organic compounds
2-Methoxy-4-[3-(3-nitrophenyl)-4,5-dihydro-1H-pyrazol-5-yl]phenol
aDepartment Phamacetical Chemistry, JSS College of Pharmacy, JSS University, Mysuru 570 015, Karnataka, India, bDepartment of Physics, Yuvaraja's College (Constituent College), University of Mysore, Mysore 570 005, Karnataka, India, and cDepartment of Pharmaceutical Chemistry, Sri Adichunchanagiri College of Pharmacy, B. G. Nagara, Mandya District 571 448, Karnataka, India
*Correspondence e-mail: devarajegowda@yahoo.com
In the title compound, C16H15N3O4, the pyrazole ring has an with the C atom substituted by the 2-methoxyphenol ring as the flap. Its mean plane makes dihedral angles of 56.78 (9) and 9.7 (1)° with the 2-methoxyphenol and 3-nitrophenyl rings, respectively. The benzene rings are inclined to one another by 49.37 (8)°. In the crystal, molecules are linked by pairs of O—H⋯N hydrogen bonds, forming inversion dimers with an R22(16) ring motif. The dimers are linked by C—H⋯O hydrogen bonds, forming slabs parallel to the ac plane. There are slipped parallel π–π interactions present within the slabs, involving inversion-related 2-methoxyphenol rings [intercentroid distance = 3.729 (1) Å] and inversion-related 3-nitrophenyl rings [intercentroid distance = 3.831 (1) Å].
Keywords: crystal structure; 1H-pyrazole; chalcones; hydrogen bonding.
CCDC reference: 1469216
Structure description
Pyrazoles and their derivatives have significant importance as biological agents and play a vital role in drug discovery. Pyrazoles have been widely exploited for their antitumor (Sankappa Rai et al., 2015), antibacterial and antifungal, antiviral, antiparasitic, anti-inflammatory, anti-diabetic, anaesthetic and analgesic properties and their anti-tubercular (Gupta & Kaskhedikar, 2013) and insecticidal activities (Hamada & Abdo, 2015). have played a crucial role in the development of and they form the skeleton for pyrazole synthesis. A classical synthesis of pyrazole involves nucleophilic addition of and in presence of a base-like KOH to follow aldol condensation (Hamada & Abdo, 2015) and yield α,β-unsaturated (chalcones), which undergo a subsequent reaction with hydrazine hydrate to afford pyrazoles. In an effort to evaluate the antitubercular activity of vanillin-based pyrazoles, we report herein on the synthesis and crystal structural of the title pyrazole derivative.
The molecular structure of the title compound is shown in Fig. 1. The pyrazole ring (N6/N6/C15–C17) has an with atom C15 as the flap. The benzene rings (C19–C14) and (C18–C23) are inclined to the mean plane of the pyrazole ring by 56.78 (9) and 9.7 (1)°, respectively, and to each other by 49.37 (8)°.
In the crystal, molecules are linked via pairs of O—H⋯N hydrogen bonds, forming inversion dimers with an R22(16) ring motif (Table 1 and Fig. 2). The dimers are linked via C—H⋯O hydrogen bonds, forming slabs parallel to the ac plane (Table 1 and Fig. 3). Within the slabs, there are slipped parallel π–π interactions present involving inversion-related 2-methoxyphenol rings [Cg2⋯Cg2i = 3.729 (1) Å, Cg2 is the centroid of ring C9–C14, interplanar distance = 3.377 (1) Å, slippage = 1.583 Å, symmetry code: (i) −x, −y + 1, −z], and inversion-related 3-nitrophenyl rings [Cg3⋯Cg3ii = 3.831 (1) Å, Cg3 is the centroid of ring C18–C23, interplanar distance = 3.356 (1) Å, slippage = 1.404 Å, symmetry code: (ii) −x + 1, − y + 1, − z + 1].
Synthesis and crystallization
To a solution of vanillin (1 mmol) and 3-nitroacetophenone (1 mmol) in absolute alcohol (25 ml) an ethanol solution of KOH (0.282 g, 10.088 mmol) was added at 298–300 K. The reaction mixture was stirred at room temperature and the progress of the reaction was monitored by TLC, using hexane:ethyl acetate (8:2). After the completion of reaction (24 h), the reaction mixture was poured into ice cold water (100 ml) and neutralized with dilute HCL. The precipitate obtained was recrystallized in ethanol. The chalcone product (1 mmol) and hydrazine hydrate (4 mmol) were dissolved in absolute alcohol (20 ml) and refluxed for 9–10 h. The reaction mixture was poured into crushed ice and stirred, the solid thus obtained was filtered off and washed with cold water, dried and recrystallized in ethanol giving colourless prismatic crystal (yield 65%). Spectroscopic data: IR (KBr disk, cm−1) 3364 (OH), 3310 (NH), 2965 (C–H), 1592 (Ar–C=C), 1513 (asym, Ar–NO2), 1340 (sym, Ar–NO2), 1260 (–OCH3); 1H NMR (CDCl3, δ p.p.m.): 8.92 (s, 1H, NH), 9.92 (s, 1H, OH), 6.96–7.64 (m, 7H, Ar–H), 6.8 (t, 1H, CH–C5), 4.72 (d, 2H, CH2), 3.84 (s, 3H, OCH3); 13C NMR (CDCl3, δ p.p.m.): 148–119 (12C, Ar—C), 110.67 (1C, C), 62.4 (1C, CH), 59.56 (1C, CH2), 48.86 (1C, OCH3); LC–MS m/z: 314.1 (M+1 100%), Elemental analysis for C16H15N3O4: found C, 61.34; H, 4.83; N, 13.41; O, 20.43%. calc. C, 61.31; H, 4.76; N, 13.44; O, 20.42%.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1469216
10.1107/S2414314616004661/su4019sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616004661/su4019Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616004661/su4019Isup3.cml
To a solution of vanillin (1 mmol) and 3-nitroacetophenone (1 mmol) in absolute alcohol (25 ml) an ethanol solution of KOH (0.282 g, 10.088 mmol) was added at 298–300 K. The reaction mixture was stirred at room temperature and the progress of the reaction was monitored by TLC, using hexane:ethyl acetate (8:2). After the completion of reaction (24 h), the reaction mixture was poured into ice cold water (100 ml) and neutralized with dilute HCL. The precipitate obtained was recrystallized in ethanol. The chalcone product (1 mmol) and hydrazine hydrate (4 mmol) were dissolved in absolute alcohol (20 ml) and refluxed for 9–10 h. The reaction mixture was poured into crushed ice and stirred, the solid thus obtained was filtered off and washed with cold water, dried and recrystallized in ethanol giving colourless prismatic crystal (yield 65%). Spectroscopic data: IR (KBr disk, cm−1) 3364 (OH), 3310 (NH), 2965 (C–H), 1592 (Ar–C=C), 1513 (asym, Ar–NO2), 1340 (sym, Ar–NO2), 1260 (–OCH3); 1H NMR (CDCl3, δ p.p.m.): 8.92 (s, 1H, NH), 9.92 (s, 1H, OH), 6.96–7.64 (m, 7H, Ar—H), 6.8 (t, 1H, CH—C5), 4.72 (d, 2H, CH2), 3.84 (s, 3H, OCH3); 13C NMR (CDCl3, δ p.p.m.): 148–119 (12 C, Ar—C), 110.67 (1 C, C), 62.4 (1 C, CH), 59.56 (1 C, CH2), 48.86 (1 C, OCH3); LC–MS m/z: 314.1 (M+1 100%), Elemental analysis for C16H15N3O4: found C, 61.34; H, 4.83; N, 13.41; O, 20.43%. calc. C, 61.31; H, 4.76; N, 13.44; O, 20.42%.
Pyrazoles and their derivatives have significant importance as biological agents and play a vital role in drug discovery. Pyrazoles have been widely exploited for their antitumor (Sankappa Rai et al., 2015), antibacterial and antifungal, antiviral, antiparasitic, anti-inflammatory, anti-diabetic, anaesthetic and analgesic properties and their anti-tubercular (Gupta & Kaskhedikar, 2013) and insecticidal activities (Hamada & Abdo, 2015). α,β-unsaturated (chalcones), which undergo a subsequent reaction with hydrazine hydrate to afford pyrazoles. In an effort to evaluate the antitubercular activity of vanillin-based pyrazoles, we report herein on the synthesis and crystal structural of the title pyrazole derivative.
have played a crucial role in the development of and they form the skeleton for pyrazole synthesis. A classical synthesis of pyrazole involves nucleophilic addition of and in presence of a base-like KOH to follow aldol condensation (Hamada & Abdo, 2015) and yieldThe molecular structure of the title compound is shown in Fig. 1. The pyrazole ring (N6/N6/C15–C17) has an
with atom C15 as the flap. The benzene rings (C19–C14) and (C18–C23) are inclined to the mean plane of the pyrazole ring by 56.78 (9) and 9.7 (1)°, respectively, and to each other by 49.37 (8)°.In the crystal, molecules are linked via pairs of O—H···N hydrogen bonds, forming inversion dimers with an R22(16) ring motif (Table 1 and Fig. 2). The dimers are linked via C—H···O hydrogen bonds, forming slabs parallel to the ac plane (Table 1 and Fig. 3). Within the slabs, there are slipped parallel π–π interactions present involving inversion-related 4-methoxyphenol rings [Cg2···Cg2i = 3.729 (1) Å, Cg2 is the centroid of ring C9–C14, interplanar distance = 3.377 (1) Å, slippage = 1.583 Å, symmetry code: (i) −x, −y + 1, −z], and inversion-related 3-nitrophenyl rings [Cg3···Cg3ii = 3.831 (1) Å, Cg3 is the centroid of ring C18–C23, interplanar distance = 3.356 (1) Å, slippage = 1.404 Å, symmetry code: (ii) −x + 1, − y + 1, − z + 1].
Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. The crystal packing of the title compound viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 1) and H atoms not involved in these interactions are omitted for clarity. | |
Fig. 3. The crystal packing of the title compound viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 1) and H atoms not involved in these interactions are omitted for clarity. |
C16H15N3O4 | Dx = 1.410 Mg m−3 |
Mr = 313.31 | Melting point: 300 K |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
a = 13.1432 (11) Å | Cell parameters from 2436 reflections |
b = 13.6130 (12) Å | θ = 4.7–64.5° |
c = 8.3381 (7) Å | µ = 0.86 mm−1 |
β = 98.495 (4)° | T = 296 K |
V = 1475.5 (2) Å3 | Prism, colourless |
