Geometric H/D isotope effect in a series of organic salts involving short O–H⋯O hydrogen bonds between carboxyl and carboxylate groups

Tong, Jin; Zhang, Wen

doi:10.1039/c9ce00734b

Cited by 11 publications

(16 citation statements)

References 39 publications

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“…The O ⋅⋅⋅ H/H ⋅⋅⋅ O contact was predominant and cover the ∼43 % area of the fingerprint region (Figure 10c). Similar to BCP 5A the H‐bond is short and in accordance with reports available in the literature [20] . Surprisingly, only weak H ⋅⋅⋅ H and C ⋅⋅⋅ H contacts were observed for the given molecules.…”

Section: Resultssupporting

confidence: 90%

“…The structure forms a one‐dimensional hydrogen‐bonded chain of BCP diacid and the corresponding dianion, along the crystallographic 2 a + c direction. The hydrogen atoms refined to an O−H distance of 1.064(16) Å, with an intermolecular H1 ⋅⋅⋅ O1 distance of 1.431(16) Å; the O ⋅⋅⋅ O contact of 2.4928(12) Å and angle of 174.5(14)°, indicating an exceptionally energetically favorable interaction, fitting the definition of a low‐barrier hydrogen bond [20] . Additional hydrogen bonding is observed between the triethylammonium cation and the BCP dianion, a strong interaction N−H ⋅⋅⋅ O (2.6731(13) Å D ⋅⋅⋅ A) and weaker charge‐assisted C−H ⋅⋅⋅ O interaction (3.110 Å D ⋅⋅⋅ A) (Figure 5b).…”

Section: Resultsmentioning

confidence: 75%

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An Insight into Non‐Covalent Interactions on the Bicyclo[1.1.1]pentane Scaffold

et al. 2020

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Bicyclo[1.1.1]pentane (BCP) is studied extensively as a bioisosteric component of drugs. Not found in nature, this molecular unit approximates the distance of a para‐disubstituted benzene which is replaced in medicines as a method of improving treatments. Predicting interactions of these drugs with specific active sites requires knowledge of the non‐covalent interactions engaged by this subunit. Structure determinations and computational analysis (Hirshfeld analysis, 2D fingerprint plots, DFT) of seven BCP derivatives chosen to probe specific and directional interactions. X‐ray analysis revealed the presence of various non‐covalent interactions including I ⋅⋅⋅ I, I ⋅⋅⋅ N, N−H ⋅⋅⋅ O, C−H ⋅⋅⋅ O, and H−C ⋅⋅⋅ H−C contacts. The preference of halogen bonding (I ⋅⋅⋅ I or I ⋅⋅⋅ N) in BCP 1–4 strictly depends upon the electronic nature and angle between bridgehead substituents. The transannular distance in co‐crystals 2 and 4 was longer as compared to monomers 1 and 3. Stronger N−H ⋅⋅⋅ O and weaker C−H ⋅⋅⋅ O contacts were observed for BCP 5 while the O ⋅⋅⋅ H interaction was a prominent contact for BCP 6. The presence of 3D BCP units prevented the π ⋅⋅⋅ π stacking between phenyl rings in 3, 4, and 7. The BCP skeleton was often rotationally averaged, indicating fewer interactions compared to bridgehead functional groups. Using DFT analysis, geometries were optimized and molecular electrostatic potentials were calculated on the BCP surfaces. These interaction profiles may be useful for designing BCP analogs of drugs.

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Section: Resultssupporting

confidence: 90%

Section: Resultsmentioning

confidence: 75%

An Insight into Non‐Covalent Interactions on the Bicyclo[1.1.1]pentane Scaffold

et al. 2020

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“…In rare cases, complete deuterium substitution can change the solid-state structure of a compound (i.e., isotope polymorphism , ). Examples are P 2 1 / c (COOH) 2 ·2H 2 O vs P 2 1 / a (COOD) 2 ·2D 2 O (different herringbone packing patterns) and trifluoroacetic acid tetrahydrate (ionic (H 5 O 2 )[(CF 3 COO) 2 H]·6H 2 O vs molecular CF 3 COOD·4D 2 O) .…”

Section: Discussionmentioning

confidence: 99%

Hydrated Metal Ion Salts of the Weakly Coordinating Fluoroanions PF₆^–, TiF₆^2–, B₁₂F₁₂^2–, Ga(C₂F₅)₄^–, B(3,5-C₆H₃(CF₃)₂)₄^–, and Al(OC(CF₃)₃)₄^–. In Search of the Weakest HOH···F Hydrogen Bonds

Lacroix

Liu²,

Strauss

2019

Inorg. Chem.

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FTIR spectra of microcrystalline samples of 11 metal ion salt hydrates of a variety of weakly coordinating fluoroanions are reported. The compounds studied were Li(H2O)4(Al(OC(CF3)3)4), Li(H2O)(B(3,5-C6H3(CF3)2)4), Li(H2O) n (Ga(C2F5)4), Li(H2O)(PF6), Li2(H2O)2(TiF6), Li2(H2O)4(B12F12), Na(H2O)(PF6), Na2(H2O)2(B12F12), K2(H2O)2(B12F12), Rb2(H2O)2(B12F12), Cs2(H2O)(B12F12), and their partially or completely deuterated isotopologs and isotopomers. The O–D···F hydrogen bonds in Li(HOD)(H2O)3(Al(OC(CF3)3)4) (ν(OD) = 2706 cm–1), Li(HOD)(B(3,5-C6H3(CF3)2)4) (ν(OD) = 2705 cm–1), and Li(HOD)(H2O) n (Ga(C2F5)4) (ν(OD) = 2697 cm–1) rival HOD absorbed in polyvinylidene difluoride (ν(OD) = 2696 cm–1) and HOD···FCH3 in a frozen Ar matrix (ν(OD) = 2685 cm–1) for the weakest hydrogen bonds between a water molecule and an F atom in any compound. As weak as they are, minor differences in O–H···F hydrogen bonds in the same fluoroanion salt can be distinguished spectroscopically. Uncoupled HOD molecules in asymmetric F···HOD···F′ hydrogen bonding environments in Rb+, Cs+, Mg2+, and Co2+ hydrates of B12F12 2– gave rise to two observable ν(OD) bands even though the two R(O···F) distances differ by only 0.010(4) Å (Mg2+), 0.033(2) Å (Co2+), 0.074(4) Å (Rb+), and 0.106(6) Å (Cs+). A plot of ν(OD) for hydrates with a single uncoupled HOD molecule per metal ion (e.g., Li(HOD)(H2O)3(Al(OC(CF3)3)4)) vs R(O···F) distance from single-crystal X-ray or neutron diffraction structures was prepared. The ν(OD) values range from 2305 to 2706 cm–1 and the R(O···F) distances range from 2.58 to 3.17 Å. The plot consists of 53 {ν(OD), R(O···F)} data points, 23 of which are new and have ν(OD) > 2600 cm–1, in contrast to a 1994 ν(OD) vs R(O···F) plot with 28 data points, none of which had ν(OD) > 2600 cm–1. There is a clear and significant difference between the new ν(OD) vs R(O···F) plot and a literature ν(OD) vs R(O···O) plot for hydrates containing O–D···O hydrogen bonds. For a given ν(OD) stretching frequency, the exponential regression curves show that R(O···F) is typically 0.1–0.2 Å shorter than R(O···O), in harmony with the lower basicity and smaller size of F atoms vs O atoms.

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“…While in many cases this assumption holds true there is a small, but increasing, number of materials where deuteration is known to affect their solid-state structures more profoundly. 1,2 There are several examples of phase boundaries shifting with isotope substitution, [3][4][5] and perturbations to atomic coordinates, 6 but more significant is the formation of entirely new crystalline phases; socalled 'isotopic polymorphism'. 7 Observation of this phenomenon has mostly been limited to inorganic crystals, including ammonium dihydrogen phosphate/arsenate, 8 and chromium oxide hydroxide.…”

Section: Introductionmentioning

confidence: 99%

Suppression of isotopic polymorphism

et al. 2021

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Geometric H/D isotope effect in a series of organic salts involving short O–H⋯O hydrogen bonds between carboxyl and carboxylate groups

Abstract: Noticeable elongations of donor–acceptor distances upon deuteration are confirmed in short O–H⋯O hydrogen bonds between carboxyl and carboxylate groups.

Cited by 11 publications

References 39 publications

An Insight into Non‐Covalent Interactions on the Bicyclo[1.1.1]pentane Scaffold

An Insight into Non‐Covalent Interactions on the Bicyclo[1.1.1]pentane Scaffold

Hydrated Metal Ion Salts of the Weakly Coordinating Fluoroanions PF₆^–, TiF₆^2–, B₁₂F₁₂^2–, Ga(C₂F₅)₄^–, B(3,5-C₆H₃(CF₃)₂)₄^–, and Al(OC(CF₃)₃)₄^–. In Search of the Weakest HOH···F Hydrogen Bonds

Suppression of isotopic polymorphism

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Geometric H/D isotope effect in a series of organic salts involving short O–H⋯O hydrogen bonds between carboxyl and carboxylate groups

Abstract: Noticeable elongations of donor–acceptor distances upon deuteration are confirmed in short O–H⋯O hydrogen bonds between carboxyl and carboxylate groups.

Cited by 11 publications

References 39 publications

An Insight into Non‐Covalent Interactions on the Bicyclo[1.1.1]pentane Scaffold

An Insight into Non‐Covalent Interactions on the Bicyclo[1.1.1]pentane Scaffold

Hydrated Metal Ion Salts of the Weakly Coordinating Fluoroanions PF6–, TiF62–, B12F122–, Ga(C2F5)4–, B(3,5-C6H3(CF3)2)4–, and Al(OC(CF3)3)4–. In Search of the Weakest HOH···F Hydrogen Bonds

Suppression of isotopic polymorphism

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Product

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Hydrated Metal Ion Salts of the Weakly Coordinating Fluoroanions PF₆^–, TiF₆^2–, B₁₂F₁₂^2–, Ga(C₂F₅)₄^–, B(3,5-C₆H₃(CF₃)₂)₄^–, and Al(OC(CF₃)₃)₄^–. In Search of the Weakest HOH···F Hydrogen Bonds