Synthesis and Structure of a Two-Dimensional Cyano-Bridged

Jan 10, 2003 - A one pot reaction between the [MoIV(CN)8]4- unit and the [Cu(cyclam)]2+ complex (cyclam = 1,4,8,11-tetraazacyclodecane) in aqueous sol...
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CRYSTAL GROWTH & DESIGN

Synthesis and Structure of a Two-Dimensional Cyano-Bridged Coordination Polymer [Cu(cyclam)]2[Mo(CN)8]‚10.5H2O (Cyclam ) 1,4,8,11-Tetraazacyclodecane)

2003 VOL. 3, NO. 2 267-272

Joulia Larionova,*,† Rodolphe Cle´rac,*,‡ Bruno Donnadieu,§ Stephanie Willemin,† and Christian Gue´rin† Laboratoire de Chimie Mole´ culaire et Organization du Solide, UMR 5637, Universite´ Montpellier II, Place E. Bataillon, 34095 Montpellier Cedex 5, France, Centre de Recherche Paul Pascal (CRPP), UPR CNRS 8641, Avenue du Dr. A. Schweitzer, 33600 Pessac, France, and Laboratoire de Chimie de Coordination, UPR CNRS 8241, 31077 Toulouse, France Received September 17, 2002

ABSTRACT: A one pot reaction between the [MoIV(CN)8]4- unit and the [Cu(cyclam)]2+ complex (cyclam ) 1,4,8,11-tetraazacyclodecane) in aqueous solution yields the new cyano-bridged coordination polymer [Cu(cyclam)]2[Mo(CN)8]‚10.5H2O. The compound presents an unusual two-dimensional framework with neutral zigzag sheet layers connected by hydrogen bonding. The thermal and magnetic behavior of this compound has been investigated. Introduction Crystal engineering of cyano-bridged molecular architectures is a considerable contemporary interest by virtue of the potential applications of such materials for example in host-guest chemistry,1 molecular electronics,2a or as a bulk magnet.2a-e These molecular and supramolecular networks possess a remarkable chemical and structural diversity. Numerous examples described in recent years demonstrate that some control is achievable in defining their architectures. General structural paradigms for systematic design of crystal lattices with predictable frameworks and desired functions are contained in a self-assembly of a system with cyanometalate building blocks and appropriate metal ion. Generally, the expectation is that the geometry of the building block will predetermine a structural organization of the system. As a matter of fact, the hexacyanometalate building blocks form highly symmetrical Prussian Blue-like structures.3 In contrast, heptacyanometalate building blocks, which are potentially incompatible with symmetrical lattices, gives rise to very anisotropic networks with an unusual topology.4 The more creative approach to the design of cyano-bridged coordination polymers has been to use metal complexes with complementary capping ligands such as NH3,5,16 aliphatic1 and aromatic amines,1,6,7a,8a ambidentate diaminoalkanes,1,7b,9b bipyridine,14e etc... These ligands play an important role in stabilizing the multidimensional structures and impose a specific network topology through their geometries and coordination binding modes. Thus, a degree of structural control may be achieved by several factors: symmetry of the cyanobridged building block and introduction of appropriate capping ligand. Indeed, on the basis of this strategy, numerous one-7, two-8 and three-dimensional9 molecular * To whom correspondence should be addressed. J.L.: E-mail: [email protected]. R.C.: E-mail: [email protected]. † Laboratoire de Chimie Mole ´ culaire et Organization du Solide. ‡ Centre de Recherche Paul Pascal. § Laboratoire de Chimie de Coordination.

Scheme 1: Tetradentate Macrocycle 1.4.8.11-Tetraazacyclodecane (Cyclam)

networks based on hexacyanometalate building blocks have been thoroughly investigated. One of the most extensively used capping ligands is a tetradentate macrocycle 1,4,8,11-tetraazacyclodecane (cyclam) (Scheme 1), which is potentially able to block four equatorial positions of the metal ion and to release its apical coordination sites. A net-based approach to framework construction10 may theoretically predict the structural dimensionality of molecular assemblies based on the connection and the number of molecular nodes. This idea was used to obtain the most likely threedimensional [Ni(cyclam)]2[Fe(CN)6]‚4H2O11 and twodimensional honeycomb-like [Ni(cyclam)]3[Fe(CN)6]2‚ 12H2O12a and [Ni(cyclam)]3[Cr(CN)6]2‚12H2O12b frameworks. Nevertheless, more unlikely one-dimensional zigzag chains [Cu(cyclam)(H2O)2]{[Cu(cyclam)]3[Fe(CN)6]}2 have also been reported.13 For octacyanometalate building blocks, we restrict ourselves here to Mo(IV) and W(IV) and offer eight bridging cyano ligands, which are potentially able to form tightly connected structured architectures. These cyano-based units have attracted some attention in recent years because of their potential application as porous materials14a,b and their remarkable photomagnetic properties.14c-e The 8-fold coordination of a metal center can lead to the formation of networks that differ considerably from those obtained with octahedrally or tetrahedrally coordinated metal cyanide ions. Therefore, it is interesting to probe its influence on a self-assembly

10.1021/cg020048j CCC: $25.00 © 2003 American Chemical Society Published on Web 01/10/2003

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of previously described systems containing additional tetradentate macrocyclic ligand. The compound described herein represents the first structurally characterized example of two-dimensional eight-coordinated cyano-bridged polymeric molybdenum (IV) complexes of this class. Experimental Procedures Syntheses. Caution! The compounds containing cyanide are potentially dangerous for health and should be handled with caution. Unless otherwise noted, all manipulations were performed at ambient temperature using reagents and solvents as received. The precursors K4[Mo(CN)8]‚2H2O and [Cu(cyclam)](NO3)2‚6H2O were prepared as already described.15,17 [Cu(cyclam)]2[Mo(CN)8]‚10.5H2O. To a solution of K4[Mo(CN)8]‚2H2O (1.0 mmol) in water (30 mL, natural pH) was added [Cu(cyclam)](NO3)2‚6H2O (2.0 mmol) in water (30 mL), which gave immediately the precipitation of a violet product. The solid was washed three times with water and then with ethanol and dried in air. Yield: 82%. Anal. calcd for C28H54N16O10.5Cu2Mo: C, 33.40; H, 5.37; N, 22.27; Cu, 12.72; Mo, 9.54. Found: C, 33.91; H, 6.18; N, 22.02; Cu, 13.12; Mo, 9.89. IR (cm-1, KBr): 3597 (m), 3526, 3449 (l), 3229 (sh), 3164 (s), 2935, 2878, 2123 (sh, m), 2100 (sh, s), 1618, 1474 (sh, m), 1453 (sh, m), 1429 (sh, m), 1387 (w), 1312 (w), 1292 (w), 1254 (w), 1105 (sh, s), 1074 (sh, m), 1062, 1017 (sh, s), 963 (sh, vs), 882 (sh, s), 439 (sh, w). UV (KBr disk): λ ) 630 nm. The crystals suitable for X-ray analysis were obtained by slow diffusion in an H-shaped tube of two 10-4 M aqueous solutions containing K4[Mo(CN)8]‚2H2O and [Cu(cyclam)](NO3)2‚6H2O, respectively. After 2 months, violet crystals with an elongated plate shape formed. The product was insoluble in most common solvents and stable in air. The composition of the crystalline compound was also established by single crystal X-ray diffraction at 180 K. [Cu(cyclam)]2[Mo(CN)8]. The title compound was dehydrated by heating under an argon atmosphere at 90 °C for 30 min. The dehydrated sample was stored in a drybox prior to use. Elemental analysis for [Cu(cyclam)]2[Mo(CN)8]‚10.5H2O after it was heated at 90 °C. Anal. calcd for C28H33N16Cu2Mo: C, 41.2; H, 4.04; N, 27.45; Cu, 15.56; Mo, 11.75. Found: C, 41.8; H, 3.78; N, 27.03; Cu, 15.76; Mo, 11.95. IR (cm-1, KBr): 3597 (m), 3526, 3229 (sh), 2935, 2878, 2123 (sh, m), 2100 (sh, s), 1474 (sh, m), 1453 (sh, m), 1429 (sh, m), 1387 (w), 1312 (w), 1292 (w), 1254 (w), 1105 (sh, s), 1074 (sh, m), 1062, 1017 (sh, s), 963 (sh, vs), 882 (sh, s), 439 (sh, w). UV (KBr disk): λ ) 630 nm. X-ray Crystallography and Structure Solution. Data were collected at 180(2) K on an IPDS STOE diffractometer using a graphite-monochromated Mo KR radiation (λ ) 0.71073 Å) and equipped with an Oxford Cryosystems Cryostream Cooler Device. The final unit cell parameters were obtained by means of a least-squares refinement performed on a set of 5000 well-measured reflections, and crystal decay was monitored during the data collection. No significant fluctuations of intensities were observed. The structure was solved by direct methods using SHELXS9718 and refined by means of least-squares procedures on a F2 with the aid of the program SHELXL97 included in the software package WinGX version 1.63.19 The atomic scattering factors were taken from international tables for X-ray crystallography.19 The quality of the low data to refined parameter ratio close to 8.5 is related to a poor diffraction of the crystal, which exhibits no intensity above θ ) 21°. Although empirical absorption corrections have been applied, no improvement in the merging factor was observed. All hydrogen atoms were located on a difference Fourier maps and refined by using a riding model, excepted concerning hydrogen atoms [H(11w), H(12w), H(21w), H(22w), H(31w), H(32w), H(51w), H(52w), H(61w), H(62w), H(71w), H(72w), H(81w), H(82w), H(91w), and H(92w)] connected respectively to oxygen atoms [O(1W), O(2W), O(3W), O(5W), O(6W), O(7W), O(8W), and O(9W)]. The coordinates of these

