Layered structures constructed by second-sphere coordination via N-H···Cl and C-H···Cl hydrogen bonding: Synthesis and crystal structures of tribenzylamine and [MCl6] (M=Sn, Re, and Te)

Article abstract of DOI:10.1080/00958971003657685

A series of second-sphere coordination complexes of tribenzylamine (L¹) and [MCI₆] (M=Sn, Re, Te) have been synthesized and characterized by spectroscopic techniques (IR, NMR) and single-crystal X-ray diffraction. The main driving force for the encapsulation of [MCl₆] and recognition with L¹ is the second-sphere coordination of metal halides by the amide protons of the ligand via hydrogen bonding (N-H···Cl-M and C-H···Cl-M); new layered structures are described. Thermal stability and irreversible behavior of second-sphere coordination complexes [L²] 0.5[TeCl₆]^2- · HCl · (H₃O)⁺ · 0.5H₂O (L²=N,N,N′,N′-tetrabenzyl-ethylenediamine) in contact with water vapor are also described.

Full text of DOI:10.1080/00958971003657685

This article was downloaded by: [Texas A&M University Libraries]
On: 11 September 2014, At: 00:33
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Journal of Coordination Chemistry
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gcoo20
Layered structures constructed by
second-sphere coordination via N–H
··· Cl and C–H ··· Cl hydrogen bonding:
synthesis and crystal structures of
tribenzylamine and [MCl6] (M = Sn, Re,
and Te)
Fang Guo a , Na Lu a , Jian Tong a , Yu-Bo Luan a & Wen-Sheng Guo
a
a College of Chemistry, Liaoning University , Shenyang 110036,
P.R. China
Published online: 01 Mar 2010.
To cite this article: Fang Guo , Na Lu , Jian Tong , Yu-Bo Luan & Wen-Sheng Guo (2010) Layered
structures constructed by second-sphere coordination via N–H ··· Cl and C–H ··· Cl hydrogen
bonding: synthesis and crystal structures of tribenzylamine and [MCl6] (M = Sn, Re, and Te), Journal
of Coordination Chemistry, 63:5, 809-818, DOI: 10.1080/00958971003657685
To link to this article: http://dx.doi.org/10.1080/00958971003657685
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Journal of Coordination Chemistry
Vol. 63, No. 5, 10 March 2010, 809–818
Layered structures constructed by second-sphere
…
…
coordination via N–H Cl and C–H Cl hydrogen
bonding: synthesis and crystal structures of tribenzylamine
and [MCl6] (M ^ Sn, Re, and Te)
FANG GUO*, NA LU, JIAN TONG, YU-BO LUAN
and WEN-SHENG GUO
College of Chemistry, Liaoning University, Shenyang 110036, P.R. China
(Received 7 September 2009; in final form 27 October 2009)
A series of second-sphere coordination complexes of tribenzylamine (L1) and [MCl6] (M ¼ Sn,
Re, Te) have been synthesized and characterized by spectroscopic techniques (IR, NMR)
and single-crystal X-ray diffraction. The main driving force for the encapsulation of [MCl6] and
recognition with L1 is the second-sphere coordination of metal halides by the amide protons of
the ligand via hydrogen bonding (N–H ꢀ ꢀ ꢀ Cl–M and C–H ꢀ ꢀ ꢀ Cl–M); new layered structures are
described. Thermal stability and irreversible behavior of second-sphere coordination complexes
[L2] ꢀ 0.5[TeCl6]2ꢁ ꢀ HCl ꢀ (H3O)þ ꢀ 0.5H2O (L2 ¼ N,N,N0,N0-tetrabenzyl-ethylenediamine) in
contact with water vapor are also described.
Keywords: Second-sphere coordination; Weak hydrogen bonding; Layered structure;
Tribenzylamine; Sn, Re, Te, Tribenzylamine
1. Introduction
Second-sphere coordination, referring to any intermolecular interactions with the pri-
mary coordination sphere of a metal ion [1, 2], has attracted immense interest due to
their unconventional physico-chemical properties [3–6] and novel structures [7–10].
Second-sphere coordination has primarily focused on cationic transition metal
complexes and is mainly provided by a host/receptor/ligand with an appropriate set
of donors, such as a crown ether or macropolycyclic ligands [11–13]. Supramolecular
synthons based on the complementarity of intermolecular interactions, such as
N–H ꢀ ꢀ ꢀ Cl, N–H ꢀ ꢀ ꢀ N, and N–H ꢀ ꢀ ꢀ O, have been widely used to construct a diverse
range of second-sphere coordination complexes due to its strength and directionality
[5–9, 14–16]. One synthon that has proved to be very effective for constructing
second-sphere coordination is N–H ꢀ ꢀ ꢀ Cl–M hydrogen bonding, through the pioneer-
ing work of Orpen [17–20]. While weak interactions have more frequently appeared in
*Corresponding author. Email: fguo@lnu.edu.cn
Journal of Coordination Chemistry
ISSN 0095-8972 print/ISSN 1029-0389 online ß 2010 Taylor & Francis
DOI: 10.1080/00958971003657685

810
F. Guo et al.
the organic crystal network [21], much less work on the construction of second-sphere
coordination complexes via weak interactions has been reported [22].
One direction in the design of functional solid materials is to recognize and accom-
modate guest molecules. A variety of frameworks based on metal–organic framework
polymers have been reported [23–26]. Second-sphere coordination recently has also
afforded an attractive route to this goal [27], in which the design and synthesis
of suitable neutral or charged second-sphere ligands that can coordinate with
first-sphere metal ions via non-covalent interactions is necessary. We have synthesized
two second-sphere ligands, tribenzylamine (L1), and N,N,N0,N0-tetrabenzyl-
ethylenediamine (L2), and prepared a series of second-sphere coordination complexes
with [MCl6]2ꢁ (M ¼ Sn, Re, Te).
The key feature of L1 and L2 is that the functional groups are located in middle
positions of the ligands instead of ꢀ, !, such as 4,40-bipyridine [18, 19], 1,4-
piperazine-bis(ethanesulfonate) [27], and 5,50-diamino-2,20-bipyridine [29]. The bulky
benzyl rings reside outside, in the hope that the bulky group can be a component of
the layer or channel framework, to generate a suitable size of cavity accessible to various
guest molecules. The structure determination of resulting complexes of
[L1]2Hþ ꢀ [SnCl6]2ꢁ (1), [L1]2Hþ ꢀ [ReCl6]2ꢁ (2), and [L1]2Hþ ꢀ [TeCl6]2ꢁ (3) show that
L1 adopts optimized conformations when recognizing different anion complexes, based
on the different shape and size of anions (table 1). Strong N–H ꢀ ꢀ ꢀ Cl and weak C–H ꢀ ꢀ ꢀ Cl
hydrogen bonds play significant roles in the construction of layered structures of these
complexes. As the interlayered channel structures of second-sphere coordination
Table 1. Crystallographic data and structure refinement summary.
[L1]2Hþ ꢀ [SnCl6]2ꢁ
[L1]2Hþ ꢀ [ReCl6]2ꢁ
[L1]2Hþ ꢀ [TeCl6]2ꢁ
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
C42H44Cl6N2Sn
908.18
294(2)
Monoclinic
P21/n
C42H44Cl6N2Re
975.69
294(2)
Monoclinic
P21/n
C42H44Cl6N2Te
915.08
294(2)
Monoclinic
P21/c
ꢂ
˚
Unit cell dimensions (A, )
a
b
c
ꢀ
ꢁ
ꢂ
11.4358(13)
13.1705(15)
14.7431(17)
90.00
106.187(2)
90.00
2132.5(4), 2
1.414
1.006
11.3993(15)
13.2331(18)
14.706(3)
90.00
107.700(2)
90.00
2113.4(5), 2
1.533
3.286
11.018(2)
22.942(5)
16.813(4)
90.00
90.901(3)
90.00
4249.5(15), 4
1.430
1.109
3
˚
Volume (A ), Z
Calculated density (g cmꢁ3
)
Absorption coefficient (mmꢁ1
F(000)
)
924
0.28 ꢃ 0.24 ꢃ 0.20
974
0.30 ꢃ 0.26 ꢃ 0.24
1848
0.30 ꢃ 0.26 ꢃ 0.20
Crystal size (mm3)
Reflections collected (unique)
Rint
11,886
0.0284
11,729
0.0276
20,874
0.0485
Data/parameters
Final R indices [I 4 2ꢃ(I )]
4368/233
R1 ¼ 0.0270,
wR2 ¼ 0.0614
R1 ¼ 0.0434,
wR2 ¼ 0.0685
1.021
4318/236
R1 ¼ 0.0227,
wR2 ¼ 0.0452
R1 ¼ 0.0418,
wR2 ¼ 0.0515
1.058
7405/460
R1 ¼ 0.0683,
wR2 ¼ 0.1672
R1 ¼ 0.0957,
wR2 ¼ 0.1844
1.059
R indices (all data)
s

