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In the title compound, C9H7N3, the allenyl form of the side chain (-CH=C=CH2) is found in preference to the propargyl form (-CH2-C[triple bond]CH). The bond distances between the C atoms in the side chain are 1.303 (3) and 1.289 (3) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103007273/ob1116sup1.cif
Contains datablocks global, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103007273/ob1116IVsup2.hkl
Contains datablock IV

CCDC reference: 214411

Comment top

1-Propargylbenzotriazole, (I), is a useful starting material for producing the versatile pyrrole derivatives (Katritzky et al., 1992, 1994). During the synthesis of 1-propargylbenzotriazole, (I), from benzotriazole and propargylbromide under basic conditions, a regioisomer with tautomeric form on the propargyl moiety, 2-allenylbenzotriazole, (IV), is also obtained as a by-product (Katritzky et al., 1996). In this paper, the molecular structure and intermolecular interactions of the title compound, (IV), in the solid state are reported.

The molecular structure of (IV) is shown in Fig. 1. The C7C8 and C8C9 bond lengths are quite similar [1.303 (3) and 1.289 (3) Å, respectively], reflecting the allenic structure. The bond angle C7C8C9 is almost linear [176.6 (2)°] and the angle N2—C7C8 is 122.4 (2)°, which indicates that the hybridization of C7 is sp2 rather than sp3. From these data, it can be concluded that the preferential formation of the allenyl structure, (IV), to the propargyl structure, (III), is demonstrated in the crystal.

In the crystal-packing diagram (Fig. 2), the two molecular planes are partially overlapped with ππ stacking. The distance between the benzotriazole rings related by a center of symmetry is 3.343 (2) Å. The formation of a weak associated dimer, which contains? a pair of intermolecular C7—H···N1' hydrogen-bonding interactions at a C···N distance of 3.395 (2) Å, is also observed (Fig. 3 and Table 2). The formation of this hydrogen-bonding dimer is a consequence of the apparent polarization of the H atom at C7 resulting from the sp2 character of the C atom (Jeffrey & Saenger, 1991).

The relative stability of the isomers (I)–(IV) was estimated by density functional theory (DFT) using Gaussian98 (Frisch et al., 1998). At the B3LYP/6–31G** calculation level, both allenyl forms, (II) and (IV), are more stable by 27.4 and 34.3 kJ mol-1 than the corresponding propargyl isomers, (I) and (III), respectively. This is consistent with the predominance of structure (IV) rather than (III), as seen in the crystal.

Experimental top

Compound (IV) was synthesized following the procedure reported by Katrintzky et al. (1992, 1996). Crystals of (IV) were obtained by slow evaporation from a saturated dicholomethane solution.

Refinement top

[In the coordinate table, the H atoms have s.u.'s, implying that they were refined, but the _refine_ls_hydrogen_treatment data name states that they were constrained. If the latter is the case, then please provide coordinate and geometry lists without s.u.'s and giving the constrained distances.]

Structure description top

1-Propargylbenzotriazole, (I), is a useful starting material for producing the versatile pyrrole derivatives (Katritzky et al., 1992, 1994). During the synthesis of 1-propargylbenzotriazole, (I), from benzotriazole and propargylbromide under basic conditions, a regioisomer with tautomeric form on the propargyl moiety, 2-allenylbenzotriazole, (IV), is also obtained as a by-product (Katritzky et al., 1996). In this paper, the molecular structure and intermolecular interactions of the title compound, (IV), in the solid state are reported.

The molecular structure of (IV) is shown in Fig. 1. The C7C8 and C8C9 bond lengths are quite similar [1.303 (3) and 1.289 (3) Å, respectively], reflecting the allenic structure. The bond angle C7C8C9 is almost linear [176.6 (2)°] and the angle N2—C7C8 is 122.4 (2)°, which indicates that the hybridization of C7 is sp2 rather than sp3. From these data, it can be concluded that the preferential formation of the allenyl structure, (IV), to the propargyl structure, (III), is demonstrated in the crystal.

In the crystal-packing diagram (Fig. 2), the two molecular planes are partially overlapped with ππ stacking. The distance between the benzotriazole rings related by a center of symmetry is 3.343 (2) Å. The formation of a weak associated dimer, which contains? a pair of intermolecular C7—H···N1' hydrogen-bonding interactions at a C···N distance of 3.395 (2) Å, is also observed (Fig. 3 and Table 2). The formation of this hydrogen-bonding dimer is a consequence of the apparent polarization of the H atom at C7 resulting from the sp2 character of the C atom (Jeffrey & Saenger, 1991).

The relative stability of the isomers (I)–(IV) was estimated by density functional theory (DFT) using Gaussian98 (Frisch et al., 1998). At the B3LYP/6–31G** calculation level, both allenyl forms, (II) and (IV), are more stable by 27.4 and 34.3 kJ mol-1 than the corresponding propargyl isomers, (I) and (III), respectively. This is consistent with the predominance of structure (IV) rather than (III), as seen in the crystal.

Computing details top

Data collection: PROCESS–AUTO (Rigaku, 1998); cell refinement: PROCESS–AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2001); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Watkin et al., 2000); software used to prepare material for publication: CrystalStructure.

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (IV). Dispalcement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. Packing diagram for the crystal structure of (IV).
[Figure 3] Fig. 3. Ditopic weak interaction using hydrogen bonding between C—H···N.
(IV) top
Crystal data top
C9H7N3F(000) = 328.00
Mr = 157.17Dx = 1.339 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.7107 Å
a = 6.8755 (7) ÅCell parameters from 7469 reflections
b = 14.5505 (2) Åθ = 3.0–27.5°
c = 7.8520 (1) ŵ = 0.09 mm1
β = 96.898 (6)°T = 123 K
V = 779.84 (8) Å3Prism, colorless
Z = 40.80 × 0.40 × 0.40 mm
Data collection top
Rigaku R-AXIS-RAPID
diffractometer
Rint = 0.030
Detector resolution: 10.00 pixels mm-1θmax = 27.5°
ω scansh = 88
7031 measured reflectionsk = 1816
1785 independent reflectionsl = 1010
1584 reflections with F2 > 2σ(F2)
Refinement top
Refinement on FH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.051 w = 1/[0.004Fo2 + 3σ2(Fo) + 0.5]
wR(F2) = 0.087(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.27 e Å3
1589 reflectionsΔρmin = 0.42 e Å3
116 parameters
Crystal data top
C9H7N3V = 779.84 (8) Å3
Mr = 157.17Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.8755 (7) ŵ = 0.09 mm1
b = 14.5505 (2) ÅT = 123 K
c = 7.8520 (1) Å0.80 × 0.40 × 0.40 mm
β = 96.898 (6)°
Data collection top
Rigaku R-AXIS-RAPID
diffractometer
1584 reflections with F2 > 2σ(F2)
7031 measured reflectionsRint = 0.030
1785 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.051116 parameters
wR(F2) = 0.087H-atom parameters constrained
S = 1.04Δρmax = 0.27 e Å3
1589 reflectionsΔρmin = 0.42 e Å3
Special details top

