PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1577.
Published online 2009 June 13. doi:  10.1107/S1600536809021369
PMCID: PMC2969301

Di-tert-butyl 3,3′-(2,2′-bi-1H-imidazole-1,1′-di­yl)dipropanoate

Abstract

In the title compound, C20H20N4O4, the complete molecule is generated by a crystallographic centre of symmetry. The conformation is stabilized by two intramolecular C—H(...)N links.

Related literature

For the background to 2, 2′-biimidazole derivatives, see: Barnett et al. (1999 [triangle], 2002 [triangle]); Liang et al. (2009 [triangle]); Zhang & Liang (2009 [triangle]); Zhang, Zhang, Ren et al. (2009 [triangle]); Zhang, Zhang, Xu et al. (2009 [triangle]). For the synthesis, see: Barnett et al. (1999 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1577-scheme1.jpg

Experimental

Crystal data

  • C20H30N4O4
  • M r = 390.48
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1577-efi1.jpg
  • a = 7.0321 (14) Å
  • b = 17.484 (4) Å
  • c = 8.9681 (18) Å
  • β = 100.80 (3)°
  • V = 1083.1 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 295 K
  • 0.48 × 0.42 × 0.14 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.960, T max = 0.988
  • 9620 measured reflections
  • 2453 independent reflections
  • 1474 reflections with I > 2σ(I)
  • R int = 0.077

Refinement

  • R[F 2 > 2σ(F 2)] = 0.077
  • wR(F 2) = 0.190
  • S = 1.02
  • 2453 reflections
  • 128 parameters
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021369/fb2148sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021369/fb2148Isup2.hkl

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

Acknowledgments

This project was sponsored by the Scientific Research Foundation of the State Education Ministry for Returned Overseas Chinese Scholars (2006701), the Critical Projects in Science and Technology Department of Zhejiang Province (2007 C21113), the Education Committee of Zhejiang Province (20061696, 2008934), the Natural Science Foundation of Ningbo City (2007 A610021) and the K. C. Wong Magna Fund of Ningbo University. We thank Professor X. Li for helpful discussions about the crystal structure and Mr W. Xu for collecting the crystal data.

supplementary crystallographic information

Comment

Biimidazole is a potentially polydentate ligand, but its chemistry is less developed in comparison to the imidazole chemistry. The reason may be a limited solubility of biimidazole in common organic solvents. Although several new disubstituted 2,2'-biimidazoles have been recently synthesized (Barnett et al., 1999; Barnett et al., 2002), a few metal complexes based on biimidazole derivatives are reported (Zhang, Zhang, Ren et al., 2009). In the course of our ongoing study, we have successfully synthesized a series of biimidazole derivatives with terminal carboxylic, hydroxyl, phosphino, imino groups which can be used as ligands in the coordination chemistry (Zhang & Liang, 2009; Zhang, Zhang, Xu et al., 2009) and cross-coupling reactions (Liang et al., 2009). These ligands exhibit rich coordination patterns and catalytic properties. Here we report the synthesis and the crystal structure of the title compound which is an intermediate of those above mentioned ligands. As shown in Fig. 1, the biimidazole ring atoms (C6, C7, C9, N1, N2 and their inversion-related partners) exhibit essentially coplanar mutual orientation [the dihedral angle is 0.00 (1)°], and the value of the torsion angle C9—N1—C10—C5 is -77.53 (30)°. In the crystal structure, there are weak C-H···N interactions (Tab. 1, Fig. 2).

Experimental

The title compound was prepared according to a published procedure (Barnett et al., 1999). 0.2 g (5 mmol) of NaOH was added to a suspension of 3 g (22.4 mmol) of 2,2'-biimidazole in 100 ml of DMF (dimethylformamide) at 80°C. The resulting mixture was stirrred for 30 min. In the course of this time the mixture gradually turned into a clear pale yellow solution. 7.12 g (55.6 mmol) butyl acrylate in 10 ml of DMF was added dropwise in several minutes to the solution and the reaction was stirred at 80°C for 8 h until the heating was stopped. The DMF was removed via vacuum distillation in a hot oil bath at 100°C. The resulting black brown oil was dissolved in water (30 ml) and extracted with CH2Cl2. The organic layer was washed with water, and then evaporated under reduced pressure to yield a white product (7.4 g, 85%). The product was dissolved in 95% ethanol (30 ml) and cooled slowly in a refrigerator to afford colourless block crystals of average size 1.5 mm×1.2 mm×0.5 mm that were suitable for the X-ray analysis.

Refinement

All the hydrogens were discernible in the difference electron density map. Nevertheless, the hydrogens were situated into the idealized positions. The C-H distances were constrained to 0.93, 0.96 and 0.97 Å for aryl, methylene and methyl hydrogens, respectively. Uiso(H) = 1.2 Ueq(Caryl); Uiso(H) = 1.2 Ueq(Cmethylene); Uiso(H) = 1.5 Ueq(Cmethyl).

Figures

Fig. 1.
View of the title molecule with the displacement ellipsoids at the 45% probability level. The labelling of the non-H atoms is also given. The symmetry code (i):-x+1, -y+1, -z+1.
Fig. 2.
A section of the title structure. The C-H···N hydrogen bonds (Tab. 1) are shown as dashed lines.

Crystal data

C20H30N4O4F(000) = 420
Mr = 390.48Dx = 1.197 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1478 reflections
a = 7.0321 (14) Åθ = 3.0–27.5°
b = 17.484 (4) ŵ = 0.08 mm1
c = 8.9681 (18) ÅT = 295 K
β = 100.80 (3)°Plate, colourless
V = 1083.1 (4) Å30.48 × 0.42 × 0.14 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer2453 independent reflections
Radiation source: fine-focus sealed tube1474 reflections with I > 2σ(I)
graphiteRint = 0.077
Detector resolution: 0 pixels mm-1θmax = 27.5°, θmin = 3.2°
ω scansh = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)k = −22→22
Tmin = 0.960, Tmax = 0.988l = −11→10
9620 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.077Hydrogen site location: difference Fourier map
wR(F2) = 0.190H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0718P)2 + 0.3943P] where P = (Fo2 + 2Fc2)/3
2453 reflections(Δ/σ)max < 0.001
128 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = −0.24 e Å3
59 constraints

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
N10.3460 (3)0.51573 (11)0.30746 (19)0.0410 (5)
N20.6689 (3)0.51901 (13)0.3698 (2)0.0522 (6)
C100.1400 (3)0.50398 (14)0.3101 (3)0.0454 (6)
H10A0.06280.52970.22370.054*
H10B0.10990.52680.40160.054*
O20.2468 (3)0.32667 (12)0.1854 (2)0.0717 (6)
O10.0366 (3)0.40123 (12)0.0365 (2)0.0774 (7)
C90.5051 (3)0.50815 (13)0.4210 (2)0.0415 (6)
C80.1171 (4)0.38275 (15)0.1612 (3)0.0525 (6)
C70.6104 (4)0.53329 (17)0.2169 (3)0.0568 (7)
H7A0.69390.54280.15010.068*
C60.4159 (4)0.53160 (15)0.1774 (2)0.0504 (6)
H6A0.34310.53960.08090.061*
C50.0864 (4)0.41992 (15)0.3056 (3)0.0520 (6)
H5A0.16440.39400.39140.062*
H5B−0.04840.41470.31440.062*
C40.2854 (6)0.2868 (2)0.0492 (4)0.0905 (11)
H4A0.31390.3238−0.02420.109*
H4B0.17240.25770.00270.109*
C30.4524 (6)0.2349 (2)0.0943 (5)0.0958 (12)
H3A0.42390.20050.17220.115*
H3B0.46640.20390.00720.115*
C20.6387 (6)0.2728 (2)0.1520 (5)0.1045 (13)
H2B0.62900.30100.24340.125*
H2C0.66530.30920.07700.125*
C10.8074 (6)0.2163 (3)0.1876 (7)0.1289 (18)
H1A0.92410.24350.22850.193*
H1B0.82290.19040.09620.193*
H1C0.78090.17950.26050.193*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0380 (10)0.0516 (11)0.0319 (9)0.0030 (9)0.0030 (7)0.0023 (8)
N20.0407 (11)0.0834 (16)0.0336 (10)0.0013 (10)0.0097 (8)0.0031 (10)
C100.0364 (11)0.0564 (15)0.0413 (12)0.0045 (11)0.0017 (9)0.0019 (10)
O20.0728 (13)0.0805 (15)0.0564 (12)0.0151 (11)−0.0018 (9)−0.0074 (10)
O10.0988 (16)0.0791 (15)0.0457 (11)0.0097 (12)−0.0087 (10)0.0001 (9)
C90.0377 (11)0.0553 (14)0.0304 (11)0.0037 (11)0.0033 (8)−0.0010 (9)
C80.0518 (14)0.0532 (15)0.0491 (15)−0.0082 (12)0.0006 (11)0.0019 (11)
C70.0522 (15)0.086 (2)0.0343 (12)−0.0015 (13)0.0134 (10)0.0047 (12)
C60.0539 (14)0.0675 (17)0.0289 (11)0.0016 (12)0.0051 (10)0.0033 (11)
C50.0474 (13)0.0629 (16)0.0444 (13)−0.0046 (12)0.0054 (10)0.0044 (12)
C40.100 (3)0.098 (3)0.069 (2)0.020 (2)0.0058 (18)−0.0199 (19)
C30.097 (3)0.095 (3)0.098 (3)−0.005 (2)0.026 (2)−0.021 (2)
C20.101 (3)0.095 (3)0.115 (3)−0.006 (2)0.013 (2)−0.001 (2)
C10.087 (3)0.101 (3)0.198 (5)0.000 (2)0.025 (3)0.031 (3)

Geometric parameters (Å, °)

N1—C91.371 (3)C6—H6A0.9300
N1—C61.376 (3)C5—H5A0.9700
N1—C101.468 (3)C5—H5B0.9700
N2—C91.331 (3)C4—C31.480 (5)
N2—C71.378 (3)C4—H4A0.9700
C10—C51.516 (3)C4—H4B0.9700
C10—H10A0.9700C3—C21.473 (5)
C10—H10B0.9700C3—H3A0.9700
O2—C81.329 (3)C3—H3B0.9700
O2—C41.475 (4)C2—C11.531 (5)
O1—C81.199 (3)C2—H2B0.9700
C9—C9i1.460 (4)C2—H2C0.9700
C8—C51.500 (4)C1—H1A0.9600
C7—C61.347 (3)C1—H1B0.9600
C7—H7A0.9300C1—H1C0.9600
C9—N1—C6106.13 (18)C10—C5—H5B109.3
C9—N1—C10130.15 (19)H5A—C5—H5B108.0
C6—N1—C10123.53 (18)O2—C4—C3108.9 (3)
C9—N2—C7104.6 (2)O2—C4—H4A109.9
N1—C10—C5112.1 (2)C3—C4—H4A109.9
N1—C10—H10A109.2O2—C4—H4B109.9
C5—C10—H10A109.2C3—C4—H4B109.9
N1—C10—H10B109.2H4A—C4—H4B108.3
C5—C10—H10B109.2C2—C3—C4115.3 (4)
H10A—C10—H10B107.9C2—C3—H3A108.4
C8—O2—C4116.1 (2)C4—C3—H3A108.4
N2—C9—N1111.59 (19)C2—C3—H3B108.4
N2—C9—C9i124.5 (2)C4—C3—H3B108.4
N1—C9—C9i123.9 (2)H3A—C3—H3B107.5
O1—C8—O2122.7 (3)C3—C2—C1112.7 (4)
O1—C8—C5124.7 (3)C3—C2—H2B109.0
O2—C8—C5112.6 (2)C1—C2—H2B109.0
C6—C7—N2110.9 (2)C3—C2—H2C109.0
C6—C7—H7A124.5C1—C2—H2C109.0
N2—C7—H7A124.5H2B—C2—H2C107.8
C7—C6—N1106.7 (2)C2—C1—H1A109.5
C7—C6—H6A126.6C2—C1—H1B109.5
N1—C6—H6A126.6H1A—C1—H1B109.5
C8—C5—C10111.6 (2)C2—C1—H1C109.5
C8—C5—H5A109.3H1A—C1—H1C109.5
C10—C5—H5A109.3H1B—C1—H1C109.5
C8—C5—H5B109.3

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C10—H10B···N2i0.972.462.960 (3)111

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FB2148).

References

  • Barnett, W. M., Baughman, R. G., Collier, H. L. & Vizuete, W. G. (1999). J. Chem. Crystallogr.29, 765–768.
  • Barnett, W. M., Baughman, R. G., Secondo, P. M. & Hermansen, C. J. (2002). Acta Cryst. C58, o565–o567. [PubMed]
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Liang, H., Zhang, T., Chen, B., Xiang, J., Shen, H. & Xie, X. (2009). Unpublished results.
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2004). CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhang, T. & Liang, H.-Z. (2009). Acta Cryst. E65, o213–o214. [PMC free article] [PubMed]
  • Zhang, T., Zhang, T., Ren, Y. & Liang, H. (2009). Acta Cryst. E65, o904. [PMC free article] [PubMed]
  • Zhang, T., Zhang, T., Xu, F. & Liang, H. (2009). Acta Cryst. E65, m543–m544. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography