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access1,3-Bis[5-(2-pyridyl)-1H-tetrazol-1-yl]propane
aDepartment of Chemistry, Key Laboratory of Medicinal Chemistry for Natural Resources, Ministry of Education, Yunnan University, Kunming 650091, People's Republic of China
*Correspondence e-mail: qhzhao@ynu.edu.cn
The title compound, C15H14N10, is a multidentate ligand obtained by the reaction of 5-(2-pyridyl)tetrazole with 1,3-dibromopropane. The molecule consists of two 5-(2-pyridyl)-1H-tetrazol-1-yl units connected by a propylene bridge in a U-like conformation. A twofold rotation axis passes through the central C atom.
Related literature
For related literature, see: Bronisz (2002![[Bronisz, R. (2002). Inorg. Chim. Acta, 340, 215-220.]](../../../../../../logos/arrows/e_arr.gif "Bronisz, R. (2002). Inorg. Chim. Acta, 340, 215-220.")
); Gallardo et al. (2004); Meyer et al. (1998).
![[Scheme 1]](hg2397scheme1.gif)
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536808015274/hg2397sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808015274/hg2397Isup2.hkl
5-(2-Pyridyl)tetrazole, (3.0 g, 20.0 mmol) was dissolved in 25 ml of 2-butanone with stirring and to the solution 1,3-dibromopropane (2.0 g, 10.0 mmol) and K2CO3 (5.5 g, 40.0 mmol) were added. The reaction mixture was heated under reflux for 24 h. After cooling the inorganic materials were filtered off and the solvent was removed under reduced pressure to afford the mixture of isomers. These isomers were separated by on silica gel (1:4–2:1 EtOAc/Petroleum ether(60-90°C). The pure compound (I) (334 mg, 1.0 mmol) was dissolved in the solvent (1:1 EtOAc/Petroleum ether), and recrystallized from EtOAc/Petroleum ether affording colorless crystals. .
Positional parameters of all H atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded, with C-H distances in the range 0.93-0.97Å and Uiso(H) = 1.2Ueq(C).
Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./hg2397fig1thm.gif) | Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level (Symmetry code(A): (-x+1,y,-z+1/2) |
| C15H14N10 | F(000) = 696 |
| Mr = 334.36 | Dx = 1.410 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 25 reflections |
| a = 14.486 (2) Å | θ = 2.7–28.3° |
| b = 9.1322 (13) Å | µ = 0.10 mm−1 |
| c = 12.8032 (19) Å | T = 298 K |
| β = 111.596 (2)° | Block, colourless |
| V = 1574.8 (4) Å3 | 0.2 × 0.2 × 0.2 mm |
| Z = 4 |
| Rigaku Scxmini 1K CCD area-detector diffractometer | 1845 independent reflections |
| Radiation source: fine-focus sealed tube | 1166 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.031 |
| Detector resolution: 8.192 pixels mm-1 | θmax = 28.3°, θmin = 2.7° |
| thin–slice ω scans | h = −15→18 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −7→12 |
| Tmin = 0.981, Tmax = 0.981 | l = −16→16 |
| 4930 measured reflections |
| 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)] = 0.044 | H-atom parameters constrained |
| wR(F2) = 0.112 | w = 1/[σ2(Fo2) + (0.0498P)2 + 0.113P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 1845 reflections | Δρmax = 0.14 e Å−3 |
| 115 parameters | Δρmin = −0.14 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0018 (5) |
| C15H14N10 | V = 1574.8 (4) Å3 |
| Mr = 334.36 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 14.486 (2) Å | µ = 0.10 mm−1 |
| b = 9.1322 (13) Å | T = 298 K |
| c = 12.8032 (19) Å | 0.2 × 0.2 × 0.2 mm |
| β = 111.596 (2)° |
| Rigaku Scxmini 1K CCD area-detector diffractometer | 1845 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1166 reflections with I > 2σ(I) |
| Tmin = 0.981, Tmax = 0.981 | Rint = 0.031 |
| 4930 measured reflections |
| R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