Synthesis and crystal structures of tribenzylamine and [MCl6] (M ¼ Sn, Re, and Te) 811
complexes formed by L2 and [MCl6] (M ¼ Cu, Co, Mn, Sn, Te) have been reported
previously [28]; herein, the thermal stability of [L2] ꢀ 0.5[TeCl6]2ꢁ ꢀ HCl ꢀ (H3O)þ ꢀ 0.5H2O
is reported.
2. Experimental
2.1. Materials and measurements
All chemicals were purchased as analytical reagents. IR spectra were obtained with
a PerkinElmer 100 FT-IR spectrometer using KBr pellets. 1H-NMR spectra were
recorded on a Mercury-Plus 300 spectrometer (VARIAN, 300 MHz) at 25ꢂC with TMS
as internal reference.
2.2. Preparation of L1
Benzylamine (5.6 mL) was added to a stirred solution of 8.5 g NaHCO3 and 10 mL
distilled water. Benzyl chloride (14.8 mL; 2–3 drops sꢁ1) was then continuously added
to the mixture. After the reaction was heated to 95ꢂC and stirred for 4 h, the mixture
was cooled to room temperature giving white precipitate, 11.343 g, yield 79.05%, m.p.
94ꢂC. IR(cmꢁ1)ꢄmax(KBr): 3082.77, 3061.78, 3027.22 (s, ArC–H), 2923.29, 2881.02
1
(s, CH2), 1601.89, 1583.78, 1493.25, 1451.78 (s, ArC–C); H-NMR ꢅH(CDCl3): 3.811
(6H, s, CH2), 7.329–7.346 (15H, m, ArH).
2.3. Preparation of [L1]2HY E [SnCl6]2Z
Protonated L1 (0.3042 g) and 15 mL ethanol were placed in a 50 mL Erlenmeyer
flask and shaken until the contents dissolved; then 14 mL of distilled water, 2 mL of
concentrated hydrochloric acid, and 4 mL solution of (NH4)2[SnCl6] were added and
the flask was allowed to stand for 3 days at room temperature. Collecting the crystals
by filtration and recrystallization gave a sizeable amount of colorless and transparent
crystals, m.p. 205–210ꢂC. IR(cmꢁ1)ꢄmax(KBr): 3539.66, 3344.81 (s, NH), 3062.77,
3034.15, 3003.85 (s, ArC–H), 2957.24, 2906.00 (s, CH2), 2684.03, 2557.76 (s, NHþ),
1
1643.07, 1586.02, 1496.24, 1455.92 (s, ArC–C). H-NMR ꢅH (DMSO): 4.263–4.364
(6H, t, CH2), 7.200–7.524 (15H, m, ArH), 10.813 (H, s, NHþ).
2.4. Preparation of [L1]2HY E [ReCl6]2Z
L1 (0.1441 g) and 15 mL ethanol were placed in a 50 mL Erlenmeyer flask and shaken
until the contents dissolved; then 14 mL of distilled water, 3 mL of concentrated
hydrochloric acid, and 7 mL solution of K2[ReCl6] were added and the flask was
allowed to stand for 3 days at room temperature. After the crystals were separated
by filtration, recrystallization gave green, transparent crystals, m.p. 246–250ꢂC.
IR (cmꢁ1)ꢄmax(KBr): 3468.13 (s, NH), 3115.14, 3065.30 (s, ArC–H), 2953.49, 2763.44
(s, CH2), 2600.18, 2326.64 (s, NHþ), 1606.32, 1586.48, 1498.63, 1457.56 (s, ArC–C).

812
F. Guo et al.
1H-NMR ꢅH(DMSO): 4.017–4.186 (6H, d, CH2), 7.403–7.502 (15H, m, ArH), 11.096
(1H, s, NHþ).
2.5. Preparation of [L1]2HY E [TeCl6]2Z
L1 (0.1435 g) and 20 mL ethanol were placed in a 50 mL Erlenmeyer flask and heated
until the contents dissolved; 7 mL of distilled water, 11 mL of concentrated hydrochloric
acid, and 10 mL solution of (NH4)2[TeCl6] were added and the flask allowed to
stand for 3 days at room temperature. Collecting the crystals by filtration and
recrystallization gave transparent yellow-green crystals, m.p. 210–213ꢂC.
IR(cmꢁ1)ꢄmax(KBr): 3445.05 (s, NH), 3031.75 (s, ArC–H), 2795.48 (s, CH2), 2599.78
(s, NHþ), 1602.59, 1585.95, 1495.20, 1454.89 (s, ArC–C). 1H-NMR ꢅH(DMSO):
4.227–4.358 (6H, t, CH2), 7.394–7.589 (15H, m, ArH), 10.600 (1H, s, NHþ).
2.6. Preparation of [L2] E 0.5[TeCl6]2ꢁ E HCl E (H3O)Y E 0.5H2O
L2 (0.1103 g) and 15 mL ethanol were placed in a 50 mL Erlenmeyer flask and heated
until the contents dissolved; 8 mL of distilled water, 10 mL of concentrated hydrochloric
acid, and 0.5 mL of (NH4)2[TeCl6] were added and the flask was allowed to stand for 3
days at room temperature. After collecting the crystals, recrystallization gave
transparent yellow-green crystals, m.p. 154ꢂC. IR(cmꢁ1)ꢄmax(KBr): 3434.27 (s, NH),
1
3006.65 (s, CH2), 2585.70 (s, NHþ), 1621.12, 1499.17, 1456.90 (s, ArC–C). H-NMR
(CDCl3): 3.868 (4H, s, CH2), 4.200 (8H, s, CH2), 7.203–7.609 (20H, m, ArH), 11.358
(2H, s, NH), 2.573 (1H, s, H2O).
2.7. X-ray crystallography
Single-crystal X-ray diffraction measurements were carried out on a Bruker Smart
CCD diffractometer equipped with a graphite monochromator at 294 K. The
determination of unit cell parameters and data collection were performed with
˚
Mo-Ka radiation (ꢆ ¼ 0.71073 A). The unit cell parameters were obtained with
least-squares refinements and the structures were determined using direct methods
and refined (based on F 2 using all independent data) by full-matrix least-squares
(SHELXTL 97). Data were reduced using the Bruker SAINT software.
3. Results and discussion
3.1. Spectroscopic analyses
IR and 1H-NMR data for both ligands and four complexes are listed in section 2. In the
complexes, proton resonances on the methylene CH2 in L1 significantly shift to lower
fields compared to those in the free ligand, 3.811 (6H, s, CH2) ! 4.263–4.364
(6H, t, CH2, 1) ! 4.017–4.186 (6H, d, CH2, 2) ! 4.227–4.358 (6H, t, CH2, 3),
indicating that these groups participate in weak hydrogen bonding, further ascertained
by the structure determination from the single-crystal X-ray diffraction analysis.

Synthesis and crystal structures of tribenzylamine and [MCl6] (M ¼ Sn, Re, and Te) 813
3.2. Layer structures constructed by L1 and [MCl6] (M ^ Sn, Re, Te)
Complexes 1 and 2 crystallize in the P21/n space group of the monoclinic system.
The metal ions (Sn and Re) are located at crystallographic inversion centers and L1 are
in a general position. Complexes 1 and 2 consist of half ion of [SnCl6]2ꢁ (or [ReCl6]2ꢁ
)
and one protonated L1 in one asymmetric unit, thus the molar ratio of [SnCl6]2ꢁ
(or [ReCl6]2ꢁ) to L1 is 1: 2. Complex 3 crystallizes in the P21/c space group of the
monoclinic system and contains two protonated L1 molecules and one [TeCl6]2ꢁ anion
in one asymmetric unit, thus the molar ratio of [TeCl6]2ꢁ to L1 is also 1 : 2.
3.2.1. [L1]2HY E [MCl6]2Z (M ^ Sn, Re) (C21H22N E 0.5SnCl6, C21H22N E0.5ReCl6).
A detailed description will be presented only for 1, as 2 is similar to 1 except for slight
variations in structural and thermal parameters which may be ascertained from the
Supplementary material.
The molecular structure of 1 with the atom numbering scheme is shown in figure 1(a).
The Sn lying on a crystallographic inversion center at (0, 1/2, 0) is bonded to six
˚
chlorides, having four short Sn–Cl bonds (2.3850(7) A, 2.4145(7) A) and two longer
˚
1
bonds(2.4927(6) A). The three benzyl groups of L are located on the pyramidal side
˚
of nitrogen, in which one benzyl (C2–C7) is significantly tilted with respect to the other
˚
benzyl group (C9–C14) with the distance of centroids of 4.030 A and the dihedral angle
of 30ꢂ between the phenyl rings. The primary sphere [SnCl6]2ꢁ is encapsulated by four
L1 through a total of 12 hydrogen bonds, including two strong N–H ꢀ ꢀ ꢀ Cl hydrogen
bonds and 10 weak C–H ꢀ ꢀ ꢀ Cl interactions to construct the building block, as seen
in figure 1(b).
The tilted benzyl ring of L1 is not involved in interactions with Clꢁ, but has ꢇ–ꢇ
˚
stacking to connect the building blocks with 3.667 A centroid–centroid distance
of phenyls, forming a 1-D chain along (1 0 1). The 1-D chain expands along b to
construct a layer structure (figure 1c). Within a layer, the Sn align along (1 0 1) at a
˚
distance of 10.339 A.
[SnCl6]2ꢁ are completely encapsulated by L1 and can be considered to be located
inside the channel surrounded by L1 (figure 1c). The adjacent distance of Sn inside
˚
the channel is 13.170 A. There is no space to accommodate solvent molecules between
the layers.
Complex 2 has similar layered structure: within a layer, the Re align along (1 0 1) at
1
˚
˚
a distance of 10.240 A and along the b-axis 13.233 A. L in 2 exhibits a slightly different
conformation compared with 1. One benzyl (C2–C7) is also tilted wiꢂth respect to the
˚
other benzyl (C9–C14) with 3.983 A distance of centroids and 29 dihedral angle
between the phenyls.
3.2.2. [L1]2HY E [TeCl6]2Z (C21H22N)2 E TeCl6). Complex 3 is different from 1 and 2.
The coordination geometry around Te is significantly distorted octahedral with Te–Cl
2ꢁ
˚
˚
distances varying between 2.413(2) A and 2.766(2) A. The primary sphere [TeCl6] is
encapsulated by five molecules of L1 through a total of nine hydrogen bonds, including
two strong N–H ꢀ ꢀ ꢀ Cl interations and seven C–H ꢀ ꢀ ꢀ Cl weak interactions, as seen
in figure 2(b); ꢇ ꢀ ꢀ ꢀ ꢇ stacking was not found in 3.
The anions of [TeCl6]2ꢁ are related to the 21 symmetry operation, making the
molecules of L1 arrange in a helical chain along the c-axis, with the Te centers at

814
F. Guo et al.
Figure 1. Structure of [L1]2Hþ ꢀ [SnCl6]2ꢁ
.

Synthesis and crystal structures of tribenzylamine and [MCl6] (M ¼ Sn, Re, and Te) 815
Figure 2. Structure of [L1]2Hþ ꢀ [TeCl6]2ꢁ
.

816
F. Guo et al.
˚
10.090 A, and expanding along the a-axis to construct the 2-Dlayer, with Te centers at a
˚
distance of 11.018 A, as seen in figure 2(c).
3.3. Interlayer channel constructed by L2 and [TeCl6]
3.3.1. The struture of the complex [L2] E 0.5[TeCl6]2Z E HCl E (H3O)Y E 0.5H2O. The
complex [L2] ꢀ 0.5[TeCl6]2ꢁ ꢀ HCl ꢀ (H3O)þ ꢀ 0.5H2O has an interlayer structure [28].
The asymmetric unit is half of [TeCl6]2ꢁ and one molecule of L2, one molecule
of hydrochloric acid, and 1.5 molecules of water (including one protonated water)
(figure 3a). The coordination around Te is not like that in 3, with Te–Cl distances
almost equal, 2.516(2)–2.539(2) A. [TeCl6]2ꢁ is surrounded by eight L2 through 10 weak
˚
C–H ꢀ ꢀ ꢀ Cl hydrogen bonds between the methylene or CH in the phenyl of L2 and
chloride of [TeCl6]2ꢁ. The building block forms a 1-D chain along the a-axis, and then
expands along b to construct the layer structure. Within the layer, the Te centers align
˚
along a at a distance of 10.350 A, which is exactly the distance of the a-axis, and align
Figure 3. Structure of [L2] ꢀ 0.5[TeCl6]2ꢁ ꢀ HCl ꢀ (H3O)þ ꢀ 0.5H2O.

