New monoclinic form of {O-EthylN-(4-nitrophenyl)thiocarbamato-κS}(tri-4-tolylphosphane-κP)gold(I): crystal structure and Hirshfeld surface analysis

The title phosphanegold(I) thiolate compound, [Au(C9H9N2O3S)(C21H21P)], is a second monoclinic polymorph (space groupP21/c) that complements a previously reportedCcpolymorph [Broker & Tiekink (2008).Acta Cryst. E64, m1582]. An SP donor set defines an approximately linear geometry about the gold atom in both forms. The key distinguishing feature between the present structure and the previously reported polymorph rests with the relative disposition of the thiolate ligand. In the title compound, the orientation is such to place the oxygen atom in close contact with the gold atom [Au...O = 2.915 (2) Å], in contrast to the aryl ring in the original polymorph. In the crystal, linear supramolecular chains along thea-axis direction mediated by C–H...π and nitro-O...π interactions are found. These pack with no directional interactions between them. The analysis of the Hirshfeld surfaces for both forms of [Au(C9H9N3O3S)(C21H21P)] indicates quite distinctive interaction profiles relating to the differences in intermolecular contacts found in their respective crystals.

Download Full-text

[(Z)-N-(3-Fluorophenyl)-O-methylthiocarbamato-κS](triphenylphosphane-κP)gold(I): crystal structure, Hirshfeld surface analysis and computational study

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989020009469 ◽

2020 ◽

Vol 76 (8) ◽

pp. 1284-1290

Author(s):

Chien Ing Yeo ◽

Sang Loon Tan ◽

Huey Chong Kwong ◽

Edward R. T. Tiekink

Keyword(s):

Computational Study ◽

Close Contact ◽

Three Dimensional ◽

Hirshfeld Surface ◽

Thiolate Ligand ◽

Intermolecular Contacts ◽

Stabilization Energies ◽

Type C ◽

Dimeric Aggregates ◽

Linear Geometry

The title phosphanegold(I) thiolate, C26H22AuFNOPS or [Au(C8H7FNOS)(C18H15P)], has the AuI centre coordinated by phosphane-P [2.2494 (8) Å] and thiolate-S [2.3007 (8) Å] atoms to define a close to linear geometry [P—Au—S = 176.10 (3)°]. The thiolate ligand is orientated so that the methoxy-O atom is directed towards the Au atom, forming an Au...O close contact of 2.986 (2) Å. In the crystal, a variety of intermolecular contacts are discerned with fluorobenzene-C—H...O(methoxy) and phenyl-C—H...F interactions leading to dimeric aggregates. These are assembled into a three-dimensional architecture by phenyl-C—H...S(thiolate) and phenyl-C—H...π(fluorobenzene, phenyl) interactions. Accordingly, the analysis of the calculated Hirshfeld surface shows 30.8% of all contacts are of the type C...H/H...C but this is less than the H...H contacts, at 44.9%. Other significant contributions to the surface come from H...F/F...H [8.1%], H...S/S...H [6.9%] and H...O/O...H [3.2%] contacts. Two major stabilization energies have contributions from the phenyl-C—H...π(fluorobenzene) and fluorobenzene-C—H...C(imine) interactions (−37.2 kcal mol−1), and from the fluorobenzene-C—H...F and phenyl-C—H...O interactions (−34.9 kcal mol−1), the latter leading to the dimeric aggregate.

Download Full-text

N-(6-Methoxypyridin-2-yl)-1-(pyridin-2-ylmethyl)-1H-pyrazole-3-carboxamide: crystal structure and Hirshfeld surface analysis

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989018011477 ◽

2018 ◽

Vol 74 (9) ◽

pp. 1254-1258

Author(s):

Vivek C. Ramani ◽

Rina D. Shah ◽

Mukesh M. Jotani ◽

Edward R. T. Tiekink

Keyword(s):

Crystal Structure ◽

Dihedral Angle ◽

Surface Analysis ◽

Intermolecular Interactions ◽

Title Compound ◽

Hirshfeld Surface ◽

Dihedral Angles ◽

Compound C ◽

Hirshfeld Surfaces ◽

Supramolecular Chains

The title compound, C16H15N5O2, adopts the shape of the letter L with the dihedral angle between the outer pyridyl rings being 78.37 (5)°; the dihedral angles between the central pyrazolyl ring (r.m.s. deviation = 0.0023 Å) and the methylene-bound pyridyl and methyoxypyridyl rings are 77.68 (5) and 7.84 (10)°, respectively. Intramolecular amide-N—H...N(pyrazolyl) and pyridyl-C—H...O(amide) interactions are evident and these preclude the participation of the amide-N—H and O atoms in intermolecular interactions. The most notable feature of the molecular packing is the formation of linear supramolecular chains aligned along the b-axis direction mediated by weak carbonyl-C=O...π(triazolyl) interactions. An analysis of the calculated Hirshfeld surfaces point to the importance of H...H (46.4%), C...H (22.4%), O...H (11.9%) and N...H (11.1%) contacts in the crystal.

