Divalent Metal Aliphatic Tricarboxylate Dipyridylamine Coordination

ARTICLE pubs.acs.org/crystal

Divalent Metal Aliphatic Tricarboxylate Dipyridylamine Coordination Polymers with New or Rare Binodal Topologies Gregory A. Farnum,† Chaun M. Gandolfo,† Ronald M. Supkowski,‡ and Robert L. LaDuca*,† † ‡

Lyman Briggs College and Department of Chemistry, Michigan State University, East Lansing, Michigan 48825, United States Department of Chemistry and Physics, King’s College, Wilkes-Barre, Pennsylvania 18711, United States

bS Supporting Information ABSTRACT: Hydrothermal synthesis has afforded four divalent metal coordination polymers containing the aliphatic tricarboxylates tricarballylate (tca) or trans-aconitate (acon) and the kinked tethering co-ligand 4,40 dipyridylamine (dpa). Diverse structural topologies are evident across this series, with coordination geometry and carboxylate binding mode serving important structure-directing roles. {[Cd2(tca)2(Hdpa)2] 3 7H2O}n (1) possesses one-dimensional (1-D) ribbon motifs with pendant Hdpa+ ligands and a new 4-connected supramolecular topology, along with co-crystallized water molecule tapes. {[Cd3(acon)2(dpa)2(H2O)2] 3 4H2O}n (2) has a 4,4connected binodal lattice with frl (4264)4(6482) topology, while the structurally related phase {[Zn3(tca)2(dpa)2] 3 2H2O}n (3) has a 4,4-connected binodal lattice with a novel (426282)4(6284) topology. [Cu(Htca)(dpa)]n (4) manifests a 3,5-connected binodal net with rare (4.62)(4.6683) topology. Thermal stability of these materials is discussed. Complexes 13 undergo blue-violet light emission on excitation with ultraviolet light.

’ INTRODUCTION The synthesis and characterization of coordination polymer solids has become a major basic research thrust over the past 10 years because of their potential technological uses in diverse areas such as gas storage,1 molecular separations,2 ion exchange,3 catalysis,4 and nonlinear optics.5 Continued research in this field is also stimulated by the discovery of beautiful underlying molecular networks,6 many of which have not yet been predicted during theoretical topological investigations.7 Aromatic dicarboxylates and tricarboxylates have proven among the most popular choice of ligands for the construction of divalent metal coordination polymers.810 Coordination geometry preferences, the disposition of carboxylate groups, and numerous accessible bridging and binding modes allow access to a wide variety of structure types and physical properties in this genre of materials. For example, [Cu3(btc)2(H2O)3]n (btc = 1,3,5-benzenetricarboxylate) can be dehydrated without decomposition, yielding a microporous material featuring large square channels11 that can absorb numerous gases such as H2, N2, CO, CO2, and NO.12 Alteration of the topologies of metal tricarboxylate coordination polymers can be achieved by inclusion of dipodal pyridyl tethers such as 4,40 -bipyridine (bpy) or N,N0 bis(4-pyridylformamide)-1,4-benzene (bpfb).13,14 Cu(btcH2)2(bpy) displays a simple one-dimensional (1-D) chain structure,13 while {[Cu3(btc)2(bpfb)3] 3 5H2O}n exhibits a 3-fold interpenetrated (3,4)-connected binodal net with a very rare (63)2(648.10)3 tfz topology.14 r 2011 American Chemical Society

In comparison to myriad coordination polymers constructed from aromatic tricarboxylates, related materials containing aliphatic tricarboxylates such as tricarballylate (tca, Scheme 1) and transaconitate (acon) have received scant attention.1522 It is possible that the lack of attention to these ligands in coordination polymer chemistry can be attributed to more difficult a priori structure prediction and design because of the greater degree of conformational freedom in contrast to their more rigid aromatic tricarboxylate prototype btc. Although {[Zn(Htca)(bpy)] 3 3H2O}n and {[Zn(Htca)(dpe)] 3 4H2O}n (dpe = 1,2-bis(4-pyridyl)ethane) show simple (4,4) grid topologies because of protonation of one tca carboxylate group resulting in a dicarboxylate ligand,15 full deprotonation can induce more interesting topologies. For instance, {[Zn3(tca)2(bpmp)(Hbpmp)2](ClO4)2 3 5H2O}n (bpmp = bis(4-pyridylmethyl)piperazine) possesses an unprecedented selfpenetrated two-dimensional (2-D) layered topology with threadedloop pseudo-rotaxane motifs. Its oxoanion-free analogue {[Zn3(H2O)4(tca)2(bpmp)2] 3 8H2O}n manifests a unique but very simple 3-fold interpenetrated (63)(658) 3,4-connected 3-D binodal network.16 [Cd3(acon)2(H2O)6]n manifests an uncommon 3-D 4-connected (4.64.8)2(42.62.82) moganite network, while {[Cd(Hacon)(2,20 -bipyridine)(H2O)] 3 H2O}n exhibits only a 1-D chain topology.17 Received: May 31, 2011 Revised: September 14, 2011 Published: October 05, 2011 4860

dx.doi.org/10.1021/cg2006869 | Cryst. Growth Des. 2011, 11, 4860–4875

Crystal Growth & Design

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Scheme 1. Ligands Used in This Study

1

empirical formula

C32H44Cd2N6O19

C32H36Cd3N6O18

formula weight

1041.53

1129.87

crystal system

orthorhombic

triclinic

space group a (Å)

Pna21 25.439(4)

P1 7.726(3)

b (Å)

10.5693(16)

8.870(3)

c (Å)

14.524(2)

14.216(5)

α ()

90

84.897(4)

β ()

90

79.723(4)

γ ()

90

73.883(4)

V (Å3)

3905.2(10)

920.1(6)

Z Dcalc (g cm3)

4 1.771

1 2.032

μ (mm1)

1.177

1.808

min/max trans

0.7409/0.8834

0.6042/0.7745

hkl ranges

0 e h e 30

9 e h e 9

12 e k e 12

10 e k e 10

17 e l e 17

0 e l e 17

total reflections

57349

17840

unique reflections R(int)

14068 0.0414

3373 0.0363

parameters/restraints

565/32

283/6

R1 (all data)

0.0511

0.0641

R1 (I > 2σ(I))

0.0450

0.0486

wR2 (all data)

0.1063

0.1099

wR2 (I > 2σ(I))

0.1033

0.1031

max/min residual (e/Å3)

1.223/0.903

0.826/1.088

GOF

1.115

1.152

data

data

2

3

4

empirical formula

C32H32N6O14Zn3

C16H15CuN3O6

formula weight

920.74

408.85

crystal system

monoclinic

monoclinic

space group

C2/c

P21/c

a (Å)

27.2048(5)

9.8770(6)

b (Å)

8.5966(1)

10.7365(6)

c (Å) α ()

17.9747(3) 90

15.2604(9) 90

β ()

122.954(1)

101.916(3)

γ ()

90

90

a

3

4

V (Å3)

3527.37(10)

1583.41(16)

Z

4

4

Dcalc (g cm3)

1.734

1.715

μ (mm1)

2.102

1.422

min/max trans hkl ranges

0.6560/0.7296 31 e h e 32

0.7759/0.8502 11 e h e 11

10 e k e 8

12 e k e 12

21 e l e 20

18 e l e 18

total reflections

15546

13444

unique reflections

3237

2909

R(int)

0.0287

0.0391

parameters/restraints

258/4

250/4

R1 (all data)a R1 (I > 2σ(I))

0.0341 0.0279

0.0683 0.0498

wR2 (all data)b

0.0705

0.1175

wR2 (I > 2σ(I))

0.0677

0.1075

max/min residual (e/Å3)

0.715/0.378

0.783/0.625

GOF

1.064

1.034

R1 = Σ Fo| |Fc /Σ|Fo|. b wR2 = {Σ[w(Fo2 Fc2)2]/Σ[wFo2]2}1/2. )

data

Table 1. Continued

)

Table 1. Crystal and Structure Refinement Data for 14

The kinked nitrogen donor disposition and hydrogen-bonding point of contact of 4,40 -dipyridylamine (dpa, Scheme 1) has proven very efficacious for the production of coordination polymer solids, many with unique or rare topologies.2327 For example, {[Ni(dpa)2(succinate)0.5]Cl}n possesses a unique selfpenetrated 5-connected framework with with 610 rld-z topology.23 {[Cd(phthalate)(dpa)(H2O)] 3 4H2O}n has an unprecedented 4-connected uninodal self-penetrated 3-D 7482 yyz network topology, constructed from the vertex sharing of [Cd(dpa)]n double helices with [Cd(pht)]n single helices.24 To date we have only been able to prepare a few dpa-containing coordination polymers with tricarboxylate ligands, [Zn(btc)(Hdpa)]n and [Cd(btc)(Hdpa)(H2O)]n, which both have 3-connected 4.82 Archimedean layer motifs.28 We were thus intrigued to investigate the possible preparation of divalent metal coordination polymers containing both dpa and aliphatic tricarboxylate ligands tca or acon. Herein we report the synthesis and structural characterization of the crystalline coordination polymer phases {[Cd2(tca)2(Hdpa)2] 3 7H2O}n (1), {[Cd3(acon)2(dpa)2(H2O)2] 3 4H2O}n (2), {[Zn3(tca)2(dpa)2] 3 2H2O}n (3), and [Cu(Htca)(dpa)]n (4). Despite common 4861

dx.doi.org/10.1021/cg2006869 |Cryst. Growth Des. 2011, 11, 4860–4875


ARTICLE

Figure 1. Coordination environments in 1.

Table 2. Selected Bond Distance (Å) and Angle () Data for 1a Cd1O1

2.210(4)

N4Cd1O4#1

117.26(18)

Cd1O7

2.213(4)

O1Cd1O3#1

158.09(19)

Cd1N4

2.300(5)

O7Cd1O3#1

95.98(17)

Cd1O4#1

2.314(5)

N4Cd1O3#1

83.72(16)

Cd1O3#1

2.386(5)

O4#1Cd1O3#1

54.75(16)

Cd2O10

2.177(4)

O10Cd2O6

104.32(18)

Cd2O6

2.234(4)

O10Cd2O12#2

111.27(16)

Cd2O12#2 Cd2N1

2.304(5) 2.311(4)

O6Cd2O12#2 O10Cd2N1

99.93(16) 88.23(14) 129.85(16)

Cd2O11#2

2.426(4)

O6Cd2N1

O1Cd1O7

105.70(19)

O12#2 Cd2N1

120.60(17)

O1Cd1N4

86.08(17)

O10Cd2O11#2

154.31(17)

125.82(16)

O6Cd2O11#2

100.17(16)

#1

114.67(17)

O12#2 Cd2O11#2

56.06(16)

O7Cd1O4#1

105.34(16)

N1Cd2O11#2

81.97(15)

O7Cd1N4 O1Cd1O4

Symmetry equivalent positions: #1 x + 1/2, y + 1/2, z 1/2; #2 x + 1/2, y 1/2, z + 1/2.

a

structural elements across this series of four coordination polymers, differences in divalent metal coordination geometry, ligand conformation, and ligand protonation promote a great diversity in the resulting crystalline structures. Thermal properties and luminescent behavior of these materials are also discussed herein.

’ EXPERIMENTAL SECTION General Considerations. Metal salts and tricarboxylic acids were purchased commercially. 4,40 -Dipyridylamine was prepared using a published procedure.29 Water was deionized above 3 MΩ-cm in-

house. IR spectra were recorded on powdered samples using a Perkin-Elmer Spectrum One instrument. The luminescence spectra were obtained with a Hitachi F-4500 fluorescence spectrometer on solid crystalline samples anchored to quartz microscope slides with Rexon Corporation RX-22P ultraviolet-transparent epoxy adhesive. Thermogravimetric analysis was performed on a TA Instruments TGA 2050 thermogravimetric analyzer with a heating rate of 10 C/ min up to 600 C. Preparation of {[Cd2(tca)2(Hdpa)2] 3 7H2O}n (1). Cd(ClO4)2 3 6H2O (75 mg, 0.18 mmol), tricarballylic acid (33 mg, 0.19 mmol), dpa (63 mg, 0.37 mmol), and 5 mL of deionized water were placed into a 15 mL screw-cap vial. The vial was sealed and heated in an oil bath at 80 C for 72 h and then cooled slowly to 25 C. Colorless blocks of 1 (69 mg, 74% yield based on Cd) were isolated after washing with distilled water, and acetone, and drying in air. Anal. Calc. for C32H44Cd2N6O19 (1): C, 36.90; H, 4.26; N, 8.07% Found: C, 37.44; H, 3.99; N, 8.72%. IR (cm1): 3046 (w, br), 1584 (s), 1514 (s), 1434 (m), 1396 (s), 1359 (m), 1318 (w), 1287 (w), 1239 (w), 1086 (m), 1069 (m), 1016 (m), 997 (w), 927 (w), 903 (w), 881 (w), 856 (w), 811 (s), 746 (w), 720 (w), 681 (w). Preparation of {[Cd3(acon)2(dpa)2(H2O)2] 3 4H2O}n (2). Cd(NO3)2 3 6H2O (62 mg, 0.18 mmol), trans-aconitic acid (33 mg, 0.19 mmol), dpa (63 mg, 0.37 mmol), and 5 mL of deionized water were placed into a 15 mL screw-cap vial. The vial was sealed and heated in an oil bath at 80 C for 72 h, and then cooled slowly to 25 C. Colorless blocks of 2 (17 mg, 25% yield based on Cd) were isolated after washing with distilled water, and acetone, and drying in air. Anal. Calc. for C32H36Cd3N6O18 (2): C, 34.02; H, 3.21; N, 7.44% Found: C, 34.61; H, 2.87; N, 7.72%. IR (cm1): 3110 (m, br), 1640 (w), 1549 (s), 1412 (w), 1391 (s), 1264 (m), 1222 (w), 1106 (w), 963 (m), 946 (w), 886 (s), 814 (w), 789 (m), 680 (m). Preparation of {[Zn3(tca)2(dpa)2] 3 2H2O}n (3). Zn(ClO4)2 3 6H2O (68 mg, 0.18 mmol), tricarballylic acid (33 mg, 0.19 mmol), dpa (63 mg, 0.37 mmol), and 5 mL of deionized water were placed into a 15 mL screw-cap vial. The vial was sealed and heated in an oil bath at 80 C for 72 h, and then cooled slowly to 25 C. Colorless blocks of 3 (23 mg, 42% yield based on Zn) were isolated after washing with distilled 4862



