実験報告書様式（トライアルユース）（ ※本報告書は英語で記述してください。ただし、産業利用課題として採択されている方は日本語で記述していただいても結構です。 ）承認日 Date of Approval 2013.7.5
承認者 Approver Takashi Ohhara
提出日 Date of Report 2013.7. 1

Experimental Report
課題番号 Project No.

装置責任者 Name of responsible person

2012B0112

Takashi OHHARA

実験課題名 Title of experiment

装置名 Name of Instrument/（BL No.）

Direct Observation of Deuterium Gas Adsorbed on Porous

SENJU (BL18)

Coordination Polymers with Viologen Surface

実施日時 Date and time of Experiment

実験責任者名 Name of principal investigator

Feb. 14, 2013, 9:00 ～ Feb. 18, 2013,

Masakazu HIGUCHI

9:00

所属 Affiliation
Kyoto University
試料、実験方法、利用の結果得られた主なデータ、考察、結論等を、記述して下さい。（適宜、図表添付のこと）
Please report your samples, experimental method and results, discussion and conclusions. Please add figures andtables for better explanation.
1. 試料 Name of sample(s) and chemical formula, or compositions including physical form.
When we made the proposal of the application, we have proposed that we would synthesize a porous
coordination polymers with viologen surface (reported in Angew. Chem. Int. Ed. 2012, 51, 8369.) to elucidate
the position of hydrogen molecules on its surface. However we could not successfully synthesized its single
crystal suitable for experiments in SENJU(BL18). Therefore, for experiments in in SENJU(BL18), wesynthesized single crystal of Ca(C4O4)(H2O), which has an adequate size, 0.7 mm x 0.7 mm x 1.0 mm, of thesingle crystal. In this proposal, we carried out a single crystal neutron diffraction measurement of this single
crystal to observe hydrogen atom of H2O in Ca(C4O4)(H2O) and hydrogen molecules in the pore.

2. 実験方法及び結果 （実験がうまくいかなかった場合、その理由を記述してください。）
Experimental method and results.

If you failed to conduct experiment as planned, please describe reasons.

MethodA 0.7 mm x 0.7 mm x 1.0 mm single crystal of Ca(C4O4)(H2O) in the quarts capillary with hydrogen molecule asgas was attached to an aluminum stick using epoxy glue and mounted to the goniometer at the end of4K-cryostat.
Neutron diffraction intensities were collected on the following conditions.
------------------------------Crystal orientation: 8Exposure time: 8 hrs. / orientationTemperature: 77 K-------------------------------

12. 実験方法及び結果（つづき） Experimental method and results (continued)
ResultIn this experiment, low temperature diffraction measurement by using the 77K-cryostat at was performed todetect hydrogen molecules in the pore. We could not success to find hydrogen molecule in the pore by theanalysis, but hydrogen atom of H2O in Ca(C4O4)(H2O) was observed, which is fundamentally of importancewhen we discuss adsorption phenomena. Figure 1 shows the single crystal structure of Ca(C4O4)(H2O) withhydrogen molecules (unfortunately hydrogen molecules were not detected) and Table 1 shows thecrystallographic parameters of Ca(C4O4)(H2O) obtained. Data processing was performed by software
STARGazer. Obtained cell parameters were a = 13.71770 Å, c = 7.6987 Å, (tetragonal). These values well agreed
with those of X-rays.

Figure 1. the single crystal structure of Ca(C4O4)(H2O).
Table 1. the crystallographic parameters of
The hydrogen atom of H2O in Ca(C4O4)(H2O) wasobserved in this experiment, which is not detected byCa(C4O4)(H2O)
Compounds

Ca(C4O4)( H2O)

Crystal system

Tetragonal

FormulaC4H2Ca1O5

oxygen atom of C4O4 with the distance of 2.7 Å, which isa, Å13.71770

the typical distance of hydrogen bond. This measurementc, Å7.6987

revealed that water molecules play the key role inV, Å31448.705

constructing the framework of Ca(C4O4)(H2O) to show

Space group

I-42dslightly zigzag 1-dimansional channel. Unfortunately

Z

8Temp, K77

X-ray single crystal measurement. As a result, weobtained the detailed information of the framework ofCa(C4O4)(H2O). Hydrogen atom in H2O coordinated toalthough we dosed hydrogen gas in the capillary with thesingle crystal of Ca(C4O4)(H2O), we could not detectedhydrogen molecules in the pore. We guess that there are

two issues to detect hydrogen molecules. One is that there is not enough hydrogen molecules to detect.
Another is that hydrogen molecules come out from the capillary inside because of high vacuum in the cryostat.

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