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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o62.
Published online 2007 December 6. doi:  10.1107/S1600536807055778
PMCID: PMC2915020

(E)-Benzo­yl[1-(2-hydroxy­ethyl)imidazolidin-2-yl­idene]acetonitrile

Abstract

In the title compound, C14H15N3O2, the C=C(H)—C=O grouping and the imidazolidine ring are coplanar as a result of an intra­molecular N—H(...)O hydrogen bond and extended electronic conjugation. Inter­molecular N—H(...)O and O—H(...)N hydrogen bonds help to establish the packing.

Related literature

For related literature, see: Wang & Huang (1996 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-00o62-scheme1.jpg

Experimental

Crystal data

  • C14H15N3O2
  • M r = 257.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00o62-efi1.jpg
  • a = 8.3748 (17) Å
  • b = 14.633 (3) Å
  • c = 10.784 (2) Å
  • β = 107.33 (3)°
  • V = 1261.6 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 113 (2) K
  • 0.10 × 0.08 × 0.06 mm

Data collection

  • Rigaku Saturn diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.982, T max = 0.994
  • 9551 measured reflections
  • 2994 independent reflections
  • 2534 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.103
  • S = 1.10
  • 2994 reflections
  • 180 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 1997 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected torsion angles (°)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807055778/hb2622sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807055778/hb2622Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank Haibin Song at Nankai University for the X-ray crystallographic determination.

supplementary crystallographic information

Comment

Heterocyclic ketene aminals (HKAs) are versatile synthons for heterocyclic synthesis. The title compound, (I), (Fig. 1), which possesses a β-hydroxyethyl group on the nitrogen atom of the imidazolidine ring, is a member of this family (Wang & Huang, 1996).

Due to the extended conjugation in the molecule, some abnormal geometrical parameters occur. For example, O2—C8 = 1.2487 (14) Å, which is longer than a normal double bond; the length of N1—C5 [1.3435 (16) Å] and N2—C5 [1.3366 (16) Å] are shorter than those of normal C—N single bonds; the length of C5—C6 [1.4348 (17) Å] double bond is longer than that of a normal C=C bond. The atoms of imidazoline ring in this compound (I) are approximately coplanar, in which, the torsion angle of C3—N1—C5—N2 is 1.74 (17)°, the torsion angle of C4—N2—C5—N1 is 11.16 (14)°, and the torsion angle of C5—N1—C3—C4 is -12.82 (13)°.

The molecules are linked by intermolecular N—H···O hydrogen bonds and O—H···N bonds (Table 1). There is also an intramolecular hydrogen bond involving the O2 and amide N2 atoms.

Experimental

The title compound was prepared according to the procedure of Wang & Huang (1996) and recrystallized from methanol in 86% yield to yield colourless prisms of (I) (m.p. 449–450 K). IR: ν= 3400 (OH), 3240 (NH), 2180 (CN), 1580 (CO), 1560, 1545 cm-1. 1H-NMR (DMSO-d6): δ= 9.83 (1H, s), 7.34–7.62 (5H, m), 4.44 (1H, s), 3.56–3.84 p.p.m. (8H, m), 13C-NMR (DMSO-d6): δ= 189.8, 163.6, 140.6, 129.8, 127.6, 127.4, 121.6, 64.5, 59.6, 50.4, 48.9, 41.6 p.p.m.. MS: m/z = 257 (M+, 29),226 (7), 212 (6), 160 (14), 105 (100). Anal. Calcd. for C14H15N3O2: C 65.35, H 5.88, N 16.33; found: C 65.39, H 5.77, N 16.42.

Refinement

The N– and O-bound H atoms were located in a difference map and freely refined. The C-bound H atoms were placed in geometrically idealized positions (C—H = 0.95–1.00 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of (I). Ellipsoids are drawn at the 40% probability level (H atoms represented by arbitrary spheres). The intramolecular hydrogen bond is indicated by a dashed line.
Fig. 2.
Packing diagram for (I), viewed down the b axis with hydrogen bonds indicated by dashed lines.

Crystal data

C14H15N3O2F000 = 544
Mr = 257.29Dx = 1.355 Mg m3
Monoclinic, P21/cMelting point = 449–450 K
Hall symbol: -P 2ybcMo Kα radiation λ = 0.71073 Å
a = 8.3748 (17) ÅCell parameters from 4329 reflections
b = 14.633 (3) Åθ = 2.3–22.5º
c = 10.784 (2) ŵ = 0.09 mm1
β = 107.33 (3)ºT = 113 (2) K
V = 1261.6 (4) Å3Prism, colourless
Z = 40.10 × 0.08 × 0.06 mm

Data collection

Rigaku Saturn diffractometer2994 independent reflections
Radiation source: rotating anode2534 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.036
Detector resolution: 7.31 pixels mm-1θmax = 27.9º
T = 113(2) Kθmin = 2.4º
ω and [var phi] scansh = −11→11
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)k = −19→18
Tmin = 0.982, Tmax = 0.994l = −14→11
9551 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.103  w = 1/[σ2(Fo2) + (0.0503P)2 + 0.2093P] where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
2994 reflectionsΔρmax = 0.32 e Å3
180 parametersΔρmin = −0.18 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
O10.30219 (13)0.59907 (7)0.03041 (9)0.0280 (2)
H10.323 (2)0.6459 (13)−0.0116 (18)0.044 (5)*
O20.91862 (10)0.56888 (6)0.57744 (8)0.0186 (2)
N10.47423 (12)0.51059 (7)0.28326 (10)0.0171 (2)
N20.72478 (13)0.46439 (7)0.39657 (10)0.0170 (2)
N30.41182 (14)0.73000 (8)0.45144 (11)0.0259 (3)
C10.30005 (16)0.63405 (9)0.15308 (12)0.0195 (3)
H1A0.19540.66870.14320.023*
H1B0.39570.67600.18760.023*
C20.31137 (15)0.55527 (9)0.24601 (11)0.0169 (3)
H2A0.28780.57810.32520.020*
H2B0.22440.50970.20490.020*
C30.49585 (16)0.42196 (9)0.22523 (12)0.0201 (3)
H3A0.46650.42640.12950.024*
H3B0.42640.37400.24830.024*
C40.68186 (16)0.40238 (9)0.28553 (12)0.0210 (3)
H4A0.70160.33780.31350.025*
H4B0.74610.41670.22440.025*
C50.61006 (14)0.53014 (8)0.38307 (11)0.0150 (2)
C60.63996 (14)0.60969 (8)0.46455 (11)0.0154 (2)
C70.51223 (15)0.67519 (9)0.45570 (11)0.0178 (3)
C80.80273 (14)0.62602 (8)0.55445 (11)0.0151 (2)
C100.79435 (15)0.79899 (9)0.56137 (12)0.0194 (3)
H100.73380.79990.47160.023*
C110.83750 (16)0.88063 (9)0.62852 (13)0.0236 (3)
H110.80660.93720.58480.028*
C120.92588 (16)0.87938 (10)0.75974 (13)0.0238 (3)
H120.95410.93520.80620.029*
C130.97302 (16)0.79694 (10)0.82305 (12)0.0225 (3)
H131.03420.79640.91270.027*
C90.83921 (14)0.71581 (8)0.62480 (11)0.0154 (2)
C140.93138 (15)0.71500 (9)0.75621 (12)0.0194 (3)
H140.96540.65860.79970.023*
H20.827 (2)0.4743 (11)0.4482 (16)0.031 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0475 (6)0.0210 (5)0.0173 (5)−0.0073 (4)0.0125 (4)−0.0009 (4)
O20.0197 (4)0.0155 (5)0.0179 (4)0.0038 (3)0.0016 (3)0.0001 (3)
N10.0172 (5)0.0146 (5)0.0186 (5)−0.0013 (4)0.0041 (4)−0.0033 (4)
N20.0173 (5)0.0137 (5)0.0188 (5)0.0001 (4)0.0033 (4)−0.0040 (4)
N30.0213 (6)0.0246 (6)0.0289 (6)0.0036 (5)0.0030 (4)−0.0091 (5)
C10.0230 (6)0.0166 (6)0.0188 (6)−0.0009 (5)0.0063 (5)−0.0014 (5)
C20.0148 (6)0.0179 (6)0.0175 (6)−0.0019 (5)0.0038 (4)−0.0002 (5)
C30.0223 (6)0.0159 (6)0.0215 (6)−0.0022 (5)0.0057 (5)−0.0054 (5)
C40.0232 (6)0.0161 (6)0.0223 (6)0.0000 (5)0.0049 (5)−0.0064 (5)
C50.0166 (6)0.0148 (6)0.0142 (5)−0.0014 (4)0.0053 (4)0.0016 (4)
C60.0172 (6)0.0129 (6)0.0160 (6)0.0005 (4)0.0050 (4)−0.0008 (4)
C70.0179 (6)0.0182 (6)0.0160 (6)−0.0020 (5)0.0031 (4)−0.0047 (5)
C80.0191 (6)0.0139 (6)0.0129 (5)0.0001 (4)0.0055 (4)0.0016 (4)
C100.0188 (6)0.0172 (6)0.0207 (6)0.0008 (5)0.0034 (5)−0.0015 (5)
C110.0222 (6)0.0159 (7)0.0331 (7)0.0005 (5)0.0087 (5)−0.0024 (5)
C120.0190 (6)0.0216 (7)0.0326 (7)−0.0043 (5)0.0102 (5)−0.0144 (5)
C130.0188 (6)0.0300 (8)0.0185 (6)−0.0027 (5)0.0055 (5)−0.0079 (5)
C90.0144 (6)0.0155 (6)0.0166 (6)−0.0007 (4)0.0052 (4)−0.0029 (4)
C140.0181 (6)0.0219 (7)0.0181 (6)0.0003 (5)0.0054 (5)−0.0014 (5)

Geometric parameters (Å, °)

O1—C11.4235 (15)C4—H4A0.9900
O1—H10.87 (2)C4—H4B0.9900
O2—C81.2487 (14)C5—C61.4348 (17)
N1—C51.3435 (16)C6—C71.4182 (17)
N1—C21.4569 (16)C6—C81.4381 (17)
N1—C31.4744 (16)C8—C91.5022 (16)
N2—C51.3366 (16)C10—C111.3879 (18)
N2—C41.4595 (16)C10—C91.3920 (17)
N2—H20.881 (16)C10—H100.9500
N3—C71.1530 (16)C11—C121.388 (2)
C1—C21.5119 (17)C11—H110.9500
C1—H1A0.9900C12—C131.384 (2)
C1—H1B0.9900C12—H120.9500
C2—H2A0.9900C13—C141.3889 (18)
C2—H2B0.9900C13—H130.9500
C3—C41.5258 (18)C9—C141.3974 (17)
C3—H3A0.9900C14—H140.9500
C3—H3B0.9900
C1—O1—H1105.2 (12)H4A—C4—H4B109.3
C5—N1—C2128.69 (10)N2—C5—N1110.10 (11)
C5—N1—C3110.22 (10)N2—C5—C6121.91 (11)
C2—N1—C3120.06 (10)N1—C5—C6127.95 (11)
C5—N2—C4111.39 (10)C7—C6—C5121.11 (11)
C5—N2—H2118.7 (11)C7—C6—C8118.52 (11)
C4—N2—H2125.1 (11)C5—C6—C8120.35 (11)
O1—C1—C2109.04 (10)N3—C7—C6177.90 (13)
O1—C1—H1A109.9O2—C8—C6123.17 (11)
C2—C1—H1A109.9O2—C8—C9117.15 (10)
O1—C1—H1B109.9C6—C8—C9119.68 (10)
C2—C1—H1B109.9C11—C10—C9120.40 (12)
H1A—C1—H1B108.3C11—C10—H10119.8
N1—C2—C1113.19 (10)C9—C10—H10119.8
N1—C2—H2A108.9C10—C11—C12119.83 (13)
C1—C2—H2A108.9C10—C11—H11120.1
N1—C2—H2B108.9C12—C11—H11120.1
C1—C2—H2B108.9C13—C12—C11120.10 (12)
H2A—C2—H2B107.8C13—C12—H12120.0
N1—C3—C4102.90 (10)C11—C12—H12120.0
N1—C3—H3A111.2C12—C13—C14120.37 (12)
C4—C3—H3A111.2C12—C13—H13119.8
N1—C3—H3B111.2C14—C13—H13119.8
C4—C3—H3B111.2C10—C9—C14119.50 (11)
H3A—C3—H3B109.1C10—C9—C8122.15 (11)
N2—C4—C3101.74 (10)C14—C9—C8118.20 (11)
N2—C4—H4A111.4C13—C14—C9119.77 (12)
C3—C4—H4A111.4C13—C14—H14120.1
N2—C4—H4B111.4C9—C14—H14120.1
C3—C4—H4B111.4
C5—N1—C2—C189.49 (14)C7—C6—C8—O2173.51 (11)
C3—N1—C2—C1−103.33 (13)C5—C6—C8—O2−8.42 (18)
O1—C1—C2—N169.56 (13)C7—C6—C8—C9−6.98 (16)
C5—N1—C3—C4−12.82 (13)C5—C6—C8—C9171.09 (10)
C2—N1—C3—C4177.82 (10)C9—C10—C11—C12−0.02 (19)
C5—N2—C4—C3−18.34 (13)C10—C11—C12—C130.94 (19)
N1—C3—C4—N217.71 (12)C11—C12—C13—C14−0.45 (19)
C4—N2—C5—N111.16 (14)C11—C10—C9—C14−1.39 (18)
C4—N2—C5—C6−166.78 (11)C11—C10—C9—C8−176.84 (11)
C2—N1—C5—N2169.93 (11)O2—C8—C9—C10133.69 (12)
C3—N1—C5—N21.74 (14)C6—C8—C9—C10−45.85 (16)
C2—N1—C5—C6−12.3 (2)O2—C8—C9—C14−41.82 (15)
C3—N1—C5—C6179.52 (11)C6—C8—C9—C14138.64 (12)
N2—C5—C6—C7−174.96 (11)C12—C13—C14—C9−0.96 (18)
N1—C5—C6—C77.49 (19)C10—C9—C14—C131.87 (18)
N2—C5—C6—C87.02 (17)C8—C9—C14—C13177.50 (10)
N1—C5—C6—C8−170.52 (11)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.881 (16)2.318 (16)2.9557 (15)129.3 (13)
N2—H2···O20.881 (16)1.953 (16)2.6252 (15)132.0 (14)
O1—H1···N3ii0.87 (2)2.04 (2)2.8794 (16)160.9 (17)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+3/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2622).

References

  • Bruker (1997). SHELXTL Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Rigaku (2005). CrystalClear Version 1.36. Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Wang, L.-B. & Huang, Z.-T. (1996). Synth. Commun.26, 459–473.

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