Syntheses and crystal structures of three supramolecular halides: (DDTD)[Zn(N3)3Cl], (DDTD)[Hg2Br6], (DDTD)[Cd4(N3)6(Cl)8] directed by DDTD dication

Article abstract of DOI:10.1080/15533174.2012.684367

The self-assembly reaction ofmetal halides with DDTD dication (DDTD = 5,8 -Diazoniadispiro[4.2.4.2] tetradecane) yielded three novel organic-inorganic hybrid mental halides (DDTD)[Zn(N₃)₃Cl] (1), (DDTD)[Hg₂Br₆] (2), and (DDTD)[Cd₄(N ₃)₆(Cl)₈] (3), which are characterized by X-ray crystallography and IR spectroscopy. The crystal structures of 1-3 show that they all crystallize in monoclinic systems. Compound 1 is mononuclear complex, compound 2 is binuclear complex, and compound 3 is a tetranuclear polymer. These compounds contained a variety of inorganic frameworks, due to the different coordinated modes of metal centers with halogen, which accordingly led to the change of the C-H...Cl(Br) interactions in the complexes. Copyright Taylor & Francis Group, LLC 2013.

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Syntheses and Crystal Structures of Three
Supramolecular Halides: (DDTD)[Zn(N3)3Cl], (DDTD)
[Hg2Br6], (DDTD)[Cd4(N3)6(Cl)8] Directed by DDTD
Dication
Yu Liang a , Zhong-Cheng Yue b , Li Li b & Xiao-Ling Guo b
a College of Chemistry and Chemical Engineering , Xinxiang University , Xinxiang , P. R. ,
China
b College of Chemistry and Molecular Engineering , Zhengzhou University , Zhengzhou , P.
R. , China
Accepted author version posted online: 28 Sep 2012.Published online: 03 Dec 2012.
To cite this article: Yu Liang , Zhong-Cheng Yue , Li Li & Xiao-Ling Guo (2013) Syntheses and Crystal Structures of Three
Supramolecular Halides: (DDTD)[Zn(N3)3Cl], (DDTD)[Hg2Br6], (DDTD)[Cd4(N3)6(Cl)8] Directed by DDTD Dication, Synthesis and
Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:1, 90-95, DOI: 10.1080/15533174.2012.684367
To link to this article: http://dx.doi.org/10.1080/15533174.2012.684367
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:90–95, 2013
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.684367
Syntheses and Crystal Structures of Three Supramolecular
Halides: (DDTD)[Zn(N3)3Cl], (DDTD)[Hg2Br6],
(DDTD)[Cd4(N3)6(Cl)8] Directed by DDTD Dication
Yu Liang,1 Zhong-Cheng Yue,2 Li Li,2 and Xiao-Ling Guo2
1College of Chemistry and Chemical Engineering, Xinxiang University, Xinxiang, P. R., China
2College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, P. R., China
halides, and obtained three novel organic-inorganic hybrid com-
pounds.
The self-assembly reaction of metal halides with DDTD dication
(DDTD = 5,8 -Diazoniadispiro[4.2.4.2] tetradecane) yielded three
novel organic-inorganic hybrid mental halides (DDTD)[Zn(N3)3Cl]
(1), (DDTD)[Hg2Br6] (2), and (DDTD)[Cd4(N3)6(Cl)8] (3), which
are characterized by X-ray crystallography and IR spectroscopy.
The crystal structures of 1–3 show that they all crystallize in mon-
oclinic systems. Compound 1 is mononuclear complex, compound
2 is binuclear complex, and compound 3 is a tetranuclear polymer.
These compounds contained a variety of inorganic frameworks,
due to the different coordinated modes of metal centers with halo-
