New Organically Templated Gallium and Indium ... - ACS Publications

New Organically Templated Gallium and Indium Selenites or Selenates with One-, Two-, and Three-Dimensional Structures Mei-Ling

Feng,†,‡

Xiu-Ling

Li,†

and Jiang-Gao

Mao*,†

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, People’s Republic of China, and Graduate School of the Chinese Academy of Sciences, Beijing, 100039, People’s Republic of China

CRYSTAL GROWTH & DESIGN 2007 VOL. 7, NO. 4 770-777

ReceiVed NoVember 21, 2006; ReVised Manuscript ReceiVed December 25, 2006

ABSTRACT: The first organically templated gallium and indium selenites or selenates have been synthesized by hydro/solvothermal methods and structurally characterized. The structure of [H2DABCO][Ga2F6(SeO3)] (1) (DABCO ) triethylenediamine) features a one-dimensional (1D) [Ga2F6(SeO3)]2- chain built from Ga3F3 trinuclear units each capped by a selenite group. The isostructural compounds [H2en][MF3(SeO3)] (en ) ethylenediamine; M ) Ga (2), In(3)) contain two-dimensional (2D) inorganic layers of [MF3(SeO3)]2- anions (M ) Ga, In). The structure of [H2pip][GaF(SeO3)(C2O4)]‚H2O (4) (pip ) piperazine) features a 1D inorganicorganic hybrid chain of [GaF(SeO3)(C2O4)]2- anions in which the oxalate anion is bidentate chelating and the selenite anion is tridentate bridging. The structure of [H2DABCO]2[Ga4F2(SeO3)6(C2O4)]‚4H2O (5) exhibits a three-dimensional (3D) pillared layered architecture in which the fluorinated gallium selenite layers are further interconnected by bridging oxalate anions (the pillar). [H2en][InF3(SeO4)] (6) features a 1D inorganic chain of [InF3(SeO4)]2- anions. The structure of the indium oxalate-selenate, [H2en]0.5[In(SeO4)(C2O4)(H2O)2] (7), contains a 1D [In(SeO4)(C2O4)(H2O)2]2- anionic chain. The template cations in all compounds are located at structural voids and are involved in hydrogen bonding (except in compound 4). Compounds 6 and 7 exhibit broad emission bands at 421 and 434 nm, respectively. Introduction Inorganic open-frameworks templated by organic amines exhibit diversity and novelty in their structures.1 The main interest in this class of compounds stems from their potential applications in the areas of catalysis, sorption, ad separation processes.1-3 A remarkable variety of organically templated inorganic open-frameworks have been reported during the last two decades.1 Generally, the inorganic skeleton of these materials is composed of a metal cation and an oxo-anion. Most of such works have been focused on the phosphate anion.1,4 In addition, open-frameworks of metal arsenates,5-7 germinates,8,9 and carbonates10 are also known. Recently, this research field has been extended to the oxo-anions of group 16 elements such as metal sulfates.11 The stereochemically active lone pair electrons of SeIV and TeIV ions have a dramatic effect on their coordination geometry as well as on the structures of their metal compounds. It has been reported that the asymmetric coordination geometry adopted by SeIV or TeIV atoms may aid in the crystallization of metal selenites in noncentrosymmetric space groups which may subsequently possess interesting physical properties such as second harmonic generation (SHG).12 As for metal selenites, organically templated transition metal selenites with various structural types have been reported.13-16 Threedimensional (3D) open-framework transition metal selenites containing both hydrogenselenite and diselenite anions were reported by Rao et al.17 A series of organically templated or organically bonded copper selenites have been reported by our group recently.18 Both organically templated and organically linked vanadium selenites have also been synthesized and structurally characterized,19,20 and a number of organically templated or bonded MoVI selenites based on polyoxomolybdate cluster units have been isolated in which the SeO3 group acts * To whom correspondence should be addressed. E-mail: mjg@ ms.fjirsm.ac.cn. † State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. ‡ Graduate School of the Chinese Academy of Sciences.

as a capping group on a MoVI cluster.21 As for the metal selenates, it is difficult to stabilize a metal selenate framework under the hydrothermal conditions especially in presence of the reducing amine templates, due to the low potential of the SeO42-/SeO32- couple (0.03 V in alkaline medium). To the best of our knowledge, the organically templated one-dimensional (1D) cadmiumII and layered or 3D lanthanideIII selenates were isolated by Rao et al.22 The organically templated lithium23 and zinc selenates24 have also been reported recently. Several organically templated uranyl selenates were obtained by Krivovichev’s group .25 The group 13 elements such as Al play an important role in molecular sieve materials.26 Many aluminophosphates have been reported, and their frameworks exhibit fascinating structural architectures: JDF-20 has the largest channel ring size of 20 among open-framework AlPOs,27 and AlPO-CJB1 is the first aluminophosphate molecular sieve with Bro¨nsted acidity.28 Although organically templated gallium and indium phosphates have been extensively studied,4 no organically templated selenites or selenates of group 13 elements (Al, Ga, In, etc.) have been prepared and structurally characterized. So far, only a few simple inorganic compounds such as Ga2(SeO3)3‚6H2O, In2(SeO3)3‚ 6H2O, Ga2(Se2O5)3, and In2(Se2O5)3 have been reported.29 We therefore started a program to explore the organically templated metal selenites or selenates of the group 13 elements. We deem that the organically templated gallium and indium selenites or selenates may provide new types of molecular sieves materials. Moreover, the introduction of the rigid linker-oxalates as a second ligand into the metal selenites or selenates may give rise to new inorganic-organic hybrid materials with a 2D or 3D open-framework structure. By using organic amines as templates and HF as a mineralizer and applying the hydro/ solvothermal synthetic technique, we synthesized seven organically templated gallium and indium selenites or selenates. These compounds crystallize in architectures ranging from 1D chains to 3D networks. Herein we report their syntheses, crystal structures, and luminescence properties.

10.1021/cg060824d CCC: $37.00 © 2007 American Chemical Society Published on Web 02/22/2007

