Push-pull intermolecular nucleophile-electrophile interactions of carbonyl groups from crystallographic data and MNDO calculations

Cossu, M.; Bachmann, Christian; N'Guessan, Thomas Yao; Viani, R.; Lapasset, J.; Aycard, Jean‐Pierre; Bodot, Hubert

doi:10.1021/jo00233a003

Cited by 10 publications

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“…As pointed out in our structure analysis of cis-1,2,3,6-tetrahydrophthalic anhydride [1] [4] and its derivatives [16], an obvious relationship between the postulated typical intermolecular interactions and the packing modes of 1 can be predicted. The study of the efficiency of these intermolecular interactions in inducing geometrical deformation of the structure of 1 is undertaken and the results obtained will be reported in an independent work.…”

mentioning

confidence: 62%

“…The packing pattern reveals a large number of close intermolecular contacts among the electrophilic C-atoms (El) and their concomitant nucleophilic O-atoms (Nu) of symmetry-related molecules I and II as well as between the H-and the O-atoms of symmetryindependent molecules I and II that are within the range of the Van der Waals interactions. The significant intermolecular NuÀEl CO ¥¥¥ CO bonds that are within the presently acceptable limit (d(O ¥¥¥ C) 3.4 ä) [16], the noncovalent angles q (O ¥¥¥ CO), and the dihedral angles f (O ¥¥¥ COC) (CO being a carbonyl group) defining the NuÀEl O ¥¥¥ C atom abstraction distance are reported in Table 2. The minimum intermolecular CO ¥¥¥ CO distance is 2.957(2) ä between molecules I and 2.926(2) ä between molecules II (Fig.…”

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confidence: 99%

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Crystal Structure of 3,4,5,6‐Tetrahydrophthalic Anhydride at 150 K

Fredj

Bagieu‐Beucher

Rejeb

et al. 2004

Helvetica Chimica Acta

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The crystal structure of 3,4,5,6-tetrahydrophthalic anhydride, ( 4,5,6,7-tetrahydroisobenzofuran-1,3-dione; 1; C 8 H 8 O 3 ) was determined and refined by an analysis of three-dimensional X-ray-diffraction data at 150 K. This bicyclic compound crystallizes in space group Pbca with two symmetry-independent molecules I and II per asymmetric unit. The cyclohexene ring in both molecules adopts a half-chair conformation. The obtained conformational descriptions of the six-membered rings in the crystal phase are consistent with conformational data derived from molecular-orbital calculations. The structure analysis evidences considerable distorsion of the partially hydrogenated six-membered ring; the furan ring is flattened in molecule I and slightly deviated from planarity in molecule II. The short intermolecular distances found for CO ¥¥¥ CO are interpreted as evidence for nonbonded interactions of the dipole ± dipole type. The rather long O ¥¥¥ H distances indicate that the C(sp 3 )-H ¥¥¥ O interactions are weak.Introduction. ± Within the context of studies on the conformations of bicyclic anhydrides, the structure of cis-1,2,3,6-tetrahydrophthalic anhydride C 8 H 8 O 3 has been determined by X-ray diffraction [1]; its crystal structure consists of two symmetryindependent molecules per asymmetric unit. Their conformations are folded, both possessing a boat form for the cyclohexene ring, in agreement with experimental NMR solution data [2] [3]. Crystal packing of the two independent molecules in the unit cell has also been investigated [4], establishing non-bonded interactions of the dipoleÀdi-pole type between local electrical dipoles of the carbonyl groups CO ¥¥¥ CO. Concomitantly, several techniques of semi-empirical and ab initio molecular-orbital calculations have been applied for the determination of the molecular geometry of this compound and its isomers, 3,4,5,6-, 1,2,5,7-, and 1,4,5,6-tetrahydrophthalic anhydrides [5]. These calculations confirmed the preference of the folded conformation for cis-1,2,3,6-tetrahydrophthalic anhydride and revealed large differences in the stereochemical behavior of these isomeric tetrahydrophthalic anhydrides. In view of the considerable interest in the structural properties of this series of anhydride isomers, it appeared desirable to have precise structural data for a selected compound to provide a check of the theory and possibly to aid in formulating refinements in the calculations. Experimental structures of the gas-phase molecules have not yet been reported, and, besides two crystallographic studies on derivatives of 3,4,5,6-tetrahydrophthalic anhydride [6] [7], no experimental data on the parent compound are available. Thus, in the present work, an investigation of the crystal structure of 3,4,5,6-tetrahydrophthalic anhydride ( 4,5,6,7-tetrahydroisobenzofuran-1,3-dione; 1) was undertaken to reveal the most stable conformation and to elucidate the structural differences between