gen, which accordingly led to the change of the C-H···Cl(Br) inter-
actions in the complexes.
EXPERIMENTAL
Material and Measurement
All reagents and solvents are of analytical pure grade and
used without further purification. The dication DDTD2+was pre-
pared as the bromide salt by direct alkylation of piperazine with
1,4-dibromoalkane in ethanol absolute. The IR spectra were
measured with a Bruker Tensor 27 spectrophotometer (Ger-
many) in the range 4000–400 cm−1 using KBr pellets.
Keywords 5, 8-Diazoniadispiro[4.2.4.2] tetradecane, crystal struc-
Synthesis of Compound (DDTD)[Zn(N3)3Cl] (1)
ture, self-assembly reaction
A CH3OH/H2O solution of DDTD (35.8 mg, 0.1 mmol)
was added to a stirring colorless solution of ZnCl2(13.6 mg,
0.1 mmol) dissolved in 10 mL DMF/H2O (volume ratio of 4:1) in
the presence of excess NaN3 (19.5 mg, 0.3 mmol). The solution
was filtrated and then slowly evaporated in a vial at room tem-
perature. Colorless crystals of (DDTD)[Zn(N3)3Cl] suitable for
X-ray analysis were obtained after a week in about 46% yield.
IR (KBr): 2061.62(s), 1639.58(w), 1458.34(w), 1343.71(w),
INTRODUCTION
Recently, inorganic-organic hybrid material, microporous
material, monomolecular magnet, and coordination polymers
are the new research fields in the crystal engineering.[1] Self-
assembly is one of the most efficient methods for the synthe-
sis of transition metal complexes, for the wide applications in
catalysis, medicine, sorption, electronics, magnetism, sensors,
sorption, photochemistry applications, and advanced materi-
als.[2–7] Particularly, in this foundation, supramolecular com-
pounds especially the coordination polymers directed by organic
cations obtain a rapid development. Organic cations connect
with polyanions by weak interactions to form stacked struc-
tures of infinite space, that is included van der Waals force,
hydrogen-bonding interactions, and electrostatic interaction.[8]
In this study, based on the principle of supramolecular self-
assembly, DDTD dication[9] and several metal halides were se-
lected to carry out orientation construction of subgroup metal
1106.77(w), 1019.24(w), 943.32(w), 643.83(w) cm−1
.
Synthesis of Compound (DDTD)[Hg2Br6] (2)
Compound (2) was obtained as white crystals by a similar re-
action procedure. Yield: 49%. IR (KBr): 1455.85(s), 1435.42(s),
1350.48(w), 1333.89(m), 1099.68(w), 1015.45(m), 996.49(m),
944.66(w), 882.96(m), 811.31(m) cm−1
.
Synthesis of Compound (DDTD)[Cd4(N3)6(Cl)8] (3)
Compound (3) was obtained as white crystals by a sim-
ilar reaction procedure. Yield: 48%. IR (KBr): 2050.70(s),
1632.43(w), 1461.06(w), 1340.16(w), 1277.63(w), 1020.74(w),
947.99(w), 916.30(w) cm−1
.
X-Ray Structural Determination
Received 13 January 2012; accepted 8 April 2012.
Crystallographic data for title compounds 1–3 were collected
at 292(3) K on a Bruker APEX-II area detector diffractometer
(Germany) equipped with graphite-monochromatized Mo-Ka
Address correspondence to Yu Liang, College of Chemistry
and Chemical Engineering, Xinxiang University, Xinxiang 453000,
People’s Republic of China. E-mail: sunrain732002@sina.com.
90

