organic compounds
1-Benzyl-5-methylindoline-2,3-dione
aPostgraduate and Research Department of Physics, National College (Autonomous), Tiruchirappalli 620 001, Tamilnadu, India, and bSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamilnadu, India
*Correspondence e-mail: sunvag@gmail.com
The title compound, C16H13NO2, is an isatin (indole-2,3-dione) derivative. The isatin moiety is almost planar with an r.m.s. deviation of 0.022 Å, and its mean plane makes a dihedral angle of 74.19 (12)° with the benzyl ring. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming C(6) chains propagating along the a-axis direction. The chains are linked via C—H⋯π interactions, forming slabs parallel to the ab plane. Within the slabs there are weak π–π interactions present involving inversion-related isatin moieties.
Keywords: crystal structure; isatin; C—H⋯O hydrogen-bonding; C—H⋯π interactions.
CCDC reference: 1458273
Structure description
Isatins (indoline-2,3-diones) are an important family of CNS (central nervous system) activities as potentiation of pentobarbitone induced necrosis. They also display analgesic, anticonvulsant, antidepressant, anti-inflammatory and antimicrobial effects on the central nervous system. Isatins are capable of crossing the blood–brain barrier (Bhrigu et al., 2010; Fathimunnisa et al., 2015; Gürsoy & Karali, 2003; Ilangovan & Satish, 2014; Mathur & Nain, 2014; Verma et al., 2004). As part of our interest in the structural investigations of isatin derivatives, we report herein on the determination and the geometry optimization of the title compound (I). Theoretical calculations of the molecular structure using MOPAC2012′s PM7 geometry optimization algorithm (Stewart, 2012; Maia et al., 2012) are in satisfactory agreement with the results of the X-ray analysis.
which are biologically active and of significant importance in medicinal chemistry. A variety of biological activities are associated with isatins includingThe molecular structure of the title compound, (I), is illustrated in Fig. 1. In the isatin (indoline-2,3-dione) moiety, which is almost planar [r.m.s. deviation of 0.022 Å; maximum deviation of 0.036 (2) Å for atom C7]. Its mean plane makes a dihedral angle of 74.19 (12)° with the benzyl ring (C10–C15). This is similar to the values observed in related structures, for example {1-benzyl-4,5,6- trimethoxyindoline-2,3-dione (II), [73.04 (7)°] and 1-benzyl- 5-fluoroindoline-2,3-dione (III), [76.82 (11)°]} (Sharmila et al., 2015). The superimposed fit (Gans & Shalloway, 2001) of the isatin group of the title compound (I) (atoms C1–C8, N1, O1 and O2) gives an r.m.s deviation of 0.065 Å with molecule (II) and 0.034 Å with molecule (III), while that with its energy-minimized counterpart gives 0.057 Å. The bond lengths and bond angles of the isatin moiety of compound (I) are also comparable with the values observed for related structures (Helliwell et al., 2012; Lötter et al., 2007). The sum of the angles around the N atom is 360°, indicating the absence of an sp3 lone pair.
In the crystal, molecules are linked via C—H⋯O hydrogen bonds, forming chains propagating along the a-axis direction (Table 1 and Fig. 2). The chains are linked by C—H⋯π interactions, forming slabs lying parallel to the ab plane. Within the slabs there are weak slipped parallel π–π interactions present involving inversion-related indoline ring systems [Cg1⋯Cg2i = 3.843 (1) Å, shortest inter-planar distance = 3.291 (1) Å, slippage 1.884 Å; Cg1 and Cg2 are the centroids of rings N1/C1/C6–C8 and C1–C6, respectively; symmetry code: (i) −x, −y + 1, −z + 1].
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A geometry optimization of (I) with Parameterized Model 7 computation was performed using MOPAC2012. Hartree–Fock closed-shell (restricted) wavefunctions were used for calculations. The HOMO and LUMO energy levels were found to be −8.962 and −1.158 eV, respectively. The total energy and
of the title molecule are −2916.87 eV and 5.244 Debye, respectively. When compared with the in the geometry optimized structure it is observed that the N1—C1 and N1—C8 bond lengths changed from 1.414 and 1.370 Å to 1.411 and 1.419 Å, respectively. The C8—N1—C1 and C8—N1—C9 bond angles decreased from 110.60 and 123.4°, respectively, to 110.12 and 122.27 °, respectively.The relative conformation about the bond joining the isatin moiety and the benzyl group of the structure is defined by the C1—N1—C9—C10 torsion angle. It shows an anti-clinal conformation [98.2 (3)°] in the syn-clinal conformation (72.38 °) in the optimized structure. However, the torsion angle C8—N1—C9—C10 remained almost the same, −81.4 (3) and −87.36°, respectively. A superimposed fit of (I) with its energy-minimized molecular structure gives an r.m.s. deviation of 0.473 Å (Fig. 3). This indicates a greater twist leading to further separation between the isatin moiety and the benzene ring. This suggests that the crystal packing is influenced by the collective effect of the intermolecular interactions.
(I), but takes aSynthesis and crystallization
To a mixture of benzyl-(2-ethynyl-4-methylphenyl)-amine (100 mg, 0.451 mmol) and I2 (22.9 mg, 0.09 mmol), dimethyl sulfoxide (3 ml) was added at ambient temperature and the mixture was heated at 373 K for 5 h in air. Progress of the reaction was monitored by thin layer Upon completion, the reaction mixture was allowed to cool to ambient temperature and quenched with aq. sodium thiosulfate and ethyl acetate. The organic phase was separated, dried over Na2SO4, filtered and concentrated. The crude product was purified by silica gel using hexane-ethyl acetate (9:1 v/v) as The title compound was obtained as a red solid (yield: 85%, 96.5 mg; mp: 416–418 K). It was dissolved in an hexane–ethyl acetate mixture (9:1 v/v) and subjected to slow evaporation at room temperature (298 K), giving red block-like crystals after 2 d. Spectroscopic analysis: 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 7.44 (s, 1H), 7.39–7.29 (m, 6H), 6.68 (d, J = 8.0 Hz, 1H), 4.93 (s, 2H), 2.32 (s, 3H); 13CNMR (100 MHz, CDCl3, δ, p.p.m.): 183.5, 158.4, 148.5, 138.7,134.7, 133.7, 129.0, 128.1, 127.4, 125.7, 117.7, 110.8, 44.0, 20.6.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1458273
10.1107/S2414314616003813/su4017sup1.cif
contains datablocks I, Global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616003813/su4017Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616003813/su4017Isup3.cml
To a mixture of benzyl-(2-ethynyl-4-methylphenyl)-amine (100 mg, 0.451 mmol) and I2 (22.9 mg, 0.09 mmol), dimethyl sulfoxide (3 ml) was added at ambient temperature and the mixture was heated at 373 K for 5 h in air. Progress of the reaction was monitored by thin layer δ, p.p.m.): 7.44 (s, 1H), 7.39–7.29 (m, 6H), 6.68 (d, J = 8.0 Hz, 1H), 4.93 (s, 2H), 2.32 (s, 3H); 13CNMR (100 MHz, CDCl3, δ, p.p.m.): 183.5, 158.4, 148.5, 138.7,134.7, 133.7, 129.0, 128.1, 127.4, 125.7, 117.7, 110.8, 44.0, 20.6.