Larionova et al. hydrogen atoms were calculated using the modeling program HYDROGEN.20 This program used a combination of geometric inspection of the environments of the H2O groups and force field calculations on the basis of hydrogen-bonding interactions. Consequently, all coordinates of these H atoms were introduced as fixed coordinates in the refinement with an isotropic thermal parameter fixed at 20% higher than those of the oxygen atoms to which they are connected. The disordered water molecules not involved in hydrogen-bonding interactions have been excluded from the calculations. Therefore, the hydrogen atoms connected on these molecules of water were not able to be located. All nonhydrogen atoms were anisotropically refined, and in the last cycles of refinement, a weighting scheme was used, where weights were calculated from the following formula: w ) 1/[σ2(Fo2) + (aP)2 + bP] where P ) (Fo2 + 2Fc2)/3. The drawing of the molecule was performed with the program ORTEP3220 with 50% probability displacement ellipsoids for nonhydrogen atoms, and the views of packing were done with the software CAMERON.22 Physical Measurements. Infrared spectra were recorded as KBr disks on a Nicolet model 510P spectrophotometer. UVvis spectra were recorded on a Cary-17D spectrometer. Thermogravimetry (TG) analysis was performed using PerkinElmer Series 7 instruments under nitrogen atmosphere from 30 to 700 °C at a heating rate of 5 °C min-1. Magnetic susceptibility data were collected with a Quantum Design MPMS-XL SQUID magnetometer. Compound 1 was measured on a finely grounded polycrystalline sample of 30.75 mg between 1.8 and 320 K at 1000 G. The data were corrected for the sample holder, and the diamagnetism contributions were calculated from the Pascal’s constants.23 The electronic paramagnetic resonance (EPR) was performed on a polycrystalline sample on a Bruker ESP-300E spectrometer equipped with a ESR900 cryostat (4.2-300 K) from Oxford Instrument. Powder X-ray data were recorded on a Bruker D5000 diffractometer using a Bragg-Brentano geometry; a Cu target and a back monochromator were used (KR1 + KR2); range 5-88° 2θ; step 0.02° 2θ.