Organically Templated Ga and In Selenites or Selenates

Experimental Section Materials and Methods. Ga2O3 (99.99%, Shanghai Chemical Reagent Co.), In2O3 (99.99%, Shanghai Chemical Reagent Co.), Ga(NO3)3‚4H2O (99%+, Shanghai Chemical Reagent Co.), In(NO3)3‚4H2O (99%+, Shanghai Chemical Reagent Co.), Na2C2O4 (99.8%, Shanghai Chemical Reagent Co.), HF (40% aqueous soln., Shanghai Chemical Reagent Co.), SeO2 (99.8%, ACROS), H2SeO4 (40% aqueous soln., Aldrich), triethylenediamine (97%, ACROS), piperazine (99%, ACROS), ethylenediamine (99%, Shanghai Chemical Reagent Co.), ethylene glycol (AR, Shanghai Chemical Reagent Co.), ethanol (AR, Shanghai Chemical Reagent Co.), and methanol (AR, Shanghai Chemical Reagent Co.) were used as received. The elemental analyses for Ga, In, and Se were carried out with an ICPQ-100 spectrometer, whereas C, H, N, and F analyses were performed on a German Elementary Vario EL III instrument. IR spectra were recorded on a Magna 750 FT-IR spectrometer photometer as KBr pellets in the range of 4000-400 cm-1. Thermogravimetric analyses were carried out with a NETZSCH STA 449C unit at a heating rate of 10 °C/ min under a nitrogen atmosphere. The XRD powder patterns were collected on a Philips X’Pert-MPD diffractometer using graphite-monochromated Cu-KR radiation in the angular range 2θ ) 5-70° with a step size of 0.02° and a counting time of 3 s per step. Photoluminescence analyses were performed on a Perkin Elemer LS55 fluorescence spectrometer. SHG measurements were performed on a homemade instrument using a Nd:YAG laser as the light source. Preparation of [H2DABCO][Ga2F6(SeO3)] (1), [H2en][GaF3(SeO3)] (2), and [H2en][InF3(SeO3)] (3). A mixture of Ga2O3 (0.0421 g, 0.22 mmol), SeO2 (0.2228 g, 2.01 mmol), triethylenediamine (0.2233 g, 2.00 mmol), 40% HF solution (0.32 mL, 6.40 mmol (Caution: toxic and highly irritating; work in a laboratory hood when handling concentrated HF) for 1 (or Ga2O3 (0.0476 g, 0.25 mmol), SeO2 (0.2730 g, 2.46 mmol), ethylenediamine (0.12 mL, 1.80 mmol), 40% HF solution (0.32 mL, 6.40 mmol) for 2 and In2O3 (0.0425 g, 0.15 mmol), SeO2 (0.2210 g, 2.00 mmol), ethylenediamine (0.12 mL, 1.80 mmol), 40% HF solution (0.32 mL, 6.40 mmol) for 3 in a mixed solvent composed of ethanol (5.0 mL) and H2O (2.0 mL) were stirred under ambient conditions until homogeneous. The resulting mixture was sealed into an autoclave equipped with a Teflon liner (25 mL) and heated at 100 °C for 5 days. The initial and final pH values of the solution did not show appreciable change and are close to 4.0 for 1 and 2, ∼3.5 for 3, respectively. Colorless plate-shaped crystals of 1-3 were collected in ca. 26, 45, and 38% yield, respectively (based on Ga or In). Elemental analysis for 1 (C6H14F6Ga2N2O3Se): Ga 28.10, Se 15.86, C 14.41, H 3.13, N 5.39, F 23.50%. Calc.: Ga 28.19, Se 15.97, C 14.57, H 2.85, N 5.66, F 23.05%. IR (KBr, cm-1): 3419 m, 3109 s, 3053 s, 2885 m, 2702 w, 1624 w, 1483 m, 1468 m, 1446 m, 1336 m, 1320 w, 1297 w, 1252 w, 1176 w, 1062 s, 871 s, 783 s, 527 m, 507 s, 468 w, 419 s. Elemental analysis for 2 (C2H10F3GaN2O3Se): Ga 22.11, Se 25.06, C 7.30, H 3.30, N 8.57, F 18.32%. Calc.: Ga 22.08, Se 25.00, C 7.61, H 3.19, N 8.87, F 18.05%. IR (KBr, cm-1): 3849 w, 3734 w, 3419 s, 3132 s, 2975 m, 2921 w, 2319 w, 1635 m, 1526 w, 1270 w, 1089 m, 1048 s, 880 m, 718 m, 566 m, 472 m. Elemental analysis for 3 (C2H10F3InN2O3Se): In 31.72, Se 21.76, C 6.24, H 3.02, N 7.54, F 15.61%. Calc.: In 31.82, Se 21.88, C 6.66, H 2.79, N 7.76, F 15.79%. IR (KBr, cm-1): 3424 w, 3126 s, 2106 w, 1650 m, 1559 m, 1519 m, 1473 w, 1350 w, 1117 m, 1072 m, 1015 w, 955 w, 832 w, 739 s, 712 s, 536 s, 438 s. Preparation of [H2pip][GaF(SeO3)(C2O4)]‚H2O (4). Compound 4 was synthesized by heating a mixture of Ga(NO3)3‚4H2O (0.1344 g, 0.41 mmol), SeO2 (0.2703 g, 2.41 mmol), Na2C2O4 (0.0438 g, 0.33 mmol), piperazine (0.1085 g, 1.26 mmol), 40% HF solution (0.08 mL, 1.60 mmol), and H2O (2 mL) at 100 °C for 5 days. The initial and final pH values were ∼3.0. Colorless prism-shaped crystals of 4 were collected in ca. 68% yield (based on C2O42-). Elemental analysis C6H14FGaN2O8Se: Ga 17.05, Se 19.27, C 17.17, H 3.52, N 6.80, F 4.36%. Calc.: Ga 17.01, Se 19.26, C 17.58, H 3.44, N 6.83, F 4.64%. IR (KBr, cm-1): 3365 s, 3010 s, 2984 w, 2824 w, 2536 m, 1678 s, 1581 m, 1432 s, 1393 w, 1284 s, 1227 w, 1088 s, 1055 m, 1009 s, 992 w, 943 w, 874 w, 836 w, 794 s, 760 s, 653 w, 588 m, 558 w, 518 m, 479 s, 459 s. Preparation of [H2DABCO]2[Ga4F2(SeO3)6(C2O4)]‚4H2O (5). Compound 5 was synthesized by heating a mixture of Ga(NO3)3‚4H2O (0.1317 g, 0.40 mmol), SeO2 (0.3331 g, 3.00 mmol), 40% HF solution (0.08 mL, 1.60 mmol), triethylenediamine (0.2253 g, 2.01 mmol),

Crystal Growth & Design, Vol. 7, No. 4, 2007 771 ethylene glycol (2 mL) and H2O (2 mL) at 100 °C for 5 days. The initial and final pH values were ∼4.0. Colorless brick-shaped crystals of 5 were collected in ca. 51% yield (based on Ga). The ethylene glycol was oxidized to oxalic acid under hydro/solvothermal conditions, probably by the oxidizing nitrate anion. Direct use of Na2C2O4 and H2C2O4 as the source of the oxalate anion resulted in only unknown powders. Elemental analysis for C14H36F2Ga4N4O26Se6: Ga 19.02, Se 32.21, C 11.38, H 2.85, N 3.72, F 2.85%. Calc.: Ga 19.01, Se 32.29, C 11.46, H 2.47, N 3.82, F 2.59%. IR (KBr, cm-1): 3627 m, 3374 s, 3039 m, 1672 s, 1596 m, 1500 w, 1479 s, 1396 w, 1360 m, 1340 w, 1249 w, 1060 s, 987 w, 850 w, 818 m, 785 m, 722 s, 552 s, 498 m, 475 m, 408 w. Preparation of [H2en][InF3(SeO4)] (6). Compound 6 was synthesized by a hydrothermal reaction of a mixture composed of In2O3 (0.0483 g, 0.17 mmol), 40% H2SeO4 solution (0.48 mL, 1.86 mmol), ethylenediamine (0.12 mL, 1.80 mmol), 40% HF solution (0.32 mL, 6.40 mmol), methanol (5 mL), and H2O (2 mL) at 100 °C for 5 days. The initial and final pH values were ∼4.0. Colorless prism-shaped crystals of 6 were collected in ca. 46% yield (based on In). Elemental analysis for C2H10F3InN2O4Se: In 30.41, Se 20.92, C 6.28, H 2.96, N 7.55, F 15.49%. Calc.: In 30.47, Se 20.95, C 6.37, H 2.67, N 7.43, F 15.12%. IR (KBr, cm-1): 3081 m, 2459 w, 2026 w, 1629 m, 1604 s, 1527 s, 1473 w, 1338 m, 1089 m, 1046 m, 1013 w, 951 s, 911 w, 864 s, 786 s, 605 w, 505 s. Preparation of [H2en]0.5[In(SeO4)(C2O4)(H2O)2] (7). Compound 7 was synthesized by heating a mixture of In(NO3)3‚4H2O (0.1458 g, 0.39 mmol), 40% H2SeO4 solution (0.24 mL, 0.93 mmol), Na2C2O4 (0.0352 g, 0.26 mmol), ethylenediamine (0.06 mL, 0.90 mmol), and H2O (2 mL) at 100 °C for 5 days. The initial and final pH values are about 3.0. Colorless needle-shaped crystals of 7 were collected in ca. 53% yield (based on C2O42-). Elemental analysis for C3H9InNO10Se: In 27.80, Se 19.13, C 8.86, H 2.56, N 3.53%. Calc.: In 27.81, Se 19.12, C 8.73, H 2.20, N 3.39%. IR (KBr, cm-1): 3451 m, 3106 m, 2027 w, 1642 s, 1575 w, 1514 w, 1469 w, 1367 m, 1323 m, 1085 w, 1046 w, 896 s, 832 m, 811 m, 781 w, 745 w, 544 w, 490 s, 444 m. X-ray Crystallography. Data collections for compounds 1-7 were performed on either Siemens Smart CCD or Rigaku Mercury CCD diffractometer equipped with graphite-monochromated Mo KR radiation (λ ) 0.71073 Å). Intensity data were collected by the narrow frame method at 293 K and corrected for Lorentz and polarization effects as well as for absorption by the SADABS program.30 All structures were solved by direct methods and refined by full-matrix least-squares cycles in SHELX-97.30 All non-hydrogen atoms were refined with anisotropic thermal parameters. Hydrogen atoms attached to C and N atoms were located at geometrically calculated positions and refined with isotropic thermal parameters. The hydrogen positions for water molecules in compounds 4, 5, and 7 were not included in the refinements. Crystallographic data and structural refinement parameters for the seven compounds are summarized in ref 31. Important bond distances are listed in Table 1. More details on the crystallographic studies as well as atom displacement parameters are given in Supporting Information.

Results and Discussion Hydro/solvothermal synthesis is an effective method for the preparation of organically templated metal selenites or selenates. Methanol, ethanol, and ethylene glycol are typically employed as solvents due to the considerable solubility of the starting metal salt, inorganic acid, and organic template in these solvents.32 In the preparation of compound 5, the ethylene glycol was oxidized to oxalic acid under hydro/solvothermal conditions. The use of 1,2-propylene glycol instead of the ethylene glycol gave the same result. Efforts to carry out the same reactions with GaCl3‚4H2O in place of Ga(NO3)3‚4H2O were tried but failed. Hence the nitrate anion probably acts as the oxidizing agent for the oxidation of ethylene glycol or 1,2-propylene glycol to oxalic acid. A similar phenomenon was observed in the oxidation of ethanol and oxidative coupling of methanol to oxalic acid under hydro/solvothermal conditions.33 The use of Na2C2O4 and H2C2O4 as the source of the oxalate anion for the preparations of 5 resulted in only unknown powders. In addition, during the preparation of compounds 1-6 the fluorine anion

772 Crystal Growth & Design, Vol. 7, No. 4, 2007

Feng et al.

Table 1. Selected Bond Lengths (Å) for Compounds 1-7a Ga(1)-F(3)#1 Ga(1)-O(2)#2 Ga(1)-F(6)#2 Ga(2)-F(2) Ga(2)-F(4) Ga(2)-O(1)#2 Hydrogen bonds: N(1)‚‚‚F(4)#1 N(2)‚‚‚F(1)#3 Ga(1)-F(1) Ga(1)-F(2) Ga(1)-O(1)#1 Hydrogen bonds: N(1)‚‚‚F(2)#4 N(2)‚‚‚F(1) N(2)‚‚‚F(2)#6 In(1)-F(1) In(1)-F(3) In(1)-O(1)#2 Hydrogen bonds: N(1)‚‚‚F(3) N(2)‚‚‚F(1)#4

[H2DABCO][Ga2F6(SeO3)] (1) 1.898(5) Ga(1)-O(3) 1.919(5) Ga(1)-F(5) 1.956(5) Ga(1)-F(6) 1.828(5) Ga(2)-F(1) 1.906(5) Ga(2)-F(3) 1.944(5) Ga(2)-F(5) 2.767(9) 2.840(9)

N(2)‚‚‚F(4)#3

2.829(9)

[H2en][GaF3(SeO3)] (2) 1.879(2) Ga(1)-F(3) 1.906(2) Ga(1)-O(3) 1.975(3) Ga(1)-O(2)#2

1.896(2) 1.966(3) 1.983(3)

2.664(4) 2.658(4) 2.662(4)

N(1)‚‚‚F(3)#5 N(2)‚‚‚F(3)#7

2.708(4) 2.727(4)

[H2en][InF3(SeO3)] (3) 2.050(2) In(1)-F(2) 2.090(2) In(1)-O(2)#1 2.136(2) In(1)-O(3)

2.081(2) 2.132(2) 2.161(2)

2.679(3) 2.653(3)

N(1)‚‚‚F(2)#3

[H2pip][GaF(SeO3)(C2O4)]‚H2O (4) Ga(1)-F(1) 1.868(3) Ga(1)-O(7) Ga(1)-O(6) 1.978(4) Ga(1)-O(5) Ga(1)-O(4)#1 1.998(4) Ga(1)-O(3)#2 Hydrogen bonds: O(1W)‚‚‚O(2) 2.731(6) [H2DABCO]2[Ga4F2(SeO3)6(C2O4)]‚4H2O (5) Ga(1)-O(6) 1.924(3) Ga(1)-O(3) Ga(1)-O(1)#1 1.977(3) Ga(1)-O(7) Ga(1)-O(11)#2 2.017(3) Ga(1)-O(10) Ga(2)-F(1) 1.855(2) Ga(2)-O(8) Ga(2)-O(9)#3 1.983(3) Ga(2)-O(5) Ga(2)-O(4)#4 2.023(3) Ga(2)-O(2) Hydrogen bonds: N(2)‚‚‚O(2W)#7 2.779(6) O(2W)‚‚‚F(1) In(1)-F(1) In(1)-F(2) In(1)-O(1)#1 Hydrogen bonds: N(1)‚‚‚F(1)#2 N(2)‚‚‚F(3)#1 N(2)‚‚‚O(2)#6

1.912(5) 1.941(4) 1.963(5) 1.844(5) 1.942(4) 1.974(4)

[H2en][InF3(SeO4)] (6) 2.017(2) In(1)-F(3) 2.086(2) In(1)-O(4) 2.137(3) 2.746(5) 2.757(5) 2.860(6)

2.725(4)

1.937(4) 1.997(4) 2.012(4)

1.938(3) 2.005(3) 2.117(3) 1.962(3) 2.011(3) 2.046(3) 2.688(5)

2.057(2) 2.131(3) In(1)-O(3)#2

N(1)‚‚‚F(2)#5 N(2)‚‚‚F(2)#6 N(2)‚‚‚F(2)#7

[H2en]0.5[In(SeO4)(C2O4)(H2O)2] (7) In(1)-O(6) 2.122(3) In(1)-O(2W) In(1)-O(1W) 2.196(3) In(1)-O(2)#1 In(1)-O(8) 2.225(3) In(1)-O(7) In(1)-O(1)#1 2.306(3) Hydrogen bonds: O(1W)‚‚‚O(3)#2 2.729(5) O(1W)‚‚‚O(4)#3 O(2W)‚‚‚O(4)#6 2.730(6) O(2W)‚‚‚O(5)#5 N(1)‚‚‚O(3)#8 2.867(5)

2.841(5) 2.833(5) 2.865(5) 2.143(3) 2.214(3) 2.252(3) 2.823(5) 2.640(6)

a Symmetry transformations used to generate equivalent atoms: For 1: #1 -x + 1, y - 1/2, -z + 1/2. #2 -x + 1, y + 1/2, -z + 1/2. #3 -x + 1, -y + 2, -z + 1. For 2: #1 -x + 1, y - 1/2, -z + 1/2. #2 -x + 1, -y, -z + 1. #3 -x + 1, y + 1/2, -z + 1/2. #4 x, y + 1, z. #5 x, -y + 1/2, z + 1/2. #6 x, -y - 1/2, z + 1/2. #7 -x, -y, -z + 1. For 3: #1 -x + 2, -y, -z + 1. #2 x, -y + 1/2, z + 1/2. #3 x, -y + 1/2, z - 1/2. #4 x, y + 1, z. For 4: #1 -x, -y - 2, -z + 3. #2 -x + 1, -y - 2, -z + 3. For 5: #1 -x, -y + 1, -z. #2 -x, -y + 2, -z. #3 -x, -y + 1, -z + 1. #4 -x - 1, -y + 1, -z + 1. #5 x, y - 1, z. #6 x - 1, y + 1, z. #7 x, y + 1, z. For 6: #1 x - 1, y, z. #2 x - 1/2, -y + 3/2, -z + 2. #3 x + 1, y, z. #4 x + 1/2, -y + 3/2, -z + 2. #5 -x, y + 1/2, -z + 3/2. #6 -x - 1/2, -y + 1, z - 1/2. #7 -x - 1, y + 1/2, -z + 3/2. For 7: #1 x - 1/2, -y + 3/2, z - 1/2. #2 -x + 1/2, y + 1/2, -z + 3/2. #3 -x + 1, -y + 2, -z + 2. #4 x + 1/2, -y + 3/2, z + 1/2. #5 x - 1/2, -y + 3/2, z + 1/2. #6 x - 1, y, z. #7 -x, -y + 1, -z + 2. #8 -x + 1, -y + 1, -z + 2.

Figure 1. (a) ORTEP drawing of the selected unit of 1. Thermal ellipsoids are drawn at 50% probability. Hydrogen atoms have been omitted for clarity. Symmetry codes for generated atoms: (A) -x + 1, y - 1/2, -z + 1/2; (B) -x + 1, y + 1/2, -z + 1/2. (b) A 1D anionic chain in 1. (c) A hydrogen-bonded layer in compound 1. The gallium octahedra are shaded in cyan; Se, O, F, C, and N are drawn as pink, red, yellow, dark gray and deep blue circles, respectively. Hydrogen bonds are drawn as dotted lines.

act as both a mineralizer and a coordination anion in the inorganic framework.34-38 Compounds 1-7 represent the first organically templated GaIII or InIII selenites or selenates. Their structures range from 1D chains to 3D open-frameworks. The structure of compound 1 features a 1D [Ga2F6(SeO3)]2anionic chain. Its asymmetric unit consists of 20 non-hydrogen atoms, 12 of which belong to the inorganic framework (two Ga atoms, six F atoms, one Se atom and three O atoms) and eight of which belong to the template cation (six C atoms and two N atoms) (Figure 1a). Both GaIII ions are octahedrally coordinated, but their coordination environments are different. Ga(1) is six-coordinated by four bridging fluorine anions and two SeO32- groups in a unidentate fashion, whereas Ga(2) is six-coordinated by three terminal fluorine anions, two bridging fluorine anions, and a SeO32- anion in a monodentate fashion. The Ga-O distances range from 1.912(5) to 1.944(5) Å and

