Literature DB >> 21587573

(E)-3-(4-Chloro-phen-yl)-3-[3-(4-chloro-phen-yl)-1H-pyrazol-1-yl]prop-2-enal.

V Susindran, S Athimoolam, S Asath Bahadur, R Manikannan, S Muthusubramanian.

Abstract

In the title compound, C(18)H(12)Cl(2)N(2)O, the pyrazole ring is almost planar [r.m.s. deviation = 0.002 Å] while the two chloro-phenyl rings are twisted out from the plane of the pyrazole ring, making dihedral angles of 5.3 (1) and 65.34 (4)°. In the crystal, centrosymmetric R(2) (2)(24) dimers are formed about crystallographic inversion centres through a pair of C-H⋯Cl inter-actions. These dimers are further linked through a C-H⋯O hydrogen bond, forming a C(8) chain extending along the a axis. C-H⋯π inter-actions are also observed.

Entities: Chemical Disease Species

Year: 2010 PMID： 21587573 PMCID： PMC2983380 DOI： 10.1107/S1600536810035646

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For the pharmacological properties of pyrazoles and their derivatives, see: Baraldi et al. (1998 ▶); Bruno et al. (1990 ▶); Chen & Li (1998 ▶); Cottineau et al. (2002 ▶); Londershausen (1996 ▶); Mishra et al. (1998 ▶); Magedov et al. (2007 ▶); Rovnyak et al. (1982 ▶); Smith et al. (2001 ▶); Velaparthi et al. (2008 ▶); Wamhoff et al. (1993 ▶). For hybridization and electron delocalization around N atoms, see: Beddoes et al. (1986 ▶); Jin et al. (2004 ▶). For hydrogen bonding, see: Desiraju & Steiner (1999 ▶) and for hydrogen-bond motifs, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C18H12Cl2N2O M = 343.20 Triclinic, a = 9.4321 (6) Å b = 9.6081 (5) Å c = 9.9439 (7) Å α = 90.533 (7)° β = 116.924 (4)° γ = 93.427 (6)° V = 801.38 (9) Å3 Z = 2 Mo Kα radiation μ = 0.41 mm−1 T = 293 K 0.16 × 0.14 × 0.12 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.884, T max = 0.993 8950 measured reflections 3464 independent reflections 2982 reflections with I > 2σ(I) R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.040 wR(F 2) = 0.116 S = 1.04 3464 reflections 211 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.20 e Å−3 Δρmin = −0.24 e Å−3 Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL/PC; molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL/PC. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810035646/fb2206sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035646/fb2206Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₈H₁₂Cl₂N₂O	Z = 2
M_r = 343.20	F(000) = 352
Triclinic, P1	D_x = 1.422 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4321 (6) Å	Cell parameters from 4879 reflections
b = 9.6081 (5) Å	θ = 2.4–24.7°
c = 9.9439 (7) Å	µ = 0.41 mm⁻¹
α = 90.533 (7)°	T = 293 K
β = 116.924 (4)°	Block, colourless
γ = 93.427 (6)°	0.16 × 0.14 × 0.12 mm
V = 801.38 (9) Å³

Bruker SMART APEX CCD area-detector diffractometer	3464 independent reflections
Radiation source: fine-focus sealed tube	2982 reflections with I > 2σ(I)
graphite	R_int = 0.018
ω scans	θ_max = 27.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −12→11
T_min = 0.884, T_max = 0.993	k = −12→12
8950 measured reflections	l = −12→12

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)] = 0.040	Hydrogen site location: difference Fourier map
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.064P)² + 0.1138P] where P = (F_o² + 2F_c²)/3
3464 reflections	(Δ/σ)_max < 0.001
211 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

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.