Refinement. Refinement using reflections with F2 > 2.0 σ(F2). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.5294 (2)0.0689 (1)0.2837 (2)0.0208 (4)
N20.3448 (2)0.0975 (1)0.2830 (2)0.0193 (4)
N30.2605 (2)0.1388 (1)0.1423 (2)0.0204 (4)
C10.4038 (3)0.1373 (1)0.0397 (2)0.0190 (4)
C20.4050 (3)0.1702 (1)0.1288 (2)0.0226 (5)
C30.5737 (3)0.1584 (1)0.2015 (3)0.0259 (5)
C40.7418 (3)0.1146 (1)0.1127 (3)0.0259 (5)
C50.7435 (3)0.0820 (1)0.0501 (3)0.0238 (5)
C60.5706 (3)0.0935 (1)0.1267 (2)0.0202 (4)
C70.2495 (3)0.0852 (1)0.4315 (2)0.0223 (4)
C80.0939 (3)0.1316 (1)0.4580 (2)0.0217 (4)
C90.0562 (3)0.1776 (1)0.4938 (3)0.0271 (5)
H10.29370.19950.18890.027*
H20.58000.18000.31490.031*
H30.85580.10790.16900.032*
H40.85570.05300.10930.029*
H50.30660.04230.50730.027*
H60.04470.23580.55550.033*
H70.18800.15550.46030.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0186 (8)0.0208 (8)0.0225 (8)0.0024 (6)0.0004 (6)0.0006 (6)
N20.0195 (8)0.0198 (7)0.0181 (8)0.0028 (6)0.0001 (6)0.0009 (6)
N30.0223 (8)0.0207 (7)0.0174 (8)0.0032 (6)0.0006 (6)0.0003 (6)
C10.0223 (9)0.0164 (8)0.0176 (9)0.0000 (6)0.0003 (6)0.0013 (6)
C20.029 (1)0.0203 (9)0.0176 (9)0.0021 (7)0.0003 (7)0.0017 (6)
C30.033 (1)0.0257 (9)0.0194 (9)0.0026 (8)0.0039 (7)0.0006 (7)
C40.0251 (9)0.0267 (9)0.027 (1)0.0023 (7)0.0082 (7)0.0015 (8)
C50.0200 (9)0.0233 (9)0.028 (1)0.0007 (7)0.0024 (7)0.0002 (7)
C60.0207 (9)0.0175 (8)0.0214 (9)0.0003 (7)0.0013 (7)0.0001 (6)
C70.0249 (9)0.0231 (9)0.0190 (9)0.0023 (7)0.0029 (7)0.0024 (7)
C80.0246 (9)0.0232 (9)0.0173 (9)0.0033 (7)0.0016 (7)0.0012 (7)
C90.0242 (9)0.032 (1)0.025 (1)0.0016 (8)0.0049 (7)0.0011 (8)
Geometric parameters (Å, º) top
N1—N21.335 (2)C3—H20.95
N1—C61.346 (2)C4—C51.362 (3)
N2—N31.329 (2)C4—H30.95
N2—C71.416 (2)C5—C61.405 (3)
N3—C11.346 (2)C5—H40.95
C1—C21.408 (2)C7—C81.303 (3)
C1—C61.414 (2)C7—H50.92
C2—C31.364 (3)C8—C91.289 (3)
C2—H10.95C9—H60.97
C3—C41.426 (3)C9—H70.968 (3)
N2—N1—C6102.63 (14)C3—C4—H3118.9
N1—N2—N3117.62 (15)C5—C4—H3119.1
N1—N2—C7119.45 (15)C4—C5—C6116.60 (18)
N3—N2—C7122.91 (15)C4—C5—H4121.9
N2—N3—C1102.28 (14)C6—C5—H4121.5
N3—C1—C2130.10 (17)N1—C6—C1108.31 (16)
N3—C1—C6109.16 (16)N1—C6—C5129.96 (17)
C2—C1—C6120.73 (18)C1—C6—C5121.73 (18)
C1—C2—C3116.85 (17)N2—C7—C8122.41 (17)
C1—C2—H1121.6N2—C7—H5114.5
C3—C2—H1121.6C8—C7—H5123.0
C2—C3—C4122.11 (18)C7—C8—C9176.57 (19)
C2—C3—H2119.1C8—C9—H6122.7
C4—C3—H2118.8C8—C9—H7121.1
C3—C4—C5121.98 (18)H6—C9—H7116.2
C6—N1—N2—N30.4 (2)C6—C1—C2—C30.5 (3)
C6—N1—N2—C7178.6 (2)N3—C1—C6—N10.6 (2)
N2—N1—C6—C10.5 (2)N3—C1—C6—C5180.0 (2)
N2—N1—C6—C5180.0 (2)C2—C1—C6—N1179.8 (2)
N1—N2—N3—C10.1 (2)C2—C1—C6—C50.7 (3)
C7—N2—N3—C1178.2 (2)C1—C2—C3—C40.1 (3)
N1—N2—C7—C8161.2 (2)C2—C3—C4—C50.1 (3)
N3—N2—C7—C817.0 (3)C3—C4—C5—C60.1 (3)
N2—N3—C1—C2179.5 (2)C4—C5—C6—N1179.8 (2)
N2—N3—C1—C60.3 (2)C4—C5—C6—C10.5 (3)
N3—C1—C2—C3179.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H5···N1i0.922.483.395 (2)178
Symmetry code: (i) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC9H7N3
Mr157.17
Crystal system, space groupMonoclinic, P21/c
Temperature (K)123
a, b, c (Å)6.8755 (7), 14.5505 (2), 7.8520 (1)
β (°) 96.898 (6)
V3)779.84 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.80 × 0.40 × 0.40
Data collection
DiffractometerRigaku R-AXIS-RAPID
Absorption correction
No. of measured, independent and
observed [F2 > 2σ(F2)] reflections
7031, 1785, 1584
Rint0.030
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.087, 1.04
No. of reflections1589
No. of parameters116
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.42

Computer programs: PROCESS–AUTO (Rigaku, 1998), PROCESS–AUTO, CrystalStructure (Rigaku/MSC, 2001), SIR97 (Altomare et al., 1999), CRYSTALS (Watkin et al., 2000), CrystalStructure.

Selected geometric parameters (Å, º) top
N1—N21.335 (2)C2—C31.364 (3)
N1—C61.346 (2)C3—C41.426 (3)
N2—N31.329 (2)C4—C51.362 (3)
N2—C71.416 (2)C5—C61.405 (3)
N3—C11.346 (2)C7—C81.303 (3)
C1—C21.408 (2)C8—C91.289 (3)
C1—C61.414 (2)
N2—N1—C6102.63 (14)C2—C3—C4122.11 (18)
N1—N2—N3117.62 (15)C3—C4—C5121.98 (18)
N1—N2—C7119.45 (15)C4—C5—C6116.60 (18)
N3—N2—C7122.91 (15)N1—C6—C1108.31 (16)
N2—N3—C1102.28 (14)N1—C6—C5129.96 (17)
N3—C1—C2130.10 (17)C1—C6—C5121.73 (18)
N3—C1—C6109.16 (16)N2—C7—C8122.41 (17)
C2—C1—C6120.73 (18)C7—C8—C9176.57 (19)
C1—C2—C3116.85 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H5···N1i0.922.483.395 (2)178
Symmetry code: (i) x+1, y, z+1.
 

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