Influence of anion variation and cation modification on the packing of tetraazamacrocyclic Au(III) complexes

Journal of Molecular Structure 1202 (2020) 127343

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Influence of anion variation and cation modification on the packing of tetraazamacrocyclic Au(III) complexes Valentina A. Afanas'eva*, Ludmila A. Glinskaya Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, 3, Acad. Lavrentiev Ave., Novosibirsk, 630090, Russia

a r t i c l e i n f o

a b s t r a c t

Article history: Received 31 May 2019 Received in revised form 7 August 2019 Accepted 1 November 2019 Available online 6 November 2019

The work presents the analysis of the packings of crystal structures of unsaturated tetraazamacrocyclic gold(III) complexes with different anions ([Au(С14H22N4)]X (X ¼ Br (I), ReO4 (II), BPh4 (III), AuBr2 (IV)) and with modified (halogenated [Au(С14Н20N4Y2)]ClO4 (Y ¼ Cl (V), Br (VI), protonated [Au(С14H23N4)](ClO4)2 (VII), [Au(С14H24N4)](H3O)(ClO4)4 (VIII) cations. Crystal-chemical regularities and features of the packings depend on the composition and structure of cations, as well as on the nature and geometry of counteranions. In the packings of the complexes IeVII whose ligands contain one or two iminate six-membered rings, the 3D supramolecular architecture of the crystal lattice is determined and stabilized by an extensive network of secondary non-covalent intermolecular interactions (non-classical H-bonds CeH… A (A ¼ p, Br, Cl, O, Au) and contacts Au/Au (O, N, p); O/Cl (Br, N). In the iminate complexes with  nonlinear inorganic anions Br, ClO 4 , ReO4 , the main structure-forming role belongs to the cations which are interconnected by non-classical H-bonds CeH…p. The halogenation of iminate rings of the cation and the protonation of one of the rings do not cause profound changes in the packing. In the structures of the complexes with a bulky organic anion BPhe 4 (III) and with a coordinatively unsaturated linear anion AuBr 2 (IV), the decisive role belongs to the anions which prevent the association of cations by forming Hbonds and contacts with them. The linear acceptor-active anion AuBr 2 has the greatest influence on the packing of diiminate macrocyclic gold(III) complexes by providing the parquet packing of the structure. The 1D crystal structure of the diprotonated diimine complex VIII is stabilized by classical H-bonds Ow eH...O of the oxonium ion and by the contacts of the central atom of the macrocyclic cation Au/O. © 2019 Elsevier B.V. All rights reserved.

Keywords: Gold(III) Tetraazamacrocyclic complexes Crystal packings Intermolecular interactions

1. Introduction In recent decades, secondary non-covalent interactions have attracted the attention of researchers in various fields of science such as mineralogy, materials science, organic and inorganic chemistry, supramolecular chemistry, biology, molecular medicine, pharmacology, etc., so that the scientific interest has largely shifted from the study of atoms and interatomic bonds to the study of molecules and intermolecular bonds. An increasing part of research is devoted to the understanding of the nature of intermolecular interactions (hydrogen bonds, short contacts, etc.). Non-covalent interactions can be used in the engineering of organic and organometallic crystals to design periodic structures with desired supramolecular organization and properties [1,2]. However, reliable prediction of crystal packings is still a non-

* Corresponding author. E-mail address: [email protected] (V.A. Afanas'eva). https://doi.org/10.1016/j.molstruc.2019.127343 0022-2860/© 2019 Elsevier B.V. All rights reserved.

trivial task [3]. In this regard, both the development of theoretical approaches to the solution of this problem and the empirical analysis of crystal chemical data are essential to identify the factors responsible for intermolecular interactions in inorganic and organometallic solids and to reveal the patterns of their architecture and, in particular, the geometry of hydrogen bonds in crystals. The understanding of these factors will allow one to purposefully create novel functional materials by designing their crystalline structures. Crystallographic studies have long recognized, classified, and discussed structural regularities and motifs formed by sets of interactions during the formation of extended crystal structures [4]. In Refs. [5e9], the models of hydrogen bonds between specific functional groups and the rules for their formation were proposed, which are useful for the understanding and design of crystal formation and the prediction of supramolecular aggregates where hydrogen bonds are predominant. In Ref. [10], the effect of H-bond donors and acceptors on the crystal packing was investigated.

