Syntheses and characterization of β-chromium(II)-orthophosphate

Glaum R.; Hammer E.; Hermes W.; P?ttgen R.

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Syntheses and characterization of β-chromium(II)-orthophosphate

机译：β-正磷酸铬铬的合成与表征

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β-Cr_3(PO_4)_2 was obtained by reducing CrPO_4 with elemental chromium. The new modification is stable between 1250 °C and its melting point at 1350 °C. Light-blue single crystal were grown by isothermal heating (T = 1300 °C, sealed double-wall silica tubes, CrI_2 as mineralizer). The crystal structure is closely related to the Mg_3(PO_4)_2 (Farringtonite) structure type (P2_1, Z = 2, a = 4.9641(5), b = 9.492(1), c = 6.4849(5) ?, β = 91.412(8)°; 2868 independent reflections, 62 variables, seven atoms in the asymmetric unit, R1 = 0.028, wR2 = 0.061). The structure consists of elongated octahedra [Cr~(II)O_6] (2.054(1) ≤ d(Cr-O) ≤ 2.743(4) ?). Electronic absorption spectra measured in the NIR/vis range for α- and β-Cr_3(PO_4) _2, α-Cr_2P_2O_7, and SrCrP _2O_7 allow an estimation of 10Dq = 9000 cm~(-1) for the [Cr~(II)O_6] chromophore. The observed transition energies for the low-symmetry chromophores match remarkably well with calculations within the framework of the angular overlap model. Comparison of the magnetic behavior of α- and β-Cr_3(PO_4) _2 (μ_(exp) = 4.90 μ_B) reveals significant differences.

机译：通过用元素铬还原CrPO_4获得β-Cr_3（PO_4）_2。新的改性剂在1250°C和1350°C的熔点之间稳定。通过等温加热（T = 1300°C，密封双壁硅胶管，CrI_2作为矿化剂）生长浅蓝色单晶。晶体结构与Mg_3（PO_4）_2（Farringtonite）结构类型密切相关（P2_1 / n，Z = 2，a = 4.9641（5），b = 9.492（1），c = 6.4849（5）α，β = 91.412（8）°; 2868个独立反射，62个变量，不对称单元中有七个原子，R1 = 0.028，wR2 = 0.061）。该结构由细长的八面体[Cr〜（II）O_6]（2.054（1）≤d（Cr-O）≤2.743（4）？）组成。在NIR / vis范围内对α-和β-Cr_3（PO_4）_2，α-Cr_2P_2O_7和SrCrP _2O_7测得的电子吸收光谱可估计[Cr〜（II）]为10Dq = 9000 cm〜（-1）。 O_6]发色团。观察到的低对称发色团的跃迁能与角度重叠模型框架内的计算非常匹配。比较α-和β-Cr_3（PO_4）_2（μ_（exp）= 4.90μ_B）的磁行为，发现存在显着差异。

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《Zeitschrift fur Anorganische und Allgemeine Chemie》 |2011年第7期|共10页
作者
Glaum R.; Hammer E.; Hermes W.; P?ttgen R.;
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正文语种 eng
中图分类化学;
关键词
Chromium; Crystal growth; Electronic spectra; Phosphates; Solid-state structures;

机译：铬;晶体生长;电子光谱;磷酸盐;固态结构;

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Syntheses and characterization of β-chromium(II)-orthophosphate

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