2,6-Diethyl­anilinium perchlorate

Wajda Smirani Sta; Mohamed Rzaigui; Salem S Al-Deyab

doi:10.1107/S1600536810004654

. 2010 Feb 13;66(Pt 3):o614. doi: 10.1107/S1600536810004654

2,6-Diethylanilinium perchlorate

Wajda Smirani Sta ^a,^*, Mohamed Rzaigui ^a,^b, Salem S Al-Deyab ^b

PMCID: PMC2983530 PMID: 21580372

Abstract

The asymmetric unit of the title molecular salt, C₁₀H₁₆N⁺·ClO₄ ⁻, contains two cations and two anions. The atoms of one of the ethyl side chains of one of the cations are disordered over two sets of sites in a 0.531 (13):0.469 (13) ratio. In the crystal, the components are linked by N—H⋯O and bifurcated N—H⋯(O,O) hydrogen bonds and weaker C—H⋯O interactions, such that the organic cations alternate with the perchlorate anions, forming ribbons in the a-axis direction.

Related literature

For background to the physical properties and potential applications of molecular salts, see: Czarnecki et al. (1994 ▶); Mylrajan & Srinivasan (1991 ▶); Toumi Akriche et al. (2010 ▶); Xiao et al. (2005 ▶). For the graph-set notation of hydrogen-bond networks, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₀H₁₆N⁺·ClO₄ ⁻
M _r = 249.69
Monoclinic,
a = 15.105 (3) Å
b = 21.192 (5) Å
c = 7.718 (6) Å
β = 98.10 (3)°
V = 2446 (2) Å³
Z = 8
Ag Kα radiation
λ = 0.56085 Å
μ = 0.17 mm⁻¹
T = 293 K
0.50 × 0.40 × 0.20 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
15750 measured reflections
11941 independent reflections
2954 reflections with I > 2σ(I)
R _int = 0.052
2 standard reflections every 120 min intensity decay: 5%

Refinement

R[F ² > 2σ(F ²)] = 0.089
wR(F ²) = 0.278
S = 0.91
11941 reflections
304 parameters
H-atom parameters not refined
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810004654/hb5332sup1.cif

e-66-0o614-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004654/hb5332Isup2.hkl

e-66-0o614-Isup2.hkl^{(572.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O6	0.89	2.41	3.029 (4)	127
N1—H1B⋯O4	0.89	2.27	3.043 (5)	146
N1—H1B⋯O2ⁱ	0.89	2.48	2.889 (4)	109
N1—H1C⋯O3ⁱⁱ	0.89	2.10	2.935 (4)	157
N1—H1C⋯O2ⁱ	0.89	2.58	2.889 (4)	101
N2—H2A⋯O1	0.89	2.17	2.971 (4)	149
N2—H2B⋯O5	0.89	2.39	2.875 (4)	114
N2—H2B⋯O7ⁱⁱⁱ	0.89	2.24	2.991 (4)	141
N2—H2C⋯O7^iv	0.89	2.03	2.805 (3)	144
C3—H3⋯O3^v	0.93	2.60	3.321 (5)	134
C13—H13⋯O8^vi	0.93	2.49	3.418 (6)	172

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

supplementary crystallographic information

Comment

A special attention is focused on the synthesis of hybrid class of inorganic-organic materials because of their interesting architectures and wide variety of physical properties. Organic substructure of these compounds is usually responsible for their molecular hyperpolarizability, electric permittivity and spontaneous polarization. The inorganic part determines thermal and mechanical stability of the crystals. The combination of these various features attributed to both organic and inorganic substructures may lead to interesting materials (Xiao et al., 2005). In particular, the association of the perchlorate anions to organic molecules could lead to materials having phase transitions, non-symmetric structures, characteristic H-bonds (Czarnecki et al., 1994; Mylrajan & Srinivasan, 1991). Among the crystals comprising perchlorate anions, the most interesting are non-centrosymmetric, due to non linear optical(ONL) properties. A pronounced second harmonic generation was found in L-leucinium perchlorate (SHG efficiency d eff= 0.44 x d eff KDP). In this paper, we report single-crystal X-ray study of 2,6-diethylanilinium perchlorate (I). Crystal structure of this latter is depicted in the figure 1. The asymmetric unit, built of two 2,6-diethylanilinium cations and two perchlorate anions, has the geometrical configuration shown in the figure 2. These four components establish between them H-bonds to form a tetra-membered ring. This ring form two slightly corrugated ribbons parallel to the a direction at y = 1/4 and 3/4. Each ribbon is built of an alternance of both inorganic and organic entities.

The first Cl(1)O₄^- is surrounded by three N(1)H₃⁺cations, to build a ribbon extended in the a direction, and generating R₂⁴(8) graph-set motifs.Whereas the second Cl(2)O₄^-, surrounded by two N(2)H₃⁺cations, leads to R₂⁴(10) graph-set motifs which form another ribbon extended in the same direction. Both parallel ribbons are attached together by N—H···O hydrogen bonds. The organic molecules are anchored on these ribbons so that to leave spacious channels (13.9 Å x 3.3 Å) parallel to the a axis. The Cl—O distances indicate rather slight distortion of the two perchlorate anions from the tetrahedral symmetry. The shortest Cl—O bond equals to 1.384 (3) Å, whereas the longest one to 1.444 (3) Å, the angles vary from 105.6 (2)° to 111.2 (2)° that are standard values for perchlorate ions (Toumi Akriche, S. et al. 2010). In this organisation, the components display different interactions (electrostatic, H-bonds, Van derWalls) to keep the three-dimensional network stability.

Experimental

An ethalonic 2,6-diethylaniline solution (5 mmol, in 5 ml) was added to an aqueous perchloric acid solution (0.5 M, 10 ml) at room temperature (293 K). Slow evaporation of the obtained mixture led to the formation of small crystals of the title compound. These were recrystallised from a mixture of water / ethanol (80% / 20%) to yield colourless blocks of (I).