Diallylaminoarenes: A new class of versatile ligands for silver(i) that consistently lead to one-dimensional polymeric metallosupramolecular assemblies

Article abstract of DOI:10.1039/c3ce41707g

Ligands comprised of a diallylamino group attached to a phenyl, 2-pyridyl, 2-pyrimidyl, 2-thiazolyl and 2-quinolyl ring react with silver(i) salts (perchlorate and/or triflate) to faithfully assemble into 1-D coordination polymers, regardless of variation

Full text of DOI:10.1039/c3ce41707g

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Diallylaminoarenes: a new class of versatile ligands for
silver(I) that consistently lead to one-dimensional
polymeric metallosupramolecular assemblies†
Cite this: CrystEngComm, 2013, 15,
9064
*
Solomon W. Kelemu and Peter J. Steel
Received 27th August 2013,
Accepted 5th September 2013
Ligands comprised of a diallylamino group attached to a phenyl, 2-pyridyl, 2-pyrimidyl, 2-thiazolyl and 2-quinolyl
ring react with silver(I) salts (perchlorate and/or triflate) to faithfully assemble into 1-D coordination polymers,
regardless of variation in the number of additional nitrogen donors, the counterion and the coordination number
(three to five) of the silver atoms.
DOI: 10.1039/c3ce41707g
www.rsc.org/crystengcomm
Introduction
THF in the presence of sodium hydride. The ligands were iso-
lated as yellow oily liquids in 46–97% yield after column chro-
Metallosupramolecular chemistry1 involves the use of bridg-
ing organic ligands and metal atoms to assemble discrete or
1-, 2- or 3-D polymeric species.2–8 We have long been engaged
in the synthesis and study of bridging heterocyclic ligands as
matography on silica gel and were characterised by 1H and 13
C
NMR, infrared spectroscopy and mass spectrometry. A number
of other diallylaminoarenes, which failed to furnish crystalline
silver complexes, were also prepared and their preparations
and spectral properties are also included in the experimental
section.
The ligands were each reacted with two equivalents of a
silver salt in acetone or toluene, in the dark. Subsequent
diffusion of diethyl ether into the reaction vial provided crys-
talline products in 36–83% yield. Single crystal X-ray struc-
ture determinations showed the consistent formation of 1-D
coordination polymers with 1 : 1 metal : ligand stoichiometry.
Attempts to further characterise these complexes using NMR
and mass spectrometry, led only to signals for the starting
ligands, indicating that the 1-D polymers lost their integrity
upon redisolution in solvent such as acetonitrile. This is con-
sistent with our previous studies showing that the silver–
alkene interaction is relatively weak.14,15,25
The product (6) from the reaction of N,N-diallylaniline (1)
with silver(I) perchlorate crystallises in the orthorhombic
space group P212121, with one molecule of (1), a coordinated
silver atom and a non-coordinated perchlorate anion in the
asymmetric unit. The structure grows into a 1-D zigzag poly-
meric assembly through the coordination of the two allyl
arms in a chelating mode and bridging through the para car-
bon atom of the benzene ring coordinated in a η1-mode, as
shown in Fig. 2. Such η1-coordination of silver with polycyclic
aromatic hydrocarbons has been well studied by Munakata
and co-workers.26 In the present case we believe that the
amine group donates electron density into the phenyl ring
resulting in a higher electron density at the para position,
thereby promoting coordination with silver. Such electron
delocalisation also explains why the amino nitrogen does not
synthons for the preparation of
a diverse range of
metallosupramolecular assemblies, including discrete cages
and helicates, as well as coordination polymers of varying
dimensionality.6,9–12 Although alkenes have long been known
to bind to silver(I),13 this interaction has, until recently, been
curiously ignored as a synthon for metallosupramolecular
chemistry. Following our initial explorations in this area,14,15
we, and others,16–24 have shown that the use of bridging
ligands containing multiple alkene subunits are indeed use-
ful synthons for the assembly of both discrete and polymeric
species.25 To date, ligands containing vinyl, allyl and allyloxy
groups as donors for coordination to silver(I) have been
used.25 We now extend this design concept to the first study
of diallylaminoarenes as ligands for silver(I). Four of these
contain heterocyclic nitrogen atoms that offer the possibility
of additional σ-donation to silver, in concert with the
π-donation from the alkene groups.
Results and discussion
The structures of the ligands employed in this study are
shown in Fig. 1. They were prepared by reaction of the corre-
sponding aminoarene with two equivalents of allyl bromide in
Department of Chemistry, University of Canterbury, Christchurch 8140, New
Zealand. E-mail: peter.steel@canterbury.ac.nz; Fax: +64 3 3642110; Tel: +64 3
3642432
† CCDC 940152 (6), 940153 (7), 940154 (8), 940155 (9), 940156 (10) and 940157
(11). For crystallographic data in CIF or other electronic format see DOI:
10.1039/c3ce41707g
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in a bridging mode (Fig. 3). In this case the two allyl arms
coordinate from opposite faces of the pyridine ring, leading
to an increased separation distance between adjacent silver
atoms of 8.219(1) Å.
The silver is four coordinate, being bound to two allyl arms
of different ligands, the pyridyl nitrogen and an oxygen atom
of the perchlorate anion. The calculated τ4 value29 for silver
is 0.76, indicating a seesaw geometry. All the silver–carbon
bond distances are within the expected range for silver–olefin
η2-type interactions.25
The complex (8) of 2-(diallylamino)-pyrimidine (3) with
silver(I) perchlorate crystallises in the orthorhombic space
group P21212. The asymmetric unit (Fig. 4a) contains two full
molecules of (3), two silver atoms, one non-coordinated per-
chlorate anion and two half perchlorate anions that lie on a
two-fold rotation axis. The diallylamine group of one of the
ligand molecules in the asymmetric unit has disorder over
two sites with 55% dominant position occupancy.
Fig. 1 Ligands employed in this study.
Once again the complex has 1 : 1 metal : ligand stoichiome-
try and extends into a 1-D zigzag polymeric chain, involving
the coordination of both nitrogen atoms of the pyrimidine
ring and the allyl arms of the ligand with two crystallographi-
cally independent silver atoms (Fig. 4b). The two silver atoms
are four coordinate, being bound to two allyl groups and two
nitrogen atoms from different ligands and have τ4 values of
0.74 and 0.68 for Ag1 and Ag2, respectively, indicating seesaw
geometries. In this case adjacent silver atoms in the chain
are separated by the two independent ligands at distances of
6.662(1) and 6.678(1) Å.
Ligand (3) was also reacted with silver(I) triflate to produce
a complex (9) that crystallises in the orthorhombic space
group P212121. The asymmetric unit contains two molecules
of (3), two silver atoms, a coordinated water molecule and
two non-coordinated triflate anions. The structure (Fig. 5)
extends into a 1-D polymer with (3) acting as a doubly chelat-
ing bridging ligand, as was its role in complex (8). However,
due to the coordinated water molecule the two silvers have
different coordination numbers; Ag1 is four coordinate, with
a seesaw geometry (τ4 = 0.74), while Ag2 is five coordinate
with a τ5 value30 of 0.14, indicating a slightly distorted square
pyramidal geometry, with an allyl group occupying the apical
position. Because of the higher coordination number of Ag2,
the Ag–C bond distances are slightly greater than those seen
in the previous structures.
Fig. 2 A section of the 1-D zigzag polymer of (6). Hydrogen atoms omitted
for clarity.
coordinate to silver in most of the structures described below.
A mixed η1-phenyl/η2-alkenyl coordination to silver has been
reported in the mononuclear complex of 4-phenylbut-1-ene.27
However, in that case the η1-coordination was supported by
chelation and the η1-interaction was somewhat weaker than
in the present case, with Ag–C bond lengths of 2.547(6) and
2.692(5) Å, compared to 2.454(2) Å in complex (6) (Table 1).
An interesting feature of the structure is that the phenyl
ring and both the allyl arms are coordinated from the same
face of the ligand, which leads to the zigzag shape of the
polymer, with the perchlorate counterions lying in the spaces
between the silvers. The silver atom has a slightly distorted
trigonal planar geometry with bond angles ranging between
115.1(2) and 125.7(2)°. The bond distances to the alkene
groups lie within the normal range for such interactions.25
Thus, the ligand (1) acts as an ambivergent28 ligand in both
chelating and bridging modes, with adjacent silver atoms sep-
arated by 6.304(1) Å.
