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Structure-Directing Self-Assembly, Structures and Characterization of Four d0‑Transition Metal Oxide/Fluoride Compounds Constructed with Imidazole/1-Methylimidazole/1-Vinylimidazole and Copper(II)/Zinc(II) Yi-Ping Tong,*,† Guo-Tian Luo,‡ Jin Zhen,† You Shen,† and Hui-Ru Liu† †

Department of Chemical Engineering, Huizhou University, Huizhou 516007, China College of Chemistry and Life Science, Gannan Normal University, Ganzhou 341000, China

‡

S Supporting Information *

ABSTRACT: Four d0 transition metal oxide/fluoride compounds of V(V), Mo(VI), and Ti(IV), with the “2D layer”, “1D zigzag chain”, “1D linear chain”, and “0D cluster” structures, have been hydrothermally synthesized, by the structure-directing self-assembly of Meimi/Viimi/imi ligands, and other transition metal Zn(II)/Cd(II) ions. The structuredirecting property of d0 transition metal oxide/fluoride anions is responsible for the tunable syntheses of novel inorganic solids with structural diversities, while the distortion of the d0 transition metal oxide/fluoride polyhedrons, owing to the second-order Jahn−Teller (SOJT) effect, is the key to engineering the structure-directing property.

T

structural changes for these anionic components can also be anticipated. The distortion may usually lead to at least one of the oxide/fluoride ligands to be terminal (μ1-O/F) or bonded to other transition metals (μ2-, μ3-, or μ4-O/F). Thus, d0 transition metal oxide/fluoride compounds hold a trend of oligomerization or polymerization via μ1- and/or μ2-, and/or μ3-, and/or μ4-O/F. The formation of mononuclear, oligomer, and polymer structures, e.g., 0D cluster, 1D chain, 2D layer, and 3D structures, for mixed d0 transition metal compounds can be anticipated. Here, we report four new mixed transition metal oxide/ fluoride compounds derived from d0 transition metal oxide/ fluoride anions and other transition metal (Cu, Zn)-based coordination cations with organic imidazole-analogue ligands. Namely, 2D layer [Cu(Meimi)2V2O6]n (1) (Meimi = 1-methyl1H-imidazole, n = ∞), 1D zigzag chain [Zn(Viimi)3MoF4O2]n (2) (Viimi =1-vinyl-1H-imidazole, n = ∞), 1D linear straight chain [Cu(Viimi)4TiF6]n (3) (n = ∞), and 0D cluster {(Himi)2[Cu(imi)4(TiF6)2]} (4) (imi = imidazole). Although a number of mixed inorganic−organic layer/chain/cluster structures have been identified and are well characterized, few examples containing mixed transition metal oxide/fluoride inorganic− organic compounds have been reported so far,7a,e,8 fewer studies have focused on the design and tunable synthesis of these solid structures. Therefore, the structure-directing properties of d0

he rational design of crystal structures based on the chemical nature of molecular components is an exciting research topic, and an emerging theme of crystal engineering in inorganic solid state chemistry.1−4 In particular, the solid structures with different dimensionality (three-dimensional (3D), two-dimensional (2D), one-dimensional (1D), and zerodimensional (0D)) are very important for exhibiting diversities of physical and chemical properties.5−7 The mixed transition metal oxide/fluoride systems continue to attract the attention of numerous research groups with widely divergent interests. Since such species are excellent components for constructing complicated inorganic solid structures.8,9 The combination of d0 transition metals (Ti, Zr, Hf, V, Nb, Ta, Mo, W) and other transition metals (Cu, Zn, Cd), together with organic ligands, leads to many interrelated and comparable metal oxide/ fluoride compounds.9b,c,10 These compounds contain similar anionic and cationic components, i.e., d0-anions [(Ti/Zr)F6]2‑, [(V/Nb/Ta)OF5]2‑, [(Mo/W)O2F4]2‑, or oligomeric/polymeric [VOn](2n‑5)‑ (n = 4−6),7b,8c,8d,9a,11,12 and cations [(Cu/Zn/ Cd)L4]2+ (L = nitrogen-containing heterocycle ligand), respectively. Though they are similar in compositions, subtle structural changes for these anionic and cationic components lead to the assembling of different structures of mixed transition metal coordination solid compounds, such as polymers with 3D, 2D, and 1D structure or clusters with 0D structure.7d,e,8a,b,9b In general, owing to the second-order Jahn−Teller (SOJT) effect, distortion of the d0 transition metal oxide/fluoride materials (i.e., the out-of-center shift of central d0 transition metal cations in polyhedrons) can be expected,13 and as a result, the subtle © 2013 American Chemical Society

