A DihalideâDecahydrate Cluster of - American Chemical Society

Article pubs.acs.org/crystal

A Dihalide−Decahydrate Cluster of [X2(H2O)10]2− in a Supramolecular Architecture of {[Na2(H2O)6(H2O@TMEQ[6])]·2(C6H5NO3)}X2(H2O)10 (TMEQ[6] = α,α′,δ,δ′-Tetramethylcucurbit[6]uril; X = Cl, Br) Wen-jian Chen, La-Sheng Long,* Rong-Bin Huang, and Lan-Sun Zheng State Key Laboratory of Physical Chemistry of Solid Surface and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China S Supporting Information *

ABSTRACT: A discrete dihalide−decahydrate cluster of [X2(H2O)10]2− has been observed in a solid-state structure of {[Na 2 (H 2 O) 6 (H 2 O@TMEQ[6])]·2(C 6 H 5 NO 3 )}X 2 (H 2 O) 10 } (TMEQ[6] = α,α′,δ,δ′-tetramethylcucurbit[6]uril; X = Cl (1), Br (2)). Its structure can be viewed as a connection of two [X(H2O)3]− clusters with a uudd water tetramer through hydrogen-bonding interactions.

■

INTRODUCTION Hydrated halide anions are a highly active area of research, since they are the most common anions in nature due to their role in many chemical, environmental, and biological processes.1 Investigation of the structures of halide−water clusters in divers environments is of key importance for our understanding of solvation phenomena,2 electrical phenomena in the troposphere and ionosphere, and the mobility of ions in chemical and biological systems.3 Although a large number of experimental and theoretical studies4 have been performed on halide−water clusters, most of these studies have focused on monochloride hydrates [X(H2O)n]−, addressing their stabilities and structures, as well as their infrared spectra.5 In contrast, theoretical and experimental studies on dihalide hydrates are rare.6 To the best of our knowledge, only four dihalide water clusters of [F2(H2O)6]2−, [Cl2(H2O)6]2−, [Cl2(H2O)2]2−, and [Br2(H2O)6]2− have been reported so far,6 although dihalide water clusters may be even more relevant in hydrophobic and low-polarity environments.6c Cucurbit[n]urils (Q[n]s, Figure 1, left)7 or their derivatives,8 are fascinating macrobicyclic compounds. Possessing intramolecular cavities, Q[n]s not only are suitable for the encapsulation of guests9 but also function as synthetic receptors10 or as building blocks for supramolecular architectures.11−15 Because Q[n]s are neutral, they often form a

cationic supramolecular framework, when coordinated with metal ions. Thus, anion−water clusters may be expected in the cationic supramolecular framework. However, owing to the poor solubility of Q[n] in water, preparation of anion−water clusters through a Q[n]-based cationic supramolecular framework remains a challenge. In an effort to increase the solubility of Q[n]s in water, it is found that chemical modification of Q[n]s through introducing methyl groups to the carbon on the waist of Q[n]s is an efficient way to improve the solubility of the Q[n]s in water.8e A typical example is that α,α′,δ,δ′tetramethylcucurbit[6]uril (TMEQ[6]) shows surprising water solubility, and on the basis of the solubility of the TMEQ[6], a series of metal−TMEQ[6] and metal−Q[n]s supramolecular architectures have been prepared in the absence16 and presence17 of aromatic molecules, respectively.17 However, utilization of the solubility of the TMEQ[6] to prepare anion− water clusters has done been less. The p-nitrophenol molecule is a neutral proton donor and acceptor and tends to form hydrogen bonding with water. Thus, introducing the p-nitrophenol in metal−TMEQ[6] systems would be helpful to stabilize the anion−water clusters. Here, we report the structures of dihalide water clusters of [X2(H2O)10]2− (X = Cl, Br), which are confined in the supramolecular architectures of {[Na 2 (H 2 O) 6 (H 2 O@ TMEQ[6])]·2(C6H5NO3)·Cl2(H2O)10}(1) and {[Na2(H2O)6(H2O@TMEQ[6])]·2(C6H5NO3)·Br2(H2O)10}(2). Significantly, the dihalide water cluster consists of two cyclic monochloride hydrates [X(H2O)3]− (X = Cl, Br) and one cyclic water tetramer (H2O)4. Received: February 6, 2013 Revised: April 16, 2013 Published: April 16, 2013

Figure 1. Molecular structure of Q[n]s (left) and TMEQ[6] (right). © 2013 American Chemical Society

2507

dx.doi.org/10.1021/cg400227k | Cryst. Growth Des. 2013, 13, 2507−2513

Crystal Growth & Design

Article

Table 1. Crystal Data and Structure Refinement Details for Compounds 1−3

a

compound

1

2

3

empirical formula formula weight crystal system space group a, Å b, Å c, Å α, deg β, deg γ, deg V, Å3 Z Dcalcd, g cm−3 T, K μ, mm−1 unique reflns obsd reflns params Rint R [I > 2σ(I)]a wR [I > 2σ(I)]b R (all data) wR (all data) GOF on F2

C52H88N26O35Na2Cl2 1754.35 monoclinic P21/c 11.958(2) 24.461(5) 15.593(6)

C52H88N26O35Na2Br2 1843.25 monoclinic P21/n 11.977(0) 24.362(1) 12.664(0)

127.32(2)

101.16(1)

3627.4(2) 2 1.604 173(2) 0.214 6366 5897 543 0.0308 0.0362 0.0952 0.0393 0.0970 1.063

3625.1(2) 2 1.687 173(2) 1.243 6374 5365 551 0.0364 0.0767 0.2138 0.0895 0.2226 1.070

C88H108N32O48Na2F2 2466.04 triclinic P1̅ 11.538(2) 15.625(3) 16.875(3) 116.83(3) 105.51(3) 91.18(3) 2580.3(1) 1 1.587 173(2) 0.140 8932 7633 788 0.0141 0.0569 0.1690 0.0644 0.1750 1.040

Conventional R on Fhkl: ∑||Fo| − |Fc||/∑|Fo|. bWeighted R on |Fhkl|2: ∑[w(Fo2 − Fc2)2]/∑[w(Fo2)2]1/2.