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Scheme 2. Binding Modes of the Tricarboxylate Ligands in 14

Figure 2. (a) [Cd(tca)]nn 1-D anionic ribbon in 1. (b) Side view of [Cd(Hdpa)(tca)]n ribbon in 1, showing pendant Hdpa ligands. water, and acetone, and drying in air. Anal. Calc. for C32H32N6O14Zn3 (3): C, 41.74; H, 3.50; N, 9.13% Found: C, 41.98; H, 3.39; N, 9.55%. IR

(cm1): 3287 (w), 2921 (w), 2852 (w), 1603 (w), 1567 (s), 1523 (s), 1493 (w), 1448 (w), 1385 (s), 1355 (s), 1315 (w), 1213 (s), 1059 (m), 4863



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Figure 3. Supramolecular 4-connected 43628 topology in 1. Hdpa linkers are shown as red bars. Purple and black spheres represent the Cd and tca nodes, respectively.

Figure 4. T4(0)A(3) classification water tape in 1.

1024 (s), 972 (w), 901 (w), 862 (w), 823 (s), 782 (w), 745 (w), 728 (w), 696 (m). Preparation of [Cu(Htca)(dpa)]n (4). Cu(ClO4)2 3 6H2O (67 mg, 0.18 mmol), tricarballylic acid (33 mg, 0.19 mmol), dpa (63 mg, 0.37 mmol), and 5 mL of deionized water were placed into a 15 mL screw-cap vial. The vial was sealed and heated in an oil bath at 80 C for 72 h, and then cooled slowly to 25 C. Purple blocks of 4 (42 mg, 57% yield based on Cu) were isolated after washing with distilled water, and acetone, and drying in air. Anal. Calc. for C16H15CuN3O6 (4): C, 47.00; H, 3.70; N, 10.28% Found: C, 46.81; H, 3.51; N, 10.04%. IR (cm1): 2923 (w), 1711 (w, br), 1582 (s), 1517 (s), 1446 (m), 1383 (s), 1347 (s), 1308 (m), 1206 (s), 1108 (w), 1062 (m), 1026 (s), 903 (w), 855 (m), 814 (s), 730 (w), 679 (w), 661 (w). X-ray Crystallography. Single crystal X-ray diffraction was performed on single crystals of 14 with a Bruker-AXS ApexII CCD instrument at 173 K. Reflection data were acquired using graphite monochromated MoKα radiation (λ = 0.71073 Å). The data were integrated via SAINT.30 Lorentz and polarization effect and empirical absorption corrections were applied with SADABS.31 The structures were solved using direct methods and refined on F2 using SHELXTL.32 All non-hydrogen atoms were refined anisotropically. Successful refinement for the structure of 1 was only possible in the acentric space group Pna21 with racemic twinning. Attempts to refine the structure in the centrosymmetric space group Pnna failed, resulting in poor wR2 values (>0.40) with numerous nonpositive definite thermal parameters. Hydrogen atoms bound to carbon atoms were placed in calculated positions and refined isotropically with a riding model. The hydrogen atoms bound to the amine nitrogen atoms of the dpa ligands were found via Fourier difference maps, then restrained at fixed positions and refined isotropically. Relevant crystallographic data for 14 are listed in Table 1.

’ RESULTS AND DISCUSSION Synthesis and Spectral Characterization. The compounds in this study were prepared cleanly as crystalline products by hydrothermal reaction of the appropriate metal perchlorate, either tricarballylic acid or trans-aconitic acid, and 4,40 -dipyridylamine. The infrared spectra for 14 were consistent with their structural characteristics as determined by single-crystal X-ray diffraction. Puckering modes of the pyridyl and phenyl rings are evident in the region between 820 cm1 and 600 cm1. Asymmetric and symmetric CO stretching modes of the deprotonated carboxylate groups of the tca or acon ligands correspond to the intense features at 1584/1514 cm1 and 1396 cm1 (for 1), 1549 cm1 and 1391 cm1 (for 2), 1567/1523 cm1 and 1385/ 1355 cm1 (for 3), or 1582/1517 cm1 and 1383/1347 cm1 (for 4). Broad yet weak bands in the region of ∼3400 cm1 to ∼3500 cm1 in the spectra arise from water molecule and protonated carboxylate OH bonds, along with NH bonds from the amine functional group of the dpa ligands. The broadness of these higher energy spectral features is caused by hydrogen bonding (see below). Structural Description of {[Cd2(tca)2(Hdpa)2] 3 7H2O}n (1). The asymmetric unit of compound 1 contains two cadmium atoms, two tca trianions, two singly protonated dpa molecules, and seven water molecules of crystallization. The cadmium atoms exhibit very distorted {CdO4N} five-coordinate geometries (τ = 0.54 and 0.41 for Cd1 and Cd2, respectively).33 Each has single oxygen donor atoms from two different tca ligands, a chelating carboxylate group from a third tca ligand, and a pyridyl nitrogen donor atom from an Hdpa+ ligand (Figure 1). Bond lengths and angles within the 4864



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Table 3. Hydrogen Bonding Distance (Å) and Angle () Data for 14 d(H 3 3 3 A)

— DHA

d(D 3 3 3 A)

O1WH1WA 3 3 3 O6W O1 WH1WB 3 3 3 O2W

1.93

179.5

2.776(7)

1.95(3)

166(7)

2.771(9)

x, y, z 1/2

O2 WH2WA 3 3 3 O4W O2 WH2WB 3 3 3 O8

1.89

179.3

2.736(5)

x 1/2, y + 1/2, z

1.94(3)

165(7)

2.763(7)

O3 WH3WA 3 3 3 O1W O3 WH3WB 3 3 3 O2 O4 WH4WA 3 3 3 O3W O4 WH4WB 3 3 3 O5

2.10(3)

157(6)

2.916(6)

x + 1/2, y + 3/2, z + 1/2

1.92(3)

159(6)

2.740(6)

x + 1, y + 1, z + 1/2

1.99(3) 2.13

145(5) 145.8

2.728(8) 2.868(7)

x + 1, y + 1, z 1/2

O5 WH5WB 3 3 3 O7W N2H2N 3 3 3 O5W

1.99(4)

148(5)

2.760(8)

x, y + 1, z

2.01(3)

151(5)

2.838(7)

DH 3 3 3 A

symmetry transformation for A

1

N3H3N 3 3 3 O6 N5H5N 3 3 3 O6W N6H6N 3 3 3 O7

x + 1/2, y + 1/2, z

1.74(2)

161(5)

2.606(6)

1.95(2)

168(6)

2.831(6)

1.75(3)

165(7)

2.609(6)

x 1/2, y + 1/2, z

x + 1, y + 2, z 1

2 O1 WH1WA 3 3 3 O2 O1 WH1WB 3 3 3 O2W O2 WH2WA 3 3 3 O4

2.00(6) 1.89(3)

143(8) 162(7)

2.751(7) 2.747(8)

1.91(2)

175(9)

2.788(8)

O2 WH2WB 3 3 3 O1W N2H2N 3 3 3 O1W

1.96(3)

168(9)

2.835(9)

2.18(9)

177(8)

2.976(8)

x + 1, y 1, z

1.95(3)

161(8)

2.799(7)

x, y + 1, z

1.84(2)

174(8)

2.726(7)

x, y + 3, z

1.911(19) 1.867(18)

165(3) 175(4)

2.747(3) 2.720(3)

x + 1/2, y 1/2, z + 1/2

1.895(18)

173(3)

2.760(3)

x, y, z + 1/2

O7H7A 3 3 3 O1 O7H7B 3 3 3 O3 3 O1W H1WA 3 3 3 O6 O1W H1WB 3 3 3 O4 N2 H2N 3 3 3 O1W 4 O2H2O 3 3 3 O4 N2H2N 3 3 3 O6

2.11(7)

122(7)

2.697(6)

x +1, y + 1/2, z + 1/2

1.91(2)

176(5)

2.781 (6)

x +1, y 1/2, z + 1/2

Figure 5. Coordination environment in 2.

coordination spheres are listed in Table 2. Subtle variances in ligand conformation and coordination environment at

cadmium result in the crystallographically distinct metal and ligand atom sets within the asymmetric unit, which enforce 4865



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Table 4. Selected Bond Distance (Å) and Angle () Data for 2a Cd1N3#1

2.323(6)

N3#2Cd1O7#3

87.0(2)

#2

Cd1N3

2.323(6)

O5Cd1O7#3

87.20(19)

Cd1O5

2.326(5)

O5#3Cd1O7#3

92.80(19)

Cd1O5#3

2.326(5)

N3#1Cd1O7

87.0(2)

Cd1O7#3

2.345(5)

N3#2Cd1O7

93.0(2)

Cd1O7

2.345(5)

O5Cd1O7

92.80(19)

Cd2O6#4

2.196(5)

O5#3Cd1O7

87.20(19)

Cd2O3#5 Cd2N1

2.219(5) 2.225(6)

O7#3Cd1O7 O6#4Cd2O3#5

179.999(1) 109.15(19)

Cd2O1

2.337(5)

O6#4Cd2N1

92.4(2)

Cd2O2

2.389(5)

O3#5Cd2N1

133.3(2)

N3#1Cd1N3#2

180.000(1)

O6#4Cd2O1

88.28(18)

N3#1Cd1O5

79.20(19)

O3#5Cd2O1

90.73(17)

N3#2Cd1O5

100.80(19)

N1Cd2O1

132.0(2)

N3#1Cd1O5#3

100.80(19)

O6#4Cd2O2

135.40(19)

N3#2Cd1O5#3 O5Cd1O5#3

79.20(19) 179.999(1)

O3#5Cd2O2 N1Cd2O2

97.32(18) 94.7(2)

N3#1Cd1O7#3

93.0(2)

O1Cd2O2

55.35(17)

Symmetry equivalent positions: #1 x + 2, y + 2, z 1; #2 x 1, y + 1, z + 1; #3 x + 1, y + 3, z; #4 x + 1, y + 2, z; #5 x + 1, y, z. a

the lower symmetry acentric space group (Pna21 instead of Pnna). Exotridentate tca ligands with a μ3-k4-O,O0 :O00 :O000 binding mode (Scheme 2) construct [Cd(tca)]nn 1-D anionic coordination polymer ribbons (Figure 2), with pendant Hdpa+ ligands providing the necessary balance. The bis(monodentate)/chelating tca carboxylate binding mode in 1 is very similar to that seen in the self-catenated layered phase {[Zn3(tca)2(bpmp)(Hbpmp)2] (ClO4)2 3 5H2O}n; however, the end-capping carboxylates in the tca ligands in 1 are chelating. Within the [Cd(tca)(Hdpa)]n neutral ribbon motif two different types of {Cd2(OC4O)2} circuits are evident. One type is bracketed by four monodentate carboxylate arms supplied by two tca ligands, yielding a Cd 3 3 3 Cd through-space distance of 6.093 Å. The other is also delineated by two tca ligands, supplying a monodentate and a chelating carboxylate arm; here the Cd 3 3 3 Cd through-space distance is slightly shorter (5.949 Å). Spanning cadmium atoms along the periphery of the ribbon patterns are the five-carbon segments of the tca ligands, which adopt an anti-anti conformation (four C-atom torsion angles = 179.7, 175.2 and 173.9, 179.5) again similar to the tca ligands in {[Zn3(tca)2(bpmp)(Hbpmp)2](ClO4)2 3 5H2O}n. The pentanedioate segments of the tca ligands in 1 connect cadmium atoms with a metalmetal contact distance of 9.453 Å (Cd1 3 3 3 Cd1) or 9.437 Å (Cd2 3 3 3 Cd2) through their chelating/monodentate bridging modes. Long-range Cd 3 3 3 O interactions (∼2.8 Å) provide an additional stabilization mechanism within the [Cd(tca)(Hdpa)]n ribbon motifs. [Cd(tca)(Hdpa)]n ribbons aggregate into a 3-D supramolecular network via strong inter-ribbon NH+ 3 3 3 O hydrogenbonding34 between pendant protonated dpa pyridyl nitrogen atoms and ligated tca carboxylate oxygen atoms. The underlying supramolecular topology can be invoked by treating the cadmium atoms and tca ligands as 4-connected nodes with Hdpa+ ligands acting as linkers between [Cd(tca)(Hdpa)]n ribbon motifs. A calculation with TOPOS software35 reveals a 4362 8 supramolecular topology (Figure 3) with the extended

point symbol [4.4.4.8.6.6]. This topology can be generated by only using four of the linkers in the prototype 9-connected hxg-d net, reducing the theoretical space group in symmetry from Pn3m to Ccca.36 To the best of our knowledge, this particular 43 62 8 topology, different from the more common 43 628 sra (SrAl2) net,37 has not yet been reported in coordination polymer chemistry. Supramolecular solvent-accessible void space within the crystal structure of 1 represents 19.6% of the unit cell volume, according to a calculation performed with PLATON.38 This incipient space contains “infinite” 1-D hydrogen-bonded water molecule tapes consisting of cyclic tetramers alternating with short three-molecule discrete chains (Figure 4), in a T4(0)A(3) classification.39 These are anchored to the coordination polymer ribbons by means of hydrogen-bonding acceptance from dpa amine groups and hydrogen-bonding donation to tca carboxylate groups. Hydrogen-bonding parameters in 1 are listed in Table 3. Structural Description of {[Cd3(acon)2(dpa)2(H2O)2] 3 4H2O}n (2). The asymmetric unit of compound 2 contains a cadmium atom on a crystallographic inversion center (Cd1), a general position cadmium atom (Cd2), a completely deprotonated acon moiety, a dpa molecule, one aqua ligand, and two water molecules of crystallization. At Cd1, the coordination environment is a symmetry-enforced {CdN2O4} octahedron, with dpa pyridyl nitrogen donors, two acon carboxylate oxygen atoms, and two aqua ligands in mutually trans positions. A distorted square pyramidal geometry (τ = 0.06) in a {CdO4N} arrangement exists at Cd2, in which the basal plane contains a dpa pyridyl donor, an oxygen donor from a monodentate carboxylate group of one acon ligand, and a chelating carboxylate group of an another acon ligand. The apical position, with a longer CdO bond length, contains a donor atom from a monodentate carboxylate group of a third acon ligand. Metrical parameters within the distinct coordination environments of 2 (Figure 5) are listed in Table 4. The acon ligands in 2 adopt an exotetradentate μ4-k5-O,O0 : 00 O :O000 :O0000 binding mode, connecting one Cd1 and three Cd2 atoms (Scheme 2). The Cd2 atoms and acon ligands construct [Cd(acon)]nn ribbon motifs similar to the [Cd(tca)]nn patterns seen in 1 (Figure 6a), but here the circuit sizes are now different. One type of circuit, defined by 16-membered {Cd2(OC5O)2} circuits, is formed by twisted pentenedioate segments of the acon ligands (four C-atom torsion angles = 6.7, 102.6). Circuits formed by smaller 14membered {Cd2(OC4O)2} circuits are built through the fumarate-like trans-ethenedicarboxylate segment of the acon ligands (four C-atom torsion angle = 173.6). The Cd 3 3 3 Cd contact distances across the {Cd2(OC5O)2} and {Cd2(OC4O)2} circuits are 6.785 and 6.937 Å, respectively. The Cd 3 3 3 Cd contact distance along the periphery of the ribbon motif is 7.726 Å, ∼1.7 Å shorter than the comparable distance in the ribbon subunits of 1. In 2, only a four-carbon acon bridge is present along the ribbon periphery. The tricarboxylate arms within the [Cd(acon)]nn ribbons in 2 are arranged in a similar fashion to related [Cu(Htca)]nn ribbons seen in {[Cu(Htca)(H2O)2]n 3 2.5H2O}n.18 Adjacent [Cd(acon)]nn ribbon motifs are linked into [Cd3(acon)2(H2O)2]n neutral layers (Figure 6b) by [Cd(H2O)2]2+ coordination complex fragments centered on the special position Cd1 atoms. Hydrogen bonding between the 4866



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Figure 6. (a) [Cd(acon)]nn 1-D anionic ribbon in 2. (b) [Cd3(acon)2(H2O)2]n layer pattern in 2. (c) 3,4-connected V2O5 prototype layer in 2. Purple and black spheres represent the Cd2 and acon nodes, respectively.

aqua ligands on Cd1 and unligated acon carboxylate atoms provides an ancillary stabilization pathway (Table 3). The topology of a [Cd3(acon)2(H2O)2]n layer pattern in 2 can be simplified by treating the Cd2 atoms and acon ligands as 3- and 4-connected nodes, respectively. In this treatment, the [Cd(H2O)2]2+ coordination complex fragments are considered simple linkers between acon ligands in neighboring chains. A view of the resulting (42638)(426) topology V2O5 prototype layer40 is shown in Figure 6c. Bridging dpa ligands connect adjacent [Cd3(acon)2(H2O)2]n layers into a 3-D [Cd3(acon)2(dpa)2(H2O)2]n coordination polymer lattice (Figure 7a). The tethering dipyridines connect Cd1 and Cd2 atoms in neighboring layers with a metalmetal contact distance of 12.148 Å. Solvent accessible voids within the polymeric framework occupy 9.0% of the unit cell volume and contain cyclic water molecule tetramers.

The 3-D net can be simplified by considering the Cd2 atoms, Cd1 atoms, and acon ligands as 4-connected nodes. The Cd2 atoms connect directly to three tca ligand nodes and one Cd1 atom through a dpa tether, while the Cd1 atoms connect to two Cd2 atoms through dpa linkers and to two acon ligand nodes. Thus, each acon ligand node connects to three Cd2 atoms and one Cd1 atom within a [Cd3(tca)2(H2O)2]n layer submotif. The resulting 4-connected network has a binodal frl “Ferey ladder” topology with a Schl€afli symbol of (4264)4(6482) (Figure 7b). The first term within this (4264)4(6482) point symbol is ascribed to both the Cd2 atom nodes and acon ligand nodes, which have the extended point symbol [4.6.4.6.6.6]. The second term in the (4264)4(6482) point represents the Cd1 atom nodes, which have the extended point symbol [6.6.62.62.82.82]. This frl topology has been seen previously only in the hybrid metal hydroxide phase 4867



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Figure 7. (a) [Cd3(acon)2(dpa)2(H2O)2]n coordination polymer lattice in 2. [Cd3(acon)2(H2O)2]n layer submotifs are shown in blue. Water molecules of crystallization are shown as orange spheres. (b) Network perspective of 4-connected binodal frl “Ferey ladder” network in 2. Purple and black spheres represent Cd and acon nodes, respectively. The bridging dpa ligands are shown as red bars.

