Design of Novel Three-Dimensional Coordination Polymers Basedon Triangular Trinuclear Copper 1,2,4-Triazolate Units

Quan-Guo Zhai, Can-Zhong Lu,* Shu-Mei Chen, Xin-Jiang Xu, and Wen-Bin Yang

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences, Fuzhou, Fujian 350002, People’s Republic of China

ReceiVed January 9, 2006; ReVised Manuscript ReceiVed March 8, 2006

ABSTRACT: By controlling the molar ratios of copper dichloride dihydrate and 1,2,4-triazole (trz), we generated a series of novelthree-dimensional coordination polymers constructed fromµ3-oxo orµ3-Cl triangular copper units, exhibiting six-connected porousself-penetrating net, graphite layer, and inorganic-organic hybrid network structures, respectively.

Introduction

The rational design of coordination polymers constructed frommetals and bridging organic ligands is now of interest, due totheir intriguing architectures1 and potential application as newmaterials.2 The utilization of polynuclear metal clusters asbuilding blocks has proved to be a versatile strategy to constructsupramolecular coordination frameworks, especially highlyconnected structures. To date, a large number of coordinationpolymers that are assembled from polynuclear metal clustershave been explored;3 however, most of the organic componentsinvolved are polycarboxylates, which are not ideal candidatesfor the predictable assembly of coordination polymers from thecrystal engineering and crystal structure prediction point ofview.4 In fact, the best targets should be in simple topologiesby employment of simple ligands and fewer components.2f,5

1,2,4-Triazole and its derivatives, which are usually studiedas precursors of compounds with importance in medicine,biology, and industry, have gained more and more attention asligands to metals due to their interesting bridging modes.Numerous papers on their coordination chemistry have shownthat they can lead to a wide variety of compounds, dependingupon the nature of the substituents; thus, a large number ofpolynuclear complexes and coordination polymers containingsubstituted triazole ligands can be found in the literature.6

However, only a few structures with unsubstituted triazole havebeen reported, which is most likely due to the fact that thisligand almost always immediately produces insoluble precipi-tates with nearly all transition-metal ions.6a Hydrothermaltechniques, which are widely used in the synthesis of inorganicmaterials and coordination polymers, can effectively surmountthe solubility problem. On the basis of this, taking into accountthe diverse bridging modes (N1,N2, N2,N4, and N1,N2,N4), wespeculate that interesting structures can be obtained withunsubstituted 1,2,4-triazole under hydrothermal conditions.Encouraged by novel 3D hybrid materials based on triazole andpolyoxometalates,7 we designed and tuned different conditionsto attain a series of copper triazolates using hydrothermaltechniques: [Cu3(µ3-O)(µ3-trz)3]2[OH]2‚15H2O (1), Cu[Cu3(µ3-O)(µ3-trz)3Cl3] (2), and [Cu2(µ3-trz)(µ3-Cl)2] (3). To our knowl-edge, no extended framework based onµ3-oxo trinuclear copper1,2,4-triazolate units has been reported to date.

Experimental SectionMaterials and General Procedures.All of the chemicals were

obtained from commercial sources and were used without further

purification. The IR spectra (KBr pellets) were recorded on a Magna750 FT-IR spectrophotometer. C, H, and N elemental analyses weredetermined on an Elementar Vario EL III elemental analyzer. Thermalstability studies were carried out on a NETSCHZ STA-449C ther-moanalyzer under air (30-800 °C range) at a heating rate of 10°Cmin-1. X-ray powder diffraction data were recorded on a RigakuMultiFlex diffractometer with a scan speed of 0.05-0.2° min-1.Magnetic measurements for powder examples of1-3 were carried outwith a Quantum Design PPMS Model 6000 magnetometer.