| wR(F2) = 0.112 | H-atom parameters constrained |
| S = 1.02 | Δρmax = 0.14 e Å−3 |
| 1845 reflections | Δρmin = −0.14 e Å−3 |
| 115 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 | Occ. (<1) | |
| C2 | 0.37119 (12) | 0.2927 (2) | −0.15496 (13) | 0.0542 (5) | |
| H2A | 0.3811 | 0.2170 | −0.1982 | 0.065* | |
| N2 | 0.39676 (9) | 0.07129 (14) | 0.09971 (10) | 0.0372 (3) | |
| N3 | 0.40148 (11) | −0.07629 (15) | 0.10268 (13) | 0.0520 (4) | |
| N4 | 0.38893 (11) | −0.11910 (16) | 0.00162 (14) | 0.0592 (4) | |
| N5 | 0.37593 (11) | −0.00222 (17) | −0.06788 (12) | 0.0527 (4) | |
| C1 | 0.36961 (10) | 0.26606 (18) | −0.04949 (12) | 0.0388 (4) | |
| N1 | 0.35696 (10) | 0.37150 (15) | 0.01654 (10) | 0.0447 (4) | |
| C3 | 0.34557 (13) | 0.50772 (19) | −0.02391 (15) | 0.0517 (5) | |
| H3B | 0.3380 | 0.5826 | 0.0215 | 0.062* | |
| C4 | 0.34441 (14) | 0.5440 (2) | −0.12819 (15) | 0.0579 (5) | |
| H4B | 0.3349 | 0.6404 | −0.1533 | 0.069* | |
| C5 | 0.35767 (15) | 0.4344 (2) | −0.19443 (15) | 0.0642 (6) | |
| H5B | 0.3575 | 0.4556 | −0.2655 | 0.077* | |
| C6 | 0.38094 (11) | 0.11518 (17) | −0.00589 (12) | 0.0382 (4) | |
| C7 | 0.40529 (11) | 0.15178 (18) | 0.20192 (12) | 0.0411 (4) | |
| H7A | 0.4022 | 0.0827 | 0.2581 | 0.049* | |
| H7B | 0.3491 | 0.2177 | 0.1851 | 0.049* | |
| C8 | 0.5000 | 0.2392 (2) | 0.2500 | 0.0418 (5) | |
| H8B | 0.4950 | 0.3021 | 0.3087 | 0.063* | 0.50 |
| H8A | 0.5050 | 0.3021 | 0.1913 | 0.063* | 0.50 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C2 | 0.0685 (12) | 0.0581 (13) | 0.0403 (9) | 0.0009 (9) | 0.0250 (8) | −0.0008 (9) |
| N2 | 0.0384 (7) | 0.0343 (8) | 0.0384 (7) | −0.0012 (6) | 0.0136 (5) | 0.0013 (6) |
| N3 | 0.0556 (9) | 0.0364 (9) | 0.0627 (10) | −0.0013 (7) | 0.0203 (7) | 0.0003 (7) |
| N4 | 0.0665 (10) | 0.0428 (9) | 0.0669 (11) | −0.0018 (7) | 0.0228 (8) | −0.0092 (8) |
| N5 | 0.0594 (9) | 0.0484 (9) | 0.0490 (9) | −0.0014 (7) | 0.0188 (7) | −0.0109 (7) |
| C1 | 0.0354 (8) | 0.0455 (10) | 0.0342 (8) | −0.0019 (7) | 0.0112 (6) | −0.0013 (7) |
| N1 | 0.0554 (8) | 0.0395 (8) | 0.0404 (8) | 0.0038 (6) | 0.0192 (6) | 0.0028 (6) |
| C3 | 0.0619 (11) | 0.0418 (10) | 0.0533 (10) | 0.0044 (8) | 0.0234 (9) | 0.0059 (9) |
| C4 | 0.0646 (12) | 0.0524 (12) | 0.0590 (11) | 0.0033 (9) | 0.0256 (9) | 0.0179 (10) |
| C5 | 0.0799 (14) | 0.0731 (15) | 0.0431 (10) | −0.0029 (11) | 0.0269 (9) | 0.0142 (10) |
| C6 | 0.0369 (8) | 0.0412 (9) | 0.0353 (8) | −0.0003 (7) | 0.0119 (6) | −0.0043 (7) |
| C7 | 0.0465 (9) | 0.0453 (10) | 0.0342 (8) | 0.0013 (7) | 0.0180 (7) | 0.0021 (7) |
| C8 | 0.0472 (13) | 0.0396 (13) | 0.0357 (11) | 0.000 | 0.0120 (9) | 0.000 |
| C2—C5 | 1.377 (2) | C3—C4 | 1.370 (2) |
| C2—C1 | 1.381 (2) | C3—H3B | 0.9300 |
| C2—H2A | 0.9300 | C4—C5 | 1.370 (3) |
| N2—N3 | 1.3493 (18) | C4—H4B | 0.9300 |
| N2—C6 | 1.3464 (18) | C5—H5B | 0.9300 |
| N2—C7 | 1.4661 (19) | C7—C8 | 1.5091 (18) |
| N3—N4 | 1.2988 (19) | C7—H7A | 0.9700 |
| N4—N5 | 1.358 (2) | C7—H7B | 0.9700 |
| N5—C6 | 1.3199 (19) | C8—C7i | 1.5091 (18) |
| C1—N1 | 1.3378 (19) | C8—H8B | 0.9700 |
| C1—C6 | 1.473 (2) | C8—H8A | 0.9700 |
| N1—C3 | 1.334 (2) | ||
| C5—C2—C1 | 118.27 (16) | C4—C5—C2 | 119.51 (16) |
| C5—C2—H2A | 120.9 | C4—C5—H5B | 120.2 |
| C1—C2—H2A | 120.9 | C2—C5—H5B | 120.2 |
| N3—N2—C6 | 108.29 (13) | N5—C6—N2 | 108.26 (14) |
| N3—N2—C7 | 119.27 (12) | N5—C6—C1 | 123.92 (14) |
| C6—N2—C7 | 132.41 (13) | N2—C6—C1 | 127.81 (14) |
| N4—N3—N2 | 106.59 (13) | N2—C7—C8 | 113.25 (11) |
| N3—N4—N5 | 110.55 (14) | N2—C7—H7A | 108.9 |
| C6—N5—N4 | 106.31 (13) | C8—C7—H7A | 108.9 |
| N1—C1—C2 | 123.13 (15) | N2—C7—H7B | 108.9 |
| N1—C1—C6 | 117.12 (13) | C8—C7—H7B | 108.9 |
| C2—C1—C6 | 119.75 (15) | H7A—C7—H7B | 107.7 |
