Crystal structure of di­cyclo­hexyl­ammonium nitrate(V)

Tomasz Rojek; Ewa Matczak-Jon

doi:10.1107/S2056989015019386

. 2015 Oct 24;71(Pt 11):o878–o879. doi: 10.1107/S2056989015019386

Crystal structure of dicyclohexylammonium nitrate(V)

Tomasz Rojek ^a, Ewa Matczak-Jon ^a,^*

PMCID: PMC4645052 PMID: 26594576

Abstract

In the title molecular salt, C₁₂H₂₄N⁺·NO₃ ⁻, the cyclohexyl rings adopt chair conformations with the exocyclic C—N bonds in equatorial orientations. In the crystal, a bifurcated N—H⋯(O,O) hydrogen bond links the cation to the anion; the ion pairs are linked via C—H⋯O hydrogen bonds, forming layers in the ac plane.

Keywords: crystal structure, dicyclohexylammonium salts, nitrate(V) salts, hydrogen bonding

Related literature

For the crystal structure of dicyclohexylammonium nitrate(III), see: Golobič et al. (1999 ▸). For other crystal structures of dicyclohexylammonium salts, see: Ng (1995 ▸); Bi et al. (2002 ▸); Lo & Ng (2008 ▸); Khawar Rauf et al. (2008 ▸); Selvakumaran et al. (2011 ▸); Ndoye et al. (2014 ▸). For crystal structures of carboxylate salts with the dicyclohexylammonium cation belonging to the low molecular weight gelators (LMWGs) class of compounds and exhibiting gelling properties, see: Trivedi et al. (2004 ▸, 2005 ▸); Sahoo & Dastidar (2012 ▸); Rojek et al. (2015 ▸).

Experimental

Crystal data

C₁₂H₂₄N⁺·NO₃ ⁻
M _r = 244.33
Orthorhombic,
a = 8.436 (2) Å
b = 18.682 (5) Å
c = 8.427 (3) Å
V = 1328.1 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.45 × 0.41 × 0.36 mm

Data collection

Kuma KM-4 difractometer with a CCD camera diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▸) T _min = 0.962, T _max = 0.969
9001 measured reflections
1759 independent reflections
1699 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.089
S = 1.09
1759 reflections
162 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: DIAMOND (Brandenburg, 1999 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015019386/su5222sup1.cif

e-71-0o878-sup1.cif^{(18.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015019386/su5222Isup2.hkl

e-71-0o878-Isup2.hkl^{(86.7KB, hkl)}

Supporting information file. DOI: 10.1107/S2056989015019386/su5222Isup3.txt

e-71-0o878-Isup3.txt^{(337.1KB, txt)}

Click here for additional data file.^{(5.5KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015019386/su5222Isup4.cml

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015019386/su5222fig1.tif

The asymmetric unit of the title molecular salt, showing the atom-numbering scheme and the symmetry-independent hydrogen bonds (orange and light-blue dashed lines; see Table 1). Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.6MB, tif)}

b ac . DOI: 10.1107/S2056989015019386/su5222fig2.tif

A view along the b axis of the crystal packing of the title molecular salt, showing the hydrogen-bonded chains assembled into a layer in the ac plane. Hydrogen bonds are drawn as yellow and light-blue dashed lines (see Table 1). H atoms on C atoms of the cyclohexane rings not involved in hydrogen bonds have been omitted for clarity.

CCDC reference: 1431025

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1NO2	0.91(2)	2.56(2)	3.292(2)	138.2(17)
N1H1NO3	0.91(2)	2.01(2)	2.8988(19)	166.7(19)
N1H2NO2ⁱ	0.86(2)	1.98(2)	2.799(2)	157.6(19)
C11H11O1ⁱⁱ	1.00	2.45	3.347(2)	149
C12H12O3ⁱⁱⁱ	1.00	2.52	3.456(3)	156
C22H22BO2	0.99	2.53	3.309(2)	136
C62H62AO1ⁱⁱ	0.99	2.59	3.506(2)	153

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

Financial support by a statutory activity subsidy from the Polish Ministry of Science and Higher Education for the Department of Chemistry of Wrocław University of Technology is gratefully acknowledged.

supplementary crystallographic information

S1. Comment

The dicyclohexylammonium cation has been widely used in the preparation of crystalline salts like chloride (Ng, 1995), nitrate(III) (Golobič et al., 1999), tungstate (Bi et al., 2002), bromide (Lo & Ng, 2008), thiocyanate (Khawar Rauf et al., 2008; Selvakumaran et al., 2011) or sulfate(VI) (Ndoye et al., 2014) salts. In recent years, there has been increased interest in dicyclohexylammonium carboxylate salts due to their potential applications as materials capable of immobilizing organic solvents to form gels, known as low molecular weight gelators - LMWGs (Trivedi et al., 2004, 2005; Sahoo & Dastidar, 2012; Rojek et al., 2015).

The title molecular salt, Fig. 1, consists of an ion pair comprising a dicyclohexylammonium cation connected to a nitrate(V) anion by N1—H1N···O3 and N1—H1N···O2 hydrogen bonds (Table 1). Additionally, the ion pair is stabilized by a C22—H22B···O2 interaction (Fig. 1 and Table 1). The N2—O2 and N2—O3 bond lengths of the nitrate(V) anion are almost equal [1.258 (2) and 1.255 (2) Å, respectively] and longer than the N2—O1 bond length [1.2353 (18) Å]. The C11—N1—C12 angle in the dicyclohexylammonium cation [117.34 (12)°] is larger than expected for a tetrahedral N atom. This is attributed to the steric hindrance imposed by the cyclohexane rings, each of which adopt a chair conformation. The N1—C11 and N1—C12 bond lengths [1.5077 (19) and 1.510 (2) Å, respectively] are similar to those observed for other dicyclohexylammonium salts (Golobič et al., 1999).

In the crystal, the N1—H2N···O2ⁱ hydrogen bonds combine ion pairs into infinite chains parallel to the c axis. The chains are additionally stabilized by C12—H12···O3ⁱⁱⁱ contacts and further packed in a parallel fashion by means of C62—H62A···O1ⁱⁱ and C11—H11···O1ⁱⁱ (symmetry codes as in Table 1) interactions giving rise to layers in the ac plane (Fig. 2).

S2. Synthesis and crystallization

Dicyclohexylamine (1 mmol, 201 ml) was added to methanol (4 ml) under vigorous stirring. The clear solution was combined with nitric(V) acid (1 M, 1 ml) and stirred for 20 min. The resulting solution was left to crystallize at room temperature. After one week, large block-shaped colourless single crystals of the title salt suitable for X-ray diffraction analysis were obtained.

S3. Refinement

The N-bound H atoms were located in a difference Fourier map and freely refined. The C-bound H atoms were positioned geometrically and refined using a riding model; C—H = 0.99 Å with U_iso(H) = 1.2U_eq(C).