Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055547/kp2142sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055547/kp2142Isup2.hkl |
CCDC reference: 672868
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.055
- wR factor = 0.137
- Data-to-parameter ratio = 15.5
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.805 1.000 Tmin(prime) and Tmax expected: 0.982 0.991 RR(prime) = 0.812 Please check that your absorption correction is appropriate. PLAT048_ALERT_1_C MoietyFormula Not Given ........................ ? PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.81 PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 3000 Deg. PLAT480_ALERT_4_C Long H...A H-Bond Reported H1A .. N6 .. 2.75 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H1A .. N7 .. 2.68 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A .. N5 .. 2.75 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.991 Tmax scaled 0.991 Tmin scaled 0.797 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 4 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 3 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
To a solution of benzotriazole in 40 ml acetone, K2CO3 (3.5 g, 25 mmol) was added and the mixture was stirred at room temperature. A solution of bromo acetonitrile (7.2 g, 60 mmol) in acetone 20 ml was dropped slowly into the mixture. After stirring for 5 h, the mixture was filtered. A filtrate was evaporated to dryness under reduced pressure. The solid residue obtained was flash- chromatographed on silica gel (eluent: light petroleum-acetic ester 7:1) affording in sequence: 2-(2H-benzotriazol-2-yl)acetonitrile (0.39 g, 5.1%), m.p. 351–352 K (Danan et al. (1997): m.p. 351 K), a 1:1 mixture of isomers 2-(2H-benzotriazol-2-yl)acetonitrile and 2-(1Hbenzotriazol-1-yl)acetonitrile (0.19 g, 2.3%) and then 2-(1Hbenzotriazol-1-yl)acetonitrile (6.71 g, 85.1%), m.p. 359–360 K (Danan et al. (1997): m.p. 360 K). The suitable crystal of the title compound for X-ray diffraction are obtained in ethanol solution after standing at room temperature for several days.
Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded, with Uiso(H) = 1.2Ueq.
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 1999).
Fig. 1. The molecular structure of (I). Displacement ellipsoids were drawn at the 30% probability level. | |
Fig. 2. The crystal packing of (I). |
C8H6N4 | Z = 4 |
Mr = 158.17 | F(000) = 328 |
Triclinic, P1 | Dx = 1.352 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2423 (16) Å | Cell parameters from 6664 reflections |
b = 9.833 (2) Å | θ = 3.1–28.8° |
c = 10.631 (2) Å | µ = 0.09 mm−1 |
α = 88.13 (3)° | T = 293 K |
β = 72.07 (3)° | Prism, colourless |
γ = 71.90 (3)° | 0.20 × 0.15 × 0.10 mm |
V = 777.3 (3) Å3 |
Rigaku Mercury2 (2x2 bin mode) diffractometer | 3559 independent reflections |
Radiation source: fine-focus sealed tube | 2183 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
CCD Profile fitting' scans | h = −10→10 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −12→12 |
Tmin = 0.805, Tmax = 1.000 | l = −13→13 |
