Conformational flexibility in amidophosphoesters: A CSD analysis completed with two new crystal structures of (C6H5O)2P(O) X = NHC7H13 and N(CH2C6H5)2]

Banafsheh Vahdani Alviri, Mehrdad Pourayoubi, Abdul Ajees Abdul Salam, Marek Necas, Arie Van Der Lee, Akshara Chithran, Krishnan Damodaran

Research output: Contribution to journalArticle

Abstract

The crystal structures of diphenyl (cycloheptylamido)phosphate, C19H24NO3P or (C6H5O)2P(O)(NHC7H13), (I), and diphenyl (dibenzylamido)phosphate, C26H24NO3P or (C6H5O)2P(O)[N(CH2C6H5)2], (II), are reported. The NHC7H13 group in (I) provides two significant hydrogen-donor sites in N - H⋯O and C - H⋯O hydrogen bonds, needed for a one-dimensional hydrogen-bond pattern along [100] in the crystal, while (II), with a (C6H5CH2)2N moiety, lacks these hydrogen bonds, but its three-dimensional supramolecular structure is mediated by C - H⋯π interactions. The conformational behaviour of the phenyl rings in (I), (II) and analogous structures from the Cambridge Structural Database (CSD) were studied in terms of flexibility, volume of the other group attached to phosphorus and packing forces. From this study, synclinal (±sc), anticlinal (±ac) and antiperiplanar (±ap) conformations were found to occur. In the structure of (II), there is an intramolecular C ortho - H⋯O interaction that imposes a +sc conformation for the phenyl ring involved. For the structures from the CSD, the +sc and ±ap conformations appear to be mainly imposed by similar C ortho - H⋯O intramolecular interactions. The large contribution of the C⋯H/H⋯C contacts (32.3%) in the two-dimensional fingerprint plots of (II) is a result of the C - H⋯π interactions. The differential scanning calorimetry (DSC) analyses exhibit peak temperatures (T m) at 109 and 81-°C for (I) and (II), respectively, which agree with the strengths of the intermolecular contacts and the melting points.

Original languageEnglish
Pages (from-to)104-116
Number of pages13
JournalActa Crystallographica Section C: Structural Chemistry
Volume76
DOIs
Publication statusPublished - 01-01-2020

Fingerprint

structural analysis
Conformations
Hydrogen bonds
phosphates
flexibility
Phosphates
Crystal structure
crystal structure
hydrogen bonds
interactions
Phosphorus
Melting point
Hydrogen
Differential scanning calorimetry
rings
melting points
phosphorus
Crystals
heat measurement
plots

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Alviri, Banafsheh Vahdani ; Pourayoubi, Mehrdad ; Salam, Abdul Ajees Abdul ; Necas, Marek ; Van Der Lee, Arie ; Chithran, Akshara ; Damodaran, Krishnan. / Conformational flexibility in amidophosphoesters : A CSD analysis completed with two new crystal structures of (C6H5O)2P(O) X = NHC7H13 and N(CH2C6H5)2]. In: Acta Crystallographica Section C: Structural Chemistry. 2020 ; Vol. 76. pp. 104-116.
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abstract = "The crystal structures of diphenyl (cycloheptylamido)phosphate, C19H24NO3P or (C6H5O)2P(O)(NHC7H13), (I), and diphenyl (dibenzylamido)phosphate, C26H24NO3P or (C6H5O)2P(O)[N(CH2C6H5)2], (II), are reported. The NHC7H13 group in (I) provides two significant hydrogen-donor sites in N - H⋯O and C - H⋯O hydrogen bonds, needed for a one-dimensional hydrogen-bond pattern along [100] in the crystal, while (II), with a (C6H5CH2)2N moiety, lacks these hydrogen bonds, but its three-dimensional supramolecular structure is mediated by C - H⋯π interactions. The conformational behaviour of the phenyl rings in (I), (II) and analogous structures from the Cambridge Structural Database (CSD) were studied in terms of flexibility, volume of the other group attached to phosphorus and packing forces. From this study, synclinal (±sc), anticlinal (±ac) and antiperiplanar (±ap) conformations were found to occur. In the structure of (II), there is an intramolecular C ortho - H⋯O interaction that imposes a +sc conformation for the phenyl ring involved. For the structures from the CSD, the +sc and ±ap conformations appear to be mainly imposed by similar C ortho - H⋯O intramolecular interactions. The large contribution of the C⋯H/H⋯C contacts (32.3{\%}) in the two-dimensional fingerprint plots of (II) is a result of the C - H⋯π interactions. The differential scanning calorimetry (DSC) analyses exhibit peak temperatures (T m) at 109 and 81-°C for (I) and (II), respectively, which agree with the strengths of the intermolecular contacts and the melting points.",
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Conformational flexibility in amidophosphoesters : A CSD analysis completed with two new crystal structures of (C6H5O)2P(O) X = NHC7H13 and N(CH2C6H5)2]. / Alviri, Banafsheh Vahdani; Pourayoubi, Mehrdad; Salam, Abdul Ajees Abdul; Necas, Marek; Van Der Lee, Arie; Chithran, Akshara; Damodaran, Krishnan.