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.

	x	y	z	U_iso*/U_eq
N1	0.32051 (15)	0.14597 (14)	0.94391 (16)	0.0637 (3)
N2	0.33330 (15)	0.11932 (14)	0.81571 (16)	0.0645 (3)
C3	0.23105 (17)	0.01018 (15)	0.74769 (19)	0.0609 (4)
C4	0.1527 (2)	−0.03430 (17)	0.8341 (2)	0.0703 (4)
H4	0.0765	−0.1085	0.8109	0.084*
C5	0.2117 (2)	0.05315 (17)	0.9566 (2)	0.0704 (4)
H5	0.1838	0.0510	1.0351	0.084*
C11	0.42212 (17)	0.24992 (16)	1.05026 (18)	0.0616 (4)
C12	0.36968 (16)	0.29488 (15)	1.16169 (18)	0.0588 (3)
C13	0.21605 (17)	0.33822 (17)	1.1154 (2)	0.0656 (4)
H13	0.1469	0.3408	1.0129	0.079*
C14	0.16603 (17)	0.37703 (17)	1.2194 (2)	0.0674 (4)
H14	0.0635	0.4053	1.1877	0.081*
C15	0.26958 (18)	0.37363 (15)	1.3718 (2)	0.0617 (4)
C16	0.42360 (18)	0.33354 (15)	1.42098 (19)	0.0625 (4)
H16	0.4931	0.3333	1.5235	0.075*
C17	0.47177 (16)	0.29416 (15)	1.31565 (18)	0.0604 (4)
H17	0.5746	0.2665	1.3479	0.072*
C31	0.21217 (16)	−0.04755 (15)	0.60370 (19)	0.0596 (4)
C32	0.2953 (2)	0.01493 (17)	0.5314 (2)	0.0679 (4)
H32	0.3586	0.0971	0.5730	0.082*
C33	0.28550 (19)	−0.04239 (17)	0.4007 (2)	0.0695 (4)
H33	0.3421	0.0002	0.3544	0.083*
C34	0.19066 (18)	−0.16420 (17)	0.33797 (18)	0.0637 (4)
C35	0.10245 (17)	−0.22597 (17)	0.4035 (2)	0.0670 (4)
H35	0.0357	−0.3059	0.3590	0.080*
C36	0.11458 (17)	−0.16782 (16)	0.5355 (2)	0.0651 (4)
H36	0.0561	−0.2099	0.5803	0.078*
C1A	0.55695 (18)	0.29870 (18)	1.0452 (2)	0.0694 (4)
H1A	0.5853	0.2553	0.9778	0.083*
C2A	0.65832 (19)	0.4138 (2)	1.1383 (2)	0.0739 (4)
O1	0.78899 (15)	0.44765 (18)	1.14726 (18)	0.0993 (5)
Cl1	0.20652 (6)	0.41935 (5)	1.50378 (6)	0.08373 (18)
Cl2	0.18660 (6)	−0.24132 (5)	0.17751 (5)	0.08459 (18)
H2A	0.612 (3)	0.475 (2)	1.198 (3)	0.102*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0550 (7)	0.0618 (7)	0.0774 (8)	0.0047 (6)	0.0326 (6)	0.0104 (6)
N2	0.0554 (7)	0.0635 (7)	0.0762 (8)	0.0042 (6)	0.0312 (6)	0.0107 (6)
C3	0.0500 (7)	0.0530 (7)	0.0810 (10)	0.0102 (6)	0.0297 (7)	0.0162 (7)
C4	0.0665 (9)	0.0589 (8)	0.0926 (12)	0.0006 (7)	0.0427 (9)	0.0115 (8)
C5	0.0654 (9)	0.0641 (9)	0.0900 (11)	0.0033 (7)	0.0426 (9)	0.0148 (8)
C11	0.0475 (7)	0.0620 (8)	0.0726 (9)	0.0099 (6)	0.0240 (7)	0.0146 (7)
C12	0.0444 (7)	0.0553 (7)	0.0743 (9)	0.0047 (6)	0.0247 (6)	0.0127 (7)
C13	0.0443 (7)	0.0698 (9)	0.0745 (9)	0.0073 (6)	0.0194 (7)	0.0093 (7)
C14	0.0446 (7)	0.0643 (9)	0.0910 (11)	0.0056 (6)	0.0285 (8)	0.0058 (8)
C15	0.0550 (8)	0.0488 (7)	0.0830 (10)	−0.0070 (6)	0.0341 (7)	0.0005 (7)
C16	0.0532 (8)	0.0544 (7)	0.0722 (9)	−0.0030 (6)	0.0225 (7)	0.0081 (7)
C17	0.0432 (7)	0.0573 (8)	0.0747 (9)	0.0061 (6)	0.0211 (6)	0.0139 (7)
C31	0.0450 (7)	0.0536 (7)	0.0775 (9)	0.0098 (6)	0.0246 (7)	0.0167 (7)
C32	0.0617 (9)	0.0571 (8)	0.0812 (10)	−0.0050 (7)	0.0300 (8)	0.0110 (7)
C33	0.0612 (9)	0.0686 (9)	0.0755 (10)	−0.0059 (7)	0.0293 (8)	0.0144 (8)
C34	0.0489 (7)	0.0652 (8)	0.0669 (9)	0.0057 (6)	0.0171 (6)	0.0132 (7)
C35	0.0483 (7)	0.0608 (8)	0.0811 (10)	−0.0025 (6)	0.0205 (7)	0.0100 (7)
C36	0.0477 (7)	0.0605 (8)	0.0856 (11)	0.0009 (6)	0.0290 (7)	0.0138 (8)
C1A	0.0498 (8)	0.0802 (10)	0.0790 (10)	0.0084 (7)	0.0292 (7)	0.0104 (8)
C2A	0.0507 (8)	0.0877 (11)	0.0792 (11)	0.0029 (8)	0.0260 (8)	0.0168 (9)
O1	0.0524 (7)	0.1234 (12)	0.1192 (12)	−0.0071 (7)	0.0379 (7)	0.0170 (9)
Cl1	0.0797 (3)	0.0800 (3)	0.1033 (4)	−0.0142 (2)	0.0546 (3)	−0.0152 (2)
Cl2	0.0784 (3)	0.0921 (3)	0.0749 (3)	−0.0089 (2)	0.0293 (2)	−0.0005 (2)

N1—N2	1.357 (2)	C16—C17	1.375 (2)
N1—C5	1.370 (2)	C16—H16	0.9300
N1—C11	1.408 (2)	C17—H17	0.9300
N2—C3	1.327 (2)	C31—C36	1.391 (2)
C3—C4	1.418 (2)	C31—C32	1.398 (2)
C3—C31	1.460 (2)	C32—C33	1.369 (2)
C4—C5	1.346 (3)	C32—H32	0.9300
C4—H4	0.9300	C33—C34	1.384 (2)
C5—H5	0.9300	C33—H33	0.9300
C11—C1A	1.351 (2)	C34—C35	1.382 (2)
C11—C12	1.474 (2)	C34—Cl2	1.7366 (18)
C12—C17	1.392 (2)	C35—C36	1.375 (2)
C12—C13	1.399 (2)	C35—H35	0.9300
C13—C14	1.374 (2)	C36—H36	0.9300
C13—H13	0.9300	C1A—C2A	1.431 (3)
C14—C15	1.384 (2)	C1A—H1A	0.9300
C14—H14	0.9300	C2A—O1	1.219 (2)
C15—C16	1.387 (2)	C2A—H2A	1.07 (2)
C15—Cl1	1.7313 (17)

N2—N1—C5	111.32 (14)	C17—C16—H16	120.5
N2—N1—C11	120.54 (13)	C15—C16—H16	120.5
C5—N1—C11	127.88 (15)	C16—C17—C12	121.30 (13)
C3—N2—N1	105.24 (13)	C16—C17—H17	119.3
N2—C3—C4	110.62 (16)	C12—C17—H17	119.3
N2—C3—C31	120.42 (14)	C36—C31—C32	117.70 (16)
C4—C3—C31	128.96 (15)	C36—C31—C3	121.53 (14)
C5—C4—C3	105.75 (15)	C32—C31—C3	120.75 (14)
C5—C4—H4	127.1	C33—C32—C31	121.34 (15)
C3—C4—H4	127.1	C33—C32—H32	119.3
C4—C5—N1	107.06 (16)	C31—C32—H32	119.3
C4—C5—H5	126.5	C32—C33—C34	119.49 (15)
N1—C5—H5	126.5	C32—C33—H33	120.3
C1A—C11—N1	119.59 (16)	C34—C33—H33	120.3
C1A—C11—C12	125.45 (15)	C35—C34—C33	120.66 (16)
N1—C11—C12	114.95 (13)	C35—C34—Cl2	120.04 (13)
C17—C12—C13	118.47 (15)	C33—C34—Cl2	119.29 (13)
C17—C12—C11	120.65 (13)	C36—C35—C34	119.15 (15)
C13—C12—C11	120.88 (14)	C36—C35—H35	120.4
C14—C13—C12	120.84 (15)	C34—C35—H35	120.4
C14—C13—H13	119.6	C35—C36—C31	121.60 (15)
C12—C13—H13	119.6	C35—C36—H36	119.2
C13—C14—C15	119.37 (14)	C31—C36—H36	119.2
C13—C14—H14	120.3	C11—C1A—C2A	123.32 (17)
C15—C14—H14	120.3	C11—C1A—H1A	118.3
C14—C15—C16	121.07 (15)	C2A—C1A—H1A	118.3
C14—C15—Cl1	119.74 (12)	O1—C2A—C1A	123.47 (19)
C16—C15—Cl1	119.20 (13)	O1—C2A—H2A	119.7 (13)
C17—C16—C15	118.93 (15)	C1A—C2A—H2A	116.7 (13)

C5—N1—N2—C3	0.51 (16)	C14—C15—C16—C17	−1.3 (2)
C11—N1—N2—C3	175.14 (12)	Cl1—C15—C16—C17	178.47 (11)
N1—N2—C3—C4	−0.49 (16)	C15—C16—C17—C12	0.5 (2)
N1—N2—C3—C31	179.66 (12)	C13—C12—C17—C16	0.7 (2)
N2—C3—C4—C5	0.30 (18)	C11—C12—C17—C16	−178.87 (13)
C31—C3—C4—C5	−179.86 (14)	N2—C3—C31—C36	175.27 (13)
C3—C4—C5—N1	0.03 (18)	C4—C3—C31—C36	−4.6 (2)
N2—N1—C5—C4	−0.34 (18)	N2—C3—C31—C32	−3.1 (2)
C11—N1—C5—C4	−174.48 (14)	C4—C3—C31—C32	177.04 (15)
N2—N1—C11—C1A	−16.7 (2)	C36—C31—C32—C33	−2.1 (2)
C5—N1—C11—C1A	156.99 (16)	C3—C31—C32—C33	176.38 (14)
N2—N1—C11—C12	164.21 (12)	C31—C32—C33—C34	0.4 (2)
C5—N1—C11—C12	−22.1 (2)	C32—C33—C34—C35	1.9 (2)
C1A—C11—C12—C17	−52.2 (2)	C32—C33—C34—Cl2	−176.72 (12)
N1—C11—C12—C17	126.86 (15)	C33—C34—C35—C36	−2.4 (2)
C1A—C11—C12—C13	128.27 (18)	Cl2—C34—C35—C36	176.17 (11)
N1—C11—C12—C13	−52.66 (19)	C34—C35—C36—C31	0.7 (2)
C17—C12—C13—C14	−1.0 (2)	C32—C31—C36—C35	1.5 (2)
C11—C12—C13—C14	178.48 (14)	C3—C31—C36—C35	−176.91 (13)
C12—C13—C14—C15	0.3 (2)	N1—C11—C1A—C2A	173.32 (15)
C13—C14—C15—C16	0.9 (2)	C12—C11—C1A—C2A	−7.7 (3)
C13—C14—C15—Cl1	−178.85 (12)	C11—C1A—C2A—O1	170.98 (18)

Cg1 is the centroid of the C31–C36 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Cl2ⁱ	0.93	2.93	3.6447 (16)	134
C14—H14···O1ⁱⁱ	0.93	2.49	3.407 (2)	167
C36—H36···Cl1ⁱⁱⁱ	0.93	2.90	3.6334 (16)	137
C17—H17···Cg1^iv	0.93	2.68	3.4919 (18)	147

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C31–C36 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯Cl2ⁱ	0.93	2.93	3.6447 (16)	134
C14—H14⋯O1ⁱⁱ	0.93	2.49	3.407 (2)	167
C36—H36⋯Cl1ⁱⁱⁱ	0.93	2.90	3.6334 (16)	137
C17—H17⋯Cg1^iv	0.93	2.68	3.4919 (18)	147

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

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