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,Journal of Chemical Crystallography

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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
Journal of Chemical Crystallography ( IF 0.4 ) Pub Date : 2022-04-15 , DOI: 10.1007/s10870-022-00941-5
Jia Xue ₁ , Yelda Hangun-Balkir ₁ , Matthew Mullaney ₁ , Richard E. Norman _{1,

2,

3} , Shamila Nadir ₂ , Justin Cody Lewis ₂ , Christine Henry-Smith ₃ , Naleen B. Jayaratna ₃ , C. A. U. Kawshalya Kumarihami ₃

Affiliation

[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.

中文翻译：

[Fe(TPA)X2](ClO4) 和 [{Fe(TPA)Y}2O](ClO4)2 的合成和结构其中 TPA = Tris-(2-pyridylmethyl)amine, X = N3, or Br, and Y = N3、Br、NCO 或 NCS

[Fe(TPA)(N ₃ ) ₂ ](ClO ₄ ) 和 [Fe(TPA)Br ₂ ](ClO ₄ )，其中 TPA 是三-(2-吡啶基甲基)胺，结晶在单斜空间群 P2 ₁ / c = 8.7029(5) Å, b = 19.168(1) Å, c = 13.5728(7) Å, β = 101.472(3)°, a = 8.944(3) Å, b = 16.578(6) Å , c = 15.108(6) Å, β = 103.18(2)°, 分别。结构分别在 150 K 时从 3397 次反射（观察到 1426 次）确定，R = 0.063（R _w = 0.097），在 115 K 时从 5617 次反射（观察到 2261 次）确定，R = 0.057（R _w = 0.065），分别。在这两种情况下，铁都是带有两个卤化物/假卤化物离子cis的假八面体。Fe-X 键叔胺的反式更短。还报道了[{Fe(TPA)X} ₂ O](ClO ₄ ) ₂的结构，其中X = N ₃、Br、N CO，以及N CS 的两种多晶型形式。叠氮化物衍生物 [CH ₃ CN 溶剂化物，单斜晶系 P2 ₁ /n，a = 11.8038(11) Å，b = 22.547(2) Å，c = 17.344(2) Å，β = 106.972(4)°，在 100 下测定K 来自 8972 次反射（观察到 4404 次），R = 0.087 (R _w = 0.145)] 具有两种不同的 Fe 环境——叔胺在一个位置与氧化桥是顺式的，在另一个位置与氧化桥是反式的；反式Fe-N _3°距离更长。Br 和N CO 衍生物都是单斜晶系，C2/c [其中 a = 16.1480(17), b = 17.2036(13), c = 16.8521(12), β = 111.204(10), 数据采集于 293 K, 3753反射（观察到 2404 个），R = 0.069 (R _w = 0.151)，a = 15.7470(9)，b = 18.2270(11)，c = 16.8950(8)，β = 110.666(3)，在 90 K 时收集的数据，5392 次反射（观察到 3028 次），分别为 R = 0.064（R _w = 0.091）]。N CS 衍生物的两种多晶型物都是单斜晶型的——一种是 P2 ₁ /c，另一种是 P2 ₁ /n [a = 11.075(2), b = 15.436(2), c = 12.351(2), β = 95.528(7) )，在 90 K 时收集的数据，5378 次反射（观察到 4345 次），R = 0.068 (R _w = 0.198)，a = 12.396(2)，b = 15.428(3)，c = 44.505(8)，β = 95.211(7)，在 110 K 时收集的数据，16,527 次反射（观察到 6540 次），R = 0.069（ R _w = 0.105)，分别]。对于 Br、N CO 和N CS 二聚体，[{Fe(TPA)X} ₂ O] ²⁺单元的每个铁是具有卤化物/伪卤化物和氧化物离子cis的拟八面体。氧化物桥是线性的，两种卤化物/伪卤化物是反的。配体的反式影响排序为 O ²⁻ ≫ Br ⁻ > Cl ⁻ > N ₃⁻ > N CO ⁻ ≥ N CS ^- > 吡啶基 > 叔胺和配体的顺式影响排序为 O ^2- ≫ N ₃^- > N CO ^- > Cl ^- ≥ Br ^- > N CS ^-。