In: Acta Crystallographica Section C: Structural Chemistry, Vol. 76, 01.01.2020, p. 104-116.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Conformational flexibility in amidophosphoesters

T2 - A CSD analysis completed with two new crystal structures of (C6H5O)2P(O) X = NHC7H13 and N(CH2C6H5)2]

AU - Alviri, Banafsheh Vahdani

AU - Pourayoubi, Mehrdad

AU - Salam, Abdul Ajees Abdul

AU - Necas, Marek

AU - Van Der Lee, Arie

AU - Chithran, Akshara

AU - Damodaran, Krishnan

PY - 2020/1/1

Y1 - 2020/1/1

N2 - The crystal structures of diphenyl (cycloheptylamido)phosphate, C19H24NO3P or (C6H5O)2P(O)(NHC7H13), (I), and diphenyl (dibenzylamido)phosphate, C26H24NO3P or (C6H5O)2P(O)[N(CH2C6H5)2], (II), are reported. The NHC7H13 group in (I) provides two significant hydrogen-donor sites in N - H⋯O and C - H⋯O hydrogen bonds, needed for a one-dimensional hydrogen-bond pattern along [100] in the crystal, while (II), with a (C6H5CH2)2N moiety, lacks these hydrogen bonds, but its three-dimensional supramolecular structure is mediated by C - H⋯π interactions. The conformational behaviour of the phenyl rings in (I), (II) and analogous structures from the Cambridge Structural Database (CSD) were studied in terms of flexibility, volume of the other group attached to phosphorus and packing forces. From this study, synclinal (±sc), anticlinal (±ac) and antiperiplanar (±ap) conformations were found to occur. In the structure of (II), there is an intramolecular C ortho - H⋯O interaction that imposes a +sc conformation for the phenyl ring involved. For the structures from the CSD, the +sc and ±ap conformations appear to be mainly imposed by similar C ortho - H⋯O intramolecular interactions. The large contribution of the C⋯H/H⋯C contacts (32.3%) in the two-dimensional fingerprint plots of (II) is a result of the C - H⋯π interactions. The differential scanning calorimetry (DSC) analyses exhibit peak temperatures (T m) at 109 and 81-°C for (I) and (II), respectively, which agree with the strengths of the intermolecular contacts and the melting points.

AB - The crystal structures of diphenyl (cycloheptylamido)phosphate, C19H24NO3P or (C6H5O)2P(O)(NHC7H13), (I), and diphenyl (dibenzylamido)phosphate, C26H24NO3P or (C6H5O)2P(O)[N(CH2C6H5)2], (II), are reported. The NHC7H13 group in (I) provides two significant hydrogen-donor sites in N - H⋯O and C - H⋯O hydrogen bonds, needed for a one-dimensional hydrogen-bond pattern along [100] in the crystal, while (II), with a (C6H5CH2)2N moiety, lacks these hydrogen bonds, but its three-dimensional supramolecular structure is mediated by C - H⋯π interactions. The conformational behaviour of the phenyl rings in (I), (II) and analogous structures from the Cambridge Structural Database (CSD) were studied in terms of flexibility, volume of the other group attached to phosphorus and packing forces. From this study, synclinal (±sc), anticlinal (±ac) and antiperiplanar (±ap) conformations were found to occur. In the structure of (II), there is an intramolecular C ortho - H⋯O interaction that imposes a +sc conformation for the phenyl ring involved. For the structures from the CSD, the +sc and ±ap conformations appear to be mainly imposed by similar C ortho - H⋯O intramolecular interactions. The large contribution of the C⋯H/H⋯C contacts (32.3%) in the two-dimensional fingerprint plots of (II) is a result of the C - H⋯π interactions. The differential scanning calorimetry (DSC) analyses exhibit peak temperatures (T m) at 109 and 81-°C for (I) and (II), respectively, which agree with the strengths of the intermolecular contacts and the melting points.

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