A unique copper coordination structure with both mono- and bi-dentate ethylenediamine ligands

Sharma, Jai; Jiang, Zhelong; Bhutani, Ankita; Behera, Piush; Shoemaker, Daniel P.

doi:10.1039/c8ce02188k

A unique copper coordination structure with both mono- and bi-dentate ethylenediamine ligands

Journal Article · Fri Mar 01 00:00:00 EST 2019 · CrystEngComm

DOI:https://doi.org/10.1039/c8ce02188k· OSTI ID:1612047

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Univ. of Illinois at Urbana-Champaign, IL (United States); DOE/OSTI
Univ. of Illinois at Urbana-Champaign, IL (United States)

The compound (ethylenediamine-N)-bis(ethylenediamine-N,N')-copper(II) bis(nitrate) is reported. It has an asymmetric unit containing Cu(II) penta-coordinating to two chelating ethylenediamine (en) and one monodentate en ligands with square-pyramidal-based geometry having severe trigonal distortion, together with two nitrate anions. It is the first crystallographic confirmation of the existence of penta-coordination with exclusively en ligands for any metal center, as well as the first monodentate en attached to Cu(II) seen in the solid state. It can be visualized as the penta-ammine effect realized solely with bi-amine ligands, defying the presumed necessity of mono-amines. X-ray crystallography establishes it to have P2₁/c space group with a = 12.83 Å, b = 9.77 Å, c = 11.91 Å, and β = 94.8° (at 100 K). Spectroscopic analysis of this compound is consistent with the crystallographic assessment of the coordination chemistry, and it is found to be a S = 1/2 paramagnet.

View Accepted Manuscript (DOE)

Research Organization:: University of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0013897

OSTI ID:: 1612047

Alternate ID(s):: OSTI ID: 1499059

Journal Information:: CrystEngComm, Journal Name: CrystEngComm Journal Issue: 17 Vol. 21; ISSN CRECF4; ISSN 1466-8033

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (51)

Synthesis and Characterization of Magnetic Iron Sulfide Nanowires Nath, M.; Choudhury, A.; Kundu, A. Advanced Materials, Vol. 15, Issue 24 https://doi.org/10.1002/adma.200306042	journal	December 2003
Nanocrystalline Ag from Supramolecular Stabilization of Metals in 4-tert-Butylcalix[4]arene Lattices Brown, Philip O.; Enright, Gary D.; Ripmeester, John A. Chemistry – An Asian Journal, Vol. 1, Issue 4 https://doi.org/10.1002/asia.200600101	journal	October 2006
Synthesis and Characterization of Magnetic Iron Sulfide Nanowires. Nath, Mannashi; Choudhury, Amitava; Kundu, Asish ChemInform, Vol. 35, Issue 10 https://doi.org/10.1002/chin.200410007	journal	March 2004
Controlled Assembly of [Nb _{6– x} W _x O ₁₉ ] ^{(8– x )–} ( x = 0–4) Lindqvist Ions with (Amine)copper Complexes Anderson, Travis M.; Rodriguez, Mark A.; Stewart, Thomas A. European Journal of Inorganic Chemistry, Vol. 2008, Issue 21 https://doi.org/10.1002/ejic.200800415	journal	July 2008
Chelates in agriculture Clemens, D. F.; Whitehurst, B. M.; Whitehurst, G. B. Fertilizer Research, Vol. 25, Issue 2 https://doi.org/10.1007/BF01095092	journal	January 1990
Structure and Spectral Characterization of Coordination Polymers Constructed by CuCN and Aliphatic Diamines Etaiw, Safaa-Eldin H.; Abdou, Safaa N.; Badr El-din, Ahmed S. Journal of Inorganic and Organometallic Polymers and Materials, Vol. 25, Issue 6 https://doi.org/10.1007/s10904-015-0252-z	journal	June 2015
Direct analysis of microbial extracts containing metabolites of ethylenediamine-type antihistamines via high-performance liquid chromatography-thermospray mass spectrometry Korfmacher, W. A.; Getek, T. A.; Hansen, E. B. Analytical Biochemistry, Vol. 185, Issue 1 https://doi.org/10.1016/0003-2697(90)90268-E	journal	February 1990
Binuclear chloropentaaminecobalt(III) complexes Alexander, M. Dale; Kilcrease, Harold G. Journal of Inorganic and Nuclear Chemistry, Vol. 35, Issue 5 https://doi.org/10.1016/0022-1902(73)80249-0	journal	May 1973
Vibrational studies of metal-ethylenediamine thiosulfates—I. Infrared and Raman spectra of the tris-ethylenediamine thiosulfates MII(en)3S2O3(MII = Zn, Cd, Fe,Ni, Co, Mn) and some of their N-deuterated analogues Gabelica, Zélimir Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 32, Issue 2 https://doi.org/10.1016/0584-8539(76)80085-2	journal	January 1976
Vibrational studies of metal-ethylenediamine thiosulfates—II. Infrared spectra of Cu(en)2S2O3 and some related bis-ethylenediamine complexes of copper (II) Gabelica, Zélimir Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 32, Issue 2 https://doi.org/10.1016/0584-8539(76)80086-4	journal	January 1976
FTIR and Raman spectra and structure of Cu(NO3)+ in aqueous solution and acetone Castro, Paul M.; Jagodzinski, Paul W. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 47, Issue 12 https://doi.org/10.1016/0584-8539(91)80008-7	journal	January 1991
Overcoming the chelate effect: hypodentate coordination of ethylenediamine, diethylenetriamine and tris(2-aminoethyl)amine in Co(III) complexes Fanshawe, Rachel L.; Mobinikhaledi, Akbar; Clark*, Charles R. Inorganica Chimica Acta, Vol. 307, Issue 1-2 https://doi.org/10.1016/S0020-1693(00)00184-5	journal	September 2000
The first X-ray crystal structures of cobalt complexes containing monodentate and bridging ethylenediamine ligands House, Donald A.; Steel, Peter J. Inorganica Chimica Acta, Vol. 288, Issue 1 https://doi.org/10.1016/S0020-1693(99)00033-X	journal	May 1999
Effect of Theophylline on Exercise-Induced Myocardial Ischaemia Crea, Filippo; Galassi, AlfredoR.; Carlos Kaski, Juan The Lancet, Vol. 333, Issue 8640 https://doi.org/10.1016/S0140-6736(89)92204-6	journal	April 1989
Chronic Toxicity and Carcinogenicity Studies of Ethylenediamine Dihydrochloride by Dietary Incorporation in Fischer 344 Rats Hermansky, S. J.; Yang, R. S. H.; Garman, R. H. Food and Chemical Toxicology, Vol. 37, Issue 7 https://doi.org/10.1016/S0278-6915(99)00051-4	journal	July 1999
Accessing magnetic chalcogenides with solvothermal synthesis: KFeS2 and KFe2S3 Han, Insung; Jiang, Zhelong; dela Cruz, Clarina Journal of Solid State Chemistry, Vol. 260 https://doi.org/10.1016/j.jssc.2018.01.003	journal	April 2018