Received: November 4, 2012 Revised: December 22, 2012 Published: January 28, 2013 446

dx.doi.org/10.1021/cg301612g | Cryst. Growth Des. 2013, 13, 446−454

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Figure 1. (a) ORTEP drawing of 1 in the asymmetric unit with 30% thermal ellipsoids. (b) View of a 2D layer of 1. Hydrogen atoms are omitted for clarity. Green, cyan, red, blue, and black circles represent V, Cu, O, N, and C atoms, respectively.

transition metal oxide/fluoride anions were also examined in detail in this paper. Complex 1, 2, 3, and 4 were obtained by the hydrothermal reactions of CuO/ZnO, V2O5/H2MoO4/TiO2 with Meimi/ Viimi/imi in hydrofluoric acid,14 and characterized structurally

by single-crystal X-ray analyses (Figures 1a, 2a, 3a, and 4a, and Table S1 in the Supporting Information).15 The hydrothermal synthetic techniques are somewhat similar to each other, though there are differences in the number of moles of reactant materials, reacting time, and temperature. The molar ratios of CuO/ZnO, 447



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Figure 2. (a) ORTEP drawing of 2 in the asymmetric unit with 30% thermal ellipsoids. (b) View of a 1D zigzag chain of 2. Hydrogen atoms are omitted for clarity. Light green, green, violet, red, blue, and black circles represent Mo, Zn, F, O, N, and C atoms, respectively. (c) The crystal stacking pattern of the 1D zigzag chains of 2. Hydrogen atoms are omitted for clarity. Light green, green, violet, red, blue, and black circles represent Mo, Zn, F, O, N, and C atoms, respectively.

for the their syntheses of 1, 2, 3, and 4.14 Despite the similarities in the reaction processes, these compounds show marked differences in structural diversities.

V2O5/H2MoO4/TiO2, and Meimi/Viimi/imi are 1:1:3, HF remained approximately constant (6 mL), and reacting time and temperature are within 4−6 days and 220−250 °C, respectively, 448



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Figure 3. (a) ORTEP drawing of 3 in the asymmetric unit with 30% thermal ellipsoids. (b) View of a 1D linear straight chain of 3. Hydrogen atoms are omitted for clarity. Green, cyan, violet, blue, and black circles represent Ti, Cu, F, N, and C atoms, respectively. (c) The crystal stacking pattern of the 1D linear straight chains of 3. Hydrogen atoms are omitted for clarity. Green, cyan, violet, blue, and black circles represent Ti, Cu, F, N, and C atoms, respectively.

zigzag backbone. Each chain has covalent V−O−Cu(Meimi)2− O−V bridges to two neighboring chains (V−O at 1.6781(18) Å and Cu−O at 1.9205(18) Å). There are two interchain bonds per VO3−VO3 repeating unit, via the O−Cu(Meimi)2−O bridge, to form the 2D framework. The covalent Cu(Meimi)2−V2O6 network reveals 2D square nets that stack in an offset arrangement

Complex 1 is a 2D layer compound, formulated as [Cu(Meimi)2V2O6]n (n = ∞). The structure contains both VO4 and CuO2N2(Meimi) cores. The crystal structure is illustrated in Figure 1b, and the selected bond parameters are listed in Table S2 in the Supporting Information. The structure is composed of one symmetry unique chain, having a repeating [−V−O−V−O−] 449



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Figure 4. (a) ORTEP drawing of 4 in the asymmetric unit with 30% thermal ellipsoids. (b) View of a 0D linear cluster of 4. Hydrogen atoms are omitted for clarity. (c) View of the intermolecular hydrogen bond (N−H···F) networks between adjacent clusters of 4. The disordered Himi+ cations are omitted for clarity. Green, cyan, red, blue, and gray circles represent Ti, Cu, F, N, and C atoms, respectively.

atom is surrounded by four different oxide atoms (one μ1-O, three μ2-O), with V−O distances at 1.610(2)−1.7984(19) Å, meaning that the vanadium atom is heavily distorted. The VO43‑ tetrahedrons are linked through two μ2-O to two neighboring vanadiums (V(V)) to form the [−V−O−V−O−] backbone. Furthermore, the V−O−V angle is bent, at 135.77(19)°, as is common for μ2-O bridging transition metal chain structures. The significance of this bent angle gives rise to 1D zigzag backbone, thus undulating 2D, not planar 2D structure for 1 is expected, in

to form little hindrance between the Meimi rings both above and below (Figure 1b). Relatively large rectangular cavities occur within a single 2D square net, at ca. 5.34 × 8.63 Å2, with the intermolecular interactions extending above and below each layer. The local bonding environment of the V(V) center is a heavily distorted tetrahedron that closely resembles those of V(V) ions described in other related structures. A list of selected bond distances and angles of 1 is given in Table S2. The vanadium 450



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M′, other d metal). Because of the second-order Jahn−Teller (SOJT) effect, the vertex oxide/fluoride atoms should be different in negative charge density. As a result the reactivity of these atoms is usually different. Two kinds of linking modes between the d0 transition metal and other transition metal via the vertex-linked oxide/fluoride atoms can be expected. One mode features the trans-directing two vertex-oxide/fluoride atoms, i.e., the two vertex-oxide/fluoride atoms are in trans arrangement, which will lead to a linear straight chains (Scheme 1), consisting of infinite alternating [−M−O/F−M′−O/F−M−]n (n = ∞, M, d0 metal, M′, other d metal), or just a limited alternating linear straight cluster structure, e.g., [M−O/F−M′−O/F−M]n (n = 1, 2, 3, etc.). The second mode, oppositely, featuring the cis-directing two vertex-oxide/fluoride atoms, may lead to a bent chain, i.e., zigzag/ helical chain, or zigzag cluster structure (Scheme 1). Besides the linkages between the d0 transition metals (M) and other transition metals (M′) via vertex-oxide/fluoride atoms, sometimes other linkages between the d0 transition metals and adjacent d0 transition metals via other vertex-oxide/fluoride atoms also occur, namely infinite alternating [−M−O/F−M−]n (n = ∞, M, d0 metal), thus a 2D layer can be anticipated (Scheme 1). For 1, in spite of the similarity in synthetic condition, compared to those of 2, 3, and 4, the vanadium tetrahedral centers have shown strong trend to polymerize via vertex-oxide atoms, forming infinite [−V−O−V−]n (n = ∞) zigzag chains, and individual zigzag chains are linked through [Cu(Meimi)2] units (i.e., V−O−Cu−O−V linkage) to form an undulating 2D network as depicted in Figure 1b. Very differently, in 2 and 3, the d0 transition metals Mo(VI) (in 2) and Ti(IV) (in 3) have shown no linkage between themselves via vertex-oxide/fluoride atoms, but linkage to zinc centers and copper centers, via vertex-oxide/fluoride atoms, respectively. Therefore, only 1D chains can be found both for 2 and for 3. The octahedral [MoO2F4]2‑ anions of 2 have been strongly distorted with the Mo(VI) cation displaced from the center of the [MoO2F4]2‑ octahedron in the direction of the cis oxide ligands or toward an edge of the octahedron. The Mo−O bonds are short (1.6884(19) and 1.7021(18) Å), and the bonds to the two trans fluorides are long (2.1018(14), and 2.1094(13) Å). Therefore, the two oxide ligands should retain little negative charge with respect to the other ligands, especially the two trans fluorides, F(3) and F(4) (Figure 2a), which are highly charged. As a result, coordination is directed in a cis fashion through the two trans fluorides, which accounts for the formation of bent or zigzag 1D chains in 2 (Figure 2b,c). However, in [TiF6]2‑ of 3, the octahedron is lightly distorted with the two axial Ti−F distances of 1.833(2) Å × 2 being longer than four equatorial Ti−F distances of 1.8191(18) Å × 4. The two axial fluoride ligands retain largely negative charge with respect to the four equatorial fluoride ligands, which are little charged. As a result, coordination is directed in a trans fashion through the two trans axial fluorides. A linear chain can be expected, in agreement with the observation found in 3 (Figure 3b,c). Therefore, owing to the structural differences between the [MoO2F4]2‑ and [TiF6]2‑ anions, they direct coordination through cis and trans ligands, respectively. For 4, it is similar to the case of 3 except that 3 has 1D linear chains, while 4 is just a 0D linear cluster. The octahedral [TiF6]2‑ anion is also lightly distorted, and results in two axial Ti−F bonds that are different from those of the four equatorial ones. Finally, coordination is directed in a trans fashion through the two trans axial fluorides, which accounts for the fact that the cluster is linear in geometric structure in 4 (Figure 4b).

