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

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[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]). For structural investigations of related compounds, see: Boche et al. (1996[Boche, G., Andrews, P., Harms, K., Marsch, M., Rangappa, K. S., Schimeczek, M. & Willeke, C. (1996). J. Am. Chem. Soc. 118, 4925-4930.]); Mouhib et al. (2011[Mouhib, H., Jelisavac, D., Stahl, W., Wang, R., Kalf, I. & Englert, U. (2011). ChemPhysChem, 12, 761-764.]). For general information on π-stacking, see: Wright (1995[Wright, J. D. (1995). Molecular Crystals, 2nd ed. Cambridge University Press.]).

[Scheme 1]

Experimental

Crystal data
  • C10H12N3+·I

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.409, Tmax = 0.972

  • 7816 measured reflections

  • 2798 independent reflections

  • 2503 reflections with I > 2σ(I)

  • Rint = 0.089

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.066

  • S = 0.96

  • 2798 reflections

  • 128 parameters

  • H-atom parameters constrained

  • Δρmax = 1.58 e Å−3

  • Δρmin = −1.35 e Å−3

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconson, USA.]); cell refinement: SAINT-Plus (Bruker, 1999[Bruker (1999). SAINT-Plus. Bruker AXS Inc., Madison, Wisconson, USA.]); data reduction: SAINT-Plus (Bruker, 1999[Bruker (1999). SAINT-Plus. Bruker AXS Inc., Madison, Wisconson, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 %.

Refinement top

H atoms were treated as riding with Caryl—H and Colefin—H 0.95 Å, Uiso(H) = 1.2Ueq(C); Cmethylene—H 0.99 Å, Uiso(H) = 1.2Ueq(C) and Cmethyl—H 0.98 Å, Uiso(H) = 1.5Ueq(C).

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+·IZ = 2
Mr = 301.13F(000) = 292
Triclinic, P1Dx = 1.763 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8839 (12) ÅCell parameters from 2049 reflections
b = 8.2265 (14) Åθ = 2.3–25.1°
c = 9.9957 (17) ŵ = 2.79 mm1
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 microsource2503 reflections with I > 2σ(I)
Multilayer optics monochromatorRint = 0.089
ω scansθmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1010
Tmin = 0.409, Tmax = 0.972k = 1010
7816 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.006P)2]
where P = (Fo2 + 2Fc2)/3
2798 reflections(Δ/σ)max = 0.002
128 parametersΔρmax = 1.58 e Å3
0 restraintsΔρmin = 1.35 e Å3
Crystal data top
C10H12N3+·Iγ = 92.201 (13)°
Mr = 301.13V = 567.20 (16) Å3
Triclinic, P1Z = 2
a = 7.8839 (12) ÅMo Kα radiation
b = 8.2265 (14) ŵ = 2.79 mm1
c = 9.9957 (17) ÅT = 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)
Tmin = 0.409, Tmax = 0.972Rint = 0.089
7816 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.066H-atom parameters constrained
S = 0.96Δρmax = 1.58 e Å3
2798 reflectionsΔρmin = 1.35 e Å3
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
xyzUiso*/Ueq
N10.7209 (4)0.1330 (4)0.4718 (3)0.0164 (7)
N20.7597 (4)0.0107 (4)0.3708 (3)0.0176 (7)
N30.6104 (4)0.0914 (4)0.2612 (3)0.0147 (7)
C10.4725 (5)0.0022 (5)0.2899 (4)0.0140 (8)
C20.5465 (5)0.1512 (5)0.4296 (4)0.0148 (8)
C30.4457 (5)0.2804 (5)0.4962 (4)0.0187 (8)
H30.49550.38320.59060.022*
C40.2706 (5)0.2495 (5)0.4171 (4)0.0211 (9)
H40.19650.33310.45890.025*
C50.1956 (5)0.0978 (5)0.2754 (4)0.0199 (9)
H50.07330.08310.22520.024*
C60.2947 (5)0.0288 (5)0.2084 (4)0.0168 (8)
H60.24540.13040.11310.020*
C70.6077 (5)0.2619 (5)0.1295 (4)0.0177 (8)
H7A0.48460.30940.06340.021*
H7B0.65020.35190.16650.021*
C80.7214 (5)0.2358 (5)0.0381 (4)0.0205 (9)
H80.70910.13960.00890.025*
C90.8387 (5)0.3421 (6)0.0034 (5)0.0271 (10)
H9A0.85270.43900.02500.033*
H9B0.90910.32180.06150.033*
C100.8626 (5)0.2617 (5)0.6012 (4)0.0220 (9)
H10A0.96400.20090.62010.033*
H10B0.82010.31030.69220.033*
H10C0.89870.36040.57810.033*
I10.77374 (3)0.33493 (3)0.22631 (3)0.01529 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0169 (18)0.0148 (17)0.0179 (17)0.0011 (13)0.0009 (14)0.0098 (14)
N20.0197 (19)0.0169 (18)0.0164 (17)0.0031 (14)0.0022 (14)0.0092 (15)
N30.0154 (17)0.0100 (16)0.0167 (16)0.0018 (12)0.0015 (13)0.0056 (14)
C10.019 (2)0.0129 (19)0.0162 (19)0.0060 (15)0.0081 (16)0.0097 (16)
C20.014 (2)0.0121 (19)0.0166 (19)0.0022 (15)0.0004 (15)0.0079 (16)
C30.027 (2)0.015 (2)0.0168 (19)0.0045 (17)0.0080 (17)0.0081 (17)
C40.027 (2)0.018 (2)0.024 (2)0.0103 (17)0.0139 (18)0.0103 (18)
C50.017 (2)0.022 (2)0.025 (2)0.0064 (16)0.0047 (17)0.0136 (19)
C60.019 (2)0.015 (2)0.0153 (19)0.0016 (16)0.0012 (16)0.0071 (16)
C70.019 (2)0.013 (2)0.019 (2)0.0038 (15)0.0043 (16)0.0047 (17)
C80.026 (2)0.014 (2)0.017 (2)0.0011 (16)0.0033 (17)0.0052 (17)
C90.023 (2)0.031 (3)0.025 (2)0.0036 (19)0.0062 (18)0.010 (2)
C100.018 (2)0.022 (2)0.019 (2)0.0017 (17)0.0013 (17)0.0061 (18)
I10.01635 (15)0.01309 (14)0.01588 (14)0.00263 (10)0.00268 (10)0.00672 (11)
Geometric parameters (Å, º) top
N1—N21.309 (4)C5—C61.375 (5)
N1—C21.370 (5)C5—H50.9500
N1—C101.460 (4)C6—H60.9500
N2—N31.322 (4)C7—C81.492 (5)
N3—C11.376 (4)C7—H7A0.9900
N3—C71.476 (4)C7—H7B0.9900
C1—C21.394 (5)C8—C91.321 (5)
C1—C61.394 (5)C8—H80.9500
C2—C31.396 (5)C9—H9A0.9500
C3—C41.370 (5)C9—H9B0.9500
C3—H30.9500C10—H10A0.9800
C4—C51.417 (5)C10—H10B0.9800
C4—H40.9500C10—H10C0.9800
N2—N1—C2112.4 (3)C5—C6—C1115.4 (3)
N2—N1—C10119.4 (3)C5—C6—H6122.3
C2—N1—C10127.7 (3)C1—C6—H6122.3
N1—N2—N3105.9 (3)N3—C7—C8111.4 (3)
N2—N3—C1111.9 (3)N3—C7—H7A109.3
N2—N3—C7119.8 (3)C8—C7—H7A109.3
C1—N3—C7128.3 (3)N3—C7—H7B109.3
N3—C1—C2104.8 (3)C8—C7—H7B109.3
N3—C1—C6132.4 (3)H7A—C7—H7B108.0
C2—C1—C6122.8 (3)C9—C8—C7122.1 (4)
N1—C2—C1105.0 (3)C9—C8—H8118.9
N1—C2—C3133.4 (4)C7—C8—H8118.9
C1—C2—C3121.6 (4)C8—C9—H9A120.0
C4—C3—C2115.8 (4)C8—C9—H9B120.0
C4—C3—H3122.1H9A—C9—H9B120.0
C2—C3—H3122.1N1—C10—H10A109.5
C3—C4—C5122.5 (4)N1—C10—H10B109.5
C3—C4—H4118.7H10A—C10—H10B109.5
C5—C4—H4118.7N1—C10—H10C109.5
C6—C5—C4121.9 (4)H10A—C10—H10C109.5
C6—C5—H5119.1H10B—C10—H10C109.5
C4—C5—H5119.1

Experimental details

Crystal data
Chemical formulaC10H12N3+·I
Mr301.13
Crystal system, space groupTriclinic, 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)
V3)567.20 (16)
Z2
Radiation typeMo Kα
µ (mm1)2.79
Crystal size (mm)0.39 × 0.04 × 0.01
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.409, 0.972
No. of measured, independent and
observed [I > 2σ(I)] reflections
7816, 2798, 2503
Rint0.089
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.066, 0.96
No. of reflections2798
No. of parameters128
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals
First citationBoche, 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
First citationBruker (1999). SAINT-Plus. Bruker AXS Inc., Madison, Wisconson, USA.
First citationBruker (2001). SMART. Bruker AXS Inc., Madison, Wisconson, USA.
First citationMouhib, H., Jelisavac, D., Stahl, W., Wang, R., Kalf, I. & Englert, U. (2011). ChemPhysChem, 12, 761–764.  Web of Science CSD CrossRef CAS PubMed
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals
First citationWright, J. D. (1995). Molecular Crystals, 2nd ed. Cambridge University Press.

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