THREE SUPRAMOLECULAR HALIDES
91
TABLE 1
Crystal data and structure refinement for compounds 1–3
1
2
3
CCDC
861543
861545
861544
Empirical formula
Formula weight
C12 H24 Cl N11 Zn
423.24
C6 H12 Br3 Hg N
538.49
C18H36Cd2Cl4N12
787.19
Crystal system
Space group
a/Å
b/Å
Monoclinic
P 2(1)/c
8.1265(7)
15.2936(14)
15.2526(14)
90.00
97.1830(10)
90.00
Monoclinic
P 2(1)/n
8.3502(5)
13.9563(9)
9.4820(6)
90.00
90.28(0
90.00
Monoclinic
P 2(1)/n
11.0474(7)
12.8270(8)
21.4646(14)
90.00
c/Å
α/◦
β/◦
99.7410(10)
90.00
γ /◦
Volume, Å3
Z
1880.8(3)
4
1.495
880
1105.00(12)
4
3.23667
960
2997.8(3)
4
1.744
Calculated density, Mgm−3
F(000)
1568
Temperature, K
Refinement method
273(2)
273(2)
273(2)
Full-matrix least-squares on
Full-matrix least-squares on
Full-matrix least-squares on
F2
F2
F2
Goodness-of-fit on F2
1.137
1.094
1.520
Final R indices [I>2sigma(I)] R1 = 0.0933, wR2 = 0.2654
R1 = 0.0574, wR2 = 0.1732
R1 = 0.0688, wR2 = 0.1810
2.974
R1 = 0.1378, wR2 = 0.3550
R1 = 0.1674, wR2 = 0.3848
5.839
R indices (all data)
Largest peak,
R1 = 0.1206, wR2 = 0.2976
2.417
Hole(e Å−3
)
–1.438
–2.271
–2.008
radiation (λ = 0.71073 Å). The structures were solved by di- [Zn-N, 1.979(1), 1.975(4), and 2.046(7) Å] in a distorted tetra-
rect methods and expanded using Fourier techniques. The non- hedral geometry. The N-Zn-N bond angles range from 102.3◦
hydrogen atoms were refined with anisotropic thermal parame- to 113.4◦, and the N-Zn-Cl bond angles range from 106.0◦ to
ters. The hydrogen atoms were assigned with common isotropic 115.0◦, deviating significantly from 109.5◦ for an ideal tetrahe-
displacement factors and included in the final refinement by dron.
using geometrical constraints. The structures were refined with
As for DDTD cation, it was distorted and not a planar struc-
full-matrix least-squares techniques on F2 using the SHELXTL- ture. Piperazine group in the cation existed in a slightly distorted
97 program package.[10] Crystal data are summarized in detail in chair geometry. The two five-membered rings containing Natom
Table 1. Selected bond lengths and angles of the title compounds also have two contorted planes with a torsion angle in the ring
1–3 are listed in Table 2.
was 36.38◦.
In each structural unit there exists C-H···Cl bond between
chlorine and DDTD, besides, there existed C-H···N weak bonds
(Figure 1). These structural units form into the infinite spatial
stack structure by this kind of weak hydrogen···chlorine and
hydrogen···nitrogen key‘s function. The Zn chloride complexes
with N3− are scarce,[11,12] and compound 1 is the first The Zn
chloride complexes with terminal -N−3 ligand.
RESULTS AND DISCUSSION
Structure of (DDTD)[Zn(N3)3Cl] (1)
Single-crystal X-ray diffraction analysis revealed that com-
pound 1 crystallized in monoclinic crystal system with space
group P2(1)/c. The structure unit and crystal pack of compound
1 are shown in Figure 1.
Compound
1 was consisted of DDTD cation and
[Zn(N3)3Cl]− anion, which was a mixed ligand adduct, where
Zn center was coordinated by three N−3 anions and a Cl atom
group to form a distorted tetrahedron (Figure 1).
Structure of (DDTD)[Hg2Br6] (2)
Single-crystal X-ray diffraction analysis revealed that com-
pound 2 consisted of a DDTD cation and [Hg2Br6]− anion which
In the crystal structure, the Zn having an environment of one was a mixed ligand adduct. The structure unit and crystal pack
chlorine atom [Zn-Cl(1), 2.3828Å] and three nitrogen atoms of compound 2 are shown in Figure 2.

