supplementary materials
3-(1H-Tetrazol-5-yl)benzoic acid
The title compound, C8H6N4O2, is a difunctional compound with a carboxylate and a tetrazole residue. In the crystal structure, molecules are linked into two-dimensional sheets by intermolecular N-H
O and O-HN hydrogen bonds.
A mixture of 3-cyanobenzoic acid (0.147 g, 1.0 mmol), Cd(NO3)2.6H2O (0.345 g, 1 mmol) and water (8 ml) was was heated in a 15-ml Teflon-lined autoclave
at 160 ° for 3 days, followed by slow cooling (5 ° h-1) to room temperature.
The resulting mixture was washed with water and collected. Then, the obtained
solids were put into 20 ml water, and 10% Na2S aqueous solution was droped
to the suspension liquid until that no precipitation appeared. The solution
was filtered and the filtrate was acidified with 50% HCl solution until the
pH value was 1.0. White products were filtered, washed with water, then dried
and collected in 76.2% yield (0.145 g) based on 3-cyanobenzoic acid. Colorless
block shaped
crystals were collected from the filtrate after the second filtration.
H atoms bonded to N and O atoms were located in a difference map and
were freely refined.
Other H atoms were positioned geometrically and refined using a
riding model with C—H = 0.93 Å and with Uiso(H) = 1.2.
Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: SHELXTL Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
Crystal data top
| C8H6N4O2 | F(000) = 392 |
| Mr = 190.17 | Dx = 1.555 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 785 reflections |
| a = 5.2501 (10) Å | θ = 2.4–28.0° |
| b = 16.805 (3) Å | µ = 0.12 mm−1 |
| c = 9.3290 (18) Å | T = 293 K |
| β = 99.188 (3)° | Block, colorless |
| V = 812.5 (3) Å3 | 0.45 × 0.14 × 0.13 mm |
| Z = 4 | |
Data collection top
Bruker APX CCD
diffractometer | 1583 independent reflections |
| Radiation source: fine-focus sealed tube | 1425 reflections with I > 2σ(I) |
| graphite | Rint = 0.018 |
| phi and ω scan | θmax = 26.0°, θmin = 2.4° |
Absorption correction: multi-scan
SADABS (Sheldrick, 2000) | h = −6→6 |
| Tmin = 0.949, Tmax = 0.985 | k = −20→20 |
| 5991 measured reflections | l = −11→11 |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.0592P)2 + 0.1634P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max < 0.001 |
| 1583 reflections | Δρmax = 0.19 e Å−3 |
| 136 parameters | Δρmin = −0.24 e Å−3 |
| 0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.018 (3) |
Crystal data top
| C8H6N4O2 | V = 812.5 (3) Å3 |
| Mr = 190.17 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 5.2501 (10) Å | µ = 0.12 mm−1 |
| b = 16.805 (3) Å | T = 293 K |
| c = 9.3290 (18) Å | 0.45 × 0.14 × 0.13 mm |
| β = 99.188 (3)° | |
Data collection top
Bruker APX CCD
diffractometer | 1583 independent reflections |
Absorption correction: multi-scan
SADABS (Sheldrick, 2000) | 1425 reflections with I > 2σ(I) |
| Tmin = 0.949, Tmax = 0.985 | Rint = 0.018 |
| 5991 measured reflections | θmax = 26.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.106 | Δρmax = 0.19 e Å−3 |
| S = 1.07 | Δρmin = −0.24 e Å−3 |
| 1583 reflections | Absolute structure: ? |
| 136 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | |
| O1 | 0.0644 (2) | 0.36005 (6) | 0.68049 (12) | 0.0471 (3) | |
| O2 | 0.3759 (2) | 0.42002 (6) | 0.58687 (13) | 0.0496 (3) | |
| H2B | 0.410 (4) | 0.3707 (14) | 0.550 (2) | 0.082 (7)* | |
| C1 | 0.1794 (3) | 0.42040 (8) | 0.65768 (15) | 0.0358 (3) | |
| C2 | 0.1127 (3) | 0.50146 (7) | 0.70380 (15) | 0.0349 (3) | |
| C3 | −0.0705 (3) | 0.51184 (8) | 0.79498 (16) | 0.0403 (4) | |
| H3A | −0.1499 | 0.4680 | 0.8296 | 0.048* | |
| C4 | −0.1332 (3) | 0.58797 (9) | 0.83368 (16) | 0.0439 (4) | |
| H4A | −0.2539 | 0.5950 | 0.8955 | 0.053* | |
| C5 | −0.0189 (3) | 0.65372 (8) | 0.78180 (16) | 0.0392 (3) | |
| H5A | −0.0640 | 0.7046 | 0.8081 | 0.047* | |
| C6 | 0.1642 (3) | 0.64386 (7) | 0.68994 (14) | 0.0338 (3) | |
| C7 | 0.2301 (2) | 0.56732 (8) | 0.65297 (14) | 0.0356 (3) | |
| H7A | 0.3544 | 0.5602 | 0.5934 | 0.043* | |
| C8 | 0.2910 (3) | 0.71171 (7) | 0.63149 (14) | 0.0338 (3) | |
| N1 | 0.2597 (2) | 0.78846 (7) | 0.66034 (13) | 0.0402 (3) | |
| N2 | 0.4101 (3) | 0.83282 (7) | 0.58804 (14) | 0.0453 (3) | |
| N3 | 0.5310 (3) | 0.78398 (7) | 0.51637 (14) | 0.0445 (3) | |
| N4 | 0.4608 (2) | 0.70804 (7) | 0.54077 (13) | 0.0394 (3) | |
| H1A | 0.147 (4) | 0.8129 (12) | 0.716 (2) | 0.067 (5)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| O1 | 0.0573 (7) | 0.0296 (5) | 0.0618 (7) | −0.0056 (4) | 0.0317 (5) | 0.0017 (4) |
| O2 | 0.0616 (7) | 0.0266 (5) | 0.0718 (7) | −0.0021 (4) | 0.0446 (6) | −0.0037 (5) |
| C1 | 0.0416 (7) | 0.0290 (7) | 0.0408 (7) | −0.0007 (5) | 0.0188 (6) | 0.0037 (5) |
| C2 | 0.0379 (7) | 0.0299 (7) | 0.0400 (7) | 0.0007 (5) | 0.0158 (6) | 0.0010 (5) |
| C3 | 0.0448 (8) | 0.0328 (7) | 0.0485 (8) | −0.0023 (6) | 0.0231 (6) | 0.0013 (6) |
| C4 | 0.0468 (8) | 0.0408 (8) | 0.0510 (8) | 0.0015 (6) | 0.0285 (7) | −0.0021 (6) |
| C5 | 0.0434 (8) | 0.0305 (7) | 0.0474 (8) | 0.0036 (5) | 0.0188 (6) | −0.0048 (6) |
| C6 | 0.0374 (7) | 0.0285 (7) | 0.0380 (7) | −0.0004 (5) | 0.0133 (5) | −0.0002 (5) |
| C7 | 0.0394 (7) | 0.0311 (7) | 0.0406 (7) | 0.0002 (5) | 0.0195 (6) | 0.0003 (5) |
| C8 | 0.0383 (7) | 0.0266 (6) | 0.0388 (7) | 0.0026 (5) | 0.0131 (5) | −0.0021 (5) |
| N1 | 0.0498 (7) | 0.0263 (6) | 0.0496 (7) | 0.0012 (5) | 0.0238 (6) | −0.0017 (5) |
| N2 | 0.0564 (8) | 0.0290 (6) | 0.0559 (8) | −0.0022 (5) | 0.0257 (6) | 0.0001 (5) |
| N3 | 0.0537 (7) | 0.0293 (6) | 0.0562 (8) | −0.0026 (5) | 0.0260 (6) | 0.0005 (5) |
| N4 | 0.0470 (7) | 0.0263 (6) | 0.0504 (7) | −0.0010 (5) | 0.0247 (5) | −0.0010 (5) |
Geometric parameters (Å, °) top
| O1—C1 | 1.2163 (16) | C5—H5A | 0.9300 |
| O2—C1 | 1.3112 (16) | C6—C7 | 1.3898 (18) |
| O2—H2B | 0.93 (2) | C6—C8 | 1.4684 (18) |
| C1—C2 | 1.4871 (18) | C7—H7A | 0.9300 |
| C2—C7 | 1.3868 (18) | C8—N4 | 1.3254 (17) |
| C2—C3 | 1.3927 (19) | C8—N1 | 1.3331 (17) |
| C3—C4 | 1.3833 (19) | N1—N2 | 1.3430 (16) |
| C3—H3A | 0.9300 | N1—H1A | 0.94 (2) |
| C4—C5 | 1.381 (2) | N2—N3 | 1.2882 (17) |
| C4—H4A | 0.9300 | N3—N4 | 1.3576 (16) |
| C5—C6 | 1.3961 (18) | | |
| | | |
| C1—O2—H2B | 114.1 (14) | C7—C6—C5 | 119.03 (12) |
| O1—C1—O2 | 122.47 (12) | C7—C6—C8 | 118.74 (11) |
| O1—C1—C2 | 124.52 (12) | C5—C6—C8 | 122.22 (12) |
| O2—C1—C2 | 113.01 (11) | C2—C7—C6 | 120.79 (12) |
| C7—C2—C3 | 119.79 (12) | C2—C7—H7A | 119.6 |
| C7—C2—C1 | 119.61 (11) | C6—C7—H7A | 119.6 |
| C3—C2—C1 | 120.59 (11) | N4—C8—N1 | 106.91 (11) |
| C4—C3—C2 | 119.44 (12) | N4—C8—C6 | 126.31 (11) |
| C4—C3—H3A | 120.3 | N1—C8—C6 | 126.77 (12) |
| C2—C3—H3A | 120.3 | C8—N1—N2 | 109.54 (11) |
| C5—C4—C3 | 120.91 (12) | C8—N1—H1A | 129.9 (12) |
| C5—C4—H4A | 119.5 | N2—N1—H1A | 120.5 (12) |
| C3—C4—H4A | 119.5 | N3—N2—N1 | 106.56 (11) |
| C4—C5—C6 | 120.02 (12) | N2—N3—N4 | 110.02 (11) |
| C4—C5—H5A | 120.0 | C8—N4—N3 | 106.96 (10) |
| C6—C5—H5A | 120.0 | | |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2B···N4i | 0.93 (2) | 1.76 (2) | 2.6664 (15) | 164 (2) |
| N1—H1A···O1ii | 0.94 (2) | 1.77 (2) | 2.7118 (16) | 179.1 (19) |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2B···N4i | 0.93 (2) | 1.76 (2) | 2.6664 (15) | 164 (2) |
| N1—H1A···O1ii | 0.94 (2) | 1.77 (2) | 2.7118 (16) | 179.1 (19) |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2. |
The authors thank the Program for Young Excellent Talents in Southeast
University for financial support.
Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Chen, X.-M. & Tong, M.-L. (2007). Acc. Chem. Res. 40, 162–170.
Demko, Z. P. & Sharpless, K. B. (2001). J. Org. Chem. 66, 7945–7950.
Rizk, A. T., Kilner, C. A. & Halcrow, M. A. (2005). CrystEngComm, 7, 359–362.
Sheldrick, G. M. (2000). SADABS, University of Göttingen.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./bt2829fig1thm.gif)
![[Figure 2]](./bt2829fig2thm.gif)
![[Figure 3]](./bt2829fig3thm.gif)
Tetrazoles have been extensively investigated in organic synthetic chemistry for several decades due to the fact that they have wide ranging applications in pharmaceuticals, especially explosives, photography, information recording systems, agriculture, and as precursors to a variety of heterocycles (Chen et al. 2007; Demko et al. 2001). They have also been used as a type of important multidentate ligands in coordination chemistry. Here, we report the crystal structure of a new tetrazole, 3-(1H-tetrazol-5-yl)benzoic acid.
The title compound, C8H6N4O2, is a difunctional compound with carboxylate and tetrazole groups. The C=O distance of the carboxylate is 1.216 (2) Å, which is much shorter than the C—O distance of 1.311 (2) Å. In the tetrazole group, the N=N distance is 1.288 (2) Å, and the N—N distances are 1.343 (2) and 1.358 (2) Å, respectively. The C—N distance is 1.333 (2) Å, being close to the C=N distance of 1.325 (2) Å, which is considered to have part double-bond character. In the crystalline state, the molecules are linked to two-dimensional hydrogen-bonding networks by intermolecular N—H···O and O—H···N hydrogen bonds. The N···O distance is 2.712 (2) Å, and the O···N distance is 2.666 (2) Å.