Organically Templated Ga and In Selenites or Selenates

the Ga-F bond lengths vary from 1.828(5) to 1.974(4) Å (Table 1), which are comparable to the reported gallium fluorophosphates.4 The selenium atom is in a ψ-SeO3 tetrahedral coordination geometry with the fourth coordination site occupied by the lone pair electrons. Each selenite group is tridentate and bridges to two Ga(1) atoms and one Ga(2) atom. The interconnection of Ga(1)F4O2 and Ga(2)F5O octahedra by bridging SeO3 anions and fluorine anions resulted in a 1D [Ga2F6(SeO3)]2- anionic chain along the b-axis (Figure 1b). Such a 1D inorganic chain can also be viewed as built from Ga3 trinuclear clusters each capped by a selenite group. Neighboring such trinuclear clusters are interconnected along b-axis by sharing GaIII ions. The two negative charges of the [Ga2F6(SeO3)]2- anion are balanced by a doubly protonated triethylenediamine cation. The H2DABCO cations are located at the interchain spaces and form hydrogen bonds with three fluorine atoms from different chains (Table 1). These hydrogen bonds result in a 2D layer motif (Figure 1c). Adjacent 2D layers are further held together via a weak van der Waals force. The use of ethylenediamine as a template instead of triethylenediamine in the preparation of 1 led to the formation of a new fluorinated gallium selenite, [H2en][GaF3(SeO3)] (2), whose structure contains a layered inorganic skeleton. Its indium analogue (compound 3) is isostructural with that of compound 2; hence, only the structure of the GaIII compound will be discussed in detail as an example. The asymmetric unit of 2 consists of 12 independent non-hydrogen atoms, eight of which belong to the inorganic framework (one Ga atom, three F atoms, one Se atom, and three O atoms), and four of which are from the template cation (two N atoms and two C atoms) (Figure 2a). The GaIII ion is octahedrally coordinated by three terminal fluorine anions and three O atoms from three selenite anions. The Ga-O distances from 1.966(3) to 1.983(3) Å are significantly longer than the Ga-F bonds [1.879(2)-1.906(2) Å] (Table 1). Similar to that in compound 1, the selenite anion in compound 2 is tridentate and bridges three GaIII ions. The interconnection of GaF3O3 octahedra by bridging selenite groups resulted in a 2D [GaF3(SeO3)]2- anionic inorganic layer. Fourmembered Ga2Se2 rings and eight-membered Ga4Se4 rings are found within the 2D layer (Figure 2b). The doubly protonated ethylenediamine cations are located at the interlayer spaces and form hydrogen bonds with five terminal fluorine anions from different layers (Table 1, Figure 2c). The 1D gallium oxalate-selenite, [H2pip][GaF(SeO3)(C2O4)]‚ H2O (4), was isolated by using piperazine as the template molecule and oxalate anion as a second metal linker. The asymmetric unit of 4 contains 19 independent non-hydrogen atoms, 12 of which belong to the anionic framework (one Ga atom, one F atom, one Se atom, two C atoms, and seven O atoms), six of which are for the template cation (two N atoms and four C atoms) and one is for the uncoordinated water molecule (Figure 3a). The GaIII atom is octahedrally coordinated by one terminal fluorine anion, one oxalate anion in a bidentate chelating fashion, and three oxygen atoms from three selenite anions. The Ga-O distances fall in the range of 1.937(4) to 2.012(4) Å, and the Ga-F bond length is 1.868(3) Å (Table 1), which are comparable to those in compounds 1-3. Each selenite anion acts as a tridentate metal linker and bridges three GaIII ions. Each oxalate anion is bidentate chelating and forms one Ga-O-C-C-O five-membered chelating ring. Each pair of GaFO5 octahedra is interconnected via a pair of bridging selenite groups into a 1D [GaF(SeO3)(C2O4)]2- anionic chain along the a-axis, forming Ga2Se2 four-membered rings (Figure 3b). The uncoordinated water molecule forms hydrogen bonds

Crystal Growth & Design, Vol. 7, No. 4, 2007 773

Figure 2. (a) ORTEP representation of the selected unit of 2. Thermal ellipsoids are drawn at 50% probability. Hydrogen atoms have been omitted for clarity. Hydrogen bonds are represented by dotted lines. Symmetry codes for generated atoms: (A) -x + 1, y - 1/2, -z + 1/2; (B) -x + 1, -y, -z + 1; (C) -x + 1, y + 1/2, -z + 1/2. (b) A 2D inorganic anionic layer in 2. (c) View of the structure of 2 down the c-axis. The gallium octahedra are shaded in cyan; Se, O, F, C, and N are drawn as pink, red, yellow, dark gray, and deep blue circles, respectively. Hydrogen bonds are drawn as dotted lines.

774 Crystal Growth & Design, Vol. 7, No. 4, 2007

Figure 3. (a) ORTEP drawing of the selected unit of 4. Thermal ellipsoids are drawn at 50% probability. Hydrogen atoms have been omitted for clarity. Symmetry codes for generated atoms: (A) -x, -y - 2, -z + 3; (B) -x + 1, -y - 2, -z + 3; (C) -x, -y, -z + 2; (D) -x + 1, -y - 1, -z + 1. (b) A 1D anionic chain in 4. (c) View of the structure of 4 down the a-axis. The gallium octahedra are shaded in cyan; Se, O, F, C, and N are drawn as pink, red, yellow, dark gray, and deep blue circles, respectively. Hydrogen bonds are drawn as dotted lines.

with the non-coordination oxalate oxygen O(2) (O(1W)‚‚‚O(2) 2.731(6) Å) (Table 1). The doubly protonated piperazine cations are located at the interchain spaces and are not involved in hydrogen bonding (Figure 3c). [H2DABCO]2[Ga4F2(SeO3)6(C2O4)]‚4H2O (5) features a pillared layered structure. As shown in Figure 4a, the asymmetric unit of 5 consists of 28 independent non-hydrogen atoms, 18 of which belong to the anionic framework (2 Ga atoms, 1 F atom, 3 Se atoms, 1 C atom, and 11 O atoms), 8 of which are

Feng et al.

Figure 4. (a) ORTEP drawing of the selected unit of 5. Thermal ellipsoids are drawn at 50% probability. Hydrogen atoms have been omitted for clarity. Hydrogen bonds are represented by dotted lines. Symmetry codes for generated atoms: (A) -x, -y + 1, -z; (B) -x, -y + 2, -z; (C) -x, -y + 1, -z + 1; (D) -x - 1, -y + 1, -z + 1. (b) A 2D fluorinated gallium selenite layer in compound 5. (c) View of the structure of 5 down the a-axis. The gallium octahedra are shaded in cyan; Se, O, F, C, and N are drawn as pink, red, yellow, dark gray, and deep blue circles, respectively.

for the template cation (2 N atoms and 6 C atoms) and another two for two uncoordinated water molecules. The Ga(1) atom is octahedrally coordinated by four SeO32- anions in a monoden-