The packing of the 1-D chains shows various intermolecular
interactions involving the anions, the phenyl π-systems and CH
groups. All of these are relatively weak and play no obvious role
in the self-assembly of the structure. The same applies to the
other 1-D polymers described below.
A similar reaction of 2-(diallylamino)-pyridine (2) with
silver(I) perchlorate gave a complex (7) that crystallises in the
monoclinic space group P21/n. The asymmetric unit contains
one molecule of (2), one silver atom and a coordinated per-
chlorate anion. Once again the structure grows into a 1-D
polymeric assembly, involving the coordination of one of the
allyl arms and the pyridyl nitrogen in a chelating mode, while
the other allyl arm coordinates to a neighbouring silver atom
Within this metallopolymer ligand (3) acts in the same
ambivergent mode as in the silver perchlorate complex (8).
Due to the presence of two independent bridging ligands,
there are two different Ag1⋯Ag2 separation distances,
6.697(1) and 6.865(1) Å. The coordinated water molecule acts
as a hydrogen bond donor to two oxygens of the non-
coordinated triflate anions, with O⋯O separations of 2.727(4)
and 2.810(4) Å.
2-(Diallylamino)-thiazole (4) failed to furnish a crystalline
product from reaction with silver(I) perchlorate, but did do
so with silver(I) triflate. This compound (10) crystallised in
¯
the triclinic space group P1, the asymmetric unit of which
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site occupancy of the diallyl arm, the thiazole sulfur and the
allyl arm of the other ligand is 63%, while for the triflate
counter anion it is 80%.
The complex (10) again extends into a 1-D coordination
polymer (Fig. 6) with, for each ligand, the thiazole nitrogen
and one allyl arm chelating to silver, while the other allyl
arm acts as a bridge to the next silver. This mode of ligand
coordination is similar to that observed for the 2-pyridyl ana-
logue (7). The sulphur atom is not coordinated. The two crys-
tallographically independent ligands bridge silver atoms
separated by 8.042(1) and 7.952(1) Å. Both three coordinate
silver atoms have distorted trigonal planar geometries, with
angles ranging between 98.1(3) and 135.7(2)°.
Fig. 3 A section of the 1-D polymer of (7). Hydrogen atoms omitted for clarity.
Finally, 8-(diallylamino)-quinoline (5) was reacted with
silver(I) perchlorate to produce a complex (11) in the mono-
clinic space group P21/n. The asymmetric unit contains one
full molecule of (5), one silver atom and a non-coordinated
perchlorate anion and again extends into a 1-D coordination
polymer. However, in this case the mode of coordination by
the ligand is somewhat different. For the first time the
diallylamino nitrogen atom is found to coordinate to the
metal. We believe that this is for two reasons: coordination
of silver to the quinoline nitrogen atom would prevent the
diallylamino group lying coplanar with the quinoline ring
(and hence prevent donation of the lone pair of the amino
group into the quinoline ring system), whilst at the same
time offering the possibility of the formation of a stable five-
membered chelate ring involving both nitrogens of the
ligand. As a consequence the ligand sacrifices one of its allyl
arms, which remains non-coordinated, whilst the other arm
bridges to an adjacent silver (Fig. 7). The silver atom is again
three coordinate but with a highly distorted trigonal geome-
try, due to the five-membered chelate ring which has a bite
angle of 76.8(1)°.
Fig. 4 (a) The asymmetric unit of complex (8). (b) A section of the 1-D polymer of (8).
Hydrogen atoms, counterions and the minor disorder components omitted for clarity.
Fig. 6 A section of the 1-D polymer of (10). Hydrogen atoms, the minor disorder
component and anions for clarity.
Fig. 5 A section of the 1-D polymer of (9). Hydrogen atoms (except for the water
molecule) and counterions omitted for clarity.
contains two full molecules of (4), two silver atoms and two
non-coordinated triflate counterions. One of the triflate
anions, the diallylamine of one of the ligand molecules, the
thiazole sulfur atom and one of the allyl arms of the second
ligand molecule are disordered over two sites. The dominant
Fig. 7 A section of the 1-D polymer of (11). Hydrogen atoms and counterions
omitted for clarity.
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Experimental section
General
2-(Diallylamino)-pyridine (2). Yield: 92%. 1H NMR
(300 MHZ, CDCl3): δ 4.11 (4H, d, J = 5.0 Hz, H6), 5.12–5.17
(4H, m, H8), 5.82–5.90 (2H, m, H7), 6.46 (1H, d, J = 8.5 Hz,
H4), 6.52 (1H, dd, J = 6.5, 5.5 Hz, H2), 7.39 (1H, dd, J = 8.5,
7.5 Hz, H3), 8.15 (1H, d, J = 6.0 Hz, H1). 13C NMR (126 MHz):
δ 50.04 C6, 106.04 C4, 111.78 C2, 115.99 C8, 133.96 C7,
137.11 C3, 147.88 C1, 157.97 C5. IR (cm−1) 3076, 3008, 2918,
2980, 2524, 2376, 2266, 1931, 1846, 1722, 1641, 1595, 1560,
1491, 1436, 1416, 1391, 1359, 1317, 1279, 1244, 1186, 1160,
1130, 1094, 1070, 1055, 1023, 993, 978, 919, 768, 732. ESI-MS:
found MH+ = 175.1229; C11H15N2 requires MH+ = 175.1230.
Unless otherwise specified, all reagents and starting mate-
rials were reagent grade, purchased from standard suppliers
and used as received. Where anhydrous solvents were
required, the HPLC-grade solvent was either distilled from
standard drying agents or dried by passing over a sealed col-
umn of activated alumina. Melting points were recorded on an
Electrothermal melting point apparatus and are uncorrected.
Elemental analysis was carried out by the Campbell Microana-
lytical Laboratory, University of Otago.
Infrared spectra were recorded on a PerkinElmer Spec-
trum One FTIR instrument operating in diffuse reflectance
mode with samples prepared as KBr mulls (KBr), or in
transmittance mode with liquid samples pressed between
KBr discs (neat). NMR spectra were recorded on a Varian
INOVA 500 or Varian Unity 300 instrument, operating
at 500 and 300 MHz, respectively, for 1H, and 125 and
75 MHz, respectively, for 13C. Mass spectra were recorded
on either a DIONEX Ultimate 3000 or Bruker MaXis 4G
spectrometer, both of which were operated in high resolu-
tion positive ion electrospray mode. Samples were dissolved
and diluted to the required concentration in HPLC grade
acetonitrile or methanol.
2-(Diallylamino)-pyrimidine (3). Yield: 46%. 1H NMR
(300 MHZ, CDCl3): δ 4.21 (4H, d, J = 5.4 Hz, H4), 5.09–5.15
(4H, m, H6), 5.78–5.91 (2H, m, H5), 6.44 (1H, t, J = 4.8 Hz, H1),
8.29 (2H, d, J = 4.8 Hz, H2). 13C NMR (75 MHz): δ 49.00 C4,
109.81 C1, 116.32 C6, 134.06 C5, 158.05 C2, 161.72 C3. IR (cm−1)
3078, 3027, 2982, 2924, 2854, 1848, 1766, 1641, 1585, 1547,
1505, 1414, 1387, 1361, 1346, 1315, 1268, 1221, 1180, 1084,
1031, 994, 980, 920, 798, 780, 688. ESI-MS: found MH+
176.1179; C10H14N3 requires MH+ = 176.1182.
=
Preparation of ligands
General procedure (based on Huang's reported31
preparation of ligand 1). Two equivalents of allylbromide
were added to
a mixture of one equivalent of the
corresponding amine and NaH in 60 ml of dry THF. The
resulting solution was refluxed for three days and
quenched with 10% ammonium chloride solution. The
organic layer was extracted with 3 × 50 ml of diethyl ether
and the extracts were washed with water and brine
solutions, respectively. The resulting solution was dried
over MgSO4, filtered and the solvent removed under
vacuum. The product was then purified by column
chromatography using silica gel (60 mesh, 200–300) and
5 : 95 ethyl acetate : petroleum ether to give the products as
yellow or red oils.
