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In the title compound, C15H12ClN3O2, the imidazolidine ring system is almost planar; the dihedral angles between it and the phenyl and pyridine rings are 74.44 (12) and 83.75 (12)°, respectively. The structure is stabilized by weak C—H...O hydrogen bonds, as well as C—H...π inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029224/at2329sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029224/at2329Isup2.hkl
Contains datablock I

CCDC reference: 657772

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Datablock: I


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Comment top

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 CN 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.

Related literature top

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).

Experimental top

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.

Refinement top

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).

Structure description top

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 CN 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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I), showing the atom labelling scheme and with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. A partial view of the crystal packing of (I), showing the formation of C—H···O hydrogen-bonded and C—H···π packing interactions, showing as dashed lines.
1-[(6-Chloropyridin-3-yl)methyl]-3-phenylimidazolidine-2,4-dione top
Crystal data top
C15H12ClN3O2F(000) = 624
Mr = 301.73Dx = 1.432 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3094 reflections
a = 7.7106 (10) Åθ = 2.7–27.0°
b = 6.3329 (9) ŵ = 0.28 mm1
c = 28.673 (4) ÅT = 297 K
β = 91.552 (2)°Block, colourless
V = 1399.6 (3) Å30.30 × 0.20 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2882 independent reflections
Radiation source: fine-focus sealed tube2353 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.087
φ and ω scansθmax = 26.5°, θmin = 2.7°
Absorption correction: multi-scanh = 99
Tmin = 0.921, Tmax = 0.946k = 77
7874 measured reflectionsl = 3335
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-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 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C15H12ClN3O2V = 1399.6 (3) Å3
Mr = 301.73Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.7106 (10) ŵ = 0.28 mm1
b = 6.3329 (9) ÅT = 297 K
c = 28.673 (4) Å0.30 × 0.20 × 0.20 mm
β = 91.552 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2882 independent reflections
Absorption correction: multi-scan2353 reflections with I > 2σ(I)
Tmin = 0.921, Tmax = 0.946Rint = 0.087
7874 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.154H-atom parameters constrained
S = 1.06Δρmax = 0.27 e Å3
2882 reflectionsΔρmin = 0.23 e Å3
190 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2372 (3)0.5225 (4)0.99690 (8)0.0533 (6)
C20.2084 (3)0.7347 (4)1.00312 (9)0.0587 (7)
H20.18930.79051.03250.070*
C30.2090 (3)0.8609 (4)0.96422 (9)0.0537 (6)
H30.19301.00590.96700.064*
C40.2335 (3)0.7713 (4)0.92095 (8)0.0428 (5)
C50.2527 (3)0.5546 (4)0.91929 (8)0.0541 (6)
H50.26320.49200.89020.065*
C60.2454 (3)0.9009 (4)0.87684 (8)0.0479 (5)
H6A0.18350.82900.85160.057*
H6B0.19001.03660.88140.057*
C70.5401 (3)1.0844 (4)0.88673 (9)0.0479 (5)
H7A0.53441.07330.92040.057*
H7B0.51171.22780.87740.057*
C80.7167 (3)1.0213 (3)0.87015 (7)0.0406 (5)
C90.5137 (3)0.7895 (4)0.83985 (8)0.0428 (5)
C100.8204 (3)0.7462 (3)0.81482 (7)0.0367 (5)
C110.8776 (3)0.5483 (3)0.82859 (8)0.0452 (5)
H110.83370.48370.85490.054*
C121.0016 (3)0.4480 (4)0.80236 (9)0.0510 (6)
H121.04130.31480.81120.061*
C131.0665 (3)0.5432 (4)0.76354 (8)0.0514 (6)
H131.15000.47450.74630.062*
C141.0083 (3)0.7397 (4)0.75001 (8)0.0494 (6)
H141.05240.80380.72370.059*
C150.8838 (3)0.8422 (4)0.77574 (8)0.0431 (5)
H150.84340.97470.76660.052*
Cl10.24657 (13)0.35783 (14)1.04586 (3)0.0857 (3)
N10.2570 (3)0.4292 (3)0.95662 (7)0.0618 (6)
N20.4254 (2)0.9345 (3)0.86390 (6)0.0447 (5)
N30.6895 (2)0.8510 (3)0.84105 (6)0.0392 (4)
O10.4589 (2)0.6335 (3)0.82032 (7)0.0632 (5)
O20.8541 (2)1.1011 (3)0.88035 (6)0.0530 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0629 (15)0.0527 (14)0.0441 (13)0.0047 (11)0.0008 (11)0.0072 (11)
C20.0751 (18)0.0575 (16)0.0437 (13)0.0037 (13)0.0053 (12)0.0116 (11)
C30.0658 (15)0.0410 (13)0.0545 (14)0.0010 (11)0.0071 (12)0.0083 (11)
C40.0385 (11)0.0436 (12)0.0464 (12)0.0019 (9)0.0023 (9)0.0044 (9)
C50.0758 (17)0.0441 (13)0.0424 (12)0.0036 (12)0.0053 (11)0.0072 (10)
C60.0429 (12)0.0516 (13)0.0492 (13)0.0053 (10)0.0011 (10)0.0053 (10)
C70.0519 (13)0.0377 (11)0.0543 (13)0.0007 (10)0.0053 (10)0.0050 (10)
C80.0499 (12)0.0316 (10)0.0404 (11)0.0004 (9)0.0015 (9)0.0035 (9)
C90.0422 (11)0.0474 (12)0.0388 (11)0.0012 (9)0.0006 (9)0.0013 (10)
C100.0360 (10)0.0366 (11)0.0373 (10)0.0022 (8)0.0017 (8)0.0030 (8)
C110.0552 (13)0.0395 (12)0.0408 (12)0.0004 (10)0.0013 (10)0.0034 (9)
C120.0567 (14)0.0399 (12)0.0560 (14)0.0107 (10)0.0047 (11)0.0009 (10)
C130.0485 (13)0.0599 (15)0.0456 (13)0.0069 (11)0.0007 (10)0.0129 (11)
C140.0457 (12)0.0615 (15)0.0413 (12)0.0044 (11)0.0049 (9)0.0039 (11)
C150.0479 (12)0.0392 (12)0.0419 (12)0.0000 (9)0.0012 (9)0.0052 (9)
Cl10.1187 (7)0.0829 (6)0.0553 (5)0.0030 (5)0.0017 (4)0.0236 (4)
N10.0920 (17)0.0422 (11)0.0513 (12)0.0049 (11)0.0054 (11)0.0003 (9)
N20.0439 (10)0.0453 (10)0.0452 (10)0.0003 (8)0.0036 (8)0.0028 (8)
N30.0399 (9)0.0372 (9)0.0406 (9)0.0015 (7)0.0012 (7)0.0038 (7)
O10.0538 (10)0.0663 (12)0.0697 (12)0.0135 (8)0.0043 (9)0.0294 (10)
O20.0480 (9)0.0454 (9)0.0657 (11)0.0098 (7)0.0012 (8)0.0099 (8)
Geometric parameters (Å, º) top
C1—N11.310 (3)C8—O21.203 (3)
C1—C21.374 (4)C8—N31.376 (3)
C1—Cl11.749 (2)C9—O11.206 (3)
C2—C31.372 (4)C9—N21.345 (3)
C2—H20.9300C9—N31.410 (3)
C3—C41.382 (3)C10—C151.376 (3)
C3—H30.9300C10—C111.382 (3)
C4—C51.382 (3)C10—N31.438 (3)
C4—C61.512 (3)C11—C121.387 (3)
C5—N11.332 (3)C11—H110.9300
C5—H50.9300C12—C131.372 (3)
C6—N21.462 (3)C12—H120.9300
C6—H6A0.9700C13—C141.375 (4)
C6—H6B0.9700C13—H130.9300
C7—N21.443 (3)C14—C151.388 (3)
C7—C81.508 (3)C14—H140.9300
C7—H7A0.9700C15—H150.9300
C7—H7B0.9700
N1—C1—C2125.3 (2)N3—C8—C7105.94 (18)
N1—C1—Cl1115.8 (2)O1—C9—N2128.4 (2)
C2—C1—Cl1118.8 (2)O1—C9—N3124.2 (2)
C3—C2—C1117.4 (2)N2—C9—N3107.36 (18)
C3—C2—H2121.3C15—C10—C11121.0 (2)
C1—C2—H2121.3C15—C10—N3119.45 (19)
C2—C3—C4119.6 (2)C11—C10—N3119.49 (19)
C2—C3—H3120.2C10—C11—C12118.7 (2)
C4—C3—H3120.2C10—C11—H11120.7
C5—C4—C3117.1 (2)C12—C11—H11120.7
C5—C4—C6120.1 (2)C13—C12—C11120.7 (2)
C3—C4—C6122.8 (2)C13—C12—H12119.6
N1—C5—C4124.4 (2)C11—C12—H12119.6
N1—C5—H5117.8C12—C13—C14120.2 (2)
C4—C5—H5117.8C12—C13—H13119.9
N2—C6—C4111.77 (18)C14—C13—H13119.9
N2—C6—H6A109.3C13—C14—C15119.9 (2)
C4—C6—H6A109.3C13—C14—H14120.0
N2—C6—H6B109.3C15—C14—H14120.0
C4—C6—H6B109.3C10—C15—C14119.5 (2)
H6A—C6—H6B107.9C10—C15—H15120.3
N2—C7—C8103.32 (18)C14—C15—H15120.3
N2—C7—H7A111.1C1—N1—C5116.0 (2)
C8—C7—H7A111.1C9—N2—C7111.67 (18)
N2—C7—H7B111.1C9—N2—C6121.88 (19)
C8—C7—H7B111.1C7—N2—C6123.74 (19)
H7A—C7—H7B109.1C8—N3—C9111.24 (17)
O2—C8—N3126.5 (2)C8—N3—C10125.55 (17)
O2—C8—C7127.5 (2)C9—N3—C10123.20 (17)
N1—C1—C2—C33.4 (4)C4—C5—N1—C11.7 (4)
Cl1—C1—C2—C3177.4 (2)O1—C9—N2—C7173.2 (2)
C1—C2—C3—C41.6 (4)N3—C9—N2—C76.8 (3)
C2—C3—C4—C51.4 (4)O1—C9—N2—C611.2 (4)
C2—C3—C4—C6176.6 (2)N3—C9—N2—C6168.84 (19)
C3—C4—C5—N13.2 (4)C8—C7—N2—C94.3 (3)
C6—C4—C5—N1174.8 (2)C8—C7—N2—C6165.91 (19)
C5—C4—C6—N279.0 (3)C4—C6—N2—C983.1 (3)
C3—C4—C6—N298.9 (3)C4—C6—N2—C776.7 (3)
N2—C7—C8—O2179.4 (2)O2—C8—N3—C9175.4 (2)
N2—C7—C8—N30.0 (2)C7—C8—N3—C94.1 (2)
C15—C10—C11—C120.5 (3)O2—C8—N3—C104.7 (3)
N3—C10—C11—C12178.9 (2)C7—C8—N3—C10175.93 (19)
C10—C11—C12—C130.0 (3)O1—C9—N3—C8173.1 (2)
C11—C12—C13—C140.3 (4)N2—C9—N3—C86.8 (2)
C12—C13—C14—C150.1 (4)O1—C9—N3—C106.9 (3)
C11—C10—C15—C140.7 (3)N2—C9—N3—C10173.14 (18)
N3—C10—C15—C14179.06 (19)C15—C10—N3—C874.4 (3)
C13—C14—C15—C100.4 (3)C11—C10—N3—C8107.2 (2)
C2—C1—N1—C51.8 (4)C15—C10—N3—C9105.5 (2)
Cl1—C1—N1—C5179.0 (2)C11—C10—N3—C972.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···O2i0.932.533.205 (3)129
C14—H14···O1ii0.932.443.221 (3)142
C6—H6A···Cg1iii0.972.803.751 (3)168
C15—H15···Cg1ii0.972.903.637 (3)137
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y+1/2, z+3/2; (iii) x1, y, z.

Experimental details

Crystal data
Chemical formulaC15H12ClN3O2
Mr301.73
Crystal system, space groupMonoclinic, P21/n
Temperature (K)297
a, b, c (Å)7.7106 (10), 6.3329 (9), 28.673 (4)
β (°) 91.552 (2)
V3)1399.6 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.28
Crystal size (mm)0.30 × 0.20 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
Tmin, Tmax0.921, 0.946
No. of measured, independent and
observed [I > 2σ(I)] reflections
7874, 2882, 2353
Rint0.087
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.154, 1.06
No. of reflections2882
No. of parameters190
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.23

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···O2i0.932.533.205 (3)129.3
C14—H14···O1ii0.932.443.221 (3)141.7
C6—H6A···Cg1iii0.972.803.751 (3)168
C15—H15···Cg1ii0.972.903.637 (3)137
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y+1/2, z+3/2; (iii) x1, y, z.
 

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