Organically Templated Ga and In Selenites or Selenates

tate fashion and one oxalate anion in a bidentate chelating fashion. The Ga(2) ion is octahedrally coordinated by a terminal fluorine anion and five SeO32- anions in a unidentate fashion. The Ga-O distances in the range from 1.924(3) to 2.046(3) Å are significantly longer than the Ga-F bonds (1.855(2) Å) (Table 1). All three selenite anions are tridentate, and each connects three metal centers. The Se(1)O3 group bridges to two Ga(1) atoms and one Ga(2) atom, whereas the other two selenite anions each connects one Ga(1) atom and two Ga(2) atoms. Each oxalate anion is tetradentate and forms two Ga(1)-OC-C-O five-membered chelating rings. The interconnection of Ga(1)O6 and Ga(2)FO5 octahedra by tridentate bridging selenite anions led to a 2D gallium fluorinated selenite layer based on Ga6Se6 12-membered rings. The selenite groups act as three connectors (Figure 4b). The above layers are further cross-linked by oxalate anions into a pillared layered architecture with large tunnels running along the a-axis (Figure 4c). The tunnel is formed by 12-membered rings each composed of six GaIII ions, four selenite anions, and two oxalate anions. The doubly protonated triethylenediamine cations and interstitial uncoordinated water molecules are located at the tunnels. Hydrogen bonds are formed among the template cation, the uncoordinated water molecules, as well as terminal fluorine anions (Table 1). The structure of [H2en][InF3(SeO4)] (6) features a 1D chain of [InF3(SeO4)]2- anions, which is similar to that in [H2en][FeF3(SO4)].32 As shown in Figure 5a, the asymmetric unit of 6 contains 13 independent non-hydrogen atoms, nine of which belong to the inorganic framework (one In atom, three F atoms, one Se atom, and four O atoms) and four for the template cation (two N atoms and two C atoms). The indiumIII ion is octahedrally coordinated by three terminal fluorine anions and three SeO42- anions in a monodentate fashion. The In-O distances ranging from 2.131(3) to 2.158(3) Å are significantly longer than the In-F bonds [2.017(2)-2.086(2) Å] (Table 1). The selenate anion adopts a tridentate bridging coordination mode. The interconnection of the InF3O3 octahedra via tridentate bridging selenate anions results in the formation of a 1D helical chain of [InF3(SeO4)]2- anions along the a-axis. Four-membered In2Se2 rings are present within the 1D chain (Figure 5b). The doubly protonated ethylenediamine cations are located at the interchain spaces; they form hydrogen bonds with non-coordination selenate O(2) as well as five terminal fluorine anions, resulting in the formation of a 3D network (Figure 5c, Table 1). [H2en]0.5[In(SeO4)(C2O4)(H2O)2] (7) represents the first organically templated metal oxalate-selenate. It features a 1D [In(SeO4)(C2O4)(H2O)2]2- anionic chain. The asymmetric unit of 7 consists of 16 independent non-hydrogen atoms, fourteen of which belong to the anionic framework (1 In atom, 1 Se atom, 2 C atoms, 10 O atoms) and remaining two for the template cation (one N atom and one C atom) (Figure 6a). Unlike that in 6, the InIII ion in compound 7 is seven-coordinated by two aqua ligands, one unidentate selenate anion, and two oxalate anions in a bidentate chelating fashion. Its coordination geometry can be described as a slightly distorted pentagonal bipyramid. O(1A), O(2A), O(7), O(8), and O(1W) form a pentagon with a mean deviation of 0.0682 Å, whereas O(6) and O(2W) occupy the two pyramidal vertices [O(6)-In(1)-O(2W) 179.6(2)°]. The In-O distances are in the range of 2.122(3)2.306(3) Å. Unlike that in compound 6, the selenate anion in compound 7 is unidentate. The oxalate anion is tetradentate and forms two In-O-C-C-O five-membered chelating rings. The interconnection of the InO7 pentagonal bipyramids via chelating

Crystal Growth & Design, Vol. 7, No. 4, 2007 775

Figure 5. (a) ORTEP drawing of the selected unit of 6. Thermal ellipsoids are drawn at 50% probability. Hydrogen atoms have been omitted for clarity. Symmetry codes for generated atoms: (A) x - 1, y, z; (B) x - 1/2, -y + 3/2, -z + 2; (C) x + 1/2, -y + 3/2, -z + 2; (D) x + 1, y, z. (b) A helical indium selenate chain in 6. (c) View of the structure of 6 down the b-axis. The indium octahedra and selenate tetrahedra are shaded in green and pink, respectively; O, F, C, and N are drawn as red, yellow, dark gray, and deep blue circles, respectively. Hydrogen bonds are drawn as dotted lines.

and bridging oxalate anions led to the formation of a 1D chain of [In(SeO4)(C2O4)(H2O)2]2- anions with the selenate anion acting as a pendent group (Figure 6b). These anionic chains are further interlinked via hydrogen bonds among the noncoordination selenate oxygens, aqua ligands, and the doubly protonated ethylenediamine cations into a 3D network (Figure 6c, Table 1). The experimental X-ray diffraction powder patterns for compounds 1-7 match well with those simulated from singlecrystal structure data, indicating that all seven compounds were isolated as single phases. Thermogravimetric curves for compounds 1-7 are shown in Figure 7. Compounds 1-3 are stable up to 245, 229, and 236 °C, respectively. Then they display two main steps of weight losses. The first step corresponds to the release of the amines, and the second one can be attributed to the removal of the fluorine and SeO2. The total weight losses are 61.0, 58.2, and 52.5%, respectively, for compounds 1, 2, and 3. The final residues are not identified, but they are expected to be mainly gallium or indium oxide. For compounds 4 and 5, the first weight loss corresponds to the release of the lattice water molecules before 255 °C (for 4) or before 130 °C (for 5). The observed weight losses of 4.3 and 4.2% are close to the

776 Crystal Growth & Design, Vol. 7, No. 4, 2007

Feng et al.

Figure 7. TGA curves for compounds 1-7.

Figure 6. (a) ORTEP drawing of the selected unit of 7. Thermal ellipsoids are drawn at 50% probability. Hydrogen atoms have been omitted for clarity. Symmetry codes for generated atoms: (A) x - 1/2, -y + 3/2, z - 1/2; (B) x + 1/2, -y + 3/2, z + 1/2; (C) -x, -y + 1, -z + 2. (b) A 1D anionic chain in 7. (c) View of the structure of 7 down the a-axis. The indium pentagonal bipyramids and selenate tetrahedra are shaded in green and pink, respectively; O, C, and N are drawn as red, dark gray, and deep blue circles, respectively. Hydrogen bonds are drawn as dotted lines.

calculated values (4.4 and 4.9%). The relatively higher temperature for the loss of water in compound 4 is probably due to its strong hydrogen bond with the non-coordination oxalate oxygen. The amine, the fluorine, and the oxalate are removed progressively in the 255-500 °C range for 4 and 286-314 °C for 5 (For 4: obs ) 47.2%, calc ) 47.6%; For 5: obs ) 24.8%, calc ) 24.7%). Finally, compounds 4 and 5 decompose continuously up to 1000 °C, which corresponds to the partial liberation of SeO2. The total weight losses at 1000 °C are 57.4% and 70.8%, respectively, for compounds 4 and 5. Their final residues were not characterized. Compounds 6 and 7 are stable up to 187 and 163 °C, respectively. Then it showed the gradual weight losses in the 187-1000 °C range for 6 and 163-1000 °C for 7 corresponding to the release of two aqua ligands (for 7), the ethylenediamine cations (for 6, 7), the fluorine (for 6), the

oxalate (for 7), and the decomposition of the selenate anions (for 6, 7) (For 6: total ) 64.0%; For 7: total ) 63.3%). The final residues were not characterized. The thermal decomposition mechanism of the metal selenate is very complicated, the selenate anion was reported to decompose into SeO2 and O2, and the final residues may be a mixture of metal oxide and metal selenide.22a The solid-state luminescent spectra of compounds 6 and 7 were investigated at room temperature (Figure S1, Supporting Information). Na2C2O4 exhibits a broad luminescent band centered at 416 nm (λex ) 345 nm), and H2SeO4 (0.03 mmol/ mL) displays a broad luminescent band centered at 395 nm (λex ) 305 nm). Compound 6 displays an emission band at λmax ) 421 nm under 354 nm excitation, whereas compound 7 exhibits a strong luminescent emission band at λmax ) 434 nm under 370 nm excitation. Both emission bands of 6 and 7 can be attributed to the intra-ligand luminescence.39 Both emission bands of 6 and 7 are red-shifted and stronger in intensity compared with those of pure ligands, which may be due to their coordination with the InIII ions, which resulted in much more rigidity of the ligands.39 Compound 6 crystallized in a noncentrosymmetric space group (P212121); hence, it may possess second nonlinear optical properties. However, results of powder SHG measurements using a Nd:YAG laser indicate the signal is very weak. Conclusion In summary, seven organically templated gallium and indium selenites or selenates have been synthesized by hydro/solvothermal methods, and their structures range from a 1D chain, a 2D layer, to a 3D pillared layered structure. In compounds 4, 5 and 7, both oxalate anion and selenite (or selenate) groups are bonded to the metal ion to form an inorganic-organic hybrid skeleton. In compounds 1-6, the F- anions are embedded into the inorganic frameworks; hence, HF can act as a mineralizer to help crystallization as well as a coordination atom. It is anticipated that many new organically templated post main group metal selenites or selenates can be synthesized by using a similar technique. Acknowledgment. We thank the Nation Nature Science Foundation of China (Nos. 20573113, 20371047 and 20521101) and NSF of Fujian Province (No. E0420003) for the financial support. Supporting Information Available: X-ray crystallographic files for compounds 1-7 in CIF format; simulated and experimental XRD

Organically Templated Ga and In Selenites or Selenates powder patterns for compounds 1-7. This material is available free of charge via the Internet at http://pubs.acs.org.

References (1) Cheetham, A. K.; Fe´rey, G.; Loiseau, T. Angew. Chem. Int. Ed. 1999, 38, 3268. (2) Moore, P. B., in Crystallochemical Aspects of the Phosphate Minerals; Niagru, J., Moore, P. B., Eds.; Springer-Verlag: Berlin, 1984. (3) (a) Feng, S. H.; Xu, R. R. Acc. Chem. Res. 2001, 34, 239; (b) Yu, J. H.; Xu, R. R. Acc. Chem. Res. 2003, 36, 481. (4) (a) Rao, C. N. R.; Natarajan, S.; Choudhury, A.; Neeraj, S.; Ayi, A. A. Acc. Chem. Res. 2001, 34, 80; (b) Liao, Y. C.; Lin, C. H.; Wang, S. L. J. Am. Chem. Soc. 2005, 127, 9986; (c) Millange, F.; Walton, R. I.; Guillou, N.; Loiseau, T.; O’Hare, D.; Fe´rey, G. Chem. Commun. 2002, 826; (d) Park, H. S.; Bull, I.; Peng, L. M.; Victer, G. Y. J.; Grey, C. P.; Parise, J. B. Chem. Mater. 2004, 16, 5350. (5) Ekambaram, S.; Sevov, S. C. Inorg. Chem. 2000, 39, 2405. (6) Chakrabarti, S.; Natarajan, S. J. Chem. Soc. Dalton Trans. 2002, 3874. (7) Harrison, W. T. A.; Phillips, M. L. F.; Chavez, A. V.; Nenoff, T. M. J. Mater. Chem. 1999, 12, 3087. (8) Reisner, B. A.; Tripathi, A.; Parise, J. B. J. Mater. Chem. 2001, 11, 887. (9) Bu, X. H.; Feng, P. Y.; Gier, T. E.; Zhao, D.; Stucky, G. D. J. Am. Chem. Soc. 1998, 120, 13389. (10) Harrison, W. T. A.; Phillips, M. L. F.; Nenoff, T. M.; MacLean, E. J.; Teat, S.; J. Maxwell, R. S. J. Chem. Soc, Dalton Trans. 2001, 546. (11) (a) Choudhury, A.; Krishnamoorthy, J.; Rao, C. N. R. Chem. Commun. 2001, 2610; (b) Paul, G.; Choudhury, A.; Rao, C. N. R. J. Chem. Soc. Dalton Trans. 2002, 3589; (c) Paul, G.; Choudhury, A.; Rao, C. N. R. Angew. Chem. Int. Ed. 2002, 41, 4297; (d) Paul, G.; Choudhury, A. and Rao, C. N. R. Chem. Commun. 2002, 1904; (e) Behera, J. N.; Paul, G.; Choudhury, A. and Rao, C. N. R. Chem. Commun. 2004, 456. (12) (a) Ra, H.-S.; Ok, K.-M.; Halasyamani, P. S. J. Am. Chem. Soc. 2003, 125, 7764; (b) Ok, K.-M.; Halasyamani, P. S. Inorg. Chem. 2004, 43, 4248; (c) Ok, K.-M.; Orzechowski, J.; Halasyamani, P. S. Inorg. Chem. 2004, 43, 964; (d) Goodey, J.; Ok, K.-M.; Broussard, J.; Hofmann, C.; Escobedo, F. V.; Halasyamani, P. S. J. Solid State Chem. 2003, 175, 3; (e) Kong, F.; Huang, S.-P.; Mao, J.-G.; Cheng, W.-D.; J. Am. Chem. Soc. 2006, 128, 7750. (13) Harrison, W. T. A.; Phillips, M. L. F.; Stanchfield, J.; Nenoff, T. M. Angew. Chem. Int. Ed. 2000, 39, 3808. (14) Choudhury, A.; Kumar U.; Rao, C. N. R. Angew. Chem., Int. Ed. 2002, 41, 158. (15) Pasha, I.; Choudhury, A.; Rao, C. N. R. Solid State Sci. 2003, 5, 257. (16) Millange, F.; Serre, C.; Cabourdin, T.; Marrot, J.; Ferey, G. Solid State Sci. 2004, 6, 229. (17) Udayakumar, D.; Rao, C. N. R. J. Mater. Chem. 2003, 13, 1635. (18) Feng, M.-L.; Prosvirin, A. V.; Mao, J.-G.; Dunbar, K. R. Chem. Eur. J. 2006, in press. (19) (a) Pasha, I.; Choudhury, A.; Rao, C. N. R. Inorg. Chem. 2003, 42, 409; (b) Nakano, H.; Ozeki, T.; Yagasaki, A. Inorg. Chem. 2001, 40, 1816. (20) (a) Shi, Z.; Zhang, D.; Feng, S.; Li, G.; Dai, Z.; Fu, W.; Chen, X.; Hua, J. J. Chem. Soc. Dalton Trans. 2002, 1873; (b) Dai, Z. M.; Chen, X. B.; Shi, Z.; Zhang, D.; Li, G.; H. Feng, S. H. Inrog. Chem. 2003, 42, 908; (c) Dai, Z. M.; Shi, Z.; Li, G. H.; Zhang, D.; Fu, W. S.; Jin, H. Y.; Xu, W.; Feng, S. H. Inrog. Chem. 2003, 42, 7396; (d) Dai, Z. M.; Shi, Z.; Li, G.; H. Chen, X. B.; Lu, X. Y.; Xu, Y. H.; Feng, S. H. J. Solid State Chem. 2003, 172, 205; (e) Dai, Z. M.; Li, G. H.; Shi, Z.; Fu, W. S.; Dong, W. J;. Xu, J.; Feng, S. H. Solid State Sci. 2004, 6, 91. (21) (a) Kortz, U.; Savelieff, M. G.; Ghali, F. Y. A.; Khalil, L. M.; Maalouf, S. A.; Sinno, D. I. Angew. Chem. Int. Ed. 2002, 41, 4070; (b) Feng, M.-L.; Mao, J.-G. Eur. J. Inorg. Chem. 2004, 3712.