Upon completion, the reaction mixture was allowed to cool to ambient temperature and quenched with aq. sodium thiosulfate and ethyl acetate. The organic phase was separated, dried over Na2SO4, filtered and concentrated. The crude product was purified by silica gel using hexane-ethyl acetate (9:1 v/v) as The title compound was obtained as a red solid (yield: 85%, 96.5 mg; mp: 416–418 K). It was dissolved in an hexane–ethyl acetate mixture (9:1 v/v) and subjected to slow evaporation at room temperature (298 K), giving red block-like crystals after 2 d. Spectroscopy analysis: 1H NMR (400 MHz, CDCl3,Isatins (indoline-2,3-diones) are an important family of
which are biologically active and of significant importance in medicinal chemistry. A variety of biological activities are associated with isatins including CNS activities as potentiation of pentobarbitone induces necrosis, analgesic, anticonvulsant, antidepressant, anti-inflammatory and antimicrobial effects on the central nervous system. Isatins are capable of crossing the blood–brain barrier (Bhrigu et al., 2010; Fathimunnisa et al., 2015; Gürsoy & Karali, 2003; Ilangovan & Satish, 2014; Mathur & Nain, 2014; Verma et al., 2004). As part of our interest in the structural investigations of isatin derivatives, we report herein on the determination and the geometry optimization of the title compound (I). Theoretical calculations of the molecular structure using MOPAC2012's PM7 geometry optimization algorithm (Stewart, 2012; Maia et al., 2012) are in satisfactory agreement with the results of the X-ray analysis.The molecular structure of the title compound, (I), is illustrated in Fig. 1. In the isatin (indoline-2,3-dione) moiety, which is almost planar [r.m.s. deviation of 0.022 Å; maximum deviation of 0.036 (2) Å for atom C7]. Its mean plane makes a dihedral angle of 74.19 (12)° with the benzyl ring (C10–C15). This is similar to the values observed in related structures, for example {1-benzyl-4,5,6- trimethoxyindoline-2,3-dione (II), [73.04 (7)°] and 1-benzyl- 5-fluoroindoline-2,3-dione (III), [76.82 (11)°]} (Sharmila et al., 2015). The superimposed fit (Gans & Shalloway, 2001) of the isatin group of the title compound (I) (atoms C1–C8, N1, O1 and O2) gives an r.m.s deviation of 0.065 Å with molecule (II) and 0.034 Å with molecule (III), while that with its energy-minimized counterpart gives 0.057 Å. The bond lengths and bond angles of the isatin moiety of compound (I) are also comparable with the values observed for related structures (Helliwell et al., 2012; Lötter et al., 2007). The sum of the angles around the N atom is 360°, indicating the absence of an sp3 lone pair.
In the crystal, molecules are linked via C—H···O hydrogen bonds, forming chains propagating along the a-axis direction (Table 1 and Fig. 2). The chains are linked by C—H···π interactions, forming slabs lying parallel to the ab plane. Within the slabs there are weak slipped parallel π–π interactions present involving inversion-related indoline ring systems [Cg1···Cg2i = 3.843 (1) Å, shortest inter-planar distance = 3.291 (1) Å, slippage 1.884 Å; Cg1 and Cg2 are the centroids of rings N1/C1/C6–C8 and C1–C6, respectively; symmetry code: (i) −x, −y + 1, −z + 1].
