2-(1H-1,2,3-Benzotriazol-1-yl)­acetonitrile

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.

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

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2Ueq.

Computing details

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

	Fig. 1. The molecular structure of (I). Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. The crystal packing of (I).

2-(1H-Benzo[d]-1,2,3-triazol-1-yl)acetonitrile

Crystal data

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) Å^3

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0585P)^2 + 0.0638P] where P = (Fo^2 + 2Fc^2)/3
3559 reflections	(Δ/σ)max < 0.001
229 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···N6^i	0.97	2.51	3.475 (3)	176
C11—H11A···N4^ii	0.97	2.62	3.468 (3)	145
C11—H11B···N2^iii	0.97	2.61	3.412 (3)	140
C1—H1A···N6^iv	0.97	2.75	3.544 (3)	140
C1—H1A···N7^iv	0.97	2.68	3.609 (3)	161
C2—H2A···N5^iv	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.