Structural Chemistry

, Volume 28, Issue 6, pp 1607–1622 | Cite as

Charge density studies of an inorganic-organic hybrid p-phenylenediammonium tetrachlorocuprate

  • Roman Gajda
  • Krzysztof Woźniak
Original Research


High quality single crystals of an inorganic-organic hybrid, p-phenylenediammonium tetrachlorocuprate (pPDA:CuCl 4 ), suitable for high-resolution X-ray data collection, have been crystallized. pPDA:CuCl 4 crystallizes at special positions in the P21/c space group of the monoclinic crystal system with only halves of the moieties in the asymmetric part of the unit cell. This compound forms a hybrid structure consisting of separate inorganic anion and organic cation layers linked by weak N-H∙∙∙Cl hydrogen bonds. The Cu atoms are located at the centers of symmetry and each of them is surrounded by six chlorine atoms thus forming a tetragonal bipyramid. Two pairs of the chlorine atoms form short Cu-Cl bonds (2.27964(4) and 2.29765(4) Å), whereas the third pair forms the longest Cu-Cl bond (2.90452(4) Å). Experimental and theoretical electron density distributions have been established. There is an excellent agreement between theoretical and experimental properties at bond critical points. The total charge of the organic cation is equal to +1.64 \( \overset{-}{\boldsymbol{e}} \) and is neutralized by the charge of the inorganic anion. The orbital population analysis of the copper 3d electrons and analysis of geometry of the tetrachlorocuprate have been performed and they clearly show presence of the Jahn-Teller effect. Comparison of some experimentally derived parameters such as area and linear density distribution with those calculated on the base of relations derived from literature shows that a longer series of experimental charge density investigations of the hybrid structures should be measured. It should allow for obtaining more reliable relations among different parameters for the hybrid structures with a strong predictive power of such relations. Analysis of residuals of measured intensities of reflections and those resulting from the refined model shows a serious underestimation of esds of measured reflections used in the refinement.


Experimental electron density Theoretical electron density Topological analysis Hybrid compound 



The authors acknowledge a financial support from the Polish National Science Centre (NCN) grant N N204 135138. The study was carried out at the Biological and Chemical Research Centre, University of Warsaw, established within the project co-financed by European Union from the European Regional Development Fund under the Operational Program Innovative Economy 2007–2013. Authors are also grateful for the CPU time in the Wrocław Center of Networking and Supercomputing (, where theoretical calculations were carried out, Grant No. 115.

Compliance with ethical standards

Ethical statement

All ethical guidelines have been adhered.

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11224_2017_969_MOESM1_ESM.docx (1.1 mb)
ESM 1 (DOCX 1129 kb)


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© Springer Science+Business Media New York 2017

Authors and Affiliations

  1. 1.Biological and Chemical Research Centre, Department of ChemistryUniversity of WarsawWarszawaPoland

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