Chiral versus racemic building blocks in supramolecular chemistry: tartrate salts of organic diamines

2002 ◽  
Vol 58 (2) ◽  
pp. 272-288 ◽  
Author(s):  
Dorcas M. M. Farrell ◽  
George Ferguson ◽  
Alan J. Lough ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bonds ◽  
Supramolecular Chemistry ◽  
Tartaric Acid ◽  
Three Dimensional ◽  
Building Blocks ◽  
Different Types ◽  
Ionic Components

In the 1:1 adducts C12H10N2·C4H6O6 formed between 1,2-bis(4′-pyridyl)ethene and racemic tartaric acid [(I), triclinic P\bar 1, Z′ = 1] and (2R,3R)-tartaric acid [(II), triclinic P1, Z′ = 2], the ionic components are linked by hard hydrogen bonds into single sheets, which are further linked by C—H...O hydrogen bonds. In the analogous adducts C10H18N2·C4H6O6 formed by 4,4′-bipyridyl with racemic tartaric acid [(III), triclinic P\bar 1, Z′ = 1] and the chiral acid [(IV), monoclinic P21, Z′ = 1], the hard hydrogen bonds generate bilayers which are again linked by C—H...O hydrogen bonds. Piperazine forms a 1:1 salt [{(C4H10N2)H2}2+]·[(C4H4O6)2−] with (2R,3R)-tartaric acid [(V), monoclinic P21] sheets, which are linked by the cations to form a pillared-layer framework. In each of the 1:2 salts formed by racemic tartaric acid with piperazine [(VI), monoclinic P21/n, Z′ = 0.5] and 1,4-diazabicyclo[2.2.2]octane (DABCO) [(VII), monoclinic P21/n, Z′ = 0.5], the cation lies across a centre of inversion, with the [{HN(CH2CH2)3NH}2+] cation disordered over two sets of sites: in both (VI) and (VII) the anions form a three-dimensional framework encapsulating large voids which accommodate the cations. The salt formed between DABCO and (2R,3R)-tartaric acid [(VIII), orthorhombic P212121, Z′ = 1] has 3:4 stoichiometry and contains four different types of ion, [{HN(CH2CH2)3NH}2+]2·[N(CH2CH2)3NH]+·3(C4H5O6)−·C4H4O6 2−: the hard hydrogen bonds generate a three-dimensional framework.

Salts of maleic and fumaric acids with organic polyamines: comparison of isomeric acids as building blocks in supramolecular chemistry

2003 ◽  
Vol 59 (1) ◽  
pp. 100-117 ◽  
Author(s):  
Katharine F. Bowes ◽  
George Ferguson ◽  
Alan J. Lough ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Supramolecular Chemistry ◽  
Fumaric Acid ◽  
Maleic Acid ◽  
Rotation Axis ◽  
Three Dimensional ◽  
Building Blocks ◽  
Ionic Components ◽  
Acid Compound

Maleic acid and fumaric acid both readily form adducts with organic diamines: maleic acid usually forms 2:1 adducts with bases, while fumaric acid usually forms 1:1 adducts, and the supramolecular stuctures within the two series are not simply related. The 1:2 adducts formed by 1,2-bis(4-pyridyl)ethane and by 4,4′-bipyridyl, respectively, with maleic acid, compounds (1) and (2), are salts [{(diamine)H2}2+]·[(C4H3O4)−]2 in which the cations lie across a centre of inversion and a twofold rotation axis, respectively. The ions are linked by N—H...O hydrogen bonds into three-ion aggregates, which are further linked by C—H...O hydrogen bonds into two- and three-dimensional arrays, respectively. In the fumarate salts formed by 2,2′-dipyridylamine (1:1) and 1,4-diazabicyclo[2.2.2]octane (1:2), compounds (3) and (4), the ionic components are linked into molecular ladders. The 1:1 adduct of 4,4′-bipyridyl and fumaric acid, compound (5), contains two neutral components, both of which lie across centres of inversion; these components are linked into chains by a single O—H...N hydrogen bond and thence into sheets by C—H...O hydrogen bonds. The corresponding adduct formed by 1,4-diazabicyclo[2.2.2]octane, compound (6), is a salt that again contains chains linked into sheets by C—H...O hydrogen bonds. In the 1:1 adducts, compounds (7), (8) and (10), that are formed between 1,2-bis(4-pyridyl)ethane, 4,4′-trimethylenedipyridine and hexamethylenetetramine, respectively, with fumaric acid, and in the 1:2 adduct, compound (9), of 2,2′-dipyridylamine and maleic acid, the chains that are generated by the hard hydrogen bonds are linked by C—H...O hydrogen bonds to form, in each case, a single three-dimensional framework. In the 1:1 adduct, compound (11), of 2,2′-bipyridyl and fumaric acid the hydrogen bonds generate two interwoven three-dimensional frameworks.

Chiral versus racemic building blocks in supramolecular chemistry: malate salts of organic diamines

2002 ◽  
Vol 58 (3) ◽  
pp. 530-544 ◽  
Author(s):  
Dorcas M. M. Farrell ◽  
George Ferguson ◽  
Alan J. Lough ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bonds ◽  
Supramolecular Chemistry ◽  
Malic Acid ◽  
Three Dimensional ◽  
Building Blocks ◽  
Partial Transfer ◽  
Molecular Components ◽  
N Vector ◽  
Hydrogen Bonded

(S)-Malic acid forms a salt with N,N′-dimethylpiperazine, [MeN(CH2CH2)2NMe]H2 2+·2C4H5O5 − (1) (triclinic, P1, Z′ = 1), in which the cations link pairs of hydrogen-bonded anion chains to form a molecular ladder. With 4,4′-bipyridyl, (S)-malic acid forms a 1:1 adduct which crystallizes from methanol to yield two polymorphs, (2) (triclinic, P1, Z′ = 1) and (3) (monoclinic, C2, Z′ = 1), while racemic malic acid with 4,4′-bipyridyl also forms a 1:1 adduct, (4) (monoclinic, P21/c, Z′ = 1). In each of (2), (3) and (4) the components are linked by O—H...N and N—H...O into chains of alternating bipyridyl and malate units, which are linked into sheets by O—H...O hydrogen bonds. In each of the 1:1 adducts (5) and (6), formed by, respectively, (S)-malic acid and racemic malic acid with 1,2-bis(4′-pyridyl)ethene, the diamine is disordered over two sets of sites, related by a 180° rotation about the N...N vector. In (5), (C12H10N2)H+·C4H5O5 − (triclinic, P1, Z′ = 1), the components are again linked by a combination of N—H...O and O—H...O hydrogen bonds into sheets, while in (6) (triclinic, P{\overline 1}, Z′ = 0.5) there is only partial transfer of the H atom from O to N and the malate component is disordered across a centre of inversion. With 1,4-diazabicyclo[2.2.2]octane, racemic malic acid forms a 1:2 salt, [(C6H12N2)H2]2+·2C4H5O5 − (7) (monoclinic, P21/c, Z′ = 2), while (S)-malic acid forms a 1:1 adduct, (8) (monoclinic, P21, Z′ = 3). There are thus six independent molecular components in each. In (7) the ions are linked by an extensive series of N—H...O and O—H...O hydrogen bonds into a three-dimensional framework, but in (8) there is extensive disorder involving all six components, and no refinement proved to be feasible.

Ethane-1,2-diphosphonic acid as a building block in supramolecular chemistry; a pillared-layer framework and framework-encapsulated cations

2001 ◽  
Vol 57 (1) ◽  
pp. 95-102 ◽  
Author(s):  
Paul S. Wheatley ◽  
Alan J. Lough ◽  
George Ferguson ◽  
Colin J. Burchell ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Supramolecular Chemistry ◽  
Building Block ◽  
Three Dimensional ◽  
Single Type ◽  
Water Molecules ◽  
Diphosphonic Acid ◽  
Different Types ◽  
O 175

The 1:1 adduct of piperazine and ethane-1,2-diphosphonic acid is a salt [C4H12N2]2+·[C2H6O6P2]2−, in which both ions lie across centres of inversion in space group P21/c. The anions are linked by a single type of O—H...O hydrogen bond [O...O, 2.562 (3) Å; H...O, 1.73 Å, O—H...O, 169°] into (6, 3) nets built from a single type of R^4_4(22) ring. The cations lie between these nets, linked to them by two types of N—H...O hydrogen bond [N...O, 2.635 (3) and 2.735 (3) Å; H...O 1.72 and 1.82 Å, N—H...O, 175 and 177°] such that the cations link adjacent sheets, thus forming a pillared-layer framework. The aquated adduct formed between trimethylenedipiperidine and ethane-1,2-diphosphonic acid is also a salt [C13H28N2]2+·[C2H6O6P2]2−·2.8[H2O], in which there are 12 different types of hydrogen bond, eight O—H...O and four N—H...O. The anions are linked into chains by pairs of O—H...O hydrogen bonds and these chains are linked by the water molecules into a continuous three-dimensional framework. Within the anion/water framework are large voids which contain pairs of cations, linked to the framework by N—H...O hydrogen bonds.

