Acta Cryst. (2010). E66, o2631 [ doi:10.1107/S1600536810037335 ]
The asymmetric unit of the title compound, C10H6N2O2, contains two independent molecules. The dihedral angles between the acetonitrile and the 1H-isoindole-1,3(2H)-dione units are 69.0 (7)° and 77.0 (5)° in the two molecules. One of the two terminal N atoms is disordered over two positions in a 0.66 (8):0,34 (8) ratio. In the crystal structure, the molecules are linked by intermolecular C-H
O hydrogen bonds.
A mixture containing 4.8 g (0.02 mol) of 2-(bromomethyl)isoindoline-1,3-dione, 6.5 g KCN (0.1 mol), and 60 ml of anhydrous acetonitrile is heated overnight at 60°C, and then filtered. The residue is washed twice with acetonitrile, and the filtrate was concentrated under vacuum. The solid obtained is purified by chromatography on silica gel column (eluent: ether / hexane: 2 / 3).
Yield= 80% (white solid); F= 122–124°C; Rf = 0.31(ether/hexane3:1).
IR (KBr) ν cm-1: 3070(CHarom),2947/2983 (CH), 1692/1709 (2 C=O), 1557/1613 (C=C). δH (CDCl3): 4.57 (2HCH2,s); 7.60–8.10 (4Harom, m). δC (CDCl3): 28.1(CH2);115.01(CN); 127.5; 132.1; 133.3(Carom); 168.28(2 C=O).
MS—EI: [M]+=186.
Elemental analysis for C10H6N2O2 Calcd(Found):C 64.51(64.62), H 3.22(3.31), N 15.02(14.94).
All H atoms were fixed geometrically and treated as riding with C—H = 0.97 Å (methyne) and 0.93Å (aromatic) with Uiso(H) = 1.2Ueq(C).
One of the terminals N was found disordered over. Two sets of positions were defined for the disordered N and the site occupation factors were refined while restraining their sum to unity. The site occupation factor of the major component was refined to 0.66 (8).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).
![[Figure 1]](./jh2206fig1thm.gif)
| Fig. 1. Two independent molecules of the title compound showing the atom-labelling scheme and 30% probability displacement ellipsoids. Only major parts of disordered N are shown. |
![[Figure 2]](./jh2206fig2thm.gif)
| Fig. 2. Partial packing view showing the formation of a chain through C—H···O hydrogen bonds shown as dashed lines. |
![[Figure 3]](./jh2206fig3thm.gif)
| Fig. 3. View of the title compound showing displacement ellipsoids at the 50% probability level. |
| C10H6N2O2 | Z = 4 |
| Mr = 186.17 | F(000) = 384 |
| Triclinic, P1 | Dx = 1.385 Mg m−3 |
| Hall symbol: -P 1 | Melting point: 395 K |
| a = 8.0960 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 8.4371 (2) Å | Cell parameters from 2714 reflections |
| c = 14.3118 (3) Å | θ = 2.7–25.3° |
| α = 85.072 (1)° | µ = 0.10 mm−1 |
| β = 79.272 (1)° | T = 296 K |
| γ = 68.421 (1)° | Block, colourless |
| V = 893.02 (4) Å3 | 0.25 × 0.24 × 0.16 mm |
