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首页> 外文期刊>Zeitschrift fur Naturforschung. A, A journal of physical sciences >Isolated versus Condensed Anion Structure: the Influence of the Cation Size and Hydrogen Bond on Structure and Phase Transition in MX_4~(2-) Complex Salts. 2,2-Dimethyl-1,3-propanediammonium Tetrabromocadmate(Ⅱ) Monohydrate, Dimethylammonium
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Isolated versus Condensed Anion Structure: the Influence of the Cation Size and Hydrogen Bond on Structure and Phase Transition in MX_4~(2-) Complex Salts. 2,2-Dimethyl-1,3-propanediammonium Tetrabromocadmate(Ⅱ) Monohydrate, Dimethylammonium

机译：分离与冷凝阴离子结构：阳离子大小和氢键对MX_4〜（2-）络合物盐结构和相变的影响。 1,2-二甲基-1,3-丙二铵四溴镉（Ⅱ）一水合物，二甲基铵

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摘要

In the course of work on the anion condensation of Cd and Zn halides, the crystal structures and ~(79,81)Br NQR spectra of 2,2-dimethyl-1,3-propanediammonium tetrabromocadmate(Ⅱ) monohy-drate (1) and dimethylammonium tetrabromozincate(Ⅱ) (2), and ~(79,81)Br NQR spectra of dimethylammonium tetrabromocadmate(Ⅱ) (3) have been studied. An isolated [CdBr_4]~(2-) ion of the salt [H_3NCH_2C(CH_3)_2CH_2NH_3]CdBr_4 • H_2O (1) is formed, with polar orthorhombic space group Pbc2_1, Z = 4, a = 645.5(3), b = 1628.3(8), c = 1389.5(6) pm. [(CH_3)_2NH_2]_2ZnBr_4 (2) has also an isolated anion lattice, with monoclinic space group, P2_1/c, Z = 4, a = 870.6(3), b = 1195.6(4), c = 1628.9(5) pm, β = 121.84(1)°. The ~(81)Br NQR spectrum of (1) is a quartet (ν in MHz, T = 77 K/ 303 K): ν_1 = 68.403/64.278; ν_2 = 65.296/62.663; ν_3 = 56.525/54.660; ν_4 = 43.211/45.422. The ~(81)Br NQR spectrum of (2) is a quartet too (ν in MHz, T = 77 K/300 K): ν_1 = 66.848/64.784; ν_2 = 63.152/ 61.883; ν_3 = 57.498/55.890; ν_4 = 49.416/50.224. The ~(81)Br NQR spectrum of [(CH_3)_2NH_2]_2CdBr_4(3) is also a quartet (ν in MHz, T= 77 K/310 K): ν_1 = 68.606/67.272; ν_2 = 65.806/63.296; ν_3 = 58.096/ 57.369; ν_4 = 55.757/53.393. The change of NQR frequencies with temperature is smooth for all three compounds. One of the ~(81)Br NQR lines in both (1) and (2) increases slightly in frequency with increasing T. In the compound (1), the H_2O coordinates to NH_3~+ groups and to bromines forming a distorted tetrahedron (Br…)_2 … H_2O…(… HN)_2, the six angles lying between 69° and 131°. The relations between the bromine NQR and the crystal structures are discussed for the title compounds.
机译：在Cd和Zn卤化物的阴离子缩合反应过程中，一溴酸盐2,2-二甲基-1,3-丙烷二铵（Ⅱ）的晶体结构和〜（79,81）Br NQR光谱（1）研究了四溴锌酸盐（Ⅱ）（2）的二甲基铵，以及四溴镉酸盐（Ⅱ）（2）的〜（79,81）Br NQR光谱。形成了盐[H_3NCH_2C（CH_3）_2CH_2NH_3] CdBr_4•H_2O（1）的分离的[CdBr_4]〜（2-）离子，极性正交空间组Pbc2_1，Z = 4，a = 645.5（3），b = 1628.3（8），c ＝ 1389.5（6）pm。 [（CH_3）_2NH_2] _2ZnBr_4（2）也具有孤立的阴离子晶格，具有单斜空间群P2_1 / c，Z = 4，a = 870.6（3），b = 1195.6（4），c = 1628.9（5） pm，β= 121.84（1）°。 （1）的〜（81）Br NQR谱是一个四重奏（νin MHz，T = 77 K / 303 K）：ν_1= 68.403 / 64.278; ν_2= 65.296 / 62.663; ν_3= 56.525 / 54.660; ν_4= 43.211 / 45.422。 （2）的〜（81）Br NQR谱也是四重奏（νin MHz，T = 77 K / 300 K）：ν_1= 66.848 / 64.784; ν_2= 63.152 / 61.883; ν_3= 57.498 / 55.890; ν_4= 49.416 / 50.224。 [（CH_3）_2NH_2] _2CdBr_4（3）的〜（81）Br NQR谱也是四重奏（νin MHz，T = 77 K / 310 K）：ν_1= 68.606 / 67.272; ν_2= 65.806 / 63.296； ν_3= 58.096 / 57.369; ν_4= 55.757 / 53.393。对于所有三种化合物，NQR频率随温度的变化是平滑的。 （1）和（2）中的〜（81）Br NQR线之一随T的增加而频率略有增加。在化合物（1）中，H_2O与NH_3〜+基团以及形成扭曲的四面体的溴配位（ Br…）_2…H_2O…（…HN）_2，六个角度在69°和131°之间。讨论了标题化合物中溴NQR和晶体结构之间的关系。

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