2-[(Adamantan-1-yl)amino­meth­yl]-4-chloro­phenol hemihydrate

Xu-Dong Jin; Xue-Yue Yin; Lu-Sha Xu; Chun-Hua Ge; Xiao-Hong Chang

doi:10.1107/S1600536812045175

. 2012 Nov 7;68(Pt 12):o3296. doi: 10.1107/S1600536812045175

2-[(Adamantan-1-yl)aminomethyl]-4-chlorophenol hemihydrate

Xu-Dong Jin ^a,^*, Xue-Yue Yin ^a, Lu-Sha Xu ^a, Chun-Hua Ge ^a, Xiao-Hong Chang ^a

PMCID: PMC3588840 PMID: 23468805

Abstract

In the title compound, C₁₇H₂₂ClNO·0.5H₂O, the water molecule O atom resides on a twofold rotation axis. In the organic molecule, the phenol group forms an intramolecular O—H⋯N hydrogen bond. In the crystal, pairs of organic molecules are hydrogen bonded through bridging solvent water molecules, forming chains along the b-axis direction.

Related literature

For the synthesis and crystal structure of 2-[(adamantan-1-ylamino)methyl]phenol, see: Wang & Tao (2012 ▶). For the synthesis and applications of amantadine derivatives, see: Camps et al. (2008 ▶). graphic file with name e-68-o3296-scheme1.jpg

Experimental

Crystal data

C₁₇H₂₂ClNO·0.5H₂O
M _r = 300.82
Monoclinic,
a = 25.469 (16) Å
b = 6.365 (4) Å
c = 18.306 (11) Å
β = 91.815 (12)°
V = 2966 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 296 K
0.35 × 0.30 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.915, T _max = 0.960
6372 measured reflections
2606 independent reflections
1798 reflections with I > 2σ(I)
R _int = 0.098

Refinement

R[F ² > 2σ(F ²)] = 0.069
wR(F ²) = 0.216
S = 1.08
2606 reflections
198 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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.

Supplementary Material

Click here for additional data file.^{(19.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812045175/ld2073sup1.cif

e-68-o3296-sup1.cif^{(19.7KB, cif)}

Click here for additional data file.^{(128.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812045175/ld2073Isup2.hkl

e-68-o3296-Isup2.hkl^{(128.1KB, hkl)}

Click here for additional data file.^{(6.3KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812045175/ld2073Isup3.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
O1—H1⋯N1	0.83 (6)	2.07 (9)	2.611 (5)	122 (7)
O1W—H1W⋯O1ⁱ	0.84 (4)	1.99 (4)	2.768 (5)	153 (5)
N1—H1A⋯O1W	0.90 (4)	2.20 (4)	3.012 (5)	150 (4)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported financially by the Foundation of Liaoning Educational Department (No. 2008T073&LT2012001), the Science and Technology Foundation of Liaoning Province (No. 20071027), the Liaoning University Foundation of 211 Project for Innovative Talents Training and the Technology Major Projects Research Foundation (No. 2011ZX09102–007–02), China.

supplementary crystallographic information

Comment

Amantadine and its derivatives attract interest because of their biological activity and many potential applications (Camps et al., 2008). As an extension of our previous work on the compounds containing an adamantane group, we synthesized the title compound by reduction of the corresponding Schiff base. It crystallizes with solvent water. Asymmetric unit contains one molecule of the title compound and one half of solvent water (Fig. 1). In the organic molecule, all bond lengths and angles are normal and comparable with another reported compound, N-(2-Hydroxybenzyl)adamantan-1-amine (Wang et al., 2012). The hydroxyl O atom is involved in hydrogen bond (Table 1) with amino N atom with the OH···N distance of 2.611 (5) Å. This intra-molecular hydrogen bond formally results in a chiral center at the nitrogen atom, but the centrosymmetric crystal represents a racemate. The intramolecular hydrogen bond forms a R²₁(6) ring which stabilizes the molecular conformation (Table 1). In the crystal, the couples of organic molecules are alternated with crystallization water molecules along b axis forming intermolecular O(W)—H···O and N—H···O(W) hydrogen bonds (Fig. 2).

Experimental

Amantadine hydrochloride (0.376 g, 2.0 mmol) and KOH (0.112 g, 2.0 mmol) were stirred in 10 ml of anhydrous alcohol for 2 h. The produced white precipitate was filtered out and the transparent filtrate was added dropwise to 5-chloro-2-hydroxybenzaldehyde (0.312 g, 2.0 mmol) in 10 ml of anhydrous alcohol under constant stirring. The resulting solution was refluxed for ca. 3 h, concentrated to about 5 ml through reduced pressure distillation and then left at room temperature. A yellow Schiff base precipitate was obtained after one week under slow solvent evaporation.

NaBH₄ (0.303 g, 8 mmol) was added into solution of the Schiff base (0.580 g, 2 mmol) in anhydrous methanol (10 ml). After 1 h stirring, a light-yellow solid, 4-chloro-2-((adamantan-1-ylamino)methyl)phenol was filtered and dried. A crystal of the title compound suitable for X-ray analysis has developed from a solution in H₂O/EtOH mixture (1:2 v/v) after 5 days of slow solvent evaporation.