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首页> 外文期刊>Acta Crystallographica, Section B. Structural Science >Structures of [Pd(NH3)(2)X-2] and its chemical transformation in the solid state
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Structures of [Pd(NH3)(2)X-2] and its chemical transformation in the solid state

机译：[Pd（NH3）（2）X-2]的结构及其固态化学转化

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摘要

Crystal structures of [Pd(NH3)(2)X-2] complexes, where X = Br or I, diamminediiodo-/-dibromopalladium(II), have been studied by X-ray powder diffraction. The series consists of five complexes: cis-[Pd(NH3)(2)Br-2] (I) [a = 13.3202 (7), b = 12.7223 (6), c = 7.05854 (3) Angstrom, Z = 8, space group Pbca], trans-[Pd(NH3)(2)Br-2] (II) [a = 6.7854 (3), b = 7.1057 (3), c = 6.6241 (2) Angstrom, alpha = 103.221 (3), beta = 102.514 (2), gamma = 100.386 (3)degrees, Z = 2, space group P (1) over bar], beta-trans-[Pd(NH3)(2)Br-2] (III) [a = 8.4315 (3), b = 8.4206 (3), c = 8.0916 (2) Angstrom, Z = 4, space group Pbca], cis-[Pd(NH3)(2)I-2] (IV) [a = 13.9060 (8), b = 13.5035 (8), c = 7.5050 (4) Angstrom, Z = 8, space group Pbca], and beta-trans-[Pd(NH3)(2)I-2] (V) [a = 8.8347 (5), b = 8.8410 (5), c = 8.6081 (2) Angstrom, Z = 4, space group Pbca]. Patterson synthesis and Rietveld refinement have been used for structural determination. Molecular structures with column- or parquet-type packing of flat complexes are characteristic of these substances. Corresponding cis- and beta-trans compounds are isostructural. The thermal transformations cis-->trans-->beta-trans (cis-->beta-trans in the case of iodine) are considered. Cl derivatives are also discussed. The transformations proceed irreversibly and are accompanied by decreasing specific volume. Owing to these features, they can be classified as chemical reactions. High-temperature X-ray powder diffraction was used to study the transformations in air. The set of data is consistent with a solid state transformation from cis to trans. According to this model, the columns of molecules remain intact during the process, and the transformation proceeds via the breaking of Pd ... X and Pd ... N intermolecular bonds. The powder diffraction data have been deposited in ICDD-JCPDS (45-0596, 46-0876, 46-0879, 47-1690, 48-1185). [References: 14]
机译：通过X射线粉末衍射研究了[Pd（NH3）（2）X-2]配合物的晶体结构，其中X = Br或I，二氨基二碘-/-二溴钯（II）。该系列由五个络合物组成：顺式[Pd（NH3）（2）Br-2]（I）[a = 13.3202（7），b = 12.7223（6），c = 7.05854（3）埃，Z = 8 ，空间群Pbca]，反式[Pd（NH3）（2）Br-2]（II）[a = 6.7854（3），b = 7.1057（3），c = 6.6241（2）埃，α= 103.221（ 3），β= 102.514（2），伽马= 100.386（3）度，Z = 2，空间组P（1）超过bar]，β-反式-[Pd（NH3）（2）Br-2]（III ）[a = 8.4315（3），b = 8.4206（3），c = 8.0916（2）埃，Z = 4，空间群Pbca]，顺式-[Pd（NH3）（2）I-2]（IV） [a = 13.9060（8），b = 13.5035（8），c = 7.5050（4）埃，Z = 8，空间群Pbca]和β-反式-[Pd（NH3）（2）I-2]]（ V）[a ＝ 8.8347（5），b ＝ 8.8410（5），c ＝ 8.6081（2）埃，Z ＝ 4，空间群Pbca]。 Patterson合成和Rietveld改进已用于结构确定。这些物质具有柱状或镶木地板型平面配合物堆积的分子结构。相应的顺式和β-反式化合物是同构的。考虑了热转变为顺式->反式->β-反式（在碘的情况下为顺式->β-反式）。还讨论了Cl衍生物。转化不可逆地进行，并伴随着比体积的减小。由于这些特征，它们可以被分类为化学反应。高温X射线粉末衍射用于研究空气中的转变。数据集与从顺式到反式的固态转化一致。根据该模型，分子柱在此过程中保持完整，并且通过Pd ... X和Pd ... N分子间键的断裂进行转化。粉末衍射数据已沉积在ICDD-JCPDS（45-0596、46-0876、46-0879、47-1690、48-1185）中。 [参考：14]

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