| C3—N1—C1 | 116.87 (14) | C7—C8—C7i | 116.09 (19) |
| N1—C3—C4 | 124.01 (17) | C7—C8—H8B | 108.3 |
| N1—C3—H3B | 118.0 | C7i—C8—H8B | 108.3 |
| C4—C3—H3B | 118.0 | C7—C8—H8A | 108.3 |
| C5—C4—C3 | 118.19 (17) | C7i—C8—H8A | 108.3 |
| C5—C4—H4B | 120.9 | H8B—C8—H8A | 107.4 |
| C3—C4—H4B | 120.9 | ||
| C6—N2—N3—N4 | 0.07 (16) | N4—N5—C6—C1 | −179.43 (14) |
| C7—N2—N3—N4 | 178.05 (12) | N3—N2—C6—N5 | −0.06 (16) |
| N2—N3—N4—N5 | −0.06 (17) | C7—N2—C6—N5 | −177.67 (14) |
| N3—N4—N5—C6 | 0.02 (18) | N3—N2—C6—C1 | 179.36 (14) |
| C5—C2—C1—N1 | −0.9 (2) | C7—N2—C6—C1 | 1.8 (2) |
| C5—C2—C1—C6 | 178.24 (15) | N1—C1—C6—N5 | 167.21 (14) |
| C2—C1—N1—C3 | 0.0 (2) | C2—C1—C6—N5 | −12.0 (2) |
| C6—C1—N1—C3 | −179.23 (13) | N1—C1—C6—N2 | −12.1 (2) |
| C1—N1—C3—C4 | 1.2 (2) | C2—C1—C6—N2 | 168.64 (14) |
| N1—C3—C4—C5 | −1.3 (3) | N3—N2—C7—C8 | 111.61 (15) |
| C3—C4—C5—C2 | 0.3 (3) | C6—N2—C7—C8 | −71.0 (2) |
| C1—C2—C5—C4 | 0.8 (3) | N2—C7—C8—C7i | −67.96 (10) |
| N4—N5—C6—N2 | 0.02 (17) |
| Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
| Crystal data | |
| Chemical formula | C15H14N10 |
| Mr | 334.36 |
| Crystal system, space group | Monoclinic, C2/c |
| Temperature (K) | 298 |
| a, b, c (Å) | 14.486 (2), 9.1322 (13), 12.8032 (19) |
| β (°) | 111.596 (2) |
| V (Å3) | 1574.8 (4) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.10 |
| Crystal size (mm) | 0.2 × 0.2 × 0.2 |
| Data collection | |
| Diffractometer | Rigaku Scxmini 1K CCD area-detector diffractometer |
| Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
| Tmin, Tmax | 0.981, 0.981 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 4930, 1845, 1166 |
| Rint | 0.031 |
| (sin θ/λ)max (Å−1) | 0.666 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.112, 1.02 |
| No. of reflections | 1845 |
| No. of parameters | 115 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.14, −0.14 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work is supported by the National Natural Science Foundation of China (No. 20561004), the Key Project of the Chinese Ministry of Education (No. 205147), the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20060673015) and the Natural Science Foundation of Yunnan Province (Nos. 2004E0008M and 2003RC13).
References
Bronisz, R. (2002). Inorg. Chim. Acta, 340, 215–220. Web of Science CSD CrossRef CAS Google Scholar
Gallardo, H., Meyer, E., Bortoluzzi, A. J., Molin, F. & Mangrich, A. S. (2004). Inorg. Chim. Acta. 357, 505–512. Web of Science CSD CrossRef CAS Google Scholar
Meyer, E., Zucco, C. & Gallardo, H. (1998). J. Mater. Chem. 8, 1351–1354. Web of Science CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
The tetrazolate anion is an ambident system in which alkylation can occur at the N-1 or N-2 position, the relative proportions of which depend upon the reaction conditions, the nature of the alkylating agent and the influence of the 5-substituent (Meyer et al., 1998; Bronisz, 2002). The crystal structure of one of the three regioisomers has already been published (Gallardo et al., 2004). In our case, no regioselectivity was observed and the three possible regioisomers were isolated in equal amounts.
The structure of the title compound (I) is similar to that observed in the paper (Gallardo et al., 2004) with bond lengths and angles in good agreement with expected values. The molecules of (I) are disposed about a crystallographic two-fold axis of symmetry with symmetrical 5-(2-pyridyl)- 2H-tetrazolyl units connected by a propylene bridge. The molecule is folded at the center of the bridge [C7-C8-C7i 116.1 (2)°; symmetry code (i) = (-x+1,y,-z+1/2)] giving a U-like conformation to the free ligand. The inter-ring dihedral angle Py/Tz is 12.00 (7)°.