DESIGNATION OF ABSOLUTE CONFIGURATION OF MULTIHETEREOCYCLIC 9,13-DICHLORO-22,22-DIPYRROLIDINE-1-YL1H,2H,13H,19H-9,13-(EPIAZENOPHOSPHAZENO)-9λ5,11λ5,13λ5-[1,3,5,2,4] BENZOXADIAZADİPHOSPHONINO[4',5':2,3][1,3,2]DIAZAPHOSPHOLO[2,1-D] [1,3,5,2,4]BENZOXADIAZADIPHOSPHONINE BY X-RAY CRYSTALLOGRAPHIC DATA

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

Research Article

Year 2019, Volume: 61 Issue: 1, 15 - 30, 31.12.2019

Gamze Elmas Aytuğ Okumuş Satiye Sevim İsaoğlu Tuncer Hökelek Zeynel Kılıç

Abstract

References

F. F. Stewart, Phosphazenes. Organophosphorus Chem. (Cambridge, UK: Royal Society of Chemistry) 44 (2015) p. 397-430.
V. Chandrasekhar and A. Chakraborty, Phosphazenes. Organophosphorus Chemistry, (Cambridge, UK: Royal Society of Chemistry) 48 (2019) p. 400-423.
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.
H. İbişoğlu, Ç. G. Yenilmez, A. Kılıç, E. Tanrıverdi, İ. Ün, H. Dal and T. Hökelek, Formation of novel spiro, spiroansa and dispiroansa derivatives of cyclotetraphosphazene from the reactions of polyfunctional amines with octachlorocyclotetraphosphazatetraene. Journal of Chemical Sciences. 121 (2009) 125-135.
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.
D. Kumar, J. Singh and A. J. Elias, Chiral multidentate oxazoline ligands based on cyclophosphazene cores: synthesis, characterization and complexation studies. Dalton Transaction, 43 (2014) 13899-13912.
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. 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.
J. Jimenez, I. Pintre, E. Gascon, C. Sanchez-Somolinos, R. Alcala, E. Cavero, J. L. Serrano and L. Oriol, Photoresponsive liquid-crystalline dendrimers based on a cyclotriphosphazene core. Macromolecular Chemistry and Physics, 215 (2014) 1551-1532.
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)cyclotriphosphazenium salts. Journal of the Turkish Chemical Society, Section A: Chemistry, 4/3 (2017) 993-1016.
R. Xu and Y. Xu, Modern Inorganic Synthetic Chemistry, Second Edition, 11 (2017) p.295.
R. Gutru, S.G. Peera, S.D. Bhat and A.K. Sahu, Synthesis of sulfonated poly(bis(phenoxy)phosphazene) based blend membranes and its effect as electrolyte in fuel cells. Solid State Ionics, 296 (2016) 127-136.
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.
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, 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, 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 (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).
E. Pidcock, Achiral molecules in non-centrosymmetric space groups. Chemical Communications, (2005) 3457.
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.
T. Hökelek, E. Kılıç and Z. Kılıç, Trans-2,6-Bis(ethylamino)-2,4,4,6,8,8-hexapiperidinocyclo- 5 5 5 5-tetraphosphazatetraene. Acta CrystallogrAPHİCA, C55 (1999) 983-985.
A. B. Chaplin, J. A. Harrison and P. J. Dyson, Revisiting the electronic structure of phosphazenes. Inorganic Chemistry, 44 (2005) 8407-8417.
E. W. Ainscough, A. M. Brodie, A. B. Chaplin, A. Derwahl, J. A. Harrison and C. A. Otter, Conformational flexibility in 2,2‘-dioxybiphenyl-chloro-cyclotetraphosphazenes and its relevance to polyphosphazene analogues. Inorganic Chemistry, 46 (2007) 2575-2583.
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.

DESIGNATION OF ABSOLUTE CONFIGURATION OF MULTIHETEREOCYCLIC 9,13-DICHLORO-22,22-DIPYRROLIDINE-1-YL1H,2H,13H,19H-9,13-(EPIAZENOPHOSPHAZENO)-9λ5,11λ5,13λ5-[1,3,5,2,4] BENZOXADIAZADİPHOSPHONINO[4',5':2,3][1,3,2]DIAZAPHOSPHOLO[2,1-D] [1,3,5,2,4]BENZOXADIAZADIPHOSPHONINE BY X-RAY CRYSTALLOGRAPHIC DATA

