Structure Analysis of Unstable Crystals using Rapid X-ray Measurement System

使用快速 X 射线测量系统分析不稳定晶体的结构

• 批准号: 04504002
• 负责人: IWASAKI Fujiko
• 金额: $ 28.1万
• 依托单位: The University of Electro-Communications
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (A)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-04504002/
• 关键词: Crystal Structure Analysis; New Diffractometer; Imaging Plate; Unstable Crystals; Phase Transformation; High Temperature X-ray Diffraction

1. Rapid collection of X-ray intensity data is especially important for determining structures of unstable crystal. A new type of X-ray diffractometer (DIP-3000) has been developed with Imaging plate as a two-dimensional detector, a kappa-goniometer and a mu-axis in order to measure diffraction intensities from a single crystal within several hours.2. A performance test and comparison of structures using a four-circle diffractometer indicated that the accuracy of the intensity data taken with our new rapid X-ray measurement system are reliable and the system can work quite satisfactorily as a tool of ordinary crystallography and very useful for unstable crystals. Total time for data collection was about 2 or 3 hours for reach crystals, on the contrast to about 3 or 4 days on the four-circle diffractometer. Although R values are larger by about 0.01 than those of four-circle diffractometer, bond lengths and angles obtained from this equipment and a four-circle diffractometer agree quite well within the estimated standard deviations.3. Using this equipment we could successfully determined the crystal structures of several new metal-carbene complexes whose crystals were very unstable. It is revealed that this equipment is very useful for crystals having a large unit cell. Intensity data could be measured within 7-10 hours, on the contrast to about 10 or 14 days on the four-circle diffractometer.4. Dynamic structural transformations and molecular motion in organic crystals were also investigated using this equipment and the mechanism of thermal rearrangement in 2,4-dinitrophenyl-o-anisidine was revealed.

1. X射线强度数据的快速收集对于确定不稳定晶体的结构尤其重要。我们开发了一种新型 X 射线衍射仪 (DIP-3000)，将成像板作为二维探测器、kappa 测角仪和 mu 轴，以便在数小时内测量单晶的衍射强度。2 。使用四环衍射仪进行的结构性能测试和比较表明，我们的新型快速X射线测量系统所获取的强度数据的准确性是可靠的，该系统作为普通晶体学的工具可以令人满意地工作，并且非常有用不稳定的晶体。对于到达晶体，数据收集的总时间约为 2 或 3 小时，而四环衍射仪的数据收集总时间约为 3 或 4 天。虽然R值比四环衍射仪的R值大约0.01，但从该设备和四环衍射仪获得的键长和角度在估计的标准偏差内非常吻合。3．使用该设备，我们可以成功确定几种新型金属卡宾配合物的晶体结构，这些配合物的晶体非常不稳定。据透露，该设备对于具有大晶胞的晶体非常有用。强度数据可以在 7-10 小时内测量，而四环衍射仪则需要大约 10 或 14 天。4。使用该设备还研究了有机晶体中的动态结构转变和分子运动，并揭示了2,4-二硝基苯基-邻甲氧基苯胺的热重排机制。

项目成果

F.Iwasaki et al.: "Crystal and Molecular Structures of Bismuth Compounds of a Spiro-σ-sulfurane Type" Acta Crystallogr.B50(in press). (1994)

F. Iwasaki 等人：“螺-σ-硫醚型铋化合物的晶体和分子结构”Acta Crystallogr.B50（出版中）。

T.Ishida et al.: "Synthesis, Second-order NLO Properties and Crystal Structures of Tetra-substituted Ethylene, Trisubstituted Schiff-base and Diphenoxymethane Derivatives" Sythetic Metals. 55-57. 2013-2918 (1993)

T.Ishida 等人：“四取代乙烯、三取代希夫碱和二苯氧基甲烷衍生物的合成、二阶 NLO 性质和晶体结构”合成金属。

M.Yasui, R.Yamazaki, T.Nogami and F.Iawasaki: "Quaternary Alkyl Halide Salts of 1,4-Diazabicyclo[2.2.2]-octanes with Halide Anion Conductivity" Acta Crystallogr.A49 suppl.183 (1993)

M.Yasui、R.Yamazaki、T.Nogami 和 F.Iawasaki：“具有卤化物阴离子电导率的 1,4-二氮杂双环[2.2.2]-辛烷的季烷基卤化物盐” Acta Crystallogr.A49 supl.183 (1993)

N.Matsumura, M.Tomura, K.Inazu, H.Inoue, N.Yamazaki and F.Iwasaki: "Synthesis and Characterization of 10-Se-3 Type Selenatetraazapentalene Derivatives with a Hypervalent Selenium" Phosphorus, Sulfur and Silicon. 67. 135-140 (1992)

N.Matsumura、M.Tomura、K.Inazu、H.Inoue、N.Yamazaki 和 F.Iwasaki：“具有高价硒的 10-Se-3 型 Selenatetraazapentalene 衍生物的合成和表征”磷、硫和硅。

T.Nogami et al.: "A New Organic Ferromagnet : 4-Benzylideneamino-2,2,6,6-tetramethylpiperidin-l-oxyl" Chemistry Letters. 29-32 (1994)

T.Nogami 等人：“一种新的有机铁磁体：4-亚苄基氨基-2,2,6,6-四甲基哌啶-1-氧基”化学快报。