research communications
Two closely related 2-(benzofuran-2-yl)-2-oxoethyl benzoates: structural differences and C—H⋯O hydrogen-bonded supramolecular assemblies
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, bDepartment of Engineering Chemistry, Vidya Vikas Institute of Engineering & Technology, Visvesvaraya Technological University, Alanahally, Mysuru 570 028, Karnataka, India, cSchool of Chemical Sciences, Universiti Sains Malaysia, Penang 11800 USM, Malaysia, dDepartment of Chemical Science, Faculty of Science, Universiti Tunku Abdul Rahman, Perak Campus, Jalan Universiti, Bandar Barat, Perak, Malaysia, eSchool of Biosciences, Taylor's University, Lakeside Campus, 47500 Subang Jaya, Selangor, Malaysia, fInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, and gDepartment of Chemistry, Science College, An-Najah National University, PO Box 7, Nablus, West Bank, Palestinian Territories
*Correspondence e-mail: chidankumar@gmail.com, khalil.i@najah.edu
The compounds 2-(1-benzofuran-2-yl)-2-oxoethyl 2-nitrobenzoate, C17H11NO6 (I), and 2-(1-benzofuran-2-yl)-2-oxoethyl 2-aminobenzoate, C17H13NO4 (II), were synthesized under mild conditions. Their molecular structures were characterized by both spectroscopic and single-crystal X-ray The molecular conformations of both title compounds are generally similar. However, different ortho-substituted moieties at the phenyl ring of the two compounds cause deviations in the torsion angles between the carbonyl group and the attached phenyl ring. In compound (I), the ortho-nitrophenyl ring is twisted away from the adjacent carbonyl group whereas in compound (II), the ortho-aminophenyl ring is almost co-planar with the carbonyl group. In the crystal of compound (I), two C—H⋯O hydrogen bonds link the molecules into chains propagating along the c-axis direction and the chains are interdigitated, forming sheets parallel to [20-1]. Conversely, pairs of N—H⋯O hydrogen bonds in compound (II) link inversion-related molecules into dimers, which are further extended by C—H⋯O hydrogen bonds into dimer chains. These chains are interconnected by π–π interactions involving the furan rings, forming sheets parallel to the ac plane.
1. Chemical context
Oxygen-containing heterocycles are the basic cores of many bioactive structures. Among these, benzofuran and its derivatives occur frequently in nature because of their stability and ease of generation. Those with substitution(s) at their C-2 and/or C-3 positions are important. Important biological activity such as anticancer (Swamy et al., 2015), anti-acetylcholinesterase (Zhou et al., 2010), antimicrobial (Ugale et al., 2012) and antioxidant (Naik et al., 2013) actions exhibited by this scaffold have attracted the attention of synthetic chemists. Some of the biological and medicinal significance of benzofuran derivatives (Nevagi et al., 2015) have been discussed in review reports. The known potential of benzofuran derivatives has motivated us to synthesise some new compounds incorporating this core structure and we herein report the synthesis and crystal structures of 2-(1-benzofuran-2-yl)-2-oxoethyl 2-nitrobenzoate (I) and 2-(1-benzofuran-2-yl)-2-oxoethyl 2-aminobenzoate (II).
2. Structural commentary
The molecular structures of the title compounds (Fig. 1) contain a benzofuran ring and an ortho-substituted [nitro- for compound (I) and amino- for compound (II)] phenyl ring, joined by a C—C(=O)—O—C(=O) carbonyl-connecting bridge. Their molecular conformations can be characterized by three as indicated by the O1—C8—C9—O3 (τ1), C9—C10—O2—C11 (τ2) and O4—C11—C12—C13 (τ3) torsion angles, respectively (Fig. 2). The torsion angle τ1 for compounds (I) and (II) is close to 0°, showing that the benzofuran ring is nearly coplanar with the C—C(=O)—O—C(=O) carbonyl bridge. Torsion angle τ2 adopts a syn-clinal conformation, as both carbonyl groups at the connecting bridges are twisted away from each other forming torsion angles of −71.43 (3)° in (I) and −70.85 (18)° in (II). For compound (I), the substituted ortho-nitrophenyl moiety is perpendicular to the adjacent carbonyl group with a τ3 torsion angle of −90.2 (4)°; this may arise from a steric repulsion force between the nitro group and carbonyl group. In contrast, the ortho-aminophenyl ring in compound (II) is almost coplanar with its adjacent carbonyl group due to the intramolecular hydrogen bond (N1—H1A⋯O4, Table 2) between the amino and carbonyl groups, which generates an S(6) ring.
3. Supramolecular features
The crystal packing of compound (I) depends mainly on two weak intermolecular hydrogen bonds. Molecules are joined into infinite chains propagating along the c-axis by C10—H10A⋯O3 hydrogen bonds (Table 1, Fig. 3), meanwhile those chains are interdigitated into a fishbone sheet extending along the [20] direction through C15—H15A⋯O5 hydrogen bonds. The fishbone sheets alternate in an up–down manner along the ab plane as shown in Fig. 4.
|
In compound (II), the molecular interactions are more abundant than in (I) because of the ortho-substituted amino group at its phenyl ring. Pairs of N1—H1A⋯O4 hydrogen bonds link molecules into inversion dimers with an R22(12) graph-set motif (Fig. 5). These dimers are further expanded by C10—H10A⋯O3 hydrogen bonds into infinite chains along the [100] direction (Fig. 6). In addition, neighbouring chains are interconnected by π–π interactions involving adjacent furan rings [centroid–centroid distance = 3.7982 (15) Å; symmetry code: −x, −y + 1, −z), forming a sheet parallel to the ac plane (Fig. 7).
