Synthesis, crystal structures, characterization and antimicrobial activities of 5-hydroxyisophthalate complexes

Article abstract of DOI:10.1007/s11243-016-0109-5

Two 5-hydroxyisophthalate complexes of nickel(II), formulated as [Ni(μ-Hhip)(2-hepy)₂]_n (1) and [Ni₂(μ-Hhip)₂(dap)₄]_n (2) (H₃hip?=?5-hydroxyisophthalic acid, 2-hepy?=?2-(2-hydrox

Full text of DOI:10.1007/s11243-016-0109-5

Transit Met Chem
DOI 10.1007/s11243-016-0109-5
Synthesis, crystal structures, characterization and antimicrobial
activities of 5-hydroxyisophthalate complexes
1
2
3
4
•
Alper Tolga C¸ olak
5
•
Handan G u¨ nay
•
Ersin Temel
•
Orhan B u¨ y u¨ kg u¨ ng o¨ r
Ferda g˘ C¸ olak
Received: 27 September 2016 / Accepted: 1 December 2016
Ó Springer International Publishing Switzerland 2016
Abstract Two 5-hydroxyisophthalate complexes of nick-
el(II), formulated as [Ni(l-Hhip)(2-hepy)2]n (1) and
Introduction
[
Ni (l-Hhip) (dap) ] (2) (H hip = 5-hydroxyisophthalic
Most of the coordination polymers described in the litera-
ture are based on polyfunctional organic ligands that link to
the d-block transition metal centres through self-assembly,
giving compounds with interesting physical properties and
2
2
4 n
3
acid, 2-hepy = 2-(2-hydroxyethyl)pyridine, dap = 1,3-di-
aminopropane), have been synthesized and characterized
by chemical and spectroscopic methods. The molecular
structures of the complexes have been determined by sin-
gle-crystal X-ray diffraction analysis. The Ni(II) centres
have distorted octahedral geometries in both crystals.
Furthermore, both complexes have 1D chain structures in
which the individual chains are linked together via
hydrogen bonds to give 3D frameworks. Evaluation of the
complexes by the agar diffusion method showed that they
have weak antibiotic activities against the tested
microorganisms.
topologies [1]. 5-Hydroxyisophthalic acid (H hip, Fig. 1)
3
has been widely reported as a useful building block for the
construction of various coordination polymers and
supramolecular networks [2–4]. Coordination polymers
involving H hip and/or anionic ligand(s) with transition
3
metals [5–7] or lanthanides [8–10] have been reported.
Nickel is very suitable for the construction of coordination
polymers of N– and/or O– ligands, because of its variable
oxidation states, different geometries, spectral and mag-
netic features and ligand field effects [11, 12]. In com-
parison with coordination polymers of H hip with other
3
transition elements, it is surprising that only eight coordi-
nation compounds with nickel(II) have been reported to
date; five of which are coordination polymers [13–21]. Our
purpose was to synthesize mixed ligand complexes using
strong ligands and investigate the spectroscopic and crys-
tallographic effects of the neutral ligands. For this purpose,
Electronic supplementary material The online version of this
article (doi:10.1007/s11243-016-0109-5) contains supplementary
material, which is available to authorized users.
&
Handan G u¨ nay
h.gunay@avrasya.edu.tr
H hip and Ni(II) have been chosen as anionic ligand and
3
1
2
3
Department of Chemistry, Faculty of Arts and Sciences,
Dumlupınar University, 43820 Kutahya, Turkey
metal centre, respectively, in both complexes. 2-(2-hy-
droxyethyl)pyridine (2-hepy, for 1) and 1,3-diamino-
propane (dap, for 2) have been chosen as neutral co-ligands
in these complexes; dap has an aliphatic structure, whilst
Department of Chemistry Technology, Vocational High
School, Avrasya University, 63010 Pelitli, Trabzon, Turkey
Department of Electric and Energy, Technical Sciences
Vocational High School, Giresun University, Giresun,
Turkey
2-hepy is aromatic. Both the 2-hepy and dap ligands have
two donor atoms: two nitrogen atoms for dap and one
nitrogen and one oxygen for 2-hepy.
4
5
Department of Physics, Faculty of Arts and Sciences,
Ondokuz Mayıs University, 55139 Kurupelit, Samsun,
Turkey
The increased occurrence of drug-resistant bacterial
infections is a major global health concern. Staphylococcus
aureus is a gram-positive bacterium that can be treated
with a number of drugs including the methicillin class of
Department of Biology, Faculty of Arts and Sciences,
Dumlupınar University, 43820 Kutahya, Turkey
123

Transit Met Chem
Fig. 1 Moleculer structures of
-hydroxyisophthalic acid
hip)
OH
analyses were recorded (Fig. S1 and S2) to assay the
purities of bulk products.
5
(H
3
HO
OH
Syntheses
O
O
Two different solutions of H hip (10 mmol, 1.82 g) in water
3
(
50 mL) were added dropwise with stirring at room tem-
antibiotics. However, the emergence of methicillin-resis-
tant S. aureus (MRSA) is a source of concern, with mil-
lions diagnosed with MRSA infections each year [22].
Candida species are commonly isolated fungal pathogens
that are responsible for many types of infection in
immunocompromised patients and hospitalized patients
with serious underlying diseases [23].
perature to two solutions of Ni(CH COO) Á4H O
3
2
2
(
10.0 mmol, 2.44 g) in water (50 mL). The solutions
immediately became suspensions, and they were stirred for
h at room temperature. 2-Hepy (10.0 mmol, 1.23 g) and
1
dap (10.0 mmol, 0.74 g) in ethanol solutions (20 mL) were
added dropwise to the suspensions in ethanol for 1 and 2,
respectively. The mixtures were stirred for 2 days at 90 °C,
then cooled to room temperature and filtered. After about a
month crystals formed; these were filtered off, washed with
In this paper, we describe the syntheses, spectroscopic
properties, thermal analyses and crystal structures of two
polynuclear Ni(II)-5-hydroxyisophthalate complexes, for-
1
0 mL of water and dried in air. Elemental Analyses (%)
mulated as, [Ni(l-Hhip)(2-hepy)2]n (1) and [Ni (l-
2
calcd. for C H N NiO (1): (484.12 g/mol), C, 54.7; H,
2
2
22
2
7
Hhip) (dap) ] (2). The antimicrobial activities of the
2
4 n
4
.9; N, 6.8; found: C, 55.1; H, 4.2; N, 5.9, (%) calcd. for
nickel (II) complexes were evaluated by the agar diffusion
method against eleven bacteria, four yeasts and one mould.
To the best of our knowledge, the antimicrobial activities
of Ni(II)-5-hydroxyisophthalate complexes have not pre-
viously been reported.
C H N Ni O (2): (774.16 g/mol), C, 43.4; H, 6.3; N,
2
8
48
8
2 10
1
4.5; found: C, 43.9; H, 6.8; N, 14.8. The mass spectra of the
complexes 1 and 2 are presented in Figs. S3 and S4. Mass
?
spectroscopy results: (1): [Ni ? (Hhip) ? 2H O(solvent)]
2
calcd. 372.99, found 372.21; [Ni ? (Hhip) ? 2(2-
?
hepy) ? H O(solvent)] calcd. 501.2, found 501.8, (2):
2
?
2Ni ? (Hhip) ? 2(dap)] calcd. 443.4, found 441.3;
[
?
Experimental
[M ? H] calcd. 774.2, found 774.6. The Ni contents were
analysed by atomic absorption spectrometry, giving values
of 12.1% for 1 (calcd. 12.16%) and 15.0% for 2 (calcd.
Materials and measurements
15.2%).
All chemicals and solvents used for the syntheses were of
reagent grade. 5-Hydroxyisophthalic acid, 2-(2-hydrox-
X-ray crystallography
yethyl)pyridine, 1,3-diaminopropane and Ni(CH COO)2-
3
4
H O were used as received from Tetra technological
2
Diffraction measurements were taken at room temperature
(296 K) on a STOE IPDS II image plate detector using a
system. Elemental analyses (C, H, and N) were obtained on
a Costech (ECS 4010) elemental analyser. An Agilent
rotation anode and graphite monochromated Mo Ka radi-
ation (k 0.71073 A˚ ). The data collection conditions,
(
6530 QTOF-LC–MS) spectrometer was used for mass
spectroscopy analyses. An Analytik Jena ContrAA 300
analyser was used in AAS to evaluate metal contents. AAS
parameters of refinement process and final refinement
parameters are summarized in Table 1. The following
procedures and software were implemented for crystallo-
graphic study: X-AREA [24] for data collection; X-Red32
for data reduction; Shelxs97 [25] for structure solving;
Shelxl97 [25] for structure refinement; Mercury [26] for
molecular visualization; WinGX [27] to prepare materials
for publication.