Z = 4 | 0.24 × 0.20 × 0.12 mm |
F(000) = 656 |
Bruker SMART CCD area-detector diffractometer | 2436 independent reflections |
Radiation source: fine-focus sealed tube | 2094 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ω and φ scans | θmax = 64.5°, θmin = 4.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −15→15 |
Tmin = 0.770, Tmax = 1.000 | k = −15→15 |
12553 measured reflections | l = −7→9 |
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)] = 0.039 | Hydrogen site location: mixed |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0633P)2 + 0.3151P] where P = (Fo2 + 2Fc2)/3 |
2436 reflections | (Δ/σ)max < 0.001 |
264 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C16H15N3O4 | V = 1475.5 (2) Å3 |
Mr = 313.31 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 13.1432 (11) Å | µ = 0.86 mm−1 |
b = 13.6130 (12) Å | T = 296 K |
c = 8.3381 (7) Å | 0.24 × 0.20 × 0.12 mm |
β = 98.495 (4)° |
Bruker SMART CCD area-detector diffractometer | 2436 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2094 reflections with I > 2σ(I) |
Tmin = 0.770, Tmax = 1.000 | Rint = 0.041 |
12553 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.23 e Å−3 |
2436 reflections | Δρmin = −0.22 e Å−3 |
264 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 | ||
O1 | 0.47950 (12) | 0.38474 (13) | 1.00496 (16) | 0.0866 (5) | |
O2 | 0.64242 (13) | 0.39816 (17) | 1.0087 (2) | 0.1116 (6) | |
O3 | −0.12236 (9) | 0.41880 (10) | −0.30456 (14) | 0.0649 (4) | |
H3 | −0.1027 | 0.4622 | −0.3609 | 0.097* | |
O4 | 0.06043 (9) | 0.50817 (9) | −0.28614 (13) | 0.0600 (3) | |
N5 | 0.55509 (13) | 0.38872 (12) | 0.93716 (19) | 0.0696 (4) | |
N6 | 0.24426 (10) | 0.37549 (11) | 0.49118 (16) | 0.0555 (4) | |
N7 | 0.15583 (11) | 0.37666 (12) | 0.37290 (16) | 0.0574 (4) | |
C8 | 0.15531 (15) | 0.55902 (15) | −0.2786 (2) | 0.0599 (5) | |
C9 | 0.05066 (11) | 0.44201 (11) | −0.16650 (17) | 0.0457 (4) | |
C10 | 0.12593 (12) | 0.41954 (12) | −0.03695 (18) | 0.0481 (4) | |
C11 | 0.10725 (12) | 0.34898 (11) | 0.07692 (18) | 0.0484 (4) | |
C12 | 0.01357 (13) | 0.30044 (13) | 0.0551 (2) | 0.0548 (4) | |
C13 | −0.06238 (13) | 0.32419 (13) | −0.0724 (2) | 0.0550 (4) | |
C14 | −0.04530 (12) | 0.39581 (12) | −0.18145 (18) | 0.0491 (4) | |
C15 | 0.18282 (13) | 0.32519 (13) | 0.22660 (18) | 0.0527 (4) | |
C16 | 0.29462 (13) | 0.35523 (15) | 0.23767 (19) | 0.0528 (4) | |
C17 | 0.32268 (12) | 0.36558 (11) | 0.41811 (18) | 0.0467 (4) | |
C18 | 0.42759 (12) | 0.36985 (11) | 0.50882 (19) | 0.0469 (4) | |
C19 | 0.51340 (14) | 0.36513 (13) | 0.4293 (2) | 0.0578 (4) | |
C20 | 0.61173 (15) | 0.36814 (15) | 0.5153 (3) | 0.0682 (5) | |
C21 | 0.62715 (15) | 0.37541 (14) | 0.6818 (3) | 0.0640 (5) | |
C22 | 0.54125 (13) | 0.38058 (12) | 0.7590 (2) | 0.0537 (4) | |
C23 | 0.44264 (13) | 0.37823 (12) | 0.6769 (2) | 0.0492 (4) | |
H8A | 0.1453 (15) | 0.6004 (15) | −0.375 (3) | 0.075 (6)* | |
H8B | 0.1670 (15) | 0.6010 (15) | −0.177 (3) | 0.069 (5)* | |
H8C | 0.2140 (16) | 0.5119 (15) | −0.281 (2) | 0.074 (6)* | |
H10 | 0.1931 (13) | 0.4536 (13) | −0.027 (2) | 0.055 (4)* | |
H12 | 0.0020 (14) | 0.2500 (14) | 0.131 (2) | 0.065 (5)* | |
H13 | −0.1337 (14) | 0.2891 (13) | −0.083 (2) | 0.062 (5)* | |
H15 | 0.1804 (14) | 0.2515 (15) | 0.249 (2) | 0.067 (5)* | |
H16A | 0.3339 (15) | 0.3090 (15) | 0.188 (2) | 0.069 (5)* | |
H16B | 0.3027 (14) | 0.4186 (16) | 0.188 (2) | 0.067 (5)* | |
H19 | 0.5030 (15) | 0.3598 (14) | 0.314 (3) | 0.072 (6)* | |
H20 | 0.6710 (17) | 0.3609 (15) | 0.457 (3) | 0.080 (6)* | |
H21 | 0.6912 (18) | 0.3768 (15) | 0.741 (3) | 0.081 (7)* | |
H23 | 0.3874 (15) | 0.3834 (13) | 0.729 (2) | 0.063 (5)* | |
H7 | 0.1015 (17) | 0.3524 (15) | 0.413 (3) | 0.076 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0900 (11) | 0.1241 (13) | 0.0460 (7) | −0.0160 (9) | 0.0117 (7) | 0.0019 (7) |
O2 | 0.0804 (10) | 0.1741 (18) | 0.0700 (10) | −0.0177 (10) | −0.0230 (8) | −0.0032 (10) |
O3 | 0.0575 (7) | 0.0804 (8) | 0.0524 (7) | −0.0051 (6) | −0.0067 (5) | 0.0029 (6) |
O4 | 0.0588 (7) | 0.0743 (8) | 0.0453 (6) | −0.0031 (5) | 0.0028 (5) | 0.0145 (5) |
N5 | 0.0723 (10) | 0.0803 (11) | 0.0516 (9) | −0.0099 (8) | −0.0066 (8) | 0.0043 (7) |
N6 | 0.0522 (8) | 0.0750 (9) | 0.0393 (7) | −0.0001 (6) | 0.0061 (6) | 0.0035 (6) |
N7 | 0.0499 (8) | 0.0837 (10) | 0.0383 (7) | −0.0016 (7) | 0.0061 (6) | 0.0030 (7) |
C8 | 0.0628 (11) | 0.0688 (12) | 0.0501 (10) | −0.0031 (9) | 0.0152 (8) | 0.0092 (9) |
C9 | 0.0539 (8) | 0.0501 (9) | 0.0338 (8) | 0.0037 (7) | 0.0088 (6) | 0.0002 (6) |
C10 | 0.0503 (8) | 0.0539 (9) | 0.0404 (8) | −0.0007 (7) | 0.0071 (7) | −0.0013 (7) |
C11 | 0.0577 (9) | 0.0504 (9) | 0.0372 (8) | 0.0039 (7) | 0.0071 (7) | −0.0003 (6) |
C12 | 0.0647 (10) | 0.0526 (9) | 0.0484 (9) | −0.0046 (8) | 0.0128 (8) | 0.0044 (7) |
C13 | 0.0570 (9) | 0.0573 (10) | 0.0508 (9) | −0.0061 (8) | 0.0080 (8) | −0.0044 (8) |
C14 | 0.0534 (9) | 0.0543 (9) | 0.0390 (8) | 0.0016 (7) | 0.0041 (7) | −0.0081 (7) |
C15 | 0.0649 (10) | 0.0511 (9) | 0.0412 (8) | 0.0012 (8) | 0.0049 (7) | 0.0046 (7) |
C16 | 0.0562 (9) | 0.0622 (11) | 0.0399 (9) | 0.0087 (8) | 0.0070 (7) | 0.0004 (8) |
C17 | 0.0540 (9) | 0.0477 (8) | 0.0387 (8) | 0.0022 (6) | 0.0081 (7) | 0.0047 (6) |
C18 | 0.0528 (9) | 0.0451 (8) | 0.0430 (8) | 0.0010 (6) | 0.0085 (7) | 0.0044 (6) |
C19 | 0.0612 (10) | 0.0660 (11) | 0.0485 (10) | 0.0005 (8) | 0.0158 (8) | 0.0066 (8) |
C20 | 0.0551 (10) | 0.0825 (13) | 0.0710 (13) | −0.0003 (9) | 0.0225 (9) | 0.0084 (10) |
C21 | 0.0501 (10) | 0.0712 (12) | 0.0691 (12) | −0.0045 (8) | 0.0034 (9) | 0.0087 (9) |
C22 | 0.0570 (9) | 0.0562 (9) | 0.0462 (9) | −0.0052 (7) | 0.0022 (7) | 0.0063 (7) |
