Two SrII coordination compounds based on tetrazole-carboxylate ligands

Article abstract of DOI:10.1515/mgmc-2016-0019

Two novel coordination compounds, [Sr(atzp)₂(H₂O)₂]·CH₃OH (1) and [Sr(dtzpha)(H₂O)₃]·4H₂O (2) [Hatzp=5-aminotetrazole-1-propionic acid, H₂dtzpha=1,3-di(tetrazol-5-yl)benzene-N2,N2'-diacetic acid)], have been generated by using 5-aminotetrazole-1-propionic acid and 1,3-di(tetrazol-5-yl)benzene-N2,N2'-diacetic acid to react with strontium salts, respectively. X-ray diffraction analysis reveals that carboxylic groups of two ligands show the same coordination mode (the μ_1,1,3-COO coordination mode), compound 1 displays a 1D structure while compound 2 shows a 2D structure, which implies the influence of the number of the carboxylic acid groups. Luminescence properties of 1 and 2 were investigated at room temperature in the solid state.

Full text of DOI:10.1515/mgmc-2016-0019

Main Group Met. Chem. 2016; 39(3-4): 105–111
Meng-Jie Cao, Li-Li Miao, Meng-Yue Guo, Gao-Wen Yang* and Qiao-Yun Li*
II
Two Sr coordination compounds based on
tetrazole-carboxylate ligands
DOI 10.1515/mgmc-2016-0019
Received April 25, 2016; accepted August 3, 2016; previously
published online August 24, 2016
ligands, in which carboxylate oxygen atoms and tetra-
zolyl nitrogen atoms both have good coordination
capacities, have been widely employed because, in the
self-assembling process, the shapes of the tetrazole-
carboxylate ligands are very important in the control of
the frameworks. Therefore, it is possible to generate the
targeted architecture through the choice of tetrazole-
carboxylate ligands.
Abstract: Two novel coordination compounds,
[
Sr(atzp) (H O) ]·CH OH (1) and [Sr(dtzpha)(H O) ]·4H O
2
2
2
3
2
3
2
(
2) [Hatzpꢀ=ꢀ5-aminotetrazole-1-propionic acid, H dtzphaꢀ=
2
ꢀ
1,3-di(tetrazol-5-yl)benzene-N2,N2′-diacetic acid)], have
been generated by using 5-aminotetrazole-1-propionic
acid and 1,3-di(tetrazol-5-yl)benzene-N2,N2′-diacetic
acid to react with strontium salts, respectively. X-ray dif-
fraction analysis reveals that carboxylic groups of two
ligands show the same coordination mode (the μ1,1,3-COO
coordination mode), compound 1 displays a 1D structure
while compound 2 shows a 2D structure, which implies
the influence of the number of the carboxylic acid groups.
Luminescence properties of 1 and 2 were investigated at
room temperature in the solid state.
Based on the above facts, we have successfully
designed two novel tetrazole-carboxylate ligands,
5
-aminotetrazole-1-propionic acid and 1,3-di(tetrazol-
5
-yl)benzene-N2,N2′-diacetic acid to construct novel
coordination compounds with fascinating structures.
After comparing 5-aminotetrazole-1-propionic acid
with 1,3-di(tetrazol-5-yl)benzene-N2,N2′-diacetic acid,
1
,3-di(tetrazol-5-yl)benzene-N2,N2′-diacetic acid has more
carboxylate group, which enables it to increase the con-
nectivity of the network and thus to promote an increase
Keywords: crystal structure; Hatzp; H dtzpha; Sr(II); tetra- of the dimensionality. So, in our study, 5-aminotetrazole-
2
zole-carboxylate ligands.
1-propionic acid and 1,3-di(tetrazol-5-yl)benzene-N2,N2′-
diacetic acid have been chosen to react with strontium
salts, thus obtaining [Sr(atzp) (H O) ]·CH OH (1) and
2
2
2
3
Introduction
[Sr(dtzpha)(H O) ]·4H O (2) (Scheme 1). The structures
2
3
2
and the luminescence properties of the compounds 1 and
It is generally acknowledged that there are many 2 also have been reported.
factors, such as metal-ligand ratio, solvents, tempera-
ture, organic ligands and so on, having an inevitable
impact on the structures of the targeted molecules (for
Results and discussion
reviews, see Dong et al., 2008; Li et al., 2014, 2015; Zou
et al., 2014a,b). For these influencing factors, organic
ligands, in particular, play a very important role in the Synthesis consideration and general
novel structures of coordination compounds. Indeed,
characterizations of 1 and 2
in multitudinous organic ligands, tetrazole-carboxylate
Compound1isstabletowardsairwhilecompound2isnot.
All general characterizations are carried out with crystal
−
1
samples. For 1–2, strong absorptions at 1660–1621 cm
*
Corresponding authors: Gao-Wen Yang and Qiao-Yun Li, Jiangsu
correspond to ν(COO) vibration of the carboxylate group.