The first bis(orotato-N,O) cadmium complex with monodentate protonated ethylenediamine ligands: Synthesis, spectrothermal properties of a cadmium(II)-orotato complex with ethylenediamine – Crystal structure of trans-[Cd(HOr)2(enH)2]·2H2O and cis-[Cd(H2O)2(phen)2](H2Or)2·2H2O Yeşilel, Okan Zafer; Ölmez, Halis; Arici, Cengiz Polyhedron, Vol. 26, Issue 14 https://doi.org/10.1016/j.poly.2007.03.060	journal	August 2007
Synthesis and modes of coordination of energetic nitramine ligands in copper(II), nickel(II), and palladium(II) complexes Palopoli, S. F.; Geib, S. J.; Rheingold, A. L. Inorganic Chemistry, Vol. 27, Issue 17 https://doi.org/10.1021/ic00290a015	journal	August 1988
Stereochemistry and Mechanism of the Reactions of Ethylenediamine with Ethylenediaminetetraacetatocobaltate(III) and Propylenediaminetetraacetatocobaltate(III) Busch, Daryle H.; Swaminathan, K.; Cooke, Dean W. Inorganic Chemistry, Vol. 1, Issue 2 https://doi.org/10.1021/ic50002a013	journal	May 1962
Raman and Infrared Spectra of Complexes of Ethylenediamine with Zinc(II), Cadmium(II), and Mercury(II) Krishnan, K.; Plane, Robert A. Inorganic Chemistry, Vol. 5, Issue 5 https://doi.org/10.1021/ic50039a031	journal	May 1966
Synthesis of a monodentate ethylenediamine complex of chromium(III) and kinetics of hydrolysis of tetraaquoethylenediaminechromium(III) cation and of pentaaquo(2-aminoethylammonium)chromium(III) cation Childers, Ray F.; Vander Zyl, K. G.; House, Donald A. Inorganic Chemistry, Vol. 7, Issue 4 https://doi.org/10.1021/ic50062a026	journal	April 1968
Monodentate ethylenediamine complex of cobalt(III) Alexander, Martin Dale; Spillert, Charles A. Inorganic Chemistry, Vol. 9, Issue 10 https://doi.org/10.1021/ic50092a028	journal	October 1970
Rate of aquation of trans-difluorobis(ethylenediamine)chromium(III) through an isolable monodentate ethylenediamine complex Pyke, Stephen C.; Linck, R. G. Inorganic Chemistry, Vol. 10, Issue 11 https://doi.org/10.1021/ic50105a017	journal	November 1971
Transition metal pentacoordination Rossi, Angelo R.; Hoffmann, Roald. Inorganic Chemistry, Vol. 14, Issue 2 https://doi.org/10.1021/ic50144a032	journal	February 1975
Spectroscopic characterization and thermal stability of copper(II) ethylenediamine complexes on solid surfaces. 2. Montmorillonite Velghe, Firmin; Schoonheydt, Robert A.; Uytterhoeven, Jan B. The Journal of Physical Chemistry, Vol. 81, Issue 12 https://doi.org/10.1021/j100527a013	journal	June 1977
A Novel Mild Route to Nanocrystalline Selenides at Room Temperature Wang, Wenzhong; Geng, Yan; Yan, Ping Journal of the American Chemical Society, Vol. 121, Issue 16 https://doi.org/10.1021/ja9832414	journal	April 1999
Spectroscopy and Structures of Copper Complexes with Ethylenediamine and Methyl-Substituted Derivatives Wang, Xu; Yang, Dong-Sheng The Journal of Physical Chemistry A, Vol. 110, Issue 24 https://doi.org/10.1021/jp061325q	journal	June 2006
Electron Paramagnetic Resonance Study of Copper–Ethylenediamine Complex Ion Intercalated in Bentonite Donoso, José Pedro; Magon, Claudio J.; Lima, José F. The Journal of Physical Chemistry C, Vol. 117, Issue 45 https://doi.org/10.1021/jp408658d	journal	October 2013
Recurrent H-bond graph motifs between metal tris-ethylenediamine cations and uncoordinated oxalate anions: Fitting a three pin plug into a two pin socket Keene, Tony D.; Hursthouse, Michael B.; Price, Daniel J. CrystEngComm, Vol. 14, Issue 1 https://doi.org/10.1039/C1CE05837A	journal	January 2012
Jahn–Teller distortions in transition metal compounds, and their importance in functional molecular and inorganic materials Halcrow, Malcolm A. Chem. Soc. Rev., Vol. 42, Issue 4 https://doi.org/10.1039/C2CS35253B	journal	January 2013
Synthesis, structure, and spectroscopic properties of copper( II ) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper( II ) perchlorate Addison, Anthony W.; Rao, T. Nageswara; Reedijk, Jan J. Chem. Soc., Dalton Trans., Issue 7 https://doi.org/10.1039/DT9840001349	journal	January 1984
Crystal structure and electronic properties of ammine[tris(2-aminoethyl)amine]copper(II) diperchlorate and potassium penta-amminecopper(II) tris(hexafluorophosphate) Duggan, Mary; Ray, Noel; Hathaway, Brian Journal of the Chemical Society, Dalton Transactions, Issue 8 https://doi.org/10.1039/dt9800001342	journal	January 1980
The electronic properties and stereochemistry of the copper(II) ion. Part I. Bis(ethylenediamine)copper(II) complexes Procter, I. M.; Hathaway, B. J.; Nicholls, P. Journal of the Chemical Society A: Inorganic, Physical, Theoretical https://doi.org/10.1039/j19680001678	journal	January 1968
The electronic properties and stereochemistry of the copper(II) ion. Part III. Some penta-ammine complexes Tomlinson, A. A. G.; Hathaway, B. J. Journal of the Chemical Society A: Inorganic, Physical, Theoretical https://doi.org/10.1039/j19680001905	journal	January 1968
263. Mechanism and steric course of octahedral aquation. Part V. The isomerisation, racemisation, and water exchange of cis- and trans-aquoamminebis(ethylenediamine)cobalt(III) salts Martin, D. F.; Tobe, M. L. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9620001388	journal	January 1962
COPPER (II) COORDINATION COMPOUNDS: CLASSIFICATION AND ANALYSIS OF CRYSTALLOGRAPHIC AND STRUCTURAL DATA: I. Mononuclear Tetra — and Pentacoordinate Compounds Melník, Milan; Kabešová, Mária; Dunaj-Jurčo, Michal Journal of Coordination Chemistry, Vol. 41, Issue 1-2 https://doi.org/10.1080/00958979708027956	journal	February 1997
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
A redetermination of bis(ethylenediamine- N , N ')bis(perchlorato- O )copper(II) Maxcy, K. R.; Turnbull, M. M. Acta Crystallographica Section C Crystal Structure Communications, Vol. 55, Issue 12 https://doi.org/10.1107/S010827019901152X	journal	December 1999
Temperature-dependent analysis of thermal motion, disorder and structures of tris(ethylenediamine)zinc(II) sulfate and tris(ethylenediamine)copper(II) sulfate Smeets, Stef; Parois, Pascal; Bürgi, Hans-Beat Acta Crystallographica Section B Structural Science, Vol. 67, Issue 1 https://doi.org/10.1107/S0108768110054571	journal	January 2011
The crystal structure of bis(ethylenediamine)copper(II) thiocyanate Brown, B. W.; Lingafelter, E. C. Acta Crystallographica, Vol. 17, Issue 3 https://doi.org/10.1107/S0365110X64000640	journal	March 1964
The crystal structure of bisethylenediaminecopper(II) nitrate Komiyama, Y.; Lingafelter, E. C. Acta Crystallographica, Vol. 17, Issue 9 https://doi.org/10.1107/S0365110X64002961	journal	September 1964
The crystal structure of bis(ethylenediamine)copper(II) fluoroborate Brown, D. S.; Lee, J. D.; Melsom, B. G. A. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 24, Issue 5 https://doi.org/10.1107/S0567740868003092	journal	May 1968
The crystal structure of the mixed valence copper cyanide ethylenediamine complex: aquobis(en)copper(II) di-[catena-di-μ-cyanocuprate(I)], Cu3(en)2(CN)4.H2O Williams, R. J.; Larson, A. C.; Cromer, D. T. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 28, Issue 3 https://doi.org/10.1107/S0567740872003310	journal	March 1972
Diaquabis(ethylenediamine-κ ² N , N ′)copper(II) bis(4-aminonaphthalene-1-sulfonate) dihydrate Li, Ming-Tian; Wang, Cheng-Gang; Wu, Yu Acta Crystallographica Section E Structure Reports Online, Vol. 61, Issue 8 https://doi.org/10.1107/S1600536805023627	journal	July 2005
Crystal structure refinement with SHELXL Sheldrick, George M. Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053229614024218	journal	January 2015
The first-row transition-metal series of tris(ethylenediamine) diacetate complexes [ M (en) ₃ ](OAc) ₂ ( M is Mn, Fe, Co, Ni, Cu, and Zn) Pham, Duyen N. K.; Roy, Mrittika; Golen, James A. Acta Crystallographica Section C Structural Chemistry, Vol. 73, Issue 6 https://doi.org/10.1107/S2053229617006738	journal	May 2017
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
One-Step Processing and Bleaching of Mechanically Separated Kenaf Fibers: Effects on Physical and Chemical Properties No authors listed Textile Research Journal, Vol. 73, Issue 4 https://doi.org/10.1177/004051750307300411	journal	April 2003
Cobalt(III) Complexes Containing Large Chelate Rings. I. Syntheses and Properties of Bis(ethylenediamine)-1,ω-diaminoalkanecobalt(III) Complexes Ogino, Hiroshi; Fujita, Junnosuke Bulletin of the Chemical Society of Japan, Vol. 48, Issue 6 https://doi.org/10.1246/bcsj.48.1836	journal	June 1975
Thermal and Photo-Responsibility of Axial Semi-Coordination Bonds in a Copper(II) Complex Akitsu, Takashiro; Einaga, Yasuaki Bulletin of the Chemical Society of Japan, Vol. 77, Issue 4 https://doi.org/10.1246/bcsj.77.763	journal	April 2004
Studies on Absorption Spectra. I. Results of Calculations on the Spectra and Configuration of Copper(II) Ions. Bjerrum, Jannik; Ballhausen, C. J.; Jørgensen, Chr. Klixbüll Acta Chemica Scandinavica, Vol. 8 https://doi.org/10.3891/acta.chem.scand.08-1275	journal	January 1954

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