Syntheses. (a) [Cu3(µ3-O)(µ3-trz) 3]2[OH] 2‚15H2O (1). A mixtureof CuCl2‚2H2O (0.17 g, 1.0 mmol) and 1,2,4-triazole (0.069 g, 1.0mmol) in 10 mL of H2O was introduced into a Parr Teflon-linedstainless steel vessel (25 cm3), after which the vessel was sealed andheated at 180°C for 5 days under autogenous pressure. The mixturewas cooled to room temperature at a rate of 0.5°C min-1. The resultingblue octahedral crystals of1 were filtered, washed with H2O, and air-dried (yield 45% based on Cu). When CuSO4‚5H2O was used insteadof CuCl2‚2H2O under the same hydrothermal conditions, the yield of1 was increased to 85% (based on Cu). However, the use of Cu(NO3)2‚3H2O and Cu(OAC)2‚H2O in our experiments did not lead to theformation of1. Anal. Calcd for C12H44Cu6N18O19: C, 12.80; H, 3.94;N, 22.39. Found: C, 12.77; H, 3.90; N, 22.41. IR (KBr pellets,λ/cm-1):

3434.64 (s), 1635.00 (s), 1514.69 (s), 1384.48 (m), 1296.08 (m),1172.64 (m), 1101.68 (s), 1000.82 (m), 882.70 (w), 667.40 (m), 617.52(w).

(b) Cu[Cu3(µ3-O)(µ3-trz) 3Cl3] (2). A mixture of CuCl2‚2H2O (0.20g, 1.2 mmol) and 1,2,4-triazole (0.062 g, 0.9 mmol) in 10 mL of H2Owas introduced into a Parr Teflon-lined stainless steel vessel (25 cm3),and then the vessel was sealed and heated at 180°C for 5 days underautogenous pressure. The mixture was cooled to room temperature ata rate of 0.5°C min-1. Almost phase-pure dark blue dodecahedralcrystals of2 were collected, washed with H2O, and air-dried (lowyield: 20% based on Cu). Anal. Calcd for C6H6Cu4N9OCl3: C, 12.41;H, 1.04; N, 21.71. Found: C, 12.47; H, 0.99; N, 22.72. IR (KBr pellets,λ/cm-1): 3425.34 (s), 3148.10 (w), 1633.86 (m), 1507.90 (vs), 1384.81(w), 1303.86 (vs), 1206.94 (vs), 1164.22 (m), 1087.40 (vs), 1041.90(w), 996.65 (m), 908.81 (w), 839.47 (m), 672.83 (m), 432.42 (m).

(c) [Cu2(µ3-trz)(µ3-Cl)2] (3). A mixture of CuCl2‚2H2O (0.34 g, 1.0mmol) and 1,2,4-triazole (0.069 g, 2.0 mmol) in 10 mL of H2O wasintroduced into a Parr Teflon-lined stainless steel vessel (25 cm3), afterwhich the vessel was sealed and heated at 180°C for 5 days underautogenous pressure. The mixture was cooled to room temperature ata rate of 0.5°C min-1. Black prismatic crystals of3 were collected,washed with H2O, and air-dried (low yield: 25% based on Cu). Anal.Calcd for C2H2Cu2N3Cl2: C, 9.03; H, 0.758; N, 15.79. Found: C, 9.10;H, 0.79; N, 15.72. IR (KBr pellets,λ/cm-1): 3426.00 (s), 3138.59 (w),1631.21 (m), 1512.19 (s), 1384.55 (w), 1290.02 (s), 11.98.25 (w),1181.60 (w), 1108.68 (s), 997.85 (m), 868.63 (m), 652.48 (s).

X-ray Crystallography. Suitable single crystals of1-3 werecarefully selected under an optical microscope and glued to thin glassfibers. Crystallographic data for all compounds were collected with aSiemens Smart CCD diffractometer with graphite-monochromated MoKR radiation (λ ) 0.710 73 Å) atT ) 293(2) K. Absorption correctionswere made using the SADABS program.8 The structures were solved

* To whom correspondence should be addressed. Tel: 86-591-83705794.Fax: 86-591-83714946. E-mail: czlu@ms.fjirsm.ac.cn.

CRYSTALGROWTH& DESIGN

2006VOL.6,NO.6

1393-1398

10.1021/cg0600142 CCC: $33.50 © 2006 American Chemical SocietyPublished on Web 04/21/2006

using direct methods and refined by full-matrix least-squares methodsonF2 by using the Shelx-97 program package.9 All non-hydrogen atomswere refined anistropically. Crystal data as well as details of datacollection and refinements for1-3 are summarized in Table 1.

