PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1226.
Published online 2008 June 7. doi:  10.1107/S1600536808015274
PMCID: PMC2961874

1,3-Bis[5-(2-pyrid­yl)-1H-tetra­zol-1-yl]propane

Abstract

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 [triangle]); Gallardo et al. (2004 [triangle]); Meyer et al. (1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1226-scheme1.jpg

Experimental

Crystal data

  • C15H14N10
  • M r = 334.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1226-efi2.jpg
  • a = 14.486 (2) Å
  • b = 9.1322 (13) Å
  • c = 12.8032 (19) Å
  • β = 111.596 (2)°
  • V = 1574.8 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 298 (2) K
  • 0.2 × 0.2 × 0.2 mm

Data collection

  • Rigaku Scxmini 1K CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.981, T max = 0.981
  • 4930 measured reflections
  • 1845 independent reflections
  • 1166 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.112
  • S = 1.02
  • 1845 reflections
  • 115 parameters
  • H-atom parameters constrained
  • Δρmax = 0.14 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015274/hg2397sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015274/hg2397Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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).

supplementary crystallographic information

Comment

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)°.

Experimental

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 column chromatography 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. .

Refinement

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).

Figures

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)

Crystal data

C15H14N10F000 = 696
Mr = 334.36Dx = 1.410 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 14.486 (2) Åθ = 2.7–28.3º
b = 9.1322 (13) ŵ = 0.10 mm1
c = 12.8032 (19) ÅT = 298 (2) K
β = 111.596 (2)ºBlock, colourless
V = 1574.8 (4) Å30.2 × 0.2 × 0.2 mm
Z = 4

Data collection

Rigaku Scxmini 1K CCD area-detector diffractometer1845 independent reflections
Radiation source: fine-focus sealed tube1166 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.031
Detector resolution: 8.192 pixels mm-1θmax = 28.3º
T = 298(2) Kθmin = 2.7º
thin–slice ω scansh = −15→18
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)k = −7→12
Tmin = 0.981, Tmax = 0.981l = −16→16
4930 measured reflections

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.044  w = 1/[σ2(Fo2) + (0.0498P)2 + 0.113P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.112(Δ/σ)max < 0.001
S = 1.02Δρmax = 0.14 e Å3
1845 reflectionsΔρmin = −0.14 e Å3
115 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0018 (5)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/UeqOcc. (<1)
C20.37119 (12)0.2927 (2)−0.15496 (13)0.0542 (5)
H2A0.38110.2170−0.19820.065*
N20.39676 (9)0.07129 (14)0.09971 (10)0.0372 (3)
N30.40148 (11)−0.07629 (15)0.10268 (13)0.0520 (4)
N40.38893 (11)−0.11910 (16)0.00162 (14)0.0592 (4)
N50.37593 (11)−0.00222 (17)−0.06788 (12)0.0527 (4)
C10.36961 (10)0.26606 (18)−0.04949 (12)0.0388 (4)
N10.35696 (10)0.37150 (15)0.01654 (10)0.0447 (4)
C30.34557 (13)0.50772 (19)−0.02391 (15)0.0517 (5)
H3B0.33800.58260.02150.062*
C40.34441 (14)0.5440 (2)−0.12819 (15)0.0579 (5)
H4B0.33490.6404−0.15330.069*
C50.35767 (15)0.4344 (2)−0.19443 (15)0.0642 (6)
H5B0.35750.4556−0.26550.077*
C60.38094 (11)0.11518 (17)−0.00589 (12)0.0382 (4)
C70.40529 (11)0.15178 (18)0.20192 (12)0.0411 (4)
H7A0.40220.08270.25810.049*
H7B0.34910.21770.18510.049*
C80.50000.2392 (2)0.25000.0418 (5)
H8B0.49500.30210.30870.063*0.50
H8A0.50500.30210.19130.063*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C20.0685 (12)0.0581 (13)0.0403 (9)0.0009 (9)0.0250 (8)−0.0008 (9)
N20.0384 (7)0.0343 (8)0.0384 (7)−0.0012 (6)0.0136 (5)0.0013 (6)
N30.0556 (9)0.0364 (9)0.0627 (10)−0.0013 (7)0.0203 (7)0.0003 (7)
N40.0665 (10)0.0428 (9)0.0669 (11)−0.0018 (7)0.0228 (8)−0.0092 (8)
N50.0594 (9)0.0484 (9)0.0490 (9)−0.0014 (7)0.0188 (7)−0.0109 (7)
C10.0354 (8)0.0455 (10)0.0342 (8)−0.0019 (7)0.0112 (6)−0.0013 (7)
N10.0554 (8)0.0395 (8)0.0404 (8)0.0038 (6)0.0192 (6)0.0028 (6)
C30.0619 (11)0.0418 (10)0.0533 (10)0.0044 (8)0.0234 (9)0.0059 (9)
C40.0646 (12)0.0524 (12)0.0590 (11)0.0033 (9)0.0256 (9)0.0179 (10)
C50.0799 (14)0.0731 (15)0.0431 (10)−0.0029 (11)0.0269 (9)0.0142 (10)
C60.0369 (8)0.0412 (9)0.0353 (8)−0.0003 (7)0.0119 (6)−0.0043 (7)
C70.0465 (9)0.0453 (10)0.0342 (8)0.0013 (7)0.0180 (7)0.0021 (7)
C80.0472 (13)0.0396 (13)0.0357 (11)0.0000.0120 (9)0.000

Geometric parameters (Å, °)

C2—C51.377 (2)C3—C41.370 (2)
C2—C11.381 (2)C3—H3B0.9300
C2—H2A0.9300C4—C51.370 (3)
N2—N31.3493 (18)C4—H4B0.9300
N2—C61.3464 (18)C5—H5B0.9300
N2—C71.4661 (19)C7—C81.5091 (18)
N3—N41.2988 (19)C7—H7A0.9700
N4—N51.358 (2)C7—H7B0.9700
N5—C61.3199 (19)C8—C7i1.5091 (18)
C1—N11.3378 (19)C8—H8B0.9700
C1—C61.473 (2)C8—H8A0.9700
N1—C31.334 (2)
C5—C2—C1118.27 (16)C4—C5—C2119.51 (16)
C5—C2—H2A120.9C4—C5—H5B120.2
C1—C2—H2A120.9C2—C5—H5B120.2
N3—N2—C6108.29 (13)N5—C6—N2108.26 (14)
N3—N2—C7119.27 (12)N5—C6—C1123.92 (14)
C6—N2—C7132.41 (13)N2—C6—C1127.81 (14)
N4—N3—N2106.59 (13)N2—C7—C8113.25 (11)
N3—N4—N5110.55 (14)N2—C7—H7A108.9
C6—N5—N4106.31 (13)C8—C7—H7A108.9
N1—C1—C2123.13 (15)N2—C7—H7B108.9
N1—C1—C6117.12 (13)C8—C7—H7B108.9
C2—C1—C6119.75 (15)H7A—C7—H7B107.7
C3—N1—C1116.87 (14)C7—C8—C7i116.09 (19)
N1—C3—C4124.01 (17)C7—C8—H8B108.3
N1—C3—H3B118.0C7i—C8—H8B108.3
C4—C3—H3B118.0C7—C8—H8A108.3
C5—C4—C3118.19 (17)C7i—C8—H8A108.3
C5—C4—H4B120.9H8B—C8—H8A107.4
C3—C4—H4B120.9
C6—N2—N3—N40.07 (16)N4—N5—C6—C1−179.43 (14)
C7—N2—N3—N4178.05 (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—C60.02 (18)N3—N2—C6—C1179.36 (14)
C5—C2—C1—N1−0.9 (2)C7—N2—C6—C11.8 (2)
C5—C2—C1—C6178.24 (15)N1—C1—C6—N5167.21 (14)
C2—C1—N1—C30.0 (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—C41.2 (2)C2—C1—C6—N2168.64 (14)
N1—C3—C4—C5−1.3 (3)N3—N2—C7—C8111.61 (15)
C3—C4—C5—C20.3 (3)C6—N2—C7—C8−71.0 (2)
C1—C2—C5—C40.8 (3)N2—C7—C8—C7i−67.96 (10)
N4—N5—C6—N20.02 (17)

Symmetry codes: (i) −x+1, y, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2397).

References

  • Bronisz, R. (2002). Inorg. Chim. Acta, 340, 215–220.
  • Gallardo, H., Meyer, E., Bortoluzzi, A. J., Molin, F. & Mangrich, A. S. (2004). Inorg. Chim. Acta.357, 505–512.
  • Meyer, E., Zucco, C. & Gallardo, H. (1998). J. Mater. Chem.8, 1351–1354.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography