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In the crystal structure of the title compound, C12H14N4O3, the dihedral angle between the phenyl and imidazole rings is 76.55 (7)°. The nitrite O atoms of the (E)-2-nitrimino­imidazolidin-1-yl group act as the acceptors of three N—H...O hydrogen bonds from the N atom of the imidazole ring, resulting in a one-dimensional chain. C—H...O hydrogen-bonding inter­actions are also observed in this complex, extending the structure into a two-dimensional supra­molecular sheet.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047939/hg2297sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047939/hg2297Isup2.hkl
Contains datablock I

CCDC reference: 667296

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.044
  • wR factor = 0.135
  • Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT230_ALERT_2_C Hirshfeld Test Diff for N3 - N4 .. 5.12 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N4 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C12 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.03
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Neonicotinoids (Yamamoto, 1996) represent a novel and distinct chemical class of insecticides with remarkable chemical and biological properties (Yamamoto Casida, 1999), which hold low degree of toxicity to mammals and aquatic life, and stability in the fields. Neonicotinoids act at the acetylcholine binding site of the nicotinic acetylcholine receptor (nAChR) of insects and the nitroimino imidazolidine is an important pharmcophore. Kagabu proposed that the nitrogen atom at the 1-position of the imidazolidine ring and one of the oxygen atoms of the nitro group play an important role in the interaction with the binding sites on nAChR (Kagabu, 1999).

The molecular structure of (I) (Fig. 1) contains no crystallographically imposed symmetry. The imidazole and benzene rings in each of the ligands are not coplanar, the dihedral angle formed by the least-squares planes of the phenyl and imidazole rings being equal to 76.55 (7)°. The dihedral angles between the mean plane of the imidazole ring and the plane of the N4/O2/O3 group are 4.67 (15)°. Selected bond lengths and angles are listed in Table 1.

Analysis of the crystal packing of (I) shows the existence of three N—H···O (two intermolecular and one intramolecular) interactions between the nitrite O atoms of the L ligand and the imidazole N atom, resulting in a one-dimensional chain along with [001] direction, as shown in Fig. 2. In this 1-D chain, a hydrogen-bonded ring, N = R2(3), is generated (Etter, 1990), which comprises one imidazole N2 atom and two O atoms of the nitrite group (O2 and O3). Furthermore, this 1-D chains are extended into 2-D supramolecular sheet via C(9)—H(B)···O(2) hydrogen bonds in bc plane [Symmetry code: x, 3/2 - y, 1/2 + z], as shown in Fig. 3. A significant intramolecular C(9)—H(9 A)···N(3) interaction is also observed, which contributes strongly to the stability of the structure. All relevant hydrogen-bonding geometries are listed in Table 2.

Related literature top

For related literature, see: Etter (1990); Kagabu (1999); Yamamoto (1996); Yamamoto & Casida (1999).

Experimental top

A suspension of 3-choro-1-phenylpropan-1-one (1.68 g, 10 mmol), nitroimino imidazolidine (1.31 g, 10 mmol) and potassium carbonate (1.38 g, 10 mmol) in 25 ml of methyl cyanide was heated to reflux for 30 min. The reaction was quenched with water and extracted with methylene chloride. The extract was washed with brine, dried over anhydrous magnesium sulfate and the solvent evaporated. The residue was purified by silica gel column chromatography to give the target compound. The crystal was grown by slow evaporation of an ethanol solution at room temperature. Anal. Calcd for C12H14N4O3: C, 55.90; H, 5.63; N, 8.69. Found: C, 55.67; H, 5.64; N, 8.66. 1H NMR (CDCl3): 3.372 (b, 2H, CH2), 3.775 (s, 6H, –NCH2N–), 7.465–7.551 (m, 2H, Ar—H), 7.623–7.579 (m, 1H, Ar—H), 7.660 (dd, 2H, Ar—H), 8.020 (s, 1H, NH).

Refinement top

Although all H atoms were visible in difference maps, they were placed in geometrically calculated positions, with C—H distances in the range 0.93–0.97 Å and N—H distances of 0.86 Å, and included in the final refinement in the riding model approximation,with Uiso(H) = 1.2Ueq(C) for aromatic and methylene H atoms.

Structure description top

Neonicotinoids (Yamamoto, 1996) represent a novel and distinct chemical class of insecticides with remarkable chemical and biological properties (Yamamoto Casida, 1999), which hold low degree of toxicity to mammals and aquatic life, and stability in the fields. Neonicotinoids act at the acetylcholine binding site of the nicotinic acetylcholine receptor (nAChR) of insects and the nitroimino imidazolidine is an important pharmcophore. Kagabu proposed that the nitrogen atom at the 1-position of the imidazolidine ring and one of the oxygen atoms of the nitro group play an important role in the interaction with the binding sites on nAChR (Kagabu, 1999).

