Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051732/at2429sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051732/at2429Isup2.hkl |
CCDC reference: 656519
The mixture containing piperonaldehyde (1.5 g, 10 mmol) and 4-chloroaniline (1.27 g, 10 mmol) was refluxed for about 6 h in ethanol, then borohydride sodium(1.52 g, 40 mmol) was added and refluxed continuely for about 2 h, then acetone (20 ml) and water (40 ml) were added in turn, and the reaction mixture was cooled and the products were filtered off, washed with ethanol and dried. Colourless crystals of (I) suitatble for X-ray structure analysis were obtained by recrystallizing the crude product from ethanol.(m.p.362–363 K).
All H atoms were located in difference Fourier maps. H atoms bonded to C and N atoms were treated as riding atoms, with C—H distances of 0.93 Å (aryl), 0.97 Å (methylene), N—H distances of 0.86 Å (amino), and with Uiso(H) = 1.2Ueq(C,N) (aryl, methylene, amino).
We have reported recently the crystyl structure of an aniline derives (Yang et al., 2007). As part of our study of the aniline derives, we report here the crystal structures of (I) (Fig.1).
The title compound (I), crystallizes in the orthorhombic space group Pca21 with Z = 4. In (I), the dihedral angle between the two benzene rings are 60.1 (1)°. Geometric parameters of (I) are normal (Allen et al., 1987) and selected geometric parameters are listed in the Table 1. The aniline N1—C9 bonds length is 1.387 (6) Å, slightly shorter than the aniline C—N bonds of the analogs reported (C—N = 1.396 Å, Silversides et al., 2006; C—N = 1.414 Å, Koşar et al., 2004; C—N = 1.396 (5) Å, Yang et al., 2007), this is probably due to the inductive negative effect of the halogen atom on the aryl residue.
In the crystal structure of (I), the molecules are linked by one C—H···Cl hydrogen bond into a simple C(13) chain (Bernstein et al., 1995) running parallel to the [010] direction. The atom C8 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H8a, to the atom Cl1 in the molecule at (x, -1 + y, z). These chains are linked by further C—H···π and C—H···Cl hydrogen bonds, resulting in a three-dimensional network structure (Table 2 and Fig. 2).
For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Koşar et al. (2004); Silversides et al. (2006); Yang et al. (2007).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
C14H12ClNO2 | Dx = 1.443 Mg m−3 |
Mr = 261.70 | Melting point: 362 K |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 904 reflections |
a = 14.4986 (13) Å | θ = 2.8–25.2° |
b = 13.9962 (14) Å | µ = 0.31 mm−1 |
c = 5.9375 (8) Å | T = 298 K |
V = 1204.9 (2) Å3 | Needle, colourless |
Z = 4 | 0.24 × 0.11 × 0.07 mm |
F(000) = 544 |
Bruker SMART CCD area-detector diffractometer | 2001 independent reflections |
Radiation source: fine-focus sealed tube | 1217 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
φ and ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→12 |
Tmin = 0.930, Tmax = 0.979 | k = −16→15 |
4750 measured reflections | l = −7→6 |
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)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0563P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.91 | (Δ/σ)max < 0.001 |
