One-dimensional coordination polymers in the crystal structures of sodium and potassium acetylacetonates

Article abstract of DOI:10.1016/j.poly.2015.03.003

Abstract The mixed ligand complexes [K₂(acac)₂(H₂O)]_∞ (I), [K₂(acac)₂(phen)(H₂O)]_∞ (II), [Na(acac)(H₂O)]_∞ (III), [Na₃(acac)₃(ⁱPrOH)]_∞ (IV), [Na₃(acac)₃(Py)]_∞ (V) and [Na₂(acac)₂(phen)]_∞ (VI) (Hacac = pentane-2,4-dione; phen = 1,10-phenanthroline; ⁱPrOH = iso-propanol; Py = pyridine) were synthesized by the reaction of the alkaline metal tert-butyloxide in dried solvent (ⁱPrOH, benzene or Py) with Hacac and phen. The products were characterized by elemental analysis, ¹H NMR and FTIR spectroscopy, and thermal analysis. The single-crystal structures were determined for the novel compounds II, IV and VI, and refined for I. The structures of I-VI consist of one-dimensional polymeric chains or ribbons which are described as a combination of formal binuclear structural blocks, [M₂(acac)₂], of four types. Quantum chemical calculations on the four isomers of [M₂(acac)₂] allowed us to explain different stabilities of the formal building blocks with M = Na and K.

Full text of DOI:10.1016/j.poly.2015.03.003

Accepted Manuscript
One-dimensional coordination polymers in the crystal structures of sodium and
potassium acetylacetonates
Dmitry M. Tsymbarenko, Igor E. Korsakov, Konstantin A. Lyssenko, Sergey I.
Troyanov
PII:
S0277-5387(15)00133-3
DOI:
http://dx.doi.org/10.1016/j.poly.2015.03.003
POLY 11226
Reference:
Polyhedron
To appear in:
Received Date:
Accepted Date:
11 August 2014
1 March 2015
Please cite this article as: D.M. Tsymbarenko, I.E. Korsakov, K.A. Lyssenko, S.I. Troyanov, One-dimensional
coordination polymers in the crystal structures of sodium and potassium acetylacetonates, Polyhedron (2015), doi:
http://dx.doi.org/10.1016/j.poly.2015.03.003
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One-dimensional coordination polymers in the crystal structures of sodium and potassium
acetylacetonates
Dmitry M. Tsymbarenko1*, Igor E. Korsakov1, Konstantin A. Lyssenko2, Sergey I. Troyanov1
1Lomonosov Moscow State University, Leninskie gory, 1-3, 119991, Moscow, Russia
2Nesmeyanov Institute of Organoelement Compounds, Vavilova St. 28, 119991, Moscow, Russia
The mixed ligand complexes [K2(acac)2(H2O)]∞ (I), [K2(acac)2(phen)(H2O)]∞ (II),
[Na(acac)(H2O)]∞ (III), [Na3(acac)3(iPrOH)]∞ (IV), [Na3(acac)3(Py)]∞ (V) and [Na2(acac)2(phen)]∞
i
(VI) (Hacac = pentane-2,4-dione; phen = 1,10-phenanthroline; PrOH = iso-propanol; Py =
pyridine) were synthesized by the reaction of the alkaline metal tert-butyloxide in dried solvent
(iPrOH, benzene or Py) with Hacac and phen. The products were characterized by elemental
1
analysis, H NMR and FTIR spectroscopy, and thermal analysis. The single-crystal structures were
determined for the novel compounds II, IV and VI, and refined for I. The structures of I-VI consist
of one-dimensional polymeric chains or ribbons which are described as a combination of formal
binuclear structural blocks, [M2(acac)2], of four types. Quantum chemical calculations on the four
isomers of [M2(acac)2] allowed us to explain different stabilities of the formal building blocks with
M = Na and K.
Keywords: Sodium; Potassium; Acetylacetone; Beta-diketone; X-ray Crystal Structure;
Coordination polymer; Mixed-ligand complex; Quantum chemical calculations.
*Corresponding author:
E-mail address: tsymbarenko@inorg.chem.msu.ru
Phone: +7 495 9390029, Fax: +7 495 9391492

Introduction
Metal β-diketonates and their mixed-ligand complexes with different ancillary neutral ligands
have successfully been used as precursors for vapor thin film deposition of functional materials [1-
3] for the last thirty years. The advantages of β-diketonate complexes as precursors results from the
easy control of the solubility or volatility by variation of substitutions and the introduction of
different ancillary ligands. A great number of excellent experimental and theoretical works devoted
to the synthesis, characterization and application of β-diketonates of transition metals [1], rare earth
elements [2,4-5] and even alkaline earth elements [6-8] have been published describing the variety
of superconductors, ferroelectric and magnetic thin films, etc. Among these functional materials
there are a lot of alkaline metal-containing ones, such as K1-xNaxNbO3 [9-10], La1-xKyMnO3 [11],
La1-xNayMnO3 [12] and (K, Rb, Cs)VO3 [13]. However, the chemistry of alkaline metal β-
diketonates as precursors is practically unexplored. These complexes were not even mentioned in
the comprehensive review by Fromm [14]. Besides, the capabilities of mixed-ligand complex
formation with neutral donor ligands have not been studied systematically, despite this being an
important approach to property modification. Only a few works devoted to the synthesis and
structures of alkaline metal β-diketonates have been reported. The known crystal structures of
sodium and potassium acetylacetonates hydrates were determined in 1970-80s [15,16]. In the case
of [K2(acac)2(H2O)], the crystal structure determination was performed at room temperature by a
photo method with low accuracy.
Examples of mixed-ligand complexes of sodium and potassium β-diketonates with organic
ligands are also very limited. Practically all the known crystal structures were determined for
incidental single-crystals: [Na4(bta)4(pypzH)2] (pypzH = 2-(3-pyrazonyl)pyridine) [18], [K(hfa)(18-
crown-6)]∞ [20], [K(Etacac)(18-crown-6)] [21] (Etacac
[Na(Etacac)(15-crown-5)] [22], [Na(hfa)(15-crown-5)]
=
C2H5OC(O)CHC(O)CH3),
(hfa 1,1,1,5,5,5-
=
hexafluoroacetylacetonate) [23]; and polymer structures of [Na3(acac)3(Py)]∞ [17] and
[Na(bzac)(HOC2H4OH)]∞ (bzac = benzoylacetonate) [19]. Most of these compounds were
characterized only by X-ray diffraction, without detailed analysis of their bulk properties.
1
Here we report a systematic study of the synthesis, X-ray crystal structures, IR and H NMR
spectroscopy data, thermal analysis and quantum chemical calculations for [K2(acac)2(H2O)]∞ (I),
[K2(acac)2(phen)(H2O)]∞
(II),
[Na(acac)(H2O)]∞
(III),
[Na3(acac)3(iPrOH)]∞
(IV),
[Na3(acac)3(Py)]∞ (V) and [Na2(acac)2(phen)]∞ (VI). The compounds II, IV and VI have not been
reported previously; in addition, we have determined the structure of I with a higher accuracy.