Results and Discussion

Preparations of the Complexes.To solve the problem thatunsubstituted 1,2,4-triazole immediately produces an insolubleprecipitate with transition-metal ions, hydrothermal techniqueswere used in our experiments. The hydrothermal reaction ofCuCl2‚2H2O with the ligand 1,2,4-triazole in a molar ratio of1:1 at 180°C produced bright blue octahedral crystals of1 inabout 45% yield. When the amount of CuCl2‚2H2O wasgradually increased, a decrease in the yield of1 was observedand then dark blue dodecahedral crystals of2 were obtained. Afurther increase in the amounts of salts led to the formation ofblack prismatic crystals of3. The almost phase-pure productswere obtained under certain stoichiometric conditions (Cu:trz) 1:1 for 1, 4:3 for 2, and 2:1 for3), whereas mixtures wereobtained under intermediate conditions. Attempts to increasethe amounts of organic ligands only led to microcrystals orprecipitates.

Structure Description. X-ray single-crystal diffraction analy-sis reveals that1 features an extended 3D six-connected self-penetrating porous structure constructed of triangular CuII

subunits (Figure 1). [Cu3(µ3-O)(µ3-trz)3]+ has a Cu3 triangle unitlinked by one centralµ3-O group; each edge is bridged by a trz

ligand in the N1,N2 bridging mode, and each copper atom iscoordinated by a N4 atom of the trz ligand from the adjacenttrinuclear unit. The coordination geometry around each CuII ioncan be described as ideal square planar with O-Cu-N andN-Cu-N angles of 180°. The Cu-O bond length is 1.9850(9)Å. Cu-N bond lengths are 1.992(5) and 2.009(6) Å. Each Cuatom forms short contacts (Cu-O ) 2.605(4) Å) with two guestwater molecules, which lie symmetrically at either side of thetrinuclear plane. Theµ3-O atom is in a standard planar triangularcoordination sphere, with Cu-O-Cu angles of 120°, which isindicative of an sp2 configuration for the oxygen atom. Thisarrangement holds the Cu atoms at average distance of 3.439(0)Å, and three triazole rings are located in the Cu3 plane to forma rigid 3-fold plane. In most of the reported triangular trinuclearcopper structures, theµ3 ligand is OH, which is located abovethe Cu3 plane in certain distances.6a,10 Each rigid trinuclearcopper cluster is interlinked by the other six identical units togenerate a turbo-shaped structure (Figure 2a), with an anglebetween two adjacent triangular planes of 60°. The resultingunique 3D self-penetrating network of a cubic topology is builtupon six-connected nodes (Figure 2b). Although a few previ-ously reported six-connected coordination polymers display self-penetration,11 the structure of1 is unprecedented because ofthe novel rigid triangular oxo-centered building blocks and therare connection modes among them.

Just like the metal-organic frameworks reported by Lin andco-workers,11c even after interpenetration, complex1 still

Table 1. Crystal Data and Structure Refinements for 1-3

1 2 3

empirical formula C12H44Cu6N18O19 C6H6Cu4N9OCl3 C2H2Cu2N3Cl2formula wt 1125.89 580.71 266.05cryst size (mm3) 0.13× 0.12× 0.10 0.10× 0.08× 0.04 0.20× 0.10× 0.10cryst descripn blue octahedron black dodecahedron black prismcryst syst cubic hexagonal orthorhombicspace group Fd3hc P63/mmc Immaa (Å) 24.8200(5) 11.6208(7) 6.764(4)b (Å) 24.8200(5) 11.6208(7) 6.981(4)c (Å) 24.8200(5) 5.9640(8) 12.338(7)V (Å3) 15 289.9(5) 697.49(11) 582.6(6)Z 16 2 4F(000) 9088 560 508F (Mg/m3) 1.956 2.765 3.033T (K) 293 293 293abs coeff (mm-1) 3.371 6.605 8.101θ for data collecn (deg) 3.28-27.44 3.51-27.46 3.30-27.47reflections collected 25 813 5216 2224no. of unique rflns (R(int)) 740 (R(int) ) 0.0619) 333 (R(int) ) 0.0552) 397 (R(int) ) 0.0187)no. of data/params 740/44 333/30 397/32goodness of fit onF2 1.010 1.085 1.087R1, wR2 (I > 2σ(I))a 0.0557, 0.1410 0.0432, 0.0823 0.0268, 0.0636R1, wR2 (all data) 0.0557, 0.1410 0.0451, 0.0831 0.0272, 0.0638