Synthesis and crystal structures of tribenzylamine and [MCl6] (M ¼ Sn, Re, and Te) 817
˚
along the b-axis at a distance of 11.687 A, which is the distance of the b-axis.
˚
The knaggy phenyls between neighboring layers construct a 4.1 ꢃ 5.8 A channel with
hydrochloric acid and water within the channel between the layers (figure 3b).
3.3.2. Thermal analysis and irreversible transformation of the complex. Thermogravi-
metric analyses (TGA) were carried out on [L2] ꢀ 0.5[TeCl6]2ꢁ ꢀHCl ꢀ (H3O)þ ꢀ 0.5H2O
from the room temperature and 230ꢂC (Supplementary material). The first stage at
25–210ꢂC corresponds to loss of water and HCl (9.81% Calcd, 10.89% Obs.). The
second stage above 210ꢂC were further decomposing of the structure. The PXRD
pattern reveals significant changes in peak positions upon heating the powder to 80ꢂC
in vacuo for 2 h (Supplementary material). Further heating to 120ꢂC for 2 h, the powder
becomes identical to the changed solid. Heating the powder to 150ꢂC for 2 h gave a
PXRD pattern with a very weak signal relative to the background, but the small peaks
did correlate with the changed solid. As supported by TGA data, guest molecules are
lost from the interlayer region at this temperature. To further study the complex, we
performed a solid–gas experiment in which the changed product was introduced into
a sealed vessel containing water and placed in equilibrium with its vapor for about
2 weeks; the dehydrated material cannot change back to the crystalline structure and
exhibits irreversible behavior in contact with the vapor of water.
4. Concluding remarks
Design of second-sphere coordination via reliable supramolecular synthons has gained
interest. Herein, tribenzylamine (L1) and N,N,N0,N0-tetrabenzyl-ethylenediamine (L2)
have been used to encapsulate [MCl6] by second-sphere coordination via hydrogen
bonds, involving strong N–H ꢀ ꢀ ꢀ Cl–M and weak C–H ꢀ ꢀ ꢀ Cl–M. The methylene or
phenyl rings of L1 and L2 provide for the construction of second-sphere coordination
complexes through C–H ꢀ ꢀ ꢀ Cl interactions. The second-sphere coordination by
[TeCl6]2ꢁ with L2 provides an interlayered framework. [TeCl6]2ꢁ locate at the
crystallography inversion centers, and the channels are constructed between
˚
the ligand parts of neighboring layers with size of 4.1 ꢃ 5.8 A, in which water and
hydrochloric acid are accommodated. Thermogravimetric studies reveal that all waters
can be removed from the channel above 80ꢂC. The crystal structure
of [L2] ꢀ 0.5[TeCl6]2ꢁ ꢀ HCl ꢀ (H3O)þ ꢀ 0.5H2O cannot be recovered after the removal of
water, as confirmed by their PXRD patterns.
Supplementary material
For more information, refer to CCDC reference numbers 720919, 720920, 720921,
and 72544.

