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The title compound, C8H6N4, crystallizes with two mol­ecules in the asymmetric unit. The two conformers have distinctive orientations of the CCN groups with respect to the benzotriazole planes are 67.0 (10) and 85.8 (8)°. C—H...N inter­actions are present in the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055547/kp2142sup1.cif
Contains datablocks I, New_Global_Publ_Block

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055547/kp2142Isup2.hkl
Contains datablock I

CCDC reference: 672868

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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

Comment top

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).

Related literature top

For related literature, see: Danan et al. (1997).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids were drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of (I).
2-(1H-Benzo[d]-1,2,3-triazol-1-yl)acetonitrile top
Crystal data top
C8H6N4Z = 4
Mr = 158.17F(000) = 328
Triclinic, P1Dx = 1.352 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.2423 (16) ÅCell parameters from 6664 reflections
b = 9.833 (2) Åθ = 3.1–28.8°
c = 10.631 (2) ŵ = 0.09 mm1
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
Data collection top
Rigaku Mercury2 (2x2 bin mode)
diffractometer
3559 independent reflections
Radiation source: fine-focus sealed tube2183 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
CCD Profile fitting' scansh = 1010
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1212
Tmin = 0.805, Tmax = 1.000l = 1313
8053 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H-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 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C8H6N4γ = 71.90 (3)°
Mr = 158.17V = 777.3 (3) Å3
Triclinic, P1Z = 4
a = 8.2423 (16) ÅMo Kα radiation
b = 9.833 (2) ŵ = 0.09 mm1
c = 10.631 (2) ÅT = 293 K
α = 88.13 (3)°0.20 × 0.15 × 0.10 mm
β = 72.07 (3)°
Data collection top
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 = 1.000Rint = 0.038
8053 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.137H-atom parameters constrained
S = 1.01Δρmax = 0.14 e Å3
3559 reflectionsΔρmin = 0.20 e Å3
229 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
xyzUiso*/Ueq
N10.5499 (4)1.0795 (3)0.1618 (3)0.1058 (9)
N20.8556 (2)0.5781 (2)0.28482 (16)0.0602 (5)
N30.8417 (2)0.74294 (17)0.14567 (15)0.0489 (4)
N40.8779 (2)0.7030 (2)0.26055 (16)0.0606 (5)
C10.8566 (3)0.8776 (2)0.0939 (2)0.0565 (5)
H1A0.90520.86520.00200.075 (7)*
H1B0.93970.90600.12670.084 (8)*
C20.7116 (3)0.5057 (2)0.0368 (2)0.0567 (5)
H2A0.68100.49250.11170.070 (7)*
C30.7191 (3)0.3982 (2)0.0533 (2)0.0635 (6)
H3A0.69320.31630.03660.072 (7)*
C40.7633 (3)0.4109 (2)0.1645 (2)0.0593 (6)
H4A0.76660.34000.22450.066 (6)*
