Morpholinium perchlorate

Mikhail S Grigoriev; Konstantin E German; Alesia Ya Maruk

doi:10.1107/S1600536807068134

. 2008 Jan 9;64(Pt 2):o390. doi: 10.1107/S1600536807068134

Morpholinium perchlorate

Mikhail S Grigoriev ^a,^*, Konstantin E German ^a, Alesia Ya Maruk ^a

PMCID: PMC2960441 PMID: 21201420

Abstract

In the title salt, C₄H₁₀NO⁺·ClO₄ ⁻, which has three independent formula units, the cations are linked into chains along [100] by N—H⋯O hydrogen bonds. Each cation acts both as a donor and as an acceptor, and every cation makes one N—H⋯O hydrogen bond with a ClO₄ ⁻ anion. The crystal studied was an inversion twin.

Related literature

See Grigoriev et al. (2007 ▶) for the structure of morpholinium tetraoxidorhenate(VII).

Experimental

Crystal data

C₄H₁₀NO⁺·ClO₄ ⁻
M _r = 187.58
Orthorhombic,
a = 8.1515 (3) Å
b = 9.5435 (4) Å
c = 28.9022 (12) Å
V = 2248.41 (16) Å³
Z = 12
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 100 (2) K
0.24 × 0.20 × 0.16 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer
Absorption correction: none
31159 measured reflections
6453 independent reflections
5928 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.062
S = 1.03
6453 reflections
323 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ▶), 2793 Friedel pairs
Flack parameter: 0.42 (3)

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a ▶); molecular graphics: SHELXTL (Sheldrick, 1997b ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068134/ng2409sup1.cif

e-64-0o390-sup1.cif^{(22.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068134/ng2409Isup2.hkl

e-64-0o390-Isup2.hkl^{(315.9KB, 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—H1C⋯O2	0.877 (9)	2.051 (13)	2.7872 (16)	141.0 (15)
N1—H1D⋯O15ⁱ	0.871 (9)	2.015 (10)	2.8642 (15)	164.7 (16)
N2—H2C⋯O14ⁱⁱ	0.884 (9)	1.980 (10)	2.8441 (14)	165.5 (16)
N2—H2D⋯O8	0.889 (9)	2.020 (11)	2.8465 (15)	154.1 (15)
N3—H3C⋯O13ⁱ	0.878 (9)	2.004 (10)	2.8690 (15)	168.0 (17)
N3—H3D⋯O9	0.870 (9)	2.039 (13)	2.7895 (17)	143.9 (16)

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

supplementary crystallographic information

Comment

The title compound, (I) (Fig. 1), contains slightly distorted tetrahedral ClO₄^- anions with Cl—O distances from 1.4353 (11) to 1.4496 (10) Å. Morpholinium cations have chair conformation.

The structure of (I) can be described as alternating cationic and anionic layers parallel to the (013) plane (Fig. 2).

Every morpholinium cation acts as proton donor in two hydrogen bonds, acceptors being O atoms of another morpholinium cation and ClO₄^- anion (Fig. 3, Table 1).

Morpholinium tetraoxidochlorate(VII) contains three independent formula units, which make two different types of zigzag chains in the [100] direction by N—H···O hydrogen bonds between cations (Fig. 3). The first type is formed by one formula unit and the second type is formed by two remaining formula units. As it is nseen in Fig. 3, two types of chains have different orientation of ClO₄^- anions.

The structure of morpholinium tetraoxidorhenate(VII) (Grigoriev et al., 2007) also contains alternating cationic and anionic layers with hydrogen bonds in perpendicular direction. But in contrast to (I), O atoms of morpholinium in (C₄H₁₀NO)[ReO₄] do not participate in hydrogen-bonding.

Experimental

Synthesis of (I) was carried out as a neutralization reaction by dissolution of stoichiometric quantity of morpholine under intensive stirring in 0.92 M water solution of HClO₄ at room temperature, followed by evaporation of the resulting solution at temperature 323 K.