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access3′,4′-Dimethoxybiphenyl-4-carbonitrile
aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
*Correspondence e-mail: hljuchuwenyi@163.com
The title compound, C15H13NO2, was prepared through a palladium-catalysed Suzuki–Miyaura coupling reaction. The dihedral angle between the biphenyl rings is 40.96 (6)°. The methoxy groups are twisted slightly out of the plane of the benzene ring [C—C—C—C torsion angles = −3.61 (18) and 12.6 (2)°]. The packing of the molecules is stabilized by van der Waals interactions.
Related literature
For general background to the synthesis and properties of 3′,4′-dimethoxybiphenyl-4-carbonitrile, see: Suzuki (1999![[Suzuki, A. (1999). J. Organomet. Chem. 576, 147-168.]](../../../../../../logos/arrows/e_arr.gif "Suzuki, A. (1999). J. Organomet. Chem. 576, 147-168.")
); Razler et al. (2009); Hou et al. (2011). For the biological activity of biphenyl derivatives, see: Kimpe et al. (1996).
![[Scheme 1]](bx2401scheme1.gif)
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536812011464/bx2401sup1.cif
Supporting information file. DOI: 10.1107/S1600536812011464/bx2401Isup2.cdx
Structure factors: contains datablock I. DOI: 10.1107/S1600536812011464/bx2401Isup3.hkl
Supporting information file. DOI: 10.1107/S1600536812011464/bx2401Isup4.cml
To a solution of 4-bromobenzonitrile (5 mmol) and 3,4-dimethoxyphenylboronic acid (6 mmol) in 20 ml water and 20 ml methanol was added Pd(OAc)2 (5 mmol) and K2CO3 (10 mmol). After stirring the reaction mixture for 8 h at 318 K. The aqueous phases were extracted with 100 ml ethyl acetate. The organic extracts were washed with 200 ml saturated aqueous sodium chloride, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting crude material was purified via silica gel (petroleum ether) to afford a translucent solid in a yield of 76%. Crystals suitable for single-crystal X-ray diffraction were obtained by recrystallization from methanol at room temperature in a total yield of 36%. Analysis found: C 75.3, H 5.6, N 6.0%; C15H13NO2 requires: C 75.3, H 5.5, N 5.9%. 1H NMR (400 MHz, CDCl3) 7.78 (m, 2H), 7.64 (m, 2H), 7.17 (dd, J = 8.3, 2.1 Hz, 1H), 7.09 (d, J = 2.1 Hz, 1H), 6.97 (d, J = 8.3 Hz, 1H), 3.96 (s, 3H), 3.94 (s, 3H).
H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms. C—H distances are in the range 0.93-0.96 Å. Uiso(H) values were constrained to be 1.2Ueq(C) (aromatic H atoms) [1.5Ueq(C) for methyl H atoms].
Considerable interest shows the palladium-catalyzed Suzuki-Miyaura coupling reaction and the biological activity of biphenyl derivatives (Suzuki, 1999; Razler et al., 2009; Kimpe et al., 1996; Hou et al., 2011). We have prepare 3',4'-dimethoxybiphenyl-4 -carbonitrile as a potential antiviral activity compound. In the title compound, Fig. 1, the dihedral angle of the biphenyl moiety is 40.96 (6)°. The methoxy groups are slightly twisted out of the plane of the benzene ring 3.65 (12) & 12.40 (13)° at C10 and C11 position respectively. The is stabilized by van der waals interactions.
For general background to the synthesis and properties of 3',4'-dimethoxybiphenyl-4-carbonitrile, see: Suzuki (1999); Razler et al. (2009); Hou et al. (2011). For the biological activity of biphenyl derivatives, see: Kimpe et al. (1996).
Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
![[Figure 1]](./bx2401fig1thm.gif) | Fig. 1. The molecular structure of the title compound I, with displacement ellipsoids drawn at the 50% probability level. |
| C15H13NO2 | F(000) = 504 |
| Mr = 239.26 | Dx = 1.274 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2577 reflections |
| a = 9.1568 (10) Å | θ = 2.9–25.8° |
| b = 7.7541 (8) Å | µ = 0.09 mm−1 |
| c = 17.6764 (19) Å | T = 295 K |
| β = 96.266 (1)° | Block, colorless |
| V = 1247.6 (2) Å3 | 0.32 × 0.30 × 0.26 mm |
| Z = 4 |
| Bruker SMART APEX CCD detector diffractometer | 2399 independent reflections |
| Radiation source: fine-focus sealed tube | 1839 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.020 |
| phi and ω scans | θmax = 26.0°, θmin = 2.9° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→11 |
| Tmin = 0.973, Tmax = 0.978 | k = −9→8 |
| 8149 measured reflections | l = −21→21 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
| wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.052P)2 + 0.1238P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 2399 reflections | Δρmax = 0.15 e Å−3 |
| 166 parameters | Δρmin = −0.12 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.017 (2) |
| C15H13NO2 | V = 1247.6 (2) Å3 |
| Mr = 239.26 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 9.1568 (10) Å | µ = 0.09 mm−1 |
| b = 7.7541 (8) Å | T = 295 K |
| c = 17.6764 (19) Å | 0.32 × 0.30 × 0.26 mm |
| β = 96.266 (1)° |
| Bruker SMART APEX CCD detector diffractometer | 2399 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1839 reflections with I > 2σ(I) |
| Tmin = 0.973, Tmax = 0.978 | Rint = 0.020 |
| 8149 measured reflections |
| R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
| wR(F2) = 0.104 | H-atom parameters constrained |
| S = 1.05 | Δρmax = 0.15 e Å−3 |
| 2399 reflections | Δρmin = −0.12 e Å−3 |
| 166 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 | ||
| O3 | 0.14237 (10) | 0.09170 (14) | 0.04364 (6) | 0.0626 (3) | |
| C8 | 0.55897 (13) | 0.10197 (17) | 0.16381 (6) | 0.0431 (3) | |
| C9 | 0.51177 (13) | −0.03577 (17) | 0.11570 (6) | 0.0420 (3) | |
| H9 | 0.5753 | −0.1271 | 0.1096 | 0.050* | |
| C5 | 0.70869 (13) | 0.10066 (16) | 0.20533 (7) | 0.0432 (3) | |
| C10 | 0.37226 (13) | −0.03711 (17) | 0.07734 (6) | 0.0425 (3) | |
| O2 | 0.31442 (9) | −0.16798 (13) | 0.03141 (5) | 0.0546 (3) | |
| C11 | 0.27761 (13) | 0.10261 (18) | 0.08472 (7) | 0.0475 (3) | |
| C13 | 0.46307 (14) | 0.23659 (19) | 0.17187 (8) | 0.0526 (4) | |