Laboratory of Advanced Functional Material, Department of
Chemistry and Material Engineering, Changshu Institute of
Technology, Changshu 215500, Jiangsu, P. R. China,
e-mail: ygwsx@126.com (G.-W. Yang);
The formation of the tetrazole group is supported by the
−1
emergence of the peak from 1400 to 1549 cm (Perkovic,
2
000). In addition, the strong and broad band centered
liqiaoyun61@126.com (Q.-Y. Li)
−1
at 3130, 3392, 3433 cm for the coordination compounds
are attributable to the O-H stretching vibration of water,
including water for both compounds 1 and 2, and metha-
nol just for compound 2.
Meng-Jie Cao, Li-Li Miao and Meng-Yue Guo: Jiangsu Laboratory
of Advanced Functional Material, Department of Chemistry and
Material Engineering, Changshu Institute of Technology, Changshu
215500, Jiangsu, P. R. China
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06ꢀꢀꢀꢀꢁꢀM.-J. Cao et al.: Sr coordination derivatives of tetrazole-carboxylates
II
1
Scheme 1:ꢀThe synthesis procedure caused by the differences in
the number of carboxylic acid groups of the ligands.
Figure 2:ꢀThe 1D chain structure of 1 which is extending along the
a axis.
Hydrogen atoms are omitted for clarity.
Crystal structure of [Sr(atzp) (H O) ]·CH OH (1)
2
2
2
3
coordination mode, forming a 1D chain extending
Single crystal X-ray diffraction reveals that compound along the a axis with the Sr···Sr distances of 4.1536 and
̅
crystallizes in triclinic space group P1. As shown in
4.1857 Å and the Sr···Sr···Sr angle of 147.352° (Figure 2).
1
Figure 1, each Sr(II) is eight-coordinated by six car- In 1, many hydrogen bonds link the layers into a 3D
boxylate-O atoms (O1, O1A, O2, O3, O3B, O5) from four supramolecular framework. Tetrazole ring provides an
5
(
-aminotetrazole-1-propionic acid ligands, two O atoms intralayer hydrogen bond [N(5)···O(7), 2.983(17) Å] to
O5, O6) from two water molecules, forming a distorted O of the uncoordinated water and amino provides an
square-antiprism structure. In 1, two adjacent Sr(II) ions intralayer hydrogen bond [N(10)···N(3), 3.014(6) Å] to N
are doubly bridged by two carboxylate groups from two of the tetrazole ring to consolidate the layer structure.
5
-aminotetrazole-1-propionic acid ligands in a μ1,1,3-COO Another hydrogen bond connects the layers through
water via hydrogen bonds [O(5)···O(2), 2.898(5) Å] to O
of the carboxylate (Figure 3).
Crystal structure of [Sr(dtzpha) (H O) ]·4H O (2)
2
3
2
̅
Compound 2 crystallizes in triclinic space group P1. As
shown in Figure 4, each Sr(II) is nine-coordinated by
Figure 1:ꢀThe coordination environment of Sr(II) in 1.
Hydrogen atoms are omitted for clarity.
Figure 3:ꢀView of 1, showing hydrogen-bonding interactions.
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M.-J. Cao et al.: Sr coordination derivatives of tetrazole-carboxylatesꢂꢁꢀꢀꢀꢂ107
II
Figure 4:ꢀThe coordination environment of Sr(II) in 2.
Hydrogen atoms are omitted for clarity.
six carboxylate-O atoms (O1, O1A, O2A, O3C, O4B, O4C) can be simplified as a (4,4) rhomboidal grid topology with
from four 1,3-di(tetrazol-5-yl)benzene-N2,N2′-diacetic diagonal lengths of 16.8821 and 17.9619 Å (Figure 5B), and
acid ligands, three water-O atoms (O5, O6, O7), forming many hydrogen bonds link the layers into a 3D supra-
a monocapped square-antiprism coordination geometry. molecular framework. Uncoordinated water provides an
In 2, both the carboxylic acids of the 1,3-di(tetrazol-5-yl) intralayer hydrogen bond [O(7)···N(1), 3.33(2) Å] to N of the
benzene-N2,N2′-diacetic acid ligand coordinate to four tetrazole ring and coordinated water provides an intra-
Sr(II) ions in a μ1,1,3-COO coordination mode, thereby layer hydrogen bond [O(5)···N(8), 3.004(9) Å] to N of the
forming a 2D layer structure (Figure 5A). The structure benzene ring to consolidate the layer structure. Another
A
B
Figure 5:ꢀ(A) The 2D chain structure of 2. Hydrogen atoms are omitted for clarity. (B) The (4,4) topology of compound 2.
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08ꢀꢀꢀꢀꢁꢀM.-J. Cao et al.: Sr coordination derivatives of tetrazole-carboxylates
II
1
Figure 6:ꢀView of 2, showing hydrogen-bonding interactions.
hydrogen bond connects the layers through water via
hydrogen bonds [O(5)···O(1), 3.174(11) Å] to O of the car-
boxylate (Figure 6).
