Isopropylammonium halidometallates. I. [CoX4]2−·X− (X = Cl, Br), ZnCl42−, and [ZnCl3−]n salts

IF 0.6 Q4 CRYSTALLOGRAPHY

Acta Crystallographica Section E: Crystallographic Communications Pub Date : 2025-08-01 DOI:10.1107/S2056989025006103

Josh Birke , Tu Nguyen , Marcus R. Bond

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Abstract

The structures of the isopropylammonium halidometallate salts (IPA⁺)₃CoX₅ (X = Cl, Br), (IPA⁺)₂ZnCl₄ and (IPA⁺)ZnCl₃ are reported along with a survey of known isopropylammonium halidometallates, and a study of IPA⁺ cation geometry (both experimental and theoretical) juxtaposed with that of the trimethylammonium TMA⁺) cation.

An exploration of the isopropylammonium (IPA⁺) metal halide structural space is conducted, initially, for cobalt(II) and zinc(II) halides as a counterpart to the more extensively studied metal halide systems containing the isomeric trimethylammonium cation. For cobalt(II) halides, the only compound obtained from slow evaporation of acidic aqueous solutions of isopropylammonium halide and cobalt(II) halide is (IPA⁺)₃CoX₄·X (X = Cl, Br), namely, tris(isopropylammonium) tetrachloridocobaltate(II) chloride, (C₃H₁₀N)₃[CoCl₄]Cl, and tris(isopropylammonium) tetrabromidocobaltate(II) bromide, (C₃H₁₀N)₃[CoBr₄]Br, regardless of the starting stoichiometric ratio of (IPA⁺)X:CoX₂. These structures consist of isolated tetrahedral CoX₄²⁻ complexes and X⁻ ions separated by IPA⁺ cations. One IPA⁺ cation hydrogen bonds to two complexes and to two halide ions to produce clusters. These clusters form stacks with hydrogen bonding from the remaining IPA⁺ cations linking the stacks into a tight, three-dimensional network. A 2:1 molar ratio of (IPA⁺)Cl and ZnCl₂ under similar growth conditions readily yields crystals of bis(isopropylammonium) tetrachloridozincate(II), (C₃H₁₀N)₂[ZnCl₄] or (IPA⁺)₂ZnCl₄, consisting only of IPA⁺ cations and isolated ZnCl₄²⁻ tetrahedra. This despite the expectation of common structural chemistry for the similarly sized Co²⁺ and Zn²⁺ ions with 51 known isostructural A₂CoCl₄ and A₂ZnCl₄ compounds out of 54 for the same monopositive A cation. Growth from a 1:1 ratio of (IPA⁺)Cl:ZnCl₂ yields crystals of poly[isopropylammonium [[dichloridozincate(II)]-μ-chlorido]], {(C₃H₁₀N)[ZnCl₃]}_n or (IPA⁺)ZnCl₃, in which parallel chains of corner-sharing ZnCl₄ tetrahedra are separated by IPA⁺ cations. This unusual zinc(II) halide chain structure has previously been observed only in [YCH₂(CH₃)₃N]ZnCl₃ salts (Y = H, halogen). In contrast to these known compounds, which are found in polar orthorhombic space groups, the structure reported here is in orthorhombic Pbca.

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Iso-propyl-ammonium halidometallates。[CoX 4]2-·X - (X = Cl, Br)， zncl2 -和[ZnCl3 -] n盐。

对异丙基铵（IPA+）金属卤化物结构空间的探索，最初是对钴（II）和锌（II）卤化物进行的，作为更广泛研究的含有三甲基铵阳离子的异构体金属卤化物体系的对应物。对于（II）卤化钴，从异丙基卤化铵和（II）卤化钴的酸性水溶液中缓慢蒸发得到的唯一化合物是（IPA+）3CoX 4·X (X = Cl, Br)，即三-（异丙基铵）四氯钴酸盐（II）氯化物（C3H10N）3[CoCl4]Cl和三-（异丙基铵）四溴化溴（C3H10N）3[CoBr4]Br，而不管（IPA+）X:CoX 2的起始化学计量比如何。这些结构由孤立的四面体CoX 42 -配合物和由IPA+阳离子分隔的X离子组成。一个IPA+阳离子氢键与两个配合物和两个卤化物离子形成团簇。这些团簇形成层叠，剩余的IPA+阳离子形成氢键，将层叠连接成一个紧密的三维网络。在相似的生长条件下，（IPA+）Cl和ZnCl2的摩尔比为2:1，容易生成双（异丙基铵）四氯锌酸盐（II），（C3H10N）2[ZnCl4]或（IPA+）2ZnCl4晶体，仅由IPA+阳离子和分离的ZnCl4 -四面体组成。尽管对于相同的单正A阳离子，54种已知的A2CoCl4和A2ZnCl4化合物中有51种具有相同大小的Co2+和Zn2+离子的共同结构化学预期。在（IPA+）Cl:ZnCl2的1:1比例下生长，得到聚[异丙基铵[[二氯锌酸盐（II）]-μ-氯]]，{(C3H10N)[ZnCl3]} n或（IPA+）ZnCl3晶体，其中平行链共享角的ZnCl4四面体被IPA+阳离子分开。这种不寻常的锌（II）卤化物链结构以前只在[YCH2(CH3)3N]ZnCl3盐（Y = H，卤素）中观察到。与这些已知化合物相反，它们是在极性正交方阵空间基团中发现的，这里报道的结构是在正交方阵Pbca中。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Acta Crystallographica Section E: Crystallographic Communications Chemistry-Chemistry (all)

CiteScore

1.90

自引率

0.00%

发文量

351

审稿时长

3 weeks

期刊介绍： Acta Crystallographica Section E: Crystallographic Communications is the IUCr''s open-access structural communications journal. It provides a fast, simple and easily accessible publication mechanism for crystal structure determinations of inorganic, metal-organic and organic compounds. The electronic submission, validation, refereeing and publication facilities of the journal ensure rapid and high-quality publication of fully validated structures. The primary article category is Research Communications; these are peer-reviewed articles describing one or more structure determinations with appropriate discussion of the science.

Iso­propyl­ammonium halidometallates. I. [CoX4]2−·X− (X = Cl, Br), ZnCl42−, and [ZnCl3−]n salts

Abstract

Isopropylammonium halidometallates. I. [CoX4]2−·X− (X = Cl, Br), ZnCl42−, and [ZnCl3−]n salts