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Acta Cryst. (2007). E63, o4045    [ doi:10.1107/S1600536807044169 ]

2-(4-Iodo-1-methyl-1H-pyrazol-3-yl)-pyridinium dichloroiodide

W. T. A. Harrison

Abstract top

In the title molecular salt, C9H9IN3+·ICl2-, the dihedral angle between the aromatic rings in the cation is 14.9 (2)°. The I-Cl bond lengths of the anion are distinctly different, by 0.149 (2) Å. The most significant interaction in the crystal structure is a bifurcated N-H...(N,Cl) hydrogen bond.

Comment top

The title compound, (I), is a molecular salt (Fig. 1), with normal geometrical parameters for the organic component (Allen et al., 1995). The dihedral angle betwen the N1/C1—C5 and N2/N3/C6—C8 rings in the cation is 14.9 (2)°. The C1—N1—C5 bond angle of 124.2 (4)° is typically expanded due to the protonation of N1 (Wang et al., 1999).

The two I—Cl bond lengths (Table 1) in the ICl2− anion in (I) are significantly different, by some 0.149 (2) Å. Sometimes (Wang et al., 1999) the two bond lengths in the ICl2− anion are constrained to be the same by symmetry. However, in C4H12N2·(ICl2)2, the difference between the two bonds of 0.22Å (Romming, 1958) is even greater than seen here. In all cases, the Cl—I—Cl bond angle is close to linear, in accordance with the predictions of VSEPR or qualitative MO theory (Greenwood & Earnshaw, 1997).

In the crystal, the components interact by way of an intra/intermolecular bifurcated N—H···(N,Cl) hydrogen bond (Table 2). A weak C—H···Cl contact also occurs. The separation of I1 and Cl1ii (ii = x, 1/2 − y, z − 1/2) of 3.5275 (13)Å is some 0.2 Å less than the van der Waals separation of I and Cl of 3.73 Å. If this is considered to be a bonding interaction, [001] chains of ion-pairs are the result (Fig. 2).

Related literature top

For background, see: Romming (1958); Greenwood & Earnshaw (1997); Wang et al. (1999). For reference structural data, see: Allen et al. (1995).

Experimental top

The title compound arose from the attempted methylation (with MeI) of 3-(2-pyridine)-pyrazole hydrochloride. Orange blocks of (I) were recoverd from the reaction. Their composition could not be determined on the basis of spectroscopic measurements and the single-crystal study was performed to identify the title compound. The mechanism of formation of (I) requires further investigation.

Refinement top

The N-bound H atom was located in a difference map and its position were freely refined with Uiso(H) = 1.2Ueq(N).

