Synthesis, crystal structure and DFT calculations of a cyanido-bridged dinuclear zinc(II) complex of cis-1,2-diaminocyclohexane (Dach) containing a dinuclear cyanidozincate(II) anion, [Zn2(Dach)4(CN)][Zn2(CN)7]·2CH3OH

Muhammad Monim-ul-Mehboob; Tobias Rüffer; Heinrich Lang; Wiktor Zierkiewicz; Abdul Rauf; Muhammad Amin; Anvarhusein A. Isab; Omar Ajouyed; Saeed Ahmad

doi:10.1016/j.molstruc.2018.05.049

Synthesis, crystal structure and DFT calculations of a cyanido-bridged dinuclear zinc(II) complex of cis-1,2-diaminocyclohexane (Dach) containing a dinuclear cyanidozincate(II) anion, [Zn₂(Dach)₄(CN)][Zn₂(CN)₇]·2CH₃OH

Muhammad Monim-ul-Mehboob
, Tobias Rüffer
, Heinrich Lang
, Wiktor Zierkiewicz
, Abdul Rauf
, Muhammad Amin
, Anvarhusein A. Isab
, Omar Ajouyed
, Saeed Ahmad^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

A zinc(II)-cyanide complex of cis-1,2-diaminocyclohexane (Dach) containing two dinuclear units, [Zn₂(Dach)₄(CN)][Zn₂(CN)₇]·2CH₃OH (1) was prepared and characterized by IR and NMR spectroscopy as well as by single crystal X-ray crystallography. Complex 1 is composed of two dinuclear ionic units, cationic [Zn₂(Dach)₄(CN)]³⁺ and anionic [Zn₂(CN)₇]^3- and two non-coordinating molecules of methanol. The Zn atoms in [Zn₂(Dach)₄(CN)]³⁺ cation adopt a square-pyramidal environment with CN ligand occupying the apical position, while the Zn atoms in [Zn₂(CN)₇]^3- anion exhibit a tetrahedral geometry. The dinuclear units are associated to each other through hydrogen bonding interactions to form a three dimensional network in the solid state. The presence of, a band around 2200 cm⁻¹ in IR spectrum and a resonance at 140 ppm in ¹³C NMR indicated the presence of cyanide in the complex. The structures of 1 and two of its analogues, [Zn(Dach)(CN)₂]₄ (2) and {[Zn(Dach)₂][Zn(CN)₄]}₂ (3) were predicted using theoretical (DFT) method. The DFT calculated values of the Gibbs free energies of the model complexes reveal that 1 is more stable than the analogous predicted complexes, 2 and 3 by 5.16 and 3.47 kcal mol⁻¹, respectively.

Original language	English
Pages (from-to)	110-118
Number of pages	9
Journal	Journal of Molecular Structure
Volume	1169
DOIs	https://doi.org/10.1016/j.molstruc.2018.05.049
State	Published - 5 Oct 2018

Bibliographical note

Publisher Copyright:
© 2018 Elsevier B.V.

Keywords

Cyanide
DFT calculations
X-ray structure
Zinc(II)
cis-1,2-Diaminocyclohexane

ASJC Scopus subject areas

Analytical Chemistry
Spectroscopy
Organic Chemistry
Inorganic Chemistry

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Monim-ul-Mehboob, M., Rüffer, T., Lang, H., Zierkiewicz, W., Rauf, A., Amin, M., Isab, A. A., Ajouyed, O., & Ahmad, S. (2018). Synthesis, crystal structure and DFT calculations of a cyanido-bridged dinuclear zinc(II) complex of cis-1,2-diaminocyclohexane (Dach) containing a dinuclear cyanidozincate(II) anion, [Zn₂(Dach)₄(CN)][Zn₂(CN)₇]·2CH₃OH. Journal of Molecular Structure, 1169, 110-118. https://doi.org/10.1016/j.molstruc.2018.05.049