analyses were recorded on 2 M 10 mL HNO solutions of
3
the complexes. Magnetic susceptibility measurements were
taken at room temperature using a Sherwood Scientific
MK1 model Gouy magnetic balance. UV–Vis spectra were
-
3
-4
obtained on aqueous solutions (10 and 10 mol/L) of
the complexes with a Shimadzu Pharmaspec UV-1700
spectrometer within the range of 800–200 nm. FTIR
-
1
spectra were recorded in the 4000–400 cm region with a
Bruker Optic, Vertex 70 FTIR spectrometer using an ATR
attachment. A Diamond TG/DTA thermal analyser was
used to record simultaneous TG, DTG and DTA curves in a
Antimicrobial activity tests
The complexes were tested for their antibacterial and
antifungal activities by the disc-diffusion method [28, 29].
In total, 16 microbial species including 11 bacteria, 4
yeasts and 1 mould were used as test organisms. The
antimicrobial activities were evaluated against gram-
2
1
static air atmosphere at a heating rate of 10 °C min in
temperature ranges of 35-1000 for 1, 35–800 °C for 2
using platinum crucibles. X-Ray powder diffraction
1
23

Transit Met Chem
8
containing approximately 10 CFU/mL for bacteria, 10
7
Table 1 Crystal data and structure refinement for complexes 1 and 2
5
CFU/mL for yeasts and 10 CFU/mL for mould was spread
on the plates of Nutrient Agar (NA). The entire surface of
the NA plates was inoculated by streaking with a sterile
swab dipped into the culture suspension. Then, paper discs
impregnated with solutions of the test compounds were
placed on the surface of the media. After pre-incubation for
1 h at 4 °C, the plates were incubated at 37 °C for 24 h for
bacterial strains, 48 h for yeast and at room temperature for
72 h for fungi. After incubation, the growth inhibition
zones around the discs were measured. Each assay was
repeated three times. Tetracycline (30 lg/disc) for bacteria
and Nystatin (100U/disc) for yeast and fungi were used as
positive controls.
Complexes
1
2
Formula
C
22
H
21 2
N NiO
7
C
28 48 8 2 10
H N Ni O
Formula weight
Crystal system
Space group
484.12
774.16
Monoclinic
P2 /c
Monoclinic
C2/c
1
˚
a (A)
17.405 (2)
17.7445 (11)
18.1032 (19)
110.953 (8)
4338.6 (8)
8
15.8230 (7)
14.7954 (5)
16.5420 (8)
107.986 (4)
3683.4 (3)
4
˚
b (A)
˚
c (A)
b (°)
3
˚
V (A )
Z
-
3
)
d
x
(mg m
-
1.482
1.396
1
l (mm
)
0.94
1.08
F
000
2008
1632
Results and discussion
T (K)
296
296
Index range, h, k, l
-21 ? 21
-19 ? 19
-18 ? 18
-20 ? 20
54,963
7637
Spectroscopic and magnetic properties
-
18 ? 18
22 ? 22
-
The UV–Vis. spectra of complexes 1 and 2 are presented in
Figs. S5 and S6. Octahedral nickel(II) complexes are
expected to show three electronic transitions in the UV–
Measured reflections
14,727
4502
Independent reflections
Reflections with I [ 2r(I)
3063
6362
3
3
3
3
Visible region; specifically A ? T , A ? T and
2
g
2g
2g
1g
R
int
0.046
0.40
0.042
3
3
2
2
A2g ? T (P), at approximately 1470–787, 847–518 and
1g
R[F [ 2r(F )]
2
wR(F )
0.037
485–344 nm, respectively [30].
0.089
\0.001
-0.44
0.55
0.096
The electronic spectra of the present complexes in water
(D/r)max
0.003
-
1
exhibit one absorption band, at 700 nm (e = 21 Lmol
-
3
)
˚
Dqmin (e A
-0.54
-1
-1
-1
cm ) and 611 nm (e = 14 Lmol cm ) for 1 and 2,
respectively; these were assigned to the A ? T d–
d transition. The A ? T (P) transition was obscured by
intra-ligand transitions, whilst the A2g ? T transition
-
3
)
˚
Dqmax (e A
0.66
3
3
2g
1g
S
1.04
1.04
3
3
2g
1g
3
3
2g
would be out of the range of our spectrophotometer. The
-
1
positive (Bacillus cereus NRRL 3711, B. subtilis NRRL-B-
complexes also show bands at 460 nm (e = 1054 Lmol
-1
-1
-1
2
00, B. pumilis NRRL 3275, Staphylococcus aureus ATCC
5923, Staphylococcus spp. and MRSA (clinic isolates)
cm ) for 1 and 320 nm (e = 1609 Lmol cm ) for 2,
assigned to intra-ligand electronic transitions (n–p* and p–p*).
