2-(3,5-Dioxo-4-aza­tri­cyclo­[5.2.1.02,6]dec-8-en-4-yl)acetic acid

Mehmet Akkurt; Aliasghar Jarrahpour; Pouria Shirvani; Muhammad Nawaz Tahir

doi:10.1107/S1600536813021764

. 2013 Aug 10;69(Pt 9):o1404. doi: 10.1107/S1600536813021764

2-(3,5-Dioxo-4-azatricyclo[5.2.1.0^2,6]dec-8-en-4-yl)acetic acid

Mehmet Akkurt ^a, Aliasghar Jarrahpour ^b, Pouria Shirvani ^b, Muhammad Nawaz Tahir ^c,^*

PMCID: PMC3884503 PMID: 24427042

Abstract

The asymmetric unit of the title compound, C₁₁H₁₁NO₄, contains two molecules, A and B, with different conformations: in molecule A, the norborne and carboxylic acid groups lie to the same side of the heterocycle, whereas in a molecule B, they lie on opposite sides. In the crystal, the A molecules form R ₂ ²(8) carboxylic acid inversion dimers, linked by pairs of O—H⋯O hydrogen bonds. The B molecules link to one of the ketone O atoms of the A molecule by an O—H⋯O interaction, resulting in tetramers (two A and two B molecules). The tetramers are linked by weak C—H⋯O interactions, generating a three-dimensional network.

Related literature

For a related structure, see: Bartkowska et al. (1997 ▶). For further synthetic details, see: Biagini et al. (1995 ▶).

Experimental

Crystal data

C₁₁H₁₁NO₄
M _r = 221.21
Triclinic,
a = 6.5060 (3) Å
b = 11.8417 (4) Å
c = 14.1794 (5) Å
α = 104.385 (2)°
β = 97.905 (2)°
γ = 99.549 (2)°
V = 1025.07 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.28 × 0.20 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.970, T _max = 0.983
15543 measured reflections
3985 independent reflections
3245 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.107
S = 1.03
3985 reflections
292 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813021764/hb7113sup1.cif

e-69-o1404-sup1.cif^{(31.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813021764/hb7113Isup2.hkl

e-69-o1404-Isup2.hkl^{(195.3KB, hkl)}

Click here for additional data file.^{(4.3KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813021764/hb7113Isup3.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⋯O2ⁱ	0.82	1.84	2.6504 (18)	170
O5—H5A⋯O3ⁱⁱ	0.82	1.86	2.6509 (18)	163
C11—H11⋯O8ⁱⁱⁱ	0.93	2.57	3.440 (2)	156
C15—H15⋯O8^iv	0.98	2.33	3.201 (2)	147
C16—H16⋯O1^iv	0.98	2.48	3.1473 (19)	125

Open in a new tab

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

Acknowledgments

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. AJ and PS thanks Shiraz University Research Council for financial support (grant No. 91-GR—SC-23).

supplementary crystallographic information

1. Comment

As shown in Fig. 1, the asymmetric unit of the title compound contains two independently molecules 1 (with N1) and 2 (with N2). The norbornene units of the molecules 1 and 2 are bound endo with respect to acetic acid. The sum of the three C—N—C angles at the imide N atom is 359.61 (13)° for molecule 1 and 359.88 (15) ° for molecule 2. In molecule 1, the N1—C2 bond length [1.448 (2) Å] is longer than the N1—C3 [1.3663 (19) Å] and N1—C6 [1.4044 (19) Å] bond lengths. In molecule 2, the corresponding bond lengths are N2—C13 of 1.442 (2) Å, N2—C17 of 1.377 (2) Å and N2—C14 of 1.384 (2) Å, respectively. As expected, this indicates a delocalized π-electron system along the imide parts of the molecules, as in a similar structure (Bartkowska et al., 1997).

In the crystal, pairs of molecules generate a dimer of the R²₂(8) motif by O—H···O hydrogen bonds; these two molecules are linked to the other two molecules by O—H···O hydrogen bonds (Table 1, Fig. 2). In addition, C—H···O hydrogen bonds contribute to the overall crystal packing.

2. Experimental

To endo-5-norbornene-2,3-dicarboxylic anhydride (16.41 g, 100.0 mmol) dissolved in DMF (30 ml) was added glycine (7.50 g, 100.0 mmol). The reaction mixture was refluxed for 24 h, coolded to room temperature, diluted with ethyl acetate (70 ml), and washed with saturated aqueous ammonium chloride solution (5×50 ml). The organic phase was dried on anhydrous Na₂SO₄, filtered and evaporated in vacuo. The residue was recrystallized (5 times) from etheyl acetate giving N-5-norbornene-2,3-dicarboxyloylglycine as a white crystalline solid (yield 61%); mp: 422–424 K (Biagini et al., 1995).