6-Amino-3-methyl-4-(3,4,5-tri­meth­oxy­phen­yl)-2,4-di­hydro­pyrano[2,3-c]pyrazole-5-carbo­nitrile

Sharma, N.; Brahmachari, G.; Banerjee, B.; Kant, R.; Gupta, V.K.

doi:10.1107/S1600536814015670

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 70| Part 8| August 2014| Pages o875-o876

doi:10.1107/S1600536814015670

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6-Amino-3-methyl-4-(3,4,5-trimethoxyphenyl)-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile

Naresh Sharma,^a Goutam Brahmachari,^b Bubun Banerjee,^b Rajni Kant ^a and Vivek K. Gupta ^a ^*

^aPost-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, and ^bLaboratory of Natural Products & Organic Synthesis, Department of Chemistry, Visva-Bharati University, Santiniketan 731 235, West Bengal, India
^*Correspondence e-mail: vivek_gupta2k2@hotmail.com

Edited by M. Gdaniec, Adam Mickiewicz University, Poland (Received 21 May 2014; accepted 4 July 2014; online 23 July 2014)

In the title compound, C₁₇H₁₈N₄O₄, the dihedral angle between the benzene ring and 2,4-dihydropyrano[2,3-c]pyrazole ring system is 89.41 (7)°. The pyran moiety adopts a strongly flattened boat conformation. In the crystal, molecules are linked by N—H⋯N, N—H⋯O, C—H⋯N and C—H⋯O hydrogen bonds into an infinite two-dimensional network parallel to (110). There are π–π interactions between the pyrazole rings in neighbouring layers [centroid–centroid distance = 3.621 (1) Å].

Keywords: crystal structure.

CCDC reference: 973484

Related literature

For background to the biological activity of synthetic pyrano[2,3-c] pyrazole compounds, see: Zaki et al. (2006 ); Abdelrazek et al. (2007 ); Mohamed et al. (2010 ); Bhavanarushi et al. (2013 ). For the synthesis of the title compound, see: Brahmachari & Banerjee (2014 ). For a related structure, see: Low et al. (2004 ).

Experimental

Crystal data

C₁₇H₁₈N₄O₄
M_r = 342.35
Triclinic, $[P \overline 1]$
a = 7.6168 (6) Å
b = 9.9967 (5) Å
c = 11.7888 (6) Å
α = 105.283 (5)°
β = 99.416 (5)°
γ = 92.221 (5)°
V = 851.05 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.805, T_max = 1.000
6228 measured reflections
3344 independent reflections
2201 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.125
S = 1.00
3344 reflections
242 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H30⋯O20ⁱ	0.94 (2)	1.96 (2)	2.882 (2)	165 (2)
N11—H40⋯N1ⁱⁱ	0.95 (2)	2.11 (2)	3.030 (3)	163 (2)
N11—H50⋯N10ⁱⁱⁱ	0.91 (2)	2.25 (2)	3.156 (3)	172 (2)
C8—H8C⋯O18ⁱ	0.96	2.52	3.305 (3)	139
C19—H19B⋯N1^iv	0.96	2.52	3.455 (4)	165
C21—H21A⋯Cg3^v	0.96	2.85	3.55	130
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x, -y+1, -z+1; (iii) -x, -y+1, -z+2; (iv) -x, -y, -z+1; (v) -x+1, -y, -z+2.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 973484

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814015670/gk2612sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814015670/gk2612Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814015670/gk2612Isup3.cml

checkCIF report

Comment top

Pyrano[2,3-c]pyrazole scaffolds represent a "privileged" structural motif well distributed in bioactive natural products and pharmaceutically potent synthetic heterocycles possessing a wide range of activities (Abdelrazek et al., 2007; Zaki et al., 2006; Mohamed et al., 2010; Bhavanarushi et al., 2013). Hence, investigation of the structural features of biologically relevant pyrano[2,3-c]pyrazole derivatives is of both scientific and practical interest. In continuation of our efforts to develop useful synthetic protocols for biologically significant molecules, we herein report an efficient and environmentally benign synthesis and the crystal structure of the title compound. In this communication we wish to report the crystal structure of 6-amino-3-methyl-4-(3,4,5-trimethoxyphenyl)-2, 4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (1) synthesized via one-pot multicomponent reaction (MCR) at room temperature using commercially available urea as inexpensive and environmentally benign organo-catalyst. The structure of the title compound 1 was elucidated by spectral methods and X-ray diffraction studies. The bond distances in the title compound are comparable to the closely related structure (Low et al., 2004). In the title compound, C₁₇H₁₈N₄O₄, the dihedral angle between the benzene ring (C12/C13/C14/C15/C16/C17) and the pyrazole ring is 87.05 (7)° and between pyrano and pyrazole rings is 4.69 (8)°. The benzene ring and the pyrazole ring are nearly planar with a maximum deviation of 0.0018 Å for the phenyl C3 atom and 0.0227 Å for the pyrazole C15 atom. The pyran moiety adopts a strongly flattened boat conformation with one mirror plane passing through the atoms C4 and O7 and the other bisecting the bonds C3A—C7A and C5—C6. In the crystal, molecules are linked by N—H···N hydrogen bonds into infinite two-dimensional network parallel to (110) . There are π - π interactions between the pyrazole rings in neighbouring networks [centroid–centroid seperation = 3.621 (1) Å, interplanar spacing = 3.333 Å, centriod shift = 1.242 Å, symmetry code: 1 - x,1 - y,1 - z].

Related literature top

For background to the biological activity of synthetic pyrano[2,3-c] pyrazole scaffolds, see: Zaki et al. (2006); Abdelrazek et al. (2007); Mohamed et al. (2010); Bhavanarushi et al. (2013). For the synthesis of the title compound, see: Brahmachari & Banerjee (2014). For a related structure, see: Low et al. (2004).

Experimental top

The synthesis of the title compound was carried out via one-pot multi-component reaction in aqueous ethanol using low-cost and environmentally benign urea as catalyst at room temperature. An oven-dried screw cap test tube was charged with a magnetic stir bar, ethyl acetoacetate (0.130 g, 1.0 mmol) and hydrazine hydrate (0.050 g, 1 mmol). The reaction mixture was then stirred at room temperature for about 10 min and 3,4,5-trimethoxybenzaldehyde (0.196 g, 1 mmol), malononitrile (0.066 g, 1.1 mmol), urea (0.007 g, 10 mol % as organo-catalyst) and EtOH:H2O (1:1 v/v; 4 ml) were added in a sequential manner (Brahmachari & Banerjee, 2014). The reaction mixture was then stirred vigorously at room temperature and the stirring was continued for 16 h. The progress of the reaction was monitored by TLC. On completion of the reaction, a solid was precipitated out, filtered off and repeatedly washed with aqueous ethanol to obtain a crude product which was purified by recrystallization from ethanol without carrying out column chromatography. The structure of the title compound was confirmed by analytical as well as spectral studies, including ¹H NMR, ¹³C NMR, and TOF-MS. Single crystal was obtained from DMSO. For crystallization 50 mg of compound was dissolved in 5 ml DMSO and left for several days at ambient temperature.

6-Amino-3-methyl-4-(3,4,5-trimethoxyphenyl)-2,4-dihydropyrano[2,3-c] pyrazole-5-carbonitrile (1). White solid. Yield 89%. Mp: 491–493 K. ¹H NMR (400 MHz, DMSO-d₆) δ /p.p.m.: 12.11(1H, s, NH), 6.87 (2H, s, NH₂), 6.47 (2H, s, aromatic H), 4.59 (1H, s, CH), 3.72 (6H, s, 2 \ OCH₃), 3.64 (3H, s, OCH₃), 1.87 (3H, s, CH₃). ¹³C NMR (100 MHz, DMSO-d₆) δ /p.p.m.: 161.39, 155.11, 153.20 (2 C), 140.49, 136.55, 136.20, 121.29, 104.98 (2 C), 97.74, 60.38, 57.33, 56.22 (2 C), 36.87, 10.34. TOF-MS: 365.1230 [M+Na]+. Elemental analysis: Calcd. (%) for C₁₇H₁₈N₄O₄: C, 59.64; H, 5.30; N, 16.37; found: C, 59.62; H, 5.28; N, 16.39.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. ORTEP view of the molecule with the atom-labeling scheme. The displacement ellipsoids are drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing arrangement of molecules viewed down the a axis.

6-Amino-3-methyl-4-(3,4,5-trimethoxyphenyl)-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile top

Crystal data top

C₁₇H₁₈N₄O₄	Z = 2
M_r = 342.35	F(000) = 360
Triclinic, P1	D_x = 1.336 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6168 (6) Å	Cell parameters from 1789 reflections
b = 9.9967 (5) Å	θ = 4.1–26.7°
c = 11.7888 (6) Å	µ = 0.10 mm⁻¹
α = 105.283 (5)°	T = 293 K
β = 99.416 (5)°	Block, colourless
γ = 92.221 (5)°	0.30 × 0.20 × 0.20 mm
V = 851.05 (9) Å³

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	3344 independent reflections
Radiation source: fine-focus sealed tube	2201 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 16.1049 pixels mm^-1	θ_max = 26.0°, θ_min = 3.5°
ω scans	h = −9→4
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −12→12
T_min = 0.805, T_max = 1.000	l = −14→14
6228 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0518P)²] where P = (F_o² + 2F_c²)/3
3344 reflections	(Δ/σ)_max < 0.001
242 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₇H₁₈N₄O₄	γ = 92.221 (5)°
M_r = 342.35	V = 851.05 (9) Å³
Triclinic, P1	Z = 2
a = 7.6168 (6) Å	Mo Kα radiation
b = 9.9967 (5) Å	µ = 0.10 mm⁻¹
c = 11.7888 (6) Å	T = 293 K
α = 105.283 (5)°	0.30 × 0.20 × 0.20 mm
β = 99.416 (5)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	3344 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	2201 reflections with I > 2σ(I)
T_min = 0.805, T_max = 1.000	R_int = 0.030
6228 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.22 e Å⁻³
3344 reflections	Δρ_min = −0.22 e Å⁻³
242 parameters

