Morpholinium hydrogen chloranilate methanol monosolvate

Kazuma Gotoh; Yuki Tahara; Hiroyuki Ishida

doi:10.1107/S1600536811047891

. 2011 Nov 16;67(Pt 12):o3335. doi: 10.1107/S1600536811047891

Morpholinium hydrogen chloranilate methanol monosolvate

Kazuma Gotoh ^a, Yuki Tahara ^a, Hiroyuki Ishida ^a,^*

PMCID: PMC3238982 PMID: 22199831

Abstract

In the crystal structure of the title compound, C₄H₁₀NO⁺·C₆HCl₂O₄ ⁻·CH₄O, the components are held together by bifurcated O—H⋯(O,O), O—H⋯(O,Cl) and N—H⋯(O,O) hydrogen bonds into a centrosymmetric 2+2+2 aggregate. The aggregates are further connected by another bifurcated N—H⋯(O, O) hydrogen bond, forming a double-tape structure along the b axis. A weak C—H⋯O interaction is observed between the tapes.

Related literature

For a related structure, see: Ishida & Kashino (1999 ▶). For ³⁵Cl nuclear quadrupole resonance studies on proton-transfer in chloranilic acid–organic base systems, see: Ikeda et al. (2005 ▶); Asaji, Hoshino et al. (2010 ▶); Asaji, Seliger et al. (2010 ▶).

Experimental

Crystal data

C₄H₁₀NO⁺·C₆HCl₂O₄ ⁻·CH₄O
M _r = 328.15
Triclinic,
a = 9.11845 (17) Å
b = 9.39881 (17) Å
c = 9.96935 (18) Å
α = 107.8089 (7)°
β = 107.5510 (7)°
γ = 110.2398 (7)°
V = 679.25 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 170 K
0.45 × 0.41 × 0.30 mm

Data collection

Rigaku R-AXIS RAPID II diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.817, T _max = 0.860
17817 measured reflections
3928 independent reflections
3636 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.077
S = 1.08
3928 reflections
197 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); 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: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S1600536811047891/lh5377sup1.cif

e-67-o3335-sup1.cif^{(23KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047891/lh5377Isup2.hkl

e-67-o3335-Isup2.hkl^{(192.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811047891/lh5377Isup3.cml

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⋯O3	0.878 (18)	2.391 (18)	3.0069 (12)	127.5 (16)
N1—H1A⋯O3ⁱ	0.878 (18)	2.180 (19)	2.9255 (13)	142.5 (16)
N1—H1B⋯O1ⁱⁱ	0.852 (19)	2.170 (19)	2.9207 (14)	146.9 (17)
N1—H1B⋯O4ⁱⁱ	0.852 (19)	2.233 (19)	2.9277 (14)	138.7 (16)
O2—H2⋯O3	0.82 (2)	2.26 (2)	2.6605 (12)	110.6 (16)
O2—H2⋯O6	0.82 (2)	1.79 (2)	2.5564 (13)	153.4 (19)
O6—H6⋯Cl2ⁱ	0.742 (19)	2.761 (19)	3.3342 (9)	136.0 (18)
O6—H6⋯O3ⁱ	0.742 (19)	2.119 (19)	2.7812 (12)	149 (2)
C8—H8A⋯O2ⁱⁱⁱ	0.99	2.51	3.4115 (15)	152

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

Acknowledgments

This work was supported by a Grant-in-Aid for Scientific Research (C) (No. 22550013) from the Japan Society for the Promotion of Science.

supplementary crystallographic information

Comment

The title compound was accidentally obtained in the preparation of morpholinium hydrogen chloranilate (Ishida & Kashino, 1999), C₄H₁₀NO⁺.C₆HCl₂O₄^-, which is an interesting model compound for investigating proton transfer in the hydrogen bond systems (Ikeda et al., 2005; Asaji, Hoshino et al., 2010; Asaji, Seliger et al., 2010).

In the title compound, the three components (Fig. 1) are held together by bifurcated O—H···(O, O), O—H···(O, Cl) and N—H···(O, O) hydrogen bonds [O2—H2···(O3, O6), O6—H6···(O3ⁱ, Cl2ⁱ) and N1—H1A···(O3, O3ⁱ); symmetry code in Table 1] into a centrosymmetric 2 + 2+2 aggregate (Fig. 2). The aggregates are connected by another N—H···(O, O) hydrogen bond between the cation and the anion [N1—H1B···(O1ⁱⁱ, O4ⁱⁱ), symmetry code in Table 1], forming a double-tape structure along the b axis (Fig. 3). The tapes are further linked a weak C—H···O interaction, forming a three-dimensional network.

Experimental

Single crystals were obtained by slow evaporation from a methanol solution (50 ml) of chloranilic acid (0.102 g) and morpholine (0.044 g) at room temperature.