The molecular structure of (I) (Fig. 1) contains no crystallographically imposed symmetry. The imidazole and benzene rings in each of the ligands are not coplanar, the dihedral angle formed by the least-squares planes of the phenyl and imidazole rings being equal to 76.55 (7)°. The dihedral angles between the mean plane of the imidazole ring and the plane of the N4/O2/O3 group are 4.67 (15)°. Selected bond lengths and angles are listed in Table 1.

Analysis of the crystal packing of (I) shows the existence of three N—H···O (two intermolecular and one intramolecular) interactions between the nitrite O atoms of the L ligand and the imidazole N atom, resulting in a one-dimensional chain along with [001] direction, as shown in Fig. 2. In this 1-D chain, a hydrogen-bonded ring, N = R2(3), is generated (Etter, 1990), which comprises one imidazole N2 atom and two O atoms of the nitrite group (O2 and O3). Furthermore, this 1-D chains are extended into 2-D supramolecular sheet via C(9)—H(B)···O(2) hydrogen bonds in bc plane [Symmetry code: x, 3/2 - y, 1/2 + z], as shown in Fig. 3. A significant intramolecular C(9)—H(9 A)···N(3) interaction is also observed, which contributes strongly to the stability of the structure. All relevant hydrogen-bonding geometries are listed in Table 2.

For related literature, see: Etter (1990); Kagabu (1999); Yamamoto (1996); Yamamoto & Casida (1999).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. The packing of (I), viewed down the b axis, showing one-dimensional chain connected by C—H···N hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted. [Symmetry code: (i) 1 - x, 1/2 + y, 1/2 - z; (ii) x, 3/2 - y, 1/2 + z].
[Figure 3] Fig. 3. A view of the two-dimensional supramolecular sheet of (I), showing the C—H···O hydrogen-bonding interactions (black dashed lines). The L molecules have been partly omitted for clarity.
(E)-3-(2-Nitriminoimidazolidin-1-yl)-1-phenylpropan-1-one top
Crystal data top
C12H14N4O3F(000) = 552
Mr = 262.27Dx = 1.383 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1967 reflections
a = 15.346 (4) Åθ = 2.7–26.2°
b = 6.0908 (15) ŵ = 0.10 mm1
c = 13.784 (3) ÅT = 294 K
β = 102.098 (4)°Block, colourless
V = 1259.8 (5) Å30.28 × 0.24 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2582 independent reflections
Radiation source: fine-focus sealed tube1534 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
φ and ω scansθmax = 26.4°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1819
Tmin = 0.972, Tmax = 0.980k = 67
6913 measured reflectionsl = 1714
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.135 w = 1/[σ2(Fo2) + (0.0576P)2 + 0.2621P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2582 reflectionsΔρmax = 0.17 e Å3
173 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.015 (3)
Crystal data top
C12H14N4O3V = 1259.8 (5) Å3
Mr = 262.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.346 (4) ŵ = 0.10 mm1
b = 6.0908 (15) ÅT = 294 K
c = 13.784 (3) Å0.28 × 0.24 × 0.20 mm
β = 102.098 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2582 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1534 reflections with I > 2σ(I)
Tmin = 0.972, Tmax = 0.980Rint = 0.039
6913 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.135H-atom parameters constrained
S = 1.00Δρmax = 0.17 e Å3
2582 reflectionsΔρmin = 0.19 e Å3
173 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
O10.89456 (9)0.4085 (3)0.57018 (12)0.0741 (5)
O20.62133 (12)0.2316 (4)0.85036 (15)0.1197 (8)
O30.54319 (14)0.0283 (4)0.77931 (16)0.1252 (8)
N10.68641 (11)0.0235 (3)0.57030 (13)0.0690 (5)
N20.58391 (13)0.2046 (4)0.62248 (17)0.0955 (7)
H20.54930.24370.66110.115*
N30.65419 (10)0.1137 (3)0.71315 (13)0.0668 (5)
N40.60406 (13)0.1005 (4)0.78249 (15)0.0814 (6)
C11.07620 (13)0.3262 (3)0.62309 (14)0.0575 (5)
H11.05770.46680.60180.069*
C21.16612 (14)0.2813 (4)0.65379 (16)0.0666 (6)
H2A1.20780.39200.65330.080*
C31.19427 (14)0.0738 (4)0.68500 (15)0.0670 (6)
H31.25470.04480.70690.080*
C41.13284 (14)0.0900 (4)0.68366 (16)0.0694 (6)
H41.15190.23130.70310.083*
C51.04285 (14)0.0474 (4)0.65363 (15)0.0613 (6)
H51.00180.15970.65340.074*
C61.01342 (12)0.1622 (3)0.62384 (12)0.0483 (5)
C70.91721 (13)0.2204 (3)0.59318 (13)0.0528 (5)
C80.84777 (12)0.0457 (3)0.59221 (14)0.0560 (5)
H8A0.85640.02120.65740.067*
H8B0.85500.06760.54510.067*
C90.75451 (12)0.1381 (4)0.56442 (15)0.0630 (6)
H9A0.74910.25950.60830.076*
H9B0.74460.19510.49730.076*
C100.66626 (17)0.2033 (5)0.5001 (2)0.0954 (9)
H10A0.71670.30170.50550.114*
H10B0.64960.14940.43260.114*
C110.58803 (18)0.3171 (5)0.5314 (2)0.1044 (10)
H11A0.53340.29810.48210.125*
H11B0.59940.47270.54270.125*
C120.63860 (12)0.0357 (4)0.64033 (16)0.0596 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0635 (9)0.0647 (10)0.0971 (12)0.0063 (8)0.0236 (8)0.0197 (8)
O20.0866 (13)0.189 (2)0.0880 (13)0.0068 (14)0.0296 (10)0.0507 (15)
O30.1108 (15)0.163 (2)0.1241 (17)0.0436 (16)0.0761 (13)0.0316 (15)
N10.0608 (10)0.0798 (13)0.0744 (12)0.0253 (9)0.0326 (9)0.0172 (10)
N20.0827 (14)0.1091 (17)0.1117 (17)0.0450 (13)0.0591 (12)0.0252 (14)
N30.0461 (9)0.0920 (14)0.0656 (11)0.0005 (9)0.0192 (8)0.0066 (10)
N40.0522 (11)0.1243 (19)0.0696 (13)0.0040 (12)0.0174 (9)0.0096 (13)
C10.0618 (12)0.0540 (12)0.0613 (12)0.0126 (10)0.0236 (10)0.0065 (9)