2. Experimental
2.1 Synthesis
All the chemical reagents and solvents were preliminarily purified. Acetylacetone was distilled
under reduced pressure and dried over 3Å molecular sieves. 1,10-Phenanthroline (Aldrich, 99%
purity) and the sodium and potassium tert-butyloxides (ChemPur, 95-99%) were purified by
sublimation in a vacuum (at 130 and 165 oC). Iso-propanol was dried by boiling with aluminum iso-
propylate under reflux and distilled. Benzene was conventionally dried by mixing with anhydrous
H2SO4 and distilled. Pyridine was dried over KOH and distilled over BaO. All solvents were stored
over 3 and 4Å molecular sieves under Ar.
2.1.1 K2(acac)2(H2O) (I) and Na(acac)(H2O) (III)
A solution of Hacac (2 mmol, 0.200 g) in iso-propanol (2 ml) was added to MOtBu (2 mmol,
0.192 or 0.224 g for M = Na or K) dissolved in iso-propanol (8 ml) under continuous stirring at 50
°C. The reaction mixture was cooled to room temperature and the colorless crystalline precipitate
that formed was isolated by filtration and dried in a vacuum. Yield: 80-90%. All operations were
carried out in air. X-ray quality single crystals were grown by slow recrystallization from iso-
propanol.
1
Anal. Calc for C10H16K2O5: C, 40.8; H, 5.5. Found: C, 40.6; H, 5.6. H NMR (d6-acetone, δ ppm):
5.1 (broad, 1H, CHacac), 1.8 (s, 6H, CH3 acac). IR (cm−1): 3500-3100 ν(O−H); 3064, 2991, 2963,
2919 ν(C−H); 1724 δ(H2O); 1617 ν(C=O); 1507 ν(C=C), δ(C=CH); 1459 δ(CH3), ν(C=Ο); 1408
ν(C=Ο), ν(C=C); 1358 δ(CH3); 1009 ρ(CH3); 908 ν(C−CH3); 760 π(C−Η); 655 πring
.
1
Anal. Calc. for C5H9O3Na: C, 42.9; H, 6.5; Found: C, 42.6; H, 6.5. H NMR (d6-acetone, δ ppm):
5.0 (s, 1H, CHacac), 1.7 (s, 6H, CH3 acac). IR (cm−1): 3432 νas(O−H); 3326 νs(O−H); 3075, 2987,
2956, 2921 ν(C−H); 1669 δ(H2O); 1608 ν(C=O); 1509 ν(C=C), δ(C=CH); 1444 δ(CH3), ν(C=Ο);
1401 ν(C=Ο), ν(C=C); 1360 δ(CH3); 1010 ρ(CH3); 912 ν(C−CH3); 767 π(C−Η); 656 πring
.
2.1.2. Na3(acac)3(iPrOH) (IV) and Na3(acac)3(Py) (V)
A solution of Hacac (2 mmol, 0.200 g) in iso-propanol or pyridine (2 ml) was added to 2
mmol (0.192 g) of NaOtBu dissolved in iso-propanol/pyridine (8 ml) under continuous stirring at 50
°C. The reaction mixture was cooled down to room temperature and the solvent was evaporated
under reduced pressure. A colorless crystalline precipitate was isolated and dried in a vacuum. All
operations were carried out under a dry Ar atmosphere using Schlenk techniques. Yield: 80-90%.
The single crystals of Na3(acac)3(iPrOH) were grown by slow recrystallization from iso-propanol in
an evacuated sealed tube.
1
Anal. Calc. for C18H29O7Na3: C, 51.7; H, 7.0; Found: C, 51.5; H, 6.9. H NMR (d6-acetone, δ