C23 | 0.0512 (9) | 0.0532 (9) | 0.0437 (9) | −0.0022 (7) | 0.0091 (7) | 0.0045 (7) |
O1—N5 | 1.215 (2) | C12—C13 | 1.384 (2) |
O2—N5 | 1.219 (2) | C12—H12 | 0.96 (2) |
O3—C14 | 1.3676 (19) | C13—C14 | 1.374 (2) |
O3—H3 | 0.8200 | C13—H13 | 1.045 (18) |
O4—C9 | 1.3640 (18) | C15—C16 | 1.515 (2) |
O4—C8 | 1.419 (2) | C15—H15 | 1.02 (2) |
N5—C22 | 1.474 (2) | C16—C17 | 1.502 (2) |
N6—C17 | 1.280 (2) | C16—H16A | 0.95 (2) |
N6—N7 | 1.409 (2) | C16—H16B | 0.97 (2) |
N7—C15 | 1.494 (2) | C17—C18 | 1.473 (2) |
N7—H7 | 0.89 (2) | C18—C23 | 1.390 (2) |
C8—H8A | 0.98 (2) | C18—C19 | 1.392 (2) |
C8—H8B | 1.02 (2) | C19—C20 | 1.383 (3) |
C8—H8C | 1.01 (2) | C19—H19 | 0.95 (2) |
C9—C10 | 1.387 (2) | C20—C21 | 1.377 (3) |
C9—C14 | 1.398 (2) | C20—H20 | 0.98 (2) |
C10—C11 | 1.398 (2) | C21—C22 | 1.381 (3) |
C10—H10 | 0.990 (17) | C21—H21 | 0.91 (2) |
C11—C12 | 1.385 (2) | C22—C23 | 1.374 (2) |
C11—C15 | 1.511 (2) | C23—H23 | 0.902 (19) |
C14—O3—H3 | 109.5 | N7—C15—C11 | 111.56 (13) |
C9—O4—C8 | 117.81 (13) | N7—C15—C16 | 99.72 (13) |
O1—N5—O2 | 123.54 (17) | C11—C15—C16 | 120.38 (14) |
O1—N5—C22 | 118.55 (15) | N7—C15—H15 | 107.2 (10) |
O2—N5—C22 | 117.90 (18) | C11—C15—H15 | 109.0 (11) |
C17—N6—N7 | 107.88 (13) | C16—C15—H15 | 108.1 (10) |
N6—N7—C15 | 107.18 (12) | C17—C16—C15 | 100.30 (13) |
N6—N7—H7 | 110.9 (13) | C17—C16—H16A | 115.4 (12) |
C15—N7—H7 | 115.4 (14) | C15—C16—H16A | 112.4 (11) |
O4—C8—H8A | 103.6 (12) | C17—C16—H16B | 108.5 (11) |
O4—C8—H8B | 109.6 (11) | C15—C16—H16B | 112.4 (11) |
H8A—C8—H8B | 110.5 (16) | H16A—C16—H16B | 107.8 (16) |
O4—C8—H8C | 111.0 (11) | N6—C17—C18 | 120.68 (14) |
H8A—C8—H8C | 111.3 (16) | N6—C17—C16 | 113.02 (14) |
H8B—C8—H8C | 110.7 (16) | C18—C17—C16 | 126.23 (14) |
O4—C9—C10 | 125.58 (14) | C23—C18—C19 | 118.64 (16) |
O4—C9—C14 | 114.39 (13) | C23—C18—C17 | 120.26 (14) |
C10—C9—C14 | 120.03 (14) | C19—C18—C17 | 121.10 (15) |
C9—C10—C11 | 120.27 (15) | C20—C19—C18 | 120.82 (17) |
C9—C10—H10 | 119.1 (10) | C20—C19—H19 | 120.6 (12) |
C11—C10—H10 | 120.6 (10) | C18—C19—H19 | 118.6 (12) |
C12—C11—C10 | 118.71 (15) | C21—C20—C19 | 120.82 (18) |
C12—C11—C15 | 117.99 (14) | C21—C20—H20 | 119.7 (13) |
C10—C11—C15 | 123.26 (15) | C19—C20—H20 | 119.3 (13) |
C11—C12—C13 | 121.03 (16) | C20—C21—C22 | 117.69 (18) |
C11—C12—H12 | 118.5 (11) | C20—C21—H21 | 122.3 (14) |
C13—C12—H12 | 120.4 (11) | C22—C21—H21 | 120.0 (14) |
C14—C13—C12 | 120.26 (16) | C23—C22—C21 | 122.83 (17) |
C14—C13—H13 | 120.1 (10) | C23—C22—N5 | 118.12 (16) |
C12—C13—H13 | 119.6 (10) | C21—C22—N5 | 119.05 (16) |
O3—C14—C13 | 118.94 (14) | C22—C23—C18 | 119.19 (15) |
O3—C14—C9 | 121.48 (14) | C22—C23—H23 | 121.6 (12) |
C13—C14—C9 | 119.56 (14) | C18—C23—H23 | 119.2 (12) |
C17—N6—N7—C15 | 23.48 (17) | C11—C15—C16—C17 | 152.25 (15) |