C50.8036 (2)0.5350 (2)0.18505 (18)0.0461 (5)
C60.7475 (3)0.6286 (2)0.01844 (18)0.0488 (5)
H6A0.74100.70000.07800.045 (5)*
C70.7945 (2)0.64060 (19)0.09500 (17)0.0408 (4)
C150.6831 (4)0.9913 (3)0.1317 (2)0.0659 (6)
N50.3078 (3)0.4137 (2)0.3596 (2)0.0753 (6)
N60.1370 (3)0.0085 (2)0.22156 (17)0.0616 (5)
N70.0731 (2)0.1280 (2)0.25838 (17)0.0597 (5)
N80.1134 (2)0.14813 (15)0.36958 (14)0.0439 (4)
C80.3127 (3)0.2251 (2)0.3148 (2)0.0632 (6)
H8A0.32440.29400.25180.071 (7)*
C90.3674 (3)0.1588 (2)0.5105 (2)0.0603 (6)
H9A0.41800.18850.57780.074 (7)*
C100.3832 (3)0.2615 (2)0.4160 (2)0.0655 (6)
H10A0.44320.35730.42250.079 (7)*
C110.0597 (3)0.2907 (2)0.4319 (2)0.0520 (5)
H11A0.02650.28510.52730.068 (6)*
H11B0.04550.35050.41100.075 (7)*
C120.2222 (3)0.0796 (2)0.30924 (18)0.0461 (5)
C130.2805 (3)0.0164 (2)0.50763 (19)0.0500 (5)
H13A0.27000.05170.57080.055 (6)*
C140.2082 (2)0.02065 (18)0.40414 (16)0.0387 (4)
C160.2010 (3)0.3579 (2)0.38981 (19)0.0510 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.1034 (19)0.0616 (15)0.122 (2)0.0069 (14)0.0132 (16)0.0147 (14)
N20.0671 (12)0.0624 (12)0.0425 (10)0.0067 (9)0.0194 (9)0.0081 (8)
N30.0574 (10)0.0486 (10)0.0394 (9)0.0118 (8)0.0184 (8)0.0033 (7)
N40.0756 (13)0.0607 (12)0.0436 (10)0.0100 (9)0.0275 (9)0.0012 (8)
C10.0684 (14)0.0537 (13)0.0537 (13)0.0253 (11)0.0218 (11)0.0055 (10)
C20.0528 (13)0.0629 (14)0.0608 (13)0.0213 (11)0.0234 (11)0.0024 (11)
C30.0571 (13)0.0528 (13)0.0880 (17)0.0217 (11)0.0289 (13)0.0072 (12)
C40.0503 (12)0.0494 (13)0.0713 (15)0.0116 (10)0.0154 (11)0.0199 (11)
C50.0404 (10)0.0479 (12)0.0394 (10)0.0033 (9)0.0087 (9)0.0058 (8)
C60.0501 (11)0.0576 (13)0.0417 (11)0.0182 (9)0.0181 (9)0.0113 (9)
C70.0380 (10)0.0405 (10)0.0397 (10)0.0085 (8)0.0101 (8)0.0021 (8)
C150.0824 (17)0.0453 (14)0.0673 (15)0.0194 (12)0.0205 (13)0.0071 (11)
N50.0905 (15)0.0630 (13)0.0790 (14)0.0374 (12)0.0224 (12)0.0048 (10)
N60.0786 (13)0.0679 (13)0.0506 (10)0.0314 (10)0.0286 (10)0.0002 (9)
N70.0709 (12)0.0662 (12)0.0538 (11)0.0270 (10)0.0314 (10)0.0129 (9)
N80.0534 (9)0.0409 (9)0.0420 (9)0.0159 (7)0.0205 (8)0.0052 (7)
C80.0680 (15)0.0441 (13)0.0694 (15)0.0219 (11)0.0041 (12)0.0145 (11)
C90.0589 (13)0.0544 (14)0.0688 (15)0.0150 (10)0.0259 (12)0.0174 (11)
C100.0593 (14)0.0394 (13)0.0856 (17)0.0079 (10)0.0135 (13)0.0048 (11)
C110.0578 (13)0.0408 (11)0.0527 (13)0.0109 (10)0.0155 (11)0.0038 (9)
C120.0515 (11)0.0459 (11)0.0434 (11)0.0221 (9)0.0108 (9)0.0029 (9)
C130.0579 (12)0.0469 (12)0.0490 (11)0.0174 (9)0.0213 (10)0.0056 (9)
C140.0413 (10)0.0361 (10)0.0389 (10)0.0156 (8)0.0097 (8)0.0060 (7)
C160.0706 (14)0.0352 (11)0.0484 (12)0.0137 (10)0.0237 (11)0.0066 (9)
Geometric parameters (Å, º) top
N1—C151.127 (3)N5—C161.138 (3)
N2—N41.303 (2)N6—N71.304 (2)
N2—C51.382 (2)N6—C121.380 (3)
N3—N41.362 (2)N7—N81.358 (2)
N3—C71.365 (2)N8—C141.362 (2)
N3—C11.443 (2)N8—C111.447 (2)
C1—C151.463 (3)C8—C101.362 (3)
C1—H1A0.9700C8—C121.402 (3)
C1—H1B0.9700C8—H8A0.9301
C2—C61.364 (3)C9—C131.365 (3)
C2—C31.402 (3)C9—C101.396 (3)
C2—H2A0.9301C9—H9A0.9300
C3—C41.359 (3)C10—H10A0.9300
C3—H3A0.9301C11—C161.460 (3)
C4—C51.400 (3)C11—H11A0.9700
C4—H4A0.9300C11—H11B0.9700
C5—C71.390 (2)C12—C141.388 (2)
C6—C71.394 (2)C13—C141.393 (2)
C6—H6A0.9300C13—H13A0.9299
N4—N2—C5108.73 (16)N7—N6—C12108.47 (15)
N4—N3—C7110.57 (16)N6—N7—N8108.51 (16)
N4—N3—C1120.34 (16)N7—N8—C14110.26 (15)
C7—N3—C1129.09 (16)N7—N8—C11120.45 (16)
N2—N4—N3108.19 (16)C14—N8—C11129.27 (15)
N3—C1—C15112.06 (18)C10—C8—C12117.2 (2)
N3—C1—H1A109.2C10—C8—H8A121.4
C15—C1—H1A109.2C12—C8—H8A121.4
N3—C1—H1B109.2C13—C9—C10122.3 (2)
C15—C1—H1B109.2C13—C9—H9A118.8
H1A—C1—H1B107.9C10—C9—H9A118.8
C6—C2—C3122.4 (2)C8—C10—C9121.8 (2)
C6—C2—H2A118.9C8—C10—H10A119.1
C3—C2—H2A118.8C9—C10—H10A119.1
C4—C3—C2121.6 (2)N8—C11—C16112.93 (17)
C4—C3—H3A119.2N8—C11—H11A109.0
C2—C3—H3A119.2C16—C11—H11A109.0
C3—C4—C5117.40 (19)N8—C11—H11B109.0
C3—C4—H4A121.3C16—C11—H11B109.0
C5—C4—H4A121.3H11A—C11—H11B107.8
N2—C5—C7108.42 (17)N6—C12—C14108.33 (17)
N2—C5—C4131.43 (19)N6—C12—C8131.67 (19)
C7—C5—C4120.16 (18)C14—C12—C8120.00 (19)
C2—C6—C7115.86 (19)C9—C13—C14115.83 (19)
C2—C6—H6A122.0C9—C13—H13A122.1
C7—C6—H6A122.1C14—C13—H13A122.1
N3—C7—C5104.10 (16)N8—C14—C12104.42 (16)
N3—C7—C6133.29 (17)N8—C14—C13132.78 (17)
C5—C7—C6122.61 (18)C12—C14—C13122.80 (17)
N1—C15—C1179.3 (3)N5—C16—C11178.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···N6i0.972.513.475 (3)176
C11—H11A···N4ii0.972.623.468 (3)145
C11—H11B···N2iii0.972.613.412 (3)140
C1—H1A···N6iv0.972.753.544 (3)140
C1—H1A···N7iv0.972.683.609 (3)161
C2—H2A···N5iv0.932.753.537 (3)143
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1; (iii) x1, y, z; (iv) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC8H6N4
Mr158.17
Crystal system, space groupTriclinic, 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)
V3)777.3 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.20 × 0.15 × 0.10
Data collection
DiffractometerRigaku Mercury2 (2x2 bin mode)
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.805, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
8053, 3559, 2183
Rint0.038
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.137, 1.01
No. of reflections3559
No. of parameters229
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.14, 0.20

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···N6i0.972.513.475 (3)176.2
C11—H11A···N4ii0.972.623.468 (3)145.4
C11—H11B···N2iii0.972.613.412 (3)140.0
C1—H1A···N6iv0.972.753.544 (3)140.0
C1—H1A···N7iv0.972.683.609 (3)161.4
C2—H2A···N5iv0.932.753.537 (3)143.3
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1; (iii) x1, y, z; (iv) x+1, y+1, z.
 

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