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In the title compound, C
10H
12N
4, 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
CCDC reference: 142784
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.
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.
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.
1-(2,4,6-trimethylphenyl)tetrazole
top
Crystal data top
C10H12N4 | F(000) = 400 |
Mr = 188.24 | Dx = 1.216 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 8.220 (2) Å | Cell parameters from 22 reflections |
b = 7.295 (1) Å | θ = 10.1–16.9° |
c = 17.470 (4) Å | µ = 0.08 mm−1 |
β = 100.97 (2)° | T = 293 K |
V = 1028.4 (4) Å3 | Prism, colourless |
Z = 4 | 0.55 × 0.50 × 0.35 mm |
Data collection top
Nicolet R3m four-circle diffractometer | Rint = 0.023 |
Radiation source: fine-focus sealed tube | θmax = 27.6°, θmin = 2.4° |
Graphite monochromator | h = −2→10 |
ω/2θ scans | k = 0→9 |
2642 measured reflections | l = −22→22 |
2386 independent reflections | 3 standard reflections every 100 reflections |
1357 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | H 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 reflections | Δρmax = 0.27 e Å−3 |
168 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.074 (9) |
Crystal data top
C10H12N4 | V = 1028.4 (4) Å3 |
Mr = 188.24 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.220 (2) Å | µ = 0.08 mm−1 |
b = 7.295 (1) Å | T = 293 K |
c = 17.470 (4) Å | 0.55 × 0.50 × 0.35 mm |
β = 100.97 (2)° | |
Data collection top
Nicolet R3m four-circle diffractometer | Rint = 0.023 |
2642 measured reflections | 3 standard reflections every 100 reflections |
2386 independent reflections | intensity decay: none |
1357 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.190 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.27 e Å−3 |
2386 reflections | Δρmin = −0.21 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
N1 | 0.9784 (2) | 0.8232 (2) | 0.16103 (10) | 0.0518 (5) | |
N2 | 0.9553 (3) | 0.6539 (3) | 0.12982 (13) | 0.0759 (6) | |
N3 | 0.8467 (3) | 0.5751 (3) | 0.16355 (15) | 0.0852 (7) | |
N4 | 0.7980 (3) | 0.6876 (3) | 0.21636 (14) | 0.0775 (6) | |
C5 | 0.8809 (3) | 0.8389 (3) | 0.21348 (15) | 0.0657 (6) | |
C11 | 1.0873 (2) | 0.9539 (3) | 0.13535 (11) | 0.0481 (5) | |
C12 | 1.0171 (2) | 1.1062 (3) | 0.09339 (11) | 0.0496 (5) | |
C13 | 1.1251 (3) | 1.2309 (3) | 0.06940 (13) | 0.0580 (5) | |
C14 | 1.2951 (3) | 1.2060 (3) | 0.08470 (13) | 0.0615 (6) | |
C15 | 1.3587 (3) | 1.0532 (3) | 0.12724 (14) | 0.0611 (6) | |
C16 | 1.2581 (2) | 0.9250 (3) | 0.15358 (12) | 0.0543 (5) | |
C17 | 0.8336 (3) | 1.1381 (4) | 0.07468 (16) | 0.0635 (6) | |
C18 | 1.4069 (4) | 1.3416 (5) | 0.0555 (2) | 0.0887 (9) | |
C19 | 1.3321 (3) | 0.7641 (4) | 0.20228 (18) | 0.0766 (7) | |
H5 | 0.875 (3) | 0.950 (4) | 0.2439 (17) | 0.093 (9)* | |
H13 | 1.078 (3) | 1.334 (3) | 0.0417 (14) | 0.072 (7)* | |
