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

Wang, K.; Li, Y.-J.; Zhang, T.-T.; Liang, H.-Z.

doi:10.1107/S1600536809021369

organic compounds

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Volume 65| Part 7| July 2009| Page o1577

doi:10.1107/S1600536809021369

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

Ke Wang,^a Yue-Jiao Li,^a Ting-Ting Zhang ^a and Hong-Ze Liang ^a ^*

^aState Key Laboratory Base of Novel Functional Materials, and Preparation Science, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
^*Correspondence e-mail: lianghongze@nbu.edu.cn

(Received 3 April 2009; accepted 5 June 2009; online 13 June 2009)

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 , 2002 ); Liang et al. (2009 ); Zhang & Liang (2009 ); Zhang, Zhang, Ren et al. (2009 ); Zhang, Zhang, Xu et al. (2009 ). For the synthesis, see: Barnett et al. (1999).

Experimental

Crystal data

C₂₀H₃₀N₄O₄
M_r = 390.48
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.077
wR(F²) = 0.190
S = 1.02
2453 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯N2ⁱ	0.97	2.46	2.960 (3)	111
Symmetry code: (i) -x+1, -y+1, -z+1.

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

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

Crystal data top

C₂₀H₃₀N₄O₄	F(000) = 420
M_r = 390.48	D_x = 1.197 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1478 reflections
a = 7.0321 (14) Å	θ = 3.0–27.5°
b = 17.484 (4) Å	µ = 0.08 mm⁻¹
c = 8.9681 (18) Å	T = 295 K
β = 100.80 (3)°	Plate, colourless
V = 1083.1 (4) Å³	0.48 × 0.42 × 0.14 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	2453 independent reflections
Radiation source: fine-focus sealed tube	1474 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
Detector resolution: 0 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −22→22
T_min = 0.960, T_max = 0.988	l = −11→10
9620 measured reflections

Refinement top

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)] = 0.077	Hydrogen site location: difference Fourier map
wR(F²) = 0.190	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0718P)² + 0.3943P] where P = (F_o² + 2F_c²)/3
2453 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³
59 constraints

Crystal data top

C₂₀H₃₀N₄O₄	V = 1083.1 (4) Å³
M_r = 390.48	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.0321 (14) Å	µ = 0.08 mm⁻¹
b = 17.484 (4) Å	T = 295 K
c = 8.9681 (18) Å	0.48 × 0.42 × 0.14 mm
β = 100.80 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2453 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1474 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.988	R_int = 0.077
9620 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.077	0 restraints
wR(F²) = 0.190	H-atom parameters constrained
S = 1.02	Δρ_max = 0.32 e Å⁻³
2453 reflections	Δρ_min = −0.24 e Å⁻³
128 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

	x	y	z	U_iso*/U_eq
N1	0.3460 (3)	0.51573 (11)	0.30746 (19)	0.0410 (5)
N2	0.6689 (3)	0.51901 (13)	0.3698 (2)	0.0522 (6)
C10	0.1400 (3)	0.50398 (14)	0.3101 (3)	0.0454 (6)
H10A	0.0628	0.5297	0.2237	0.054*
H10B	0.1099	0.5268	0.4016	0.054*
O2	0.2468 (3)	0.32667 (12)	0.1854 (2)	0.0717 (6)
O1	0.0366 (3)	0.40123 (12)	0.0365 (2)	0.0774 (7)
C9	0.5051 (3)	0.50815 (13)	0.4210 (2)	0.0415 (6)
C8	0.1171 (4)	0.38275 (15)	0.1612 (3)	0.0525 (6)
C7	0.6104 (4)	0.53329 (17)	0.2169 (3)	0.0568 (7)
H7A	0.6939	0.5428	0.1501	0.068*
C6	0.4159 (4)	0.53160 (15)	0.1774 (2)	0.0504 (6)
H6A	0.3431	0.5396	0.0809	0.061*
C5	0.0864 (4)	0.41992 (15)	0.3056 (3)	0.0520 (6)
H5A	0.1644	0.3940	0.3914	0.062*
H5B	−0.0484	0.4147	0.3144	0.062*
C4	0.2854 (6)	0.2868 (2)	0.0492 (4)	0.0905 (11)
H4A	0.3139	0.3238	−0.0242	0.109*
H4B	0.1724	0.2577	0.0027	0.109*
C3	0.4524 (6)	0.2349 (2)	0.0943 (5)	0.0958 (12)
H3A	0.4239	0.2005	0.1722	0.115*
H3B	0.4664	0.2039	0.0072	0.115*
C2	0.6387 (6)	0.2728 (2)	0.1520 (5)	0.1045 (13)
H2B	0.6290	0.3010	0.2434	0.125*
H2C	0.6653	0.3092	0.0770	0.125*
C1	0.8074 (6)	0.2163 (3)	0.1876 (7)	0.1289 (18)
H1A	0.9241	0.2435	0.2285	0.193*
H1B	0.8229	0.1904	0.0962	0.193*
H1C	0.7809	0.1795	0.2605	0.193*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0380 (10)	0.0516 (11)	0.0319 (9)	0.0030 (9)	0.0030 (7)	0.0023 (8)
N2	0.0407 (11)	0.0834 (16)	0.0336 (10)	0.0013 (10)	0.0097 (8)	0.0031 (10)
C10	0.0364 (11)	0.0564 (15)	0.0413 (12)	0.0045 (11)	0.0017 (9)	0.0019 (10)
O2	0.0728 (13)	0.0805 (15)	0.0564 (12)	0.0151 (11)	−0.0018 (9)	−0.0074 (10)
O1	0.0988 (16)	0.0791 (15)	0.0457 (11)	0.0097 (12)	−0.0087 (10)	0.0001 (9)
C9	0.0377 (11)	0.0553 (14)	0.0304 (11)	0.0037 (11)	0.0033 (8)	−0.0010 (9)
C8	0.0518 (14)	0.0532 (15)	0.0491 (15)	−0.0082 (12)	0.0006 (11)	0.0019 (11)
C7	0.0522 (15)	0.086 (2)	0.0343 (12)	−0.0015 (13)	0.0134 (10)	0.0047 (12)
C6	0.0539 (14)	0.0675 (17)	0.0289 (11)	0.0016 (12)	0.0051 (10)	0.0033 (11)
C5	0.0474 (13)	0.0629 (16)	0.0444 (13)	−0.0046 (12)	0.0054 (10)	0.0044 (12)
C4	0.100 (3)	0.098 (3)	0.069 (2)	0.020 (2)	0.0058 (18)	−0.0199 (19)
C3	0.097 (3)	0.095 (3)	0.098 (3)	−0.005 (2)	0.026 (2)	−0.021 (2)
C2	0.101 (3)	0.095 (3)	0.115 (3)	−0.006 (2)	0.013 (2)	−0.001 (2)
C1	0.087 (3)	0.101 (3)	0.198 (5)	0.000 (2)	0.025 (3)	0.031 (3)