C8—O4—C9—C10 | −0.2 (2) | N7—N6—C17—C18 | 175.02 (13) |
C8—O4—C9—C14 | 179.31 (15) | N7—N6—C17—C16 | −2.02 (19) |
O4—C9—C10—C11 | −178.96 (14) | C15—C16—C17—N6 | −19.28 (19) |
C14—C9—C10—C11 | 1.6 (2) | C15—C16—C17—C18 | 163.88 (14) |
C9—C10—C11—C12 | 1.7 (2) | N6—C17—C18—C23 | 4.3 (2) |
C9—C10—C11—C15 | −176.05 (14) | C16—C17—C18—C23 | −179.11 (16) |
C10—C11—C12—C13 | −3.1 (2) | N6—C17—C18—C19 | −176.06 (15) |
C15—C11—C12—C13 | 174.84 (15) | C16—C17—C18—C19 | 0.6 (2) |
C11—C12—C13—C14 | 1.0 (3) | C23—C18—C19—C20 | 0.4 (2) |
C12—C13—C14—O3 | −178.94 (14) | C17—C18—C19—C20 | −179.32 (16) |
C12—C13—C14—C9 | 2.4 (2) | C18—C19—C20—C21 | 0.3 (3) |
O4—C9—C14—O3 | −1.8 (2) | C19—C20—C21—C22 | −0.7 (3) |
C10—C9—C14—O3 | 177.69 (14) | C20—C21—C22—C23 | 0.4 (3) |
O4—C9—C14—C13 | 176.82 (14) | C20—C21—C22—N5 | −179.81 (17) |
C10—C9—C14—C13 | −3.7 (2) | O1—N5—C22—C23 | 6.1 (2) |
N6—N7—C15—C11 | −162.14 (14) | O2—N5—C22—C23 | −174.65 (18) |
N6—N7—C15—C16 | −33.87 (16) | O1—N5—C22—C21 | −173.77 (18) |
C12—C11—C15—N7 | −79.11 (19) | O2—N5—C22—C21 | 5.5 (3) |
C10—C11—C15—N7 | 98.68 (18) | C21—C22—C23—C18 | 0.3 (3) |
C12—C11—C15—C16 | 164.65 (16) | N5—C22—C23—C18 | −179.53 (14) |
C10—C11—C15—C16 | −17.5 (2) | C19—C18—C23—C22 | −0.6 (2) |
N7—C15—C16—C17 | 30.07 (15) | C17—C18—C23—C22 | 179.03 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···N7i | 0.82 | 2.31 | 2.863 (2) | 126 |
C19—H19···O1ii | 0.95 (2) | 2.57 (2) | 3.510 (2) | 168.0 (16) |
C21—H21···O3iii | 0.91 (2) | 2.60 (2) | 3.330 (2) | 137.8 (19) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y, z−1; (iii) x+1, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···N7i | 0.82 | 2.31 | 2.863 (2) | 126 |
C19—H19···O1ii | 0.95 (2) | 2.57 (2) | 3.510 (2) | 168.0 (16) |
C21—H21···O3iii | 0.91 (2) | 2.60 (2) | 3.330 (2) | 137.8 (19) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y, z−1; (iii) x+1, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H15N3O4 |
Mr | 313.31 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 13.1432 (11), 13.6130 (12), 8.3381 (7) |
β (°) | 98.495 (4) |
V (Å3) | 1475.5 (2) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.86 |
Crystal size (mm) | 0.24 × 0.20 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.770, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12553, 2436, 2094 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.586 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.113, 1.00 |
No. of reflections | 2436 |
No. of parameters | 264 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.22 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).
Acknowledgements
The authors thank the XRD Facility, IOE, University of Mysore, Mysore, India, for the X-ray data collection.
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