5-Chloro­methyl-1,3-dimethyl-1H-pyrazole

Yang, G.; Xu, H.; Yang, H.; Yu, H.

doi:10.1107/S1600536810042844

organic compounds

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Volume 66| Part 11| November 2010| Page o3006

https://doi.org/10.1107/S1600536810042844

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5-Chloromethyl-1,3-dimethyl-1H-pyrazole

Guiqiu Yang,^a ^* Hongcai Xu,^b Huibin Yang ^c and Haibo Yu ^c

^aShenyang University of Chemical Technology, Shenyang 110142, People's Republic of China, ^bPharmaceutical Division, Shenyang University of Chemical Technology, Shenyang 110142, People's Republic of China, and ^cAgrochemicals Division, Shenyang Research Institute of Chemical Industry, Shenyang 110021, People's Republic of China
^*Correspondence e-mail: yangguiqiu@gmail.com

(Received 29 September 2010; accepted 21 October 2010; online 31 October 2010)

The pyazole ring in the title compound, C₆H₉ClN₂, is almost planar (r.m.s. deviation = 0.003 Å). In the crystal, molecules are linked by C—H⋯N interactions, forming [100] chains.

Related literature

For a related structure, see: Baldy et al. (1985 ).

Experimental

Crystal data

C₆H₉ClN₂
M_r = 144.60
Triclinic, $[P \overline 1]$
a = 6.5210 (7) Å
b = 7.3111 (7) Å
c = 7.9854 (8) Å
α = 88.383 (1)°
β = 77.563 (2)°
γ = 85.725 (2)°
V = 370.71 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 296 K
0.28 × 0.22 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.890, T_max = 0.919
1906 measured reflections
1304 independent reflections
1135 reflections with I > 2σ(I)
R_int = 0.011

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.105
S = 1.05
1304 reflections
85 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯N2ⁱ	0.97	2.50	3.446 (3)	164
Symmetry code: (i) x+1, y, z.

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); 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: https://doi.org/10.1107/S1600536810042844/hb5664sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042844/hb5664Isup2.hkl

checkCIF report

Related literature top

For a related structure, see: Baldy et al. (1985).

Experimental top

N,N-Dimethylformamide(0.96 g, 11 mmol) was add to a 100 ml three necked-bottle, and phosphoryl trichloride(6.13 g, 40 mmol) was added slowly under ice-bath, then added (1,3-dimethyl-1H-pyrazole-5-yl)methanol(1.26 g, 10 mmol) at room temperature in portions. The reaction mixture was heated to reflux and reacted for 6 h. After separation through silica gel column chromatography (fluent: ethyl acetate/petroleum ether=1/5). The title product compound was obtained as a white solid (0.36 g, 22%) and recrystallised from methylene chloride to yield colourless blocks of (I).

Anal. Calcd for C₆H₉N₂: C, 49.84; H, 6.27; N, 19.37. Found: C, 49.81; H, 6.30; N, 19.40. ¹H NMR(CDCl3): 2.22(s,3H, CH₃), 3.84 (s,3H, N—CH₃), 4.53(s, 2H, CH₂), 6.04 (s, 1H, Pyrazole-H).

Structure description top

For a related structure, see: Baldy et al. (1985).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 molecular structure of (I), with 30% probability displacement ellipsoids.

5-Chloromethyl-1,3-dimethyl-1H-pyrazole top

Crystal data top

C₆H₉ClN₂	Z = 2
M_r = 144.60	F(000) = 152
Triclinic, P1	D_x = 1.295 Mg m⁻³
Hall symbol: -P 1	Melting point = 361–364 K
a = 6.5210 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.3111 (7) Å	Cell parameters from 1109 reflections
c = 7.9854 (8) Å	θ = 2.6–26.7°
α = 88.383 (1)°	µ = 0.43 mm⁻¹
β = 77.563 (2)°	T = 296 K
γ = 85.725 (2)°	BLOCK, colorless
V = 370.71 (6) Å³	0.28 × 0.22 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	1304 independent reflections
Radiation source: fine-focus sealed tube	1135 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.011
φ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→4
T_min = 0.890, T_max = 0.919	k = −7→8
1906 measured reflections	l = −9→8

Refinement top

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)] = 0.038	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0513P)² + 0.1537P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1304 reflections	Δρ_max = 0.22 e Å⁻³
85 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.43 (3)

Crystal data top

C₆H₉ClN₂	γ = 85.725 (2)°
M_r = 144.60	V = 370.71 (6) Å³
Triclinic, P1	Z = 2
a = 6.5210 (7) Å	Mo Kα radiation
b = 7.3111 (7) Å	µ = 0.43 mm⁻¹
c = 7.9854 (8) Å	T = 296 K
α = 88.383 (1)°	0.28 × 0.22 × 0.20 mm
β = 77.563 (2)°

