Cyclo­octanaminium hydrogen succinate monohydrate

Sanaz Khorasani; Manuel A Fernandes

doi:10.1107/S1600536812011208

. 2012 Mar 28;68(Pt 4):o1204. doi: 10.1107/S1600536812011208

Cyclooctanaminium hydrogen succinate monohydrate

Sanaz Khorasani ^a, Manuel A Fernandes ^a,^*

PMCID: PMC3344141 PMID: 22606144

Abstract

In the title hydrated salt, C₈H₁₈N⁺·C₄H₅O₄ ⁻·H₂O, the cyclooctyl ring of the cation is disordered over two positions in a 0.833 (3):0.167 (3) ratio. The structure contains various O—H.·O and N—H⋯O interactions, forming a hydrogen-bonded layer of molecules perpendicular to the c axis. In each layer, the ammonium cation hydrogen bonds to two hydrogen succinate anions and one water molecule. Each hydrogen succinate anion hydrogen bonds to neighbouring anions, forming a chain of molecules along the b axis. In addition, each hydrogen succinate anion hydrogen bonds to two water molecules and the ammonium cation.

Related literature

For studies involving hydrogen-bonding interactions, see: Latimer & Rodebush (1920 ▶); Pimentel & McClellan (1960 ▶); Lemmerer (2011a ▶,b ▶). For graph-set motifs, see: Bernstein et al. (1995 ▶); Etter et al. (1990 ▶).

Experimental

Crystal data

C₈H₁₈N⁺·C₄H₅O₄ ⁻·H₂O
M _r = 263.33
Orthorhombic,
a = 8.4221 (6) Å
b = 14.3704 (9) Å
c = 23.7031 (16) Å
V = 2868.8 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.46 × 0.42 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
12354 measured reflections
3461 independent reflections
2245 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.145
S = 1.04
3461 reflections
198 parameters
30 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-NT (Bruker, 2005 ▶); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and SCHAKAL99 (Keller, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812011208/sj5211sup1.cif

e-68-o1204-sup1.cif^{(30.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812011208/sj5211Isup2.hkl

e-68-o1204-Isup2.hkl^{(166.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812011208/sj5211Isup3.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
O3—H3⋯O1ⁱ	0.84	1.72	2.5586 (18)	179
N1—H1A⋯O2ⁱⁱ	0.91	1.93	2.834 (2)	175
N1—H1B⋯O1Wⁱⁱⁱ	0.91	1.91	2.804 (2)	168
N1—H1C⋯O1	0.91	1.89	2.7866 (19)	168
N1—H1A⋯O2ⁱⁱ	0.91	1.93	2.834 (2)	175
O1W—H1WA⋯O2	0.83 (3)	1.99 (3)	2.807 (2)	167 (3)
O1W—H1WB⋯O4^iv	0.85 (3)	2.03 (3)	2.855 (2)	165 (2)

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

Acknowledgments

This work was supported by the National Research Foundation, Pretoria (NRF, GUN 77122) and the University of the Witwatersrand.

supplementary crystallographic information

Comment

Intramolecular and intermolecular hydrogen bonding is of great importance in chemical and biological systems. As a consequence it has been studied extensively since the 1920's (Latimer & Rodebush, 1920; Pimentel & McClellan, 1960) and is still an area of intense interest. In the crystal engineering field, hydrogen bonding plays an important role in organizing molecules, assembling them to create supramolecules and controlling their dimensions in one-, two- or three-dimensions. This is a requirement in order to create functional materials by design. Ammonium carboxylate salts, by having strong charge-assisted N—H..O hydrogen bonds, can be used to align molecules in desired directions, which is also useful for creating functional materials (Lemmerer, 2011a; Lemmerer, 2011b).

The title compound (Fig.1) crystallizes in Pbca and contains three independent molecules: a cyclooctanaminium cation disordered over two positions in a 0833 (3):0.167 (3) ratio, a hydrogen succinate anion, and a water molecule (Scheme 1). The crystal structure consists of a hydrogen bonded layer composed of several different hydrogen bonds between the three molecules (Fig. 2). The hydrogen succinate anions are linked via an intermolecular O3—H3···O1 hydrogen bond to form chains of molecules along the b axis described by the graph set C7 (Fig. 3) (Etter et al., 1990; Bernstein et al., 1995). All three independent molecules are linked via hydrogen bonding to form a ring described by the graph set motif R³₅(12). The three ammonium hydrogen atoms are involved in strong hydrogen bonds with the O atoms of the neighbouring succinate anions (N—H1C···O1 and N—H1A···O2) and a hydrogen bond with the water molecule (N—H1B···O1W). The water molecule act as both hydrogen acceptor (accepts the H atom from N) and donor (donates H atoms to the succinate anions) to surrounding molecules. The combination of these hydrogen bonds leads to a two-dimensional hydrogen bonded layer of molecules perpedicular to the c axis. A list hydrogen bonding interactions are given in Table 1.

Experimental

The title compound was obtained after a failed synthesis. Succinic acid [succinic anhydride having reacted with water in the reagent bottle over time (years)] was dissolved in dioxane followed by the addition of an equimolar amount of cyclooctylamine. After 6 h, thionyl chloride in dioxane was slowly added to the reaction mixture at room temperature. The mixture was then kept at 50 °C for 6 h, followed by neutralization of excess thionyl chloride by pouring the mixture into a beaker containing ice. The mixture was then filtered and the solvent removed under reduced pressure. This was then redissolved in methanol which after a few days of evaporation yielded crystals suitable for analysis by X-ray diffraction.