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According to the results of the structural analysis of a number of carbene proligands [11], weak non-covalent (anion…p, p…p) interactions combine with intermolecular hydrogen bonds, thus contributing to the assembly of the supramolecular framework. Counter-ions play a significant role in the formation of metal complexes, determining not only the type of ligand coordination but also the coordination geometry of the central atom [12e14]. The effect of the anion species on the supramolecular ensemble was studied in Refs. [15e20]. For instance, the structural studies of the packing features in thiamineeanion systems revealed that these features are closely related to the nature of the anions and especially to the ability of anions to accept hydrogen bonds [15]. In Ref. [19], it was demonstrated that different geometries of counterions (bromide, nitrate, and dihydrogen phosphate) and their different potentiality to form hydrogen-bonds result in markedly different hydrogen-bonding arrangements of small organic molecules (3-acetylanilinium salts) and, consequently, result in the differences between their supramolecular aggregations. In Ref. [20], it was shown that the styryl dye crystal packing depends on the size   of the anion: small inorganic anions such as ClO 4 , BF4 , PF6 aid the formation of cation stacking motifs of the “head-to-tail” type, whereas the bulky BPhe 4 anion suppresses the cation tendency to form this motif. The supramolecular architecture of gold compounds containing various types of secondary bonds where gold can participate (Au/Au, Au…M, Au$$$NM, DeH…Au, Au…p), often in combination with hydrogen bonds, p-stacking, etc., was analyzed in Ref. [21]. It was shown that various types of intermolecular vander-Waals interactions alone or in cooperation with other types of intermolecular interactions can act as a versatile bonding motif for the self-assembly of gold complexes. In Ref. [22], it was demonstrated how influential weak intermolecular interactions Au…X, Au/Au, X…X can be in determining the structure of dihalodicyanoaurate(III) salts, as well as the utility of these interactions in structural design. A supramolecular one-dimensional array containing cations and anions stacked alternatingly in columns is formed by intermolecular gold(III)…h6-arene interactions in the solid-state structure of the (2,6-diphenylpyridine) gold(III) derivative [23,24]. According to the study of nearly planar gold(III) bis(2 pyridylmethyl)-amidocomplexes with various anions (BF 4 , PF6 , AuCl ) [25], the structure of the BF complex has no strong in2 4 teractions between the cation and the anion; the other two complexes are packed in columns and contain aurophilic bonds. We synthesized and investigated the physicochemical properties of a number of acyclic and macrocyclic (deprotonated and protonated) tetraazametal gold(III) complexes in which nitrogen atoms in different electronic states (amine >NH2, iminate >N , imine >N¼) are coordinated to the central atoms of the cations (see review [26]). It seemed reasonable to conduct a comparative analysis of the mutual arrangement of ions in the packings of the studied complexes to identify the regularities of the crystal structures of these complexes, to clarify the role of cations and anions in the formation of the packings, and to study how the packings are influenced by the factors such as the electronic state of nitrogen atoms in the coordination polyhedron and the presence of substituents in the six-membered iminate rings. The analysis of crystal packings in gold(III) acyclic iminate complexes with various anions [Au(C9H19N4)]X2 (X ¼ I, ClO4, PF6) and halogen-substituted cations [Au(C9H18N4Y)](ClO4)2 (Y ¼ Cl, Br) [27,28] showed that the 3D supramolecular architecture of their crystal lattices is determined and stabilized by an extensive network of intermolecular interactions (hydrogen bonds N(C)eH… A, CeH/Au(p) and short contacts Au…A (A ¼ I, O, F)). The decisive role in the formation of the structure of the studied acyclic complexes of gold(III) is up to the flat acyclic cation

[Au(C9H19N4)]2þ which provides a potential possibility to form numerous classical and non-classical cationecationic and cationeanionic H-bonds. The packing architecture of these complexes is not changed significantly when the monoatomic inorganic anion is replaced by a polyatomic anion or when the proton in the b-position of the six-member delocalized ring is replaced by a halogen. The characteristic features of these packings (cation double stacks and anion chains extended along the short axis and linked into 2D layers) as well as the geometry of their local fragments determined by the set of secondary interactions remain the same. A comparative analysis of the crystal structures of tetraazamacrocyclic gold(III) complexes [Au(С14H22N4)]Br (I), [Au(С14H23N4)](ClO4)2 (VII), [Au(С14H24N4)](H3O)(ClO4)4 (VIII) with deprotonated, monoprotonated, and diprotonated ligands was carried out in Ref. [29]. It was shown that 3D packings of complexes I and VII with two and one iminate delocalized six-membered heterocycles AuN2C3, respectively, are determined and stabilized by extensive networks of weak non-classical H-bonds (CeH…p, CeH/Au, CeH/Br(O)) and (in VII) short contacts Au(N)/O. The structures of these complexes contain 2D-cationic (I) and 2Dcation-anionic (VII) networks. The 1D cation-anionic stacks in the structure of diprotonated VIII are formed due to classical H-bonds OweH...O and Au/O contacts. The packings of the complexes are topologically similar to those exhibited by acyclic gold(III) complexes with one iminate ring in the heterocycle [27,28]. In this work, it is analyzed how the crystal packing of [Au(С14H22N4)]X complexes is affected by the type of the counteranion Xe and by the halogenation of six-membered delocalized rings of the [Au(C14H22N4)]þ cation. A set of anions X ¼ Br, ClO 4, e  ReO 4 , BPh4 , AuBr2 were used to estimate the effect of the following anion characteristics on the packing of the complexes: monatomic e polyatomic anion; nonmetal anion e metal anion; anion size (compact inorganic anion e bulky organic anion); anion shape (spherical, tetrahedral, linear). The discussion of the effect of ligand modification on the packing contains the results reported previously in Ref. [29]. Synthetic procedures and descriptions of physicochemical properties of complexes IeIV, complexes V, VI and complexes VII, VIII were presented in Refs. [30e33], in Refs. [34,35], and in Refs. [36,37], respectively. Tables S1eS4 contain selected data of chemical and physicochemical analyses for IeVIII. Tables S5 and S6 list geometrical parameters of intermolecular interactions in the crystal structures of complexes IeVIII. For the analysis of СeН…p and Au…p contacts, we used the geometrical criteria reported in Refs. [38,39], respectively. 1.1. Description of crystal structures All analyzed complexes (IeVIII) have ionic crystal structures consisting of discrete macrocyclic complex cations ([Au(C14H22N4)]þ (IeIV), [Au(C14H20N4Y2)]þ (Y ¼ Cl (V), Br(VI)), [Au(C14H23N4)]2þ (VII), [Au(C14H24N4)]3þ (VIII)) (Scheme 1) and outer-sphere anions Xe (X ¼ Br (I), ReO4 (II), BPh4 (III), AuBr2 (IV), ClO4 (VeVIII). Structure VIII contains also an oxonium cation H3Oþ. The coordination sphere of the Au atom includes four nitrogen atoms with AueN distances equal to 1.974(2)e1.996(5) Å. The coordination squares AuN4 are slightly distorted (D max ¼ 0.03 Å). The six-membered iminate rings of complexes IeVII are planar (the average deviation of non-hydrogen atoms from their root-meansquare atomic planes does not exceed 0.085 Å); they are negatively charged and contain C and N atoms in the sp2-state. The lengths of NeC (1.303(9)e1.35(1) Å) and CeC (1.37(2)e1.41(2) Å) bonds in these rings are intermediate between those of single and double bonds, respectively [40]. In the protonated six-membered

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Scheme 1. Structures of tetraazamacrocyclic cations of Au(III) complexes IeVIII.

rings of VII and VIII cations, the average NeC bond lengths (1.25(1)e1.288(7) Å) indicate localization of p-electrons and the formation of diimine bonds. The lengths of the bonds between carbon atoms (1.477(9)e1.500(9) Å) correspond to single CeC bonds. Methyl groups are bonded to the carbon atoms of sixmembered rings. Five-membered ethylenediamine rings of the macrocycles are non-planar and have ordinary envelope or gauche conformations like in most complexes with ethylenediamine bridges and in non-bridging ethylenediamine chelate rings. Complex cations are almost planar, the mean square deviations of all non-hydrogen atoms do not exceed 0.184 Å. 1.1.1. Diiminate complexes [Au(C14H22N4)]X (X ¼ Br (I), ReO4 (II), BPh4 (III), AuBr2 (IV)) In the diiminate complex I with the bromide anion, the cations are bound into two-dimensional layers by the interactions CeH…p [2,41,42] formed by hydrogen atoms H(72) and H(73) of the bridging methyl groups C(7)H3 of cations and p-electron clouds of delocalized six-membered rings of above- and below-lying cations (Fig. 1a1,2; Tables S5 and S6 (see complementary file)). As a result, each cation participates in the formation of four chains of two independent bonds CeH…p. The cation layers contain flat cation ribbons stretched in the direction ab (or eab); the distance between the planes of the ribbons is 3.5 Å. The anions are also bridging and are located between the cationic layers and bind them with cationeanionic non-classical H-bonds CeH/Br to form a 3D

1 H-bonds and contacts in Figs. 1e11 are marked as follows: CeH…p (bright green), CeH/Au (orange), CeH/Cl (plum), CeH/Br (violet), CeH/F (teal), CeH/O (red), Au/Au (gold), Au/Cl (turquiose), Au…p (rose), Au/N (light blue), Au/O (light orange), O/Cl (green), O/Br (aqua), O/N (dark blue), p…p (grey). 2 Atoms in Figs. 1e11 are marked as follows: Au (orange), C (grey), N (blue), Br (turquiose), Cl (green), F (bright green), B (plum), P (brown), H (grey).

structure (Fig. 1b). The neighboring layers are rotated through an angle of 111 relative to each other. In the diiminate complex II with the metal anion, only double cation stacks are formed due to the CeH…p interactions. Each cation is penetrated by two chains of CeH…p bonds (Fig. 2a). In contrast to the bromide complex I, the ReO 4 anions are located in the space between the cationic double stacks to link them, due to the bonds CeH/O formed by methylene groups, into 2D layers parallel to the plane ac. The flat cationeanionic ribbons are stretched along the direction [102] of the layers. The distances between the ribbons of the layer are 3.7 and 3.8 Å. The bonds CeH/O of methyl groups bind the layers into a 3D structure (Fig. 2b). In the structure of complex III with the bulky organic anion BPhe 4 (Fig. 3a), the central atoms B of the anions are located in the space between the cationeanionic layers formed by each of crystallographically independent cations K(1) and K(1A). The cations in the layers (Fig. 3b) are not connected directly to each other; they are parallel, but they do not form flat ribbons, in contrast to the case of diiminate complexes with inorganic anions. The angle between the planes of cations K(1) and K(1A) is 118 . Four acceptor-active phenyl rings of the anions participate in the formation of intraand interlayer cationeanionic H-bonds CeH…p to form a 3D structure. The architecture of the complex IV with a linear anion [33] fundamentally differs from the architectures of the complexes with spherical and tetrahedral anions (including complex III with a tetraphenylborate anion): in IV, double cationeanionic ribbons are stretched in the direction [101] and form a herringbone packing (Fig. 4a). The main structural unit of the packing of complex IV is a flat ribbon of alternating cations [Au(С14Н22N4)]þ and anions AuBr 2 (Fig. 4b). The linear anion AuBr 2 is located almost perpendicular to

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Fig. 1. (a) 2D cation layer in the (001) plane. (b) The packing diagram for (I) viewed along the special axis [110]. Only interlayer interactions are shown (dashed lines).

Fig. 2. (a) 2D cationeanionic layer in the (010) plane. (b) The packing diagram for (II) viewed along the a axes. Only the interlayer interactions are shown (dashed lines).

the axis of the ribbon (85о); also, the distance between the bromine atoms of the anion (4.8 Å) is close to the distance between the C atoms of the methyl groups of delocalized cation rings (5.0 and 4.9 Å). The cationeanionic ribbons are pair-wise parallel and are bound by the cationeanionic contacts Au(1)…Au(2), N(3)…Au(2), Au(2)… p and the non-classical H-bond C(13)eH(13A)…Br(2) to form a double cationeanionic ribbon; the distance between the planes of the double ribbon is 3.4 Å. The flat “faces” of the double ribbon, which contain not only cationic donor groups (CH3, CH2, CH) but also acceptor atoms Au(2) and Br of the anions AuBr 2 , occur in spatial accessibility for the formation of non-classical H-bonds. The double ribbons are combined with the adjacent double ribbons due to non-classical H-bonds CeH/Au(2) and СeН…Br (Table S5) to form a herringbone structure (Fig. 4a). Note that the angle between the planes of the double ribbons arranged in a herringbone pattern (108о) virtually corresponds to the HCH angle between the CH bonds of cation methyl groups (109.5о). The 3D structure IV contains only cationeanionic bonds and contacts (CeH/Br, Au(2); Au(2)…Au(1), N, p) (Table S5) which are quite large in number:

atoms Au and Br of the anion form twelve H-bonds and contacts. 1.1.2. Diiminate complexes with halogenated ligands [Au(C14H20N4Y2)]ClO4 (Y ¼ Cl (V), Br (VI) In structures V and VI containing two halogenated iminate rings, stack-layered 3D packings are realized (Figs. 5 and 6). Twodimensional layers are formed by cationecationic bonds CeH…p. The cationic ribbons are also observed in 2D layers of complexes V, VI; the distances between the ribbons are 3.5, 3.8 Å (V) and 3.4, 4.0 Å (VI). The cationic layers are connected into a 3D structure by the contacts of halogen atoms in the b-position of six-membered rings with bridge anions located in the interlayer space (Figs. 5a and 6a); each bridge anion lies in the planes of two cationic ribbons of adjacent layers. 1.1.3. Mono- and diprotonated complexes [Au(C14H23N4)](ClO4)2 (VII), [Au(C14H24N4)](H3O)(ClO4)4 (VIII) The structure of the iminatoeimine complex VII with the monoprotonated cation [Au(C14H23N4)]2þ contains double stacks (Fig. 7a) where delocalized cationic rings are penetrated by two

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Fig. 3. (a) The packing diagram for (III) viewed along the a axis. (b) 2D cationeanionic layer in the (001) plane formed by the cation K(1) and anions BPhe 4 . The phenyl rings C(20)e C(25) of anions are omitted for clarity.

Fig. 4. (a) The packing diagram of (IV) viewed along the special axis [101]. The contacts Au…p are omitted for clarity. (b) A pair of parallel cationeanionic ribbons stretched in the direction [101].

Fig. 5. (a) The packing diagram of (V) viewed along the b axis. (b) 2D cation layer in the (100) plane.

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Fig. 6. (a) The packing diagram for (VI) viewed along the b axis. (b) 2D cation layer in the (100) plane.

Fig. 7. (a) The packing diagram for (VII) viewed along the a axis. Only the interlayer interactions are shown (dashed lines). (b) The cationeanionic pseudo-layer in the (010) plane.

chains of bonds CeH…p, and the protonated rings of translationally identical cations are connected by the contacts of nitrogen atoms of imine rings with O(6) and O(8) atoms of the bridge Cl(2) O 4 anions [29]. The double cationeanionic stacks in VII are tied due to cationeanionic bonds C(12)eH(121)…O(7) into twodimensional networks in the bc and ebc directions of the crystal lattice; as a result, a 3D structure is formed (Fig. 7a). In the planes parallel to ac, the double stacks form pseudo-layers (Fig. 7b) containing flat cationeanionic ribbons which are parallel to each other and are symmetry-generated via inversion centers. The angle between the plane of the ribbon and the plane of the pseudo-layer is about 78 ; the distances between the planes of the ribbons in the pseudo-layer are 3.6 and 3.9 Å. In the crystal structure of the diprotonated imine complex VIII, a 1D stacked structure is realized, which is formed due to the contacts of O(2) atoms of the flat cationeanionic associates {[Н3О](ClO4)4}3e with the central gold(III) atoms of the macrocyclic [Au(С14Н24N4)]3þ cations (Fig. 8a) [29]. The planes of macrocyclic cations and those of {[Н3О](ClO4)4}3e associates in the cationeanionic stacks are parallel. In the planes parallel to ab (as well as in the planes parallel to bc), cationeanionic pseudo-layers are realized (Fig. 8b) which consist of parallel macrocyclic cations and {[Н3О](ClO4)4}3e associates. The pseudo-layers contain flat cationeanionic ribbons arranged parallel to each other; the distance between the planes of the ribbons is 3.9 Å.

The neighboring pseudo-layers in VII and VIII are rotated relative to each other so that the angles between the planes of the cations of adjacent layers for these complexes are 24 and 39 , respectively.

2. Discussion Macrocyclic cations of analyzed complexes are flat and have ten peripheral hydrogen-containing groups (CH3, CH2, CH), which are potential donors of weak CeH…A bonds [43,44]. Methyl groups in the a-position of six-membered rings of the cations have a rotational degree of freedom around the CeC axis and can orient in the structures in a way to participate in the formation of non-classical CH-bonds. The ligands of the cations in complexes IeVI contain two delocalized rings; the cation of complex VII has a single delocalized ring. The coordinatively unsaturated central atom Au(III) and iminate rings with a p-delocalized electron can exhibit weak acceptor properties [41,45]. The planar structure of the macrocyclic gold(III) cation provides spatial accessibility of both delocalized iminate rings and of the central atom Au(III) for the formation of H-bonds and contacts. The oxonium-ion in VIII is a strong donor of H-bonds OweH...O [43]. The counter-anions used in this work (spherical bromide anion, tetrahedral perchlorate and perrhenate anions, bulky tetraphenylborate anion, linear dibromoaurite anion) are good acceptors of

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Fig. 8. (a) The packing diagram for (VIII) viewed along the b axis. (b) The cationeanionic pseudo-layer in the (001) plane.