Data collection top

Bruker SMART CCD diffractometer	1304 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1135 reflections with I > 2σ(I)
T_min = 0.890, T_max = 0.919	R_int = 0.011
1906 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.05	Δρ_max = 0.22 e Å⁻³
1304 reflections	Δρ_min = −0.31 e Å⁻³
85 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	1.05348 (10)	0.89562 (8)	0.28229 (8)	0.0675 (3)
N1	0.7203 (2)	0.6178 (2)	0.1574 (2)	0.0414 (4)
N2	0.5716 (3)	0.4983 (2)	0.2188 (2)	0.0450 (4)
C1	1.0872 (3)	0.6828 (3)	0.1664 (3)	0.0509 (5)
H1A	1.1141	0.7093	0.0443	0.061*
H1B	1.2085	0.6102	0.1904	0.061*
C2	0.8994 (3)	0.5757 (3)	0.2144 (2)	0.0408 (5)
C3	0.8653 (3)	0.4224 (3)	0.3159 (3)	0.0453 (5)
H3	0.9593	0.3600	0.3737	0.054*
C4	0.6600 (3)	0.3784 (3)	0.3150 (2)	0.0435 (5)
C5	0.5411 (4)	0.2246 (3)	0.4043 (3)	0.0586 (6)
H5A	0.3958	0.2440	0.3976	0.088*
H5B	0.5518	0.2198	0.5224	0.088*
H5C	0.5991	0.1110	0.3504	0.088*
C6	0.6713 (4)	0.7699 (3)	0.0489 (3)	0.0579 (6)
H6A	0.5882	0.8648	0.1187	0.087*
H6B	0.5937	0.7284	−0.0304	0.087*
H6C	0.7997	0.8172	−0.0134	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0728 (5)	0.0529 (4)	0.0782 (5)	−0.0180 (3)	−0.0135 (3)	−0.0100 (3)
N1	0.0373 (9)	0.0436 (9)	0.0435 (9)	−0.0058 (7)	−0.0085 (7)	0.0046 (7)
N2	0.0381 (9)	0.0480 (10)	0.0493 (9)	−0.0092 (7)	−0.0085 (7)	0.0007 (7)
C1	0.0387 (11)	0.0513 (12)	0.0616 (13)	−0.0059 (9)	−0.0065 (9)	−0.0068 (10)
C2	0.0346 (10)	0.0425 (10)	0.0449 (10)	−0.0009 (8)	−0.0073 (8)	−0.0066 (8)
C3	0.0455 (11)	0.0434 (11)	0.0487 (11)	0.0015 (9)	−0.0157 (9)	−0.0001 (8)
C4	0.0467 (11)	0.0402 (10)	0.0417 (10)	−0.0053 (8)	−0.0044 (8)	−0.0028 (8)
C5	0.0652 (15)	0.0492 (12)	0.0589 (13)	−0.0133 (11)	−0.0054 (11)	0.0036 (10)
C6	0.0584 (14)	0.0556 (13)	0.0635 (14)	−0.0074 (11)	−0.0219 (11)	0.0140 (11)

Geometric parameters (Å, º) top

Cl1—C1	1.808 (2)	C3—C4	1.401 (3)
N1—C2	1.354 (2)	C3—H3	0.9300
N1—N2	1.357 (2)	C4—C5	1.490 (3)
N1—C6	1.449 (3)	C5—H5A	0.9600
N2—C4	1.330 (3)	C5—H5B	0.9600
C1—C2	1.478 (3)	C5—H5C	0.9600
C1—H1A	0.9700	C6—H6A	0.9600
C1—H1B	0.9700	C6—H6B	0.9600
C2—C3	1.368 (3)	C6—H6C	0.9600

C2—N1—N2	111.77 (16)	N2—C4—C3	110.45 (17)
C2—N1—C6	128.92 (17)	N2—C4—C5	120.51 (19)
N2—N1—C6	119.29 (16)	C3—C4—C5	129.03 (19)
C4—N2—N1	105.36 (15)	C4—C5—H5A	109.5
C2—C1—Cl1	111.73 (14)	C4—C5—H5B	109.5
C2—C1—H1A	109.3	H5A—C5—H5B	109.5
Cl1—C1—H1A	109.3	C4—C5—H5C	109.5
C2—C1—H1B	109.3	H5A—C5—H5C	109.5
Cl1—C1—H1B	109.3	H5B—C5—H5C	109.5
H1A—C1—H1B	107.9	N1—C6—H6A	109.5
N1—C2—C3	106.40 (17)	N1—C6—H6B	109.5
N1—C2—C1	123.08 (18)	H6A—C6—H6B	109.5
C3—C2—C1	130.52 (19)	N1—C6—H6C	109.5
C2—C3—C4	106.02 (17)	H6A—C6—H6C	109.5
C2—C3—H3	127.0	H6B—C6—H6C	109.5
C4—C3—H3	127.0

C2—N1—N2—C4	−0.5 (2)	Cl1—C1—C2—C3	−104.4 (2)
C6—N1—N2—C4	−178.81 (18)	N1—C2—C3—C4	−0.1 (2)
N2—N1—C2—C3	0.3 (2)	C1—C2—C3—C4	−179.3 (2)
C6—N1—C2—C3	178.48 (19)	N1—N2—C4—C3	0.4 (2)
N2—N1—C2—C1	179.62 (17)	N1—N2—C4—C5	−179.94 (17)
C6—N1—C2—C1	−2.2 (3)	C2—C3—C4—N2	−0.2 (2)
Cl1—C1—C2—N1	76.5 (2)	C2—C3—C4—C5	−179.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···N2ⁱ	0.97	2.50	3.446 (3)	164

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₆H₉ClN₂
M_r	144.60
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.5210 (7), 7.3111 (7), 7.9854 (8)
α, β, γ (°)	88.383 (1), 77.563 (2), 85.725 (2)
V (Å³)	370.71 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.28 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.890, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	1906, 1304, 1135
R_int	0.011
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.105, 1.05
No. of reflections	1304
No. of parameters	85
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.31

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), 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
C1—H1B···N2ⁱ	0.97	2.50	3.446 (3)	164

Symmetry code: (i) x+1, y, z.

References

Baldy, A., Elguero, J., Fawe, R., Pierrot, M. & Vincent, E. J. (1985). J. Am. Chem. Soc. 107, 5290-5291. CSD CrossRef CAS Web of Science Google Scholar
Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o3006

https://doi.org/10.1107/S1600536810042844

Open

access