Download Full-text

Bis[2-(4,5-diphenyl-1H-imidazol-2-yl)-4-nitrophenolato]copper(II) dihydrate: crystal structure and Hirshfeld surface analysis

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989019013720 ◽

2019 ◽

Vol 75 (11) ◽

pp. 1664-1671 ◽

Cited By ~ 1

Author(s):

Sailesh Chettri ◽

Dhiraj Brahman ◽

Biswajit Sinha ◽

Mukesh M. Jotani ◽

Edward R. T. Tiekink

Keyword(s):

Chelate Ring ◽

Three Dimensional ◽

Hirshfeld Surface ◽

Molecular Structures ◽

Coordination Geometry ◽

Bidentate Ligands ◽

Metal Centre ◽

Hirshfeld Surfaces ◽

Square Planar ◽

Intermolecular Contacts

The crystal and molecular structures of the title CuII complex, isolated as a dihydrate, [Cu(C21H14N3O3)2]·2H2O, reveals a highly distorted coordination geometry intermediate between square-planar and tetrahedral defined by an N2O2 donor set derived from two mono-anionic bidentate ligands. Furthermore, each six-membered chelate ring adopts an envelope conformation with the Cu atom being the flap. In the crystal, imidazolyl-amine-N—H...O(water), water-O—H...O(coordinated, nitro and water), phenyl-C—H...O(nitro) and π(imidazolyl)–π(nitrobenzene) [inter-centroid distances = 3.7452 (14) and 3.6647 (13) Å] contacts link the components into a supramolecular layer lying parallel to (101). The connections between layers forming a three-dimensional architecture are of the types nitrobenzene-C—H...O(nitro) and phenyl-C—H...π(phenyl). The distorted coordination geometry for the CuII atom is highlighted in an analysis of the Hirshfeld surface calculated for the metal centre alone. The significance of the intermolecular contacts is also revealed in a study of the calculated Hirshfeld surfaces; the dominant contacts in the crystal are H...H (41.0%), O...H/H...O (27.1%) and C...H/H...C (19.6%).

Download Full-text

2,2′-(Disulfanediyl)dibenzoic acid N,N-dimethylformamide monosolvate: crystal structure, Hirshfeld surface analysis and computational study

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989020008257 ◽

2020 ◽

Vol 76 (7) ◽

pp. 1150-1157

Author(s):

Sang Loon Tan ◽

Edward R. T. Tiekink

Keyword(s):

Benzene Ring ◽

Computational Study ◽

Three Dimensional ◽

Hirshfeld Surface ◽

Title 1 ◽

Torsion Angles ◽

Carboxylic Acid Groups ◽

Hirshfeld Surfaces ◽

Intermolecular Contacts ◽

Benzene Rings

The title 1:1 solvate, C14H10O4S2·C3H7NO, features a twisted molecule of 2,2′-dithiodibenzoic acid (DTBA), with the central C—S—S—C torsion angle being −88.57 (6)°, and a molecule of dimethylformamide (DMF). The carboxylic acid groups are, respectively, close to co-planar and twisted with respect to the benzene rings to which they are connected as seen in the CO2/C6 torsion angles of 1.03 (19) and 7.4 (2)°. Intramolecular, hypervalent S←O interactions are noted [S...O = 2.6140 (9) and 2.6827 (9) Å]. In the crystal, four-molecule aggregates are formed via DTBA-O—H...O(DMF) and DTBA-O—H...O(DTBA) hydrogen bonding, the latter via an eight-membered {...OHCO}2 homosynthon. These are linked into supramolecular layers parallel to (011) via benzene-C—H...O(DTBA) and DTBA-C=O...π(benzene) interactions, with the connections between these, giving rise to a three-dimensional architecture, being of the type benzene-C—H...π(benzene). An analysis of the calculated Hirshfeld surfaces indicates, in addition to the aforementioned intermolecular contacts, the presence of stabilizing interactions between a benzene ring and a quasi-π-system defined by O—H...O hydrogen bonds between a DTBA dimer, i.e. the eight-membered {...OCOH}2 ring system, and between a benzene ring and a quasi-π(OCOH...OCH) system arising from the DTBA-O—H...O(DMF) hydrogen bond. The inter-centroid separations are 3.65 and 3.49 Å, respectively.

