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

Zhuang, Y.; Zhang, S.-S.; Yin, X.-H.; Zhao, K.; Lin, C.-W.

doi:10.1107/S1600536808015006

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1224

doi:10.1107/S1600536808015006

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

Yue Zhuang,^a Shan-Shan Zhang,^b Xian-Hong Yin,^b ^* Kai Zhao ^a and Cui-Wu Lin ^c

^aDepartment of Chemistry, Guangxi University for Nationalities, Nanning 530004, People's Republic of China, ^bDepartment of Chemistry, Guangxi University, Nanning 530006, People's Republic of China, and ^cCollege of Chemistry and Chemical Engineering, Guangxi University, Nanning 530006, People's Republic of China
^*Correspondence e-mail: yxhphd@163.com

(Received 10 April 2008; accepted 18 May 2008; online 7 June 2008)

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 $[\overline{1}]$ ).

Related literature

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

Experimental

Crystal data

C₁₁H₉Cl₂N₃O
M_r = 270.11
Triclinic, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.044
wR(F²) = 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

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) -x+1, -y+1, -z+1.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015006/bg2182sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015006/bg2182Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 2008).

Figures top

	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.

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

Crystal data top

C₁₁H₉Cl₂N₃O	Z = 2
M_r = 270.11	F(000) = 276
Triclinic, P1	D_x = 1.488 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.344 (1) Å	Cell parameters from 1363 reflections
b = 8.7981 (12) Å	θ = 2.2–27.4°
c = 9.6490 (14) Å	µ = 0.52 mm⁻¹
α = 75.554 (2)°	T = 298 K
β = 89.627 (3)°	Block, colourless
γ = 86.819 (2)°	0.50 × 0.49 × 0.48 mm
V = 602.79 (15) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2102 independent reflections
Radiation source: fine-focus sealed tube	1543 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.780, T_max = 0.787	k = −9→10
3145 measured reflections	l = −9→11

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0468P)² + 0.2168P] where P = (F_o² + 2F_c²)/3
2101 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₁H₉Cl₂N₃O	γ = 86.819 (2)°
M_r = 270.11	V = 602.79 (15) Å³
Triclinic, P1	Z = 2
a = 7.344 (1) Å	Mo Kα radiation
b = 8.7981 (12) Å	µ = 0.52 mm⁻¹
c = 9.6490 (14) Å	T = 298 K
α = 75.554 (2)°	0.50 × 0.49 × 0.48 mm
β = 89.627 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2102 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1543 reflections with I > 2σ(I)
T_min = 0.780, T_max = 0.787	R_int = 0.038
3145 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.04	Δρ_max = 0.22 e Å⁻³
2101 reflections	Δρ_min = −0.27 e Å⁻³
154 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
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 (Å²) top

	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, º) top

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, º) top

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) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₉Cl₂N₃O
M_r	270.11
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.344 (1), 8.7981 (12), 9.6490 (14)
α, β, γ (°)	75.554 (2), 89.627 (3), 86.819 (2)
V (Å³)	602.79 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.50 × 0.49 × 0.48

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.780, 0.787
No. of measured, independent and observed [I > 2σ(I)] reflections	3145, 2102, 1543
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.126, 1.04
No. of reflections	2101
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.27

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y+1, −z+1.

Acknowledgements

The authors thank the National Natural Science Foundation of China (20761002). This research was sponsored by the Fund of the Talent Highland Research Program of Guangxi University (205121), the Science Foundation of the State Ethnic Affairs Commission (07GX05), the Development Foundation of Guangxi Research Institute of Chemical Industry and the Science Foundation of Guangxi University for Nationalities (0409032, 0409012, 0509ZD047).

References

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Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar