Synthesis and characterization of the mixed-linker copper(II) coordination polymer [Cu(HO3PC6H4SO3)(C 10N2H8)]·H2O

Article abstract of DOI:10.1002/zaac.201100202

A new copper(II) phosphonatobenzenesulfonate incorporating 4,4′-bipyridine (4,4′-bipy) as auxiliary ligand has been discovered through systematic high-throughput (HT) screening of the system Cu(NO ₃)₂·3H₂O/H₂O ₃PC₆H₄SO₃H/4,4′-bipy using different solvents. The hydrothermal synthesis of [Cu(HO₃PC ₆H₄SO₃)(C₁₀H₈N ₂)]·H₂O (1) was further optimized by screening various copper(II) salts. The crystal structure of 1 was determined by single-crystal X-ray diffraction and unveiled the presence of isolated sixfold coordinated Jahn-Teller-distorted Cu²⁺ ions. The isolated CuN ₂O₄ octahedra are interconnected by phosphonate and sulfonate groups to form chains along the c-axis. The organic groups, namely phenyl rings and 4,4′-bipy molecules cross-link the chains into a three-dimensional framework. Water molecules are found in the narrow voids in the structure which are held by weak hydrogen bonds. Upon dehydration, the structure of 1 undergoes a phase transition, which was confirmed by TG measurements and temperature dependent X-ray powder diffraction. The new structure of 1-h was refined with Rietveld methods. Detailed inspection of the structure revealed the directional switching of the Jahn-Teller distortion upon de/rehydration. Weak ferro-/ferrimagnetic interactions were observed by magnetic investigations of 1, which switch to antiferromagnetic below 3.5 K. Compounds 1 and 1-h are further characterized by thermogravimetric and elemental analysis as well as IR spectroscopy. Copyright

Full text of DOI:10.1002/zaac.201100202

ARTICLE
DOI: 10.1002/zaac.201100202
Synthesis and Characterization of the Mixed-Linker Copper(II)
Coordination Polymer [Cu(HO3PC6H4SO3)(C10N2H8)]·H2O
Palanikumar Maniam[a] and Norbert Stock*[a]
Dedicated to Professor Hanskarl Müller-Buschbaum on the Occasion of His 80th Birthday
Keywords: High-throughput screening; Copper; Coordination polymers; Phosphonato-sulfonates; X-ray diffraction
Abstract. A new copper(II) phosphonatobenzenesulfonate incorporat- molecules are found in the narrow voids in the structure which are
ing 4,4'-bipyridine (4,4'-bipy) as auxiliary ligand has been discovered
through systematic high-throughput (HT) screening of the system
Cu(NO3)2·3H2O/H2O3PC6H4SO3H/4,4'-bipy using different solvents.
The hydrothermal synthesis of [Cu(HO3PC6H4SO3)(C10H8N2)]·H2O
(1) was further optimized by screening various copper(II) salts. The
crystal structure of 1 was determined by single-crystal X-ray diffrac-
tion and unveiled the presence of isolated sixfold coordinated Jahn–
Teller-distorted Cu2+ ions. The isolated CuN2O4 octahedra are inter-
connected by phosphonate and sulfonate groups to form chains along
the c-axis. The organic groups, namely phenyl rings and 4,4'-bipy mol-
held by weak hydrogen bonds. Upon dehydration, the structure of 1
undergoes a phase transition, which was confirmed by TG measure-
ments and temperature dependent X-ray powder diffraction. The new
structure of 1-h was refined with Rietveld methods. Detailed inspec-
tion of the structure revealed the directional switching of the Jahn–
Teller distortion upon de/rehydration. Weak ferro-/ferrimagnetic inter-
actions were observed by magnetic investigations of 1, which switch
to antiferromagnetic below 3.5 K. Compounds 1 and 1-h are further
characterized by thermogravimetric and elemental analysis as well as
ecules cross-link the chains into a three-dimensional framework. Water IR spectroscopy.
Examples from our previous work comprise the use of link-
Introduction
ers containing phosphonate and carboxylate groups,[14,15] phos-
phonate and amine groups such as imino-bis(methylphosphon-
ate) units[16] or imino-bis(methylphosphonate) and carboxylate
units.[17,18] Linkers containing phosphonic and sulfonic acid
groups have only been recently investigated. By using the flex-
ible linkers 2-phosphonoethane- and 4-phosphonobutane-sul-
fonic acid, our group has explored the synthesis of several hy-
brid compounds with different ions such as Cu2+,[19,20] Sr2+,[21]
Ba2+,[22] and lanthanide ions.[23–25] Rigid phosphonoarylsul-
fonic acids, i.e. 3-phosphonobenzenesulfonic acid were em-
ployed by the group of Mao,[26–30] 5-phosphono-1,3-disulfonic
acid and 4-fluoro-3-sulfobenzylphosphonic acid by the group
of Montoneri,[31,32] mostly in combination with amine linkers.
The synthesis of most metal phosphonates is accomplished
under hydrothermal conditions. Such reactions are often
known to be strongly dependent on the process parameters, e.g.
reaction time, temperature, heating rate, and the compositional
parameters, e.g. molar composition of the starting materials,
pH of the reaction mixture or overall concentration. An elegant
way for the exploration of these complex systems can be car-
ried out using high-throughput (HT) methods.[33–35] These al-
low a systematic and efficient investigation of large parameter
spaces giving rise to the accelerated discovery of new com-
pounds and optimization of synthesis parameters. Due to the
large amounts of data, reaction and structural trends can be
derived. Our recent work on 4-phosphonobenzenesulfonic acid
(H3L) with HT methods has highlighted the discovery of sev-
The field of inorganic-organic hybrid compounds encom-
passes many types of materials; i.e. amorphous nanocompos-
ites, such as self-assembled mesoporous materials, to crystal-
line products.[1] One intensively studied class of these
compounds is coordination polymers.[2,3] The organic building
units that are mostly deployed in these materials are based on
carboxylates (R–CO2 ) and amines.[4–7] On the other hand, sul-
–
–
fonate (R–SO3 ) and phosphonate (R–PO32–) based compounds
have been less intensively investigated.[8–11] The restriction of
structural diversity with these functional groups compared to
–
the –CO2 counterpart is mostly caused by the more flexible
coordination modes as well as the higher number of coordinat-
ing atoms. Therefore, in general dense materials are
formed.[12,13] We are interested in the utilization of organic
linker molecules containing two or more different functional
groups for the synthesis of inorganic-organic hybrid com-
pounds. In addition to the number of functional groups, their
structure, coordination modes, as well as charge and acidity
have a strong effect on the final crystal structure formation.
* Prof. Dr. N. Stock
E-Mail: stock@ac.uni-kiel.de
[a] Institut für Anorganische Chemie,
Christian-Albrechts-Universität,
Max-Eyth-Strasse 2
24118 Kiel, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201100202 or from the
author.
Z. Anorg. Allg. Chem. 2011, 637, 1145–1151
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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P. Maniam, N. Stock
ARTICLE
eral compounds incorporating this linker and Cu2+ ions.[36] oxidation during the synthesis.[18] In addition, the deployment
Various CuO clusters ranging from mononuclear CuO6, binu- of the suitable copper(II) salt could also prevent the co-crystal-
clear Cu2O8, hexanuclear Cu6O24 to infinite chains of edge- lization of unwanted phases.[36] In a HT-screening experiment
sharing CuO5/CuO6 were observed in these phosphonosulfo- with 24 individual reactions, other copper salts in addition to
nate compounds. We concentrated on the usage of copper(II) Cu(NO3)2·3H2O were tested with 4,4'-bipy under hydrothermal
as the metal ion as it usually displays diverse coordinating conditions (Tab. S2). The reaction involving CuCl2·2H2O only
characteristics arising from Jahn–Teller distortion as well as yielded α-[Cu(4,4'-bipy)Cl2] which was identified via XRPD
the catalytic potential through coordinatively unsaturated cop- and elemental analysis.[43] Cu(CH3COO)2·H2O always gener-
per sites.[37,38] By inserting auxiliary ligands such as amines, ated mixed phases of 1 with unidentified crystalline impurities
new structural motives could be obtained as seen in the work and traces of Cu2O. The use of CuSO4·5H2O resulted only in
of Mao et al.[26–30] In order to gain insight into these structural mixtures of 1 with a small amount of crystalline impurities.
