Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801000198/ci6001sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801000198/ci6001Isup2.hkl |
CCDC reference: 159717
To a stirred suspension of 1.12 g (46.5 mmol) of NaH in dry THF (30 ml) under dry argon gas was added a solution of 5.00 g (161.2 mmol) of 3,4-(methylenedioxy)phenylacetonitrile and 4.90 g (31.0 mmol) of 2-bromopyridine in dry THF (30 ml). The mixture was stirred at room temperature for 1 h and then at reflux overnight. After cooling, the THF was removed and water (50 ml) added while cooling in an ice bath. The aqueous layer was extracted with 3 × 50 ml of EtOAc and the combined organic layer washed with water and then extracted with 4 × 30 ml of 6M HCl solution. The combined aqueous layer was adjusted to pH 11 with 15% NaOH and extracted with 3 × 50 ml EtOAc. The organic layer was washed with water, dried over Na2SO4, filtered and the solvent removed in vacuo. Column chromatography with EtOAc–hexane (1:4) gave 5.83 g (79%) of the title compound as a pale yellow powder with m.p. 338–340 K. 1H NMR (CDCl3) δ 5.22 (1H, s), 5.94 (2H, s), 6.78 (1H, d), 6.87 (1H, d), 6.91 (1H, dd), 7.24 (1H, ddd), 7.36 (1H, d), 7.69 (1H, ddd), 8.59 (1H, ddd). 13C NMR (CDCl3) δ 44.9, 101.4, 108.1, 108.6, 119.0, 121.2, 121.8, 123.0, 128.2, 137.5, 147.7, 148.3, 149.9, 155.4. Analysis calculated for C14H10N2O2 (238.24): C 70.58, H 4.23%; found: C 70.80, H 4.20%. ES—MS [M + H]+ = 239.1. Crystals were obtained from the slow evaporation of a CDCl3 solution of the compound.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1997-1999); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.
Fig. 1. The molecular structure of (I). Displacement ellipsoids are shown at the 50% probability level (Johnson, 1976). |
C14H10N2O2 | Z = 2 |
Mr = 238.25 | F(000) = 248 |
Triclinic, P1 | Dx = 1.415 Mg m−3 |
a = 8.851 (2) Å | Mo Kα radiation, λ = 0.7107 Å |
b = 11.435 (4) Å | Cell parameters from 25 reflections |
c = 5.831 (1) Å | θ = 8.0–30.0° |
α = 94.42 (2)° | µ = 0.10 mm−1 |
β = 92.79 (2)° | T = 173 K |
γ = 107.65 (2)° | Block, colourless |
V = 559.1 (3) Å3 | 0.48 × 0.48 × 0.11 mm |
Rigaku AFC-7R diffractometer | Rint = 0.050 |
Radiation source: rotating anode | θmax = 27.5°, θmin = 3.5° |
Graphite monochromator | h = −11→11 |
ω–2θ scans | k = −14→14 |
2731 measured reflections | l = 0→7 |
2564 independent reflections | 3 standard reflections every 400 reflections |
1911 reflections with I > 2σ(I) | intensity decay: 0.2% |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters not refined |
S = 1.05 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
2564 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C14H10N2O2 | γ = 107.65 (2)° |
Mr = 238.25 | V = 559.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.851 (2) Å | Mo Kα radiation |
b = 11.435 (4) Å | µ = 0.10 mm−1 |
c = 5.831 (1) Å | T = 173 K |
α = 94.42 (2)° | 0.48 × 0.48 × 0.11 mm |
β = 92.79 (2)° |
Rigaku AFC-7R diffractometer | Rint = 0.050 |
2731 measured reflections | 3 standard reflections every 400 reflections |
2564 independent reflections | intensity decay: 0.2% |
1911 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters not refined |
S = 1.05 | Δρmax = 0.25 e Å−3 |
2564 reflections | Δρmin = −0.25 e Å−3 |
163 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 | ||
O1 | 0.19247 (14) | 0.58173 (10) | −0.00247 (19) | 0.0375 (3) | |
O3 | 0.13809 (14) | 0.46384 (10) | −0.35548 (18) | 0.0386 (3) | |
N1' | 0.19430 (14) | 0.02168 (11) | −0.2951 (2) | 0.0296 (3) | |
N1'' | 0.57051 (15) | 0.18918 (12) | −0.4895 (2) | 0.0350 (3) | |
C1 | 0.42803 (15) | 0.17724 (11) | −0.1053 (2) | 0.0238 (3) | |
H1 | 0.5083 | 0.1830 | 0.0252 | 0.029* | |
C1'' | 0.50785 (15) | 0.18228 (12) | −0.3225 (2) | 0.0266 (3) | |
C2 | 0.13269 (19) | 0.57686 (13) | −0.2365 (3) | 0.0343 (3) | |
H2A | 0.1986 | 0.6481 | −0.3105 | 0.041* | |
H2B | 0.0220 | 0.5799 | −0.2420 | 0.041* | |
C2' | 0.29507 (15) | 0.05452 (11) | −0.1064 (2) | 0.0229 (3) | |
C3' | 0.27971 (17) | −0.01189 (12) | 0.0840 (2) | 0.0282 (3) | |
H3' | 0.3547 | 0.0149 | 0.2142 | 0.034* | |
C3A | 0.22371 (16) | 0.41604 (12) | −0.2071 (2) | 0.0258 (3) | |
C4 | 0.27607 (15) | 0.31587 (12) | −0.2512 (2) | 0.0248 (3) | |
H4 | 0.2541 | 0.2687 | −0.3972 | 0.030* | |
C4' | 0.15207 (18) | −0.11859 (13) | 0.0801 (3) | 0.0323 (3) | |
H4' | 0.1385 | −0.1670 | 0.2073 | 0.039* | |
C5 | 0.36395 (15) | 0.28657 (11) | −0.0692 (2) | 0.0226 (3) | |
C5' | 0.04548 (17) | −0.15317 (12) | −0.1110 (3) | 0.0319 (3) | |
H5' | −0.0438 | −0.2252 | −0.1174 | 0.038* | |
C6' | 0.07089 (17) | −0.08098 (13) | −0.2933 (3) | 0.0328 (3) | |
H6' | −0.0032 | −0.1054 | −0.4247 | 0.039* | |
C6 | 0.39230 (16) | 0.35490 (12) | 0.1439 (2) | 0.0261 (3) | |
H6 | 0.4504 | 0.3322 | 0.2648 | 0.031* | |
C7 | 0.33715 (17) | 0.45677 (13) | 0.1851 (2) | 0.0284 (3) | |
H7 | 0.3560 | 0.5035 | 0.3313 | 0.034* | |
C7A | 0.25502 (16) | 0.48561 (12) | 0.0046 (2) | 0.0267 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0475 (7) | 0.0333 (6) | 0.0375 (6) | 0.0211 (5) | 0.0073 (5) | 0.0013 (4) |
O3 | 0.0516 (7) | 0.0420 (6) | 0.0327 (6) | 0.0311 (5) | −0.0017 (5) | 0.0033 (5) |
N1' | 0.0298 (6) | 0.0271 (6) | 0.0291 (6) | 0.0053 (5) | −0.0047 (5) | 0.0044 (5) |
N1'' | 0.0326 (7) | 0.0406 (7) | 0.0346 (7) | 0.0136 (6) | 0.0054 (5) | 0.0087 (5) |
C1 | 0.0228 (6) | 0.0243 (6) | 0.0246 (6) | 0.0074 (5) | −0.0010 (5) | 0.0048 (5) |
C1'' | 0.0234 (6) | 0.0256 (6) | 0.0317 (7) | 0.0089 (5) | −0.0015 (5) | 0.0052 (5) |
C2 | 0.0374 (8) | 0.0318 (7) | 0.0392 (8) | 0.0168 (6) | 0.0094 (6) | 0.0086 (6) |
C2' | 0.0229 (6) | 0.0222 (6) | 0.0254 (6) | 0.0097 (5) | 0.0013 (5) | 0.0029 (5) |
C3' | 0.0316 (7) | 0.0272 (7) | 0.0270 (7) | 0.0105 (6) | 0.0013 (5) | 0.0053 (5) |
C3A | 0.0249 (6) | 0.0274 (6) | 0.0261 (6) | 0.0086 (5) | 0.0026 (5) | 0.0063 (5) |
C4 | 0.0252 (6) | 0.0249 (6) | 0.0238 (6) | 0.0071 (5) | 0.0008 (5) | 0.0022 (5) |
C4' | 0.0385 (8) | 0.0285 (7) | 0.0332 (7) | 0.0122 (6) | 0.0100 (6) | 0.0109 (6) |
C5 | 0.0201 (6) | 0.0208 (6) | 0.0253 (6) | 0.0031 (5) | 0.0017 (5) | 0.0050 (5) |
C5' | 0.0265 (7) | 0.0227 (6) | 0.0457 (9) | 0.0054 (5) | 0.0079 (6) | 0.0034 (6) |
C6' | 0.0289 (7) | 0.0294 (7) | 0.0370 (8) | 0.0057 (6) | −0.0043 (6) | 0.0020 (6) |
C6 | 0.0249 (6) | 0.0275 (6) | 0.0236 (6) | 0.0038 (5) | 0.0013 (5) | 0.0055 (5) |
C7 | 0.0295 (7) | 0.0276 (6) | 0.0249 (6) | 0.0039 (5) | 0.0056 (5) | 0.0002 (5) |
C7A | 0.0254 (7) | 0.0233 (6) | 0.0319 (7) | 0.0067 (5) | 0.0091 (5) | 0.0043 (5) |
O1—C7A | 1.3748 (17) | C2'—C3' | 1.3819 (18) |
O1—C2 | 1.430 (2) | C3'—C4' | 1.387 (2) |
O3—C3A | 1.3720 (16) | C3A—C4 | 1.3717 (19) |
O3—C2 | 1.4339 (18) | C3A—C7A | 1.384 (2) |
N1'—C2' | 1.3359 (18) | C4—C5 | 1.4055 (18) |
N1'—C6' | 1.3404 (18) | C4'—C5' | 1.375 (2) |
N1''—C1'' | 1.1403 (19) | C5—C6 | 1.3853 (19) |
C1—C1'' | 1.4765 (19) | C5'—C6' | 1.382 (2) |
C1—C5 | 1.5264 (18) | C6—C7 | 1.402 (2) |
C1—C2' | 1.5332 (18) | C7—C7A | 1.367 (2) |
C7A—O1—C2 | 105.72 (11) | O3—C3A—C7A | 109.97 (12) |
C3A—O3—C2 | 105.56 (11) | C3A—C4—C5 | 116.53 (12) |
C2'—N1'—C6' | 116.71 (12) | C5'—C4'—C3' | 118.88 (13) |
C1''—C1—C5 | 110.09 (10) | C6—C5—C4 | 120.95 (12) |
C1''—C1—C2' | 110.49 (11) | C6—C5—C1 | 119.29 (12) |
C5—C1—C2' | 111.25 (10) | C4—C5—C1 | 119.76 (12) |
N1''—C1''—C1 | 178.35 (14) | C6'—C5'—C4' | 118.66 (13) |
O1—C2—O3 | 107.98 (11) | N1'—C6'—C5' | 123.63 (14) |
N1'—C2'—C3' | 123.81 (12) | C5—C6—C7 | 121.46 (13) |
N1'—C2'—C1 | 115.68 (11) | C7A—C7—C6 | 116.79 (13) |
C3'—C2'—C1 | 120.43 (12) | O1—C7A—C7 | 128.36 (13) |
C2'—C3'—C4' | 118.31 (13) | O1—C7A—C3A | 109.75 (13) |
C4—C3A—O3 | 127.67 (12) | C7—C7A—C3A | 121.88 (13) |
C4—C3A—C7A | 122.35 (13) |
Experimental details
Crystal data | |
Chemical formula | C14H10N2O2 |
Mr | 238.25 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.851 (2), 11.435 (4), 5.831 (1) |
α, β, γ (°) | 94.42 (2), 92.79 (2), 107.65 (2) |
V (Å3) | 559.1 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.48 × 0.48 × 0.11 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2731, 2564, 1911 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.139, 1.05 |
No. of reflections | 2564 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.25, −0.25 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1997-1999), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 1997), TEXSAN.
The title compound, (I), is an intermediate in the synthesis of potential cocaine antagonists. It was prepared by a nucleophilic substitution reaction involving 2-bromopyridine and 1,3-benzodioxo-5-ylmethyl cyanide. The mean deviation of the atoms from the 1,3-benzodioxo group is 0.054 Å with the major deviation of 0.100 (2) Å associated with C2. The dihedral angle between this plane and that through the pyridyl group is 67.73 (6)°. Molecules associate in the crystal to form chains held by alternating π···π and C—H···π interactions. Centrosymmetrically (1 - x, 1 - y, -z) related 1,3-benzodioxo groups are aligned so as to place the six-membered rings in close proximity. The distance separating the ring centroids is calculated to be 3.584 (2) Å (Spek, 1990). These pairs are capped on each sides by a symmetry related H5' atom (-x, -y, -z) which -forms an interaction of the type C–H···π with the C3a–C7a aromatic ring so that the H···ring centroid separation is 2.73 Å and the angle at H5' is 157°.