Crystal structures and Hirshfeld surface analyses of the di- and tri-hydrates of (5α,17E)-17-hydrazonoandrostan-3-ol: Significant differences in the hydrogen bonding patterns and supramolecular arrangements

Ligia R Gomes, John N. Low, Alan B Turner, Thomas C Baddeley, James L Wardell (Corresponding Author)

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Abstract

The crystal structures, Hirshfeld surface analyses and electrostatic potential surfaces of the di- and tri-hydrates of (5α,17E)-17-hydrazonoandrostan-3-ol, 3, namely [3·(H2O)2] and [3·(H2O)3], are reported. The trihydrate, isolated from a solution of 3 in moist methanol, recrystallizes in the orthorhombic space group, P212121, while that of the dihydrate, isolated from a 1:1 aqueous methanol solution, recrystallizes in the monoclinic space group, P21. The asymmetric unit of the trihydrate involves one steroid and three water molecules, while that of the dihydrate has two similar but independent steroid molecules and four hydrate molecules. Very similar conformations are found for the steroid molecules in both hydrates. As expected, the different mole ratios of water: steroid have major influences on the structures. In both cases, complex crystal structures are constructed from various classical hydrogen bonds, involving the hydrate molecules and the hydroxy and hydrazonyl moieties of the steroid. In the trihydrate, there are no direct connections between the steroid molecules, instead the water molecules link the steroid molecules, with only weak van der Waals forces between the steroid molecules. There are some direct links between the steroid molecules in the dihydrate, involving OH(steroid hydroxyl)⋯O(steroid oxo) hydrogen bonds, in a head to head fashion, and OH⋯N(hydrazonyl) hydrogen bonds, in a head to tail fashion. However, the major occurrence throughout the structure is of steroid molecules linked by water molecules.

Original languageEnglish
Pages (from-to)92-103
Number of pages12
JournalSteroids
Volume140
Early online date29 Sep 2018
DOIs
Publication statusPublished - 31 Dec 2018

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Hydrogen Bonding
Hydrates
Hydrogen bonds
Crystal structure
Steroids
Molecules
Hydrogen
Water
Methanol
Van der Waals forces
Static Electricity
Hydroxyl Radical
Conformations
Electrostatics

Keywords

  • hydrogen bonds
  • crystal structures
  • Hirshfeld surface analysis
  • hydrazones
  • androsterones
  • molecular electrostatic potential

Cite this

@article{d1854102d0a24a76ba3a36cd0d98fd2f,
title = "Crystal structures and Hirshfeld surface analyses of the di- and tri-hydrates of (5α,17E)-17-hydrazonoandrostan-3-ol: Significant differences in the hydrogen bonding patterns and supramolecular arrangements",
abstract = "The crystal structures, Hirshfeld surface analyses and electrostatic potential surfaces of the di- and tri-hydrates of (5α,17E)-17-hydrazonoandrostan-3-ol, 3, namely [3·(H2O)2] and [3·(H2O)3], are reported. The trihydrate, isolated from a solution of 3 in moist methanol, recrystallizes in the orthorhombic space group, P212121, while that of the dihydrate, isolated from a 1:1 aqueous methanol solution, recrystallizes in the monoclinic space group, P21. The asymmetric unit of the trihydrate involves one steroid and three water molecules, while that of the dihydrate has two similar but independent steroid molecules and four hydrate molecules. Very similar conformations are found for the steroid molecules in both hydrates. As expected, the different mole ratios of water: steroid have major influences on the structures. In both cases, complex crystal structures are constructed from various classical hydrogen bonds, involving the hydrate molecules and the hydroxy and hydrazonyl moieties of the steroid. In the trihydrate, there are no direct connections between the steroid molecules, instead the water molecules link the steroid molecules, with only weak van der Waals forces between the steroid molecules. There are some direct links between the steroid molecules in the dihydrate, involving OH(steroid hydroxyl)⋯O(steroid oxo) hydrogen bonds, in a head to head fashion, and OH⋯N(hydrazonyl) hydrogen bonds, in a head to tail fashion. However, the major occurrence throughout the structure is of steroid molecules linked by water molecules.",
keywords = "hydrogen bonds, crystal structures, Hirshfeld surface analysis, hydrazones, androsterones, molecular electrostatic potential",
author = "Gomes, {Ligia R} and Low, {John N.} and Turner, {Alan B} and Baddeley, {Thomas C} and Wardell, {James L}",
note = "Acknowledgements The authors thank the National Crystallographic Service, University of Southampton for the data collection, and for their help and advice. This work was supported by the Portuguese Foundation for Science and Technology (FCT) UID/Multi/04546/2013 and by CNPq, Brazil.",
year = "2018",
month = "12",
day = "31",
doi = "10.1016/j.steroids.2018.09.010",
language = "English",
volume = "140",
pages = "92--103",
journal = "Steroids",
issn = "0039-128X",
publisher = "Elsevier Inc.",