| Bruker APEXII CCD detector diffractometer | 2885 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.034 |
| graphite | θmax = 27.0°, θmin = 1.5° |
| ω and φ scans | h = −10→10 |
| 18332 measured reflections | k = −10→10 |
| 3906 independent reflections | l = −17→18 |
| 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.128 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0697P)2 + 0.070P] where P = (Fo2 + 2Fc2)/3 |
| 3906 reflections | (Δ/σ)max = 0.005 |
| 267 parameters | Δρmax = 0.19 e Å−3 |
| 6 restraints | Δρmin = −0.19 e Å−3 |
| C10H6N2O2 | γ = 68.421 (1)° |
| Mr = 186.17 | V = 893.02 (4) Å3 |
| Triclinic, P1 | Z = 4 |
| a = 8.0960 (2) Å | Mo Kα radiation |
| b = 8.4371 (2) Å | µ = 0.10 mm−1 |
| c = 14.3118 (3) Å | T = 296 K |
| α = 85.072 (1)° | 0.25 × 0.24 × 0.16 mm |
| β = 79.272 (1)° |
| Bruker APEXII CCD detector diffractometer | 2885 reflections with I > 2σ(I) |
| 18332 measured reflections | Rint = 0.034 |
| 3906 independent reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
| wR(F2) = 0.128 | Δρmax = 0.19 e Å−3 |
| S = 1.05 | Δρmin = −0.19 e Å−3 |
| 3906 reflections | Absolute structure: ? |
| 267 parameters | Flack parameter: ? |
| 6 restraints | Rogers parameter: ? |
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 | Occ. (<1) | |
| C11 | 0.73565 (18) | 0.39842 (17) | 0.04371 (10) | 0.0471 (3) | |
| C16 | 0.75085 (18) | 0.49910 (17) | −0.03635 (10) | 0.0461 (3) | |
| C10 | 0.7395 (2) | 0.48752 (18) | 0.12747 (11) | 0.0497 (3) | |
| C17 | 0.7711 (2) | 0.65409 (18) | −0.00671 (11) | 0.0527 (4) | |
| C18 | 0.7772 (2) | 0.76260 (19) | 0.15037 (12) | 0.0582 (4) | |
| H18A | 0.8360 | 0.8327 | 0.1112 | 0.070* | |
| H18B | 0.8503 | 0.7049 | 0.1984 | 0.070* | |
| C15 | 0.7474 (2) | 0.4505 (2) | −0.12523 (12) | 0.0612 (4) | |
| H15 | 0.7559 | 0.5195 | −0.1788 | 0.073* | |
| C14 | 0.7309 (2) | 0.2948 (2) | −0.13128 (13) | 0.0685 (5) | |
| H14 | 0.7291 | 0.2577 | −0.1903 | 0.082* | |
| C19 | 0.5995 (3) | 0.8711 (2) | 0.19668 (15) | 0.0745 (5) | |
| C12 | 0.7182 (3) | 0.2438 (2) | 0.03696 (14) | 0.0670 (5) | |
| H12 | 0.7075 | 0.1754 | 0.0906 | 0.080* | |
| C13 | 0.7170 (3) | 0.1937 (2) | −0.05234 (15) | 0.0750 (5) | |
| H13 | 0.7065 | 0.0893 | −0.0589 | 0.090* | |
| C20 | 0.91639 (18) | 0.46404 (18) | 0.38170 (10) | 0.0462 (3) | |
| C26 | 0.72827 (18) | 0.4498 (2) | 0.52338 (10) | 0.0495 (3) | |
| C21 | 0.78905 (18) | 0.56105 (19) | 0.46334 (10) | 0.0472 (3) | |
| C27 | 0.81143 (19) | 0.2782 (2) | 0.48113 (11) | 0.0512 (4) | |
| C28 | 1.0390 (2) | 0.1584 (2) | 0.33559 (12) | 0.0598 (4) | |
| H28A | 1.1202 | 0.0741 | 0.3727 | 0.072* | |