4. Database survey
A survey of the Cambridge Structural Database (Groom et al., 2016) revealed five benzofuran structures (Kumar et al., 2015) similar to the title compounds: ITAXUY, ITAYAF, ITAYEJ, ITAYIN and ITAYOT. The molecular structures of the studied and previous compounds differ only at their substituted phenyl rings. By comparing their torsion angles at the C(=O)—O—C(=O) carbonyl bridges, the title compounds exhibit a syn-clinal conformation similar to ITAXUY, ITAYEJ and ITAYIN with respect to their torsion angles which range from 75 to 80°.
5. Synthesis and crystallization
The synthesis was carried out by reacting 1-(benzofuran-2-yl)-2-bromoethan-1-one (1 mmol) with 2-nitrobenzoic acid (1 mmol) for compound (I) and 2-aminobenzoic acid (1 mmol) for compound (II) in 8 ml of N,N-dimethylformamide in the presence of a catalytic amount of anhydrous potassium carbonate at room temperature. The reaction solution was stirred for about two h and monitored by (TLC). After the reaction was complete, the resultant mixture was then added to a beaker of ice-cooled water to form a precipitate. The precipitate was then filtered, rinsed with distilled water and dried. Crystals suitable for X-ray analysis were obtained by slow evaporation using a suitable solvent.
2-(Benzofuran-2-yl)-2-oxoethyl 2-nitrobenzoate (I):
Solvents used to grow crystal: acetone + methanol 1:1 v/v); yield: 80%, m.p. 381–383 K; 1H NMR (500MHz, CDCl3) in ppm: δ 8.041–8.025 (d, 1H, J = 7.9Hz, 14CH), 7.995–7.980 (d, 1H, J = 7.9Hz, 17CH), 7.796–7.763 (m, 2H, 2CH, 3CH), 7.726–7.695 (t, 1H, J = 7.9Hz, 15CH), 7.673 (s, 1H, 7CH), 7.644–7.627 (d, 1H, J = 8.4Hz, 5CH), 7.578–7.544 (t, 1H, J = 8.4Hz, 4CH), 7.398–7.366 (t, 1H, J = 7.9Hz, 16CH), 5.609 (s, 2H, 10CH2). 13C NMR (125 MHz, CDCl3) in ppm: 182.94 (C9), 165.67 (C11), 155.80 (C1), 150.25 (C13), 133.31 (C16), 132.04 (C15), 130.39 (C17), 130.10 (C8), 128.97 (C3), 127.23 (C12), 126.70 (C6), 124.34 (C5), 124.11 (C4), 123.60 (C14), 113.75 (C7), 112.57 (C2), 67.10 (C10). FT–IR (ATR (solid) cm−1): 3089 (Ar C—H, ν), 2953 (C—H, ν), 1744, 1686 (C=O, ν), 1612 (C=C, ν), 1554, 1422 (Ar C=C, ν), 1529, 1344 (N=O, ν), 1278, 1123 (C—O, ν).
2-(Benzofuran-2-yl)-2-oxoethyl 2-aminobenzoate (II):
Solvents used to grow crystal: acetone + acetonitrile (1:1 v/v); yield: 83%; m.p. 432–434 K; 1H NMR (500 MHz, DMSO) in ppm: δ 8.083 (s, 1H, 7CH), 7.907–7.891 (d, 1H, J = 8.1Hz, 17CH), 7.848–7.832 (d, 1H, J = 8.1Hz, 14CH), 7.787–7.770 (d, 1H, J = 8.5Hz, 2CH), 7.617–7.583 (t, 1H, J = 8.5Hz, 3CH), 7.437–7.405 (t, 1H, J = 8.1Hz, 15CH), 7.329–7.295 (t, 1H, J = 8.5Hz, 4CH), 6.824–6.807 (d, 1H, J = 8.5Hz, 5CH), 6.669 (br–s, 2H, 1NH2), 6.607–6.574 (t, 1H, J = 8.1Hz, 16CH), 5.591 (s, 2H, 10CH2). 13C NMR (125MHz, DMSO) in ppm: 184.08 (C9), 166.60 (C11), 154.96 (C1), 151.62 (C15), 149.63 (C13), 134.49 (C8), 130.78 (C17), 128.88 (C3), 126.49 (C6), 124.28 (C5), 123.84 (C4), 116.63 (C14), 114.84 (C16), 114.66 (C7), 112.31 (C2), 107.87 (C2), 65.63 (C10). FT–IR (ATR (solid) cm−1): 3473, 3360 (N—H, ν), 3078 (Ar C—H, ν), 2942 (C—H, ν), 1697, 1676 (C=O, ν), 1615 (C=C, ν), 1583, 1487 (Ar C=C, ν), 1244, 1112 (C—O, ν).
