Bis(adamantan-1-aminium) carbonate

Nowakowska, M.; Gamble, C.; Levendis, D.C.

doi:10.1107/S1600536812011828

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1159

doi:10.1107/S1600536812011828

Open

access

Bis(adamantan-1-aminium) carbonate

Monika Nowakowska,^a Caryn Gamble ^a and Demetrius C. Levendis ^a ^*

^aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg, PO Wits 2050, South Africa
^*Correspondence e-mail: demetrius.levendis@wits.ac.za

(Received 8 March 2012; accepted 19 March 2012; online 24 March 2012)

In the title compound, 2C₁₀H₁₈N⁺·CO₃²⁻, the adamantan-1-aminium cation forms three N—H⋯O hydrogen bonds to three carbonate ions, resulting in a layer parallel to (001) with the adamantane groups located on its surface so that adjacent layers form only C—H⋯H—C contacts. The carbonate anions occupy special positions of 32 symmetry, whereas the adamantan-1-aminium cations occupy special positions of 3 symmetry.

Related literature

For related structures, see: de Vries et al. (2011 ); Mullica et al. (1999 ); He & Wen (2006 ); Liu et al. (2009 ); Zhao et al. (2003 ). For applications of adamantane–ammonium salts in virology, see: Hoffmann (1973 ); Dolin et al. (1982 ); Bright et al. (2005 ); Betakova (2007 ). For applications of amines for the capture of CO₂ from the atmosphere, see: Yang et al. (2008 ).

Experimental

Crystal data

2C₁₀H₁₈N⁺·CO₃²⁻
M_r = 364.52
Trigonal, $[P \overline 3c 1]$
a = 6.4340 (6) Å
c = 25.474 (2) Å
V = 913.25 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.30 × 0.22 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
3187 measured reflections
629 independent reflections
493 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.107
S = 1.08
629 reflections
45 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.999 (16)	1.778 (15)	2.764 (1)	168.7 (18)
Symmetry code: (i) -y+1, x-y+1, z.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus and XPREP (Bruker 2005); 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 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812011828/gk2467sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011828/gk2467Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812011828/gk2467Isup3.cml

checkCIF report

Comment top

It has been reported that 1-aminoadamantane hydrochloride (marketed as Symmetrel) is effective in the prevention and treatment of the influenza (A) virus (Hoffmann, 1973; Dolin et al., 1982; Bright et al., 2005). However recent studies suggest that the virus is becoming increasingly resistant to this anti-influenza drug (Betakova, 2007).

In an attempt to crystallize pure 1-aminoadamantane from ethanol we obtained instead adamantan-1-aminium carbonate, illustrated in Fig. 1, suggesting that the amine had captured atmospheric CO₂. We report the structure here. It is known that organic amines can trap CO₂ as the ammonium carbonate salt and this property is being explored as a way to capture carbon dioxide from the atmosphere (Yang et al., 2008).

Each carbonate ion of the title compound forms hydrogen bonds to six adamantane-ammonium ions, as shown in Fig. 2, forming a two-dimensional layer of adamantan-1-aminium carbonates parallel to (001). The hydrophobic adamantane layers interact with the neighbouring layers of adamantane-ammonium molecules via C—H···H–C contacts (see Fig. 3).

It is noted here that the structure of adamantan-1-aminium bicarbonate (Liu et al., 2009) reported in the literature is isomorphous to adamantan-1-aminium nitrate (Zhao et al., 2003). The former structure has unusually short H···H intermolecular contacts between NH₃⁺ group H atom and bicarbonate H atom of 1.50 Å In addition the geometry of the hydrogen carbonate ion is very similar to that of the nitrate ion. A re-investigation of these structures is warranted.

Related literature top

For related structures, see: de Vries et al. (2011); Mullica et al. (1999); He & Wen (2006); Liu et al. (2009); Zhao et al. (2003). For applications of adamantane–ammonium salts in virology, see: Hoffmann (1973); Dolin et al. (1982); Bright et al. (2005); Betakova (2007). For applications of amines for the capture of CO₂ from the atmosphere, see: Yang et al. (2008).

Experimental top

Crystals were grown by slow evaporation of an ethanol solution of the title compound, 0.500 g in 10 ml of ethanol, and afforded colourless plates after three days under ambient conditions. Crystals decompose, with an emission of gas bubbles (presumably CO₂), at 423–428 K.