| H28B | 1.1114 | 0.2015 | 0.2857 | 0.072* | |
| C22 | 0.7336 (2) | 0.7317 (2) | 0.48390 (12) | 0.0600 (4) | |
| H22 | 0.7740 | 0.8068 | 0.4433 | 0.072* | |
| C29 | 0.9423 (2) | 0.0764 (2) | 0.29222 (14) | 0.0661 (5) | |
| C23 | 0.6146 (2) | 0.7856 (2) | 0.56814 (14) | 0.0715 (5) | |
| H23 | 0.5744 | 0.8996 | 0.5843 | 0.086* | |
| C25 | 0.6098 (2) | 0.5045 (3) | 0.60702 (12) | 0.0640 (4) | |
| H25 | 0.5686 | 0.4297 | 0.6475 | 0.077* | |
| C24 | 0.5549 (2) | 0.6749 (3) | 0.62815 (13) | 0.0725 (5) | |
| H24 | 0.4758 | 0.7154 | 0.6842 | 0.087* | |
| O11 | 0.72249 (19) | 0.44907 (16) | 0.21083 (8) | 0.0739 (4) | |
| O12 | 0.7926 (2) | 0.77161 (16) | −0.05386 (10) | 0.0863 (4) | |
| O20 | 1.00395 (15) | 0.51155 (14) | 0.31593 (8) | 0.0613 (3) | |
| O21 | 0.79522 (16) | 0.14499 (15) | 0.50949 (9) | 0.0727 (4) | |
| N11 | 0.76467 (16) | 0.63694 (14) | 0.09160 (9) | 0.0497 (3) | |
| N21 | 0.92041 (16) | 0.29721 (15) | 0.39635 (8) | 0.0494 (3) | |
| N22 | 0.8731 (3) | 0.0080 (2) | 0.25846 (16) | 0.1020 (7) | |
| N12A | 0.4599 (15) | 0.972 (4) | 0.222 (2) | 0.100 (4) | 0.66 (8) |
| N12B | 0.466 (4) | 0.916 (6) | 0.252 (3) | 0.085 (6) | 0.34 (8) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C11 | 0.0471 (8) | 0.0391 (7) | 0.0555 (8) | −0.0166 (6) | −0.0054 (6) | −0.0037 (6) |
| C16 | 0.0411 (7) | 0.0434 (7) | 0.0506 (8) | −0.0148 (6) | 0.0017 (6) | −0.0064 (6) |
| C10 | 0.0539 (8) | 0.0439 (8) | 0.0529 (9) | −0.0215 (6) | −0.0049 (6) | −0.0009 (6) |
| C17 | 0.0550 (8) | 0.0447 (8) | 0.0597 (9) | −0.0227 (7) | −0.0037 (7) | 0.0018 (7) |
| C18 | 0.0611 (9) | 0.0469 (8) | 0.0728 (10) | −0.0233 (7) | −0.0141 (8) | −0.0108 (7) |
| C15 | 0.0567 (9) | 0.0693 (10) | 0.0519 (9) | −0.0200 (8) | 0.0035 (7) | −0.0102 (8) |
| C14 | 0.0631 (10) | 0.0669 (11) | 0.0705 (11) | −0.0135 (8) | −0.0062 (8) | −0.0307 (9) |
| C19 | 0.0700 (12) | 0.0728 (12) | 0.0872 (14) | −0.0258 (10) | −0.0134 (10) | −0.0353 (10) |
| C12 | 0.0875 (12) | 0.0422 (8) | 0.0784 (12) | −0.0294 (8) | −0.0189 (9) | 0.0008 (8) |
| C13 | 0.0835 (12) | 0.0453 (9) | 0.1006 (15) | −0.0209 (9) | −0.0214 (11) | −0.0213 (9) |
| C20 | 0.0446 (7) | 0.0517 (8) | 0.0462 (8) | −0.0201 (6) | −0.0124 (6) | 0.0007 (6) |
| C26 | 0.0418 (7) | 0.0632 (9) | 0.0449 (8) | −0.0185 (7) | −0.0123 (6) | 0.0011 (7) |
| C21 | 0.0432 (7) | 0.0540 (8) | 0.0462 (8) | −0.0167 (6) | −0.0127 (6) | −0.0035 (6) |
| C27 | 0.0455 (8) | 0.0578 (9) | 0.0532 (8) | −0.0209 (7) | −0.0143 (6) | 0.0073 (7) |
| C28 | 0.0518 (9) | 0.0554 (9) | 0.0701 (10) | −0.0151 (7) | −0.0088 (8) | −0.0125 (8) |
| C22 | 0.0573 (9) | 0.0558 (9) | 0.0674 (10) | −0.0164 (7) | −0.0166 (8) | −0.0072 (8) |
| C29 | 0.0628 (10) | 0.0485 (9) | 0.0830 (12) | −0.0116 (8) | −0.0123 (9) | −0.0185 (8) |
| C23 | 0.0590 (10) | 0.0699 (11) | 0.0766 (12) | −0.0041 (8) | −0.0181 (9) | −0.0257 (10) |
| C25 | 0.0492 (9) | 0.0898 (13) | 0.0496 (9) | −0.0219 (8) | −0.0069 (7) | −0.0001 (8) |
| C24 | 0.0517 (9) | 0.0973 (15) | 0.0572 (10) | −0.0114 (9) | −0.0049 (8) | −0.0202 (10) |
| O11 | 0.1064 (10) | 0.0764 (8) | 0.0524 (7) | −0.0494 (8) | −0.0150 (6) | 0.0068 (6) |
| O12 | 0.1289 (12) | 0.0668 (8) | 0.0810 (9) | −0.0601 (8) | −0.0181 (8) | 0.0195 (7) |
| O20 | 0.0651 (7) | 0.0686 (7) | 0.0530 (6) | −0.0320 (6) | −0.0011 (5) | 0.0014 (5) |
| O21 | 0.0695 (7) | 0.0627 (7) | 0.0869 (9) | −0.0291 (6) | −0.0133 (6) | 0.0184 (6) |
| N11 | 0.0584 (7) | 0.0396 (6) | 0.0556 (7) | −0.0229 (5) | −0.0072 (6) | −0.0052 (5) |
| N21 | 0.0499 (7) | 0.0496 (7) | 0.0498 (7) | −0.0186 (5) | −0.0072 (5) | −0.0065 (5) |
| N22 | 0.0928 (13) | 0.0766 (11) | 0.1438 (18) | −0.0253 (10) | −0.0265 (12) | −0.0498 (12) |
| N12A | 0.078 (2) | 0.098 (7) | 0.114 (8) | −0.013 (4) | −0.013 (4) | −0.048 (7) |
| N12B | 0.079 (5) | 0.081 (10) | 0.088 (10) | −0.020 (6) | 0.005 (5) | −0.040 (7) |
| C11—C12 | 1.376 (2) | C20—N21 | 1.3944 (18) |
| C11—C16 | 1.381 (2) | C20—C21 | 1.481 (2) |
| C11—C10 | 1.480 (2) | C26—C21 | 1.380 (2) |
| C16—C15 | 1.378 (2) | C26—C25 | 1.381 (2) |
| C16—C17 | 1.482 (2) | C26—C27 | 1.482 (2) |
| C10—O11 | 1.2052 (18) | C21—C22 | 1.382 (2) |
| C10—N11 | 1.3903 (18) | C27—O21 | 1.2066 (17) |
| C17—O12 | 1.1989 (18) | C27—N21 | 1.3958 (19) |
| C17—N11 | 1.395 (2) | C28—N21 | 1.4445 (19) |
| C18—N11 | 1.4511 (18) | C28—C29 | 1.460 (2) |
| C18—C19 | 1.458 (2) | C28—H28A | 0.9700 |
| C18—H18A | 0.9700 | C28—H28B | 0.9700 |
| C18—H18B | 0.9700 | C22—C23 | 1.388 (2) |
| C15—C14 | 1.380 (2) | C22—H22 | 0.9300 |
| C15—H15 | 0.9300 | C29—N22 | 1.125 (2) |
| C14—C13 | 1.369 (3) | C23—C24 | 1.372 (3) |
| C14—H14 | 0.9300 | C23—H23 | 0.9300 |
| C12—C13 | 1.383 (3) | C25—C24 | 1.383 (3) |
| C12—H12 | 0.9300 | C25—H25 | 0.9300 |
| C13—H13 | 0.9300 | C24—H24 | 0.9300 |
| C20—O20 | 1.2021 (17) | ||
| C12—C11—C16 | 120.65 (14) | C21—C26—C27 | 108.31 (13) |
| C12—C11—C10 | 130.71 (15) | C25—C26—C27 | 130.42 (15) |
| C16—C11—C10 | 108.64 (12) | C26—C21—C22 | 121.60 (14) |
| C15—C16—C11 | 121.80 (13) | C26—C21—C20 | 108.40 (13) |
| C15—C16—C17 | 130.20 (14) | C22—C21—C20 | 129.99 (14) |
| C11—C16—C17 | 108.00 (13) | O21—C27—N21 | 124.00 (15) |
| O11—C10—N11 | 123.96 (14) | O21—C27—C26 | 130.39 (15) |
| O11—C10—C11 | 130.57 (14) | N21—C27—C26 | 105.61 (12) |
| N11—C10—C11 | 105.46 (12) | N21—C28—C29 | 112.91 (13) |
| O12—C17—N11 | 124.60 (15) | N21—C28—H28A | 109.0 |
| O12—C17—C16 | 129.75 (15) | C29—C28—H28A | 109.0 |
| N11—C17—C16 | 105.63 (12) | N21—C28—H28B | 109.0 |
| N11—C18—C19 | 111.30 (13) | C29—C28—H28B | 109.0 |
| N11—C18—H18A | 109.4 | H28A—C28—H28B | 107.8 |
| C19—C18—H18A | 109.4 | C21—C22—C23 | 116.75 (17) |
| N11—C18—H18B | 109.4 | C21—C22—H22 | 121.6 |
| C19—C18—H18B | 109.4 | C23—C22—H22 | 121.6 |
| H18A—C18—H18B | 108.0 | N22—C29—C28 | 177.51 (18) |
| C16—C15—C14 | 117.07 (16) | C24—C23—C22 | 121.71 (17) |
| C16—C15—H15 | 121.5 | C24—C23—H23 | 119.1 |
| C14—C15—H15 | 121.5 | C22—C23—H23 | 119.1 |
| C13—C14—C15 | 121.47 (16) | C26—C25—C24 | 117.30 (17) |
| C13—C14—H14 | 119.3 | C26—C25—H25 | 121.4 |
| C15—C14—H14 | 119.3 | C24—C25—H25 | 121.4 |
| C11—C12—C13 | 117.66 (16) | C23—C24—C25 | 121.36 (16) |
| C11—C12—H12 | 121.2 | C23—C24—H24 | 119.3 |
| C13—C12—H12 | 121.2 | C25—C24—H24 | 119.3 |
| C14—C13—C12 | 121.34 (16) | C10—N11—C17 | 112.21 (12) |
| C14—C13—H13 | 119.3 | C10—N11—C18 | 123.66 (13) |
| C12—C13—H13 | 119.3 | C17—N11—C18 | 124.11 (12) |
| O20—C20—N21 | 124.84 (14) | C20—N21—C27 | 112.00 (12) |
| O20—C20—C21 | 129.50 (14) | C20—N21—C28 | 123.18 (12) |
| N21—C20—C21 | 105.65 (12) | C27—N21—C28 | 124.49 (13) |
| C21—C26—C25 | 121.28 (15) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C13—H13···O12i | 0.93 | 2.51 | 3.386 (2) | 158 |
| C15—H15···O20ii | 0.93 | 2.45 | 3.144 (2) | 132 |
| C18—H18B···O20 | 0.97 | 2.42 | 3.372 (2) | 167 |
| C28—H28A···O21iii | 0.97 | 2.39 | 3.298 (2) | 156 |
| Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z; (iii) −x+2, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C13—H13···O12i | 0.93 | 2.51 | 3.386 (2) | 158 |
| C15—H15···O20ii | 0.93 | 2.45 | 3.144 (2) | 132 |
| C18—H18B···O20 | 0.97 | 2.42 | 3.372 (2) | 167 |
| C28—H28A···O21iii | 0.97 | 2.39 | 3.298 (2) | 156 |
| Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z; (iii) −x+2, −y, −z+1. |
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With the aim of developing new tetrazolic derived, an analog isosteric of the glycine, we have prepared 2-(1,3-dioxoisoindolin-2-yl)acetonitrile,a key intermediate, starting from 2-(bromomethyl)isoindoline-1,3-dione.
The asymmetric unit of the new synthetized 2-(1,3-dioxoisoindolin-2-yl)acetonitrile, C10H6N2O2, contains two independent molecules. The dihedral angles between the acetonitrile and the 1H-isoindole-1,3(2H)-dione are 69.0 (7)° and 77.0 (5)°, respictively.
One of the two terminal N is disordered over two positions with occupancy of 0.66 (8) for the major site. In the crystal structure, the molecules are linked by intermolecular C—H···O hydrogen bonds.