Дихлородицианоаураты органилтрифенилфосфония [Ph3PR][Au(CN)2Cl2] (R = n-Pr, i-Bu, n-Hp): синтез и строение

D. P. Shevchenko; A. E. Khabina

doi:10.14529/10.14529/chem210406

Authors

D. P. Shevchenko South Ural State University
A. E. Khabina South Ural State University

DOI:

https://doi.org/10.14529/10.14529/chem210406

Keywords:

дихлородицианоаурат калия, бромиды органилтрифенилфосфония, комплекс, золото, синтез, строение, рентгеноструктурный анализ

Abstract

The interaction of potassium dichlorodicyanoaurate with n-propyl-, i-butyl- and n-heptyltriphenylphosphonium bromides in water followed by the recrystallization from acetonitrile leads to the dichlorodicyanoaurate complexes [Ph₃P(n-Pr)][Au(CN)₂Cl₂] (1), [Ph₃P(i‑Bu)][Au(CN)₂Cl₂] (2), and [Ph₃P(n-Hp)][Au(CN)₂Cl₂] (3). Compounds 1 and 2 have been identified by the IR spectroscopy; structure of compound 3 has been determined by the X-ray diffraction analysis. According to the X-ray data, complex 3 consists of n-heptyltriphenylphosphonium cation and two types of crystallographically independent centrosymmetric square-planar dichlorodicyanoaurate anions. The phosphorus atom in the cation has a slightly distorted tetrahedral coordination with the CPC bond angles within the interval 108.3(5)–110.5(5)°; the P–C distances are 1.801(10)–1.832(10) Å. The square-planar coordination of the gold atoms in centrosymmetric anions [Au(CN)₂Cl₂]^- is almost undistorted: the CAuC and ClAuCl trans-angles equal 180°, the CAuCl cis-angles vary in a narrow range 74.5(9)–105.5(9)°. The Au–Cl bond lengths in anions do not exceed the sum of the covalent radii of the gold and chlorine atoms and equal 2.406(3), 2.388(3) Å; the Au–C bond lengths are 2.021(14), 2.037(13); they are close to the sum of the covalent radii of the gold and carbon atoms. The structural organization in crystals 3 is caused by the H∙∙∙N≡C(2.55–2.63 Å) and С–H∙∙∙Cl–Au (2.87 Å) hydrogen bonds. Moreover, the structure contains the additional С–H∙∙∙π(Ph) contacts with the distances from the hydrogen atom to the plane of the benzene ring that are equal to 2.80 Å. Complete tables of atomic coordinates, bond lengths, and valence angles are deposited in the Cambridge structural data Bank (No. 2094701 for 3; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).

Author Biographies

D. P. Shevchenko, South Ural State University

студент, химический факультет , Институт естественных и точных наук,

A. E. Khabina, South Ural State University

студент, химический факультет, Институт естественных и точных наук

References

Kumar, K. Effect of Noble Metals on Luminescence and Single-Molecule Magnet Behavior in the Cyanido-Bridged Ln–Ag and Ln–Au (Ln = Dy, Yb, Er) Complexes / K. Kumar, O. Stefańczyk, S. Chorazy // Inorg. Chem. – 2019. – V. 58, № 9. – P. 5677–5687. DOI: 10.1021/acs.inorgchem.8b03634.

Photophysical Investigation of Silver/Gold Dicyanometallates and Tetramethylammonium Networks: An Experimental and Theoretical Investigation / A.D. Nicholas, R.M. Bullard, R.D. Pike et al. // Eur. J. Inorg. Chem. – 2019. – V. 2019, № 7. – P. 956–962. DOI: 10.1002/ejic.201801407.

Cyanide‐Assembled d10 Coordination Polymers and Cycles: Excited State Metallophilic Modulation of Solid‐State Luminescence / A. Belyaev, T. Eskelinen, T. Dau et al. // Chem. Eur. J. – 2017. – V. 24, № 6. P. 1404–1415. DOI: 10.1002/chem.201704642.

Polymorphism of Zn[Au(CN)2]2 and Its Luminescent Sensory Response to NH3 Vapor / M.J. Katz, T. Ramnial, H.-Z. Yu et al. // J. Am. Chem. Soc. – 2008. – V. 130, № 32. – P. 10662–10673. DOI: 10.1021/ja801773p.

Ovens, J.S. Designing Tunable White‐Light Emission from an Aurophilic CuI/AuI Coordination Polymer with Thioether Ligands / J.S. Ovens, R.R. Christensen, D.B. Leznoff // Chem. Eur. J. – 2016. – V. 22, № 24. – P. 8234–8239. DOI: 10.1002/chem.201505075.

The Use of Polarizable [AuX2(CN)2]− (X = Br, I) Building Blocks Toward the Formation of Birefringent Coordination Polymers / J.S. Ovens, A.R. Geisheimer, A.A. Bokov et al. // Inorg. Chem. – 2010. – V. 49, № 20. – P. 9609–9616. DOI: 10.1021/ic101357y.

Katz, M.J. Highly Birefringent Cyanoaurate Coordination Polymers: The Effect of Polarizable C−X Bonds (X = Cl, Br) / M.J. Katz, D.B. Leznoff // J. Am. Chem. Soc. – 2009. – V. 131, № 51. – P. 18435–18444. DOI: 10.1021/ja907519c.

Thompson, J.R. Birefringent, Emissive Cyanometallate-Based Coordination Polymer Materials Containing Group(II) Metal-Terpyridine Building Blocks / J.R. Thompson, K.A.S. Goodman-Rendall, D.B. Leznoff // Polyhedron. – 2016. – V. 108. – P. 93–99. DOI: 10.1016/j.poly.2015.12.026.

Structural Design Parameters for Highly Birefringent Coordination Polymers / J.R. Thompson, M.J. Katz, V.E. Williams et al. // Inorg. Chem. – 2015. – V. 54, № 13. – P. 6462–6471. DOI: 10.1021/acs.inorgchem.5b00749.

Lefebvre, J. Cu[Au(CN)2]2(DMSO)2: Golden Polymorphs That Exhibit Vapochromic

Behavior / J. Lefebvre, R.J. Batchelor, D.B. Leznoff // J. Am. Chem. Soc. – 2004. – V. 126, № 49. – P. 16117–16125. DOI: 10.1021/ja049069n.

Vapochromic Behaviour of M[Au(CN)2]2-Based Coordination Polymers (M = Co, Ni) / J. Lefebvre J, J.L. Korčok, M.J. Katz et al. // Sensors. – 2012. – V. 12, № 3. – P. 3669–3692. DOI: 10.3390/s120303669.

Varju, B.R. Mixed Cu(i)/Au(i) Coordination Polymers as Reversible Turn-on Vapoluminescent Sensors for Volatile Thioethers / B.R. Varju, J.S. Ovens, D.B. Leznoff // Chem. Commun. – 2017. – V. 53, № 48. – P. 6500–6503. DOI: 10.1039/C7CC03428H.

Ovens, J.S. Raman Detected Sensing of Volatile Organic Compounds by Vapochromic Cu[AuX2(CN)2]2 (X = Cl, Br) Coordination Polymer Materials / J.S. Ovens, D.B. Leznoff // Chem.

Mater. – 2015. – V. 27, № 5. – P. 1465–1478. DOI: 10.1021/cm502998w.

Ovens, J.S. Thermal Expansion Behavior of MI[AuX2(CN)2]-Based Coordination Polymers (M = Ag, Cu; X = CN, Cl, Br) / J.S. Ovens, D.B. Leznoff // Inorg. Chem. – 2017. – V. 56, № 13. – P. 7332–7343. DOI: 10.1021/acs.inorgchem.6b03153.

Ovens, J.S. Probing Halogen⋯Halogen Interactions via Thermal Expansion Analysis /

J.S. Ovens, D.B. Leznoff // CrystEngComm. – 2018. – V. 20, №13. – P. 1769–1773 DOI: 10.1039/C7CE02167D.

Lefebvre, J. Synthesis, Structure and Magnetic Properties of 2-D and 3-D [cation]{M[Au(CN)2]3} (M = Ni, Co) Coordination Polymers / J. Lefebvre, D. Chartrand, D.B. Leznoff // Polyhedron. – 2007. – V. 26, № 9–11. – P. 2189–2199. DOI: 10.1016/j.poly.2006.10.045.

Magnetic Properties of Isostructural M(H2O)4[Au(CN)4]2-based Coordination Polymers (M = Mn, Co, Ni, Cu, Zn) by SQUID and μSR Studies / A.R. Geisheimer, W. Huang, V. Pacradouni et al // Dalton Trans. – 2011. – V. 40, № 29. – P. 7505–7516. DOI: 10.1039/C0DT01546F.

A New Basic Motif in Cyanometallate Coordination Polymers: Structure and Magnetic Behavior of M(μ‐OH2)2[Au(CN)2]2 (M = Cu, Ni) / J. Lefebvre, F. Callaghan, M.J. Katz et al. // Chem. Eur. J. – 2006. – V. 12, № 26. – P. 6748–6761. DOI: 10.1002/chem.200600303.

Magnetic Frustration and Spin Disorder in Isostructural M(μ-OH2)2[Au(CN)2]2 (M = Mn, Fe, Co) Coordination Polymers Containing Double Aqua-Bridged Chains: SQUID and μSR Studies / J. Lefebvre, P. Tyagi, S. Trudel et al. // Inorg. Chem. – 2008. – V. 48, № 1. – P. 55–67. DOI: 10.1021/ic801094m.

Шевченко, Д.П. Строение дигалогенодицианоауратных комплексов [Ph3PR][Au(CN)2Hal2], Hal = Cl, R = Me, СH2Ph; Hal = Br, R = цикло-C6H11; Hal = I, R = Ph / Д.П. Шевченко, А.Е. Хабина // Вестник ЮУрГУ. Серия «Химия». – 2021. – Т. 13, № 1. – С. 58–67. DOI: 10.14529/chem210106.

Синтез и строение дицианодибромоаурата метилтрифенилфосфония [Ph3PMe][Au(CN)2Br2] / А.Н. Ефремов, В.В. Шарутин, О.К. Шарутина и др. // Изв. вузов. Химия и хим. технология. – 2020. – Т. 63, № 3. – С. 10–15. DOI: 10.6060/ivkkt.20206303.6097.

Синтез и строение комплексов золота [Ph3PR]+[Au(CN)2I2-trans]−, R = Et, CH2Ph, Ph / В.В. Шарутин, О.К. Шарутина, Н.М. Тарасова и др. // Изв АН. Сер. хим. – 2020. – Т. 69, № 10. – С. 1892–1896).

Дицианодибромоаураты алкилтрифенилфосфония [Ph3PAlk][Au(CN)2Br2], Alk = CH2C6H4(OH)-2, CH2C6H11-cyclo, CH2Ph, CH2C6H4CN-4 / В.В. Шарутин, О.К. Шарутина, Н.М. Тарасова и др. // Журн. неорг. химии. – 2020. – Т. 65, № 2. – С. 171–178. DOI: 10.31857/S0044457X20020154.

Шарутин, В.В. Строение минорных продуктов реакций дииододицианоаурата калия с галогенидами тетраорганилфосфора и -сурьмы // В.В. Шарутин / Вест. Южно-Уральского Гос.

Ун-та. Сер. хим. – 2020. – Т. 12, № 2. – С. 74–84. DOI: 10.14529/chem200208.

Синтез и строение дицианодииодоауратов тетра(пара-толил)сурьмы [p-Tol4Sb][Au(CN)2I2] и алкилтрифенилфосфония [Ph3PAlk][Au(CN)2I2], Alk = Me, CH2CN / В.В. Шарутин, О.К. Шарутина, А.Н. Ефремов и др. // Коорд. химия. – 2020. – Т. 46, № 9. – С. 554–561. DOI: 10.31857/S0132344X20090030 .

Bruker. SMART and SAINT-Plus. Versions 5.0. Data Collection and Processing Software for the SMART System. Bruker AXS Inc., Madison, Wisconsin, USA, 1998.

Bruker. SHELXTL/PC. Versions 5.10. An Integrated System for Solving, Refining and Displaying Crystal Structures From Diffraction Data. Bruker AXS Inc., Madison, Wisconsin, USA, 1998.

OLEX2: Complete Structure Solution, Refinement and Analysis Program / O.V. Dolomanov, L.J. Bourhis, R.J. Gildea et al. // J. Appl. Cryst. – 2009. – V. 42. – P. 339–341. DOI: 10.1107/S0021889808042726.

Covalent Radii Revisited / B. Cordero, V. Gómez, A.E. Platero-Prats et al. // Dalton Trans. – 2008. – № 21. – P. 2832–2838. DOI: 10.1039/B801115J.

Consistent Van der Waals Radii for the Whole Main Group / M. Mantina, A.C. Chamberlin, R. Valero et al. // J. Phys. Chem. A. – 2009. – V. 113, №19. – P. 5806–5812. DOI: 10.1021/jp8111556.

Nishio, M. The CH/π Hydrogen Bond in Chemistry. Conformation, Supramolecules, Optical Resolution and Interactions Involving Carbohydrates / M. Nishio // Phys. Chem. Chem. Phys. – 2011. – № 13. – P. 13873–13900. DOI: 10.1039/C1CP20404A