Structure description top

For related structures, see: de Vries et al. (2011); Mullica et al. (1999); He & Wen (2006); Liu et al. (2009); Zhao et al. (2003). For applications of adamantane–ammonium salts in virology, see: Hoffmann (1973); Dolin et al. (1982); Bright et al. (2005); Betakova (2007). For applications of amines for the capture of CO₂ from the atmosphere, see: Yang et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus and XPREP (Bruker 2005); 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), Mercury (Macrae et al., 2008) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are shown at the 50% probability level. The atoms C2f to C4f are generated by the symmetry (1-y,x-y,z); C2g to C4g by (1-x+y, 1-x,z); O1a by (-y,x-y,z) and O2b by (-x+y,-x,z).
	Fig. 2. Intermolecular N—H···O hydrogen bonded (dashed lines) layers along [001] showing only the C-NH₃ and CO₃ groups for clarity.
	Fig. 3. A view down the b axis of the unit cell of the title compound showing the hydrogen bonded layers. Notice that the carbonate ions occupy sites with 32 symmetry whereas cations occupy the sites of 3 symmetry.

Bis(adamantan-1-aminium) carbonate top

Crystal data top

2C₁₀H₁₈N⁺·CO₃²⁻	D_x = 1.326 Mg m⁻³
M_r = 364.52	Mo Kα radiation, λ = 0.71069 Å
Trigonal, P3c1	Cell parameters from 819 reflections
Hall symbol: -P 3 2"c	θ = 3.2–25.8°
a = 6.4340 (6) Å	µ = 0.09 mm⁻¹
c = 25.474 (2) Å	T = 173 K
V = 913.25 (14) Å³	Prism, colourless
Z = 2	0.30 × 0.22 × 0.08 mm
F(000) = 400

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.062
Graphite monochromator	θ_max = 26.4°, θ_min = 1.6°
φ and ω scans	h = −8→5
3187 measured reflections	k = −2→8
629 independent reflections	l = −31→31
493 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0587P)² + 0.010P] where P = (F_o² + 2F_c²)/3
629 reflections	(Δ/σ)_max < 0.001
45 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

2C₁₀H₁₈N⁺·CO₃²⁻	Z = 2
M_r = 364.52	Mo Kα radiation
Trigonal, P3c1	µ = 0.09 mm⁻¹
a = 6.4340 (6) Å	T = 173 K
c = 25.474 (2) Å	0.30 × 0.22 × 0.08 mm
V = 913.25 (14) Å³

Data collection top

Bruker APEXII CCD diffractometer	493 reflections with I > 2σ(I)
3187 measured reflections	R_int = 0.062
629 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.22 e Å⁻³
629 reflections	Δρ_min = −0.18 e Å⁻³
45 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.6667	0.3333	0.16486 (9)	0.0236 (6)
C2	0.9213 (2)	0.5034 (2)	0.14518 (6)	0.0278 (4)
H2A	1.032	0.4505	0.1584	0.033*
H2B	0.977	0.6678	0.1583	0.033*
C3	0.9215 (2)	0.5033 (3)	0.08498 (6)	0.0309 (4)
H3	1.0877	0.614	0.0719	0.037*
C4	0.8365 (3)	0.2482 (3)	0.06502 (6)	0.0346 (4)
H4A	0.838	0.2474	0.0262	0.042*
H4B	0.9464	0.1932	0.0777	0.042*
C5	0	0	0.25	0.0219 (7)
N1	0.6667	0.3333	0.22372 (8)	0.0278 (5)
O1	0	0.1993 (2)	0.25	0.0343 (4)
H1	0.732 (4)	0.502 (3)	0.2358 (7)	0.060 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0198 (8)	0.0198 (8)	0.0312 (12)	0.0099 (4)	0	0
C2	0.0195 (8)	0.0205 (7)	0.0415 (9)	0.0087 (6)	−0.0018 (6)	−0.0014 (6)
C3	0.0217 (8)	0.0262 (8)	0.0404 (9)	0.0085 (6)	0.0061 (6)	0.0039 (6)
C4	0.0317 (9)	0.0350 (9)	0.0397 (8)	0.0185 (8)	0.0055 (6)	−0.0016 (7)
C5	0.0214 (10)	0.0214 (10)	0.0228 (15)	0.0107 (5)	0	0
N1	0.0253 (7)	0.0253 (7)	0.0328 (11)	0.0127 (3)	0	0
O1	0.0299 (8)	0.0221 (6)	0.0536 (10)	0.0149 (4)	−0.0091 (7)	−0.0045 (3)