Luminescent properties
The luminescence properties of 1–2 and the free ligands
were investigated in the solid state at room temperature.
As shown in Figure 7, the free ligands, 5-aminotetra-
zole-1-propionic acid and 1,3-di(tetrazol-5-yl)benzene-
N2,N2′-diacetic acid exhibit maximum emissions at
4
33 and 360 nm upon excitations at 371 and 315 nm,
respectively. Compounds 1 and 2 exhibit photolumi-
Figure 7:ꢀ(A) Emission spectra of compound 1 and 5-aminotetra-
nescence with maximum emissions at 405 and 409 nm
zole-1-propionic acid in the solid state at room temperature (for
upon excitations at 357 and 336 nm, respectively. Hence 5-aminotetrazole-1-propionic acid λ ꢁꢃ=ꢃꢁ371 nm, for 1 λ ꢁꢃ=ꢃꢁ357 nm).
ex
ex
fluorescent emissions could be tentatively assigned to (B) Emission spectra of compound 2 and 1,3-di(tetrazol-5-yl)
benzene-N2,N2′-diacetic acid in the solid state at room temperature
the intraligand fluorescent emissions. Compared to the
[
for 1,3-di(tetrazol-5-yl)benzene-N2,N2′-diacetic acid λ ꢁꢃ=ꢃꢁ315 nm,
ex
corresponding ligands, a blue shift of 28 nm for com-
pound 1 and a red shift of 49 nm for compound 2 have
been observed, respectively, which implies that the
for 2 λ ꢁꢃ=ꢃꢁ336 nm].
ex
shifts may be attributed to the coordination effects of with distinctly different structures. For 1, the bidentate
Sr with the two ligands (Zou et al., 2014a,b). Gener- 5-aminotetrazole-1-propionic acid ligand is capable of
II
ally, the intraligand fluorescence emission wavelength coordinating the neighboring Sr(II) ions through two car-
is determined by the energy gap between the π and π* boxylate-O atoms in a μ1,1,3-COO coordination mode to form
molecular orbitals of the free ligand, which is related a 1D chain. However, in 2, the 1,3-di(tetrazol-5-yl)benzene-
to the extent of π conjugation (Li et al., 2011; Wu et al., N2,N2′-diacetic acid ligand acts as a hexadentate ligand
2
015; Zou et al., 2015).
to coordinate four Sr(II) ions via four carboxylate-O atoms
in a μ1,1,3-COO coordination mode to form a 2D structure,
demonstrating that the differences between the coordina-
tion structures are reflected in the number of carboxylic
acid groups. The photoluminescence measurements show
Conclusion
1
and 2 exhibit strong photoluminescence at room tem-
In this study, under the same experimental condi- perature in the solid state.
tions, the reaction of 5-aminotetrazole-1-propionic acid
Inspired by these observations, the approach that
and 1,3-di(tetrazol-5-yl)benzene-N2,N2′-diacetic acid changes the shape of tetrazole-carboxylate ligands via
with strontium salts, respectively gives two compounds controlling the number of carboxylic acid is expected to
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M.-J. Cao et al.: Sr coordination derivatives of tetrazole-carboxylatesꢂꢁꢀꢀꢀꢂ109
II
triethylammonium chloride. 5-Aminotetrazole-1-propionic acid
be effective for further construction of novel coordination
frameworks.
(
Hatzp) was prepared by the reaction of 5-aminotetrazole with
3-bromopropionic acid in sodium hydroxide solution, while the
reaction of 1,3-di(tetrazol-5-yl)benzene with chloroacetic acid in
sodium hydroxide solution gave mostly 1,3-di(tetrazol-5-yl)benzene-
N2,N2′-diacetic acid(H dtzpha) products (Shen et al., 2015, 2016;
2
Experimental section
Materials and instrumentation
Wang et al., 2016; Yang et al., 2016). For Hatzp: anal. calcd for
C H N O : C, 43.64; H, 3.05; N, 33.93%. Found: C, 43.89; H, 3.11; N,
1
2
10
8
4
34.33%. IR (KBr, cm−1): 3337(m); 3160(m); 1721(s); 1670(s); 1415(m);
1
596(w); 1225(w); 1472(w); 1372(s); 1257(m); 1096(m); 1063(m);
1
7
88(w); 695(m). HNMR (DMSO, δppm): 4.71, 5.82(-CH ); 9.52(-NH );
General chemicals were commercially available reagents of analyti-
cal grade and were used without further purification. The elemental
analyses for C, H, and N were performed on a PE-2400 Microana-
lyzer (PerkinElmer, USA). All NMR spectra were taken on a Bruker
AVANCEIII-HD-400 MHz spectrometer (Bruker, Switzerland). The IR
spectra were recorded on a thermo NICOLET-380 instrument (Thermo
2
2
1
3
1
1
1.49(-COOH). CNMR (DMSO, δppm): 30.50(-CH -); 56.85(-N-CH -);
2
2
50.52(Cꢀ=ꢀN); 173.88(Cꢀ=ꢀO). For H dtzpha: anal. calcd for C H N O :
2
8
10
8
4
C, 34.05; H, 3.57; N, 39.70%. Found: C, 34.33; H, 3.60; N, 39.56%. IR
−1
(
KBr, cm ): 3263(s); 3108(m); 2990(m); 1719(s); 1550(s); 1423(w);
1
1
236(w); 1045(w); 1457(w); 817(w); 744(w); 664(w); 532(w). HNMR
−1
(DMSO, δppm): 5.28(-N-CH -); 7.70, 8.07, 8.26(-C H ); 11.98(-COOH).
