Synthesis and solid-state structures of 1,3- and 1,4-bis(diethylgallyl) benzene

Article abstract of DOI:10.1515/znb-2009-11-1218

The compounds 1,3-bis(diethylgallyl)benzene (3) and 1,4-bis(diethylgallyl) benzene (6) were prepared by reaction of the corresponding chloromercuriobenzenes with an excess of triethylgallium by applying pressure and higher temperatures. These compounds very easily undergo redistribution reactions in solution and in the solid state. Extremely air-sensitive crystals suitable for an X-ray crystal structure analysis were obtained from triethylgallium as solvent. The structural studies revealed the presence of tetra-coordinated carbon and gallium atoms in symmetric aryl-diethylgallyl bridging units. The coordination behavior of 3 and 6 in the solid state is quite different from that of the corresponding methyl-substituted compounds.

Full text of DOI:10.1515/znb-2009-11-1218

Z. Kristallogr. NCS 2016; aop
Open Access
ZChri-QyiasntgaXilonsg,tXriuu-YcintguSroeng aonfd Xdu-iLaiaqnguNiae*-bis(2-methyl-1H-
imidazole-4,5-dicarboxylato-κ2-O,N)cadmium(II)
tetrahydrate, C12H22CdN4O14
Table 1: Data collection and handling.
Crystal:
Colourless, blocks
Size 0.22 × 0.20 × 0.16 mm
Mo Kα radiation (0.71073 Å)
11.5 cm−1
Wavelength:
µ:
Diꢀractometer, scan mode:
2θmax, completeness:
N(hkl)measured, N(hkl)unique, Rint
Criterion for Iobs, N(hkl)gt:
Bruker APEXII, φ and ω
59.0°, >99%
:
3874, 1879, 0.023
Iobs > 2 σ(Iobs), 1863
164
N(param)reꢁned
:
Programs:
SHELX [10], Bruker programs [11]
Table 2: Fractional atomic coordinates and isotropic or equivalent
DOI 10.1515/ncrs-2016-0068
Received March 4, 2016; accepted June 13, 2016; available
online June 25, 2016
isotropic displacement parameters (Å2).
Atom
x
y
z
Uiso*/Ueq
Abstract
Cd1
O1
1.0000
0.9506(3)
0.8494(3)
0.6709(3)
0.7244(3)
0.7573
0.6869(3)
0.8578(3)
0.7542(3)
0.8039(4)
0.6999
1.0000
1.2382(2)
1.3403(2)
0.9966(3)
1.2393(3)
1.2755
1.1638(4)
0.9324(2)
0.8366(3)
0.6378(3)
0.6723
0.0000
0.05901(19)
0.2426(2)
0.69875(19)
0.5169(2)
0.4248
−0.1149(3)
0.2449(2)
0.4890(2)
0.3565(3)
0.2909
0.03118(11)
0.0387(4)
0.0408(4)
0.0393(4)
0.0416(4)
0.062*
0.0604(6)
0.0269(4)
0.0284(4)
0.0393(5)
0.059*
¯
C12H22CdN4O14, triclinic, P1 (no. 2), a = 7.188(2) Å, b =
8.895(3) Å, c = 9.771(3) Å, α = 63.148(3)°, β = 76.750(3)°,
γ = 66.225(3)°, V = 509.2(3) Å3, Z = 1, Rgt(F) = 0.0253,
wRref(F2) = 0.0676, T = 296(2) K.
O2
O4
O3
H3
O5
CCDC no.: 1484775
N1
The crystal structure is shown in the ꢀgure. Tables 1 and
2 contain details of the measurement method and a list of
the atoms including atomic coordinates and displacement
parameters.
N2
C1
H1A
H1B
H1C
C2
0.7753
0.9337
0.5575
0.5787
0.4581
0.3167
0.059*
0.059*
0.8083(3)
0.8322(3)
0.8804(4)
0.7670(3)
0.7169(3)
0.3235(3)
0.3486(5)
0.716(6)
0.251(5)
0.263(5)
0.692(6)
0.577(4)
0.334(7)
0.334(7)
0.7998(3)
1.0586(3)
1.2241(3)
1.0005(3)
1.0797(3)
0.3294(3)
0.4207(4)
0.768(5)
0.270(4)
0.424(3)
1.064(3)
1.218(4)
0.521(3)
0.411(5)
0.3627(3)
0.2981(2)
0.1921(3)
0.4507(2)
0.5653(3)
1.0042(2)
0.2413(3)
0.578(2)
0.0283(4)
0.0259(4)
0.0304(5)
0.0268(4)
0.0298(5)
0.0526(5)
0.0689(7)
0.083*
Source of material
The title compound was synthesized by a hydrothermal
method under autogenous pressure. A mixture of CdCl2·H2O
C3
C5
C4
C6
O6
*Corresponding author: Xu-Liang Nie, Key Laboratory of Natural
Product Research and Development/College of Sciences, Jiangxi
Agricultural University, Nanchang 330045, People’s Republic of
China, e-mail: niexuliang1981@163.com
Zhi-Qiang Xiong: Center of Analysis and Testing, Nanchang
Hangkong University, Nanchang 330063, People’s Republic of
China
O7
H2
H3W
H4W
H1W
H2W
H5W
H6W
1.056(4)
0.936(4)
0.083*
0.083*
−0.100(5)
−0.081(5)
0.229(4)
0.083*
0.083*
0.083*
Xiu-Ying Song: College of Sciences, Jiangxi Agricultural University,
Nanchang 330045, People’s Republic of China
0.166(3)
0.083*
© 2016 Zhi-Qiang Xiong et al., published by De Gruyter.
This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.
- 10.1515/ncrs-2016-0068
Downloaded from De Gruyter Online at 09/12/2016 03:49:10AM
via free access

2
|
Xiong et al.: C12H22CdN4O14
(0.029 g, 0.1 mmol), 2-methyl-1H-imidazole-4,5-dicarboxylic molecular O—H· · · O hydrogen bonds link the molecules into
acid (H3MIDA) (0.034 g, 0.2 mmol) and distilled water (15 mL) a three-dimensional hydrogen bonds network.
was sealed in a teꢁon-lined stainless reactor (25 mL) and
Acknowledgements: This work was supported by the
Research Foundation of Educational Department of Jiangxi
Province[GJJ13261]. X-ray data were collected at Instrumental
Analysis Center Nanchang Hangkong University, Nanchang,
330063, People’s Republic of China.
heated at 120°C for 72 h, and then cooled to room temper-
ature. The red block crystals were ꢀltered and washed with
water and ethanol. Yield: 75% (based on H3MIDA). Analysis
calculated for C12H22CdN4O14: C, 25.80; H, 3.97; N, 10.03%;
found: C, 24.99; H, 4.19; N, 9.71%.
References
Experimental details
All H atoms were included in calculated positions and re-
ꢀned as riding atoms, with C—H = 0.96–0.97 Å, O—H = 0.81–
0.82 Å and N—H = 0.77 Å, with Uiso(H) = 1.5 Ueq(C) for methyl
H atoms and 1.2 Ueq(C) for all other H atoms.
1. Lu, W. G.; Su, C. Y.; Lu, T. B.; Jiang, L.; Chen, J. M.: Two stable
3D metal-organic frameworks constructed by nanoscale cages
via sharing the single-layer walls. J. Am. Chem. Soc. 128 (2006)
34–35.
2. Zou, R. Q.; Sakurai, H.; Xu. Q.: Preparation, adsorption-
properties, and catalytic activity of 3D porous metal-
organic frameworks composed of cubic building blocks and
alkali-metal ions. Angew. Chem., Int. Ed. 45 (2006) 2542–2546.
3. Sun, Y. Q.; Yang, G. Y.: Organic-inorganic hybrid materials
constructed from inorganic lanthanide sulfate skeletons and
organic 4,5-imidazoledicarboxylic acid. Dalton Trans. 34 (2007)
3771–3781.
4. Lu, W. G.; Gu, J. Z.; Jiang, L.; Tan, M. Y.; Lu, T.B.: Four 3D porous
metal-organic frameworks with various layered and pillared
motifs. Cryst. Growth Des. 8 (2008) 986–994.
5. Liu, C. B.; Nie, X. L.; Wen, H. L.: Diaquabis(5-carboxy-2-methyl-
1H-idazole-4-carboxylato-κ2N3,O4)cobalt(II). Acta Crystallogr.
E63 (2007) m2244–2246.
6. Nie, X. L.; Wen, H. L.; Wu, Z. S.; Liu, D. B.; Liu, C. B.:
Diaquabis (5-carboxy-2-methyl-1H-imidazole-4-carboxylato-
κ2N3,O4)cadmium(II). Acta Crystallogr. E63 (2007) m753–m755.
7. Wen, H. L.; Lai, B. W.; Wu, X. Q.; Nie, X. L.: Crystal structure
of diaqua-bis(2-methyl-1H-imidazole-4,5-dicarboxylato-κ-
O,N)nickel, [Ni(H2O)2(C6H5N2O4)2]. Z. Kristallogr. NCS 224
(2009) 455–456.
8. Tu, Y. G.; Xiong, Z. Q.; Song, X. Y.; Nie, X. L.; Wen, S. H.;
Liu, G. B.: The ꢀrst two-dimensional supramolecular network
constructed by Na(I) with 2-methylimidazole-4,5-dicarboxylate
building blocks. Chin. J. Struct. Chem. 30 (2011) 1770–1774.
9. Nie, X. L.; Xiong, H.; Tu, Y. G.; Huang, C. G.: Binuclear
parallelepiped three-dimensional Ca(II) coordination polymer
constructed by 2-methylimidazole-4,5-dicarboxylate ligand.
Chin. J. Inorg. Chem. 27 (2014) 1962–1968.
Discussion
The design and synthesis of metal-organic frameworks
(MOFs) have attracted much attention, not only owing to
their intriguing variety of architectures but also because of
their potential applications as microporous, magnetic, non-
linear optical, and ꢁuorescent materials [1, 2]. Extensive
investigation has focused on the construction of coordination
polymers using 4,5-imidazoledicarboxylates and derivatives
as bridging ligands [3, 4]. However, the reports of coordina-
tion polymer with 2-methyl-1H-imidazole-4,5-dicarboxylato
ligands are still rare [5–9]. Recently, our group reported
ꢀve coordination polymers with 2-methyl-1H-imidazole-4,5-
dicarboxylate ligand. The reported coordination polymers not
only show beautiful and interesting topological structures, for
instance 0-D, 1-D, 2-D and 3-D but also exhibits very ꢁexible
coordination modes [5–9]. Therefore, we have been engaged
in synthesizing new MOFs with H2MIA-ligand. The structure
of the title compound is related to the previously reported
cadmium(II) complex [6]. The literature known Cd(II) com-
plex crystallizes in the monoclinic space group P21/c and
contains no co-crystallized water molecules. The title com-
pound consists of one cadmium(II) ion, two 4-carboxy-2-
methyl-1H-imidazole-5-carboxylate anions, two coordinated
water molecules, four free water molecules. There are four
more free water in the title complex more than the reported
cadmium (II) complex. So there are more intermolecular O—
H· · · O hydrogen bonds in the title complex and the inter-
10. Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr.
A64 (2008) 112–122.
11. Bruker. APEX2, SAINT and SADABS. Bruker AXS Inc., Madison,
WI, USA, 2009.
- 10.1515/ncrs-2016-0068
Downloaded from De Gruyter Online at 09/12/2016 03:49:10AM
via free access