■

the basis of TMEQ[6]. Anal. Calcd for 3: C, 42.86; H, 4.41; N, 18.18. Found: C, 42.95; H, 4.51; N, 18.27. X-ray Crystallography. A suitable single crystal was picked up with paratone oil and mounted on a Bruker Apex-2000 diffractometer using graphite monochromated Mo Kα radiation (λ = 0.71073 Å) with ω/2θ scan mode at 173 K. The data were corrected for Lorentz and polarization effects (SAINT),18a and semiempirical absorption corrections based on equivalent reflections were applied (SADABS).18a The structure was elucidated by direct methods and refined by the fullmatrix least-squares method on F2 with the SHELXS-97 and SHELXL97 program packages, respectively.18b,c All the non-hydrogen atoms were refined anisotropically, and the hydrogen atoms were calculated in ideal positions with isotropic displacement parameters set to 1.2 × Ueq of the attached atom (1.5 × Ueq for methyl hydrogen atoms). Analytical expressions for neutral-atom scattering factors were employed, and anomalous dispersion corrections were incorporated. The disordered Br1 atom locates over two positions, which split to Br1 with 53% occupancy and Br1′ with 47% occupancy in compound 2, and the disordered F atom locates over two positions, which split to F1 with 51% occupancy and F1′ with 49% occupancy in compound 3. Details of the crystal parameters, data collection conditions, and refinement parameters for the compounds 1−3 are summarized in Table 1. The CCDC numbers for compounds 1, 2, and 3 are 861214, 902321, and 902320, respectively. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/data_request/cif, or by Emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, U.K.; Fax: +44 1223 336033.

EXPERIMENTAL SECTION

Synthesis. Chemicals, such as sodium fluoride, sodium chloride, sodium bromide, and p-nitrophenol, were of reagent grade and used without further purification. The TMeQ[6] (Figure 1, right) was prepared by procedures reported previously.8e The C, H, and N microanalyses were carried out with a CE instruments EA 1110 elemental analyzer. TGA curves were prepared on an SDT Q600 Thermal Analyzer. X-ray powder diffraction studies (PXRD) were performed using a Panalytical X-Pert PRO diffractometer with Cu−Kα radiation (λ = 0.15418 nm, 40.0 kV, 30.0 mA). The calculated PXRD patterns were produced using Mercury 2.4 and single-crystal reflection data. Preparation of {[Na2(H2O)6(H2O@TMEQ[6])]·2(C6H5NO3)· Cl2(H2O)10} (1). TMeQ[6] (0.275 g, 0.25 mmol), p-nitrophenol (0.141 g, 1.01 mmol), and NaCl (0.059 g, 1.01 mmol) were dissolved in 20.0 mL of water while stirring at 70 °C. The mixture was heated to 100 °C and refluxed for 1 h. The filtrate was left to stand at room temperature in an open beaker (25 mL). After 2 days, yellow crystals of 1 were obtained and collected in a yield of 47.5% on the basis of TMEQ[6]. Anal. Calcd for 1: C, 35.60; H, 5.06; N, 20.76. Found: C, 35.55; H, 5.04; N, 20.72. Preparation of {[Na2(H2O)6(H2O@TMEQ[6])]·2(C6H5NO3)·Br2(H2O)10} (2). TMeQ[6] (0.275 g, 0.25 mmol), p-nitrophenol (0.141 g, 1.01 mmol), and NaBr (0.104 g, 1.01 mmol) were dissolved in 20.0 mL of water with stirring at 70 °C. The mixture was heated to 100 °C and refluxed for 1 h. The filtrate was left to stand at room temperature in an open beaker (25 mL). After 2 days, yellow crystals of 2 were obtained and collected in a yield of 55.7% on the basis of TMEQ[6]. Anal. Calcd for 2: C, 33.88; H, 4.81; N, 19.76. Found: C, 33.82; H, 4.75; N, 19.72. Preparation of {[Na2(H2O)6(C6H5NO3)2(2H2O@ TMEQ[6])]·6(C6H5NO3)}F2(H2O)4} (3). TMeQ[6] (0.275 g, 0.25 mmol), p-nitrophenol (0.141g, 1.01 mmol), and NaF (0.043 g, 1.02 mmol) were dissolved in 20.0 mL of water with stirring at 70 °C. The mixture was heated to 100 °C and refluxed for 1 h. The filtrate was left to stand at room temperature in an open beaker (25 mL). After 2 days, yellow crystals of 3 were obtained and collected in a yield of 50.5% on

■

RESULTS AND DISCUSSION Complex 1 crystallized in the monoclinic, P21/c space group. Single-crystal structure analysis at 173 K shows that the asymmetric unit of 1 consists of half a TMeQ[6] molecule, one p-nitrophenol molecule, one sodium ion, one chloride anion, three coordinated and 5.5 guest water molecules. Each sodium ion (Na1) in 1 is coordinated by six oxygen atoms with four from water molecules (O4W, O8W, O9W, and O9Wi), and two 2508



Article

Figure 2. (a) View of 1D chain structure in 1. (b) Interaction of two neighboring 1D chains with [Cl2(H2O)10]2−. (c) Packing diagram of 1. Hydrogen atoms are omitted for clarity, and dashed lines indicate hydrogen-bonding interactions (symmetry codes: (i) −x − 1, −y, −z).

