Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006128/cf6165sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006128/cf6165Isup2.hkl |
CCDC reference: 185785
p-Phenylenediamine (0.81 g, 7.5 mmol) was dissolved in dehydrated methanol (50 ml). To this solution, freshly distilled 4-acetylpyridine (1.16 ml, 15 mmol) was added dropwise and then the reaction mixture was refluxed for 6 h, maintaining dry conditions. On evaporation of the solvent, a brown solid was obtained, which, on recrystallization from acetonitrile, gave light-brown needle-like crystals suitable for X-ray analysis. Yield 1.436 g (61%), m.p. 471–473 K. The product was characterized by elemental analyses as well as by 1H and 13C NMR spectra. Analysis found (calculated): C 76.43 (76.40%), H 5.71 (5.77%), N 17.89 (17.83%). 1H NMR (200 MHz, CDCl3, TMS): δ 8.76 (d, J = 4 Hz, 4H), 7.75 (d, J = 4 Hz, 4H), 7.33 (m, 4H), 2.29 (s, 6H, methyl H). 13C NMR (200 MHz, CDCl3, TMS): δ 164.54, 150.14, 149.61, 142.67, 122.24, 121.19, 15.66.
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski, 1985); data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
C20H18N4 | F(000) = 166 |
Mr = 314.38 | Dx = 1.287 Mg m−3 |
Triclinic, P1 | Melting point: 198-200 deg. C K |
a = 5.8900 (3) Å | Mo Kα radiation, λ = 0.71070 Å |
b = 8.0690 (3) Å | Cell parameters from 1279 reflections |
c = 8.8480 (5) Å | θ = 3.3–27.9° |
α = 94.7670 (18)° | µ = 0.08 mm−1 |
β = 92.0520 (18)° | T = 110 K |
γ = 104.1570 (17)° | Prism, light brown |
V = 405.65 (3) Å3 | 0.35 × 0.20 × 0.20 mm |
Z = 1 |
Nonius KappaCCD diffractometer | 1279 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 27.9°, θmin = 3.3° |
Detector resolution: 56 microns pixels mm-1 | h = 0→7 |
ϕ and ω scans | k = −10→10 |
1775 measured reflections | l = −11→11 |
1775 independent 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 0.88 | w = 1/[σ2(Fo2) + (0.0943P)2 + 0.2375P] where P = (Fo2 + 2Fc2)/3 |
1775 reflections | (Δ/σ)max = 0.017 |
110 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C20H18N4 | γ = 104.1570 (17)° |
Mr = 314.38 | V = 405.65 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.8900 (3) Å | Mo Kα radiation |
b = 8.0690 (3) Å | µ = 0.08 mm−1 |
c = 8.8480 (5) Å | T = 110 K |
α = 94.7670 (18)° | 0.35 × 0.20 × 0.20 mm |
β = 92.0520 (18)° |
Nonius KappaCCD diffractometer | 1279 reflections with I > 2σ(I) |
1775 measured reflections | Rint = 0.000 |
1775 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.22 e Å−3 |
1775 reflections | Δρmin = −0.23 e Å−3 |
110 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 | ||
N1 | 0.7027 (3) | 0.84831 (19) | 0.46098 (17) | 0.0251 (4) | |
C2 | 0.4989 (3) | 0.8073 (2) | 0.3773 (2) | 0.0252 (4) | |
H2 | 0.4084 | 0.8900 | 0.3778 | 0.030* | |
C3 | 0.8263 (3) | 0.7294 (2) | 0.45633 (19) | 0.0222 (4) | |
H3 | 0.9726 | 0.7555 | 0.5132 | 0.027* | |
C4 | 0.7534 (3) | 0.5697 (2) | 0.37323 (19) | 0.0199 (4) | |
H4 | 0.8481 | 0.4899 | 0.3743 | 0.024* | |
C5 | 0.5401 (3) | 0.5280 (2) | 0.28844 (18) | 0.0169 (4) | |
C6 | 0.4123 (3) | 0.6529 (2) | 0.2907 (2) | 0.0227 (4) | |
H6 | 0.2672 | 0.6317 | 0.2331 | 0.027* | |
C7 | 0.4466 (3) | 0.3570 (2) | 0.20043 (19) | 0.0186 (4) | |
C8 | 0.6123 (3) | 0.2431 (2) | 0.1772 (3) | 0.0338 (5) | |
H8A | 0.6386 | 0.1950 | 0.2726 | 0.051* | |
H8B | 0.7620 | 0.3105 | 0.1455 | 0.051* | |
H8C | 0.5443 | 0.1496 | 0.0985 | 0.051* | |
N9 | 0.2324 (2) | 0.32075 (17) | 0.15220 (16) | 0.0194 (3) | |
C10 | 0.1237 (3) | 0.1575 (2) | 0.07524 (18) | 0.0169 (4) | |
C11 | 0.0548 (3) | 0.1448 (2) | −0.07819 (18) | 0.0201 (4) | |
H11 | 0.0912 | 0.2442 | −0.1320 | 0.024* | |
C12 | 0.0661 (3) | 0.0107 (2) | 0.15348 (19) | 0.0208 (4) | |
H12 | 0.1101 | 0.0177 | 0.2586 | 0.025* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0269 (9) | 0.0218 (8) | 0.0248 (8) | 0.0049 (6) | −0.0007 (6) | −0.0034 (6) |
