- Materials and Methods.
All the reagents were commer-cially available and used as received except for H
(obpdc) which was purified by recrystallization before use. IR data were recorded on KBr pellets using a Varian FTS 1000 instru-ment.
Synthesis of [H2N(CH3)2][Zn3(µ3-OH)Ti(obpdc)3(O3CH)] (1).
Titanium(IV) isopropoxide (29.6 µL, 0.10 mmol) was added to a solution of H
obpdc (77.7 mg, 0.30 mmol) in DMF (3.5 mL) to form an orange colored turbid mixture. After stirring for 30 min zinc nitrate hexahydrate (51.4 mg, 0.17 mmol) and formic acid (3.8 µL, 0.1 mmol) were added to it. The final mixture was well-stirred for 2 h at room temperature and then filtered. The solution was heated in a sealed glass vial with the following steps: 1 day at 75 °C, 2 days at 95-100 °C and 1 day at 120 °C. The product was separated from the orange-colored suspension, thoroughly washed with fresh DMF and soaked in dichloromethane before drying under vacuum at room temperature for 12 h and then at 100 °C for 5 h (42.7 mg, 68％). Calcd: C, 48.4; H, 2.8; N, 1.3; Ti, 4.3％. Found: C, 48.7; H, 2.9; N, 1.2; Ti, 4.1％.
X-ray Powder Diffraction.
X-ray powder diffraction patterns were recorded at the 2D SMC beamline of the Pohang Accelerator Laboratory, Korea. Crystalline samples were thoroughly ground in an agate mortar and packed in a capillary tube (0.3 mm diameter). Debye-Scherrer diffraction data were collected on an ADSC Quantum-210 detector with a fixed wavelength (λ = 1.40000 Å) and an exposure of 60 sec. The ADX program
was used for data collection, and Fit2D program
was used to convert the 2D to 1D patterns.
X-ray Single-crystal Diffraction.
Single-crystals of as-synthesized
were directly picked up from the mother liquor with a cryoloop attached to a goniohead, and trans-ferred to a cold stream of liquid nitrogen (−173 °C). The data collection was carried out using synchrotron X-ray on a ADSC Quantum 210 CCD detector with a silicon (111) double-crystal monochromator at 2D SMC beamline of the Pohang Accelerator Laboratory, Korea. The ADSC Quantum- 210 ADX program
was used for data collection, and HKL3000sm (Ver. 703r)
was used for cell refinement, data integration, and absorption correction. After space group determination, the structures were solved by direct methods and subsequent difference Fourier techniques (SHEXLTL).
All the non-hydrogen atoms were refined anisotropically, and hydrogen atoms were added to their geometrically ideal positions. The diffused electron densities in the void space could not be modeled properly, and were removed from the reflection data using the SQUEEZE routine of PLATON.
The results of SQUEEZE process were attached to the CIF file. The crystal data and results of structure refinements are summarized in Table S1. Crystallographic data for the structure reported here have been deposited with CCDC (Deposition No. CCDC-981813 (
)). These data can be obtained free of charge
http://www.ccdc.cam.ac.uk/conts/retrieving.html or from CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, E-mail: email@example.com
Gas sorption isotherms were measured in a bath of liquid nitrogen (77 K) with a Belsorp Mini-II. The gases used were of the highest quality available (N60 for H
, N50 for Ar and N
, and N45 for O
). Typically, 100-150 mg of solvent-exchanged samples were evacuated under a dynamic vacuum at room temperature for 12 h. The equilibrium criteria were set consistent throughout all the measurements (change in adsorption amounts less than 0.1 cm
/g within 180 sec). Complete gas sorption isotherms are shown in Fig. S2.
Supporting Information.Summary of crystal data, FT-IR spectra, complete gas sorption isotherms and crystallo-graphic data in CIF format for1.
Arvai A. J.
ADSC Quantum-210 ADX Program
Area Detector System Corporation
Poway, CA, USA
Fit2D Program, ESRF; 6 Rue Jules Horowitz, BP 220 38043, Grenoble CEDEX 9
Methods in Enzymology; Carter, C. W., Jr., Sweet, R. M., Eds., Part A
Sheldrick G. M.
SHELXTL-PLUS, Crystal Structure Analysis Package
Bruker Analytical X-Ray
Madison, WI, USA