–実験報告書様式（一般利用課題・成果公開利用）（ ※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。 ）提出日 Date of Report

MLF	 Experimental Report
課題番号 Project No. 2014A0027

装置責任者 Name of responsible person

実験課題名 Title of experiment

Takashi Ohhara

Neutron Diffraction Study of Metal Complex Using Porous

装置名 Name of Instrument/（BL No.）

Coordination Complexes as Crystalline Hosts

BL-18

実験責任者名 Name of principal investigator

実施日 Date of Experiment

Yasuhide Inokuma

2014/11/15~2014/11/25

所属 Affiliation
DepartmentofAppliedChemistry,GraduateSchoolofEngineering, The University of Tokyo
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.
Guest included porous coordination crystal(C6H5)3GeH ⊂[(TPT)2(ZnI2)3]nSize: 2.0 × 1.0 × 0.3 mm

TPT(tri(4-pyridyl)1,3,5-triazine)

32. 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.

This experiment is aimed to show the applicability of recently developed new technique called ‘Crystalline
Sponge Method’ for neutron diffraction analysis of non-crystalline organometallic hydride compounds.

A

porous coordination network crystal [(TPT)2(ZnI2)3]n is used as a crystalline sponge that absorb organometallic
compounds from a contacting solution to align them in the crystal pores so that they can be analyzed by X-ray
diffraction analysis.

Although the method was so far limited to single crystal X-ray analysis because of the host

crystal size, this time we succeeded to synthesize millimeter–sized crystals that would match the requirement ofneutron diffraction analysis.

Metal hydride complexes are of interesting because of their reactivity and catalyticactivities.

One of the most important data of metal hydride complexes is the position (i.e. H-M bond length) of

the hydride.

X-ray diffraction analysis, however, cannot precisely determine the positions of hydride ligands.

Given general interest of metal hydride complexes, we designed the project of neutron diffraction analysis ofthem using big size crystalline sponges.

12.

実験方法及び結果（つづき） Experimental method and results (continued)
The sample crystal was preparedby soaking method.

A crystalof [(TPT)2(ZnI2)3]n was placed inaquartz

capillarywithacyclohexane/nitrobenzene
solution of triphenyl germanium
hydride at room temperature over15 days.

The end of thecapillary was sealed with wax
Fig. 1. A diffraction image of Ph3GeH@[(TPT)2(ZnI2)3]n.

andsubjectedtoneutron

diffraction analysis using SENJUat BL-18 in MLF over 8 days at 40 K.

The data analysis was carried out with 10887 reflections up to 1.0 Åresolution using STARGazer program. (Fig. 1)

The lattice parameters were determined to be monoclinic C2/c

a=35.376(4), b=15.0635(10), c= 30.459(5), β=102.605(10)˚.

Using the coordinates of non-hydrogen atoms

obtained from single crystal X-ray data, the neutron diffraction data was refined and hydrogen atoms weregenerated.

We could see the nuclear densities for hydrogen atoms with the R1 value of 0.3111 for 1211 observedreflections (|Fo| > 2σ(Fo)). (Fig. 2) The bond distance between Ge-H was thus estimated to be 1.6 Å.
Since the measurement temperature of neutron diffraction was 40 K which is different from that of X-ray analysis(90 K), it is necessary to re-measure the X-ray data at the same temperature to publish the result.

We are now

negotiating with a collaborator of
Spring-8 about the possibility of
low-temperature measurement ofX-ray data.

Fig. 2. Nuclear density map (contour at σ = -1.0) of crystal
Ph3GeH@[(TPT)2(ZnI2)3]n.

2