2001 reflections | Δρmax = 0.30 e Å−3 |
163 parameters | Δρmin = −0.21 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 848 Freidel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (13) |
C14H12ClNO2 | V = 1204.9 (2) Å3 |
Mr = 261.70 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 14.4986 (13) Å | µ = 0.31 mm−1 |
b = 13.9962 (14) Å | T = 298 K |
c = 5.9375 (8) Å | 0.24 × 0.11 × 0.07 mm |
Bruker SMART CCD area-detector diffractometer | 2001 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1217 reflections with I > 2σ(I) |
Tmin = 0.930, Tmax = 0.979 | Rint = 0.079 |
4750 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.130 | Δρmax = 0.30 e Å−3 |
S = 0.91 | Δρmin = −0.21 e Å−3 |
2001 reflections | Absolute structure: Flack (1983), 848 Freidel pairs |
163 parameters | Absolute structure parameter: −0.02 (13) |
1 restraint |
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 | ||
Cl1 | 0.37654 (9) | 1.15071 (8) | 1.1159 (3) | 0.0662 (5) | |
N1 | 0.3911 (3) | 0.7548 (3) | 0.7777 (7) | 0.0531 (10) | |
H1 | 0.4207 | 0.7130 | 0.8556 | 0.064* | |
O1 | 0.3321 (3) | 0.3804 (2) | 0.7531 (7) | 0.0641 (10) | |
O2 | 0.3978 (2) | 0.3355 (2) | 0.4179 (7) | 0.0639 (11) | |
C1 | 0.3476 (3) | 0.7259 (3) | 0.5713 (10) | 0.0566 (14) | |
H1a | 0.3718 | 0.7640 | 0.4482 | 0.068* | |
H1b | 0.2818 | 0.7378 | 0.5815 | 0.068* | |
C2 | 0.3637 (3) | 0.6218 (3) | 0.5221 (9) | 0.0474 (12) | |
C3 | 0.3375 (3) | 0.5532 (3) | 0.6795 (8) | 0.0494 (14) | |
H3 | 0.3122 | 0.5707 | 0.8174 | 0.059* | |
C4 | 0.3501 (3) | 0.4608 (3) | 0.6250 (10) | 0.0448 (11) | |
C5 | 0.3891 (3) | 0.4328 (3) | 0.4238 (10) | 0.0476 (12) | |
C6 | 0.4156 (3) | 0.4980 (3) | 0.2673 (10) | 0.0517 (13) | |
H6 | 0.4412 | 0.4796 | 0.1303 | 0.062* | |
C7 | 0.4028 (3) | 0.5935 (3) | 0.3221 (9) | 0.0508 (13) | |
H7 | 0.4212 | 0.6400 | 0.2197 | 0.061* | |
C8 | 0.3467 (4) | 0.3028 (4) | 0.6030 (13) | 0.0714 (16) | |
H8a | 0.3799 | 0.2520 | 0.6792 | 0.086* | |
H8b | 0.2879 | 0.2776 | 0.5526 | 0.086* | |
C9 | 0.3864 (3) | 0.8482 (3) | 0.8544 (9) | 0.0451 (12) | |
C10 | 0.3341 (3) | 0.9186 (3) | 0.7439 (9) | 0.0509 (13) | |
H10 | 0.3014 | 0.9032 | 0.6141 | 0.061* | |
C11 | 0.3314 (3) | 1.0091 (3) | 0.8266 (10) | 0.0507 (13) | |
H11 | 0.2961 | 1.0547 | 0.7522 | 0.061* | |
C12 | 0.3785 (3) | 1.0349 (3) | 1.0138 (8) | 0.0476 (13) | |
C13 | 0.4303 (3) | 0.9661 (3) | 1.1291 (10) | 0.0476 (12) | |
H13 | 0.4620 | 0.9818 | 1.2601 | 0.057* | |
C14 | 0.4333 (3) | 0.8749 (3) | 1.0443 (8) | 0.0478 (13) | |
H14 | 0.4686 | 0.8294 | 1.1190 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0658 (8) | 0.0487 (7) | 0.0839 (11) | 0.0012 (6) | −0.0075 (9) | −0.0143 (8) |
N1 | 0.066 (3) | 0.038 (2) | 0.056 (3) | 0.0058 (19) | −0.009 (2) | 0.001 (2) |
O1 | 0.078 (3) | 0.050 (2) | 0.064 (2) | −0.003 (2) | 0.016 (2) | 0.010 (2) |
O2 | 0.070 (3) | 0.048 (2) | 0.074 (3) | −0.0013 (16) | 0.005 (2) | −0.006 (2) |
C1 | 0.073 (3) | 0.046 (3) | 0.051 (4) | −0.002 (2) | −0.006 (3) | −0.003 (3) |
C2 | 0.046 (3) | 0.047 (3) | 0.049 (3) | 0.000 (2) | −0.006 (2) | −0.002 (3) |
C3 | 0.051 (3) | 0.045 (3) | 0.052 (4) | 0.004 (2) | 0.004 (2) | −0.006 (2) |
C4 | 0.042 (3) | 0.048 (3) | 0.045 (3) | −0.0022 (19) | 0.003 (3) | −0.002 (3) |
