Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026414/pk2022sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026414/pk2022Isup2.hkl |
CCDC reference: 654892
To a stirring solution of cis-(±)2-(2,5-di(pyridin-2-yl)-4,5-dihydro-1H-imidazol-4-yl)pyridine (0.3 g, 0.9966 mmol) in dichloromethane (10 ml) was added Et3N (0.5 g, 4.9807 mmol). After an additional 5 min, benzoyl chloride (0.28 g, 1.9931 mmol) and 4-dimethylaminopyridine (0.012 g, 0.0982 mmol) was added. The solution was stirred for 22 h at room temperature. The resulting mixture was washed with 0.1 N NaOH (3 × 10 ml). The organic layer was dried over MgSO4, filtered, and the solvent removed under reduced pressure. The remaining solid was crystallized from CH2Cl2/pentane by gas phase diffusion providing colourless crystals that were dried under high vacuum. Yield (0.1930 g, 48%) Mp: 248–250 °K. IR (KBr): 3039, 2929, 2852, 1651, 1613, 1589, 1473, 1438, 1354, 1147, 996, 784, 704 cm-1. 1H NMR (CDCl3, 500 MHz): d8.34 (ta, J = 4.8, 2H), 8.24 (da, J = 4.6, 2.0, 0.8 Hz,1H), 7.85 (d, J = 7.5 Hz,1H), 7.62 (td, J = 7.7, 2.0 Hz, 1H), 7.42–7.38 (m, 3H),7.32 (td, J = 7.5, 1.6, Hz, 1H), 7.23–7.16 (m, 2H), 7.15 (ddd, J = 7.6,4.8, 1.1 Hz, 1H), 7.09 (t, J = 7.6 Hz, 3H), 6.95(ddd, J = 7.4, J = 4.9, J = 1.0 Hz,1H), 6.91(ddd, J = 7.5,4.8, 1.0 Hz, 1H), 6.08 (d, J = 9.1 Hz, 1H), 6.05 (d, J = 9.1 Hz, 1H). 13C NMR (CDCl3 125.7 MHz): 168.83, 161.43, 157.52, 156.53, 150.14, 149.04, 148.96, 148.89, 148.33, 136.11, 135.88, 153.47, 131.04, 128.43, 127.77, 124.41, 122.85, 122.34, 121.97, 121.90, 75.40, 70.36. EMIES m/e (int. rel.): [M+H]+ 406 (100%).
The sample partially decomposed in the X-ray beam (13% decay). Refinement of H atoms was carried out using a riding model, with distances constrained to 0.93 Å for aromatic CH, 0.98 Å for methine CH. Isotropic U parameters were fixed at Uiso(H) = 1.2Ueq(carrier atom) for aromatic CH and methine CH.
The coordination chemistry of transition metals with polypyridyl ligands has progressed considerably during the last decade, and has been widely used for the construction of coordination polymers and other supramolecular structures (Itoh et al., 2005; Albrechy, 2001; Leininger et al., 2000). Complex metal-organic coordination polymers, macrocycles, networks and other metallosupramolecular structures can be constructed by self-assembly from small, easily prepared building blocks, which are combined either through coordinative bonds, hydrogen bonding (Majumder et al., 2006; Burchell et al. 2006; Gallego et al. 2004), π-π (Zou et al., 2006; Liu et al., 2005; Roesky et al., 2003; Wang et al., 2006) or CH/π interactions (Chen et al., 2002; Janiak et al., 2000). Such supramolecular architectures have attracted considerable attention due to the useful electronic, magnetic, optical and catalytic properties of these materials (Lehn, 1995; Séneque et al., 2001). In this direction, previous work in our laboratory has been focused on the coordination chemistry of the ligand cis-(±)2-(2,5-di(pyridin-2-yl)-4,5-dihydro-1H-imidazol-4-yl)pyridine (Larter et al., 1998) with transition metals such as Ni(II), Cu(II), Zn(II) (Parra-Hake et al., 2000) and Cd(II) (Campos-Gaxiola et al., 2007).
As part of our ongoing research on the chemistry of polypyridine ligands we have synthesized Cis-(±)-phenyl[2,4,5-tri(pyridin-2-yl)-4,5- dihydroimidazol-1-yl]methanone (I) in order to modify the coordination environment that could assist in the formation of coordination macromolecules. To gain insight on the new coordination capabilities, the X-ray crystal structure of the title compound has been carried out (Fig. 1).
In the crystal structure, adjacent units are linked together by strong and weak edge-to-face C—H···π interactions (Fig. 2) between pyridyl protons and the pyridyl ring [H···π 3.250 (4) Å and C—H···π 129.3 (2)°], phenyl protons and the pyridyl ring [H···π 2.917 (4) Å and C—H···π 154.0 (2)°](Yang et al., 2006; Jennings et al., 2001; Planas et al., 2006; Jayaraman et al., 2006; Reger et al., 2001), to form one-dimensional chains along the [001] direction. In addition, adjacent units are arranged into a two-dimensional network propagated along the (011) plane via intermolecular C—H···N hydrogen bond interactions between the H-atoms of phenyl or pyridyl rings and pyridyl N atoms as well as C—H···O interactions between pyridyl protons and the O atom of carbonyl group (Fig. 3). The hydrogen bond distances are within the range found for other reported structures (Oxtoby et al., 2003; Thallapally et al., 2003; Kapildev et al., 2005). These interactions may be attributed to the orientation of the aromatic rings, which help to stabilize the structure.
For related literature, see: Albrechy (2001); Burchell & Puddephatt (2006); Campos-Gaxiola, Höpfl & Parra-Hake (2007); Chen & Liu (2002); Gallego et al. (2004); Itoh et al. (2005); Janiak (2000); Jayaraman et al. (2006); Jennings et al. (2001); Kapildev et al. (2005); Larter et al. (1998); Lehn (1995); Leininger et al. (2000); Liu et al. (2005); Majumder et al. (2006); Oxtoby et al. (2003); Parra-Hake et al. (2000); Planas et al. (2006); Reger et al. (2001); Roesky & Andruh (2003); Séneque et al. (2001); Thallapally et al. (2003); Wang et al. (2006); Yang et al. (2006); Zou et al. (2006). It would be helpful to the reader if this long list could be split up into groups concerning different topics, e.g. supramolecular structures, hydrogen bonding, related compounds etc. Please rearrange and rephrase accordingly.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
C25H19N5O | Z = 2 |
Mr = 405.45 | F(000) = 424 |
Triclinic, P1 | Dx = 1.341 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.004 (3) Å | Cell parameters from 39 reflections |
b = 10.085 (4) Å | θ = 4.6–11.6° |
c = 13.432 (4) Å | µ = 0.09 mm−1 |
α = 108.65 (4)° | T = 298 K |
β = 93.56 (3)° | Prismatic, colourless |
γ = 99.84 (4)° | 0.5 × 0.42 × 0.14 mm |
V = 1004.2 (7) Å3 |
Bruker P4 diffractometer | Rint = 0.030 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.2° |
Graphite monochromator | h = 0→9 |
2θ/ω scans | k = −11→11 |
3758 measured reflections | l = −15→15 |
3483 independent reflections | 3 standard reflections every 97 reflections |
1931 reflections with I > 2σ(I) | intensity decay: 13.7% |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0581P)2] where P = (Fo2 + 2Fc2)/3 |
3483 reflections | (Δ/σ)max = 0.010 |
280 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C25H19N5O | γ = 99.84 (4)° |
Mr = 405.45 | V = 1004.2 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.004 (3) Å | Mo Kα radiation |
b = 10.085 (4) Å | µ = 0.09 mm−1 |
c = 13.432 (4) Å | T = 298 K |
α = 108.65 (4)° | 0.5 × 0.42 × 0.14 mm |
β = 93.56 (3)° |
Bruker P4 diffractometer | Rint = 0.030 |
3758 measured reflections | 3 standard reflections every 97 reflections |
3483 independent reflections | intensity decay: 13.7% |
1931 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.15 e Å−3 |
3483 reflections | Δρmin = −0.21 e Å−3 |
280 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 | 0.4369 (4) | 0.1653 (3) | 0.7048 (2) | 0.0388 (7) | |
C2 | 0.4347 (4) | 0.1829 (3) | 0.5448 (2) | 0.0433 (8) | |
H2B | 0.5467 | 0.1729 | 0.5211 | 0.052* | |
C3 | 0.4522 (4) | 0.3372 (3) | 0.6233 (2) | 0.0435 (8) | |
H3B | 0.5464 | 0.4015 | 0.6087 | 0.052* | |
C4 | 0.4006 (4) | 0.1088 (3) | 0.7916 (2) | 0.0388 (7) | |
C5 | 0.3979 (4) | −0.0332 (3) | 0.7776 (3) | 0.0479 (8) | |
H5B | 0.4261 | −0.0932 | 0.7152 | 0.057* | |
C6 | 0.3527 (5) | −0.0842 (4) | 0.8574 (3) | 0.0589 (10) | |
H6A | 0.3497 | −0.1795 | 0.8500 | 0.071* | |
C7 | 0.3124 (4) | 0.0069 (4) | 0.9475 (3) | 0.0578 (10) | |
H7A | 0.2817 | −0.0248 | 1.0029 | 0.069* | |
C8 | 0.3181 (4) | 0.1471 (4) | 0.9550 (3) | 0.0539 (9) | |
H8A | 0.2899 | 0.2086 | 1.0167 | 0.065* | |
C9 | 0.3068 (4) | 0.1464 (3) | 0.4479 (2) | 0.0415 (8) | |
C10 | 0.1672 (4) | 0.0362 (3) | 0.4222 (3) | 0.0513 (9) | |
H10A | 0.1478 | −0.0208 | 0.4644 | 0.062* | |
C11 | 0.0569 (5) | 0.0117 (4) | 0.3332 (3) | 0.0625 (10) | |
H11A | −0.0397 | −0.0612 | 0.3146 | 0.075* | |
C12 | 0.0912 (5) | 0.0962 (4) | 0.2719 (3) | 0.0583 (10) | |
H12A | 0.0182 | 0.0819 | 0.2112 | 0.070* | |
C13 | 0.2343 (5) | 0.2014 (4) | 0.3016 (3) | 0.0557 (9) | |
H13A | 0.2579 | 0.2573 | 0.2589 | 0.067* | |
C14 | 0.2925 (4) | 0.3986 (3) | 0.6281 (2) | 0.0407 (8) | |
C15 | 0.2940 (5) | 0.5330 (3) | 0.6216 (3) | 0.0561 (9) | |
H15A | 0.3945 | 0.5878 | 0.6131 | 0.067* | |
C16 | 0.1466 (6) | 0.5843 (4) | 0.6277 (3) | 0.0683 (11) | |
H16A | 0.1453 | 0.6745 | 0.6236 | 0.082* | |
C17 | 0.0008 (5) | 0.5011 (4) | 0.6399 (3) | 0.0669 (11) | |
H17A | −0.1013 | 0.5337 | 0.6449 | 0.080* | |
C18 | 0.0088 (5) | 0.3687 (4) | 0.6447 (3) | 0.0587 (9) | |
H18A | −0.0912 | 0.3117 | 0.6514 | 0.070* | |
C19 | 0.5967 (4) | 0.4186 (3) | 0.8071 (2) | 0.0459 (8) | |
C20 | 0.6959 (4) | 0.3814 (3) | 0.8878 (2) | 0.0401 (8) | |
C21 | 0.7149 (4) | 0.4693 (3) | 0.9926 (3) | 0.0479 (8) | |
H21A | 0.6591 | 0.5457 | 1.0118 | 0.057* | |
C22 | 0.8166 (5) | 0.4436 (4) | 1.0685 (3) | 0.0590 (10) | |
H22A | 0.8246 | 0.5001 | 1.1392 | 0.071* | |
C23 | 0.9049 (5) | 0.3364 (4) | 1.0408 (3) | 0.0632 (10) | |
H23A | 0.9764 | 0.3222 | 1.0921 | 0.076* | |
C24 | 0.8890 (4) | 0.2488 (4) | 0.9372 (3) | 0.0565 (9) | |
H24A | 0.9488 | 0.1749 | 0.9185 | 0.068* | |
C25 | 0.7838 (4) | 0.2708 (3) | 0.8608 (3) | 0.0465 (8) | |
H25A | 0.7721 | 0.2107 | 0.7908 | 0.056* | |
N1 | 0.5004 (3) | 0.3120 (2) | 0.72264 (18) | 0.0417 (6) | |
N2 | 0.3949 (3) | 0.0892 (3) | 0.6083 (2) | 0.0443 (7) | |
N3 | 0.3616 (3) | 0.1996 (3) | 0.8789 (2) | 0.0448 (7) | |
N4 | 0.3427 (3) | 0.2286 (3) | 0.3890 (2) | 0.0505 (7) | |
N5 | 0.1514 (4) | 0.3169 (3) | 0.6402 (2) | 0.0522 (7) | |
O1 | 0.6116 (3) | 0.5423 (2) | 0.80961 (17) | 0.0641 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0382 (18) | 0.0368 (17) | 0.0389 (18) | 0.0068 (14) | 0.0009 (14) | 0.0105 (15) |
C2 | 0.0434 (19) | 0.0461 (18) | 0.0357 (18) | 0.0063 (15) | 0.0033 (15) | 0.0092 (15) |
C3 | 0.047 (2) | 0.0443 (18) | 0.0369 (18) | 0.0011 (15) | 0.0008 (15) | 0.0160 (14) |
C4 | 0.0349 (17) | 0.0384 (17) | 0.0388 (18) | 0.0022 (14) | −0.0060 (14) | 0.0119 (15) |
C5 | 0.053 (2) | 0.0417 (19) | 0.047 (2) | 0.0091 (16) | −0.0030 (16) | 0.0156 (16) |
C6 | 0.069 (3) | 0.043 (2) | 0.063 (2) | 0.0028 (18) | −0.011 (2) | 0.0245 (19) |
C7 | 0.061 (2) | 0.060 (2) | 0.053 (2) | −0.0052 (19) | −0.0043 (18) | 0.0316 (19) |
C8 | 0.056 (2) | 0.064 (2) | 0.042 (2) | 0.0058 (18) | 0.0062 (17) | 0.0199 (18) |
C9 | 0.048 (2) | 0.0400 (18) | 0.0363 (18) | 0.0123 (16) | 0.0086 (15) | 0.0102 (15) |
C10 | 0.052 (2) | 0.051 (2) | 0.048 (2) | 0.0009 (17) | 0.0044 (17) | 0.0180 (17) |
C11 | 0.050 (2) | 0.064 (2) | 0.059 (2) | −0.0017 (18) | −0.0064 (19) | 0.009 (2) |
C12 | 0.054 (2) | 0.063 (2) | 0.050 (2) | 0.0173 (19) | −0.0115 (18) | 0.0091 (19) |
C13 | 0.069 (3) | 0.055 (2) | 0.046 (2) | 0.016 (2) | −0.0006 (19) | 0.0208 (18) |
C14 | 0.048 (2) | 0.0377 (18) | 0.0313 (17) | 0.0019 (15) | −0.0016 (14) | 0.0093 (14) |
C15 | 0.065 (2) | 0.041 (2) | 0.057 (2) | −0.0011 (18) | −0.0061 (18) | 0.0183 (17) |
C16 | 0.084 (3) | 0.044 (2) | 0.077 (3) | 0.017 (2) | −0.013 (2) | 0.024 (2) |
C17 | 0.067 (3) | 0.061 (2) | 0.066 (3) | 0.023 (2) | −0.003 (2) | 0.008 (2) |
C18 | 0.054 (2) | 0.058 (2) | 0.064 (2) | 0.0099 (19) | 0.0120 (19) | 0.0217 (19) |
C19 | 0.049 (2) | 0.0395 (19) | 0.0426 (19) | −0.0007 (16) | 0.0011 (16) | 0.0103 (15) |
C20 | 0.0380 (18) | 0.0421 (18) | 0.0351 (18) | −0.0026 (15) | −0.0020 (14) | 0.0129 (15) |
C21 | 0.046 (2) | 0.0458 (19) | 0.046 (2) | 0.0005 (16) | 0.0052 (16) | 0.0133 (16) |
C22 | 0.065 (2) | 0.063 (2) | 0.0367 (19) | −0.005 (2) | −0.0083 (18) | 0.0106 (17) |
C23 | 0.059 (2) | 0.070 (3) | 0.058 (3) | −0.002 (2) | −0.0115 (19) | 0.030 (2) |
C24 | 0.050 (2) | 0.053 (2) | 0.067 (3) | 0.0056 (17) | −0.0057 (19) | 0.0248 (19) |
C25 | 0.0432 (19) | 0.049 (2) | 0.0407 (19) | −0.0006 (16) | 0.0011 (15) | 0.0117 (15) |
N1 | 0.0479 (16) | 0.0360 (14) | 0.0337 (14) | −0.0023 (12) | −0.0069 (12) | 0.0095 (11) |
N2 | 0.0532 (17) | 0.0366 (14) | 0.0405 (16) | 0.0062 (12) | 0.0007 (13) | 0.0117 (12) |
N3 | 0.0463 (16) | 0.0445 (15) | 0.0422 (16) | 0.0042 (13) | 0.0040 (13) | 0.0157 (13) |
N4 | 0.0567 (18) | 0.0476 (16) | 0.0436 (16) | 0.0035 (14) | 0.0008 (14) | 0.0152 (14) |
N5 | 0.0569 (19) | 0.0499 (17) | 0.0538 (18) | 0.0121 (15) | 0.0124 (15) | 0.0213 (14) |
O1 | 0.0910 (19) | 0.0381 (14) | 0.0542 (15) | −0.0024 (13) | −0.0156 (13) | 0.0157 (11) |
C1—N2 | 1.267 (4) | C12—H12A | 0.9300 |
C1—N1 | 1.416 (4) | C13—N4 | 1.340 (4) |
C1—C4 | 1.476 (4) | C13—H13A | 0.9300 |
C2—N2 | 1.473 (4) | C14—N5 | 1.331 (4) |
C2—C9 | 1.509 (4) | C14—C15 | 1.384 (4) |
C2—C3 | 1.552 (4) | C15—C16 | 1.363 (5) |
C2—H2B | 0.9800 | C15—H15A | 0.9300 |
C3—N1 | 1.477 (4) | C16—C17 | 1.368 (5) |
C3—C14 | 1.509 (4) | C16—H16A | 0.9300 |
C3—H3B | 0.9800 | C17—C18 | 1.369 (5) |
C4—N3 | 1.330 (4) | C17—H17A | 0.9300 |
C4—C5 | 1.380 (4) | C18—N5 | 1.331 (4) |
C5—C6 | 1.371 (4) | C18—H18A | 0.9300 |
C5—H5B | 0.9300 | C19—O1 | 1.222 (3) |
C6—C7 | 1.361 (5) | C19—N1 | 1.366 (4) |
C6—H6A | 0.9300 | C19—C20 | 1.483 (4) |
C7—C8 | 1.377 (4) | C20—C25 | 1.383 (4) |
C7—H7A | 0.9300 | C20—C21 | 1.385 (4) |
C8—N3 | 1.332 (4) | C21—C22 | 1.381 (4) |
C8—H8A | 0.9300 | C21—H21A | 0.9300 |
C9—N4 | 1.327 (4) | C22—C23 | 1.358 (5) |
C9—C10 | 1.373 (4) | C22—H22A | 0.9300 |
C10—C11 | 1.369 (4) | C23—C24 | 1.373 (5) |
C10—H10A | 0.9300 | C23—H23A | 0.9300 |
C11—C12 | 1.369 (5) | C24—C25 | 1.384 (4) |
C11—H11A | 0.9300 | C24—H24A | 0.9300 |
C12—C13 | 1.362 (5) | C25—H25A | 0.9300 |
N2—C1—N1 | 114.6 (3) | C12—C13—H13A | 118.3 |
N2—C1—C4 | 122.2 (3) | N5—C14—C15 | 122.2 (3) |
N1—C1—C4 | 122.7 (3) | N5—C14—C3 | 116.2 (3) |
N2—C2—C9 | 113.5 (3) | C15—C14—C3 | 121.6 (3) |
N2—C2—C3 | 105.2 (2) | C16—C15—C14 | 119.3 (3) |
C9—C2—C3 | 114.1 (2) | C16—C15—H15A | 120.3 |
N2—C2—H2B | 107.9 | C14—C15—H15A | 120.3 |
C9—C2—H2B | 107.9 | C15—C16—C17 | 119.0 (3) |
C3—C2—H2B | 107.9 | C15—C16—H16A | 120.5 |
N1—C3—C14 | 111.5 (2) | C17—C16—H16A | 120.5 |
N1—C3—C2 | 98.9 (2) | C18—C17—C16 | 118.4 (4) |
C14—C3—C2 | 115.8 (3) | C18—C17—H17A | 120.8 |
N1—C3—H3B | 110.1 | C16—C17—H17A | 120.8 |
C14—C3—H3B | 110.1 | N5—C18—C17 | 123.8 (4) |
C2—C3—H3B | 110.1 | N5—C18—H18A | 118.1 |
N3—C4—C5 | 123.3 (3) | C17—C18—H18A | 118.1 |
N3—C4—C1 | 116.2 (3) | O1—C19—N1 | 119.1 (3) |
C5—C4—C1 | 120.3 (3) | O1—C19—C20 | 121.1 (3) |
C6—C5—C4 | 118.7 (3) | N1—C19—C20 | 119.5 (3) |
C6—C5—H5B | 120.6 | C25—C20—C21 | 118.8 (3) |
C4—C5—H5B | 120.6 | C25—C20—C19 | 122.2 (3) |
C7—C6—C5 | 118.9 (3) | C21—C20—C19 | 118.7 (3) |
C7—C6—H6A | 120.5 | C22—C21—C20 | 120.1 (3) |
C5—C6—H6A | 120.5 | C22—C21—H21A | 119.9 |
C6—C7—C8 | 118.6 (3) | C20—C21—H21A | 119.9 |
C6—C7—H7A | 120.7 | C23—C22—C21 | 120.6 (3) |
C8—C7—H7A | 120.7 | C23—C22—H22A | 119.7 |
N3—C8—C7 | 123.8 (3) | C21—C22—H22A | 119.7 |
N3—C8—H8A | 118.1 | C22—C23—C24 | 120.2 (3) |
C7—C8—H8A | 118.1 | C22—C23—H23A | 119.9 |
N4—C9—C10 | 123.1 (3) | C24—C23—H23A | 119.9 |
N4—C9—C2 | 114.1 (3) | C23—C24—C25 | 119.9 (3) |
C10—C9—C2 | 122.8 (3) | C23—C24—H24A | 120.1 |
C11—C10—C9 | 118.8 (3) | C25—C24—H24A | 120.1 |
C11—C10—H10A | 120.6 | C24—C25—C20 | 120.4 (3) |
C9—C10—H10A | 120.6 | C24—C25—H25A | 119.8 |
C10—C11—C12 | 118.9 (3) | C20—C25—H25A | 119.8 |
C10—C11—H11A | 120.5 | C19—N1—C1 | 132.2 (3) |
C12—C11—H11A | 120.5 | C19—N1—C3 | 121.1 (2) |
C13—C12—C11 | 118.8 (3) | C1—N1—C3 | 106.6 (2) |
C13—C12—H12A | 120.6 | C1—N2—C2 | 107.4 (2) |
C11—C12—H12A | 120.6 | C4—N3—C8 | 116.6 (3) |
N4—C13—C12 | 123.3 (3) | C9—N4—C13 | 117.1 (3) |
N4—C13—H13A | 118.3 | C14—N5—C18 | 117.3 (3) |
N2—C2—C3—N1 | 25.5 (3) | N1—C19—C20—C21 | −145.6 (3) |
C9—C2—C3—N1 | 150.6 (3) | C25—C20—C21—C22 | −1.7 (5) |
N2—C2—C3—C14 | −93.6 (3) | C19—C20—C21—C22 | −175.4 (3) |
C9—C2—C3—C14 | 31.4 (4) | C20—C21—C22—C23 | 3.0 (5) |
N2—C1—C4—N3 | −144.7 (3) | C21—C22—C23—C24 | −2.4 (6) |
N1—C1—C4—N3 | 26.8 (4) | C22—C23—C24—C25 | 0.6 (5) |
N2—C1—C4—C5 | 31.4 (4) | C23—C24—C25—C20 | 0.7 (5) |
N1—C1—C4—C5 | −157.1 (3) | C21—C20—C25—C24 | −0.2 (5) |
N3—C4—C5—C6 | 0.0 (5) | C19—C20—C25—C24 | 173.3 (3) |
C1—C4—C5—C6 | −175.8 (3) | O1—C19—N1—C1 | −168.1 (3) |
C4—C5—C6—C7 | −0.1 (5) | C20—C19—N1—C1 | 18.4 (5) |
C5—C6—C7—C8 | 0.2 (5) | O1—C19—N1—C3 | 16.1 (5) |
C6—C7—C8—N3 | −0.3 (5) | C20—C19—N1—C3 | −157.4 (3) |
N2—C2—C9—N4 | −178.9 (3) | N2—C1—N1—C19 | −160.5 (3) |
C3—C2—C9—N4 | 60.5 (4) | C4—C1—N1—C19 | 27.4 (5) |
N2—C2—C9—C10 | 0.0 (4) | N2—C1—N1—C3 | 15.7 (3) |
C3—C2—C9—C10 | −120.6 (3) | C4—C1—N1—C3 | −156.4 (3) |
N4—C9—C10—C11 | −1.8 (5) | C14—C3—N1—C19 | −85.2 (3) |
C2—C9—C10—C11 | 179.4 (3) | C2—C3—N1—C19 | 152.4 (3) |
C9—C10—C11—C12 | 1.2 (5) | C14—C3—N1—C1 | 98.1 (3) |
C10—C11—C12—C13 | 0.2 (5) | C2—C3—N1—C1 | −24.3 (3) |
C11—C12—C13—N4 | −1.1 (5) | N1—C1—N2—C2 | 2.3 (3) |
N1—C3—C14—N5 | −62.1 (3) | C4—C1—N2—C2 | 174.4 (3) |
C2—C3—C14—N5 | 49.9 (4) | C9—C2—N2—C1 | −143.8 (3) |
N1—C3—C14—C15 | 117.1 (3) | C3—C2—N2—C1 | −18.3 (3) |
C2—C3—C14—C15 | −130.9 (3) | C5—C4—N3—C8 | −0.1 (4) |
N5—C14—C15—C16 | 0.0 (5) | C1—C4—N3—C8 | 175.9 (3) |
C3—C14—C15—C16 | −179.2 (3) | C7—C8—N3—C4 | 0.2 (5) |
C14—C15—C16—C17 | −0.1 (5) | C10—C9—N4—C13 | 0.9 (5) |
C15—C16—C17—C18 | −0.5 (6) | C2—C9—N4—C13 | 179.8 (3) |
C16—C17—C18—N5 | 1.4 (6) | C12—C13—N4—C9 | 0.6 (5) |
O1—C19—C20—C25 | −132.3 (3) | C15—C14—N5—C18 | 0.7 (4) |
N1—C19—C20—C25 | 41.0 (4) | C3—C14—N5—C18 | 180.0 (3) |
O1—C19—C20—C21 | 41.1 (5) | C17—C18—N5—C14 | −1.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13A···O1i | 0.93 | 2.57 | 3.469 (5) | 163 |
C15—H15A···N4i | 0.93 | 2.56 | 3.483 (5) | 171 |
C5—H5B···N4ii | 0.93 | 2.69 | 3.515 (5) | 149 |
C21—H21A···N3iii | 0.93 | 2.56 | 3.413 (5) | 153 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C25H19N5O |
Mr | 405.45 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.004 (3), 10.085 (4), 13.432 (4) |
α, β, γ (°) | 108.65 (4), 93.56 (3), 99.84 (4) |
V (Å3) | 1004.2 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.5 × 0.42 × 0.14 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3758, 3483, 1931 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.140, 0.99 |
No. of reflections | 3483 |
No. of parameters | 280 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.21 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13A···O1i | 0.93 | 2.57 | 3.469 (5) | 162.6 |
C15—H15A···N4i | 0.93 | 2.56 | 3.483 (5) | 171.1 |
C5—H5B···N4ii | 0.93 | 2.69 | 3.515 (5) | 149.0 |
C21—H21A···N3iii | 0.93 | 2.56 | 3.413 (5) | 153.1 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+2. |
The coordination chemistry of transition metals with polypyridyl ligands has progressed considerably during the last decade, and has been widely used for the construction of coordination polymers and other supramolecular structures (Itoh et al., 2005; Albrechy, 2001; Leininger et al., 2000). Complex metal-organic coordination polymers, macrocycles, networks and other metallosupramolecular structures can be constructed by self-assembly from small, easily prepared building blocks, which are combined either through coordinative bonds, hydrogen bonding (Majumder et al., 2006; Burchell et al. 2006; Gallego et al. 2004), π-π (Zou et al., 2006; Liu et al., 2005; Roesky et al., 2003; Wang et al., 2006) or CH/π interactions (Chen et al., 2002; Janiak et al., 2000). Such supramolecular architectures have attracted considerable attention due to the useful electronic, magnetic, optical and catalytic properties of these materials (Lehn, 1995; Séneque et al., 2001). In this direction, previous work in our laboratory has been focused on the coordination chemistry of the ligand cis-(±)2-(2,5-di(pyridin-2-yl)-4,5-dihydro-1H-imidazol-4-yl)pyridine (Larter et al., 1998) with transition metals such as Ni(II), Cu(II), Zn(II) (Parra-Hake et al., 2000) and Cd(II) (Campos-Gaxiola et al., 2007).
As part of our ongoing research on the chemistry of polypyridine ligands we have synthesized Cis-(±)-phenyl[2,4,5-tri(pyridin-2-yl)-4,5- dihydroimidazol-1-yl]methanone (I) in order to modify the coordination environment that could assist in the formation of coordination macromolecules. To gain insight on the new coordination capabilities, the X-ray crystal structure of the title compound has been carried out (Fig. 1).
In the crystal structure, adjacent units are linked together by strong and weak edge-to-face C—H···π interactions (Fig. 2) between pyridyl protons and the pyridyl ring [H···π 3.250 (4) Å and C—H···π 129.3 (2)°], phenyl protons and the pyridyl ring [H···π 2.917 (4) Å and C—H···π 154.0 (2)°](Yang et al., 2006; Jennings et al., 2001; Planas et al., 2006; Jayaraman et al., 2006; Reger et al., 2001), to form one-dimensional chains along the [001] direction. In addition, adjacent units are arranged into a two-dimensional network propagated along the (011) plane via intermolecular C—H···N hydrogen bond interactions between the H-atoms of phenyl or pyridyl rings and pyridyl N atoms as well as C—H···O interactions between pyridyl protons and the O atom of carbonyl group (Fig. 3). The hydrogen bond distances are within the range found for other reported structures (Oxtoby et al., 2003; Thallapally et al., 2003; Kapildev et al., 2005). These interactions may be attributed to the orientation of the aromatic rings, which help to stabilize the structure.