A geometry optimization of (I) with Parameterized Model 7 computation was performed using MOPAC2012. Hartree–Fock closed-shell (restricted) wavefunctions were used for calculations. The HOMO and LUMO energy levels were found to be −8.962 and −1.158 eV, respectively. The total energy and
of the title molecule are −2916.87 eV and 5.244 Debye, respectively. When compared with the in the geometry optimized structure it is observed that the N1—C1 and N1—C8 bond lengths changed from 1.414 and 1.370 Å to 1.411 and 1.419 Å, respectively. The C8—N1—C1 and C8—N1—C9 bond angles decreased from 110.60 and 123.4°, respectively, to 110.12 and 122.27 °, respectively.The relative conformation about the bond joining the isatin moiety and the benzyl group of the structure is defined by the C1—N1—C9—C10 torsion angle. It shows an anti-clinal conformation [98.2 (3)°] in the
(I), but takes a syn-clinal conformation (72.38 °) in the optimized structure. However, the torsion angle C8—N1—C9—C10 remained almost the same, −81.4 (3) and −87.36°, respectively. A superimposed fit of (I) with its energy-minimized molecular structure gives an r.m.s. deviation of 0.473 Å (Fig. 3). This indicates a greater twist leading to further separation between the isatin moiety and the benzene ring. This suggests that the crystal packing is influenced by the collective effect of the intermolecular interactions.Data collection: APEX2 (Bruker, 2004); cell
APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: QMOL (Gans & Shalloway, 2001), Mercury (Macrae et al., 2008) and MOPAC (Stewart, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title compound (I), showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. Crystal packing of the title compound (I), viewed along the b axis, showing the C—H···O hydrogen bonds as dashed lines (see Table 1), and C—H···π interactions as black lines. H atoms not involved in these interactions have been omitted for clarity. | |
Fig. 3. A superimposed fit of the title compound (red) and its energy-minimized counterpart (blue). |
C16H13NO2 | Dx = 1.302 Mg m−3 |
Mr = 251.27 | Melting point < 418 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
a = 14.6122 (15) Å | Cell parameters from 2925 reflections |
b = 8.3882 (9) Å | θ = 5.6–44.9° |
c = 20.911 (2) Å | µ = 0.09 mm−1 |
V = 2563.1 (5) Å3 | T = 293 K |
Z = 8 | Block, red |
F(000) = 1056 | 0.35 × 0.30 × 0.25 mm |
Bruker Kappa APEXII CCD diffractometer | 3091 independent reflections |
Radiation source: fine-focus sealed tube | 1652 reflections with I > 2σ(I) |
Grapite monochromator | Rint = 0.051 |
ω and φ scan | θmax = 28.3°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −11→18 |
Tmin = 0.970, Tmax = 0.979 | k = −11→11 |