Results and Discussion The slow diffusion in an H-shaped tube of two aqueous solutions containing K4[Mo(CN)8]‚2H2O and [Cu(cyclam)](NO3)2, respectively, allows violet crystalline elongated plates to be obtained. The infrared C-N stretch (2134 (sh, m) cm-1) is shifted toward higher frequencies from those of K4[Mo(CN)8]‚2H2O (2101 (s), 2120 (s) cm-1) clearly showing a coordination of a few CN groups to copper ions. The stretches observed at 2123 (sh, m) and 2101 (sh, s) cm-1 show that free CN groups are also present in this compound. The IR feature is confirmed by the X-ray crystallographic analysis at 180 K (Tables 1 and 2). The [Cu(cyclam)]2[Mo(CN)8]‚10.5H2O (1) crystallizes in a monoclinic system with P21/n space group with a neutral two-dimensional structure containing one molybdenum and two copper sites. The structural arrangement may be described as a strongly distorted cyano-bridged {Mo(CN)8Cu(cyclam)}4 eight metal ring represented in Figure 1. Each Mo atom is linked by cyano bridges to two different copper sites, Cu1 and Cu2, respectively. The molybdenum atom is surrounded by two -C-NCu1 linkages, two -C-N-Cu2 linkages, and four terminal cyano groups. The Mo-C bond lengths range from 2.117 (16) to 2.191(17) Å, with an average value of 2.148 Å. It should be noted that one interesting aspect of this structure is the geometry at the Mo site. In principle, for 8-fold coordination, ML8 the reference polyhedron is taken as the D2d-dodecahedron. Two alternative

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Table 1: Crystallographic Data for [Cu(cyclam)]2[Mo(CN)8]‚10.5H2O empirical formula formula weight temp wavelength cryst system, space group unit cell dimens

C28H54N16O10.5Cu2Mo 1005.89 180(2) K 0.71073 Å monoclinic, P21/c

a ) 10.278(5) Å b ) 25.507(5) Å c ) 17.398(5) Å β ) 99.581(5) ° volume 4497(3) Å3 Z, calcd density 4, 1.486 Mg/m3 absorption coeff 1.278 mm-1 F(000) 2072 index ranges -9 e h e 9, -25 e k e 25, -17 e l e 17e reflns collected/unique 19351/4553 [R(int) ) 0.1854] refinement method full-matrix least-squares on F2 data/restraints/params 4553/0/533 goodness-of-fit on F2 1.034 scheme of ponderation weight ) 1/[σ2(Fo2) + (0.133P)2 + 32.343P] where P ) (Fo2 + 2Fc2)/3a Tmin - Tmax 0.23-0.693 final R indices [I > 2σ(I)] R1 ) 0.0938, wR2 ) 0.2391 R indices (all data) R1 ) 0.1233, wR2 ) 0.2613 extinction coeff 0.0016(7) largest diff peak and hole (1.048 and -1.107)e Å-3 Table 2: Selected Bond Lengths (Å) and Angles (°) for [Cu(cyclam)]2[Mo(CN)8]‚10.5H2O C(1) -Mo C(3)-Mo C(5)-Mo C(7)-Mo C(1)-N(1) C(3)-N(3) C(5)-N(5) C(7)-N(7) N(4)-Cu(2) N(12)-Cu(1) N(14)-Cu(1) N(22)-Cu(2) N(24)-Cu(2) C(11)-C(12) C(13)-N(12) C(14)-C(15) C(16)-N(13) C(17)-N(14) C(18)-C(19) C(20)-N(11) C(21)-C(22) C(23)-N(22) C(24)-C(25) C(26)-N(23) C(27)-C(28) C(29)-C(30) C(30)-N(21)

2.18(2) 2.132(16) 2.162(19) 2.156(17) 1.17(2) 1.171(18) 1.144(19) 1.187(18) 2.422(15) 1.998(16) 2.013(17) 2.027(14) 2.032(13) 1.57(4) 1.34(4) 1.48(5) 1.32(4) 1.58(3) 1.53(4) 1.69(3) 1.53(2) 1.49(2) 1.52(2) 1.48(2) 1.56(2) 1.48(2) 1.45(2)

C(2)-Mo C(4)-Mo C(6)-Mo C(8)-Mo C(2)-N(2) C(4)-N(4) C(6)-N(6) C(8)-N(8) N(11)-Cu(1) N(13)-Cu(1) N(21)-Cu(2) N(23)-Cu(2) C(11)-N(11) C(12)-N(12) C(13)-C(14) C(15)-N(13) C(16)-C(17) C(18)-N(14) C(19)-C(20) C(21)-N(21) C(22)-C(23) C(24)-N(22) C(25)-N(23) C(26)-C(27) C(28)-N(24) C(29)-N(24)

2.163(17) 2.116(14) 2.15(2) 2.197(18) 1.125(18) 1.181(18) 1.17(2) 1.153(18) 1.950(18) 2.018(17) 2.017(11) 2.019(11) 1.24(4) 1.55(3) 1.59(5) 1.57(4) 1.55(4) 1.29(3) 1.43(3) 1.475(19) 1.49(2) 1.477(19) 1.448(19) 1.50(2) 1.44(2) 1.499(19)

polyhedra, the D4d-square antiprism and the C2v-bicapped trigonal prism, can be generated from the dodecahedron by stretching one or two edges, respectively.23 It is interesting to notice that in all previously reported extended networks based on the octacyanomolybdenum(IV) building block,14 the [Mo(CN)8]4- unit rearranges itself from the dodecahedral structure (D2d) of the starting K4[Mo(CN)8]‚2H2O15 compound to produce square antiprismatic geometry (D4d). In the title compound, following the dihedral angles analysis, the geometry of the Mo site may by viewed essentially as the intermediate geometry between the square antiprism and the bicapped trigonal prism. The Cu1 and Cu2 atoms are surrounded by the four nitrogen atoms of the cyclam ligand in the equatorial

Figure 1. View of the octagonal {Mo(CN)8Cu(cyclam)}4 unit. Water molecules are omitted for clarity.

plane and two other -N-C-Mo linkages in the apical direction (Figure 1). The Cu-N bond lengths range from 1.955(18) to 2.035(13) Å and from 2.202(16) to 2.421(17) Å for equatorial and apical directions, respectively. The apical C1-N1-Cu1-C4-N4- and C1-N1-Cu2C4-N4- angles are close to 180°; they equal 175.25 and 175.5°, respectively. The geometry around the Cu1 and Cu2 sites may be described as a distorted octahedron as usually observed for the Jahn-Teller distortion of Cu(II). A striking aspect of the structure lies in the fact that the Mo-C-N-Cu linkages in the eight metal ring are far from being linear. Although the Mo-C-N- bond angles are close to 180° and range from 177.58(1) to 176.30(5)° (the mean value is 177.32°), the Cu-N-C bond angles significantly deviate from 180°.16 The latter range from 131.85(3) to 144.73(4)° (the mean value is 138.18°). Both the valence bond and the molecular orbital descriptions of the CtN-M system indicate that the N-M bond should be collinear with the triple bond. This situation holds for most of the cyano-bridged coordination polymers observed to date, although a few compounds with angles about 130° have been reported. For example, one of the CtN-Cu angles in [{Cu(dien)}2Fe(CN)6]n‚6nH2O is 136.2(8)°,16a and [{Cu(dien)2Fe(CN)6}n][Cu(H2O)(dien)Fe(CN)6]n‚4nH2O has CtN-Cu angles of 139 and 140°.16b In a recently reported structure determination of a cyano-bridged dinuclear compound [(CN)3Pt(µ-CN)Cu(NH3)4], the Ct N-Cu angles of 120.8(8)° were observed.16c In the title compound, the Cu-Mo separation across a cyano bridge ranges from 5.38 to 5.521 Å. These structural motifs are linked together through the molybdenum atoms to form a strongly distorted sheet layer

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Figure 2. View of the structure in the ac plane, showing a corrugated gridlike plan. Water molecules are omitted for clarity.

