2,2′-(2,2′-Biimidazole-1,1′-di­yl)diethanoic acid

Zhang, T.; Zhang, T.; Ren, Y.; Liang, H.

doi:10.1107/S1600536809010897

organic compounds

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Volume 65| Part 4| April 2009| Page o904

doi:10.1107/S1600536809010897

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2,2′-(2,2′-Biimidazole-1,1′-diyl)diethanoic acid

Tingting Zhang,^a Tao Zhang,^a Yingtao Ren ^a and Hongze 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 22 March 2009; accepted 24 March 2009; online 28 March 2009)

In the title compound, C₁₀H₁₀N₄O₄, the two imidazole rings adopt a trans conformation and are inclined to one another at a dihedral angle of 55.64 (4)°. In the crystal structure, molecules are linked by intermolecular O—H⋯N hydrogen bonds into chains running parallel to [010] and layers are formed from these by intermolecular C—H⋯O hydrogen bonds. Additional C—H⋯O hydrogen bonds produce a three-dimensional network.

Related literature

For the use of 2,2′-biimidazole ligands in metal complex formation, see: Pereira et al. (2006 ); Ion et al. (2007 ). For related structures, see: Barnett et al. (1999 , 2002 ); Zhang & Liang (2009 ). For preparation of the starting material, see: Barnett et al. (1996 ).

Experimental

Crystal data

C₁₀H₁₀N₄O₄
M_r = 250.22
Orthorhombic, P b c a
a = 8.4327 (17) Å
b = 15.116 (3) Å
c = 16.702 (3) Å
V = 2129.0 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 295 K
0.51 × 0.27 × 0.2 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.961, T_max = 0.978
18907 measured reflections
2436 independent reflections
2159 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.086
S = 1.05
2436 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2ⁱ	0.87	1.75	2.6137 (13)	176
O3—H10⋯N4ⁱⁱ	0.85	1.72	2.5666 (13)	176
C4—H2⋯N4	0.97	2.54	3.2234 (17)	127
C4—H3⋯O2ⁱⁱⁱ	0.97	2.24	3.0675 (16)	142
C2—H5⋯O4^iv	0.93	2.48	3.2286 (16)	138
C8—H7⋯O1^v	0.93	2.55	3.3610 (15)	146
C9—H8⋯N2	0.97	2.62	3.2611 (16)	124
C9—H9⋯O4^vi	0.97	2.59	3.3391 (15)	135
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) -x, -y+1, -z+1; (vi) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

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/S1600536809010897/sj2599sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809010897/sj2599Isup2.hkl

checkCIF report

Comment top

2,2'-Biimidazole (H₂biim) derivatives as versatile ligands are widely used in the construction of metal complexes (Pereira et al., 2006; Ion et al., 2007). Here, we report the synthesis and crystal structure of the title compound. As shown in Fig.1, the two imidazole rings adopt a trans conformation and are inclined to one another at dihedral angle of 55.64 (4)°. while most unconjugated disubstituted biimidazole derivatives show an almost coplanar orientation of the two imidazole rings (Barnett, et al., 1999, 2002). This is probably due to the presence of the strong intermolecular O–H···N hydrogen bonds as observed before (Zhang & Liang, 2009). The values of the C1—N1—C4—C5 and C6—N3—C9—C10 torsion angles are -119.21 (11)° and -111.87 (12)°, respectively.

In the crystal, molecules are linked by intermolecular O–H···N hydrogen bonds into chains running parallel to [010] (Table 1, Fig.2). The chains are linked by intermolecular C–H···O hydrogen bonds into layers. The layers are further held together via C–H···O hydrogen bonds into a three-dimensional network.

Related literature top

For the use of 2,2'-biimidazole ligands in metal complex formation, see: Pereira et al. (2006); Ion et al. (2007). For related structures, see: Barnett et al. (1999, 2002); Zhang & Liang (2009). For preparation of the starting material, see: Barnett et al. (1996).

