DETERMINATION OF ABSOLUTE CONFIGURATION OF 8,8,10,10TETRACHLORO-20,21-DIHYDRO-18H,23H-6,12-EPIAZENO-6λ5,8λ5,10λ5, 12λ5[1,3,2]BENZOXAZAPHOSPHONINO[2',3':8,9][1,3,5,7,9,2,4,6,8] PENTAAZATETRAPHOSPHACYCLOUNDSYNO[2,1-B][1,3,2] BENZOXAZAPHOSPHONINE USING X-RAY CRYSTALLOGRAPHY

Gamze Elmas; Aytuğ Okumuş; Satiye Sevim İsaoğlu; Tuncer Hökelek; Zeynel Kılıç

Research Article

Year 2019, Volume: 61 Issue: 1, 1 - 14, 31.12.2019

Gamze Elmas Aytuğ Okumuş Satiye Sevim İsaoğlu Tuncer Hökelek Zeynel Kılıç

Abstract

References

V. Chandrasekhar and R. S. Narayanan, Phosphazenes. Organophosphorus Chemistry, (Cambridge, UK: Royal Society of Chemistry) 45 (2016) p. 375-437.
V. Chandrasekhar and R. S. Narayanan, Phosphazenes. Organophosphorus Chemistry, (Cambridge, UK: Royal Society of Chemistry) 46 (2017) p. 342-417.
V. Chandrasekhar and A. Chakraborty, Phosphazenes. Organophosphorus Chemistry, (Cambridge, UK: Royal Society of Chemistry) 48 (2019) p. 400-423.
X. Liu, J. P. Breon, C. Chen and H. R. Allcock, Substituent exchange reactions of trimeric and tetrameric aryloxycyclophosphazenes with sodium 2,2,2-trifluoroethoxide. Dalton Transaction, 41 (2012) 2100-2109.
G. Elmas, The reactions of 2-trans-6-bis(4-fluorobenzyl)spirocyclotetraphosphazene with primary amines:spectroscopic and crystallographic characterizations. Phosphorus, Sulfur, and Silicon and the Related Elements, 192 (2017) 1224-1232.
G. Elmas, A. Okumuş, Z. Kılıç, M. Çam, L. Açık and T. Hökelek, Phosphorus-nitrogen compounds. Part 40. The syntheses of (4-fluorobenzyl) pendant armed cyclotetraphosphazene derivatives: Spectroscopic, crystallographic and stereogenic properties, DNA interactions and antimicrobial activities. Inorganica Chimica Acta, 476 (2018) 110-122.
G. Elmas, A. Okumuş, R. Cemaloğlu, Z. Kılıç, S. P. Çelik, L. Açık, B. Ç. Tunalı, M. Türk, N. A. Çerçi, R. Güzel and T. Hökelek, Phosphorus-nitrogen compounds. Part 38. Syntheses, characterizations,cytotoxic, antituberculosis and antimicrobial activities and DNA interactions of spirocyclotetraphosphazenes with bis-ferrocenyl pendant arms. Journal of Organometallic Chemistry, 853 (2017) 93-106.
G. Mutlu, G. Elmas, Z. Kılıç, T. Hökelek, L. Y. Koç, M. Türk, L. Açık, B. Aydın and H. Dal, Phosphorus-nitrogen compounds: Part 31. Syntheses, structural and stereogenic properties, in vitro cytotoxic and antimicrobial activities, DNA interactions of novel bicyclotetraphosphazenes containing bulky side group. Inorganica Chimica Acta, 436 (2015) 69-81.
G. Elmas, A. Okumuş, L.Y. Koç, H. Soltanzade, Z. Kılıç, T. Hökelek, H. Dal, L. Açık, Z. Üstündağ, D. Dündar and M. Yavuz, Phosphorus-nitrogen compounds. Part 29. Syntheses, crystal structures, spectroscopic and stereogenic properties, electrochemical investigations, antituberculosis, antimicrobial and cytotoxic activities and DNA interactions of ansa-spiro-ansa cyclotetraphosphazenes. Europane Journal of Medicinal Chemistry, 87 (2014) 662-676.
T. S. Cameron, A. Linden, G. Guerch, J. P. Bonnet and J. Labarre, Crystal and molecular structure of the spiransa and dispiransa cyclophosphazenic derivatives from spermidine and spermine. Journal of Molecular Structure, 212 (1989) 295-304.
A. Uslu and S. Yeşilot, Chiral configurations in cyclophosphazene chemistry. Coordination Chemistry Reviews, 291 (2015) 28-67.
K. Kajiyama, Y. Setone, K. Aoyagi and H. Yuge, Chiral HPLC Separation, Absolute Structural Elucidation, and Determination of Stereochemical Stability of trans‐ Bis[2‐(2‐ pyridinyl)aminophenolato] Cyclotriphosphazene. Chirality, 28 (2016) 556-561.
G. Elmas, Syntheses and structural characterizations of 2-pyridyl(N/O)spirocyclotriphosphazene derivatives. Phosphorus, Sulfur, and Silicon and the Related Elements,194/1-2 (2019) 13-24.
A. Binici, A. Okumuş, G. Elmas, Z. Kılıç, N. Ramazanoğ lu, L. Açık, H. Şimşek, B.Ç. Tunalı, M. Türk, R. Güzel and T. Hökelek. Phosphorus–nitrogen compounds. Part 42. The comparative syntheses of 2-cis-4-ansa(N/O) and spiro(N/O) cyclotetraphosphazene derivatives: spectroscopic and crystallographic characterization, antituberculosis and cytotoxic activity studies. New Journal of Chemistry, 43 (2019) 6856-6873.