Figure 3. The structure of [Cl2(H2O)10]2− in 1. Dashed lines indicate hydrogen bonds (symmetry codes: (i) x, −1/2 − y, −1/2 + z; (ii) −1 − x, −1/2 + y, 1/2 − z; (iii) −1 + x, −1/2 − y, −1/2 + z; (iv) −1 − x, −1 − y, −z; (v) −x, −1/2 + y, 1/2 − z).

Figure 4. Structure of [Br2(H2O)10]2− in 2. Dashed lines indicate hydrogen bonds (symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) −x, 1 − y, 1 − z; (iii) −1 + x, y, z).

from carbonyl oxygen atoms (O3 and O6) of a TMeQ[6] molecule. The bond lengths of Na−Owater are in the range of 2.410(2)−2.455(3) Å, and the bond lengths of Na−Ocarbonyl are in the range of 2.326(4)−2.410(2) Å, comparable to those of 2.197(3)−2.451(1) Å for Na−Owater and 2.368(3)−2.375(4) Å for Na−Ocarbonyl in the complex of {[Na2(H2O)8(TMeQ[6])2]·2Cl·24H2O} reported previously.16 Two neighboring TMeQ[6] molecules are bridged by a [Na2(H2O)6]2+ ion

through two carbonyl oxygen atoms from one TMeQ[6] directly coordinated to the Na+ in the [Na2(H2O)6]2+, forming a one-dimensional chain structure of {[Na2(H2O)6(H2O@ TMEQ[6])]}n2n+ (Figure 2a). This 1D chain is different from that constructed from TMeQ[6] and sodium in the absence of p-nitrophenol.16 Two neighboring 1D chains are connected by 2509



Article

O1W···O3W = 2.885(2) Å, O1W−H1O1···O3W = 2.10 Å, ∠O1W−H1O1···O3W = 171.2°; O3W···O5W = 2.770(2) Å, O3W−H2O3···O5W = 2.01 Å, ∠O3W−H2O3···O5W = 161.1°; ∠O1W···Cl1···O5W = 72.1°, ∠O1W···O3W···O5W = 82.0°. The average Cl···O separation is 3.153(2) Å, comparable to that of 3.112 Å in the calculated [Cl(H2O)3]−,4n and slightly shorter than that of 3.227 Å reported by Curnow and coworkers in the [Cl2(H2O)6)]2− cluster.6c The average O···O separation of 2.828(2) Å is comparable to that of 2.832 Å in the [Cl2(H2O)6)]2− cluster,6c but significantly shorter than that of 2.938 Å in the calculated [Cl(H2O)3]−.4n The O···Cl···O angle in the present monochloride hydrates [Cl(H2O)3]− is 72.1°, 10.5° smaller than that in the calculated [Cl(H2O)3]−,4n while the O···O···O angle of [Cl(H2O)3]− in the present structure is 82.0°, 5.3° smaller than that in the [Cl2(H2O)6)]2− cluster.6c The uudd cyclic water tetramer has been reported,19 and it is not the most stable mode of cyclic water tetramer calculated by Gregory in 1996.20 The hydrogen bond distances and angles within the water tetramer in 1 are the following: O2Wi···O6Wv = 2.872(2) Å, O2W i···O6W iii = 2.705(2) Å, O2W i − H2O2···O6Wv = 165.6°, ∠O6Wiii−H2O6···O2Wi = 166.8°. The average hydrogen bond distance within the water tetramer is 2.788(2) Å, shorter than that of 2.834 Å in the uudd water tetramer reported previously,19 but longer than that of 2.743 Å calculated in the discrete udud water tetramer,21 and that of 2.78 Å estimated in the udud water tetramer of (D2O)4 in the gas phase.22 The hydrogen bond distance of Cl1···O2Wi between the [Cl(H2O)3]− and the water tetramer is 3.042(2) Å, shorter than that of 3.246(2) Å for Cl1···O1W and 3.059(2) Å for Cl1···O5W within the [Cl(H2O)3]−. Single-crystal structure analysis reveals that compound 2 is the isomorph of 1. A similar 1D supramolecular chain of {[Na2(H2O)6(H2O@TMEQ[6])]}n2n+ in 1 is also observed in 2 (Supporting Information, Figure S1a). Two neighboring 1D chains are connected by the discrete dibromide−decahydrate cluster through hydrogen-bonding interactions (Supporting Information, Figure S1b), generating a 3D supramolecular architecture of 2 (Supporting Information, Figure S1c), similar to that in 1. The bond lengths of Na−Owater and Na−Ocarbonyl are 2.402(4)−2.462(5) and 2.332(3)−2.422(3) Å, respectively, comparable to those of 2.410(2)−2.455(3) Å for Na−Owater and 2.326(4)−2.410(2) Å for Na−Ocarbonyl in 1. The dibromide water cluster is formed through a uudd water tetramer as a proton donor hydrogen-bonded to two [Br(H2O)3]− clusters as proton acceptors (Figure 4). The bromide atom in the cluster is disordered and locates at two positions with Br1 in 53% occupancy and Br1′ in 47% occupancy, respectively. The hydrogen bond distances and angles within the [Br(H2O)3]− are the following: Br1···O1W = 3.052(4) Å, O1W−H1O1···Br1 = 2.35 Å, ∠Br1···H1O1−O1W = 142.7°; Br1′···O1W = 3.304(4) Å, O1W−H1O1···Br1′ = 2.51 Å, ∠Br1′···H1O1−O1W = 159.0°; Br1···O6W = 3.169(7) Å, O6W−H2O6···Br1 = 2.36 Å, ∠Br1···H2O6−O6W = 166.7°; Br1′···O6W = 3.935(7) Å, O6W−H2O6···Br1′ = 3.12 Å, ∠Br1′···H2O6−O6W = 174.2°; O6W···O7Wi = 2.885(5) Å, O6W−H1O6···O7Wi = 2.04 Å, ∠O6W−H1O6···O7Wi = 169.0°; O7Wi···O1W = 2.776(5) Å, O7Wi−H1O7···O1W = 1.99 Å, ∠O7Wi−H1O7···O1W = 158.9°; ∠O6W···Br1···O1W = 71.6°, ∠O6W···Br1′···O1W = 59.6°, ∠O6W···O7Wi···O1W = 80.0°. The average Br···O separation is 3.368(3) Å, comparable to that of 3.367(5) Å reported by Khavasi and co-workers in the [Br2(H2O)6]2− cluster.6e The average O···O separation of 2.831(5) Å is very close to that of 2.828(2) Å in the [Cl(H2O)3]− in 1, but significantly shorter