Experimental top

1,1'-Di(cyanomethyl)-2,2'-biimidazole (Barnett et al., 1996) (0.5 g, 2.36 mmol) was dissolved in 1 M aqueous sulfuric acid (50 ml) and heated at 100°C for 6 h before cooling to room temperature. A white precipitate of the title compound was obtained by adjusting pH to 5, filtered, washed with water, and finally dried in vacuo (yield: 0.35 g, 59.4%). The solid was dissolved in hot N,N-dimethylformamide and cooled to room temperaure slowly to afford colorless block-like crystals.

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. A view of (I), showing the labeling of the non-H atoms and 45% probability ellipsoids.
	Fig. 2. A perspective view of a one-dimensional chain running parallel to [010], showing the packing mode and the O–H···N. hydrogen bonds as dashed lines. All H atoms not involved in the hydrogen-bond motifs have been omitted for clarity.

2,2'-(2,2'-Biimidazole-1,1'-diyl)diethanoic acid top

Crystal data top

C₁₀H₁₀N₄O₄	F(000) = 1040
M_r = 250.22	D_x = 1.561 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 17425 reflections
a = 8.4327 (17) Å	θ = 3.1–27.5°
b = 15.116 (3) Å	µ = 0.12 mm⁻¹
c = 16.702 (3) Å	T = 295 K
V = 2129.0 (7) Å³	Prism, colorless
Z = 8	0.51 × 0.27 × 0.2 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	2436 independent reflections
Radiation source: fine-focus sealed tube	2159 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 0 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −19→19
T_min = 0.961, T_max = 0.978	l = −21→21
18907 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0416P)² + 1.0303P] where P = (F_o² + 2F_c²)/3
2436 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₀H₁₀N₄O₄	V = 2129.0 (7) Å³
M_r = 250.22	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.4327 (17) Å	µ = 0.12 mm⁻¹
b = 15.116 (3) Å	T = 295 K
c = 16.702 (3) Å	0.51 × 0.27 × 0.2 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	2436 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2159 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.978	R_int = 0.026
18907 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.05	Δρ_max = 0.33 e Å⁻³
2436 reflections	Δρ_min = −0.21 e Å⁻³
163 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
O1	0.09214 (10)	0.31447 (5)	0.31089 (5)	0.01700 (19)
H1	0.1441	0.2674	0.2969	0.050*
O2	0.21420 (10)	0.38341 (5)	0.20945 (5)	0.01586 (18)
O4	0.24120 (10)	0.83984 (6)	0.49664 (5)	0.01865 (19)
N3	0.11682 (11)	0.68000 (6)	0.44503 (5)	0.0121 (2)
O3	0.10682 (10)	0.91340 (5)	0.40169 (5)	0.01702 (19)
H10	0.1596	0.9575	0.4189	0.050*
C5	0.12876 (13)	0.38415 (7)	0.26763 (6)	0.0124 (2)
N1	0.11865 (11)	0.54801 (6)	0.26858 (5)	0.0123 (2)
