Structures and magnetism of two manganese crowns assembled with 2,4-dihydroxyacetophenone oxime

Article abstract of DOI:10.1080/00958972.2012.756103

Reactions of 2,4-dihydroxyacetophenone oxime with manganese salts yielded two manganese crowns, [Mn₃(μ₃-O)(4-OH-Me-sao) ₃(HCOO)(MeOH)₅].MeOH (1) and [Mn₃(μ ₃-O)(4-OH-Mesao) 3(CH₃

Full text of DOI:10.1080/00958972.2012.756103

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Structures and magnetism of two
manganese crowns assembled with 2,4-
dihydroxyacetophenone oxime
a
a
a
a
LEI-LEI LI , SU-NA WANG , JING LU , FAN CAO , LING-QIAN
b
a
a
KONG , JIAN-MIN DOU & DA-CHENG LI
a
Shandong Provincial Key Laboratory of Chemical Energy Storage
and Novel Cell Technology , School of Chemistry and Chemical
Engineering, Liaocheng University , Liaocheng , China
b
Department of Chemistry and Biology , Dongchang College,
Liaocheng University , Liaocheng , China
Accepted author version posted online: 05 Dec 2012.Published
online: 21 Jan 2013.
To cite this article: LEI-LEI LI , SU-NA WANG , JING LU , FAN CAO , LING-QIAN KONG , JIAN-
MIN DOU & DA-CHENG LI (2013) Structures and magnetism of two manganese crowns assembled
with 2,4-dihydroxyacetophenone oxime, Journal of Coordination Chemistry, 66:2, 306-315, DOI:
10.1080/00958972.2012.756103
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Journal of Coordination Chemistry
Vol. 66, No. 2, 20 January 2013, 306–315
Structures and magnetism of two manganese crowns
assembled with 2,4-dihydroxyacetophenone oxime
LEI-LEI LI†, SU-NA WANG†, JING LU†, FAN CAO†, LING-QIAN KONG‡, JIAN-MIN
DOU†* and DA-CHENG LI†*
†
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell
Technology, School of Chemistry and Chemical Engineering, Liaocheng University,
Liaocheng, China
‡
Department of Chemistry and Biology, Dongchang College, Liaocheng University,
Liaocheng, China
(Received 19 August 2012; in final form 11 October 2012)
Reactions of 2,4-dihydroxyacetophenone oxime with manganese salts yielded two manganese
crowns, [Mn (μ -O)(4-OH-Me-sao) (HCOO)(MeOH) ]·MeOH (1) and [Mn (μ -O)(4-OH-Me-
sao) (CH COO)(MeOH) ]·MeOH (2) (4-OH-Me-saoH =2,4-dihydroxyacetophenone oxime). Both
compounds possess [Mn -O)] cores which contain 9-MC-3 metallacrown (MC) rings with
3
3
3
5
3
3
3
3
5
2
III
7+
3
(μ
3
the repeating pattern [–Mn–N–O–]. However, the difference in the structures of both compounds is
coordinated carboxylates. In 1 and 2, the MC molecules are connected with each other through
intermolecular hydrogen bonds, generating similar 3-D supramolecular networks. Magnetic
properties reveal that in 1 and 2 the metal ions exhibit ferromagnetic exchange coupling.
III
7+
Keywords: [Mn
3 3
(μ -O)] core; 9-MC-3 metallacrown; Magnetic properties; 2,4-Dihydroxyaceto-
phenone oxime
1. Introduction
In 1989, Pecoraro reported the synthesis and characterization of metallacrown (MC)
II
III
compounds, [VO(shi)(MeOH)]3 and {Mn (OAc) [Mn (shi) ](DMF) }·2DMF [1]. Since
2
4
6
then, many researchers have studied such compounds owing to their intrinsic magnetism
2–4]. MCs, which are inorganic structural and functional analogs to crown ethers, are a
[
new class of metallamacrocyclic molecules [5] with a wide range of potential applications,
such as catalysis [6], selective separation agents [7, 8], recognition agents [9], and
single-molecule magnets [10]. Many structural types of MCs have been reported, such as
9
-MC-3, 12-MC-4, 15-MC-5, 24-MC-8, etc. [11–13]. They can also be utilized as building
blocks to construct 1-D, 2-D, and 3-D coordination polymers [14].
Oxime acids have been reported to construct MCs [15]. Phenolic oximes have gained
renewed attention owing to their propensity to generate polynuclear compounds, in
which both the oximate and the phenolate bridge. A series of phenolic oximes (HsaoH2,
*
Corresponding authors. Email: jmdou@lcu.edu.cn (J.-M. Dou); lidacheng@lcu.edu.cn (D.-C. Li)
Journal of Coordination Chemistry
ISSN 0095-8972 print/ISSN 1029-0389 online Ó 2012 Taylor & Francis
http://dx.doi.org/10.1080/00958972.2012.756103

Structures and magnetism of two manganese crowns
307
Me–saoH , Et–saoH , etc.) have been explored to construct 9-MC-3 MCs [16], especially
2
2
III
manganese crowns, for example, [Mn O(Et–sao) (MeOH) ](ClO ) consists of a 9-MC-3
manganese crown ring, which is capped by a ClO4 in a η : η : η : μ fashion [16g].
3
3
3
4
1
ꢀ
1
1
3
Some of them exhibit single-molecule magnetic behavior [16b–16f,16k], for example,
III
[
Mn O(Et–sao) (O CPh(Cl) )(MeOH) (H O)] is a low nuclearity single-molecule magnet
3 3 2 2 3 2
with anisotropy barrier Ueff ꢁ 51 K, which is almost the largest effective barrier [16f].
However, manganese clusters with 2,4-dihydroxyacetophenone oxime have remained unre-
ported. In this manuscript, we report syntheses and structures of two manganese crowns
based on this ligand, [Mn (μ -O)(4-OH-Me-sao) (HCOO)(MeOH) ]·MeOH (1) and
3
3
3
5
[
Mn (μ -O)(4-OH-Mesao) (CH COO)(MeOH) ]·MeOH (2). Both compounds possess
3 3 3 3 5
III
7+
similar [Mn (μ -O)] cores which contain 9-MC-3 MC rings with the repeating pattern
3
3
[
–Mn–N–O–]. In 1 and 2, the MC molecules are connected into similar 3-D supramolecu-
lar networks through intermolecular hydrogen bonds. Magnetic properties reveal that the
metal ions exhibit ferromagnetic exchange coupling in 1 and 2.
2
2
. Experimental
.1. Materials and physical measurements
All manipulations were performed under aerobic conditions using materials as received
reagent grade). 2,4-Dihydroxyacetophenone oxime was synthesized by reaction of 2,4-
(
dihydroxyacetophenone with hydroxylamine and sodium acetate in a mixture of MeOH/
H O, as described in the literature [17]. Elemental analyses (C, H, N) were performed by
2
a Perkin-Elmer 2400 elemental analytical instrument. IR spectra were recorded as KBr
ꢀ
1
pellets on a Nicolet-460 FT-IR spectrophotometer from 4000 to 400 cm . Structures were
characterized by a Bruker Smart-1000 CCD diffractometer. Variable-temperature direct
current (dc) magnetic susceptibility measurements down to 2.0 K were carried out on a
Quantum Design MPMS-XL SQUID magnetometer equipped with a 0.1 T dc magnet.
Caution! Although we encountered no problems, care should be taken when using the
potentially explosive perchlorates.
2
2
.2. Synthesis
.2.1. Preparation of [Mn (μ -O)(4-OH-Me-sao) (HCOO)(MeOH) ]·MeOH (1).
A
3
3
3
5
solution of Mn(ClO ) ꢂ6H O (181 mg, 0.5 mmol) and 2,4-dihydroxyacetophenone oxime
4
2
2
(83.5 mg, 0.5 mmol) in MeOH was treated with a molar equivalent of MeONa and stirred
for 1 h to form a black solution. After filtration the solution was left to evaporate slowly
and black block X-ray quality crystals were formed after one week. Yield: 30% (based on
Mn(ClO ) ꢂ6H O). C H Mn N O (913.53): calcd C 40.76, H 5.08, N 4.60; found C
4
2
2
31 46
3 3 18
ꢀ1
4
1
0.13, H 4.67, N 4.27. IR(KBr, cm ): 3423(s), 1617(s), 1529(m), 1436(w), 1384(w),
369(w), 1333(w), 1300(w), 1251(m), 1177(m), 1158(w), 1122(w), 1070(s), 1037(m), 992
(s), 963(m), 851(w), 808(w), 763(m), 736(w), 669(s), 612(m), 535(m), 479(w), 444(w).
2
.2.2. Preparation of [Mn (μ -O)(4-OH-Me-sao) (CH COO)(MeOH) ]·MeOH (2).
A
3
3
3
3
5
similar procedure to 1 was followed, except that Mn(CH COO) ꢂ4H O was used instead.
3
2
2
Yield: 36.83% (based on Mn(CH COO) ꢂ4H O). C H Mn N O
(927.55): calcd
3
2
2
32 48
3 3 18
ꢀ
1
C 41.44, H 5.22, N 4.53, found C 40.27, H 4.79, N 4.06. IR(KBr, cm ): 3397.6(m),

3
08
L.-L. Li et al.
1604.7(s), 1529.5(s), 1433.3(m), 1384.2(w), 1369.0(w), 1332.5(w), 1304.1(w), 1252.0(m),
1178.3(m), 1152.7(w), 1070.3(m), 1037.9(m), 992.0(s), 964.0(w), 851.6(w), 808.0(w),
765.5(w), 669.9(s), 612.4(w), 536.2(w), 479.3(w), 444.3(w).
2.2.3. X-ray structural studies. Data of the compounds were obtained on a Bruker
Smart-1000 CCD diffractometer using graphite-monochromated Mo Kα radiation. The2
structures were solved by direct methods and refined by full-matrix least-squares on F
using SHELXTL-97 crystallographic software package [18, 19]. The non-hydrogen atoms
2
were refined anisotropically by full-matrix least-squares calculations on F . Anisotropic
thermal parameters were applied to all non-hydrogen atoms. The refinement details and
selected bond distances and angles of 1 and 2 are listed in tables 1 and 2, respectively.
3
3
. Results and discussion
.1. Syntheses
2
+
The syntheses were performed under aerobic conditions with reactions of Mn salts and
,4-dihydroxyacetophenone oxime in a molar ratio of 1 : 1 in basic methanol solution. All
2
II
Mn ions are +3, indicating Mn was oxidized by atmospheric O and the oxidation
process was base-assisted [16a, 20]. The Mn and Na salts have large influences on the
2
2
+
+
Table 1. Details of the crystal parameters, data collection, and refinement for 1 and 2.
Compound
1
2
Formula
C
31
H
46Mn
3
N
3
O
18
C
32
H
3 3 18
48Mn N O
Formula weight
Crystal system
Space group
913.53
Monoclinic
P2(1)/c
927.55
Monoclinic
P2(1)/c
Unit cell dimensions
a (Å)
b (Å)
c (Å)
a (°)
b (°)
c (°)
8.4810(8)
42.080(3)
12.7191(13)
90
117.160(2)
90
4038.7(6)
4
8.5170(8)
42.440(4)
12.6151(11)
90
117.120(2)
90
4058.5(6)
4
3
V (Å )
Z
ꢀ3
D
calc (Mg m
)
1.502
1.518
F(0 0 0)
1888
1920
h Range (°)
2.31–25.02
2.32–25.02
Index ranges
ꢀ10 ꢃ h ꢃ 9,
ꢀ8 ꢃ h ꢃ 10,
ꢀ
ꢀ
49 ꢃ k ꢃ 33,
15 ꢃ l ꢃ 15
ꢀ50 ꢃ k ꢃ 50,
ꢀ14 ꢃ l ꢃ 15
16,518/6897
0.1308
Measd./unique
int) reflns.
20,019/7048
0.0615
(R
Final R indices [I > 2σ (I)]
R = 0.1005
wR = 0.2197
R = 0.1273
wR = 0.2330
1.127
R = 0.1186
wR = 0.2547
R = 0.1620
wR = 0.2754
1.126
R indices (all data)
2
GOF on F

Structures and magnetism of two manganese crowns
Table 2. Selected bond lengths (Å) and angles (°) for 1 and 2.
309
1
Mn(1)–O(10)
Mn(1)–O(2)
Mn(1)–O(7)
1.884(5)
1.889(5)
1.928(6)
2.002(7)
2.266(6)
2.325(7)
119.2(3)
Mn(2)–O(10)
Mn(2)–O(5)
Mn(2)–O(1)
1.897(6)
1.878(6)
1.944(5)
2.009(7)
2.249(6)
2.297(6)
120.9(3)
Mn(3)–O(10)
Mn(3)–O(8)
Mn(3)–O(4)
1.896(5)
1.901(6)
1.916(6)
2.010(7)
2.255(7)
2.340(6)
118.4(3)
Mn(1)–N(1)
Mn(2)–N(2)
Mn(3)–N(3)
Mn(1)–O(15)
Mn(1)–O(11)
Mn(1)–O(10)–Mn(3)
Mn(2)–O(16)
Mn(2)–O(12)
Mn(1)–O(10)–Mn(2)
Mn(3)–O(17)
Mn(3)–O(14)
Mn(3)–O(10)–Mn(2)
2
Mn(1)–O(10)
Mn(1)–O(8)
Mn(1)–O(1)
Mn(1)–N(3)
Mn(1)–O(15)
Mn(1)–O(13)
Mn(3)–O(10)–Mn(2)
1.893(6)
1.882(7)
1.912(7)
2.001(8)
2.258(7)
2.356(7)
121.0(3)
Mn(2)–O(10)
Mn(2)–O(2)
Mn(2)–O(4)
1.890(6)
1.877(6)
1.951(6)
2.006(7)
2.255(7)
2.304(7)
118.6(3)
Mn(3)–O(10)
Mn(3)–O(5)
Mn(3)–O(7)
1.875(6)
1.864(7)
1.929(7)
1.995(8)
2.273(7)
2.323(7)
119.1(3)
Mn(2)–N(1)
Mn(3)–N(2)
Mn(2)–O(16)
Mn(2)–O(11)
Mn(3)–O(10)–Mn(1)
Mn(3)–O(17)
Mn(3)–O(14)
Mn(2)–O(10)–Mn(1)
ꢀ
resulting structures. Formate (HCOO ) in 1 may be the result of oxidation of CH OH
3
[20].
3
.2. Crystal structures of [Mn (μ -O)(4-OH-Me-sao) (HCOO)(MeOH) ]·H O (1)
3
3
3
5
2
As shown in figure 1(a), 1 crystallizes in the monoclinic space group P2(1)/c and the
asymmetric unit consists of three doubly deprotonated 2,4-dihydroxyacetophenone oxime
ligands, three Mn ions, one μ -O, one formate, five coordinated methanols, and one free
3
methanol. The oxidation states of Mn ions were confirmed by a combination of charge
balance, bond-valence sum (BVS) calculations, and bond-length considerations (table 3)
III
7+
[
21–23]. The trinuclear compound contains a [Mn (μ -O)] oxo-centered core, in which
3 3
the three manganeses are bridged by the central oxygen 0.133 Å below the [Mn ] plane.
3
2
ꢀ
The three Mn-O bonds range from 1.884(5) to 1.897(6) Å, comparable with those of
reported compounds containing similar cores [24–27]. The three oximates η : η : η : μ
1
1
1
using their –N–O– oxime moieties span each edge of the [Mn ] plane forming a 9-MC-3
3
MC ring with the repeating pattern [–Mn–N–O–]. The Mn–N–O–Mn torsion angles are
3
7.5(2)°, 41.3(4)°, and 40.0(7)°, respectively. The other coordination sites of the three
metal centers are furnished by formate and two MeOH on the “upper” triangular [Mn3]
plane and three MeOH on the “lower” triangular [Mn ] plane, constructing an octahedral
3
III
coordination geometry around each Mn . The average bond lengths of Mn–O/N are 1.926
(3)–1.932(6) Å in the equatorial plane and 2.273(6)–2.298(1) Å at the axial position, close
to those of other manganese complexes [16, 28], displaying a classical Jahn–Teller (JT)
elongation. These JT axes are approximately parallel and perpendicular to the [Mn ] trian-
3
gular plane.
O–Hꢂ ꢂ ꢂO hydrogen bonding interactions connect these clusters into 3-D supramolecular
networks (figure 1(b)), similar to that of [Mn(H bptc)(2,2’-bpy) ]·H O [29]. Three MeOH
2
2
2
on the “lower” triangular face (O15, O16, and O17) interact with uncoordinated oxygen
ꢀ
O13 of HCOO on the “upper” triangular face of another molecule, linking adjacent clus-
ters into 1-D chains along the a axis. These chains are connected with each other through
O–Hꢂ ꢂ ꢂO hydrogen bonding interactions between lattice methanols (O18) and oximate
oxygens O2 as well as the uncoordinated phenolic hydroxyl O9, forming 2-D supramolec-
ular layers. Adjacent 2-D supramolecular layers are linked into 3-D supramolecular

3
10
L.-L. Li et al.
Figure 1. The molecular structure (a) and 3-D network structure (b) of 1.
networks by O–Hꢂ ꢂ ꢂO hydrogen bonds (O3–Hꢂ ꢂ ꢂO8 and O6–Hꢂ ꢂ ꢂO1). The data of these
hydrogen bonds are collected in table 4.
3
.3. Crystal structures of [Mn (μ -O)(4-OH-Me-sao) (CH COO)(MeOH) ]·MeOH (2)
3 3 3 3 5
Compound 2 crystallizes in the monoclinic space group P2(1)/c and is also a 9-MC-3 MC
figure 2(a)). Acetate takes place of formate. The central oxygen (O10) is 0.129 Å below
(

Structures and magnetism of two manganese crowns
Table 3. BVS calculations for 1 and 2.
311
2
+
3+
4+
1
2
Mn1
Mn2
Mn3
Mn1
Mn2
Mn3
3.216411
3.207430
3.132503
3.237867
3.216467
3.160382
2.977307
2.968346
2.898971
2.997104
2.977052
2.988841
3.068347
3.060151
2.988684
3.088913
3.068574
3.147424
Table 4. Data of hydrogen bonds of 1 and 2.
D–Hꢂ ꢂ ꢂA
d(Hꢂ ꢂ ꢂA) (Å)
\DHA (°)
d(Dꢂ ꢂ ꢂA) (Å)
1
O(15)–H(15)ꢂ ꢂ ꢂO(13) #3
O(16)–H(16)ꢂ ꢂ ꢂO(13) #3
O(17)–H(17)ꢂ ꢂ ꢂO(13) #3
O(3)–H(3)ꢂ ꢂ ꢂO(8) #1
O(6)–H(6)ꢂ ꢂ ꢂO(1) #5
O(9)–H(9)ꢂ ꢂ ꢂO(16) #2
O(18)–H(18)ꢂ ꢂ ꢂO(2) #4
O6–H6ꢂ ꢂ ꢂO8 #2
1.962
1.878
1.991
1.938
1.931
1.771
2.000
1.980
1.797
1.938
1.907
1.922
1.978
2.029
175.43
165.35
159.26
161.60
161.15
166.74
170.63
164.99
176.57
160.21
167.82
165.81
158.54
171.69
2.780
2.679
2.773
2.729
2.720
2.576
2.812
2.780
2.616
2.736
2.714
2.725
2.758
2.843
2
O9–H9ꢂ ꢂ ꢂO18 #1
O3–H3ꢂ ꢂ ꢂO8 #5
O15–H15ꢂ ꢂ ꢂO12 #4
O16–H16ꢂ ꢂ ꢂO12 #4
O17–H17ꢂ ꢂ ꢂJ124
O18–H18ꢂ ꢂ ꢂO5 #3
Symmetry transformations used to generate equivalent atoms for 1: #1 x, y, z + 1; #2 x, y, zꢀ1; #3 x + 1, y, z; #4
xꢀ1, y, z; #5 xꢀ1, ꢀy + 1/2, zꢀ1/2; for 2: #1 x, y, z + 1; #2 x, y, zꢀ1; #3 x + 1, y, z; #4 xꢀ1, y, z; #5 x + 1, ꢀy
+
1/2, z + 1/2.
the triangular [Mn ] plane. The torsion angles are 43.6(9)°, 38.3(9)°, and 39.7(2)°. In 2,
3
adjacent molecules are also connected with each other by intermolecular hydrogen bonds
to form a 3-D supramolecular network (figure 2(b)).
3
.4. Magnetic studies
Variable-temperature, solid-state dc magnetic susceptibility measurements were carried out
on both polycrystalline samples in a field of 0.1 T and a temperature range of 2–300 K. As
plotted in figure 3, different coordinated carboxyl in both complexes has little effect on
magnetic properties. Both 1 and 2 exhibit ferromagnetic coupling exchanges within the
metal centers. The χ T values of 1 and 2 are almost the same. At room temperature, the
M
3
ꢀ1
values of χ T are 9.72 (1) and 10.00 cm mol K (2), comparable to those of analogous
M
9
-MC-3 manganese crowns [16], and increase steadily as the temperature decreases, reach-
3
ꢀ1
ing maximum values of 16.99 (1) and 17.43 cm mol K (2), and then drop to 11.26 (1)
and 12.3 cm mol K (2) at 2.0 K, respectively. The χ T values at room temperature are
3
ꢀ1
M
larger than expected for three non-interacting Mn(III) centers with g = 2.0 (9.00
3
ꢀ1
cm mol K) [27], which may indicate that ferromagnetic interactions may have occurred
at room temperature. The decrease at low temperature may be assigned to the Zeeman
effect, zero-field splitting, and/or intermolecular interactions.

3
12
L.-L. Li et al.
Figure 2. The molecular structure (a) and 3-D network structure (b) of 2.
M M
Figure 3. (a)–(b) Plots of χ T and 1/χ vs. T for 1 and 2; the solid lines represent the best theoretical fit of the
data.

Structures and magnetism of two manganese crowns
313
Figure 4. The magnetic coupling interactions within the 9-MC-3 unit.
In order to have a better estimation of the exchange coupling parameters, the experimen-
tal magnetic data were successfully simulated. For 1 and 2, the interactions between
adjacent molecules are very weak, and only the intramolecular coupling interactions are
considered. The Heisenberg spin Hamiltonian was written as (figure 4):
^
^ ^
^ ^
^ ^
3 2 3
H ¼ ꢀ2J S S ꢀ 2J S S ꢀ 2J S S
ð1Þ
1
1
2
2
1
3
ꢀ
ꢀ
1
ꢀ1
ꢀ4
The best fits are J = 0.12 cm , J = J = 0.96 cm , and g = 1.96, with R = 1.8 ꢄ 10
1
2
3
1
ꢀ5
for 1, while J = J = J = 0.25 cm , and g = 2.0, with R = 2.7 ꢄ 10 for 2. The magneto-
1
2
3
III
structural relations for analogous [Mn ] compounds have been well established [30]. The
6
coupling is largely dependent upon the Mn–O–N–Mn torsion angles; the ferromagnetic
exchange interaction is attributed to Mn–O–N–Mn torsion angles above the “magic area”
of 30.4°–31.3° [15, 27, 31], whereas antiferromagnetic interaction arises from the Mn–O–
N–Mn torsion angle below the magic area. That is, when the Mn–O–N–Mn torsion angle
is larger than ca. 31.3°, J > 0 (F), and if the Mn–N–O–Mn torsion angle is lower than ca.
3
0.4°, then J < 0 (AF) [16 h]. For 1 and 2, the Mn–O–N–Mn torsion angles are 38.0–44.0
with ferromagnetic coupling existing. Of course, other interactions such as those between
adjacent 9-MC-3 along the chain also have influence on the coupling, and the resulting
ferromagnetic interactions should be the synergistic effect of both of them.
4
. Conclusion
We have described the structures and magnetic properties of two manganese MCs assem-
bled from 2,4-dihydroxyacetophenone oxime. Both compounds possess 9-MC-3 MC rings
with the repeating pattern [–Mn–N–O–]. In 1 and 2, the MC molecules are connected with
each other by intermolecular hydrogen bonds into similar 3-D supramolecular networks. It
is difficult to understand the relationship between structures and magnetic properties in
these trinuclear manganese complexes since all contributions to the exchange must be con-
sidered, such as ligand type, bond length and angles, weak interactions between molecules,
etc. The magneto-structural investigations of the two complexes indicate the Mn–O–N–Mn
torsion angles within the MCs play a dominant role in the magnetic coupling consistent
with earlier work on analogous [Mn ] compounds.
6

3
14
L.-L. Li et al.
Supplementary material
Crystallographic data have been deposited with the Cambridge Crystallographic Data
Centre (CCDC) as deposition numbers CCDC-834672 for 1 and 838577 for 2. The data
may be obtained free of charge from the CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK, via Fax (+44 1223 336033) or email (deposit@ccdc.cam.ac.uk).
Acknowledgements
This work was supported by the National Natural Science Foundation of P.R. China (Nos.
2
0671048, 21041002) and Shandong Province Higher School Science and Technology
Plan Projects (No. J10LB61).
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