Figure 8. Coordination environments in 3. 4868



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[V(OH)]2(pyromellitate)]n.41 The topology of 2 differs greatly from one of the only previously reported 3-D cadmium aconitate phases, [Cd3(acon)2(H2O)6]n,18 which has a (4.64.8)2(42.62.82) mog network. Despite the similar conformations of the acon ligands in 2 and [Cd3(acon)2(H2O)6]n, the dual chelating binding mode of the acon ligands and the absence of dipodal neutral tethering ligands in the latter phase Table 5. Selected Bond Distance (Å) and Angle () Data for 3a 1.9528(17)

O2#1Zn1N1#1

Zn1O2

1.9528(17)

O2Zn1N1

96.98(8)

Zn1N1#1

2.021(2)

O2#1Zn1N1

126.41(8)

Zn1N1

Zn1O2 #1

96.98(8)

2.022(2)

N1#1Zn1N1

104.04(12)

#2

Zn2O5

1.9250(19)

O5#2Zn2O3#3

113.00(10)

Zn2O3#3

1.9764(19)

O5#2Zn2O1

101.75(8)

Zn2O1

2.0301(17)

O3#3Zn2O1

97.73(8)

Zn2N3#4 O2Zn1O2#1

2.036(2) 108.97(11)

O5#2Zn2N3#4 O3#3Zn2N3#4

136.03(10) 105.16(8)

O2Zn1N1#1

126.40(8)

O1Zn2N3#4

93.72(7)

Symmetry equivalent positions: #1 x, y, z + 1/2; #2 x, y 1, z; #3 x, y, z; #4 x 1/2, y + 1/2, z 1/2.

a

enforce a different topology on the final 3-D coordination polymer topology. Structural Description of {[Zn3(tca)2(dpa)2] 3 2H2O}n (3). The asymmetric unit of compound 3 contains a zinc atom on a crystallographic 2-fold axis (Zn1), a general position zinc atom (Zn2), a fully deprotonated tca moiety, a dpa molecule, and one unligated water molecule. The coordination geometries at Zn1 and Zn2 are both tetrahedral, but with {ZnN2O2} and {ZnNO3} environments, respectively. All nitrogen donors belong to dpa pyridyl rings, while monodentate carboxylate groups of tca ligands provide all oxygen donors. Pertinent bond lengths and angles within the coordination environments of 3 (Figure 8) are listed in Table 5. The tca ligands in 3 adopt an exotetradentate μ4-k4-O:O0 :O00 : 000 O binding mode, conjoining one Zn1 and three Zn2 atoms (Scheme 2). The tricarboxylate ligands and Zn2 atoms form [Zn(tca)]nn ribbon motifs similar to the [Cd(tca)]nn ribbons seen in 1 (Figure 9a), with only {Zn2(OC4O)2} circuits. As in 1, there are two different types of 14-membered circuits that alternate along the ribbon axis. The Zn 3 3 3 Zn contact distances across the different {Zn2(OC4O)2} circuits are 5.434 and 6.921 Å, respectively. The narrower circuit is defined by gauche conformation tca four-carbon segments (torsion angle = 55.0), while the larger circuit shows an anti disposition of its

Figure 9. (a) [Zn(tca)]nn ribbon motif in 3. (b) Neutral [Zn3(tca)2]n coordination polymer layer in 3. Ribbon submotifs are shown in blue. 4869



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Figure 10. [Zn3(tca)2(dpa)2]n coordination polymer network in 3. [Zn3(tca)2]n layers are shown in blue. (b) New binodal 4-connected (426282)4(6284) topology of 3. Gray and purple spheres represent Zn1 and Zn2 atom nodes, and black spheres denote tca ligand nodes. Tethering dpa ligands are shown as red rods.

tca four-carbon segments (torsion angle = 172.4). The full fivecarbon span of the tca ligands, with a gauche-anti conformation (torsion angles = 65.6, 174.4), bridges zinc atoms along the periphery of the ribbon motifs, with a Zn 3 3 3 Zn contact distance of 8.597 Å. Within the [Zn(tca)]nn ribbons in 3, all tca carboxylate groups possess a monodentate binding mode, avoiding any of the chelation seen in 1 and 2. Parallel [Zn(tca)]nn ribbons are connected by special position (Zn1)2+ ions to construct neutral [Zn3(tca)2]n coordination polymer layers (Figure 9b). These resemble the [Cd3(acon)2]n layers in 2 and also possess a (42638)(426) V2O5 topology 3,4connected binodal network (Figure 8c). These layers are pillared into a 3-D [Zn3(tca)2(dpa)2]n coordination polymer network by tethering dpa ligands (Figure 10a), in a manner similar to that seen in the 3-D [Cd3(acon)2(dpa)2]n net of 2. Isolated water

molecules of crystallization are anchored to the coordination polymer matrix by hydrogen-bonding acceptance from the amine groups of the dpa ligands and hydrogen-bonding donation to tca carboxylate groups. The unligated water molecules occupy a solvent-accessible incipient space comprising 3.7% of the unit cell volume. In 3, the Zn1 atoms, Zn2 atoms, and the tca ligands act as 4-connnected nodes with a connectivity pattern very similar to that in 2. However, the tetrahedral coordination at zinc in 3 promotes a very different underlying topology than that of 2, in which the dpa tethers are arranged in a strictly trans orientation across octahedral cadmium coordination environments. The overall 4-connected 3-D binodal lattice in 3 has a (4 26282)4(6 284) topology (Figure 10b), with a larger number of eight-membered rings than the network of 2, 4870



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Figure 11. Coordination environment in 4.

Table 6. Selected Bond Distance (Å) and Angle () Data for 4a Cu1O5#1

1.958(3)

O5#1Cu1O1

166.92(15)

Cu1O1 Cu1N3#2

1.978(3) 2.007(3)

O5#1Cu1N3#2 O1Cu1N3#2

88.22(14) 88.18(13)

Cu1N1

2.017(3)

O5#1Cu1N1

92.28(13)

Cu1O3#3

2.425(4)

O1Cu1N1

91.41(12)

N3#2Cu1O3#3

95.19(14)

N3#2Cu1N1

179.38(14)

N1Cu1O3#3

84.44(13)

O5#1Cu1O3#3

89.27(18)

O1Cu1O3#3

103.59(16)

Symmetry equivalent positions: #1 x, y + 1/2, z 1/2; #2 x + 1, y + 1/2, z + 1/2; #3 x + 1, y + 1/2, z + 1/2.. a

because of the kinked disposition of the dpa donors. The extended point symbol for 3 is (4.83.4.85.6.84)4(6.6.82.82. 84.84), with the first symbol representing the Zn2 and tca nodes. To the best of our knowledge, this (426282)4(6 284) binodal topology has neither been reported nor theoretically predicted. Two previous zinc tricarballylate coordination polymers, the grid-like 2-D phases {[Zn(Htca)(bpy)] 3 3H2O}n and {[Zn(Htca)(dpe)] 3 4H2O}n,15 show their tca ligands adopting simple bis(monodentate) binding modes along with protonation of the third carboxylate terminus. While the terminal carboxylate groups of the tca ligands in 3 show a similar bis(monodentate) binding mode, the additional binding of the central carboxylate group to [Zn(dpa)2]2+ fragments promotes a 3-D instead of a 2-D topology. Structural Description of [Cu(Htca)(dpa)]n (4). The asymmetric unit of compound 4 contains a divalent copper ion, a singly protonated Htca dianion, and a dpa molecule. The coordination environment at copper (Figure 11) is a distorted {CuN2 O3} square pyramid (τ = 0.21) with the basal plane containing trans dpa pyridyl nitrogen donors and trans carboxylate oxygen donors from two Htca ligands. Residing in the long JahnTeller distorted apical position is an oxygen donor atom from a third Htca ligand. Bond

lengths and angles within the coordination sphere of 4 are listed in Table 6. Exotridentate tca ligands with a μ3-k3-O:O0 :O00 tris(monodentate) binding mode link basal and apical coordination sites at copper ions to construct neutral [Cu(Htca)]n layers (Figure 12a) that are oriented parallel to the bc crystal planes. These consist of two types of circuits, 28-membered {Cu4(OC4O)4} and 16-membered {Cu2(OC5O)2} rings. The latter rings are formed by the full span of the five-carbon segment of the tca ligands in an anti-anti conformation (torsion angles = 168.3, 169.1). As measured by Cu 3 3 3 Cu or C 3 3 3 C contact distances, the smaller 16-membered circuits have apertures with dimensions ∼5.7 7.8 Å, while the windows in the larger 28-membered rings measure ∼7.5 12.5 Å. All copper atom and tca ligand nodes in this layer motif are 3-connected in an underlying ruffled 4.82 grid pattern (Figure 12b). The [Cu(Htca)]n layers in 4 therefore contrast topologically with the (6,3) herringbone [Zn(tca)]n layers in {[(CH3)4N][Zn(tca)(H2O)] 3 H2O}n,19 despite a similar 3-connectivity of metal and tca nodes within the layers and a similar tris(monodentate) tca binding mode. [Cu(Htca)]n 4.82 layers are pillared by tethering dpa ligands to form a non-interpenetrated [Cu(Htca)(dpa)]n 3-D coordination polymer network (Figure 13a). The interlayer throughligand Cu 3 3 3 Cu distance is 11.166 Å, although the shortest Cu 3 3 3 Cu contact between [Cu(Htca)]n layers is 8.540 Å. In this network, the 3-connected tca ligand nodes link Cu atom nodes only within [Cu(Htca)]n layer submotifs, while the Cu atom nodes are 5-connected. According to TOPOS software, the resulting 3,5-connected binodal net has a very rarely observed but simple (4.62)(4.6683) topology (Figure 13b). Among the few previously reported examples of this topology are [Cd(μ3-SO4)(bis(4-pyridylformyl)piperazine)]n42 and {[Mn(succinate)(4,40 -bipyridine)(H2O)] 3 0.5(4,40 bipyridine)}n.43 Nevertheless, the extended point symbol for 4 (4.62.62)(4.6.6.6.6.62.62.8.85.88), and its 5-connected coordination sequence (5, 13, 28, 49, 75, 108, 145, 189, 240, 295), differs from [Cd(μ3-SO4)(bis(4-pyridylformyl)piperazine)]n. The comparable extended point symbol for this 3-D cadmium phase is (4.62.62)(4.62.62.63.63.63.63.8.8.88) and its 4871



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Figure 12. (a) Neutral [Cu(Htca)]n layer in 4. (b) Schematic perspective of ruffled 4.82 grid layer submotif in 4. Blue and black spheres represent Cu and tca nodes, respectively.

5-connected coordination sequence is as follows: 5, 13, 26, 45, 69, 98, 133, 173, 218, 269. It is plausible that the subtle difference between the network of 4 and previous (4.62)(4.6683) rigid-rod binodal nets arises from the kinked donor disposition of the dpa ligands, which thus cannot span the shortest Cu 3 3 3 Cu interlayer distance in 4. Luminescence Spectra of 13. Irradiation of complexes 13 with ultraviolet light (λex = 320 nm for 1 and 3, 345 nm for 2) in the solid state resulted in modestly intense blue-violet visible light emission with λmax values of ∼370 nm (1), ∼405 nm (2), and ∼355 nm (3) (Figure 14). The emissive behavior is ascribed to ligand-centered electronic transitions between ππ* or πn molecular orbital manifolds within the aromatic pyridyl rings of the dpa ligands.44 Thermogravimetric Analysis. For compound 1, ejection of the water molecules of crystallization was essentially complete by 125 C, with a mass loss of 11.0% corresponding well

with the predicted value of 12.1%. The mass then remained stable until ∼210 C, with likely pyrolysis of the 1D coordination polymer chains above this temperature. At 600 C, the final mass remnant of 21.0% matches very well with a deposition of Cd metal (21.5%). The mass of compound 2 remained stable until ∼125 C, whereupon dehydration commenced. Water loss was complete by ∼210 C, with a mass loss of 13% roughly consistent with the predicted value (10%). Pyrolysis of the organic ligands occurred around 325 C. Dehydration of 3 occurred between 100 and 170 C (4.0% mass loss, 3.9% calc’d). Pyrolysis of the organic components was observed above 350 C. For 4, the mass remained stable until 220 C, with ligand combustion occurring above this temperature. The mass remnant of 22.5% was consistent with a deposition of CuO (19.3% calc’d). Thermograms for 14 are shown in Supporting Information Figures S1S4. 4872