2-(Diallylamino)-thiazole (4). Yield 82%. 1H NMR
(300 MHZ, CDCl3): δ 4.06 (4H, d, J = 5.7 Hz, H4), 5.18–5.24
(4H, m, H6), 5.79–5.89 (2H, m, H5), 6.46 (1H, d, J = 3.6 Hz, H2),
7.15 (1H, d, J = 3.6 Hz, H1). 13C NMR (126 MHz): δ 53.26 C4,
106.55 C2, 117.96 C6, 132.60 C5, 139.60 C1, C3 not
observed. IR (cm−1) 3475, 3079, 2923, 1717, 1641, 1531,
1417, 1364, 1310, 1225, 1198, 1126, 1055, 992, 925, 749.
ESI-MS: found MNa+ = 203.0622; C9H12N2SNa requires MNa+ =
203.0613.
N,N-Diallylaniline (1). Yield: 97%. 1H NMR (300 MHZ,
CDCl3): δ 3.95 (4H, d, J = 4.8 Hz, H5), 5.14–5.21 (4H, m, H7),
5.82–5.94 (2H, m, H6), 6.62 (1H, t, J = 7.2 Hz, H1), 6.69 (2H,
d, J = 9.0 Hz, H3), 7.16 (2H, dd, J = 9.0, 7.2 Hz, H2). 13C NMR
(75 MHz): δ 52.85 C5, 112.45 C3, 116.04 C7, 116.38 C1,
129.17 C2, 134.17 C6, 148.83 C4. IR (cm−1) 3090, 3056, 2956,
1690, 1643, 1599, 1505, 1232, 1181, 989, 919, 745. ESI-MS:
found MH+ = 174.1277; C12H16N requires MH+ = 174.1277.
8-(Diallylamino)-quinoline (5). Yield: 88%. 1H NMR
(300 MHz, CDCl3): δ 4.16 (4H, d, J = 6.3 Hz, H7), 5.13 (2H, dd,
J = 10.3, 1.4 Hz, H9), 5.18 (2H, dd, J = 17.5, 1.4 Hz, H9′),
5.86–6.00 (2H, m, H8), 7.10 (1H, dd, J = 6.5, 2.5 Hz, H6),
7.32–7.40 (3H, m, H2, H4, H5), 8.08 (1H, dd, J = 8.4, 1.8 Hz, H3),
8.89 (1H, dd, J = 4.2, 1.8 Hz, H1). 13C NMR (126 MHz):
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δ 55.80 C7, 117.67 C9, 118.78 C4, 121.04 C6, 121.12 C5,
126.53 C2, 129.99 C12, 135.43 C8, 136.70 C3, 143.29 C11,
147.59 C10, 148.11 C1. IR (cm−1) 3073, 2977, 1841, 1662,
1640, 1607, 1595, 1566, 1499, 1470, 1390, 1242, 1100, 918,
791. ESI-MS: found MNa+ = 247.1218; C15H16N2Na requires
MNa+ = 247.1206.
917, 805, 725. ESI-MS: found MNa+ = 291.1838; C18H24N2Na
requires MNa+ = 291.1832.
1
4-(N,N-Diallylamino)azobenzene. Yield: 65%. 1H NMR
(500 MHz, CDCl3): δ 4.02 (4H, d, J = 4.5 Hz, H9), 5.17–5.22
(4H, m, H11), 5.84–5.92 (2H, m, H10), 6.76 (2H, d, J = 9.0 Hz, H7),
7.38 (2H, dd, J = 7.0, 7.5 Hz, H2), 7.47 (1H, t, J = 8.0 Hz, H1),
7.83–7.86 (4H, m, H3, H6). 13C NMR (126 MHz): δ 53.05 C9,
112.00 C7, 116.70 C11, 122.44 C3, 125.21 C6, 129.17 C2,
129.63 C1, 133.13 C10, 144.11 C5, 151.32 C8, 153.47 C4.
IR (cm−1) 3081, 3008, 2980, 2909, 2642, 1700, 1642, 1600,
1566, 1513, 1461, 1448, 1435, 1414, 1392, 1356, 1334, 1313,
1236, 1177, 1155, 1140, 1069, 1019, 990, 921, 821, 767, 723,
689. ESI-MS: found MNa+ = 300.1473; C18H19N3Na requires
MNa+ = 300.1471.
1,5-Bis(N,N-diallyamino)naphthalene. Yield: 70%. H NMR
(300 MHz, CDCl3): δ 3.79 (8H, d, J = 6.0 Hz, C6), 5.15 (4H, dd,
10.2, 1.5 Hz, H8), 5.25 (4H, dd, 17.1, 1.5 Hz, H8′), 5.82–5.95
(4H, m, H7), 7.08 (2H, d, J = 7.5 Hz, H2), 7.39 (2H, dd, J =
7.5, 8.1 Hz, H3), 8.04 (2H, d, J = 8.4 Hz, H4). 13C NMR (126
MHz, CDCl3): δ 56.28 C6, 117.10 C8, 117.60 C2, 119.27 C4,
124.70 C3, 131.58 C5, 135.22 C7, 148.06 C1. IR (cm−1) 3075,
3007, 2978, 2923, 2814, 1847, 1642, 1588, 1505, 1436, 1409,
1357, 1239, 1203, 1174, 1145, 1105, 1034, 992, 919, 785. ESI-
MS: found MH+ = 319.2168; C22H27N2 requires MH+
319.2169.
=
1,3-Bis(N,N-diallyamino)benzene. Yield: 53%. 1H NMR
(500 MHz, CDCl3): δ 3.91(8H, d, J = 5.0 Hz, H5), 5.16 (4H, dd,
J = 10.0, 1.5 Hz, H7), 5.21 (4H, dd, J = 17.0, 1.5 Hz, H7′),
5.84–5.91 (4H, m, H6), 6.10–6.14 (3H, m, H2, H4), 7.05 (1H, t,
J = 8.0 Hz, H1). 13C NMR (126 MHz): δ 53.25 C5, 97.44 C4,
101.95 C2, 116.12 C7, 129.75 C1, 134.87 C6, 150.14 C3.
IR (cm−1) 3077, 3005, 2924, 2853, 1838, 1641, 1603, 1571,
1505, 1459, 1416, 1357, 1335, 1288, 1248, 1205, 1179, 1128,
1
2,7-Bis(N,N-diallyamino)naphthalene. Yield: 45%. H NMR
(300 MHz, DMSO): δ 4.01 (8H, d, J = 4.8 Hz, H5), 5.16–5.24
(8H, m, H7), 5.86–5.98 (4H, m, H6), 6.68 (2H, s, H4), 6.81
(2H, d, J = 9.0 Hz, H2), 7.48 (2H, d, J = 9.0 Hz, H1). 13C NMR
(126 MHz, CDCl3): δ 52.79 C5, 104.69 C4, 112.40 C2, 116.06
C7, 128.35 C1, 134.26 C6, 147.14 C3, C7 and C8 not observed.
IR (cm−1) 3079, 3006, 2978, 2907, 1842, 1738, 1624, 1518,
1475, 1430, 1399, 1358, 1288, 1251, 1217, 1194, 1129, 1022,
991, 951, 917, 846, 813, 748. ESI-MS: found MH+ = 319.2180;
C22H27N2 requires MH+ = 319.2169.
1042, 991, 960, 916, 809, 744, 687. ESI-MS: found MH+
269.2018; C18H25N2 requires MH+ = 269.2012.
=
1,4-Bis(N,N-diallyamino)benzene. Yield: 78%. 1H NMR
(300 MHz, CDCl3): δ 3.83 (8H, d, J = 3.9 Hz, H3), 5.14
(4H, dd, J = 10.2, 1.5 Hz, H5), 5.20 (4H, dd, J = 17.4, 1.5 Hz, H5′),
5.80–5.91 (4H, m, H4), 6.70 (4H, s, H1). 13C NMR (75 MHz,
CDCl3): δ 54.06 C3, 115.42 C1, 116.43 C5, 135.19 C4,
142.00 C2. IR (cm−1) 3077, 3005, 2977, 2912, 1842, 1641,
1612, 1517, 1417, 1356, 1333, 1285, 1231, 1182, 1068, 992,
Preparation of complexes
General procedure. A solution of one equivalent of the
diallylaminoarene dissolved in acetone was added to an
acetone solution of the silver salt. Diffusion of diethyl ether
into the mixture at room temperature in the dark led to the
formation of colourless crystals of the complexes listed below.
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[Ag(1)ClO4]n (6): Yield: 54%. M.p. 123–125 °C. IR (cm−1
3056, 2978, 2918, 2868, 2610, 2016, 1642, 1598, 1546, 1505,
1458, 1421, 1340, 1234, 1096, 989, 952, 823, 749, 695, 626.
Elem. anal. found: C, 37.99; H, 4.03; N, 3.95. Calc. for
C12H15NAgClO4: C, 37.87; H, 3.97; N, 3.68.
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)
1490, 1434, 1418, 1248, 1174, 1049, 992, 927, 861, 767, 750,
656, 610, 579, 521. Elem. anal. found: C, 27.40; H, 2.68; N,
6.31. Calc. for C9H12N2SAgSO3CF3: C, 27.47; H, 2.77; N, 6.41.
[Ag(5)ClO4]n (11): Yield: 59%. M.p. 149–151 °C. IR (cm−1)
3547, 3474, 3413, 3047, 2854, 1716, 1637, 1536, 1485, 1428,
1351, 1265, 1235, 1147, 1110, 1089, 941, 828, 760, 660, 627.
Elem. anal. found: C, 41.45; H, 3.78; N, 6.21. Calc. for
C15H16N2AgClO4: C, 41.74; H, 3.74; N, 6.49.
[Ag(2)ClO4]n (7): Yield: 74%. M.p. 89–91 °C. IR (cm−1) 3060,
3008, 2918, 2862, 2021, 1648, 1599, 1547, 1490, 1438, 1245,
1094, 979, 941, 768, 734, 627. Elem. anal. found: C, 34.93;
H, 3.77; N, 6.78. Calc. for C11H14N2AgClO4: C, 34.63; H, 3.70;
N, 7.34.
[Ag(3)ClO4]n (8): Yield: 42%. M.p. 219–221 °C. IR (cm−1
)
Crystallography
3078, 2982, 2913, 2013, 1641, 1586, 1547, 1507, 1415, 1388,
1362, 1269, 1087, 981, 941, 816, 798, 781, 690, 626. Elem.
anal. found: C, 30.67; H, 3.24; N, 10.49. Calc. for
C10H13N3AgClO4.0.5H2O: C, 30.67; H, 3.60, N, 10.73.
X-Ray crystallographic data collection was carried out with a
Bruker APEXII instrument, using graphite-monochromated
Mo Kα (λ = 0.71073 Å) radiation All structures were solved
using direct methods with SHELXS and refined on F2 using
all data by full matrix least-squares procedures with
SHELXL.32 Unless otherwise stated all non-hydrogen atoms
were refined with anisotropic displacement parameters.
Hydrogen atoms were included in calculated positions with
isotropic displacement parameters 1.2 or 1.5 times the isotro-
pic equivalent of their carrier carbon atoms. Experimental
details are listed in Table 2.
[Ag(3)OTf]n (9): Yield: 83%. M.p. 151–153 °C. IR (cm−1
)
3507, 3083, 3009, 2907, 2288, 1643, 1586, 1548, 1508, 1429,
1387, 1364, 1254, 1180, 1113, 1084, 1033, 993, 966, 944, 798,
688, 639, 576, 519. Elem. anal. found: C, 30.60; H, 2.96; N,
9.51. Calc. for C10H13N3AgSO3CF3: C, 30.57; H, 3.03; N, 9.72.
[Ag(4)OTf]n (10): Yield: 36%. M.p. 109–111 °C. IR (cm−1
)
3716, 3637, 3079, 3011, 2982, 2905, 1722, 1641, 1623, 1531,
Table 2 X-Ray experimental details
Complex
(6)
(7)
(8)
(9)
(10)
(11)
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
Unit cell dimensions:
a/Å
b/Å
c/Å
α/°
β/°
C12H15NO4ClAg C11H14N2O4ClAg C20H26N6O8Cl2Ag2 C22H28N6O7F6S2Ag2 C20H24N4O6F6S4Ag2 C15H16N2O4ClAg
380.57
115
381.56
114
765.11
114
Orthorhombic
P21212
882.36
114
Orthorhombic
P212121
874.41
117
Triclinic
¯
P1
431.62
116
Monoclinic
P21/n
Orthorhombic Monoclinic
P212121
P21/n
8.8079(4)
12.2447(4)
12.5250(6)
90
90
90
12.6852(4)
8.1924(3)
12.8192(5)
90
99.738(2)
90
15.3229(9)
21.2905(11)
8.0381(4)
90
90
90
11.6969(3)
12.9740(3)
20.0150(5)
90
90
90
7.8652(3)
14.0587(5)
14.8864(6)
113.746(2)
92.329(2)
90.687(2)
1504.73(10)
2
12.1378(4)
10.7654(3)
13.2121(4)
90
111.584(2)
90
γ/°
Volume/Å3
Z
1350.82(10)
4
1313.00(8)
4
2622.3(2)
4
3037.39(13)
4
1605.35(8)
4
Density (calculated)
1.871
1.930
1.938
1.930
1.930
1.786
Mg m−3
Absorption
coefficient mm−1
F(000)
1.698
1.749
1.754
1.516
1.658
1.443
760
0.30 × 0.18 ×
0.13
760
0.70 × 0.68 ×
0.33
1520
0.29 × 0.09 ×
0.06
1752
0.36 × 0.09 ×
0.06
864
0.49 × 0.30 ×
0.10
864
0.50 × 0.32 ×
0.10
Crystal size/mm3
Theta range for data
collection (°)
Reflections collected
Independent
5.7 to 55.0°
5.92 to 52.9°
3.82 to 52.8°
4.04 to 50.1°
5.16 to 53.97°
5.22 to 50.1°
31 161
3097[0.0537]
26 401
2682[0.0329]
14 890
5371[0.0355]
58 870
5366[0.0623]
30 605
6154[0.0442]
28 656
2846[0.0597]
reflections [R(int)]
Completeness %
Data/restraints/parameters
Goodness-of-fit on F2
Final R1 indices
[I > 2σ(I)]
100
3097/0/173
1.054
R1 = 0.0181,
wR2 = 0.0448
R1 = 0.0190,
wR2 = 0.0451
0.37/−0.44
100
2682/0/172
1.105
R1 = 0.0216,
wR2 = 0.0564
R1 = 0.0236,
wR2 = 0.0580
0.43/−0.66
100
5371/24/399
0.935
R1 = 0.0478,
wR2 = 0.1080
R1 = 0.0832,
wR2 = 0.1199
0.91/−0.60
100
5366/0/414
0.994
R1 = 0.0210,
wR2 = 0.0423
R1 = 0.0237,
wR2 = 0.0431
0.46/−0.33
100
6154/0/455
1.250
R1 = 0.0451,
wR2 = 0.1241
R1 = 0.0578,
wR2 = 0.1297
1.38/−1.24
100
2846/0/218
0.981
R1 = 0.0362,
wR2 = 0.1012
R1 = 0.0494,
wR2 = 0.1068
0.98/−0.45
Final R indices
[all data]
Largest diff.
peak/hole/e Å−3
Flack parameter where
applicable
−0.04(2)
—
0.05(2)
−0.02(2)
—
—
9070
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Paper
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Conclusions
We have shown that ligands containing a diallylamino group
attached to
a (hetero)aromatic ring represent versatile
synthons for silver-based metallosupramolecular synthesis.
Despite the fact that the five ligands studied exhibit a variety
of coordination modes (Fig. 8), they faithfully assemble into
1-D coordination polymers, regardless of the number of addi-
tional nitrogen donors, by adjusting the coordination require-
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Acknowledgements
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We thank the University of Canterbury, College of Science,
for a scholarship for SWK and the RSNZ Marsden fund for
generous financial support.
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This journal is © The Royal Society of Chemistry 2013
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