Figure 5. Hydrogen-bonding interactions of [Cl2(H2O)10]2− with its immediate environment. Dashed lines indicate hydrogen bonds (symmetry codes: (i) x, −1/2 − y, −1/2 + z; (ii) −1 − x, −1/2 + y, 1/2 − z; (iii) −1 + x, −1/2 − y, −1/2 + z; (iv) −1 − x, −1 − y, −z; (v) −x, −1/2 + y, 1/2 − z; (vi) x, −1/2 − y, 1/2 + z; (vii) 1 + x, −1/2 − y, 1/2 + z; (viii) −1 − x, −1/2 + y, −1/2 − z; (ix) −2 − x, −1/2 + y, −1/2 − z).

Figure 6. Hydrogen-bonding interactions of [Br2(H2O)10]2− with its immediate environment. Dashed lines indicate hydrogen bonds (symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) −x, 1 − y, 1 − z; (iii) −1 + x, y, z; (iv) −1 + x, y, 1 + z; (v) −x, 1 − y, −z; (vi) x, y, 1 + z; (vii) −1 + x, y, 1 + z).

the discrete dichloride−decahydrate cluster through hydrogenbonding interactions (Figure 2b), generating a 3D supramolecular architecture of 1 (Figure 2c). Interestingly, the dichloride water cluster is formed through a uudd water tetramer as a proton donor hydrogen-bonded to two [Cl(H2O)3]− clusters as proton acceptors (Figure 3). Structurally, the anion water cluster looks like a “cut-open and flattened” cubane. It was mentioned that, although two dichloride water clusters have experimentally been found in the compounds of sodium [2.2.2]cryptand6b and [C3(NiPr2)3]Cl·3H 2 O (C 3 (NiPr 2 ) 3 = tris(diisopropylamino)-cyclopropenium cation), respectively,6c the dichloride water cluster in the present work has not been observed yet. In the [Cl(H2O)3]− cluster, O3W acted as both a proton donor and acceptor and forms hydrogen-bonding interactions with O5W and O1W, respectively, while O1W and O5W, respectively, act as a proton donor to form hydrogen-bonding interactions with chloride anion (Cl1). Its configuration is much different from that of the most stable monochloride hydrate of [Cl(H2O)3]− calculated by Xantheas in 19964n and by Merrill in 2003,4j respectively. The hydrogen bond distances and angles within the monochloride hydrates [Cl(H2O)3]− are the following: Cl1···O1W = 3.246(2) Å, O1W−H2O1···Cl1 = 2.46 Å, ∠Cl1···H2O1−O1W = 163.9°; Cl1···O5W = 3.059(2) Å, O5W−H2O5···Cl1 = 2.28 Å, ∠Cl1···H2O5−O5W = 152.3°; 2510



Article

Figure 7. (a) View of 1D chain structure in 3. (b) Interaction of two neighboring 1D chains with [F2(H2O)2]2−. (c) Packing diagram of 3. Hydrogen atoms are omitted for clarity, and dashed lines indicate hydrogen-bonding interactions (symmetry codes: (i) −x + 1, −y + 1, −z).

Figure 8. The cluster [F2(H2O)2]2− in 3 (left). Interaction of [F2(H2O)2]2− with its immediate environment (right). Dashed lines indicate hydrogen bonds (symmetry codes: (i) 1 − x, −y, −z).

than that of 2.879(7) Å in the [Br2(H2O)6]2− cluster.6e The O···Br···O angle in [Br(H2O)3]− is 65.6°, 6.5° smaller than that of the O···Cl···O angle in the [Cl(H2O)3]− in 1, while the O···O···O angle in [Br(H2O)3]− is 80.0°, 2.0° smaller than that in the monochloride hydrates [Cl(H2O)3]− in 1. The hydrogen bond distances and angles within the water tetramer in 2 are the following: O2W···O5W = 2.832(8) Å, O5Wii···O2W = 2.610(8) Å, O2W−H 2O2 ···O5W = 166.9°, ∠O5W ii − H1O5···O2W = 153.2°. The average hydrogen bond distance within the cyclic water tetramer is 2.721(8) Å, shorter than that of 2.788(2) Å in the uudd water tetramer in 1. To reveal the formation of the dichloride water cluster and dibromide water cluster in the present work, the hydrogenbonding interactions between the anion water cluster and its

surroundings were investigated. As shown in Figure 5, the water molecules O3W and O6Wv and their symmetry-related O3Wiv and O6Wiii are only involved in O−H···O hydrogen bonding within the [Cl2(H2O)10]2− cluster, whereas the water molecules O1W, O2Wi, and O5W and their symmetry-related O1Wiv, O2Wii, and O5Wiv are, respectively, involved in O−H···O and O−H···Cl hydrogen bonding within the [Cl2(H2O)10]2− cluster. The water molecules O3W, O5W, and O6Wv and their symmetry-related O3Wiv, O5Wiv, and O6Wiii are invariably hydrogen-bonded to their surroundings. Especially, the water molecules of O6Wv and its symmetry-related O6Wiii form two stronger O−H···O intermolecular hydrogen bonding with the hydroxyl oxygen atoms (O9v and O9iii) of pnitrophenol and the coordination water O8Wv and O8Wiii, 2511



