2-(3-Oxocyclo­hex-1-enylamino)acetic acid

Liu, L.; Liu, L.-Z.; Liu, X.-Z.; Bi, B.; Xu, L.

doi:10.1107/S1600536809039646

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2776

https://doi.org/10.1107/S1600536809039646

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2-(3-Oxocyclohex-1-enylamino)acetic acid

Li Liu,^a Li-Zhen Liu,^a Xi-Zheng Liu,^a Bo Bi ^a and Lin Xu ^a ^*

^aKey Laboratory of Polyoxometalate Science of the Ministry of Education, Northeast Normal University, Changchun 130024, People's Republic of China
^*Correspondence e-mail: liul515@nenu.edu.cn, linxu@nenu.edu.cn

(Received 23 September 2009; accepted 29 September 2009; online 17 October 2009)

The six-membered ring of the title compound, C₈H₁₁NO₃, adopts an envelope shape with the C atom in the meta position of the carbonyl representing the flap. This atom is disordered over two positions in an 0.865 (6): 0.135 (6) ratio. In the crystal, a two-dimensional supramolecular network parallel to the ac plane is built up from O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For a related structure, see: Lalancette et al. (2001 )

Experimental

Crystal data

C₈H₁₁NO₃
M_r = 169.18
Monoclinic, P 2₁ /n
a = 5.138 (1) Å
b = 12.983 (3) Å
c = 12.345 (3) Å
β = 92.89 (3)°
V = 822.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 291 K
0.35 × 0.31 × 0.23 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.964, T_max = 0.977
7743 measured reflections
1854 independent reflections
1461 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.117
S = 1.13
1854 reflections
127 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 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
N1—H1⋯O1ⁱ	0.853 (9)	2.190 (10)	3.0266 (17)	166.9 (17)
O2—H2⋯O3ⁱⁱ	0.862 (10)	1.676 (10)	2.5369 (16)	176 (2)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x+{\script{3\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809039646/ng2648sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039646/ng2648Isup2.hkl

checkCIF report

Comment top

As shown in the scheme, the title compound is a resonance body of the (E)-2-(3-oxocyclohexylideneamino)acetic acid, which can be verified by the existence of the shorter single C—C bond distance and the emergence of the imino group (Figure 1). The C5 atom of the cyclohexane is disordered over two positions with site occupation 0.84 and 0.16 for C5, C5' and their appended H atoms, respectively.

In the crystal structure, a two-dimensional supramolecular network is built up by O—H···O and N—H···O hydrogen bonds between the ketone, the imino group and the carboxyl, along ac plane (Table 1, Figure 2).

Related literature top

For a related structure, see: Lalancette et al. (2001)

Experimental top

Title compound was prepared from 1,3-cyclohexanedione (11.2 g, 0.1 mol) and 2-aminoacetic acid (7.5 g, 0.1 mol) in 100 ml DMSO solution at 100 °C for 24 h. Needle crystals for X-ray diffraction analysis were produced from a ethanol and cyclohexane mixed solution.

Structure description top

For a related structure, see: Lalancette et al. (2001)

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 30% probability level for non-H atoms.
	Fig. 2. A partial packing view, showing the two-dimensional network. Dashed lines indicate the hydrogen-bonding interactions and no involving H atoms have been omitted.

2-(3-Oxocyclohex-1-enylamino)acetic acid top

Crystal data top

C₈H₁₁NO₃	F(000) = 360
M_r = 169.18	D_x = 1.366 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6177 reflections
a = 5.138 (1) Å	θ = 3.1–27.5°
b = 12.983 (3) Å	µ = 0.11 mm⁻¹
c = 12.345 (3) Å	T = 291 K
β = 92.89 (3)°	Block, colorless
V = 822.4 (3) Å³	0.35 × 0.31 × 0.23 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	1854 independent reflections
Radiation source: fine-focus sealed tube	1461 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→5
T_min = 0.964, T_max = 0.977	k = −16→16
7743 measured reflections	l = −15→15