The C-bound H atoms were placed geometrically (C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl C). The methyl group was allowed to rotate, but not to tip, to best fit the electron density.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) (50% displacement ellipsoids, arbitrary spheres for the H atoms, hydrogen bonds indicated by double dashed lines).
[Figure 2] Fig. 2. An [001] chain in (I) arising from N—H···Cl hydrogen bonds and possible I···Cl interactions. Symmetry code: (ii) x, 1/2 − y, z − 1/2.
2-(4-Iodo-1-methyl-1H-pyrazol-3-yl)-pyridinium dichloroiodide top
Crystal data top
C9H9IN3+·Cl2I–F000 = 896
Mr = 483.89Dx = 2.241 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5028 reflections
a = 8.4261 (4) Åθ = 2.5–25.0º
b = 8.0183 (4) ŵ = 4.74 mm−1
c = 21.4692 (10) ÅT = 293 (2) K
β = 98.604 (1)ºBlock, orange
V = 1434.20 (12) Å30.29 × 0.19 × 0.12 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer		2523 independent reflections
Radiation source: fine-focus sealed tube2256 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.029
T = 293(2) Kθmax = 25.0º
ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Bruker, 1999)		h = −10→9
Tmin = 0.340, Tmax = 0.601k = −7→9
8399 measured reflectionsl = −25→25
Refinement top
Refinement on F2Hydrogen site location: difmap and geom
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.027  w = 1/[σ2(Fo2) + (0.0376P)2 + 1.477P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.069(Δ/σ)max = 0.002
S = 1.04Δρmax = 1.35 e Å−3
2523 reflectionsΔρmin = −1.15 e Å−3
150 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0015 (2)
Secondary atom site location: difference Fourier map
Crystal data top
C9H9IN3+·Cl2I–V = 1434.20 (12) Å3
Mr = 483.89Z = 4
Monoclinic, P21/cMo Kα
a = 8.4261 (4) ŵ = 4.74 mm−1
b = 8.0183 (4) ÅT = 293 (2) K
c = 21.4692 (10) Å0.29 × 0.19 × 0.12 mm
β = 98.604 (1)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		2523 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)		2256 reflections with I > 2σ(I)
Tmin = 0.340, Tmax = 0.601Rint = 0.029
8399 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027150 parameters
wR(F2) = 0.069H atoms treated by a mixture of
independent and constrained refinement
S = 1.04Δρmax = 1.35 e Å−3
2523 reflectionsΔρmin = −1.15 e Å−3
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 > 2sigma(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
xyzUiso*/Ueq
C10.3644 (5)0.1154 (6)0.6860 (2)0.0506 (11)
H1A0.33970.07880.72460.061*
C20.2569 (6)0.0942 (7)0.6326 (2)0.0626 (13)
H20.15850.04290.63390.075*
C30.2985 (6)0.1513 (8)0.5760 (2)0.0641 (14)
H30.22640.13960.53900.077*
C40.4438 (6)0.2244 (6)0.5744 (2)0.0526 (11)
H40.47040.26200.53630.063*
C50.5527 (5)0.2428 (5)0.62949 (19)0.0361 (8)
C60.7118 (5)0.3184 (5)0.63513 (18)0.0362 (8)
C70.8107 (5)0.3601 (5)0.59068 (18)0.0401 (9)
C80.9446 (5)0.4287 (5)0.6250 (2)0.0444 (10)
H81.03360.47010.60910.053*
C91.0300 (6)0.4922 (8)0.7394 (2)0.0732 (17)
H9A1.00870.43790.77710.110*
H9B1.01170.60990.74260.110*
H9C1.13950.47300.73400.110*
N10.5052 (4)0.1889 (4)0.68311 (17)0.0395 (8)
H10.570 (6)0.193 (6)0.713 (2)0.047*
N20.7823 (4)0.3587 (4)0.69377 (15)0.0396 (8)
N30.9241 (4)0.4256 (5)0.68572 (16)0.0437 (8)
I10.77668 (4)0.33639 (5)0.493422 (14)0.06943 (16)
I20.37423 (3)0.26801 (3)0.869408 (12)0.04377 (12)
Cl10.62989 (15)0.1392 (2)0.83096 (6)0.0648 (3)
Cl20.13126 (16)0.3839 (2)0.90614 (6)0.0740 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.045 (2)0.060 (3)0.049 (3)−0.008 (2)0.017 (2)−0.002 (2)
C20.041 (2)0.082 (4)0.065 (3)−0.024 (2)0.008 (2)−0.010 (3)
