2-Meth­oxy-4-[3-(3-nitro­phen­yl)-4,5-di­hydro-1H-pyrazol-5-yl]phenol

Inturi, B.; Roopashree, K.R.; Pujar, G.V.; Mohammed, I.A.; Devarajegowda, H.C.

doi:10.1107/S2414314616004661

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 3| March 2016| x160466

doi:10.1107/S2414314616004661

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2-Methoxy-4-[3-(3-nitrophenyl)-4,5-dihydro-1H-pyrazol-5-yl]phenol

Bharathkumar Inturi,^a K. R. Roopashree,^b Gurubasavaraj V. Pujar,^a Irfan Ali Mohammed ^c and H. C. Devarajegowda ^b ^*

^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

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 29 February 2016; accepted 17 March 2016; online 22 March 2016)

In the title compound, C₁₆H₁₅N₃O₄, the pyrazole ring has an envelope conformation, 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

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Chemical scheme

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 ). Chalcones have played a crucial role in the development of heterocyclic compounds, and they form the skeleton for pyrazole synthesis. A classical synthesis of pyrazole involves nucleophilic addition of ketones and aldehydes in presence of a base-like KOH to follow aldol condensation (Hamada & Abdo, 2015) and yield α,β-unsaturated ketones (chalcones), which undergo a subsequent cyclization 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 envelope conformation 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)°.

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

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].

Table 1
Hydrogen-bond geometry (Å, °)

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.

Figure 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.

Figure 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.

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₅N₃O₄
M_r	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 )
T_min, T_max	0.770, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12553, 2436, 2094
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.22
Computer programs: SMART and SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ), and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1469216

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616004661/su4019sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616004661/su4019Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616004661/su4019Isup3.cml

checkCIF report

Experimental top

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%.

Structure description top

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). Chalcones have played a crucial role in the development of heterocyclic compounds, and they form the skeleton for pyrazole synthesis. A classical synthesis of pyrazole involves nucleophilic addition of ketones and aldehydes in presence of a base-like KOH to follow aldol condensation (Hamada & Abdo, 2015) and yield α,β-unsaturated ketones (chalcones), which undergo a subsequent cyclization 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.

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].

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: 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).

Figures top

	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.

2-Methoxy-4-[3-(3-nitrophenyl)-4,5-dihydro-1H-pyrazol-5-yl]phenol top

Crystal data top

C₁₆H₁₅N₃O₄	D_x = 1.410 Mg m⁻³
M_r = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	2436 independent reflections
Radiation source: fine-focus sealed tube	2094 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ω and φ scans	θ_max = 64.5°, θ_min = 4.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −15→15
T_min = 0.770, T_max = 1.000	k = −15→15
12553 measured reflections	l = −7→9

Refinement top

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(F_o²) + (0.0633P)² + 0.3151P] where P = (F_o² + 2F_c²)/3
2436 reflections	(Δ/σ)_max < 0.001
264 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₆H₁₅N₃O₄	V = 1475.5 (2) Å³
M_r = 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)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2436 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2094 reflections with I > 2σ(I)
T_min = 0.770, T_max = 1.000	R_int = 0.041
12553 measured reflections

Refinement top

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	Δρ_max = 0.23 e Å⁻³
2436 reflections	Δρ_min = −0.22 e Å⁻³
264 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.770, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12553, 2436, 2094
R_int	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
Δρ_max, Δρ_min (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.

References

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