5,5,7,12,14,14-Hexamethyl-1,8-diaza-4,11-diazoniacyclotetradeca-4,11-diene dichloride trihydrate

In the title compound, C16H34N4 2+·2Cl−·3H2O, the two protonated N atoms in the macrocyclic ring of the dication are located at diagonally opposite positions. There are two intramolecular N—H⋯N hydrogen bonds in the cation. The crystal structure features O—H⋯Cl, O—H⋯O, C—H⋯Cl and N—H⋯Cl hydrogen bonds.

In the title compound, C 16 H 34 N 4 2+ Á2Cl À Á3H 2 O, the two protonated N atoms in the macrocyclic ring of the dication are located at diagonally opposite positions. There are two intramolecular N-HÁ Á ÁN hydrogen bonds in the cation. The crystal structure features O-HÁ Á ÁCl, O-HÁ Á ÁO, C-HÁ Á ÁCl and N-HÁ Á ÁCl hydrogen bonds.

Related literature
For related structures, see: Bi et al. (2008); He et al. (2010); Heeg et al. (1981); Heinlein & Tebbe (1985); Kennedy et al. (2011); Rohovec et al. (1999). For bond-length data, see: Allen et al. (1987). For the preparation, see: Curtis & Hay (1966); Curtis et al. (1975). For applications of macrocyclic compounds, see: Mittal et al. (2008); Yatsimirskii (1990 Table 1 Hydrogen-bond geometry (Å , ). Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2009 The structures of tetraazacyclotetradeca-4,11-diene macrocyclic complexes with metal such as cobalt, nickel, zinc have been extensively studied (Heeg et al., 1981;He et al., 2010;Heinlein et al., 1985). Some macrocyclic compounds and their complexes have been applied as ionophores for metal ions determination and catalyst for several reactions (Mittal et al., 2008;Yatsimirskii 1990). However, the structure of the macrocyclic salts are still less reported. So far, the macrocyclic salts with perchlorate, bromide and iodide anion have been reported (Rohovec et al., 1999;Kennedy et al., 2011;Bi et al., 2008). The unit-cell parameters for the bromide and iodide salt are similar and the two salts are indeed isostructural. The title compound (I) is similar to those salts but the presence of trihydrate water molecules caused the unit-cell parameters to be different. The unit cell of the salt consists of symmetrically generated macrocyclic dication, two chloride anions atoms and three water molecules of crystallization (Fig.1). The bond lengths are in normal ranges (Allen et al. 2003) and comparable to those in the bromide and iodide salts. There are seven intramolecular hydrogen

Refinement
All H atoms attached to C atoms were fixed geometrically and treated as riding with C-H= 0.96 Å for methyl or 0.97 Å for methylene groups with U iso (H)=1.2U eq (C) and 1.5U eq (C) for methylene and methyl groups respectively. The hydrogen atoms attached to nitrogen and oxygen atoms were located from the Fourier difference map and refined isotropiclly. The supplementary materials sup-2 Acta Cryst. (2012). E68, o1476-o1477 rotating model was applied in the refinement of the methyl hydrogen atoms.

Figure 1
The molecular structure of (I), with displacement ellipsods are drawn at the 50% probability level. The dashed line indicate intramolecular hydrogen bond. The unlabelled atoms are symmetrically generated (1-x, 1-y,-z).

Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.