| H13 | 0.4923 | 0.3277 | 0.2043 | 0.063* | |
| C4 | 0.82954 (14) | 0.04428 (19) | 0.17115 (8) | 0.0520 (4) | |
| H4 | 0.8170 | 0.0075 | 0.1208 | 0.062* | |
| C3 | 0.96813 (15) | 0.04188 (19) | 0.21075 (9) | 0.0568 (4) | |
| H3 | 1.0483 | 0.0055 | 0.1869 | 0.068* | |
| C12 | 0.32371 (15) | 0.23763 (19) | 0.13225 (8) | 0.0554 (4) | |
| H12 | 0.2609 | 0.3300 | 0.1378 | 0.066* | |
| C6 | 0.73122 (15) | 0.15651 (19) | 0.28075 (7) | 0.0522 (3) | |
| H6 | 0.6519 | 0.1970 | 0.3043 | 0.063* | |
| C7 | 0.86821 (15) | 0.1529 (2) | 0.32089 (8) | 0.0585 (4) | |
| H7 | 0.8809 | 0.1900 | 0.3712 | 0.070* | |
| C2 | 0.98743 (15) | 0.09404 (18) | 0.28652 (8) | 0.0552 (4) | |
| C14 | 0.40771 (15) | −0.30952 (19) | 0.01883 (8) | 0.0569 (4) | |
| H14A | 0.4924 | −0.2685 | −0.0033 | 0.085* | |
| H14B | 0.3552 | −0.3904 | −0.0152 | 0.085* | |
| H14C | 0.4384 | −0.3652 | 0.0664 | 0.085* | |
| C15 | 0.05399 (16) | 0.2429 (2) | 0.03800 (10) | 0.0692 (5) | |
| H15A | 0.0321 | 0.2764 | 0.0878 | 0.104* | |
| H15B | −0.0359 | 0.2199 | 0.0064 | 0.104* | |
| H15C | 0.1061 | 0.3343 | 0.0160 | 0.104* | |
| C1 | 1.13159 (18) | 0.0889 (2) | 0.32852 (10) | 0.0703 (5) | |
| N1 | 1.24412 (18) | 0.0863 (2) | 0.36292 (10) | 0.1005 (6) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O3 | 0.0425 (5) | 0.0668 (7) | 0.0749 (7) | 0.0073 (5) | −0.0095 (4) | −0.0125 (5) |
| C8 | 0.0431 (7) | 0.0452 (8) | 0.0406 (6) | −0.0020 (6) | 0.0025 (5) | −0.0018 (5) |
| C9 | 0.0407 (7) | 0.0414 (7) | 0.0437 (6) | 0.0013 (5) | 0.0044 (5) | −0.0018 (5) |
| C5 | 0.0457 (7) | 0.0389 (7) | 0.0440 (7) | −0.0037 (5) | 0.0001 (5) | −0.0005 (5) |
| C10 | 0.0433 (7) | 0.0435 (7) | 0.0405 (6) | −0.0040 (6) | 0.0042 (5) | −0.0042 (5) |
| O2 | 0.0467 (5) | 0.0526 (6) | 0.0624 (6) | −0.0005 (4) | −0.0030 (4) | −0.0167 (4) |
| C11 | 0.0381 (6) | 0.0545 (8) | 0.0489 (7) | 0.0007 (6) | 0.0001 (5) | −0.0031 (6) |
| C13 | 0.0518 (8) | 0.0512 (9) | 0.0536 (8) | 0.0016 (6) | −0.0002 (6) | −0.0143 (6) |
| C4 | 0.0487 (8) | 0.0546 (9) | 0.0515 (7) | −0.0009 (6) | 0.0000 (6) | −0.0093 (6) |
| C3 | 0.0471 (8) | 0.0523 (9) | 0.0700 (9) | 0.0002 (6) | 0.0014 (6) | −0.0052 (7) |
| C12 | 0.0479 (7) | 0.0523 (9) | 0.0650 (9) | 0.0094 (6) | 0.0022 (6) | −0.0118 (7) |
| C6 | 0.0526 (7) | 0.0568 (9) | 0.0466 (7) | −0.0028 (7) | 0.0023 (6) | −0.0042 (6) |
| C7 | 0.0647 (9) | 0.0609 (10) | 0.0467 (7) | −0.0092 (7) | −0.0077 (7) | −0.0009 (6) |
| C2 | 0.0519 (8) | 0.0429 (8) | 0.0665 (9) | −0.0068 (6) | −0.0128 (7) | 0.0069 (6) |
| C14 | 0.0606 (8) | 0.0495 (9) | 0.0602 (8) | 0.0003 (7) | 0.0044 (7) | −0.0145 (6) |
| C15 | 0.0512 (8) | 0.0735 (11) | 0.0792 (10) | 0.0127 (8) | −0.0097 (7) | 0.0050 (8) |
| C1 | 0.0652 (10) | 0.0561 (10) | 0.0830 (11) | −0.0044 (8) | −0.0216 (9) | 0.0080 (8) |
| N1 | 0.0749 (10) | 0.0913 (12) | 0.1230 (14) | −0.0034 (9) | −0.0452 (10) | 0.0111 (10) |
| O3—C11 | 1.3681 (15) | C4—H4 | 0.9300 |
| O3—C15 | 1.4217 (18) | C3—C2 | 1.392 (2) |
| C8—C13 | 1.3814 (18) | C3—H3 | 0.9300 |
| C8—C9 | 1.4038 (17) | C12—H12 | 0.9300 |
| C8—C5 | 1.4828 (16) | C6—C7 | 1.3724 (18) |
| C9—C10 | 1.3794 (16) | C6—H6 | 0.9300 |
| C9—H9 | 0.9300 | C7—C2 | 1.383 (2) |
| C5—C4 | 1.3880 (18) | C7—H7 | 0.9300 |
| C5—C6 | 1.3954 (17) | C2—C1 | 1.4426 (19) |
| C10—O2 | 1.3695 (15) | C14—H14A | 0.9600 |
| C10—C11 | 1.4023 (18) | C14—H14B | 0.9600 |
| O2—C14 | 1.4231 (17) | C14—H14C | 0.9600 |
| C11—C12 | 1.3795 (19) | C15—H15A | 0.9600 |
| C13—C12 | 1.3870 (18) | C15—H15B | 0.9600 |
| C13—H13 | 0.9300 | C15—H15C | 0.9600 |
| C4—C3 | 1.3809 (18) | C1—N1 | 1.1381 (18) |
| C11—O3—C15 | 117.49 (11) | C11—C12—C13 | 120.43 (12) |
| C13—C8—C9 | 118.70 (11) | C11—C12—H12 | 119.8 |
| C13—C8—C5 | 121.20 (11) | C13—C12—H12 | 119.8 |
| C9—C8—C5 | 120.10 (11) | C7—C6—C5 | 121.27 (13) |
| C10—C9—C8 | 120.72 (11) | C7—C6—H6 | 119.4 |
| C10—C9—H9 | 119.6 | C5—C6—H6 | 119.4 |
| C8—C9—H9 | 119.6 | C6—C7—C2 | 120.02 (12) |
| C4—C5—C6 | 118.15 (11) | C6—C7—H7 | 120.0 |
| C4—C5—C8 | 121.65 (11) | C2—C7—H7 | 120.0 |
| C6—C5—C8 | 120.20 (11) | C7—C2—C3 | 119.67 (12) |
| O2—C10—C9 | 125.07 (11) | C7—C2—C1 | 120.31 (14) |
| O2—C10—C11 | 115.12 (11) | C3—C2—C1 | 120.01 (14) |
| C9—C10—C11 | 119.81 (11) | O2—C14—H14A | 109.5 |
| C10—O2—C14 | 117.66 (10) | O2—C14—H14B | 109.5 |
| O3—C11—C12 | 124.69 (12) | H14A—C14—H14B | 109.5 |
| O3—C11—C10 | 115.83 (11) | O2—C14—H14C | 109.5 |
| C12—C11—C10 | 119.46 (11) | H14A—C14—H14C | 109.5 |
| C8—C13—C12 | 120.83 (12) | H14B—C14—H14C | 109.5 |
| C8—C13—H13 | 119.6 | O3—C15—H15A | 109.5 |
| C12—C13—H13 | 119.6 | O3—C15—H15B | 109.5 |
| C3—C4—C5 | 121.05 (12) | H15A—C15—H15B | 109.5 |
| C3—C4—H4 | 119.5 | O3—C15—H15C | 109.5 |
| C5—C4—H4 | 119.5 | H15A—C15—H15C | 109.5 |
| C4—C3—C2 | 119.80 (14) | H15B—C15—H15C | 109.5 |
| C4—C3—H3 | 120.1 | N1—C1—C2 | 178.6 (2) |
| C2—C3—H3 | 120.1 | ||
| C13—C8—C9—C10 | −0.17 (18) | C5—C8—C13—C12 | 179.36 (12) |
| C5—C8—C9—C10 | 179.33 (11) | C6—C5—C4—C3 | 0.6 (2) |
| C13—C8—C5—C4 | −139.90 (14) | C8—C5—C4—C3 | −179.25 (12) |
| C9—C8—C5—C4 | 40.61 (18) | C5—C4—C3—C2 | 1.0 (2) |
| C13—C8—C5—C6 | 40.26 (18) | O3—C11—C12—C13 | 179.70 (13) |
| C9—C8—C5—C6 | −139.23 (13) | C10—C11—C12—C13 | 0.7 (2) |
| C8—C9—C10—O2 | −177.57 (11) | C8—C13—C12—C11 | 0.9 (2) |
| C8—C9—C10—C11 | 1.74 (18) | C4—C5—C6—C7 | −1.3 (2) |
| C9—C10—O2—C14 | −3.61 (18) | C8—C5—C6—C7 | 178.53 (12) |
| C11—C10—O2—C14 | 177.05 (11) | C5—C6—C7—C2 | 0.4 (2) |
| C15—O3—C11—C12 | 12.6 (2) | C6—C7—C2—C3 | 1.2 (2) |
| C15—O3—C11—C10 | −168.41 (13) | C6—C7—C2—C1 | −179.64 (14) |
| O2—C10—C11—O3 | −1.71 (16) | C4—C3—C2—C7 | −2.0 (2) |
| C9—C10—C11—O3 | 178.92 (11) | C4—C3—C2—C1 | 178.93 (14) |
| O2—C10—C11—C12 | 177.36 (12) | C7—C2—C1—N1 | 0 (7) |
| C9—C10—C11—C12 | −2.01 (19) | C3—C2—C1—N1 | 179 (100) |
| C9—C8—C13—C12 | −1.1 (2) |
Experimental details
| Crystal data | |
| Chemical formula | C15H13NO2 |
| Mr | 239.26 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 295 |
| a, b, c (Å) | 9.1568 (10), 7.7541 (8), 17.6764 (19) |
| β (°) | 96.266 (1) |
| V (Å3) | 1247.6 (2) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.09 |
| Crystal size (mm) | 0.32 × 0.30 × 0.26 |
| Data collection | |
| Diffractometer | Bruker SMART APEX CCD detector |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
| Tmin, Tmax | 0.973, 0.978 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 8149, 2399, 1839 |
| Rint | 0.020 |
| (sin θ/λ)max (Å−1) | 0.617 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.104, 1.05 |
| No. of reflections | 2399 |
| No. of parameters | 166 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.15, −0.12 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).
Acknowledgements
We thank the National Natural Science Foundation of China (No. 20872030), the Foundation of Heilongjiang Education Committee (No. 12511383) and the Key Laboratory of Chemical Engineering Processes and Technology for High-efficiency Conversion, College of Heilongjiang Province and Heilongjiang University, China, for supporting this study.
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Considerable interest shows the palladium-catalyzed Suzuki-Miyaura coupling reaction and the biological activity of biphenyl derivatives (Suzuki, 1999; Razler et al., 2009; Kimpe et al., 1996; Hou et al., 2011). We have prepare 3',4'-dimethoxybiphenyl-4 -carbonitrile as a potential antiviral activity compound. In the title compound, Fig. 1, the dihedral angle of the biphenyl moiety is 40.96 (6)°. The methoxy groups are slightly twisted out of the plane of the benzene ring 3.65 (12) & 12.40 (13)° at C10 and C11 position respectively. The crystal structure is stabilized by van der waals interactions.