@article{6c753ce00a2b4533845b78cfa277491f,

title = "Synthesis, crystal structure and DFT calculations of a cyanido-bridged dinuclear zinc(II) complex of cis-1,2-diaminocyclohexane (Dach) containing a dinuclear cyanidozincate(II) anion, [Zn2(Dach)4(CN)][Zn2(CN)7]·2CH3OH",

abstract = "A zinc(II)-cyanide complex of cis-1,2-diaminocyclohexane (Dach) containing two dinuclear units, [Zn2(Dach)4(CN)][Zn2(CN)7]·2CH3OH (1) was prepared and characterized by IR and NMR spectroscopy as well as by single crystal X-ray crystallography. Complex 1 is composed of two dinuclear ionic units, cationic [Zn2(Dach)4(CN)]3+ and anionic [Zn2(CN)7]3- and two non-coordinating molecules of methanol. The Zn atoms in [Zn2(Dach)4(CN)]3+ cation adopt a square-pyramidal environment with CN ligand occupying the apical position, while the Zn atoms in [Zn2(CN)7]3- anion exhibit a tetrahedral geometry. The dinuclear units are associated to each other through hydrogen bonding interactions to form a three dimensional network in the solid state. The presence of, a band around 2200 cm−1 in IR spectrum and a resonance at 140 ppm in 13C NMR indicated the presence of cyanide in the complex. The structures of 1 and two of its analogues, [Zn(Dach)(CN)2]4 (2) and \{[Zn(Dach)2][Zn(CN)4]\}2 (3) were predicted using theoretical (DFT) method. The DFT calculated values of the Gibbs free energies of the model complexes reveal that 1 is more stable than the analogous predicted complexes, 2 and 3 by 5.16 and 3.47 kcal mol−1, respectively.",

keywords = "Cyanide, DFT calculations, X-ray structure, Zinc(II), cis-1,2-Diaminocyclohexane",

author = "Muhammad Monim-ul-Mehboob and Tobias R{\"u}ffer and Heinrich Lang and Wiktor Zierkiewicz and Abdul Rauf and Muhammad Amin and Isab, \{Anvarhusein A.\} and Omar Ajouyed and Saeed Ahmad",

note = "Publisher Copyright: {\textcopyright} 2018 Elsevier B.V.",

year = "2018",

month = oct,

day = "5",

doi = "10.1016/j.molstruc.2018.05.049",

language = "English",

volume = "1169",

pages = "110--118",

journal = "Journal of Molecular Structure",

issn = "0022-2860",

publisher = "Elsevier BV",

}

Monim-ul-Mehboob, M, Rüffer, T, Lang, H, Zierkiewicz, W, Rauf, A, Amin, M, Isab, AA, Ajouyed, O & Ahmad, S 2018, 'Synthesis, crystal structure and DFT calculations of a cyanido-bridged dinuclear zinc(II) complex of cis-1,2-diaminocyclohexane (Dach) containing a dinuclear cyanidozincate(II) anion, [Zn₂(Dach)₄(CN)][Zn₂(CN)₇]·2CH₃OH', Journal of Molecular Structure, vol. 1169, pp. 110-118. https://doi.org/10.1016/j.molstruc.2018.05.049

Synthesis, crystal structure and DFT calculations of a cyanido-bridged dinuclear zinc(II) complex of cis-1,2-diaminocyclohexane (Dach) containing a dinuclear cyanidozincate(II) anion, [Zn₂(Dach)₄(CN)][Zn₂(CN)₇]·2CH₃OH. / Monim-ul-Mehboob, Muhammad; Rüffer, Tobias; Lang, Heinrich et al.
In: Journal of Molecular Structure, Vol. 1169, 05.10.2018, p. 110-118.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Synthesis, crystal structure and DFT calculations of a cyanido-bridged dinuclear zinc(II) complex of cis-1,2-diaminocyclohexane (Dach) containing a dinuclear cyanidozincate(II) anion, [Zn2(Dach)4(CN)][Zn2(CN)7]·2CH3OH

AU - Monim-ul-Mehboob, Muhammad

AU - Rüffer, Tobias

AU - Lang, Heinrich

AU - Zierkiewicz, Wiktor

AU - Rauf, Abdul

AU - Amin, Muhammad

AU - Isab, Anvarhusein A.

AU - Ajouyed, Omar

AU - Ahmad, Saeed

PY - 2018/10/5

Y1 - 2018/10/5

N2 - A zinc(II)-cyanide complex of cis-1,2-diaminocyclohexane (Dach) containing two dinuclear units, [Zn2(Dach)4(CN)][Zn2(CN)7]·2CH3OH (1) was prepared and characterized by IR and NMR spectroscopy as well as by single crystal X-ray crystallography. Complex 1 is composed of two dinuclear ionic units, cationic [Zn2(Dach)4(CN)]3+ and anionic [Zn2(CN)7]3- and two non-coordinating molecules of methanol. The Zn atoms in [Zn2(Dach)4(CN)]3+ cation adopt a square-pyramidal environment with CN ligand occupying the apical position, while the Zn atoms in [Zn2(CN)7]3- anion exhibit a tetrahedral geometry. The dinuclear units are associated to each other through hydrogen bonding interactions to form a three dimensional network in the solid state. The presence of, a band around 2200 cm−1 in IR spectrum and a resonance at 140 ppm in 13C NMR indicated the presence of cyanide in the complex. The structures of 1 and two of its analogues, [Zn(Dach)(CN)2]4 (2) and {[Zn(Dach)2][Zn(CN)4]}2 (3) were predicted using theoretical (DFT) method. The DFT calculated values of the Gibbs free energies of the model complexes reveal that 1 is more stable than the analogous predicted complexes, 2 and 3 by 5.16 and 3.47 kcal mol−1, respectively.

AB - A zinc(II)-cyanide complex of cis-1,2-diaminocyclohexane (Dach) containing two dinuclear units, [Zn2(Dach)4(CN)][Zn2(CN)7]·2CH3OH (1) was prepared and characterized by IR and NMR spectroscopy as well as by single crystal X-ray crystallography. Complex 1 is composed of two dinuclear ionic units, cationic [Zn2(Dach)4(CN)]3+ and anionic [Zn2(CN)7]3- and two non-coordinating molecules of methanol. The Zn atoms in [Zn2(Dach)4(CN)]3+ cation adopt a square-pyramidal environment with CN ligand occupying the apical position, while the Zn atoms in [Zn2(CN)7]3- anion exhibit a tetrahedral geometry. The dinuclear units are associated to each other through hydrogen bonding interactions to form a three dimensional network in the solid state. The presence of, a band around 2200 cm−1 in IR spectrum and a resonance at 140 ppm in 13C NMR indicated the presence of cyanide in the complex. The structures of 1 and two of its analogues, [Zn(Dach)(CN)2]4 (2) and {[Zn(Dach)2][Zn(CN)4]}2 (3) were predicted using theoretical (DFT) method. The DFT calculated values of the Gibbs free energies of the model complexes reveal that 1 is more stable than the analogous predicted complexes, 2 and 3 by 5.16 and 3.47 kcal mol−1, respectively.

KW - Cyanide

KW - DFT calculations

KW - X-ray structure

KW - Zinc(II)

KW - cis-1,2-Diaminocyclohexane

UR - https://www.scopus.com/pages/publications/85047269191

U2 - 10.1016/j.molstruc.2018.05.049

DO - 10.1016/j.molstruc.2018.05.049

M3 - Article

AN - SCOPUS:85047269191

SN - 0022-2860

VL - 1169

SP - 110

EP - 118

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

ER -

Monim-ul-Mehboob M, Rüffer T, Lang H, Zierkiewicz W, Rauf A, Amin M et al. Synthesis, crystal structure and DFT calculations of a cyanido-bridged dinuclear zinc(II) complex of cis-1,2-diaminocyclohexane (Dach) containing a dinuclear cyanidozincate(II) anion, [Zn₂(Dach)₄(CN)][Zn₂(CN)₇]·2CH₃OH. Journal of Molecular Structure. 2018 Oct 5;1169:110-118. doi: 10.1016/j.molstruc.2018.05.049