Heterometallic manganese(III) coordination polymers with Schiff bases (H2Salpn) and dicyanometallates

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Abstract

Single crystals of the Mn(III) complexes with tetradentate (N2O2) Schiff bases (L) and dicyanometallates [Mn(L)M(CN)2]n, where L = Salpn2– = N,N’-bis(salicylidene)-1,3-diaminopropane, M = M = Ag+ (I), Au+ (II) were obtained for the first time. The molecular structures of I and II were determined by X-ray diffraction (CCDC no. 2351118 (I), 2351119 (II)). It was found that the dicyanometallate anion [M(CN)2]ˉ in the crystal structure of these compounds acts as a bridge binding the Mn(III) moieties with the Schiff base into 1D. Using quantum chemical calculations, the (3, –1) type critical points were found near the C‒H…Ag/Au contact; this attests to the existence of weak hydrogen bonds between these atoms.

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About the authors

V. A. Kopotkov

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Author for correspondence.
Email: vakopotkov@icp.ac.ru
Russian Federation, Chernogolovka, Moscow oblast

L. V. Zorina

Osipyan Institute of Solid State Physics, Russian Academy of Sciences

Email: vakopotkov@icp.ac.ru
Russian Federation, Chernogolovka, Moscow oblast

S. V. Simonov

Osipyan Institute of Solid State Physics, Russian Academy of Sciences

Email: vakopotkov@icp.ac.ru
Russian Federation, Chernogolovka, Moscow oblast

A. N. Utenyshev

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: vakopotkov@icp.ac.ru
Russian Federation, Chernogolovka, Moscow oblast

K. V. Bozhenko

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: vakopotkov@icp.ac.ru
Russian Federation, Chernogolovka, Moscow oblast

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Supplementary files

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2. Scheme 1

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3. Scheme 2

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4. Fig. 1. Molecular structure of complex I (thermal ellipsoids at 50% level, hydrogen atoms not shown). Symmetry operation: * x, 1.5–y, z–0.5.

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5. Fig. 2. Polymer chain [Mn(L)Ag(CN)2]n in structure I (a). Parallel chains on the projection of the structure along the b axis (C and H atoms of ligand L are omitted) (b).

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6. Fig. 3. The nearest environment of the Mn(L)+ cation in structure I. The Mn…Mn distances are 7.3657(1) Å (blue dotted line 1) and 7.3795(8) Å (red dotted line 2). The C–H…O/N/Ag hydrogen contacts are shown as thin red/blue/gray dotted lines with the designation of atoms (bond geometry – see Tables 3, 4).

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7. Fig. 4. Critical points in the dimer of I (a) and II (b) (green points – CP (3, –1)). The numbering of atoms does not coincide with the numbering in Fig. 1–3. Points CP6 (a) and CP3 (b) correspond to the minimum H…Ag/Au distance of 2.77 Å in the structures of I and II.

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