Structure and properties of bis(1-phenyl-1h-tetrazole-5-thiolate)diiron tetranitrosyl

N. A. Sanina, G. I. Kozub, T. A. Kondrat'Eva, G. V. Shilov, D. V. Korchagin, N. S. Emel'Yanova, O. Kh Poleshchuk, A. V. Chernyak, A. V. Kulikov, F. B. Mushenok, N. S. Ovanesyan, S. M. Aldoshin

    Research output: Contribution to journalArticle

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    Abstract

    New tetranitrosyl binuclear iron complex [Fe2(SC 7H5N4)2(NO)4] (I) has been synthesized by interaction of aqueous solutions of anionic salts [Fe(S 2O3)2(NO)2]3- and [SC7H5N4]-. The latter one was synthesized by reduction of bis-(1-phenyl-1H-tetrazole-5-yl) disulfide with hydrazine hydrate in ethanol at T = 25 C. Molecular and crystalline structure of I was determined by X-ray analysis; the complex has binuclear structure of "μ-SCN" type with ∼4.02 Å between the iron atoms. Shortened O⋯O contacts (2.81 Å) between the NO groups of similar type are observed. Parameters of Mössbauer spectrum for I are: isomer shift δFe = 0.311(1) mm/s, quadrupole splitting ΔEQ = 1.044(1) mm/s, line width Γ = 0.267(1) mm/s at 85 K. From SQUID magnetometry data, the temperature and field dependences of the magnetic moment of I are well described in the frame of a simple model of binuclear iron complex with magnetic centers S1 = S2 = . In solution, binuclear structure of the complex remains, though the NO groups are non-equivalent. For solutions of I five-line hyperfine structure of spectrum (HFS) is observed, g-factor = 2.03. For polycrystals of I, no HFS was observed due to averaged exchange interaction between the electron spins of adjacent complexes. In polycrystals of I, the number of spins per one binuclear complex is <2, this being the evidence of antiferromagnetic exchange interaction of unpaired electrons of two iron atoms. The average number of spins in crystals (0.65) and solutions (0.55) are close. The maximum amount of NO generated by I in 1% dimethylsulfoxide (DMSO) aqueous solution is ∼13.8 nM, it halves in 8 min after decomposition starts, and reaches ∼3.8 nM in anaerobic conditions at T = 25 C, pH 7.0. This is due, according to quantum-chemical calculations, to the presence of a more stable FeNO bond in I than in its isostructural analog - nitrosyl iron complex with 1-methyltetrazole-5-yl (II).

    Original languageEnglish
    Pages (from-to)183-189
    Number of pages7
    JournalJournal of Molecular Structure
    Volume1041
    DOIs
    Publication statusPublished - 10 Jun 2013

    Fingerprint

    Iron
    hydrazine
    Exchange interactions
    Polycrystals
    Atoms
    Electrons
    SQUIDs
    X ray analysis
    Dimethyl Sulfoxide
    Magnetic moments
    Disulfides
    Isomers
    Linewidth
    Ethanol
    Salts
    1H-tetrazole
    Crystalline materials
    Decomposition
    Crystals
    Temperature

    Keywords

    • 1-Phenyl-1H-tetrazole-5-thiol
    • EPR
    • IR-
    • NO donors
    • Sulfur-nitrosyl iron complexes
    • X-ray analysis

    ASJC Scopus subject areas

    • Analytical Chemistry
    • Spectroscopy
    • Organic Chemistry
    • Inorganic Chemistry

    Cite this

    Sanina, N. A., Kozub, G. I., Kondrat'Eva, T. A., Shilov, G. V., Korchagin, D. V., Emel'Yanova, N. S., ... Aldoshin, S. M. (2013). Structure and properties of bis(1-phenyl-1h-tetrazole-5-thiolate)diiron tetranitrosyl. Journal of Molecular Structure, 1041, 183-189. https://doi.org/10.1016/j.molstruc.2013.03.021

    Structure and properties of bis(1-phenyl-1h-tetrazole-5-thiolate)diiron tetranitrosyl. / Sanina, N. A.; Kozub, G. I.; Kondrat'Eva, T. A.; Shilov, G. V.; Korchagin, D. V.; Emel'Yanova, N. S.; Poleshchuk, O. Kh; Chernyak, A. V.; Kulikov, A. V.; Mushenok, F. B.; Ovanesyan, N. S.; Aldoshin, S. M.

    In: Journal of Molecular Structure, Vol. 1041, 10.06.2013, p. 183-189.

    Research output: Contribution to journalArticle

    Sanina, NA, Kozub, GI, Kondrat'Eva, TA, Shilov, GV, Korchagin, DV, Emel'Yanova, NS, Poleshchuk, OK, Chernyak, AV, Kulikov, AV, Mushenok, FB, Ovanesyan, NS & Aldoshin, SM 2013, 'Structure and properties of bis(1-phenyl-1h-tetrazole-5-thiolate)diiron tetranitrosyl', Journal of Molecular Structure, vol. 1041, pp. 183-189. https://doi.org/10.1016/j.molstruc.2013.03.021
    Sanina NA, Kozub GI, Kondrat'Eva TA, Shilov GV, Korchagin DV, Emel'Yanova NS et al. Structure and properties of bis(1-phenyl-1h-tetrazole-5-thiolate)diiron tetranitrosyl. Journal of Molecular Structure. 2013 Jun 10;1041:183-189. https://doi.org/10.1016/j.molstruc.2013.03.021
    Sanina, N. A. ; Kozub, G. I. ; Kondrat'Eva, T. A. ; Shilov, G. V. ; Korchagin, D. V. ; Emel'Yanova, N. S. ; Poleshchuk, O. Kh ; Chernyak, A. V. ; Kulikov, A. V. ; Mushenok, F. B. ; Ovanesyan, N. S. ; Aldoshin, S. M. / Structure and properties of bis(1-phenyl-1h-tetrazole-5-thiolate)diiron tetranitrosyl. In: Journal of Molecular Structure. 2013 ; Vol. 1041. pp. 183-189.
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    title = "Structure and properties of bis(1-phenyl-1h-tetrazole-5-thiolate)diiron tetranitrosyl",
    abstract = "New tetranitrosyl binuclear iron complex [Fe2(SC 7H5N4)2(NO)4] (I) has been synthesized by interaction of aqueous solutions of anionic salts [Fe(S 2O3)2(NO)2]3- and [SC7H5N4]-. The latter one was synthesized by reduction of bis-(1-phenyl-1H-tetrazole-5-yl) disulfide with hydrazine hydrate in ethanol at T = 25 C. Molecular and crystalline structure of I was determined by X-ray analysis; the complex has binuclear structure of {"}μ-SCN{"} type with ∼4.02 {\AA} between the iron atoms. Shortened O⋯O contacts (2.81 {\AA}) between the NO groups of similar type are observed. Parameters of M{\"o}ssbauer spectrum for I are: isomer shift δFe = 0.311(1) mm/s, quadrupole splitting ΔEQ = 1.044(1) mm/s, line width Γ = 0.267(1) mm/s at 85 K. From SQUID magnetometry data, the temperature and field dependences of the magnetic moment of I are well described in the frame of a simple model of binuclear iron complex with magnetic centers S1 = S2 = . In solution, binuclear structure of the complex remains, though the NO groups are non-equivalent. For solutions of I five-line hyperfine structure of spectrum (HFS) is observed, g-factor = 2.03. For polycrystals of I, no HFS was observed due to averaged exchange interaction between the electron spins of adjacent complexes. In polycrystals of I, the number of spins per one binuclear complex is <2, this being the evidence of antiferromagnetic exchange interaction of unpaired electrons of two iron atoms. The average number of spins in crystals (0.65) and solutions (0.55) are close. The maximum amount of NO generated by I in 1{\%} dimethylsulfoxide (DMSO) aqueous solution is ∼13.8 nM, it halves in 8 min after decomposition starts, and reaches ∼3.8 nM in anaerobic conditions at T = 25 C, pH 7.0. This is due, according to quantum-chemical calculations, to the presence of a more stable FeNO bond in I than in its isostructural analog - nitrosyl iron complex with 1-methyltetrazole-5-yl (II).",
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    author = "Sanina, {N. A.} and Kozub, {G. I.} and Kondrat'Eva, {T. A.} and Shilov, {G. V.} and Korchagin, {D. V.} and Emel'Yanova, {N. S.} and Poleshchuk, {O. Kh} and Chernyak, {A. V.} and Kulikov, {A. V.} and Mushenok, {F. B.} and Ovanesyan, {N. S.} and Aldoshin, {S. M.}",
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    T1 - Structure and properties of bis(1-phenyl-1h-tetrazole-5-thiolate)diiron tetranitrosyl

    AU - Sanina, N. A.

    AU - Kozub, G. I.

    AU - Kondrat'Eva, T. A.

    AU - Shilov, G. V.

    AU - Korchagin, D. V.

    AU - Emel'Yanova, N. S.

    AU - Poleshchuk, O. Kh

    AU - Chernyak, A. V.

    AU - Kulikov, A. V.

    AU - Mushenok, F. B.

    AU - Ovanesyan, N. S.

    AU - Aldoshin, S. M.

    PY - 2013/6/10

    Y1 - 2013/6/10

    N2 - New tetranitrosyl binuclear iron complex [Fe2(SC 7H5N4)2(NO)4] (I) has been synthesized by interaction of aqueous solutions of anionic salts [Fe(S 2O3)2(NO)2]3- and [SC7H5N4]-. The latter one was synthesized by reduction of bis-(1-phenyl-1H-tetrazole-5-yl) disulfide with hydrazine hydrate in ethanol at T = 25 C. Molecular and crystalline structure of I was determined by X-ray analysis; the complex has binuclear structure of "μ-SCN" type with ∼4.02 Å between the iron atoms. Shortened O⋯O contacts (2.81 Å) between the NO groups of similar type are observed. Parameters of Mössbauer spectrum for I are: isomer shift δFe = 0.311(1) mm/s, quadrupole splitting ΔEQ = 1.044(1) mm/s, line width Γ = 0.267(1) mm/s at 85 K. From SQUID magnetometry data, the temperature and field dependences of the magnetic moment of I are well described in the frame of a simple model of binuclear iron complex with magnetic centers S1 = S2 = . In solution, binuclear structure of the complex remains, though the NO groups are non-equivalent. For solutions of I five-line hyperfine structure of spectrum (HFS) is observed, g-factor = 2.03. For polycrystals of I, no HFS was observed due to averaged exchange interaction between the electron spins of adjacent complexes. In polycrystals of I, the number of spins per one binuclear complex is <2, this being the evidence of antiferromagnetic exchange interaction of unpaired electrons of two iron atoms. The average number of spins in crystals (0.65) and solutions (0.55) are close. The maximum amount of NO generated by I in 1% dimethylsulfoxide (DMSO) aqueous solution is ∼13.8 nM, it halves in 8 min after decomposition starts, and reaches ∼3.8 nM in anaerobic conditions at T = 25 C, pH 7.0. This is due, according to quantum-chemical calculations, to the presence of a more stable FeNO bond in I than in its isostructural analog - nitrosyl iron complex with 1-methyltetrazole-5-yl (II).

    AB - New tetranitrosyl binuclear iron complex [Fe2(SC 7H5N4)2(NO)4] (I) has been synthesized by interaction of aqueous solutions of anionic salts [Fe(S 2O3)2(NO)2]3- and [SC7H5N4]-. The latter one was synthesized by reduction of bis-(1-phenyl-1H-tetrazole-5-yl) disulfide with hydrazine hydrate in ethanol at T = 25 C. Molecular and crystalline structure of I was determined by X-ray analysis; the complex has binuclear structure of "μ-SCN" type with ∼4.02 Å between the iron atoms. Shortened O⋯O contacts (2.81 Å) between the NO groups of similar type are observed. Parameters of Mössbauer spectrum for I are: isomer shift δFe = 0.311(1) mm/s, quadrupole splitting ΔEQ = 1.044(1) mm/s, line width Γ = 0.267(1) mm/s at 85 K. From SQUID magnetometry data, the temperature and field dependences of the magnetic moment of I are well described in the frame of a simple model of binuclear iron complex with magnetic centers S1 = S2 = . In solution, binuclear structure of the complex remains, though the NO groups are non-equivalent. For solutions of I five-line hyperfine structure of spectrum (HFS) is observed, g-factor = 2.03. For polycrystals of I, no HFS was observed due to averaged exchange interaction between the electron spins of adjacent complexes. In polycrystals of I, the number of spins per one binuclear complex is <2, this being the evidence of antiferromagnetic exchange interaction of unpaired electrons of two iron atoms. The average number of spins in crystals (0.65) and solutions (0.55) are close. The maximum amount of NO generated by I in 1% dimethylsulfoxide (DMSO) aqueous solution is ∼13.8 nM, it halves in 8 min after decomposition starts, and reaches ∼3.8 nM in anaerobic conditions at T = 25 C, pH 7.0. This is due, according to quantum-chemical calculations, to the presence of a more stable FeNO bond in I than in its isostructural analog - nitrosyl iron complex with 1-methyltetrazole-5-yl (II).

    KW - 1-Phenyl-1H-tetrazole-5-thiol

    KW - EPR

    KW - IR-

    KW - NO donors

    KW - Sulfur-nitrosyl iron complexes

    KW - X-ray analysis

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