Fisher Scientific, USA) as KBr disk (4000–400 cm ). Photolumines-
cent spectra were performed on a Hitachi F-4600 spectrofluorometer
2
6
4
1
3
CNMR (DMSO, δppm): 49.98(-N-CH -); 119.12, 129.68, 130.36,
2
1
34.36(Cꢀ=ꢀC); 166.13(Cꢀ=ꢀN); 167.21(-COOH).
(
Hitachi, Japan). Single crystal X-ray diffraction was carried out by a
Rigaku SCXmini CCD diffractometer.
Synthesis of [Sr(atzp) (H O) ]·CH OH (1)
2
2
2
3
Synthesis of 5-aminotetrazole-1-propionic acid (Hatzp)
5
-Aminotetrazole-1-propionic acid (Hatzp) (0.0114 g, 0.1 mmol) was
and 1,3-di(tetrazol-5-yl)benzene-N2,N2′-diacetic acid
dissolved in 0.5 mL distilled water, and the pH value was adjusted to
6 with KOH (0.2 mol/L). SrCl ·6H O (0.0267 g, 0.1 mmol) and methanol
(
H dtzpha)
2
2
2
(
3 mL) were added to the solution. The mixture was heated at 60°C in
5
-Aminotetrazole and 1,3-di(tetrazol-5-yl)benzene were prepared a thermostat water bath for 1 h, then cooled to the room temperature,
by [2ꢁ+ꢁ3] cycloaddition reactions, by treating dicyandiamide and filtered; the block crystals 1 was obtained in mother liquors. For
or 1,3-dicyanobenzene with NaN3 in toluene in the presence of 1, yield: 54% based on Sr2 consumed. Anal. calcd for C H N O Sr:
+
9
20 10
7
Table 1:ꢀSelected crystallographic data and structure refinement for 1–2.
Compound
Empirical formula
Formula mass
Crystal system
Space group
a (Å)
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢁ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢂ
C H N O Sr
C H N O Sr·ꢊ(H O)
ꢄ
ꢅꢆ ꢇꢆ
ꢈ
ꢇꢅ ꢇꢅ 8 ꢉ ꢅ
ꢊꢉꢈ.ꢄꢈ
Triclinic
Pꢇ
ꢋꢅꢌ.ꢄ8
Triclinic
̅
Pꢇ
̅
8.ꢆꢆꢅ8(ꢇꢉ)
ꢇꢆ.8ꢌꢅ(ꢅ)
ꢇꢇ.8ꢅꢅ(ꢅ)
ꢈꢋ.ꢌꢋ(ꢌ)
ꢈꢄ.ꢇꢉ(ꢌ)
ꢈ8.ꢌꢋ(ꢌ)
ꢄꢉꢆ.ꢄ(ꢌ)
ꢅ
ꢄ.ꢌꢌꢋ8(ꢇꢆ)
ꢇꢆ.ꢋꢋ8ꢇ(ꢇꢅ)
ꢇꢇ.ꢊꢊꢌꢌ(ꢇꢌ)
ꢇꢆꢆ.ꢇꢋꢆꢆ(ꢇꢋ)
ꢄꢋ.ꢉꢈꢌꢆ(ꢇꢊ)
ꢇꢆꢉ.ꢅꢆꢌꢆ(ꢇꢌ)
ꢇꢆꢋꢌ.ꢆ(ꢅ)
ꢅ
b (Å)
c (Å)
α (°)
β (°)
γ (°)
ꢌ
V (Å )
Z
T/K
ꢅꢄꢇ(ꢅ)
ꢅꢄꢉ(ꢅ)
−
ꢌ
Dcalcd (g.cm )
ꢇ.ꢉꢇꢈ
ꢇ.ꢉꢋꢌ
−
ꢇ
μ (mm )
ꢅ.8ꢉꢆ
ꢅ.ꢉꢅꢈ
Reflections collected
Unique reflections (Rint)
No. observations [Iꢃ>ꢃꢅσ(I)]
No. variables
ꢇꢆꢆꢈꢌ
ꢉꢇꢉꢌ
ꢊꢌ8ꢌ (ꢆ.ꢆꢌ8ꢌ) ꢃ
ꢌꢋꢉꢋ (ꢆ.ꢆꢇꢋꢋ)
ꢌꢇꢈꢈ
ꢌꢈꢉꢊ
ꢅꢌꢋ
ꢃ
ꢃ
ꢅꢉꢉ
ꢆ.ꢆꢉꢇꢈ, ꢆ.ꢇ8ꢊꢊ
ꢆ.8ꢌꢉ
ꢇ.ꢈꢈꢌ
−ꢆ.8ꢅꢋ
a
b
R , wR [Iꢃ>ꢃꢅσ(I)]
ꢆ.ꢆꢋꢅꢅ, ꢆ.ꢇꢊꢊꢌꢃ
ꢇ
ꢅ
c
GOF
ꢇ.ꢆꢉꢄ
ꢇ.ꢆꢉꢆ
−ꢆ.8ꢈꢋ
ꢃ
ꢃ
ꢃ
ꢌ
Δ/ρmax (e/Å )
ꢌ
Δ/ρmin (e/Å )
a
Rꢁꢁ=ꢁꢁΣ||F |−|F |/Σ|F |. Rwꢁꢃ=ꢃꢁ[Σw(F ꢁ−ꢁF ) /Σw(F ) ] . GOFꢁꢃ=ꢃꢁ{Σ[w((F ꢁ−ꢁF ) )/(nꢁ−ꢁp)]}1/2, where n, number of reflections; p, total numbers of
b
2
2
2
2
2
1/2
c
2
2 2
o
c
o
o
c
o
o
c
parameters refined.
