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There are two symmetry-independent molecules in the unit cell of the title compound, C
7H
5N
5O
3. The tetrazole and phenyl rings are essentially planar and are not coplanar in either molecule [dihedral angles 30.2 (1) and 7.0 (1)°]. In the structure, four molecules are connected by O—H
N bridges, forming four-membered molecular aggregates which are linked together by a complex three-dimensional hydrogen-bond network.
Supporting information
CCDC reference: 174841
The title compound was prepared by heterocyclization of 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 = 0.92 (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.
1-(2-hydroxy-5-nitrophenyl)-1
H-tetrazole
top
Crystal data top
C7H5N5O3 | Z = 4 |
Mr = 207.16 | F(000) = 424 |
Triclinic, P1 | Dx = 1.592 Mg m−3 |
a = 7.116 (2) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 9.452 (2) Å | Cell parameters from 25 reflections |
c = 13.895 (3) Å | θ = 12.5–19.8° |
α = 86.43 (2)° | µ = 0.13 mm−1 |
β = 84.17 (2)° | T = 293 K |
γ = 68.42 (2)° | Prism, colourless |
V = 864.3 (4) Å3 | 0.54 × 0.40 × 0.30 mm |
Data collection top
Nicolet R3m four-circle diffractometer | Rint = 0.019 |
Radiation source: fine-focus sealed tube | θmax = 30.1°, θmin = 1.5° |
Graphite monochromator | h = 0→10 |
ω/2θ scans | k = −12→13 |
5619 measured reflections | l = −19→19 |
5062 independent reflections | 3 standard reflections every 100 reflections |
3704 reflections with I > 2σ(I) | intensity decay: 0.1% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.143 | All H-atom parameters refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0837P)2 + 0.0881P] where P = (Fo2 + 2Fc2)/3 |
5062 reflections | (Δ/σ)max = 0.001 |
311 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C7H5N5O3 | γ = 68.42 (2)° |
Mr = 207.16 | V = 864.3 (4) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.116 (2) Å | Mo Kα radiation |
b = 9.452 (2) Å | µ = 0.13 mm−1 |
c = 13.895 (3) Å | T = 293 K |
α = 86.43 (2)° | 0.54 × 0.40 × 0.30 mm |
β = 84.17 (2)° | |
Data collection top
Nicolet R3m four-circle diffractometer | Rint = 0.019 |
5619 measured reflections | 3 standard reflections every 100 reflections |
5062 independent reflections | intensity decay: 0.1% |
3704 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.143 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.25 e Å−3 |
5062 reflections | Δρmin = −0.27 e Å−3 |
311 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 | |
N1A | −0.23274 (18) | 0.27927 (11) | 0.65678 (7) | 0.0391 (2) | |
