4-[(4-Bromo­phenyl)amino]-2-methyl­idene-4-oxo­butanoic acid

B Narayana; Prakash S Nayak; Balladka K Sarojini; Jerry P Jasinski

doi:10.1107/S1600536814012872

. 2014 Jun 14;70(Pt 7):o779–o780. doi: 10.1107/S1600536814012872

4-[(4-Bromophenyl)amino]-2-methylidene-4-oxobutanoic acid

B Narayana ^a, Prakash S Nayak ^a, Balladka K Sarojini ^b, Jerry P Jasinski ^c,^*

PMCID: PMC4120590 PMID: 25161566

Abstract

In the title compound, C₁₁H₁₀BrNO₃, two independent molecules (A and B) crystallize in the asymmetric unit. The dihedral angles between the mean planes of the 4-bromophenyl ring and amide group are 24.8 (7) in molecule A and 77.1 (6)° in molecule B. The mean plane of the methylidene group is further inclined by 75.6 (4) in molecule A and 72.5 (6)° in molecule B from that of the amide group. In the crystal, N—H⋯O hydrogen bonds formed by amide groups and O—H⋯O hydrogen bonds formed by carboxylic acid groups are observed and supported additionally by weak C—H⋯O interactions between the methylidene and amide groups. Together, these link the molecules into chains of dimers along [110] and form R ₂ ²(8) graph-set motifs.

Related literature

For the pharmacological activity of amide derivatives, see: Galanakis et al. (2004 ▶); Kumar & Knaus (1993 ▶); Ban et al. (1998 ▶); Ukrainets et al. (2006 ▶), Lesyk & Zimenkovsky (2004 ▶); Gududuru et al. (2004 ▶). For related structures, see: Nayak et al. (2013a ▶,b ▶). For standard bond lengths, see: Allen et al. (1987 ▶). graphic file with name e-70-0o779-scheme1.jpg

Experimental

Crystal data

C₁₁H₁₀BrNO₃
M _r = 284.11
Triclinic,
a = 6.2782 (4) Å
b = 8.3251 (5) Å
c = 21.3244 (12) Å
α = 96.462 (5)°
β = 92.026 (5)°
γ = 95.390 (5)°
V = 1101.38 (11) Å³
Z = 4
Cu Kα radiation
μ = 5.04 mm⁻¹
T = 173 K
0.44 × 0.28 × 0.14 mm

Data collection

Agilent Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.162, T _max = 1.000
7163 measured reflections
4131 independent reflections
3490 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.076
wR(F ²) = 0.227
S = 1.03
4131 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 2.73 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus et al., 2012 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814012872/bt6983sup1.cif

e-70-0o779-sup1.cif^{(28.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012872/bt6983Isup2.hkl

e-70-0o779-Isup2.hkl^{(226.6KB, hkl)}

Click here for additional data file.^{(4.1KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814012872/bt6983Isup3.cml

CCDC reference: 1006395

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3A—H3A⋯O2B ⁱ	0.84	1.85	2.685 (5)	174
N1A—H1A⋯O1B ⁱⁱ	0.88	2.06	2.933 (5)	170
O3B—H3B⋯O2A ⁱⁱⁱ	0.84	1.82	2.654 (5)	170
N1B—H1B⋯O1A ^iv	0.88	2.04	2.848 (6)	152
C5B—H5BB⋯O1A ^v	0.95	2.54	3.464 (7)	164

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

Acknowledgments

BN thanks the UGC for financial assistance through a BSR one-time grant for the purchase of chemicals. PSN thanks Mangalore University for research facilities and DST–PURSE financial assistance. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

S1. Comment

Amide bonds play a major role in the elaboration and composition of biological systems, which are the main chemical bonds that link amino acid building blocks together to give proteins. Amide bonds are not limited to biological systems and are indeed present in a huge array of molecules, including major marketed drugs. Amide derivatives possessing anti-inflammatory (Galanakis et al., 2004; Kumar et al., 1993; Ban et al., 1998), antimicrobial (Ukrainets et al., 2006), anti-tubercular (Lesyk et al., 2004) and antiproliferative (Gududuru et al., 2004) activities are reported in the literature. Crystal structures of some related amide derivatives include, viz., 4-(4-iodoanilino)-2-methylene-4-oxobutanoic acid and 4-(3-fluoro-4-methylanilino)-2-methylidene-4-oxobutanoic acid (Nayak et al., 2013a,b). Hence in view of its pharmacological importance, the title compound 4-[(4-bromophenyl)amino]-2-methylidene-4-oxobutanoic acid (I), C₁₁H₁₀BrNO₃, was synthesized from 3-methylidenedihydrofuran-2,5-dione with good yields and its crystal structure is reported here.

In the title compound, two independent molecules (A & B) crystallize in the asymmetric unit (Fig. 1). The N–C(=O) bond lengths of 1.359 (6)A (A) and 1.346 (6)Å (B) are indicative of amide-type resonance. The bond lengths of the remaining atoms are in normal ranges (Allen et al., 1987). In the crystal, classical N—H···O and O—H···O hydrogen bonds are observed supported additionally by weak C—H···O intermolecular interactions between the 2-methylidene and amide groups (Table 1, Fig. 2) linking the molecules into chains of dimers along [1 1 0]. The N—H···O hydrogen bonds are supported by the carbonyl oxygen atom of the amide functionality as the acceptor. The carboxylic acid groups form a dimeric hydrogen bonding pattern commonly seen for many carbolylic acids into R₂²(8) graph-set motifs (Fig. 3). The dihedral angles between the mean planes of the 4-bromophenyl ring (C6A–C11A or C6B–C11B) and oxoamine group (N1A/C1A/O1A/C2A or N1B/C1B/O1B/C2B) are 24.8 (7)° (A) and 77.1 (6)° (B), respectively. The mean plane of the 2-methylidene group (C2A–C5A or C2B–C5B) is further inclined by 75.6 (4)° (A) and 72.5 (6)° (B) from that of the oxoamine group (N1A/C1A/O1A/C2A or N1B/C1B/O1B/C2B).

S2. Experimental

3-Methylidenedihydrofuran-2,5-dione (0.112 g, 1 mmol) was dissolved in 30 ml acetone and stirred at ambient temperature. 4-Bromoaniline (0.172 g, 1 mmol) in 20 mL acetone was added over 30 mins (Fig. 4). After sirring for 1.5 h the slurry was filtered. The solid was washed with acetone and dried to give title compound, C₁₁H₁₀BrNO₃. Single crystals were grown from methanol by the slow evaporation method (yield 0.248 g, 87.32%; m.p.: 441–443 K).