818
F. Guo et al.
Acknowledgment
This work was supported by the National Science Foundation of China
(No. 20772054, 20903052).
References
[1] S.J. Loeb. In Comprehensive Supramolecular Chemistry, J.L. Atwood, J.E. Davies, D.D. MacNicol,
F. Vogtle (Eds), Vol. 1, p. 733, Elsevier, New York (1996).
¨
[2] S.A. Dalrymple, M. Parvez, G.K.H. Shimizu. Chem. Commun., 2672 (2001).
[3] K. Zamaraev. New J. Chem., 3, 18 (1994).
[4] V.A. Russell, C.C. Evans, W. Li, M.D. Ward. Science, 276, 575 (1997).
[5] R.L. Lucas, M.K. Zart, J. Murkerjee, T.N. Sorrell, D.R. Powell, A.S. Borovik. J. Am. Chem. Soc., 128,
15476 (2006).
[6] R.A. Pires, T.G. Nunes, I. Abrahams, G.E. Hawkes. J. Mater. Sci., 19, 1687 (2008).
[7] S. Ferlay, O. Fe
[8] S.L. Renard, I. Sylvestre, S.A. Barrett, C.A. Kilner, M.A. Halcrow. Inorg. Chem., 45, 8711 (2006).
[9] A. Singh, R. Pal Sharma, P. Brandao, V. Felix, P. Venugopalan. J. Mol. Struct., 892, 452 (2008).
´
lix, M.W. Hosseini, J. Planeixa, N. Kyritsakas. Chem. Commun., 702 (2002).
´
˘
[10] B.A. Blight, J.A. Wisner, M.C. Jennings. Chem. Commun., 4593 (2006).
[11] A.M. Madalan, N. Avarvarib, M. Andruh. New J. Chem., 30, 521 (2006).
[12] K. Kavallieratos, C.M. Bertao, R.H. Crabtree. J. Org. Chem., 64, 1675 (1999).
[13] K. Kavallieratos, S.R. de Gala, D.J. Austin, R.H. Crabtree. J. Am. Chem. Soc., 119, 2325 (1997).
[14] J.C. Mareque Rivas, L. Brammer. Inorg. Chem., 37, 4756 (1998).
[15] D.A. Beauchamp, S.J. Loeb. Chem. Eur. J., 8, 5084 (2002).
[16] G.R. Desiraju. Angew. Chem. Int. Ed., 46, 8342 (2007).
[17] A. Angeloni, P.C. Crawford, A.G. Orpen, T.J. Podesta, B.J. Shore. Eur. J. Chem., 10, 3783 (2004).
[18] C.J. Adams, H.M. Colquhoun, P.C. Crawford, M. Lusi, A.G. Orpen. Angew. Chem. Int. Ed., 46, 1124
(2007).
[19] B. Dolling, A.L. Gillon, A.G. Orpen, J. Starbuck, X. Wang. Chem. Commun., 567 (2001).
[20] P.C. Crawford, A.L. Gillon, J. Green, A.G. Orpen, T.J. Podesta, S.V. Pritchard. CrystEngComm, 6, 419
(2004).
[21] G.R. Desiraju, T. Steiner. The Weak Hydrogen Bond in Structural Chemistry and Biology, Oxford
University Press, Oxford (1999).
[22] (a) F. Zordan, L. Brammer, F.P. Sherwood. J. Am. Chem. Soc., 127, 5979 (2005); (b) L. Brammer,
´
G. Mınguez Espallargas, H. Adams. CrystEngComm, 5, 343 (2003); (c) F. Zordarysn, L. Brammer.
Acta Crystallogr., B60, 512 (2004).
[23] S.I. Noro, S. Kitagawa, M. Kondo, K. Seki. Angew. Chem. Int. Ed., 39, 2082 (2000).
[24] M. Eddaoudi, J. Kim, M. O’Keeffe, O.M. Yaghi. J. Am. Chem. Soc., 124, 376 (2002).
[25] M.J. Zaworotko. Angew. Chem. Int. Ed., 39, 3052 (2000).
[26] K. Biradha, C. Seward, M.J. Zaworotko. Angew. Chem. Int. Ed., 38, 492 (1999).
[27] D.S. Reddy, S. Duncan, G.K.H. Shimizu. Angew. Chem. Int. Ed., 42, 1360 (2003).
[28] (a) L. Yuan, F. Guo, S. Zhang, Z.Q. Hu, F. Xia, W.S. Guo. Chem. J. Chin. Univ., 28, 1897 (2007);
(b) Z.Q. Hu, C.L. Hu, Y.B. Luan, F. Xia, F. Guo, W.S. Guo. Acta Chim. Sinica, 67, 213 (2009).
[29] X.J. Yang, B. Wu, C. Janiak, W.H. Sun, H.M. Hu. Z. Anorg. Allg. Chem., 630, 1564 (2004).