Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103007273/ob1116sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103007273/ob1116IVsup2.hkl |
CCDC reference: 214411
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.
[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.]
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 C7═C8 and C8═C9 bond lengths are quite similar [1.303 (3) and 1.289 (3) Å, respectively], reflecting the allenic structure. The bond angle C7═C8═C9 is almost linear [176.6 (2)°] and the angle N2—C7═C8 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 π–π 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.
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.
C9H7N3 | F(000) = 328.00 |
Mr = 157.17 | Dx = 1.339 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.7107 Å |
a = 6.8755 (7) Å | Cell parameters from 7469 reflections |
b = 14.5505 (2) Å | θ = 3.0–27.5° |
c = 7.8520 (1) Å | µ = 0.09 mm−1 |
β = 96.898 (6)° | T = 123 K |
V = 779.84 (8) Å3 | Prism, colorless |
Z = 4 | 0.80 × 0.40 × 0.40 mm |
Rigaku R-AXIS-RAPID diffractometer | Rint = 0.030 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5° |
ω scans | h = −8→8 |
7031 measured reflections | k = −18→16 |
1785 independent reflections | l = −10→10 |
1584 reflections with F2 > 2σ(F2) |
Refinement on F | H-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 = 1.04 | Δρmax = 0.27 e Å−3 |
1589 reflections | Δρmin = −0.42 e Å−3 |
116 parameters |
C9H7N3 | V = 779.84 (8) Å3 |
Mr = 157.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.8755 (7) Å | µ = 0.09 mm−1 |
b = 14.5505 (2) Å | T = 123 K |
c = 7.8520 (1) Å | 0.80 × 0.40 × 0.40 mm |
β = 96.898 (6)° |
Rigaku R-AXIS-RAPID diffractometer | 1584 reflections with F2 > 2σ(F2) |
7031 measured reflections | Rint = 0.030 |
1785 independent reflections |
R[F2 > 2σ(F2)] = 0.051 | 116 parameters |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.27 e Å−3 |
1589 reflections | Δρmin = −0.42 e Å−3 |
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). |
x | y | z | Uiso*/Ueq | ||
N1 | 0.5294 (2) | 0.0689 (1) | 0.2837 (2) | 0.0208 (4) | |
N2 | 0.3448 (2) | 0.0975 (1) | 0.2830 (2) | 0.0193 (4) | |
N3 | 0.2605 (2) | 0.1388 (1) | 0.1423 (2) | 0.0204 (4) | |
C1 | 0.4038 (3) | 0.1373 (1) | 0.0397 (2) | 0.0190 (4) | |
C2 | 0.4050 (3) | 0.1702 (1) | −0.1288 (2) | 0.0226 (5) | |
C3 | 0.5737 (3) | 0.1584 (1) | −0.2015 (3) | 0.0259 (5) | |
C4 | 0.7418 (3) | 0.1146 (1) | −0.1127 (3) | 0.0259 (5) | |
C5 | 0.7435 (3) | 0.0820 (1) | 0.0501 (3) | 0.0238 (5) | |
