Syntheses and Structures of [Fe(TPA)X2](ClO4) and [{Fe(TPA)Y}2O](ClO4)2 Where TPA = Tris-(2-pyridylmethyl)amine, X = N3, or Br, and Y = N3, Br, NCO, or NCS

IF 0.4 4区化学 Q4 CRYSTALLOGRAPHY

Journal of Chemical Crystallography Pub Date : 2022-04-15 DOI:10.1007/s10870-022-00941-5

Jia Xue, Yelda Hangun-Balkir, Matthew Mullaney, Shamila Nadir, Justin Cody Lewis, Christine Henry-Smith, Naleen B. Jayaratna, C. A. U. Kawshalya Kumarihami, Richard E. Norman

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引用次数: 1

Abstract

[Fe(TPA)(N₃)₂](ClO₄) and [Fe(TPA)Br₂](ClO₄), where TPA is tris-(2-pyridylmethyl)amine, crystallize in the monoclinic space group P2₁/c with a = 8.7029(5) Å, b = 19.168(1) Å, c = 13.5728(7) Å, β = 101.472(3)°, and a = 8.944(3) Å, b = 16.578(6) Å, c = 15.108(6) Å, β = 103.18(2)°, respectively. The structures were determined at 150 K from 3397 reflections (1426 observed) with R = 0.063 (R_w = 0.097), and at 115 K from 5617 reflections (2261 observed) with R = 0.057 (R_w = 0.065), respectively. In both cases, the iron is pseudo-octahedral with the two halide/pseudohalide ions cis. The Fe–X bond trans to the tertiary amine is shorter. The structures of [{Fe(TPA)X}₂O](ClO₄)₂ where X = N₃, Br, NCO, and two polymorphic forms of NCS, are also reported. The azide derivative [CH₃CN solvate, monoclinic P2₁/n, a = 11.8038(11) Å, b = 22.547(2) Å, c = 17.344(2) Å, β = 106.972(4)°, determined at 100 K from 8972 reflections (4404 observed) with R = 0.087 (R_w = 0.145)] has two distinct Fe environments—the tertiary amine is cis to the oxido bridge at one site and is trans to the oxido bridge at the other site; the trans Fe–N_3° distance is longer. Both the Br and NCO derivatives are monoclinic, C2/c [with a = 16.1480(17), b = 17.2036(13), c = 16.8521(12), β = 111.204(10), data collected at 293 K, 3753 reflections (2404 observed), R = 0.069 (R_w = 0.151), and a = 15.7470(9), b = 18.2270(11), c = 16.8950(8), β = 110.666(3), data collected at 90 K, 5392 reflections (3028 observed), R = 0.064 (R_w = 0.091), respectively]. Both polymorphs of the NCS derivative are monoclinic—one is P2₁/c and the other P2₁/n [a = 11.075(2), b = 15.436(2), c = 12.351(2), β = 95.528(7), data collected at 90 K, 5378 reflections (4345 observed), R = 0.068 (R_w = 0.198), and a = 12.396(2), b = 15.428(3), c = 44.505(8), β = 95.211(7), data collected at 110 K, 16,527 reflections (6540 observed), R = 0.069 (R_w = 0.105), respectively]. For the Br, NCO and NCS dimers, each iron of the [{Fe(TPA)X}₂O]²⁺ unit is pseudo-octahedral with the halide/pseudohalide and oxide ions cis. The oxide bridge is linear, and the two halides/pseudohalides are anti. The ranking of trans influence of the ligands is O²⁻ ≫ Br⁻ > Cl⁻ > N₃⁻ > NCO⁻ ≥ NCS⁻ > pyridyl > tertiary amine and the ranking of cis influence of the ligands is O²⁻ ≫ N₃⁻ > NCO⁻ > Cl⁻ ≥ Br⁻ > NCS⁻.

Graphical Abstract

The X-ray structures of two monomeric [Fe(TPA)(X)₂](ClO₄), where TPA is tris-(2-pyridylmethyl)amine and X = N₃, and Br, and four dimeric [{Fe(TPA)Y}₂O](ClO₄)₂, where Y =N₃, Br, NCO, and NCS are presented and discussed.

Abstract Image

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[Fe(t2)和Structures的[ClO4) (ClO4)和[ClO4) (ClO4)两个地方的TPA = Tris-(2-pyridylmethyl)amine, X = N3，或Br, Y = N3, Br, NCO，或NCS

(Fe (TPA) (N3) 2) (ClO4)和(Fe (TPA) Br2] (ClO4), TPA是三羟甲基氨基甲烷——(2-pyridylmethyl)胺液结晶的单斜晶体的空间群P21 / c = 8.7029 (5) a, b = 19.168 (1) a, c = 13.5728(7),β= 101.472(3)°,和一个= 8.944 (3)a, b = 16.578 (6) a, c = 15.108(6),分别为β= 103.18(2)°。在150 K和115 K下，分别有3397次反射(1426次)和5617次反射(2261次)，R = 0.057 (Rw = 0.065)， R = 0.063 (Rw = 0.097)。在这两种情况下，铁都是与两个卤化物/伪卤化物离子顺式排列的伪八面体。转至叔胺的Fe-X键较短。本文还报道了[{Fe(TPA)X}2O](ClO4)2在X = N3、Br、NCO和两种NCS的多态形式下的结构。叠氮化物衍生物[CH3CN溶剂化物，单斜P21/n, a = 11.8038(11) Å， b = 22.547(2) Å， c = 17.344(2) Å， β = 106.972(4)°，在100 K下由8972次反射(观察到4404次)，R = 0.087 (Rw = 0.145)测定]具有两种不同的铁环境-叔胺在一个位点顺式氧化桥，在另一个位点反式氧化桥;Fe-N3°反相距离较长。Br和NCO衍生物均为单斜晶，C2/c[其中a = 16.1480(17)， b = 17.2036(13)， c = 16.8521(12)， β = 111.204(10)，在293 K下收集数据，3753次反射(2404次观测)，R = 0.069 (Rw = 0.151)， a = 15.7470(9)， b = 18.2270(11)， c = 16.8950(8)， β = 110.666(3)，在90 K下收集数据，5392次反射(3028次观测)，R = 0.064 (Rw = 0.091)]。NCS衍生物的两个多态性都是单斜的，一个是P21/c，另一个是P21/n [a = 11.075(2)， b = 15.436(2)， c = 12.351(2)， β = 95.528(7)， 90 K采集数据，5378次反射(4345次观测)，R = 0.068 (Rw = 0.198)， a = 12.396(2)， b = 15.428(3)， c = 44.505(8)， β = 95.211(7)， 110 K采集数据，16,527次反射(6540次观测)，R = 0.069 (Rw = 0.105)]。对于Br、NCO和NCS二聚体，[{Fe(TPA)X}2O]2+单元的每个铁都是假八面体，卤化物/伪卤化物和氧化物离子顺式排列。氧化物桥是线性的，两个卤化物/伪卤化物是反的。配体的反式影响顺序为:O2−> Br−> Cl−> N3−> NCO−≥NCS−>吡啶基>叔胺;顺式影响顺序为:O2−> N3−> NCO−> Cl−≥Br−> NCS−。摘要本文给出并讨论了两种单体[Fe(TPA)(X)2](ClO4)的X射线结构，其中TPA为三-(2-吡啶基甲基)胺，X =N3和Br，以及四种二聚体[{Fe(TPA)Y}2O](ClO4)2, Y =N3, Br, NCO和NCS。

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来源期刊

Journal of Chemical Crystallography 化学-光谱学

CiteScore

1.50

自引率

12.50%

发文量

审稿时长

6.3 months

期刊介绍： Journal of Chemical Crystallography is an international and interdisciplinary publication dedicated to the rapid dissemination of research results in the general areas of crystallography and spectroscopy. Timely research reports detail topics in crystal chemistry and physics and their relation to problems of molecular structure; structural studies of solids, liquids, gases, and solutions involving spectroscopic, spectrometric, X-ray, and electron and neutron diffraction; and theoretical studies.