Article

respectively (O9v−H9···O6Wv, O6Wv−H1O6···O8Wv, O9iii− H9···O6Wiii, and O6Wiii−H1O6···O8Wiii). Similarly, the water molecules O7Wi and O5W and their symmetry-related O7Wiii and O5Wii are only involved in O− H···O hydrogen bonding within the [Br2(H2O)10]2− cluster, and the water molecules O1W, O2W, and O6W and their symmetry-related O1Wii, O2Wii, and O6Wii are, respectively, involved in O−H···O and O−H···Cl hydrogen bonding within the [Br2(H2O)10]2− cluster. The water molecules O7Wi, O1W, and O5W and their symmetry-related O7Wiii, O1Wii, and O5Wii are hydrogen-bonded to their surroundings, and the water molecules of O5W and its symmetry-related O5Wii form two stronger O−H···O intermolecular hydrogen bonding with the hydroxyl oxygen atoms (O9 and O9ii) of p-nitrophenol and the coordination water O4W and O4Wii, respectively (O9− H9···O5W, O5W−H2O5···O4W, O9ii−H9···O5Wii, and O5Wii− H2O5···O4Wii) (Figure 6). On the basis of the hydrogenbonding interactions between the water clusters and their surroundings in 1 and 2, it is clear that the formation of the dihalide (Cl, Br) water cluster in the present work is closely related to the hydrogen-bonding interactions between the dihalide (Cl, Br) water cluster and its surroundings. Details of these hydrogen-bonding interactions, along with their symmetry codes, are given in the Supporting Information (Tables S1 and S2). Complex 3 crystallized in the triclinic, P1̅ space group. Single-crystal structure analysis at 173 K shows that the asymmetric unit of 3 consists of half a TMeQ[6] molecule, one sodium ion, one fluoride anion, one coordinated and three guest p-nitrophenol molecules, and three coordinated and three guest water molecules. Each sodium ion (Na1) in 3 is coordinated by seven oxygen atoms with three from water molecules (O1W, O2W, and O3W), two from carbonyl oxygen atoms (O1 and O2) of a TMeQ[6] molecule, and two from the nitro group (O17 and O18 atoms) of a p-nitrophenol molecule. Connection of neighboring [Na2(H2O)6(C6H5NO3)2(2H2O@TMEQ[6])]2+ units through a phenolic oxygen atom (O16) of p-nitrophenol from one [Na2(H2O)6(C6H5NO3)2(2H2O@TMEQ[6])]2+ unit as a proton donor and the coordination water O2W from the neighboring [Na 2(H 2O)6 (C6 H5 NO3 )2 (2H 2O@ TMEQ[6])]2+ unit as a proton acceptor leads to the formation of a 1D chain structure of {[Na2(H2O)6(C6H5NO3)2(2H2O@ TMEQ[6])]2+}n (Figure 7 a). Two neighboring 1D chains linked by the discrete difluoride−dihydrate through hydrogenbonding interactions with F− as a proton acceptor and the coordination water O1W as a donor (Figure 7 b) generates a 3D supramolecular architecture of 3 (Figure 7 c). It was noted that both the 1D chain in 3 and the 3D supramolecular architecture of 3 are much different from those of 1 and 2. This result indicates that the anion water cluster is an important factor influencing the supramolecular architecture, since the synthetic condition between 1 and 3 is very similar. Unambiguously, the F− anion forming the [F2(H2O)2]2− cluster with water in 3, instead of [F2(H2O)10]2− as Cl− and Br− anions, is related to its ionic radius being smaller than that of Cl− and Br− anions, which results in the F− anion hydrogenbonded to fewer water molecules when compared with Cl− and Br− anions. The bond lengths of Na−Owater are in the range of 2.414(2)−2.491(2) Å, and the bond lengths of Na−Ocarbonyl are in the range of 2.367(2)−2.389(2) Å, comparable to those of 2.197(3)−2.451(1) Å for Na−Owater and 2.368(3)−2.375(4) Å

for Na−Ocarbonyl in the complex of {[Na2(H2O)8(TMeQ[6])2]·2Cl·24H2O} reported previously.16 The hydrogen bond distances and angles within the difluoride hydrates [F2(H2O)2]2− (Figure 8, left) are the following: F1···O5W = 2.745(7) Å, O5W−H1O5···F1 = 1.89 Å, ∠F1···H1O5−O5W = 165.2°; F1′···O5W = 1.889(6) Å, O5W− H1O5···F1′ = 1.10 Å, ∠F1′···H1O5−O5W = 146.7°; F1i ···O5W = 2.423(7) Å, O5W−H2O5···F1i = 1.83 Å, ∠F1i···H2O5−O5W = 127.1°. Details of these hydrogen-bonding interactions, along with their symmetry codes, are given in the Supporting Information (Table S3).

■

CONCLUSION In conclusion, a discrete dihalide−decahydrate cluster of [X2(H2O)10]2− (X = Cl, Br) has been observed in a supramolecular architecture. The [X2(H2O)10]2− cluster not only functions as a structure motif of the supramolecular architecture but also represents the first example of the dihalide−decahydrate cluster formed by a uudd water tetramer as a proton donor hydrogen-bonded to two [X(H2O)3]− clusters as proton acceptors. Significantly, when NaF was used, the difluoride−dihydrate cluster of [F2(H2O)2]2− was obtained at the similar synthetic condition. Moreover, both the 1D chain in 3 and the 3D supramolecular architecture of 3 are much different from those of 1 and 2. Thus, the present work not only helps us to understand the influence of the surrounding on the structure of anion water but also helps us to understand the role of the anion water in the construction of supramolecular architectures.

