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The title compound, C
8H
13N
5, is a novel functionally substituted 5-alkyltetrazole. The substituent on the tetrazole C atom is symmetrical, with intrinsic symmetry close to
m. There is intermolecular N—H
N hydrogen bonding between adjacent tetrazole rings, which is responsible for the formation of one-dimensional polymeric chains running along the
c axis. The polycrystalline compound exhibits frequency doubling for incident light (λ = 1064 nm) from a YAG:Nd pulsed laser.
Supporting information
CCDC reference: 217151
The title compound was obtained unexpectedly during the cycloaddition of the azide ion to tetramethylsuccinonitrile according to the method described by Finnegan et al. (1958). Although there was a twofold excess of azide ions, only one nitrile group was involved in the reaction. A mixture of tetramethylsuccinonitrile (11.0 g, 81 mmol), sodium azide (10.5 g, 162 mmol) and ammonium chloride (8.7 g, 162 mmol) in dimethylformamide (130 ml) was stirred at 388–403 K for 40 h. The solvent was removed at reduced pressure on a steam bath, and the residue was dissolved in water (100 ml) and acidified with concentrated hydrochloric acid (15 ml). The precipitate was filtered, washed with several portions of water and dried. Crystallization from ethyl acetate gave the title compound (9.4 g, yield 65%; m.p. 462–463 K, decomposition, uncorrected). 1H NMR (100 MHz, DMSO-d6, p.p.m.): δ 1.29 (s, 6H, 2CH3), 1.58 (s, 6H, 2CH3); 13C NMR (25 MHz, DMSO-d6, p.p.m.): δ 26.5 (2CH3), 26.9 (2CH3), 42.8 and 43.9 (2Cquaternary), 127.7 (CN), 164.0 (Ctetrazole). Single crystals were grown by recrystallization from ethyl acetate at 288–293 K.
Methyl H atoms were included in calculated positions, (C—H = 0.96 Å) and refined using a riding model, with Uiso(H) values equal to 1.5Ueq of the corresponding C atom. The tetrazole H atom was localized from a ΔF map and refined using a riding model, with N—H distances of 0.86 Å and a Uiso(H) value equal to 1.2Ueq of the N atom. Because the compound contains only C, N and H atoms, absolute structure determination was not intended.
Data collection: R3m software (Nicolet, 1980); cell refinement: R3m software (Nicolet, 1980); data reduction: R3m software (Nicolet, 1980); 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),
PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Crystal data top
C8H13N5 | F(000) = 384 |
Mr = 179.23 | Dx = 1.245 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 25 reflections |
a = 15.070 (3) Å | θ = 17.7–22.8° |
b = 6.4292 (12) Å | µ = 0.08 mm−1 |
c = 9.8694 (18) Å | T = 293 K |
V = 956.2 (3) Å3 | Prism, colourless |
Z = 4 | 0.44 × 0.32 × 0.30 mm |
Data collection top
Nicolet R3m four-circle diffractometer | Rint = 0.028 |
Radiation source: fine-focus sealed tube | θmax = 30.1°, θmin = 2.7° |
Graphite monochromator | h = −1→21 |
ω/2θ scans | k = 0→9 |
1571 measured reflections | l = 0→13 |
1475 independent reflections | 3 standard reflections every 100 reflections |
1309 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0702P)2 + 0.0423P] where P = (Fo2 + 2Fc2)/3 |
1475 reflections | (Δ/σ)max < 0.001 |
122 parameters | Δρmax = 0.17 e Å−3 |
1 restraint | Δρmin = −0.17 e Å−3 |
Crystal data top
C8H13N5 | V = 956.2 (3) Å3 |
Mr = 179.23 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 15.070 (3) Å | µ = 0.08 mm−1 |
b = 6.4292 (12) Å | T = 293 K |
c = 9.8694 (18) Å | 0.44 × 0.32 × 0.30 mm |
Data collection top
Nicolet R3m four-circle diffractometer | Rint = 0.028 |
1571 measured reflections | 3 standard reflections every 100 reflections |
1475 independent reflections | intensity decay: none |
1309 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 1 restraint |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.17 e Å−3 |
1475 reflections | Δρmin = −0.17 e Å−3 |
122 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 | |
N1 | 0.75734 (10) | 0.3535 (2) | 0.46059 (15) | 0.0322 (3) | |
H1 | 0.7471 | 0.3264 | 0.5445 | 0.039* | |
N2 | 0.81473 (11) | 0.4977 (3) | 0.41459 (17) | 0.0401 (4) | |
N3 | 0.81126 (11) | 0.4909 (3) | 0.28457 (17) | 0.0400 (4) | |
N4 | 0.75213 (11) | 0.3427 (3) | 0.24388 (15) | 0.0346 (3) | |
C5 | 0.71891 (8) | 0.25916 (19) | 0.35541 (19) | 0.0278 (2) | |
C6 | 0.64829 (8) | 0.09268 (19) | 0.36315 (19) | 0.0295 (2) | |
C7 | 0.55467 (8) | 0.2038 (2) | 0.3643 (2) | 0.0327 (3) | |
C8 | 0.48574 (10) | 0.0404 (3) | 0.3690 (3) | 0.0458 (4) | |
N9 | 0.43087 (12) | −0.0813 (3) | 0.3724 (4) | 0.0774 (7) | |
C10 | 0.65740 (15) | −0.0501 (4) | 0.2392 (2) | 0.0437 (5) | |
H10A | 0.6516 | 0.0308 | 0.1580 | 0.065* | |
H10B | 0.6118 | −0.1543 | 0.2417 | 0.065* | |
H10C | 0.7145 | −0.1161 | 0.2406 | 0.065* | |
C11 | 0.66184 (16) | −0.0389 (4) | 0.4914 (2) | 0.0441 (5) | |
H11A | 0.7204 | −0.0979 | 0.4906 | 0.066* | |
H11B | 0.6186 | −0.1485 | 0.4936 | 0.066* | |
H11C | 0.6551 | 0.0475 | 0.5700 | 0.066* | |
C12 | 0.53751 (15) | 0.3332 (4) | 0.2365 (3) | 0.0519 (6) | |
H12A | 0.5437 | 0.2465 | 0.1579 | 0.078* | |
H12B | 0.5796 | 0.4451 | 0.2320 | 0.078* | |
H12C | 0.4785 | 0.3891 | 0.2396 | 0.078* | |
C13 | 0.54138 (15) | 0.3413 (4) | 0.4893 (2) | 0.0513 (6) | |
H13A | 0.4829 | 0.4005 | 0.4875 | 0.077* | |
H13B | 0.5847 | 0.4508 | 0.4892 | 0.077* | |
H13C | 0.5482 | 0.2588 | 0.5697 | 0.077* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0296 (6) | 0.0390 (8) | 0.0279 (6) | −0.0027 (6) | −0.0014 (5) | −0.0019 (5) |
N2 | 0.0333 (7) | 0.0450 (10) | 0.0421 (8) | −0.0086 (7) | −0.0004 (6) | −0.0025 (7) |
N3 | 0.0362 (8) | 0.0420 (10) | 0.0418 (8) | −0.0076 (7) | 0.0047 (6) | 0.0031 (7) |
N4 | 0.0332 (6) | 0.0415 (8) | 0.0293 (6) | −0.0037 (7) | 0.0017 (5) | 0.0015 (6) |
C5 | 0.0254 (4) | 0.0323 (5) | 0.0258 (5) | 0.0018 (4) | −0.0001 (6) | −0.0007 (7) |
C6 | 0.0302 (5) | 0.0301 (5) | 0.0281 (5) | −0.0016 (4) | −0.0004 (6) | −0.0024 (7) |
C7 | 0.0277 (5) | 0.0369 (6) | 0.0336 (6) | −0.0033 (4) | −0.0008 (7) | 0.0005 (8) |
C8 | 0.0366 (7) | 0.0574 (9) | 0.0435 (9) | −0.0119 (6) | 0.0016 (8) | −0.0010 (9) |
N9 | 0.0578 (10) | 0.0816 (12) | 0.0927 (17) | −0.0347 (9) | 0.0012 (13) | 0.0014 (16) |
C10 | 0.0493 (10) | 0.0394 (11) | 0.0423 (9) | −0.0006 (9) | 0.0024 (8) | −0.0118 (8) |
C11 | 0.0506 (11) | 0.0416 (11) | 0.0402 (9) | −0.0062 (9) | −0.0064 (8) | 0.0134 (8) |
C12 | 0.0372 (10) | 0.0614 (15) | 0.0570 (13) | 0.0068 (10) | −0.0018 (9) | 0.0198 (11) |
C13 | 0.0379 (10) | 0.0622 (15) | 0.0536 (12) | 0.0051 (10) | 0.0044 (8) | −0.0228 (11) |
Geometric parameters (Å, º) top
N1—C5 | 1.334 (2) | C8—N9 | 1.139 (2) |
N1—N2 | 1.347 (2) | C10—H10A | 0.9600 |
N1—H1 | 0.8600 | C10—H10B | 0.9600 |
N2—N3 | 1.285 (2) | C10—H10C | 0.9600 |
N3—N4 | 1.365 (2) | C11—H11A | 0.9600 |
N4—C5 | 1.323 (2) | C11—H11B | 0.9600 |
C5—C6 | 1.5113 (16) | C11—H11C | 0.9600 |
C6—C10 | 1.535 (3) | C12—H12A | 0.9600 |
C6—C11 | 1.536 (3) | C12—H12B | 0.9600 |
C6—C7 | 1.5817 (17) | C12—H12C | 0.9600 |
C7—C8 | 1.4784 (19) | C13—H13A | 0.9600 |
C7—C13 | 1.531 (3) | C13—H13B | 0.9600 |
C7—C12 | 1.532 (3) | C13—H13C | 0.9600 |
| | | |
C5—N1—N2 | 109.23 (15) | C6—C10—H10B | 109.5 |
C5—N1—H1 | 125.4 | H10A—C10—H10B | 109.5 |
N2—N1—H1 | 125.4 | C6—C10—H10C | 109.5 |
N3—N2—N1 | 106.69 (17) | H10A—C10—H10C | 109.5 |
N2—N3—N4 | 110.12 (17) | H10B—C10—H10C | 109.5 |
C5—N4—N3 | 106.59 (15) | C6—C11—H11A | 109.5 |
N4—C5—N1 | 107.37 (11) | C6—C11—H11B | 109.5 |
N4—C5—C6 | 126.58 (17) | H11A—C11—H11B | 109.5 |
N1—C5—C6 | 126.02 (16) | C6—C11—H11C | 109.5 |
C5—C6—C10 | 108.68 (15) | H11A—C11—H11C | 109.5 |
C5—C6—C11 | 109.76 (15) | H11B—C11—H11C | 109.5 |
C10—C6—C11 | 108.36 (12) | C7—C12—H12A | 109.5 |
C5—C6—C7 | 107.96 (10) | C7—C12—H12B | 109.5 |
C10—C6—C7 | 110.82 (14) | H12A—C12—H12B | 109.5 |
C11—C6—C7 | 111.21 (15) | C7—C12—H12C | 109.5 |
C8—C7—C13 | 107.03 (17) | H12A—C12—H12C | 109.5 |
C8—C7—C12 | 107.06 (18) | H12B—C12—H12C | 109.5 |
C13—C7—C12 | 109.15 (14) | C7—C13—H13A | 109.5 |
C8—C7—C6 | 107.80 (12) | C7—C13—H13B | 109.5 |
C13—C7—C6 | 112.52 (15) | H13A—C13—H13B | 109.5 |
C12—C7—C6 | 112.96 (15) | C7—C13—H13C | 109.5 |
N9—C8—C7 | 178.1 (2) | H13A—C13—H13C | 109.5 |
C6—C10—H10A | 109.5 | H13B—C13—H13C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N4i | 0.86 | 1.97 | 2.8004 (18) | 162 |
Symmetry code: (i) −x+3/2, y, z+1/2. |
Experimental details
Crystal data |
Chemical formula | C8H13N5 |
Mr | 179.23 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 293 |
a, b, c (Å) | 15.070 (3), 6.4292 (12), 9.8694 (18) |
V (Å3) | 956.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.44 × 0.32 × 0.30 |
|
Data collection |
Diffractometer | Nicolet R3m four-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1571, 1475, 1309 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.705 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.108, 1.04 |
No. of reflections | 1475 |
No. of parameters | 122 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.17 |
Selected geometric parameters (Å, º) topN1—C5 | 1.334 (2) | C6—C11 | 1.536 (3) |
N1—N2 | 1.347 (2) | C6—C7 | 1.5817 (17) |
N2—N3 | 1.285 (2) | C7—C8 | 1.4784 (19) |
N3—N4 | 1.365 (2) | C7—C13 | 1.531 (3) |
N4—C5 | 1.323 (2) | C7—C12 | 1.532 (3) |
C5—C6 | 1.5113 (16) | C8—N9 | 1.139 (2) |
C6—C10 | 1.535 (3) | | |
| | | |
C5—N1—N2 | 109.23 (15) | C5—N4—N3 | 106.59 (15) |
N3—N2—N1 | 106.69 (17) | N4—C5—N1 | 107.37 (11) |
N2—N3—N4 | 110.12 (17) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N4i | 0.86 | 1.97 | 2.8004 (18) | 161.7 |
Symmetry code: (i) −x+3/2, y, z+1/2. |
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Interest in 5-monosubstituted tetrazoles has arisen for several reasons. The N-unsubstituted tetrazolyl group –CN4H is a non-classic isostere for the carboxylic group and hence may be a suitable substitutent for it in drug design (Herr, 2002). Moreover, 5-monosubstituted tetrazoles, since they are coordinated by diverse modes, are interesting ligands for transition metal complexes and possess some unique properties (Yelamos et al., 2001). To date, only one 5-alkyltetrazole and two functionally substituted 5-alkyltetrazoles have been structurally characterized [Cambridge Structural Database (CSD); Version 5.24 of November 2002; Allen, 2002], namely 5-methyltetrazole (Ohno et al., 1999), 5-trichloromethyltetrazole (Geisenberg et al., 1987) and zwitterionic 5-(1-piperidiniomethyl)tetrazole (Lyakhov et al., 2003). In this paper, we report the synthesis and the molecular and crystal structures of a novel representative of functionally substituted 5-alkyltetrazoles, viz. 2,2,3-trimethyl-3-(1H-1,2,3,4-tetrazol-5-yl)butanenitrile, (I) (Fig. 1).
The tetrazole ring geometry is typical of the 5-substituted tetrazoles listed in the CSD. The N2—N3 [1.285 (2) Å] and N4—C5 [1.323 (2) Å] formal double bonds are the shortest bonds in the ring, and the ring is planar within 0.001 (1) Å.
The bond distances and angles in the substitutent on the C atom of the tetrazole ring are consistent with those observed previously for similar fragments (CSD). The substitutent is almost symmetrical, with intrinsic symmetry close to m (a pseudo-mirror plane is perpendicular to the tetrazole ring plane). If the tetrazole ring was also symmetrical, the space group would be the centric Pcam group. However, the tetrazole ring H atom is unambiguosly located only at one N atom, and the tetrazole ring is non-symmetrical, so the obtained data correspond to the acentric Pca21 space group. These results are supported by an investigation of the optical properties of (I). The polycrystalline compound exhibits visually detected frequency doubling for an incedent pumping light (λ=1064 nm, 10 ns pulses, 100 mJ pulse−1) from a YAG:Nd pulsed laser.
There are classical intermolecular N1—H1···N4(3/2 − x, y, 1/2 + z) hydrogen bonds between adjacent tetrazole rings in the structure of (I). These bonds are responsible for the formation of one-dimensional polymeric chains that extend along the c axis (Fig. 2).