}

TY - JOUR

T1 - Crystal structures and Hirshfeld surface analyses of the di- and tri-hydrates of (5α,17E)-17-hydrazonoandrostan-3-ol

T2 - Significant differences in the hydrogen bonding patterns and supramolecular arrangements

AU - Gomes, Ligia R

AU - Low, John N.

AU - Turner, Alan B

AU - Baddeley, Thomas C

AU - Wardell, James L

N1 - Acknowledgements The authors thank the National Crystallographic Service, University of Southampton for the data collection, and for their help and advice. This work was supported by the Portuguese Foundation for Science and Technology (FCT) UID/Multi/04546/2013 and by CNPq, Brazil.

PY - 2018/12/31

Y1 - 2018/12/31

N2 - The crystal structures, Hirshfeld surface analyses and electrostatic potential surfaces of the di- and tri-hydrates of (5α,17E)-17-hydrazonoandrostan-3-ol, 3, namely [3·(H2O)2] and [3·(H2O)3], are reported. The trihydrate, isolated from a solution of 3 in moist methanol, recrystallizes in the orthorhombic space group, P212121, while that of the dihydrate, isolated from a 1:1 aqueous methanol solution, recrystallizes in the monoclinic space group, P21. The asymmetric unit of the trihydrate involves one steroid and three water molecules, while that of the dihydrate has two similar but independent steroid molecules and four hydrate molecules. Very similar conformations are found for the steroid molecules in both hydrates. As expected, the different mole ratios of water: steroid have major influences on the structures. In both cases, complex crystal structures are constructed from various classical hydrogen bonds, involving the hydrate molecules and the hydroxy and hydrazonyl moieties of the steroid. In the trihydrate, there are no direct connections between the steroid molecules, instead the water molecules link the steroid molecules, with only weak van der Waals forces between the steroid molecules. There are some direct links between the steroid molecules in the dihydrate, involving OH(steroid hydroxyl)⋯O(steroid oxo) hydrogen bonds, in a head to head fashion, and OH⋯N(hydrazonyl) hydrogen bonds, in a head to tail fashion. However, the major occurrence throughout the structure is of steroid molecules linked by water molecules.

AB - The crystal structures, Hirshfeld surface analyses and electrostatic potential surfaces of the di- and tri-hydrates of (5α,17E)-17-hydrazonoandrostan-3-ol, 3, namely [3·(H2O)2] and [3·(H2O)3], are reported. The trihydrate, isolated from a solution of 3 in moist methanol, recrystallizes in the orthorhombic space group, P212121, while that of the dihydrate, isolated from a 1:1 aqueous methanol solution, recrystallizes in the monoclinic space group, P21. The asymmetric unit of the trihydrate involves one steroid and three water molecules, while that of the dihydrate has two similar but independent steroid molecules and four hydrate molecules. Very similar conformations are found for the steroid molecules in both hydrates. As expected, the different mole ratios of water: steroid have major influences on the structures. In both cases, complex crystal structures are constructed from various classical hydrogen bonds, involving the hydrate molecules and the hydroxy and hydrazonyl moieties of the steroid. In the trihydrate, there are no direct connections between the steroid molecules, instead the water molecules link the steroid molecules, with only weak van der Waals forces between the steroid molecules. There are some direct links between the steroid molecules in the dihydrate, involving OH(steroid hydroxyl)⋯O(steroid oxo) hydrogen bonds, in a head to head fashion, and OH⋯N(hydrazonyl) hydrogen bonds, in a head to tail fashion. However, the major occurrence throughout the structure is of steroid molecules linked by water molecules.

KW - hydrogen bonds

KW - crystal structures

KW - Hirshfeld surface analysis

KW - hydrazones

KW - androsterones

KW - molecular electrostatic potential

U2 - 10.1016/j.steroids.2018.09.010

DO - 10.1016/j.steroids.2018.09.010

M3 - Article

VL - 140

SP - 92

EP - 103

JO - Steroids

JF - Steroids

SN - 0039-128X

ER -