Crystal Growth & Design, Vol. 7, No. 4, 2007 777 (22) (a) Pasha, I.; Choudhury, A.; Rao, C. N. R. J. Solid State Chem. 2003, 174, 386. (b) Behera, J. N.; Ayi, A. A.; Rao, C. N. R. Chem. Commun. 2004, 968. (c) Udayakumar, D.; Dan, M.; Rao, C. N. R. Eur. J. Inorg. Chem. 2004, 1733. (23) Plocek, J.; Havlicek, D.; Nemec, I.; Cisarova, I.; Micka, Z. J. Solid State Chem. 2003, 170, 308. (24) Feng, M.-L.; Mao, J.-G. J. Solid State Chem. 2004, 177, 3529. (25) (a) Krivovichev, S. V.; Kahlenberg, V. J. Am. Chem. Soc. 2005, 127, 1072; (b) Krivovichev, S. V.; Kahlenberg, V. Eur. J. Inorg. Chem. 2005, 1653; (c) Krivovichev, S. V.; Kahlenberg, V. Z. Anorg. Allg. Chem. 2005, 631, 2352. (26) Wilson, S. T.; Lok, B. M.; Messian, C. A.; Cannan, T. R.; Flanigen, E. M. J. Am. Chem. Soc. 1982, 104, 1146. (27) Huo, Q.; Xu, R.; Li, S.; Ma, Z.; Thomas, J. M.; Jones, R. H.; Chippindale, A. M. J. Chem. Soc. Chem. Commun. 1992, 875. (28) Yan, W.; Yu, J.; Xu, R.; Zhu, G.; Xiao, F.; Han, Y.; Sugiyama, K.; Terasaki, O. Chem. Mater. 2000, 12, 2517. (29) (a) Vlaev, L. T.; Nikolova, M. M.; and Gospodinov, G. G. J. Solid State Chem. 2004, 177, 2663; (b) Ok, K.-M.; Halasyamani, P. S. Chem. Mater. 2002, 14, 2360. (30) (a) Sheldrick, G. M. Program SADABS; Universita¨t Go¨ttingen, 1995; (b) CrystalClear version 1.3.5. Rigaku Corp., Woodlands, TX, 1999; (c) Sheldrick, G. M. SHELXTL, Crystallographic Software Package, SHELXTL, Version 5.1; Bruker-AXS: Madison, WI, 1998. (31) Crystal data for 1: C6H14F6Ga2N2O3Se, formula weight 494.59, space group P21/c, a ) 12.6161(16) Å, b ) 7.2700(6) Å, c ) 13.6053(17) Å, β ) 104.746(6)°, V ) 1206.8(2) Å3, Z ) 4, µ ) 7.568 mm-1, R1 (I > 2σ(I)) ) 0.0524, wR2 (I > 2σ(I)) ) 0.1318; for 2: C2H10F3GaN2O3Se, formula weight 315.80, space group P21/c, a ) 9.1107(6) Å, b ) 8.0382(6) Å, c ) 10.8302(9) Å, β ) 90.045(7)°, V ) 793.13(10) Å3, Z ) 4, µ ) 8.085 mm-1, R1 (I > 2σ(I)) ) 0.0350, wR2 (I > 2σ(I)) ) 0.0886; for 3: C2H10F3InN2O3Se, formula weight 360.90, space group P21/c, a ) 9.3066(5) Å, b ) 8.3012(5) Å, c ) 11.2923(7) Å, β ) 92.329(4)°, V ) 871.68(9) Å3, Z ) 4, µ ) 6.911 mm-1, R1 (I > 2σ(I)) ) 0.0239, wR2 (I > 2σ(I)) ) 0.0500; for 4: C6H14FGaN2O8Se, formula weight 409.87, space group P1h, a ) 6.377 Å, b ) 9.2820(2) Å, c ) 11.4112(1) Å, R ) 66.531(11)°, β ) 77.448(13)°, γ ) 71.889(12)°, V ) 585.47(6) Å3, Z ) 2, µ ) 5.513 mm-1, R1 (I > 2σ(I)) ) 0.0410, wR2 (I > 2σ(I)) ) 0.1042; for 5: C14H36F2Ga4N4O26Se6, formula weight 1467.11, space group P1h, a ) 8.99410(10) Å, b ) 9.4963(3) Å, c ) 11.29590(10) Å, R ) 77.128(10)°, β ) 68.073(8)°, γ ) 83.776(12)°, V ) 872.17(3) Å3, Z ) 1, µ ) 9.433 mm-1, R1 (I > 2σ(I)) ) 0.0317, wR2 (I > 2σ(I)) ) 0.0724; for 6: C2H10F3InN2O4Se, formula weight 376.90, space group P212121, a ) 6.8035(15) Å, b ) 9.861(2) Å, c ) 12.956(3) Å, V ) 869.2(3) Å3, Z ) 4, µ ) 6.945 mm-1, R1 (I > 2σ(I)) ) 0.0217, wR2 (I > 2σ(I)) ) 0.0514; for 7: C3H9InNO10Se, formula weight 412.89, space group P21/n, a ) 8.3749(16) Å, b ) 12.118(2) Å, c ) 10.648(3) Å, β ) 110.478(8)°, V ) 1012.3(4) Å3, Z ) 4, µ ) 5.976 mm-1, R1 (I > 2σ(I)) ) 0.0321, wR2 (I > 2σ(I)) ) 0.0696. (32) Paul, G.; Choudury, A.; Rao, C. N. R. Chem. Mater. 2003, 15, 1174. (33) Evans, O. R.; Lin, W. Cryst. Growth Des. 2001, 1, 9. (34) Estermann, M.; McCusker, L. B.; Baerlocher, C.; Merrouche, A.; Kessler, H. Nature 1991, 352, 320. (35) Paillaud, J. L.; Marler, B.; Kessler, H. Chem. Commun. 1996, 1293. (36) Cavellec, M.; Riou, D.; Ninclaus, C.; Greneche, J. M., Fe´rey, G. Zeolites 1996, 17, 250. (37) Riou, D.; Taulelle, F.; Fe´rey, G. Inorg. Chem. 1996, 35, 6392. (38) Kemnitz, E.; Wloka, M.; Trojanov, S.; Stiewe, A. Angew. Chem., Int. Ed. 1996, 35, 2677-2678. (39) Chen, C.; Liu, Y.; Wang, S.; Li, G.; Bi, M.; Yi, Z.; Pang, W. Chem. Mater. 2006, 18, 2950.

CG060824D