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Wolfgang Hnle Walter Schmettow Karl Peters Jen‐Hui Chang Hans Georg von Schnering 《无机化学与普通化学杂志》2004,630(12):1858-1862
The novel ternary polyphosphides M4P21I (M = K, Rb) have been synthesized from the elements in single crystalline form, representing further examples for the formation of mixed crystals between simple salts and binary phosphides. They form as ruby‐red platelets and dark‐red prisms, respectively, and are only slightly sensitive to moisture and oxygen. The compounds are isotypic (Ccmm (no 63); Z = 4; oP104; K4P21I: a = 12.853Å; b = 21.795Å; c = 9.748Å; 1168 hkl, R = 0.033; Rb4P21I: a = 13.281Å; b = 21.868Å; c = 9.771Å; 777 hkl, R = 0.053) and feature corrugated 2D networks formed from two different types of polymerized P7 units. The networks form large cavities filled by M+ and I‐ ions. Zigzag chains of condensed trigonal M6 prisms, centered by the I‐ anions, separate the polyphosphide nets. The mean homoatomic P‐P bond length (d = 2.216Å) corresponds to a P‐P single bond. However, the individual P‐P distances vary with position and function (2.126 ‐ 2.247Å) and these are compared with those of the isolated P21‐3 anion. 相似文献
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