N2A | −0.1978 (3) | 0.13495 (15) | 0.63400 (10) | 0.0790 (6) | |
N3A | −0.1855 (4) | 0.05921 (16) | 0.71514 (11) | 0.0901 (7) | |
N4A | −0.2115 (2) | 0.15010 (14) | 0.79045 (9) | 0.0538 (3) | |
C5A | −0.2415 (3) | 0.28493 (17) | 0.75238 (9) | 0.0490 (3) | |
H5A | −0.263 (3) | 0.370 (3) | 0.7874 (17) | 0.080 (6)* | |
C6A | −0.2466 (2) | 0.39313 (13) | 0.58251 (8) | 0.0345 (2) | |
C7A | −0.3695 (2) | 0.54479 (13) | 0.60096 (8) | 0.0365 (3) | |
C8A | −0.3799 (2) | 0.65539 (14) | 0.52821 (9) | 0.0410 (3) | |
H8A | −0.469 (3) | 0.760 (2) | 0.5431 (14) | 0.059 (5)* | |
C9A | −0.2735 (2) | 0.61563 (15) | 0.43936 (9) | 0.0403 (3) | |
H9A | −0.279 (3) | 0.694 (2) | 0.3885 (12) | 0.052 (5)* | |
C10A | −0.1573 (2) | 0.46415 (14) | 0.42333 (8) | 0.0365 (3) | |
C11A | −0.1411 (2) | 0.35108 (14) | 0.49369 (8) | 0.0368 (3) | |
H11A | −0.052 (3) | 0.245 (2) | 0.4815 (12) | 0.048 (4)* | |
N12A | −0.0407 (2) | 0.42126 (14) | 0.33021 (8) | 0.0465 (3) | |
O1A | −0.47239 (18) | 0.57488 (12) | 0.68793 (7) | 0.0496 (3) | |
H1A | −0.527 (4) | 0.677 (3) | 0.6941 (17) | 0.088 (7)* | |
O2A | −0.0357 (2) | 0.52364 (14) | 0.27241 (7) | 0.0590 (3) | |
O3A | 0.0505 (3) | 0.28802 (15) | 0.31489 (9) | 0.0869 (5) | |
N1B | 0.29712 (18) | 0.04553 (11) | 0.83583 (7) | 0.0390 (2) | |
N2B | 0.3183 (3) | 0.10098 (16) | 0.74517 (9) | 0.0747 (5) | |
N3B | 0.3500 (4) | −0.00811 (17) | 0.68734 (10) | 0.0808 (6) | |
N4B | 0.3511 (2) | −0.13475 (14) | 0.73721 (9) | 0.0543 (3) | |
C5B | 0.3167 (3) | −0.09933 (15) | 0.82844 (10) | 0.0465 (3) | |
H5B | 0.301 (3) | −0.168 (2) | 0.8801 (14) | 0.063 (5)* | |
C6B | 0.26941 (19) | 0.13924 (13) | 0.91701 (8) | 0.0339 (2) | |
C7B | 0.2350 (2) | 0.08549 (13) | 1.01118 (8) | 0.0353 (3) | |
C8B | 0.2084 (2) | 0.18041 (15) | 1.08861 (9) | 0.0421 (3) | |
H8B | 0.183 (3) | 0.1464 (19) | 1.1551 (12) | 0.046 (4)* | |
C9B | 0.2206 (2) | 0.32217 (15) | 1.07342 (9) | 0.0419 (3) | |
H9B | 0.204 (3) | 0.387 (2) | 1.1268 (14) | 0.061 (5)* | |
C10B | 0.25793 (19) | 0.37022 (13) | 0.97979 (9) | 0.0358 (3) | |
C11B | 0.2813 (2) | 0.28149 (13) | 0.90095 (8) | 0.0353 (2) | |
H11B | 0.301 (2) | 0.3158 (19) | 0.8370 (12) | 0.045 (4)* | |
N12B | 0.27468 (19) | 0.51941 (12) | 0.96311 (9) | 0.0429 (3) | |
O1B | 0.23081 (17) | −0.05484 (10) | 1.02257 (7) | 0.0473 (3) | |
H1B | 0.222 (3) | −0.078 (3) | 1.0888 (17) | 0.082 (7)* | |
O2B | 0.2482 (2) | 0.59981 (13) | 1.03256 (9) | 0.0621 (3) | |
O3B | 0.3140 (2) | 0.55774 (13) | 0.88040 (8) | 0.0649 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1A | 0.0570 (7) | 0.0298 (5) | 0.0302 (5) | −0.0179 (4) | 0.0041 (4) | 0.0024 (4) |
N2A | 0.1544 (17) | 0.0322 (6) | 0.0437 (7) | −0.0302 (8) | 0.0071 (9) | −0.0001 (5) |
N3A | 0.173 (2) | 0.0363 (7) | 0.0498 (8) | −0.0312 (10) | 0.0084 (10) | 0.0081 (6) |
N4A | 0.0795 (9) | 0.0423 (6) | 0.0375 (6) | −0.0237 (6) | 0.0040 (6) | 0.0104 (5) |
C5A | 0.0789 (10) | 0.0422 (7) | 0.0301 (6) | −0.0294 (7) | 0.0013 (6) | 0.0054 (5) |
C6A | 0.0477 (7) | 0.0312 (5) | 0.0267 (5) | −0.0184 (5) | 0.0009 (4) | 0.0019 (4) |
C7A | 0.0487 (7) | 0.0335 (5) | 0.0286 (5) | −0.0181 (5) | 0.0033 (5) | −0.0016 (4) |
C8A | 0.0530 (8) | 0.0311 (6) | 0.0379 (6) | −0.0155 (5) | −0.0003 (5) | 0.0024 (4) |
C9A | 0.0538 (8) | 0.0376 (6) | 0.0322 (5) | −0.0211 (5) | −0.0029 (5) | 0.0066 (4) |
C10A | 0.0486 (7) | 0.0402 (6) | 0.0244 (5) | −0.0218 (5) | 0.0013 (4) | 0.0006 (4) |
C11A | 0.0482 (7) | 0.0342 (6) | 0.0288 (5) | −0.0173 (5) | 0.0019 (5) | −0.0007 (4) |
N12A | 0.0655 (8) | 0.0511 (7) | 0.0264 (5) | −0.0274 (6) | 0.0044 (5) | −0.0005 (4) |
O1A | 0.0722 (7) | 0.0374 (5) | 0.0327 (4) | −0.0164 (5) | 0.0145 (4) | −0.0051 (4) |
O2A | 0.0790 (8) | 0.0651 (7) | 0.0327 (5) | −0.0309 (6) | 0.0065 (5) | 0.0102 (4) |
O3A | 0.1449 (14) | 0.0517 (7) | 0.0478 (6) | −0.0264 (8) | 0.0363 (8) | −0.0119 (5) |
N1B | 0.0575 (7) | 0.0274 (5) | 0.0303 (5) | −0.0147 (4) | 0.0009 (4) | 0.0010 (4) |
N2B | 0.1519 (17) | 0.0432 (7) | 0.0296 (6) | −0.0406 (9) | 0.0088 (7) | 0.0000 (5) |
N3B | 0.1589 (18) | 0.0499 (8) | 0.0356 (6) | −0.0438 (10) | 0.0088 (8) | −0.0070 (5) |
N4B | 0.0803 (9) | 0.0377 (6) | 0.0431 (6) | −0.0200 (6) | 0.0017 (6) | −0.0077 (5) |
C5B | 0.0687 (9) | 0.0298 (6) | 0.0405 (6) | −0.0180 (6) | −0.0023 (6) | −0.0013 (5) |
C6B | 0.0438 (6) | 0.0267 (5) | 0.0289 (5) | −0.0113 (4) | 0.0008 (4) | 0.0013 (4) |
C7B | 0.0450 (7) | 0.0286 (5) | 0.0318 (5) | −0.0144 (5) | 0.0004 (5) | 0.0046 (4) |
C8B | 0.0572 (8) | 0.0381 (6) | 0.0300 (5) | −0.0185 (6) | 0.0037 (5) | 0.0017 (4) |
C9B | 0.0559 (8) | 0.0367 (6) | 0.0331 (6) | −0.0180 (6) | 0.0013 (5) | −0.0025 (5) |
C10B | 0.0431 (6) | 0.0280 (5) | 0.0363 (6) | −0.0143 (5) | 0.0011 (5) | 0.0009 (4) |
C11B | 0.0460 (7) | 0.0279 (5) | 0.0308 (5) | −0.0138 (5) | 0.0018 (5) | 0.0026 (4) |
N12B | 0.0534 (7) | 0.0324 (5) | 0.0458 (6) | −0.0202 (5) | −0.0002 (5) | −0.0009 (4) |
O1B | 0.0746 (7) | 0.0328 (4) | 0.0374 (5) | −0.0252 (5) | −0.0006 (4) | 0.0072 (3) |
O2B | 0.0948 (9) | 0.0432 (5) | 0.0563 (6) | −0.0344 (6) | −0.0005 (6) | −0.0126 (5) |
O3B | 0.1042 (10) | 0.0453 (6) | 0.0532 (6) | −0.0418 (6) | 0.0105 (6) | 0.0042 (5) |
Geometric parameters (Å, º) top
N1A—C5A | 1.327 (2) | N1B—C5B | 1.334 (2) |