parallel to the ac plane, as shown in Figure 2. The layers are not planar but form infinite staircase structures aligning along the c direction with the zigzag Cu(cyclam)-Mo-Cu(cyclam) angle of 104.99°, as shown in Figure 3. The shortest interlayer separation of 8.110 and 8.462 Å is for Cu1‚‚‚Cu1 and Cu1‚‚‚Mo, respectively. The view of the structure in the bc plane (Figure 3) shows the channels in the network situated between the zigzag layers. The cyclam ligands block the channels along the b and c axes, but along the a axis, an open channel of about 3.08 × 7.57 Å2 remains. The 10 disordered crystallized water molecules accommodate these channels. Hydrogen atom positions have been calculated in order to determine the most consistent hydrogen-bonding interactions.20 As a matter of fact, seven water molecules, O(1W), O(2W), O(3W), O(6W), O(7W), O(8W), and O(9W), from 10 form hydrogen bonds, but only two of these, O(7W) and O(9W), participate in the hydrogen-bonded network connecting each gridlike sheet layer to the two nearest neighbors. The interlayer hydrogen-bonded pathway N6‚‚‚H(71W)‚ ‚‚O(9W)-H(91W)‚‚‚N6 with distances of 2.580, 2.225, and 2.069 Å, respectively, is shown in Figure 3 by dashed lines. Like the two-dimensional networks formed by hexacyanometalate building blocks,8,13 the network retains the solvent molecules. The thermogravimetric analysis (TGA) effectuated under an argon atmosphere from room temperature up to 700 °C exhibits three well-pronounced weight loss steps as the temperature was increased. These steps can

be determined by inflection points at 90, 210, and 280 °C corresponding to weight losses of -18.7, -8.3, and -26.4%, respectively. The first weight loss step corresponds well with the loss of 10 crystallized water molecules located in the channels between the layers. The residues from heating the sample to 120 °C for 1 h retained the same inorganic structure as shown by infrared spectra and X-ray powder diffraction. At a temperature above 210 °C, decomposition of the original structure occurs. The temperature dependence of the magnetic susceptibility (χM) for a polycrystalline sample of 1 is presented in Figure 4. It was recorded under an applied field of 1000 Oe. Down to 1.8 K, χM can be fitted using the Curie-Weiss law (χM ) C/(T - θ)) with C ) 0.754 emu K mol-1 and θ ) -0.3 K. The Curie constant (C) is in agreement with the expected value for two Cu2+ ions with S ) 1/2 and g ) 2.01 ( 0.05. The g value was confirmed by EPR measurements at room temperature, which show an unsymmetrical resonance line (∆H ) 87 G) at an average g value of 2.06. The negative sign of the Weiss constant obtained from the Curie-Weiss fitting reveals the presence of weak antiferromagnetic interactions between the Cu2+ ions through the diamagnetic NC-Mo(IV)-CN bridge. The main conclusion of the present work concerns the synthetic possibilities opened by the ability of [Mo(CN)8]4to form molecular networks with different dimensionality. It should be noted that structurally characterized polynuclear compounds based on the use of [Mo(CN)8]4-

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Figure 3. Global view of the crystal structure of 1 in the bc plane showing the channels with a hydrogen-bonded network.

ligand (cyclam) has been crystallized and structurally characterized. This compound belongs to an important class of coordination systems24 able to accept guest water molecules in the cavity. Additionally, given that the diamagnetic MoIV ion is photooxidized to paramagnetic MoV ion, this compound may also exhibit interesting photomagnetic properties. Supporting Information Available: X-ray crystallographic files, in CIF format, containing data for structure of [Cu(cyclam)]2[Mo(CN)8]‚10.5H2O. This material is available free of charge via the Internet at http://pubs.acs.org.

References

Figure 4. Temperature dependence of χMT for 1 under a field of 1 kOe.

as a building block are still rare and only the mixed valence two-dimensional compound {[Mn(L)]6[MoIII(CN)7][Mo(CN)8]2}‚19.5H2O (L ) 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16pentaene) has already been reported.14d A new twodimensional coordination polymer [Cu(cyclam)]2[Mo(CN)8]‚10.5H2O with the use of a macrocyclic capping

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