Cobalt, nickel and copper complexes with glycinamide: Structural insights and magnetic properties

Article abstract of DOI:10.1039/c9ra03693h

Ten new compounds of Co, Ni and Cu with glycinamide (HL = glycinamide): [Co(H₂O)₂(HL)₂]Cl₂ (1a), [Co(H₂O)₂(HL)₂]Br_1.06Cl_0.94 (1b), [Co(H₂O)₂(HL)₂]I₂ (1c), [Ni(H₂O)₂(HL)₂]Cl₂ (2a), [Ni(H₂O)₂(HL)₂]Br_0.94Cl_1.06 (2b), [Ni(H₂O)₂(HL)₂]I₂ (low and room temperature polymorph, 2c_LT and 2c_RT), [CuCl₂(HL)₂] (3a), [CuBr_1.3Cl_0.7(HL)₂] (3b) and {[Cu(HL)₂]₂[Cu₂I₆]}_n (3c), as well as glycinamide hydroiodide (H₂LI) and a new polymorph of glycinamide hydrochloride (β-H₂LCl) were prepared and characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermal analysis (TG/DTA) and ESR spectroscopy. 1a, 1b, 2a and 2b are isostructural, as well as 1c and 2c_RT, while the Cu compounds (3a-c) have entirely different molecular structures. All investigated compounds are mononuclear with exception of the 1D coordination polymer 3c. Compound 3c contains copper ions in the mixed oxidation state Cu(i) and Cu(ii) with interesting magnetic properties. Paramagnetic behaviour was found in 1a, 1b, 3a and 3b. Temperature induced polymorphic transformation was observed in 2c. Compounds 1a and 3a showed moderate antiproliferative activity and selectivity toward the human breast tumor cell line MCF-7.

Full text of DOI:10.1039/c9ra03693h

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Cobalt, nickel and copper complexes with
glycinamide: structural insights and magnetic
Cite this: RSC Adv., 2019, 9, 21637
properties†
a
a
a
a
Darko Vusak,
Neven Smrecki, Biserka Prugovecki, * Ivica Đilovic,
ˇ ˇ ´
ˇ
a
b
b
Inka Kirasic, Dijana Zˇ ilic,
Senada Muratovic and Dubravka Matkovic-
´
´
´
´
a
Cˇ alogovic
´
Ten new compounds of Co, Ni and Cu with glycinamide (HL ¼ glycinamide): [Co(H
2
O)
2
2 2
(HL) ]Cl (1a),
[
(
[
Co(H
2b), [Ni(H
CuBr1.3Cl0.7(HL)
2
O)
2
(HL)
2
]Br1.06Cl0.94 (1b), [Co(H
(HL) ]I (low and room temperature polymorph, 2cLT and 2cRT), [CuCl
] (3b) and {[Cu(HL) [Cu ]} (3c), as well as glycinamide hydroiodide (H LI) and a new
LCl) were prepared and characterized by single-crystal X-
2 2 2 2 2 2 2 2 2 2 2
O) (HL) ]I (1c), [Ni(H O) (HL) ]Cl (2a), [Ni(H O) (HL) ]Br0.94Cl1.06
2
O)
2
2
2
2 2
(HL) ] (3a),
2
2
]
2
2
I
6
n
2
polymorph of glycinamide hydrochloride (b-H
2
ray diffraction, infrared spectroscopy, thermal analysis (TG/DTA) and ESR spectroscopy. 1a, 1b, 2a and 2b
are isostructural, as well as 1c and 2cRT, while the Cu compounds (3a–c) have entirely different
molecular structures. All investigated compounds are mononuclear with exception of the 1D
coordination polymer 3c. Compound 3c contains copper ions in the mixed oxidation state Cu(I) and
Cu(II) with interesting magnetic properties. Paramagnetic behaviour was found in 1a, 1b, 3a and 3b.
Temperature induced polymorphic transformation was observed in 2c. Compounds 1a and 3a showed
moderate antiproliferative activity and selectivity toward the human breast tumor cell line MCF-7.
Received 16th May 2019
Accepted 17th June 2019
DOI: 10.1039/c9ra03693h
rsc.li/rsc-advances
complexes with ligands analogous to those of amino acids side
chains are useful in protein crystallography for interpretation
The orchestrated transport, exchange and incorporation of and validation of protein structural data.
Introduction
11–15
various metal ions in different metalloproteins is vital for their
function. Metal ions are constituents of many proteins and have complexes possess various biological activities such as anti-
Amino acids/amino acid derivatives and their metal
1
6
17–20
either catalytic or structural functions. They are usually coor- retroviral,
antibacterial and antifungal,
and anti-
21
dinated by the side chain functionalities of peptides (histidyl, proliferative effects on tumor cells, with potential applications
carboxylate, hydroxyl or amide groups), solvent molecules and in biomedicine. Copper coordination compounds, especially
1,2
ions. The search for small molecules with the desired struc- those with mixed oxidation states, are also of special interest
22–24
tural and functional plasticity to perform, or even enhance, because of their magnetic properties.
Cobalt and nickel
bioinspired processes – from mimicking and electron transfer polynuclear compounds showed interesting ferro- and antifer-
to recognition and catalysis – has become an integral part of romagnetic properties, specically compounds containing the
24–26
3
–9
everyday research. Derivatization of ubiquitous amino acids carboxylic group, such as amino acids and their derivatives.
seems to be an obvious synthetic choice to provide coordination There are fewer published papers on magnetic measurements
environments complementary to those found in metal- and structural studies of such cobalt and nickel compounds
10
loproteins.
Accurately determined structures of metal than for copper compounds.
Glycinamide (HL) is the simplest amino acid amide, being
cheap, readily available and easily synthesized. In bio-systems
its derivative glycinamide ribonucleotide is known as an inter-
mediate in de novo biosynthesis of purine. Moreover, glycil-
prolyl-glycinamide and its metabolites (glycine, glycinamide,
proline, glycil-proline and prolyl-glicinamide) were tested in
a
Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a,
HR-10000 Zagreb, Croatia. E-mail: biserka@chem.pmf.hr
27
b
Laboratory for Magnetic Resonances, Division of Physical Chemistry, Rudꢀer Bo ˇs kovi ´c
Institute, Bijeni ˇc ka 54, HR-10000 Zagreb, Croatia
†
Electronic supplementary information (ESI) available: crystal and molecular
structure data of b-H LCl, H
complexes, Hirshfeld surface analysis of a and b-H
2
2
LI, 1a–c, 2a,b, 2cRT, 2cLT, 3a–c, TG analysis of vitro as potential HIV-1 replication inhibitors. It was shown that
2
LCl, crystallographic data,
only glycil-prolyl-glycinamide and glycinamide showed
bond lengths and angles, torsion angles, geometric parameters of
intermolecular hydrogen bonds, conformational analysis of chelate rings. CCDC
16
a pronounced inhibitory effect.
