1-[5-(Anthracen-9-yl)-3-(4-nitro­phen­yl)-4,5-dihydro-1H-pyrazol-1-yl]ethan-1-one

Bao-Li Dong; Ming-Liang Wang; Yong-Hua Li

doi:10.1107/S1600536810053365

. 2011 Jan 15;67(Pt 2):o386. doi: 10.1107/S1600536810053365

1-[5-(Anthracen-9-yl)-3-(4-nitrophenyl)-4,5-dihydro-1H-pyrazol-1-yl]ethan-1-one

Bao-Li Dong ^a, Ming-Liang Wang ^a,^*, Yong-Hua Li ^a

PMCID: PMC3051795 PMID: 21523061

Abstract

In the title compound, C₂₅H₁₉N₃O₃, steric repulsion between the methine H atom and one of the anthryl H atoms seems to be concomitant with the considerable distortion of the anthryl fragment from planarity. The side rings of the anthryl subtend an angle of 9.57 (8)°, which is an extreme value among the known reliably determined structures. This angle correlates with the length of the bond by which the anthryl is attached to the rest of the molecule. In the anthryl fragment, the maximum deviation of one of the C atoms from the mean plane is 0.126 (3) Å and regards the carrier C atom involved in the repulsion between the anthryl and the methine H atoms. The interplanar angle between the pyrazoline ring and the anthryl fragment is 88.36 (5)° and that between the pyrazoline and 4-nitrophenyl rings is 8.80 (15)°. Weak intermolecular C—H⋯N, C—H⋯π and π–π interactions [centroid–centroid distances of 3.7659 (17), 3.9477 (15) and 3.8972 (15) Å] are pesent in the structure.

Related literature

For the related structure 1′,2′,3′,4′-tetrahydro-1,3-diphenyl-4-p-tolylspiro[2-pyrazoline-5,2′-naphthalen]-1′-one, see: Krishna et al. (1999 ▶). For examples of the synthetic utility applied in the case of the title compound, see: Akama et al. (1996 ▶); Fahrni et al. (2003 ▶); Wei et al. (2007 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C₂₅H₁₉N₃O₃
M _r = 409.43
Orthorhombic,
a = 22.888 (5) Å
b = 9.4031 (19) Å
c = 8.9688 (18) Å
V = 1930.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.962, T _max = 0.982
19272 measured reflections
2352 independent reflections
2131 reflections with I > 2σ(I)
R _int = 0.062

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.097
S = 1.07
2352 reflections
288 parameters
69 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL/PC.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810053365/fb2230sup1.cif

e-67-0o386-sup1.cif^{(19.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053365/fb2230Isup2.hkl

e-67-0o386-Isup2.hkl^{(115.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1, Cg2 and Cg3 are the centroids of the N1,N2,C15–C17, C5–C7,C12–C14 and C7–C12 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯N1	0.93	2.47	3.047 (3)	120
C8—H8A⋯N2	0.93	2.54	3.391 (3)	152
C8—H8A⋯Cg1	0.93	2.29	2.979 (3)	142
C15—H15A⋯Cg2ⁱ	0.99	2.90 (3)	3.731 (3)	142
C4—H4A⋯Cg3ⁱ	0.976	2.95	3.824 (3)	150

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Pyrazoline derivatives are widely studied compounds. Some of them are capable of prototropic tautomerism (Akama et al., 1996). Others show elevated fluorescence. Therefore they have been widely used as fluorescence probes in some elaborated chemosensors (Fahrni et al., 2003) as well as hole-transport materials in electrophotography and electroluminescence (Wei et al., 2007). Here we report the structure of the title compound, a new derivative of pyrazoline.

In the pyrazoline ring, all the atoms are coplanar with the maximum deviation of 0.0258 (14)° for atom N1. The bond length of N2═C17 [1.2865 (31) Å] agrees with normal C═N bond (1.28 Å). The bond distance of N1—N2 [1.3796 (25) Å] conforms to the expected value (Krishna et al., 1999), too. The mean plane of pyrazoline ring makes interplanar angles of 8.80 (15)° and 88.36 (5)° with 4-nitrophenyl ring and the anthryl fragment, respectively.

The most interesting feature of the title structure is the distortion of the anthryl from planarity. The side rings of the anthryl fragment, i. e. the benzene rings C1\C2\C3\C4\C5\C14 and C7\C8\C9\C10\C11\C12, contain the angle 9.57 (8)°. In the anthryl fragment, the maximum deviation is 0.126 (3) Å from C4 atom to the mean plane of the ring. It can be related to the repulsion between the methine H15A and the anthryl H4A atoms (Fig. 1). The non-bonding distance between these two hydrogens equals to 1.95 Å. The attached atom H4A is also situated out of the plane of the ring.

Fig. 2 was obtained from the search on the Cambridge Crystallographic Structure Database (Allen, 2002; version CSD 5.31 with the last upgrade from Sept. 1 2010) carried out on the structures with R-factor < 0.05, with no disorder, no errors, with exclusion of the powder diffraction determinations and the polymeric structures or structures containing ions. This plot shows the correlation of the interplanar angle of the side anthryl rings with the C—C distance corresponding to C15—C6 (1.520 Å) in the title structure. It can be seen that the loss of planarity of the anthryl fragment is correlated to the lengthening of the bond by which is the anthryl attached to the the rest of the molecule. The present structure is situated at the extreme of the plot in Fig. 2.

There are present only weak intermolecular interactions in the structure: C—H···N, C—H···π- electron ring interactions (Tab. 1). Moreover, there are also π-electron ring -π-electron ring interactions present in the structure: Between the pyrazoline ring N1\N2\C17\C16\C15 and the benzene C1\C2\C3\C4\C5\C14 ring [symmetry code: -x,1-y,1/2+z] with the centroid-centroid distance equal to 3.7659 (17) Å; between the pyrazoline ring N1\N2\C17\C16\C15 and the benzene C5\C6\C7\C12\C13\C14 ring [symmetry code: x, y, z] with the centroid-centroid distance equal to 3.9477 (15) Å and between the pyrazoline ring N1\N2\C17\C16\C15 and the benzene C5\C6\C7\C12\C13\C14 ring [symmetry code: -x, 1-y, 1/2+z] with the centroid-centroid distance equal to 3.8972 (15) Å.

Experimental

3-(9-anthryl)-1-(4-nitrophenylprop)-2-en-1-one (3 mmol) and 0.6 g of hydrazine hydrate aqueous solution (1:1 w/w) were dissolved in 10 ml of glacial acetic acid. The mixture was stirred for 8 h at 391 K to give an orange solid. The product was then isolated and recrystallized from acetonitrile. The average size of light yellow single-crystals of the title structure equalled to 2.0 mm×1.0 mm×1.0 mm.