3-Allyl-1-methyl-1H-benzotriazol-3-ium iodide

Buttrus, N.H.; Sabah, A.A.; Taqa, A.A.; Englert, U.

doi:10.1107/S1600536812035611

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2735

doi:10.1107/S1600536812035611

Open

access

3-Allyl-1-methyl-1H-benzotriazol-3-ium iodide

Nabeel H. Buttrus,^a Assim A. Sabah,^b Amer A. Taqa ^c ^* and Ulli Englert ^d

^aChemistry Department, College of Science, Mosul University, Iraq, ^bScience Department, College of Basic Education, Mosul University, Iraq, ^cDEPS Department, College of Dentistry, Mosul University, Iraq, and ^dInstitut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany
^*Correspondence e-mail: amertaqa@hotmail.com

(Received 1 April 2012; accepted 13 August 2012; online 23 August 2012)

In the crystal structure of 1-methyl-3-allyl benzotriazolium iodide, C₁₀H₁₂N₃⁺·I⁻, centrosymmetric dimers of coplanar cations are π-stacked with an interplanar distance of 3.453 (6) Å. The iodide anions are situated above and below the formally positive charged triazolium rings.

Related literature

For information on the Cambridge Structural Database, see: Allen (2002 ). For structural investigations of related compounds, see: Boche et al. (1996 ); Mouhib et al. (2011 ). For general information on π-stacking, see: Wright (1995 ).

Experimental

Crystal data

C₁₀H₁₂N₃⁺·I⁻
M_r = 301.13
Triclinic, $[P \overline 1]$
a = 7.8839 (12) Å
b = 8.2265 (14) Å
c = 9.9957 (17) Å
α = 114.093 (2)°
β = 104.033 (15)°
γ = 92.201 (13)°
V = 567.20 (16) Å³
Z = 2
Mo Kα radiation
μ = 2.79 mm⁻¹
T = 100 K
0.39 × 0.04 × 0.01 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.409, T_max = 0.972
7816 measured reflections
2798 independent reflections
2503 reflections with I > 2σ(I)
R_int = 0.089

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.066
S = 0.96
2798 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 1.58 e Å⁻³
Δρ_min = −1.35 e Å⁻³

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 1999 ); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812035611/im2367sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035611/im2367Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812035611/im2367Isup3.cml

checkCIF report

Comment top

The asymmetric unit of the title compound 1 (Fig. 1) comprises an organic cation and an iodide anion in general positions. The heteroaromatic cation is planar within error, with a maximum deviation of 0.008 (3) Å from the least-squares plane for the nitrogen atoms N1 and N2. Neighbouring cations are related by inversion and hence coplanar for reasons of symmetry. The shortest intermolecular interaction amounts to C2···C2ⁱ = 3.453 (6) Å (i = 1 - x,-y,1 - z). Due to the antiparallel arrangement of the coplanar benzotriazolium cations, the formally positive part of each heteroaromatic system is located on top of the carbocyclic moiety of its neighbour, thus ensuring both efficient space filling and efficient dipole matching for the π-stacking (Wright, 1995). An iodide counter anion is located 3.5172 (3) Å above and below each triazolium ring of such a cation pair. This packing motif is shown in Fig. 2. Shortest interactions between the hydrogen atoms of neighbouring stacks and iodide anions amount to 3.02 Å for I1···H7Bⁱⁱ (ii = x,1 + y,z). No relevant interhalide contacts occur, all being longer than 5 Å. Eight other benzotriazolium salts have been documented (Version 1.13, including the updates of August 2011) in the CSD data base (Allen, 2002), among them the closely related dimethylbenzotriazolium iodide studied by Boche et al. (1996). According to the database, the average N–N distance in the heteroaromatic five membered ring is 1.316 Å (min 1.300, max 1.338 Å); we find values of 1.309 (4) Å for N1—N2 and 1.322 (4) Å for N2—N3. The interatomic distance of 1.321 (5) Å of the allylic double bond C8—C9 closely matches the result recently obtained for the corresponding bond in allyl acetate where an interatomic distance of 1.3257 (18) Å was found by high-resolution X-ray diffraction (Mouhib et al., 2010).

Related literature top

For information on the Cambridge Structural Database, see: Allen (2002). For structural investigations of related compounds, see: Boche et al. (1996); Mouhib et al. (2011). For general information on π-stacking, see: Wright (1995).

Experimental top

To a solution of benzotriazole (1.19 g, 0.01 mol) in 10 ml of EtOH, first CH₃I (0.62 ml, 0.01 mol) and then 10 ml of 10% aqueous KOH were added. The mixture was refluxed for 1h. Then allyl chloride (5 ml) was added and refluxing was continued for 1h. The reaction mixture was extracted with n-hexane (3-5) times, in order to remove the excess of CH₃I . The mixture was filtered and the solvent removed under vacuum. The residue was crystallized from ethanol to give yellow crystals (yield 75%). M.p. 148-150 °C. Elemental analysis: found C: 39.56; H: 4.40; N: 13.70, Calcd. C: 39.89; H: 4.02; N: 13.95 %.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1: Displacement ellipsoid plot (Spek, 2009) of the asymmetric unit of 1 with thermal ellipsoids at the 50% probability level; H atoms have been omitted.

Fig. 2: Packing of the title compound: Two π-stacked cations related by inversion (i = 1 - x,-y,1 - z) and two counter anions are shown; H atoms have been omitted for clarity.

3-Allyl-1-methyl-1H-benzotriazol-3-ium iodide top

Crystal data top

C₁₀H₁₂N₃⁺·I⁻	Z = 2
M_r = 301.13	F(000) = 292
Triclinic, P1	D_x = 1.763 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8839 (12) Å	Cell parameters from 2049 reflections
b = 8.2265 (14) Å	θ = 2.3–25.1°
c = 9.9957 (17) Å	µ = 2.79 mm⁻¹
α = 114.093 (2)°	T = 100 K
β = 104.033 (15)°	Rod, yellow
γ = 92.201 (13)°	0.39 × 0.04 × 0.01 mm
V = 567.20 (16) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2798 independent reflections
Radiation source: Incoatec microsource	2503 reflections with I > 2σ(I)
Multilayer optics monochromator	R_int = 0.089
ω scans	θ_max = 28.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.409, T_max = 0.972	k = −10→10
7816 measured reflections	l = −13→13

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.006P)²] where P = (F_o² + 2F_c²)/3
2798 reflections	(Δ/σ)_max = 0.002
128 parameters	Δρ_max = 1.58 e Å⁻³
0 restraints	Δρ_min = −1.35 e Å⁻³

Crystal data top

C₁₀H₁₂N₃⁺·I⁻	γ = 92.201 (13)°
M_r = 301.13	V = 567.20 (16) Å³
Triclinic, P1	Z = 2
a = 7.8839 (12) Å	Mo Kα radiation
b = 8.2265 (14) Å	µ = 2.79 mm⁻¹
c = 9.9957 (17) Å	T = 100 K
α = 114.093 (2)°	0.39 × 0.04 × 0.01 mm
β = 104.033 (15)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2798 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2503 reflections with I > 2σ(I)
T_min = 0.409, T_max = 0.972	R_int = 0.089
7816 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 0.96	Δρ_max = 1.58 e Å⁻³
2798 reflections	Δρ_min = −1.35 e Å⁻³
128 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
N1	0.7209 (4)	0.1330 (4)	0.4718 (3)	0.0164 (7)
N2	0.7597 (4)	−0.0107 (4)	0.3708 (3)	0.0176 (7)
N3	0.6104 (4)	−0.0914 (4)	0.2612 (3)	0.0147 (7)
C1	0.4725 (5)	0.0022 (5)	0.2899 (4)	0.0140 (8)
C2	0.5465 (5)	0.1512 (5)	0.4296 (4)	0.0148 (8)
C3	0.4457 (5)	0.2804 (5)	0.4962 (4)	0.0187 (8)
H3	0.4955	0.3832	0.5906	0.022*
C4	0.2706 (5)	0.2495 (5)	0.4171 (4)	0.0211 (9)
H4	0.1965	0.3331	0.4589	0.025*
C5	0.1956 (5)	0.0978 (5)	0.2754 (4)	0.0199 (9)
H5	0.0733	0.0831	0.2252	0.024*
C6	0.2947 (5)	−0.0288 (5)	0.2084 (4)	0.0168 (8)
H6	0.2454	−0.1304	0.1131	0.020*
C7	0.6077 (5)	−0.2619 (5)	0.1295 (4)	0.0177 (8)
H7A	0.4846	−0.3094	0.0634	0.021*
H7B	0.6502	−0.3519	0.1665	0.021*
C8	0.7214 (5)	−0.2358 (5)	0.0381 (4)	0.0205 (9)
H8	0.7091	−0.1396	0.0089	0.025*
C9	0.8387 (5)	−0.3421 (6)	−0.0034 (5)	0.0271 (10)
H9A	0.8527	−0.4390	0.0250	0.033*
H9B	0.9091	−0.3218	−0.0615	0.033*
C10	0.8626 (5)	0.2617 (5)	0.6012 (4)	0.0220 (9)
H10A	0.9640	0.2009	0.6201	0.033*
H10B	0.8201	0.3103	0.6922	0.033*
H10C	0.8987	0.3604	0.5781	0.033*
I1	0.77374 (3)	0.33493 (3)	0.22631 (3)	0.01529 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0169 (18)	0.0148 (17)	0.0179 (17)	0.0011 (13)	0.0009 (14)	0.0098 (14)
N2	0.0197 (19)	0.0169 (18)	0.0164 (17)	0.0031 (14)	0.0022 (14)	0.0092 (15)
N3	0.0154 (17)	0.0100 (16)	0.0167 (16)	0.0018 (12)	0.0015 (13)	0.0056 (14)
C1	0.019 (2)	0.0129 (19)	0.0162 (19)	0.0060 (15)	0.0081 (16)	0.0097 (16)
C2	0.014 (2)	0.0121 (19)	0.0166 (19)	−0.0022 (15)	−0.0004 (15)	0.0079 (16)
C3	0.027 (2)	0.015 (2)	0.0168 (19)	0.0045 (17)	0.0080 (17)	0.0081 (17)
C4	0.027 (2)	0.018 (2)	0.024 (2)	0.0103 (17)	0.0139 (18)	0.0103 (18)
C5	0.017 (2)	0.022 (2)	0.025 (2)	0.0064 (16)	0.0047 (17)	0.0136 (19)
C6	0.019 (2)	0.015 (2)	0.0153 (19)	0.0016 (16)	0.0012 (16)	0.0071 (16)
C7	0.019 (2)	0.013 (2)	0.019 (2)	0.0038 (15)	0.0043 (16)	0.0047 (17)
C8	0.026 (2)	0.014 (2)	0.017 (2)	−0.0011 (16)	0.0033 (17)	0.0052 (17)
C9	0.023 (2)	0.031 (3)	0.025 (2)	0.0036 (19)	0.0062 (18)	0.010 (2)
C10	0.018 (2)	0.022 (2)	0.019 (2)	−0.0017 (17)	−0.0013 (17)	0.0061 (18)
I1	0.01635 (15)	0.01309 (14)	0.01588 (14)	0.00263 (10)	0.00268 (10)	0.00672 (11)

Geometric parameters (Å, º) top

N1—N2	1.309 (4)	C5—C6	1.375 (5)
N1—C2	1.370 (5)	C5—H5	0.9500
N1—C10	1.460 (4)	C6—H6	0.9500
N2—N3	1.322 (4)	C7—C8	1.492 (5)
N3—C1	1.376 (4)	C7—H7A	0.9900
N3—C7	1.476 (4)	C7—H7B	0.9900
C1—C2	1.394 (5)	C8—C9	1.321 (5)
C1—C6	1.394 (5)	C8—H8	0.9500
C2—C3	1.396 (5)	C9—H9A	0.9500
C3—C4	1.370 (5)	C9—H9B	0.9500
C3—H3	0.9500	C10—H10A	0.9800
C4—C5	1.417 (5)	C10—H10B	0.9800
C4—H4	0.9500	C10—H10C	0.9800

N2—N1—C2	112.4 (3)	C5—C6—C1	115.4 (3)
N2—N1—C10	119.4 (3)	C5—C6—H6	122.3
C2—N1—C10	127.7 (3)	C1—C6—H6	122.3
N1—N2—N3	105.9 (3)	N3—C7—C8	111.4 (3)
N2—N3—C1	111.9 (3)	N3—C7—H7A	109.3
N2—N3—C7	119.8 (3)	C8—C7—H7A	109.3
C1—N3—C7	128.3 (3)	N3—C7—H7B	109.3
N3—C1—C2	104.8 (3)	C8—C7—H7B	109.3
N3—C1—C6	132.4 (3)	H7A—C7—H7B	108.0
C2—C1—C6	122.8 (3)	C9—C8—C7	122.1 (4)
N1—C2—C1	105.0 (3)	C9—C8—H8	118.9
N1—C2—C3	133.4 (4)	C7—C8—H8	118.9
C1—C2—C3	121.6 (4)	C8—C9—H9A	120.0
C4—C3—C2	115.8 (4)	C8—C9—H9B	120.0
C4—C3—H3	122.1	H9A—C9—H9B	120.0
C2—C3—H3	122.1	N1—C10—H10A	109.5
C3—C4—C5	122.5 (4)	N1—C10—H10B	109.5
C3—C4—H4	118.7	H10A—C10—H10B	109.5
C5—C4—H4	118.7	N1—C10—H10C	109.5
C6—C5—C4	121.9 (4)	H10A—C10—H10C	109.5
C6—C5—H5	119.1	H10B—C10—H10C	109.5
C4—C5—H5	119.1

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₃⁺·I⁻
M_r	301.13
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.8839 (12), 8.2265 (14), 9.9957 (17)
α, β, γ (°)	114.093 (2), 104.033 (15), 92.201 (13)
V (Å³)	567.20 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.79
Crystal size (mm)	0.39 × 0.04 × 0.01

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.409, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	7816, 2798, 2503
R_int	0.089
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.066, 0.96
No. of reflections	2798
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.58, −1.35

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

The authors gratefully acknowledge the cooperation of the Dean of the College of Dentistry and the Dean of College of Science.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Boche, G., Andrews, P., Harms, K., Marsch, M., Rangappa, K. S., Schimeczek, M. & Willeke, C. (1996). J. Am. Chem. Soc. 118, 4925–4930. CSD CrossRef CAS Web of Science Google Scholar
Bruker (1999). SAINT-Plus. Bruker AXS Inc., Madison, Wisconson, USA. Google Scholar
Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconson, USA. Google Scholar
Mouhib, H., Jelisavac, D., Stahl, W., Wang, R., Kalf, I. & Englert, U. (2011). ChemPhysChem, 12, 761–764. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wright, J. D. (1995). Molecular Crystals, 2nd ed. Cambridge University Press. Google Scholar