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In the title compound, C14H10N2O2, the dihedral angle formed between the substituted pyridine ring and 1,3-benzodioxole group is 67.73 (6)°. The crystal features chains of mol­ecules held together by alternating π...π and C—H...π interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801000198/ci6001sup1.cif
Contains datablocks general, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801000198/ci6001Isup2.hkl
Contains datablock I

CCDC reference: 159717

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.039
  • wR factor = 0.139
  • Data-to-parameter ratio = 15.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry




Comment top

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°.

Experimental top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are shown at the 50% probability level (Johnson, 1976).
(I) top
Crystal data top
C14H10N2O2Z = 2
Mr = 238.25F(000) = 248
Triclinic, P1Dx = 1.415 Mg m3
a = 8.851 (2) ÅMo Kα radiation, λ = 0.7107 Å
b = 11.435 (4) ÅCell parameters from 25 reflections
c = 5.831 (1) Åθ = 8.0–30.0°
α = 94.42 (2)°µ = 0.10 mm1
β = 92.79 (2)°T = 173 K
γ = 107.65 (2)°Block, colourless
V = 559.1 (3) Å30.48 × 0.48 × 0.11 mm
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.050
Radiation source: rotating anodeθmax = 27.5°, θmin = 3.5°
Graphite monochromatorh = 1111
ω–2θ scansk = 1414
2731 measured reflectionsl = 07
2564 independent reflections3 standard reflections every 400 reflections
1911 reflections with I > 2σ(I) intensity decay: 0.2%
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H-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 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C14H10N2O2γ = 107.65 (2)°
Mr = 238.25V = 559.1 (3) Å3
Triclinic, P1Z = 2
a = 8.851 (2) ÅMo Kα radiation
b = 11.435 (4) ŵ = 0.10 mm1
c = 5.831 (1) ÅT = 173 K
α = 94.42 (2)°0.48 × 0.48 × 0.11 mm
β = 92.79 (2)°
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.050
2731 measured reflections3 standard reflections every 400 reflections
2564 independent reflections intensity decay: 0.2%
1911 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.139H-atom parameters not refined
S = 1.05Δρmax = 0.25 e Å3
2564 reflectionsΔρmin = 0.25 e Å3
163 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
O10.19247 (14)0.58173 (10)0.00247 (19)0.0375 (3)
O30.13809 (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)
C10.42803 (15)0.17724 (11)0.1053 (2)0.0238 (3)
H10.50830.18300.02520.029*
C1''0.50785 (15)0.18228 (12)0.3225 (2)0.0266 (3)
C20.13269 (19)0.57686 (13)0.2365 (3)0.0343 (3)
H2A0.19860.64810.31050.041*
H2B0.02200.57990.24200.041*
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)
H3'0.35470.01490.21420.034*
C3A0.22371 (16)0.41604 (12)0.2071 (2)0.0258 (3)
C40.27607 (15)0.31587 (12)0.2512 (2)0.0248 (3)
H40.25410.26870.39720.030*
C4'0.15207 (18)0.11859 (13)0.0801 (3)0.0323 (3)
H4'0.13850.16700.20730.039*
C50.36395 (15)0.28657 (11)0.0692 (2)0.0226 (3)
C5'0.04548 (17)0.15317 (12)0.1110 (3)0.0319 (3)
H5'0.04380.22520.11740.038*
C6'0.07089 (17)0.08098 (13)0.2933 (3)0.0328 (3)
H6'0.00320.10540.42470.039*
C60.39230 (16)0.35490 (12)0.1439 (2)0.0261 (3)
H60.45040.33220.26480.031*
C70.33715 (17)0.45677 (13)0.1851 (2)0.0284 (3)
H70.35600.50350.33130.034*
C7A0.25502 (16)0.48561 (12)0.0046 (2)0.0267 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0475 (7)0.0333 (6)0.0375 (6)0.0211 (5)0.0073 (5)0.0013 (4)
O30.0516 (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)
C10.0228 (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)
C20.0374 (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)
C3A0.0249 (6)0.0274 (6)0.0261 (6)0.0086 (5)0.0026 (5)0.0063 (5)
C40.0252 (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)
C50.0201 (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)
C60.0249 (6)0.0275 (6)0.0236 (6)0.0038 (5)0.0013 (5)0.0055 (5)
C70.0295 (7)0.0276 (6)0.0249 (6)0.0039 (5)0.0056 (5)0.0002 (5)
C7A0.0254 (7)0.0233 (6)0.0319 (7)0.0067 (5)0.0091 (5)0.0043 (5)
Geometric parameters (Å, º) top
O1—C7A1.3748 (17)C2'—C3'1.3819 (18)
O1—C21.430 (2)C3'—C4'1.387 (2)
O3—C3A1.3720 (16)C3A—C41.3717 (19)
O3—C21.4339 (18)C3A—C7A1.384 (2)
N1'—C2'1.3359 (18)C4—C51.4055 (18)
N1'—C6'1.3404 (18)C4'—C5'1.375 (2)
N1''—C1''1.1403 (19)C5—C61.3853 (19)
C1—C1''1.4765 (19)C5'—C6'1.382 (2)
C1—C51.5264 (18)C6—C71.402 (2)
C1—C2'1.5332 (18)C7—C7A1.367 (2)
C7A—O1—C2105.72 (11)O3—C3A—C7A109.97 (12)
C3A—O3—C2105.56 (11)C3A—C4—C5116.53 (12)
C2'—N1'—C6'116.71 (12)C5'—C4'—C3'118.88 (13)
C1''—C1—C5110.09 (10)C6—C5—C4120.95 (12)
C1''—C1—C2'110.49 (11)C6—C5—C1119.29 (12)
C5—C1—C2'111.25 (10)C4—C5—C1119.76 (12)
N1''—C1''—C1178.35 (14)C6'—C5'—C4'118.66 (13)
O1—C2—O3107.98 (11)N1'—C6'—C5'123.63 (14)
N1'—C2'—C3'123.81 (12)C5—C6—C7121.46 (13)
N1'—C2'—C1115.68 (11)C7A—C7—C6116.79 (13)
C3'—C2'—C1120.43 (12)O1—C7A—C7128.36 (13)
C2'—C3'—C4'118.31 (13)O1—C7A—C3A109.75 (13)
C4—C3A—O3127.67 (12)C7—C7A—C3A121.88 (13)
C4—C3A—C7A122.35 (13)

Experimental details

Crystal data
Chemical formulaC14H10N2O2
Mr238.25
Crystal system, space groupTriclinic, 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)
V3)559.1 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.48 × 0.48 × 0.11
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2731, 2564, 1911
Rint0.050
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.139, 1.05
No. of reflections2564
No. of parameters163
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)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.

 

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