a R1 ) ∑(|Fo| - |Fc|)/∑|Fo|; wR2 ) [∑w(Fo2 - Fc

2)2/∑w(Fo2)2]0.5.

Figure 1. Trinuclear copper units in1-3.

1394 Crystal Growth & Design, Vol. 6, No. 6, 2006 Zhai et al.

presents a tubular framework as viewed from thea, b, or cdirection (Figure 2c). The wall of each tube consists of a unitthat is formed by four trinuclear clusters connected with eachother as shown in Figure 2d. Taking the van der Waals radiiinto account, the aperture may only admit the passage of asphere with a 4.5 Å diameter. If this highly open structure isviewed from the [-1,0,1] axis, a larger channel can be seenwith cross dimensions of ca. 11.1× 5.9 Å (Figure S1;Supporting Information). The channels are fully occupied bythe severely disordered HO- or H2O guests. The total solvent-accessible volume of the channel is approximately 6458.4 Å3,which accounts for 42.2% of the total cell volume. In compari-son with the only two reported porous metal-organic frame-works constructed from 1,2,4-triazole ligands, [ZnF(atrz)]‚guest12 and [Ag6Cl(atrz)4]‚OH‚6H2O13 (atrz ) 3-amino-1,2,4-

triazole), this solvent-accessible volume is the largest. In contrastto a vast number of porous coordination polymers constructedby tetrameric Zn4O clusters,1a only a few examples based ontriangular oxo-centered building units have been reported.2c,14

Further, it should be pointed out that examples of triangulartrinuclear complexes obtained with 1,2,4-triazole or its deriva-tives are very rare, though quite a few of them were obtainedwith pyrazole. To our knowledge, only a few discrete trinuclearcomplexes with substituted 1,2,4-triazole have been investi-gated,10 and no extended framework has been reported to date.

The crystal structure of2 shows that it is also constructedfrom a triangular trinuclear unit (Figure 1), which is similar tothat of complex1 except that each copper atom is coordinatedby one terminal Cl atom (Cu-Cl ) 2.347(2) Å, N-Cu-Cl )92.94(14)°) instead of the N4 atom; thus, the six-connected unit

Figure 2. (a) Building block unit including the asymmetric units present in1. (b) Schematic illustrating the six-connected self-penetrating net. Thetrinuclear building blocks are shown as orange balls. (c) Stick representation (left) and space-filling diagram (right) of the tubular channels formedin 1 along thea, b, or c axis. (d) Tubular structure of each channel. A yellow cylinder indicates the tube interior. Color scheme in (a), (c), and (d):Cu, cyan; O, red; N, blue; C, white. Hydrogen atoms and guest H2O or HO- units are omitted for clarity.

Coordination Polymers Based on Trinuclear Cu Units Crystal Growth & Design, Vol. 6, No. 6, 20061395

becomes a three-connected one (Figure 3a). However, in[Cu3(µ3-O)(µ-pz)3Cl3]2-,15 which has a similar structure, onepyrazole rotates out of the Cu3O plane and the other twopyrazoles are bent out on either side of this plane by 33.0°.The second crystallographically unique copper atom (Cu(2))coordinates to three N4 atoms from three adjacent trinuclearunits, assuming an ideal trigonal-planar coordination geometry(Cu-N ) 1.966(7) Å). The rule of charge balance indicatesthe valence of Cu(2) to be+2. Although there have been manyreports on trigonally coordinated CuI complexes with cyanideligands or other mixed systems, three-coordinated CuII is veryrare. The whole network of2 exhibits three-connected 2D 63

