3-Aza­bicyclo­[3.3.1]nonane-2,4-dione–acetic acid (1/1)

Hulme, A.T.; Johnston, A.; Florence, A.J.; Tocher, D.A.

doi:10.1107/S1600536806000602

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 2| February 2006| Pages o545-o547

https://doi.org/10.1107/S1600536806000602

3-Azabicyclo[3.3.1]nonane-2,4-dione–acetic acid (1/1)

Ashley T. Hulme,^a ^* Andrea Johnston,^b Alastair J. Florence ^b and Derek A. Tocher ^a

^aChristopher Ingold Laboratory, Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, England, and ^bStrathclyde Institute for Biomedical Science, 27 Taylor Street, University of Strathclyde, Glasgow G4 0NR, Scotland
^*Correspondence e-mail: a.hulme@ucl.ac.uk

(Received 23 December 2005; accepted 5 January 2006; online 11 January 2006)

3-Azabicyclo[3.3.1]nonane-2,4-dione (cyclohexane-1,3-dicarboximide, C₈H₁₁NO₂) forms a 1:1 solvate with acetic acid (C₂H₄O₂). The crystal structure comprises hydrogen-bonded chains containing alternating cyclohexane-1,3-dicarboximide and acetic acid molecules.

Comment

The title solvate, (I), was first produced during an automated parallel crystallization screen on cyclohexane-1,3-dicarboximide. It was identified as a new crystal structure, different from the known unsolvated form (Howie & Skakle, 2001 ), by examination of its powder diffraction pattern, collected on a multi-sample X-ray powder diffractometer (Florence et al., 2003 ). It was crystallized by crash cooling a subsaturated solution in glacial acetic acid from 383 to 288 K, and gave crystals of suitable size and quality for single-crystal X-ray diffraction.

The asymmetric unit of (I) contains one molecule of cyclohexane-1,3-dicarboximide and one molecule of acetic acid (Fig. 1). The structure exhibits a chain hydrogen-bonding motif [graph set C₂²(8)], with cyclohexane-1,3-dicarboximide and acetic acid molecules alternating in the chain. The pair of hydrogen bonds (Table 1) to the acetic acid carboxyl group is in an anti configuration and only one of the carbonyl O atoms in the cyclohexane-1,3-dicarboximide molecule is used in the hydrogen bonding forming the chain (Fig. 2). There are no hydrogen bonds between different chains, but the chains stack upon one another, forming a column parallel to [001]. The alkyl substituents of the cyclohexane-1,3-dicarboximide molecules lie to the sides of the column, with the hydrogen-bonding substituents comprising the middle of the column (Fig. 3). Adjacent chains in the column have the cyclohexane-1,3-dicarboximide alkyl groups on alternating sides of the column.

The chain motif in this structure is closely related to the chain motif observed in both the anhydrous form of cyclohexane-1,3-dicarboximide and in the crystal structure of acetic acid. Fig. 4 shows overlays of the chain motif of (I) with the chain from the unsolvated cyclohexane-1,3-dicarboximide structure (Howie & Skakle, 2001) and with the chain from the orthorhombic form of acetic acid (Boese et al., 1999 ). From these overlays it can be seen that the basic hydrogen-bonded backbone is the same in each of these structures.

Figure 1
A view of the asymmetric unit of (I)

. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as spheres. The dashed line indicates an N—H⋯O hydrogen bond.

Figure 2
View perpendicular to the bc plane, showing the chain hydrogen-bonding motif present in (I)

. Dotted blue lines indicate hydrogen bonds.

Figure 3
View perpendicular to the ac plane, showing the stacking of hydrogen-bonded chains.

Figure 4
(a) Overlay of the chain present in (I)

(normal colours) with the chain from unsolvated cyclohexane-1,3-dicarboxylic acid (blue). Dotted lines indicate hydrogen bonds; (b) overlay of the chain present in (I)

with the chain from acetic acid (blue).

Experimental

3-Azabicyclo[3.3.1]nonane-2,4-dione (100 mg) was dissolved in glacial acetic acid (2 ml) at 383 K and crash cooled to 288 K to obtain single crystals of (I).

Crystal data

C₈H₁₁NO₂·C₂H₄O₂
M_r = 213.23
Triclinic, $[P \overline 1]$
a = 6.6224 (7) Å
b = 7.3580 (8) Å
c = 10.7995 (12) Å
α = 103.598 (2)°
β = 93.378 (2)°
γ = 97.272 (2)°
V = 505.22 (10) Å³
Z = 2
D_x = 1.402 Mg m⁻³
Mo Kα radiation
Cell parameters from 2712 reflections
θ = 3.1–28.3°
μ = 0.11 mm⁻¹
T = 150 (2) K
Block, colourless
0.35 × 0.29 × 0.17 mm

Data collection

Bruker SMART APEX diffractometer
Narrow-frame ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 1996 )T_min = 0.963, T_max = 0.982
4424 measured reflections
2313 independent reflections
2121 reflections with I > 2σ(I)
R_int = 0.013
θ_max = 28.3°
h = −8 → 8
k = −9 → 9
l = −14 → 13

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.098
S = 1.04
2313 reflections
196 parameters
All H-atom parameters refined
w = 1/[σ²(F_o²) + (0.0565P)² + 0.1277P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O50—H50⋯O1ⁱ	0.88 (2)	1.84 (2)	2.6849 (12)	160.2 (18)
N1—H1⋯O51	0.917 (16)	1.962 (16)	2.8752 (12)	174.0 (14)
Symmetry code: (i) x, y-1, z.

All H atoms were located in a difference map and were refined isotropically; C—H bond lengths range from 0.94 (2) to 1.00 (2) Å.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: MERCURY (Bruno et al., 2002 ) and SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806000602/ci6743sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806000602/ci6743Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury (Bruno et al., 2002) and SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXL97.

3-azabicyclo[3.3.1]nonane-2,4-dione–acetic acid (1/1) top

Crystal data top

C₈H₁₁NO₂·C₂H₄O₂	Z = 2
M_r = 213.23	F(000) = 228
Triclinic, P1	D_x = 1.402 Mg m⁻³
Hall symbol: -P 1	Melting point = 462–467 K
a = 6.6224 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.3580 (8) Å	Cell parameters from 2712 reflections
c = 10.7995 (12) Å	θ = 3.1–28.3°
α = 103.598 (2)°	µ = 0.11 mm⁻¹
β = 93.378 (2)°	T = 150 K
γ = 97.272 (2)°	Block, colourless
V = 505.22 (10) Å³	0.35 × 0.29 × 0.17 mm

Data collection top

Bruker SMART APEX diffractometer	2313 independent reflections
Radiation source: fine-focus sealed tube	2121 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ω rotation with narrow frames scans	θ_max = 28.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.963, T_max = 0.982	k = −9→9
4424 measured reflections	l = −14→13

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)] = 0.036	Hydrogen site location: difference Fourier map
wR(F²) = 0.098	All H-atom parameters refined
S = 1.04	w = 1/[σ²(F_o²) + (0.0565P)² + 0.1277P] where P = (F_o² + 2F_c²)/3
2313 reflections	(Δ/σ)_max = 0.001
196 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