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Figure 13. (a) [Cu(Htca)(dpa)]n 3-D coordination polymer network in 4. [Cu(Htca)]n layers are shown in blue. (b) 3,5-connected binodal net with (4.62)(4.6683) topology in 4. Blue and black spheres represent Cu and tca nodes, respectively. Red bars denote the dpa tethering ligands.

to promote formation of rare and novel coordination polymer networks, in conjunction with dipyridylamine tethering coligands. Coordination geometry at the divalent metal plays a predominant structure directing effect in this system of materials, along with protonation of either the tricarboxylate or dipyridylamine ligands. In the case of compounds 2 and 3, similar V2O5type metal tricarboxylate subnets are formed, with different 3-D topologies fostered by the variances in coordination geometry at cadmium and zinc, respectively. For the copper derivative 4, the kinked nature of the dipyridylamine ligand appears to instill a subtly different 3,5-connected binodal topology than that seen in similar species built from pillaring of Archimedean nets with rectangular and octagonal circuits. Figure 14. Luminescence spectra for 13.

’ CONCLUSIONS The conformationally flexible tricarballylate and trans-aconitate tricarboxylate ligands have been utilized as connecting nodes

’ ASSOCIATED CONTENT

bS

Supporting Information. Thermograms for 14. CIF files for 14. This material is available free of charge via the Internet at http://pubs.acs.org. Crystallographic data (excluding structure factors) for 14 have been deposited with the

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Crystal Growth & Design Cambridge Crystallographic Data Centre with Nos. 808593, 808592, 808595, and 808594, respectively. Copies of the data can be obtained free of charge via the Internet at http://www. ccdc.cam.ac.uk/conts/retrieving.html or by post at CCDC, 12 Union Road, Cambridge CB2 1EZ, U.K. (fax: 441223336033, e-mail: [email protected]).

’ AUTHOR INFORMATION Corresponding Author

*Mailing address: Lyman Briggs College, E-30 Holmes Hall, Michigan State University, East Lansing, MI 48825 USA. E-mail: [email protected].

’ ACKNOWLEDGMENT We acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work. C.M.G. thanks the MSU Honors College for his Professorial Assistantship. ’ REFERENCES (1) (a) Han, S. S.; Mendoza-Cortes, J. L.; Goddard, W. A., III Chem. Soc. Rev. 2009, 38, 1460–1476and references therein. (b) Roswell, J. L. C.; Yaghi, O. M. Angew. Chem., Int. Ed. Engl. 2005, 44, 4670– 4679. (c) Kondo, M.; Okubo, T.; Asami, A.; Noro, S.-I.; Yoshitomi, T.; Kitagawa, S.; Ishii, T.; Matsuzaka, H. Angew. Chem., Int. Ed. Engl. 1999, 38, 140–143. (d) Sudik, A. C.; Millward, A. R.; Ockwig, N. W.; Cote, A. P.; Kim, J.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 7110–7118. (2) (a) Li, J.-R.; Kuppler, R. J.; Zhou, H.-C. Chem. Soc. Rev. 2009, 38, 1477–1504and references therein. (b) Seo, J. S.; Whang, D.; Lee, H.; Jun, S. I.; Oh, J.; Jeon, Y. J.; Kim, K. Nature 2000, 404, 982–986. (c) Cingolani, A.; Galli, S.; Masciocchi, N.; Pandolfo, L.; Pettinari, C.; Sironi, A. J. Am. Chem. Soc. 2005, 127, 6144–6145. (3) (a) Fang, Q.-R.; Zhu, G.-S.; Xue, M.; Sun, J.-Y.; Qiu, S.-L. Dalton Trans. 2006, 2399–2402. (b) Zhang, X.-M.; Tong, M.-L.; Lee, H. K.; Chen, X.-M. J. Solid State Chem. 2001, 160, 118–122. (c) Yaghi, O. M.; Li, H.; Groy, T. L. Inorg. Chem. 1997, 36, 4292–4293. (4) (a) Lee, J. Y.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450–1459and references therein. (b) Ma, L.; Abney, C.; Lin, W. Chem. Soc. Rev. 2009, 38, 1248–1256and references therein. (c) Baca, S. G.; Reetz, M. T.; Goddard, R.; Filippova, I. G.; Simonov, Y. A.; Gdaniec, M.; Gerbeleu, N. Polyhedron 2006, 25, 1215–1222. (d) Han, H.; Zhang, S.; Hou, H.; Fan, Y.; Zhu, Y. Eur. J. Inorg. Chem. 2006, 8, 1594–1600. (e) Mori, W.; Takamizawa, S.; Kato, C. N.; Ohmura, T.; Sato, T. Microporous Mesoporous Mater. 2004, 73, 15–30. (5) (a) Dai, J. C.; Wu, X. T.; Fu, Z. Y.; Cui, C. P.; Hu, S. M.; Du, W. X.; Wu, L. M.; Zhang, H. H.; Sun, R. Q. Inorg. Chem. 2002, 41, 1391–1396. (b) Chen, W.; Wang, J. Y.; Chen, C.; Yue, Q.; Yuan, H. M.; Chen, J. S.; Wang, S. N. Inorg. Chem. 2003, 42, 944–946. (c) Hao, N.; Shen, E.; Li, Y. B.; Wang, E. B.; Hu, C. W.; Xu, L. Eur. J. Inorg. Chem. 2004, 4102–4107. (6) Blatov, V. A.; Carlucci, L.; Ciani, G.; Proserpio, D. M. CrystEngComm 2004, 6, 377–395. (7) The theoretically derived EPINET database of Euclidean Patterns in Non-Euclidean Tilings can be accessed at http://epinet.anu. edu.au (8) For example:(a) Groeneman, R. H.; MacGillivray, L. R.; Atwood, J. L. Inorg. Chem. 1999, 38, 208–209. (b) Tao, J.; Tong, M. L.; Chen, X. M. Dalton Trans. 2000, 3669–3674. (c) Manna, S. C.; Konar, S.; Zangrando, E.; Okamoto, K.; Ribas, J.; Chaudhuri, N. R. Eur. J. Inorg. Chem. 2005, 4646–4654. (9) (a) Bourne, S. A.; Mondal, A.; Zaworotko, M. J. Cryst. Eng. 2001, 4, 25–36. (b) Moulton, B.; Lu, J.; Hajndl, R.; Hariharan, S.; Zaworotko, M. J. Angew. Chem., Int. Ed. 2002, 41, 2821–2824. (c) Yang, S. Y.; Long, L. S.; Huang, R. B.; Zheng, L. S. Chem. Commun. 2002, 472–474.

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