18203 measured reflections | l = −27→27 |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0579P)2 + 0.8201P] where P = (Fo2 + 2Fc2)/3 |
3091 reflections | (Δ/σ)max = 0.001 |
173 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C16H13NO2 | V = 2563.1 (5) Å3 |
Mr = 251.27 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.6122 (15) Å | µ = 0.09 mm−1 |
b = 8.3882 (9) Å | T = 293 K |
c = 20.911 (2) Å | 0.35 × 0.30 × 0.25 mm |
Bruker Kappa APEXII CCD diffractometer | 3091 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1652 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.979 | Rint = 0.051 |
18203 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.19 e Å−3 |
3091 reflections | Δρmin = −0.16 e Å−3 |
173 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.08992 (12) | 0.2173 (2) | 0.53228 (9) | 0.0517 (5) | |
O1 | −0.04615 (12) | 0.0928 (2) | 0.55743 (9) | 0.0698 (5) | |
O2 | −0.11076 (11) | 0.2770 (2) | 0.44577 (9) | 0.0714 (5) | |
C1 | 0.11891 (14) | 0.3272 (2) | 0.48514 (11) | 0.0454 (5) | |
C2 | 0.20581 (15) | 0.3881 (3) | 0.47456 (11) | 0.0507 (6) | |
H2 | 0.2553 | 0.3570 | 0.4996 | 0.061* | |
C3 | 0.21631 (15) | 0.4966 (3) | 0.42539 (11) | 0.0512 (6) | |
H3 | 0.2743 | 0.5383 | 0.4180 | 0.061* | |
C4 | 0.14499 (15) | 0.5465 (3) | 0.38655 (11) | 0.0513 (6) | |
C5 | 0.05881 (15) | 0.4812 (3) | 0.39747 (11) | 0.0509 (6) | |
H5 | 0.0096 | 0.5107 | 0.3719 | 0.061* | |
C6 | 0.04655 (13) | 0.3728 (3) | 0.44619 (11) | 0.0462 (5) | |
C7 | −0.03384 (15) | 0.2825 (3) | 0.46708 (11) | 0.0522 (6) | |
C8 | −0.00124 (16) | 0.1836 (3) | 0.52531 (12) | 0.0545 (6) | |
C9 | 0.14700 (17) | 0.1481 (3) | 0.58222 (13) | 0.0619 (7) | |
H9A | 0.2105 | 0.1525 | 0.5689 | 0.074* | |
H9B | 0.1307 | 0.0368 | 0.5877 | 0.074* | |
C10 | 0.13695 (15) | 0.2328 (3) | 0.64541 (12) | 0.0555 (6) | |
C11 | 0.0863 (2) | 0.1681 (4) | 0.69456 (16) | 0.0836 (9) | |
H11 | 0.0596 | 0.0684 | 0.6893 | 0.100* | |
C12 | 0.0745 (2) | 0.2489 (6) | 0.75132 (17) | 0.1014 (12) | |
H12 | 0.0397 | 0.2038 | 0.7838 | 0.122* | |
C13 | 0.1143 (2) | 0.3966 (6) | 0.76008 (16) | 0.0959 (11) | |
H13 | 0.1073 | 0.4502 | 0.7987 | 0.115* | |
C14 | 0.1636 (2) | 0.4628 (4) | 0.71219 (16) | 0.0877 (9) | |
H14 | 0.1894 | 0.5633 | 0.7175 | 0.105* | |
C15 | 0.17557 (18) | 0.3809 (4) | 0.65538 (14) | 0.0709 (8) | |
H15 | 0.2105 | 0.4267 | 0.6231 | 0.085* | |
C16 | 0.15996 (18) | 0.6691 (3) | 0.33497 (13) | 0.0728 (8) | |
H16A | 0.1522 | 0.6202 | 0.2938 | 0.109* | |
H16B | 0.2208 | 0.7113 | 0.3384 | 0.109* | |
H16C | 0.1164 | 0.7539 | 0.3398 | 0.109* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0366 (11) | 0.0446 (11) | 0.0739 (13) | 0.0017 (8) | −0.0005 (8) | −0.0055 (10) |
O1 | 0.0533 (11) | 0.0584 (11) | 0.0978 (14) | −0.0094 (9) | 0.0173 (9) | −0.0061 (10) |
O2 | 0.0309 (9) | 0.0824 (13) | 0.1009 (13) | −0.0079 (8) | −0.0058 (8) | −0.0110 (11) |
C1 | 0.0340 (12) | 0.0393 (12) | 0.0629 (14) | 0.0024 (9) | 0.0021 (9) | −0.0144 (10) |