Special details top

Experimental. CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01–02-2013 CrysAlis171. NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
N1	0.2660 (2)	0.39361 (17)	0.45176 (13)	0.0399 (4)
N2	0.4190 (2)	0.32739 (18)	0.44265 (15)	0.0420 (4)
C3	0.5002 (3)	0.3075 (2)	0.54703 (17)	0.0403 (5)
C3A	0.3973 (3)	0.36369 (18)	0.63060 (16)	0.0332 (5)
C4	0.4095 (3)	0.37099 (18)	0.76047 (15)	0.0329 (4)
H4	0.5116	0.4362	0.8064	0.039*
C5	0.2393 (3)	0.43016 (19)	0.79658 (15)	0.0340 (5)
C6	0.1121 (3)	0.4790 (2)	0.72636 (16)	0.0377 (5)
O7	0.11958 (19)	0.47720 (15)	0.61077 (11)	0.0469 (4)
C7A	0.2595 (3)	0.4131 (2)	0.56623 (16)	0.0353 (5)
C8	0.6670 (3)	0.2363 (3)	0.5545 (2)	0.0644 (7)
H8A	0.6381	0.1384	0.5413	0.097*
H8B	0.7392	0.2738	0.6322	0.097*
H8C	0.7317	0.2505	0.4947	0.097*
C9	0.2164 (3)	0.44234 (19)	0.91550 (16)	0.0354 (5)
N10	0.1998 (2)	0.45179 (18)	1.01250 (14)	0.0487 (5)
N11	−0.0360 (3)	0.5354 (2)	0.75602 (17)	0.0532 (5)
C12	0.4390 (3)	0.22862 (19)	0.78092 (15)	0.0329 (5)
C13	0.3050 (3)	0.1214 (2)	0.73981 (16)	0.0393 (5)
H13	0.1912	0.1378	0.7066	0.047*
C14	0.3410 (3)	−0.0109 (2)	0.74832 (16)	0.0413 (5)
C15	0.5115 (3)	−0.03574 (19)	0.79687 (16)	0.0394 (5)
C16	0.6430 (3)	0.0735 (2)	0.84271 (17)	0.0387 (5)
C17	0.6066 (3)	0.20604 (19)	0.83509 (16)	0.0363 (5)
H17	0.6945	0.2797	0.8663	0.044*
O18	0.2197 (2)	−0.12489 (15)	0.71128 (13)	0.0599 (5)
C19	0.0428 (4)	−0.1075 (3)	0.6622 (3)	0.0823 (9)
H19A	−0.0082	−0.0431	0.7213	0.123*
H19B	−0.0270	−0.1956	0.6379	0.123*
H19C	0.0435	−0.0718	0.5942	0.123*
O20	0.5514 (2)	−0.17034 (13)	0.79545 (11)	0.0522 (4)
C21	0.5144 (4)	−0.2128 (2)	0.89635 (19)	0.0656 (8)
H21A	0.5801	−0.1499	0.9684	0.098*
H21B	0.5494	−0.3052	0.8905	0.098*
H21C	0.3889	−0.2117	0.8979	0.098*
O22	0.8041 (2)	0.04130 (15)	0.89463 (14)	0.0568 (4)
C23	0.9389 (3)	0.1526 (3)	0.9471 (3)	0.0761 (8)
H23A	0.9602	0.1989	0.8882	0.114*
H23B	1.0471	0.1167	0.9763	0.114*
H23C	0.9006	0.2176	1.0122	0.114*
H40	−0.119 (3)	0.569 (2)	0.703 (2)	0.072 (8)*
H30	0.442 (3)	0.290 (2)	0.365 (2)	0.063 (7)*
H50	−0.072 (3)	0.543 (2)	0.8274 (19)	0.055 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0455 (11)	0.0444 (11)	0.0312 (9)	0.0059 (8)	0.0110 (8)	0.0099 (7)
N2	0.0508 (12)	0.0445 (11)	0.0330 (9)	0.0095 (8)	0.0158 (9)	0.0091 (8)
C3	0.0465 (13)	0.0395 (12)	0.0386 (11)	0.0069 (9)	0.0128 (10)	0.0132 (9)
C3A	0.0377 (12)	0.0316 (11)	0.0321 (10)	0.0048 (8)	0.0098 (9)	0.0091 (8)
C4	0.0360 (11)	0.0307 (11)	0.0313 (10)	0.0023 (8)	0.0046 (8)	0.0082 (8)
C5	0.0399 (12)	0.0357 (11)	0.0270 (9)	0.0085 (9)	0.0056 (9)	0.0090 (8)
C6	0.0469 (13)	0.0412 (12)	0.0275 (10)	0.0104 (9)	0.0088 (9)	0.0114 (9)
O7	0.0494 (9)	0.0688 (11)	0.0315 (7)	0.0247 (8)	0.0135 (7)	0.0226 (7)
C7A	0.0393 (12)	0.0383 (12)	0.0321 (10)	0.0065 (9)	0.0127 (9)	0.0120 (9)
C8	0.0692 (18)	0.0812 (19)	0.0544 (14)	0.0381 (15)	0.0274 (13)	0.0243 (13)
C9	0.0389 (12)	0.0350 (11)	0.0328 (11)	0.0116 (8)	0.0059 (9)	0.0094 (9)
N10	0.0560 (13)	0.0601 (13)	0.0333 (10)	0.0164 (9)	0.0119 (9)	0.0144 (9)
N11	0.0534 (13)	0.0800 (15)	0.0365 (10)	0.0348 (11)	0.0180 (10)	0.0236 (10)
C12	0.0405 (12)	0.0333 (11)	0.0262 (9)	0.0066 (9)	0.0092 (9)	0.0078 (8)
C13	0.0405 (12)	0.0394 (12)	0.0380 (11)	0.0050 (9)	0.0081 (9)	0.0097 (9)
C14	0.0549 (14)	0.0334 (12)	0.0341 (11)	−0.0029 (10)	0.0125 (10)	0.0049 (9)
C15	0.0609 (15)	0.0302 (11)	0.0328 (10)	0.0104 (10)	0.0199 (10)	0.0106 (9)
C16	0.0448 (13)	0.0408 (12)	0.0357 (10)	0.0137 (10)	0.0132 (9)	0.0143 (9)
C17	0.0402 (12)	0.0342 (11)	0.0352 (10)	0.0036 (9)	0.0084 (9)	0.0101 (9)
O18	0.0702 (12)	0.0415 (10)	0.0623 (10)	−0.0144 (8)	0.0072 (9)	0.0098 (8)
C19	0.0618 (19)	0.0663 (19)	0.103 (2)	−0.0226 (14)	0.0191 (17)	−0.0026 (16)
O20	0.0901 (13)	0.0325 (8)	0.0418 (8)	0.0183 (8)	0.0266 (8)	0.0130 (7)
C21	0.111 (2)	0.0492 (15)	0.0487 (13)	0.0143 (14)	0.0246 (14)	0.0269 (12)
O22	0.0504 (10)	0.0523 (10)	0.0726 (11)	0.0182 (8)	0.0060 (8)	0.0266 (9)
C23	0.0474 (16)	0.0711 (19)	0.106 (2)	0.0087 (13)	−0.0095 (15)	0.0304 (16)

