1-[5-(4-Meth­oxy­phen­yl)-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl]ethanone

Abbas, A.; Hussain, S.; Hafeez, N.; Lo, K.M.; Hasan, A.

doi:10.1107/S1600536810045861

1-[5-(4-Methoxyphenyl)-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl]ethanone

A. Abbas, S. Hussain, N. Hafeez, K. M. Lo and A. Hasan

The title molecule, C₁₈H₁₈N₂O₂, is V-shaped with the pyrazoline moiety being inclined to the adjacent phenyl ring by an angle of 6.49 (9)°, while the 4-methoxy-substituted ring is inclined to the pyrazoline ring by 82.99 (9)°. In the crystal, adjacent molecules are linked by C—H

O interactions, forming chains propagating in [100]. There are also C—H

π interactions involving adjacent molecules and those related by an inversion center.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810045861/su2223sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810045861/su2223Isup2.hkl Contains datablock I

CCDC reference: 803177

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.050
wR factor = 0.164
Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT923_ALERT_1_B S    values in the CIF and FCF Differ by .......       0.03

Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         15
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          5
PLAT922_ALERT_1_C wR2 * 100.0 in the CIF and FCF Differ by .......       0.39
PLAT927_ALERT_1_C Reported and Calculated  wR2 * 100.0 Differ by .       0.39

Alert level G
PLAT793_ALERT_4_G The Model has Chirality at C8      (Verify) ....          R

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Pyrazoline systems are well known nitrogen-containing heterocyclic compounds which possess a wide range of biological and pharmacological activities such as antitumor (Hatheway et al., 1978), immunosuppressive (Lombardino et al.,1981), psychoanaleptic (Parmar et al., 1974), anti-inflammation (Rathish et al., 2009), and anticancer (Subbaramaiah et al., 2002). In continuation of previous structural studies of alkoxy group bearing pyrazoline derivatives (Abbas et al., 2010), the title compound was synthesized and its crystal structure is reported on herein.

The molecular structure of the title compound is shown in Fig. 1. All the bond lengths and bond angles are similar to those observed in similar structures (Fahrni et al., 2003; Bai et al., 2009; Lu et al., 2008). In the pyrazolinyl ring, the C8—N2 and C10=N1 bond lengths, 1.483 (2) and 1.2860 (18) Å, respectively, are comparable with those in similar structures [C—N 1.482 (2)–1.515 (9) A°, C=N 1.291 (2)–1.300 (10) A°]. The N1—N2 bond length of 1.3867 (16) Å is slightly longer than that found in a similar structure [N–N 1.373 (2)–1.380 (8) A°] (Jian et al., 2008). The plane containing the pyrazoline moiety is inclined to the adjacent phenyl ring (C16-C21) by 6.49 (9)\%, while the 4-methoxy substituted phenyl ring (C2-C7) is inclined to the pyrazoline moiety by 82.99 (9) °.

In the crystal adjacent molecules are linked by a C-H···O interaction forming chains propagating in [100]. There are also C-H···π interactions involving adjacent molecules and those related by an inversion center; see Table 1 for details.

Related literature top

For biological and pharmacological activity of 2-pyrazoline derivatives, see: Hatheway et al. (1978); Lombardino et al. (1981); Parmar et al. (1974); Rathish et al. (2009); Subbaramaiah et al. (2002). For the synthesis and crystal structure of alkoxy group-bearing 2-pyrazoline derivatives, see: Abbas et al. (2010); Bai et al. (2009); Lu et al. (2008); Fahrni et al. (2003); Jian et al. (2008).

Experimental top

To a mixture of (E)-3-(4-(methoxy)phenyl)-1-phenylprop-2-en-1-one (2.94 g, 10 mmol) and hydrazine hydrate (1.0 g, 20 mmol) in acetic acid (25 ml), were added two drops of concentrated hydrochloric acid. The mixture was refluxed for 5 h. The precipitated solids were filtered, dried and recrystallized from ethanol. The crystals, suitable for X-ray diffraction analysis, were obtained from a mixture of ethyl acetate and dichloromethane (v:v / 1:1) by slow evaporation.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: pubCIF (Westrip, 2010).

Figures top

Fig. 1. A view of the molecular structure of the title molecule, showing the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

1-[5-(4-Methoxyphenyl)-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl]ethanone top

Crystal data top

C₁₈H₁₈N₂O₂	Z = 2
M_r = 294.34	F(000) = 312
Triclinic, P1	D_x = 1.292 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2762 (9) Å	Cell parameters from 2249 reflections
b = 7.2081 (9) Å	θ = 3.1–26.2°
c = 18.570 (2) Å	µ = 0.09 mm⁻¹
α = 85.939 (9)°	T = 296 K
β = 85.384 (9)°	Block, white
γ = 64.709 (8)°	0.30 × 0.30 × 0.20 mm
V = 756.51 (17) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	3448 independent reflections
Radiation source: fine-focus sealed tube	2584 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→7
T_min = 0.975, T_max = 0.983	k = −9→9
7199 measured reflections	l = −24→24

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.164	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0912P)² + 0.0545P] where P = (F_o² + 2F_c²)/3
3448 reflections	(Δ/σ)_max < 0.001
201 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₈H₁₈N₂O₂	γ = 64.709 (8)°
M_r = 294.34	V = 756.51 (17) Å³
Triclinic, P1	Z = 2
a = 6.2762 (9) Å	Mo Kα radiation
b = 7.2081 (9) Å	µ = 0.09 mm⁻¹
c = 18.570 (2) Å	T = 296 K
α = 85.939 (9)°	0.30 × 0.30 × 0.20 mm
β = 85.384 (9)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3448 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2584 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.983	R_int = 0.026
7199 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.164	H-atom parameters constrained
S = 1.08	Δρ_max = 0.18 e Å⁻³
3448 reflections	Δρ_min = −0.26 e Å⁻³
201 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.

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
O1	0.4631 (3)	−0.2736 (2)	0.45861 (9)	0.0843 (5)
C3	0.4986 (3)	−0.0139 (3)	0.37307 (9)	0.0537 (4)
H3	0.6618	−0.0701	0.3751	0.064*
C4	0.3831 (3)	0.1595 (3)	0.32925 (9)	0.0500 (4)
H4	0.4709	0.2180	0.3018	0.060*
O2	−0.1965 (2)	0.2057 (2)	0.21830 (7)	0.0643 (4)
C16	0.4222 (3)	0.6534 (2)	0.08234 (9)	0.0494 (4)
H16	0.3703	0.5800	0.0546	0.059*
N2	0.0349 (2)	0.3699 (2)	0.20010 (7)	0.0452 (3)
N1	0.1673 (2)	0.44578 (18)	0.15426 (7)	0.0401 (3)
C1	0.7049 (4)	−0.3530 (3)	0.47300 (13)	0.0760 (6)
H1A	0.7996	−0.3994	0.4291	0.114*
H1B	0.7424	−0.4661	0.5077	0.114*
H1C	0.7366	−0.2475	0.4920	0.114*
C2	0.3689 (3)	−0.1025 (3)	0.41372 (9)	0.0564 (4)
C5	0.1405 (3)	0.2471 (2)	0.32553 (8)	0.0456 (4)
C8	0.0129 (3)	0.4317 (2)	0.27581 (8)	0.0472 (4)
H8	−0.1543	0.4988	0.2920	0.057*
C9	0.1164 (3)	0.5910 (3)	0.26675 (9)	0.0511 (4)
H9A	−0.0054	0.7288	0.2738	0.061*
H9B	0.2381	0.5615	0.3005	0.061*
C10	0.2176 (2)	0.5667 (2)	0.19012 (8)	0.0388 (3)
C11	0.3582 (3)	0.6705 (2)	0.15576 (8)	0.0399 (3)
C15	0.5613 (3)	0.7436 (3)	0.05020 (10)	0.0601 (5)
H15	0.6047	0.7297	0.0011	0.072*
C14	0.6364 (3)	0.8549 (3)	0.09092 (11)	0.0597 (5)
H14	0.7331	0.9138	0.0694	0.072*
C13	0.5693 (3)	0.8791 (3)	0.16288 (10)	0.0558 (4)
H13	0.6178	0.9566	0.1899	0.067*
C12	0.4290 (3)	0.7881 (2)	0.19563 (9)	0.0481 (4)
H12	0.3823	0.8059	0.2444	0.058*
C17	−0.0737 (3)	0.2610 (2)	0.17608 (9)	0.0460 (4)
C18	−0.0336 (3)	0.2129 (3)	0.09780 (10)	0.0546 (4)
H18A	0.1118	0.0928	0.0906	0.082*
H18B	−0.0251	0.3269	0.0697	0.082*
H18C	−0.1617	0.1882	0.0828	0.082*
C6	0.0143 (3)	0.1551 (3)	0.36706 (9)	0.0538 (4)
H6	−0.1492	0.2116	0.3657	0.065*
C7	0.1271 (3)	−0.0172 (3)	0.40986 (10)	0.0599 (5)
H7	0.0396	−0.0774	0.4366	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0905 (11)	0.0808 (10)	0.0967 (11)	−0.0527 (9)	−0.0259 (9)	0.0337 (8)
C3	0.0521 (9)	0.0614 (10)	0.0550 (10)	−0.0316 (8)	0.0020 (7)	−0.0057 (8)
C4	0.0551 (9)	0.0630 (10)	0.0458 (8)	−0.0396 (8)	0.0082 (7)	−0.0047 (7)
O2	0.0651 (8)	0.0827 (9)	0.0682 (8)	−0.0548 (7)	0.0016 (6)	0.0011 (7)
C16	0.0627 (10)	0.0455 (8)	0.0521 (9)	−0.0349 (8)	0.0060 (7)	−0.0092 (7)
N2	0.0524 (8)	0.0529 (7)	0.0433 (7)	−0.0356 (6)	0.0019 (6)	−0.0019 (6)
N1	0.0424 (6)	0.0418 (6)	0.0435 (7)	−0.0257 (5)	−0.0004 (5)	0.0006 (5)
C1	0.0838 (15)	0.0640 (12)	0.0780 (14)	−0.0283 (11)	−0.0145 (11)	0.0035 (10)
C2	0.0732 (12)	0.0592 (10)	0.0508 (9)	−0.0416 (9)	−0.0063 (8)	0.0018 (8)
C5	0.0541 (9)	0.0554 (9)	0.0390 (7)	−0.0353 (8)	0.0072 (6)	−0.0070 (6)
C8	0.0514 (9)	0.0537 (9)	0.0443 (8)	−0.0307 (7)	0.0068 (7)	−0.0067 (7)
C9	0.0660 (10)	0.0497 (9)	0.0473 (9)	−0.0343 (8)	0.0059 (7)	−0.0084 (7)
C10	0.0407 (7)	0.0358 (7)	0.0438 (8)	−0.0201 (6)	−0.0016 (6)	−0.0021 (6)
C11	0.0418 (7)	0.0324 (7)	0.0492 (8)	−0.0194 (6)	−0.0034 (6)	0.0003 (6)
C15	0.0774 (12)	0.0567 (10)	0.0590 (10)	−0.0433 (9)	0.0167 (9)	−0.0087 (8)
C14	0.0634 (11)	0.0516 (10)	0.0783 (13)	−0.0400 (9)	0.0057 (9)	−0.0007 (9)
C13	0.0650 (11)	0.0491 (9)	0.0698 (11)	−0.0387 (8)	−0.0122 (9)	−0.0011 (8)
C12	0.0571 (9)	0.0458 (8)	0.0504 (9)	−0.0297 (7)	−0.0062 (7)	−0.0014 (7)
C17	0.0424 (8)	0.0482 (8)	0.0566 (9)	−0.0282 (7)	−0.0051 (7)	0.0034 (7)
C18	0.0631 (10)	0.0573 (10)	0.0587 (10)	−0.0387 (9)	−0.0103 (8)	−0.0033 (8)
C6	0.0554 (10)	0.0712 (11)	0.0497 (9)	−0.0426 (9)	0.0052 (7)	−0.0016 (8)
C7	0.0717 (12)	0.0772 (12)	0.0520 (9)	−0.0541 (10)	0.0013 (8)	0.0071 (8)

Geometric parameters (Å, º) top

O1—C2	1.370 (2)	C8—C9	1.537 (2)
O1—C1	1.415 (2)	C8—H8	0.9800
C3—C2	1.384 (2)	C9—C10	1.501 (2)
C3—C4	1.388 (2)	C9—H9A	0.9700
C3—H3	0.9300	C9—H9B	0.9700
C4—C5	1.382 (2)	C10—C11	1.467 (2)
C4—H4	0.9300	C11—C12	1.389 (2)
O2—C17	1.2202 (19)	C15—C14	1.380 (3)
C16—C15	1.374 (2)	C15—H15	0.9300
C16—C11	1.389 (2)	C14—C13	1.369 (3)
C16—H16	0.9300	C14—H14	0.9300
N2—C17	1.3544 (19)	C13—C12	1.388 (2)
N2—N1	1.3867 (16)	C13—H13	0.9300
N2—C8	1.483 (2)	C12—H12	0.9300
N1—C10	1.2860 (18)	C17—C18	1.495 (2)
C1—H1A	0.9600	C18—H18A	0.9600
C1—H1B	0.9600	C18—H18B	0.9600
C1—H1C	0.9600	C18—H18C	0.9600
C2—C7	1.379 (3)	C6—C7	1.370 (3)
C5—C6	1.393 (2)	C6—H6	0.9300
C5—C8	1.516 (2)	C7—H7	0.9300

C2—O1—C1	118.98 (16)	C8—C9—H9B	111.2
C2—C3—C4	119.52 (16)	H9A—C9—H9B	109.1
C2—C3—H3	120.2	N1—C10—C11	120.66 (14)
C4—C3—H3	120.2	N1—C10—C9	113.99 (13)
C5—C4—C3	121.48 (15)	C11—C10—C9	125.34 (13)
C5—C4—H4	119.3	C16—C11—C12	118.70 (14)
C3—C4—H4	119.3	C16—C11—C10	120.40 (13)
C15—C16—C11	120.83 (15)	C12—C11—C10	120.90 (14)
C15—C16—H16	119.6	C16—C15—C14	119.84 (17)
C11—C16—H16	119.6	C16—C15—H15	120.1
C17—N2—N1	122.42 (13)	C14—C15—H15	120.1
C17—N2—C8	124.22 (13)	C13—C14—C15	120.30 (15)
N1—N2—C8	113.24 (11)	C13—C14—H14	119.8
C10—N1—N2	108.02 (12)	C15—C14—H14	119.8
O1—C1—H1A	109.5	C14—C13—C12	120.07 (15)
O1—C1—H1B	109.5	C14—C13—H13	120.0
H1A—C1—H1B	109.5	C12—C13—H13	120.0
O1—C1—H1C	109.5	C13—C12—C11	120.19 (16)
H1A—C1—H1C	109.5	C13—C12—H12	119.9
H1B—C1—H1C	109.5	C11—C12—H12	119.9
O1—C2—C7	115.83 (16)	O2—C17—N2	119.62 (16)
O1—C2—C3	124.75 (17)	O2—C17—C18	123.10 (14)
C7—C2—C3	119.42 (16)	N2—C17—C18	117.28 (13)
C4—C5—C6	117.83 (15)	C17—C18—H18A	109.5
C4—C5—C8	122.07 (14)	C17—C18—H18B	109.5
C6—C5—C8	120.04 (15)	H18A—C18—H18B	109.5
N2—C8—C5	110.93 (13)	C17—C18—H18C	109.5
N2—C8—C9	100.75 (12)	H18A—C18—H18C	109.5
C5—C8—C9	115.68 (13)	H18B—C18—H18C	109.5
N2—C8—H8	109.7	C7—C6—C5	121.05 (16)
C5—C8—H8	109.7	C7—C6—H6	119.5
C9—C8—H8	109.7	C5—C6—H6	119.5
C10—C9—C8	102.96 (12)	C6—C7—C2	120.69 (16)
C10—C9—H9A	111.2	C6—C7—H7	119.7
C8—C9—H9A	111.2	C2—C7—H7	119.7
C10—C9—H9B	111.2

C2—C3—C4—C5	0.4 (3)	C8—C9—C10—C11	−173.86 (14)
C17—N2—N1—C10	170.50 (14)	C15—C16—C11—C12	2.7 (2)
C8—N2—N1—C10	−5.73 (17)	C15—C16—C11—C10	−177.55 (15)
C1—O1—C2—C7	−171.49 (18)	N1—C10—C11—C16	5.5 (2)
C1—O1—C2—C3	8.9 (3)	C9—C10—C11—C16	−173.24 (14)
C4—C3—C2—O1	179.81 (17)	N1—C10—C11—C12	−174.79 (13)
C4—C3—C2—C7	0.2 (3)	C9—C10—C11—C12	6.5 (2)
C3—C4—C5—C6	−0.3 (2)	C11—C16—C15—C14	−0.8 (3)
C3—C4—C5—C8	−177.65 (15)	C16—C15—C14—C13	−1.2 (3)
C17—N2—C8—C5	70.55 (18)	C15—C14—C13—C12	1.3 (3)
N1—N2—C8—C5	−113.30 (14)	C14—C13—C12—C11	0.7 (3)
C17—N2—C8—C9	−166.43 (15)	C16—C11—C12—C13	−2.7 (2)
N1—N2—C8—C9	9.72 (16)	C10—C11—C12—C13	177.64 (14)
C4—C5—C8—N2	77.68 (18)	N1—N2—C17—O2	−176.77 (14)
C6—C5—C8—N2	−99.57 (17)	C8—N2—C17—O2	−1.0 (2)
C4—C5—C8—C9	−36.3 (2)	N1—N2—C17—C18	3.8 (2)
C6—C5—C8—C9	146.50 (15)	C8—N2—C17—C18	179.57 (14)
N2—C8—C9—C10	−9.34 (15)	C4—C5—C6—C7	−0.3 (3)
C5—C8—C9—C10	110.31 (14)	C8—C5—C6—C7	177.01 (16)
N2—N1—C10—C11	179.75 (12)	C5—C6—C7—C2	1.0 (3)
N2—N1—C10—C9	−1.36 (17)	O1—C2—C7—C6	179.48 (17)
C8—C9—C10—N1	7.31 (17)	C3—C2—C7—C6	−0.8 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg3 are the centroids of the N1,N2,C8–C10 and C11–C16 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2ⁱ	0.93	2.47	3.331 (2)	154
C1—H1C···Cg1ⁱⁱ	0.96	2.96	3.755 (2)	141
C12—H12···Cg1ⁱⁱⁱ	0.93	2.96	3.7783 (18)	148
C18—H18A···Cg3^iv	0.96	2.63	3.544 (2)	159

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₈N₂O₂
M_r	294.34
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.2762 (9), 7.2081 (9), 18.570 (2)
α, β, γ (°)	85.939 (9), 85.384 (9), 64.709 (8)
V (Å³)	756.51 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.975, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	7199, 3448, 2584
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.164, 1.08
No. of reflections	3448
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.26

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), pubCIF (Westrip, 2010).