Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029224/at2329sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029224/at2329Isup2.hkl |
CCDC reference: 657772
checkCIF/PLATON results
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The mixture of 3-phenylimidazolidine-2,4-dione (0.53 g, 3 mmol) and potassium carbonate (0.41 g, 3 mmol) dissolved in 10 ml of acetonitrile was stirred magnetically for 10–15 min. Then the solution of 2-chloro-5-(chloromethyl)pyridine (3 mmol, 0.49 g) in 10 ml of acetonitrile was added dropwise at 273 K for 30 min. The mixture was stirred for 1 h at room temperature, then refluxed for 3 h. The workup involved stripping of the solvent followed by an addition of water and extraction of the product mixture into dichloromethane, after phase separation, drying over anhydrous sodium sulfate, filtration and evaporation, the crude product was recrystallized from ethyl acetate and petroleum etherto give the product as colourless crystals; yield 57%; m.p. 377–379 K.
H atoms bonded to C were placed at calculated positions, with C—H distances of 0.97 and 0.93 Å for H atoms bonded to sp3 and sp2 C atoms, respectively. They were refined using a riding model, with Uiso(H) = 1.2Ueq(C).
Imidazolidine-2,4-diones became of recent importance in the research and development of agrochemicals due to their widespread biological activites. Some of them have been used as herbicides, fungicides, etc. (Lee et al., 1997; Hirai et al., 1999). Neonicotinoid insecticides as nicotinic acetylcholine receptor inhibitors have attracted increasing attention because of their safety, low toxicity, wide range of activities and high potency. It has been found that most biologically active nicotinic compounds contain the (aminomethyl)-pyridine moiety. As a continuation of our search for new biologically active heterocyclic compounds, we report here the crystal structure of the title compound, (I) (Fig.1).
Selected bonds in (I) are listed in Table 1. In the crystal structure, the C7—N2, C8—N3, C9—N2 and C9—N3 bonds are significantly shorter than a normal single C—N bond (1.47 Å; Sasada, 1984) and close to the value for a C═N bond (1.28 Å; Wang et al., 1998), which is indicative of signficant double-bond character. Weak C—H···O hydrogen bond (Table 2) and C—H···π interactions contribute to the stability of the crystal structure.
Many derivatives of imidazolidine have been prepared; biological and pharmaceutical activities have been studied by Lee et al. (1997) and Hirai et al., (1999).
For related literature, see: Sasada (1984); Wang et al. (1998).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
C15H12ClN3O2 | F(000) = 624 |
Mr = 301.73 | Dx = 1.432 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3094 reflections |
a = 7.7106 (10) Å | θ = 2.7–27.0° |
b = 6.3329 (9) Å | µ = 0.28 mm−1 |
c = 28.673 (4) Å | T = 297 K |
β = 91.552 (2)° | Block, colourless |
V = 1399.6 (3) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2882 independent reflections |
Radiation source: fine-focus sealed tube | 2353 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.087 |
φ and ω scans | θmax = 26.5°, θmin = 2.7° |
Absorption correction: multi-scan | h = −9→9 |
Tmin = 0.921, Tmax = 0.946 | k = −7→7 |
7874 measured reflections | l = −33→35 |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0605P)2 + 0.5771P] where P = (Fo2 + 2Fc2)/3 |
2882 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C15H12ClN3O2 | V = 1399.6 (3) Å3 |
Mr = 301.73 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.7106 (10) Å | µ = 0.28 mm−1 |
b = 6.3329 (9) Å | T = 297 K |
c = 28.673 (4) Å | 0.30 × 0.20 × 0.20 mm |
β = 91.552 (2)° |
Bruker SMART CCD area-detector diffractometer | 2882 independent reflections |
Absorption correction: multi-scan | 2353 reflections with I > 2σ(I) |
Tmin = 0.921, Tmax = 0.946 | Rint = 0.087 |
7874 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.27 e Å−3 |
2882 reflections | Δρmin = −0.23 e Å−3 |
190 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 | 0.2372 (3) | 0.5225 (4) | 0.99690 (8) | 0.0533 (6) | |
C2 | 0.2084 (3) | 0.7347 (4) | 1.00312 (9) | 0.0587 (7) | |
H2 | 0.1893 | 0.7905 | 1.0325 | 0.070* | |
C3 | 0.2090 (3) | 0.8609 (4) | 0.96422 (9) | 0.0537 (6) | |
H3 | 0.1930 | 1.0059 | 0.9670 | 0.064* | |
C4 | 0.2335 (3) | 0.7713 (4) | 0.92095 (8) | 0.0428 (5) | |
C5 | 0.2527 (3) | 0.5546 (4) | 0.91929 (8) | 0.0541 (6) | |
H5 | 0.2632 | 0.4920 | 0.8902 | 0.065* | |
C6 | 0.2454 (3) | 0.9009 (4) | 0.87684 (8) | 0.0479 (5) | |
H6A | 0.1835 | 0.8290 | 0.8516 | 0.057* | |
H6B | 0.1900 | 1.0366 | 0.8814 | 0.057* | |
C7 | 0.5401 (3) | 1.0844 (4) | 0.88673 (9) | 0.0479 (5) | |
H7A | 0.5344 | 1.0733 | 0.9204 | 0.057* | |
H7B | 0.5117 | 1.2278 | 0.8774 | 0.057* | |
C8 | 0.7167 (3) | 1.0213 (3) | 0.87015 (7) | 0.0406 (5) | |
C9 | 0.5137 (3) | 0.7895 (4) | 0.83985 (8) | 0.0428 (5) | |
C10 | 0.8204 (3) | 0.7462 (3) | 0.81482 (7) | 0.0367 (5) | |
C11 | 0.8776 (3) | 0.5483 (3) | 0.82859 (8) | 0.0452 (5) | |
H11 | 0.8337 | 0.4837 | 0.8549 | 0.054* | |
C12 | 1.0016 (3) | 0.4480 (4) | 0.80236 (9) | 0.0510 (6) | |
H12 | 1.0413 | 0.3148 | 0.8112 | 0.061* | |
C13 | 1.0665 (3) | 0.5432 (4) | 0.76354 (8) | 0.0514 (6) | |
H13 | 1.1500 | 0.4745 | 0.7463 | 0.062* | |