Geometric parameters (Å, º) top

N1—C9	1.371 (3)	C6—H6A	0.9300
N1—C6	1.376 (3)	C5—H5A	0.9700
N1—C10	1.468 (3)	C5—H5B	0.9700
N2—C9	1.331 (3)	C4—C3	1.480 (5)
N2—C7	1.378 (3)	C4—H4A	0.9700
C10—C5	1.516 (3)	C4—H4B	0.9700
C10—H10A	0.9700	C3—C2	1.473 (5)
C10—H10B	0.9700	C3—H3A	0.9700
O2—C8	1.329 (3)	C3—H3B	0.9700
O2—C4	1.475 (4)	C2—C1	1.531 (5)
O1—C8	1.199 (3)	C2—H2B	0.9700
C9—C9ⁱ	1.460 (4)	C2—H2C	0.9700
C8—C5	1.500 (4)	C1—H1A	0.9600
C7—C6	1.347 (3)	C1—H1B	0.9600
C7—H7A	0.9300	C1—H1C	0.9600

C9—N1—C6	106.13 (18)	C10—C5—H5B	109.3
C9—N1—C10	130.15 (19)	H5A—C5—H5B	108.0
C6—N1—C10	123.53 (18)	O2—C4—C3	108.9 (3)
C9—N2—C7	104.6 (2)	O2—C4—H4A	109.9
N1—C10—C5	112.1 (2)	C3—C4—H4A	109.9
N1—C10—H10A	109.2	O2—C4—H4B	109.9
C5—C10—H10A	109.2	C3—C4—H4B	109.9
N1—C10—H10B	109.2	H4A—C4—H4B	108.3
C5—C10—H10B	109.2	C2—C3—C4	115.3 (4)
H10A—C10—H10B	107.9	C2—C3—H3A	108.4
C8—O2—C4	116.1 (2)	C4—C3—H3A	108.4
N2—C9—N1	111.59 (19)	C2—C3—H3B	108.4
N2—C9—C9ⁱ	124.5 (2)	C4—C3—H3B	108.4
N1—C9—C9ⁱ	123.9 (2)	H3A—C3—H3B	107.5
O1—C8—O2	122.7 (3)	C3—C2—C1	112.7 (4)
O1—C8—C5	124.7 (3)	C3—C2—H2B	109.0
O2—C8—C5	112.6 (2)	C1—C2—H2B	109.0
C6—C7—N2	110.9 (2)	C3—C2—H2C	109.0
C6—C7—H7A	124.5	C1—C2—H2C	109.0
N2—C7—H7A	124.5	H2B—C2—H2C	107.8
C7—C6—N1	106.7 (2)	C2—C1—H1A	109.5
C7—C6—H6A	126.6	C2—C1—H1B	109.5
N1—C6—H6A	126.6	H1A—C1—H1B	109.5
C8—C5—C10	111.6 (2)	C2—C1—H1C	109.5
C8—C5—H5A	109.3	H1A—C1—H1C	109.5
C10—C5—H5A	109.3	H1B—C1—H1C	109.5
C8—C5—H5B	109.3

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···N2ⁱ	0.97	2.46	2.960 (3)	111

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₀H₃₀N₄O₄
M_r	390.48
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	7.0321 (14), 17.484 (4), 8.9681 (18)
β (°)	100.80 (3)
V (Å³)	1083.1 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.48 × 0.42 × 0.14

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.960, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	9620, 2453, 1474
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.077, 0.190, 1.02
No. of reflections	2453
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.24

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···N2ⁱ	0.97	2.46	2.960 (3)	111

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

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.

References

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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1577

doi:10.1107/S1600536809021369

Open

access