H-bonds. Even though the organic anion BPhe 4 has a negligible local charge on each C atom of phenyl rings (0.19 e on the whole ring [46]), the presence of four phenyl rings with a total of eight negatively charged aromatic faces makes this anion a unique hydrogen bond acceptor. Moreover, the anion BPhe 4 is effective both as an Hacceptor and as an H-donor. The dibromoaurite ion AuBr 2 is the strongest acceptor of H-bonds among all anions used in this study due to the coordination unsaturation of the central gold atom and of bromine atoms located at the ends of the linear segment and bearing negative charges. A detailed comparative analysis of the structures of the analyzed complexes allowed us to reveal not only factors affecting the packing of their crystal structures, but also the regularities and specific features in the packings. First of all, it should be noted that the packings of the crystal structures of the studied tetraazamacrocyclic gold(III) complexes depend both on the composition and structure of the constituent ions and on the ability of these ions to form intermolecular Hbonds and contacts. The nature of the anion and the composition of the cation play important roles in determining the self-assembly of cations. 3D crystal structures of the complexes IeVII, which cations contain delocalized six-membered rings, are stabilized by intermolecular non-covalent interactions (non-classical H-bonds and contacts). The topological pictures of the packings of the complexes  IeII, VeVII with small inorganic nonlinear anions (Br, ClO 4 , ReO4 ) are largely similar: the structures of these complexes are 3D stacklayered and are characterized by the presence of two-dimensional cationic layers (in I, V, VI) or doubled cationic stacks (in II, VII) where the cations are linked by the chains of cationecationic bonds  CeH…p penetrating the iminate rings. The anions Br, ClO 4 , ReO4 aid the formation of cation-cationic stacking motifs. A similar conclusion concerning the role of compact inorganic anions ClO 4,  BF 4 , PF6 was made in the work of Kuz'mina et al. [20], who studied the influence of the anion nature on styryl dye crystal packing. The cations in the 2D layers in I, II, V, VI and in pseudo-layers in VII are parallel and symmetry generated by inversion centers. The layers (pseudo-layers) contain flat cationic (I, V, VI) or cationeanionic (II, VII) ribbons, which are also connected by the centers of symmetry. In the immediate proximity to the planes of

the cationic ribbons (in I, V, VI), there are the nearest off-layer anions. The geometrical characteristics of the arrangement of the cations in the layers (the distance between the planes of cationic ribbons equal to 3.4e4.0 Å, the proximity of the angles between the planes of the cations and the planes of the layers (pseudo-layers) to right angles (75e90о)) create the prerequisites for the realization of cationecationic bonds CeH…p. In the bromide and perchlorate complexes (I, V, VI, VII), where the axes of the cations are rotated relative to the axes of the ribbons through an angle of 15e18 , the donor groups in the CeH…p bonds are methyl groups; in complex II with a metal-anion, this angle is equal to 86 , and the methylene groups of five-membered rings are donors. At the same time, the structures of complexes I, II, VVII with  small inorganic nonlinear anions Br, ClO 4 , and ReO4 have particular characteristics. Thus, the anions in their packings are placed differently and perform different functions. In the structures of diiminate bromide and perchlorate complexes I, V, VI, they are located in the planes parallel to the planes of cationic layers and bind them into 3D structures. In the diiminate perrhenate complex II, the anions ReO 4 are located between the double stacks to link them into 2D layers and to combine the 2D layers into a 3D structure. Note that no fundamental changes occur in the character of the packing when one of the six-membered rings of the macrocyclic gold(III) cation is protonated (in VII). The structure VII contains double cationeanionic stacks, on the periphery of which the perchlorate anions are located; in this complex, the cationeanionic contacts N/O, Au/O of the atoms of the imine ring participate in the formation of double stacks in the complex. These stacks are bound in a three-dimensional supramolecular structure by cationeanionic interactions CeH/O. The halogenation of iminate rings of the cation does not lead to profound changes in the packing. In halogen-substituted complexes V and VI, like in the unsubstituted complex I, the cationecationic CeH…p interactions are crucial for the formation of stack-layered packings. The replacement of the hydrogen atom in the b-position of a six-membered delocalized ring with a halogen without changing the packing pattern affects the character of the bonds between the layers. In the bromide complex I, the layers are linked by CH bonds between bridging bromide anions and methyl

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groups of the cations of the neighboring layers, while in the halogen-substituted complexes V and VI, the O atoms of the bridging perchlorate anions form contacts with halogen atoms of cation six-membered rings rather than with methyl groups. A similar conclusion was reported in our earlier works devoted to the analysis of packings of acyclic iminate gold(III) complexes with inorganic anions: the basic scheme of the packing and characteristic features of its structural elements are preserved when the  monatomic anion (I) is replaced by polyatomic anions (ClO 4 , PF6 ) or when hydrogen atoms are replaced by a halogen in the sixmembered ring of the cation [27,28]. In contrast to the complexes with compact inorganic non-linear anions, in the packings of diiminate complexes III and IV with a bulky BPhe 4 and with a coordinatively unsaturated linear anion AuBr 2 , the decisive role belongs to the anions. These anions prevent the association of cations by competing with them for acceptor sites. So, there are no cation-cationic interactions in the complex III with the bulky organic anion BPhe 4 . This anion with four phenyl rings having eight p-electron surfaces initiates the formation of a large number of cationeanionic interactions CeH…p. In Ref. [20], when studying styryl dye crystals with different anions, it was also demonstrated that the bulky BPhe 4 anion suppresses the formation of cation stacking motifs. In complex IV, the coordinatively unsaturated linear anion is also crucial for the architecture of the packing. The cations and anions in IV are lined up into flat ribbons due to the bonds and contacts formed by the anion AuBr 2 ; the cations and the anions of each ribbon in IV are interconnected. The ribbons are doubled also due to cationeanionic contacts and non-classical H-bonds formed by the anion AuBr 2 , and these doubled cationeanionic ribbons are packed in a herringbone structure. It is worth mentioning that the structures of complexes I, II, VeVII with compact inorganic anions also contain flat cationic or cationeanionic ribbons, but the ions of each ribbon are not linked to each other. Besides, in contrast to the complex IV, the ribbons in the structures of these complexes with non-linear anions are connected into two-dimensional cationic or cationeanionic layers whose cations are linked by cation-cationic H-bonds CeH…p. In the structure IV, the ribbons are only doubled and no cationecationic interactions take place. The introduction of oxonium, a strong H-bond donor, into the composition of the diprotonated complex VIII significantly affects its structure by changing the set of structure-forming interactions. Since p-electrons of both six-membered rings in complex VIII are localized on double C]N bonds, these rings lack acceptor properties for CeH…p interactions which bind cations in diiminate and iminatoeimine complexes into layers or double stacks. The 1D chain structure of the diimine complex VIII is determined by classical bonds OweH...O of the oxonium cation and by the Au/O contacts of the central atom of the macrocyclic cation that completes the coordination of Au up to six. In the structures of analyzed complexes, different anions have different abilities to form H-bonds and contacts. The inorganic spherical anion Br forms only two H-bonds in I. The tetrahedral metal-anion ReO 4 (II) participates in the formation of four H-bonds. The perchlorate anions in VeVII participate in the formation of short contacts: two contacts with halogen atoms in halogensubstituted V and VI, and three contacts with the central gold atom and N atoms of the imine rings in the monoprotonated complex VII; in VII perchlorate anions Cl(1)O4 and Cl(2)O4 form also one and two H-bonds, respectively. Among the complexes with inorganic anions, the greatest number of intermolecular interactions are observed in the complex IV with the linear anion AuBr 2 : nine bonds CeH…A (A ¼ Au(2), Br) and three contacts Au(2) …Au(1), Au(2)…N(3), Au(2)…p. In structure III, the organic

tetraphenylborate anion is both an acceptor (eight H-bonds) and a donor (three H-bonds) of non-classical bonds CeH…p. In complex VIII, the macrocyclic cation has no iminate rings and none of its constituent groups exhibits H-donor and H-acceptor properties. The four perchlorate anions of this complex are acceptors of eight classical H-bonds with the oxonium ion. The anions used as counter-ions in this work not only form different numbers of H-bonds and contacts but are associated with different numbers of macrocyclic cations: the bromide-anion in I is linked to two cations, the perchlorate anion in VeVII is linked to threeefour cations, the perrhenate anion (in II) is linked to four e cations, and the linear AuBr 2 anion and the bulky organic BPh4 anion (in IV and III) are linked to seven cations. In the diimine complex VIII, the perchlorate anion forms only one contact with the macrocyclic cation. For comparison, we analyzed the effect of counter-anions on the crystal packing of gold(III) amidocomplexes [AuCl(BPMAeH)]X (X ¼ BF4 (IX), PF6 (X), AuCl2 (XI)) synthesized by Cao et al. [25]. The structure of the [AuCl(BPMAeH)]þ cation of these complexes is similar to that of the cations of the complexes we studied. Namely, the cation is flat (D ¼ 0.101 Å), its coordination polyhedron AuN3Cl is a distorted square. The cation contains two six-membered delocalized heterocyclic rings (Py) and two five-membered heterocycles with methylene groups. However, unlike tetraazamacrocyclic cations considered in our study, the [AuCl(BPMAeH)]þ cation has no terminal methyl groups. Like in the present work,   compact pseudo-spherical (BF 4 , PF6 ) and linear (AuCl2 ) inorganic anions were used in Ref. [25] as counter-anions.

The authors of [25] revealed the presence of 1D chains in the structures of complexes X and XI. In X, the chains are formed due to the interactions between central atoms of the square-planar antiparallel cations, which are supplemented by p…p stacking interactions between the pyridyl groups; in XI, the complex is packed in cation-anionic columns by short aurophilic bonds Au(III)/Au(I) and Au(I)/Cl contacts. No detailed analysis of crystal structure architectures of the complexes and intermolecular H-bonds and contacts realized in their structures was reported in Ref. [25]. We generated the packing diagrams for the amidocomplexes IXeXI (Figs. 9e11) using the following data from the CCDC database: NIBWUR for IX, NIBXAY for X, NIBXEC for XI. There is an analogy between the packing architectures of tetraazamacrocyclic gold(III) complexes studied in our work and amidocomplexes studied in Ref. [25]. Like in complexes IVII containing delocalized six-membered rings, 3D supramolecular structures of gold(III) amidocomplexes IXeXI (Figs. 9e11) are stabilized by intermolecular cation-cationic and cation-anionic interactions (Table S7). The geometry and type of counter-anions not only determine relative positions of the ions in the packings but also influence the formation of cation associates. Thus, anion chains occur between cation layers in the tetrafluoroborate complex IX (Fig. 9a) and between doubled cation stacks in complex X with hexafluorophosphate anion (Fig. 10a) (for comparison: in IeVII, interlayer and inter-stack arrangements of anions are observed in I, V, VI (Figs. 1, 5 and 6) and in II, VII (Figs. 2 and 7), respectively). In the amidocomplex XI with linear dichloroaurite anion, like in the tetraazamacrocyclic complex IV with dibromoaurite anion, the anions are located between the cations

V.A. Afanas'eva, L.A. Glinskaya / Journal of Molecular Structure 1202 (2020) 127343

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Fig. 9. (a) The packing diagram for (IX) viewed along the b axis. (b) 2D cationic network in the (100) plane.

Fig. 10. (a) The packing diagram for (X) viewed along the a axis. The interactions into double cationic stacks are omitted for clarity. (b) 2D cationeanionic layer in the (010) plane.

Fig. 11. (a) The packing diagram for (XI) viewed along the b axis. (b) 2D cationeanionic layer viewed along special axis [101].

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within planar cation-anion ribbons (Fig. 11b, cf. Fig. 4b). The structures of amidocomplexes IXeXI, like those of tetraazamacrocyclic complexes IVII, contain cation associates, and their dimension depends on the nature of the counter-anion. 2D cation networks are realized in IX containing BF4 anion (Fig. 9b), and 1D cation chains are realized in X with PF-6 anion (Fig. 10b). The architecture of complex XI with linear AuCl 2 is characterized by the

formation. These anions prevent the association of cations by forming cationeanionic H-bonds and contacts with them. The linear acceptor-active anion AuBr 2 has the greatest influence on the packing of the analyzed macrocyclic gold(III) complexes to provide, along with the complementary structure of the cation, the herringbone packing of the structure.

presence of only 0D cation dimers formed due to p…p interactions (Cg…Cg ¼ 3.601 Å; dpln ¼ 3.42 Å) between pyridine rings of the cations of the cation-anion layer along the special axis [101] (Fig. 11b). In our complexes with nonlinear inorganic anions, the cations are also connected into 2D layers (I, V, VI) or into 1D double stacks (II, VII); no cation associates are present in complex IV with a linear anion. It is noteworthy that cation-cationic bonds СН…p, which are decisive in the formation of packings of tetraazamacrocyclic IVII,

Acknowledgements

are absent in amidocomplexes. But the cation-cationic p…p interactions are present in structures of all amidocomplexes (Table S7; Figs. 9b, 10b and 11b). In these complexes, like in IeVII, the anions are bridging and are responsible for connecting cationic associates into 3D structures. The linear dibromo- and dichloroaurite anions creating the largest number of H bonds and contacts in the tetraazamacrocyclic complex IV and in the amidocomplex XI are crucial for the formation of 3D packings in both complexes. It is characteristic that in these complexes, cations and anions form flat cation-anion ribbons, and these ribbons are the main structural elements in their structures. But in the tetraazamacrocyclic complex IV, the doubled ribbons are linked into a herringbone structure, whereas in the amidocomplex XI, whose cation has no methyl groups, the ribbons are parallel and linked into 2D layers (in the directions [101] and [010]). 3. Conclusions The features of the packings of the analyzed unsaturated tetraazamacrocyclic gold(III) complexes are determined both by the composition and structure of the cation and by the nature and geometry of the counter-anion. The most important key factor to affect the packing of gold(III) macrocyclic complexes is the ability of the ions composing the complex to form intermolecular nonclassical H-bonds and contacts. In the packings of crystal structures of all complexes whose ligands contain iminate six-membered rings (IeVII), the 3D supramolecular architecture of the crystal lattice is determined and stabilized by an extensive network of secondary non-covalent intermolecular interactions (non-classical H-bonds CeH…A (A ¼ p, Br, Cl, O, Au) and contacts Au/Au(O, N, p); O/Cl(Br, N). The 1D crystal structure of the diprotonated complex VIII is stabilized by classical H-bonds OweH...O and by Au/O contacts. In the complexes I, II, VeVII with iminate six-membered rings  and with inorganic non-linear anions (Br, ClO 4 , ReO4 ), the packing architecture depends mainly on the structure of the tetraazamacrocyclic cation: namely, its planarity, the presence of sixmembered delocalized iminate rings, the presence of four terminal methyl groups capable to rotate around the axis Csp2eCsp3 to take a “comfortable” position for the formation of CeH…p bonds between the cations. The halogenation of iminate rings of the cation and the protonation of one of them do not lead to radical changes in the packing. The counter-anions are placed between the layers or between the stacks of the layers (or pseudo-layers) and do not prevent the formation of layered structures. In diiminate complexes with a bulky BPhe 4 anion or with a linear AuBr 2 anion, the anions play a decisive role in the structure

This research was supported by the Ministry of Science and Education of the Russian Federation. Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.molstruc.2019.127343. References [1] D. Braga, F. Grepioni, Acc. Chem. Res. 33 (2000) 601e608. , S.D. Zari [2] G.A. Bogdanovi c, A. Spasojevi c-de Bire c, Eur. J. Inorg. Chem. (2002) 1599e1602. [3] W.D.S. Motherwell, H.L. Ammon, J.D. Dunitz, et al., Acta Crystallogr. B58 (2002) 647e661. [4] F.H. Allen, W.D.S. Motherwell, Acta Crystallogr. B58 (2002) 407e422. [5] M.C. Etter, Acc. Chem. Res. 23 (1990) 120e126. [6] F. Garcia-Tellado, S.J. Geib, S. Goswami, A.D. Hamilton, J. Am. Chem. Soc. 113 (1991) 9265e9269. [7] M.C. Etter, J. Phys. Chem. 95 (1991) 4601e4610. [8] M.C. Etter, S.M. Reutzel, J. Am. Chem. Soc. 113 (1991) 2586e2598. [9] J. Bernstein, R.E. Davis, L. Shimoni, N.-L. Chang, Angew. Chem., Int. Ed. Engl. 34 (1995) 1555e1573. [10] S. Friedrichs, P.G. Jones, Z. Naturforschung 59b (2004) 49e57. [11] T. Samanta, L. Dey, J. Dinda, S.K. Chattopadhyay, S.K. Seth, J. Mol. Struct. 1068 (2014) 58e70. [12] Y.J. Zhao, M.C. Hong, Y.C. Liang, et al., Polyhedron 20 (2001) 2619e2625. [13] H.-Y. Zhao, X.Y.-B. Qiu, P.-W. Shen, J. Mol. Struct. 733 (2005) 95e99. [14] W.P. Su, M.C. Hong, J.B. Weng, et al., Inorg. Chim. Acta 331 (2002) 8e15. [15] N.-H. Hu, H.-Q. Jia, J.-W. Xu, K. Aoki, Acta Crystallogr. 61 (2005) o457eo459. [16] M.-L. Tong, X.-M. Chen, B.-H. Ye, Inorg. Chem. 37 (1998) 5278e5281. [17] D. Whang, K. Kim, J. Am. Chem. Soc. 119 (1997) 451e452. [18] P. Manna, S.K. Seth, A. Das, et al., Inorg. Chem. 51 (2012) 3557e3571. [19] D. Cin ci c, B. Kaitner, Acta Crystallogr. C64 (2008) o561eo565. [20] L.G. Kuz'mina, A.I. Vedernikov, A.V. Churakov, et al., CrystEngComm 16 (2014) 5364e5378. [21] A. Laguna (Ed.), Modern Supramolecular Gold Chemistry. Gold-Metal Interactions and Applications, Wiley-VCH, Weinheim, 2008, p. 505. [22] J.S. Ovens, K.N. Truong, D.B. Leznoff, Dalton Trans. 41 (2012) 1345e1351. [23] J.D. Crowley, I.M. Steele, B. Bosnich, Inorg. Chem. 44 (2005) 2989e2991. [24] H. Ehlich, A. Schier, H. Schmidbaur, Z. Naturforschung 57b (2002) 890e894. [25] L. Cao, M.C. Jennings, R.J. Puddephatt, Inorg. Chem. 46 (2007) 1361e1368. [26] V.A. Afanas’eva, L.A. Glinskaya, R.F. Klevtsova, I.V. Mironov, Russ. J. Coord. Chem. 36 (2010) 697e703. [27] V.A. Afanas’eva, L.A. Glinskaya, I.V. Korolkov, Russ. J. Coord. Chem. 39 (2013) 257e270. [28] V.A. Afanas’eva, L.A. Glinskaya, N.V. Kurat’eva, Russ. J. Coord. Chem. 40 (2014) 484e494. [29] V.A. Afanas’eva, L.A. Glinskaya, S.A. Gromilov, Russ. J. Coord. Chem. 42 (2016) 85e95. [30] L.A. Glinskaya, V.A. Afanas’eva, R.F. Klevtsova, J. Struct. Chem. 45 (2004) 124e129. [31] V.A. Afanas’eva, L.A. Glinskaya, S.A. Gromilov, et al., J. Struct. Chem. 56 (2015) 787e791. [32] V.A. Afanas’eva, L.A. Glinskaya, D.A. Piryazev, et al., Inorg. Chem. Commun. 83 (2017) 70e75. [33] V.A. Afanas’eva, L.A. Glinskaya, R.F. Klevtsova, et al., Russ. J. Coord. Chem. 37 (2011) 325e332. [34] V.A. Afanas’eva, L.A. Glinskaya, R.F. Klevtsova, et al., J. Struct. Chem. 44 (2003) 68e73. [35] V.A. Afanas’eva, L.A. Glinskaya, R.F. Klevtsova, et al., J. Struct. Chem. 48 (2007) 289e299. [36] V.A. Afanas’eva, I.V. Mironov, L.A. Glinskaya, et al., J. Struct. Chem. 45 (2004) 1014e1021. [37] V.A. Afanas’eva, L.A. Glinskaya, R.F. Klevtsova, L.A. Sheludyakova, J. Struct. Chem. 46 (2005) 131e136. [38] M. Nishio, Y. Umezawa, J. Fantini, et al., Phys. Chem. Chem. Phys. 16 (2014) 12648e12683. [39] E.R.T. Tiekink, J. Zukerman-Schpector, CrystEngComm 11 (2009) 1176e1186. [40] L. Pauling, The Nature of the Chemical Bond and the Structure of Molecules

V.A. Afanas'eva, L.A. Glinskaya / Journal of Molecular Structure 1202 (2020) 127343 and Crystals: an Introduction to Modern Structural Chemistry, Cornell University Press, Ithaca. NY, 1960, p. 644. [41] H. Suezawa, T. Yoshida, Y. Umezawa, et al., Eur. J. Inorg. Chem. (2002) 3148e3155. [42] M. Nishio, CrystEngComm 6 (2004) 130e158.

11

[43] G.A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford University Press, New York, 1997. [44] T. Steiner, Acta Crystallogr. B54 (1998) 456e463. [45] L. Brammer, Dalton Trans. 16 (2003) 3145e3157. [46] P.K. Bakshi, A. Linden, B.R. Vincent, et al., Can. J. Chem. 72 (1994) 1273e1293.