possibilities, HT-screening of various solvents and copper(II) The most suitable copper salt was determined to be
salts with an auxiliary diamine ligand, namely 4,4'-bipyridine Cu(NO3)2·3H2O since it resulted mostly in the pure phase 1
(4,4'-bipy) was performed. This systematic investigation has depending on the molar composition of the reaction mixtures.
resulted in the discovery and the synthesis optimization of a Looking closely at the various Cu(NO3)23H2O/H3L/4,4'-bipy
new mixed-ligand coordination polymer. Here, we report the molar ratios used, the optimal reactant composition was deter-
synthesis, structural and magnetic characterization of a new mined to be 1:1:1. This molar ratio was successfully used for
copper(II)-coordination polymer containing H3L and 4,4'-bipy, the synthesis scale up in glass tubes (see Exp. Sect.).
[Cu(HL)(4,4'-bipy)]·H2O (1) and its structural conversion to
the dehydrated compound [Cu(HL)(4,4'-bipy)] (1-h).
Crystal Structure
The asymmetric unit of 1 is comprised of two Cu2+ ions, one
Results and Discussion
HT-Screening of Solvents
doubly deprotonated (HL)2– ion, two 4,4'-bipy and a single wa-
ter molecule (Figure 1).
Solubility of each reactant in the respective solvent plays an
essential role in determining the outcome of a synthesis.[39]
Nonetheless, most metal phosphonates or sulfonates are syn-
thesized in aqueous solution. In order to see the effects of other
solvents on the synthesis, acetonitrile, 2-propanol and N,N-
dimethylformamide (DMF) were also screened with
Cu(NO3)2·3H2O, H3L and 4,4'-bipy (Tab. S1). All screening
reactions in this stage were performed at a reaction temperature
of 130 °C. The molar ratios of Cu2+:H3L:4,4'-bipy were varied
in the range of 1 to 3 in 1.0 steps. According to the X-ray
powder diffraction (XRPD) measurements, 2-propanol-based
syntheses yielded various mixed-phase products most of which
contained 1. Due to strong overlap of the reflections the identi-
fication of the other products was not accomplished. DMF-
based reactions generated mixed phases mostly comprised of
1, elemental copper, Cu2O and [Cu(4,4'-bipy)(OH)],[40] which
indicates that DMF can also act as a reducing agent under
certain conditions.[41] Acetonitrile-based reactions produced
mixed phases in which green crystals were obtained. These
were determined by XRPD measurements to be the known
compound [Cu2(CH3COO)4(4,4'-bipy)]·CH3CN.[42] The acetate
ion resulted from the in situ hydrolysis of acetonitrile. In gen-
eral, the organic solvents are advantageous to increase the sol-
ubilility of some amine ligands. Nevertheless, the usage of or-
ganic solvent is disadvantageous for our purposes as no new
mixed-ligand coordination polymer was obtained. Only with
water based synthesis led unequivocally to a new mixed-ligand
compound, [Cu(HL)(4,4'-bipy)]·H2O (1).
Figure 1. The asymmetric unit of compound 1. The coordinative Cu–
N and Cu–O bonds are depicted by broken lines. Thermal ellipsoids
are drawn at 50 % probability.
The X-ray scattering factors of phosphorus and sulfur are
very similar. Nevertheless, the distinction can be made by
comparison of the P–O and S–O bond lengths. The P–O bond
lengths of 1.489(2)–1.571(2) Å in 1 are longer than the S–
O bonds, which are between 1.438(2) and 1.456(3) Å. These
observations agree well with the values in the literature and
facilitate the assignment of sulfur and phosphorus
atoms.[19,36,44]
The Cu2+ ions are surrounded by four oxygen atoms of the
sulfonate and phosphonate ions as well as two nitrogen atoms
of the 4,4'-bipy molecules to form a distorted CuN2O4 octahe-
dra. The oxygen atoms of phosphonate ions and the nitrogen
atoms lie on the equatorial positions in the octahedra whereas
the oxygen atoms from the sulfonate ions are in the axial posi-
tions. The typical Jahn–Teller distortion can be observed with
the elongated Cu–O axial bonds in the 2.556(2)–2.620(3) Å
range (Figure 2A). The equatorial Cu–O and Cu–N bonds are
HT-Screening of Copper(II) Salts
The counterions of the copper salts affect the pH of the reac- in the range of 1.930(2)–1.942(2) Å and 2.008(3)–2.025(3) Å,
tion mixture and can also induce in situ side-reactions such as respectively. These octahedra are interconnected via sulfur and
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The Mixed-Linker CuII Coordination Polymer [Cu(HO3PC6H4SO3)(C10N2H8)]·H2O
phosphorus atoms along the c-axis to form infinite chains (Fig-
ure 2A). The chains are cross-linked along the b-axis through
4,4'-bipy molecules and also through (HL)2– ions in the (101)
plane (Figure 3). A three-dimensional structure is thus formed.
