Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101016006/av1091sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101016006/av1091Isup2.hkl |
CCDC reference: 179276
For related literature, see: Allen & Kennard (1993); Lyakhov et al. (2000, 2001); Matsunaga et al. (1999); Schmidt et al. (1993); Voitekhovich et al. (2001).
The title compound was prepared by heterocyclization of anthranilic acid and 2-amino-4-nitrophenol with ethyl orthoformate and sodium azide in acetic acid (Voitekhovich et al., 2001). Single crystals were grown by slow crystallization from an acetonitrile solution.
H-atom positions were found from the ΔF map and all associated parameters were refined freely [C—H = 0.93 (2)–0.99 (2) Å].
Data collection: R3m Software (Nicolet, 1980); cell refinement: R3m Software; data reduction: R3m Software; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.
C8H6N4O2 | F(000) = 392 |
Mr = 190.17 | Dx = 1.546 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 3.841 (1) Å | Cell parameters from 25 reflections |
b = 16.073 (4) Å | θ = 17.9–24.1° |
c = 13.234 (3) Å | µ = 0.12 mm−1 |
β = 91.15 (2)° | T = 293 K |
V = 816.9 (3) Å3 | Prism, colourless |
Z = 4 | 0.74 × 0.30 × 0.18 mm |
Nicolet R3m four-circle diffractometer | Rint = 0.019 |
Radiation source: fine-focus sealed tube | θmax = 30.1°, θmin = 2.0° |
Graphite monochromator | h = 0→5 |
ω/2θ scans | k = 0→22 |
2822 measured reflections | l = −18→18 |
2410 independent reflections | 3 standard reflections every 100 reflections |
1888 reflections with I > 2σ(I) | intensity decay: 2.2% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | All H-atom parameters refined |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0582P)2 + 0.1169P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2410 reflections | Δρmax = 0.26 e Å−3 |
152 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.077 (7) |
C8H6N4O2 | V = 816.9 (3) Å3 |
Mr = 190.17 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 3.841 (1) Å | µ = 0.12 mm−1 |
b = 16.073 (4) Å | T = 293 K |
c = 13.234 (3) Å | 0.74 × 0.30 × 0.18 mm |
β = 91.15 (2)° |
Nicolet R3m four-circle diffractometer | Rint = 0.019 |
2822 measured reflections | 3 standard reflections every 100 reflections |
2410 independent reflections | intensity decay: 2.2% |
1888 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.113 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.26 e Å−3 |
2410 reflections | Δρmin = −0.16 e Å−3 |
152 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.7659 (2) | 0.11787 (5) | 0.37068 (6) | 0.0325 (2) | |
N2 | 0.9448 (3) | 0.10356 (6) | 0.45845 (7) | 0.0444 (3) | |
N3 | 0.9235 (3) | 0.17065 (7) | 0.51131 (8) | 0.0476 (3) | |
N4 | 0.7335 (3) | 0.22903 (6) | 0.46038 (7) | 0.0423 (2) | |
C5 | 0.6410 (3) | 0.19511 (7) | 0.37417 (9) | 0.0393 (3) | |
H5 | 0.516 (4) | 0.2200 (10) | 0.3189 (13) | 0.056 (4)* | |
C6 | 0.7118 (3) | 0.05210 (6) | 0.29889 (7) | 0.0311 (2) | |
C7 | 0.7803 (3) | 0.06150 (6) | 0.19593 (7) | 0.0302 (2) | |
C8 | 0.7050 (3) | −0.00590 (7) | 0.13267 (8) | 0.0370 (2) | |
H8 | 0.747 (4) | −0.0004 (9) | 0.0594 (13) | 0.053 (4)* | |
C9 | 0.5729 (3) | −0.07948 (7) | 0.17030 (10) | 0.0432 (3) | |
H9 | 0.518 (4) | −0.1234 (11) | 0.1251 (12) | 0.057 (4)* | |
C10 | 0.5144 (4) | −0.08788 (7) | 0.27227 (10) | 0.0451 (3) | |
H10 | 0.429 (4) | −0.1382 (11) | 0.2960 (12) | 0.059 (4)* | |
C11 | 0.5800 (3) | −0.02159 (7) | 0.33665 (9) | 0.0399 (3) | |
H11 | 0.548 (4) | −0.0264 (10) | 0.4080 (13) | 0.058 (4)* | |
C12 | 0.9455 (3) | 0.13766 (6) | 0.15292 (8) | 0.0328 (2) | |
O1 | 1.0738 (3) | 0.19278 (5) | 0.20294 (6) | 0.0468 (2) | |
O2 | 0.9448 (3) | 0.13685 (6) | 0.05348 (6) | 0.0568 (3) | |
