Three closely related 1-[(1,3-benzodioxol-5-yl)methyl]-4-(halobenzoyl)piperazines: similar molecular structures but different intermolecular interactions

Ninganayaka Mahesha; Belakavadi K. Sagar; Hemmige S. Yathirajan; Tetsundo Furuya; Tomoyuki Haraguchi; Takashiro Akitsu; Christopher Glidewell

doi:10.1107/S2056989019000458

Three closely related 1-[(1,3-benzodioxol-5-yl)methyl]-4-(halobenzoyl)piperazines: similar molecular structures but different intermolecular interactions

Ninganayaka Mahesha, Belakavadi K. Sagar, Hemmige S. Yathirajan, Tetsundo Furuya, Tomoyuki Haraguchi, Takashiro Akitsu, Christopher Glidewell

School of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

In each of the compounds 1-[(1,3-benzodioxol-5-yl)methyl]-4-(3-fluorobenzoyl)piperazine, C₁₉H ₁₉FN ₂O ₃ (I), 1-[(1,3-benzodioxol-5-yl)methyl]-4-(2,6-difluorobenzoyl)piperazine, C₁₉H ₁₈F ₂N ₂O ₃ (II), and 1-[(1,3-benzodioxol-5-yl)methyl]-4-(2,4-dichlorobenzoyl)piperazine, C₁₉H ₁₉Cl ₂N ₂O ₃ (III), the piperazine rings adopt a chair conformation with the (1,3-benzodioxol-5-yl)methyl substituent occupying an equatorial site: the five-membered rings are all slightly folded across the O⋯O line leading to envelope conformations. The dihedral angle between the planar amidic fragment and the haloaryl ring is 62.97 (5)° in (I) but 77.72 (12)° and 75.50 (5)° in (II) and (III), respectively. Despite their similarity in constitution and conformation, the supramolecular interactions in (I)–(III) differ: in (I), a combination of C—H⋯O and C—H⋯π(arene) hydrogen bonds links the molecules into a three-dimensional framework structure, but there are no hydrogen bonds of any sort in either (II) or (III), although the structure of (III) contains a short Cl⋯Cl contact between inversion-related pairs of molecules.

Original language	English
Pages (from-to)	202-207
Journal	Acta Crystallographica Section E Crystallographic Communications
Volume	75
Issue number	2
DOIs	https://doi.org/10.1107/S2056989019000458
Publication status	Published - 1 Feb 2019

Keywords

Piperazines
Crystal structure
Molecular conformation
Hydrogen bonding
Supramolecular assembly

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Three closely related 1-[(1,3-benzodioxol-5-yl)methyl]-4-(halobenzoyl)piperazines: similar molecular structures but different intermolecular interactions (crystallography data)
Mahesha, N. (Creator), Sagar, B. K. (Creator), Yathirajan, H. S. (Creator), Furuya, T. (Creator), Haraguchi, T. (Creator), Akitsu, T. (Creator) & Glidewell, C. (Creator), Cambridge Crystallographic Data Centre, 2019
https://doi.org/10.5517/ccdc.csd.cc21fdb7 and 2 more links, https://doi.org/10.5517/ccdc.csd.cc21fdc8, https://doi.org/10.5517/ccdc.csd.cc21fdd9 (show fewer)
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Mahesha, N., Sagar, B. K., Yathirajan, H. S., Furuya, T., Haraguchi, T., Akitsu, T., & Glidewell, C. (2019). Three closely related 1-[(1,3-benzodioxol-5-yl)methyl]-4-(halobenzoyl)piperazines: similar molecular structures but different intermolecular interactions. Acta Crystallographica Section E Crystallographic Communications, 75(2), 202-207. https://doi.org/10.1107/S2056989019000458

@article{322f369a6689422b9111cf98f66d1ad9,

title = "Three closely related 1-[(1,3-benzodioxol-5-yl)methyl]-4-(halobenzoyl)piperazines: similar molecular structures but different intermolecular interactions",

abstract = "In each of the compounds 1-[(1,3-benzodioxol-5-yl)methyl]-4-(3-fluorobenzoyl)piperazine, C19H 19FN 2O 3 (I), 1-[(1,3-benzodioxol-5-yl)methyl]-4-(2,6-difluorobenzoyl)piperazine, C19H 18F 2N 2O 3 (II), and 1-[(1,3-benzodioxol-5-yl)methyl]-4-(2,4-dichlorobenzoyl)piperazine, C19H 19Cl 2N 2O 3 (III), the piperazine rings adopt a chair conformation with the (1,3-benzodioxol-5-yl)methyl substituent occupying an equatorial site: the five-membered rings are all slightly folded across the O⋯O line leading to envelope conformations. The dihedral angle between the planar amidic fragment and the haloaryl ring is 62.97 (5)° in (I) but 77.72 (12)° and 75.50 (5)° in (II) and (III), respectively. Despite their similarity in constitution and conformation, the supramolecular interactions in (I)–(III) differ: in (I), a combination of C—H⋯O and C—H⋯π(arene) hydrogen bonds links the molecules into a three-dimensional framework structure, but there are no hydrogen bonds of any sort in either (II) or (III), although the structure of (III) contains a short Cl⋯Cl contact between inversion-related pairs of molecules.",

keywords = "Piperazines, Crystal structure, Molecular conformation, Hydrogen bonding, Supramolecular assembly",

author = "Ninganayaka Mahesha and Sagar, {Belakavadi K.} and Yathirajan, {Hemmige S.} and Tetsundo Furuya and Tomoyuki Haraguchi and Takashiro Akitsu and Christopher Glidewell",

note = "HSY is grateful to the UGC, New Delhi for the award of a BSR Faculty Fellowship for three years. BKS thanks the UGC for the award of a Rajeev Gandhi Fellowship.",

year = "2019",

month = feb,

day = "1",

doi = "10.1107/S2056989019000458",

language = "English",

volume = "75",

pages = "202--207",

journal = "Acta Crystallographica Section E Crystallographic Communications",

issn = "2056-9890",

publisher = "International Union of Crystallography",

number = "2",

}

Mahesha, N, Sagar, BK, Yathirajan, HS, Furuya, T, Haraguchi, T, Akitsu, T & Glidewell, C 2019, 'Three closely related 1-[(1,3-benzodioxol-5-yl)methyl]-4-(halobenzoyl)piperazines: similar molecular structures but different intermolecular interactions', Acta Crystallographica Section E Crystallographic Communications, vol. 75, no. 2, pp. 202-207. https://doi.org/10.1107/S2056989019000458

Three closely related 1-[(1,3-benzodioxol-5-yl)methyl]-4-(halobenzoyl)piperazines: similar molecular structures but different intermolecular interactions. / Mahesha, Ninganayaka; Sagar, Belakavadi K.; Yathirajan, Hemmige S. et al.
In: Acta Crystallographica Section E Crystallographic Communications, Vol. 75, No. 2, 01.02.2019, p. 202-207.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Three closely related 1-[(1,3-benzodioxol-5-yl)methyl]-4-(halobenzoyl)piperazines

T2 - similar molecular structures but different intermolecular interactions

AU - Mahesha, Ninganayaka

AU - Sagar, Belakavadi K.

AU - Yathirajan, Hemmige S.

AU - Furuya, Tetsundo

AU - Haraguchi, Tomoyuki

AU - Akitsu, Takashiro

AU - Glidewell, Christopher

N1 - HSY is grateful to the UGC, New Delhi for the award of a BSR Faculty Fellowship for three years. BKS thanks the UGC for the award of a Rajeev Gandhi Fellowship.

PY - 2019/2/1

Y1 - 2019/2/1

N2 - In each of the compounds 1-[(1,3-benzodioxol-5-yl)methyl]-4-(3-fluorobenzoyl)piperazine, C19H 19FN 2O 3 (I), 1-[(1,3-benzodioxol-5-yl)methyl]-4-(2,6-difluorobenzoyl)piperazine, C19H 18F 2N 2O 3 (II), and 1-[(1,3-benzodioxol-5-yl)methyl]-4-(2,4-dichlorobenzoyl)piperazine, C19H 19Cl 2N 2O 3 (III), the piperazine rings adopt a chair conformation with the (1,3-benzodioxol-5-yl)methyl substituent occupying an equatorial site: the five-membered rings are all slightly folded across the O⋯O line leading to envelope conformations. The dihedral angle between the planar amidic fragment and the haloaryl ring is 62.97 (5)° in (I) but 77.72 (12)° and 75.50 (5)° in (II) and (III), respectively. Despite their similarity in constitution and conformation, the supramolecular interactions in (I)–(III) differ: in (I), a combination of C—H⋯O and C—H⋯π(arene) hydrogen bonds links the molecules into a three-dimensional framework structure, but there are no hydrogen bonds of any sort in either (II) or (III), although the structure of (III) contains a short Cl⋯Cl contact between inversion-related pairs of molecules.

AB - In each of the compounds 1-[(1,3-benzodioxol-5-yl)methyl]-4-(3-fluorobenzoyl)piperazine, C19H 19FN 2O 3 (I), 1-[(1,3-benzodioxol-5-yl)methyl]-4-(2,6-difluorobenzoyl)piperazine, C19H 18F 2N 2O 3 (II), and 1-[(1,3-benzodioxol-5-yl)methyl]-4-(2,4-dichlorobenzoyl)piperazine, C19H 19Cl 2N 2O 3 (III), the piperazine rings adopt a chair conformation with the (1,3-benzodioxol-5-yl)methyl substituent occupying an equatorial site: the five-membered rings are all slightly folded across the O⋯O line leading to envelope conformations. The dihedral angle between the planar amidic fragment and the haloaryl ring is 62.97 (5)° in (I) but 77.72 (12)° and 75.50 (5)° in (II) and (III), respectively. Despite their similarity in constitution and conformation, the supramolecular interactions in (I)–(III) differ: in (I), a combination of C—H⋯O and C—H⋯π(arene) hydrogen bonds links the molecules into a three-dimensional framework structure, but there are no hydrogen bonds of any sort in either (II) or (III), although the structure of (III) contains a short Cl⋯Cl contact between inversion-related pairs of molecules.

KW - Piperazines

KW - Crystal structure

KW - Molecular conformation

KW - Hydrogen bonding

KW - Supramolecular assembly

U2 - 10.1107/S2056989019000458

DO - 10.1107/S2056989019000458

M3 - Article

SN - 2056-9890

VL - 75

SP - 202

EP - 207

JO - Acta Crystallographica Section E Crystallographic Communications

JF - Acta Crystallographica Section E Crystallographic Communications

IS - 2

ER -

Three closely related 1-[(1,3-benzodioxol-5-yl)methyl]-4-(halobenzoyl)piperazines: similar molecular structures but different intermolecular interactions

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Three closely related 1-[(1,3-benzodioxol-5-yl)methyl]-4-(halobenzoyl)piperazines: similar molecular structures but different intermolecular interactions (crystallography data)

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