C6 | 0.5706 (3) | 0.0935 (1) | 0.1267 (2) | 0.0202 (4) | |
C7 | 0.2495 (3) | 0.0852 (1) | 0.4315 (2) | 0.0223 (4) | |
C8 | 0.0939 (3) | 0.1316 (1) | 0.4580 (2) | 0.0217 (4) | |
C9 | −0.0562 (3) | 0.1776 (1) | 0.4938 (3) | 0.0271 (5) | |
H1 | 0.2937 | 0.1995 | −0.1889 | 0.027* | |
H2 | 0.5800 | 0.1800 | −0.3149 | 0.031* | |
H3 | 0.8558 | 0.1079 | −0.1690 | 0.032* | |
H4 | 0.8557 | 0.0530 | 0.1093 | 0.029* | |
H5 | 0.3066 | 0.0423 | 0.5073 | 0.027* | |
H6 | −0.0447 | 0.2358 | 0.5555 | 0.033* | |
H7 | −0.1880 | 0.1555 | 0.4603 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0186 (8) | 0.0208 (8) | 0.0225 (8) | 0.0024 (6) | 0.0004 (6) | 0.0006 (6) |
N2 | 0.0195 (8) | 0.0198 (7) | 0.0181 (8) | 0.0028 (6) | −0.0001 (6) | 0.0009 (6) |
N3 | 0.0223 (8) | 0.0207 (7) | 0.0174 (8) | 0.0032 (6) | −0.0006 (6) | 0.0003 (6) |
C1 | 0.0223 (9) | 0.0164 (8) | 0.0176 (9) | 0.0000 (6) | −0.0003 (6) | −0.0013 (6) |
C2 | 0.029 (1) | 0.0203 (9) | 0.0176 (9) | 0.0021 (7) | 0.0003 (7) | 0.0017 (6) |
C3 | 0.033 (1) | 0.0257 (9) | 0.0194 (9) | −0.0026 (8) | 0.0039 (7) | 0.0006 (7) |
C4 | 0.0251 (9) | 0.0267 (9) | 0.027 (1) | −0.0023 (7) | 0.0082 (7) | −0.0015 (8) |
C5 | 0.0200 (9) | 0.0233 (9) | 0.028 (1) | −0.0007 (7) | 0.0024 (7) | −0.0002 (7) |
C6 | 0.0207 (9) | 0.0175 (8) | 0.0214 (9) | −0.0003 (7) | −0.0013 (7) | 0.0001 (6) |
C7 | 0.0249 (9) | 0.0231 (9) | 0.0190 (9) | 0.0023 (7) | 0.0029 (7) | 0.0024 (7) |
C8 | 0.0246 (9) | 0.0232 (9) | 0.0173 (9) | −0.0033 (7) | 0.0016 (7) | 0.0012 (7) |
C9 | 0.0242 (9) | 0.032 (1) | 0.025 (1) | 0.0016 (8) | 0.0049 (7) | −0.0011 (8) |
N1—N2 | 1.335 (2) | C3—H2 | 0.95 |
N1—C6 | 1.346 (2) | C4—C5 | 1.362 (3) |
N2—N3 | 1.329 (2) | C4—H3 | 0.95 |
N2—C7 | 1.416 (2) | C5—C6 | 1.405 (3) |
N3—C1 | 1.346 (2) | C5—H4 | 0.95 |
C1—C2 | 1.408 (2) | C7—C8 | 1.303 (3) |
C1—C6 | 1.414 (2) | C7—H5 | 0.92 |
C2—C3 | 1.364 (3) | C8—C9 | 1.289 (3) |
C2—H1 | 0.95 | C9—H6 | 0.97 |
C3—C4 | 1.426 (3) | C9—H7 | 0.968 (3) |
N2—N1—C6 | 102.63 (14) | C3—C4—H3 | 118.9 |
N1—N2—N3 | 117.62 (15) | C5—C4—H3 | 119.1 |
N1—N2—C7 | 119.45 (15) | C4—C5—C6 | 116.60 (18) |
N3—N2—C7 | 122.91 (15) | C4—C5—H4 | 121.9 |
N2—N3—C1 | 102.28 (14) | C6—C5—H4 | 121.5 |
N3—C1—C2 | 130.10 (17) | N1—C6—C1 | 108.31 (16) |
N3—C1—C6 | 109.16 (16) | N1—C6—C5 | 129.96 (17) |
C2—C1—C6 | 120.73 (18) | C1—C6—C5 | 121.73 (18) |
C1—C2—C3 | 116.85 (17) | N2—C7—C8 | 122.41 (17) |
C1—C2—H1 | 121.6 | N2—C7—H5 | 114.5 |
C3—C2—H1 | 121.6 | C8—C7—H5 | 123.0 |
C2—C3—C4 | 122.11 (18) | C7—C8—C9 | 176.57 (19) |
C2—C3—H2 | 119.1 | C8—C9—H6 | 122.7 |
C4—C3—H2 | 118.8 | C8—C9—H7 | 121.1 |
C3—C4—C5 | 121.98 (18) | H6—C9—H7 | 116.2 |
C6—N1—N2—N3 | −0.4 (2) | C6—C1—C2—C3 | −0.5 (3) |
C6—N1—N2—C7 | −178.6 (2) | N3—C1—C6—N1 | −0.6 (2) |
N2—N1—C6—C1 | 0.5 (2) | N3—C1—C6—C5 | 180.0 (2) |
N2—N1—C6—C5 | 180.0 (2) | C2—C1—C6—N1 | −179.8 (2) |
N1—N2—N3—C1 | 0.1 (2) | C2—C1—C6—C5 | 0.7 (3) |
C7—N2—N3—C1 | 178.2 (2) | C1—C2—C3—C4 | 0.1 (3) |
N1—N2—C7—C8 | 161.2 (2) | C2—C3—C4—C5 | 0.1 (3) |
N3—N2—C7—C8 | −17.0 (3) | C3—C4—C5—C6 | 0.1 (3) |
N2—N3—C1—C2 | 179.5 (2) | C4—C5—C6—N1 | −179.8 (2) |
N2—N3—C1—C6 | 0.3 (2) | C4—C5—C6—C1 | −0.5 (3) |
N3—C1—C2—C3 | −179.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H5···N1i | 0.92 | 2.48 | 3.395 (2) | 178 |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C9H7N3 |
Mr | 157.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 123 |
a, b, c (Å) | 6.8755 (7), 14.5505 (2), 7.8520 (1) |
β (°) | 96.898 (6) |
V (Å3) | 779.84 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.80 × 0.40 × 0.40 |
Data collection | |
Diffractometer | Rigaku R-AXIS-RAPID |
Absorption correction | – |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 7031, 1785, 1584 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.087, 1.04 |
No. of reflections | 1589 |
No. of parameters | 116 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
N1—N2 | 1.335 (2) | C2—C3 | 1.364 (3) |
N1—C6 | 1.346 (2) | C3—C4 | 1.426 (3) |
N2—N3 | 1.329 (2) | C4—C5 | 1.362 (3) |
N2—C7 | 1.416 (2) | C5—C6 | 1.405 (3) |
N3—C1 | 1.346 (2) | C7—C8 | 1.303 (3) |
C1—C2 | 1.408 (2) | C8—C9 | 1.289 (3) |
C1—C6 | 1.414 (2) | ||
N2—N1—C6 | 102.63 (14) | C2—C3—C4 | 122.11 (18) |
N1—N2—N3 | 117.62 (15) | C3—C4—C5 | 121.98 (18) |
N1—N2—C7 | 119.45 (15) | C4—C5—C6 | 116.60 (18) |
N3—N2—C7 | 122.91 (15) | N1—C6—C1 | 108.31 (16) |
N2—N3—C1 | 102.28 (14) | N1—C6—C5 | 129.96 (17) |
N3—C1—C2 | 130.10 (17) | C1—C6—C5 | 121.73 (18) |
N3—C1—C6 | 109.16 (16) | N2—C7—C8 | 122.41 (17) |
C2—C1—C6 | 120.73 (18) | C7—C8—C9 | 176.57 (19) |
C1—C2—C3 | 116.85 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H5···N1i | 0.92 | 2.48 | 3.395 (2) | 178 |
Symmetry code: (i) −x+1, −y, −z+1. |
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 C7═C8 and C8═C9 bond lengths are quite similar [1.303 (3) and 1.289 (3) Å, respectively], reflecting the allenic structure. The bond angle C7═C8═C9 is almost linear [176.6 (2)°] and the angle N2—C7═C8 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 π–π 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.