T. L. Greaves and C. J. Drummond, Protic Ionic Liquids: Properties and Applications. Chemical Reviews, 108 (2008) 206-237.
H. R. Allcock, Recent developments in polyphosphazene materials science. Current Opinion in Solid State and Materials Science, 10 (2006) 231-240.
M. K. Harrup, K. L. Gering, H. W. Rollins, S. V. Sazhin, M. T. Benson, D. K. Jamison, C. J. Michelbacher and T. A. Luther, Phosphazene based additives for ımprovement of safety and battery lifetimes in lithium-ıon batteries. ESC Transaction, 41 (2012) 13-25.
G. Elmas, A. Okumuş, P. Sevinç, Z. Kılıç, L. Açık, M. Atalan, M. Türk, G. Deniz and T. Hökelek, Phosphorus-nitrogen compounds. Part 37. Syntheses and structural characterizations, biological activities of mono and bis(4-fluorobenzyl) spirocyclotetraphosphazenes. New Journal of Chemistry, 41 (2017) 5818-5835.
A. Okumuş, G. Elmas, R. Cemaloğlu, B. Aydın, A. Binici, H. Şimşek, L. Açık, M. Türk, R. Güzel, Z. Kılıç and T. Hökelek, Phosphorus–nitrogen compounds. Part 35. Syntheses, spectroscopic and electrochemical properties, and antituberculosis, antimicrobial and cytotoxic activities of mono-ferrocenyl-spirocyclotetraphosphazenes. New Journal of Chemistry, 40 (2016) 5588-5603.
G. Elmas, A. Okumuş, Z. Kılıç, S.P. Çelik and L. Açık, The spectroscopic and thermal properties, antibacterial and antifungal Activity and DNA interactions of 4-(fluorobenzyl)spiro(N/O)cyclotri phosphazenium salts. Journal of the Turkish Chemical Society, Section A: Chemistry, 4/3 (2017) 993-1016.
A. Okumuş, G. Elmas, Z. Kılıç, N. Ramazanoğlu, L. Açık, M. Türk and G. Akça, The reactions of N3P3Cl6 with monodentate and bidentate ligands: The syntheses and structural characterizations, In vitro antimicrobial activities and DNA interactions of 4- fluorobenzyl(N/O)spirocylotriphosphazenes. Turkish Journal of Chemistry, 41 (2017) 525-547.
G. Elmas, A. Okumuş, Z. Kılıç, L. Y. Gönder, L. Açık and T. Hökelek, The Syntheses and Structural Characterizations, Antimicrobial Activity and In vitro DNA Binding of 4-fluorobenzylspıro(N/O)cyclotriphosphazenes and Their Phosphazenium salts. Journal of the Turkish Chemical Society, Section A: Chemistry, 3 (2016) 25-46.
G. Elmas, Syntheses and spectroscopic investigations of 2-pyridyl(N/N)spirocyclotriphosphazenes. Journal of the Turkish Chemical Society, Section A: Chemistry, 5/2 (2018) 621-634.
G. Elmas (nee Egemen), A. Okumuş, Z. Kılıç, T. Hökelek, L. Açık, H. Dal, N. Ramazanoğlu and L. Y. Koç, Phosphorus−nitrogen compounds. Part 24. Syntheses, crystal structures, spectroscopic and stereogenic properties, biological activities, and DNA interactions of novel spiro-ansa-spiro- and ansaspiro-ansacyclotetraphosphazenes. Inorganic Chemistry, 51 (2012) 12841-12856.
Bruker SADABS, Bruker AXS Inc. Madison, Wisconsin, USA (2005).
G. M. Sheldrick, SHELXS-97, SHELXL-97 University of Gottingen, Gottingen, Germany (1997).
D. Cremer and J. A. Pople, General definition of ring puckering coordinates. Journal of American Chemical Society, 97 (1975) 1354-1358.
F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, G. Orpen and R. Taylor, Tables of bond lengths determined by X-ray and neutron diffraction. Part 1. Bond lengths in organic compounds. Journal of the Chemical Society, Perkin Transactions 2. 12 (1987) 1-19.
S. Safran, T. Hökelek, S. Bilge, Ş. Demiriz, A. Natsagdorj, and Z. Kılıç, Crystal Structure of 8,8-dichloro-1,2,10,11,13,14-hexahydro-6λ5,8λ5,10λ5-6,10-nitrilo[1,3,5,7,2,4,6]tetrazatriphosphoninobis [1,3,2]oxazaphosphorine. Analytical Sciences X-ray Structure Analysis Online, 21 (2005) x77-x78.
A. J. Wagner, A. Vos, The crystal structure of compounds with (N-P)n rings. IV. The stable modification (T form) of tetrameric phosphonitrilic chloride, N4P4Cl8. Acta Crystallograhica Section B. B24 (1968) 707-713.
A. B. Chaplin, J. A. Harrison and P. J. Dyson, Revisiting the electronic structure of phosphazenes. Inorganic Chemistry, 44 (2005) 8407-8417.
L. J. Farrugia, ORTEP-3 for Windows- a version of ORTEP-III with a Graphical User Interface (GUI). Journal of Applied Crystallography, 30 (1997) 565-566.

DETERMINATION OF ABSOLUTE CONFIGURATION OF 8,8,10,10TETRACHLORO-20,21-DIHYDRO-18H,23H-6,12-EPIAZENO-6λ5,8λ5,10λ5, 12λ5[1,3,2]BENZOXAZAPHOSPHONINO[2',3':8,9][1,3,5,7,9,2,4,6,8] PENTAAZATETRAPHOSPHACYCLOUNDSYNO[2,1-B][1,3,2] BENZOXAZAPHOSPHONINE USING X-RAY CRYSTALLOGRAPHY

Year 2019, Volume: 61 Issue: 1, 1 - 14, 31.12.2019

Gamze Elmas Aytuğ Okumuş Satiye Sevim İsaoğlu Tuncer Hökelek Zeynel Kılıç

Abstract

The title compound, 8, 8, 10, 10-tetrachloro-20,21-dihydro-18H, 23H-6, 12epiazeno-6λ5, 8λ5, 10λ5, 12λ5-[1,3,2] benzoxazaphosphonino [2',3':8,9][1,3,5,7,9,2,4,6,8] pentaazatetraphosphacyclo undsyno [2,1-b] [1,3,2] benzoxazaphosphonine; C16H16Cl4N6O2P4, a cyclotetraphosphazene, has a tetrachloro-2, 4-spiro-ansa-spiro (tetrachloro-2,4-sas) architecture in which the bicyclic structure has consisted of eightmembered tetrameric N4P4 and seven-membered ansa (N1/P1/P1′/N4′/C8′/C8/N4) rings fused with a common PNP fragment. The asymmetric unit possesses one-half of the molecule. P1 and P1′ atoms are stereogenic centres. In addition, there is a mirror plane passing through the N3 and N1 atoms in the molecule, and therefore, this compound is in meso form (RS/SR). According to the checkcif result, it is found that the absolute configuration of P1 and/or P1′ phosphorus centers is RS, displaying that in the solid-state there is only one enantiomer in the unit cell. The space group is P bnm with cell parameters of a = 6.2692(2), b = 15.8111(3), c = 22.9393(4) Å.

Keywords

Cyclotetraphosphazene, spiro-ansa-spiro-Structure, X-ray crystallography

References

V. Chandrasekhar and R. S. Narayanan, Phosphazenes. Organophosphorus Chemistry, (Cambridge, UK: Royal Society of Chemistry) 45 (2016) p. 375-437.
V. Chandrasekhar and R. S. Narayanan, Phosphazenes. Organophosphorus Chemistry, (Cambridge, UK: Royal Society of Chemistry) 46 (2017) p. 342-417.
V. Chandrasekhar and A. Chakraborty, Phosphazenes. Organophosphorus Chemistry, (Cambridge, UK: Royal Society of Chemistry) 48 (2019) p. 400-423.
X. Liu, J. P. Breon, C. Chen and H. R. Allcock, Substituent exchange reactions of trimeric and tetrameric aryloxycyclophosphazenes with sodium 2,2,2-trifluoroethoxide. Dalton Transaction, 41 (2012) 2100-2109.
G. Elmas, The reactions of 2-trans-6-bis(4-fluorobenzyl)spirocyclotetraphosphazene with primary amines:spectroscopic and crystallographic characterizations. Phosphorus, Sulfur, and Silicon and the Related Elements, 192 (2017) 1224-1232.
G. Elmas, A. Okumuş, Z. Kılıç, M. Çam, L. Açık and T. Hökelek, Phosphorus-nitrogen compounds. Part 40. The syntheses of (4-fluorobenzyl) pendant armed cyclotetraphosphazene derivatives: Spectroscopic, crystallographic and stereogenic properties, DNA interactions and antimicrobial activities. Inorganica Chimica Acta, 476 (2018) 110-122.
G. Elmas, A. Okumuş, R. Cemaloğlu, Z. Kılıç, S. P. Çelik, L. Açık, B. Ç. Tunalı, M. Türk, N. A. Çerçi, R. Güzel and T. Hökelek, Phosphorus-nitrogen compounds. Part 38. Syntheses, characterizations,cytotoxic, antituberculosis and antimicrobial activities and DNA interactions of spirocyclotetraphosphazenes with bis-ferrocenyl pendant arms. Journal of Organometallic Chemistry, 853 (2017) 93-106.
G. Mutlu, G. Elmas, Z. Kılıç, T. Hökelek, L. Y. Koç, M. Türk, L. Açık, B. Aydın and H. Dal, Phosphorus-nitrogen compounds: Part 31. Syntheses, structural and stereogenic properties, in vitro cytotoxic and antimicrobial activities, DNA interactions of novel bicyclotetraphosphazenes containing bulky side group. Inorganica Chimica Acta, 436 (2015) 69-81.
G. Elmas, A. Okumuş, L.Y. Koç, H. Soltanzade, Z. Kılıç, T. Hökelek, H. Dal, L. Açık, Z. Üstündağ, D. Dündar and M. Yavuz, Phosphorus-nitrogen compounds. Part 29. Syntheses, crystal structures, spectroscopic and stereogenic properties, electrochemical investigations, antituberculosis, antimicrobial and cytotoxic activities and DNA interactions of ansa-spiro-ansa cyclotetraphosphazenes. Europane Journal of Medicinal Chemistry, 87 (2014) 662-676.
T. S. Cameron, A. Linden, G. Guerch, J. P. Bonnet and J. Labarre, Crystal and molecular structure of the spiransa and dispiransa cyclophosphazenic derivatives from spermidine and spermine. Journal of Molecular Structure, 212 (1989) 295-304.
A. Uslu and S. Yeşilot, Chiral configurations in cyclophosphazene chemistry. Coordination Chemistry Reviews, 291 (2015) 28-67.
K. Kajiyama, Y. Setone, K. Aoyagi and H. Yuge, Chiral HPLC Separation, Absolute Structural Elucidation, and Determination of Stereochemical Stability of trans‐ Bis[2‐(2‐ pyridinyl)aminophenolato] Cyclotriphosphazene. Chirality, 28 (2016) 556-561.
G. Elmas, Syntheses and structural characterizations of 2-pyridyl(N/O)spirocyclotriphosphazene derivatives. Phosphorus, Sulfur, and Silicon and the Related Elements,194/1-2 (2019) 13-24.
A. Binici, A. Okumuş, G. Elmas, Z. Kılıç, N. Ramazanoğ lu, L. Açık, H. Şimşek, B.Ç. Tunalı, M. Türk, R. Güzel and T. Hökelek. Phosphorus–nitrogen compounds. Part 42. The comparative syntheses of 2-cis-4-ansa(N/O) and spiro(N/O) cyclotetraphosphazene derivatives: spectroscopic and crystallographic characterization, antituberculosis and cytotoxic activity studies. New Journal of Chemistry, 43 (2019) 6856-6873.
T. L. Greaves and C. J. Drummond, Protic Ionic Liquids: Properties and Applications. Chemical Reviews, 108 (2008) 206-237.
H. R. Allcock, Recent developments in polyphosphazene materials science. Current Opinion in Solid State and Materials Science, 10 (2006) 231-240.
M. K. Harrup, K. L. Gering, H. W. Rollins, S. V. Sazhin, M. T. Benson, D. K. Jamison, C. J. Michelbacher and T. A. Luther, Phosphazene based additives for ımprovement of safety and battery lifetimes in lithium-ıon batteries. ESC Transaction, 41 (2012) 13-25.
G. Elmas, A. Okumuş, P. Sevinç, Z. Kılıç, L. Açık, M. Atalan, M. Türk, G. Deniz and T. Hökelek, Phosphorus-nitrogen compounds. Part 37. Syntheses and structural characterizations, biological activities of mono and bis(4-fluorobenzyl) spirocyclotetraphosphazenes. New Journal of Chemistry, 41 (2017) 5818-5835.
A. Okumuş, G. Elmas, R. Cemaloğlu, B. Aydın, A. Binici, H. Şimşek, L. Açık, M. Türk, R. Güzel, Z. Kılıç and T. Hökelek, Phosphorus–nitrogen compounds. Part 35. Syntheses, spectroscopic and electrochemical properties, and antituberculosis, antimicrobial and cytotoxic activities of mono-ferrocenyl-spirocyclotetraphosphazenes. New Journal of Chemistry, 40 (2016) 5588-5603.
G. Elmas, A. Okumuş, Z. Kılıç, S.P. Çelik and L. Açık, The spectroscopic and thermal properties, antibacterial and antifungal Activity and DNA interactions of 4-(fluorobenzyl)spiro(N/O)cyclotri phosphazenium salts. Journal of the Turkish Chemical Society, Section A: Chemistry, 4/3 (2017) 993-1016.
A. Okumuş, G. Elmas, Z. Kılıç, N. Ramazanoğlu, L. Açık, M. Türk and G. Akça, The reactions of N3P3Cl6 with monodentate and bidentate ligands: The syntheses and structural characterizations, In vitro antimicrobial activities and DNA interactions of 4- fluorobenzyl(N/O)spirocylotriphosphazenes. Turkish Journal of Chemistry, 41 (2017) 525-547.
G. Elmas, A. Okumuş, Z. Kılıç, L. Y. Gönder, L. Açık and T. Hökelek, The Syntheses and Structural Characterizations, Antimicrobial Activity and In vitro DNA Binding of 4-fluorobenzylspıro(N/O)cyclotriphosphazenes and Their Phosphazenium salts. Journal of the Turkish Chemical Society, Section A: Chemistry, 3 (2016) 25-46.
G. Elmas, Syntheses and spectroscopic investigations of 2-pyridyl(N/N)spirocyclotriphosphazenes. Journal of the Turkish Chemical Society, Section A: Chemistry, 5/2 (2018) 621-634.
G. Elmas (nee Egemen), A. Okumuş, Z. Kılıç, T. Hökelek, L. Açık, H. Dal, N. Ramazanoğlu and L. Y. Koç, Phosphorus−nitrogen compounds. Part 24. Syntheses, crystal structures, spectroscopic and stereogenic properties, biological activities, and DNA interactions of novel spiro-ansa-spiro- and ansaspiro-ansacyclotetraphosphazenes. Inorganic Chemistry, 51 (2012) 12841-12856.
Bruker SADABS, Bruker AXS Inc. Madison, Wisconsin, USA (2005).
G. M. Sheldrick, SHELXS-97, SHELXL-97 University of Gottingen, Gottingen, Germany (1997).
D. Cremer and J. A. Pople, General definition of ring puckering coordinates. Journal of American Chemical Society, 97 (1975) 1354-1358.
F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, G. Orpen and R. Taylor, Tables of bond lengths determined by X-ray and neutron diffraction. Part 1. Bond lengths in organic compounds. Journal of the Chemical Society, Perkin Transactions 2. 12 (1987) 1-19.
S. Safran, T. Hökelek, S. Bilge, Ş. Demiriz, A. Natsagdorj, and Z. Kılıç, Crystal Structure of 8,8-dichloro-1,2,10,11,13,14-hexahydro-6λ5,8λ5,10λ5-6,10-nitrilo[1,3,5,7,2,4,6]tetrazatriphosphoninobis [1,3,2]oxazaphosphorine. Analytical Sciences X-ray Structure Analysis Online, 21 (2005) x77-x78.
A. J. Wagner, A. Vos, The crystal structure of compounds with (N-P)n rings. IV. The stable modification (T form) of tetrameric phosphonitrilic chloride, N4P4Cl8. Acta Crystallograhica Section B. B24 (1968) 707-713.
A. B. Chaplin, J. A. Harrison and P. J. Dyson, Revisiting the electronic structure of phosphazenes. Inorganic Chemistry, 44 (2005) 8407-8417.
L. J. Farrugia, ORTEP-3 for Windows- a version of ORTEP-III with a Graphical User Interface (GUI). Journal of Applied Crystallography, 30 (1997) 565-566.

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Details

Primary Language	English
Subjects	Chemical Engineering
Journal Section	Research Articles
Authors	Gamze Elmas 0000-0003-4877-3697 Aytuğ Okumuş 0000-0002-2169-5695 Satiye Sevim İsaoğlu This is me Tuncer Hökelek 0000-0002-8602-4382 Zeynel Kılıç 0000-0003-1061-8122
Publication Date	December 31, 2019
Acceptance Date	August 9, 2019
Published in Issue	Year 2019 Volume: 61 Issue: 1

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Vancouver	Elmas G, Okumuş A, İsaoğlu SS, Hökelek T, Kılıç Z. DETERMINATION OF ABSOLUTE CONFIGURATION OF 8,8,10,10TETRACHLORO-20,21-DIHYDRO-18H,23H-6,12-EPIAZENO-6λ5,8λ5,10λ5, 12λ5[1,3,2]BENZOXAZAPHOSPHONINO[2’,3’:8,9][1,3,5,7,9,2,4,6,8] PENTAAZATETRAPHOSPHACYCLOUNDSYNO[2,1-B][1,3,2] BENZOXAZAPHOSPHONINE USING X-RAY CRYSTALLOGRAPHY. Commun. Fac. Sci. Univ. Ank. Ser. B. 2019;61(1):1-14.

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