N2	0.23979 (12)	0.67789 (6)	0.26608 (5)	0.0145 (2)
N4	0.23766 (12)	0.55062 (6)	0.44669 (6)	0.0148 (2)
C6	0.18459 (13)	0.61528 (7)	0.40021 (6)	0.0121 (2)
C8	0.12794 (14)	0.65457 (7)	0.52369 (6)	0.0147 (2)
H7	0.0916	0.6857	0.5681	0.018*
C10	0.14467 (13)	0.84266 (7)	0.44296 (6)	0.0127 (2)
C1	0.18552 (13)	0.61380 (7)	0.31285 (6)	0.0120 (2)
C4	0.04544 (14)	0.46687 (7)	0.29809 (7)	0.0146 (2)
H3	−0.0647	0.4654	0.2814	0.017*
H2	0.0477	0.4670	0.3562	0.017*
C9	0.04736 (13)	0.76275 (7)	0.41703 (7)	0.0137 (2)
H9	−0.0594	0.7682	0.4381	0.016*
H8	0.0405	0.7617	0.3591	0.016*
C3	0.13028 (14)	0.57281 (7)	0.18970 (6)	0.0148 (2)
H4	0.0941	0.5413	0.1455	0.018*
C7	0.20265 (14)	0.57488 (8)	0.52384 (7)	0.0159 (2)
H6	0.2264	0.5419	0.5693	0.019*
C2	0.20507 (14)	0.65256 (8)	0.18896 (7)	0.0154 (2)
H5	0.2291	0.6850	0.1432	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0212 (4)	0.0099 (4)	0.0199 (4)	0.0007 (3)	0.0056 (3)	0.0007 (3)
O2	0.0179 (4)	0.0146 (4)	0.0151 (4)	0.0005 (3)	0.0031 (3)	−0.0006 (3)
O4	0.0233 (4)	0.0155 (4)	0.0172 (4)	−0.0035 (3)	−0.0063 (3)	0.0016 (3)
N3	0.0147 (4)	0.0096 (4)	0.0120 (4)	0.0001 (4)	−0.0002 (3)	−0.0005 (3)
O3	0.0196 (4)	0.0103 (4)	0.0212 (4)	−0.0015 (3)	−0.0053 (3)	0.0019 (3)
C5	0.0118 (5)	0.0114 (5)	0.0140 (5)	−0.0021 (4)	−0.0025 (4)	−0.0014 (4)
N1	0.0143 (4)	0.0092 (4)	0.0134 (4)	−0.0002 (4)	0.0011 (3)	−0.0010 (3)
N2	0.0187 (5)	0.0116 (4)	0.0131 (5)	−0.0011 (4)	0.0000 (4)	0.0015 (3)
N4	0.0184 (5)	0.0121 (4)	0.0138 (4)	0.0022 (4)	0.0008 (4)	0.0017 (3)
C6	0.0141 (5)	0.0092 (5)	0.0132 (5)	−0.0008 (4)	0.0002 (4)	0.0000 (4)
C8	0.0178 (5)	0.0154 (5)	0.0108 (5)	−0.0012 (4)	0.0012 (4)	0.0001 (4)
C10	0.0140 (5)	0.0118 (5)	0.0124 (5)	0.0008 (4)	0.0023 (4)	−0.0009 (4)
C1	0.0137 (5)	0.0087 (5)	0.0135 (5)	0.0009 (4)	0.0001 (4)	−0.0004 (4)
C4	0.0151 (5)	0.0102 (5)	0.0184 (5)	−0.0023 (4)	0.0034 (4)	−0.0010 (4)
C9	0.0152 (5)	0.0098 (5)	0.0160 (5)	0.0017 (4)	−0.0016 (4)	0.0000 (4)
C3	0.0168 (5)	0.0154 (5)	0.0122 (5)	0.0020 (4)	−0.0005 (4)	−0.0020 (4)
C7	0.0198 (5)	0.0162 (5)	0.0118 (5)	−0.0003 (4)	0.0007 (4)	0.0024 (4)
C2	0.0191 (5)	0.0153 (5)	0.0119 (5)	0.0007 (4)	0.0002 (4)	0.0012 (4)

Geometric parameters (Å, º) top

O1—C5	1.3140 (13)	N4—C6	1.3260 (14)
O1—H1	0.8677	N4—C7	1.3718 (14)
O2—C5	1.2098 (14)	C6—C1	1.4592 (15)
O4—C10	1.2117 (14)	C8—C7	1.3594 (17)
N3—C6	1.3579 (14)	C8—H7	0.9300
N3—C8	1.3720 (14)	C10—C9	1.5230 (15)
N3—C9	1.4583 (13)	C4—H3	0.9700
O3—C10	1.3116 (13)	C4—H2	0.9700
O3—H10	0.8513	C9—H9	0.9700
C5—C4	1.5217 (15)	C9—H8	0.9700
N1—C1	1.3614 (14)	C3—C2	1.3605 (17)
N1—C3	1.3733 (14)	C3—H4	0.9300
N1—C4	1.4589 (14)	C7—H6	0.9300
N2—C1	1.3259 (14)	C2—H5	0.9300
N2—C2	1.3752 (14)

C5—O1—H1	113.0	N2—C1—C6	125.43 (10)
C6—N3—C8	107.30 (9)	N1—C1—C6	123.50 (10)
C6—N3—C9	127.61 (9)	N1—C4—C5	112.49 (9)
C8—N3—C9	125.08 (9)	N1—C4—H3	109.1
C10—O3—H10	109.5	C5—C4—H3	109.1
O2—C5—O1	125.04 (10)	N1—C4—H2	109.1
O2—C5—C4	123.44 (10)	C5—C4—H2	109.1
O1—C5—C4	111.49 (9)	H3—C4—H2	107.8
C1—N1—C3	106.98 (9)	N3—C9—C10	111.88 (9)
C1—N1—C4	127.30 (9)	N3—C9—H9	109.2
C3—N1—C4	125.72 (9)	C10—C9—H9	109.2
C1—N2—C2	105.96 (9)	N3—C9—H8	109.2
C6—N4—C7	106.27 (9)	C10—C9—H8	109.2
N4—C6—N3	110.50 (10)	H9—C9—H8	107.9
N4—C6—C1	124.91 (10)	C2—C3—N1	106.48 (9)
N3—C6—C1	124.37 (10)	C2—C3—H4	126.8
C7—C8—N3	106.36 (9)	N1—C3—H4	126.8
C7—C8—H7	126.8	C8—C7—N4	109.57 (10)
N3—C8—H7	126.8	C8—C7—H6	125.2
O4—C10—O3	125.52 (10)	N4—C7—H6	125.2
O4—C10—C9	122.99 (10)	C3—C2—N2	109.69 (10)
O3—C10—C9	111.47 (9)	C3—C2—H5	125.2
N2—C1—N1	110.89 (9)	N2—C2—H5	125.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.87	1.75	2.6137 (13)	176
O3—H10···N4ⁱⁱ	0.85	1.72	2.5666 (13)	176
C4—H2···N4	0.97	2.54	3.2234 (17)	127
C4—H3···O2ⁱⁱⁱ	0.97	2.24	3.0675 (16)	142
C2—H5···O4^iv	0.93	2.48	3.2286 (16)	138
C8—H7···O1^v	0.93	2.55	3.3610 (15)	146
C9—H8···N2	0.97	2.62	3.2611 (16)	124
C9—H9···O4^vi	0.97	2.59	3.3391 (15)	135

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₄O₄
M_r	250.22
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	295
a, b, c (Å)	8.4327 (17), 15.116 (3), 16.702 (3)
V (Å³)	2129.0 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.51 × 0.27 × 0.2

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.961, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	18907, 2436, 2159
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.086, 1.05
No. of reflections	2436
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.21

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
O1—H1···N2ⁱ	0.87	1.75	2.6137 (13)	176
O3—H10···N4ⁱⁱ	0.85	1.72	2.5666 (13)	176
C4—H2···N4	0.97	2.54	3.2234 (17)	127
C4—H3···O2ⁱⁱⁱ	0.97	2.24	3.0675 (16)	142
C2—H5···O4^iv	0.93	2.48	3.2286 (16)	138
C8—H7···O1^v	0.93	2.55	3.3610 (15)	146
C9—H8···N2	0.97	2.62	3.2611 (16)	124
C9—H9···O4^vi	0.97	2.59	3.3391 (15)	135

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

Acknowledgements

This project was sponsored by the Scientific Research Foundation of the State Education Ministry for Returned Overseas Chinese Scholars (2006331), the Critical Projects in Science and Technology Department of Zhejiang Province (2007 C21113), the Education Committee of Zhejiang Province (20061696), the Natural Science Foundation of Ningbo City (2007 A610021), the K. C. Wong Magna Fund in Ningbo University and Ningbo University (2005062). We thank Mr W. Xu for collecting the crystal data.

References

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