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mentioning

confidence: 62%

mentioning

confidence: 99%

Crystal Structure of 3,4,5,6‐Tetrahydrophthalic Anhydride at 150 K

Fredj

Bagieu‐Beucher

Rejeb

et al. 2004

Helvetica Chimica Acta

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“…Moreover it is noticeable that the averaged value of dihedrals angles corresponding to the oxygen and carbon atom C=O as nucleophilic and electrophilic reagents which are found respectively in the average equal to 91.4° (HOpt) and to 91° (FullOpt) are close the bisecter criterium (=90°) [14]. Results from >O…C=O intermolecular interactions ( [45.5°-96.9°] (FullOpt); in the crystal of cis-1,2,3,6-tetrahydrophthalic anhydride, the  packing does not depend on (>O…C=O) angle and appear to be mainly on the  (CO...CO) control [14]. This can be correlated with anhydride crystal data which show an almost random distribution of  (>O…C=O) from 48.7° to 96.8° for >O…C=O intermolecular interactions [2,13].…”

Section: Results Of Theoretical Calculations and Comparison With Expementioning

confidence: 89%

“…But even more gratifying than the direct comparison is the agreement in many trends when crystal packing of 3,4,5,6-tetrahydrophthalic anhydride is compared to that of cis-1,2,3,6-THP anhydride: the shortest intermolecular C=O….C=O contacts in the 3,4,5,6-tetrahydrophthalic anhydride structure, in the range [2.957 Å to 3.191 Å], are between symmetry related of formular group, while in cis-1,2,3,6-tetrahydrophthalic anhydride, the closest contacts [3.023 Å to 3.30 Å] appear among symmetry independent molecules. The calculated non covalent  angles values corresponding to the d (C=O....C=O) abstraction distances in the 3,4,5,6-THP anhydride crystal packing deviate significantly from the ideal value which is assumed to be 105° [13,14] in comparison with the values calculated for cis-1,2,3,6-THP anhydride. The angles may be more accurate for C=O…C=O abstraction owing to the localisation of -electron density in the case of the cis-1,2,3,6-THP anhydride closer to the centre of the C=O bond; a trend opposite to that expected for C=O….C=O abstraction in 3,4,5,6-tetrahydrophthalic anhydride which may include electrostatic interactions as pointed out above.…”

Section: -3456-tetrahydrophthalic Anhydridementioning

confidence: 93%

“…Their crystal structures exhibit an interesting columnar packing pattern, sustained by an extensive network of non-bonded intermolecular C=O…C=O interactions of dipole-dipole type [3,13]. Discussion of these intermolecular interactions in terms of typical geometrical criteria [14] allows us to argue that there is an obvious relationship between these specific intermolecular interactions and the packing modes of these crystal isomers. The cis-1,2,3,6-THP anhydride isomer (Form I) showed polymorphism: M. Bolte et al [15] crystallised it from a solution in ether at 173 K and found an orthorhombic structure with Z=8 in space group Pca2 1 .…”

Section: Introductionmentioning

confidence: 99%

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Modelling of crystal structure of cis-1,2,3,6 and 3,4,5,6-tetrahydrophthalic anhydrides using lattice energy calculations

Fredj¹,

Day

2015

J Mol Model

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Lattice energy calculations using a model potential have been performed to model the crystal structures of cis-1,2,3,6-and 3,4,5,6-tetrahydrophthalic anhydrides. The optimized molecular models using the DFT method at the B3LYP/6-31G** level were found consistent with the available experimental evidence and allow to reproduce all differences observed in crystal packing between cis-1,2,3,6-and 3,4,5,6-tetrahydrophthalic anhydrides. Calculations provide evidence for the presence of dipole-dipole C=O…C=O intermolecular interactions and support the idea that the molecules distort from their ideal geometries, improving packing in both crystals. The search for minima in the lattice energy of both crystals amongst the more common space groups with Z'=1, using a simulated annealing crystal structure prediction procedure followed by lattice energy minimisation shows that the observed structure of 3,4,5,6-tetrahydrophthalic anhydride (Z'=2) is the thermodynamically most stable and allow us to justify why 3,4,5,6-tetrahydropthalic anhydride crystallises in such complex structure with 16 molecules in the unit cell. The computational model was successful to predict the second observed form at 173 K for cis-1,2,3,6-tetrahydropthalic anhydride as a polymorph and could predict several hypothetical structures with Z'=1 which appear competitive with the observed structures. The results of phonon estimates of zero point intermolecular vibrational energy and entropy suggest that crystal structures of cis-1,2,3,6-tetrahydropthalic anhydride cannot be predicted just on the basis of lattice energy, there are yet, other factors than thermodynamics favoring the observed structures.

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Organic Addition and Elimination Reactions; Transformation Paths of Carbonyl Derivatives

Cieplak¹

1994

Structure Correlation

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Push-pull intermolecular nucleophile-electrophile interactions of carbonyl groups from crystallographic data and MNDO calculations

Cited by 10 publications

References 0 publications

Crystal Structure of 3,4,5,6‐Tetrahydrophthalic Anhydride at 150 K

Crystal Structure of 3,4,5,6‐Tetrahydrophthalic Anhydride at 150 K

Modelling of crystal structure of cis-1,2,3,6 and 3,4,5,6-tetrahydrophthalic anhydrides using lattice energy calculations

Organic Addition and Elimination Reactions; Transformation Paths of Carbonyl Derivatives

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