3,5-Bis(4-fluoro-phen-yl)-4,5-dihydro-1H-pyrazole-1-carbaldehyde.

In the title mol-ecule, C(16)H(12)F(2)N(2)O, the pyrazole ring adopts a slight envelope conformation with the methyl-ene C atom deviating by 0.114 (3) Å from the mean plane of the other four atoms [maximum deviation = 0.021 (3) Å]. The dihedral angles between the four essentially planar atoms of the pyrazole ring and the fluoro-substituted benzene rings are 2.6 (2) and 82.2 (2)°. The dihedral angle between the two benzene rings is 83.7 (2)°. The crystal packing is stabilized by weak inter-molecular C-H⋯O hydrogen bonds.

Related literature

For the biological activity of pyrazolines, see: Hes et al. (1978 ▶); Manna et al. (2005 ▶); Amir et al. (2008 ▶); Regaila et al. (1979 ▶); Sarojini et al. (2010 ▶). For their importance in organic synthesis, see: Bhaskarreddy et al. (1997 ▶); Klimova et al. (1999 ▶). For related structures, see: Butcher et al. (2007 ▶); Cui & Li (2010 ▶); Fun et al. (2010a ▶,b ▶); Jasinski et al. (2010a ▶,b ▶); Baktır et al. (2011 ▶).

Experimental

Crystal data

C16H12F2N2O

M = 286.28

Triclinic,

a = 6.2141 (9) Å

b = 6.7802 (8) Å

c = 17.9857 (9) Å

α = 96.727 (4)°

β = 90.254 (4)°

γ = 116.791 (5)°

V = 670.39 (13) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 294 K

0.30 × 0.20 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▶) T min = 0.968, T max = 0.989

14070 measured reflections

2736 independent reflections

1011 reflections with I > 2σ(I)

R int = 0.095

Refinement

R[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.206

S = 0.94

2736 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.33 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681101587X/lh5239sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681101587X/lh5239Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681101587X/lh5239Isup3.cml

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

C16H12F2N2O	Z = 2
Mr = 286.28	F(000) = 296
Triclinic, P1	Dx = 1.418 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2141 (9) Å	Cell parameters from 1748 reflections
b = 6.7802 (8) Å	θ = 2.3–26.3°
c = 17.9857 (9) Å	µ = 0.11 mm−1
α = 96.727 (4)°	T = 294 K
β = 90.254 (4)°	Prism, pale yellow
γ = 116.791 (5)°	0.30 × 0.20 × 0.10 mm
V = 670.39 (13) Å3

Rigaku R-AXIS RAPID-S diffractometer	2736 independent reflections
Radiation source: Sealed Tube	1011 reflections with I > 2σ(I)
Graphite Monochromator	Rint = 0.095
Detector resolution: 10.0000 pixels mm-1	θmax = 26.5°, θmin = 3.4°
dtprofit.ref scans	h = −7→7
Absorption correction: multi-scan (Blessing, 1995)	k = −8→8
Tmin = 0.968, Tmax = 0.989	l = −22→22
14070 measured reflections

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.206	H-atom parameters constrained
S = 0.94	w = 1/[σ2(Fo2) + (0.0812P)2] where P = (Fo2 + 2Fc2)/3
2736 reflections	(Δ/σ)max < 0.001
191 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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.

	x	y	z	Uiso*/Ueq
F1	−0.7910 (4)	0.0976 (4)	0.04914 (14)	0.1334 (11)
F2	0.7113 (5)	1.4342 (4)	0.49400 (14)	0.1284 (11)
O1	0.9124 (4)	0.8903 (4)	0.23729 (12)	0.0822 (9)
N1	0.3094 (4)	0.6264 (4)	0.16479 (13)	0.0621 (9)
N2	0.5069 (4)	0.7082 (4)	0.21640 (12)	0.0621 (9)
C1	−0.1494 (6)	0.4185 (7)	0.08534 (18)	0.1019 (16)
C2	−0.3750 (7)	0.3162 (8)	0.0481 (2)	0.120 (2)
C3	−0.5702 (6)	0.1944 (7)	0.0858 (2)	0.0937 (16)
C4	−0.5512 (6)	0.1715 (5)	0.1584 (2)	0.0798 (14)
C5	−0.3241 (6)	0.2737 (5)	0.19570 (18)	0.0718 (12)
C6	−0.1199 (5)	0.3980 (5)	0.15912 (16)	0.0643 (11)
C7	0.1190 (5)	0.5070 (5)	0.19872 (15)	0.0583 (11)
C8	0.1722 (5)	0.4922 (5)	0.27855 (16)	0.0728 (12)
C9	0.4427 (5)	0.6519 (5)	0.29283 (15)	0.0650 (11)
C10	0.5095 (5)	0.8590 (5)	0.34783 (15)	0.0637 (11)
C11	0.3760 (6)	0.9769 (6)	0.34948 (17)	0.0713 (11)
C12	0.4417 (7)	1.1706 (6)	0.39825 (19)	0.0820 (16)
C13	0.6424 (7)	1.2450 (6)	0.4449 (2)	0.0873 (16)
C14	0.7786 (7)	1.1343 (6)	0.44657 (19)	0.0870 (14)
C15	0.7124 (6)	0.9408 (6)	0.39679 (17)	0.0774 (14)
C16	0.7313 (6)	0.8185 (5)	0.19475 (18)	0.0696 (12)
H1	−0.01520	0.50270	0.06000	0.1230*
H2	−0.39330	0.33040	−0.00210	0.1440*
H4	−0.68760	0.08870	0.18310	0.0960*
H5	−0.30840	0.25880	0.24590	0.0860*
H8A	0.13880	0.34140	0.28510	0.0870*
H8B	0.07740	0.53940	0.31210	0.0870*
H9	0.52740	0.57050	0.30870	0.0780*
H11	0.23920	0.92430	0.31700	0.0850*
H12	0.35050	1.24820	0.39910	0.0990*
H14	0.91270	1.18720	0.48020	0.1040*
H15	0.80540	0.86500	0.39630	0.0930*
H16	0.75090	0.84190	0.14480	0.0830*

	U11	U22	U33	U12	U13	U23
F1	0.0603 (14)	0.164 (2)	0.142 (2)	0.0304 (15)	−0.0376 (13)	−0.0172 (17)
F2	0.1089 (18)	0.1004 (17)	0.133 (2)	0.0232 (15)	0.0018 (15)	−0.0407 (15)
O1	0.0474 (13)	0.0936 (18)	0.0902 (17)	0.0222 (13)	−0.0112 (12)	−0.0025 (13)
N1	0.0507 (15)	0.0728 (18)	0.0553 (14)	0.0242 (14)	−0.0057 (12)	−0.0030 (12)
N2	0.0451 (15)	0.0734 (18)	0.0576 (14)	0.0203 (14)	−0.0060 (11)	−0.0010 (12)
C1	0.059 (2)	0.159 (4)	0.061 (2)	0.027 (2)	−0.0034 (17)	0.011 (2)
C2	0.070 (3)	0.187 (5)	0.074 (2)	0.037 (3)	−0.015 (2)	0.001 (3)
C3	0.052 (2)	0.105 (3)	0.107 (3)	0.028 (2)	−0.022 (2)	−0.016 (2)
C4	0.051 (2)	0.072 (2)	0.104 (3)	0.0191 (18)	−0.0005 (18)	0.004 (2)
C5	0.059 (2)	0.069 (2)	0.080 (2)	0.0242 (18)	−0.0004 (17)	0.0038 (17)
C6	0.053 (2)	0.075 (2)	0.0613 (18)	0.0286 (18)	−0.0030 (14)	−0.0025 (15)
C7	0.0502 (19)	0.066 (2)	0.0554 (17)	0.0254 (16)	0.0004 (14)	0.0000 (14)
C8	0.063 (2)	0.074 (2)	0.068 (2)	0.0199 (18)	−0.0071 (15)	0.0074 (16)
C9	0.061 (2)	0.070 (2)	0.0583 (17)	0.0253 (17)	−0.0090 (14)	0.0073 (15)
C10	0.0568 (19)	0.072 (2)	0.0541 (17)	0.0232 (17)	−0.0080 (14)	0.0042 (15)
C11	0.065 (2)	0.084 (2)	0.0618 (18)	0.032 (2)	−0.0040 (15)	0.0066 (17)
C12	0.085 (3)	0.086 (3)	0.075 (2)	0.040 (2)	0.0065 (19)	0.0061 (19)
C13	0.082 (3)	0.077 (3)	0.080 (2)	0.022 (2)	0.002 (2)	−0.0147 (19)
C14	0.069 (2)	0.095 (3)	0.078 (2)	0.026 (2)	−0.0154 (18)	−0.011 (2)
C15	0.064 (2)	0.091 (3)	0.066 (2)	0.029 (2)	−0.0137 (16)	−0.0044 (18)
C16	0.050 (2)	0.081 (2)	0.072 (2)	0.0268 (18)	−0.0002 (16)	0.0009 (17)

F1—C3	1.352 (5)	C10—C15	1.385 (5)
F2—C13	1.358 (4)	C11—C12	1.380 (5)
O1—C16	1.225 (4)	C12—C13	1.356 (6)
N1—N2	1.390 (4)	C13—C14	1.363 (6)
N1—C7	1.299 (4)	C14—C15	1.388 (5)
N2—C9	1.478 (4)	C1—H1	0.9300
N2—C16	1.337 (5)	C2—H2	0.9300
C1—C2	1.379 (6)	C4—H4	0.9300
C1—C6	1.370 (4)	C5—H5	0.9300
C2—C3	1.360 (6)	C8—H8A	0.9700
C3—C4	1.344 (5)	C8—H8B	0.9700
C4—C5	1.387 (5)	C9—H9	0.9800
C5—C6	1.388 (5)	C11—H11	0.9300
C6—C7	1.461 (5)	C12—H12	0.9300
C7—C8	1.497 (4)	C14—H14	0.9300
C8—C9	1.534 (5)	C15—H15	0.9300
C9—C10	1.506 (4)	C16—H16	0.9300
C10—C11	1.386 (5)
N2—N1—C7	107.5 (2)	C13—C14—C15	118.4 (4)
N1—N2—C9	113.9 (2)	C10—C15—C14	120.9 (4)
N1—N2—C16	120.5 (2)	O1—C16—N2	123.4 (3)
C9—N2—C16	125.6 (3)	C2—C1—H1	119.00
C2—C1—C6	121.0 (4)	C6—C1—H1	119.00
C1—C2—C3	119.0 (3)	C1—C2—H2	120.00
F1—C3—C2	118.6 (3)	C3—C2—H2	121.00
F1—C3—C4	119.2 (4)	C3—C4—H4	121.00
C2—C3—C4	122.2 (4)	C5—C4—H4	121.00
C3—C4—C5	118.7 (3)	C4—C5—H5	120.00
C4—C5—C6	120.9 (3)	C6—C5—H5	120.00
C1—C6—C5	118.1 (3)	C7—C8—H8A	111.00
C1—C6—C7	121.1 (3)	C7—C8—H8B	111.00
C5—C6—C7	120.8 (3)	C9—C8—H8A	111.00
N1—C7—C6	120.7 (3)	C9—C8—H8B	111.00
N1—C7—C8	113.8 (3)	H8A—C8—H8B	109.00
C6—C7—C8	125.5 (3)	N2—C9—H9	109.00
C7—C8—C9	103.6 (2)	C8—C9—H9	109.00
N2—C9—C8	100.7 (2)	C10—C9—H9	109.00
N2—C9—C10	111.1 (2)	C10—C11—H11	119.00
C8—C9—C10	116.5 (3)	C12—C11—H11	119.00
C9—C10—C11	121.5 (3)	C11—C12—H12	121.00
C9—C10—C15	120.4 (3)	C13—C12—H12	121.00
C11—C10—C15	118.1 (3)	C13—C14—H14	121.00
C10—C11—C12	121.4 (4)	C15—C14—H14	121.00
C11—C12—C13	118.4 (4)	C10—C15—H15	120.00
F2—C13—C12	119.9 (4)	C14—C15—H15	120.00
F2—C13—C14	117.3 (4)	O1—C16—H16	118.00
C12—C13—C14	122.8 (4)	N2—C16—H16	118.00
C7—N1—N2—C9	−4.2 (3)	C5—C6—C7—N1	−178.8 (3)
C7—N1—N2—C16	173.1 (3)	C5—C6—C7—C8	2.3 (5)
N2—N1—C7—C8	−1.3 (4)	C1—C6—C7—N1	0.1 (5)
N2—N1—C7—C6	179.7 (3)	C6—C7—C8—C9	−175.2 (3)
C16—N2—C9—C10	66.3 (4)	N1—C7—C8—C9	5.9 (4)
C16—N2—C9—C8	−169.7 (3)	C7—C8—C9—N2	−7.3 (3)
C9—N2—C16—O1	−1.5 (5)	C7—C8—C9—C10	112.8 (3)
N1—N2—C9—C8	7.4 (3)	C8—C9—C10—C11	−40.0 (4)
N1—N2—C9—C10	−116.5 (3)	C8—C9—C10—C15	142.1 (3)
N1—N2—C16—O1	−178.4 (3)	N2—C9—C10—C15	−103.5 (3)
C2—C1—C6—C7	−179.8 (4)	N2—C9—C10—C11	74.4 (4)
C6—C1—C2—C3	0.3 (7)	C9—C10—C15—C14	178.6 (3)
C2—C1—C6—C5	−0.9 (6)	C9—C10—C11—C12	−177.9 (3)
C1—C2—C3—C4	0.5 (7)	C15—C10—C11—C12	0.0 (5)
C1—C2—C3—F1	179.0 (4)	C11—C10—C15—C14	0.6 (5)
F1—C3—C4—C5	−179.3 (3)	C10—C11—C12—C13	0.3 (5)
C2—C3—C4—C5	−0.8 (6)	C11—C12—C13—C14	−1.3 (6)
C3—C4—C5—C6	0.2 (5)	C11—C12—C13—F2	−179.5 (3)
C4—C5—C6—C1	0.6 (5)	F2—C13—C14—C15	−179.8 (3)
C4—C5—C6—C7	179.5 (3)	C12—C13—C14—C15	1.9 (6)
C1—C6—C7—C8	−178.8 (3)	C13—C14—C15—C10	−1.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1i	0.93	2.50	3.421 (5)	171
C11—H11···O1ii	0.93	2.39	3.296 (5)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O1i	0.93	2.50	3.421 (5)	171
C11—H11⋯O1ii	0.93	2.39	3.296 (5)	165

Symmetry codes: (i) ; (ii) .