C2 | 0.0238 (9) | 0.0188 (9) | 0.0329 (10) | 0.0077 (7) | −0.0007 (7) | −0.0034 (8) |
C3 | 0.0213 (9) | 0.0233 (9) | 0.0198 (8) | 0.0030 (7) | −0.0032 (7) | −0.0009 (7) |
C4 | 0.0186 (9) | 0.0200 (9) | 0.0214 (8) | 0.0050 (6) | 0.0003 (6) | 0.0031 (7) |
C5 | 0.0159 (8) | 0.0163 (8) | 0.0173 (8) | 0.0019 (6) | 0.0022 (6) | 0.0008 (6) |
C6 | 0.0185 (9) | 0.0214 (9) | 0.0270 (9) | 0.0046 (6) | −0.0029 (7) | −0.0022 (7) |
C7 | 0.0165 (8) | 0.0181 (8) | 0.0204 (8) | 0.0036 (6) | 0.0008 (6) | 0.0001 (7) |
C8 | 0.0197 (9) | 0.0255 (10) | 0.0534 (13) | 0.0069 (7) | −0.0026 (9) | −0.0145 (9) |
N9 | 0.0181 (7) | 0.0156 (7) | 0.0233 (7) | 0.0038 (5) | −0.0023 (6) | −0.0027 (6) |
C10 | 0.0136 (8) | 0.0145 (8) | 0.0218 (8) | 0.0044 (6) | −0.0012 (6) | −0.0036 (6) |
C11 | 0.0220 (9) | 0.0168 (8) | 0.0206 (8) | 0.0030 (6) | 0.0001 (7) | 0.0018 (7) |
C12 | 0.0229 (9) | 0.0216 (9) | 0.0176 (8) | 0.0064 (7) | −0.0014 (6) | −0.0007 (7) |
N1—C2 | 1.342 (2) | C7—C8 | 1.503 (2) |
N1—C3 | 1.338 (2) | C8—H8A | 0.980 |
C2—C6 | 1.380 (2) | C8—H8B | 0.980 |
C2—H2 | 0.950 | C8—H8C | 0.980 |
C3—C4 | 1.391 (2) | N9—C10 | 1.420 (2) |
C3—H3 | 0.950 | C10—C11 | 1.391 (2) |
C4—C5 | 1.392 (2) | C10—C12 | 1.398 (2) |
C4—H4 | 0.950 | C11—C12i | 1.384 (2) |
C5—C6 | 1.397 (2) | C11—H11 | 0.950 |
C5—C7 | 1.494 (2) | C12—C11i | 1.384 (2) |
C6—H6 | 0.950 | C12—H12 | 0.950 |
C7—N9 | 1.273 (2) | ||
C2—N1—C3 | 116.17 (15) | C5—C7—C8 | 117.48 (14) |
N1—C2—C6 | 124.20 (16) | C7—C8—H8A | 109.5 |
N1—C2—H2 | 117.9 | C7—C8—H8B | 109.5 |
C6—C2—H2 | 117.9 | H8A—C8—H8B | 109.5 |
N1—C3—C4 | 123.92 (16) | C7—C8—H8C | 109.5 |
N1—C3—H3 | 118.0 | H8A—C8—H8C | 109.5 |
C4—C3—H3 | 118.0 | H8B—C8—H8C | 109.5 |
C3—C4—C5 | 119.30 (15) | C7—N9—C10 | 120.88 (14) |
C3—C4—H4 | 120.3 | C11—C10—C12 | 118.95 (15) |
C5—C4—H4 | 120.3 | C11—C10—N9 | 119.64 (14) |
C4—C5—C6 | 117.03 (15) | C12—C10—N9 | 121.18 (15) |
C4—C5—C7 | 122.34 (15) | C12i—C11—C10 | 120.86 (15) |
C6—C5—C7 | 120.62 (15) | C12i—C11—H11 | 119.6 |
C2—C6—C5 | 119.36 (16) | C10—C11—H11 | 119.6 |
C2—C6—H6 | 120.3 | C11i—C12—C10 | 120.18 (15) |
C5—C6—H6 | 120.3 | C11i—C12—H12 | 119.9 |
N9—C7—C5 | 116.66 (15) | C10—C12—H12 | 119.9 |
N9—C7—C8 | 125.86 (15) |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C20H18N4 |
Mr | 314.38 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 110 |
a, b, c (Å) | 5.8900 (3), 8.0690 (3), 8.8480 (5) |
α, β, γ (°) | 94.7670 (18), 92.0520 (18), 104.1570 (17) |
V (Å3) | 405.65 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.35 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1775, 1775, 1279 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.153, 0.88 |
No. of reflections | 1775 |
No. of parameters | 110 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.23 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski, 1985), DENZO, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.
The title compound, (I), is a 1 + 2 Schiff base ligand of p-phenylenediamine and 4-acetylpyridine, with two peripheral pyridine and two inner imino N atoms. This type of ligand is being extensively used as bridging spacers in the design of supramolecular metallo-organic hybrid polymers (Patra & Goldberg, 2002; Diskin-Posner et al., 2001; Fei et al., 2001). Here we report on the synthesis and structure (at low temperature) of a new ligand in this series, N,N'-bis[1-(4-pyridyl)ethylidene]-p-phenylenediamine. The terminal pyridyl groups are coplanar, and they form a dihedral angle of 60.3 (1)° with the central benzene ring. The crystal structure consists of parallel zones of stacked molecules. In every zone, there are face-to-face (between the pyridyl rings of neighboring species) and edge-to-face (between a pyridyl ring of one molecule and the central benzene ring of an adjacent molecule) stacking interactions (Fig. 2).