C5 | 0.043 (3) | 0.038 (3) | 0.062 (4) | −0.003 (2) | −0.006 (3) | −0.011 (3) |
C6 | 0.052 (3) | 0.059 (3) | 0.045 (3) | −0.001 (2) | 0.011 (2) | −0.005 (3) |
C7 | 0.058 (3) | 0.048 (3) | 0.047 (3) | −0.007 (2) | 0.005 (2) | 0.001 (3) |
C8 | 0.080 (4) | 0.046 (3) | 0.088 (5) | −0.006 (2) | 0.013 (4) | 0.000 (4) |
C9 | 0.045 (3) | 0.045 (3) | 0.045 (3) | −0.004 (2) | −0.001 (2) | 0.000 (2) |
C10 | 0.053 (3) | 0.046 (3) | 0.054 (3) | 0.003 (2) | −0.012 (2) | −0.005 (3) |
C11 | 0.046 (3) | 0.041 (3) | 0.065 (4) | 0.005 (2) | −0.009 (3) | 0.002 (3) |
C12 | 0.035 (3) | 0.046 (3) | 0.061 (4) | −0.005 (2) | 0.000 (2) | −0.008 (3) |
C13 | 0.047 (3) | 0.052 (3) | 0.043 (3) | −0.004 (2) | −0.004 (3) | −0.002 (3) |
C14 | 0.050 (3) | 0.044 (3) | 0.049 (3) | 0.001 (2) | −0.005 (2) | 0.003 (2) |
N1—C9 | 1.387 (6) | C5—C6 | 1.358 (7) |
N1—C1 | 1.436 (6) | C6—C7 | 1.388 (6) |
N1—H1 | 0.8600 | C6—H6 | 0.9300 |
O1—C4 | 1.383 (6) | C7—H7 | 0.9300 |
O1—C8 | 1.420 (7) | C8—H8a | 0.9700 |
O2—C5 | 1.368 (5) | C8—H8b | 0.9700 |
O2—C8 | 1.402 (7) | C9—C14 | 1.368 (7) |
Cl1—C12 | 1.730 (4) | C9—C10 | 1.406 (6) |
C1—C2 | 1.504 (6) | C10—C11 | 1.359 (6) |
C1—H1a | 0.9700 | C10—H10 | 0.9300 |
C1—H1b | 0.9700 | C11—C12 | 1.354 (7) |
C2—C7 | 1.374 (7) | C11—H11 | 0.9300 |
C2—C3 | 1.393 (6) | C12—C13 | 1.400 (6) |
C3—C4 | 1.346 (6) | C13—C14 | 1.373 (6) |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.379 (8) | C14—H14 | 0.9300 |
C9—N1—C1 | 121.7 (4) | C2—C7—H7 | 118.8 |
C9—N1—H1 | 119.2 | C6—C7—H7 | 118.8 |
C1—N1—H1 | 119.2 | O2—C8—O1 | 108.7 (4) |
C4—O1—C8 | 104.5 (4) | O2—C8—H8a | 110.0 |
C5—O2—C8 | 104.8 (4) | O1—C8—H8a | 110.0 |
N1—C1—C2 | 111.7 (4) | O2—C8—H8b | 110.0 |
N1—C1—H1a | 109.3 | O1—C8—H8b | 110.0 |
C2—C1—H1b | 109.3 | H8a—C8—H8b | 108.3 |
N1—C1—H1b | 109.3 | C14—C9—N1 | 120.3 (5) |
C2—C1—H1b | 109.3 | C14—C9—C10 | 117.5 (5) |
H1a—C1—H1b | 107.9 | N1—C9—C10 | 122.2 (5) |
C7—C2—C3 | 119.6 (4) | C11—C10—C9 | 120.0 (5) |
C7—C2—C1 | 120.7 (5) | C11—C10—H10 | 120.0 |
C3—C2—C1 | 119.7 (5) | C9—C10—H10 | 120.0 |
C4—C3—C2 | 117.7 (4) | C12—C11—C10 | 122.1 (5) |
C4—C3—H3 | 121.2 | C12—C11—H11 | 118.9 |
C2—C3—H3 | 121.2 | C10—C11—H11 | 118.9 |
C3—C4—C5 | 122.5 (5) | C11—C12—C13 | 119.2 (4) |
C3—C4—O1 | 128.7 (5) | C11—C12—Cl1 | 122.0 (4) |
C5—C4—O1 | 108.8 (4) | C13—C12—Cl1 | 118.8 (4) |
C6—C5—O2 | 128.7 (5) | C14—C13—C12 | 118.5 (4) |
C6—C5—C4 | 121.2 (5) | C14—C13—H13 | 120.7 |
O2—C5—C4 | 110.1 (5) | C12—C13—H13 | 120.7 |
C5—C6—C7 | 116.7 (5) | C9—C14—C13 | 122.7 (5) |
C5—C6—H6 | 121.7 | C9—C14—H14 | 118.6 |
C7—C6—H6 | 121.7 | C13—C14—H14 | 118.6 |
C2—C7—C6 | 122.4 (5) | ||
C9—N1—C1—C2 | 179.0 (4) | C1—C2—C7—C6 | −177.6 (4) |
N1—C1—C2—C7 | −124.2 (5) | C5—C6—C7—C2 | −1.2 (7) |
N1—C1—C2—C3 | 56.8 (6) | C5—O2—C8—O1 | −17.6 (6) |
C7—C2—C3—C4 | −1.4 (7) | C4—O1—C8—O2 | 17.3 (5) |
C1—C2—C3—C4 | 177.6 (4) | C1—N1—C9—C14 | −175.9 (5) |
C2—C3—C4—C5 | 1.3 (7) | C1—N1—C9—C10 | 4.4 (7) |
C2—C3—C4—O1 | 178.1 (4) | C14—C9—C10—C11 | −0.1 (7) |
C8—O1—C4—C3 | 172.6 (5) | N1—C9—C10—C11 | 179.6 (5) |
C8—O1—C4—C5 | −10.3 (5) | C9—C10—C11—C12 | 0.5 (8) |
C8—O2—C5—C6 | −171.0 (5) | C10—C11—C12—C13 | −1.3 (8) |
C8—O2—C5—C4 | 11.1 (5) | C10—C11—C12—Cl1 | 178.9 (4) |
C3—C4—C5—C6 | −1.2 (8) | O2i—Cl1—C12—C11 | 167.7 (5) |
O1—C4—C5—C6 | −178.5 (4) | O2i—Cl1—C12—C13 | −12.2 (10) |
C3—C4—C5—O2 | 176.9 (4) | C11—C12—C13—C14 | 1.6 (7) |
O1—C4—C5—O2 | −0.4 (5) | Cl1—C12—C13—C14 | −178.5 (3) |
O2—C5—C6—C7 | −176.7 (4) | N1—C9—C14—C13 | −179.3 (4) |
C4—C5—C6—C7 | 1.0 (7) | C10—C9—C14—C13 | 0.5 (7) |
C3—C2—C7—C6 | 1.4 (7) | C12—C13—C14—C9 | −1.2 (7) |
Symmetry code: (i) x, y+1, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8a···Cl1ii | 0.97 | 2.96 | 3.741 (7) | 139 |
C11—H11···Cl1iii | 0.93 | 2.95 | 3.819 (5) | 155 |
C8—H8b···Cl1iv | 0.97 | 3.00 | 3.874 (5) | 151 |
C6—H6···Cg1v | 0.93 | 2.80 | 3.50 (2) | 133 |
C13—H13···Cg2vi | 0.93 | 2.70 | 3.51 (2) | 146 |
Symmetry codes: (ii) x, y−1, z; (iii) −x+1/2, y, z−1/2; (iv) −x+1/2, y−1, z−1/2; (v) −x+1, −y+1, z−1/2; (vi) −x+1, −y+2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H12ClNO2 |
Mr | 261.70 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 298 |
a, b, c (Å) | 14.4986 (13), 13.9962 (14), 5.9375 (8) |
V (Å3) | 1204.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.24 × 0.11 × 0.07 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.930, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4750, 2001, 1217 |
Rint | 0.079 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.130, 0.91 |
No. of reflections | 2001 |
No. of parameters | 163 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.21 |
Absolute structure | Flack (1983), 848 Freidel pairs |
Absolute structure parameter | −0.02 (13) |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8a···Cl1i | 0.97 | 2.96 | 3.741 (7) | 138.7 |
C11—H11···Cl1ii | 0.93 | 2.95 | 3.819 (5) | 155.4 |
C8—H8b···Cl1iii | 0.97 | 3.00 | 3.874 (5) | 151.1 |
C6—H6···Cg1iv | 0.93 | 2.80 | 3.50 (2) | 132.5 |
C13—H13···Cg2v | 0.93 | 2.70 | 3.51 (2) | 146.0 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y, z−1/2; (iii) −x+1/2, y−1, z−1/2; (iv) −x+1, −y+1, z−1/2; (v) −x+1, −y+2, z+1/2. |
We have reported recently the crystyl structure of an aniline derives (Yang et al., 2007). As part of our study of the aniline derives, we report here the crystal structures of (I) (Fig.1).
The title compound (I), crystallizes in the orthorhombic space group Pca21 with Z = 4. In (I), the dihedral angle between the two benzene rings are 60.1 (1)°. Geometric parameters of (I) are normal (Allen et al., 1987) and selected geometric parameters are listed in the Table 1. The aniline N1—C9 bonds length is 1.387 (6) Å, slightly shorter than the aniline C—N bonds of the analogs reported (C—N = 1.396 Å, Silversides et al., 2006; C—N = 1.414 Å, Koşar et al., 2004; C—N = 1.396 (5) Å, Yang et al., 2007), this is probably due to the inductive negative effect of the halogen atom on the aryl residue.
In the crystal structure of (I), the molecules are linked by one C—H···Cl hydrogen bond into a simple C(13) chain (Bernstein et al., 1995) running parallel to the [010] direction. The atom C8 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H8a, to the atom Cl1 in the molecule at (x, -1 + y, z). These chains are linked by further C—H···π and C—H···Cl hydrogen bonds, resulting in a three-dimensional network structure (Table 2 and Fig. 2).