ppm): 5.0 (s, 3H, CHacac), 3.9 (m, 1H, CHiPrOH), 3.4 (d, 1H, OH), 1.7 (s, 18H, CH3 acac), 1.1 (d, 6H,
CH3 iPrOH). IR (cm−1): 3435 ν(O−H); 3071, 2977, 2918, 2850 ν(C−H); 1615 ν(C=O); 1512 ν(C=C),
δ(C=CH); 1457 δ(CH3), ν(C=Ο); 1404, 1387 ν(C=Ο), ν(C=C); 1011 ρ(CH3); 911 ν(C−CH3); 767
π(C−Η); 656 πring; 1163, 1126, 1110, 816 (iPrOH).
1
Anal. Calc. for C20H26O6Na3N: C, 53.9; H, 5.8; N, 3.2; Found: C, 53.7; H, 5.9; N, 3.1. H
NMR (d6-acetone, δ ppm): 8.6 (s, 2H, CHPy), 7.8 (m, 1H, CHPy), 7.3 (m, 2H, CHPy), 5.0 (s, 3H,
CHacac), 1.7 (s, 18H, CH3 acac). IR (cm−1): 2989, 2959, 2937, 2919, 2851 ν(C−H); 1615 ν(C=O);
1512 ν(C=C), δ(C=CH); 1456 δ(CH3), ν(C=Ο); 1404, 1387 ν(C=Ο), ν(C=C); 1011 ρ(CH3); 912
ν(C−CH3); 766 π(C−Η); 660 πring; 3083, 3019, 3000, 1122, 1055, 705 (Py).
2.1.3 K2(acac)2(phen)(H2O) (II)
The solution of acetylacetone (1.98 mmol, 0.198 g) in iso-propanol (3 ml) was added to
KOtBu (1.89 mmol, 0.212 g) and 1,10-phenanthroline (0.99 mmol, 0.178 g) dissolved in the
mixture iso-propanol:benzene (1:1, 20 ml) under continuous stirring at 50°C. The reaction mixture
was cooled down to room temperature and small colorless crystals were obtained. Precipitate was
filtrated of and dried in vacuum. The single crystals were grown by slow recrystallization from iso-
propanol/benzene mixture.
Anal. Calc. for C22H24K2N2O5: C, 55.7; H, 5.1; N, 5.9. Found: C, 55.2; H, 5.1; N, 6.0. 1H NMR (d6-
Acetonte, δ ppm): 9.1 (q, 2H, CHphen), 8.5 (q, 2H, CHphen), 8.0 (s, 2H, CHphen), 7.8 (q, 2H, CHphen),
5.1 (broad, 1H, CHacac), 1.8 (s, 6H, CH3acac). IR (cm−1): 3414 νas(O−H); 3351 νs(O−H); 3055, 2977,
2956, 2915, 2852 ν(C−H); 1699 δ(H2O); 1617 ν(C=O); 1510 ν(C=C), δ(C=CH); 1465 δ(CH3),
ν(C=Ο); 1423 ν(C=Ο), ν(C=C); 1007 ρ(CH3); 902 ν(C−CH3); 753 π(C−Η); 650 πring; 1588, 1565,
1140, 1098, 843, 733, 708 (phen).
2.1.4 Na2(acac)2(phen) (VI)
Acetylacetone (1.66 mmol, 0.166 g) was added dropwise to NaOtBu (1.66 mmol, 0.159 g) and
1,10-phenanthroline (1.66 mmol, 0.299 g) dissolved in an iso-propanol:benzene mixture (1:1, 10
ml) under continuous stirring at room temperature. The reaction mixture was placed into a Λ-like
evacuated sealed tube and the solvent was slowly distilled off over 6 weeks. As a result, single
crystals of VI were obtained together with crystals of III, IV and phen as by-products.
2.2 Physical techniques
1H NMR spectra in d6-acetone with TMS as an internal standard were recorded using a Bruker
AVANCE-400 (400 MHz) spectrometer. FT-IR spectra in the 4000-650 cm-1 range were measured

on a Perkin-Elmer Spectrum One FTIR spectrometer in the Frustrated Total Internal Reflection
mode. TG curves were recorded on a Q-1500D Derivatograph (in air and N2 atmosphere) with a
10°/min heating rate. The C, H and N contents were determined by conventional elemental analysis.
Powder XRD data were collected using an Enraf-Nonius FR-552 Guinier-Johanson camera and
STOE Stadi P diffractometer (curved Ge monochromator, Cu-Kα1 radiation, λ = 1.54056 Å) at
room temperature.
Single crystal X-ray diffraction data were collected on Bruker SMART 1000 and Oxford X-
Calibur 2 diffractometers with CCD area detectors (the data were corrected for absorption by
SADABS [24] and ABSPACK [25]) and STOE IPDS with an imaging plate (without absorption
correction) using Mo Kα radiation (λ = 0.71073 Å, graphite monochromator). The crystal structures
were solved by direct methods and refined anisotropically for all non-H atoms with the full-matrix
F2 least-squares technique (SHELXTL PLUS) [26]. Hydrogen atoms of water molecules were
found in the difference Fourier synthesis; other H atoms were placed in geometrically calculated
positions. All hydrogen atoms were refined in a riding mode. Details of the data collection and
refinement parameters are summarized in Table 1.
2.3. Theoretical simulation
Quantum chemical calculations of the molecular geometries and ligand-to-metal bonding energies
were carried out in a framework of the Density Functional Theory (B3LYP) with the 6-31G(d) basis
set on all atoms in the Firefly 7.1.g package [27]. All geometry optimizations were performed
without any symmetry constrains in the C1 point group symmetry. The optimized molecular
geometries were checked by Hessian calculations. The system energy change values (∆E) due to
addition reactions (A+B = C) were calculated as:
∆E = EC – EA – EB - EBSSE
,
where EBSSE is the basis set superposition error, calculated by the Boys and Bernardi approach [28].

Table 1. Crystal and refinement data for the structures [K2(acac)2(H2O)]∞ (I), [K2(acac)2(phen)(H2O)]∞ (II),
[Na3(acac)3(iPrOH)]∞ (IV) and [Na2(acac)2(phen)]∞ (VI).
I
II
IV
VI
Formula
K2C10H14O4·(H2O) C22H24K2N2O5
C18H29Na3O7
426.38
C22H22N2Na2O4
424.40
XcaliburTM
2
Formula weight
Diffractometer
294.42
474.63
SMART 1000
SMART 1000
STOE IPDS
Data collection method
Temperature (K)
Crystal system
Space group
φ- and ω- scans
120
φ- and ω- scans
120
φ-scan
100
φ- and ω- scans
106
Triclinic
Monoclinic
Monoclinic
Monoclinic
P 21/n
P 21/n
C 2/c
P 1
7.352(3)
12.917(4)
10.4897(5)
11.6645(8)
a (Å)
8.750(4)
10.696(5)
87.875(9)
87.262(8)
88.631(8)
686.6(5)
7.2201(16)
25.181(6)
12.4028(4)
17.4433(9)
16.7097(11)
22.3126(14)
b (Å)
c (Å)
α (º)
90
90
90
103.166(5)
94.795(4)
95.432(6)
β (º)
γ (º)
V (Å3)
90
90
90
2286.8(10)
2261.46(17)
4329.4(5)
Z
2
4
4
8
Color, habit
Colorless, needle
Colorless, plate
Colorless, block
Colorless, plate
0.60 × 0.10 × 0.05 0.20 × 0.10 × 0.04 0.60 × 0.30 × 0.30 0.50 × 0.20 × 0.10
Crystal dimensions (mm)
Dcalc (g cm-3)
µ (mm-1)
1.424
1.379
1.252
1.302
0.70
0.45
0.14
0.12
Unique reflections (Rint)
3184 (0.068)
5494 (0.066)
6095 (0.089)
5019 (0.117)
Observed reflections [I >
2σ(I)]
2124
3299
4489
2035
Parameters
158
286
271
275
R1[I > 2σ(I)], ωR2
Goodness-of-fit on F2
Absorption correction
Tmin, Tmax
0.068, 0.166
1.08
0.075, 0.175
1.06
0.054, 0.111
1.09
0.043, 0.076
0.71
SADABS
0.680, 0.966
-0.70, 0.72
SADABS
0.916, 0.982
-0.49, 0.72
none
ABSPACK
0.946, 0.986
-0.24, 0.23
-
ρmin, ρmax (e Å-3)
-0.26, 0.39

3. Results and discussion
3.1. Synthesis
The synthesis of alkaline β-diketonates is a rather common interjacent stage for the
preparation of 3d- and 4f-metal β-diketonates [29]. In this case, sodium and potassium β-
diketonates were synthesized in situ from alkalis and β-diketone in aqua-alcohol solution. The solid
compounds obtained via this reaction were the hydrated sodium and potassium β-diketonates [15-
16].
To isolate the anhydrous alkaline metal β-diketonates, we used another known method of
synthesis, performing the reaction in dried solvents and using MOtBu instead of MOH (M = Na, K).
The syntheses of compounds I-VI were performed by the reaction of MOtBu, Hacac and phen (for
II and VI) in dried solvents – iso-propanol, benzene or pyridine - in air or under Ar atmosphere.
1
The composition of the obtained compounds was confirmed by CHN analysis, IR and H NMR
spectroscopy. The identity of powder samples and single crystals was proved by a comparison of
powder XRD patterns with theoretical ones calculated from single crystal data.
The reaction between MOtBu and Hacac in air resulted in the formation of hydrated
compounds, K2(acac)2(H2O) (I) and Na(acac)(H2O) (III), in spite of using dried solvents. The large
ionic radii and unsaturated coordination sphere of alkaline elements lead to the formation of mixed-
ligand complexes, even with traces of water. The addition of the bidenate ancillary ligand
phenanthroline does not prevent the coordination of water molecules: in case of potassium,
K2(acac)2(phen)(H2O) (II) was obtained, while for sodium, the mixed-ligand complex with phen
was not formed and only III was isolated. The syntheses using Schlenk techniques in dry Ar
atmosphere leads to the formation of the anhydrous complexes Na3(acac)3(iPrOH) (IV) and
Na3(acac)3(Py) (V), but Na2(acac)2(phen) (VI) was not isolated by conventional methods, even
under dry Ar. Only slow crystallization in an evacuated sealed tube allowed us to obtain several
small single crystals of VI. In order to understand the origins of the differences in the synthesis and
composition of II and VI one should consider the X-ray structures and quantum chemical
simulations.
3.2. X-ray crystal structures
The 1D polymer structures of I-VI have chain (I, III) or ribbon (II, IV-VI) motifs with
additional bridging and chelating functions of acac ligands (tetra- or hexadentate). For convenience,
the description of the structures can be represented as consisting of formal binuclear building
blocks, [M2(acac)2]. Four types of [M2(acac)2] building blocks can be found in the structures of I-
VI, which differ by their metal-oxygen cores (A-D blocks, Fig. 1).
The A-block has a nearly square {M2O2} metal-oxygen core (Fig. 1). Each acac- ligand forms

one chelate cycle only with one M cation, and coordinates to the other M as a bridging
ligand.
In the B-block four oxygen atoms of two acac- ligands in the equatorial plane and two apical
M atoms form a distorted octahedral metal-oxygen core {M2O4} (Fig. 1). Each M cation takes part
in two chelate cycles with both bi-chelating acac- ligands.
The C-block has a distorted square or tetrahedral metal-oxygen core {M2O2} (Fig. 1). In the
C-block two M-atoms have different coordination environments. Two acac- ligands coordinate to
M1 as chelating ligands, while the same acac- ligands coordinate to M2 only as bridging ligands.
The D-block has a trigonal bipyramidal metal-oxygen core (Fig. 1). Like in the A-block, each
acac- ligand formes one chelate cycle only with one M cation and coordinates to the other M as a
bridging ligand. Additionally, a donor ligand µ2-L bridges to the M atoms.
Thus, the descriptions of structures I-VI go two ways: (i) the coordination environment of the
alkaline ions and (ii) the building block types and their arrangment in the polymeric structure.
Fig. 1. The geometry of the A-D binuclear building blocks in the structures I-VI. Blue dash lines
show the metal-oxygen core of the blocks. The arrows show the additional interactions with
neighboring building blocks or terminal ligands. M = Na, K; L – O donor atom (H2O, acac, iPrOH)
or N donor atom (Py, phen).
3.2.1 [K2(acac)2(H2O)]∞ (I) and [K2(acac)2(phen)(H2O)]∞ (II)
The crystal structure of I at room temperature (IR) with low accuracy (σ(C−C) = 0.03 Å) was
reported by Shibata et al. in 1975 [16]. Here, we present the results of a modern low temperature
diffraction experiment (IL). The structures IR and IL were found to be identical, so the thermally
induced phase transition reported previously for structurally flexible coordination compounds of
alkaline-earth β-diketonates [30] was not observed for I.
The asymmetric unit cell of I consists of two seven-fold coordinated potassium cations (K1

