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In the title compound, C10H12N4, the tetrazole and phenyl rings are planar to within 0.001 (2) and 0.006 (2) Å, respectively. The two rings are not coplanar and have a dihedral angle of 69.07 (9)° between them. Each mol­ecule is connected with two adjacent ones by C—H...N bridges between atoms of tetrazole rings forming chains parallel with the y axis of the unit cell.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199014742/av1031sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199014742/av1031Isup2.hkl
Contains datablock I

CCDC reference: 142784

Comment top

An increasing interest in research of 1-monosubstituted tetrazoles is due to possibility of their application in synthesis of medicines (Wittenberger, 1994) and as ligands for complexes with thermal and light-induced spin transitions (Lavrenova & Larionov, 1998) or ferromagnetic ordering (Gaponik, 1998). However a rather small number of structures of this type have been described: 1-methyl-tetrazole (Palmer & Parsons, 1996), 1-phenyl-tetrazole (Matsunaga et al., 1999) and hydrated 1-(3-pyrazolyl)tetrazole (Reimlinger et al., 1970). The crystal structure of a new compound, (I), has been determined and is presented here.

Bond distances within the tetrazole ring differ significantly. The shortest bond is between the atoms N2 and N3 [1.294 (3) Å]. This value in question is close to the N4—C5 bond distance of 1.303 (3) Å. N3—N4 and N1—N2 bonds are the longest in the ring [1.351 (2) Å and 1.349 (2) Å, respectively]. These data are consistent with the formulation of formal double bonds N4—C5 and N2—N3. Tetrazole ring is planar - the r.m.s. deviation of ring atoms from the least-squares plane through them is 0.001 (2) Å.

The bond distances and angles in the phenyl fragment are consistent with those observed previously for the phenyl ring. It is planar within 0.006 (2) Å.

The tetrazole and phenyl rings are not coplanar with a dihedral angle of 69.07 (9)° between the planes. Such conformation is due to a steric interaction between the tetrazole ring C5—H atom and methyl group of the phenyl ring. The N1—C11 bond length is 1.437 (2) Å, which is almost the same as a normal NC(phenyl) single-bond length. These facts indicate that the conjugation effects between the phenyl and tetrazole rings in the title compound are negligible.

Inspection of the packing of the molecules reveals that they are linked by C—H···N bridges between tetrazole rings forming chains parallel with the y axis of the unit cell. The dihedral angle between the adjacent tetrazole rings is 41.1°.

Experimental top

The title compound was prepared by heterocyclization of 2,4,6-trimethylaniline with ethylorthoformate and sodium azide in acetic acid (Gaponik et al., 1985). Single crystals of (I) used for analysis were grown by recrystallization from an ethanol solution.

Refinement top

H atom positions were found from the ΔF map. Refinement of methyl H atom positions was performed with fixed displacement parameters. Other H atoms were refined isotropically.

Computing details top

Data collection: R3m Software (Nicolet, 19XX); cell refinement: R3m Software; data reduction: R3m Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-III for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with the atom-numbering scheme.
[Figure 2] Fig. 2. Packing diagram of the title compound.
1-(2,4,6-trimethylphenyl)tetrazole top
Crystal data top
C10H12N4F(000) = 400
Mr = 188.24Dx = 1.216 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
a = 8.220 (2) ÅCell parameters from 22 reflections
b = 7.295 (1) Åθ = 10.1–16.9°
c = 17.470 (4) ŵ = 0.08 mm1
β = 100.97 (2)°T = 293 K
V = 1028.4 (4) Å3Prism, colourless
Z = 40.55 × 0.50 × 0.35 mm
Data collection top
Nicolet R3m four-circle
diffractometer
Rint = 0.023
Radiation source: fine-focus sealed tubeθmax = 27.6°, θmin = 2.4°
Graphite monochromatorh = 210
ω/2θ scansk = 09
2642 measured reflectionsl = 2222
2386 independent reflections3 standard reflections every 100 reflections
1357 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.190 w = 1/[σ2(Fo2) + (0.0849P)2 + 0.3158P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.004
2386 reflectionsΔρmax = 0.27 e Å3
168 parametersΔρmin = 0.21 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.074 (9)
Crystal data top
C10H12N4V = 1028.4 (4) Å3
Mr = 188.24Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.220 (2) ŵ = 0.08 mm1
b = 7.295 (1) ÅT = 293 K
c = 17.470 (4) Å0.55 × 0.50 × 0.35 mm
β = 100.97 (2)°
Data collection top
Nicolet R3m four-circle
diffractometer
Rint = 0.023
2642 measured reflections3 standard reflections every 100 reflections
2386 independent reflections intensity decay: none
1357 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.190H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.27 e Å3
2386 reflectionsΔρmin = 0.21 e Å3
168 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
N10.9784 (2)0.8232 (2)0.16103 (10)0.0518 (5)
N20.9553 (3)0.6539 (3)0.12982 (13)0.0759 (6)
N30.8467 (3)0.5751 (3)0.16355 (15)0.0852 (7)
N40.7980 (3)0.6876 (3)0.21636 (14)0.0775 (6)
C50.8809 (3)0.8389 (3)0.21348 (15)0.0657 (6)
C111.0873 (2)0.9539 (3)0.13535 (11)0.0481 (5)
C121.0171 (2)1.1062 (3)0.09339 (11)0.0496 (5)
C131.1251 (3)1.2309 (3)0.06940 (13)0.0580 (5)
C141.2951 (3)1.2060 (3)0.08470 (13)0.0615 (6)
C151.3587 (3)1.0532 (3)0.12724 (14)0.0611 (6)
C161.2581 (2)0.9250 (3)0.15358 (12)0.0543 (5)
C170.8336 (3)1.1381 (4)0.07468 (16)0.0635 (6)
C181.4069 (4)1.3416 (5)0.0555 (2)0.0887 (9)
C191.3321 (3)0.7641 (4)0.20228 (18)0.0766 (7)
H50.875 (3)0.950 (4)0.2439 (17)0.093 (9)*
H131.078 (3)1.334 (3)0.0417 (14)0.072 (7)*
H151.474 (3)1.034 (4)0.1388 (15)0.077 (7)*
H17A0.767 (4)1.028 (4)0.0547 (17)0.094 (9)*
H17B0.809 (4)1.227 (4)0.0308 (17)0.090*
H17C0.790 (3)1.192 (4)0.1157 (17)0.090*
H18A1.348 (4)1.444 (4)0.0329 (17)0.090*
H18B1.435 (3)1.287 (4)0.0086 (17)0.090*
H18C1.502 (4)1.367 (4)0.0948 (17)0.090*
H19A1.296 (3)0.765 (4)0.2523 (17)0.090*
H19B1.448 (4)0.762 (4)0.2032 (17)0.090*
H19C1.303 (4)0.660 (4)0.1765 (17)0.090*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0498 (9)0.0442 (9)0.0642 (10)0.0009 (7)0.0178 (8)0.0037 (7)
N20.0941 (15)0.0520 (11)0.0877 (14)0.0104 (10)0.0327 (12)0.0140 (10)
N30.0925 (16)0.0601 (12)0.1078 (17)0.0236 (11)0.0309 (14)0.0047 (12)
N40.0658 (12)0.0683 (12)0.1054 (17)0.0109 (10)0.0344 (12)0.0040 (12)
C50.0595 (13)0.0574 (13)0.0883 (16)0.0055 (10)0.0344 (12)0.0049 (12)
C110.0455 (10)0.0461 (10)0.0554 (10)0.0005 (8)0.0160 (8)0.0015 (8)
C120.0451 (10)0.0487 (10)0.0560 (10)0.0045 (8)0.0121 (8)0.0041 (8)
C130.0585 (12)0.0538 (12)0.0632 (12)0.0034 (10)0.0153 (10)0.0049 (10)
C140.0549 (12)0.0624 (13)0.0698 (13)0.0045 (10)0.0183 (10)0.0054 (10)
C150.0436 (11)0.0705 (14)0.0706 (13)0.0020 (10)0.0139 (10)0.0047 (11)
C160.0472 (10)0.0565 (11)0.0604 (11)0.0047 (9)0.0135 (9)0.0024 (9)
C170.0499 (12)0.0618 (14)0.0785 (15)0.0071 (11)0.0114 (11)0.0030 (12)
C180.0717 (17)0.091 (2)0.107 (2)0.0164 (15)0.0253 (16)0.0242 (18)
C190.0628 (15)0.0777 (17)0.0893 (19)0.0156 (13)0.0142 (14)0.0190 (15)
Geometric parameters (Å, º) top
N1—C51.332 (3)C16—C191.508 (3)
N1—N21.349 (2)C5—H50.98 (3)
N1—C111.437 (2)C13—H130.94 (3)
N2—N31.294 (3)C15—H150.94 (3)
N3—N41.351 (3)C17—H17A1.00 (3)
N4—C51.303 (3)C17—H17B1.00 (3)
C11—C121.395 (3)C17—H17C0.94 (3)
C11—C161.395 (3)C18—H18A0.93 (3)
C12—C131.390 (3)C18—H18B0.98 (3)
C12—C171.500 (3)C18—H18C0.95 (3)
C13—C141.384 (3)C19—H19A0.97 (3)
C14—C151.386 (3)C19—H19B0.95 (3)
C14—C181.504 (3)C19—H19C0.89 (3)
C15—C161.384 (3)
C5—N1—N2107.5 (2)C14—C13—H13121 (2)
C5—N1—C11130.6 (2)C12—C13—H13117 (2)
N2—N1—C11121.9 (2)C16—C15—H15118 (2)
N3—N2—N1106.2 (2)C14—C15—H15120 (2)
N2—N3—N4111.1 (2)C12—C17—H17A115 (2)
C5—N4—N3105.3 (2)C12—C17—H17B109 (2)
N4—C5—N1110.0 (2)H17A—C17—H17B104 (2)
C12—C11—C16122.54 (18)C12—C17—H17C114 (2)
C12—C11—N1118.20 (16)H17A—C17—H17C110 (2)
C16—C11—N1119.26 (17)H17B—C17—H17C105 (2)
C13—C12—C11117.14 (18)C14—C18—H18A112 (2)
C13—C12—C17120.42 (19)C14—C18—H18B106 (2)
C11—C12—C17122.44 (18)H18A—C18—H18B99 (2)
C14—C13—C12122.3 (2)C14—C18—H18C111 (2)
C13—C14—C15118.3 (2)H18A—C18—H18C116 (3)
C13—C14—C18120.5 (2)H18B—C18—H18C113 (2)
C15—C14—C18121.2 (2)C16—C19—H19A110 (2)
C16—C15—C14122.2 (2)C16—C19—H19B109 (2)
C15—C16—C11117.48 (19)H19A—C19—H19B117 (2)
C15—C16—C19120.7 (2)C16—C19—H19C110 (2)
C11—C16—C19121.8 (2)H19A—C19—H19C111 (3)
N4—C5—H5127 (2)H19B—C19—H19C100 (3)
N1—C5—H5123 (2)
C5—N1—N2—N30.2 (3)N1—C11—C12—C170.2 (3)
C11—N1—N2—N3177.7 (2)C11—C12—C13—C141.1 (3)
N1—N2—N3—N40.2 (3)C17—C12—C13—C14179.3 (2)
N2—N3—N4—C50.2 (3)C12—C13—C14—C151.7 (3)
N3—N4—C5—N10.0 (3)C12—C13—C14—C18178.2 (3)
N2—N1—C5—N40.1 (3)C13—C14—C15—C160.9 (4)
C11—N1—C5—N4177.6 (2)C18—C14—C15—C16178.9 (3)
C5—N1—C11—C1267.4 (3)C14—C15—C16—C110.4 (3)
N2—N1—C11—C12109.9 (2)C14—C15—C16—C19177.7 (2)
C5—N1—C11—C16112.1 (3)C12—C11—C16—C151.0 (3)
N2—N1—C11—C1670.6 (3)N1—C11—C16—C15179.49 (18)
C16—C11—C12—C130.3 (3)C12—C11—C16—C19177.0 (2)
N1—C11—C12—C13179.80 (17)N1—C11—C16—C192.4 (3)
C16—C11—C12—C17179.26 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···N4i0.98 (3)2.43 (3)3.290 (3)147 (2)
Symmetry code: (i) x+3/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC10H12N4
Mr188.24
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)8.220 (2), 7.295 (1), 17.470 (4)
β (°) 100.97 (2)
V3)1028.4 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.55 × 0.50 × 0.35
Data collection
DiffractometerNicolet R3m four-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2642, 2386, 1357
Rint0.023
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.190, 1.06
No. of reflections2386
No. of parameters168
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.27, 0.21

Computer programs: R3m Software (Nicolet, 19XX), R3m Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-III for Windows (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
N1—C51.332 (3)C11—C121.395 (3)
N1—N21.349 (2)C11—C161.395 (3)
N1—C111.437 (2)C12—C131.390 (3)
N2—N31.294 (3)C13—C141.384 (3)
N3—N41.351 (3)C14—C151.386 (3)
N4—C51.303 (3)C15—C161.384 (3)
C5—N1—N2107.5 (2)N2—N3—N4111.1 (2)
C5—N1—C11130.6 (2)C5—N4—N3105.3 (2)
N2—N1—C11121.9 (2)N4—C5—N1110.0 (2)
N3—N2—N1106.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···N4i0.98 (3)2.43 (3)3.290 (3)147 (2)
Symmetry code: (i) x+3/2, y+1/2, z+1/2.
 

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