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
O51	0.24026 (16)	−0.08875 (12)	0.46398 (8)	0.0339 (2)
O50	0.21208 (13)	−0.22994 (11)	0.62416 (8)	0.0249 (2)
C51	0.2222 (2)	0.10010 (16)	0.67523 (11)	0.0274 (3)
H51A	0.102 (3)	0.087 (3)	0.7168 (18)	0.049 (5)*
H51B	0.333 (3)	0.116 (3)	0.7374 (18)	0.052 (5)*
H51C	0.223 (2)	0.207 (2)	0.6374 (16)	0.039 (4)*
C50	0.22593 (16)	−0.07895 (15)	0.57639 (10)	0.0206 (2)
H50	0.216 (3)	−0.330 (3)	0.5621 (18)	0.047 (5)*
O2	0.33694 (14)	−0.05870 (11)	0.15566 (8)	0.0301 (2)
O1	0.24571 (12)	0.42653 (11)	0.47939 (7)	0.02418 (19)
N1	0.29922 (14)	0.18908 (12)	0.31657 (9)	0.0207 (2)
H1	0.280 (2)	0.107 (2)	0.3685 (15)	0.034 (4)*
C8	0.10302 (17)	0.51372 (15)	0.21090 (10)	0.0231 (2)
H8A	0.006 (2)	0.551 (2)	0.2742 (14)	0.030 (4)*
H8B	0.127 (2)	0.613 (2)	0.1658 (14)	0.026 (3)*
C7	0.01654 (17)	0.32663 (16)	0.11624 (10)	0.0238 (2)
H7A	−0.032 (2)	0.233 (2)	0.1632 (13)	0.026 (3)*
H7B	−0.102 (2)	0.344 (2)	0.0648 (14)	0.032 (4)*
C6	0.17583 (17)	0.24951 (16)	0.02883 (10)	0.0237 (2)
H6A	0.207 (2)	0.329 (2)	−0.0312 (14)	0.029 (4)*
H6B	0.120 (2)	0.121 (2)	−0.0245 (14)	0.030 (4)*
C5	0.33876 (16)	0.11110 (15)	0.19154 (10)	0.0216 (2)
C4	0.37781 (16)	0.24459 (15)	0.10551 (10)	0.0219 (2)
H4	0.473 (2)	0.194 (2)	0.0481 (14)	0.026 (3)*
C3	0.46373 (17)	0.44298 (15)	0.18455 (11)	0.0226 (2)
H3A	0.599 (2)	0.445 (2)	0.2288 (14)	0.029 (3)*
H3B	0.481 (2)	0.529 (2)	0.1269 (13)	0.024 (3)*
C2	0.31151 (16)	0.50773 (14)	0.28069 (10)	0.0199 (2)
H2	0.361 (2)	0.629 (2)	0.3366 (13)	0.023 (3)*
C1	0.28424 (15)	0.37591 (14)	0.36779 (10)	0.0189 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O51	0.0602 (6)	0.0212 (4)	0.0231 (4)	0.0102 (4)	0.0106 (4)	0.0071 (3)
O50	0.0346 (4)	0.0192 (4)	0.0213 (4)	0.0040 (3)	0.0055 (3)	0.0052 (3)
C51	0.0358 (6)	0.0203 (5)	0.0246 (6)	0.0054 (4)	0.0021 (5)	0.0019 (4)
C50	0.0201 (5)	0.0191 (5)	0.0228 (5)	0.0028 (4)	0.0022 (4)	0.0053 (4)
O2	0.0410 (5)	0.0172 (4)	0.0324 (4)	0.0074 (3)	0.0093 (4)	0.0035 (3)
O1	0.0325 (4)	0.0207 (4)	0.0198 (4)	0.0045 (3)	0.0057 (3)	0.0046 (3)
N1	0.0255 (5)	0.0165 (4)	0.0215 (4)	0.0045 (3)	0.0051 (3)	0.0063 (3)
C8	0.0276 (5)	0.0207 (5)	0.0240 (5)	0.0084 (4)	0.0064 (4)	0.0080 (4)
C7	0.0235 (5)	0.0266 (6)	0.0221 (5)	0.0034 (4)	0.0023 (4)	0.0078 (4)
C6	0.0299 (6)	0.0214 (5)	0.0186 (5)	0.0006 (4)	0.0045 (4)	0.0039 (4)
C5	0.0209 (5)	0.0186 (5)	0.0251 (5)	0.0047 (4)	0.0048 (4)	0.0036 (4)
C4	0.0246 (5)	0.0188 (5)	0.0224 (5)	0.0034 (4)	0.0101 (4)	0.0031 (4)
C3	0.0230 (5)	0.0193 (5)	0.0253 (5)	0.0002 (4)	0.0082 (4)	0.0053 (4)
C2	0.0242 (5)	0.0145 (5)	0.0206 (5)	0.0011 (4)	0.0047 (4)	0.0033 (4)
C1	0.0174 (5)	0.0177 (5)	0.0209 (5)	0.0022 (4)	0.0018 (4)	0.0037 (4)

Geometric parameters (Å, º) top

O51—C50	1.2092 (14)	C8—H8B	0.971 (15)
O50—C50	1.3259 (13)	C7—C6	1.5306 (15)
O50—H50	0.88 (2)	C7—H7A	0.982 (14)
C51—C50	1.4919 (15)	C7—H7B	0.971 (15)
C51—H51A	0.944 (19)	C6—C4	1.5402 (16)
C51—H51B	0.943 (19)	C6—H6A	0.984 (15)
C51—H51C	0.970 (17)	C6—H6B	0.995 (15)
O2—C5	1.2163 (14)	C5—C4	1.5126 (15)
O1—C1	1.2271 (13)	C4—C3	1.5264 (15)
N1—C1	1.3744 (13)	C4—H4	0.960 (14)
N1—C5	1.3916 (14)	C3—C2	1.5275 (14)
N1—H1	0.917 (16)	C3—H3A	0.989 (15)
C8—C7	1.5290 (16)	C3—H3B	0.989 (14)
C8—C2	1.5443 (15)	C2—C1	1.5043 (14)
C8—H8A	0.982 (15)	C2—H2	0.960 (14)

C50—O50—H50	108.9 (12)	C7—C6—H6B	110.0 (8)
C50—C51—H51A	108.4 (11)	C4—C6—H6B	110.4 (9)
C50—C51—H51B	108.5 (12)	H6A—C6—H6B	106.3 (12)
H51A—C51—H51B	107.1 (16)	O2—C5—N1	119.51 (10)
C50—C51—H51C	111.6 (10)	O2—C5—C4	123.15 (10)
H51A—C51—H51C	108.6 (14)	N1—C5—C4	117.33 (9)
H51B—C51—H51C	112.4 (15)	C5—C4—C3	110.52 (9)
O51—C50—O50	122.45 (10)	C5—C4—C6	109.11 (9)
O51—C50—C51	124.54 (10)	C3—C4—C6	109.86 (9)
O50—C50—C51	113.01 (9)	C5—C4—H4	106.4 (9)
C1—N1—C5	125.83 (9)	C3—C4—H4	111.2 (8)
C1—N1—H1	117.6 (10)	C6—C4—H4	109.6 (8)
C5—N1—H1	116.5 (10)	C4—C3—C2	108.09 (8)
C7—C8—C2	112.96 (9)	C4—C3—H3A	111.1 (8)
C7—C8—H8A	110.6 (9)	C2—C3—H3A	110.9 (8)
C2—C8—H8A	109.4 (8)	C4—C3—H3B	109.1 (8)
C7—C8—H8B	110.0 (8)	C2—C3—H3B	109.9 (8)
C2—C8—H8B	105.8 (8)	H3A—C3—H3B	107.8 (12)
H8A—C8—H8B	107.9 (12)	C1—C2—C3	109.90 (9)
C8—C7—C6	111.94 (9)	C1—C2—C8	109.72 (8)
C8—C7—H7A	109.7 (8)	C3—C2—C8	110.67 (9)
C6—C7—H7A	109.1 (8)	C1—C2—H2	104.9 (8)
C8—C7—H7B	109.7 (9)	C3—C2—H2	111.7 (8)
C6—C7—H7B	109.7 (9)	C8—C2—H2	109.8 (8)
H7A—C7—H7B	106.6 (12)	O1—C1—N1	119.50 (10)
C7—C6—C4	111.82 (9)	O1—C1—C2	123.37 (9)
C7—C6—H6A	110.7 (9)	N1—C1—C2	117.12 (9)
C4—C6—H6A	107.5 (9)

C2—C8—C7—C6	−48.40 (12)	C6—C4—C3—C2	62.97 (11)
C8—C7—C6—C4	50.44 (12)	C4—C3—C2—C1	60.65 (11)
C1—N1—C5—O2	−175.89 (10)	C4—C3—C2—C8	−60.69 (11)
C1—N1—C5—C4	2.79 (16)	C7—C8—C2—C1	−67.27 (11)
O2—C5—C4—C3	−154.70 (11)	C7—C8—C2—C3	54.18 (11)
N1—C5—C4—C3	26.67 (13)	C5—N1—C1—O1	178.96 (10)
O2—C5—C4—C6	84.40 (13)	C5—N1—C1—C2	0.47 (15)
N1—C5—C4—C6	−94.23 (11)	C3—C2—C1—O1	148.81 (10)
C7—C6—C4—C5	62.82 (11)	C8—C2—C1—O1	−89.28 (12)
C7—C6—C4—C3	−58.48 (11)	C3—C2—C1—N1	−32.76 (12)
C5—C4—C3—C2	−57.48 (12)	C8—C2—C1—N1	89.15 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O50—H50···O1ⁱ	0.88 (2)	1.84 (2)	2.6849 (12)	160.2 (18)
N1—H1···O51	0.917 (16)	1.962 (16)	2.8752 (12)	174.0 (14)

Symmetry code: (i) x, y−1, z.

Acknowledgements

The authors acknowledge the Research Councils UK Basic Technology Programme for supporting `Control and Prediction of the Organic Solid State' (URL: www.cposs.org.uk). The authors also thank the Cambridge Crystallographic Data Centre for financial support of this work.

References

Boese, R., Blaser, D., Latz, R. & Baumen, A. (1999). Acta Cryst. C55, IUC9900001. CrossRef IUCr Journals Google Scholar
Bruker (1998). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M. K., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397. Web of Science CrossRef CAS IUCr Journals Google Scholar
Florence, A. J., Baumgartner, B., Weston, C., Shankland, N., Kennedy, A. R., Shankland, K. & David, W. I. F. (2003). J. Pharm. Sci. 92, 1930–1938. Web of Science CSD CrossRef PubMed CAS Google Scholar
Howie, R. A. & Skakle, J. M. S. (2001). Acta Cryst. E57, o822–o824. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.