6. Refinement
Crystal data, data collection and structure . All C-bound H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(parent atom). The N-bound H atoms of compound (II) were located in a difference-Fourier map and refined freely.
details for both compounds are summarized in Table 3Supporting information
https://doi.org/10.1107/S2056989017009422/qm2116sup1.cif
contains datablocks I, II. DOI:Structure factors: contains datablock mo_bzf12_0m. DOI: https://doi.org/10.1107/S2056989017009422/qm2116Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989017009422/qm2116IIsup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989017009422/qm2116Isup4.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989017009422/qm2116IIsup5.cml
For both compounds, data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT2013 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b). Molecular graphics: SHELXL2013 (Sheldrick, 2015b) and Mercury (Macrae et al., 2006) for (I); SHELXL2013 (Sheldrick, 2015b) for (II). For both compounds, software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015b) and PLATON (Spek, 2009).C17H11NO6 | Dx = 1.477 Mg m−3 |
Mr = 325.27 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 3687 reflections |
a = 9.3022 (10) Å | θ = 2.3–25.3° |
b = 28.482 (3) Å | µ = 0.11 mm−1 |
c = 5.5208 (6) Å | T = 100 K |
V = 1462.7 (3) Å3 | Block, colourless |
Z = 4 | 0.27 × 0.16 × 0.13 mm |
F(000) = 672 |
Bruker APEXII DUO CCD area-detector diffractometer | 3358 independent reflections |
Radiation source: fine-focus sealed tube | 2915 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
φ and ω scans | θmax = 27.6°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −12→12 |
Tmin = 0.933, Tmax = 0.985 | k = −36→37 |
15875 measured reflections | l = −7→7 |
Refinement on F2 | 1 restraint |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0345P)2 + 0.279P], where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
3358 reflections | Δρmax = 0.18 e Å−3 |
217 parameters | Δρmin = −0.17 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.5075 (2) | 0.27391 (8) | 0.1493 (4) | 0.0290 (5) | |
O1 | 0.72961 (19) | 0.53112 (6) | 0.6220 (3) | 0.0309 (4) | |
O2 | 0.51143 (18) | 0.39614 (6) | 0.2506 (3) | 0.0289 (4) | |
O3 | 0.5376 (2) | 0.45933 (6) | 0.6044 (4) | 0.0328 (4) | |
O4 | 0.6811 (2) | 0.36342 (6) | 0.4887 (4) | 0.0350 (5) | |
O5 | 0.5946 (2) | 0.30243 (6) | 0.0721 (4) | 0.0343 (4) | |
O6 | 0.4877 (2) | 0.23524 (7) | 0.0592 (4) | 0.0460 (6) | |
C1 | 0.8415 (3) | 0.56187 (8) | 0.5803 (5) | 0.0270 (6) | |
C2 | 0.8830 (3) | 0.59794 (10) | 0.7294 (6) | 0.0362 (6) | |
H2A | 0.8343 | 0.6045 | 0.8768 | 0.043* | |
C3 | 0.9982 (3) | 0.62384 (10) | 0.6543 (6) | 0.0412 (7) | |
H3A | 1.0313 | 0.6488 | 0.7539 | 0.049* | |
C4 | 1.0686 (3) | 0.61491 (10) | 0.4372 (6) | 0.0413 (8) | |
H4A | 1.1475 | 0.6341 | 0.3910 | 0.050* | |
C5 | 1.0259 (3) | 0.57859 (11) | 0.2866 (6) | 0.0380 (7) | |
H5A | 1.0743 | 0.5725 | 0.1385 | 0.046* | |
C6 | 0.9074 (3) | 0.55093 (9) | 0.3613 (5) | 0.0278 (6) | |
C7 | 0.8303 (3) | 0.51167 (9) | 0.2669 (5) | 0.0284 (6) | |
H7A | 0.8489 | 0.4958 | 0.1187 | 0.034* | |
C8 | 0.7272 (3) | 0.50142 (9) | 0.4259 (5) | 0.0312 (6) | |
C9 | 0.6161 (3) | 0.46488 (9) | 0.4317 (5) | 0.0286 (6) | |
