DOI: 10.

1021/cg900475q

Lanthanide Carboxyphosphonates Ln(O3PCH2- 2009, Vol. 9

NC5H9-COO)(H2O)2 3 xH2O with Open Framework Structures 4445–4449
Containing Parallelogram-like Channels

Deng-Ke Cao,* Shou-Zeng Hou, Yi-Zhi Li, and Li-Min Zheng*

State Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, School of
Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China

Received April 30, 2009; Revised Manuscript Received June 22, 2009

ABSTRACT: On the basis of (4-carboxypiperidyl)-N-methylenephosphonic acid (4-cpmpH3), four isostructural lanthanide

phosphonates Ln(O3PCH2-NC5H9-COO)(H2O)2 3 xH2O [Ln=Eu(1), Gd(2), Tb(3), Dy(4)] have been synthesized. All exhibit
three-dimensional open framework structures, in which inorganic double chains made up of {Ln2O14} dimers and {PO3C}
linkages are connected through organic moieties of 4-cpmp3-. Uniform parallelogram-like channels are observed in the [100]
direction. Luminescent properties of 1 and 3, and the magnetic properties of 2 are investigated.

Introduction Lu), based on N-(phosphonomethyl)iminodiacetic anion

(H4PMIDA), are reported which exhibit three-dimensional
Metal phosphonates with open frameworks or porous
(3D) open framework structures with helical tunnels.14 The
structures have received great attention because of their
reactions of 1-phosphonomethylproline with lanthanide salts
potential applications in adsorption, separation, ion ex-
result in chiral porous compounds Ln[(S)-HO3PCH2NHC4-
change, catalysis, etc.1-3 On the other hand, lanthanide-based
H7CO2]3 3 2H2O (Ln=Tb, Dy, Eu, Gd) built from 1D triple-
compounds are interesting luminescent materials because they
strand helical chains.15 A few lanthanide oxalatophospho-
could emit over the entire spectral range: near-infrared (Nd3þ,
nates with open framework structures are also described.6,16
Yb3þ), red (Eu3þ, Pr3þ, Sm3þ), green (Er3þ, Tb3þ), and blue
In this paper, we describe four new isostructural lanthanide
(Tm3þ, Ce3þ).4 Consequently, design and syntheses of porous
carboxyphosphonates Ln(O3PCH2-NC5H9-COO)(H2O)2 3
lanthanide phosphonates are attractive in developing new
xH2O [Ln = Eu(1), Gd(2), Tb(3), Dy(4)]. All exhibit open
materials with multifunctions.5-8
framework structures containing parallelogram-like channels.
To prepare lanthanide phosphonates with open framework
or porous structures, one efficient approach is using phos-
phonate ligands with additional functional groups such as a Experimental Section
second phosphonate or carboxylate group. Thus, by using N, Materials and Methods. (4-Carboxypiperidyl)-N-methylenephos-
N-piperazine(bis-methylenephosphonic acid) [H2O3PCH2- phonic acid (4-cpmpH3) was prepared according to the literature
N(C2H4)2NCH2PO3H2, LH4], compounds La2(LH2)2(LH4)Cl2, method.17 All other reagents were purchased as reagent grade
La2(LH2)2(LH3)Cl,9 Gd2(LH2)3 3 3H2O, and Nd2(LH2)3 3 chemicals and used without further purification. Elemental analyses
9H2O10 were obtained which show open framework struc- were performed on a Perkin-Elmer 240C elemental analyzer. The IR
tures in which the inorganic chains composed of corner- spectra were obtained as KBr disks on a VECTOR 22 spectrometer.
Magnetic susceptibility data of compound 2 were obtained on
sharing {LaO7} and {PO3C} polyhedra are linked through
microcrystalline sample (8.13 mg), using a Quantum Design
organic moieties. Mixed ligated compounds [Ln2(HL0 )(H2L)2- MPMS-XL7 SQUID magnetometer. Diamagnetic corrections were
(H2O)4] 3 8H2O (Ln = La, Nd; H3L0 = m-sulfophenylphos- made for both the sample holder and the compound estimated from
phonic acid) were also obtained which contain tetranuclear Pascal’s constants.18
cluster units interconnected by the same phosphonate ligand Syntheses of Ln(O3PCH2-NC5H9-COO)(H2O)2 3 xH2O [Ln3þ
(H2L2-).11 Large pore is achieved in [Ln(H2L00 (NO3)- =Eu (1), Gd (2), Tb (3), Dy (4)]. Compounds 1-4 were synthesized
(H2O)2] 3 2H2O 3 2MeOH where 26,28-dihydroxy-25,27- di- following a similar procedure. In a general synthesis, a mixture of 4-
cpmpH3 3 2H2O (0.10 mmol, 0.0259 g) and Ln(CH3COO)3 3 4H2O
methoxycalix[4]arene-11,23-diphosphonate (L00 4-) are linked (0.1 mmol) in 8 mL of H2O, adjusted to a certain pH with 2 M HCl
by Ln3þ ions.12 (3.96 for 1, 3.46 for 2, 3.54 for 3, and 3.46 for 4), was kept in a Teflon-
With regard to compounds containing both phosphonate lined autoclave at 140 °C for 24 h. After slowly being cooled to room
and carboxylate groups, Pr4(H2O)7(O3PCH2-NC5H9- temperature, colorless needlelike crystals were collected.
COO)4(H2O)5 provides the first open framework lanthanide For compound 1: Yield: 28.2 mg (66.2%). Anal. found (calcd)
carboxyphosphonate, where one-dimensional (1D) inorganic for C7H15NO7PEu 3 2H2O: C, 19.61 (18.91); H, 4.04 (4.28);
N, 3.19 (3.15)%. IR (KBr, cm-1): 3582 (b,s), 2951(w), 2922(w),
chains made up of corner- and edge-sharing {PrO8} and 2852(w), 2811(w), 2756(w), 2669(w), 1655(w), 1624(w), 1543(s),
{PrO9} are linked by (4-carboxypiperidyl)-N-methylenepho- 1448(s), 1384(w), 1361(w), 1336(w), 1305(w), 1290(w), 1267-
sphonate.13 Isostructural lanthanide carboxyphosphonates (w), 1239(w), 1218(w), 1152(s), 1119(m), 1073(s), 1052(m), 1031(m),
Ln(HPMIDA)(H2O)2 3 H2O (Ln = Gd, Tb, Dy, Y, Er, Yb, 1009(s), 953(w), 939(w), 878(w), 812(w), 788(w), 767(m), 663(w),
604(m), 574(w), 505(w), 470.55(w), 461(w), 444(w).
For compound 2: Yield: 22.1 mg (51.3%). Anal. found (calcd) for
*Corresponding author. E-mail: lmzheng@nju.edu.cn (L.-M.Z.), dkcao@ C7H15NO7PGd 3 2H2O: C, 19.39 (18.69); H, 3.80 (4.23); N, 3.17
nju.edu.cn (D.K.C.); fax: þ86-25-83314502. (3.11)%. IR (KBr, cm-1): 3419 (b,s), 2937(w), 2949(w), 2921(w),