agreement with the experimental observation. The local squareplanar coordination of the Cu(II) ions is common, with two longer bonds to the nitrogen atoms (1.997(2) Å × 2) of the Meimi ligands and two shorter bonds to oxygen atoms (1.9205(18) Å × 2). Complexes 2 and 3 are 1D zigzag chain and 1D linear straight chain, respectively, formulated as [Zn(Viimi)3MoF4O2]n (n = ∞) for the former and [Cu(Viimi)4TiF6]n (n = ∞) for the latter. For 2, the structure contains both MoF4O2 and ZnO2N3(Viimi) cores. The chains are constructed from alternating [Zn(Viimi)3]2+ cations and [MoF4O2]2‑ anions, which are bound to one another through shared fluoride anions (Figure 2b). The geometry of the zinc centers is trigonal bipyramidal, and the three equatorial coordination sites on the zinc center are occupied by Viimi ligands, through Zn−N distances of 2.005(2), 2.010(2), and 2.023(2) Å (Table S2). The two axial Zn−F distances are 2.0942(14) and 2.1650(14) Å. The geometry of the [MoF4O2]2‑ anion is octahedral, with Mo−F distances of 1.9124(18), 1.9394(18), 2.1018(14), and 2.1094(13) Å, and Mo−O distances of 1.6884(19) and 1.7021(18) Å. While in 3, the 1D linear straight chains are constructed from alternating [Cu(Viimi)4]2+ cations and [TiF6]2‑ anions via the shared fluoride anions (Figure 3b). The geometry of the copper centers is octahedral, and shows an obvious Jahn−Teller effect. The four equatorial coordination sites on the copper center are occupied by Viimi ligands, through Cu−N distances of 2.016(2) Å × 4. The two axial Cu−F distances are 2.315(2) Å × 2 (Table S2). The geometry of the [TiF6]2‑ anion is octahedral, with Ti−F distances of 1.8191(18) Å × 4, and 1.833(2) Å × 2. Complex 4 {(Himi)2[Cu(imi)4(TiF6)2]} is built from anionic [Cu(imi)4(TiF6)2]2‑ clusters (Figure 4b), which link to imidazolium (Himi+) cations via intermolecular hydrogen bond interactions (Figure S1). These 0D anionic clusters comprise two smaller complex anions ([TiF6]2‑) coordinated to a central [Cu(imi)4]2+ cation (Figure 4b). The coordination environment around the d9 Jahn−Teller copper ion consists of four equatorial imi ligands through Cu−N distances of 2.006(4) Å × 4 (Table S2) and two very long axial Cu−F bonds (2.524(3) Å × 2) to the respective complex anions ([TiF6]2‑). The F−Cu−F angle is 180°, and the anionic [Cu(imi)4(TiF6)2]2‑ clusters are, therefore, linear in geometric structure. Ti(IV) center of [TiF6]2‑ anion is slightly distorted from the center of the F− octahedron away from the Cu. This results in the short axial Ti−F(1) distance (1.823(5) Å), trans to the long Ti− F(3) distance (1.826(5) Å) (Table S2). The Himi+ cations are highly disordered, and link to any of the four equatorial fluorides by means of intermolecular N−H···F hydrogen bonds. The crystal packing is related to the anti-fluorite structure. The anionic clusters can be thought of as closest-packed structure, with the disordered Himi+ cations occupying “tetrahedral holes”. The fact that the anion in this structure is not spheres but instead has only 4fold symmetry explains the reduction of the crystal system from cubic to tetragonal. Alternatively, the structure may be viewed as (110) planes of parallel, end to end clusters, with each plane shifted c/2 from the one above and below it and Himi+ cations occupying the spaces between the anions. The d0 transition metal oxide/fluoride anions play a very important role in constructing the complicated crystal structures, as they are structure-directing. These anions are usually [MOxF6‑x] (x = 0−6), [MOxF5‑x] (x = 0−5), and [MOxF4‑x] (x = 0−4). The vertex oxide/fluoride, as bridging atoms, is easily coordinated to other transition metal centers, e.g., Cu(II) and Zn(II), to form 1D chains [−M−O/F−M′−O/F−] (M, d0 metal, 451