H15 | 1.474 (3) | 1.034 (4) | 0.1388 (15) | 0.077 (7)* | |
H17A | 0.767 (4) | 1.028 (4) | 0.0547 (17) | 0.094 (9)* | |
H17B | 0.809 (4) | 1.227 (4) | 0.0308 (17) | 0.090* | |
H17C | 0.790 (3) | 1.192 (4) | 0.1157 (17) | 0.090* | |
H18A | 1.348 (4) | 1.444 (4) | 0.0329 (17) | 0.090* | |
H18B | 1.435 (3) | 1.287 (4) | 0.0086 (17) | 0.090* | |
H18C | 1.502 (4) | 1.367 (4) | 0.0948 (17) | 0.090* | |
H19A | 1.296 (3) | 0.765 (4) | 0.2523 (17) | 0.090* | |
H19B | 1.448 (4) | 0.762 (4) | 0.2032 (17) | 0.090* | |
H19C | 1.303 (4) | 0.660 (4) | 0.1765 (17) | 0.090* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0498 (9) | 0.0442 (9) | 0.0642 (10) | −0.0009 (7) | 0.0178 (8) | −0.0037 (7) |
N2 | 0.0941 (15) | 0.0520 (11) | 0.0877 (14) | −0.0104 (10) | 0.0327 (12) | −0.0140 (10) |
N3 | 0.0925 (16) | 0.0601 (12) | 0.1078 (17) | −0.0236 (11) | 0.0309 (14) | −0.0047 (12) |
N4 | 0.0658 (12) | 0.0683 (12) | 0.1054 (17) | −0.0109 (10) | 0.0344 (12) | 0.0040 (12) |
C5 | 0.0595 (13) | 0.0574 (13) | 0.0883 (16) | −0.0055 (10) | 0.0344 (12) | −0.0049 (12) |
C11 | 0.0455 (10) | 0.0461 (10) | 0.0554 (10) | 0.0005 (8) | 0.0160 (8) | −0.0015 (8) |
C12 | 0.0451 (10) | 0.0487 (10) | 0.0560 (10) | 0.0045 (8) | 0.0121 (8) | −0.0041 (8) |
C13 | 0.0585 (12) | 0.0538 (12) | 0.0632 (12) | 0.0034 (10) | 0.0153 (10) | 0.0049 (10) |
C14 | 0.0549 (12) | 0.0624 (13) | 0.0698 (13) | −0.0045 (10) | 0.0183 (10) | 0.0054 (10) |
C15 | 0.0436 (11) | 0.0705 (14) | 0.0706 (13) | 0.0020 (10) | 0.0139 (10) | 0.0047 (11) |
C16 | 0.0472 (10) | 0.0565 (11) | 0.0604 (11) | 0.0047 (9) | 0.0135 (9) | 0.0024 (9) |
C17 | 0.0499 (12) | 0.0618 (14) | 0.0785 (15) | 0.0071 (11) | 0.0114 (11) | −0.0030 (12) |
C18 | 0.0717 (17) | 0.091 (2) | 0.107 (2) | −0.0164 (15) | 0.0253 (16) | 0.0242 (18) |
C19 | 0.0628 (15) | 0.0777 (17) | 0.0893 (19) | 0.0156 (13) | 0.0142 (14) | 0.0190 (15) |
Geometric parameters (Å, º) top
N1—C5 | 1.332 (3) | C16—C19 | 1.508 (3) |
N1—N2 | 1.349 (2) | C5—H5 | 0.98 (3) |
N1—C11 | 1.437 (2) | C13—H13 | 0.94 (3) |
N2—N3 | 1.294 (3) | C15—H15 | 0.94 (3) |
N3—N4 | 1.351 (3) | C17—H17A | 1.00 (3) |
N4—C5 | 1.303 (3) | C17—H17B | 1.00 (3) |
C11—C12 | 1.395 (3) | C17—H17C | 0.94 (3) |
C11—C16 | 1.395 (3) | C18—H18A | 0.93 (3) |
C12—C13 | 1.390 (3) | C18—H18B | 0.98 (3) |
C12—C17 | 1.500 (3) | C18—H18C | 0.95 (3) |
C13—C14 | 1.384 (3) | C19—H19A | 0.97 (3) |
C14—C15 | 1.386 (3) | C19—H19B | 0.95 (3) |
C14—C18 | 1.504 (3) | C19—H19C | 0.89 (3) |
C15—C16 | 1.384 (3) | | |
| | | |
C5—N1—N2 | 107.5 (2) | C14—C13—H13 | 121 (2) |
C5—N1—C11 | 130.6 (2) | C12—C13—H13 | 117 (2) |
N2—N1—C11 | 121.9 (2) | C16—C15—H15 | 118 (2) |
N3—N2—N1 | 106.2 (2) | C14—C15—H15 | 120 (2) |
N2—N3—N4 | 111.1 (2) | C12—C17—H17A | 115 (2) |
C5—N4—N3 | 105.3 (2) | C12—C17—H17B | 109 (2) |
N4—C5—N1 | 110.0 (2) | H17A—C17—H17B | 104 (2) |
C12—C11—C16 | 122.54 (18) | C12—C17—H17C | 114 (2) |
C12—C11—N1 | 118.20 (16) | H17A—C17—H17C | 110 (2) |
C16—C11—N1 | 119.26 (17) | H17B—C17—H17C | 105 (2) |
C13—C12—C11 | 117.14 (18) | C14—C18—H18A | 112 (2) |
C13—C12—C17 | 120.42 (19) | C14—C18—H18B | 106 (2) |
C11—C12—C17 | 122.44 (18) | H18A—C18—H18B | 99 (2) |
C14—C13—C12 | 122.3 (2) | C14—C18—H18C | 111 (2) |
C13—C14—C15 | 118.3 (2) | H18A—C18—H18C | 116 (3) |
C13—C14—C18 | 120.5 (2) | H18B—C18—H18C | 113 (2) |
C15—C14—C18 | 121.2 (2) | C16—C19—H19A | 110 (2) |
C16—C15—C14 | 122.2 (2) | C16—C19—H19B | 109 (2) |
C15—C16—C11 | 117.48 (19) | H19A—C19—H19B | 117 (2) |
C15—C16—C19 | 120.7 (2) | C16—C19—H19C | 110 (2) |
C11—C16—C19 | 121.8 (2) | H19A—C19—H19C | 111 (3) |
N4—C5—H5 | 127 (2) | H19B—C19—H19C | 100 (3) |
N1—C5—H5 | 123 (2) | | |
| | | |
C5—N1—N2—N3 | 0.2 (3) | N1—C11—C12—C17 | 0.2 (3) |
C11—N1—N2—N3 | −177.7 (2) | C11—C12—C13—C14 | 1.1 (3) |
N1—N2—N3—N4 | −0.2 (3) | C17—C12—C13—C14 | −179.3 (2) |
N2—N3—N4—C5 | 0.2 (3) | C12—C13—C14—C15 | −1.7 (3) |
N3—N4—C5—N1 | 0.0 (3) | C12—C13—C14—C18 | 178.2 (3) |
N2—N1—C5—N4 | −0.1 (3) | C13—C14—C15—C16 | 0.9 (4) |
C11—N1—C5—N4 | 177.6 (2) | C18—C14—C15—C16 | −178.9 (3) |
C5—N1—C11—C12 | −67.4 (3) | C14—C15—C16—C11 | 0.4 (3) |
N2—N1—C11—C12 | 109.9 (2) | C14—C15—C16—C19 | −177.7 (2) |
C5—N1—C11—C16 | 112.1 (3) | C12—C11—C16—C15 | −1.0 (3) |
N2—N1—C11—C16 | −70.6 (3) | N1—C11—C16—C15 | 179.49 (18) |
C16—C11—C12—C13 | 0.3 (3) | C12—C11—C16—C19 | 177.0 (2) |
N1—C11—C12—C13 | 179.80 (17) | N1—C11—C16—C19 | −2.4 (3) |
C16—C11—C12—C17 | −179.26 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···N4i | 0.98 (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 formula | C10H12N4 |
Mr | 188.24 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.220 (2), 7.295 (1), 17.470 (4) |
β (°) | 100.97 (2) |
V (Å3) | 1028.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.55 × 0.50 × 0.35 |
|
Data collection |
Diffractometer | Nicolet R3m four-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2642, 2386, 1357 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.651 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.190, 1.06 |
No. of reflections | 2386 |
No. of parameters | 168 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.21 |
Selected geometric parameters (Å, º) topN1—C5 | 1.332 (3) | C11—C12 | 1.395 (3) |
N1—N2 | 1.349 (2) | C11—C16 | 1.395 (3) |
N1—C11 | 1.437 (2) | C12—C13 | 1.390 (3) |
N2—N3 | 1.294 (3) | C13—C14 | 1.384 (3) |
N3—N4 | 1.351 (3) | C14—C15 | 1.386 (3) |
N4—C5 | 1.303 (3) | C15—C16 | 1.384 (3) |
| | | |
C5—N1—N2 | 107.5 (2) | N2—N3—N4 | 111.1 (2) |
C5—N1—C11 | 130.6 (2) | C5—N4—N3 | 105.3 (2) |
N2—N1—C11 | 121.9 (2) | N4—C5—N1 | 110.0 (2) |
N3—N2—N1 | 106.2 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···N4i | 0.98 (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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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 N—C(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°.