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

J 2020

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

ALVIRI, Banafsheh Vahdani, Mehrdad POURAYOUBI, Abdul Ajees Abdul SALAM, Marek NEČAS, Arie VAN DER LEE et. al.

Basic information

Original name

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

Authors

ALVIRI, Banafsheh Vahdani, Mehrdad POURAYOUBI, Abdul Ajees Abdul SALAM, Marek NEČAS (203 Czech Republic, guarantor, belonging to the institution), Arie VAN DER LEE, Akshara CHITHRAN and Krishnan DAMODARAN

Edition

Acta Crystallographica Section C: Structural Chemistry, Chester, International Union of Crystallography, 2020, 2053-2296

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10406 Analytical chemistry

Country of publisher

United Kingdom of Great Britain and Northern Ireland

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 1.172

RIV identification code

RIV/00216224:14310/20:00117096

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1107/S2053229619016619

UT WoS

000506846200013

Keywords in English

amidophosphoester; conformational flexibility; Cambridge Structural Database; crystal structure; hydrogen bonding; energy framework

Abstract

V originále

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 Cortho—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 Cortho—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 (Tm) at 109 and 81 °C for (I) and (II), respectively, which agree with the strengths of the intermolecular contacts and the melting points.

Links

LM2015043, research and development project

Name: Česká infrastruktura pro integrativní strukturní biologii (Acronym: CIISB)

Investor: Ministry of Education, Youth and Sports of the CR

Citovat

ALVIRI, Banafsheh Vahdani, Mehrdad POURAYOUBI, Abdul Ajees Abdul SALAM, Marek NEČAS, Arie VAN DER LEE, Akshara CHITHRAN and Krishnan DAMODARAN. Conformational flexibility in amidophosphoesters: a CSD analysis completed with two new crystal structures of (C6H5O)2P(O)X [X = NHC7H13 and N(CH2C6H5)2]. Acta Crystallographica Section C: Structural Chemistry. Chester: International Union of Crystallography, 2020, vol. 76, No 1, p. 104-116. ISSN 2053-2296. Available from: https://dx.doi.org/10.1107/S2053229619016619.

@article{1699476,
   author = {Alviri, Banafsheh Vahdani and Pourayoubi, Mehrdad and Salam, Abdul Ajees Abdul and Nečas, Marek and van der Lee, Arie and Chithran, Akshara and Damodaran, Krishnan},
   article_location = {Chester},
   article_number = {1},
   doi = {http://dx.doi.org/10.1107/S2053229619016619},
   keywords = {amidophosphoester; conformational flexibility; Cambridge Structural Database; crystal structure; hydrogen bonding; energy framework},
   language = {eng},
   issn = {2053-2296},
   journal = {Acta Crystallographica Section C: Structural Chemistry},
   title = {Conformational flexibility in amidophosphoesters: a CSD analysis completed with two new crystal structures of (C6H5O)2P(O)X [X = NHC7H13 and N(CH2C6H5)2]},
   url = {https://doi.org/10.1107/S2053229619016619},
   volume = {76},
   year = {2020}
}

TY  - JOUR
ID  - 1699476
AU  - Alviri, Banafsheh Vahdani - Pourayoubi, Mehrdad - Salam, Abdul Ajees Abdul - Nečas, Marek - van der Lee, Arie - Chithran, Akshara - Damodaran, Krishnan
PY  - 2020
TI  - Conformational flexibility in amidophosphoesters: a CSD analysis completed with two new crystal structures of (C6H5O)2P(O)X [X = NHC7H13 and N(CH2C6H5)2]
JF  - Acta Crystallographica Section C: Structural Chemistry
VL  - 76
IS  - 1
SP  - 104-116
EP  - 104-116
PB  - International Union of Crystallography
SN  - 20532296
KW  - amidophosphoester
KW  - conformational flexibility
KW  - Cambridge Structural Database
KW  - crystal structure
KW  - hydrogen bonding
KW  - energy framework
UR  - https://doi.org/10.1107/S2053229619016619
L2  - https://doi.org/10.1107/S2053229619016619
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 Cortho—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 Cortho—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 (Tm) at 109 and 81 °C for (I) and (II), respectively, which agree with the strengths of the intermolecular contacts and the melting points.
ER  -

ALVIRI, Banafsheh Vahdani, Mehrdad POURAYOUBI, Abdul Ajees Abdul SALAM, Marek NEČAS, Arie VAN DER LEE, Akshara CHITHRAN and Krishnan DAMODARAN. Conformational flexibility in amidophosphoesters: a CSD analysis completed with two new crystal structures of (C6H5O)2P(O)X [X = NHC7H13 and N(CH2C6H5)2]. \textit{Acta Crystallographica Section C: Structural Chemistry}. Chester: International Union of Crystallography, 2020, vol.~76, No~1, p.~104-116. ISSN~2053-2296. Available from: https://dx.doi.org/10.1107/S2053229619016619.

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