Geometric parameters (Å, º) top

N1—C7A	1.321 (2)	C12—C17	1.386 (2)
N1—N2	1.368 (2)	C13—C14	1.388 (3)
N2—C3	1.351 (2)	C13—H13	0.9300
N2—H30	0.94 (2)	C14—O18	1.366 (2)
C3—C3A	1.377 (3)	C14—C15	1.390 (3)
C3—C8	1.481 (3)	C15—C16	1.384 (3)
C3A—C7A	1.378 (3)	C15—O20	1.387 (2)
C3A—C4	1.501 (2)	C16—O22	1.369 (2)
C4—C5	1.523 (3)	C16—C17	1.387 (3)
C4—C12	1.524 (2)	C17—H17	0.9300
C4—H4	0.9800	O18—C19	1.413 (3)
C5—C6	1.360 (2)	C19—H19A	0.9600
C5—C9	1.415 (2)	C19—H19B	0.9600
C6—N11	1.336 (3)	C19—H19C	0.9600
C6—O7	1.369 (2)	O20—C21	1.429 (2)
O7—C7A	1.371 (2)	C21—H21A	0.9600
C8—H8A	0.9600	C21—H21B	0.9600
C8—H8B	0.9600	C21—H21C	0.9600
C8—H8C	0.9600	O22—C23	1.420 (3)
C9—N10	1.151 (2)	C23—H23A	0.9600
N11—H40	0.95 (2)	C23—H23B	0.9600
N11—H50	0.91 (2)	C23—H23C	0.9600
C12—C13	1.380 (3)

C7A—N1—N2	101.46 (15)	C17—C12—C4	118.71 (16)
C3—N2—N1	113.28 (17)	C12—C13—C14	119.61 (19)
C3—N2—H30	129.5 (14)	C12—C13—H13	120.2
N1—N2—H30	116.4 (14)	C14—C13—H13	120.2
N2—C3—C3A	106.36 (18)	O18—C14—C13	125.0 (2)
N2—C3—C8	121.06 (19)	O18—C14—C15	114.81 (18)
C3A—C3—C8	132.59 (18)	C13—C14—C15	120.19 (18)
C3—C3A—C7A	103.61 (16)	C16—C15—O20	120.11 (19)
C3—C3A—C4	133.13 (18)	C16—C15—C14	119.79 (17)
C7A—C3A—C4	123.20 (18)	O20—C15—C14	120.06 (17)
C3A—C4—C5	106.47 (15)	O22—C16—C15	115.96 (17)
C3A—C4—C12	110.49 (15)	O22—C16—C17	124.12 (18)
C5—C4—C12	114.14 (14)	C15—C16—C17	119.92 (19)
C3A—C4—H4	108.5	C12—C17—C16	119.95 (18)
C5—C4—H4	108.5	C12—C17—H17	120.0
C12—C4—H4	108.5	C16—C17—H17	120.0
C6—C5—C9	117.19 (18)	C14—O18—C19	118.08 (18)
C6—C5—C4	125.60 (16)	O18—C19—H19A	109.5
C9—C5—C4	117.11 (15)	O18—C19—H19B	109.5
N11—C6—C5	127.32 (18)	H19A—C19—H19B	109.5
N11—C6—O7	109.26 (16)	O18—C19—H19C	109.5
C5—C6—O7	123.42 (19)	H19A—C19—H19C	109.5
C6—O7—C7A	115.23 (15)	H19B—C19—H19C	109.5
N1—C7A—O7	119.07 (17)	C15—O20—C21	114.32 (16)
N1—C7A—C3A	115.30 (18)	O20—C21—H21A	109.5
O7—C7A—C3A	125.62 (16)	O20—C21—H21B	109.5
C3—C8—H8A	109.5	H21A—C21—H21B	109.5
C3—C8—H8B	109.5	O20—C21—H21C	109.5
H8A—C8—H8B	109.5	H21A—C21—H21C	109.5
C3—C8—H8C	109.5	H21B—C21—H21C	109.5
H8A—C8—H8C	109.5	C16—O22—C23	117.11 (17)
H8B—C8—H8C	109.5	O22—C23—H23A	109.5
N10—C9—C5	179.2 (2)	O22—C23—H23B	109.5
C6—N11—H40	122.9 (15)	H23A—C23—H23B	109.5
C6—N11—H50	124.7 (13)	O22—C23—H23C	109.5
H40—N11—H50	112.3 (19)	H23A—C23—H23C	109.5
C13—C12—C17	120.38 (17)	H23B—C23—H23C	109.5
C13—C12—C4	120.79 (17)

C7A—N1—N2—C3	0.3 (2)	C4—C3A—C7A—O7	1.5 (3)
N1—N2—C3—C3A	−0.3 (2)	C3A—C4—C12—C13	−69.8 (2)
N1—N2—C3—C8	179.5 (2)	C5—C4—C12—C13	50.1 (2)
N2—C3—C3A—C7A	0.2 (2)	C3A—C4—C12—C17	106.20 (19)
C8—C3—C3A—C7A	−179.6 (2)	C5—C4—C12—C17	−133.86 (17)
N2—C3—C3A—C4	177.34 (19)	C17—C12—C13—C14	−2.8 (3)
C8—C3—C3A—C4	−2.4 (4)	C4—C12—C13—C14	173.21 (16)
C3—C3A—C4—C5	−172.4 (2)	C12—C13—C14—O18	179.75 (17)
C7A—C3A—C4—C5	4.2 (2)	C12—C13—C14—C15	−0.6 (3)
C3—C3A—C4—C12	−48.0 (3)	O18—C14—C15—C16	−176.85 (16)
C7A—C3A—C4—C12	128.68 (19)	C13—C14—C15—C16	3.5 (3)
C3A—C4—C5—C6	−5.9 (2)	O18—C14—C15—O20	5.5 (3)
C12—C4—C5—C6	−128.09 (19)	C13—C14—C15—O20	−174.18 (15)
C3A—C4—C5—C9	177.73 (15)	O20—C15—C16—O22	−5.8 (3)
C12—C4—C5—C9	55.6 (2)	C14—C15—C16—O22	176.56 (17)
C9—C5—C6—N11	−1.5 (3)	O20—C15—C16—C17	174.73 (16)
C4—C5—C6—N11	−177.8 (2)	C14—C15—C16—C17	−3.0 (3)
C9—C5—C6—O7	178.23 (17)	C13—C12—C17—C16	3.3 (3)
C4—C5—C6—O7	1.9 (3)	C4—C12—C17—C16	−172.74 (16)
N11—C6—O7—C7A	−175.81 (17)	O22—C16—C17—C12	−179.90 (17)
C5—C6—O7—C7A	4.4 (3)	C15—C16—C17—C12	−0.4 (3)
N2—N1—C7A—O7	−179.27 (16)	C13—C14—O18—C19	−1.1 (3)
N2—N1—C7A—C3A	−0.2 (2)	C15—C14—O18—C19	179.25 (19)
C6—O7—C7A—N1	172.79 (16)	C16—C15—O20—C21	94.3 (2)
C6—O7—C7A—C3A	−6.2 (3)	C14—C15—O20—C21	−88.0 (2)
C3—C3A—C7A—N1	0.0 (2)	C15—C16—O22—C23	−177.29 (19)
C4—C3A—C7A—N1	−177.51 (16)	C17—C16—O22—C23	2.2 (3)
C3—C3A—C7A—O7	179.01 (18)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H30···O20ⁱ	0.94 (2)	1.96 (2)	2.882 (2)	165 (2)
N11—H40···N1ⁱⁱ	0.95 (2)	2.11 (2)	3.030 (3)	163 (2)
N11—H50···N10ⁱⁱⁱ	0.91 (2)	2.25 (2)	3.156 (3)	172 (2)
C8—H8C···O18ⁱ	0.96	2.52	3.305 (3)	139
C19—H19B···N1^iv	0.96	2.52	3.455 (4)	165
C21—H21A···Cg3^v	0.96	2.85	3.55	130