Geometric parameters (Å, º) top

C1—N1	1.500 (3)	C3—C4	1.534 (2)
C1—C2	1.5295 (14)	C3—H3	1
C2—C3	1.5335 (19)	C4—H4A	0.99
C2—H2A	0.99	C4—H4B	0.99
C2—H2B	0.99	C5—O1	1.2820 (13)
C3—C4ⁱ	1.532 (2)	N1—H1	0.999 (16)

N1—C1—C2	109.13 (9)	C2—C3—C4	109.40 (12)
C2ⁱⁱ—C1—C2	109.81 (9)	C2—C3—H3	109.5
C1—C2—C3	109.18 (12)	C4—C3—H3	109.5
C1—C2—H2A	109.8	C3ⁱⁱ—C4—C3	109.57 (13)
C3—C2—H2A	109.8	C3—C4—H4A	109.8
C1—C2—H2B	109.8	C3—C4—H4B	109.8
C3—C2—H2B	109.8	H4A—C4—H4B	108.2
H2A—C2—H2B	108.3	O1ⁱⁱⁱ—C5—O1	120
C4ⁱ—C3—C2	109.29 (11)	C1—N1—H1	107.9 (11)
C4ⁱ—C3—C4	109.58 (14)

N1—C1—C2—C3	179.92 (8)	C1—C2—C3—C4	−59.84 (12)
C2ⁱⁱ—C1—C2—C3	60.34 (13)	C4ⁱ—C3—C4—C3ⁱⁱ	−59.76 (18)
C2ⁱ—C1—C2—C3	−60.50 (13)	C2—C3—C4—C3ⁱⁱ	60.04 (15)
C1—C2—C3—C4ⁱ	60.13 (13)

Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (iii) −y, x−y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^iv	0.999 (16)	1.778 (15)	2.7644 (11)	168.7 (18)

Symmetry code: (iv) −y+1, x−y+1, z.

Experimental details

Crystal data
Chemical formula	2C₁₀H₁₈N⁺·CO₃²⁻
M_r	364.52
Crystal system, space group	Trigonal, P3c1
Temperature (K)	173
a, c (Å)	6.4340 (6), 25.474 (2)
V (Å³)	913.25 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.22 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3187, 629, 493
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.107, 1.08
No. of reflections	629
No. of parameters	45
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.18

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2005), SAINT-Plus and XPREP (Bruker 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), Mercury (Macrae et al., 2008) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.999 (16)	1.778 (15)	2.7644 (11)	168.7 (18)

Symmetry code: (i) −y+1, x−y+1, z.

Acknowledgements

The University of the Witwatersrand and the Molecular Sciences Institute are acknowledged for providing the infrastructure required for this work.

References

Betakova, T. (2007). Curr. Pharm. Des. 13, 3231–3235. Web of Science CrossRef PubMed CAS Google Scholar
Bright, R. A., Medina, M. J., Xu, X. Y., Gilda, P. O., Wallis, T. R., Davis, X. H. M., Povinelli, L., Cox, N. J. & Klimov, A. I. (2005). Lancet, 366, 1175–1181. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2005). APEX2, SAINT-Plus and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolin, R., Reichman, R. C., Madore, H. P., Maynard, R., Lindon, P. M. & Weber-Jones, J. (1982). N. Engl. J. Med. 307, 580–584. CrossRef CAS PubMed Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
He, Y.-H. & Wen, Y.-H. (2006). Acta Cryst. E62, o1312–o1313. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hoffmann, C. E. (1973). Selective Inhibitors of Viral Functions, edited by W. A. Carter, p. 199. Cleveland, USA: CRC Press. Google Scholar
Liu, J.-F., Xian, H.-D., Li, H.-Q. & Zhao, G.-L. (2009). Z. Kristallogr. 224, 69–70. CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mullica, D. F., Scott, T. G., Farmer, J. M. & Kautz, J. A. (1999). J. Chem. Crystallogr. 29, 845–848. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vries, E. J. C. de, Gamble, C. & Nowakowska, M. (2011). Acta Cryst. E67, o1339. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yang, H., Xu, Z., Fan, M., Gupta, R., Bland, A. E. & Wright, I. J. (2008). Environ. Sci. 20, 14–27. CrossRef CAS Google Scholar
Zhao, G.-L., Feng, Y.-L., Hu, X.-C. & Kong, L.-K. (2003). Chin. J. Struct. Chem. 22, 321. Google Scholar