■

ASSOCIATED CONTENT

S Supporting Information *

View of 1D chain structure in 2; tables of the parameters of the hydrogen bond in 1, 2, and 3; XRD patterns for 1, 2, and 3, and TGA curves for 1, 2, and 3. This material is available free of charge via the Internet at http://pubs.acs.org.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel/Fax: (+)86-592-2183047. Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS We acknowledge the 973 project from MSTC (Grant No. 2012CB821704) and the National Natural Science Foundation of China (Grant Nos. 20825103 90922031 and 21021061).

■

REFERENCES

(1) (a) Infantes, L.; Motherwell, S. CrystEngComm 2002, 4, 454. (b) Infantes, L.; Chisholm, J.; Motherwell, S. CrystEngComm 2003, 5, 480. (c) Mascal, M.; Infantes, L.; Chisholm, J. Angew. Chem., Int. Ed. 2006, 45, 32. (d) Zhu, W. H.; Wang, Z. M.; Gao, S. Dalton Trans. 2006, 765. (e) Wang, J.; Zheng, L. L.; Li, C. J.; Zheng, Y. Z.; Tong, M. L. Cryst. Growth Des. 2006, 6, 357. (f) Ghosh, S. K.; Bharadwaj, P. K. Inorg. Chem. 2003, 42, 8250. (g) Karabach, Y. Y.; Kirillov, A. M.; Guedes da Silva, M. F. C.; Kopylovich, M. N.; Pombeiro, A. J. L. Cryst. Growth Des. 2006, 6, 2200. (h) Wang, X. B.; Yang, X.; Nicholas, J. B.; Wang, L. S. Science 2001, 294, 1322. (i) Robertson, W. H.; Diken, E. G.; Price, E. A.; Shin, J. W.; Johnson, M. A. Science 2003, 299, 1367. (2) (a) Ohtaki, H.; Radnai, T. Chem. Rev. 1993, 93, 1157. (b) Marcus, Y. Ion Solvation; Wiley: Chichester, U.K., 1986. (c) Richens, D. T. The 2512