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Scheme 1. Structure-Directing Self-Assembling Modes of d0 Transition Metal Oxide/Fluoride Anions via Vertex-Oxide/Fluoride Atoms To Form 1D Zigzag/Linear Chains, 0D Zigzag/Linear Clusters, and 2D Layer Compounds

It should be noted that the coordination of [TiF6]2‑ anion to [Cu(imi)4]2+ via axial fluoride in 4 is very weak as indicated by the long Cu−F bonds (2.524(3) Å × 2), ca. 0.209 and 0.171 Å longer than those observed in 3 and other documents previously, respectively.8a,9c The weak covalent interaction between [TiF6]2‑ anion and [Cu(imi)4]2+ cation means that the alternating repeating units of [−Ti−F−Cu−F−Ti−] can be easily interrupted by other weak interactions, e.g., intermolecular hydrogen bond interactions; thus, linear cluster (0D) with limited repeating of [−Ti−F−Cu−F−Ti−], but not 1D linear chains with infinite repeat of [−Ti−F−Cu−F−Ti−], can be expected. The 0D cluster with linear structure in 4 can be easily explained by the observed fact that there are strong intermolecular hydrogen bonds (N−H···F(3), 3.232(4) Å) between the axial fluoride (F(3)) and NH group of imi organic ligands of adjacent clusters (Figure 4c), and other intermolecular hydrogen bonds (N− H···F(2) 2.80(3), 2.88(2), 3.119(4), and 3.02(2) Å) between the equatorial fluorides (F(2)) and NH groups of imi organic ligand of adjacent clusters and Himi+ cations (Figure S1). As for the variation of organic ligands (imi, Meimi, and Viimi), there is no obvious relation between the dimensionality of the networks and size of organic ligands that has been observed. This may be due to several factors determining the dimensionality of the network structures. Though the synthetic conditions of 1, 2, 3, and 4 are somewhat similar, and the organic ligands are

imidazole-analogues, the variations of d0 transition metals (V(V), Mo(VI), and Ti(IV)) lead to formation of four main structure types in these systems: the “2D layer”, “1D zigzag chain”, “1D linear chain”, and “0D cluster” structures (Figures 1b, 2b, 3b, and 4b). The reason for their structural diversities is ascribed to the structuredirecting property of d0 transition metal oxide/fluoride anions. The successful performance of the present synthetic procedure is helpful for looking for other d0 transition metal oxide/fluoride compounds with novel structures or property. To summarize, we have described four novel d0 transition metal oxide/fluoride compounds with V(V), Mo(VI), and Ti(IV): the “2D layer”, “1D zigzag chain”, “1D linear chain”, and “0D cluster” structures. The structure-directing property of d0 transition metal oxide/fluoride anions is responsible for the tunable syntheses of novel inorganic solids with structural diversities, while the distortion of the d0 transition metal oxide/fluoride polyhedrons, owing to the second-order Jahn−Teller (SOJT) effect, is the key to engineering the structure-directing property.

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ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data (Table S1), selected geometric parameters (Table S2), Figure S1, and CIF format files for 1−4. This material is available free of charge via the Internet at http://pubs. acs.org. 452



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(8) (a) Maggard, P. A.; Kopf, A. L.; Stern, C. L.; Poeppelmeier, K. R. CrystEngComm 2004, 6 (74), 451. (b) Maggard, P. A.; Stern, C. L.; Poeppelmeier, K. R. J. Am. Chem. Soc. 2001, 123, 7742. (9) (a) Mahenthirarajah, T.; Lightfoot, P. Chem.Commun. 2008, 1401. (b) Izumi, H. K.; Kirsch, J. E.; Stern, C. L.; Poeppelmeier, K. R. Inorg. Chem. 2005, 44, 884. (c) Welk, M. E.; Stern, C. L.; Poeppelmeier, K. R.; Norquist, A. J. Cryst. Growth Des. 2007, 7 (5), 956. (10) (a) Aldous, D. W.; Stephens, N. F.; Lightfoot, P. Dalton Trans. 2007, 2271. (b) Maggard, P. A.; Nault, T. S.; Stern, C. L.; Poeppelmeier, K. R. J. Solid State Chem. 2003, 175, 27. (11) (a) Tong, Y.-P.; Luo, G.-T.; Jin, Z.; Lin, Y.-W. Aust. J. Chem. 2011, 64, 973. (b) Tong, Y.-P.; Luo, G.-T.; Zhou, W.; Ng, S. W. Inorg. Chem. Commun. 2010, 13, 1281. (12) Abrahams, B. F.; Haywood, M. G.; Robson, R. Polyhedron 2007, 26, 300. (13) (a) Kunz, M.; Brown, I. D. J. Solid State Chem. 1995, 115, 395. (b) Jacco, J. C. SPIE Int. Soc. Opt. Eng. 1988, 968, 93. (14) Synthesis details follow. For 1, a mixture of CuO (0.081 g, 1 mmol), V2O5 (0.095 g, 0.5 mmol), Meimi (0.249 g, 3 mmol), hydrofluoric acid (40%, 6 mL), and water (10 mL) was stirred for about 5 h at room temperature, sealed in a 23-mL Teflon-lined stainless steel autoclave, heated at 230 °C for 5 days, and then slowly cooled to room temperature at a rate of 5 °C per an hour. Finally, little green crystals of 1 suitable for single crystal X-ray diffraction analysis were collected from the final reaction system. Yield: 38% based on CuO. Anal. (%). Calcd for 1 (C8H12CuN4O6V2): C, 22.57; N, 13.16; H, 2.84. Found: C, 22.63; N, 13.05; H, 2.88. For 2, a mixture of ZnO (0.083 g, 1 mmol), H2MoO4 (0.162 g, 1 mmol), Viimi (0.289 g, 3 mmol), hydrofluoric acid (40%, 6 mL), and water (10 mL) was stirred for about 5 h at room temperature, sealed in a 23-mL Teflon-lined stainless steel autoclave, heated at 220 °C for 5 days, and then slowly cooled to room temperature at a rate of 5 °C per an hour. Finally, colorless crystals of 2 suitable for single crystal X-ray diffraction analysis were collected from the final reaction system. Yield: 46% based on ZnO. Anal. (%). Calcd for 2 (C15H18F4MoN6O2Zn): C, 32.66; N, 15.23; H, 3.29. Found: C, 32.76; N, 15.29; H, 3.32. For 3, a mixture of CuO (0.084 g, 1 mmol), TiO2 (0.082 g, 1 mmol), Viimi (0.276 g, 3 mmol), hydrofluoric acid (40%, 6 mL), and water (10 mL) was stirred for about 5 h at room temperature, sealed in a 23-mL Teflonlined stainless steel autoclave, heated at 250 °C for 4 days, and then slowly cooled to room temperature at a rate of 5 °C per an hour. Finally, dark green crystals of 3 suitable for single crystal X-ray diffraction analysis were collected from the final reaction system. Yield: 50% based on CuO. Anal. (%). Calcd for 3 (C20H24CuF6N8Ti): C, 39.91; N, 18.62; H, 4.02. Found: C, 39.82; N, 18.67; H, 3.96. For 4, a mixture of CuO (0.081 g, 1 mmol), TiO2 (0.086 g, 1 mmol), imi (3 mmol, 0.211 g), hydrofluoric acid (40%, 6 mL), and water (10 mL) was stirred for about 5 h at room temperature, sealed in a 23-mL Teflon-lined stainless steel autoclave, heated at 220 °C for 6 days, and then slowly cooled to room temperature at a rate of 5 °C per an hour. Finally, light blue crystals of 4 suitable for single crystal X-ray diffraction analysis were collected from the final reaction system. Yield: 30% based on CuO. Anal. (%). Calcd for 4 (C18H26CuF12N12Ti2): C, 27.10; N, 21.07; H, 3.29. Found: C, 27.18; N, 21.03; H, 3.18. (15) Crystal data follow. For 1, C8H12CuN4O6V2, Mr = 425.64, monoclinic, space group P21/c, a = 9.6731(8) Å, b = 5.3414(5) Å, c = 15.4107(10) Å, β = 121.766(4)°, V = 676.97(10) Å3, Z = 2, Dcalcd = 2.088 g cm−3, μ = 2.940 mm−1, F(000) = 422, GOF = 1.084, R1 = 0.0263, wR2 = 0.0769. A total of 4410 reflections were collected, of which 1449 (Rint = 0.0213) were unique. For 2, C15H18F4MoN6O2Zn, Mr = 551.66, monoclinic, space group P21/c, a = 11.4692(2) Å, b = 11.9788(2) Å, c = 18.2487(3) Å, β = 123.049(1)°, V = 2101.49(6) Å3, Z = 4, Dcalcd = 1.744 g cm−3, μ = 1.795 mm−1, F(000) = 1096, GOF = 1.023, R1 = 0.0317, wR2 = 0.0738. A total of 19 837 reflections were collected, of which 5164 (Rint = 0.0377) were unique. For 3, C20H24CuF6N8Ti, Mr = 601.91, tetragonal, space group P42/n, a = 12.3189(1) Å, b = 12.3189(1) Å, c = 8.2962(1) Å, V = 1258.99(2) Å3, Z = 2, Dcalcd = 1.588 g cm−3, μ = 1.231 mm−1, F(000) = 610, GOF = 1.075, R1 = 0.0353, wR2 = 0.1235. A total of 5850 reflections were collected, of which 1500 (Rint = 0.0213) were unique. For 4, C18H26CuF12N12Ti2, Mr = 1620.1(2), tetragonal, space

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Corresponding Author

*E-mail: [email protected]. Fax: +86 752 2527229. Phone: +86 752 2527229. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors gratefully acknowledge support from the National Natural Science Foundation of China (No. 21271080), the Natural Science Foundation of Guangdong Province, China (No. S2012010010311), the Science and Technology Planning Project of Guangdong Province, China (No. 2011B010400042), and the Research Foundation for High-Ranking Talent Projects of the Educational Commission of Guangdong Province, China (2010).

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ABBREVIATIONS Meimi, 1-methyl-1H-imidazole; Viimi, 1-vinyl-1H-imidazole; imi, imidazole; SOJT, the second-order Jahn−Teller; 3D, three-dimensional; 2D, two-dimensional; 1D, one-dimensional; 0D, zero-dimensional

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REFERENCES

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Communication

group I4/mmm, a = 10.1096(5) Å, b = 10.1096(5) Å, c = 15.8515(16) Å, V = 1620.1(2) Å3, Z = 2, Dcalcd = 1.636 g cm−3, μ = 1.232 mm−1, F(000) = 798, GOF = 1.146, R1 = 0.0434, wR2 = 0.1335. A total of 5363 reflections were collected, of which 573 (Rint = 0.0303) were unique. Intensity data were collected on a Bruker SMART CCD diffractometer equipped with a graphite-monochromated Mo Kα radiation (λ = 0.710 73 Å) at 293(2) K using the ω−2θ scan technique. The structures were solved by direct methods and refined by full-matrix least-squares fitting on F2 by SHELXTL-97. All nonhydrogen atoms were located from the initial solution and refined with anisotropic thermal parameters. CCDC reference numbers are 760087, 780693, 804452, and 763288 for 1, 2, 3, and 4, respectively. These data can be obtained free of charge via www. ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, U.K.; fax (+44) 1223-336-033; or [email protected]).

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Fluo - American Chemical Society

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