Square tetravalent chalcogen bonds in dimeric aggregates: a joint crystallographic survey and theoretical study

Chalcogen bonds (ChBs) involving hypervalent chalcogen atoms have been the target of several recent crystallographic and theoretical studies. In this work, we firstly gathered a large number of crystal structures...

Crystal structure of 1,2-bis(4-fluorophenyl)-1-hydroxy-2,3,8-trimethoxyacenaphthene: formation of a five-membered intramolecular O—H...O hydrogen-bonded ring

The structure of the title compound, C27H22F2O4, at 193 K has triclinic (P\overline{1}) symmetry. The hydroxy and methoxy groups at the 1,2-positions of the acenaphthene core display a cis configuration. Both substituents are involved in the formation of a five-membered intramolecular O—H...O hydrogen-bonded ring. The 4-fluorophenyl rings make dihedral angles of 87.02 (7) and 51.86 (8)° with the naphthalene ring system. In the crystal, a pair of non-classical C—H...O hydrogen bonds forms centrosymmetric dimeric structures. The dimeric aggregates are linked in the ac plane through non-classical C—H...F hydrogen bonds and C—H...π interactions.

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

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.

(N,N-Diisopropyldithiocarbamato)triphenyltin(IV): crystal structure, Hirshfeld surface analysis and computational study

The crystal and molecular structures of the title triorganotin dithiocarbamate, [Sn(C6H5)3(C7H14NS2)], are described. The molecular geometry about the metal atom is highly distorted being based on a C3S tetrahedron as the dithiocarbamate ligand is asymmetrically chelating to the tin centre. The close approach of the second thione-S atom [Sn...S = 2.9264 (4) Å] is largely responsible for the distortion. The molecular packing is almost devoid of directional interactions with only weak phenyl-C—H...C(phenyl) interactions, leading to centrosymmetric dimeric aggregates, being noted. An analysis of the calculated Hirshfeld surface points to the significance of H...H contacts, which contribute 66.6% of all contacts to the surface, with C...H/H...C [26.8%] and S...H/H...H [6.6%] contacts making up the balance.

A new monoclinic polymorph ofN-(3-methylphenyl)ethoxycarbothioamide: crystal structure and Hirshfeld surface analysis

The title compound, C10H13NOS, is a second monoclinic polymorph (space groupP21/c,Z′ = 2) of the previously reportedC2/c(Z= 1) polymorph [Tadbuppa & Tiekink (2005).Z. Kristallogr. New Cryst. Struct.220, 395–396]. Two independent molecules comprise the asymmetric unit of the new polymorph and each of these exists as a thioamide–thione tautomer. In each molecule, the central CNOS chromophore is strictly planar [r.m.s. deviations = 0.0003 and 0.0015 Å] and forms dihedral angles of 6.17 (5) and 20.78 (5)° with the N-bound 3-tolyl rings, thereby representing the major difference between the molecules. The thione-S and thioamide-N—H atoms aresynin each molecule and this facilitates the formation of an eight-membered thioamide {...SCNH}2synthon between them; the dimeric aggregates are consolidated by pairwise 3-tolyl-C—H...S interactions. In the extended structure, supramolecular layers parallel to (102) are formedviaa combination of 3-tolyl-C—H...π(3-tolyl) and weak π–π interactions [inter-centroid distance between 3-tolyl rings = 3.8535 (12) Å]. An analysis of the Hirshfeld surfaces calculated for both polymorphs reveals the near equivalence of one of the independent molecules of theP21/cform to that in theC2/cform.

1-{(E)-[(2E)-3-(4-Methoxyphenyl)-1-phenylprop-2-en-1-ylidene]amino}-3-phenylurea: crystal structure and Hirshfeld surface analysis

The title compound, C23H21N3O2, is constructed about an almost planar disubstituted aminourea residue (r.m.s. deviation = 0.0201 Å), which features an intramolecular amine-N—H...N(imine) hydrogen bond. In the `all-trans' chain connecting this to the terminal methoxybenzene residue, the conformation about each of the imine and ethylene double bonds isE. In the crystal, amide-N—H...O(carbonyl) hydrogen bonds connect centrosymmetrically related molecules into dimeric aggregates, which also incorporate ethylene-C—H...O(amide) interactions. The dimers are linked by amine–phenyl-C—H...π(imine–phenyl) and methoxybenzene-C—H...π(amine–phenyl) interactions to generate a three-dimensional network. The importance of C—H...π interactions in the molecular packing is reflected in the relatively high contributions made by C...H/H...C contacts to the Hirshfeld surface,i.e. 31.6%.

Bis(N′-{(E)-[(2E)-1,3-diphenylprop-2-en-1-ylidene]amino}-N-ethylcarbamimidothioato-κ2N′,S)zinc(II): crystal structure and Hirshfeld surface analysis

The title ZnIIcomplex, [Zn(C18H18N3S)2], (I), features two independent but chemically equivalent molecules in the asymmetric unit. In each, the thiosemicarbazonate monoanion coordinates the ZnIIatomviathe thiolate-S and imine-N atoms, with the resulting N2S2donor set defining a distorted tetrahedral geometry. The five-membered ZnSCN2chelate rings adopt distinct conformations in each independent molecule,i.e.one ring is almost planar while the other is twisted about the Zn—S bond. In the crystal, the two molecules comprising the asymmetric unit are linked by amine-N—H...N(imine) and amine-N—H...S(thiolate) hydrogen bondsviaan eight-membered heterosynthon, {...HNCN...HNCS}. The dimeric aggregates are further consolidated by benzene-C—H...S(thiolate) interactions and are linked into a zigzag supramolecular chain along thecaxisviaamine-N—H...S(thiolate) hydrogen bonds. The chains are connected into a three-dimensional architectureviaphenyl-C—H...π(phenyl) and π–π interactions, the latter occurring between chelate and phenyl rings [inter-centroid separation = 3.6873 (11) Å]. The analysis of the Hirshfeld surfaces calculated for (I) emphasizes the different interactions formed by the independent molecules in the crystal and the impact of the π–π interactions between chelate and phenyl rings.

The 1:1 co-crystal of 2-bromonaphthalene-1,4-dione and 1,8-dihydroxyanthracene-9,10-dione: crystal structure and Hirshfeld surface analysis

The asymmetric unit of the title co-crystal, C10H5BrO2·C14H8O4[systematic name: 2-bromo-1,4-dihydronaphthalene-1,4-dione–1,8-dihydroxy-9,10-dihydroanthracene-9,10-dione (1/1)], features one molecule of each coformer. The 2-bromonaphthoquinone molecule is almost planar [r.m.s deviation of the 13 non-H atoms = 0.060 Å, with the maximum deviations of 0.093 (1) and 0.099 (1) Å being for the Br atom and a carbonyl-O atom, respectively]. The 1,8-dihydroxyanthraquinone molecule is planar (r.m.s. deviation for the 18 non-H atoms is 0.022 Å) and features two intramolecular hydroxy-O—H...O(carbonyl) hydrogen bonds. Dimeric aggregates of 1,8-dihydroxyanthraquinone molecules assemble through weak intermolecular hydroxy-O—H...O(carbonyl) hydrogen bonds. The molecular packing comprises stacks of molecules of 2-bromonaphthoquinone and dimeric assembles of 1,8-dihydroxyanthraquinone with the shortest π–π contact within a stack of 3.5760 (9) Å occurring between the different rings of 2-bromonaphthoquinone molecules. The analysis of the Hirshfeld surface reveals the importance of the interactions just indicated but, also the contribution of additional C—H...O contacts as well as C=O...π interactions to the molecular packing.

[N,N-Bis(2-hydroxyethyl)dithiocarbamato-κ2S,S′]bis(triphenylphosphane-κP)copper(I) chloroform monosolvate: crystal structure, Hirshfeld surface analysis and solution NMR measurements

The title compound, [Cu(C5H5NO2S2)(C18H15P)2]·CHCl3, features a tetrahedrally coordinated CuIatom within a P2S2donor set defined by two phosphane P atoms and by two S atoms derived from a symmetrically coordinating dithiocarbamate ligand. Both intra- and intermolecular hydroxy-O—H...O(hydroxy) hydrogen bonding is observed: the former closes an eight-membered {...HOC2NC2O} ring, whereas the latter connects centrosymmetrically related molecules into dimeric aggregatesviaeight-membered {...H—O...H—O}2synthons. The complex molecules are arranged to form channels along thecaxis in which reside the chloroform molecules, being connected by Cl...π(arene) and short S...Cl [3.3488 (9) Å] interactions. The intermolecular interactions have been investigated further by Hirshfeld surface analysis, which shows the conventional hydrogen bonding to be very localized with the main contributors to the surface, at nearly 60%, being H...H contacts. Solution NMR studies indicate that whilst the same basic molecular structure is retained in solution, the triphenylphosphane ligands are highly labile, exchanging rapidly with free Ph3P at room temperature.