

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042158/si2032sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042158/si2032Isup2.hkl |
CCDC reference: 642432
The title compound, (I) was synthesized starting from 4-nitrobenzyl(triphenyl) phosphonium chlorine (II) (2.2 mmol), which was obtained by reacting 4-nitrobenzyl chlorine with triphenylphosphite (Shi et al., 2002), In compound (II), 4-nitrobenzaldehyde (2.0 mmol) and NaOH (3.0 mmol) were added to. The mixture was thoroughly ground in an open mortar at room temperature, next it was heated about 15 min at 45–50° C in an oven, and next it was ground again for 1–2 min. Above-mentioned procedure was repeated until the reaction was completed by TLC monitoring. After the mixture was cooled down to the room temperature, water (20 ml) was added to. Then the mixture was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate. Subsequently it was filtered and concentrated. The yellow product was collected and then was purified by column chromatography on silica gel (petroleum ether/ethyl acetate, 40:1). Suitable crystals of the title compound were obtained by evaporation of an acetonitrile solution, yield: 7.5% (based on 4-nitrobenzaldehyde). IR (cm-1, KBr, pellet): v(C=C) 3081(m), 1591(s), 1488(s), 715(s). 1HNMR (CDCl3)(400 MHz; TMS p.p.m.), δ(p.p.m.): 6.83(s, 2H, –C=C–), 7.24–7.35(m, 4H, Ar), 8.10–8.12(d, 4H, Ar).
H atoms bonded to C were located geometrically; they were treated as riding, with distances C—H = 0.93 Å and Uiso(H)=1.2 times Ueq(C).
In recent years, the stilbene and its derivatives have been the subject of many photophysical investigations (Albota et al., 1998; Reinhardt et al., 1998). Many researches have been directed toward the synthesis of geometrically pure stilbenes, and many perfect methods have been developed (Cella et al., 2006; Ferré-Filmon et al., 2004; Jeffery et al., 2003). Though a number of 4,4'-disubstituted stilbenes are obtained easily, and some trans-stilbene derivatives had been crystallographically characterized (Hulliger et al., 2002; De Borger et al., 2005; Zhang et al., 2005), the crystal stuctures of cis-stilbene derivatives (Traetteberg et al.,1975; Tirado-Rives et al., 1984) has been seldom reported up to the precent, and it is still a challenge topic.
The molecular structure of the title compound is illustrated in Fig. 1, where the molecule adopts a cis configuration with two aryl groups of cis-stilbene resideing on the same side. The bond angles (Table 1) <C(14)—C(13)—C(4) (129.41 (14)°) and <C(13)—C(14)—C(10) (128.71 (13)°) severely deviate from 120° due to the comparatively strong steric hindrance between the two aryl groups. There is a dihedral angle of 56.67° between two planes defined by N(1)/O(1)/O(2)/C(1)—C(6)/C(13) and N(2)/O(3)/O(4)/C(7)—C(12)/C(14). The torsion angles of C(3)—C(4)—C(13)—C(14) (149.55 (16)°) and C(9)—C(10)—C(14)—C(13) (138.17 (17)°) are also significantly deviated from 180°, which indicates that the whole molecule is non-coplanar.
Within the cell of the crystal structure, the molecules are held together by hydrogen bonding interactions (Fig. 2), where the phenyl groups donate hydrogen atoms (H(2) and H(9)) to the oxygen atoms (O(3) and O(4)) to form weak non-classical intermolecular C—H···O hydrogen bonds (Table 2).
For synthesis of geometrically pure (cis or trans) stilbenes, see: Cella & Stefani (2006); Ferré-Filmon et al. (2004); Jeffery & Ferber (2003); Shi & Xu (2002). For photophysical investigations on stilbenes and their derivatives, see: Albota et al. (1998); Reinhardt et al. (1998). For related trans-stilbene structures, see: Hulliger et al. (2002); De Borger et al. (2005); Zhang et al. (2005). For rarely reported cis-stilbene structures, see: Traetteberg & Frantsen (1975); Tirado-Rives et al. (1984).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2003).
C14H10N2O4 | F(000) = 560 |
Mr = 270.24 | Dx = 1.426 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 195 reflections |
a = 6.8922 (4) Å | θ = 2.0–27.5° |
b = 22.8669 (13) Å | µ = 0.11 mm−1 |
c = 8.0727 (5) Å | T = 298 K |
β = 98.469 (2)° | Block, yellow |
V = 1258.41 (13) Å3 | 0.50 × 0.20 × 0.19 mm |
Z = 4 |
Bruker SMART CCD APEXII diffractometer | 2951 independent reflections |
Radiation source: fine-focus sealed tube | 2179 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 8.4 pixels mm-1 | θmax = 27.8°, θmin = 1.8° |
ω scans | h = −9→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | k = −26→29 |
Tmin = 0.973, Tmax = 0.981 | l = −10→9 |
9077 measured reflections |
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) = 0.116 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0487P)2 + 0.1997P] where P = (Fo2 + 2Fc2)/3 |
2951 reflections | (Δ/σ)max = 0.001 |
182 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C14H10N2O4 | V = 1258.41 (13) Å3 |
Mr = 270.24 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.8922 (4) Å | µ = 0.11 mm−1 |
b = 22.8669 (13) Å | T = 298 K |
c = 8.0727 (5) Å | 0.50 × 0.20 × 0.19 mm |
β = 98.469 (2)° |
Bruker SMART CCD APEXII diffractometer | 2951 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 2179 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.981 | Rint = 0.019 |
9077 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.19 e Å−3 |
2951 reflections | Δρmin = −0.16 e Å−3 |
182 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 | ||
C1 | 0.2049 (2) | 0.73977 (6) | 0.61613 (16) | 0.0503 (3) | |
N2 | 0.74204 (17) | 0.46581 (6) | 1.07266 (16) | 0.0558 (3) | |
C12 | 0.7579 (2) | 0.56150 (6) | 0.93698 (17) | 0.0509 (3) | |
H12A | 0.7621 | 0.5794 | 1.0409 | 0.061* | |
C7 | 0.74826 (19) | 0.50148 (6) | 0.92206 (16) | 0.0461 (3) | |
C6 | 0.2168 (2) | 0.67990 (6) | 0.63390 (18) | 0.0511 (3) | |
H6A | 0.1232 | 0.6594 | 0.6824 | 0.061* | |
N1 | 0.0403 (2) | 0.77052 (6) | 0.67462 (16) | 0.0642 (4) | |
C2 | 0.3426 (2) | 0.77145 (6) | 0.54582 (18) | 0.0576 (4) | |
H2A | 0.3333 | 0.8119 | 0.5367 | 0.069* | |
C5 | 0.3704 (2) | 0.65114 (6) | 0.57828 (18) | 0.0510 (3) | |
H5A | 0.3801 | 0.6107 | 0.5900 | 0.061* | |
O2 | −0.07476 (19) | 0.74209 (6) | 0.74400 (18) | 0.0808 (4) | |
C10 | 0.75668 (19) | 0.56807 (6) | 0.63870 (17) | 0.0467 (3) | |
C11 | 0.7613 (2) | 0.59447 (6) | 0.79455 (18) | 0.0517 (3) | |
H11A | 0.7667 | 0.6350 | 0.8027 | 0.062* | |
C4 | 0.5118 (2) | 0.68122 (6) | 0.50478 (16) | 0.0479 (3) | |
O4 | 0.7539 (2) | 0.49014 (6) | 1.20713 (14) | 0.0825 (4) | |
C9 | 0.7531 (2) | 0.50730 (6) | 0.63014 (18) | 0.0553 (4) | |
H9A | 0.7554 | 0.4890 | 0.5275 | 0.066* | |
C13 | 0.6705 (2) | 0.65123 (7) | 0.43457 (18) | 0.0557 (4) | |
H13A | 0.7087 | 0.6689 | 0.3407 | 0.067* | |
C8 | 0.7464 (2) | 0.47360 (6) | 0.77084 (19) | 0.0558 (4) | |
