Crystal structure of 6-amino-4-(3-bromo-4-meth­oxy­phen­yl)-3-methyl-2,4-di­hydro­pyrano[2,3-c]pyrazole-5-carbo­nitrile dimethyl sulfoxide monosolvate

Sammer Yousuf; Huma Bano; Munira Taj Muhammad; Khalid Mohammed Khan

doi:10.1107/S2056989015010543

. 2015 Jun 6;71(Pt 7):o453–o454. doi: 10.1107/S2056989015010543

Crystal structure of 6-amino-4-(3-bromo-4-methoxyphenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile dimethyl sulfoxide monosolvate

Sammer Yousuf ^a,^*, Huma Bano ^a, Munira Taj Muhammad ^a, Khalid Mohammed Khan ^a

PMCID: PMC4518963 PMID: 26279904

Abstract

In the pyrazole molecule of the title solvate, C₁₅H₁₃BrN₄O₂·C₂H₆OS, the dihedral angle between the benzene ring and the mean plane of the dihydropyrano[2,3-c]pyrazole ring system [r.m.s deviation = 0.031 (2) Å] is 86.71 (14)°. In the crystal, the pyrazole molecules are linked by N—H⋯N hydrogen bonds, forming a layer parallel to (10-1). The pyrazole and dimethyl sulfoxide molecules are connected by an N—H⋯O hydrogen bond.

Keywords: crystal structure, pyrazole derivative, hydrogen bonding

Related literature

For the applications and biological activities of pyrazole derivative, see: Balbia et al. (2011 ▸); Insuasty et al. (2010 ▸); Szabó et al. (2008 ▸); Perchellet et al. (2006 ▸); Tanitame et al. (2004 ▸, 2005 ▸); Abadi et al. (2003 ▸). For crystal structures of related compounds, see: Sharma et al. (2014 ▸). graphic file with name e-71-0o453-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₃BrN₄O₂·C₂H₆OS
M _r = 439.33
Monoclinic,
a = 13.4982 (6) Å
b = 8.3470 (4) Å
c = 17.7173 (8) Å
β = 101.510 (1)°
V = 1956.05 (16) Å³
Z = 4
Mo Kα radiation
μ = 2.23 mm⁻¹
T = 273 K
0.54 × 0.51 × 0.33 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▸) T _min = 0.345, T _max = 0.479
9464 measured reflections
3642 independent reflections
2776 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.149
S = 1.04
3642 reflections
247 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.15 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Data collection: SMART (Bruker, 2000 ▸); cell refinement: SAINT (Bruker, 2000 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ▸) and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015010543/is5403sup1.cif

e-71-0o453-sup1.cif^{(26.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010543/is5403Isup2.hkl

e-71-0o453-Isup2.hkl^{(178.6KB, hkl)}

Click here for additional data file.^{(6.9KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015010543/is5403Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015010543/is5403fig1.tif

The molecular structure of the title compound with displacement ellipsoids drawn at 30% probability level. H atoms have been omitted.

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015010543/is5403fig2.tif

A crystal packing view of the title compound. Only H atoms involved in the hydrogen bonds (dashed lines) are shown.

CCDC reference: 1404448

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N2H2AO3ⁱ	0.82(3)	1.96(4)	2.762(5)	166(4)
N3H3AN4ⁱⁱ	0.84(4)	2.26(4)	3.080(5)	165(3)
N3H3BN1ⁱⁱⁱ	0.86(3)	2.14(4)	2.983(4)	169(3)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors acknowledge the financial support of the Higher Education Commission of Pakistan (HEC) through research projects Nos. 20–1910 and 20–2216 under the National Research Program for Universities.

supplementary crystallographic information

S1. Comment

The pyrazole moiety containing compounds represent an important group of pharmaceutically active molecules with a wide range of biological activities including antifungal (Tanitame et al., 2004), antibacterial (Tanitame et al., 2005), anti-diabetic, (Balbia et al., 2011), anti-inflammatory (Szabo et al., 2008) and antiangiogenesis (Abadi et al., 2003). The pyrazole derivatives are also known to have antiproliferative (Perchellet et al., 2006) and anti-tumor (Insuasty et al., 2010) activities. The title compound was synthesize as a part of our ongoing research to synthesize and evaluate the biological activities of structural analogues of dihydropyrano[2,3-c] pyrazole derivatives. In continuation of our efforts to purify enantiomerically pure compounds from racemic mixtures by using simple crystallization techniques the title compound was crystallize as dimethyl sulfoxide (DMSO) solvate from racemic mixture by dissolving in DMSO at room temperature.

The structure of title compound is similar to that of previously published 6-amino-3-methyl-4-(3,4,5-trimethoxy-phenyl)-2,4-dihydropyrano[2,3-c]- pyrazole-5-carbonitrile (Sharma et al., 2014) with the difference that trimethoxy sustituted phenyl ring is replaced by methoxy substituted bromo benzene ring (Fig. 1). The dihedral angles between the benzene (C1–C6) / pyran (O1/C7–C9/C10/C11) rings and the benzene (C1–C6) / pyrazole (N1/N2/C8/C9/C13) rings are 87.53 (15) and 86.04 (18)°, respectively. The bond lengths and angles are similar as in structurally related benzohydrazide derivatives (Sharma et al., 2014). The crystal structure stabilize by intermolecular N—H···O and N—H···N interactions to form a layer parallel to (101) (Table 2 and Fig. 2).

S2. Experimental

The title compound was synthesized as follows. Dichloromethane (10 ml), 1.0 equivalent (1 mmol) of triethylamine and pyrazolone were taken in a round bottom flask and allowed to stirred for 2 minutes at room temperature followed by the addition of 1.0 equivalent of corresponding pre-synthesized benzylidene from malononitrile and allowed to stir for additional 25–30 min. The progress of reaction was monitored by TLC. The desired product was appeared in the form of precipitates. The precipitates were washed with water to remove the unreacted pyrazolone to obtain pure products. Yeild 79%; m.p. 215 °C. The precipitates were redissolved in DMSO and allow to stand at room temperature for whole night followed by the removal of DMSO under freeze drying condition to obtain single crystals suitable for X-ray diffraction.