scholarly journals Two-dimensional coordination polymeric structures in caesium complexes with ring-substituted phenoxyacetic acids

2014 ◽  
Vol 70 (6) ◽  
pp. 606-612 ◽  
Author(s):  
Graham Smith ◽  
Daniel E. Lynch
Keyword(s):  
Acetic Acid ◽  
Water Molecule ◽  
Complex Iii ◽  
Phenoxyacetic Acid ◽  
Two Dimensional ◽  
Coordination Polyhedra ◽  
Bidentate Chelate ◽  
Phenoxyacetic Acids ◽  
Ligand Species ◽  
Polymeric Structures

The two-dimensional polymeric structures of the caesium complexes with the phenoxyacetic acid analogues (4-fluorophenoxy)acetic acid, (3-chloro-2-methylphenoxy)acetic acid and the herbicidally active (2,4-dichlorophenoxy)acetic acid (2,4-D), namely poly[[μ5-(4-fluorophenoxy)acetato][μ4-(4-fluorophenoxy)acetato]dicaesium], [Cs2(C8H6FO3)2]n, (I), poly[aqua[μ5-(3-chloro-2-methylphenoxy)acetato]caesium], [Cs(C9H8ClO3)(H2O)]n, (II), and poly[[μ7-(2,4-dichlorophenoxy)acetato][(2,4-dichlorphenoxy)acetic acid]caesium], [Cs(C8H5Cl2O3)(C8H6Cl2O3)]n, (III), are described. In (I), the Cs+cations of the two individual irregular coordination polyhedra in the asymmetric unit (one CsO7and the other CsO8) are linked by bridging carboxylate O-atom donors from the two ligand molecules, both of which are involved in bidentate chelateOcarboxy,Ophenoxyinteractions, while only one has a bidentate carboxylateO,O′-chelate interaction. Polymeric extension is achieved through a number of carboxylate O-atom bridges, with a minimum Cs...Cs separation of 4.3231 (9) Å, giving layers which lie parallel to (001). In hydrated complex (II), the irregular nine-coordination about the Cs+cation comprises a single monodentate water molecule, a bidentateOcarboxy,Ophenoxychelate interaction and six bridging carboxylate O-atom bonding interactions, giving a Cs...Cs separation of 4.2473 (3) Å. The water molecule forms intralayer hydrogen bonds within the two-dimensional layers, which lie parallel to (100). In complex (III), the irregular centrosymmetric CsO6Cl2coordination environment comprises two O-atom donors and two ring-substituted Cl-atom donors from two hydrogen bis[(2,4-dichlorophenoxy)acetate] ligand species in a bidentate chelate mode, and four O-atom donors from bridging carboxyl groups. The duplex ligand species lie across crystallographic inversion centres, linked through a short O—H...O hydrogen bond involving the single acid H atom. Structure extension gives layers which lie parallel to (001). The present set of structures of Cs salts of phenoxyacetic acids show previously demonstrated trends among the alkali metal salts of simple benzoic acids with no stereochemically favourable interactive substituent groups for formation of two-dimensional coordination polymers.

Low-dimensional coordination polymeric structures in alkali metal complex salts of the herbicide (2,4-dichlorophenoxy)acetic acid (2,4-D)

2015 ◽  
Vol 71 (2) ◽  
pp. 140-145 ◽  
Author(s):  
Graham Smith
Keyword(s):  
Acetic Acid ◽  
Hydrogen Bonds ◽  
Water Molecule ◽  
Rotation Axis ◽  
Layer Structure ◽  
Complex Iii ◽  
Polymeric Chain ◽  
Two Dimensional ◽  
Dichlorophenoxy Acetic Acid ◽  
Polymeric Structures

The Li, Rb and Cs complexes with the herbicide (2,4-dichlorophenoxy)acetic acid (2,4-D), namely poly[[aqua[μ3-(2,4-dichlorophenoxy)acetato-κ3O1:O1:O1′]lithium(I)] dihydrate], {[Li(C8H5Cl2O3)(H2O)]·2H2O}n, (I), poly[μ-aqua-bis[μ3-(2,4-dichlorophenoxy)acetato-κ4O1:O1′:O1′,Cl2]dirubidium(I)], [Rb2(C8H5Cl2O3)2(H2O)]n, (II), and poly[μ-aqua-bis[μ3-(2,4-dichlorophenoxy)acetato-κ5O1:O1′:O1′,O2,Cl2]dicaesium(I)], [Cs2(C8H5Cl2O3)2(H2O)]n, (III), respectively, have been determined and their two-dimensional polymeric structures are described. In (I), the slightly distorted tetrahedral LiO4coordination involves three carboxylate O-atom donors, of which two are bridging, and a monodentate aqua ligand, together with two water molecules of solvation. Conjoined six-membered ring systems generate a one-dimensional coordination polymeric chain which extends alongband interspecies water O—H...O hydrogen-bonding interactions give the overall two-dimensional layers which lie parallel to (001). In hemihydrate complex (II), the irregular octahedral RbO5Cl coordination about Rb+comprises a single bridging water molecule which lies on a twofold rotation axis, a bidentateOcarboxy,Cl-chelate interaction and three bridging carboxylate O-atom bonding interactions from the 2,4-D ligand. A two-dimensional coordination polymeric layer structure lying parallel to (100) is formed through a number of conjoined cyclic bridges, including a centrosymmetric four-membered Rb2O2ring system with an Rb...Rb separation of 4.3312 (5) Å. The coordinated water molecule forms intralayer aqua–carboxylate O—H...O hydrogen bonds. Complex (III) comprises two crystallographically independent (Z′ = 2) irregular CsO6Cl coordination centres, each comprising two O-atom donors (carboxylate and phenoxy) and a ring-substituted Cl-atom donor from the 2,4-D ligand species in a tridentate chelate mode, two O-atom donors from bridging carboxylate groups and one from a bridging water molecule. However, the two 2,4-D ligands are conformationally very dissimilar, with one phenoxyacetate side chain being synclinal and the other being antiperiplanar. The minimum Cs...Cs separation is 4.4463 (5) Å. Structure extension gives coordination polymeric layers which lie parallel to (001) and are stabilized by intralayer water–carboxylate O—H...O hydrogen bonds.

scholarly journals Two-dimensional hydrogen-bonded polymers in the crystal structures of the ammonium salts of phenoxyacetic acid, (4-fluorophenoxy)acetic acid and (4-chloro-2-methylphenoxy)acetic acid

2014 ◽  
Vol 70 (12) ◽  
pp. 528-532 ◽  
Author(s):  
Graham Smith
Keyword(s):  
Hydrogen Bonding ◽  
Acetic Acid ◽  
Water Molecule ◽  
Rotation Axis ◽  
Ammonium Salts ◽  
Phenoxyacetic Acid ◽  
Two Dimensional ◽  
The Core ◽  
Ammonium N ◽  
Hydrogen Bonded

The structures of the ammonium salts of phenoxyacetic acid, NH4+·C8H6O3−, (I), (4-fluorophenoxy)acetic acid, NH4+·C8H5FO3−, (II), and the herbicidally active (4-chloro-2-methylphenoxy)acetic acid (MCPA), NH4+·C9H8ClO3−·0.5H2O, (III) have been determined. All have two-dimensional layered structures based on inter-species ammonium N—H...O hydrogen-bonding associations, which give core substructures consisting primarily of conjoined cyclic motifs. The crystals of (I) and (II) are isomorphous with the core comprisingR12(5),R12(4) and centrosymmetricR42(8) ring motifs, giving two-dimensional layers lying parallel to (100). In (III), the water molecule of solvation lies on a crystallographic twofold rotation axis and bridges two carboxyl O atoms in anR44(12) hydrogen-bonded motif, creating twoR43(10) rings, which together with a conjoined centrosymmetricR42(8) ring incorporating both ammonium cations, generate two-dimensional layers lying parallel to (100). No π–π ring associations are present in any of the structures.

scholarly journals Crystal structures of the potassium and rubidium salts of (3,5-dichlorophenoxy)acetic acid: two isotypic coordination polymers

2015 ◽  
Vol 71 (10) ◽  
pp. 1177-1180 ◽  
Author(s):  
Graham Smith
Keyword(s):  
Hydrogen Bond ◽  
Acetic Acid ◽  
Water Molecule ◽  
Coordination Polymers ◽  
Rotation Axis ◽  
Side Chain ◽  
Two Dimensional ◽  
Alkali Cations ◽  
Dichlorophenoxy Acetic Acid ◽  
Polymeric Structures

The two-dimensional coordination polymeric structures of the hydrated potassium and rubidium salts of (3,5-dichlorophenoxy)acetic acid (3,5-D), namely, poly[μ-aqua-bis[μ3-2-(3,5-dichlorophenoxy)acetato]dipotassium], [K2(C8H5Cl2O3)2(H2O)]n, and poly[μ-aqua-bis[μ3-2-(3,5-dichlorophenoxy)acetato]dirubidium], [Rb2(C8H5Cl2O3)2(H2O)]n, respectively, have been determined and are described. The two compounds are isotypic and the polymeric structure is based on centrosymmetric dinuclear bridged complex units. The irregular six-coordination about the alkali cations comprises a bridging water molecule lying on a twofold rotation axis, the phenoxy O-atom donor and a triple bridging carboxylate O atom of the oxoacetate side chain of the 3,5-D ligand, and the second carboxyate O-atom donor also bridging. The K—O and Rb—O bond-length ranges are 2.7238 (15)–2.9459 (14) and 2.832 (2)–3.050 (2) Å, respectively, and the K...K and Rb...Rb separations in the dinuclear units are 4.0214 (7) and 4.1289 (6) Å, respectively. Within the layers which lie parallel to (100), the coordinating water molecule forms an O—H...O hydrogen bond to the single bridging carboxylate O atom.

Two-dimensional coordination polymeric structures in the sodium, potassium and rubidium complex salts with (4-fluorophenoxy)acetic acid

2017 ◽  
Vol 73 (11) ◽  
pp. 979-983 ◽  
Author(s):  
Graham Smith
Keyword(s):  
Acetic Acid ◽  
The Other ◽  
Water Molecules ◽  
Two Dimensional ◽  
Primary Metal ◽  
Sodium Potassium ◽  
Distorted Octahedral ◽  
Bidentate Chelate ◽  
Complex Salts ◽  
Polymeric Structures

The structures of the sodium, potassium and rubidium complex salts of (4-fluorophenoxy)acetic acid (PFPA), namely poly[μ-aqua-aqua-μ-[2-(4-fluorophenoxy)acetato]-κ3 O 1,O 2:O 1′-sodium], [Na(C8H6FO3)(H2O)2] n , (I), and isotypic poly[μ5-[2-(4-fluorophenoxy)acetato]-κ5 O 1,O 2:O 1,O 1′:O 1′:O 1′:O 1′-potassium], [K(C8H6FO3)] n , (II), and poly[μ5-[2-(4-fluorophenoxy)acetato]-κ5 O 1,O 2:O 1,O 1′:O 1′:O 1′:O 1′-rubidium], [Rb(C8H6FO3)] n , (III), have been determined and their coordination polymeric structures described. In the structure of (I), the very distorted octahedral NaO6 coordination polyhedron comprises two bidentate chelating O-atom donors (carboxylate and phenoxy) of the PFPA ligand and three O-atom donors from water molecules, one monodentate and the other μ2-bridging between inversion-related Na centres in a cyclic manner. A bridging carboxylate donor generates two-dimensional polymer layers lying parallel to (001), in which intralayer water O—H...O hydrogen-bonding associations are also present. Structures (II) and (III) are isotypic, each having an irregular MO7 stereochemistry, with the primary metal–ligand bidentate chelate similar to that in (I) and extended into a two-dimensional polymeric layered structure, lying parallel to (100), through five additional bridging carboxylate O atoms. Two of these bonds are from an O,O′-bidentate chelate interaction and the other three are from μ3-O-atom bridges, generating cyclic links with short M...M separations [3.9064 (17) Å for (II) and 4.1001 (8) for (III)], the shortest being a centrosymmetric four-membered cyclic link. In the crystals of (I)–(III), intralayer C—H...F interactions are present, but no π–π ring interactions are found.

scholarly journals Coordination polymeric structures in the sodium salt of 4-chloro-3-nitrobenzoic acid and the sodium and potassium salts of 4-nitroanthranilic acid

2013 ◽  
Vol 69 (12) ◽  
pp. 1472-1477 ◽  
Author(s):  
Graham Smith
Keyword(s):  
Hydrogen Bonding ◽  
Water Molecule ◽  
Coordination Polyhedron ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Two Dimensional ◽  
Π Interactions ◽  
Nitrobenzoic Acid ◽  
Distorted Octahedral ◽  
Polymeric Structures

The structures of the hydrated sodium salts of 4-chloro-3-nitrobenzoic acid {poly[aqua(μ4-4-chloro-3-nitrobenzoato)sodium(I)], [Na(C7H3ClNO4)(H2O)]n, (I)} and 2-amino-4-nitrobenzoic acid {poly[μ-aqua-aqua(μ3-2-amino-4-nitrobenzoato)sodium(I)], [Na(C7H5N2O4)(H2O)2]n, (II)}, and the hydrated potassium salt of 2-amino-4-nitrobenzoic acid {poly[μ-aqua-aqua(μ5-2-amino-4-nitrobenzoato)potassium(I)], [K(C7H5N2O4)(H2O)]n, (III)} have been determined and their complex polymeric structures described. All three structures are stabilized by intra- and intermolecular hydrogen bonding and strong π–π ring interactions. In the structure of (I), the distorted trigonal bipyrimidal NaO5coordination polyhedron comprises a monodentate water molecule and four bridging carboxylate O-atom donors, generating a two-dimensional polymeric structure lying parallel to (001). Intra-layer hydrogen-bonding associations and strong inter-ring π–π interactions are present. Structure (II) has a distorted octahedral NaO6stereochemistry, with four bridging O-atom donors, two from a single carboxylate group and two from a single nitro group and three from the two water molecules, one of which is bridging. Na centres are linked through centrosymmetric four-membered duplex water bridges and through 18-membered duplex head-to-tail ligand bridges. Similar centrosymmetric bridges are found in the structure of (III), and in both (II) and (III) strong inter-ring π–π interactions are found. A two-dimensional layered structure lying parallel to (010) is generated in (II), whereas in (III) the structure is three-dimensional. With (III), the irregular KO7coordination polyhedron comprises a doubly bridging water molecule, a single bidentate bridging carboxylate O-atom donor and three bridging O-atom donors from the two nitro groups. A three-dimensional structure is generated. These coordination polymer structures are among the few examples of metal complexes of any type with either 4-chloro-3-nitrobenzoic acid or 4-nitroanthranilic acid.

scholarly journals Poly[μ5-{hydrogen bis[(E)-cinnamato]}-caesium]

2014 ◽  
Vol 70 (2) ◽  
pp. m43-m44 ◽  
Author(s):  
Graham Smith
Keyword(s):  
Hydrogen Bond ◽  
Coordination Polymer ◽  
Cinnamic Acid ◽  
Component Ratio ◽  
Two Dimensional ◽  
Polymeric Complex ◽  
Coordination Polyhedra ◽  
Rotation Axes ◽  
Structure Extension ◽  
Ligand Species

In the structure of the title polymeric complex, [Cs(C9H7O2)(C9H8O2)]n, a caesium salt oftrans-cinnamic acid, the Cs+ions of the two individual irregular CsO8coordination polyhedra lie on twofold rotation axes and are linked by four bridging carboxyl O-atom donors from two cinnamate ligand species. These two ligand components are interlinked through a delocalized H atom within a short O...H...O hydrogen bond. Structure extension gives a two-dimensional coordination polymer which lies parallel to (001). The structure was determined from a crystal twinned by non-merohedry, with a twin component ratio of approximately 1:1.