topology 16 with three-coordinated copper atoms and cyclictrinuclear units as hexagonal nodes (Figure 3b). When Cu‚‚‚Cu short contacts (2.9820(4) Å) are taken into account as linkersand the Cu(2) atoms act as five-connected nodes, the 2Dnetworks are stacked in an ABAB... fashion to form the layeredgraphite structure (Figure 3c). As in Cu2(im)3 or Cu3(im)4,17

there exist infinite linear copper chains (Cu-Cu-Cu ) 180°)along thec axis (Figure S2; Supporting Information).

For 3, µ3-Cl triangular mixed-valence copper units (Figure1) form novel 2D inorganic layers (Figure 4a), which are linkedby µ3-trz ligands to generate a 3D organic-inorganic hybridframework (Figure 4b and Figure S4 (Supporting Information)).The 2D inorganic layer can be viewed as two wavy sheetspenetrated together along thea direction (Figure S3; SupportingInformation). Cu(1) has a trigonal-planar geometry (Cu-N )1.931(5) Å; Cu-Cl ) 2.2849(15) Å; N-Cu-Cl ) 128.62(4)°;Cl-Cu-Cl ) 102.76(8)°), which can be assigned a charge of+1 on the base of charge neutrality. The bivalent Cu(2) is ashortened octahedron, N(CuCl4)N, in which two apical positionsare occupied by nitrogen atoms (Cu-N ) 1.935(3) Å and Cu-Cl ) 2.5789(13) Å). Although hybrid coordination polymersbased on copper halides and aromatic nitrogen-donor ligandsare well-known, compound3 is of interest with respect to thefollowing aspects: (i) it exhibits unique 2D inorganic layers

Figure 3. (a) Local coordination geometry of ligands and metals in the structure of2. (b) The 2D 63 net viewed along thec axis. The trinuclearbuilding blocks are shown as orange balls. (c) 3D graphite structure in2 linked by Cu‚‚‚Cu short contacts. Color scheme: Cu, cyan; O, red; N,blue; C, white; Cl, green. Hydrogen atoms are omitted for clarity.

1396 Crystal Growth & Design, Vol. 6, No. 6, 2006 Zhai et al.

which are different from those of basic copper halide skeletons18

such as square dimers, cubane tetramers, zigzag chains, double-stranded ladders, hexagonal grid chains, et al.; (ii) it has mixed-valence copper atoms; (iii) it presents the first example of 1,2,4-triazoles as organic components in the filed of inorganic-organic hybrid copper halides.

TG Analysis, Heating-Cooling and Dehydration-Hydra-tion Experiments. TGA of 1 (Figure S6; Supporting Informa-tion) first shows a weight loss (found 24.02%) from 130 to 300°C, which is attributed to the loss of guest water molecules(calcd 24.48%). The weight loss observed between 300 and 450°C was slight; after that a sharp weight loss started and endedat 625°C. The total weight loss in the temperature range 300-625 °C was 37.03%, which corresponds to the loss of triazolegroups (calcd 36.27%). For2 and3, similar weight losses wereobserved in the temperature range 300-750 °C, which weredue to the decomposition of organic components and chlorine(Figure S6). The N2 sorption experiments for1 showed thatonly surface adsorption had occurred, indicating that nitrogenmolecules could not diffuse into the channels at this temperature.On the other hand, heating-cooling and dehydration-hydrationexperiments were carried out according to the TGA results and

monitored by X-ray powder diffraction techniques (XRPD,Figure S7 (Supporting Information)). In comparison to theoriginal crystals, the dehydrated solid obtained by heating1 at300 °C for 30 min showed an almost identical XRPD (curvesb and e in Figure S7). The loss of water caused1 to changecolor from bright blue to cyan. When1 was heated to 350°C,some of the characteristic peaks became weak or disappeared,but the intensity of the lines could be recovered after thisdehydrated solid was immersed in water (curve i in Figure S7),which suggests that the dehydration of1 is reversible. Furtherheating at 400 and 450°C led to a severe disappearance ofcharacteristic peaks, indicating that the decomposition hadbegun. When this finding is combined with the slight weightloss between 300 and 450°C, it can be concluded that the[Cu3(µ3-O)(µ3-trz)3]+ framework is rather stable, which may beattributed to the whole rigid building blocks and the self-penetrating nets. It should be pointed out that, though a highthermal stability of porous metal-organic frameworks is themost desirable quality for application purposes, it has been rarelyachieved to date.2,13,14

ESR and Magnetic Properties.The ESR spectra of1-3(Figure S8a; Supporting Information) were recorded on poly-crystalline samples at room temperature. The following param-eters were obtained:g ) 2.1519 for1, g ) 2.1002 for2, andg ) 2.0060 for3. The temperature-dependent molar magneticsusceptibility for three complexes is measured at 5 kOe in thetemperature range 2-300 K (Figure S8). TheøMT values for1and2 at room temperature are 0.508 and 0.571 cm3 K mol-1,which are much lower than the valued expected for three (for1) or four (for 2) uncoupled copper(II) ions. With decreasingtemperature, the gradually decreasingøMT value indicates thepresence of antiferromagnetic interactions. The magnetic dataobey the Curie-Weiss law in the temperature region (20-300K for 1 and 2-300 K for2), and fitting in the range gives valuesof C ) 0.5133 cm3 K mol-1, Θ ) -57.65 K andC ) 0.4373cm3 K mol-1, Θ ) -6.373 K, respectively. It should be notedthat there exists a small “plateau” in theøM versusT curve of1 at 0.0053 cm3 mol-1 in the range 12-17 K. A similar resulthas been founded in the magnetic behavior of Na3[Co6(OH)-(C8H4O4)6]‚H2O,19 which containsµ3-O triangular cobalt units.The “plateau” indicates that there exists a residual moment,which may be due to the stabilization of an uncompensatedmoment by the frustration effect in the triangular motifs.19 For3, antiferromagnetic behavior is observed down to 5 K, and afurther decrease of the temperature causes a sharp increase oføMT, suggesting the presence of ferromagnetic interactions. Themagnetic data in the range of 5-300 K were well fitted to theCurie-Weiss law withC ) 0.3692 cm3 K mol-1 and Θ )-9.066 K, indicating antiferromagnetic interactions betweenCu2+ ions. Further study on the magnetic properties is underway.

Conclusions

Three novel 3D coordination polymers exhibiting differenttopological structures have been successfully synthesized andcharacterized, which are all constructed by triangular trinuclearcopper units. This is the first time that trinuclearµ3-O subunitshave been obtained with unsubstituted triazole ligands. Theisolation of these complexes demonstrates that using hydro-thermal techniques can effectively surmount the solubilityproblem of metal-1,2,4-triazolate systems, as expected. On thebasis of this work, further synthesis and structural studies ofother transition metals with unsubstituted 1,2,4-triazole are underway in our laboratory.

Figure 4. (a) 2D network in3 constructed fromµ3-Cl trinuclear mixed-valance copper units. (b) 3D structure formed by the 2D network andµ3-trz. Color scheme: Cu, cyan; N, blue; C, white; Cl, green. Hydrogenatoms are omitted for clarity.

Coordination Polymers Based on Trinuclear Cu Units Crystal Growth & Design, Vol. 6, No. 6, 20061397

Acknowledgment. This work was supported by the 973program of the MOST (Grant No. 001CB108906), the NationalScience Foudation of China (Grant Nos. 20425313, 90206040,20521101, 20333070, and 20303021), the Natural ScienceFoundation of Fujian Province (Grant No. 2005HZ01-1), andthe Chinese Academy of Science.

Supporting Information Available: X-ray crystallographic dataas a CIF file, tables of bond lengths and angles, and figures givingadditional plots of the structures, infrared spectra, thermogravimetricanalysis, XRPD patterns for1, ESR spectra, and magnetic results for1-3. This material is available free of charge via the Internet at http://pubs.acs.org.

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1398 Crystal Growth & Design, Vol. 6, No. 6, 2006 Zhai et al.