r 2009 American Chemical Society Published on Web 07/14/2009 pubs.acs.org/crystal

4446 Crystal Growth and Design, Vol. 9, No. 10, 2009 Cao et al.

Table 1. Crystallographic Data and Refinement Parameters for 1-4

compound 1 2 3 4
empirical formula C7H17NO8PEu C7H17NO8PGd C7H17NO8PTb C7H17NO8PDy
fw 426.15 431.44 433.11 436.69
crystal system monoclinic monoclinic monoclinic monoclinic
space group P21/c P21/c P21/c P21/c
a (Å) 5.5520(5) 5.515(2) 5.5294(7) 5.5286(12)
b (Å) 13.3686(14) 13.393(3) 13.3523(17) 13.314(2)
c (Å) 20.797(2) 20.8105(14) 20.642(3) 20.599(2)
β (°) 95.577(3) 95.382(3) 95.378(3) 95.244(3)
V (Å3) 1536.3(3) 1530.4(7) 1517.3(3) 1509.9(4)
Z 4 4 4 4
Fcalcd (g 3 cm-3) 1.842 1.873 1.896 1.921
F(000) 832 836 840 844
goodness-of-fit on F2 1.034 1.018 1.077 1.080
R1, wR2 [I > 2σ(I)]a 0.0519, 0.1232 0.0433, 0.0847 0.0412, 0.1115 0.0587, 0.1730
R1, wR2 (All data)a 0.0717, 0.1291 0.0639, 0.0890 0.0496, 0.1152 0.0749, 0.1804
(ΔF)max, (ΔF)min(e Å-3) 1.146, -2.718 1.052, -2.323 2.392, -1.840 1.883, -2.870
a
R1 = Σ||Fo| - |Fc||/Σ|Fo|. wR2 = [Σw(Fo2 - Fc2)2/Σw(Fo2)2]1/2.

2852(w), 2810(w), 2755(w), 2669(w), 1658(w), 1550(s), 1450(s), Table 2. Selected Bond Lengths [Å] and Angles [o] for 1-4a
1384(w), 1363(w), 1336(w), 1306(w), 1267(w), 1240(w), 1219(w),
1 2 3 4
1144(s), 1117(s), 1069(m), 1046(m), 1035(m), 1011(s), 992(m),
955(w), 940(w), 879(w), 813(w), 789(w), 767(w), 716(w), 633(w), Ln1-O1 2.407(6) 2.404(4) 2.398(5) 2.399(8)
608(w), 561(w), 544(w), 504(w), 460(w), 443(w). Ln1-O2 2.534(5) 2.536(4) 2.526(4) 2.520(7)
For compound 3: Yield 12.2 mg (28.2%). Anal. found (calcd) Ln1-O1W 2.41(11) 2.39(9) 2.39(9) 2.38(15)
for C7H15NO7PTb 3 2H2O: C, 19.31 (18.62); H, 3.98 (4.21); Ln1-O2W 2.37(12) 2.36(9) 2.36(10) 2.36(16)
N, 3.13 (3.10)%. IR (KBr, cm-1): 3425 (b,s), 3116(w), 2954(w), Ln1-O3B 2.280(5) 2.273(4) 2.267(4) 2.262(7)
2924(w), 2856(w), 2810(w), 2756(w), 2344(w), 1647(w), 1550(s), Ln1-O2C 2.283(5) 2.274(4) 2.278(4) 2.275(7)
1450(s), 1384(w), 1367(w), 1336(w), 1308(w), 1268(w), 1219- Ln1-O4D 2.476(6) 2.479(4) 2.462(5) 2.458(8)
Ln1-O5D 2.482(5) 2.484(4) 2.476(4) 2.474(7)
(w), 1136(s), 1070(m), 1037(m), 1012(s), 956(w), 941(w), 852(w),
O1-P1 1.540(5) 1.534(4) 1.536(4) 1.531(7)
814(w), 768(w), 714(w), 669(w), 644(w), 617(w), 558(w), 504(w),
O2-P1 1.562(5) 1.558(4) 1.557(4) 1.557(8)
461(w), 443(w). O3-P1 1.513(5) 1.520(4) 1.509(4) 1.507(7)
For compound 4: Yield 19.1 mg (43.7%). Anal. found (calcd) C7-O4 1.257(10) 1.258(8) 1.252(8) 1.250(13)
for C7H15NO7PDy 3 2H2O: C, 19.14 (18.47); H, 3.74 (4.18); C7-O5 1.243(9) 1.233(8) 1.233(8) 1.230(13)
N, 3.20 (3.08)%. IR (KBr, cm-1): 3347 (b,s), 2951(w), 2919(w),
2852(w), 2810(w), 2754(w), 2668(w), 2362(w), 2343(w), 1655(w), O1-Ln1-O2 59.40(17) 59.34(13) 59.48(14) 59.5(2)
1625(w), 1545(s), 1448(s), 1383(w), 1363(w), 1349(w), 1304(w), O1-Ln1-O1W 79(3) 79(2) 80(2) 80(3)
1286(w), 1267(w), 1239(w), 1213(w), 1154(s), 1119(m), 1069- O2W-Ln1-O1 74(3) 75(2) 74(2) 74(4)
(s), 1052(m), 1037(m), 1012(s), 997(m), 954(w), 939(w), 927(w), O1W-Ln1-O2 77(3) 77(2) 77(2) 77(4)
814(w), 789(w), 766(m), 662(w), 606(m), 566(w), 504(m), 472(w), O2W-Ln1-O2 134(3) 134(2) 134(2) 134(4)
460(w), 443(w). O2W-Ln1-O1W 95(4) 95(3) 95(3) 95(5)
X-ray Crystallographic Analyses. Single crystals of dimensions O2C-Ln1-O1 125.79(18) 125.56(15) 125.82(15) 125.9(3)
0.07  0.05  0.04 mm3 for 1, 0.08  0.06  0.05 mm3 for 2, 0.08  O3B-Ln1-O1 85.72(18) 86.32(14) 85.54(15) 85.4(3)
0.07  0.05 mm3 for 3, 0.08  0.06  0.04 mm3 for 4 were used for O1-Ln1-O4D 146.08(19) 146.21(15) 146.10(16) 146.1(3)
structural determinations on a Bruker SMART APEX CCD dif- O1-Ln1-O5D 138.96(19) 139.03(14) 138.96(15) 139.1(3)
fractometer using graphite-monochromatized Mo KR radiation O2C-Ln1-O2 66.5(2) 66.37(17) 66.44(17) 66.6(3)
(λ=0.71073 Å) at room temperature. A hemisphere of data were O3B-Ln1-O2 85.55(18) 85.28(15) 85.21(15) 85.2(3)
O4D-Ln1-O2 141.72(18) 141.54(15) 141.64(15) 141.6(2)
collected in the θ range 1.81-25.99° for 1, 1.81-26.00° for 2, 1.82-
O5D-Ln1-O2 137.96(18) 138.46(15) 138.08(14) 138.1(2)
25.50o for 3, and 1.82-25.00° for 4 using a narrow-frame method
O2C-Ln1-O1W 86(3) 86(2) 86(2) 86(4)
with scan widths of 0.30° in ω and an exposure time of 10 s/frame. O3B-Ln1-O1W 161(3) 161(2) 161(2) 161(3)
Numbers of observed and unique reflections are 8187 and 3013 O1W-Ln1-O4D 125(2) 125(2) 125(2) 125(3)
(Rint =0.0422) for 1, 8003 and 2964 (Rint =0.0292) for 2, 7704 and O1W-Ln1-O5D 73(2) 73(2) 73(2) 73(3)
2822 (Rint = 0.0232) for 3, 7456 and 2663 (Rint = 0.0414) for 4, O2C-Ln1-O2W 159(3) 159(2) 160(2) 159(4)
respectively. The data were integrated using the Siemens SAINT O3B-Ln1-O2W 92(3) 93(2) 92(2) 92(4)
program,19 with the intensities corrected for Lorentz factor, polar- O2W-Ln1-O4D 80(3) 80(2) 80(2) 80(4)
ization, air absorption, and absorption due to variation in the path O2W-Ln1-O5D 78(3) 78(2) 78(2) 78(4)
length through the detector faceplate. Multiscan absorption correc- O3B-Ln1-O2C 93.6(2) 93.33(16) 93.46(16) 93.5(3)
tions were applied. The structures were solved by direct methods O3B-Ln1-O4D 73.54(18) 73.23(15) 73.84(15) 73.9(2)
and refined on F2 by full matrix least-squares using SHELXTL.20 O2C-Ln1-O5D 82.4(2) 82.50(16) 82.49(17) 82.3(3)
All the non-hydrogen atoms were located from the Fourier maps O2C-Ln1-O4D 82.9(2) 83.12(16) 82.84(16) 82.7(3)
and were refined anisotropically. All H atoms were refined isotro- O3B-Ln1-O5D 125.52(17) 124.91(15) 125.68(14) 125.7(2)
pically, with the isotropic vibration parameters related to the non-H O4D-Ln1-O5D 52.00(18) 51.70(15) 51.87(14) 51.8(2)
atom to which they are bonded. For compounds 1-4, crystal- P1-O1-Ln1 101.0(3) 101.0(2) 100.9(2) 100.9(4)
lographic and refinement details are listed in Table 1, and selected P1-O2-Ln1 95.2(3) 94.9(2) 95.1(2) 95.2(3)
bond lengths and angles are given in Table 2. P1-O2-Ln1C 151.0(3) 151.0(3) 151.1(3) 151.1(5)
P1-O3-Ln1B 141.3(3) 140.4(2) 141.3(2) 141.3(4)
C7-O4-Ln1A 93.4(5) 93.5(4) 93.7(4) 93.8(6)
Results and Discussion C7-O5-Ln1A 93.5(5) 94.0(4) 93.5(4) 93.6(6)
Syntheses. Compounds 1-4 were prepared through Ln1C-O2-Ln1 113.5(2) 113.63(17) 113.56(17) 113.4(3)
hydrothermal reactions of 4-cpmpH3 and equal molar cor- a
Symmetry codes: A: x þ 1, -y þ 1/2, z þ 1/2; B: -x þ 1, -y, -z;
responding lanthanide acetates at 140 °C for 24 h. It is found C: -x, -y, -z; D: x - 1, -y þ 1/2, z - 1/2.
Article Crystal Growth and Design, Vol. 9, No. 10, 2009 4447

Figure 1. Building unit of structure 1 with atomic labeling scheme Figure 2. One inorganic chain in structure 1.
(50% probability). All H atoms are omitted for clarity.
forming a dimer of {Eu2O14} with the Eu1C-O2-Eu1 bond
Scheme 1 angle of 113.5(2)o. The dimers are connected by {PO3C}
tetrahedra through corner- or edge-sharing, resulting in a 1D
double chain running along the a-axis (Figure 2). Within the
chain, the Eu 3 3 3 Eu distances over μ3-O2, O1-P1-O3, and
O2-P1-O3 bridges are 4.031, 5.485, and 5.552 Å, respec-
tively. The chain is further linked to its four equivalent
neighbors through the coordination of the phosphonate
and carboxylate oxygens to the Eu atoms, leading to a 3D
open framework containing uniform large parallelogram-
like channels with the size of 15.978  9.777 Å (van der Waals
radii not accounted) (Figure 3). The lattice water mole-
cules fill in these channels and are involved in hydrogen
bonding networks formed among phosphonate oxygens
(O3, O4) and lattice waters (O3W, O4W, O5W). The three
shortest contacts are 2.779 Å for O3W 3 3 3 O4a, 3.029 Å for
O4W 3 3 3 O5Wb, and 3.034 Å for O4W 3 3 3 O3Wc (symmetry
codes: a: x - 1, -y þ 1/2, z þ 1/2; b: -x, -y þ 1, -z þ 1; c:
x, -y þ 1/2, z - 1/2).
The structures of 2-4 are analogous to 1 except that the
Eu atom in 1 is replaced by Gd in 2, Tb in 3, and Dy in 4. The
crystal cell volume decreases in the decreasing sequence of ionic
radii with Eu>Gd>Tb>Dy. The Ln-O distances and O-
Ln-O bond angles are 2.273(4)-2.536(4) Å and 51.70(15)-
161(2)o for 2, 2.267(4)-2.526(4) Å and 51.87(14)-161(2)o for
3, and 2.262(7)-2.520(7) Å and 51.8(2)-161(3)o for 4, respec-
tively. The sizes of the channels are 15.978  9.792 Å in 2,
15.920  9.734 Å in 3, and 15.879  9.733 Å in 4.
The open-framework structures of 1-4 are different from
that the pH values play a key role in the formation of four that of Pr4(H2O)7(O3PCH2-NC5H9-COO)4(H2O)5. In the
compounds. The pH value above 4.0 results in flocculent latter case, chains of edge-sharing {PrO8} and {PrO9} poly-
mixture, whereas the pH value below 3 leads to a lower yield, hedra are observed, which are interconnected via organic
and even clear solution. Compounds with good crystal acids to create an open framework structure. While in 1-4,
quality and high yields are obtained in the pH values between the inorganic chain is built from dimers of edge-sharing
3.5 and 4.0. {LnO8} connected by {PO3C} linkages. Further, each chain
Crystal structures. Compounds 1-4 are isostructural and is linked by its four equivalents via eight 4-cpmp3- ligands
crystallize in monoclinic space group P21/c. As shown in in Pr4(H2O)7(O3PCH2-NC5H9-COO)4(H2O)5, instead of
Figure 1, the building unit of 1 contains one Eu atom, one four 4-cpmp3- in 1-4. Finally, the coordination modes of
4-cpmp3- ligand, two coordination and one lattice water 4-cpmp3- in 1-4 (Scheme 1a) are also different from those in
molecules. Each Eu is eight-coordinated by four phospho- Pr4(H2O)7(O3PCH2-NC5H9-COO)4(H2O)5 (Scheme 1b-d).
nate oxygens (O1, O2, O2C, and O3B) from three equivalent It is worth noting that a few transition metal phosphonates
4-cpmp3- ligands, two carboxylate oxygens (O4D and O5D) based on 4-cpmp3- were also reported, including Mn(O3-
from the fourth equivalent 4-cpmp3- ligand and two water PCH2-NHC5H9-COO),17 Zn(O3PCH2-NHC5H9-COO),
oxygens (O1W and O2W). The Eu-O bond lengths and the and Co3(O3PCH2-NHC5H9-COO)2(O3PCH2-NC5H10)-
O-Eu-O bond angles are in the normal range of 2.280(5)- (H2O).21 Their structures, however, are all pillared layered,
2.534(5) Å and 52.00(18)-161(3)°, respectively. and the 4-cpmpH2- ligand adopts two other coordination
Each 4-cpmp3- serves as a pentadentate ligand, binding modes (Scheme 1e,f).
four Eu atoms through three phosphonate oxygens (O1, O2, Thermal Analysis. In order to explore the thermal stability
O3) and two carboxylate oxygens (O4, O5) (Scheme 1a). The of these materials, the TG curves of 1-4 were measured. The
phosphonate oxygen O2 bridges two equivalent Eu atoms, first step decomposition appears in the temperature range
4448 Crystal Growth and Design, Vol. 9, No. 10, 2009 Cao et al.

Figure 3. (a) Structure 1 packed along the a-axis. The lattice water molecules are omitted for clarity. (b) The channel in structure 1.

Figure 4. Room temperature emission spectra of 1 (left) and 3 (right).

50-235 °C, with a weight loss of about 17.1% for 1, 15.6%

for 2, 16.7% for 3, and 15.0% for 4. These values are in
agreement with the theoretical values expected for the release
of two coordinated and two lattice water molecules (16.2%
for 1, 16.0% for 2, 16.0% for 3, 15.8% for 4). A plateau
appears in the range 235-348 °C in all four cases, above
which a rapid weight loss occurs, corresponding to the
decomposition of the organic ligands and the collapse of
the structure. In order to determine whether the framework
is maintained after dehydration, compounds 1-4 were
heated at 110 °C for 2 h. The X-ray diffraction (XRD)
measurements reveal that the dehydrated samples become
amorphous.
Luminescent and Magnetic Properties. The solid-state
luminescent properties of compounds 1 and 3 were investi- Figure 5. The χM and χM-1 vs T plot for 2.
gated at room temperature under excitation at 395 nm for 1,
and 376 nm for 3, respectively. As shown in Figure 4, a Curie constant of 7.67 cm3 3 K 3 mol-1 and a very small
compound 1 emits strong red luminescence characteristic Weiss constant θ=-0.054 K which suggests that compound
for the f-f transitions of Eu3þ ion. The emission bands 2 is paramagnetic.
at 592, 616, 698 and 650 nm are attributed to 5D0 f 7FJ (J=
1-4) transitions. Compound 3 shows four emission bands at Acknowledgment. This work is supported by the National
489 nm (5D4 f 7F6), 545 nm (5D4 f 7F5), 583 nm, 590 nm Basic Research Program of China (2007CB925102), the
(5D4 f 7F4), and 622 nm (5D4 f 7F3). The most intensive one NSFC (No. 20631030) and the NSFC for the Creative
is 5D4 f 7F5, in accordance with the typical Tb3þ ion Research Group (No. 20721002).
emission spectrum.22 The observed luminescent lifetimes Supporting Information Available: This material is available free
are τ1 = 0.84 μs (43.21%), τ2 = 3.04 μs (20.31%), and τ3 = of charge via the Internet at http://pubs.acs.org.
18.76 μs (36.48%) for 1, and τ1=1.12 μs (61.35%), τ2=11.95 μs
(38.65%) for 3. References
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Curie-Weiss law in the whole temperature range, leading to Llewellyn, P. L. J. Am. Chem. Soc. 2008, 130, 15967.
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