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10ꢀꢀꢀꢀꢁꢀM.-J. Cao et al.: Sr coordination derivatives of tetrazole-carboxylates
II
1
C, 23.10; H, 4.31; N, 29.93%. Found: C, 23.33; H, 4.42; N, 30.34%. IR was adjusted to 6 with KOH (0.2 mol/L). SrCl ·6H O (0.0267 g, 0.1 mmol)
2
2
−
1
(
KBr, cm ): 3392(s), 1653(m), 1638(m), 1549(s), 1493(w), 1443(m), and methanol (3 mL) were added to the solution. The mixture was
1
269(w), 1126(w), 1087(w), 956(w), 674(m).
heated at 60°C in a thermostat water bath for 1 h, then cooled to the
room temperature, and filtered; the block crystals 2 were obtained in
2+
mother liquors. For 2, yield: 40% based on Sr consumed. Anal. calcd
Synthesis of [Sr(dtzpha)(H O) ]·4H O (2)
2
3
2
for C H N O Sr: C, 27.51; H, 3.85; N, 21.39%. Found: C, 27.73; H, 3.78;
12
20
8
10
−1
N, 21.59%. IR (KBr, cm ): 3433(s), 3130(s), 1660(m), 1621(s), 1453(m),
1
,3-Di(tetrazol-5-yl)benzene-N2,N2′-diacetic acid (H dtzpha) (0.0332 1433(m), 1400(s), 1205(w), 1139(w), 1069(m), 951(w), 862(w), 834(w),
2
g, 0.1 mmol) was dissolved in 1 mL distilled water, and the pH value 814(w), 742(m), 680(w).
Table 2:ꢀSelected bond distances and angles for compounds 1 and 2 (Å/°).
Compound ꢁ
Sr(ꢇ)-O(ꢌB)
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢅ.ꢋꢆꢋ(ꢌ)ꢃ