and K2), two acetylacetonate-anions (µ4-O1−C1−C2−C3−µ2-O2 and µ4-O3−C6−C7−C8−µ2-O4)
and a water molecule (µ2-O1w) (Fig. 2). The H2O molecules form a framework of hydrogen bonds
with acac-anions of neighboring chains, resulting in their association into sheets parallel to the
(001) plane.
Fig. 2. A fragment of the polymeric [K2(acac)2(H2O)]∞ chain in I. Empty lines show the acac
ligands, dashed lines show H-bonds. H-atoms are partially omitted for clarity. Symmetry codes: (i)
−x, −y+2, −z; (ii) −x+1, −y+2, −z; (iii) x, −y+1, z.
The K1 and K2 cations have similar coordination environments, formed by four oxygen atoms
(O1i – O4i or O1 – O4 respectively) of two chelate-bridging acac-anions, two bridging oxygen
atoms (O1, O3 or O1ii, O3ii ) of two other acac− ligands and a bridging water molecule (O1w or
O1wii) (Fig. 2). The average K-O distance in I is equal to 2.85(11) Å, and only the K1-O1 and K2-
O3 distances (3.007(3) and 3.044(3) Å respectively) are significantly longer due to enhanced
bridging functions of µ4-O1 and µ4-O3 (Table S1). Therefore, the coordination number of K1 and
K2 is 6+1.
The polymeric chain in I can be represented as a combination of edge- and corner-sharing B-
and D- formal building blocks (Fig. 3). The B-block [K2(acac)2] contains a distorted octahedral
metal-oxygen core {K1iK2O1O2O3O4}. Neighboring B-blocks are connected via bridging K1–O3,
K2ii–O3, K1–O1, K2ii–O1 and K1–O1w, K2–O1wii interactions forming a trigonal bipyramidal
{K1K2iiO1O3O1w} D-block metal-oxygen core.

Fig. 3. Metal-oxygen framework and building blocks in the polymeric chain [K2(acac)2(H2O)]∞ (I).
In the asymmetric unit cell of II there are two potassium cations (K1 and K2) in different
coordination environments, two acac– anions (O1-C1-C2-C3-O2 and O3-C6-C7-C8-O4), phen (N1-
C15-C16-N2) and a water molecule (H2O1w). The seven-coordinated K1 is surrounded by four O-
atoms of two chelating acac– anions (µ2-O1, µ3-O2 and µ3-O3, µ2-O4), two bridging atoms (O2i and
O3i) of two other acac– anions and µ2-O1wii of water (Fig.4). Therefore, the coordination
environment of K1 is similar to that in I, while the average K-Oacac distance, 2.77 Å, is slightly
shorter than in I (2.85 Å, Table 2).
Table 2. Selected geometrical parameters in II.
II
Bond distances (Å)
K1—O1
K1—O2
K1—O3
K1—O4
K1—O2i
K1—O3i
K1—O1wii
K2—O1
K2—O2
K2—O3
K2—O4
K2—O1wiii
K2—N1
K2—N2
2.856(3)
2.691(3)
2.731(3)
2.862(3)
2.680(3)
2.693(3)
2.984(3)
2.970(3)
2.749(3)
2.742(3)
2.918(3)
2.866(4)
2.880(4)
2.856(4)
Hydrogen bond geometry (Å,°)
Fig. 4. A fragment of the polymeric ribbon
[K2(acac)2(phen)(H2O)]∞ in II. Empty lines
show the acac ligands, dashed lines show H-
bonds. H-atoms are partially omitted for clarity.
D···A
D–H···A
O1w-H1wa···O1 2.782(4) 152
−x+1/2, y−1/2, −z+1/2; (ii)
Symmetry codes: (i)
−x+1/2, y+1/2, −z+1/2; (iii) x, y+1, z.
−1/2, −z+1/2;
(ii) −x+1/2, y+1/2,
O1w-H1wb···O4 2.779(4) 138
Symmetry codes: (i) −x+1/2,
−z+1/2; (iii) x, y+1, z.
y
The coordination environment of K2 with CN=7 (Fig. 4) is formed by four O-atoms of two
chelating acac– anions (µ2-O1, µ3-O2 and µ3-O3, µ2-O4), a chelating phen ligand (N1 and N2) and a
bridging water (µ2-O1wiii). The average K-Nphen distance (2.868 Å) is close to that observed for

hexacoordinated (2.871
Å
in K(thd)(phen)2 [31]) and heptacoordinated (2.834
Å in
K2(Piv)2(phen)(H2O) [32]) potassium atoms and is in good agreement with typical values of K-Nphen
distances in other known potassium complexes with phen [33].
The ribbons in II can be represented as a combination of the same B- and D- formal building
blocks (Fig. 5). In contrast to I, these blocks share faces and vertices. The B-block consists of K1,
K2 and two acac- anions and has a distorted octahedral metal-oxygen core {K1K2O1O2O3O4}.
Connection of K1ii and µ2-O1wiii to the {K2O2O3} triangular face of the B-block leads to the
formation of the trigonal-bipyramidal metal-oxygen core of the D-block.
Fig. 5. Metal-oxygen framework and building blocks in the polymeric ribbon
[K2(acac)2(phen)(H2O)]∞ (II).
The neighboring ribbons contact each other through alternating face-to-face π-π stacked phen
ligands (the inter-planar distance is 3.48 Å, the molecular centroids separation is 3.87 Å). The water
molecule and O atoms of the acac– anions form two intra-ribbon H-bonds (d(O1w-H1wa-O1) =
2.782(4) Å, d (O1w-H2wa-O4) = 2.779(4) Å) in contrast to I which has only inter-ribbon H-bonds.
3.2.2. [Na(acac)(H2O)]∞ (III), [Na3(acac)3(iPrOH)]∞ (IV) and [Na2(acac)2(phen)]∞ (VI)
Although the structure of III was reported earlier [15], we discuss it here using our formal
building block approach. The distorted octahedral coordination environment of the Na atom in III
consists of one bidentate-chelating acac–, two bridging acac– and two bridging water molecules
(Fig. 6). The chains in III can be represented as corner-shared D-blocks.