H2 | 1.036 (5) | 0.1855 (13) | 0.0298 (16) | 0.080 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0431 (5) | 0.0293 (4) | 0.0254 (4) | −0.0005 (3) | 0.0045 (3) | 0.0000 (3) |
N2 | 0.0636 (7) | 0.0407 (5) | 0.0288 (4) | 0.0019 (4) | −0.0024 (4) | 0.0009 (4) |
N3 | 0.0683 (7) | 0.0442 (5) | 0.0303 (5) | −0.0023 (5) | 0.0001 (4) | −0.0042 (4) |
N4 | 0.0557 (6) | 0.0367 (5) | 0.0347 (5) | −0.0012 (4) | 0.0070 (4) | −0.0071 (4) |
C5 | 0.0504 (6) | 0.0323 (5) | 0.0352 (5) | 0.0039 (4) | 0.0020 (5) | −0.0046 (4) |
C6 | 0.0386 (5) | 0.0269 (4) | 0.0280 (4) | 0.0011 (4) | 0.0036 (4) | −0.0013 (3) |
C7 | 0.0355 (5) | 0.0279 (4) | 0.0273 (4) | 0.0016 (4) | 0.0029 (3) | 0.0002 (3) |
C8 | 0.0439 (6) | 0.0364 (5) | 0.0308 (5) | 0.0007 (4) | 0.0036 (4) | −0.0053 (4) |
C9 | 0.0521 (7) | 0.0317 (5) | 0.0458 (6) | −0.0033 (5) | 0.0035 (5) | −0.0092 (4) |
C10 | 0.0575 (7) | 0.0289 (5) | 0.0491 (7) | −0.0063 (5) | 0.0073 (5) | 0.0009 (4) |
C11 | 0.0530 (7) | 0.0328 (5) | 0.0343 (5) | −0.0042 (5) | 0.0082 (5) | 0.0030 (4) |
C12 | 0.0380 (5) | 0.0320 (5) | 0.0287 (5) | 0.0016 (4) | 0.0027 (4) | 0.0027 (3) |
O1 | 0.0646 (6) | 0.0407 (5) | 0.0351 (4) | −0.0158 (4) | 0.0023 (4) | 0.0012 (3) |
O2 | 0.0951 (8) | 0.0477 (5) | 0.0276 (4) | −0.0212 (5) | 0.0052 (4) | 0.0046 (3) |
N1—C5 | 1.332 (1) | C8—C9 | 1.3835 (16) |
N1—N2 | 1.357 (1) | C8—H8 | 0.991 (17) |
N1—C6 | 1.434 (1) | C9—C10 | 1.3792 (18) |
N2—N3 | 1.289 (1) | C9—H9 | 0.947 (17) |
N3—N4 | 1.359 (2) | C10—C11 | 1.3842 (16) |
N4—C5 | 1.307 (2) | C10—H10 | 0.930 (17) |
C5—H5 | 0.956 (16) | C11—H11 | 0.958 (18) |
C6—C11 | 1.3853 (14) | C12—O1 | 1.205 (1) |
C6—C7 | 1.4012 (13) | C12—O2 | 1.316 (1) |
C7—C8 | 1.3958 (14) | O2—H2 | 0.92 (2) |
C7—C12 | 1.496 (1) | ||
C5—N1—N2 | 107.74 (9) | C9—C8—H8 | 119.8 (9) |
C5—N1—C6 | 131.51 (9) | C7—C8—H8 | 118.8 (9) |
N2—N1—C6 | 120.42 (9) | C10—C9—C8 | 120.27 (10) |
N3—N2—N1 | 106.63 (10) | C10—C9—H9 | 120.4 (10) |
N2—N3—N4 | 110.35 (10) | C8—C9—H9 | 119.3 (10) |
C5—N4—N3 | 106.18 (10) | C9—C10—C11 | 119.71 (11) |
N4—C5—N1 | 109.10 (10) | C9—C10—H10 | 118.7 (10) |
N4—C5—H5 | 128.1 (9) | C11—C10—H10 | 121.6 (10) |
N1—C5—H5 | 122.7 (10) | C10—C11—C6 | 119.96 (10) |
C11—C6—C7 | 121.34 (9) | C10—C11—H11 | 121.3 (9) |
C11—C6—N1 | 116.14 (9) | C6—C11—H11 | 118.6 (9) |
C7—C6—N1 | 122.50 (9) | O1—C12—O2 | 123.30 (10) |
C8—C7—C6 | 117.31 (9) | O1—C12—C7 | 124.34 (10) |
C8—C7—C12 | 119.41 (9) | O2—C12—C7 | 112.33 (9) |
C6—C7—C12 | 123.19 (9) | C12—O2—H2 | 109.9 (13) |
C9—C8—C7 | 121.37 (10) | ||
C5—N1—N2—N3 | 0.09 (13) | C11—C6—C7—C12 | −175.62 (10) |
C6—N1—N2—N3 | −174.01 (9) | N1—C6—C7—C12 | 5.72 (15) |
N1—N2—N3—N4 | 0.11 (14) | C6—C7—C8—C9 | −0.94 (16) |
N2—N3—N4—C5 | −0.28 (14) | C12—C7—C8—C9 | 175.84 (11) |
N3—N4—C5—N1 | 0.33 (14) | C7—C8—C9—C10 | −0.38 (19) |
N2—N1—C5—N4 | −0.27 (14) | C8—C9—C10—C11 | 1.6 (2) |
C6—N1—C5—N4 | 172.94 (10) | C9—C10—C11—C6 | −1.5 (2) |
C5—N1—C6—C11 | −122.17 (13) | C7—C6—C11—C10 | 0.19 (18) |
N2—N1—C6—C11 | 50.32 (14) | N1—C6—C11—C10 | 178.93 (11) |
C5—N1—C6—C7 | 56.55 (16) | C8—C7—C12—O1 | −166.81 (11) |
N2—N1—C6—C7 | −130.95 (11) | C6—C7—C12—O1 | 9.77 (17) |
C11—C6—C7—C8 | 1.04 (16) | C8—C7—C12—O2 | 11.29 (14) |
N1—C6—C7—C8 | −177.62 (10) | C6—C7—C12—O2 | −172.12 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N4i | 0.92 (2) | 1.83 (2) | 2.729 (1) | 169 (2) |
C5—H5···O1ii | 0.96 (2) | 2.31 (2) | 3.112 (2) | 141 (1) |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C8H6N4O2 |
Mr | 190.17 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 3.841 (1), 16.073 (4), 13.234 (3) |
β (°) | 91.15 (2) |
V (Å3) | 816.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.74 × 0.30 × 0.18 |
Data collection | |
Diffractometer | Nicolet R3m four-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2822, 2410, 1888 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.705 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.113, 1.04 |
No. of reflections | 2410 |
No. of parameters | 152 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.26, −0.16 |
Computer programs: R3m Software (Nicolet, 1980), R3m Software, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 1999), SHELXL97.
N1—C5 | 1.332 (1) | N4—C5 | 1.307 (2) |
N1—N2 | 1.357 (1) | C7—C12 | 1.496 (1) |
N1—C6 | 1.434 (1) | C12—O1 | 1.205 (1) |
N2—N3 | 1.289 (1) | C12—O2 | 1.316 (1) |
N3—N4 | 1.359 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N4i | 0.92 (2) | 1.83 (2) | 2.729 (1) | 169 (2) |
C5—H5···O1ii | 0.96 (2) | 2.31 (2) | 3.112 (2) | 141 (1) |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x−1, y, z. |
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This work is a part of a systematic investigation of the molecular and crystal structures of 1-aryltetrazoles which are of great interest in the field of theoretical and experimental chemistry. To date, the structures of the following 1-aryltetrazoles have been reported: 1-phenyltetrazole (Matsunaga et al., 1999), 1-(2,4,6-trimethylphenyl)tetrazole (Lyakhov et al., 2000) and 4-nitro-2-(1H-tetrazol-1-yl)phenol (Lyakhov et al., 2001). In this paper, we present the crystal structure of 2-(1H-tetrazol-1-yl)benzoic acid, (I) (Fig. 1).
The tetrazole ring is planar to within 0.001 (1) Å. The endocyclic angles vary from 106.2 (1) to 109.1 (1)°. The N1—N2 and N3—N4 bonds are similar and longer than N2—N3, while the N1—C5 bond length is somewhat longer than N4—C5. This is a typical geometry of the 1-substituted tetrazole ring. All the bond lengths and angles of the ring are within the ranges found for tetrazole-containing structures generated by a search of the Cambridge Structural Database (Allen et al., 1993). The tetrazole-ring geometry shows that there is strong π-delocalization in the N1—C5—N4 fragment, whereas single and double bonds are in the other part of the ring.
The benzene ring is planar to within 0.007 (1) Å. The bond distances and angles are consistent with those observed previously for the benzene ring. The bond lengths and angles of the carboxyl group also have typical values. The dihedral angle between the COO plane and the least-squares plane of the benzene ring is 11.8 (2)°. The bridge N1—C6 bond lies almost in the planes of the tetrazole and benzene rings. The angles between the N1—C6 bond and the least-squares planes of the benzene and tetrazole rings are 1.62 (7) and 5.22 (7)°, respectively.
The benzene and tetrazole rings are not coplanar in the molecule, the dihedral angle between the rings being 52.90 (4)°. It is interesting to compare this value with that of a free molecule of (I). The ab initio calculations on an isolated molecule using the HF/6–311G** basis set were performed using the GAMESS program (Schmidt et al., 1993). Geometry optimization with respect to all variables results in a dihedral angle between the benzene and tetrazole rings of 69.5°. This value is somewhat larger than that in the crystal of (I). The data obtained confirm a presumption (Lyakhov et al., 2001) that the decrease in the dihedral angle in the crystals of 1-aryltetrazoles is due to molecular packing.
Inspection of the packing of the molecules in (I) reveals the following. There are two types of hydrogen bonds, O2—H2···N4 and C5—H5···O1 (Desiraju, 1999), between the molecules in the structure of (I). O2—H2···N4 bridges are responsible for the formation of infinite one-dimensional zigzag chains parallel to the [101] direction. These chains are linked together by C5—H5···O1 hydrogen bonds, forming two-dimensional networks parallel to the xz plane (Fig. 2). Only van der Waals interactions take place between these networks in the structure.