C2 | 0.0306 (12) | 0.0482 (13) | 0.0732 (15) | 0.0031 (9) | −0.0054 (10) | −0.0107 (12) |
C3 | 0.0335 (12) | 0.0478 (14) | 0.0724 (16) | −0.0018 (10) | 0.0057 (10) | −0.0117 (12) |
C4 | 0.0403 (14) | 0.0526 (15) | 0.0609 (15) | 0.0040 (10) | 0.0061 (10) | −0.0112 (11) |
C5 | 0.0347 (13) | 0.0600 (16) | 0.0580 (14) | 0.0078 (10) | −0.0015 (9) | −0.0152 (12) |
C6 | 0.0300 (11) | 0.0466 (13) | 0.0622 (14) | 0.0011 (9) | 0.0014 (9) | −0.0183 (11) |
C7 | 0.0326 (12) | 0.0508 (14) | 0.0733 (15) | 0.0013 (10) | 0.0037 (10) | −0.0214 (12) |
C8 | 0.0412 (14) | 0.0425 (13) | 0.0799 (16) | −0.0041 (10) | 0.0109 (11) | −0.0168 (12) |
C9 | 0.0467 (15) | 0.0422 (14) | 0.097 (2) | 0.0067 (11) | −0.0007 (12) | 0.0067 (13) |
C10 | 0.0364 (13) | 0.0557 (15) | 0.0743 (17) | 0.0056 (11) | −0.0050 (10) | 0.0184 (13) |
C11 | 0.069 (2) | 0.088 (2) | 0.094 (2) | −0.0067 (16) | −0.0008 (16) | 0.038 (2) |
C12 | 0.084 (2) | 0.147 (4) | 0.072 (2) | 0.001 (2) | 0.0058 (18) | 0.039 (2) |
C13 | 0.073 (2) | 0.148 (4) | 0.067 (2) | 0.019 (2) | −0.0126 (16) | −0.003 (2) |
C14 | 0.077 (2) | 0.100 (3) | 0.087 (2) | −0.0068 (18) | −0.0110 (17) | −0.009 (2) |
C15 | 0.0583 (17) | 0.076 (2) | 0.0782 (19) | −0.0132 (14) | 0.0028 (13) | 0.0065 (16) |
C16 | 0.0578 (18) | 0.086 (2) | 0.0751 (17) | 0.0021 (14) | 0.0087 (13) | 0.0009 (16) |
N1—C8 | 1.370 (3) | C9—C10 | 1.508 (4) |
N1—C1 | 1.414 (3) | C9—H9A | 0.9700 |
N1—C9 | 1.457 (3) | C9—H9B | 0.9700 |
O1—C8 | 1.209 (3) | C10—C11 | 1.378 (4) |
O2—C7 | 1.210 (3) | C10—C15 | 1.380 (4) |
C1—C2 | 1.386 (3) | C11—C12 | 1.377 (5) |
C1—C6 | 1.388 (3) | C11—H11 | 0.9300 |
C2—C3 | 1.382 (3) | C12—C13 | 1.381 (5) |
C2—H2 | 0.9300 | C12—H12 | 0.9300 |
C3—C4 | 1.386 (3) | C13—C14 | 1.353 (5) |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.392 (3) | C14—C15 | 1.384 (4) |
C4—C16 | 1.506 (3) | C14—H14 | 0.9300 |
C5—C6 | 1.377 (3) | C15—H15 | 0.9300 |
C5—H5 | 0.9300 | C16—H16A | 0.9600 |
C6—C7 | 1.464 (3) | C16—H16B | 0.9600 |
C7—C8 | 1.549 (3) | C16—H16C | 0.9600 |
C8—N1—C1 | 110.60 (19) | C10—C9—H9A | 109.1 |
C8—N1—C9 | 123.4 (2) | N1—C9—H9B | 109.1 |
C1—N1—C9 | 126.00 (19) | C10—C9—H9B | 109.1 |
C2—C1—C6 | 120.2 (2) | H9A—C9—H9B | 107.8 |
C2—C1—N1 | 128.7 (2) | C11—C10—C15 | 117.5 (3) |
C6—C1—N1 | 111.11 (19) | C11—C10—C9 | 121.4 (3) |
C3—C2—C1 | 117.6 (2) | C15—C10—C9 | 121.1 (2) |
C3—C2—H2 | 121.2 | C12—C11—C10 | 121.1 (3) |
C1—C2—H2 | 121.2 | C12—C11—H11 | 119.5 |
C2—C3—C4 | 123.5 (2) | C10—C11—H11 | 119.5 |
C2—C3—H3 | 118.3 | C11—C12—C13 | 120.2 (3) |
C4—C3—H3 | 118.3 | C11—C12—H12 | 119.9 |
C3—C4—C5 | 117.7 (2) | C13—C12—H12 | 119.9 |
C3—C4—C16 | 121.1 (2) | C14—C13—C12 | 119.6 (3) |
C5—C4—C16 | 121.2 (2) | C14—C13—H13 | 120.2 |
C6—C5—C4 | 119.9 (2) | C12—C13—H13 | 120.2 |
C6—C5—H5 | 120.0 | C13—C14—C15 | 119.9 (3) |
C4—C5—H5 | 120.0 | C13—C14—H14 | 120.0 |
C5—C6—C1 | 121.1 (2) | C15—C14—H14 | 120.0 |
C5—C6—C7 | 131.8 (2) | C10—C15—C14 | 121.7 (3) |
C1—C6—C7 | 107.1 (2) | C10—C15—H15 | 119.2 |
O2—C7—C6 | 130.9 (2) | C14—C15—H15 | 119.2 |