Fig. 6. The fragment of the polymeric chain [Na(acac)(H2O)]∞ (III) and formal building blocks.
−x, y+1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2.
Symmetry codes: (i)
In the structure of IV, the asymmetric unit cell contains three pentacoordinated Na cations in
distorted square-pyramidal coordination environments, three acetylacetonate-anions (O1-C2-C3-
C4-O2, O3-C7-C8-C9-O4, O5-C12-C13-C14-O6) and one iso-propanol molecule (O7-C16-
C17(C18)). To confirm the square-pyramidal coordination geometry around the Na cation we have
calculated the geometric parameter τ = (β – α)/60. The α and β values are the two largest basal
angles in the polyhedra. Thus, τ = 0 corresponds to an ideal square-pyramid, while τ = 1
corresponds to an ideal trigonal bipyramid [34]. The coordination environment of Na1 consists of
four oxygen atoms of two chelating acac ligands (µ3-O1, µ3-O2 and µ2-O3, µ2-O4) in the basal
plane and an apical O7 atom of iso-propanol (τ = 0.14). The Na1 atom is displaced by 0.97 Å from
the basal plane (Fig. 7a).
Fig. 7. Structure of [Na3(acac)3(iPrOH)]∞ (IV): a) fragment of the polymeric ribbon; b) metal-
oxygen framework and building blocks. Empty lines show the acac ligands. H-atoms are omitted for
clarity. Symmetry codes:(i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) −x+1, −y+2, −z.

The Na2 and Na3 atoms are coordinated by oxygen atoms of acac ligands only (Fig. 7a). The
Na2 atom connects to two oxygen atoms (µ3-O1i and µ3-O2i) of a bi-chelating acac ligand and two
bridging oxygen atoms (µ3-O2 and µ2-O5) in the basal plane and one apical µ2-O4 (τ = 0.15). The
Na3 atom is coordinated by two oxygen atoms (µ2-O5i and µ2-O6i) of a chelating acac ligand and
two bridging oxygen atoms (µ3-O1 and µ2-O6ii) in the basal plane and one apical µ2-O3 (τ = 0.20).
The Na2 and Na3 atoms are located at 0.44 and 0.47 Å from the basal plane of the square pyramid,
respectively. Therefore, the fashion of the chelating acac ligand coordination is the main difference
in the coordination environments of Na2 and Na3. Bonding of one acac (µ3-O1 and µ3-O2) as a bi-
chelating ligand leads to an increase of the Na1-O1 and Na1-O2 distances compared with Na1-O4
and Na1-O3 (Table 3).
Table 3. Selected geometrical parameters in IV and V [17].
V
IV
Bond distances (Å)
Na1—O1
Na1—O2
Na1—O3
Na1—O4
2.3642(13)
2.3125(13)
2.2641(14)
2.2936(14)
3.354(2)
2.307(2)
2.229(2)
2.302(2)
2.423(2)
2.311(2)
2.332(2)
2.286(2)
2.481(2)
2.447(2)
2.336(2)
2.305(2)
2.314(2)
2.291(2)
2.321(2)
Na1—O7(N1) 2.3238(15)
Na2—O2
Na2—O4
Na2—O5
Na2—O1i
Na2—O2i
Na3—O1
Na3—O3
Na3—O5i
Na3—O6i
Na3—O6ii
2.2877(13)
2.3026(14)
2.2662(14)
2.4661(14)
2.4330(14)
2.3790(13)
2.3307(13)
2.3026(13)
2.3172(13)
2.3272(13)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y+1, z.
The ribbons in IV can be represented as the central chain of corner-shared A-blocks and pairs
of corner-shared C-blocks alternating on both sides of the central chain (Fig. 7b). The metal-oxygen
cores of the A-blocks are {Na2O2Na2iO2i}, {Na2iO1Na3O5i} and {Na3O6iNa3iiiO6ii}. The cores
of the C-blocks are {Na1O1Na3O3} and {Na1O2Na2O4}.
So, on going from structure III to IV, the replacement of H2O by iPrOH occurs, followed by

decreasing the metal to neutral ligand molar ratio from 1:1 to 3:1 and rearrangement of the chains
into ribbons in the crystal structures.
i
In the case of the replacement of PrOH by Py (i.e. going from IV to V) neither the metal to
neutral ligand molar ratio nor the ribbon structure changes. The corresponding bond lengths in
structures IV and V are very close, the difference is less than 0.04 Å (Table 3). Meanwhile, the
packing of ribbons in IV and V differ significantly (Fig. S1). The planes on neighboring ribbons in
IV are parallel to each other, while in V these planes form a herring-bone motif in the ab projection
(with a dihedral angle of 73.16°).
The asymmetric unit cell in the mixed-ligand complex VI contains two sodium cations in
different coordination environments, two acac anions (O1-C2-C3-C4-O2 and O3-C7-C8-C9-O4),
and a phen ligand. The sodium to neutral bidentate phen ligand molar ratio is equal to 2:1. The Na1
atom, in a nearly octahedral environment (Fig. 8a), is coordinated by chelating acac (µ2-O1 and µ2-
O2), chelating phen (N1 and µ2-N2) and two bridging acac- ligands (µ2-O1i and µ2-O3). The Na2
atpm, in a distorted square-pyramidal coordination environment (Fig. 8a), connects to a chelating
acac ligand (µ2-O3 and µ2-O4ii), bridging acac- ligands (µ2-O2 and µ2-O4) and an apical µ2-N2 of a
phen ligand (τ = 0.18).
Fig. 8. Structure of [Na2(acac)2(phen)]∞ (VI): a) fragment of the polymeric ribbon; b) metal-
oxygen framework and building blocks. Empty lines show the acac ligands. H-atoms are omitted for
clarity. Symmetry codes:(i) −x+1, y, −z+1/2; (ii) −x+3/2, −y+1/2, −z+1.

The Na1-N1 distance, 2.48 Å (Table 4), is typical for the Na-Nphen bond length (2.45-2.49 Å
[35]), while the bridging Na1-N2 and Na2-N2 bonds, 2.70-2.81 Å, are significantly longer and
exceed the sum of the ionic radii (2.48 Å) by 0.22-0.33 Å, and thus correspond to weak interactions.
Thus, the CN is 5+1 for Na1 and 4+1 for Na2.
Polymer ribbons along the [101] direction are formed due to µ2-bridging oxygen atoms of
acac ligands and µ2-N2 atoms of phen ligands. These ribbons could be described as corner-shared
alternating A- and D- building blocks (Fig. 8b). The atoms Na1, Na1i, O1 and O1i form the
distorted square metal-oxygen core of the A-block. Atoms Na1, Na2, O2, O3 and N2 form the
trigonal bipyramidal core of the D-block.
Table 4. Selected geometrical parameters in VI.
VI
Bond distances (Å)
Na1—O1
Na1—O3
Na1—O1i
Na1—O2
Na1—N1
Na1—N2
Na2—O2
Na2—O4
Na2—O4ii
Na2—O3
Na2—N2
2.3199(16)
2.3286(17)
2.3328(15)
2.3493(16)
2.4809(19)
2.8118(18)
2.2195(16)
2.2531(16)
2.2631(15)
2.2854(15)
2.702(2)
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, −y+1/2, −z+1.
In the crystal structure of VI the ribbons interact with each other due to edge-to-face stacking
of alternating phen ligands with the chelating rings of two acac ligands (the molecular centroids
separations are 5.10 and 4.97 Å, and the dihedral angles are 87 and 60°). The phen ligands of
neighboring ribbons are parallel to each other (with an inter-planar distance of 3.417 Å), but with a
lateral displacement of 6.14 Å. While the two neighboring phen ligands in one ribbon are also
parallel (inter-planar distance 3.28(5) Å), their centroids are shifted by 7.69 Å. Thus, there are no
face-to-face stacking interactions between two phen molecules.
Consequently, for four sodium polymers (III-VI) the A-, C- and D-blocks were observed.
These blocks are in different pairwise combinations in structures IV-VI. At the same time, for the

potassium polymers only B- and D-blocks were observed in both structures I and II.
3.3. Theoretical study of mixed ligand complex formation
Theoretical simulations of the binuclear molecules [M2(acac)2] as molecular analogues of A-D
building blocks were carried out to understand the structural isomerism of these building blocks, to
compare their energies and to reveal the most stable ones. The geometries of the four isomers of the
[M2(acac)2] molecules were optimized (Fig. 9).These calculated isomers, α-, β-, γ- and δ-
[M2(acac)2], have the same metal-oxygen core as in the building blocks A-, B-, C- and D-
respectively, Fig. 1. The only difference was made in the D- and δ- pair; namely, in the simulated
molecule δ-[M2(acac)2] the trigonal bipyramidal core was constructed only by acac-ligands (one bi-
chelating and one chelate-bridging), while in the D-block, the core included a donor atom of the L
ligand (Fig. 1).
Fig. 9. Geometry of the simulated [M2(acac)2] isomers (M = Na and K). Dashed lines complete the
polyhedron of the metal-oxygen core. H-atoms are omitted for clarity.
Table 5. Selected parameters of the simulated isomers of the [M2(acac)2] molecules and binuclear
building [M2(acac)2] blocks in the structures I-VI
Simulated [M2(acac)2] molecules
CN1) <dM-O>2), Å Erel3), kJ/mol
Experimental [M2(acac)2] blocks
Fragment
CN1) <dM-O>2), Å
Molecule
M = Na
A-block (IV, V)
A-block (VI)
-
5, 5
2.35(7)
2.31(6)
-
α-[Na2(acac)2] 3, 3
2.197
0
5, 5
β-[Na2(acac)2] 4, 4
γ-[Na2(acac)2] 4, 2
2.345
2.222
+47.7
+37.6
C-block (IV, V)
D-block (III)
D-block (VI)
5, 5
6, 6
5, 5
2.32(4)
2.38(5)
2.30(6)
δ-[Na2(acac)2] 4, 3
2.268
+12.2

M = K
+11.3
α-[K2(acac)2]
β-[K2(acac)2]
γ-[K2(acac)2]
δ-[K2(acac)2]
3, 3
4, 4
4, 2
4, 3
2.578
-
B-block (I)
B-block (II)
-
-
6+1, 6+1 2.82(11)
2.691
2.602
+4.7
6, 7
2.79(12)
-
+35.7
D-block (I)
D-block (II)
6+1, 6+1 2.85(10)
6, 7 2.81(10)
2.636
0
1) Coordination number of two M-atoms in [M2(acac)2]
2) Average intra-block M-O distance
3) Energy of [M2(acac)2] isomer relative to the most stable one (with Erel = 0)
The stabilities and relative energies of the different [M2(acac)2] isomers depend mainly on two
competitive factors - the strength of the M-O interactions and their number. The average M-O
distance (<dM-O>) and coordination number (CN) corresponding to these two factors are listed in
Table 5. For [Na2(acac)2], the strength of the M-O interactions is the dominant factor; α-
[Na2(acac)2], with the shortest <dM-O>, is the most stable isomer. While for [K2(acac)2], with larger
K cations, the CN factor becomes more important. Indeed, the CN values for the most stable δ and
β isomers, with very close relative energies, are higher than for the α and γ isomers, in spite of
weaker M-O interactions (Table 5).
The M-O distances in the α-δ isomers of the M2(acac)2 molecules are slightly shorter (by 0.03-
0.13 Å for M = Na and by 0.13-0.21 Å for M = K) than in the corresponding A-D blocks of the
crystal structures. This is due to a lower CN of M in the simulated [M2(acac)2] molecules than in the
building blocks A-D.
Note, the energy difference between all isomers does not exceed 40 kJ/mol, which is
comparable to the energy of the H-bonds and intermolecular interactions. This explains the presence
of all types of building blocks, except the most unstable ones, in structures I-VI.
The formation of dimeric [M2(acac)2] molecules was also considered as the first stage of
polymerization. This process competes with the formation of mononuclear mixed-ligand
complexes, [M(acac)L].
The formation of the most stable binuclear molecules [M2(acac)2] was simulated and the
system energy change ∆E was calculated:
2 Na(acac) = α-[Na2(acac)2], ∆E = -143 kJ/mol
2 K(acac) = δ-[K2(acac)2], ∆E = -111 kJ/mol
(1)
(2)
The theoretical simulations of mixed-ligand complexes were carried out for the isolated

molecules [Na(acac)(phen)] and [K(acac)(phen)]. As a result, the optimized molecules have a planar
geometry. In [M(acac)(phen)], the phen and acac ligands act as chelating ligands and CN = 4 (Fig.
10). The weak attractive interaction between the aromatic hydrogen atom and oxygen atom of acac
lead to broken axial symmetry and bond length differences in the M-N1/M-N2 and M-O1/M-O2
pairs (Table 6).
Na(acac) + phen = Na(acac)(phen), ∆E = -100 kJ/mol
K(acac) + phen = K(acac)(phen), ∆E = -75 kJ/mol
(3)
(4)
Fig. 10. Geometry of the simulated M(acac)(phen) molecule (M = Na and K).
The calculated ∆E values for reactions (3) and (4) show that the formation of mixed ligand
complexes is energetically favorable, but the formation of [M2(acac)2] dimers leads to lower
energies (reactions (1) and (2)). This agrees with the experimental results from the syntheses and X-
ray structure analyses. Indeed, the addition of the phen ligand to polymeric chains of hydrates I and
III leads to mixed-ligand complexes II and VI, which retain the polymeric structure.
Table 6. Selected distances (Å) in the simulated [M(acac)(phen)] molecules
Distance
M-O1
M-O2
M-N1
M-N2
M = Na
2.170
2.199
2.516
2.401
M = K
2.518
2.554
2.995
2.805
The phen binding ∆E value for M = K is smaller due to the larger ionic radius and lower
positive charge surface density. A similar tendency was observed in [36] according to quantum
chemical calculations of the interaction of the M+ cation (M = Li, Na, K) with the neutral phen
ligand. The absolute ∆E values reported in [36] (-254 and -172 kJ/mol for Na and K respectively)

seem to be significantly overestimated due to the small basis set used for the calculations and the
absence of an anion in the model to compensate the positive charge of the central atom.
The calculated M-N distances (Table 6) are close to those observed in structures II and VI.
The M-O distances in both modelled [M(acac)(phen)] and [M2(acac)2] molecules are rather close,
but are shorter than the experimental M-O distances in the polymeric structures I-VI.
3.4. Thermal behavior
Thermal analyses in air and N2 were carried out for the three compounds I, II and III. The
i
anhydrous complexes IV-VI are unstable in air and rapidly lose PrOH, Py and phen respectively,
with the formation of III.
The TG curve of I in N2 shows the complete elimination of H2O at 90-130 °C (exp. weight
loss 6%, calc. 6%) with the formation of anhydrous “K(acac)”, which is stable in the range 130-220
°C. In air, the first stage of weight loss (24%) occurs at 95-250 °C and corresponds to elimination of
H2O accompanied by partial decomposition. The total weight loss of I in air at 800 °C (55%)
corresponds to the formation of K2CO3 (calc. weight loss 53%).
For III, in both atmospheres, the first stage of weight loss corresponds to complete
elimination of H2O (70-110 °C, exp. 13%, calc. 13%), followed by the formation of anhydrous
“Na(acac)”, which is stable in the range 110-170 °C. The total weight loss at 600 °C in air
corresponds to the formation of Na2CO3 (exp. 64%, calc. 62%).
Heating of II in both atmospheres leads to the complete elimination of coordinated H2O at 90-
155 °C (exp. 4%, calc. 4%), followed by elimination of phen at 163-295 °C (exp. 39%, calc. 38%),
which overlaps with the range of the thermal stability of “K(acac)”. Similarly to I, the total weight
loss of II in air at 800 °C (70%) corresponds to the formation of K2CO3 (calc. weight loss 71%).
4. Conclusions
A comprehensive overview of the results of the synthesis and crystal structures for
[K2(acac)2(H2O)]∞ (I), [K2(acac)2(phen)(H2O)]∞ (II), [Na(acac)(H2O)]∞ (III), [Na3(acac)3(iPrOH)]∞
(IV), [Na3(acac)3(Py)]∞ (V) and [Na2(acac)2(phen)]∞ (VI) allowed us to reveal key factors of the
i
M(acac) (M = Na and K) reactions with ancillary neutral ligands (H2O, PrOH, Py and phen). The
compounds I-VI have one-dimentional polymeric structures. The chains or ribbons can be
represented as a combination of corner-, edge- or face-shared formal binuclear [M2(acac)2] building
blocks of four types (A-D). A theoretical simulation of the molecular analogs of these blocks
showed that the stability of the blocks changed in the row A>D>>C>B (M = Na) or D≈B>A>>C (M
= K). In spite of the structural flexibility of alkaline metal coordination compounds, these building
blocks were found to be rather rigid units. These four types of formal blocks appear not only in the

polymeric acetylacetonates I-VI but also in oligomeric structures of sodium and potassium
hexafluoroacetylacetonates, which will be reported later.
In general, one could expect that the formation of mixed-ligand complexes results in an
increasing CN of the central atom accompanied by transformation of the polymeric structure into
structures of lower nuclearity. Indeed, such transformations are widely used to decrease the
nuclearity of various metal acetylacetonates. However, for polymeric alkaline metal
acetylacetonates, this rule does not work. The coordination of additional neutral donor ligands to
polymeric chains of acetylacetonates retains the polymeric motif, but changes the types of blocks in
some cases. It is noteworthy that the formation of mixed ligand complexes of M(acac) does not
necessarily lead to an increase in CN (e.g. CN = 6 in III, but in VI CN = 5 and 6).
Appendix A. Supplementary data.
CCDC 904026 (I), 904027 (IV), 904028 (II) and 904029 (VI) contain the supplementary
crystallographic
data.
These
data
can
be
obtained
free
of
charge
via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk. Supplementary data associated with this article can be found in the online
version.
Acknowledgments
The authors are grateful to the Research Computing Center of M.V. Lomonosov Moscow
State University for access to Supercomputer SKIF-MGU “Chebyshev”. The authors are very
thankful to Prof. N.P. Kuzmina and Dr. A.V. Mironov (Lomonosov Moscow State University) for
useful advice and discussion. D.T. is also thankful to Prof. R. Fischer and Mrs. M. Winter (Ruhr-
University Bochum) for the assistance with the X-ray experiment.
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Six mixed ligand acetylacetonates of Na and K with H2O, 1,10-phenanthroline, iso-propanol and
pyridine were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis,
1H NMR and FTIR spectroscopy. All the compounds have one-dimensional polymeric structures
described as a combination of formal binuclear building blocks, [M2(acac)2], of four types.