scholarly journals Crystal structure of 4-(dimethylamino)pyridiniumcis-diaquabis(oxalato-κ2O,O′)ferrate(III) hemihydrate

2015 ◽  
Vol 71 (8) ◽  
pp. 934-936 ◽  
Author(s):  
Edith Dimitri Djomo ◽  
Frédéric Capet ◽  
Justin Nenwa ◽  
Michel M. Bélombé ◽  
Michel Foulon
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Bond Length ◽  
Three Dimensional ◽  
Coordination Environment ◽  
Distorted Octahedral Coordination ◽  
Dimensional Network ◽  
Distorted Octahedral ◽  
Ionic Components ◽  
Distorted Octahedral Coordination Environment

The FeIIIions in the hybrid title salt, (C7H11N2)[Fe(C2O4)2(H2O)2]·0.5H2O, show a distorted octahedral coordination environment, with four O atoms from two chelating oxalate dianions and two O atoms from twocisaqua ligands. The average Fe—O(oxalate) bond length [2.00 (2) Å] is shorter than the average Fe—O(water) bond length [2.027 (19) Å]. The ionic components are connectedviaintermolecular N—H...O and O—H...O hydrogen bonds into a three-dimensional network.

Associations of squaric acid and its anions as multiform building blocks of hydrogen-bonded molecular crystals

2001 ◽  
Vol 57 (6) ◽  
pp. 859-865 ◽  
Author(s):  
Gastone Gilli ◽  
Valerio Bertolasi ◽  
Paola Gilli ◽  
Valeria Ferretti
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Engineering ◽  
Negative Charge ◽  
Three Dimensional ◽  
Molecular Crystals ◽  
Building Blocks ◽  
Squaric Acid ◽  
Orthosilicic Acid ◽  
Molecular Plane ◽  
Dimensional Crystal

Squaric acid, H2C4O4 (H2SQ), is a completely flat diprotic acid that can crystallize as such, as well as in three different anionic forms, i.e. H2SQ·HSQ−, HSQ− and SQ2−. Its interest for crystal engineering studies arises from three notable factors: (i) its ability of donating and accepting hydrogen bonds strictly confined to the molecular plane; (ii) the remarkable strength of the O—H...O bonds it may form with itself which are either of resonance-assisted (RAHB) or negative-charge-assisted [(−)CAHB] types; (iii) the ease with which it may donate a proton to an aromatic base which, in turn, back-links to the anion by strong low-barrier N—H+...O1/2− charge-assisted hydrogen bonds. Analysis of all the structures so far known shows that, while H2SQ can only crystallize in an extended RAHB-linked planar arrangement and SQ2− tends to behave much as a monomeric dianion, the monoanion HSQ− displays a number of different supramolecular patterns that are classifiable as β-chains, α-chains, α-dimers and α-tetramers. Partial protonation of these motifs leads to H2SQ·HSQ− anions whose supramolecular patterns include ribbons of dimerized β-chains and chains of emiprotonated α-dimers. The topological similarities between the three-dimensional crystal chemistry of orthosilicic acid, H4SiO4, and the two-dimensional one of squaric acid, H2C4O4, are finally stressed.

Supramolecular chemistry of amine–phenol adducts; novel three-dimensional framework structures in adducts of bis(2-aminoethyl)amine with 4,4′-sulfonyldiphenol, 1,1,1-tris(4-hydroxyphenyl)ethane and 3,5-dihydroxybenzoic acid, and in the methanol-solvated adduct of tris(2-aminoethyl)amine with 4,4′-biphenol

2000 ◽  
Vol 56 (1) ◽  
pp. 68-84 ◽  
Author(s):  
Christopher Glidewell ◽  
George Ferguson ◽  
Richard M. Gregson ◽  
Charles F. Campana
Keyword(s):  
Hydrogen Bonds ◽  
Supramolecular Chemistry ◽  
Three Dimensional ◽  
Two Dimensional ◽  
Asymmetric Unit ◽  
Dihydroxybenzoic Acid ◽  
Nearest Neighbours ◽  
Molecular Components

Bis(2-aminoethyl)amine–4,4′-sulfonyldiphenol (1/3) (1) (orthorhombic Pccn with Z′ = 0.5) is a salt, [HN(CH2CH2NH3)2]2+.[O2S(C6H4O)2]2−.[O2S(C6H4OH)2]2, containing both dianionic and neutral bis-phenol units. The neutral and anionic bis-phenol units are linked by strong O—H...O− hydrogen bonds to form ladders built from R{_4}{^4}(48) rings: each ladder is interwoven with its two nearest neighbours to form a continuous two-dimensional sheet. The amine cations play two roles: they link each ladder to its two next-nearest neighbours by means of N—H...O hydrogen bonds and they also link each sheet to the two neighbouring sheets, again via N—H...O hydrogen bonds, thus generating a three-dimensional framework. Bis(2-aminoethyl)amine–1,1,1-tris(4-hydroxyphenyl)ethane–methanol (1/4/1) (2) (triclinic P1¯ with Z′ = 0.5) consists entirely of neutral fragments. The tris-phenol units are linked by O—H...O hydrogen bonds into molecular ladders built from R{_4}{^4}(48) rings: these ladders are linked by the amine units, firstly into sheets and thence into a three-dimensional framework. Bis(2-aminoethyl)amine–3,5-dihydroxybenzoic acid (1/2) (3) (monoclinic P21/c with Z′ = 1) is a salt [HN(CH2CH2NH3)2]2+.[{(HO)2C6H3COO}−]2. The 3,5-dihydroxybenzoate anions are linked by O—H...O hydrogen bonds into interwoven and cross-connected (001) sheets linked by further O—H...O hydrogen bonds into a three-dimensional framework. The (001) sheets are further linked by ladders formed from both cations and anions. Tris(2-aminoethyl)amine–4,4′-biphenol–methanol (1/3/1), (4) (monoclinic P21), is a salt [{(H2NCH2CH2)2N(CH2CH2NH3)}+]2.[OC6H4C6H4O]2−.[HOC6H4C6H4OH]5.[MeOH]2, with Z′ = 1. The asymmetric unit, containing ten independent molecular components, can be regarded as a supermolecule held together by a total of 13 independent hydrogen bonds, of O—H...O, O—H...N and N—H...O types. The supermolecules are linked by O—H...O and N—H...O hydrogen bonds into two-dimensional sheets, generated by translation; further N—H...O hydrogen bonds around the 21 screw axes link neighbouring sheets together into a three-dimensional framework.

Oligosiloxanediols as building blocks for supramolecular chemistry: hydrogen-bonded adducts with amines form supramolecular structures in zero, one and two dimensions

2000 ◽  
Vol 56 (2) ◽  
pp. 273-286 ◽  
Author(s):  
Brian O'Leary ◽  
Trevor R. Spalding ◽  
George Ferguson ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bonds ◽  
Supramolecular Chemistry ◽  
Building Blocks ◽  
Two Dimensions ◽  
Supramolecular Structures ◽  
Structural Motif ◽  
Two Dimensional ◽  
The Third ◽  
A Chain ◽  
Hydrogen Bonded

The structure of 1,1,3,3,5,5-hexaphenyltrisiloxane-1,5-diol–pyrazine (4/1), (C36H32O4Si3)4·C4H4N2 (1), contains finite centrosymmetric aggregates; the diol units form dimers, by means of O—H...O hydrogen bonds, and pairs of such dimers are linked to the pyrazine by means of O—H...N hydrogen bonds. In 1,1,3,3,5,5-hexaphenyltrisiloxane-1,5-diol–pyridine (2/3), (C36H32O4Si3)2·(C5H5N)3 (2), the diol units are linked into centrosymmetric pairs by means of disordered O—H...O hydrogen bonds: two of the three pyridine molecules are linked to the diol dimer by means of ordered O—H...N hydrogen bonds, while the third pyridine unit, which is disordered across a centre of inversion, links the diol dimers into a C 3 3(9) chain by means of O—H...N and C—H...O hydrogen bonds. In 1,1,3,3-tetraphenyldisiloxane-1,3-diol–hexamethylenetetramine (1/1), (C24H22O3Si2)·C6H12N4 (3), the diol acts as a double donor and the hexamethylenetetramine acts as a double acceptor in ordered O—H...N hydrogen bonds and the structure consists of C 2 2(10) chains of alternating diol and amine units. In 1,1,3,3-tetraphenyldisiloxane-1,3-diol–2,2′-bipyridyl (1/1), C24H22O3Si2·C10H8N2 (4), there are two independent diol molecules, both lying across centres of inversion and therefore both containing linear Si—O—Si groups: each diol acts as a double donor of hydrogen bonds and the unique 2,2′-bipyridyl molecule acts as a double acceptor, thus forming C 2 2(11) chains of alternating diol and amine units. The structural motif in 1,1,3,3-tetraphenyldisiloxane-1,3-diol–pyrazine (2/1), (C24H22O3Si2)2·C4H4N2 (5), is a chain-of-rings: pairs of diol molecules are linked by O—H...O hydrogen bonds into centrosymmetric R 2 2(12) dimers and these dimers are linked into C 2 2(13) chains by means of O—H...N hydrogen bonds to the pyrazine units. 1,1,3,3-Tetraphenyldisiloxane-1,3-diol–pyridine (1/1), C24H22O3Si2·C5H5N (6), and 1,1,3,3-tetraphenyldisiloxane-1,3-diol–pyrimidine (1/1), C24H22O3Si2·C4H4N2 (7), are isomorphous: in each compound the amine unit is disordered across a centre of inversion. The diol molecules form C(6) chains, by means of disordered O—H...O hydrogen bonds, and these chains are linked into two-dimensional nets built from R 6 6(26) rings, by a combination of O—H...N and C—H...O hydrogen bonds.

scholarly journals Six tris(bipyridyl)iron(II) complexes with 2-substituted 1,1,3,3-tetracyanopropenide, perchlorate and tetrafluoridoborate anions; order versus disorder, hydrogen bonding and C—N...π interactions

2018 ◽  
Vol 74 (12) ◽  
pp. 1717-1726
Author(s):  
Abderezak Addala ◽  
Zouaoui Setifi ◽  
Yukio Morimoto ◽  
Beñat Artetxe ◽  
Takashi Matsumoto ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Compound I ◽  
Π Interactions ◽  
Chain Compounds ◽  
Compound Ii ◽  
Ionic Components

Structures are reported for six closely related salts of tris(bipyridyl)iron(II) cations, namely tris(2,2′-bipyridine)iron(II) bis(1,1,3,3-tetracyano-2-methoxypropenide) 0.776-hydrate, [Fe(C10H8N2)3](C8H3N4O)2.0.776H2O, (I), tris(2,2′-bipyridine)iron(II) 1,1,3,3-tetracyano-2-(propylsulfanyl)propenide perchlorate, [Fe(C10H8N2)3](C10H7N4S)(ClO4), (II), tris(5,5′-dimethyl-2,2′-bipyridine)iron(II) 1,1,3,3-tetracyano-2-methoxypropenide tetrafluoridoborate ethanol 0.926-solvate, [Fe(C12H12N2)3](C8H3N4O)(BF4).0.926C2H2O, (III), tris(5,5′-dimethyl-2,2′-bipyridine)iron(II) 1,1,3,3-tetracyano-2-ethoxypropenide tetrafluoridoborate, [Fe(C12H12N2)3](C9H5N4O)(BF4), (IV), tris(5,5′-dimethyl-2,2′-bipyridine)iron(II) 1,1,3,3-tetracyano-2-(ethylsufanyl)propenide tetrafluoridoborate, [Fe(C12H12N2)3](C9H5N4S)(BF4), (V), and tris(5,5′-dimethyl-2,2′-bipyridine)iron(II) 1,1,3,3-tetracyano-2-propoxypropenide tetrafluoridoborate, [Fe(C12H12N2)3](C10H7N4O)(BF4), (VI). In compound (I), one of the anions is disordered over two sets of atomic sites with equal occupancies while, in the second anion, just one of the C(CN)2 units is disordered, again over two sets of atomic sites with equal occupancies: the anionic components are linked by multiple C—H...N hydrogen bonds to form a three-dimensional framework. In compound (II), the polynitrile anion is disordered over two sets of atomic sites with occupancies in the approximate ratio 3:1, while the perchlorate anion is disordered over three sets of atomic sites: there are C—N...π interactions between the cations and the polynitrile anion. The polynitrile anion in compound (III) is fully ordered, but the tetrafluoridoborate anion is disordered over two sets of atomic sites with occupancies 0.671 (4) and 0.329 (4): the cations and the tetrafluoridoborate anions are linked by C—H...F interactions to form an interrupted chain. Compounds (IV) and (V) are isostructural and all of the ionic components are fully ordered in both of them: the cations and tetrafluoridoborate anions are linked into C 2 2(12) chains. The polynitrile anion in compound (VI) is disordered over two sets of atomic sites with approximately equal occupancies, and here the chains formed by the cations and the tetrafluoridoborate anions are of the C 2 2(13) type.

The Solution and Solid State Structure of L-Carnitine L-Tartrate

1998 ◽  
Vol 53 (8) ◽  
pp. 788-791 ◽  
Author(s):  
Hubert Schmidbaur ◽  
Annette Schier ◽  
Angela Bayler
Keyword(s):  
Solid State ◽  
Hydrogen Bonds ◽  
Aqueous Solutions ◽  
Tartaric Acid ◽  
Title Compound ◽  
State Structure ◽  
Hygroscopic Properties ◽  
Anions And Cations ◽  
Ionic Components ◽  
Tartrate Anion

Abstract L-Carnitine forms a salt-like 2:1 adduct with L-tartaric acid which crystallizes in the or-thorhombic space group P212121 with Z = 4 formula units in the unit cell. The lattice is composed of an L-tartrate dianion and two crystallographically independent L-carnitinium cations. The two cations show only very minor differences in their conformation. Anions and cations are arranged in separate stacks which are linked via hydrogen bonds. The tartrate anion and the carnitinium cations show standard geometries known from the structures of other salts of these ions, like the L-carnitine component of the R,L-carnitinium chloride or the dianion in alkali tartrates. The title compound has galenic advantages as an L-carnitine drug because of its non-hygroscopic properties. Aqueous solutions have been shown to contain solvated ionic components, i.e. L-tartrate and L-hydrogentartrate anions, L-tartaric acid (15:70:15) and carnitinium cations. The title compound can therefore be classified as a genuine L-carnitinium salt of L-tartaric acid.

Synthesis and characterization of two novel bimetallic macrocyclic complexes generated from 1,2,4-triazole-containing semi-rigid ligands andM(NO3)2units (M= Ni and Zn)

2016 ◽  
Vol 72 (4) ◽  
pp. 285-290 ◽  
Author(s):  
Xiang-Wen Wu ◽  
Shi Yin ◽  
Wan-Fu Wu ◽  
Jian-Ping Ma
Keyword(s):  
Hydrogen Bonds ◽  
Mixed Solvents ◽  
Three Dimensional ◽  
Building Blocks ◽  
Macrocyclic Complexes ◽  
Organic Ligands ◽  
Dimensional Structure ◽  
Two Dimensional ◽  
Coordination Environment ◽  
Dimensional Network

Bimetallic macrocyclic complexes have attracted the attention of chemists and various organic ligands have been used as molecular building blocks, but supramolecular complexes based on semi-rigid organic ligands containing 1,2,4-triazole have remained rare until recently. It is easier to obtain novel topologies by making use of asymmetric semi-rigid ligands in the self-assembly process than by making use of rigid ligands. A new semi-rigid ligand, 3-[(pyridin-4-ylmethyl)sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine (L), has been synthesized and used to generate two novel bimetallic macrocycle complexes, namely bis{μ-3-[(pyridin-4-ylmethyl)sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine}bis[(methanol-κO)(nitrato-κ2O,O′)nickel(II)] dinitrate, [Ni2(NO3)2(C17H14N6S)2(CH3OH)2](NO3)2, (I), and bis{μ-3-[(pyridin-4-ylmethyl)sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine}bis[(methanol-κO)(nitrato-κ2O,O′)zinc(II)] dinitrate, [Zn2(NO3)2(C17H14N6S)2(CH3OH)2](NO3)2, (II), by solution reactions with the inorganic saltsM(NO3)2(M= Ni and Zn, respectively) in mixed solvents. In (I), two NiIIcations with the same coordination environment are linked byLligands through Ni—N bonds to form a bimetallic ring. Compound (I) is extended into a two-dimensional network in the crystallographicacplaneviaN—H...O, O—H...N and O—H...O hydrogen bonds, and neighbouring two-dimensional planes are parallel and form a three-dimensional structureviaπ–π stacking. Compound (II) contains two bimetallic rings with the same coordination environment of the ZnIIcations. The ZnIIcations are bridged byLligands through Zn—N bonds to form the bimetallic rings. One type of bimetallic ring constructs a one-dimensional nanotubeviaO—H...O and N—H...O hydrogen bonds along the crystallographicadirection, and the other constructs zero-dimensional molecular cagesviaO—H...O and N—H...O hydrogen bonds. They are interlinked into a two-dimensional network in theacplane through extensive N—H...O hydrogen bonds, and a three-dimensional supramolecular architecture is formedviaπ–π interactions between the centroids of the benzene rings of the quinoline ring systems.

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