N1A—N2A | 1.346 (2) | N1B—N2B | 1.350 (2) |
N1A—C6A | 1.427 (2) | N1B—C6B | 1.431 (2) |
N2A—N3A | 1.290 (2) | N2B—N3B | 1.287 (2) |
N3A—N4A | 1.350 (2) | N3B—N4B | 1.343 (2) |
N4A—C5A | 1.300 (2) | N4B—C5B | 1.307 (2) |
C5A—H5A | 0.92 (2) | C5B—H5B | 0.96 (2) |
C6A—C11A | 1.378 (2) | C6B—C11B | 1.381 (2) |
C6A—C7A | 1.401 (2) | C6B—C7B | 1.405 (2) |
C7A—O1A | 1.337 (1) | C7B—O1B | 1.337 (1) |
C7A—C8A | 1.395 (2) | C7B—C8B | 1.397 (2) |
C8A—C9A | 1.377 (2) | C8B—C9B | 1.376 (2) |
C8A—H8A | 0.98 (2) | C8B—H8B | 0.98 (2) |
C9A—C10A | 1.384 (2) | C9B—C10B | 1.384 (2) |
C9A—H9A | 0.99 (2) | C9B—H9B | 0.96 (2) |
C10A—C11A | 1.383 (2) | C10B—C11B | 1.381 (2) |
C10A—N12A | 1.458 (2) | C10B—N12B | 1.461 (2) |
C11A—H11A | 0.99 (2) | C11B—H11B | 0.94 (2) |
N12A—O3A | 1.207 (2) | N12B—O3B | 1.220 (2) |
N12A—O2A | 1.227 (2) | N12B—O2B | 1.222 (2) |
O1A—H1A | 0.91 (3) | O1B—H1B | 0.93 (2) |
| | | |
C5A—N1A—N2A | 108.0 (1) | C5B—N1B—N2B | 107.2 (1) |
C5A—N1A—C6A | 131.5 (1) | C5B—N1B—C6B | 132.8 (1) |
N2A—N1A—C6A | 120.5 (1) | N2B—N1B—C6B | 120.0 (1) |
N3A—N2A—N1A | 105.9 (1) | N3B—N2B—N1B | 106.9 (1) |
N2A—N3A—N4A | 111.1 (1) | N2B—N3B—N4B | 110.6 (1) |
C5A—N4A—N3A | 105.5 (1) | C5B—N4B—N3B | 106.1 (1) |
N4A—C5A—N1A | 109.5 (1) | N4B—C5B—N1B | 109.2 (1) |
N4A—C5A—H5A | 124 (2) | N4B—C5B—H5B | 124 (1) |
N1A—C5A—H5A | 126 (2) | N1B—C5B—H5B | 127 (1) |
C11A—C6A—C7A | 121.4 (1) | C11B—C6B—C7B | 121.0 (1) |
C11A—C6A—N1A | 119.2 (1) | C11B—C6B—N1B | 118.7 (1) |
C7A—C6A—N1A | 119.4 (1) | C7B—C6B—N1B | 120.3 (1) |
O1A—C7A—C8A | 123.6 (1) | O1B—C7B—C8B | 123.0 (1) |
O1A—C7A—C6A | 117.5 (1) | O1B—C7B—C6B | 118.4 (1) |
C8A—C7A—C6A | 118.8 (1) | C8B—C7B—C6B | 118.6 (1) |
C9A—C8A—C7A | 120.5 (1) | C9B—C8B—C7B | 120.8 (1) |
C9A—C8A—H8A | 123 (1) | C9B—C8B—H8B | 119 (1) |
C7A—C8A—H8A | 117 (1) | C7B—C8B—H8B | 121 (1) |
C8A—C9A—C10A | 118.9 (1) | C8B—C9B—C10B | 118.9 (1) |
C8A—C9A—H9A | 121 (1) | C8B—C9B—H9B | 121 (1) |
C10A—C9A—H9A | 121 (1) | C10B—C9B—H9B | 120 (1) |
C11A—C10A—C9A | 122.5 (1) | C11B—C10B—C9B | 122.3 (1) |
C11A—C10A—N12A | 118.1 (1) | C11B—C10B—N12B | 118.4 (1) |
C9A—C10A—N12A | 119.3 (1) | C9B—C10B—N12B | 119.3 (1) |
C6A—C11A—C10A | 117.8 (1) | C6B—C11B—C10B | 118.4 (1) |
C6A—C11A—H11A | 121 (1) | C6B—C11B—H11B | 119 (1) |
C10A—C11A—H11A | 121 (1) | C10B—C11B—H11B | 122 (1) |
O3A—N12A—O2A | 123.3 (1) | O3B—N12B—O2B | 123.2 (1) |
O3A—N12A—C10A | 118.7 (1) | O3B—N12B—C10B | 118.3 (1) |
O2A—N12A—C10A | 117.8 (1) | O2B—N12B—C10B | 118.5 (1) |
C7A—O1A—H1A | 108 (2) | C7B—O1B—H1B | 108 (1) |
| | | |
C5A—N1A—N2A—N3A | −0.4 (2) | C5B—N1B—N2B—N3B | −0.3 (2) |
C6A—N1A—N2A—N3A | 177.50 (17) | C6B—N1B—N2B—N3B | 177.07 (16) |
N1A—N2A—N3A—N4A | 0.0 (3) | N1B—N2B—N3B—N4B | −0.2 (3) |
N2A—N3A—N4A—C5A | 0.3 (3) | N2B—N3B—N4B—C5B | 0.6 (3) |
N3A—N4A—C5A—N1A | −0.6 (2) | N3B—N4B—C5B—N1B | −0.8 (2) |
N2A—N1A—C5A—N4A | 0.6 (2) | N2B—N1B—C5B—N4B | 0.7 (2) |
C6A—N1A—C5A—N4A | −176.96 (14) | C6B—N1B—C5B—N4B | −176.21 (15) |
C5A—N1A—C6A—C11A | 148.61 (16) | C5B—N1B—C6B—C11B | 171.40 (15) |
N2A—N1A—C6A—C11A | −28.7 (2) | N2B—N1B—C6B—C11B | −5.2 (2) |
C5A—N1A—C6A—C7A | −32.3 (2) | C5B—N1B—C6B—C7B | −7.3 (2) |
N2A—N1A—C6A—C7A | 150.32 (16) | N2B—N1B—C6B—C7B | 176.15 (15) |
C11A—C6A—C7A—O1A | 177.62 (12) | C11B—C6B—C7B—O1B | −178.09 (12) |
N1A—C6A—C7A—O1A | −1.41 (19) | N1B—C6B—C7B—O1B | 0.57 (19) |
C11A—C6A—C7A—C8A | −1.8 (2) | C11B—C6B—C7B—C8B | 1.4 (2) |
N1A—C6A—C7A—C8A | 179.18 (12) | N1B—C6B—C7B—C8B | −179.94 (12) |
O1A—C7A—C8A—C9A | −178.39 (13) | O1B—C7B—C8B—C9B | 177.87 (13) |
C6A—C7A—C8A—C9A | 1.0 (2) | C6B—C7B—C8B—C9B | −1.6 (2) |
C7A—C8A—C9A—C10A | 0.4 (2) | C7B—C8B—C9B—C10B | 0.6 (2) |
C8A—C9A—C10A—C11A | −1.1 (2) | C8B—C9B—C10B—C11B | 0.7 (2) |
C8A—C9A—C10A—N12A | −178.72 (13) | C8B—C9B—C10B—N12B | −178.93 (13) |
C7A—C6A—C11A—C10A | 1.2 (2) | C7B—C6B—C11B—C10B | −0.2 (2) |
N1A—C6A—C11A—C10A | −179.82 (12) | N1B—C6B—C11B—C10B | −178.88 (12) |
C9A—C10A—C11A—C6A | 0.3 (2) | C9B—C10B—C11B—C6B | −0.9 (2) |
N12A—C10A—C11A—C6A | 177.97 (12) | N12B—C10B—C11B—C6B | 178.74 (11) |
C11A—C10A—N12A—O3A | 6.6 (2) | C11B—C10B—N12B—O3B | −1.9 (2) |
C9A—C10A—N12A—O3A | −175.66 (16) | C9B—C10B—N12B—O3B | 177.69 (14) |
C11A—C10A—N12A—O2A | −171.25 (13) | C11B—C10B—N12B—O2B | 177.92 (13) |
C9A—C10A—N12A—O2A | 6.5 (2) | C9B—C10B—N12B—O2B | −2.5 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N4Bi | 0.91 (3) | 1.78 (3) | 2.665 (2) | 165 (2) |
O1B—H1B···N4Aii | 0.93 (2) | 1.78 (2) | 2.703 (2) | 171 (2) |
C5A—H5A···O2Biii | 0.92 (3) | 2.55 (2) | 3.234 (2) | 131 (2) |
C5B—H5B···O3Biv | 0.96 (2) | 2.56 (2) | 3.283 (2) | 132 (1) |
C8B—H8B···O3Av | 0.98 (2) | 2.57 (2) | 3.320 (2) | 133 (1) |
C8B—H8B···N3Aii | 0.98 (2) | 2.56 (2) | 3.465 (2) | 153 (1) |
C9A—H9A···N2Bvi | 0.98 (2) | 2.56 (2) | 3.540 (2) | 176 (2) |
C9B—H9B···O2Av | 0.96 (2) | 2.58 (2) | 3.417 (2) | 145 (2) |
C11B—H11B···O2Avi | 0.94 (2) | 2.53 (2) | 3.191 (2) | 128 (1) |
Symmetry codes: (i) x−1, y+1, z; (ii) −x, −y, −z+2; (iii) −x, −y+1, −z+2; (iv) x, y−1, z; (v) x, y, z+1; (vi) −x, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C7H5N5O3 |
Mr | 207.16 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.116 (2), 9.452 (2), 13.895 (3) |
α, β, γ (°) | 86.43 (2), 84.17 (2), 68.42 (2) |