C14 | 1.0083 (3) | 0.7397 (4) | 0.75001 (8) | 0.0494 (6) | |
H14 | 1.0524 | 0.8038 | 0.7237 | 0.059* | |
C15 | 0.8838 (3) | 0.8422 (4) | 0.77574 (8) | 0.0431 (5) | |
H15 | 0.8434 | 0.9747 | 0.7666 | 0.052* | |
Cl1 | 0.24657 (13) | 0.35783 (14) | 1.04586 (3) | 0.0857 (3) | |
N1 | 0.2570 (3) | 0.4292 (3) | 0.95662 (7) | 0.0618 (6) | |
N2 | 0.4254 (2) | 0.9345 (3) | 0.86390 (6) | 0.0447 (5) | |
N3 | 0.6895 (2) | 0.8510 (3) | 0.84105 (6) | 0.0392 (4) | |
O1 | 0.4589 (2) | 0.6335 (3) | 0.82032 (7) | 0.0632 (5) | |
O2 | 0.8541 (2) | 1.1011 (3) | 0.88035 (6) | 0.0530 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0629 (15) | 0.0527 (14) | 0.0441 (13) | −0.0047 (11) | −0.0008 (11) | 0.0072 (11) |
C2 | 0.0751 (18) | 0.0575 (16) | 0.0437 (13) | −0.0037 (13) | 0.0053 (12) | −0.0116 (11) |
C3 | 0.0658 (15) | 0.0410 (13) | 0.0545 (14) | −0.0010 (11) | 0.0071 (12) | −0.0083 (11) |
C4 | 0.0385 (11) | 0.0436 (12) | 0.0464 (12) | 0.0019 (9) | 0.0023 (9) | −0.0044 (9) |
C5 | 0.0758 (17) | 0.0441 (13) | 0.0424 (12) | 0.0036 (12) | 0.0053 (11) | −0.0072 (10) |
C6 | 0.0429 (12) | 0.0516 (13) | 0.0492 (13) | 0.0053 (10) | 0.0011 (10) | 0.0053 (10) |
C7 | 0.0519 (13) | 0.0377 (11) | 0.0543 (13) | 0.0007 (10) | 0.0053 (10) | −0.0050 (10) |
C8 | 0.0499 (12) | 0.0316 (10) | 0.0404 (11) | −0.0004 (9) | 0.0015 (9) | 0.0035 (9) |
C9 | 0.0422 (11) | 0.0474 (12) | 0.0388 (11) | −0.0012 (9) | 0.0006 (9) | −0.0013 (10) |
C10 | 0.0360 (10) | 0.0366 (11) | 0.0373 (10) | −0.0022 (8) | −0.0017 (8) | −0.0030 (8) |
C11 | 0.0552 (13) | 0.0395 (12) | 0.0408 (12) | −0.0004 (10) | 0.0013 (10) | 0.0034 (9) |
C12 | 0.0567 (14) | 0.0399 (12) | 0.0560 (14) | 0.0107 (10) | −0.0047 (11) | −0.0009 (10) |
C13 | 0.0485 (13) | 0.0599 (15) | 0.0456 (13) | 0.0069 (11) | 0.0007 (10) | −0.0129 (11) |
C14 | 0.0457 (12) | 0.0615 (15) | 0.0413 (12) | −0.0044 (11) | 0.0049 (9) | 0.0039 (11) |
C15 | 0.0479 (12) | 0.0392 (12) | 0.0419 (12) | 0.0000 (9) | −0.0012 (9) | 0.0052 (9) |
Cl1 | 0.1187 (7) | 0.0829 (6) | 0.0553 (5) | −0.0030 (5) | −0.0017 (4) | 0.0236 (4) |
N1 | 0.0920 (17) | 0.0422 (11) | 0.0513 (12) | 0.0049 (11) | 0.0054 (11) | 0.0003 (9) |
N2 | 0.0439 (10) | 0.0453 (10) | 0.0452 (10) | −0.0003 (8) | 0.0036 (8) | −0.0028 (8) |
N3 | 0.0399 (9) | 0.0372 (9) | 0.0406 (9) | −0.0015 (7) | 0.0012 (7) | −0.0038 (7) |
O1 | 0.0538 (10) | 0.0663 (12) | 0.0697 (12) | −0.0135 (8) | 0.0043 (9) | −0.0294 (10) |
O2 | 0.0480 (9) | 0.0454 (9) | 0.0657 (11) | −0.0098 (7) | 0.0012 (8) | −0.0099 (8) |
C1—N1 | 1.310 (3) | C8—O2 | 1.203 (3) |
C1—C2 | 1.374 (4) | C8—N3 | 1.376 (3) |
C1—Cl1 | 1.749 (2) | C9—O1 | 1.206 (3) |
C2—C3 | 1.372 (4) | C9—N2 | 1.345 (3) |
C2—H2 | 0.9300 | C9—N3 | 1.410 (3) |
C3—C4 | 1.382 (3) | C10—C15 | 1.376 (3) |
C3—H3 | 0.9300 | C10—C11 | 1.382 (3) |
C4—C5 | 1.382 (3) | C10—N3 | 1.438 (3) |
C4—C6 | 1.512 (3) | C11—C12 | 1.387 (3) |
C5—N1 | 1.332 (3) | C11—H11 | 0.9300 |
C5—H5 | 0.9300 | C12—C13 | 1.372 (3) |
C6—N2 | 1.462 (3) | C12—H12 | 0.9300 |
C6—H6A | 0.9700 | C13—C14 | 1.375 (4) |
C6—H6B | 0.9700 | C13—H13 | 0.9300 |
C7—N2 | 1.443 (3) | C14—C15 | 1.388 (3) |
C7—C8 | 1.508 (3) | C14—H14 | 0.9300 |
C7—H7A | 0.9700 | C15—H15 | 0.9300 |
C7—H7B | 0.9700 | ||
N1—C1—C2 | 125.3 (2) | N3—C8—C7 | 105.94 (18) |
N1—C1—Cl1 | 115.8 (2) | O1—C9—N2 | 128.4 (2) |
C2—C1—Cl1 | 118.8 (2) | O1—C9—N3 | 124.2 (2) |
C3—C2—C1 | 117.4 (2) | N2—C9—N3 | 107.36 (18) |
C3—C2—H2 | 121.3 | C15—C10—C11 | 121.0 (2) |
C1—C2—H2 | 121.3 | C15—C10—N3 | 119.45 (19) |
C2—C3—C4 | 119.6 (2) | C11—C10—N3 | 119.49 (19) |
C2—C3—H3 | 120.2 | C10—C11—C12 | 118.7 (2) |
C4—C3—H3 | 120.2 | C10—C11—H11 | 120.7 |
C5—C4—C3 | 117.1 (2) | C12—C11—H11 | 120.7 |
C5—C4—C6 | 120.1 (2) | C13—C12—C11 | 120.7 (2) |
C3—C4—C6 | 122.8 (2) | C13—C12—H12 | 119.6 |
N1—C5—C4 | 124.4 (2) | C11—C12—H12 | 119.6 |
N1—C5—H5 | 117.8 | C12—C13—C14 | 120.2 (2) |
C4—C5—H5 | 117.8 | C12—C13—H13 | 119.9 |
N2—C6—C4 | 111.77 (18) | C14—C13—H13 | 119.9 |
N2—C6—H6A | 109.3 | C13—C14—C15 | 119.9 (2) |
C4—C6—H6A | 109.3 | C13—C14—H14 | 120.0 |
N2—C6—H6B | 109.3 | C15—C14—H14 | 120.0 |
C4—C6—H6B | 109.3 | C10—C15—C14 | 119.5 (2) |
H6A—C6—H6B | 107.9 | C10—C15—H15 | 120.3 |
N2—C7—C8 | 103.32 (18) | C14—C15—H15 | 120.3 |
N2—C7—H7A | 111.1 | C1—N1—C5 | 116.0 (2) |
C8—C7—H7A | 111.1 | C9—N2—C7 | 111.67 (18) |
N2—C7—H7B | 111.1 | C9—N2—C6 | 121.88 (19) |
C8—C7—H7B | 111.1 | C7—N2—C6 | 123.74 (19) |
H7A—C7—H7B | 109.1 | C8—N3—C9 | 111.24 (17) |
O2—C8—N3 | 126.5 (2) | C8—N3—C10 | 125.55 (17) |
O2—C8—C7 | 127.5 (2) | C9—N3—C10 | 123.20 (17) |
N1—C1—C2—C3 | −3.4 (4) | C4—C5—N1—C1 | 1.7 (4) |
Cl1—C1—C2—C3 | 177.4 (2) | O1—C9—N2—C7 | 173.2 (2) |
C1—C2—C3—C4 | 1.6 (4) | N3—C9—N2—C7 | −6.8 (3) |
C2—C3—C4—C5 | 1.4 (4) | O1—C9—N2—C6 | 11.2 (4) |
C2—C3—C4—C6 | −176.6 (2) | N3—C9—N2—C6 | −168.84 (19) |
C3—C4—C5—N1 | −3.2 (4) | C8—C7—N2—C9 | 4.3 (3) |
C6—C4—C5—N1 | 174.8 (2) | C8—C7—N2—C6 | 165.91 (19) |
C5—C4—C6—N2 | −79.0 (3) | C4—C6—N2—C9 | 83.1 (3) |
C3—C4—C6—N2 | 98.9 (3) | C4—C6—N2—C7 | −76.7 (3) |
N2—C7—C8—O2 | −179.4 (2) | O2—C8—N3—C9 | 175.4 (2) |
N2—C7—C8—N3 | 0.0 (2) | C7—C8—N3—C9 | −4.1 (2) |
C15—C10—C11—C12 | 0.5 (3) | O2—C8—N3—C10 | −4.7 (3) |
N3—C10—C11—C12 | 178.9 (2) | C7—C8—N3—C10 | 175.93 (19) |
C10—C11—C12—C13 | 0.0 (3) | O1—C9—N3—C8 | −173.1 (2) |
C11—C12—C13—C14 | −0.3 (4) | N2—C9—N3—C8 | 6.8 (2) |
C12—C13—C14—C15 | 0.1 (4) | O1—C9—N3—C10 | 6.9 (3) |
C11—C10—C15—C14 | −0.7 (3) | N2—C9—N3—C10 | −173.14 (18) |
N3—C10—C15—C14 | −179.06 (19) | C15—C10—N3—C8 | −74.4 (3) |
C13—C14—C15—C10 | 0.4 (3) | C11—C10—N3—C8 | 107.2 (2) |
C2—C1—N1—C5 | 1.8 (4) | C15—C10—N3—C9 | 105.5 (2) |
Cl1—C1—N1—C5 | −179.0 (2) | C11—C10—N3—C9 | −72.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O2i | 0.93 | 2.53 | 3.205 (3) | 129 |
C14—H14···O1ii | 0.93 | 2.44 | 3.221 (3) | 142 |
C6—H6A···Cg1iii | 0.97 | 2.80 | 3.751 (3) | 168 |
C15—H15···Cg1ii | 0.97 | 2.90 | 3.637 (3) | 137 |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C15H12ClN3O2 |
Mr | 301.73 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 297 |
a, b, c (Å) | 7.7106 (10), 6.3329 (9), 28.673 (4) |
β (°) | 91.552 (2) |
V (Å3) | 1399.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan |
Tmin, Tmax | 0.921, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7874, 2882, 2353 |
Rint | 0.087 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.154, 1.06 |
No. of reflections | 2882 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.23 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O2i | 0.93 | 2.53 | 3.205 (3) | 129.3 |
C14—H14···O1ii | 0.93 | 2.44 | 3.221 (3) | 141.7 |
C6—H6A···Cg1iii | 0.97 | 2.80 | 3.751 (3) | 168 |
C15—H15···Cg1ii | 0.97 | 2.90 | 3.637 (3) | 137 |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x−1, y, z. |
Imidazolidine-2,4-diones became of recent importance in the research and development of agrochemicals due to their widespread biological activites. Some of them have been used as herbicides, fungicides, etc. (Lee et al., 1997; Hirai et al., 1999). Neonicotinoid insecticides as nicotinic acetylcholine receptor inhibitors have attracted increasing attention because of their safety, low toxicity, wide range of activities and high potency. It has been found that most biologically active nicotinic compounds contain the (aminomethyl)-pyridine moiety. As a continuation of our search for new biologically active heterocyclic compounds, we report here the crystal structure of the title compound, (I) (Fig.1).
Selected bonds in (I) are listed in Table 1. In the crystal structure, the C7—N2, C8—N3, C9—N2 and C9—N3 bonds are significantly shorter than a normal single C—N bond (1.47 Å; Sasada, 1984) and close to the value for a C═N bond (1.28 Å; Wang et al., 1998), which is indicative of signficant double-bond character. Weak C—H···O hydrogen bond (Table 2) and C—H···π interactions contribute to the stability of the crystal structure.