C30.049 (3)0.092 (4)0.048 (3)−0.012 (3)−0.002 (2)−0.006 (3)
C40.050 (3)0.070 (3)0.036 (2)−0.012 (2)0.002 (2)0.002 (2)
C50.040 (2)0.035 (2)0.033 (2)−0.0018 (16)0.0070 (16)−0.0017 (16)
C60.041 (2)0.0326 (19)0.035 (2)−0.0001 (16)0.0065 (17)0.0037 (16)
C70.044 (2)0.047 (2)0.030 (2)−0.0020 (18)0.0090 (17)0.0002 (17)
C80.042 (2)0.050 (2)0.044 (2)−0.0015 (19)0.0155 (18)0.0034 (19)
C90.056 (3)0.112 (5)0.048 (3)−0.034 (3)−0.006 (2)−0.004 (3)
N10.0387 (19)0.0448 (19)0.0348 (18)−0.0024 (15)0.0047 (14)0.0016 (15)
N20.0344 (17)0.051 (2)0.0330 (17)−0.0054 (15)0.0022 (14)0.0047 (15)
N30.0359 (17)0.055 (2)0.0395 (19)−0.0069 (16)0.0026 (14)0.0007 (16)
I10.0779 (3)0.0981 (3)0.03559 (19)−0.0296 (2)0.01929 (16)−0.00920 (16)
I20.04535 (18)0.04520 (18)0.03920 (18)−0.00216 (12)0.00128 (12)0.00301 (11)
Cl10.0531 (6)0.0988 (10)0.0434 (6)0.0133 (6)0.0107 (5)0.0076 (6)
Cl20.0652 (8)0.0984 (10)0.0581 (8)0.0316 (8)0.0079 (6)−0.0003 (7)
Geometric parameters (Å, °) top
C1—N11.334 (6)C7—C81.367 (6)
C1—C21.361 (7)C7—I12.073 (4)
C1—H1A0.9300C8—N31.341 (5)
C2—C31.391 (7)C8—H80.9300
C2—H20.9300C9—N31.449 (6)
C3—C41.363 (7)C9—H9A0.9600
C3—H30.9300C9—H9B0.9600
C4—C51.392 (6)C9—H9C0.9600
C4—H40.9300N1—H10.78 (5)
C5—N11.346 (5)N2—N31.345 (4)
C5—C61.460 (6)I2—Cl22.4819 (13)
C6—N21.348 (5)I2—Cl12.6308 (13)
C6—C71.398 (5)
N1—C1—C2120.0 (4)C8—C7—I1123.9 (3)
N1—C1—H1A120.0C6—C7—I1131.2 (3)
C2—C1—H1A120.0N3—C8—C7107.5 (4)
C1—C2—C3118.1 (4)N3—C8—H8126.2
C1—C2—H2120.9C7—C8—H8126.2
C3—C2—H2120.9N3—C9—H9A109.5
C4—C3—C2120.6 (4)N3—C9—H9B109.5
C4—C3—H3119.7H9A—C9—H9B109.5
C2—C3—H3119.7N3—C9—H9C109.5
C3—C4—C5120.3 (4)H9A—C9—H9C109.5
C3—C4—H4119.9H9B—C9—H9C109.5
C5—C4—H4119.9C1—N1—C5124.2 (4)
N1—C5—C4116.8 (4)C1—N1—H1120 (4)
N1—C5—C6116.7 (4)C5—N1—H1116 (4)
C4—C5—C6126.5 (4)N3—N2—C6104.6 (3)
N2—C6—C7110.8 (3)C8—N3—N2112.2 (3)
N2—C6—C5116.6 (3)C8—N3—C9127.8 (4)
C7—C6—C5132.6 (4)N2—N3—C9119.9 (4)
C8—C7—C6104.8 (3)Cl2—I2—Cl1178.86 (5)
N1—C1—C2—C3−0.2 (8)C5—C6—C7—I10.9 (7)
C1—C2—C3—C40.9 (9)C6—C7—C8—N30.4 (5)
C2—C3—C4—C5−0.1 (8)I1—C7—C8—N3179.1 (3)
C3—C4—C5—N1−1.4 (7)C2—C1—N1—C5−1.4 (7)
C3—C4—C5—C6−179.8 (5)C4—C5—N1—C12.1 (6)
N1—C5—C6—N2−13.3 (5)C6—C5—N1—C1−179.3 (4)
C4—C5—C6—N2165.1 (4)C7—C6—N2—N30.2 (4)
N1—C5—C6—C7166.8 (4)C5—C6—N2—N3−179.7 (3)
C4—C5—C6—C7−14.7 (7)C7—C8—N3—N2−0.3 (5)
N2—C6—C7—C8−0.4 (5)C7—C8—N3—C9−176.6 (5)
C5—C6—C7—C8179.4 (4)C6—N2—N3—C80.1 (5)
N2—C6—C7—I1−179.0 (3)C6—N2—N3—C9176.7 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N20.78 (5)2.32 (5)2.683 (5)109 (4)
N1—H1···Cl10.78 (5)2.54 (5)3.216 (4)146 (5)
C2—H2···Cl2i0.932.773.664 (5)160
Symmetry codes: (i) −x, y−1/2, −z+3/2.
Selected geometric parameters (Å, °) top
I2—Cl22.4819 (13)I2—Cl12.6308 (13)
Cl2—I2—Cl1178.86 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N20.78 (5)2.32 (5)2.683 (5)109 (4)
N1—H1···Cl10.78 (5)2.54 (5)3.216 (4)146 (5)
C2—H2···Cl2i0.932.773.664 (5)160
Symmetry codes: (i) −x, y−1/2, −z+3/2.
Acknowledgements top

We thank M. R. St J. Foreman and M. John Plater for supplying the sample.

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1995). International Tables for Crystallography, Vol. C, pp. 685–706. Dordrecht: Kluwer.

Bruker (1999). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Greenwood, N. N. & Earnshaw, A. (1997). Chemistry of the Elements, 2nd ed., p 897. London: Butterworth-Heinmann.

Romming, C. (1958). Acta Chem. Scand. 12, 668–b>000. Final page?

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Wang, Z.-M., Wang, Y.-Q., Liao, C.-S. & Yan, C.-H. (1999). Acta Cryst. C55, 1506–1508.