(3,6-Dichloro­pyridin-2-yl)(3,5-dimethyl-1H-pyrazol-1-yl)methanone

Abstract

In the crystal structure of the title compound, C₁₁H₉Cl₂N₃O, mol­ecules are held together by short inter­molecular Cl⋯Cl contacts [3.319 (1) Å] and C—H⋯N hydrogen bonds, forming two-dimensional networks parallel to (01).

Related literature

For related literature, see: Mann et al. (1992 ▶); Perevalov et al. (2001 ▶).

Experimental

Crystal data

• C₁₁H₉Cl₂N₃O

• M _r = 270.11

• Triclinic,

• a = 7.3440 (10) Å

• b = 8.7981 (12) Å

• c = 9.6490 (14) Å

• α = 75.554 (2)°

• β = 89.627 (3)°

• γ = 86.819 (2)°

• V = 602.79 (15) ų

• Z = 2

• Mo Kα radiation

• μ = 0.52 mm⁻¹

• T = 298 (2) K

• 0.50 × 0.49 × 0.48 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.780, T _max = 0.787

• 3145 measured reflections

• 2102 independent reflections

• 1543 reflections with I > 2σ(I)

• R _int = 0.038

Refinement

• R[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 0.126

• S = 1.04

• 2101 reflections

• 154 parameters

• H-atom parameters constrained

• Δρ_max = 0.22 e Å⁻³

• Δρ_min = −0.27 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11C⋯N1i	0.96	2.56	3.514 (4)	174

Symmetry code: (i) .

supplementary crystallographic information

Comment

The chemical and pharmacological properties of pyrazoles have been investigated extensively, owing to their chelating ability with metal ions and their potentially beneficial chemical and biological activities (Mann et al., 1992, Perevalov et al., 2001). As part of our studies on the synthesis and characterization of these compounds, we report here the synthesis and crystal structure of (3,6-dichloropyridin-2-yl)(3,5-dimethyl-1H-pyrazol-1-yl)methanone.

The crystal structure of the monomeric title compound is built up by C₁₁H₉Cl₂N₃O molecules (Fig.1), linked by intermolecular C—H···N hydrogen bonds along [100] (Table 1) and by Cl···Cl short contacts along the [011] direction (Cl1···Cl1ⁱⁱ: 3.319 (1)Å, (ii): 2-x, 1-y, 1-z) , forming a two-dimensional network parallel to (011).

The short C=O bond length (1.199 (3)Å) indicates that the molecule is in a keto form (Fig.1). The two rings are nearly perpendicular to each other (dihedral angle: 82.319 (84) °), and this fact helps in minimizing steric effects between them. Finally, there is an intermolecular π—π contact between pyridine groups with and intercentroid distance of 3.40 (1) Å, which contributes to the stability of the crystal packing.

Experimental

A solution of 3,6-dichloropicolinoyl chloride (10 mmol) in 50 ml toluene was added to a solution of 3,5-dimethyl-1H-pyrazole (10 mmol) in 10 ml toluene. The reaction mixture was refluxed for 1 h with stirring then the resulting white precipitate was obtained by filtration, washed several times with ethanol and dried in vacuo (yield 90%). Elemental analysis calculate: Elemental analysis: found: C, 48.89; H, 3.33; N, 15.56; calc. for C₁₁H₉Cl₂N₃O: C, 48.99; H, 3.23; N, 15.46.

Refinement

Data collection: 2102 independent reflections but 2101 in Refinement. H atoms on C atoms were positoned geometrically and refined using a riding model with C—H = 0.96Å and U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The structure of the title compound (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Fig. 2.

Crystal packing of (I) showing the short contacts interactions as dashed lines.

Crystal data

C11H9Cl2N3O	Z = 2
Mr = 270.11	F000 = 276
Triclinic, P1	Dx = 1.488 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 7.3440 (10) Å	Cell parameters from 1363 reflections
b = 8.7981 (12) Å	θ = 2.2–27.4º
c = 9.6490 (14) Å	µ = 0.52 mm−1
α = 75.554 (2)º	T = 298 (2) K
β = 89.627 (3)º	Block, colourless
γ = 86.819 (2)º	0.50 × 0.49 × 0.48 mm
V = 602.79 (15) Å3

Data collection

Bruker SMART CCD area-detector diffractometer	2102 independent reflections
Radiation source: fine-focus sealed tube	1543 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.038
T = 298(2) K	θmax = 25.0º
φ and ω scans	θmin = 2.2º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.780, Tmax = 0.787	k = −9→10
3145 measured reflections	l = −9→11

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H-atom parameters constrained
wR(F2) = 0.126	w = 1/[σ2(Fo2) + (0.0468P)2 + 0.2168P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2101 reflections	Δρmax = 0.22 e Å−3
154 parameters	Δρmin = −0.27 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.60627 (11)	0.85128 (9)	0.94981 (8)	0.0634 (3)
Cl2	0.90422 (12)	0.19393 (9)	0.92556 (10)	0.0712 (3)
N1	0.8160 (3)	0.4899 (3)	0.8173 (2)	0.0434 (5)
N2	0.6305 (3)	0.7559 (2)	0.5846 (2)	0.0415 (5)
N3	0.4844 (3)	0.6627 (2)	0.6266 (2)	0.0421 (5)
O1	0.8838 (3)	0.8463 (3)	0.6636 (2)	0.0712 (7)
C1	0.7630 (4)	0.7572 (3)	0.6853 (3)	0.0440 (6)
C2	0.7517 (3)	0.6330 (3)	0.8231 (2)	0.0368 (6)
C3	0.6925 (3)	0.6653 (3)	0.9493 (3)	0.0407 (6)
C4	0.6996 (4)	0.5468 (3)	1.0739 (3)	0.0469 (7)
H4	0.6596	0.5662	1.1598	0.056*
C5	0.7666 (4)	0.4004 (3)	1.0686 (3)	0.0488 (7)
H5	0.7746	0.3181	1.1508	0.059*
C6	0.8220 (4)	0.3782 (3)	0.9384 (3)	0.0445 (7)
C7	0.7566 (5)	0.9440 (4)	0.3653 (3)	0.0670 (9)
H7A	0.7593	1.0332	0.4056	0.101*
H7B	0.7259	0.9789	0.2654	0.101*
H7C	0.8743	0.8890	0.3764	0.101*
C8	0.6167 (4)	0.8362 (3)	0.4409 (3)	0.0483 (7)
C9	0.4615 (4)	0.7924 (3)	0.3939 (3)	0.0548 (8)
H9	0.4145	0.8254	0.3013	0.066*
C10	0.3819 (4)	0.6865 (3)	0.5110 (3)	0.0444 (6)
C11	0.2080 (4)	0.6066 (4)	0.5140 (3)	0.0622 (8)
H11A	0.1074	0.6782	0.5223	0.093*
H11B	0.2091	0.5166	0.5944	0.093*
H11C	0.1953	0.5733	0.4272	0.093*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0743 (6)	0.0459 (4)	0.0697 (5)	0.0120 (4)	0.0039 (4)	−0.0172 (4)
Cl2	0.0775 (6)	0.0408 (4)	0.0948 (7)	0.0118 (4)	−0.0144 (5)	−0.0188 (4)
N1	0.0444 (13)	0.0417 (13)	0.0441 (13)	0.0003 (10)	−0.0022 (10)	−0.0110 (10)
N2	0.0448 (13)	0.0369 (12)	0.0379 (12)	−0.0010 (10)	0.0017 (10)	−0.0006 (9)
N3	0.0440 (13)	0.0414 (12)	0.0388 (12)	−0.0010 (10)	0.0006 (10)	−0.0062 (9)
O1	0.0706 (15)	0.0756 (16)	0.0611 (14)	−0.0326 (13)	−0.0013 (11)	0.0012 (11)
C1	0.0466 (16)	0.0413 (15)	0.0422 (15)	−0.0033 (13)	0.0020 (12)	−0.0066 (12)
C2	0.0338 (13)	0.0387 (14)	0.0360 (13)	−0.0027 (11)	−0.0032 (10)	−0.0058 (11)
C3	0.0382 (14)	0.0390 (14)	0.0438 (15)	0.0000 (12)	−0.0031 (11)	−0.0084 (12)
C4	0.0507 (17)	0.0510 (17)	0.0380 (15)	−0.0034 (13)	−0.0011 (12)	−0.0088 (12)
C5	0.0527 (18)	0.0462 (17)	0.0406 (15)	−0.0082 (13)	−0.0079 (13)	0.0036 (12)
C6	0.0415 (15)	0.0343 (14)	0.0559 (17)	0.0001 (11)	−0.0102 (12)	−0.0083 (12)
C7	0.079 (2)	0.062 (2)	0.0488 (18)	−0.0075 (18)	0.0099 (16)	0.0091 (15)
C8	0.0604 (19)	0.0408 (15)	0.0373 (15)	0.0049 (13)	0.0037 (13)	0.0009 (12)
C9	0.064 (2)	0.0595 (19)	0.0359 (15)	0.0079 (16)	−0.0081 (14)	−0.0047 (13)
C10	0.0488 (16)	0.0445 (15)	0.0382 (14)	0.0057 (12)	−0.0024 (12)	−0.0090 (12)
C11	0.0570 (19)	0.076 (2)	0.0561 (19)	−0.0005 (17)	−0.0078 (15)	−0.0219 (16)

Geometric parameters (Å, °)

Cl1—C3	1.722 (3)	C5—C6	1.375 (4)
Cl2—C6	1.732 (3)	C5—H5	0.9300
N1—C6	1.325 (3)	C7—C8	1.496 (4)
N1—C2	1.334 (3)	C7—H7A	0.9600
N2—C1	1.382 (3)	C7—H7B	0.9600
N2—N3	1.383 (3)	C7—H7C	0.9600
N2—C8	1.392 (3)	C8—C9	1.340 (4)
N3—C10	1.316 (3)	C9—C10	1.419 (4)
O1—C1	1.199 (3)	C9—H9	0.9300
C1—C2	1.502 (3)	C10—C11	1.488 (4)
C2—C3	1.380 (3)	C11—H11A	0.9600
C3—C4	1.380 (4)	C11—H11B	0.9600
C4—C5	1.366 (4)	C11—H11C	0.9600
C4—H4	0.9300
C6—N1—C2	117.4 (2)	C5—C6—Cl2	119.8 (2)
C1—N2—N3	118.3 (2)	C8—C7—H7A	109.5
C1—N2—C8	130.2 (2)	C8—C7—H7B	109.5
N3—N2—C8	111.5 (2)	H7A—C7—H7B	109.5
C10—N3—N2	104.7 (2)	C8—C7—H7C	109.5
O1—C1—N2	123.1 (2)	H7A—C7—H7C	109.5
O1—C1—C2	121.5 (2)	H7B—C7—H7C	109.5
N2—C1—C2	115.3 (2)	C9—C8—N2	105.3 (2)
N1—C2—C3	122.1 (2)	C9—C8—C7	131.3 (3)
N1—C2—C1	114.8 (2)	N2—C8—C7	123.4 (3)
C3—C2—C1	123.0 (2)	C8—C9—C10	107.6 (2)
C4—C3—C2	119.4 (3)	C8—C9—H9	126.2
C4—C3—Cl1	120.5 (2)	C10—C9—H9	126.2
C2—C3—Cl1	120.03 (19)	N3—C10—C9	110.9 (2)
C5—C4—C3	118.7 (3)	N3—C10—C11	120.8 (2)
C5—C4—H4	120.6	C9—C10—C11	128.3 (2)
C3—C4—H4	120.6	C10—C11—H11A	109.5
C4—C5—C6	118.1 (2)	C10—C11—H11B	109.5
C4—C5—H5	121.0	H11A—C11—H11B	109.5
C6—C5—H5	121.0	C10—C11—H11C	109.5
N1—C6—C5	124.3 (3)	H11A—C11—H11C	109.5
N1—C6—Cl2	115.9 (2)	H11B—C11—H11C	109.5
C1—N2—N3—C10	179.3 (2)	Cl1—C3—C4—C5	179.1 (2)
C8—N2—N3—C10	−0.6 (3)	C3—C4—C5—C6	−0.7 (4)
N3—N2—C1—O1	−171.8 (3)	C2—N1—C6—C5	0.0 (4)
C8—N2—C1—O1	8.1 (5)	C2—N1—C6—Cl2	179.37 (18)
N3—N2—C1—C2	11.2 (3)	C4—C5—C6—N1	0.5 (4)
C8—N2—C1—C2	−169.0 (2)	C4—C5—C6—Cl2	−178.9 (2)
C6—N1—C2—C3	−0.2 (4)	C1—N2—C8—C9	−179.9 (3)
C6—N1—C2—C1	175.1 (2)	N3—N2—C8—C9	0.0 (3)
O1—C1—C2—N1	−98.9 (3)	C1—N2—C8—C7	1.1 (5)
N2—C1—C2—N1	78.2 (3)	N3—N2—C8—C7	−179.1 (3)
O1—C1—C2—C3	76.4 (4)	N2—C8—C9—C10	0.5 (3)
N2—C1—C2—C3	−106.5 (3)	C7—C8—C9—C10	179.5 (3)
N1—C2—C3—C4	0.0 (4)	N2—N3—C10—C9	0.9 (3)
C1—C2—C3—C4	−174.9 (2)	N2—N3—C10—C11	−179.3 (2)
N1—C2—C3—Cl1	−178.62 (19)	C8—C9—C10—N3	−0.9 (3)
C1—C2—C3—Cl1	6.4 (3)	C8—C9—C10—C11	179.3 (3)
C2—C3—C4—C5	0.4 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11C···N1i	0.96	2.56	3.514 (4)	174

Symmetry codes: (i) −x+1, −y+1, −z+1.