Glycinamide is capable of building various hydrogen
1
915361–1915372. For ESI and crystallographic data in CIF or other electronic
bonding architectures, having four N–H hydrogen atoms in the
format see DOI: 10.1039/c9ra03693h
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neutral form as potential HB-donors and an amide oxygen as
28
the acceptor. In the Cambridge Structural Database (CSD)
there are only six structures containing the glycinamide frag-
2
9
ment:
complexes,
glycinamide
hydrochloride,
two
rhodium
30,31
32
a bimetallic (Mn, Cr) ferrimagnet, a ruthenium
33
34
complex and an iridium complex. This is surprising because
coordination of metal ions by amide groups of simple amides,
peptides and proteins is of great interest due to their impor-
35
tance in biological systems. Different modes of coordination
to the metal ion were found. In the reported rhodium(III)
complexes glycinamide acts as a monodentate ligand coordi-
nating rhodium through the amine nitrogen atom. In the
manganese complex glycinamide acts as a bidentate N,O-
coordinating ligand through the amine nitrogen and amide
oxygen atoms, while in the ruthenium and iridium complexes
0
the glycinamidato group acts as a bidentate N,N -coordinating
ligand through nitrogen atoms from amide and amino groups
(
Scheme 1).
As a part of our ongoing research on preparation and Scheme 2 Preparation of the glycinamide complexes with Co, Ni and Cu.
structural investigation of metal complexes with amino acids
21,36–39
and their derivatives,
and nickel(II) complexes with N-alkyliminodiacetamide. In the general formula [M(H
order to expand our knowledge on the properties of amino Cl, I). On the other hand, copper(II) gave different and less
acetamide complexes in the solid state, we report synthesis and soluble compounds [CuX (HL)
] (X ¼ Cl, Br/Cl) (3a and 3b). A
solid-state characterization (X-ray structural analysis, IR and partial reduction of copper(II) to copper(I) occurred when KI was
ESR spectroscopy, TG/DTA analysis) of cobalt, nickel and copper introduced into the solution of CuCl , H LCl and NaHCO
complexes with glycinamide. Structural characterization of leading to the formation of a 1D coordination polymer
glycinamide hydroiodide (H LI) and a new polymorph of glyci- {[Cu(HL) [Cu ]} (3c). Compound 3a can also be prepared by
LCl) is also given. Reactions of NG mechanochemical synthesis, using Cu(OH) and H LCl,
LCl with cobalt(II), nickel(II) and copper(II) halides, acetate or offering a very fast and clean route to the desired product
hydroxides yielded ten novel compounds: nine mononuclear (Scheme 2).
we have prepared various copper(II) nickel(II) gave water-soluble compounds 1a–c, 2a,b and 2cRT of
40
2
O)
2
(HL)
2
]X
2
(M ¼ Co, Ni; X ¼ Cl, Br/
2
2
2
2
3
2
]
2
2 6 n
I
2
namide hydrochloride (b-H
H
2
2
2
2
[
[
Co(H
Co(H
2
O)
O)
2
2
(HL)
(HL)
2
2
]Cl
]I
2
(1a), [Co(H
2
O)
2
(HL)
2
]Br1.06Cl0.94 (1b),
O) (HL)
All compounds are air-stable. Thermal stability of the
cobalt(II) and nickel(II) compounds (1a–c, 2a,b and 2cRT) is
2
2
(1c), [Ni(H O) (HL)
2
2
2
]Cl
2
(2a), [Ni(H
2
2
2
]
Br0.94Cl1.06 (2b), [Ni(H O) (HL) ]I (low and room temperature characterized by the initial loss of coordinated water molecules
2
2
2 2
ꢀ
polymorphs, 2cLT and 2cRT), [Ni(H O) (HL) ]I (2c); [CuCl (HL) ] in the range 100–120 C, followed by further decomposition
2
2
2
2
2
2
ꢀ
(
3a); [CuBr1.3Cl0.7(HL) ] (3b) and a 1D coordination polymer starting between 220 and 265 C. Copper(II) compounds (3a–c)
2
{
[Cu(HL)
2
]
2
[Cu
2
I
6
]}
n
(3c).
are less stable than cobalt(II) and nickel(II) compounds and
decompose at signicantly lower temperatures in the range
ꢀ
1
(
60–195 C. Full thermal analyses data are given in Table S1
Results and discussion
Synthesis and properties of the complex compounds
ESI†).
Infrared spectra of the compounds are characterized by the
presence of very strong and sharp bands of the carbonyl group
Reactions of H
were performed in aqueous solutions, and the reactions of
LCl with metal hydroxides mechanochemically by neat
2
LCl with metal halides and sodium bicarbonate
41,42
stretching, n(C]O)
occurring in the range of 1674–
ꢁ
1
1
644 cm . Comparing the spectra of cobalt(II), nickel(II) and
H
2
copper(II) complexes with chlorides and bromides, the n(C]O)
bands occur at the highest wavenumbers in the spectra of
copper(II) complexes. Carbonyl stretching in protonated glyci-
grinding (NG), Scheme 2. Synthesis of 1c was performed in an
aqueous solution by using cobalt(II) acetate and surplus of
potassium iodide. When metal bromides were used as reactants
mixed halide compounds 1b, 2b and 3b were obtained (bromide
ions originated from the metal bromide, while the chloride ions
originated from glycinamide hydrochloride). Cobalt(II) and
namide, b-H LCl, was observed at higher wavenumber then in
2
ꢁ
1
any of the complexes, at 1688 cm , showing weakening of the
C]O bond upon coordination to the metal ion. The amide II
41
ꢁ1
band, which appears at 1594 cm in the spectrum of b-H
2
LCl,
was found in the similar region in the spectra of all compounds
ꢁ
1
ꢁ1
(
1570–1600 cm ) and at 1555 cm for compound 3c. The
bands of antisymmetric and symmetric stretching of the amide
ꢁ1
amino groups are observed in the range 3300–3100 cm
,
+
ꢁ
indicating that these are involved in hydrogen bonding, as
evidenced by the crystal structures of all nine complexes. A
Scheme 1 Structural diagrams of H L and HL/L modes of binding in
complexes in the solid state.
2
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sharp band of medium intensity, which was assigned as O–H similar, however the most notable difference between the two
ꢁ1
stretching, n(OH, H O), was observed at roughly 3430 cm in structures is in the surrounding of the oxygen atom.
2
the spectra of compounds 1a–c, 2a–c. The band is, of course,
absent in the spectra of compounds 3a–c. IR spectra of repre- groups of the neighbouring H2L ion, while in a-H LCl the
sentative compounds are given in Fig. S1 (ESI†).
In b-H LCl the oxygen atom is in contact with CH and NH
2 2 2
+
2
+
oxygen atom is surrounded by two –NH
H/H contacts.
3
groups, having more
Molecular and crystal structures of b-H LCl and H LI
2
2
Both H
2
LCl polymorphs crystallize in monoclinic space groups,
Molecular and crystal structures of 1a–c, 2a,b, 2cLT and 2cRT
In cobalt(II) and nickel(II) compounds [M(H O) (HL) ]X (M ¼
a in P2 /c and b in P2 /m, while H LI crystallizes in the ortho-
rhombic crystal system, space group Pca2 (Table S2, ESI†). ORTEP
drawings of b-H LCl and H LI are given in Fig. S2 (ESI†). Selected
1
1
2
2
2
2
2
1
Co, Ni; X ¼ Cl, Br/Cl, I), the metal(II) cation is octahedrally
coordinated by two N,O-donating glycinamide ligands and two
water molecules (Fig. S4, ESI†). 1a, 1b, 2a and 2b are iso-
structural and crystallize in the tetragonal crystal system. 1c and
2cRT are also isostructural and crystallize in the orthorhombic
crystal system (Tables S2 and S5, ESI†). Two glycinamide
molecules are bound to the metal ion via amido O and amino N-
atoms in a cis-fashion, and two water molecules occupy the axial
coordination sites. Selected bond distances and angles in
2
2
29
bond distances and angles in the crystal structures of a-H
LCl and H LI are presented in Table S3 (ESI†). Structures of the
L] ions are different in the two polymorphs: torsion angle N1–
2
LCl, b-
H
[H
2
2
2
+
ꢀ
ꢀ
C1–C2–N2 is 149.64(15) in a-H
LI. In a-H LCl, centrosymmetric [H
R (10)] are bridged by eight chloride ions thus forming sheets
2
LCl, and 180 in b-H
2
LCl and
+
H
2
2
2
L] dimers [graph-set
2
2
ꢀ
parallel to the crystallographic (101) plane (Fig. 1a). In b-H LCl and
2
+
ꢁ
H LI chains of [H L] ions [C(4)] are mutually connected via Cl or
2
ꢁ
2
+
[
M(H O) (HL) ]X (M ¼ Co, Ni; X ¼ Cl, Br/Cl, I) can be found in
I ions (Fig. 1b and c). Each [H
2
L] ion is hydrogen bonded to four
Cl or I ions in a 3D charge-assisted hydrogen bond framework
Fig. 1b, c and Table S4, ESI†). Fingerprint plots and Hirshfeld
surface analysis for H LCl polymorphs are given in Fig. S3 (ESI†).
Most of the intermolecular contacts in a-H LCl and b-H LCl are
2
2
2
2
ꢁ
ꢁ
Tables S6 and S7 in ESI.†
The same building block, a dimer, is found in the iso-
structural Co(II) and Ni(II) compounds 1a, 1b, 2a and 2b
(
2
(Fig. 2a). A dimer consists of complex ion pairs mutually con-
2
2
nected by four hydrogen bonds of the Ow–H/O type [graph-set
Fig. 1 HB-interactions in crystal structures of: (a) a-H
and (c) H LI. In the a-H LCl polymorph, a layer of [H
2 2 2
2
LCl; (b) b-H
2
LCl
L] and Cl ions is
parallel to the crystallographic (10 1ꢀ) plane, while in b-H LCl and H LI
L] ions is parallel to the crystallographic (010) and (001) Fig.
+
ꢁ
2
2
+
an array of [H
plane, respectively (picture on the left). Hydrogen bonding of [H
with four surrounding halides is presented on the right. Atoms are bonds (arrays of cyan cylinders). (b) Zig-zag chain of complex ions of
2
2
(a) Discrete centrosymmetric dimers in [Ni(HL)
2 2 2
(H O) ]
+
2
L]
Br0.94Cl1.06 (2b) formed through intermolecular Ow–H/O hydrogen
2+
represented as small spheres of arbitrary radii (a-H
hydrogen atoms) or ellipsoids (at 50% probability level; b-H
LI).
2
LCl and all [Co(HL)
2
(H
(H
2 2
O) ]
in 1c. (c) Zig-zag chain of complex ions of
in 2cLT. Atom labelling is analogous to 1c, except for
2+
2
LCl and [Ni(HL)
2
2 2
O) ]
H
2
water molecules (O1W) which are symmetrically equivalent.
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2
R
2
(6)] (Fig. 2a, Tables S8 and S9, ESI†). Halide ions (Cl or Br/Cl)
are placed between almost perpendicular dimers forming
chains parallel to crystallographic a axis (Fig. S5, ESI†). The
remaining hydrogen bond donors N–H and O–H are used for
counter ion hydrogen bonding, thus forming a three dimen-
sional framework.
In 1c, 2cRT and 2cLT the complex ions are connected by Ow–H/
O hydrogen bonds forming zig-zag chains along the a-axis (Fig. 2b
and c, Tables S8 and S9, ESI†). In 1c and 2cRT six-membered
2
hydrogen bond rings are formed, R (6) (Fig. 2b), while in 2c
2
LT
2
the hydrogen bond rings are eight-membered, R (8) (Fig. 2c).
2
Iodide ions are hydrogen bonded by N–H and O–H groups from
three neighbouring cations thus forming a three dimensional
framework (Fig. S6–S9, Tables S8 and S9, ESI†).
Fig. 4 (a) Molecular structure of 3c with atom labelling scheme. Cu(II)
are coordinated octahedrally in the cis-HL fashion. Two Cu(I) ions, Cu2
ii
Two polymorphs 2cRT and 2cLT are both cis-octahedral and Cu2 are both coordinated tetrahedrally with a shared edge.
Symmetry operators i ¼ ꢁx, y ꢁ 1, ꢁz; ii ¼ x + 1, y ꢁ 1, z ꢁ 1. (b) double
complexes with axial positions occupied by water molecules. At
room temperature the orthorhombic polymorph 2cRT is the
stable one, while at low temperature (<220 K) it transforms into
the monoclinic polymorph 2cLT. The main difference between
chain of the coordination polymer.
