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

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.044
• wR factor = 0.112
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           28.27
           From the CIF: _diffrn_reflns_theta_full          28.27
           From the CIF: _reflns_number_total               1845
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         1956
           Completeness (_total/calc)             94.33%
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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)°.

Related literature

For related literature, see: Bronisz (2002); Gallardo et al. (2004); Meyer et al. (1998).

S2. 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. .

S3. 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 U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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).

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)

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

Crystal data

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) Å^3	0.2 × 0.2 × 0.2 mm
Z = 4

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.0498P)^2 + 0.113P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (5)

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 (Ų)

	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

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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

Geometric parameters (Å, º)

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—C7^i	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—C7^i	116.09 (19)
N1—C3—C4	124.01 (17)	C7—C8—H8B	108.3
N1—C3—H3B	118.0	C7^i—C8—H8B	108.3
C4—C3—H3B	118.0	C7—C8—H8A	108.3
C5—C4—C3	118.19 (17)	C7^i—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—C7^i	−67.96 (10)
N4—N5—C6—N2	0.02 (17)

Symmetry code: (i) −x+1, y, −z+1/2.