Download Full-text

Rationalising molecular crystal structures using Hirshfeld surfaces

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314099653 ◽

2014 ◽

Vol 70 (a1) ◽

pp. C34-C34

Author(s):

Mark Spackman

Keyword(s):

Crystal Packing ◽

Close Contact ◽

Hirshfeld Surface ◽

Electrostatic Energy ◽

Quantum Mechanical ◽

Hirshfeld Surfaces ◽

Visual Approach ◽

Energy Of Interaction ◽

Molecular Wavefunctions ◽

Patterns Of Interaction

Hirshfeld surface analysis [1] has very quickly become a routine tool for rationalising and visualising intermolecular interactions in crystals. The serendipitous discovery of an intriguing and novel way to identify the space `belonging' to a molecule in a crystal has led to the development of a suite of computational tools that facilitate a deeper understanding of how molecules pack in crystals and why it makes sense that a particular crystal packing occurs [2]. We have previously used the Hirshfeld surface as a vehicle for mapping inherent shape and curvature, surface-mediated distances between closest atoms, as well as quantum mechanical properties such as molecular orbital density, electron density and electrostatic potential. Combining visualisation tools like these with quantum mechanical wavefunctions – and hence properties derived from these wavefunctions – offers a powerful and unique opportunity to investigate intuitive concepts like `electrostatic complementarity' [3]. With this in mind we have been investigating ways to subdivide Hirshfeld surfaces into discrete patches that can be identified with specific pairs of molecules in close contact in crystals, and testing different expressions to quantify our ideas on electrostatic complementarity. Coupled with this appealing visual approach we also compute the electrostatic energy of interaction between the respective molecular wavefunctions. This combination of approaches within an easy to use software package will be powerful enough to not only routinely explore and visualise the patterns of interaction exhibited by molecules in crystals, but also provide meaningful energies of interaction between relevant pairs of molecules. In this way we can readily attach some real significance – energetics – to what are more usually classified as close contacts of various kinds.

Download Full-text

4-[(1-Benzyl-1H-1,2,3-triazol-4-yl)methoxy]benzene-1,2-dicarbonitrile: crystal structure, Hirshfeld surface analysis and energy-minimization calculations

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989016004722 ◽

2016 ◽

Vol 72 (4) ◽

pp. 563-569

Author(s):

Norzianah Shamsudin ◽

Ai Ling Tan ◽

David J. Young ◽

Mukesh M. Jotani ◽

A. Otero-de-la-Roza ◽

...

Keyword(s):

Crystal Structure ◽

Surface Analysis ◽

Energy Minimization ◽

Phenyl Ring ◽

Hirshfeld Surface ◽

Hirshfeld Surface Analysis ◽

Dihedral Angles ◽

Compound C ◽

Intermolecular Contacts ◽

Supramolecular Chains

In the solid state, the title compound, C18H13N5O, adopts a conformation whereby the phenyl ring and methoxy–benzene-1,2-dicarbonitrile residue (r.m.s. deviation of the 12 non-H atoms = 0.041 Å) lie to opposite sides of the central triazolyl ring, forming dihedral angles of 79.30 (13) and 64.59 (10)°, respectively; the dihedral angle between the outer rings is 14.88 (9)°. This conformation is nearly 7 kcal mol−1higher in energy than the energy-minimized structure which has asyndisposition of the outer rings, enabling intramolecular π–π interactions. In the crystal, methylene-C—H...N(triazolyl) and carbonitrile-N...π(benzene) interactions lead to supramolecular chains along theaaxis. Supramolecular layers in theabplane arise as the chains are connected by benzene-C—H...N(carbonitrile) interactions; layers stack with no directional interactions between them. The specified intermolecular contacts along with other, weaker contributions to the supramolecular stabilization are analysed in a Hirshfeld surface analysis.