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1; (iii) −x, −y+1, −z+2; (iv) −x, −y, −z+1; (v) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H30···O20ⁱ	0.94 (2)	1.96 (2)	2.882 (2)	165 (2)
N11—H40···N1ⁱⁱ	0.95 (2)	2.11 (2)	3.030 (3)	163 (2)
N11—H50···N10ⁱⁱⁱ	0.91 (2)	2.25 (2)	3.156 (3)	172 (2)
C8—H8C···O18ⁱ	0.96	2.52	3.305 (3)	139
C19—H19B···N1^iv	0.96	2.52	3.455 (4)	165
C21—H21A···Cg3^v	0.96	2.85	3.55	130

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1; (iii) −x, −y+1, −z+2; (iv) −x, −y, −z+1; (v) −x+1, −y, −z+2.

Acknowledgements

RK acknowledges the Department of Science & Technology for the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. GB is thankful to the CSIR, New Delhi, for financial support [grant No. 02 (110)/12/EMR-II]. BB is grateful to the UGC, New Delhi for the award of a Senior Research Fellowship.

References

Abdelrazek, F. M., Metz, P., Kataeva, O., Jager, A. & El-Mahrouky, S. F. (2007). Arch. Pharm. 340, 543–548. Web of Science CSD CrossRef CAS Google Scholar
Bhavanarushi, S., Kanakaiah, V., Yakaiah, E., Saddanapu, V., Addlagatta, A. & Rani, V. J. (2013). Med. Chem. Res. 22, 2446–2454. Web of Science CrossRef CAS Google Scholar
Brahmachari, G. & Banerjee, B. (2014). ACS Sustainable Chem. Eng. 2, 411–422. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Low, J. N., Cobo, J., Portilla, J., Quiroga, J. & Glidewell, C. (2004). Acta Cryst. E60, o1034–o1037. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mohamed, N. R., Khaireldin, N. Y., Fahmy, A. F. & El-Sayed, A. A. (2010). Der Pharma Chem. 2, 400–417. CAS Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zaki, M. E. A., Soliman, H. A., Hiekal, O. A. & Rashad, A. E. Z. (2006). Z. Naturforsch. Teil C, 61, 1–5. CAS Google Scholar

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Volume 70| Part 8| August 2014| Pages o875-o876

doi:10.1107/S1600536814015670

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6-Amino-3-methyl-4-(3,4,5-tri­meth­­oxy­phen­yl)-2,4-di­hydro­pyrano[2,3-c]pyrazole-5-carbo­nitrile

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organic compounds

6-Amino-3-methyl-4-(3,4,5-trimethoxyphenyl)-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile