Research Abstract

This document briey describes a few aspects of my research during my PhD including crystal engineering studies of salts of Nickel(II) bisdithiooxalate and bisdithiosquarate and their organic analogues: the chloranilate and anilate dianions. Also described is work involving formation of metal oxalate coordination polymers with pendant pyridine ligands by solid state methods.

Salts and cocrystals of 1,2-dicarbonyls

2.2. RESULTS AND DISCUSSION

Figure 2.17: Methyl-methyl interactions in 2 (labelled here as b2 ) and 3 (c2 ); in the analagous PdCl4 salt (TANDIW) the separation is 3.31 A.

The crystal engineer wishes to have control over the structure of crystal to the same degree that an organic chemist can perform a covalent synthesis of his target molecule.[1] Use of the Desiraju-Wuest molecular tectonics paradigm[7, 13] has brought us closer to realising this aim by studying intermolecular interactions, SALTS such as hydrogen-bonds, that can form CHAPTER robust synthons;2. andNICKEL(II) the molecular units, or tectons, that give rise to these synthons. Hydrogen-bonds often form robust and
CHAPTER 2. NICKEL(II) SALTS

2 Figure 2.18: Symmetric R1 (4) motif formed in crystalline [4-Hpic]2 [PdCl4 ]

Figure 1: Similar hydrogen packing and hydrogen bonding can occur between pyridinium cations and both (left ) [MCl4 ]2 [4] and (right ) [Ni(dts)2 ]2 dianions.

controllable interactions between tectons and are thus a prime tool for the crystal Figure 2.20: Undulating (top) engineer. Crystal enginering studies using planar transition metal tetrachlorides have shown that these form robust, three-centre hydrogen bonds with pyridinium cations, generating an R2 1 (4) motif (g. 1, left).[5, 8] Further studies sought to replace the metal tetrachloride tecton while retaining a similar three-centre hydrogen 2 unit contains half a [Ni(dts) dianion an 2] bonded synthon. This was achieved by replacement with 1,2-dicarbonyl based complexes leading to work involving the bis-ligated complexes of dithiooxneutralnickel(II) supermolecule and its associated hy alate (dto) (g. 2).[3, 12] During my PhD I studied pyridinium salts of nickel(II) proton does further not hydrogen-bond this study to examine the ef- within the bisdithiooxalate ([Ni(dto)2 ]2 ) and extended fect on hydrogen bonding in the crystallone structures adjusting the dimensions pairof of the carbonyl, butof the positions 2 this tecton and using nickel(II) bisdithiosquarate dianions ([Ni(dts)2 ] ). These 2 seen in 2 symmetry and as as such an struct dianionic tectons feature the same functionality and [Ni(dto) di2 ] analogous anions but are both larger and have a slightly greater bite angle between the though the neutral supermolecules are not 1,2-dicarbonyl hydrogen-bond acceptors (g. 2). As expected the same hydrogen bonded motif (R2 nickelsupermolecule complexes of dto and dts but neutral is S-shaped and pac 1 (5)) is found in both 2 the packing is dierent, with sheets formed in the case of [Ni(dts)2 ] salts and
2 Figure 2.19: Asymmetric R1 (4) motif formed in crystalline [4-Hpic]2 [PtCl4 ]

72

arrangement as seen in 2 and shown in gure 1 and the cell parameters means that the pow some degree of isostructurality. Short conta CH protons (see tab. 2.4) although hydrog be weak 29,30 and their existence has had tim A notable feature of 3 when considered as

X=O

O
substitute sulfur

-O

O-

-S

S-

[ox]2O O

[dto]2extend C framework
O

2-

S M S

S
add divalent TM

substitute sulfur

-S

S-

-O

O-

[dts]2O O

[sq]2-

Figure 2: Tecton derivation while preserving the 1,2-dicarbonyl acceptor- from oxalate to dithiooxalate to dithiosquarate.

ribbons in salts of [Ni(dto)2 ]2 . Interestingly though, in some cases crystal structures of [Ni(dts)2 ]2 dianions with isomeric and isosteric picolinium cations lead to isostructural crystal stuctures (g. 3). These studies were extended to use other tectons featuring the 1,2-dicarbonyl moiety in the form of chloranilate dianions and 2,5-dihydroxybenzoquinone (g. 4). In these structures the R2 1 (5) hydrogenbonded synthon is preserved in salts but the small separation in the pKa values of the pyridine derivatives and the oxidobenzoquinones means that cocrystals, rather than salts can form leading the formation of a D(2)( N H-O-C) synthon.

Solid state preparation of metal oxalates

Oxalate is a bidentate ligand with strong chelating properties. In combination with metal ions it chelates in a bis-bidentate fashion forming an oxalate bridge. In complexes of Cu, Co and Ni oxalate can bind in an cis- or trans fashion leading to zig-zagging or linear chains. Pyridine ligands may coordinate to the vacant site, or displace solvent ligands. These ligands may either be monodentate ligand such as pyridine or bidentate ligand such as 4,4 -bipyridine, in the case of bidentate ligands this leads to the formation of two-dimensional nets.[11, 10, 14] Recently, solid state reactions have become much more prevalent in research and have been used to form a variety of hydrogen bonded crystals and coordination polymers.[9, 2] I investigated the used of these solid state methods in the formation of these co-ordination polymers from the linear metal oxalate precursors. Many of these

CHAPTER 2. NICKEL(II) SALTS

O H3C N+ H O H H S Ni S O O H N+ CH3 Ni S S Ni H3C

2.2. RESULTS AND DISCUSSION

O H N+ H H S O H CH3 S O N+ O S S Ni

Figure 3: 4-picolinium and 3-picolinium and isosteric and isomeric. Despite the dierFigure 2.23: Hydrogen-bonding interactions and short C-H O contacts in 2 and23 . ent location of the pyridinium proton when crystallised with [Ni(dts)2 ] dianions the resulting crystal structures are isostructural.
83 to the plane of the dianion but in 3 the surrounding cations are organised in a planar arrangement and there is no longer and structural similarity with the pyridinium analogue. Many O of these structures exhibit contacts between the meta-CH proton and a dicarbonyl oxygen or a sulfur. In the case of 3a, while there are still six cations arranged in the same plane around the 2X OO O dianion, the anking cations are tilted relative to the dianion, as in the published structure of S S 1a. Structures 1a, 2a and 3a all show a preference for the cations to be tilted out of the plane Organic analogue M of the dianion and therefore form ribbons that run at angles to one another. The [Ni(dts)2 ] 2 S S -O O X cations, dianion, II, is O 10.6 A in length, this being roughly double the maximum dimension of the which are all approximately 4.3 A(excluding hydrogen atoms), allowing them to lie alongside the O dianion in the same plane.
2 , a good tecton; right, its organic analogue, a 2,5Figure Left,2a[Ni(dto) The 4: structures and 3a are unlike the case of 2 and 3, where despite the dierence 2 ]dissimilar, in the hydrogen-bond donor position a similar supermolecular arrangement is formed. 2a forms dioxidobenzoquinone.

from single crystal X-ray analyses[6] allowing a library of powder diraction patterns to be compiled for comparison. Many of these literature compounds were grown using [2 - H-pic] 2 [Ni(dts)2 ] (4) 4 crystallised in the space group P 21 /n. The asymmetric unit con2 tains one [Ni(dts) dianion andit two crystallographically 2-H-picolinium cations. hydrothermal techniques but was found that independent simply grinding these compounds 2] In contrast with structures 1 and 2 , which form centrosymmetric supermolecules, the neutral together by hand in a pestle and mortar can yield these coordination polymers; supermolecule of 4 contains two dierent hydrogen-bonding motifs. Of these two, one is conalthough reaction occurs much more rapidly in a ball mill. Reactions were found sistent with the NH [dts] synthon (similar to C) as seen in 1 and 2, and as in these cases, to even allow conversion of the naked trans-ligated polymer to the cis-ligated the large O O separation means that only a single hydrogen-bond forms to one carbonyl. The form second of the coordination polymer. However, this found to be athe case only 2-picolinium cation hydrogen-bonds to an exotopic lonewas pair of one carbonyl, similar mode to that seen in 3. 4 may be seen as to a hybrid between these two hydrogen-bonding modes: for monodentate ligands, attempts form two-dimensional frameworks with 4,4 bipyridine did not lead to formation of the products. Analysis was carried out 75 using powder X-ray diraction and IR analysis.

the linear hydrogen-bonded supermolecule (with bifurcated endotopic hydrogen-bond) and these units are linked by van der Waals interactions between the para-CH groups. 3a also forms the bifurcated hydrogen-bond as in synthon C and as a consequence the 3-methyl group is positioned so that it are points out of theknown side of the supermolecule forming short contacts with determined the carbonyl compounds already and their structures have been oxygen of an adjacent [Ni(dto)2 ] 2 dianion.

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