H8A | 0.7408 | 0.4330 | 0.7637 | 0.067* | |
C3 | 0.4939 (2) | 0.74179 (6) | 0.48956 (18) | 0.0558 (4) | |
H3A | 0.5863 | 0.7626 | 0.4403 | 0.067* | |
C14 | 0.7668 (2) | 0.60270 (6) | 0.48576 (18) | 0.0547 (4) | |
H14A | 0.8520 | 0.5886 | 0.4159 | 0.066* | |
O3 | 0.7226 (2) | 0.41327 (5) | 1.05662 (17) | 0.0904 (5) | |
O1 | 0.0264 (3) | 0.82307 (6) | 0.6530 (2) | 0.1119 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0558 (8) | 0.0524 (8) | 0.0401 (7) | 0.0075 (6) | −0.0014 (6) | 0.0029 (6) |
N2 | 0.0534 (7) | 0.0586 (8) | 0.0569 (8) | 0.0048 (6) | 0.0129 (5) | 0.0068 (6) |
C12 | 0.0553 (8) | 0.0506 (8) | 0.0465 (7) | 0.0015 (6) | 0.0065 (6) | −0.0062 (6) |
C7 | 0.0421 (7) | 0.0482 (7) | 0.0481 (7) | 0.0033 (5) | 0.0070 (5) | 0.0044 (6) |
C6 | 0.0507 (8) | 0.0504 (8) | 0.0512 (8) | −0.0043 (6) | 0.0040 (6) | 0.0036 (6) |
N1 | 0.0750 (9) | 0.0613 (8) | 0.0553 (7) | 0.0157 (7) | 0.0059 (6) | 0.0005 (6) |
C2 | 0.0779 (11) | 0.0422 (7) | 0.0512 (8) | 0.0033 (7) | 0.0042 (7) | 0.0103 (6) |
C5 | 0.0537 (8) | 0.0424 (7) | 0.0559 (8) | −0.0028 (6) | 0.0051 (6) | 0.0042 (6) |
O2 | 0.0701 (8) | 0.0792 (8) | 0.0976 (9) | 0.0015 (7) | 0.0268 (7) | −0.0105 (7) |
C10 | 0.0443 (7) | 0.0483 (7) | 0.0476 (7) | 0.0032 (6) | 0.0072 (5) | −0.0004 (6) |
C11 | 0.0595 (9) | 0.0410 (7) | 0.0545 (8) | 0.0008 (6) | 0.0074 (6) | −0.0025 (6) |
C4 | 0.0526 (8) | 0.0488 (7) | 0.0406 (6) | −0.0002 (6) | 0.0012 (5) | 0.0073 (5) |
O4 | 0.1144 (11) | 0.0847 (9) | 0.0501 (7) | −0.0059 (7) | 0.0176 (6) | 0.0030 (6) |
C9 | 0.0694 (10) | 0.0494 (8) | 0.0475 (8) | 0.0031 (7) | 0.0096 (7) | −0.0072 (6) |
C13 | 0.0613 (9) | 0.0585 (9) | 0.0491 (8) | −0.0027 (7) | 0.0138 (6) | 0.0099 (6) |
C8 | 0.0693 (10) | 0.0406 (7) | 0.0576 (8) | 0.0020 (6) | 0.0101 (7) | −0.0024 (6) |
C3 | 0.0639 (9) | 0.0515 (8) | 0.0515 (8) | −0.0042 (7) | 0.0074 (6) | 0.0155 (6) |
C14 | 0.0574 (9) | 0.0575 (9) | 0.0514 (8) | 0.0016 (7) | 0.0157 (6) | 0.0016 (6) |
O3 | 0.1400 (13) | 0.0519 (7) | 0.0849 (9) | 0.0025 (7) | 0.0352 (8) | 0.0156 (6) |
O1 | 0.1440 (14) | 0.0671 (8) | 0.1377 (14) | 0.0428 (9) | 0.0643 (12) | 0.0231 (8) |
C1—C6 | 1.378 (2) | C5—C4 | 1.3948 (19) |
C1—C2 | 1.381 (2) | C5—H5A | 0.93 |
C1—N1 | 1.4709 (19) | C10—C9 | 1.3913 (19) |
N2—O4 | 1.2119 (16) | C10—C11 | 1.3916 (19) |
N2—O3 | 1.2135 (17) | C10—C14 | 1.477 (2) |
N2—C7 | 1.4700 (18) | C11—H11A | 0.93 |
C12—C11 | 1.378 (2) | C4—C3 | 1.394 (2) |
C12—C7 | 1.3785 (19) | C4—C13 | 1.473 (2) |
C12—H12A | 0.93 | C9—C8 | 1.379 (2) |
C7—C8 | 1.376 (2) | C9—H9A | 0.93 |
C6—C5 | 1.376 (2) | C13—C14 | 1.327 (2) |
C6—H6A | 0.93 | C13—H13A | 0.93 |
N1—O1 | 1.2158 (17) | C8—H8A | 0.93 |
N1—O2 | 1.2231 (18) | C3—H3A | 0.93 |
C2—C3 | 1.376 (2) | C14—H14A | 0.93 |
C2—H2A | 0.93 | ||
C6—C1—C2 | 122.03 (14) | C9—C10—C11 | 118.43 (13) |
C6—C1—N1 | 118.60 (13) | C9—C10—C14 | 119.78 (13) |
C2—C1—N1 | 119.38 (13) | C11—C10—C14 | 121.70 (13) |
O4—N2—O3 | 122.82 (13) | C12—C11—C10 | 121.08 (13) |
O4—N2—C7 | 118.66 (13) | C12—C11—H11A | 119.5 |
O3—N2—C7 | 118.51 (13) | C10—C11—H11A | 119.5 |
C11—C12—C7 | 118.57 (13) | C3—C4—C5 | 117.97 (13) |
C11—C12—H12A | 120.7 | C3—C4—C13 | 119.32 (13) |
C7—C12—H12A | 120.7 | C5—C4—C13 | 122.61 (13) |
C8—C7—C12 | 122.21 (13) | C8—C9—C10 | 121.31 (13) |
C8—C7—N2 | 118.63 (13) | C8—C9—H9A | 119.3 |
C12—C7—N2 | 119.16 (12) | C10—C9—H9A | 119.3 |
C5—C6—C1 | 118.53 (13) | C14—C13—C4 | 129.41 (13) |
C5—C6—H6A | 120.7 | C14—C13—H13A | 115.3 |
C1—C6—H6A | 120.7 | C4—C13—H13A | 115.3 |
O1—N1—O2 | 123.27 (15) | C7—C8—C9 | 118.35 (13) |
O1—N1—C1 | 118.33 (15) | C7—C8—H8A | 120.8 |
O2—N1—C1 | 118.40 (13) | C9—C8—H8A | 120.8 |
C3—C2—C1 | 118.50 (13) | C2—C3—C4 | 121.48 (14) |
C3—C2—H2A | 120.8 | C2—C3—H3A | 119.3 |
C1—C2—H2A | 120.8 | C4—C3—H3A | 119.3 |
C6—C5—C4 | 121.48 (13) | C13—C14—C10 | 128.73 (13) |
C6—C5—H5A | 119.3 | C13—C14—H14A | 115.6 |
C4—C5—H5A | 119.3 | C10—C14—H14A | 115.6 |
C11—C12—C7—C8 | 1.5 (2) | C14—C10—C11—C12 | −177.96 (13) |
C11—C12—C7—N2 | −179.22 (12) | C6—C5—C4—C3 | 0.3 (2) |
O4—N2—C7—C8 | 176.23 (14) | C6—C5—C4—C13 | −176.04 (13) |
O3—N2—C7—C8 | −4.7 (2) | C11—C10—C9—C8 | 2.5 (2) |
O4—N2—C7—C12 | −3.1 (2) | C14—C10—C9—C8 | 179.12 (14) |
O3—N2—C7—C12 | 175.97 (14) | C3—C4—C13—C14 | 149.55 (16) |
C2—C1—C6—C5 | −0.5 (2) | C5—C4—C13—C14 | −34.2 (2) |
N1—C1—C6—C5 | 179.65 (12) | C12—C7—C8—C9 | −0.5 (2) |
C6—C1—N1—O1 | −177.33 (16) | N2—C7—C8—C9 | −179.73 (13) |
C2—C1—N1—O1 | 2.8 (2) | C10—C9—C8—C7 | −1.6 (2) |
C6—C1—N1—O2 | 3.4 (2) | C1—C2—C3—C4 | −1.1 (2) |
C2—C1—N1—O2 | −176.45 (14) | C5—C4—C3—C2 | 0.4 (2) |
C6—C1—C2—C3 | 1.1 (2) | C13—C4—C3—C2 | 176.81 (14) |
N1—C1—C2—C3 | −179.03 (12) | C4—C13—C14—C10 | −7.1 (3) |
C1—C6—C5—C4 | −0.2 (2) | C9—C10—C14—C13 | 138.17 (17) |
C7—C12—C11—C10 | −0.5 (2) | C11—C10—C14—C13 | −45.4 (2) |
C9—C10—C11—C12 | −1.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O3i | 0.93 | 2.45 | 3.3606 (18) | 166 |
C9—H9A···O4ii | 0.93 | 2.58 | 3.4381 (18) | 153 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C14H10N2O4 |
Mr | 270.24 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 6.8922 (4), 22.8669 (13), 8.0727 (5) |
β (°) | 98.469 (2) |
V (Å3) | 1258.41 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.50 × 0.20 × 0.19 |
Data collection | |
Diffractometer | Bruker SMART CCD APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.973, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9077, 2951, 2179 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.655 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.116, 1.05 |
No. of reflections | 2951 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.16 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2003).
C1—C6 | 1.378 (2) | C2—C3 | 1.376 (2) |
C1—C2 | 1.381 (2) | C5—C4 | 1.3948 (19) |
C1—N1 | 1.4709 (19) | C4—C3 | 1.394 (2) |
C6—C5 | 1.376 (2) | C4—C13 | 1.473 (2) |
N1—O1 | 1.2158 (17) | C13—C14 | 1.327 (2) |
N1—O2 | 1.2231 (18) | ||
C9—C10—C14 | 119.78 (13) | C5—C4—C13 | 122.61 (13) |
C11—C10—C14 | 121.70 (13) | C14—C13—C4 | 129.41 (13) |
C3—C4—C13 | 119.32 (13) | C13—C14—C10 | 128.73 (13) |
C3—C4—C13—C14 | 149.55 (16) | C9—C10—C14—C13 | 138.17 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O3i | 0.93 | 2.45 | 3.3606 (18) | 166 |
C9—H9A···O4ii | 0.93 | 2.58 | 3.4381 (18) | 153 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, y, z−1. |
In recent years, the stilbene and its derivatives have been the subject of many photophysical investigations (Albota et al., 1998; Reinhardt et al., 1998). Many researches have been directed toward the synthesis of geometrically pure stilbenes, and many perfect methods have been developed (Cella et al., 2006; Ferré-Filmon et al., 2004; Jeffery et al., 2003). Though a number of 4,4'-disubstituted stilbenes are obtained easily, and some trans-stilbene derivatives had been crystallographically characterized (Hulliger et al., 2002; De Borger et al., 2005; Zhang et al., 2005), the crystal stuctures of cis-stilbene derivatives (Traetteberg et al.,1975; Tirado-Rives et al., 1984) has been seldom reported up to the precent, and it is still a challenge topic.
The molecular structure of the title compound is illustrated in Fig. 1, where the molecule adopts a cis configuration with two aryl groups of cis-stilbene resideing on the same side. The bond angles (Table 1) <C(14)—C(13)—C(4) (129.41 (14)°) and <C(13)—C(14)—C(10) (128.71 (13)°) severely deviate from 120° due to the comparatively strong steric hindrance between the two aryl groups. There is a dihedral angle of 56.67° between two planes defined by N(1)/O(1)/O(2)/C(1)—C(6)/C(13) and N(2)/O(3)/O(4)/C(7)—C(12)/C(14). The torsion angles of C(3)—C(4)—C(13)—C(14) (149.55 (16)°) and C(9)—C(10)—C(14)—C(13) (138.17 (17)°) are also significantly deviated from 180°, which indicates that the whole molecule is non-coplanar.
Within the cell of the crystal structure, the molecules are held together by hydrogen bonding interactions (Fig. 2), where the phenyl groups donate hydrogen atoms (H(2) and H(9)) to the oxygen atoms (O(3) and O(4)) to form weak non-classical intermolecular C—H···O hydrogen bonds (Table 2).