Tetra­ethyl­ammonium bicarbonate trihydrate

Heping Li; Yimin Hou; Yunxia Yang

doi:10.1107/S1600536811026080

. 2011 Jul 9;67(Pt 8):o1991. doi: 10.1107/S1600536811026080

Tetraethylammonium bicarbonate trihydrate

Heping Li ^a, Yimin Hou ^a, Yunxia Yang ^b,^*

PMCID: PMC3213447 PMID: 22091026

Abstract

In the title compound, C₈H₂₀N⁺·CHO₃ ⁻·3H₂O, the bicarbonate anion, which has a small mean deviation from the plane of 0.0014 Å, fully utilises its three O and one H atom to form various O—H⋯O hydrogen bonds with the three water molecules in the asymmetric unit, generating a hydrogen-bonded layer, which extends along (10 Inline graphic ). The tetraethylammonium cations, as the guest species, are accommodated between every two neighboring layers, constructing a sandwich-like structure with an interlayer distance of 7.28 Å.

Related literature

For the crystal structure of tetraethylammonium bicarbonate monohydrate clathrate, see: Li et al. (2003 ▶). For O—H⋯O hydrogen bonds, see: Steiner (2002 ▶). For polymorphism see Kumar et al. (2002 ▶).

Experimental

Crystal data

C₈H₂₀N⁺·CHO₃ ⁻·3H₂O
M _r = 245.32
Monoclinic,
a = 7.6633 (1) Å
b = 12.9627 (3) Å
c = 14.2683 (3) Å
β = 99.932 (1)°
V = 1396.13 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.61 × 0.29 × 0.18 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.854, T _max = 1.000
8465 measured reflections
3480 independent reflections
2466 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.138
S = 1.02
3480 reflections
166 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811026080/nr2008sup1.cif

e-67-o1991-sup1.cif^{(16.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811026080/nr2008Isup2.hkl

e-67-o1991-Isup2.hkl^{(170.7KB, 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
O1W—H1WA⋯O2ⁱ	0.83 (1)	2.00 (1)	2.8239 (16)	177 (2)
O1W—H1WB⋯O3Wⁱⁱ	0.82 (1)	2.05 (1)	2.8666 (19)	173 (2)
O2W—H2WA⋯O1	0.83 (1)	1.97 (1)	2.7980 (15)	172 (2)
O2W—H2WB⋯O1Wⁱⁱⁱ	0.82 (1)	2.01 (1)	2.8229 (16)	171 (2)
O3—H3⋯O1^iv	0.83 (1)	1.85 (1)	2.6676 (15)	172 (2)
O3W—H3WA⋯O2	0.83 (1)	2.06 (1)	2.8422 (18)	157 (2)
O3W—H3WB⋯O2W	0.81 (1)	2.07 (2)	2.8099 (19)	152 (3)

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

Acknowledgments

We thank Northwest Normal University for supporting this study.

supplementary crystallographic information

Comment

Polymorphism is the existence of the same chemical substance in at least two different crystalline arrangements of molecules (Kumar et al. 2002). It is helpful to understand polymorphism to explore different crystal structures which are not qualified polymorphs but are also constructed with the same components. In 2003, the crystal structure of tetraethylammonium bicarbonate monohydrate clathrate (C₈H₂₀N⁺.CHO₃^-.H₂O, 1) has been reported (Li et al. 2003). Here we reported the crystal structure of tetraethylammonium bicarbonate trihydrate clathrate (C₈H₂₀N⁺.CHO₃^-.3H₂O, 2), in which the same components were used to obtain the crystal but the difference of the amount of water molecules in the asymmetric unit results in the final different packing model compared with compound 1. In addition, it should be noted that, in our experiment, 4,4'-oxybis(benzoic acid) was used to be the host molecule to obtain the acid-base inclusion compound, but after the data collection and determination, it was found that bicarbonate anion, which was finally determined according to the corresponding C—O bond lengths and O—C—O angles existed in the similar crystal structure of compound 1, take the place of the acid to interact with the related base to generate compound 2. In compound 1, one bicarbonate anion and one water molecule interacting with each other through O—H···O hydrogen bonds constitute a zigzag ribbon and are arranged in un-closed channels generated from tetraethylammonium cations. Comparatively, one bicarbonate anion and three water molecules in compound 2 form more O—H···O hydrogen bonds to construct the hydrogen-bonded layer and tetraethylammonium cations are contained between the layers to display the typical sandwich-like structure. Obviously, the amount of water molecules has significant effect on constructing different crystal structure between compound 1 and2. Noticeably, in compound 2, the strongest O—H···O hydrogen bond is between the centro-symmetric related bicarbonate anions (the distance of O···O is 2.6654 (16) Å) and other weaker O—H···O contacts involve the participation of water molecules (the corresponding values are from 2.7991 (16) Å to 2.868 (2) Å), which can be compared with the related O···O intervals of compound 1 (O···O distances are 2.619 Å and 2.868 Å) and the corresponding values (2.68 Å ~ 3.11 Å) of the reference (Steiner, 2002).

Experimental

4,4'-Oxybis(benzoic acid) (0.25 mmol, 0.065 g) was dissolved in a water-ethanol (50 ml/100 ml v/v) mixture. Tetraethylammonium hydroxide (25% aqueous solution) was added to neutralize the acid. The mixture was stirred for about 2 h and set aside to crystallize. Unexpectedly, the crystals involved 4,4'-oxybis(benzoic acid) were not obtained. Instead, colorless block crystals of the title compound were separated after several weeks.