8053 measured reflections |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0585P)2 + 0.0638P] where P = (Fo2 + 2Fc2)/3 |
3559 reflections | (Δ/σ)max < 0.001 |
229 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C8H6N4 | γ = 71.90 (3)° |
Mr = 158.17 | V = 777.3 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.2423 (16) Å | Mo Kα radiation |
b = 9.833 (2) Å | µ = 0.09 mm−1 |
c = 10.631 (2) Å | T = 293 K |
α = 88.13 (3)° | 0.20 × 0.15 × 0.10 mm |
β = 72.07 (3)° |
Rigaku Mercury2 (2x2 bin mode) diffractometer | 3559 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 2183 reflections with I > 2σ(I) |
Tmin = 0.805, Tmax = 1.000 | Rint = 0.038 |
8053 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.14 e Å−3 |
3559 reflections | Δρmin = −0.20 e Å−3 |
229 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.5499 (4) | 1.0795 (3) | 0.1618 (3) | 0.1058 (9) | |
N2 | 0.8556 (2) | 0.5781 (2) | 0.28482 (16) | 0.0602 (5) | |
N3 | 0.8417 (2) | 0.74294 (17) | 0.14567 (15) | 0.0489 (4) | |
N4 | 0.8779 (2) | 0.7030 (2) | 0.26055 (16) | 0.0606 (5) | |
C1 | 0.8566 (3) | 0.8776 (2) | 0.0939 (2) | 0.0565 (5) | |
H1A | 0.9052 | 0.8652 | −0.0020 | 0.075 (7)* | |
H1B | 0.9397 | 0.9060 | 0.1267 | 0.084 (8)* | |
C2 | 0.7116 (3) | 0.5057 (2) | −0.0368 (2) | 0.0567 (5) | |
H2A | 0.6810 | 0.4925 | −0.1117 | 0.070 (7)* | |
C3 | 0.7191 (3) | 0.3982 (2) | 0.0533 (2) | 0.0635 (6) | |
H3A | 0.6932 | 0.3163 | 0.0366 | 0.072 (7)* | |
C4 | 0.7633 (3) | 0.4109 (2) | 0.1645 (2) | 0.0593 (6) | |
H4A | 0.7666 | 0.3400 | 0.2245 | 0.066 (6)* | |
C5 | 0.8036 (2) | 0.5350 (2) | 0.18505 (18) | 0.0461 (5) | |
C6 | 0.7475 (3) | 0.6286 (2) | −0.01844 (18) | 0.0488 (5) | |
H6A | 0.7410 | 0.7000 | −0.0780 | 0.045 (5)* | |
C7 | 0.7945 (2) | 0.64060 (19) | 0.09500 (17) | 0.0408 (4) | |
C15 | 0.6831 (4) | 0.9913 (3) | 0.1317 (2) | 0.0659 (6) | |
N5 | 0.3078 (3) | 0.4137 (2) | 0.3596 (2) | 0.0753 (6) | |
N6 | 0.1370 (3) | −0.0085 (2) | 0.22156 (17) | 0.0616 (5) | |
N7 | 0.0731 (2) | 0.1280 (2) | 0.25838 (17) | 0.0597 (5) | |
N8 | 0.1134 (2) | 0.14813 (15) | 0.36958 (14) | 0.0439 (4) | |
C8 | 0.3127 (3) | −0.2251 (2) | 0.3148 (2) | 0.0632 (6) | |
H8A | 0.3244 | −0.2940 | 0.2518 | 0.071 (7)* | |
C9 | 0.3674 (3) | −0.1588 (2) | 0.5105 (2) | 0.0603 (6) | |
H9A | 0.4180 | −0.1885 | 0.5778 | 0.074 (7)* | |
C10 | 0.3832 (3) | −0.2615 (2) | 0.4160 (2) | 0.0655 (6) | |
H10A | 0.4432 | −0.3573 | 0.4225 | 0.079 (7)* | |
C11 | 0.0597 (3) | 0.2907 (2) | 0.4319 (2) | 0.0520 (5) | |
H11A | 0.0265 | 0.2851 | 0.5273 | 0.068 (6)* | |
H11B | −0.0455 | 0.3505 | 0.4110 | 0.075 (7)* | |
C12 | 0.2222 (3) | −0.0796 (2) | 0.30924 (18) | 0.0461 (5) | |
C13 | 0.2805 (3) | −0.0164 (2) | 0.50763 (19) | 0.0500 (5) | |
H13A | 0.2700 | 0.0517 | 0.5708 | 0.055 (6)* | |
C14 | 0.2082 (2) | 0.02065 (18) | 0.40414 (16) | 0.0387 (4) | |
C16 | 0.2010 (3) | 0.3579 (2) | 0.38981 (19) | 0.0510 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.1034 (19) | 0.0616 (15) | 0.122 (2) | −0.0069 (14) | −0.0132 (16) | 0.0147 (14) |
N2 | 0.0671 (12) | 0.0624 (12) | 0.0425 (10) | −0.0067 (9) | −0.0194 (9) | 0.0081 (8) |
N3 | 0.0574 (10) | 0.0486 (10) | 0.0394 (9) | −0.0118 (8) | −0.0184 (8) | 0.0033 (7) |
N4 | 0.0756 (13) | 0.0607 (12) | 0.0436 (10) | −0.0100 (9) | −0.0275 (9) | 0.0012 (8) |
C1 | 0.0684 (14) | 0.0537 (13) | 0.0537 (13) | −0.0253 (11) | −0.0218 (11) | 0.0055 (10) |
C2 | 0.0528 (13) | 0.0629 (14) | 0.0608 (13) | −0.0213 (11) | −0.0234 (11) | 0.0024 (11) |
C3 | 0.0571 (13) | 0.0528 (13) | 0.0880 (17) | −0.0217 (11) | −0.0289 (13) | 0.0072 (12) |
C4 | 0.0503 (12) | 0.0494 (13) | 0.0713 (15) | −0.0116 (10) | −0.0154 (11) | 0.0199 (11) |
C5 | 0.0404 (10) | 0.0479 (12) | 0.0394 (10) | −0.0033 (9) | −0.0087 (9) | 0.0058 (8) |
C6 | 0.0501 (11) | 0.0576 (13) | 0.0417 (11) | −0.0182 (9) | −0.0181 (9) | 0.0113 (9) |
C7 | 0.0380 (10) | 0.0405 (10) | 0.0397 (10) | −0.0085 (8) | −0.0101 (8) | 0.0021 (8) |
C15 | 0.0824 (17) | 0.0453 (14) | 0.0673 (15) | −0.0194 (12) | −0.0205 (13) | 0.0071 (11) |
N5 | 0.0905 (15) | 0.0630 (13) | 0.0790 (14) | −0.0374 (12) | −0.0224 (12) | 0.0048 (10) |
N6 | 0.0786 (13) | 0.0679 (13) | 0.0506 (10) | −0.0314 (10) | −0.0286 (10) | 0.0002 (9) |
N7 | 0.0709 (12) | 0.0662 (12) | 0.0538 (11) | −0.0270 (10) | −0.0314 (10) | 0.0129 (9) |
N8 | 0.0534 (9) | 0.0409 (9) | 0.0420 (9) | −0.0159 (7) | −0.0205 (8) | 0.0052 (7) |
C8 | 0.0680 (15) | 0.0441 (13) | 0.0694 (15) | −0.0219 (11) | −0.0041 (12) | −0.0145 (11) |
C9 | 0.0589 (13) | 0.0544 (14) | 0.0688 (15) | −0.0150 (10) | −0.0259 (12) | 0.0174 (11) |
C10 | 0.0593 (14) | 0.0394 (13) | 0.0856 (17) | −0.0079 (10) | −0.0135 (13) | 0.0048 (11) |
C11 | 0.0578 (13) | 0.0408 (11) | 0.0527 (13) | −0.0109 (10) | −0.0155 (11) | 0.0038 (9) |
C12 | 0.0515 (11) | 0.0459 (11) | 0.0434 (11) | −0.0221 (9) | −0.0108 (9) | −0.0029 (9) |
C13 | 0.0579 (12) | 0.0469 (12) | 0.0490 (11) | −0.0174 (9) | −0.0213 (10) | 0.0056 (9) |
C14 | 0.0413 (10) | 0.0361 (10) | 0.0389 (10) | −0.0156 (8) | −0.0097 (8) | 0.0060 (7) |
C16 | 0.0706 (14) | 0.0352 (11) | 0.0484 (12) | −0.0137 (10) | −0.0237 (11) | 0.0066 (9) |
N1—C15 | 1.127 (3) | N5—C16 | 1.138 (3) |
N2—N4 | 1.303 (2) | N6—N7 | 1.304 (2) |
N2—C5 | 1.382 (2) | N6—C12 | 1.380 (3) |
N3—N4 | 1.362 (2) | N7—N8 | 1.358 (2) |
N3—C7 | 1.365 (2) | N8—C14 | 1.362 (2) |
N3—C1 | 1.443 (2) | N8—C11 | 1.447 (2) |
C1—C15 | 1.463 (3) | C8—C10 | 1.362 (3) |
C1—H1A | 0.9700 | C8—C12 | 1.402 (3) |
C1—H1B | 0.9700 | C8—H8A | 0.9301 |
C2—C6 | 1.364 (3) | C9—C13 | 1.365 (3) |
C2—C3 | 1.402 (3) | C9—C10 | 1.396 (3) |
C2—H2A | 0.9301 | C9—H9A | 0.9300 |
C3—C4 | 1.359 (3) | C10—H10A | 0.9300 |
C3—H3A | 0.9301 | C11—C16 | 1.460 (3) |
C4—C5 | 1.400 (3) | C11—H11A | 0.9700 |
C4—H4A | 0.9300 | C11—H11B | 0.9700 |
C5—C7 | 1.390 (2) | C12—C14 | 1.388 (2) |
C6—C7 | 1.394 (2) | C13—C14 | 1.393 (2) |
C6—H6A | 0.9300 | C13—H13A | 0.9299 |
N4—N2—C5 | 108.73 (16) | N7—N6—C12 | 108.47 (15) |
N4—N3—C7 | 110.57 (16) | N6—N7—N8 | 108.51 (16) |
N4—N3—C1 | 120.34 (16) | N7—N8—C14 | 110.26 (15) |
C7—N3—C1 | 129.09 (16) | N7—N8—C11 | 120.45 (16) |
N2—N4—N3 | 108.19 (16) | C14—N8—C11 | 129.27 (15) |
N3—C1—C15 | 112.06 (18) | C10—C8—C12 | 117.2 (2) |
N3—C1—H1A | 109.2 | C10—C8—H8A | 121.4 |
C15—C1—H1A | 109.2 | C12—C8—H8A | 121.4 |
N3—C1—H1B | 109.2 | C13—C9—C10 | 122.3 (2) |
C15—C1—H1B | 109.2 | C13—C9—H9A | 118.8 |
H1A—C1—H1B | 107.9 | C10—C9—H9A | 118.8 |
C6—C2—C3 | 122.4 (2) | C8—C10—C9 | 121.8 (2) |
C6—C2—H2A | 118.9 | C8—C10—H10A | 119.1 |
C3—C2—H2A | 118.8 | C9—C10—H10A | 119.1 |
C4—C3—C2 | 121.6 (2) | N8—C11—C16 | 112.93 (17) |
C4—C3—H3A | 119.2 | N8—C11—H11A | 109.0 |
C2—C3—H3A | 119.2 | C16—C11—H11A | 109.0 |
C3—C4—C5 | 117.40 (19) | N8—C11—H11B | 109.0 |
C3—C4—H4A | 121.3 | C16—C11—H11B | 109.0 |
C5—C4—H4A | 121.3 | H11A—C11—H11B | 107.8 |
N2—C5—C7 | 108.42 (17) | N6—C12—C14 | 108.33 (17) |
N2—C5—C4 | 131.43 (19) | N6—C12—C8 | 131.67 (19) |
C7—C5—C4 | 120.16 (18) | C14—C12—C8 | 120.00 (19) |
C2—C6—C7 | 115.86 (19) | C9—C13—C14 | 115.83 (19) |
C2—C6—H6A | 122.0 | C9—C13—H13A | 122.1 |
C7—C6—H6A | 122.1 | C14—C13—H13A | 122.1 |
N3—C7—C5 | 104.10 (16) | N8—C14—C12 | 104.42 (16) |
N3—C7—C6 | 133.29 (17) | N8—C14—C13 | 132.78 (17) |
C5—C7—C6 | 122.61 (18) | C12—C14—C13 | 122.80 (17) |
N1—C15—C1 | 179.3 (3) | N5—C16—C11 | 178.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···N6i | 0.97 | 2.51 | 3.475 (3) | 176 |
C11—H11A···N4ii | 0.97 | 2.62 | 3.468 (3) | 145 |
C11—H11B···N2iii | 0.97 | 2.61 | 3.412 (3) | 140 |
C1—H1A···N6iv | 0.97 | 2.75 | 3.544 (3) | 140 |
C1—H1A···N7iv | 0.97 | 2.68 | 3.609 (3) | 161 |
C2—H2A···N5iv | 0.93 | 2.75 | 3.537 (3) | 143 |
Symmetry codes: (i) x+1, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C8H6N4 |
Mr | 158.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.2423 (16), 9.833 (2), 10.631 (2) |
α, β, γ (°) | 88.13 (3), 72.07 (3), 71.90 (3) |
V (Å3) | 777.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury2 (2x2 bin mode) diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.805, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8053, 3559, 2183 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.137, 1.01 |
No. of reflections | 3559 |
No. of parameters | 229 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.20 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···N6i | 0.97 | 2.51 | 3.475 (3) | 176.2 |
C11—H11A···N4ii | 0.97 | 2.62 | 3.468 (3) | 145.4 |
C11—H11B···N2iii | 0.97 | 2.61 | 3.412 (3) | 140.0 |
C1—H1A···N6iv | 0.97 | 2.75 | 3.544 (3) | 140.0 |
C1—H1A···N7iv | 0.97 | 2.68 | 3.609 (3) | 161.4 |
C2—H2A···N5iv | 0.93 | 2.75 | 3.537 (3) | 143.3 |
Symmetry codes: (i) x+1, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z. |
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The title compound is obtained with high yield through the gentle reation of benzoletriazole and bromo acetonitrile in the presence of K2CO3 as catalyst. Colourless crystals of the title compound are obtained at room temperature after 3 days. The molecular structure with two molecules in the asymmetric unit (Fig. 1) shows almost linear acetonitrile moieties [bonding angles are 178.0 (2) and 179.3 (3) °]. The crystal packing is dominated by C—H···N interactions (Fig. 2, Table 1).