O2—C7—C8 | 123.7 (2) | C4—C16—H16A | 109.5 |
C6—C7—C8 | 105.36 (19) | C4—C16—H16B | 109.5 |
O1—C8—N1 | 126.8 (2) | H16A—C16—H16B | 109.5 |
O1—C8—C7 | 127.4 (2) | C4—C16—H16C | 109.5 |
N1—C8—C7 | 105.78 (19) | H16A—C16—H16C | 109.5 |
N1—C9—C10 | 112.60 (19) | H16B—C16—H16C | 109.5 |
N1—C9—H9A | 109.1 | ||
C8—N1—C1—C2 | −178.0 (2) | C1—N1—C8—O1 | 179.0 (2) |
C9—N1—C1—C2 | 2.3 (3) | C9—N1—C8—O1 | −1.3 (4) |
C8—N1—C1—C6 | 1.5 (2) | C1—N1—C8—C7 | 0.2 (2) |
C9—N1—C1—C6 | −178.2 (2) | C9—N1—C8—C7 | 179.89 (19) |
C6—C1—C2—C3 | 1.4 (3) | O2—C7—C8—O1 | −1.6 (4) |
N1—C1—C2—C3 | −179.2 (2) | C6—C7—C8—O1 | 179.5 (2) |
C1—C2—C3—C4 | −0.2 (3) | O2—C7—C8—N1 | 177.2 (2) |
C2—C3—C4—C5 | −1.0 (3) | C6—C7—C8—N1 | −1.7 (2) |
C2—C3—C4—C16 | 178.1 (2) | C8—N1—C9—C10 | −81.4 (3) |
C3—C4—C5—C6 | 1.0 (3) | C1—N1—C9—C10 | 98.2 (3) |
C16—C4—C5—C6 | −178.1 (2) | N1—C9—C10—C11 | 103.5 (3) |
C4—C5—C6—C1 | 0.2 (3) | N1—C9—C10—C15 | −74.2 (3) |
C4—C5—C6—C7 | −177.8 (2) | C15—C10—C11—C12 | 0.2 (4) |
C2—C1—C6—C5 | −1.4 (3) | C9—C10—C11—C12 | −177.5 (3) |
N1—C1—C6—C5 | 179.02 (19) | C10—C11—C12—C13 | −0.5 (5) |
C2—C1—C6—C7 | 176.97 (19) | C11—C12—C13—C14 | 1.1 (5) |
N1—C1—C6—C7 | −2.6 (2) | C12—C13—C14—C15 | −1.4 (5) |
C5—C6—C7—O2 | 1.9 (4) | C11—C10—C15—C14 | −0.5 (4) |
C1—C6—C7—O2 | −176.2 (2) | C9—C10—C15—C14 | 177.2 (2) |
C5—C6—C7—C8 | −179.3 (2) | C13—C14—C15—C10 | 1.2 (5) |
C1—C6—C7—C8 | 2.6 (2) |
Cg3 is the centroid of the benzyl ring, C10–C15. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2i | 0.93 | 2.53 | 3.446 (3) | 169 |
C5—H5···Cg3ii | 0.93 | 2.91 | 3.818 (3) | 165 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x, −y+1, −z+1. |
Cg3 is the centroid of the benzyl ring, C10–C15. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2i | 0.93 | 2.53 | 3.446 (3) | 169 |
C5—H5···Cg3ii | 0.93 | 2.91 | 3.818 (3) | 165 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H13NO2 |
Mr | 251.27 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 14.6122 (15), 8.3882 (9), 20.911 (2) |
V (Å3) | 2563.1 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.35 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.970, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18203, 3091, 1652 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.164, 1.05 |
No. of reflections | 3091 |
No. of parameters | 173 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.16 |
Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), QMOL (Gans & Shalloway, 2001), Mercury (Macrae et al., 2008) and MOPAC (Stewart, 2012), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).
Acknowledgements
NS thanks the Sophisticated Analytical Instrument Facility (SAIF), Sophisticated Test and Instrumentation Centre (STIC), Cochin University, Cochin, Kerala, India, for help with the data collection and Professor A. Ilangovan, School of Chemistry, Bharathidasan University, India, for fruitful discussions.
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