scholarly journals catena-Poly[[diaqua[μ2-4-(4-carboxyphenoxy)benzoato](μ2-4,4′-oxydibenzoato)praseodymium(III)] monohydrate]

2013 ◽  
Vol 69 (11) ◽  
pp. m586-m587
Author(s):  
Ping Li ◽  
Duo-Meng Su ◽  
Chang-Ge Zheng
Keyword(s):  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Water Molecule ◽  
Network Structure ◽  
Three Dimensional ◽  
Water Molecules ◽  
Two Dimensional ◽  
Dimensional Network ◽  
Bidentate Chelate ◽  
Single Water Molecule

In the title compound, {[Pr(C14H8O5)(C14H9O5)(H2O)2]·H2O}n, the PrIIIcation is eight-coordinated by six carboxyl O atoms from both a monoanionic 4-(4-carboxyphenoxy)benzoate and a dianionic 4,4′-oxydibenzoate ligand (four bridging with two from a bidentate chelate interaction), and two O-atom donors from water molecules. A single water molecule of solvation is also present. The complex units are linked through carboxylO:O′ bridges giving a two-dimensional sheet polymer lying parallel to (001). An overall three-dimensional network structure is generated through intermolecular carboxylic acid and water O—H...O hydrogen bonds and weak C—H...O interactions.

scholarly journals Poly[μ-aqua-μ5-[2-(2,3,6-trichlorophenyl)acetato]-caesium]

2013 ◽  
Vol 69 (12) ◽  
pp. m628-m628 ◽  
Author(s):  
Graham Smith
Keyword(s):  
Hydrogen Bonding ◽  
Acetic Acid ◽  
Water Molecule ◽  
Title Complex ◽  
Two Dimensional ◽  
Hydrogen Bonding Interactions ◽  
Cl Atom

In the structure of the title complex, [Cs(C8H4Cl3O2)(H2O)]n, the caesium salt of the commercial herbicide fenac [(2,3,6-trichlorophenyl)acetic acid], the irregular eight-coordination about Cs+comprises a bidentateO:Cl-chelate interaction involving a carboxylate-O atom and anortho-related ring-substituted Cl atom, which is also bridging, a triple-bridging carboxylate-O atom and a bridging water molecule. A two-dimensional polymer is generated, lying parallel to (100), within which there are water–carboxylate O—H...O hydrogen-bonding interactions.

Metal-Betaine Interactions.XIV. Silver(I) 3-Carboxylato-1-pyridinioacetate Monohydrate, [Ag{C5H4(COO)NCH2.COO}]n.nH2O

1991 ◽  
Vol 44 (12) ◽  
pp. 1783 ◽  
Author(s):  
XM Chen ◽  
TCW Mak
Keyword(s):  
Oxygen Atom ◽  
Water Molecule ◽  
Lattice Water Molecule ◽  
Membered Ring ◽  
Zigzag Chain ◽  
Two Dimensional ◽  
Metal Centre ◽  
Lattice Water ◽  
Dimensional Network ◽  
Tetrahedral Environment

The complex silver(I) 3-carboxylato-1-pyridinioacetate monohydrate, [Ag{C5H4(COO)NCH2.COO}]n.nH2O, crystallizes in space group P21/c (No. 14), with Z-4, a 12.233(6), b 5.049(1), c 14.418(7)Ǻ, and β 94.96(4)°; the structure was refined to RF -0.057 for 1721 observed [I ≥ 3σ(I)] Mo Kα data. The silver(I) atom is coordinated by four carboxylato oxygen atoms in a distorted tetrahedral environment [Ag-O 2.284(5)-2.570(5)Ǻ]. The tridentate acetato group bridges the Ag1 atoms into a zigzag chain featuring an uncommon [Ag2( carboxylato -O,O′)(carboxylato-μ-1,1-O)] six- membered ring, and the coordination sphere about each metal centre is completed by the unidentate aromatic carboxylato group, resulting in a two-dimensional network in the solid. The lattice water molecule forms hydrogen bonds with the uncoordinated oxygen atom of the aromatic carboxylato group [2.755(9)Ǻ] and the coordinated oxygen atom of the acetato group [2.936(9)Ǻ].

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