4
ꢁ
ii
[Cu I ] unit are I2 and I2 (ii ¼ x + 1, y ꢁ 1, z ꢁ 1) with the
2
6
the two is the orientation of water molecules (rotation by approx.
corresponding Cu2–I bond lengths of 2.6696(12) and 2.7228(9)
ꢀ
4
ꢁ
9
0 ), which consequently changes the intermolecular interac-
˚
A. The [Cu I ]
unit (Cu(I) oxidation state) and the four
units are connected through the I1 and I3 bridging
atoms (and their centrosymmetrically related atoms). Cu(II)–I
2
6
2
+
tions, as seen in Hirshfeld surface plots (Fig. S10, ESI†). In 2cRT
one water molecule (O1w) forms Ow–H/O hydrogen bonds with
two carbonyl oxygen atoms of adjacent complexes, while the
other water molecule forms two Ow–H/I hydrogen bonds. Aer
[
2
Cu(HL) ]
˚
˚
bonds are longer and amount to 3.1632(8) A and 3.2963(8) A
Table S12, ESI†). These two copper centers have different
(
ꢀ
rotation by 90 at low temperature, both water molecules form
coordination geometries having the main inuence on the bond
lengths. Those octahedrally coordinated generally have Cu–I
both Ow–H/O and Ow–H/I hydrogen bonds (Table S9, ESI†).
˚
distances greater than 3 A although the radius of Cu(II) is
smaller than of Cu(I). These results are in agreement with
Molecular and crystal structures of 3a–c
I
II
23,43–45
similar Cu /Cu mixed oxidation state complexes.
Coor-
The octahedral coordination environment around the Cu(II) dination preferences of both Cu centres are also fullled: Cu(I)
ions in the structures of 3a and 3b consists of two N,O-bidentate ions are tetrahedrally and Cu(II) ions octahedrally coordinated.
2
+
glycinamide ligands and two halide ions (Cl or Br/Cl) (Fig. 3 and
In the [Cu(HL)2] unit two glycinamide molecules bidentately
S11, ESI†). Cu(II) complex molecules are trans isomers. In the chelate Cu(II) ions in a cis-fashion while iodide ions are found in
crystal structures of 3a and 3b all amide H-atoms participate in axial positions. The inner chelate bond lengths indicate partial
hydrogen bonds with the neighboring halide ions (in total, every electron delocalization in the amide group, and the Jahn–Teller
46
halide ion is hydrogen bonded by two amide N–H and one effect also inuences elongation of the Cu1–I bonds.
amino N–H hydrogen bond donor) forming a very dense three
Neighbouring 1D chains are connected by hydrogen bonds
dimensional framework (Fig. S12, S13 and Table S11, ESI†).
between amide N–H bifurcated donors and O- and axial I-atom
In terms of the crystal structure, the most interesting acceptors. These interactions are almost perpendicular to the
compound is 3c. It is a 1D coordination polymer built up of chain propagation, Fig. S14 and S15 (ESI†). Inside one chain the
4
ꢁ
2+
dinuclear copper [Cu
2
I
6
]
and [Cu(HL)
2
]
units (Fig. 4a). The glycinamide amino groups serve as N–H donors to iodide ions
connectivity within this polymer is unique among the copper that are coordinated to the Cu(I) ions (Table S13, ESI†).
complexes since it is the only copper complex where the
All compounds have two chelate rings in the equatorial
4
ꢁ
[
[
Cu
2
I
6
]
unit links four Cu(II) complex units, in this case plane, however the ring conformations are somewhat different.
2
+
Cu(HL)2] (Fig. 4b). The two bridging atoms within the In isostructural 1a, 1b, 2a, 2b, as well as in 3c one 5 membered
chelate ring adopts an envelope, and the other a half chair
Table
1 Conformations of chelate rings of the investigated
compounds
5
membered chelate ring
Compound
conformations
1
1
a, 1b, 2a, 2b and 3c
c and 2cRT
Envelope and half chair
Planar
Fig. 3 Molecular structure of 3a with the atom labelling scheme. Cu(II) 3a, 3b and 2cLT
is located on the center of inversion (space group P2 /n).
Half chair
1
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conformation. In 1c and 2cRT both rings are planar, while in 3a,
H ¼ m B$g$S
(1)
B
3b and 2cLT the chelate rings are in a half chair conformation
(Table 1). A more detailed conformational analysis is given in
B
In eqn (1), the constant m is the Bohr magneton, g is the g-
Table S14 (ESI†).
tensor, B is the magnetic eld vector and S is the spin operator.
Hyperne interaction between electron spin S ¼ 1/2 and nuclear
spin I ¼ 3/2 for Cu(II) ion was not detected probably due to weak
interactions between Cu(II) ions (the nearest Cu/Cu distances
Magnetic properties
1a–b, 2a–c, 3a–c were investigated by X-band electron spin/
˚
are around 6.5 A). For octahedral Co(II) ions in the high-spin
paramagnetic resonance (ESR/EPR) spectroscopy.
state S ¼ 3/2, it is assumed that magnetic anisotropy is very
Ni(II) complexes (2a, 2b and 2cRT, 2cLT (<220 K)) were ESR
silent i.e. from room down to 4 K no ESR signal was detected.
This effect could be related to a high value of the zero-eld
splitting (ZFS) parameter of the Ni(II) ion or with the spin-
relaxation phenomena. Additionally, it is also possible that,
due to Jahn–Teller distortion, Ni(II) ions have a low-spin
conguration (S ¼ 0), instead of high-spin (S ¼ 1) expected
for octahedral complexes.
large and therefore only the lowest states (m ¼ 1/2 and m ¼ ꢁ1/
50
2
) are thermally occupied. As a result only one ESR line with
51
very anisotropic g-values is observed. Also, hyperne interac-
tion for Co(II) ions were not detected. Therefore, the spectra for
both Cu(II) and Co(II) ions were simulated using anisotropic g-
tensor and allowing only linewidth for assumed Lorentzian
lineshape to change with temperature. The obtained g-values,
together with the parameters used for the simulations, are given
in Table S15 (ESI†). For 3a and 3b complexes, it was necessary to
include gstrain values in the simulation. Namely, small varia-
tions in the local geometry in Cu(II) octahedra can cause
distribution of ESR parameters around some average g-values,
47
Representative spectra of 1a, 3a and 3c, obtained at several
selected temperatures, are shown in Fig. 5 while the corre-
sponding spectra of 1b and 3b are shown in Fig. S16, ESI.†
The simulation of the spectra was performed by EasySpin
48
soware using the following form of the spin-Hamiltonian for
52
described by the gstrain parameter. This effect is not observed
49
Cu(II) and Co(II) ions:
for 1a and 1b complexes because of their very broad ESR lines.
The obtained g-values are the same for 3a and 3b complexes, as
expected due to their similar crystal structures. Here obtained
results for the g-values are in agreement with the g-values for
49–51,53
Cu(II) and Co(II) ions that can be found in the literature.
Contrary to the paramagnetic behaviour of 1a, 1b, 3a and 3b
samples, 3c shows the most interesting magnetic behaviour,
due to its linear 1D structure which contains dinuclear copper
4
ꢁ
˚
units [Cu I ] (Cu/Cu distance in the dimer is 3.2057 A).
2
6
Beside the unusual ESR spectra, it was noticed that when the
compound was heated from 5 K to 78 K, the spectra show
different patterns compared to the spectra recorded when the
compound was cooled from 78 K to 5 K, Fig. 5. This observation
points to possible interesting magnetic behaviour of this
compound. Further investigation of 3c should also include
magnetic susceptibility measurement.
Biological assays
Antiproliferative activities of 1a and 3a were tested on human
lung (H 460), breast (MCF-7) and colon carcinoma (HCT116) cell
lines (paragraph biological activity in the ESI†). The tested
compounds showed moderate antiproliferative activity towards
the MCF-7 cell line, and minor to negligible activity towards
HCT116 and H 460 cell lines. However, the effects of the two
compounds were almost identical, pointing to negligible
structural inuence on their biological/antitumor activity (Table
S16, ESI†).
Experimental
Materials and methods
Fig. 5 Experimental (red lines) and simulated (black lines) ESR spectra of
polycrystalline samples of the investigated complexes. The ESR intensities
of the spectra at different temperatures are presented in the real ratios.
The narrow lines labeled with asterisks originate from the ESR cavity.
All chemicals for the syntheses were purchased from commer-
cial sources (Aldrich, Acros or Alfa Aesar) and used as received
without further purication. Glycinamide hydrochloride was
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prepared by aminolysis of chloroacetamide according to the
method of E. Fischer. CHN analyses were performed on a Per-
Preparation of complex compounds
[Co(H O) (HL) ]Cl (1a). Cobalt(II) chloride hexahydrate
54
2
2
2
2
kinElmer 2400 Series II CHNS analyzer in the Analytical Services (0.24 g, 1.0 mmol), glycinamide hydrochloride (0.22 g, 2.0
Laboratories of the RuCer Bo ˇs kovi ´c Institute, Zagreb, Croatia. The mmol) and sodium bicarbonate (0.15 g, 1.8 mmol) were mixed
ꢁ
1
IR spectra were obtained in the range 4000–450 cm on a Per- in 10 mL of water. The mixture was stirred for few minutes, until
kinElmer Spectrum Two™ FTIR-spectrometer in the ATR mode. the effervescence subsided, and was le to stand at room
TGA measurements were performed at a heating rate of temperature. Rose-red crystals, suitable for X-ray structural
ꢀ
ꢁ1
ꢀ
1
0 C min in the temperature range of 25–800 C, under an analysis, were obtained. Anal. calc. for C H N O Cl Co: C
4 16 4 4 2
ꢁ
1
e
oxygen ow of 100 mL min on a Mettler-Toledo TG/SDTA 851
15.30, H 5.14, N 17.84%. Found: C 15.42, H 4.66, N 17.83%. IR
ꢁ
1
instrument. Approximately 5–10 mg of each sample was placed in (ATR, cm ): 3424(w), 3277(s), 3245(s), 3129(m), 2956(w),
a standard alumina crucible (70 mL). The NMR spectra of the 2929(w), 2781(w), 1665(vs), 1595(s), 1461(m), 1422(m), 1343(w),
ligand were recorded on a Bruker AV 600 spectrometer, operating 1313(w), 1196(w), 1134(vs), 1043(s), 944(w), 858(w), 767(w),
1
at 600.130 MHz for the H nucleus and at 150.903 MHz for the 656(s), 601(s), 545(w), 488(w).
1
3
C nucleus. The samples of the ligand were measured in DMSO-
solutions at 298 K, using 5 mm NMR tubes. The chemical mmol), glycinamide hydrochloride (0.22 g, 2.0 mmol) and
shis in ppm were referenced to TMS.
sodium bicarbonate (0.15 g, 1.8 mmol) were mixed in 10 mL of
[Co(H O) (HL) ]Br1.06Cl0.94 (1b). Cobalt(II) bromide (0.22 g, 1.0
2 2 2
d
6
The ESR measurements were performed on a Bruker Elexsys water. The mixture was stirred for few minutes, until the effer-
80 FT/CW spectrometer from room down to liquid helium vescence subsided, and was le to stand at room temperature.
5
temperature. The microwave frequency was around 9.7 GHz Rose-red crystals, suitable for X-ray structural analysis, were
with the magnetic eld modulation amplitude of 0.5 mT and obtained. Anal. calc. for C H N O Br1.06Cl0.94Co: C 13.32, H
4
16 4 4
modulation frequency of 100 kHz. 3a and 3b complexes, due to 4.47, N 15.53%. Found: C 13.31, H 3.98, N 15.34%. IR
55
ꢁ1
observed passage effect at low temperatures, were recorded (ATR, cm ): 3428(w), 3272(s), 3243(s), 3144(m), 2951(w),
with modulation amplitude of 0.1 mT and modulation 2925(w), 2771(w), 1659(vs), 1586(s), 1455(m), 1417(m), 1340(w),
frequency of 1 kHz.
1312(w), 1193(w), 1129(s), 1040(s), 939(w), 856(w), 754(w),
35(s), 587(s), 542(w), 488(w).
Co(H O) (HL) ]I (1c). Cobalt(II) acetate dihydrate (0.108 g,
6
[
2
2
2 2
Synthetic procedures
0.5 mmol), glycinamide hydrochloride (0.111 g, 1.0 mmol) and
potassium iodide (0.166 g, 1.0 mmol) were mixed in 10 mL of
water. Pink crystals, suitable for X-ray structural analysis, were
obtained. Anal. calc. for C H N O I Co: C 9.67, H 3.25, N
Preparation of glycinamide hydrochloride, H LCl and H LI
b-H LCl. CAUTION – the experiment should be performed in
2
a fume hood!
2
2
4
16 4 4 2
ꢁ
1
1
3
1.27%. Found: C 9.72, H 3.41, N 11.25%. IR (ATR, cm ):
335(s), 3317(s), 3273(s), 3242(s), 3145(s), 2929(m), 2784(w),
Chloroacetamide (18.6 g; 0.2 mol) was mixed with a concen-
trated ammonia solution (200 mL) and the mixture was heated
ꢀ
1662(s), 1596(s), 1461(m), 1420(m), 1312(m), 1193(w), 1131(m),
1042(s), 940(w), 853(w), 766(w), 658(m), 596(m), 544(w), 493(w).
at 100 C for 30 min. The reaction mixture was then concen-
ꢀ
trated at z80 C‡ until the product started to crystallize (the
[
Ni(H
2
O)
2
(HL)
2
]Cl
2
(2a). Nickel(II) chloride hexahydrate

nal volume was about 20–30 mL) and immediately mixed with
(0.24 g, 1.0 mmol), glycinamide hydrochloride (0.22 g, 2.0
ethanol (200 mL). The reaction mixture was le to stand over-
night in a refrigerator and the product was ltered off, washed
with ethanol (50 mL) and air-dried. Additional amount of the
product can be obtained by evaporation of the ltrate at room
temperature.§ When prepared in this manner, the product can
be used without any further purication.
mmol) and sodium bicarbonate (0.15 g, 1.8 mmol) were mixed
in 10 mL of water. The mixture was stirred for few minutes, until
the effervescence subsided, and was le to stand at room
temperature. Light blue crystals, suitable for X-ray structural
analysis, were obtained. Anal. calc. for C
4 16 4 4 2
H N O Cl Ni: C
ꢀ
1
15.31, H 5.14, N 17.86%. Found: C 15.27, H 4.68, N 17.74%. IR
White crystals, yield: 16.8 g (76%); mp 210 C. H NMR
ꢁ
1
a
(ATR, cm ): 3432(w), 3285(s), 3250(s), 3114(m), 2958(w),
2933(w), 2786(w), 1677(vs), 1595(s), 1463(m), 1422(m), 1341(w),
1313(w), 1193(w), 1134(s), 1042(s), 946(w), 860(w), 768(w),
(
DMSO-d , d, ppm): 3.50 (s, 2H) CH , 7.49 (s, br, 1H) NH , 8.05
6
2
b
+ 13
(s, br, 1H) NH , 8.27 (s, br, 3H) NH . C NMR (DMSO-d , d,
3
6
ꢁ
1
2 2
ppm): 39.85 CH , 167.66 CONH . IR (ATR, cm ): 3364(w),
659(s), 605(s), 548(w), 495(w).
3
1
1
263(w), 3184(w), 2997(m), 2893(w), 2773(w), 2566(w), 1688(s),
594(m), 1578(m), 1464(s), 1417(s), 1314(s), 1151(w), 1093(m),
038(m), 891(s), 826(m), 528(w), 479(w).
[
Ni(H O) (HL) ]Br0.94Cl1.06 (2b). Nickel(II) bromide (0.22 g, 1.0
2
2
2
mmol), glycinamide hydrochloride (0.22 g, 2.0 mmol) and
sodium bicarbonate (0.15 g, 1.8 mmol) were mixed in 10 mL of
water. The mixture was stirred for few minutes, until the effer-
vescence subsided, and was le to stand at room temperature.
Light blue crystals, suitable for X-ray structural analysis, were
H
2
LI. Green crystals of H
2
LI were obtained from a solution
LCl (0.110 g, 1.0 mmol)
containing CoI (0.156 g, 0.5 mmol), H
2
2
and NaHCO (0.076 g, 0.9 mmol) and 10 mL of water in a very
3
low yield. Crystals decomposed aer several weeks.
obtained. Anal. calc. for C
4 16 4 4
H N O Br0.94Cl1.06Ni: C 13.51, H
4
.53, N 15.75%. Found: C 13.66, H 4.06, N 15.81%. IR
‡
The reaction mixture becomes orange-coloured when overheated, leading to
a very impure yellow-orange product which is not easily puried.
Crystals obtained by slow evaporation of the ltrate were suitable for X-ray 2927(w), 2778(w), 1663(vs), 1592(s), 1458(m), 1418(m), 1338(w),
structural analysis.
ꢁ
1
(ATR, cm ): 3437(w), 3280(s), 3247(w), 3142(m), 2956(w),
§
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1
6
312(w), 1191(w), 1131(s), 1040(s), 941(w), 858(w), 755(w), X-ray crystallography
40(s), 592(s), 544(w), 495(w).
The single-crystal X-ray diffraction data of b-H LCl, H LI, 1a–c,
2
2
[
Ni(H O) (HL) ]I , (2cRT). Nickel(II) iodide (0.31 g, 1.0 mmol),
2 2 2 2
2
a, 2b, 2cLT, 2cRT, 3a–c were collected by u-scans on an Oxford
Diffraction Xcalibur3 CCD diffractometer with graphite-
monochromated MoK radiation. Data reduction was per-
glycinamide hydrochloride (0.22 g, 2.0 mmol), sodium bicar-
bonate (0.15 g, 1.8 mmol) were mixed in 10 mL of water. Blue
crystals, suitable for X-ray structural analysis, were obtained.
a
56
formed using the CrysAlis soware package. Solution, rene-
ment and analysis of the structures were done using the
programs integrated in the WinGX system. All structures were
Anal. calc. for C
4 16 4 4 2
H N O I Ni: C 9.67, H 3.25, N 11.28%. Found:
ꢁ
1
C 9.35, H 3.64, N 11.40%. IR (ATR, cm ): 3343(s), 3322(s),
57
3
1
9
275(s), 3179(s), 2939(m), 2758(w), 1646(s), 1596(s), 1575(s),
461(m), 1411(m), 1318(m), 1297(m), 1193(w), 1120(m), 1036(s),
35(w), 846(w), 766(w), 682(m), 594(s), 556(m), 505(m).
solved by the direct methods using SHELXS and the renement
procedure was performed by the full-matrix least-squares
2
58,59
method based on F against all reections using SHELXL.
[
CuCl (HL) ] (3a). Copper(II) chloride dihydrate (0.17 g, 1.0
2 2
The non-hydrogen atoms were rened anisotropically. All
hydrogen atoms were located in the difference Fourier maps.
Because of poor geometry for some of them they were placed in
calculated positions and rened using the riding model. In
structures 1b, 2b and 3b bromide and chloride ions statistically
occupy almost the same site (slightly longer distances are
associated with the bromide ion). Displacement parameters of
these ions were restrained to the same values. Occupancies were
rened to the nal ratios Br/Cl: 1.06 : 0.94 in 1b, 0.94 : 1.06 in
mmol), glycinamide hydrochloride (0.22 g, 2.0 mmol) and
sodium bicarbonate (0.15 g, 1.8 mmol) were mixed in 10 mL of
water. The mixture was stirred for few minutes, until the effer-
vescence subsided, and was le to stand at room temperature.
Dark blue crystals, suitable for X-ray structural analysis, were
obtained. Anal. calc. for C H N O Cl Cu: C 17.00, H 4.28, N
4
16
4
2
2
ꢁ
1
19.82%. Found: C 17.18, H 3.81, N 19.82%. IR (ATR, cm ):
3290(m), 3217(w), 3144(m), 2987(w), 2953(w), 2757(w), 1674(m),
1632(vs), 1579(vs), 1462(m), 1416(m), 1343(m), 1290(w),
1180(w), 1122(vs), 1101(vs), 1056(m), 948(m), 857(w), 777(m),
692(s), 651(s), 563(m), 509(m), 460(m).
2
b, and 1.3 : 0.7 in 3b. Geometrical calculations were done
60
using PLATON. Drawings of the structures were prepared
61
using PLATON and MERCURY program. The crystallographic
data are summarized in Tables S2 and S5, see ESI.†
2
[CuBr1.3Cl0.7(HL) ] (3b). Copper(II) bromide (0.22 g, 1.0
mmol), glycinamide hydrochloride (0.22 g, 2.0 mmol) and
sodium bicarbonate (0.15 g, 1.8 mmol) were mixed in 10 mL of
water. The mixture was stirred for few minutes, until the effer-
vescence subsided, and was le to stand at room temperature.
Dark blue crystals, suitable for X-ray structural analysis, were
Crystal data for b-H LCl. C H N OCl, M ¼ 110.55, mono-
2
2
7 2
˚
clinic, a ¼ 4.6688(9), b ¼ 6.2057(13), c ¼ 8.898(2) A, b ¼
ꢀ
˚
3
1
(
0
0
01.486(19) , V ¼ 252.65(10) A , T ¼ 293 K, space group P2
1
/m
no. 11), Z ¼ 2, 1268 reections measured, 543 unique (Rint
¼
2
.024). Final R(F, I > 2s(I)) value was 0.0369, wR
.0977, S ¼ 1.09. CCDC 1915366.†
2
(F , I > 2s(I)) ¼
obtained. Anal. calc. for C
4 16 4 2
H N O Br1.3Cl0.7Cu: C 14.11, H
3.55, N 16.46%. Found: C 13.97, H 4.18, N 16.18%. IR
Crystal data for H
2
LI. C
2
H
7
N
2
OI, M ¼ 202.00, orthorhombic,
ꢁ
1
(ATR, cm ): 3282(m), 3209(w), 3137(m), 2981(w), 2949(w),
3
˚
˚
a ¼ 4.6880(1), b ¼ 18.6082(4), c ¼ 6.7363(2) A, V ¼ 587.64(2) A , T
2
1
8
746(w), 1669(m), 1633(vs), 1572(vs), 1456(m), 1415(m),
339(m), 1290(w), 1177(w), 1118(vs), 1100(vs), 1055(m), 946(m),
52(w), 755(m), 677(s), 646(s), 560(m), 506(m), 460(m).
¼
295 K, space group Pbcm (no. 57), Z ¼ 4, 4855 reections
measured, 929 unique (R ¼ 0.023). Final R(F, I > 2s(I)) value was
int
2
0
.0188, wR
2
(F , I > 2s(I)) ¼ 0.0430, S ¼ 1.11. CCDC 1915367.†
II
I
{
[Cu (HL) ] [Cu I ]} (3c). Copper(II) chloride dihydrate
2 2 2 6 n
Crystal data for 1a. C
4
H
16
N
4
O
4
CoCl
2
, M ¼ 314.04, tetragonal,
(0.17 g, 1 mmol), glycinamide hydrochloride (0.22 g, 2.0 mmol)
˚
a ¼ 11.3145(2), b ¼ 11.3145(2), c ¼ 37.9735(8) A, V ¼ 4861.3(2)
and sodium bicarbonate (0.15 g, 1.8 mmol) were mixed in 10 mL
of water. Aer the effervescence subsided, solid potassium
iodide (0.35 g, 2 mmol) was added into the solution. The colour
changed from dark blue to olive-green, leading to brown crys-
tals, suitable for X-ray structural analysis. Anal. calc. for C4-
3
˚
A , T ¼ 293 K, space group I4
1
cd (no. 110), Z ¼ 16, 26 763
reections measured, 2660 unique (Rint ¼ 0.024). Final R(F, I >
2
2
s(I)) value was 0.0169, wR (F , I > 2s(I)) ¼ 0.0426, S ¼ 1.13.
2
CCDC 1915368.†
Crystal data for 1b. C H N O CoBr1.06Cl0.94, M ¼ 360.88,
4
16 4 4
H N O I Cu : C 7.32, H 1.84, N 8.54%. Found: C 7.44, H 2.12, N
1
2
4
2 3
2
˚
tetragonal, a ¼ 11.3708(2), b ¼ 11.3708(2), c ¼ 38.3225(14) A, V ¼
ꢁ1
8.36%. IR (ATR, cm ): 3380(m), 3310(vs), 3267(vs), 3201(s),
3119(s), 2953(w), 2912(w), 1672(m), 1644(vs), 1555(vs), 1457(m),
1401(m), 1321(w), 1293(w), 1174(w), 1108(s), 1054(m), 1034(m),
929(w), 852(w), 687(w), 620(m), 583(m), 548(m), 480(m).
3
˚
4
954.9(3) A , T ¼ 150 K, space group I4
1
cd (no. 110), Z ¼ 16,
1
5 188 reections measured, 2501 unique (Rint ¼ 0.036). Final
2
R(F, I > 2s(I)) value was 0.0238, wR
.03. CCDC 1915361.†
2
(F , I > 2s(I)) ¼ 0.0538, S ¼
1
Crystal data for 1c. C H N O CoI , M ¼ 496.94, ortho-
4
16
4
4
2
˚
rhombic, a ¼ 7.3966(4), b ¼ 19.1784(8), c ¼ 10.1512(4) A, V ¼
Crystallization of complex compounds
3
˚
1
4
440.00(11) A , T ¼ 150 K, space group Pnma (no. 62), Z ¼ 4,
All compounds crystallized from aqueous solutions by slow
evaporation of solvent at room temperature. 1a, 1b, 2a, 2b, 3a,
and 3b crystalized aer several days. Coordination polymer 3c
crystallized within minutes upon addition of potassium iodide
due to very low solubility. On the other hand, 1c and 2cRT are
highly soluble in water, hence crystallization occurred aer
several months.
648 reections measured, 1606 unique (Rint ¼ 0.042). Final R(F,
2
I > 2s(I)) value was 0.0327, wR
CCDC 1915362.†
2
(F , I > 2s(I)) ¼ 0.0602, S ¼ 1.03.
Crystal data for 2a. C
4
H
16
N
4
O
4
NiCl
2
, M ¼ 313.82, tetragonal,
3
˚
˚
a ¼ 11.2394(5), b ¼ 11.2394(5), c ¼ 37.594(4) A, V ¼ 4749.0(7) A , T
¼
150 K, space group I4 cd (no. 110), Z ¼ 16, 21 338 reections
1
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Paper
measured, 4042 unique (Rint ¼ 0.030). Final R(F, I > 2s(I)) value 1 : 1 (1.06 : 0.94 in Co(II) complexes; 0.94 : 1.06 in Ni(II)
2
was 0.0269, wR (F , I > 2s(I)) ¼ 0.0592, S ¼ 1.08. CCDC 1915364.† compounds). Copper(II) ion, on the other hand, has slightly more
2
Crystal data for 2b. C H N O NiBr Cl , M ¼ 355.61, preference towards the bromide ion, which resulted in Br to Cl
4
16
4
4
0.94 1.06
˚
tetragonal, a ¼ 11.3175(3), b ¼ 11.3175(3), c ¼ 38.0842(14) A, V ¼ ratio 1.3 : 0.7. Copper showed interesting chemical behavior in
3
˚
4
1
878.1(3) A , T ¼ 150 K, space group I4
1
cd (no. 110), Z ¼ 16, reaction of copper(II) ions, glycinamide and iodide ions. Cop-
1 070 reections measured, 2662 unique (Rint ¼ 0.028). Final per(II) was partially reduced to copper(I) and the coordination
2
R(F, I > 2s(I)) value was 0.0223, wR
2
(F , I > 2s(I)) ¼ 0.0485, S ¼ polymer 3c was formed with mixed oxidation states of copper. 1D
polymer 3c contains double chains of copper(II) coordinated by
1
.10. CCDC 1915369.†
Crystal data for 2cRT. C
4
H
16
N
4
O
4
NiI
2
, M ¼ 496.72, ortho- two glycinamide ligands in a cis conguration bridged by
4ꢁ
˚
rhombic, a ¼ 7.5456(3), b ¼ 18.9706(7), c ¼ 10.1902(3) A, V ¼ [Cu I ] species. 3c also showed possible interesting magnetic
2
6
3
˚
1
458.67(9) A , T ¼ 295 K, space group Pnma (no. 62), Z ¼ 4, 5770 properties which will be investigated in more details in further
reections measured, 1626 unique (R ¼ 0.024). Final R(F, I > research. 1a and 3a were tested for antiproliferative activity. Both
int
2
2
s(I)) value was 0.0299, wR
2
(F , I > 2s(I)) ¼ 0.0698, S ¼ 1.09. compounds showed no activity towards HCT116 and H 460 cell
ꢁ
3
CCDC 1915363.†
lines, but moderate activity (GI50 just above 10 mmol dm ) and
Crystal data for 2cLT. C
4
H
16
N
4
O
4
NiI
2
, M ¼ 496.72, mono- selectivity was found towards the MCF-7 cell line.
˚
clinic, a ¼ 7.2589(7), b ¼ 10.3706(10), c ¼ 19.2258(17) A, b ¼
CCDC 1915361–1915372 contain the supplementary crystal-
ꢀ
˚
3
9
8.742(9) , V ¼ 1430.5(2) A , T ¼ 150 K, space group I2/a (no. 15), lographic data for this paper.†
Z ¼ 4, 2506 reections measured, 2506 unique (R ¼ 0.038).
int
2
Final R(F, I > 2s(I)) value was 0.0353, wR (F , I > 2s(I)) ¼ 0.1020, S
2
Conflicts of interest
¼
1.19. CCDC 1915370.†
Crystal data for 3a. C
4
H
12
N
4
O
2
CuCl
2
, M ¼ 282.62, mono- There are no conicts of interest to declare.
˚
clinic, a ¼ 6.8813(2), b ¼ 7.7420(2), c ¼ 9.2635(2) A, b ¼
ꢀ
˚
3
1
1
0
0
01.779(3) , V ¼ 483.12(2) A , T ¼ 293 K, space group P2
1
/n (no.
Acknowledgements
4), Z ¼ 2, 11 873 reections measured, 1159 unique (Rint
¼
2
.016). Final R(F, I > 2s(I)) value was 0.0151, wR
.0479, S ¼ 0.98. CCDC 1915371.†
2
(F , I > 2s(I)) ¼ Financial support by the Croatian Science Foundation (grant no.
IP-2014-09-4274 and IP-2018-01-3168) is gratefully acknowledged.
Crystal data for 1b. C H N O CuBr1.3Cl0.7, M ¼ 340.41, The authors are grateful to Dr Marijeta Kralj and Dr Lidija Uzelac
4
12 4 2
˚
monoclinic, a ¼ 7.0098(5), b ¼ 7.8128(3), c ¼ 9.4100(5) A, b ¼ for testing compounds for antiproliferative activity.
ꢀ
˚
3
1
1
0
0
01.963(6) , V ¼ 504.16(5) A , T ¼ 293 K, space group P2
1
/n (no.
4), Z ¼ 2, 4025 reections measured, 1092 unique (Rint
¼
Notes and references
2
.028). Final R(F, I > 2s(I)) value was 0.0238, wR
.0571, S ¼ 1.12. CCDC 1915372.†
2
(F , I > 2s(I)) ¼
1 C. Kutzscher, P. M u¨ ller, S. Raschke and S. Kaskel, in The
Chemistry of Metal–Organic Frameworks: Synthesis,
Characterization, and Applications, ed. S. Kaskel, Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim, 1st edn, 2016, Chiral
Linker Systems, pp. 387–418.
Crystal data for 3c. C
4
H
12
N
4
O
2
Cu
2
I
3
, M ¼ 655.96, triclinic,
˚
a ¼ 8.0185(4), b ¼ 8.6901(4), c ¼ 11.0929(5) A, a ¼ 84.575(4), b ¼
ꢀ
˚
3
7
7.367(4), g ¼ 72.679(4) , V ¼ 719.69(6) A , T ¼ 293 K, space
ꢀ
group P1 (no. 2), Z ¼ 2, 7861 reections measured, 3084 unique
2
ˇ
´
´
(R
int ¼ 0.039). Final R(F, I > 2s(I)) value was 0.0259, wR
2
(F , I >
2 I. Dokmani ´c , M. Sikic and S. Tomic, Acta Crystallogr., Sect. D:
2
s(I)) ¼ 0.0686, S ¼ 0.84. CCDC 1915365.†
Biol. Crystallogr., 2008, 64(3), 257–263.
3
4
P. J. Almhjell and J. H. Mills, Curr. Opin. Struct. Biol., 2018,
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K. U ˇz arevi ´c , I. Halasz, I. Đilovi ´c , N. Bregovi ´c , M. Rub ˇc i ´c ,
5
Conclusions
D. Matkovi ´c -Calogovic and V. Tomisic, Angew. Chem., Int.
ˇ
´
ˇ ´
New cobalt(II), nickel(II) and copper(II) compounds with glyci-
namide were prepared and characterized by X-ray crystallog-
raphy, IR spectroscopy and thermal analysis.
Cobalt(II) and nickel(II) compounds 1a–1c and 2a–2c have an
analogous chemical composition, [M(HL) (H O) ]X . In these
compounds two glycinamide ligands coordinate Co(II) or Ni(II)
ions in the N,O-bidentate chelating mode arranged in a cis-
conguration, while water molecules occupy the axial coordina-
tion sites. Halide ions are counter-ions in all six mentioned
complexes. Copper compounds 3a and 3b are trans isomers with
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