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0593P)² + 0.1182P] where P = (F_o² + 2F_c²)/3
1854 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.18 e Å⁻³
8 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₈H₁₁NO₃	V = 822.4 (3) Å³
M_r = 169.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.138 (1) Å	µ = 0.11 mm⁻¹
b = 12.983 (3) Å	T = 291 K
c = 12.345 (3) Å	0.35 × 0.31 × 0.23 mm
β = 92.89 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1854 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1461 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.977	R_int = 0.032
7743 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	8 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.18 e Å⁻³
1854 reflections	Δρ_min = −0.19 e Å⁻³
127 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	Occ. (<1)
C5'	−0.308 (3)	1.0310 (8)	0.2164 (12)	0.043 (4)	0.135 (6)
H5'1	−0.4453	1.0472	0.2648	0.052*	0.135 (6)
H5'2	−0.2880	1.0900	0.1693	0.052*	0.135 (6)
C5	−0.1653 (5)	1.01745 (14)	0.16773 (17)	0.0444 (7)	0.865 (6)
H5A	−0.0283	0.9987	0.1202	0.053*	0.865 (6)
H5B	−0.2226	1.0867	0.1489	0.053*	0.865 (6)
C1	0.0056 (2)	0.90870 (10)	0.31865 (10)	0.0301 (3)
C2	−0.1357 (3)	0.82688 (10)	0.27717 (11)	0.0331 (3)
H2A	−0.0941	0.7608	0.3015	0.040*
C3	−0.3418 (3)	0.83987 (10)	0.19878 (10)	0.0323 (3)
C4	−0.3913 (3)	0.94381 (12)	0.15005 (13)	0.0439 (4)
H4A	−0.5440	0.9734	0.1811	0.053*
H4B	−0.4292	0.9360	0.0727	0.053*
C6	−0.0589 (3)	1.01603 (11)	0.28306 (13)	0.0445 (4)
H6A	0.0968	1.0583	0.2897	0.053*
H6B	−0.1866	1.0450	0.3297	0.053*
C7	0.2932 (3)	0.79797 (11)	0.43069 (11)	0.0348 (3)
H7A	0.3407	0.7560	0.3698	0.042*
H7B	0.1534	0.7633	0.4661	0.042*
C8	0.5245 (3)	0.80897 (10)	0.50935 (10)	0.0324 (3)
H1	0.274 (3)	0.9517 (10)	0.4179 (13)	0.053 (5)*
H2	0.762 (3)	0.7271 (19)	0.5786 (16)	0.089 (8)*
N1	0.2035 (2)	0.89704 (9)	0.39184 (9)	0.0350 (3)
O1	0.5998 (2)	0.89070 (8)	0.54410 (10)	0.0549 (4)
O2	0.6287 (2)	0.72005 (8)	0.53416 (8)	0.0425 (3)
O3	−0.4844 (2)	0.76566 (8)	0.16931 (9)	0.0468 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C5'	0.044 (7)	0.025 (5)	0.059 (7)	0.005 (4)	−0.011 (5)	0.004 (4)
C5	0.0481 (13)	0.0335 (9)	0.0494 (12)	−0.0016 (8)	−0.0183 (10)	0.0112 (7)
C1	0.0275 (6)	0.0328 (7)	0.0291 (6)	0.0012 (5)	−0.0077 (5)	−0.0014 (5)
C2	0.0330 (7)	0.0294 (7)	0.0353 (7)	−0.0022 (5)	−0.0134 (5)	0.0034 (5)
C3	0.0288 (6)	0.0369 (7)	0.0302 (6)	−0.0024 (5)	−0.0083 (5)	−0.0024 (5)
C4	0.0399 (8)	0.0430 (8)	0.0464 (8)	0.0020 (6)	−0.0205 (6)	0.0053 (6)
C6	0.0435 (8)	0.0295 (7)	0.0579 (9)	0.0025 (6)	−0.0221 (7)	−0.0043 (6)
C7	0.0318 (7)	0.0362 (7)	0.0350 (7)	−0.0053 (5)	−0.0132 (6)	0.0044 (5)
C8	0.0305 (6)	0.0356 (7)	0.0300 (6)	−0.0006 (5)	−0.0093 (5)	0.0010 (5)
N1	0.0328 (6)	0.0323 (6)	0.0379 (6)	−0.0032 (5)	−0.0172 (5)	−0.0015 (4)
O1	0.0560 (7)	0.0383 (6)	0.0662 (7)	0.0015 (5)	−0.0378 (6)	−0.0078 (5)
O2	0.0438 (6)	0.0385 (6)	0.0431 (6)	0.0038 (4)	−0.0195 (5)	0.0021 (4)
O3	0.0441 (6)	0.0423 (6)	0.0510 (6)	−0.0104 (4)	−0.0254 (5)	−0.0008 (5)

Geometric parameters (Å, º) top

C5'—C4	1.448 (12)	C3—C4	1.494 (2)
C5'—C6	1.500 (12)	C4—H4A	0.9700
C5'—H5'1	0.9700	C4—H4B	0.9700
C5'—H5'2	0.9700	C6—H6A	0.9700
C5—C6	1.499 (2)	C6—H6B	0.9700
C5—C4	1.511 (2)	C7—N1	1.4403 (17)
C5—H5A	0.9700	C7—C8	1.5030 (18)
C5—H5B	0.9700	C7—H7A	0.9700
C1—N1	1.3344 (17)	C7—H7B	0.9700
C1—C2	1.3710 (18)	C8—O1	1.2013 (17)
C1—C6	1.4931 (19)	C8—O2	1.3025 (17)
C2—C3	1.4082 (18)	N1—H1	0.853 (9)
C2—H2A	0.9300	O2—H2	0.862 (10)
C3—O3	1.2533 (16)

C4—C5'—C6	115.4 (8)	C5'—C4—H4B	132.6
C4—C5'—H5'1	108.4	C3—C4—H4B	108.9
C6—C5'—H5'1	108.4	C5—C4—H4B	108.9
C4—C5'—H5'2	108.4	H4A—C4—H4B	107.7
C6—C5'—H5'2	108.4	C1—C6—C5	110.84 (13)
H5'1—C5'—H5'2	107.5	C1—C6—C5'	116.9 (4)
C6—C5—C4	111.72 (16)	C5—C6—C5'	38.4 (6)
C6—C5—H5A	109.3	C1—C6—H6A	109.5
C4—C5—H5A	109.3	C5—C6—H6A	109.5
C6—C5—H5B	109.3	C5'—C6—H6A	130.6
C4—C5—H5B	109.3	C1—C6—H6B	109.5
H5A—C5—H5B	107.9	C5—C6—H6B	109.5
N1—C1—C2	122.41 (12)	C5'—C6—H6B	72.0
N1—C1—C6	117.07 (12)	H6A—C6—H6B	108.1
C2—C1—C6	120.52 (12)	N1—C7—C8	111.08 (11)
C1—C2—C3	121.96 (12)	N1—C7—H7A	109.4
C1—C2—H2A	119.0	C8—C7—H7A	109.4
C3—C2—H2A	119.0	N1—C7—H7B	109.4
O3—C3—C2	121.05 (13)	C8—C7—H7B	109.4
O3—C3—C4	119.49 (12)	H7A—C7—H7B	108.0
C2—C3—C4	119.46 (12)	O1—C8—O2	125.30 (13)
C5'—C4—C3	116.0 (5)	O1—C8—C7	122.99 (12)
C5'—C4—C5	38.9 (6)	O2—C8—C7	111.71 (11)
C3—C4—C5	113.54 (12)	C1—N1—C7	123.16 (11)
C5'—C4—H4A	71.8	C1—N1—H1	117.2 (13)
C3—C4—H4A	108.9	C7—N1—H1	119.6 (13)
C5—C4—H4A	108.9	C8—O2—H2	111.1 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.85 (1)	2.19 (1)	3.0266 (17)	167 (2)
O2—H2···O3ⁱⁱ	0.86 (1)	1.68 (1)	2.5369 (16)	176 (2)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+3/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₁NO₃
M_r	169.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	5.138 (1), 12.983 (3), 12.345 (3)
β (°)	92.89 (3)
V (Å³)	822.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.35 × 0.31 × 0.23

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.964, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	7743, 1854, 1461
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.117, 1.13
No. of reflections	1854
No. of parameters	127
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.853 (9)	2.190 (10)	3.0266 (17)	166.9 (17)
O2—H2···O3ⁱⁱ	0.862 (10)	1.676 (10)	2.5369 (16)	176 (2)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+3/2, −y+3/2, z+1/2.

Acknowledgements

This study was supported by the Open Topics Foundation for the Key Laboratory of Polyoxometalate Science of the Ministry of Education of Northeast Normal University.

References

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Lalancette, R. A. & Thompson, H. W. (2001). Acta Cryst. C57, 1434–1435. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar