1-{3-(4-Chloro­phen­yl)-5-[4-(propan-2-yl)phen­yl]-4,5-di­hydro-1H-pyrazol-1-yl}propan-1-one

Narayana, B.; Salian, V.V.; Sarojini, B.K.; Jasinski, J.P.

doi:10.1107/S1600536814013075

1-{3-(4-Chlorophenyl)-5-[4-(propan-2-yl)phenyl]-4,5-dihydro-1H-pyrazol-1-yl}propan-1-one

B. Narayana, V. V. Salian, B. K. Sarojini and J. P. Jasinski

In the title compound, C₂₁H₂₃ClN₂O, the dihedral angle between the benzene rings is 83.2 (6)°, while the mean plane of the pyrazole ring [r.m.s. deviation = 0.043 (1) Å] makes dihedral angles of 3.4 (3) and 86.2 (1)° with the benzene rings. In the crystal, a pair of weak C—H

O interactions between the benzene ring and the propan-1-one group link the molecules into an inversion dimer with an R₂²(16) graph-set motif. In addition, a weak π–π stacking interaction [centroid–centroid distance = 3.959 (4) Å] connects the dimers into a tape running along [201].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536814013075/is5364sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536814013075/is5364Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536814013075/is5364Isup3.cml Supplementary material

CCDC reference: 1006823

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.002 Å
R factor = 0.047
wR factor = 0.133
Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         11 Why ?

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT793_ALERT_4_G The Model has Chirality at C3      .............          R Verify
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          1 Why ?
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         93 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   1 ALERT type 5 Informative message, check

Comment top

Pyrazolines are important nitrogen containing five-membered heterocyclic compounds. Pyrazoline derivatives possess important biological activities, including antitumor (Taylor et al., 1992), immunosuppressive (Lombardino & Otterness, 1977), anticancer (Manna et al., 2005), antimicrobial, analgesic and antioxidant activities (Samshuddin et al., 2012a,b).

In the title compound, the dihedral angle between the benzene rings is 83.2 (6)°, while the pyrazole ring is separated from each of the benzene rings by 3.4 (3)° (C16–C21) and 86.2 (1)° (C7–C12), respectively (Fig. 1). Bond lengths are in normal ranges (Allen et al., 1987). In the crystal, a weak C—H···O intermolecular interaction between the benzene ring and the propan-1-one group is observed forming dimers in an R₂²(16) ring-set motif (Fig. 2). In addition, a weak π–π intermolecular stacking interaction [Cg3···Cg3 (1 - x, 2 - y, 1 - z) = 3.959 (4) Å; Cg3: C16–C21] is present and influences the crystal packing.

Related literature top

For the biological activity of pyrazolines, see: Taylor et al. (1992); Lombardino & Otterness (1977); Manna et al. (2005); Samshuddin et al. (2012a,b). For standard bond lengths, see: Allen et al. (1987). For a related structure, see: Narayana et al., (2014).

Experimental top

To a mixture of (2E)-1-(4-chlorophenyl)-3-[4-(propan-2-yl)phenyl] prop-2-en-1-one (2.85 g, 0.01 mol) and hydrazine hydrate (0.5 mL, 0.01 mol) in 20 mL propionic acid was refluxed for 8 h (Fig. 3). The reaction mixture was cooled and poured into 50 mL ice-cold water. The precipitate formed was collected by filtration and purified by recrystallization from ethanol. Single crystals were grown from DMF by the slow evaporation method. (m.p.: 365–367 K).

Structure description top

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus et al., 2012); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. ORTEP drawing of the title compound showing the labeling scheme with 30% probability displacement ellipsoids.
	Fig. 2. Molecular packing of the title compound viewed along the a axis. Dashed lines indicate weak C—H···O intermolecular interactions between the benzene ring and the ketone group forming dimers with an R₂²[16] ring motif. H atoms not involved in these interactions have been removed for clarity.
	Fig. 3. Synthesis of the title compound.

1-{3-(4-Chlorophenyl)-5-[4-(propan-2-yl)phenyl]-4,5-dihydro-1H-pyrazol-1-yl}propan-1-one top

Crystal data top

C₂₁H₂₃ClN₂O	Z = 2
M_r = 354.86	F(000) = 376
Triclinic, P1	D_x = 1.286 Mg m⁻³
a = 6.6042 (3) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.1188 (9) Å	Cell parameters from 2712 reflections
c = 14.4806 (12) Å	θ = 4.6–72.1°
α = 98.444 (7)°	µ = 1.92 mm⁻¹
β = 90.650 (6)°	T = 173 K
γ = 106.542 (6)°	Irregular, colourless
V = 916.13 (12) Å³	0.36 × 0.28 × 0.16 mm

Data collection top

Agilent Eos Gemini diffractometer	3519 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3170 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 16.0416 pixels mm^-1	θ_max = 72.2°, θ_min = 4.6°
ω scans	h = −6→8
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	k = −12→12
T_min = 0.583, T_max = 0.736	l = −14→17
5565 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.047	w = 1/[σ²(F_o²) + (0.0778P)² + 0.2126P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.133	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.31 e Å⁻³
3519 reflections	Δρ_min = −0.27 e Å⁻³
230 parameters	Extinction correction: SHELXL2012 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0079 (10)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₁H₂₃ClN₂O	γ = 106.542 (6)°
M_r = 354.86	V = 916.13 (12) Å³
Triclinic, P1	Z = 2
a = 6.6042 (3) Å	Cu Kα radiation
b = 10.1188 (9) Å	µ = 1.92 mm⁻¹
c = 14.4806 (12) Å	T = 173 K
α = 98.444 (7)°	0.36 × 0.28 × 0.16 mm
β = 90.650 (6)°

Data collection top

Agilent Eos Gemini diffractometer	3519 independent reflections
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	3170 reflections with I > 2σ(I)
T_min = 0.583, T_max = 0.736	R_int = 0.039
5565 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.05	Δρ_max = 0.31 e Å⁻³
3519 reflections	Δρ_min = −0.27 e Å⁻³
230 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Cl1	0.09015 (7)	0.80472 (5)	0.39149 (3)	0.04238 (19)
O1	1.2342 (2)	0.71922 (13)	0.84127 (9)	0.0348 (3)
N1	0.9973 (2)	0.77738 (13)	0.75592 (9)	0.0247 (3)
N2	0.8703 (2)	0.75374 (13)	0.67523 (9)	0.0239 (3)
C1	0.7420 (2)	0.82811 (16)	0.68834 (11)	0.0234 (3)
C2	0.7635 (2)	0.91195 (18)	0.78502 (11)	0.0272 (4)
H2A	0.6352	0.8793	0.8198	0.033*
H2B	0.7900	1.0126	0.7822	0.033*
C3	0.9569 (2)	0.88334 (16)	0.83017 (11)	0.0243 (3)
H3	0.9150	0.8405	0.8876	0.029*
C4	1.1291 (2)	0.69830 (16)	0.76809 (11)	0.0249 (3)
C5	1.1314 (3)	0.58555 (16)	0.68676 (12)	0.0280 (4)
H5A	0.9900	0.5161	0.6769	0.034*
H5B	1.1619	0.6280	0.6292	0.034*
C6	1.2960 (3)	0.51247 (19)	0.70421 (14)	0.0363 (4)
H6A	1.2959	0.4423	0.6498	0.054*
H6B	1.2625	0.4668	0.7596	0.054*
H6C	1.4361	0.5811	0.7145	0.054*
C7	1.1482 (2)	1.00998 (15)	0.85394 (10)	0.0219 (3)
C8	1.2222 (3)	1.10049 (17)	0.78993 (11)	0.0258 (3)
H8	1.1504	1.0837	0.7302	0.031*
C9	1.3995 (3)	1.21478 (17)	0.81238 (11)	0.0271 (3)
H9	1.4486	1.2740	0.7672	0.033*
C10	1.5071 (3)	1.24473 (16)	0.89944 (11)	0.0252 (3)
C11	1.4312 (3)	1.15487 (17)	0.96358 (11)	0.0278 (4)
H11	1.5005	1.1732	1.0239	0.033*
C12	1.2564 (3)	1.03921 (17)	0.94090 (11)	0.0262 (3)
H12	1.2095	0.9787	0.9856	0.031*
C13	1.7049 (3)	1.36693 (17)	0.92541 (12)	0.0297 (4)
H13	1.7213	1.3878	0.9952	0.036*
C14	1.9003 (3)	1.3267 (2)	0.89069 (16)	0.0432 (5)
H14A	1.8869	1.3024	0.8224	0.065*
H14B	1.9124	1.2463	0.9183	0.065*
H14C	2.0270	1.4056	0.9091	0.065*
C15	1.6934 (3)	1.49961 (19)	0.89028 (16)	0.0450 (5)
H15A	1.8187	1.5766	0.9146	0.067*
H15B	1.5659	1.5228	0.9119	0.067*
H15C	1.6884	1.4847	0.8218	0.067*
C16	0.5854 (2)	0.82406 (16)	0.61440 (11)	0.0245 (3)
C17	0.5637 (3)	0.73309 (19)	0.52963 (12)	0.0315 (4)
H17	0.6547	0.6753	0.5189	0.038*
C18	0.4115 (3)	0.7264 (2)	0.46142 (12)	0.0338 (4)
H18	0.3968	0.6641	0.4042	0.041*
C19	0.2804 (3)	0.81191 (18)	0.47760 (12)	0.0301 (4)
C20	0.2989 (3)	0.90336 (18)	0.56024 (12)	0.0294 (4)
H20	0.2088	0.9619	0.5702	0.035*
C21	0.4514 (2)	0.90838 (17)	0.62857 (11)	0.0272 (4)
H21	0.4644	0.9703	0.6858	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0387 (3)	0.0443 (3)	0.0417 (3)	0.0081 (2)	−0.0167 (2)	0.0083 (2)
O1	0.0367 (7)	0.0342 (7)	0.0332 (7)	0.0118 (5)	−0.0104 (5)	0.0020 (5)
N1	0.0265 (7)	0.0227 (6)	0.0223 (6)	0.0062 (5)	−0.0045 (5)	−0.0024 (5)
N2	0.0236 (7)	0.0228 (6)	0.0230 (6)	0.0046 (5)	−0.0026 (5)	0.0009 (5)
C1	0.0214 (7)	0.0229 (7)	0.0230 (7)	0.0026 (6)	0.0013 (6)	0.0021 (6)
C2	0.0218 (8)	0.0321 (8)	0.0249 (8)	0.0072 (6)	−0.0007 (6)	−0.0033 (6)
C3	0.0251 (8)	0.0242 (7)	0.0219 (7)	0.0063 (6)	0.0014 (6)	−0.0002 (6)
C4	0.0228 (7)	0.0204 (7)	0.0287 (8)	0.0024 (6)	−0.0017 (6)	0.0032 (6)
C5	0.0273 (8)	0.0223 (7)	0.0333 (9)	0.0075 (6)	−0.0015 (6)	0.0004 (6)
C6	0.0329 (9)	0.0277 (8)	0.0497 (11)	0.0117 (7)	0.0013 (8)	0.0043 (7)
C7	0.0226 (7)	0.0218 (7)	0.0209 (7)	0.0079 (6)	0.0004 (6)	−0.0012 (5)
C8	0.0306 (8)	0.0272 (8)	0.0198 (7)	0.0101 (6)	−0.0031 (6)	0.0019 (6)
C9	0.0336 (9)	0.0234 (7)	0.0253 (8)	0.0085 (6)	0.0030 (6)	0.0066 (6)
C10	0.0262 (8)	0.0210 (7)	0.0278 (8)	0.0074 (6)	0.0019 (6)	0.0006 (6)
C11	0.0286 (8)	0.0287 (8)	0.0224 (8)	0.0043 (7)	−0.0036 (6)	0.0010 (6)
C12	0.0291 (8)	0.0271 (8)	0.0206 (7)	0.0051 (6)	0.0009 (6)	0.0040 (6)
C13	0.0317 (9)	0.0237 (8)	0.0287 (8)	0.0022 (7)	0.0000 (7)	0.0005 (6)
C14	0.0292 (9)	0.0395 (10)	0.0530 (12)	0.0027 (8)	−0.0010 (8)	−0.0028 (9)
C15	0.0456 (11)	0.0261 (9)	0.0575 (13)	0.0008 (8)	−0.0035 (9)	0.0079 (8)
C16	0.0213 (7)	0.0266 (8)	0.0234 (8)	0.0037 (6)	−0.0003 (6)	0.0036 (6)
C17	0.0333 (9)	0.0350 (9)	0.0269 (8)	0.0139 (7)	−0.0009 (7)	−0.0013 (7)
C18	0.0358 (9)	0.0380 (9)	0.0260 (8)	0.0115 (7)	−0.0040 (7)	−0.0014 (7)
C19	0.0262 (8)	0.0321 (9)	0.0296 (8)	0.0028 (7)	−0.0047 (6)	0.0085 (7)
C20	0.0251 (8)	0.0291 (8)	0.0351 (9)	0.0089 (6)	0.0004 (7)	0.0067 (7)
C21	0.0244 (8)	0.0268 (8)	0.0284 (8)	0.0056 (6)	0.0014 (6)	0.0012 (6)

Geometric parameters (Å, º) top

Cl1—C19	1.7391 (17)	C9—C10	1.389 (2)
O1—C4	1.218 (2)	C10—C11	1.393 (2)
N1—N2	1.3812 (18)	C10—C13	1.520 (2)
N1—C3	1.4858 (19)	C11—H11	0.9500
N1—C4	1.365 (2)	C11—C12	1.386 (2)
N2—C1	1.282 (2)	C12—H12	0.9500
C1—C2	1.509 (2)	C13—H13	1.0000
C1—C16	1.468 (2)	C13—C14	1.529 (3)
C2—H2A	0.9900	C13—C15	1.525 (2)
C2—H2B	0.9900	C14—H14A	0.9800
C2—C3	1.546 (2)	C14—H14B	0.9800
C3—H3	1.0000	C14—H14C	0.9800
C3—C7	1.515 (2)	C15—H15A	0.9800
C4—C5	1.518 (2)	C15—H15B	0.9800
C5—H5A	0.9900	C15—H15C	0.9800
C5—H5B	0.9900	C16—C17	1.401 (2)
C5—C6	1.516 (2)	C16—C21	1.391 (2)
C6—H6A	0.9800	C17—H17	0.9500
C6—H6B	0.9800	C17—C18	1.382 (2)
C6—H6C	0.9800	C18—H18	0.9500
C7—C8	1.393 (2)	C18—C19	1.388 (3)
C7—C12	1.390 (2)	C19—C20	1.382 (3)
C8—H8	0.9500	C20—H20	0.9500
C8—C9	1.387 (2)	C20—C21	1.389 (2)
C9—H9	0.9500	C21—H21	0.9500

N2—N1—C3	113.63 (12)	C9—C10—C13	122.90 (14)
C4—N1—N2	121.84 (13)	C11—C10—C13	119.59 (15)
C4—N1—C3	124.15 (13)	C10—C11—H11	119.4
C1—N2—N1	108.33 (12)	C12—C11—C10	121.14 (15)
N2—C1—C2	114.20 (14)	C12—C11—H11	119.4
N2—C1—C16	120.84 (14)	C7—C12—H12	119.4
C16—C1—C2	124.92 (14)	C11—C12—C7	121.25 (14)
C1—C2—H2A	111.2	C11—C12—H12	119.4
C1—C2—H2B	111.2	C10—C13—H13	107.4
C1—C2—C3	102.65 (13)	C10—C13—C14	110.30 (14)
H2A—C2—H2B	109.2	C10—C13—C15	113.48 (15)
C3—C2—H2A	111.2	C14—C13—H13	107.4
C3—C2—H2B	111.2	C15—C13—H13	107.4
N1—C3—C2	100.81 (12)	C15—C13—C14	110.46 (16)
N1—C3—H3	109.6	C13—C14—H14A	109.5
N1—C3—C7	112.12 (12)	C13—C14—H14B	109.5
C2—C3—H3	109.6	C13—C14—H14C	109.5
C7—C3—C2	114.82 (13)	H14A—C14—H14B	109.5
C7—C3—H3	109.6	H14A—C14—H14C	109.5
O1—C4—N1	120.11 (15)	H14B—C14—H14C	109.5
O1—C4—C5	123.92 (14)	C13—C15—H15A	109.5
N1—C4—C5	115.96 (14)	C13—C15—H15B	109.5
C4—C5—H5A	109.3	C13—C15—H15C	109.5
C4—C5—H5B	109.3	H15A—C15—H15B	109.5
H5A—C5—H5B	108.0	H15A—C15—H15C	109.5
C6—C5—C4	111.61 (14)	H15B—C15—H15C	109.5
C6—C5—H5A	109.3	C17—C16—C1	120.97 (14)
C6—C5—H5B	109.3	C21—C16—C1	120.24 (14)
C5—C6—H6A	109.5	C21—C16—C17	118.76 (15)
C5—C6—H6B	109.5	C16—C17—H17	119.6
C5—C6—H6C	109.5	C18—C17—C16	120.78 (16)
H6A—C6—H6B	109.5	C18—C17—H17	119.6
H6A—C6—H6C	109.5	C17—C18—H18	120.5
H6B—C6—H6C	109.5	C17—C18—C19	119.09 (16)
C8—C7—C3	121.51 (14)	C19—C18—H18	120.5
C12—C7—C3	120.69 (14)	C18—C19—Cl1	119.18 (14)
C12—C7—C8	117.80 (14)	C20—C19—Cl1	119.38 (14)
C7—C8—H8	119.6	C20—C19—C18	121.45 (16)
C9—C8—C7	120.73 (14)	C19—C20—H20	120.5
C9—C8—H8	119.6	C19—C20—C21	118.94 (15)
C8—C9—H9	119.2	C21—C20—H20	120.5
C8—C9—C10	121.58 (14)	C16—C21—H21	119.5
C10—C9—H9	119.2	C20—C21—C16	120.97 (15)
C9—C10—C11	117.48 (15)	C20—C21—H21	119.5

Cl1—C19—C20—C21	−179.97 (12)	C3—C7—C8—C9	−179.03 (14)
O1—C4—C5—C6	−5.7 (2)	C3—C7—C12—C11	−179.83 (14)
N1—N2—C1—C2	−1.75 (18)	C4—N1—N2—C1	170.50 (14)
N1—N2—C1—C16	−179.56 (13)	C4—N1—C3—C2	−167.46 (14)
N1—C3—C7—C8	66.98 (18)	C4—N1—C3—C7	69.93 (19)
N1—C3—C7—C12	−112.81 (16)	C7—C8—C9—C10	−1.2 (2)
N1—C4—C5—C6	175.14 (14)	C8—C7—C12—C11	0.4 (2)
N2—N1—C3—C2	5.53 (16)	C8—C9—C10—C11	0.5 (2)
N2—N1—C3—C7	−117.09 (14)	C8—C9—C10—C13	178.43 (15)
N2—N1—C4—O1	−177.75 (14)	C9—C10—C11—C12	0.7 (2)
N2—N1—C4—C5	1.4 (2)	C9—C10—C13—C14	−83.6 (2)
N2—C1—C2—C3	5.09 (18)	C9—C10—C13—C15	40.9 (2)
N2—C1—C16—C17	3.7 (2)	C10—C11—C12—C7	−1.1 (3)
N2—C1—C16—C21	−178.10 (14)	C11—C10—C13—C14	94.32 (19)
C1—C2—C3—N1	−5.77 (15)	C11—C10—C13—C15	−141.14 (17)
C1—C2—C3—C7	114.94 (14)	C12—C7—C8—C9	0.8 (2)
C1—C16—C17—C18	177.91 (16)	C13—C10—C11—C12	−177.35 (15)
C1—C16—C21—C20	−178.43 (14)	C16—C1—C2—C3	−177.20 (14)
C2—C1—C16—C17	−173.90 (16)	C16—C17—C18—C19	0.4 (3)
C2—C1—C16—C21	4.3 (2)	C17—C16—C21—C20	−0.1 (2)
C2—C3—C7—C8	−47.29 (19)	C17—C18—C19—Cl1	179.47 (14)
C2—C3—C7—C12	132.92 (15)	C17—C18—C19—C20	0.0 (3)
C3—N1—N2—C1	−2.67 (17)	C18—C19—C20—C21	−0.5 (3)
C3—N1—C4—O1	−5.3 (2)	C19—C20—C21—C16	0.6 (2)
C3—N1—C4—C5	173.88 (13)	C21—C16—C17—C18	−0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.95	2.51	3.419 (2)	161

Symmetry code: (i) −x+3, −y+2, −z+2.