Á Á ÁO1i
There are, in addition, a second set of ꢂ±ꢂ interactions
between inversion-related 2,6-DHB ligands. The centroid of
Symmetry codes: (i) 1 ‡ x; y; z; (ii) x; y; 1 z.
ꢁ
Acta Cryst. (2004). C60, m605±m608
Wang and Okabe
[Ag(C6H4NO2)(C10H9N3)] and [Ag(C7H5O4)(C10H9N3)] m607

metal-organic compounds
Ê
and OÐH distances of 0.82 A, and with Uiso(H) values of
1.2Ueq(C,N) and 1.5Ueq(O).
Compound (II)
Crystal data
For compound (I), data collection: RAPID-AUTO (Rigaku, 2003);
cell re®nement: RAPID-AUTO. For compound (II), data collection:
CrystalStructure (Rigaku/MSC, 2004) and CRYSTALS (Watkin et al.,
1996); cell re®nement: CrystalStructure and CRYSTALS. For both
compounds, data reduction: CrystalStructure and CRYSTALS;
program(s) used to solve structure: SIR97 (Altomare et al., 1999) and
DIRDIF99 (Beurskens et al., 1999); program(s) used to re®ne struc-
ture: SHELXL97 (Sheldrick, 1997) and WinGX (Farrugia, 1999);
molecular graphics: PLATON (Spek, 2003); software used to prepare
material for publication: WordPerfect.
[Ag(C7H5O4)(C10H9N3)]
Mr = 432.18
Triclinic, P1
Z = 2
Dx = 1.822 Mg m
Mo Kꢄ radiation
3
Ê
a = 7.56 (1) A
Cell parameters from 6495
re¯ections
Ê
b = 9.23 (1) A
c = 12.01 (2) A
ꢅ = 3.1±27.6ꢀ
ꢁ = 1.31 mm
T = 296 K
Ê
1
ꢄ = 71.29 (5)ꢀ
ꢃ = 82.87 (5)ꢀ
ꢈ = 87.44 (5)ꢀ
Prism, colorless
0.30 Â 0.15 Â 0.10 mm
3
Ê
V = 787.6 (19) A
Data collection
Rigaku R-AXIS RAPID
diffractometer
! scans
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
Tmin = 0.672, Tmax = 0.878
7753 measured re¯ections
3567 independent re¯ections
2402 re¯ections with I > 2ꢆ(I)
Rint = 0.033
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FG1780). Services for accessing these data are
described at the back of the journal.
ꢅmax = 27.5ꢀ
h = 9 ! 9
k = 11 ! 11
References
l = 15 ! 15
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Re®nement
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.050
wR(F2) = 0.153
S = 1.02
3567 re¯ections
228 parameters
H-atom parameters constrained
w = 1/[ꢆ2(F2o) + (0.0754P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢆ)max = 0.002
3
Ê
Áꢇmax = 0.61 e A
3
Ê
1.28 e A
Áꢇmin
=
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Table 3
Selected geometric parameters (A, ) for (II).
ꢀ
Ê
È
Kall, P. O., Grins, J., Fahlman, M. & Soderlind, F. (2001). Polyhedron, 20, 2747±
2753.
Ag1ÐN11
Ag1ÐN21
2.320 (5)
2.286 (5)
Ag1ÐO2
Ag1ÐO61iii
2.222 (4)
2.703 (4)
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1998±EP2939.)
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E58, m203±m205.
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Nihon Yukagakkaishi, 46, 1399±1402.
O2ÐAg1ÐN21
O2ÐAg1ÐN11
N11ÐAg1ÐN21
133.99 (15)
138.13 (16)
80.97 (15)
O2ÐAg1ÐO61iii
N21ÐAg1ÐO61iii
N11ÐAg1ÐO61iii
95.21 (16)
120.49 (15)
78.52 (14)
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Hydrogen-bonding geometry (A, ) for (II).
ꢀ
Ê
È
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280.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
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CRYSTALS. Issue 10. Chemical Crystallography Laboratory, Oxford,
England.
O21ÐH21Á Á ÁO2
O61ÐH61Á Á ÁO1
N3ÐH3Á Á ÁO1iv
C25ÐH25Á Á ÁO21v
0.82
0.82
0.86
0.93
1.81
1.80
2.08
2.60
2.538 (6)
2.525 (6)
2.927 (6)
3.519 (8)
146
147
170
171
Symmetry codes: (iv) 1 x; 1 y; 1 z; (v) x; y 1; z.
Zhu, H. L., Chen, Q., Peng, W. L., Qi, S. J., Xu, A. J. & Chen, X. M. (2001).
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m218±m220.
For both (I) and (II), all H atoms were clearly visible in difference
Fourier maps. H atoms were then allowed for as riding atoms in the
Ê
re®nements, with CÐH distances of 0.93 A, NÐH distances of 0.86 A
Ê
ꢁ
m608 Wang and Okabe [Ag(C6H4NO2)(C10H9N3)] and [Ag(C7H5O4)(C10H9N3)]
Acta Cryst. (2004). C60, m605±m608