92
Y. LIANG ET AL.
TABLE 2
Selected bonds lengths (Å) and angles (◦) for compounds 1–3
Compound 1
Zn(1)-N(4)
Zn(1)-N(1)
Zn(1)-N(7)
Zn(1)-Cl(1)
N(4)-Zn(1)-N(1)
1.975 (7)
1.979 (5)
2.046 (6)
2.3828 (12)
N(4)-Zn(1)-N(7)
N(1)-Zn(1)-N(7)
N(4)-Zn(1)-Cl(1)
N(1)-Zn(1)-Cl(1)
N(7)-Zn(1)-Cl(1)
113.4 (3)
110.4 (3)
115.0 (3)
106.0 (2)
109.28 (18)
102.3 (3)
Compound 2
Compound 3
Hg(1)-Br(1)
Hg(1)-Br(3)
Br(1)-Hg(1)-Br(2)
2.615
2.510
115.907 (36)
Hg(1)-Br(2)
Br(1)-Hg(1)-Br(3)
Br(2)-Hg(1)-Br(3)
2.489
108.362 (31)
134.353 (40)
Cd(1)-N(1)
Cd(1)-N(4)
Cd(1)-Cl(2)
Cd(1)-Cl(1)
Cd(2)-N(7)
Cd(2)-N(1)
Cd(2)-N(7)#1
Cd(2)-N(4)#1
Cd(2)-Cl(3)
2.198 (11)
2.341 (16)
2.5324 (19)
2.611 (2)
2.397 (11)
2.407 (10)
2.432 (13)
2.490 (14)
2.6658 (19)
2.6735 (18)
112.5 (5)
N(4)-Cd(1)-Cl(1)
Cl(2)-Cd(1)-Cl(1)
N(7)-Cd(2)-N(1)
101.6 (4)
104.16 (7)
79.1 (5)
75.6 (4)
97.5 (4)
98.6 (6)
177.4 (5)
83.1 (5)
92.0 (3)
90.2 (3)
163.8 (3)
88.7 (4)
160.1 (3)
89.1 (3)
93.4 (4)
N(7)-Cd(2)-N(7)#1
N(1)-Cd(2)-N(7)#1
N(7)-Cd(2)-N(4)#1
N(1)-Cd(2)-N(4)#1
N(7)#1-Cd(2)-N(4)#1
N(7)-Cd(2)-Cl(3)
N(1)-Cd(2)-Cl(3)
N(7)#1-Cd(2)-Cl(3)
N(4)#1-Cd(2)-Cl(3)
N(7)-Cd(2)-Cl(4)
N(1)-Cd(2)-Cl(4)
N(4)#1-Cd(2)-Cl(4)
Cd(2)-Cl(4)
N(1)-Cd(1)-N(4)
N(1)-Cd(1)-Cl(2)
N(4)-Cd(1)-Cl(2)
N(1)-Cd(1)-Cl(1)
N(7)#1-Cd(2)-Cl(4)
122.5 (3)
110.9 (4)
102.1 (3)
90.3 (3)
The structure unit consists of two Hg centers, six Br− ions,
and one DDTD. Every Hg atom is four-coordinated with four
Br atoms to form deformed tetrahedron geometry, and two Br−
ions serve as bridging ligands to link two Hg ions, giving rise
to a four-membered ring (Figure 2). The bond lengths of Hg-
Br arrange from 2.4885 Å to 3.5871 Å, bond angles vary from
78.97◦ to 134.35◦.
In each structural unit, there exists C-H···Br bond between
bromine and DDTD (Figure 2). These structural units form
into the infinite spatial stack structure by this kind of weak
hydrogen···bromine key function.
ions and two N−3 ions to form deformed tetrahedron geometry.
The other Cd ion is hexa-coordinated, surrounded by two Cl−
ions and four N−3 ions to form deformed octahedron geometry
(Figure 3).
Four N−3 ions serve as bridging ligands to link four Cd ions,
giving rise to an eight-membered ring, and the eight atoms not
in a plane, the Cd 1 and Cd 1# deviated from the plane. The Cd 2
and Cd 2# were connected by two N−3 ions as bridging ligands,
giving rise to a four-membered ring. The bond lengths of Cd-Cl
arrange from 2.5324 Å to 2.6735 Å, and Cd-N bond lengths
arrange from 2.198 Å to 2.490 Å. The Cl(1)-Cd(1)-Cl(2) bond
angle is 104.16◦, Cl(3)-Cd(2)-Cl(4) bond angle is 104.18◦. The
N-Cd-N bond angle varies from 75.6◦ to 112.5◦, N-Cd-Cl bond
Structure of (DDTD)[Cd4(N3)6(Cl)8] (3)
Single-crystal X-ray diffraction analysis revealed that com- angle varies from 90.3◦ to 160.1◦.
pound 3 consisted of DDTD cation and [Cd4(N3)6(Cl)8]− anion,
In each structural unit, there exists C-H···Cl bond between
which was a mixed ligand adduct. The structure unit and crystal chlorine and DDTD, besides, the C-H···N bond also existed
pack of compound 3 are shown in Figure 3.
(Figure 3). These structural units form into the infinite spatial
The structure unit consists of four Cd centers, six N−3 ions, stack structure by this kind of weak hydrogen···chlorine and
eight Cl− ions, and two DDTD. There are two kinds of co- hydrogen···nitrogen key function. There are several Cd com-
ordinate environments about the Cd atoms. One Cd ion is plexes with N−3 [13,14], and to the author’s knowledge compound
tetra-coordinated, and each atom is surrounded by two Cl− 3 is the first Cd chloride tetramer with N3− ligand.

THREE SUPRAMOLECULAR HALIDES
93
FIG. 1. (a) The basic structural unit of compound 1. (b) Crystal pack of compound 1. (c) Weak C-H···Cl and C-H···N hydrogen bonds in 1.

94
Y. LIANG ET AL.
FIG. 3. (a) The structure unit of compound 3. (b) The crystal pack of 3. (c)
Weak C-H··Br and C-H···N hydrogen bonds in 3.
FIG. 2. (a) The structure unit of compound 2. (b) The crystal pack of 2. (c)
Weak C-H·Br hydrogen bonds in 2.

THREE SUPRAMOLECULAR HALIDES
95
SUPPLEMENTARY MATERIALS
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Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallographic Data Center,
CCDC No. 861543 for compound 1, CCDC No.861545 for
compound 2, CCDC No.861544 for compound 3. Copies of this
information may be obtained free of charge from The Direc-
tor, CCDC, 12 Union Road, Cambridge, CB21EZ, UK (fax:
44-1223-336-033; email: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
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