C10 | 0.6080 (3) | 0.43440 (9) | 0.2082 (5) | 0.0299 (6) | |
H10A | 0.5737 | 0.4533 | 0.0691 | 0.036* | |
H10B | 0.7047 | 0.4221 | 0.1685 | 0.036* | |
C11 | 0.5621 (3) | 0.36359 (9) | 0.4045 (5) | 0.0272 (6) | |
C12 | 0.4463 (3) | 0.32984 (8) | 0.4742 (5) | 0.0250 (5) | |
C13 | 0.4219 (3) | 0.28707 (9) | 0.3614 (4) | 0.0247 (5) | |
C14 | 0.3186 (3) | 0.25567 (9) | 0.4415 (5) | 0.0307 (6) | |
H14A | 0.3052 | 0.2264 | 0.3622 | 0.037* | |
C15 | 0.2354 (3) | 0.26790 (10) | 0.6397 (5) | 0.0345 (6) | |
H15A | 0.1640 | 0.2469 | 0.6979 | 0.041* | |
C16 | 0.2562 (3) | 0.31066 (10) | 0.7531 (5) | 0.0348 (6) | |
H16A | 0.1978 | 0.3191 | 0.8874 | 0.042* | |
C17 | 0.3614 (3) | 0.34129 (10) | 0.6725 (5) | 0.0319 (6) | |
H17A | 0.3755 | 0.3704 | 0.7535 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0311 (11) | 0.0268 (11) | 0.0292 (12) | 0.0017 (9) | 0.0055 (10) | −0.0006 (10) |
O1 | 0.0304 (10) | 0.0307 (9) | 0.0316 (9) | 0.0006 (8) | 0.0030 (8) | 0.0025 (8) |
O2 | 0.0337 (10) | 0.0216 (9) | 0.0314 (9) | 0.0024 (7) | −0.0008 (9) | 0.0025 (8) |
O3 | 0.0371 (10) | 0.0267 (9) | 0.0346 (10) | 0.0017 (8) | 0.0038 (9) | −0.0001 (8) |
O4 | 0.0278 (10) | 0.0305 (10) | 0.0467 (12) | 0.0005 (8) | −0.0025 (9) | 0.0064 (9) |
O5 | 0.0374 (10) | 0.0291 (9) | 0.0364 (11) | 0.0010 (8) | 0.0133 (9) | 0.0021 (9) |
O6 | 0.0516 (13) | 0.0338 (11) | 0.0527 (13) | −0.0047 (10) | 0.0184 (11) | −0.0161 (10) |
C1 | 0.0267 (13) | 0.0262 (12) | 0.0280 (13) | 0.0043 (10) | −0.0017 (11) | 0.0067 (11) |
C2 | 0.0419 (16) | 0.0360 (16) | 0.0307 (14) | 0.0065 (13) | −0.0075 (13) | −0.0020 (12) |
C3 | 0.0426 (17) | 0.0341 (15) | 0.0470 (18) | 0.0033 (13) | −0.0196 (15) | 0.0017 (14) |
C4 | 0.0293 (15) | 0.0395 (17) | 0.055 (2) | −0.0040 (13) | −0.0109 (15) | 0.0193 (15) |
C5 | 0.0326 (15) | 0.0502 (18) | 0.0312 (15) | 0.0123 (13) | 0.0035 (13) | 0.0142 (13) |
C6 | 0.0281 (13) | 0.0299 (14) | 0.0256 (13) | 0.0072 (11) | −0.0027 (11) | 0.0043 (11) |
C7 | 0.0316 (14) | 0.0247 (13) | 0.0289 (13) | 0.0081 (11) | −0.0035 (12) | −0.0022 (11) |
C8 | 0.0349 (14) | 0.0230 (12) | 0.0357 (15) | 0.0058 (11) | −0.0062 (13) | −0.0002 (11) |
C9 | 0.0293 (13) | 0.0222 (12) | 0.0342 (14) | 0.0065 (11) | −0.0007 (12) | 0.0042 (11) |
C10 | 0.0343 (14) | 0.0208 (12) | 0.0345 (15) | 0.0017 (11) | 0.0044 (12) | 0.0032 (11) |
C11 | 0.0299 (14) | 0.0217 (12) | 0.0299 (14) | 0.0059 (11) | 0.0028 (12) | −0.0010 (11) |
C12 | 0.0234 (12) | 0.0244 (12) | 0.0273 (13) | 0.0056 (10) | 0.0004 (11) | 0.0021 (11) |
C13 | 0.0233 (12) | 0.0281 (13) | 0.0227 (12) | 0.0052 (10) | 0.0021 (10) | 0.0008 (11) |
C14 | 0.0301 (13) | 0.0308 (14) | 0.0313 (13) | −0.0033 (11) | −0.0001 (12) | −0.0007 (12) |
C15 | 0.0275 (13) | 0.0436 (16) | 0.0324 (14) | −0.0054 (12) | 0.0042 (12) | 0.0049 (13) |
C16 | 0.0289 (14) | 0.0471 (17) | 0.0286 (13) | 0.0011 (13) | 0.0069 (12) | −0.0014 (14) |
C17 | 0.0320 (14) | 0.0343 (15) | 0.0295 (14) | 0.0050 (12) | 0.0012 (12) | −0.0051 (12) |
N1—O6 | 1.223 (3) | C6—C7 | 1.427 (4) |
N1—O5 | 1.224 (3) | C7—C8 | 1.333 (4) |
N1—C13 | 1.465 (3) | C7—H7A | 0.9500 |
O1—C8 | 1.374 (3) | C8—C9 | 1.467 (4) |
O1—C1 | 1.380 (3) | C9—C10 | 1.511 (4) |
O2—C11 | 1.343 (3) | C10—H10A | 0.9900 |
O2—C10 | 1.431 (3) | C10—H10B | 0.9900 |
O3—C9 | 1.211 (3) | C11—C12 | 1.494 (4) |
O4—C11 | 1.201 (3) | C12—C13 | 1.387 (3) |
C1—C2 | 1.372 (4) | C12—C17 | 1.389 (4) |
C1—C6 | 1.391 (4) | C13—C14 | 1.385 (4) |
C2—C3 | 1.365 (4) | C14—C15 | 1.385 (4) |
C2—H2A | 0.9500 | C14—H14A | 0.9500 |
C3—C4 | 1.389 (5) | C15—C16 | 1.383 (4) |
C3—H3A | 0.9500 | C15—H15A | 0.9500 |
C4—C5 | 1.385 (4) | C16—C17 | 1.384 (4) |
C4—H4A | 0.9500 | C16—H16A | 0.9500 |
C5—C6 | 1.416 (4) | C17—H17A | 0.9500 |
C5—H5A | 0.9500 | ||
O6—N1—O5 | 123.8 (2) | O3—C9—C10 | 122.6 (2) |
O6—N1—C13 | 118.3 (2) | C8—C9—C10 | 115.1 (2) |
O5—N1—C13 | 117.9 (2) | O2—C10—C9 | 109.6 (2) |
C8—O1—C1 | 105.8 (2) | O2—C10—H10A | 109.8 |
C11—O2—C10 | 114.1 (2) | C9—C10—H10A | 109.8 |
C2—C1—O1 | 126.0 (3) | O2—C10—H10B | 109.8 |
C2—C1—C6 | 124.4 (3) | C9—C10—H10B | 109.8 |
O1—C1—C6 | 109.6 (2) | H10A—C10—H10B | 108.2 |
C3—C2—C1 | 116.3 (3) | O4—C11—O2 | 124.9 (2) |
C3—C2—H2A | 121.8 | O4—C11—C12 | 124.2 (2) |
C1—C2—H2A | 121.8 | O2—C11—C12 | 110.7 (2) |
C2—C3—C4 | 122.2 (3) | C13—C12—C17 | 117.8 (2) |
C2—C3—H3A | 118.9 | C13—C12—C11 | 124.6 (2) |
C4—C3—H3A | 118.9 | C17—C12—C11 | 117.5 (2) |
C5—C4—C3 | 121.3 (3) | C14—C13—C12 | 122.5 (2) |
C5—C4—H4A | 119.4 | C14—C13—N1 | 117.8 (2) |
C3—C4—H4A | 119.4 | C12—C13—N1 | 119.7 (2) |
C4—C5—C6 | 117.6 (3) | C13—C14—C15 | 118.5 (3) |
C4—C5—H5A | 121.2 | C13—C14—H14A | 120.7 |
C6—C5—H5A | 121.2 | C15—C14—H14A | 120.7 |
C1—C6—C5 | 118.1 (3) | C16—C15—C14 | 120.1 (3) |
C1—C6—C7 | 105.7 (2) | C16—C15—H15A | 120.0 |
C5—C6—C7 | 136.1 (3) | C14—C15—H15A | 120.0 |
C8—C7—C6 | 107.0 (2) | C15—C16—C17 | 120.6 (3) |
C8—C7—H7A | 126.5 | C15—C16—H16A | 119.7 |
C6—C7—H7A | 126.5 | C17—C16—H16A | 119.7 |
C7—C8—O1 | 111.9 (2) | C16—C17—C12 | 120.5 (3) |
C7—C8—C9 | 132.6 (3) | C16—C17—H17A | 119.8 |
O1—C8—C9 | 115.5 (2) | C12—C17—H17A | 119.8 |
O3—C9—C8 | 122.3 (3) | ||
C8—O1—C1—C2 | 179.6 (2) | O3—C9—C10—O2 | −7.9 (3) |
C8—O1—C1—C6 | −0.3 (3) | C8—C9—C10—O2 | 171.4 (2) |
O1—C1—C2—C3 | 179.2 (2) | C10—O2—C11—O4 | −5.4 (4) |
C6—C1—C2—C3 | −0.8 (4) | C10—O2—C11—C12 | 169.6 (2) |
C1—C2—C3—C4 | 1.1 (4) | O4—C11—C12—C13 | −90.2 (4) |
C2—C3—C4—C5 | −0.8 (4) | O2—C11—C12—C13 | 94.7 (3) |
C3—C4—C5—C6 | 0.3 (4) | O4—C11—C12—C17 | 86.9 (3) |
C2—C1—C6—C5 | 0.3 (4) | O2—C11—C12—C17 | −88.2 (3) |
O1—C1—C6—C5 | −179.7 (2) | C17—C12—C13—C14 | −1.0 (4) |
C2—C1—C6—C7 | −179.7 (2) | C11—C12—C13—C14 | 176.1 (2) |
O1—C1—C6—C7 | 0.3 (3) | C17—C12—C13—N1 | 179.1 (2) |
C4—C5—C6—C1 | 0.0 (4) | C11—C12—C13—N1 | −3.8 (4) |
C4—C5—C6—C7 | −180.0 (3) | O6—N1—C13—C14 | −2.8 (3) |
C1—C6—C7—C8 | −0.1 (3) | O5—N1—C13—C14 | 177.0 (2) |
C5—C6—C7—C8 | 179.9 (3) | O6—N1—C13—C12 | 177.1 (2) |
C6—C7—C8—O1 | −0.1 (3) | O5—N1—C13—C12 | −3.1 (3) |
C6—C7—C8—C9 | −179.1 (3) | C12—C13—C14—C15 | 1.0 (4) |
C1—O1—C8—C7 | 0.3 (3) | N1—C13—C14—C15 | −179.1 (2) |
C1—O1—C8—C9 | 179.4 (2) | C13—C14—C15—C16 | 0.0 (4) |
C7—C8—C9—O3 | 174.5 (3) | C14—C15—C16—C17 | −1.0 (4) |
O1—C8—C9—O3 | −4.5 (3) | C15—C16—C17—C12 | 1.0 (4) |
C7—C8—C9—C10 | −4.9 (4) | C13—C12—C17—C16 | 0.1 (4) |
O1—C8—C9—C10 | 176.2 (2) | C11—C12—C17—C16 | −177.3 (2) |
C11—O2—C10—C9 | −71.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···O3i | 0.99 | 2.59 | 3.471 (4) | 148 |
C15—H15A···O5ii | 0.95 | 2.58 | 3.380 (3) | 142 |
Symmetry codes: (i) x, y, z−1; (ii) x−1/2, −y+1/2, z+1. |
C17H13NO4 | Z = 2 |
Mr = 295.28 | F(000) = 308 |
Triclinic, P1 | Dx = 1.441 Mg m−3 |
a = 5.1839 (12) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.853 (3) Å | Cell parameters from 5796 reflections |
c = 12.269 (3) Å | θ = 2.4–27.9° |
α = 93.562 (3)° | µ = 0.10 mm−1 |
β = 91.167 (3)° | T = 297 K |
γ = 98.714 (3)° | Block, orange |
V = 680.6 (3) Å3 | 0.40 × 0.32 × 0.21 mm |
Bruker APEXII DUO CCD area-detector diffractometer | 3105 independent reflections |
Radiation source: fine-focus sealed tube | 2214 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
φ and ω scans | θmax = 27.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −6→6 |
Tmin = 0.871, Tmax = 0.978 | k = −14→14 |
17052 measured reflections | l = −15→15 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0462P)2 + 0.1899P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
3105 reflections | Δρmax = 0.18 e Å−3 |
207 parameters | Δρmin = −0.18 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.6563 (4) | 0.67887 (18) | 0.63733 (16) | 0.0583 (4) | |
H1A | 0.611 (4) | 0.617 (2) | 0.5840 (19) | 0.069 (7)* | |
H1B | 0.797 (5) | 0.682 (2) | 0.6702 (19) | 0.074 (7)* | |
O1 | 0.2314 (2) | 0.47254 (11) | 0.10178 (9) | 0.0478 (3) | |
O2 | 0.0514 (2) | 0.72867 (11) | 0.41702 (9) | 0.0500 (3) | |
O3 | 0.3365 (3) | 0.67869 (12) | 0.24247 (11) | 0.0587 (4) | |
O4 | 0.2949 (3) | 0.59366 (11) | 0.47797 (11) | 0.0579 (4) | |
C1 | 0.1297 (3) | 0.35882 (16) | 0.05120 (14) | 0.0448 (4) | |
C2 | 0.2360 (4) | 0.3001 (2) | −0.03521 (16) | 0.0581 (5) | |
H2A | 0.3890 | 0.3356 | −0.0667 | 0.070* | |
C3 | 0.1032 (5) | 0.1866 (2) | −0.07204 (17) | 0.0677 (6) | |
H3A | 0.1669 | 0.1434 | −0.1309 | 0.081* | |
C4 | −0.1240 (5) | 0.1334 (2) | −0.02449 (18) | 0.0672 (6) | |
H4A | −0.2072 | 0.0551 | −0.0514 | 0.081* | |
C5 | −0.2283 (4) | 0.19380 (18) | 0.06135 (17) | 0.0585 (5) | |
H5A | −0.3814 | 0.1581 | 0.0926 | 0.070* | |
C6 | −0.0976 (3) | 0.31045 (16) | 0.10033 (14) | 0.0452 (4) | |
C7 | −0.1376 (3) | 0.40069 (16) | 0.18454 (14) | 0.0453 (4) | |
H7A | −0.2762 | 0.3957 | 0.2318 | 0.054* | |
C8 | 0.0625 (3) | 0.49452 (16) | 0.18298 (13) | 0.0429 (4) | |
C9 | 0.1355 (3) | 0.60838 (16) | 0.25240 (14) | 0.0439 (4) | |
C10 | −0.0582 (3) | 0.63287 (18) | 0.33799 (14) | 0.0507 (4) | |
H10A | −0.2107 | 0.6571 | 0.3031 | 0.061* | |
H10B | −0.1141 | 0.5567 | 0.3741 | 0.061* | |
C11 | 0.2338 (3) | 0.69697 (16) | 0.48521 (13) | 0.0431 (4) | |
C12 | 0.3415 (3) | 0.79867 (15) | 0.56403 (13) | 0.0407 (4) | |
C13 | 0.5539 (3) | 0.78708 (16) | 0.63365 (13) | 0.0441 (4) | |
C14 | 0.6573 (4) | 0.89064 (19) | 0.70265 (15) | 0.0567 (5) | |
H14A | 0.7996 | 0.8855 | 0.7486 | 0.068* | |
C15 | 0.5549 (4) | 0.9990 (2) | 0.70424 (16) | 0.0611 (5) | |
H15A | 0.6289 | 1.0667 | 0.7506 | 0.073* | |
C16 | 0.3431 (4) | 1.00947 (18) | 0.63798 (16) | 0.0603 (5) | |
H16A | 0.2715 | 1.0831 | 0.6403 | 0.072* | |
C17 | 0.2401 (4) | 0.91065 (17) | 0.56910 (15) | 0.0515 (4) | |
H17A | 0.0976 | 0.9179 | 0.5240 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0538 (10) | 0.0643 (11) | 0.0604 (11) | 0.0199 (9) | −0.0078 (8) | 0.0097 (9) |
O1 | 0.0432 (7) | 0.0505 (7) | 0.0489 (7) | 0.0035 (5) | 0.0037 (5) | 0.0054 (5) |
O2 | 0.0511 (7) | 0.0514 (7) | 0.0492 (7) | 0.0158 (6) | −0.0066 (6) | −0.0011 (6) |
O3 | 0.0505 (8) | 0.0579 (8) | 0.0635 (8) | −0.0041 (6) | 0.0051 (6) | −0.0002 (6) |
O4 | 0.0647 (8) | 0.0426 (7) | 0.0680 (8) | 0.0158 (6) | −0.0080 (7) | 0.0023 (6) |
C1 | 0.0456 (9) | 0.0457 (10) | 0.0441 (9) | 0.0097 (8) | −0.0051 (7) | 0.0072 (8) |
C2 | 0.0588 (12) | 0.0676 (13) | 0.0508 (11) | 0.0174 (10) | 0.0053 (9) | 0.0058 (9) |
C3 | 0.0846 (16) | 0.0697 (14) | 0.0532 (12) | 0.0292 (12) | −0.0042 (11) | −0.0027 (10) |
C4 | 0.0846 (16) | 0.0519 (12) | 0.0630 (13) | 0.0095 (11) | −0.0195 (12) | −0.0043 (10) |
C5 | 0.0565 (11) | 0.0540 (11) | 0.0622 (12) | −0.0018 (9) | −0.0073 (9) | 0.0083 (10) |
C6 | 0.0457 (9) | 0.0462 (10) | 0.0442 (9) | 0.0075 (8) | −0.0060 (7) | 0.0081 (8) |
C7 | 0.0399 (9) | 0.0523 (10) | 0.0438 (9) | 0.0047 (8) | 0.0017 (7) | 0.0087 (8) |
C8 | 0.0408 (9) | 0.0489 (10) | 0.0409 (9) | 0.0105 (7) | −0.0014 (7) | 0.0093 (7) |
C9 | 0.0405 (9) | 0.0458 (10) | 0.0458 (9) | 0.0065 (8) | −0.0051 (7) | 0.0080 (7) |
C10 | 0.0432 (10) | 0.0576 (11) | 0.0508 (10) | 0.0083 (8) | −0.0033 (8) | −0.0008 (8) |
C11 | 0.0422 (9) | 0.0447 (10) | 0.0444 (9) | 0.0098 (7) | 0.0042 (7) | 0.0093 (7) |
C12 | 0.0416 (9) | 0.0414 (9) | 0.0403 (8) | 0.0078 (7) | 0.0058 (7) | 0.0064 (7) |
C13 | 0.0417 (9) | 0.0511 (10) | 0.0404 (9) | 0.0064 (8) | 0.0069 (7) | 0.0104 (7) |
C14 | 0.0538 (11) | 0.0684 (13) | 0.0461 (10) | 0.0039 (10) | −0.0026 (8) | 0.0032 (9) |
C15 | 0.0724 (13) | 0.0573 (12) | 0.0488 (11) | −0.0023 (10) | 0.0052 (9) | −0.0049 (9) |
C16 | 0.0776 (14) | 0.0471 (11) | 0.0579 (11) | 0.0156 (10) | 0.0074 (10) | −0.0006 (9) |
C17 | 0.0565 (11) | 0.0482 (10) | 0.0520 (10) | 0.0152 (9) | 0.0008 (8) | 0.0034 (8) |
N1—C13 | 1.363 (2) | C6—C7 | 1.419 (2) |
N1—H1A | 0.91 (2) | C7—C8 | 1.340 (2) |
N1—H1B | 0.82 (2) | C7—H7A | 0.9300 |
O1—C1 | 1.371 (2) | C8—C9 | 1.453 (2) |
O1—C8 | 1.373 (2) | C9—C10 | 1.507 (3) |
O2—C11 | 1.3469 (19) | C10—H10A | 0.9700 |
O2—C10 | 1.420 (2) | C10—H10B | 0.9700 |
O3—C9 | 1.208 (2) | C11—C12 | 1.457 (2) |
O4—C11 | 1.209 (2) | C12—C17 | 1.394 (2) |
C1—C2 | 1.371 (3) | C12—C13 | 1.405 (2) |
C1—C6 | 1.382 (2) | C13—C14 | 1.396 (3) |
C2—C3 | 1.363 (3) | C14—C15 | 1.361 (3) |
C2—H2A | 0.9300 | C14—H14A | 0.9300 |
C3—C4 | 1.387 (3) | C15—C16 | 1.376 (3) |
C3—H3A | 0.9300 | C15—H15A | 0.9300 |
C4—C5 | 1.370 (3) | C16—C17 | 1.358 (3) |
C4—H4A | 0.9300 | C16—H16A | 0.9300 |
C5—C6 | 1.393 (3) | C17—H17A | 0.9300 |
C5—H5A | 0.9300 | ||
C13—N1—H1A | 119.3 (14) | O3—C9—C10 | 122.21 (16) |
C13—N1—H1B | 117.8 (16) | C8—C9—C10 | 115.14 (15) |
H1A—N1—H1B | 118 (2) | O2—C10—C9 | 111.46 (14) |
C1—O1—C8 | 105.72 (13) | O2—C10—H10A | 109.3 |
C11—O2—C10 | 115.04 (13) | C9—C10—H10A | 109.3 |
C2—C1—O1 | 125.63 (17) | O2—C10—H10B | 109.3 |
C2—C1—C6 | 124.29 (18) | C9—C10—H10B | 109.3 |
O1—C1—C6 | 110.08 (15) | H10A—C10—H10B | 108.0 |
C3—C2—C1 | 115.8 (2) | O4—C11—O2 | 121.09 (16) |
C3—C2—H2A | 122.1 | O4—C11—C12 | 126.02 (15) |
C1—C2—H2A | 122.1 | O2—C11—C12 | 112.89 (14) |
C2—C3—C4 | 122.1 (2) | C17—C12—C13 | 118.93 (16) |
C2—C3—H3A | 119.0 | C17—C12—C11 | 120.32 (15) |
C4—C3—H3A | 119.0 | C13—C12—C11 | 120.72 (15) |
C5—C4—C3 | 121.3 (2) | N1—C13—C14 | 119.72 (17) |
C5—C4—H4A | 119.3 | N1—C13—C12 | 122.51 (17) |
C3—C4—H4A | 119.3 | C14—C13—C12 | 117.76 (16) |
C4—C5—C6 | 117.9 (2) | C15—C14—C13 | 121.56 (18) |
C4—C5—H5A | 121.1 | C15—C14—H14A | 119.2 |
C6—C5—H5A | 121.1 | C13—C14—H14A | 119.2 |
C1—C6—C5 | 118.65 (17) | C14—C15—C16 | 120.74 (19) |
C1—C6—C7 | 105.84 (15) | C14—C15—H15A | 119.6 |
C5—C6—C7 | 135.50 (18) | C16—C15—H15A | 119.6 |
C8—C7—C6 | 106.96 (16) | C17—C16—C15 | 119.00 (18) |
C8—C7—H7A | 126.5 | C17—C16—H16A | 120.5 |
C6—C7—H7A | 126.5 | C15—C16—H16A | 120.5 |
C7—C8—O1 | 111.38 (15) | C16—C17—C12 | 121.99 (18) |
C7—C8—C9 | 132.36 (17) | C16—C17—H17A | 119.0 |
O1—C8—C9 | 116.19 (14) | C12—C17—H17A | 119.0 |
O3—C9—C8 | 122.65 (17) | ||
C8—O1—C1—C2 | 179.91 (16) | O1—C8—C9—C10 | 177.70 (13) |
C8—O1—C1—C6 | −0.32 (16) | C11—O2—C10—C9 | −70.85 (18) |
O1—C1—C2—C3 | 179.33 (15) | O3—C9—C10—O2 | −13.3 (2) |
C6—C1—C2—C3 | −0.4 (3) | C8—C9—C10—O2 | 166.80 (13) |
C1—C2—C3—C4 | −0.5 (3) | C10—O2—C11—O4 | −0.3 (2) |
C2—C3—C4—C5 | 1.0 (3) | C10—O2—C11—C12 | 179.52 (14) |
C3—C4—C5—C6 | −0.5 (3) | O4—C11—C12—C17 | −175.17 (17) |
C2—C1—C6—C5 | 0.8 (3) | O2—C11—C12—C17 | 5.1 (2) |
O1—C1—C6—C5 | −178.95 (14) | O4—C11—C12—C13 | 6.8 (3) |
C2—C1—C6—C7 | −179.49 (16) | O2—C11—C12—C13 | −172.97 (14) |
O1—C1—C6—C7 | 0.74 (17) | C17—C12—C13—N1 | 176.84 (17) |
C4—C5—C6—C1 | −0.3 (2) | C11—C12—C13—N1 | −5.1 (2) |
C4—C5—C6—C7 | −179.90 (18) | C17—C12—C13—C14 | −1.8 (2) |
C1—C6—C7—C8 | −0.87 (18) | C11—C12—C13—C14 | 176.29 (15) |
C5—C6—C7—C8 | 178.74 (18) | N1—C13—C14—C15 | −177.67 (18) |
C6—C7—C8—O1 | 0.71 (18) | C12—C13—C14—C15 | 1.0 (3) |
C6—C7—C8—C9 | −176.21 (16) | C13—C14—C15—C16 | 0.6 (3) |
C1—O1—C8—C7 | −0.26 (17) | C14—C15—C16—C17 | −1.3 (3) |
C1—O1—C8—C9 | 177.21 (13) | C15—C16—C17—C12 | 0.4 (3) |
C7—C8—C9—O3 | 174.59 (17) | C13—C12—C17—C16 | 1.1 (3) |
O1—C8—C9—O3 | −2.2 (2) | C11—C12—C17—C16 | −176.94 (17) |
C7—C8—C9—C10 | −5.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4 | 0.91 (2) | 2.05 (2) | 2.700 (3) | 127.7 (18) |
N1—H1A···O4i | 0.91 (2) | 2.49 (2) | 3.246 (2) | 141.4 (18) |
C10—H10A···O3ii | 0.97 | 2.50 | 3.444 (2) | 165 |
C17—H17A···O2 | 0.93 | 2.35 | 2.687 (2) | 101 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z. |
Acknowledgements
LYT thanks Universiti Sains Malaysia for the USM Fellowship Scheme and the Malaysian Government for a MyBrain15 (MyMaster) scholarship. HCK thanks the Malaysian Government for a MyBrain15 (MyPhD) scholarship. The authors extend their appreciation to Vidya Vikas Research & Development Center for the facilities and encouragement.
References
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kumar, C., Then, L., Chia, T., Chandraju, S., Win, Y.-F., Sulaiman, S., Hashim, N., Ooi, K., Quah, C. & Fun, H.-K. (2015). Molecules, 20, 16566–16581. CrossRef CAS PubMed Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Naik, N., Vijay, K., Dias, S. M. & Ranga, S. (2013). Int. J. Pharm. Pharm. Sci. 5, 242–247. CAS Google Scholar
Nevagi, R. J., Dighe, S. N. & Dighe, S. N. (2015). Eur. J. Med. Chem. 97, 561–581. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Swamy, P. M. G., Prasad, Y. R., Ashvini, H. M., Giles, D., Shashidhar, B. V. & Agasimundin, Y. S. (2015). Med. Chem. Res. 24, 3437–3452. CrossRef CAS Google Scholar
Ugale, V., Patel, H., Patel, B. & Bari, S. (2012). Arab. J. Chem. 10, S389–A396. CrossRef Google Scholar
Zhou, X., Li, M., Wang, X.-B., Wang, T. & Kong, L.-Y. (2010). Molecules, 15, 8593–8601. CrossRef CAS PubMed Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.