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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o3006.
Published online 2010 October 31. doi:  10.1107/S1600536810042844
PMCID: PMC3009082

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

Abstract

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 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3006-scheme1.jpg

Experimental

Crystal data

  • C6H9ClN2
  • M r = 144.60
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3006-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.105
  • S = 1.05
  • 1304 reflections
  • 85 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.31 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810042844/hb5664sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810042844/hb5664Isup2.hkl

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

supplementary crystallographic information

Experimental

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).

Refinement

Although all H atoms were visible in difference maps, they werefinally placed in geometrically calculated positions, with C-Hdistances in the range 0.93–0.96Å and N—H distances of 0.86 Å, andincluded in the final refinement in the riding model approximation,with Uiso(H) = 1.2Ueq(C, N) and Uiso(H) = 1.5Ueq(C).

Figures

Fig. 1.
The molecular structure of (I), with 30% probability displacement ellipsoids.

Crystal data

C6H9ClN2Z = 2
Mr = 144.60F(000) = 152
Triclinic, P1Dx = 1.295 Mg m3
Hall symbol: -P 1Melting point = 361–364 K
a = 6.5210 (7) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.3111 (7) ÅCell parameters from 1109 reflections
c = 7.9854 (8) Åθ = 2.6–26.7°
α = 88.383 (1)°µ = 0.43 mm1
β = 77.563 (2)°T = 296 K
γ = 85.725 (2)°BLOCK, colorless
V = 370.71 (6) Å30.28 × 0.22 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer1304 independent reflections
Radiation source: fine-focus sealed tube1135 reflections with I > 2σ(I)
graphiteRint = 0.011
[var phi] and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −7→4
Tmin = 0.890, Tmax = 0.919k = −7→8
1906 measured reflectionsl = −9→8

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.105w = 1/[σ2(Fo2) + (0.0513P)2 + 0.1537P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1304 reflectionsΔρmax = 0.22 e Å3
85 parametersΔρmin = −0.30 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.43 (3)

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 (Å2)

xyzUiso*/Ueq
Cl11.05348 (10)0.89562 (8)0.28229 (8)0.0675 (3)
N10.7203 (2)0.6178 (2)0.1574 (2)0.0414 (4)
N20.5716 (3)0.4983 (2)0.2188 (2)0.0450 (4)
C11.0872 (3)0.6828 (3)0.1664 (3)0.0509 (5)
H1A1.11410.70930.04430.061*
H1B1.20850.61020.19040.061*
C20.8994 (3)0.5757 (3)0.2144 (2)0.0408 (5)
C30.8653 (3)0.4224 (3)0.3159 (3)0.0453 (5)
H30.95930.36000.37370.054*
C40.6600 (3)0.3784 (3)0.3150 (2)0.0435 (5)
C50.5411 (4)0.2246 (3)0.4043 (3)0.0586 (6)
H5A0.39580.24400.39760.088*
H5B0.55180.21980.52240.088*
H5C0.59910.11100.35040.088*
C60.6713 (4)0.7699 (3)0.0489 (3)0.0579 (6)
H6A0.58820.86480.11870.087*
H6B0.59370.7284−0.03040.087*
H6C0.79970.8172−0.01340.087*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0728 (5)0.0529 (4)0.0782 (5)−0.0180 (3)−0.0135 (3)−0.0100 (3)
N10.0373 (9)0.0436 (9)0.0435 (9)−0.0058 (7)−0.0085 (7)0.0046 (7)
N20.0381 (9)0.0480 (10)0.0493 (9)−0.0092 (7)−0.0085 (7)0.0007 (7)
C10.0387 (11)0.0513 (12)0.0616 (13)−0.0059 (9)−0.0065 (9)−0.0068 (10)
C20.0346 (10)0.0425 (10)0.0449 (10)−0.0009 (8)−0.0073 (8)−0.0066 (8)
C30.0455 (11)0.0434 (11)0.0487 (11)0.0015 (9)−0.0157 (9)−0.0001 (8)
C40.0467 (11)0.0402 (10)0.0417 (10)−0.0053 (8)−0.0044 (8)−0.0028 (8)
C50.0652 (15)0.0492 (12)0.0589 (13)−0.0133 (11)−0.0054 (11)0.0036 (10)
C60.0584 (14)0.0556 (13)0.0635 (14)−0.0074 (11)−0.0219 (11)0.0140 (11)

Geometric parameters (Å, °)

Cl1—C11.808 (2)C3—C41.401 (3)
N1—C21.354 (2)C3—H30.9300
N1—N21.357 (2)C4—C51.490 (3)
N1—C61.449 (3)C5—H5A0.9600
N2—C41.330 (3)C5—H5B0.9600
C1—C21.478 (3)C5—H5C0.9600
C1—H1A0.9700C6—H6A0.9600
C1—H1B0.9700C6—H6B0.9600
C2—C31.368 (3)C6—H6C0.9600
C2—N1—N2111.77 (16)N2—C4—C3110.45 (17)
C2—N1—C6128.92 (17)N2—C4—C5120.51 (19)
N2—N1—C6119.29 (16)C3—C4—C5129.03 (19)
C4—N2—N1105.36 (15)C4—C5—H5A109.5
C2—C1—Cl1111.73 (14)C4—C5—H5B109.5
C2—C1—H1A109.3H5A—C5—H5B109.5
Cl1—C1—H1A109.3C4—C5—H5C109.5
C2—C1—H1B109.3H5A—C5—H5C109.5
Cl1—C1—H1B109.3H5B—C5—H5C109.5
H1A—C1—H1B107.9N1—C6—H6A109.5
N1—C2—C3106.40 (17)N1—C6—H6B109.5
N1—C2—C1123.08 (18)H6A—C6—H6B109.5
C3—C2—C1130.52 (19)N1—C6—H6C109.5
C2—C3—C4106.02 (17)H6A—C6—H6C109.5
C2—C3—H3127.0H6B—C6—H6C109.5
C4—C3—H3127.0
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—C30.3 (2)C1—C2—C3—C4−179.3 (2)
C6—N1—C2—C3178.48 (19)N1—N2—C4—C30.4 (2)
N2—N1—C2—C1179.62 (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—N176.5 (2)C2—C3—C4—C5−179.8 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1B···N2i0.972.503.446 (3)164

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5664).

References

  • Baldy, A., Elguero, J., Fawe, R., Pierrot, M. & Vincent, E. J. (1985). J. Am. Chem. Soc.107, 5290-5291.
  • Bruker (2001). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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