Year 2019, Volume: 61 Issue: 1, 15 - 30, 31.12.2019

Gamze Elmas Aytuğ Okumuş Satiye Sevim İsaoğlu Tuncer Hökelek Zeynel Kılıç

Abstract

The title compound, 9,13-dichloro-22,22-dipyrrolidine-1-yl-1H,2H,13H,19H-9,13-(epiazenophosphazeno)-9λ5,11λ5,13λ5-1,3,5,2,4]benzoxadiazadiphosphonino [4',5':2,3][1,3,2]diazaphospholo[2,1-d][1,3,5,2,4]benzoxadiazadiphosphonine;
2(C24H32Cl2N8O2P4). 0.5 C6H12, a cyclotetraphosphazene derivative, has a geminaldipyrrolidino-2-trans-6-dichloro-ansa-spiro-ansa (gem-dipyrrolidino-2-trans-6-dichloroasa) structure in which the tricyclic parts are consisted of three eight-membered rings,
containing a tetrameric N4P4 and two ansa rings. However, all these rings are not planar. The asymmetric unit contains two crystallographically independent molecules and one half of the cyclohexane solvent molecule. In both molecules, it is expected that two P (P1 and P3/P1′ and P3′) atoms are stereogenic centres. Both gem-dipyrrolidino-2-trans-6-dichloro-asa molecules have trans structures according to the Cl atoms, and they are in the racemic forms. Besides, it is found that the absolute configurations of P1, P3 and P1′, P3′ phosphorus centers are RR and SS, respectively. The title compound has P-1 space group, a Sohncke chiral space
group, with the cell parameters of a = 9.6682(2), b = 13.8587(3), c = 24.0250(4) Å, � =105.249(2)°, � = 96.298(3)° and � = 98.367(3)°.

Keywords

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

References

F. F. Stewart, Phosphazenes. Organophosphorus Chem. (Cambridge, UK: Royal Society of Chemistry) 44 (2015) p. 397-430.
V. Chandrasekhar and A. Chakraborty, Phosphazenes. Organophosphorus Chemistry, (Cambridge, UK: Royal Society of Chemistry) 48 (2019) p. 400-423.
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.
H. İbişoğlu, Ç. G. Yenilmez, A. Kılıç, E. Tanrıverdi, İ. Ün, H. Dal and T. Hökelek, Formation of novel spiro, spiroansa and dispiroansa derivatives of cyclotetraphosphazene from the reactions of polyfunctional amines with octachlorocyclotetraphosphazatetraene. Journal of Chemical Sciences. 121 (2009) 125-135.
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.
D. Kumar, J. Singh and A. J. Elias, Chiral multidentate oxazoline ligands based on cyclophosphazene cores: synthesis, characterization and complexation studies. Dalton Transaction, 43 (2014) 13899-13912.
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. 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.
J. Jimenez, I. Pintre, E. Gascon, C. Sanchez-Somolinos, R. Alcala, E. Cavero, J. L. Serrano and L. Oriol, Photoresponsive liquid-crystalline dendrimers based on a cyclotriphosphazene core. Macromolecular Chemistry and Physics, 215 (2014) 1551-1532.
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)cyclotriphosphazenium salts. Journal of the Turkish Chemical Society, Section A: Chemistry, 4/3 (2017) 993-1016.
R. Xu and Y. Xu, Modern Inorganic Synthetic Chemistry, Second Edition, 11 (2017) p.295.
R. Gutru, S.G. Peera, S.D. Bhat and A.K. Sahu, Synthesis of sulfonated poly(bis(phenoxy)phosphazene) based blend membranes and its effect as electrolyte in fuel cells. Solid State Ionics, 296 (2016) 127-136.
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.
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, 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, 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 (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).
E. Pidcock, Achiral molecules in non-centrosymmetric space groups. Chemical Communications, (2005) 3457.
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.
T. Hökelek, E. Kılıç and Z. Kılıç, Trans-2,6-Bis(ethylamino)-2,4,4,6,8,8-hexapiperidinocyclo- 5 5 5 5-tetraphosphazatetraene. Acta CrystallogrAPHİCA, C55 (1999) 983-985.
A. B. Chaplin, J. A. Harrison and P. J. Dyson, Revisiting the electronic structure of phosphazenes. Inorganic Chemistry, 44 (2005) 8407-8417.
E. W. Ainscough, A. M. Brodie, A. B. Chaplin, A. Derwahl, J. A. Harrison and C. A. Otter, Conformational flexibility in 2,2‘-dioxybiphenyl-chloro-cyclotetraphosphazenes and its relevance to polyphosphazene analogues. Inorganic Chemistry, 46 (2007) 2575-2583.
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.

There are 30 citations in total.

Details

Primary Language	English
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
Publication Date	December 31, 2019
Acceptance Date	August 26, 2019
Published in Issue	Year 2019 Volume: 61 Issue: 1

Cite

Vancouver	Elmas G, Okumuş A, İsaoğlu SS, Hökelek T, Kılıç Z. DESIGNATION OF ABSOLUTE CONFIGURATION OF MULTIHETEREOCYCLIC 9,13-DICHLORO-22,22-DIPYRROLIDINE-1-YL1H,2H,13H,19H-9,13-(EPIAZENOPHOSPHAZENO)-9λ5,11λ5,13λ5-[1,3,5,2,4] BENZOXADIAZADİPHOSPHONINO[4’,5’:2,3][1,3,2]DIAZAPHOSPHOLO[2,1-D] [1,3,5,2,4]BENZOXADIAZADIPHOSPHONINE BY X-RAY CRYSTALLOGRAPHIC DATA. Commun. Fac. Sci. Univ. Ank. Ser. B. 2019;61(1):15-30.

Download Cover Image

Article Files

Full Text

Communications Faculty of Sciences University of Ankara Series B Chemistry and Chemical Engineering

This work is licensed under a Creative Commons Attribution 4.0 International License.