ꢅ.ꢋꢋꢊ(ꢌ)ꢃ
Sr (ꢇ)-O(ꢇA)
Sr (ꢇ)-O(ꢊ)
Sr(ꢇ)-O(ꢅ)
Sr (ꢇ)-O(ꢌ)
O(ꢌB)-Sr(ꢇ)-O(ꢉ) ꢃ
O(ꢌB)-Sr(ꢇ)-O(ꢊ) ꢃ
O(ꢉ)-Sr(ꢇ)-O(ꢊ)
O(ꢇA)-Sr(ꢇ)-O(ꢋ) ꢃ
O(ꢊ)-Sr(ꢇ)-O(ꢋ)
O(ꢇA)-Sr(ꢇ)-O(ꢅ) ꢃ
O(ꢊ)-Sr(ꢇ)-O(ꢅ)
O(ꢌB)-Sr(ꢇ)-O(ꢇ) ꢃ
O(ꢉ)-Sr(ꢇ)-O(ꢇ)
O(ꢋ)-Sr(ꢇ)-O(ꢇ)
O(ꢌB)-Sr(ꢇ)-O(ꢌ) ꢃ
O(ꢉ)-Sr(ꢇ)-O(ꢌ)
O(ꢋ)-Sr(ꢇ)-O(ꢌ)
O(ꢇ)-Sr(ꢇ)-O(ꢌ)
ꢃ
ꢃ
ꢃ
ꢃ
ꢅ.ꢋꢆꢈ(ꢌ)
ꢅ.ꢋꢈꢄ(ꢌ)
Sr(ꢇ)-O(ꢉ)
Sr(ꢇ)-O(ꢋ)
ꢅ.ꢉꢌꢅ(ꢌ)ꢃ
ꢅ.ꢉꢈꢈ(ꢌ)
Sr(ꢇ)-O(ꢇ)
ꢅ.ꢉꢄꢆ(ꢌ)ꢃ
ꢅ.ꢈꢋꢉ(ꢌ)
O(ꢌB)-Sr(ꢇ)-O(ꢇA)
O(ꢇA)-Sr(ꢇ)-O(ꢉ)
O(ꢇA)-Sr(ꢇ)-O(ꢊ)
O(ꢌ)-Sr(ꢇ)-O(ꢋ)
O(ꢉ)-Sr(ꢇ)-O(ꢋ)
O(ꢌ)-Sr(ꢇ)-O(ꢅ)
O(ꢉ)-Sr(ꢇ)-O(ꢅ)
O(ꢋ)-Sr(ꢇ)-O(ꢅ)
O(ꢇA)-Sr(ꢇ)-O(ꢇ)
O(ꢊ)-Sr(ꢇ)-O(ꢇ)
O(ꢅ)-Sr(ꢇ)-O(ꢇ)
O(ꢇA)-Sr(ꢇ)-O(ꢌ)
O(ꢊ)-Sr(ꢇ)-O(ꢌ)
O(ꢅ)-Sr(ꢇ)-O(ꢌ)
ꢇꢋꢆ.8ꢋ(ꢇꢇ)ꢃ
ꢈꢈ.ꢄꢋ(ꢇꢇ)ꢃ
ꢈꢉ.ꢆꢄ(ꢇꢇ)ꢃ
ꢈꢅ.ꢆꢋ(ꢇꢇ)ꢃ
ꢇꢆꢄ.ꢉ8(ꢇꢌ)ꢃ
8ꢇ.ꢋꢄ(ꢇꢆ)ꢃ
8ꢆ.ꢋ8(ꢇꢅ)ꢃ
ꢇꢋꢆ.ꢄꢉ(ꢇꢆ)ꢃ
ꢈꢅ.ꢈꢊ(ꢇꢇ)ꢃ
ꢈꢋ.ꢆ8(ꢇꢅ)ꢃ
ꢊ8.ꢈꢊ(ꢄ)ꢃ
8ꢈ.ꢈꢊ(ꢇꢇ)
ꢇꢅꢌ.ꢌꢆ(ꢇꢆ)
ꢇꢊ8.ꢊꢋ(ꢇꢇ)
88.8ꢄ(ꢇꢆ)
8ꢈ.ꢋꢆ(ꢇꢌ)
ꢇꢅꢆ.ꢆꢄ(ꢇꢆ)
ꢄꢈ.ꢅꢋ(ꢇꢌ)
ꢇꢌꢆ.ꢆꢈ(ꢇꢆ)
8ꢆ.ꢌꢌ(ꢇꢇ)
ꢇꢋꢈ.ꢆꢄ(ꢇꢆ)
ꢈꢋ.8ꢊ(ꢇꢇ)
ꢇꢋꢉ.ꢉꢉ(ꢇꢅ)
8ꢇ.ꢅꢌ(ꢇꢇ)
ꢄꢈ.ꢊ8(ꢇꢆ)
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢇꢅꢌ.8ꢈ(ꢇꢆ)ꢃ
ꢊ8.ꢋꢉ(ꢄ)ꢃ
8ꢆ.ꢉꢄ(ꢇꢆ)ꢃ
ꢃ
ꢃ
ꢃ
Compound ꢂ
Sr(ꢇ)-O(ꢇ)
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢅ.ꢈꢆꢌ(ꢋ)ꢃ
ꢅ.ꢈꢋꢉ(ꢈ)ꢃ
Sr(ꢇ)-O(ꢊB)
Sr(ꢇ)-O(ꢋ)
Sr(ꢇ)-O(ꢊC)
Sr(ꢇ)-O(ꢇA)
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢅ.ꢈꢇ8(ꢋ)
ꢅ.8ꢅꢉ(ꢈ)
ꢅ.ꢄꢆꢉ(ꢋ)
ꢅ.ꢄꢇꢆ(ꢋ)
Sr(ꢇ)-O(ꢉ)
Sr(ꢇ)-O(ꢈ)
ꢅ.ꢄꢅ8(ꢉ)ꢃ
Sr(ꢇ)-O(ꢌC)
ꢅ.ꢄꢆ8(ꢋ)ꢃ
ꢅ.ꢄꢌꢊ(ꢉ)ꢃ
Sr(ꢇ)-O(ꢅA)
O(ꢇ)-Sr(ꢇ)-O(ꢊB)
O(ꢊB)-Sr(ꢇ)-O(ꢉ)
O(ꢊB)-Sr(ꢇ)-O(ꢋ)
O(ꢌC)-Sr(ꢇ)-O(ꢈ)
O(ꢇA)-Sr(ꢇ)-O(ꢈ)
O(ꢇ)-Sr(ꢇ)-O(ꢊC)
O(ꢉ)-Sr(ꢇ)-O(ꢊC)
O(ꢌC)-Sr(ꢇ)-O(ꢅA)
O(ꢊB)-Sr(ꢇ)-O(ꢌC)
O(ꢋ)-Sr(ꢇ)-O(ꢌC)
O(ꢊC)-Sr(ꢇ)-O(ꢌC)
O(ꢊB)-Sr(ꢇ)-O(ꢇA)
O(ꢋ)-Sr(ꢇ)-O(ꢇA)
O(ꢊC)-Sr(ꢇ)-O(ꢇA)
O(ꢇA)-Sr(ꢇ)-O(ꢅA)
O(ꢉ)-Sr(ꢇ)-O(ꢅA)
O(ꢇ)-Sr(ꢇ)-O(ꢈ)
O(ꢉ)-Sr(ꢇ)-O(ꢈ)
ꢇꢋꢅ.ꢋꢅ(ꢇ8)ꢃ
8ꢌ.ꢊꢄ(ꢇꢈ)ꢃ
ꢈꢈ.ꢊꢉ(ꢇꢋ)ꢃ
ꢉꢆ.ꢊꢌ(ꢇꢉ)ꢃ
ꢈꢌ.ꢈꢋ(ꢇꢈ)ꢃ
ꢇꢇꢄ.ꢇꢆ(ꢇꢌ)ꢃ
ꢉ8.ꢅꢄ(ꢇꢉ)ꢃ
ꢇꢊꢆ.8ꢄ(ꢇꢋ)ꢃ
ꢇꢇꢅ.ꢈꢄ(ꢇꢅ)ꢃ
ꢇꢊꢅ.ꢋ(ꢅ)ꢃ
ꢊꢊ.ꢉꢈ(ꢇꢅ)ꢃ
ꢇꢇꢉ.ꢅꢋ(ꢇꢌ)ꢃ
ꢉꢉ.ꢄꢇ(ꢇ8)ꢃ
ꢇꢋꢄ.ꢄ8(ꢇ8)ꢃ
ꢇꢇꢇ.ꢇꢈ(ꢇꢌ)ꢃ
ꢇꢊꢈ.ꢈ(ꢅ)ꢃ
O(ꢇ)-Sr(ꢇ)-O(ꢉ)
O(ꢇ)-Sr(ꢇ)-O(ꢋ)
O(ꢉ)-Sr(ꢇ)-O(ꢋ)
ꢈꢉ.ꢅꢅ(ꢇꢈ)
ꢈꢄ.ꢋꢅ(ꢇ8)
ꢈꢋ.ꢇ(ꢅ)
O(ꢊC)-Sr(ꢇ)-O(ꢈ) ꢃ
O(ꢅA)-Sr(ꢇ)-O(ꢈ) ꢃ
O(ꢊB)-Sr(ꢇ)-O(ꢊC)ꢃ
O(ꢋ)-Sr(ꢇ)-O(ꢊC) ꢃ
O(ꢇ)-Sr(ꢇ)-O(ꢌC) ꢃ
O(ꢉ)-Sr(ꢇ)-O(ꢌC) ꢃ
O(ꢊC)-Sr(ꢇ)-O(ꢅA)ꢃ
O(ꢇ)-Sr(ꢇ)-O(ꢇA) ꢃ
O(ꢉ)-Sr(ꢇ)-O(ꢇA) ꢃ
O(ꢇA)-Sr(ꢇ)-O(ꢅA)ꢃ
O(ꢌC)-Sr(ꢇ)-O(ꢇA)ꢃ
O(ꢊB)-Sr(ꢇ)-O(ꢅA)ꢃ
O(ꢋ)-Sr(ꢇ)-O(ꢅA) ꢃ
O(ꢊB)-Sr(ꢇ)-O(ꢈ) ꢃ
8ꢄ.ꢆꢈ(ꢇꢋ)
8ꢊ.ꢉꢌ(ꢇꢈ)
ꢉ8.ꢅꢊ(ꢇꢊ)
ꢇꢌꢇ.ꢉꢋ(ꢇꢉ)
ꢈꢈ.8ꢋ(ꢇꢊ)
ꢈꢆ.ꢈꢇ(ꢇꢄ)
ꢇꢅꢋ.ꢊꢇ(ꢇꢅ)
ꢉꢉ.8ꢌ(ꢇꢈ)
ꢇꢌꢆ.ꢊꢋ(ꢇꢈ)
ꢊꢊ.ꢌꢋ(ꢇꢌ)
ꢇꢅꢈ.ꢄꢌ(ꢇꢌ)
ꢈꢈ.ꢅꢈ(ꢇꢌ)
ꢈꢋ.ꢉ(ꢅ)
ꢈꢊ.ꢉꢌ(ꢇꢈ)ꢃ
ꢇꢅꢉ.ꢄ(ꢅ)ꢃ
ꢇꢌꢅ.8ꢊ(ꢇꢋ)
ꢇꢌ8.ꢄꢋ(ꢇꢈ)
O(ꢋ)-Sr(ꢇ)-O(ꢈ)
ꢃ
Symmetry code: For 1: A: 1ꢁ−ꢁx, 1ꢁ−ꢁy, −z; B: 2ꢁ−ꢁx, 1ꢁ−ꢁy, ꢁ−z. For 2: A: 2ꢁ−ꢁx, −y, 2ꢁ−ꢁz; B: 1ꢁ+ꢁx, −ꢁ1ꢁ+ꢁy, 1ꢁ+ꢁz; C: 2ꢁ−ꢁx, 1ꢁ−ꢁy, 1ꢁ−ꢁz; D: 2ꢁ−ꢁx, −y, 1ꢁ−ꢁz.
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M.-J. Cao et al.: Sr coordination derivatives of tetrazole-carboxylatesꢂꢁꢀꢀꢀꢂ111
II
X-ray crystallography
Li, W. X.; Zou, J. H.; Wang, B. B.; Li, S.; Yang, G. W.; Li, Q.Y.; Qiu,
B.; Zhu, D. L. Four structurally diverse coordination complexes
based on a new flexible ligand. Transition Met. Chem. 2014, 39,
Suitable single crystals of compounds 1–2 were mounted on a Rigaku
SCXmini CCD diffractometer equipped with a graphite-monochro-
mated Mo-Kα radiation (λꢁꢀ=ꢀꢁ0.071073 Å) at 291 K. All absorption cor-
rections were performed using the Crystal-Clear programs. The crystal
421–429.
Li, Q. Y.; Tian, H.; Li, X.Y.; Zou, J. H.; Mei, G. D.; Qiu, L. J.; Wei, B.;
Yang, G. W. Substituted group directed assembly of zinc coordi-
nation compounds based on bifunctional ligands, from mono, di
2
structures of 1–2 were solved by direct methods and refined on F by
†
to tristetrazole-carboxylate . RSC Adv. 2015, 5, 43741–43749.
full-matrix least-squares using anisotropic displacement parameters
for all nonhydrogen atoms (Sheldrick, 1997). For 1–2, more relevant
refinement data and parameters are summarized in Table 1, and
selected bond lengths and angles are given in Table 2.
Perkovic, M. W. Allosteric manipulation of photoexcited state relaxa-
II
tion in (bpy)2Ru (binicotinic acid). Inorg. Chem. Commun. 2000,
3
9, 4962–496ꢍ.
Sheldrick, M. SHELXS-97 and SHELXL-97 program for the refinement
of crystal structures (University of Göttingen, Göttingen, 1997).
Shen, L.; Min, Y. T.; Wang, J.; Xu, Y.; Chen, H. J.; Yang, J.; Zhang,
X.; Wu, M. L.; Yang, G. W.; Wei, B. Coordination architectures
of lanthanum complexes based on bifunctional 5-substituted
tetrazole-carboxylate ligands. Z. Anorg. Allg. Chem. 2015, 642,
Supplementary crystallographic
data
CCDC 1451996 and 1451997 contain the supplementary
crystallographic data for 1 and 2 in this article. 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 UnionRoad, Cambridge
CB21EZ, UK; Fax:(+44) 1223-336-033; or e-mail: deposit@
ccdc.cam.ac.uk.
1
74–1ꢍ1.
Shen, L.; Cao, M. J.; Zhang, F. F.; Wu, Q.; Zhao, L.Y.; Lu, Y. M.;
Li, Q. Y.; Yang, G. Y.; Wei, B.; Zou, J. H. Three new manganese(II)
coordination complexes based on tetrazole carboxylate ligands.
Transition Met. Chem. 2016, 41, 125–131.
Wang, J.; Zhang, F. F.; Wei, B.; Wu, Q.; Cao, M. J.; Bai, Y.; Yang, G. W.
Counterion-directed assembly of praseodymium(III) compounds
based on the flexible ligand 5-aminotetrazole-1-propionic acid
(
Hatzp). Z. Anorg. Allg. Chem. 2016, 642, 169–173.
Wu, Q.; Cao, M. J.; Wei, B.; Bai, Y.; Tian, H.; Wang, J.; Liu, Q.; Li, Q.
Y.; Yang, G. W. pH dependent synthesis of structurally diverse
praseodymium(III) coordination polymers based on isomeric
ligands. Inorg. Chem. Commun. 2015, 62, 111–114.
Acknowledgments: The authors acknowledge the start-up
grant from Changshu Institute of Technology.
Yang, J.; Wang, J.; Wei, B.; Shen, L.; Tian, H.; Min, Y. T.; Cheng, H. J.;
Xu, Y.; Huang, J.; Wang, C. C.; et al. Coordination architectures of
copper(II) coordination polymers constructed from bifunctional
5-substituted-tetrazole-carboxylate ligands. Transition Met.
Chem. 2016, 41, 35–43.
Zou, J. H.; Cui, H. J.; Xu, B.; Zhu, D. L.; Li, Q. Y.; Yang, G. W.; Hua, Y.
C. Three new alkaline earth coordination compounds based on
Funding: Changshu Institute of Technology (Grant No.
1
2KFJJ010).
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