Article

Chemistry of Aqua Ions; Wiley: Chichester, U.K., 1997. (d) Castleman, A. W.; Bowen, K. H. J. Phys. Chem. 1996, 100, 12911. (3) (a) Markovich, G.; Pollack, S.; Giniger, R.; Cheshnovsky, O. J. Chem. Phys. 1994, 101, 9344. (b) Roeselova, M.; Jacoby, G.; Kaldor, U.; Jungwirth, P. Chem. Phys. Lett. 1998, 293, 309. (c) Janoschek, R. J. Mol. Struct. 1982, 84, 237. (d) Sodaye, S.; Suresh, G.; Pandey, A. K.; Goswami, A. Radiochim. Acta. 2006, 94, 347. (e) Kumar, R.; Pandey, A. K.; Sharma, M. K.; Panicker, L. V.; Sodaye, S.; Suresh, G.; Ramagiri, S. V.; Bellare, J. R.; Goswami, A. J. Phys. Chem. B 2011, 115, 5856. (4) (a) Kemp, D. D.; Gordon, M. S. J. Phys. Chem. A 2005, 109, 7688. (b) Robertson, W. H.; Johnson, M. A. Annu. Rev. Phys. Chem. 2003, 54, 173. (c) Ayala, R.; MartRnez, J. M.; Pappalardo, R. R.; Marcos, E. S. J. Chem. Phys. 2003, 119, 9538. (d) Custelcean, R.; Gorbunova, M. G. J. Am. Chem. Soc. 2005, 127, 16362. (e) Lakshminarayanan, P. S.; Suresh, E.; Ghosh, P. Angew. Chem. 2006, 118−3891;(f) Angew. Chem., Int. Ed. 2006, 45, 3807. (g) Siu, C. K.; Balaj, O. P.; Bondybey, V. E.; Beyer, M. K. J. Am. Chem. Soc. 2007, 129, 3238. (h) Koizumi, S.; Yasumatsu, H.; Otani, S.; Kondow, T. J. Chem. Phys. 2004, 121, 4833. (i) Sobolewski, A. L.; Domcke, W. J. Phys. Chem. A 2003, 107, 1557. (j) Merrill, G. N.; Webb, S. P. J. Phys. Chem. A 2003, 107, 7852. (k) Perera, L.; Berkowitz, M. L. J. Phys. Chem. 1993, 99, 4222. (l) Ayotte, P.; Weddle, G. H.; Kim, J.; Johnson, M. A. J. Am. Chem. Soc. 1998, 120, 12361. (m) Hall, R. J.; Hillier, I. H.; Vincent, M. A. Chem. Phys. Lett. 2000, 320, 139. (n) Xantheas, S. S. J. Phys. Chem. 1996, 100, 9703. (5) (a) Markovich, G.; Giniger, R.; Levin, M.; Cheshnovsky, O. Z. Phys. D: At., Mol. Clusters 1991, 20, 69. (b) Markovich, G.; Pollack, S.; Giniger, R.; Cheshnovsky, O. J. Chem. Phys. 1994, 101, 9344. (c) Ritzhaupt, G.; Devlin, J. P. J. Phys. Chem. 1991, 95, 90. (d) Ayotte, P.; Marchand, P.; Daschbach, J. L.; Smith, R. S.; Kay, B. D. J. Phys. Chem. A 2011, 115, 6002. (6) (a) Arunachalam, M.; Ghosh, P. Chem. Commun. 2009, 5389. (b) Dalley, N. K.; Krakowiak, K. E.; Bradshaw, J. S.; Kou, X.; Izatt, R. M. J. Heterocycl. Chem. 1995, 32, 1201. (c) Butchard, J. R.; Curnow, O. J.; Garrett, D. J.; Maclagan, R. G. A. R. Angew. Chem., Int. Ed. 2006, 45, 7550. (d) Kopylovich, M. N.; Tronova, E. A.; Haukka, M.; Kirillov, A. M.; Kukushkin, V. Yu.; Fraústo da Silva, J. J. R.; Pombeiro, A. J. L. Eur. J. Inorg. Chem. 2007, 4621. (e) Bakhoda, A.; Khavasi, H. R.; Safari, N. Cryst. Growth Des. 2011, 11, 933. (7) (a) Behrend, R.; Meyer, E.; Rusche, F. Justus Liebigs Ann. Chem. 1905, 339, 1. (b) Freeman, W. A.; Mock, W. L.; Shih, N. Y. J. Am. Chem. Soc. 1981, 103, 7367. (c) Kim, J.; Jung, I. S.; Kim, S. Y.; Lee, E.; Kang, J. K.; Sakamoto, S.; Yamaguchi, K.; Kim, K. J. Am. Chem. Soc. 2000, 122, 540. (d) Day, A. I.; Arnold, A. P. Method for Synthesis Cucurbiturils. Patent WO 0068232, 2000; p 8. (e) Day, A. I.; Arnold, A. P.; Blanch, R. J.; Snushall, B. J. J. Org. Chem. 2001, 66, 8094. (f) Day, A. I.; Blanch, R. J.; Arnold, A.; Lorenzo, P. S.; Lewis, G. R.; Dance, I. Angew. Chem., Int. Ed. 2002, 41, 275. (8) (a) Flinn, A.; Hough, G. C.; Stoddart, J. F.; Williams, D. J. Angew. Chem., Int. Ed. 1992, 31, 1475. (b) Zhao, J. Z.; Kim, H. J.; Oh, J.; Kim, S. Y.; Lee, J. W.; Sakamoto, S.; Yamaguchi, K.; Kim, K. Angew. Chem., Int. Ed. 2001, 40, 4233. (c) Isobe, H.; Sato, S.; Nakamura, E. Org. Lett. 2002, 4, 1287. (d) Jon, S. Y.; Selvapalam, N.; Oh, D. H.; Kang, J. K.; Kim, S. Y.; Jeon, Y. J.; Lee, J. W.; Kim, K. J. Am. Chem. Soc. 2003, 125, 10186. (e) Zhao, Y. J.; Xue, S. F.; Zhu, Q. J.; Tao, Z.; Zhang, J. X.; Wei, Z. B.; Long, L. S.; Hu, M. L.; Xiao, H. P.; Day, A. I. Chin. Sci. Bull. 2004, 49, 1111. (f) Huang, W. H.; Zavalij, P. Y.; Isaacs, L. Angew. Chem., Int. Ed. 2007, 46, 7425. (g) Huang, W. H.; Zavalij, P. Y.; Isaacs, L. J. Am. Chem. Soc. 2008, 130, 8446. (9) (a) Jeon, Y. J.; Bharadwaj, P. K.; Choi, S. W.; Lee, J. W.; Kim, K. Angew. Chem., Int. Ed. 2002, 41, 4474. (b) Colquhoun, H. M.; Zhu, Z. X. Angew. Chem., Int. Ed. 2004, 43, 5040. (c) Fuller, A. M.; Leigh, D. A.; Lusby, P. J.; Oswald, I. D. H.; Parsons, S.; Walker, D. B. Angew. Chem., Int. Ed. 2004, 43, 3914. (d) Lee, J. W.; Samal, S.; Selvapalam, N.; Kim, H. J.; Kim, K. Acc. Chem. Res. 2003, 36, 621. (e) Kim, H.; Kim, Y.; Yoon, M.; Lim, S.; Park, S. M.; Seo, G.; Kim, K. J. Am. Chem. Soc. 2010, 132, 12200. (10) (a) Kim, H. J.; Heo, J.; Jeon, W. S.; Lee, E.; Kim, J.; Sakamoto, S.; Yamaguchi, K.; Kim, K. Angew. Chem., Int. Ed. 2001, 40, 1526.

(b) Ko, Y. H.; Kim, K.; Kang, J. K.; Chun, H.; Lee, J. W.; Sakamoto, S.; Yamaguchi, K.; Fettinger, J. C.; Kim, K. J. Am. Chem. Soc. 2004, 126, 1932. (11) (a) Lee, E.; Heo, J.; Kim, K. Angew. Chem., Int. Ed. 2000, 39, 2699. (b) Lee, E.; Kim, J.; Heo, J.; Whang, D.; Kim, K. Angew. Chem., Int. Ed. 2001, 40, 399. (c) Park, K. M.; Kim, S. Y.; Heo, J.; Whang, D.; Sakamoto, S.; Yamaguchi, K.; Kim, K. J. Am. Chem. Soc. 2002, 124, 2140. (12) (a) Gerasko, O. A.; Sokolov, M. N.; Fedin, V. P. Pure Appl. Chem. 2004, 76, 1633. (b) Samsonenko, D. G.; Gerasko, O. A.; Virovets, A. V.; Fedin, V. P. Russ. Chem. Bull. 2005, 54, 1557. (c) Liu, J. X.; Long, L. S.; Huang, R. B.; Zheng, L. S. Cryst. Growth Des. 2006, 6, 2611. (d) Kasuga, N. C.; Umeda, M.; Kidokoro, H.; Ueda, K.; Hattori, K.; Yamaguchi, K. Cryst. Growth Des. 2009, 9, 1494. (e) Heo, J.; Kim, J.; Whang, D.; Kim, K. Inorg. Chim. Acta 2000, 297, 307. (13) (a) Mit’kina, T. V.; Gerasko, O. A.; Sokolov, M. N.; Naumov, D. Yu.; Fedin, V. P. Russ. Chem. Bull. 2004, 53, 80. (b) Liu, J. X.; Dong, C. H.; Long, L. S.; Huang, R. B.; Zheng, L. S. Dalton Trans. 2009, 36, 7344. (14) (a) Gerasko, O. A.; Mainicheva, E. A.; Naumova, M. I.; Yurjeva, O. P.; Albreola, A.; Vicent, C.; Llusar, R.; Fedin, V. P. Eur. J. Inorg. Chem. 2008, 416. (b) Thuéry, P. Cryst. Growth Des. 2008, 8, 4132. (c) Gerasko, O. A.; Mainicheva, E. A.; Naumova, M. I.; Neumaier, M.; Kappes, M. M.; Lebedkin, S.; Fenske, D.; Fedin, V. P. Inorg. Chem. 2008, 47, 8869. (d) Thuéry, P. Inorg. Chem. 2009, 48, 4497. (e) Thuéry, P. Inorg. Chem. 2009, 48, 825. (f) Thuéry, P. Inorg. Chem. 2009, 48, 4497. (g) Thue’ry, P. CrystEngComm. 2009, 11, 1150. (h) Thuéry, P. Cryst. Growth Des. 2009, 9, 1208. (i) Thuéry, P.; Masci, B. Cryst. Growth Des. 2010, 10, 716. (j) Thuéry, P. Inorg. Chem. 2010, 49, 9078. (15) (a) Hernandez-Molina, R.; Sokolov, M. N.; Sykes, A. G. Acc. Chem. Res. 2001, 34, 223. (b) Hernandez-Molina, R.; Sokolov, M. N.; Clausen, M.; Clegg, W. Inorg. Chem. 2006, 45, 10567. (c) HernandezMolina, R.; Kalinina, I.; Sokolov, M.; Clausen, M.; Gonzalez Platas, J.; Vicent, C.; Llusar, R. Dalton Trans. 2007, 550. (d) Abramov, P. A.; Sokolov, M. N.; Virovets, A. V.; Peresypkina, E. V.; Fedin, V. P. J. Cluster Sci. 2007, 18, 597. (e) Algarra, A. G.; Sokolov, M. N.; Gonzalez-Platas, J.; Fernandez-Trujillo, M. J.; Basallote, M. G.; Hernandez-Molina, R. Inorg. Chem. 2009, 48, 3639. (f) Gushchin, A. L.; Ooi, B.; Harris, P.; Vicent, C.; Sokolov, M. N. Inorg. Chem. 2009, 48, 3832. (16) Chen, W. J.; Yu, D. H.; Xiao, X.; Zhang, Y. Q.; Zhu, Q. J.; Xue, S. F.; Tao, Z.; Wei, G. Inorg. Chem. 2011, 50, 6956. (17) (a) Chen, K.; Cong, H.; Xiao, X.; Zhang, Y. Q.; Xue, S. F.; Tao, Z.; Zhu, Q. J.; Wei, G. CrystEngComm 2011, 13, 5105. (b) Feng, X.; Chen, K.; Zhang, Y. Q.; Xue, S. F.; Zhu, Q. J.; Tao, Z.; Day, A. I. CrystEngComm 2011, 13, 5049. (c) Feng, X.; Du, H.; Xiao, X.; Luo, S. X.; Xue, S. X.; Zhang, Y. Q.; Zhu, Q. J.; Tao, Z.; Zhang, X. Y.; Gang, W. Cryst. Growth Des. 2010, 10, 2901. (d) Chen, K.; Liang, L. L.; Cong, H.; Xiao, X.; Zhang, Y. Q.; Xue, S. F.; Zhu, Q. J.; Tao, Z. CrystEngComm 2012, 14, 3862. (e) Chen, K.; Feng, X.; Liang, L. L.; Zhang, Y. Q.; Zhu, Q. J.; Xue, S. F.; Tao, Z. Crystal Growth Des. 2011, 11, 5712. (f) Chen, K.; Liang, L. L.; Liu, H. J.; Tao, Z.; Xue, S. F.; Zhang, Y. Q.; Zhu, Q. J. CrystEngComm 2012, 14, 8049. (g) Chen, K.; Liang, L. L.; Liu, H. J.; Zhang, Y. Q.; Xue, S. F.; Tao, Z.; Xiao, X.; Zhu, Q. J.; Lindoy, L. F.; Wei, G. CrystEngComm 2012, 14, 7994. (18) (a) SAINT and SADABS; Bruker AXS Inc.: Madison, WI, 2005. (b) Sheldrick, G. M. SHELXTL Program Package, version 5.1; Bruker AXS, Inc.: Madison, WI, 1998. (c) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112. (19) Long, L. S.; Wu, Y. R.; Huang, R. B.; Zheng, L. S. Inorg. Chem. 2004, 43, 3798. (20) Gregory, J. K.; Clary, D. C. J. Phys. Chem. 1996, 100, 18014. (21) (a) Xantheas, S. S. J. Chem. Phys. 1994, 100, 7523. (b) Xantheas, S. S. J. Chem. Phys. 1995, 102, 4505. (22) Cruzan, J. D.; Braly, L. B.; Liu, K.; Brown, M. G.; Loeser, J. G.; Saykally, R. J. Science 1996, 271, 59.

2513


A DihalideâDecahydrate Cluster of - American Chemical Society

Recommend Documents

A DihalideâDecahydrate Cluster of - American Chemical Society