Weak hydrogen bonds (D···A = 2.614(3)–2.819(3) Å) are ob-
served between the water molecule and the oxygen atoms from
the phosphonate and sulfonate ions (Figure 2A). The water
molecules act twice as H-donor and once as H-acceptor.
Figure 3. View along [001] showing the linkage of the chains of
CuN2O4 octahedra to each other by the phenyl rings of (HL)2– ions,
and by the 4,4'-bipy ligands. The same arrangement is observed in both
compounds 1 and 1-h. Hydrogen atoms from the aromatic groups were
omitted for clarity.
most apparent changes are a longer cell parameter a (+7.8 %)
and a shorter cell parameter c (–3.7 %). The cell parameter b,
which is exactly the distance between the chains connected by
the 4,4’-bipy ligands, does not change significantly (Figure 3).
Typically, structural phase transitions are due to temperature
changes,[45] but in compound 1, the transition to 1-h seems to
be caused by the dehydration of the compound as the dehy-
drated phase 1-h is stable at room temperature. By exposing
1-h to moisture, the structure converts gradually to the crystal
structure of 1, which was confirmed by XRPD analysis (Figure
S1).
A possible explanation for the lengthening of cell parameter
a could be the lack of the hydrogen bonds from the water
molecules in 1. This produces a repulsion of the chains from
each other and thus increasing the cell length along the a-axis.
Looking closer at the atomic arrangements in 1-h, the elon-
gated Cu–O axial bonds of the Jahn–Teller distorted CuN2O4
octahedra are no longer between the oxygen atoms of sulfonate
groups, but instead between the oxygen atoms of the phos-
phonate groups (Figure 2A, Figure 2B). This is similar to a so-
called “Jahn–Teller switching”, which has been reported with
several copper(II) containing compounds. In a Jahn–Teller dis-
2+
Figure 2. The chain-like interconnection of the CuN2O4 Jahn–Teller
distorted octahedra by the sulfonate and phosphonate groups along the
c-axis for the compound 1 (A) and 1-h (B). The chains are linked to
each other via the phenyl rings of the (HL)2– ions. The elongated Cu–
O axial bonds in 1 originate from sulfonate groups (A). In 1-h, the
elongation of Cu–O axial bonds involves the oxygen atoms of the
phosphonate groups (B). Hydrogen atoms from the aromatic groups
were omitted for clarity.
torted Cu(D2O)6 octahedra in the deuterated Tutton salt,
Cu(D2O)6(ND4)2(SO4)2, the elongated axial bonds flip to dif-
ferent pairs of water molecules compared to hydrogenous
compound.[46] A pressure dependent “switching” also occurs
in this compound upon raising the pressure from 1 to 1.5
bar.[47] The changes in the local coordination environment of
Cu2+ ion between compounds 1 and 1-h can be attributed to
the lack of hydrogen bonding from water molecules. Neverthe-
Thermal treatment at 250 °C leads to the removal of the H2O less, the reasoning behind this observation cannot be solely
melecules (see Thermal investigations). Changes in the unit dependent on the water molecules, but also on the influence of
cell parameters were observed with no symmetry changes. The the remainder of the whole structure.
Z. Anorg. Allg. Chem. 2011, 1145–1151
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P. Maniam, N. Stock
ARTICLE
Magnetic Investigations
Thermal Investigations
To investigate the magnetic properties of 1, the temperature
dependence of its susceptibility was investigated by applying
a magnetic field of H = 1 T in the temperature range of 2–300
K. The Cu2+ ions are only found in isolated CuN2O4 polyhedra
and are connected by phosphonate and sulfonate groups
(Cu···Cu = 5.356(1) Å). Due to the long exchange pathway,
weak magnetic interactions are expected. Looking at the χ–1
vs. T plot fitted using the Curie–Weiss law χ = C/(T–θw), an
almost linear curve is observed which confirms the Curie–
Weiss paramagnetism (Figure 4, top). A Weiss constant of 10.2
K was determined which indicates weak ferro-/ferrimagnetic
interactions. This result is also supported by the plot of χ·T vs.
T in Figure 4 (bottom) that shows the domination of weak
ferro-/ferrimagnetic behavior from 300 K to 3.5 K. At 3.5 K,
the interaction switches to antiferromagnetic (see inset in Fig-
ure 4, bottom). The average effective magnetic moment of
1.69(4) μB calculated from the fitted data from 40–300 K com-
pares well with the theoretical spin-only value of 1.73 μB (Fig-
ure 4). Upon further cooling from 40 K to 2 K, the μeff value
dips exponentially which indicates complex magnetic interac-
tions.
TG/DTA measurements have yielded much insight in the
composition and the thermal stability of compound 1 (Figure
S3). The solid product after the TG analysis was characterized
by XRPD measurement. The endothermic dehydration of 1 is
observed at 200 °C (weight loss % calcd./obs.: 3.9/4.1). The
second weight loss stage (200–450 °C) is attributed to the loss
of 4,4'-bipy molecules (% calcd./obs.: 32.9/32.0). The final
step in the TG curve can be assigned to the disintegration of
the -C6H4-SO3 fragment of the (HL)2– ions (% calcd./obs.:
33.0/32.1). The light blue colored solid residue was identified
as Cu2P2O7 by XRPD (% calcd./obs.: 31.8/31.7).
Temperature dependent XRPD measurements gave important
evidence on the phase transition of 1 to 1-h (Figure 5). Com-
pound 1 is stable in the temperature range of 20–250 °C. Upon
complete dehydration at 250 °C, 1-h is formed, which decom-
poses at 340 °C. The obvious discrepancy in phase transition
temperatures between TG (200 °C) and temperature dependent
XRPD analyses (250 °C) is due to the difference in the sample
setup (refer to Experimental Section).
Figure 5. Results of the temperature-dependent XRPD investigation
of a capillary tube sample shows the phase transition from 1 to 1-h at
250 °C.
Conclusions
High-throughput methods have helped to identify and opti-
mize the reaction conditions that led to the new mixed-linker
coordination polymer [Cu(HL)(4,4'-bipy)]·H2O. Surprisingly
the choice of Cu-salt and solvent has a strong influence on the
structure formed. Thus, only the reaction in water led to a sin-
gle-phase product of 1. Although only very small pores are
present in the structure of 1, occluded water molecules can be
reversibly removed. The often in coordination polymers ob-
served structural flexibility leads in 1 to a substantial change
in the coordination environment of the Jahn–Teller distorted
CuN2O4 polyhedra. In 1 the elongated Cu–O axial bonds stem
from the sulfonate groups whereas upon dehydration, they
Figure 4. Results of the magnetic susceptibility measurements for 1.
Plots of paramagnetic and reciprocal paramagnetic susceptibility (top)
as well as χ·T and effective magnetic moment as function of tempera-
ture are shown. The inset graph displays the switching from ferro-/
ferrimagnetic to antiferromagnetic interactions at 3.5 K.
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The Mixed-Linker CuII Coordination Polymer [Cu(HO3PC6H4SO3)(C10N2H8)]·H2O
(OH) 3410 cm–1, ν(Ar-H) 3080 w, δ(OH) 1650 m, ν(C=C) 1600 m,
ν(C=N) 1410 m, νasym(P–O, S–O) 1190 s, νsym(P–O, S–O) 1090 m,
δ(Ar-H) 810 m, 645 s.
originate from the phosphonate groups. Such switching phe-
nomenon in the coordination environment of the Jahn–Teller
distorted octahedra has been rarely observed in the literature.
[Cu(HL)(4,4'-bipy)] (1-h): 1-h was obtained by activating compound
1 at 200 °C under vacuum for 12 h. To avoid rehydration of 1-h to 1,
the dehydrated substance was stored in a vacuum desiccator with KOH
and P2O5 as the desiccant. C16H13CuN2O6PS (molecular mass:
455.88 g/mol); C 42.0 (calcd. 42.2); H 3.1 (2.9); N 6.1 (6.1); S 6.8
(7.0)%. IR (ATR): ν(Ar-H) 3070 cm–1 w, ν(C=C) 1610 m, ν(C=N)
1410 m, νasym(P–O, S–O) 1140 s, νsym(P–O, S–O) 1000 m, δ(Ar-H)
810 m, 642 s.
Experimental Section
Materials and Characterization Methods: All chemicals were com-
mercially available and used without further purification (Sigma–Al-
drich and ABCR), except for 4-phosphonobenzene-sulfonic acid (H3L)
which was synthesized according to the procedure reported
previously.[48] The three step synthesis of H3L was performed with 4-
bromobenzenesulfonyl chloride as the starting reactant. High-through-
put XRPD experiments were carried out in transmission mode using a
STOE high-throughput powder diffractometer (Cu-Kα1, λ = 1.5406 Å)
equipped with an image-plate position-sensitive detector (IPPSD).
MIR spectra were recorded with an ATI Matheson Genesis spectrome-
ter in the spectral range 4000–400 cm–1 using the KBr disc method as
well as an ALPHA-ST-IR Bruker spectrometer equipped with an ATR
unit. Thermogravimetric analyses were carried out in air atmosphere
(75 mL·min–1, 30–800 °C, 4 °C·min–1) using a NETZSCH STA 409
CD analyzer. The temperature dependent XRPD analysis in Debye–
Scherrer mode was carried out on a STOE Stadi-P diffractometer (Cu-
Kα1, λ = 1.5406 Å), equipped with a STOE high temperature capillary
furnace, using 0.3 mm quartz capillary tubes. CHNS analyses were
performed with an Eurovektor EuroEA Elemental Analyzer. The semi-
quantitative elemental analyses were performed with a Phillips ESEM
XL 30 hot cathode scanning electron microscope equipped with energy
dispersive X-ray (EDX) EDAX analyzer for elemental analysis. Mag-
netic measurements for compound 1 was performed with a Physical
Property Measuring System (PPMS) from Quantum Design (9 T mag-
net), at 1 T (DC field), respectively, in the temperature range of 2 to
X-ray Crystallography: A suitable crystal of the compound was care-
fully selected from the HT experiments using a polarizing microscope.
Single-crystal X-ray diffraction for 1 was performed with a STOE
IPDS-1 diffractometer equipped with a fine-focus sealed tube (Mo-Kα
radiation, λ = 0.71073 Å). For data reduction and absorption correction
the programs XRED and XSHAPE were used.[50] The single crystal
structure was solved by direct methods and refined using the program
package SHELXTL.[51] Experimental data and results of the structure
determination of 1 are given in Table 1.
Table 1. Crystallographic data and details on the structure determina-
tion from single crystal of [Cu(HL)(4,4'-bipy)]·H2O (1) and from Riet-
veld refinement of [Cu(HL)(4,4'-bipy)] (1-h).
1
1-h
formula
MW /g·mol–1
crystal system
space group
a /Å
C16H15CuN2O7PS
473.87
C16H13CuN2O6PS
455.89
monoclinic
C2 (no. 5)
15.7374(12)
11.0896(6)
10.6253(8)
108.243(6)
1761.14(22)
4
monoclinic
C2 (no. 5)
16.9581(7)
b /Å
11.1033(3)
300
K (ZFC). Diamagnetic susceptibility of compound 1 (–
c /Å
10.2310(5)
237.51 × 10–6 cm3·mol–1) was calculated using the tables in the litera-
ture and diamagnetic correction was applied during the data
analysis.[49]
β /°
103.866(2)
V /Å3
1870.27(10)
Z
4
ρcalcd. /g·cm–3
T /K
1.787
1.572
High-Throughput Experiments: The reaction system Cu2+/H3L/4,4'-
bipy/solvent was investigated using various molar ratios Cu2+/H3L/4,4'-
bipy employing high-throughput methods (process and compositional
parameters are listed in Tab. S1–S2 in the Supporting Information).
Each HT experiment was performed under solvothermal conditions in
a custom-made stainless steel high-throughput reactor system contain-
ing 48 PTFE inserts each. The PTFE inserts have a maximum volume
of 300 μL.[34] All reagents were manually dosed using aqueous solu-
tions of the reactants. The concentrations as well as the exact amounts
of starting materials are given in the Table S1–S2. The evaluation of
the HT experiments is based on XRPD measurements.
293 (5)
583 (5)
μ /mm–1
min/max transm.
1.495
–
–
0.770 / 0.862
2–29.2
θ
min, θmax /°
4–40
meas. reflns.
unique reflns.
16314
4619
–
–
reflns. [Fo > 4σ(Fo)] 4368
–
parameter
258
70
R-values
Rint = 0.038
R1,wR2 [all data]
= 0.036, 0.071
R1,wR2 [Fo > 4σ(Fo)]
= 0.032, 0.069
1.085
Rexp = 0.023
RBragg = 0.008
Rp = 0.032
Rwp = 0.042
1.805
GoF
[Cu(HL)(4,4'-bipy)]·H2O (1): In a typical HT experiment 1 was ob-
tained by the following procedure (molar ratio Cu2+:H3L:4,4'-bipy =
1:1:1). Aqueous solutions of Cu(NO3)2·3H2O (0.02 mmol, 40 μL), H3L
(0.02 mmol, 20 μL), 4,4'-bipy (0.02 mmol, 20 μL) and additional H2O
Δpmax, Δpmin /e·Å–3 0.43, –0.38
–
(120 μL) were mixed in a 300 μL reactor and heated for 48 h at The crystal structure of 1-h was determined on the basis of X-ray
130 °C. The scale-up of 1 was accomplished using glass tubes powder diffraction data. The XRPD pattern of a capillary-filled sample
(DURAN® culture tubes 12 × 100 mm D50 GL 14 M.KAP, SCHOTT was recorded with a STOE Stadi-P powder diffractometer in Debye–
261351155). Cu(NO3)2 3H2O·(500 μL, 0.2 mmol), H3L (500 μL, Scherrer geometry using Ge(111) monochromated Cu-Kα1 radiation.
0.2 mmol), and 4,4'-bipy (1000 μL, 0.2 mmol) were combined and The details of XRPD measurements are as following; 2θ range = 8–
sonicated for 10 min. The mixture was heated at 130 °C for 48 h. The 80°, step width = 0.01, data points = 4800, no. of observed reflec-
synthesis yielded a light blue powder (40 mg, 42 mol-% based on H3L, tions = 105, T = 583(5) K. EXPO2009 software with TREOR indexing
final pH value of reaction mixture = 1–2) which was identified by algorithm was used to determine the cell parameters.[52] The Rietveld
XRPD. C16H15CuN2O7PS (molecular mass: 473.87 g/mol); C 40.6 refinement (Figure 6) was performed with the TOPAS package[53] us-
(calcd. 40.5); H 2.9 (3.2); N 6.2 (6.0); S 6.8 (6.8)%. IR (KBr): ν = ing the structure of 1 as the starting model. Preferred orientation of
˜
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P. Maniam, N. Stock
ARTICLE
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Figure 6. Observed (circles) and calculated (line) XRPD pattern as
well as the difference profile of the Rietveld refinement of 1-h; Al-
lowed Bragg reflex positions are marked by vertical lines.
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Crystallographic data (excluding structure factors) for the structures 1
and 1-h reported in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no. CCDC-
822923 (1) and -823351 (1-h). Copies of the data can be obtained free
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Supporting Information (see footnote on the first page of this article):
Experimental details of the HT-investigations; selected bond lengths
and angles; comparison of measured and simulated XRPD patterns, IR
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Acknowledgement
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The authors thank Inke Jeß and Professor Christian Näther for the
acquisition of the single-crystal data, Beatrix Seidlhofer for TG meas-
urements, Henning Lühmann and Maren Rassmussen for magnetic
measurements. This work was supported by the Deutsche Forschungs-
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