The effect of environment on molecular structure: The crystalline-state stereochemistry of N-methylated adamantane 1,3-diammonium salts

Itzhak Ergaz, Rubén Alfredo Toscano, Guillermo Delgado, Avital Steinberg, Robert Glaser

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


The expected achiral C2v,-symmetry was observed by solution-state 1H and 13C NMR spectroscopic measurements performed for each of the N-methylated 1,3-diaminoadamantane diammonium salts studied. 1,3-Diaminoadamantane dihydrochloride crystallized in the orthorhombic achiral system Pna21 and at 294(2) K: a = 10.910(1) Å, b = 15.515(2) Å, c = 7.246(1) Å, V = 1226.5(3) Å3, and Z = 4. N,N,N′,N′-Tetramethyl-1,3-diaminoadamantane dihydrochloride gave monohydrate crystals in the monoclinic achiral system C2/c and at 173(2) K: a = 17.482(2) Å, b = 22.194(2) Å, c = 9.660(1) Å, β = 120.173(2)°, V = 3240.2(6) Å3, and Z = 8. N,N,N,N′,N′,N′-Hexamethyl-1,3-diaminoadamantane diiodide afforded monohydrate crystals in the orthorhombic chiral system P2 12121 and at 298(2) K: a = 9.6400(10) Å, b = 13.982(2) Å, c = 15.601(2) Å, V = 2102.8(5) Å3, and Z = 4. 5,7,N,N,N,N′,N′,N′-Octamethyl-1,3- diaminoadamantane dibromide gave dihydrate crystals belonging to the triclinic achiral system P1̄ and at 294(2) K: a = 9.154(1) Å, b = 14.825(2) Å, c = 16.722(2) Å, α = 108.774(2)°, β = 90.969(2)°, γ = 90.791(2)°, V = 2147.8(5) Å3, and Z = 4. All the diammonium dications in these crystals occupied "general positions of symmetry" within the crystal lattice, which resulted in their complete desymmetrization to C1-symmetry. Their molecular geometries still exhibited some degree of "pseudosymmetry", since the distortions were fairly small in magnitude. Continuous symmetry measures (CSM) were made to study the effect of the crystal lattice environment upon the distortion of the molecular structure. The CSM showed that the crystalline diammonium salts were either predominantly C2 pseudosymmetric if the N-methylated ammonium units were skewed in the same directions, or predominantly Cs pseudosymmetric (σ) if these units were twisted in opposite directions. In the crystalline compounds studied in this series, there were no examples with predominantly pseudomirror symmetry via a σ-plane encompassing both nitrogen atoms, since this would have required a chemical (structural) constraint in favor a staggered arrangement for the C-N+-C-C-C-N+-C fragment that was not obligated by the local site asymmetric environments in the various crystals. The values of S(total), the total CSM distortion from solution-state ideal C 2v,-symmetry exhibited by the general positioned dication moieties, were augmented with increasing N-methylation, while the relationships between the two external periphery subunits [R1R2R3N(1) and N(2)R1R2R3] became more distorted than those of the adamantane Q10 core fragments.

Original languageEnglish
Pages (from-to)1399-1405
Number of pages7
JournalCrystal Growth and Design
Issue number4
StatePublished - 1 Apr 2008

ASJC Scopus subject areas

  • Chemistry (all)
  • Materials Science (all)
  • Condensed Matter Physics


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