Download Full-text

Crystal structures and Hirshfeld surface analyses of (N-hexyl-N-methyldithiocarbamato-κ2 S,S′)triphenyltin(IV) and [N-methyl-N-(2-phenylethyl)dithiocarbamato-κ2 S,S′]triphenyltin(IV)

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989018005133 ◽

2018 ◽

Vol 74 (5) ◽

pp. 630-637 ◽

Cited By ~ 2

Author(s):

Rapidah Mohamad ◽

Normah Awang ◽

Nurul Farahana Kamaludin ◽

Mukesh M. Jotani ◽

Edward R. T. Tiekink

Keyword(s):

Crystal Structures ◽

Close Approach ◽

Molecular Packing ◽

Hirshfeld Surface ◽

Molecular Structures ◽

Crystal And Molecular Structures ◽

Hirshfeld Surfaces ◽

Dithiocarbamate Ligand ◽

Supramolecular Chains

The crystal and molecular structures of two triphenyltin dithiocarbamate compounds, viz. [Sn(C6H5)3(C8H16NS2)], (I), and [Sn(C6H5)3(C10H12NS2)], (II), are described. The dithiocarbamate ligand in each molecule coordinates in an asymmetric fashion resulting in heavily distorted tetrahedral C3S coordination geometries for the Sn atoms, with the distortions traced to the close approach of the non-coordinating thione-S atom. The molecular packing in both compounds features C—H...π(Sn-phenyl) interactions. In (I), the donors are Sn-phenyl-C—H groups leading to centrosymmetric aggregates, while in (II), the donors are both Sn-phenyl-C—H and methyl-C—H groups leading to supramolecular chains propagating along the b axis. The identified aggregates assemble into their respective crystals with no directional interactions between them. An analysis of the Hirshfeld surfaces show distinctive patterns, but an overwhelming predominance (>99% in each case) of H...H, C...H/H...C and S...H/H...S contacts on the respective Hirshfeld surface.

Download Full-text

Crystal structure and Hirshfeld surface analysis of a zinc xanthate complex containing the 2,2′-bipyridine ligand

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989019014968 ◽

2019 ◽

Vol 75 (12) ◽

pp. 1857-1860

Author(s):

Adnan M. Qadir ◽

Sevgi Kansiz ◽

Georgina M. Rosair ◽

Necmi Dege ◽

Inna S. Safyanova

Keyword(s):

Hydrogen Bonds ◽

Surface Analysis ◽

Rotation Axis ◽

Hirshfeld Surface ◽

Coordination Geometry ◽

Tetrahedral Coordination ◽

Intermolecular Contacts ◽

Bipyridine Ligand ◽

Supramolecular Chains ◽

Distorted Tetrahedral Coordination

In the title compound, (2,2′-bipyridine-κ2 N,N′)bis(2-methoxyethyl xanthato-κS)zinc(II), [Zn(C4H7O2S2)2(C10H8N2)], the ZnII ion is coordinated to two N atoms of the 2,2′-bipyridine ligand and two S atoms from two 2-methoxyethyl xanthate ligands. The ZnII ion lies on a crystallographic twofold rotation axis and has distorted tetrahedral coordination geometry. In the crystal, molecules are linked by weak C—H...O hydrogen bonds, forming supramolecular chains propagating along the a-axis direction. Weak intramolecular C—H...S hydrogen bonds are also observed. The intermolecular contacts in the crystal were further analysed using Hirshfield surface analysis, which indicates that the most significant contacts are H...H (36.3%), followed by S...H/H...S (24.7%), C...H/H...C (15.1%), O...H/H...O (14.4%), N...H/H...N (4.1%) and C...C (2.9%).

Download Full-text

Synthesis, molecular structure and Hirshfeld surface analysis of (4-methoxyphenyl)[2-(methylsulfanyl)thiophen-3-yl]methanone

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989018016043 ◽

2018 ◽

Vol 74 (12) ◽

pp. 1800-1803

Author(s):

S. Nagaraju ◽

M. A. Sridhar ◽

C.S. Pradeepa Kumara ◽

M. P. Sadashiva ◽

B. N. Lakshminarayana ◽

...

Keyword(s):

Molecular Structure ◽

Dihedral Angle ◽

Surface Analysis ◽

Title Compound ◽

Hirshfeld Surface ◽

Triclinic Space Group ◽

Compound C ◽

Hirshfeld Surfaces ◽

Phenyl Rings ◽

Layer Stacking

The title compound, C13H12O2S2, crystallizes in the triclinic space group P\overline{1}. The molecular structure is substantially twisted, with a dihedral angle of 43.70 (2)° between the 2-(methylsulfanyl)thiophene and 4-methoxyphenyl rings. In the crystal, molecules are linked through C—H...O interactions and form a bifurcated layer stacking along the b-axis direction and enclosing R 2 2(10) ring motifs. The phenyl rings are involved in π–π interactions with a centroid–centroid separation of 3.760 (2) Å. The Hirshfeld surfaces were studied and the contributions of the various intermolecular interactions were quantified.

Download Full-text