V (Å3) | 864.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.54 × 0.40 × 0.30 |
|
Data collection |
Diffractometer | Nicolet R3m four-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5619, 5062, 3704 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.705 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.143, 1.04 |
No. of reflections | 5062 |
No. of parameters | 311 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.25, −0.27 |
Selected geometric parameters (Å, º) topN1A—C5A | 1.327 (2) | N1B—C5B | 1.334 (2) |
N1A—N2A | 1.346 (2) | N1B—N2B | 1.350 (2) |
N1A—C6A | 1.427 (2) | N1B—C6B | 1.431 (2) |
N2A—N3A | 1.290 (2) | N2B—N3B | 1.287 (2) |
N3A—N4A | 1.350 (2) | N3B—N4B | 1.343 (2) |
N4A—C5A | 1.300 (2) | N4B—C5B | 1.307 (2) |
| | | |
C5A—N1A—N2A | 108.0 (1) | C5B—N1B—N2B | 107.2 (1) |
N3A—N2A—N1A | 105.9 (1) | N3B—N2B—N1B | 106.9 (1) |
N2A—N3A—N4A | 111.1 (1) | N2B—N3B—N4B | 110.6 (1) |
C5A—N4A—N3A | 105.5 (1) | C5B—N4B—N3B | 106.1 (1) |
N4A—C5A—N1A | 109.5 (1) | N4B—C5B—N1B | 109.2 (1) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N4Bi | 0.91 (3) | 1.78 (3) | 2.665 (2) | 165 (2) |
O1B—H1B···N4Aii | 0.93 (2) | 1.78 (2) | 2.703 (2) | 171 (2) |
C5A—H5A···O2Biii | 0.92 (3) | 2.55 (2) | 3.234 (2) | 131 (2) |
C5B—H5B···O3Biv | 0.96 (2) | 2.56 (2) | 3.283 (2) | 132 (1) |
C8B—H8B···O3Av | 0.98 (2) | 2.57 (2) | 3.320 (2) | 133 (1) |
C8B—H8B···N3Aii | 0.98 (2) | 2.56 (2) | 3.465 (2) | 153 (1) |
C9A—H9A···N2Bvi | 0.98 (2) | 2.56 (2) | 3.540 (2) | 176 (2) |
C9B—H9B···O2Av | 0.96 (2) | 2.58 (2) | 3.417 (2) | 145 (2) |
C11B—H11B···O2Avi | 0.94 (2) | 2.53 (2) | 3.191 (2) | 128 (1) |
Symmetry codes: (i) x−1, y+1, z; (ii) −x, −y, −z+2; (iii) −x, −y+1, −z+2; (iv) x, y−1, z; (v) x, y, z+1; (vi) −x, −y+1, −z+1. |
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1-Monosubstituted aryltetrazoles have attracted considerable theoretical and experimental interest. On the one hand, they are used as valuable intermediates in the synthesis of arylcyanamides (Gaponik et al., 1990) and different nitrogen-containing heterocycles (Voitekhovich et al., 2001). On the other hand, they attract interest as models for investigation of the interaction between tetrazole and phenyl rings. Previously, only the structures of 1-phenyltetrazole (Matsunaga et al., 1999) and 1-(2,4,6-trimethylphenyl)tetrazole (Lyakhov et al., 2000) have been described. In this paper, we present the crystal structure of a new compound, 4-Nitro-2-(1H-tetrazol-1-yl)phenol, (I). There are two symmetry-independent molecules in the structure denoted by letters A and B.
The tetrazole rings of molecules A and B have very similar geometries; they are planar to within 0.004 (2) and 0.005 (2) Å, respectively. Endocyclic angles vary from 105.5 (1) to 111.1 (1)° and from 106.1 (1) to 110.6 (1)° for molecules A and B, respectively. The N1—N2 and N3—N4 bonds are similar and longer than N2—N3, while the C5—N1 bond is longer than C5—N4 in both molecules. All the formal single endocyclic bonds are considerably shorter than those usually found for normal single bonds, but somewhat longer than normal double bonds (International Tables for Crystallography, 1992, Vol. C, pp. 707–791). This suggests that there is some conjugation in the tetrazole rings of (I), however, significant differences in the endocyclic bond lengths show that there is still considerable localization of charge within the ring.
The bond distances and angles in the phenyl fragments of (I) are consistent with those observed previously. The rings nearly planar to within 0.009 (1) and 0.008 (1) Å for molecules A and B, respectively.
The phenyl and tetrazole rings are not coplanar in either molecule, the dihedral angle between them being 30.2 (1) and 7.0 (1)° in molecules A and B, respectively. To compare these values with that of a free molecule of (I), an ab initio calculation of a single molecule in the 6–311 G** basis set using the GAMESS program (Schmidt et al., 1993) was carried out. Geometry optimization with respect to all variables results in a dihedral angle between the phenyl and tetrazole rings of 39.6°. It should be noted that in the crystal of 1-phenyltetrazole, the dihedral angle between the rings is 11.8 (1)° (Matsunaga et al., 1999), whereas the angle of 38.6° was obtained from an MP2/6–31 G* calculation for a free molecule of 1-phenyltetrazole (Matsunaga et al., 1999). The introduction of an ortho-substituent on the phenyl ring must result in more steric hindrance compared with 1-phenyltetrazole and, as a result, the dihedral angle between the rings increases. Such s situation is also seen in the crystal structure of 1-(2,4,6-trimethylphenyl)tetrazole, where the dihedral angle is 69.07 (9)° (Lyakhov et al., 2000), and also in molecule A of (I). In the case of molecule B of (I), a rather small dihedral angle is obtained. Taking these results into account, it may be presumed that the decrease in the dihedral angle in the crystal is due to molecular packing. In the structure of (I), this effect is larger for molecule B than for molecule A.
From an inspection of the packing of the molecules in (I), the following may be noted. There are two types of hydrogen bonds, O1A—H1A···N4B and O1B—H1B···N4A, between molecules A and B, resulting in the formation of four-membered aggregates in the structure (Fig. 2). C8B—H8B···N3A interactions may be considered as additional weak hydrogen bonds between molecules A and B in the four-membered aggregates. Connection of these aggregates is achieved mainly through C9A—H9A···N2B hydrogen bonds (N2A does not form similar bonds). There are also C—H···O contacts (Desiraju, 1996) between the nitro O atoms and the H atoms of the phenyl rings, thereby forming an additional connection between the aggregates. The molecules in the structure of (I) are thus linked together by a complex three-dimensional hydrogen-bond network.