C20.0551 (13)0.0727 (15)0.0761 (15)0.0174 (11)0.0232 (11)0.0169 (12)
C30.0563 (12)0.0864 (17)0.0583 (13)0.0008 (12)0.0119 (10)0.0079 (12)
C40.0686 (14)0.0687 (14)0.0697 (14)0.0024 (12)0.0117 (11)0.0087 (11)
C50.0660 (13)0.0586 (13)0.0601 (12)0.0130 (10)0.0148 (10)0.0075 (10)
C60.0539 (11)0.0547 (12)0.0395 (10)0.0108 (9)0.0171 (8)0.0027 (8)
C70.0624 (12)0.0554 (13)0.0448 (11)0.0102 (10)0.0207 (9)0.0042 (9)
C80.0558 (11)0.0613 (13)0.0538 (11)0.0144 (10)0.0178 (9)0.0012 (9)
C90.0553 (12)0.0714 (15)0.0659 (13)0.0175 (10)0.0210 (10)0.0018 (11)
C100.0881 (17)0.105 (2)0.107 (2)0.0444 (16)0.0515 (15)0.0386 (17)
C110.0877 (18)0.113 (2)0.128 (2)0.0473 (17)0.0580 (17)0.0403 (19)
C120.0395 (10)0.0732 (14)0.0682 (13)0.000.0164 (9)0.0008 (11)
Geometric parameters (Å, º) top
O1—C71.220 (2)C3—H30.9300
O2—N41.216 (3)C4—C51.381 (3)
O3—N41.214 (3)C4—H40.9300
N1—C121.332 (2)C5—C61.387 (3)
N1—C91.450 (2)C5—H50.9300
N1—C101.451 (3)C6—C71.491 (3)
N2—C121.318 (3)C7—C81.504 (3)
N2—C111.443 (3)C8—C91.511 (3)
N2—H20.8600C8—H8A0.9700
N3—C121.338 (3)C8—H8B0.9700
N3—N41.349 (2)C9—H9A0.9700
C1—C21.383 (3)C9—H9B0.9700
C1—C61.390 (2)C10—C111.525 (3)
C1—H10.9300C10—H10A0.9700
C2—C31.375 (3)C10—H10B0.9700
C2—H2A0.9300C11—H11A0.9700
C3—C41.370 (3)C11—H11B0.9700
C12—N1—C9126.26 (18)O1—C7—C8119.96 (18)
C12—N1—C10111.61 (17)C6—C7—C8119.49 (17)
C9—N1—C10122.04 (16)C7—C8—C9111.77 (17)
C12—N2—C11113.02 (18)C7—C8—H8A109.3
C12—N2—H2123.5C9—C8—H8A109.3
C11—N2—H2123.5C7—C8—H8B109.3
C12—N3—N4116.87 (19)C9—C8—H8B109.3
O3—N4—O2119.6 (2)H8A—C8—H8B107.9
O3—N4—N3124.2 (2)N1—C9—C8112.88 (18)
O2—N4—N3116.2 (2)N1—C9—H9A109.0
C2—C1—C6120.3 (2)C8—C9—H9A109.0
C2—C1—H1119.9N1—C9—H9B109.0
C6—C1—H1119.9C8—C9—H9B109.0
C3—C2—C1120.4 (2)H9A—C9—H9B107.8
C3—C2—H2A119.8N1—C10—C11103.03 (19)
C1—C2—H2A119.8N1—C10—H10A111.2
C4—C3—C2119.7 (2)C11—C10—H10A111.2
C4—C3—H3120.2N1—C10—H10B111.2
C2—C3—H3120.2C11—C10—H10B111.2
C3—C4—C5120.6 (2)H10A—C10—H10B109.1
C3—C4—H4119.7N2—C11—C10102.15 (19)
C5—C4—H4119.7N2—C11—H11A111.3
C4—C5—C6120.34 (19)C10—C11—H11A111.3
C4—C5—H5119.8N2—C11—H11B111.3
C6—C5—H5119.8C10—C11—H11B111.3
C5—C6—C1118.72 (19)H11A—C11—H11B109.2
C5—C6—C7122.99 (17)N2—C12—N1109.5 (2)
C1—C6—C7118.29 (18)N2—C12—N3132.64 (19)
O1—C7—C6120.55 (17)N1—C12—N3117.82 (18)
C12—N3—N4—O34.6 (3)C12—N1—C9—C8105.8 (2)
C12—N3—N4—O2177.2 (2)C10—N1—C9—C870.6 (3)
C6—C1—C2—C30.2 (3)C7—C8—C9—N1175.57 (16)
C1—C2—C3—C41.3 (3)C12—N1—C10—C116.7 (3)
C2—C3—C4—C51.6 (3)C9—N1—C10—C11176.4 (2)
C3—C4—C5—C60.4 (3)C12—N2—C11—C107.1 (3)
C4—C5—C6—C11.2 (3)N1—C10—C11—N27.8 (3)
C4—C5—C6—C7178.32 (17)C11—N2—C12—N13.2 (3)
C2—C1—C6—C51.5 (3)C11—N2—C12—N3178.0 (2)
C2—C1—C6—C7178.05 (16)C9—N1—C12—N2179.2 (2)
C5—C6—C7—O1177.96 (18)C10—N1—C12—N22.6 (3)
C1—C6—C7—O11.6 (3)C9—N1—C12—N30.3 (3)
C5—C6—C7—C81.1 (3)C10—N1—C12—N3176.4 (2)
C1—C6—C7—C8179.35 (16)N4—N3—C12—N22.3 (4)
O1—C7—C8—C92.1 (3)N4—N3—C12—N1178.99 (19)
C6—C7—C8—C9177.01 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.862.603.272 (3)136
N2—H2···O3i0.862.493.260 (3)150
C9—H9B···O2ii0.972.503.314 (3)141
N2—H2···O30.862.112.605 (3)116
C9—H9A···N30.972.422.814 (2)104
Symmetry codes: (i) x+1, y1/2, z+3/2; (ii) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC12H14N4O3
Mr262.27
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)15.346 (4), 6.0908 (15), 13.784 (3)
β (°) 102.098 (4)
V3)1259.8 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.28 × 0.24 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.972, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
6913, 2582, 1534
Rint0.039
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.135, 1.00
No. of reflections2582
No. of parameters173
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.19

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.862.603.272 (3)136.4
N2—H2···O3i0.862.493.260 (3)150.0
C9—H9B···O2ii0.972.503.314 (3)140.9
N2—H2···O30.862.112.605 (3)116.0
C9—H9A···N30.972.422.814 (2)103.5
Symmetry codes: (i) x+1, y1/2, z+3/2; (ii) x, y+1/2, z1/2.
 

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