Complexes 1 and 2 exhibit magnetic moment values of 2.84
and 2.86 BM, respectively, corresponding to two unpaired
electrons per nickel(II) centre. These values are close to the
spin-only value for two unpaired electrons of 2.83 BM.
The IR spectra of complexes 1 and 2 are presented in
2
and gram-negative (Escherichia coli ATCC 25922, E.
aerogenes ATCC 13048 A. hydrophilia NRRL 406, Mo-
raxella catarhalis and Salmonella spp. (clinic isolate)
bacteria, yeast cultures (Candida albicans ATCC 10231,
Sacchoromyces baulardii (wild), S. cerevisa (wild), Can-
dida spp. (clinic isolate) and fungi culture (Aspergillus
niger ATCC 10949). Bacterial and fungal cultures were
maintained on Nutrient slants at 4 °C and were subcultured
in petri dishes prior to use.
-1
Figs. S7 and S8. An absorption peak at 3319 cm is assigned
to the m(NH ) stretching vibration of the secondary amine
group of the dap ligand in complex 2. Bands at 3233 and
2
-1
3256 cm are attributed to m(OH) of the Hhip ligand for 1
and 2 complexes, respectively, whilst bands at 3071 (for 1)
In the disc-diffusion method, sterile paper discs (about
-1
6
mm) impregnated with 10 lL of the test compounds
and 3056 (for 2) cm are assigned to C–H vibrations from
-1
(
dissolved in water at concentrations of 100 and 200 lg)
the ligands. Peaks at 1606 and 1607 cm are attributes to the
ligands C=C and C=N vibrations. In these complexes, each
carboxylate group coordinates to nickel(II) ion in a mon-
odentate mode, so the difference between asymmetric and
symmetric vibration (Dm) of carboxylate group should be
were used. The test bacteria were transferred to tubes
containing 4–5 mL of Nutrient broth. The test cultures
were incubated at 37 °C until visibly turbid. The density of
the cultures was adjusted to 0.5 Mc Farland (at 625 nm,
-1
0
.08–0.1 absorbance) with sterile saline. A suspension
approximately 218 cm [31]. For complex 1, peaks at 1487
123

Transit Met Chem
Fig. 2 Molecular structures of complex 1 (upper figure) and 2 (bottom figure) showing the atom numbering scheme (i: 2 - x, 1 -y, 1 - z, ii: 1 -
x, 1 - y, -z for 1; i: 1 ? x, y, 1 ? z, ii: -1 ? x, y, -1 ? z for 2)
-
1
and 1270 cm are due to asymmetric modes, whilst peaks at
stable until 103 °C. Endothermic peaks between 103 and
417 °C correspond to the loss of two 2-hepy ligands
(DTGmax = 191, 240 and 270 °C, found 50.4, calc.
51.2%). It is difficult to comment on the calculated mass
losses for this complex because of the lack of smooth
plateaus; however, the DTG curves indicate that the
decomposition occurs in three steps. In the following stage,
an exothermic peak between 270 and 429 °C corresponds
to the loss of Hhip ligand (DTGmax = 382 °C, found 33.1,
calcd. 34.0%). The final decomposition product is NiO
-1
1
537 and 1345 cm are due to symmetric vibrations of the
carboxylate groups. Hence, in complex 1, Dm = 217 and
-1
-1
92 cm . For complex 2, peaks at 1542 and 1352 cm are
1
due to asymmetric and symmetric vibrations of carboxylate
-1
groups; hence, in complex 2, Dm = 190 cm . These results
confirm that the carboxylate groups are monodentate in these
-1
complexes. Peaks at 529 and 491 cm are assigned to Ni–O,
-1
4
80 and 474 cm
to Ni–N vibrations for 1 and 2,
respectively.
(found 16.7, calcd. 15.4%). Complex 2 is stable until
Thermal analyses
97 °C. Endothermic peaks between 97 and 360 °C corre-
spond to the loss of four dap ligands (DTGmax = 165, 328
and 354 °C, found 36.4, calcd 38.2%). In the second stage,
an exothermic peak between 360 and 440 °C corresponds
The TG-DTG and DTA curves of the complexes are shown
in Figs. S9 for 1 and S10 and for 2. Complex 1 is
1
23

Transit Met Chem
Table 2 Selected geometric
˚
˚
Bond distances (A)
parameters (A, °) and the details
of intra/inter-molecular
interactions for complex 1
N1–Ni1
Ni2–N2
2.082 (2)
2.053 (2)
2.0565 (16)
Ni1–O2
Ni2–O4
Ni2–O7
2.1110 (14)
2.0836 (15)
2.0953 (17)
Ni1–O1
Bond angles (°)
i
O1 –Ni1–N1
i
O1 –Ni1–O2
91.30 (8)
88.23 (8)
85.63 (7)
94.37 (7)
90.09 (8)
89.91 (8)
88.97 (6)
91.77 (6)
88.23 (6)
89.82 (7)
90.18 (7)
88.23 (6)
91.03 (6)
O1–Ni1–N1
O1–Ni1–O2
N1–Ni1–O2
i
N1 –Ni1–O2
i
O1 –Ni1–O2
ii
O4 –Ni2–O7
ii
N2–Ni2–O4
ii
N2 –Ni2–O4
ii
i
N2–Ni2–O7
ii
N2 –Ni2–O7
O4–Ni2–O7
˚
Hydrogen Bonds (A, °)
D–HÁÁÁA
D–H
0.97
HÁÁÁA
2.43
DÁÁÁA
D–HÁÁÁA
131.3
C21–H21AÁÁÁO4
3.155 (4)
3.012 (3)
3.156 (3)
2.973 (3)
3.379 (4)
2.873 (2)
2.627 (2)
i
C1–H1ÁÁÁO1
0.93
2.50
115.2
i
C6–H6AÁÁÁO2
0.97
2.43
131.0
ii
C16–H16ÁÁÁO7
0.93
2.44
117.0
iii
C1–H1ÁÁÁO5
0.93
2.57
146.1
iv
O6–H6CÁÁÁO3
0.82
2.06
169 (7)
168 (3)
O1–H1OÁÁÁO3
0.79 (3)
1.85 (3)
Symmetry codes (i) –x ? 2, -y ? 1, -z ? 1; (ii) –x ? 1, -y ? 1, -z; (iii) x ? 1/2, -y ? 1/2, z ? 1/2;
iv) –x ? 3/2, y - 1/2, -z ? 1/2
(
Fig. 3 3D supramolecular network of complex 1 (hydrogen atoms were omitted for clarity)
123

Transit Met Chem
Table 3 Selected geometric
˚
˚
Bond distances (A)
parameters (A, °) and the details
of intra/inter-molecular
interactions for complex 2
N1–Ni1
2.1132 (18)
2.115 (2)
N7–Ni2
N8–Ni2
O3–Ni2
O5–Ni1
O8–Ni2
2.116 (2)
N2–Ni1
2.0942 (17)
2.0966 (14)
2.1016 (13)
2.0974 (14)
2.1023 (13)
i
N3–Ni1
2.1107 (18)
2.1050 (2)
2.126 (2)
N4–Ni1
N5–Ni2
N6–Ni2
2.0992 (17)
O10–Ni1
Bond angles (°)
O5–Ni1–O10
O5–Ni1–N4
O10–Ni1–N4
O5–Ni1–N3
O10–Ni1–N3
N4–Ni1–N3
O5–Ni1–N2
O10–Ni1–N2
N4–Ni1–N2
N3–Ni1–N2
O5–Ni1–N1
O10–Ni1–N1
N4–Ni1–N1
N6–Ni2–N5
N7–Ni2–N5
176.38 (7)
97.49 (7)
86.01 (8)
85.51 (7)
95.56 (6)
87.95 (8)
84.58 (8)
91.95 (9)
177.12 (10)
90.22 (9)
92.65 (7)
86.42 (7)
89.95 (8)
92.06 (8)
179.19 (9)
N3–Ni1–N1
N2–Ni1–N1
N8–Ni2–O3
177.01 (7)
91.95 (9)
92.97 (6)
86.77 (6)
179.61 (6)
179.40 (8)
86.58 (6)
93.67 (6)
92.69 (8)
87.14 (8)
93.16 (8)
87.69 (8)
87.56 (8)
93.62 (8)
86.08 (8)
ii
N8–Ni2–O8
ii
O3 –Ni2–O8
N8–Ni2–N6
ii
O3 –Ni2–N6
O8–Ni2–N6
N8–Ni2–N7
ii
O3 –Ni2–N7
O8–Ni2–N7
N6–Ni2–N7
N8–Ni2–N5
ii
O3 –Ni2–N5
O8–Ni2–N5
˚
Hydrogen Bonds (A, °)
D–HÁÁÁA
N1–H1AÁÁÁO4
N3–H3BÁÁÁO9
N6–H6AÁÁÁO7
D–H
HÁÁÁA
DÁÁÁA
D–HÁÁÁA
138 (3)
135 (2)
153 (2)
151 (2)
168 (2)
157 (3)
174 (3)
1644 (3)
157 (2)
174 (2)
166 (3)
156
0.90 (3)
0.85 (3)
0.85 (3)
0.85 (3)
0.88 (3)
0.81 (3)
0.89 (3)
0.83 (3)
0.90 (3)
0.87 (3)
0.89 (3)
0.97
2.32 (3)
2.34 (3)
2.23 (3)
2.28 (3)
2.37 (3)
2.33 (3)
2.28 (3)
1.83 (3)
2.22 (3)
2.25 (3)
1.75 (3)
2.72
3.049 (3)
2.996 (3)
3.011 (2)
3.046 (3)
3.240 (3)
3.091 (3)
3.166 (2)
2.644 (2)
3.076 (2)
3.119 (3)
2.631 (2)
3.630(4)
3.651(3)
3.573(3)
iii
N8–H8BÁÁÁO2
iv
N1–H1BÁÁÁO2
iv
N4–H4BÁÁÁO2
v
N6–H6BÁÁÁO1
v
O6–H6CÁÁÁO9
vi
N8–H8AÁÁÁO6
vi
N3–H3AÁÁÁO7
vii
O1–H1CÁÁÁO4
viii
C18-H18BÁÁÁCg1
ix
C24-H24AÁÁÁCg2
0.97
2.78
150
x
C26-H26AÁÁÁCg1
0.97
2.90
127
Symmetry codes (i) –x ? 2, -y ? 1, -z ? 1; (ii) –x ? 1, -y ? 1, -z, (iii) x ? 1, y, z ? 1; (iv) -x, y - 1/
, -z ? 1/2; (v) -x ? 1, ?y-1/2,-z ? 3/2; (vi) -x ? 1, ?y ? 1/2, -z ? 3/2; (vii) -x, y ? 1/2,
z ? 1/2; (viii) x, -y ? 3/2, z ? 1/2; (ix) -x ? 1, -y ? 1, -z ? 2; (x) x ? 1, -y ? 3/2, z ? 1/2
2
-
to the loss of two Hhip ligands (DTGmax = 383 °C, found
6.7, calcd. 47.9). The final decomposition product is NiO
found 17.7, calcd. 19.3%).
and two 2-hepy ligands. Ni1 is hexa-coordinated in a
distorted octahedral geometry. The two 2-hepy ligands
chelate through their nitrogen and oxygen atoms. The
Hhip ligand coordinates by two oxygen atoms of two
different monodentate carboxylate groups, meaning that it
is bidentate overall. Ni1 and Ni2 have the same coordi-
nation environments, but there are differences in the bond
distances between the oxygen or nitrogen atoms of the
coordinated 2-hepy ligands.
4
(
Crystal structure of complex 1
Complex 1 crystallized in the monoclinic crystal system
with space group C2/c. As shown in Fig. 2, one Ni(II)
centre in the asymmetric unit is coordinated by one Hhip
1
23

Transit Met Chem
The Ni–O and Ni–N bond lengths are in the ranges of
˚
crystallizes in the monoclinic crystal system in the space
˚
and 2.053(2)–2.082(2) A,
2
.0565(16)-2.1110(14)
A
group P2 /c. There are two Ni(II) centres, two Hhip
1
respectively (Table 2), which are in the normal ranges
observed for Ni(II)-5-hydroxyisophthalate complexes
ligand(s) and four dap ligands in the asymmetric unit. As
depicted in Fig. 2, atoms Ni1 and Ni2 have the same
coordination, but the bond distances between the nitrogen
atoms of coordinated dap ligands and the metals are
somewhat different. Both Ni1 and Ni2 are hexa-coordi-
nated in a distorted octahedral geometry, coordinated by
two chelating dap ligands via their nitrogen atoms, plus
two oxygen atoms of two hip ligands in different cells. The
Ni–O and Ni–N bond lengths are in the ranges of
[
15–17]. The crystal structure of complex 1 reveals an
infinite 1D coordination polymer. These 1D layers are
extended into a 2D framework through weak hydrogen
bonds between Hhip ligands (O6–H6CÁÁÁO3) and between
Hhip and 2-hepy ligands (C1–H1ÁÁÁO5) (Fig. S11). These
2
2
2
2
hydrogen bonds generate adjacent R (22) and R (14) ring
motifs [32]. There is an intramolecular hydrogen bond
between the hydroxyl group and the carboxylate oxygen-
˚
atom (O1–O3), with an O–O distance of 2.627 (2) A. All
˚
˚
2.0966(14)–2.1023(13) A and 2.0942(17)–2.126(2) A,
respectively (Table 3), which are similar to the values
observed in related Ni(II)-5-hydroxyisophthalate com-
plexes [22, 23].
these interactions give rise to a 3D supramolecular net-
work (Fig. 3). The channel volume per unit was estimated
3
to be 53.3 A (1.2% of the total) by using the PLATON
˚
For complex 2, the channel volume per unit was esti-
3
mated as 3683.4 A (9.8% of the total) by using the
˚
program [33].
PLATON program. The crystal packing is mainly stabi-
lized by intramolecular (N1–H1AÁÁÁO4, N3–H3BÁÁÁO9 and
N6–H6AÁÁÁO7) and inter-molecular (Table 3) hydrogen
bonds (Fig S12). The combinations of these hydrogen
Crystal structure of complex 2
Single-crystal X-ray diffraction analysis reveals that com-
2
1
plex 2 possesses a 1D polynuclear structure which
bonds generate R (12)(13)(15) and R (6) ring motifs [33].
2 2
Fig. 4 C–HÁÁÁp interactions in complex 2
123

Transit Met Chem
Fig. 5 3D framework of complex 2 (hydrogen atoms were omitted for clarity)
As shown in Fig. 4, there is a weak electrostatic interaction
and C24–
is shorter than the Ni–N bond distance for dap (in
complex 2), suggesting that the Ni–N bond in complex 1
is stronger than that in complex 2.
(
C18–H18BÁÁÁCg1,
C26–H26AÁÁÁCg1
H24AÁÁÁCg2) between the ligand and phenyl group (Cg1:
C1/6 and Cg2: C9/14). These various interactions give rise
to a three-dimensional supramolecular framework (Fig. 5).
All the carboxylic acid groups of H hip are deprotonated
3
in all complexes in agreement with the IR data in which the
characteristic absorption bands of –COOH groups at
-
1
1
700–1750 cm were not observed. In both complexes, the
2
-
Antimicrobial activities
anionic Hhip ligands coordinate to the metal with same
coordination mode. Complex 1 did not show any significant
antimicrobial activity against the tested microorganisms,
whilst complex 2 showed weak antimicrobial activities.
The antimicrobial activities of the complexes assessed by
the agar diffusion method are presented in Table S1.
Complex 1 showed weak antimicrobial activities against B.
pumilus, S. cerevisia and S. baulardii only with inhibition
zones of 7 mm at 200 lg/disc test concentration. Complex
2
showed weak antimicrobial activities against B. subtilis,
Salmonella spp., A. hydrophilia, S. baulardii, S. cerevisia
7 mm) at 200 lg/disc test concentration.
Supplementary data
(
This work was supported by Dumlupinar University, Pro-
ject No. 2012/22. CCDC 1031887 and 1031881 contain
supplementary crystallographic data for complexes 1 and 2.
These data can be obtained free of charge via http://www.
ccdc.cam.ac.uk/conts/retrieving.html, or from the Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (?44) 1223-336-033; or
e-mail: deposit@ccdc.cam.ac.uk.
Conclusion
In this work, two new complexes were synthesized, and
their structures were characterized by single-crystal
X-ray diffraction. Both complexes are one-dimensional
coordination polymers. Although hydrothermal synthesis
methods often used in the syntheses of these types of
structures, these complexes were successfully synthesized
using easy one-pot methods at room temperature. Crys-
tallographic analysis show that the bond distance
between Ni(II) and the N atom of 2-hepy (in complex 1)
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