4-Nitro­benzoic acid–2,2′-biimidazole (2/1)

Liu, X.; Zhu, W.

doi:10.1107/S1600536810015643

organic compounds

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https://doi.org/10.1107/S1600536810015643

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4-Nitrobenzoic acid–2,2′-biimidazole (2/1)

Xin Liu ^a and Weiqun Zhu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: zhuwq@sdu.edu.cn

(Received 20 April 2010; accepted 28 April 2010; online 8 May 2010)

In the title adduct, C₇H₅NO₄·0.5C₆H₆N₄, the complete biimidazole molecule is generated by a crystallographic inversion centre. In the crystal, N—H⋯O and O—H⋯N hydrogen bonds connects the 4-nitrobenzoic acid and 2,2′-biimidazole units, affording multi-dimensional frameworks with graph-set descriptor R₂²(9).

Related literature

For the potential applications of coordination complexes as functional materials and enzymes, see: Zhang et al. (2003 ) For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₇H₅NO₄·0.5C₆H₆N₄
M_r = 234.19
Monoclinic, P 2₁ /c
a = 4.852 (1) Å
b = 10.9245 (10) Å
c = 19.7981 (10) Å
β = 90.496 (1)°
V = 1049.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.986, T_max = 0.991
5185 measured reflections
1849 independent reflections
1264 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.134
S = 1.00
1849 reflections
158 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N1	0.85 (1)	1.75 (1)	2.580 (2)	168 (3)
N2—H2⋯O1ⁱ	0.86	1.89	2.742 (2)	173
Symmetry code: (i) -x+2, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810015643/bx2278sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810015643/bx2278Isup2.hkl

checkCIF report

Comment top

Recently, the design and synthesis of coordination complexes have attracted much attention due to their diversity structures as well as potential applications as functional materials and enzymes (Zhang et al. , 2003). Here, we report one by-product of the hydrothermal reaction of FeCl₃ with 4-nitrobenzoic acid and biimidazole. The asymmetric unit of (I) consists of a 4-nitrobenzoic acid molecule and half biimidazole molecule, Fig 1. In the 4-nitrobenzoic acid molecule, the nitro group is rotated 10.6 (3)° from aromatic ring. N—H···O and O—H···N hydrogen bonds connects the C₇H₅NO₄ . 0.5C₆H₆N₄ units to affords a macrocycle with graph-set descriptor R²₂(9) (Bernstein et al., 1995), Fig2.

Related literature top

For the potential applications of coordination complexes as functional materials and enzymes, see: Zhang et al. (2003) For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of 4-nitrobenzoic acid (1 mmoL, 0.17 g), biimidazole (1 mmoL, 0.14 g), and iron trichloride (1 mmoL, 0.27 g) in 12 ml distilled water sealed in a 25 ml Teflon-lined stainless steel autoclave was kept at 433 K for three days. Colorless crystals suitable for the single X-ray diffraction were obtained.

Structure description top

For the potential applications of coordination complexes as functional materials and enzymes, see: Zhang et al. (2003) For hydrogen-bond motifs, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing the atom-labelling scheme and with displacement ellipsoids at the 30% probability level. Unlabeled atoms are related to labeled atoms by the symmetry code (-x, 2-y, 1-z).

4-Nitrobenzoic acid–2,2'-biimidazole (2/1) top

Crystal data top

C₇H₅NO₄·0.5C₆H₆N₄	F(000) = 484
M_r = 234.19	D_x = 1.482 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1230 reflections
a = 4.852 (1) Å	θ = 2.8–22.0°
b = 10.9245 (10) Å	µ = 0.12 mm⁻¹
c = 19.7981 (10) Å	T = 296 K
β = 90.496 (1)°	Block, colourless
V = 1049.4 (2) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1849 independent reflections
Radiation source: fine-focus sealed tube	1264 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
phi and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −5→5
T_min = 0.986, T_max = 0.991	k = −12→9
5185 measured reflections	l = −23→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.078P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1849 reflections	Δρ_max = 0.25 e Å⁻³
158 parameters	Δρ_min = −0.15 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (4)

Crystal data top

C₇H₅NO₄·0.5C₆H₆N₄	V = 1049.4 (2) Å³
M_r = 234.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.852 (1) Å	µ = 0.12 mm⁻¹
b = 10.9245 (10) Å	T = 296 K
c = 19.7981 (10) Å	0.12 × 0.10 × 0.08 mm
β = 90.496 (1)°

Data collection top

Bruker APEXII CCD diffractometer	1849 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1264 reflections with I > 2σ(I)
T_min = 0.986, T_max = 0.991	R_int = 0.034
5185 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	1 restraint
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.25 e Å⁻³
1849 reflections	Δρ_min = −0.15 e Å⁻³
158 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.3475 (4)	0.7795 (2)	0.58109 (11)	0.0548 (6)
C2	−0.2424 (4)	0.54924 (18)	0.67279 (9)	0.0493 (5)
C3	−0.1097 (4)	0.5072 (2)	0.61681 (10)	0.0577 (6)
H3	−0.1475	0.4298	0.5995	0.069*
C4	0.0825 (4)	0.5826 (2)	0.58629 (11)	0.0586 (6)
H4	0.1753	0.5557	0.5482	0.070*
C5	0.1368 (4)	0.69760 (19)	0.61233 (10)	0.0502 (5)
C6	−0.0063 (4)	0.7371 (2)	0.66845 (10)	0.0565 (6)
H6	0.0283	0.8148	0.6858	0.068*
C7	−0.1990 (4)	0.66362 (19)	0.69917 (11)	0.0551 (6)
H7	−0.2963	0.6908	0.7366	0.066*
C9	0.9965 (4)	0.95887 (18)	0.47185 (10)	0.0468 (5)
C10	0.8856 (5)	0.8140 (2)	0.40287 (11)	0.0676 (7)
H10	0.7961	0.7472	0.3836	0.081*
C11	1.0980 (5)	0.8751 (2)	0.37532 (11)	0.0678 (7)
H11	1.1813	0.8580	0.3342	0.081*
H2A	0.566 (4)	0.7886 (19)	0.5083 (11)	0.080*
N1	0.8218 (3)	0.86605 (16)	0.46396 (9)	0.0549 (5)
N2	1.1672 (3)	0.96604 (16)	0.41881 (8)	0.0550 (5)
H2	1.2968	1.0188	0.4135	0.066*
N3	−0.4451 (4)	0.46869 (19)	0.70582 (9)	0.0596 (5)
O1	0.4057 (3)	0.87721 (14)	0.60756 (8)	0.0689 (5)
O2	0.4566 (3)	0.73838 (16)	0.52653 (8)	0.0739 (5)
O3	−0.5946 (4)	0.50989 (16)	0.74887 (10)	0.0873 (6)
O4	−0.4548 (4)	0.36262 (17)	0.68800 (10)	0.0926 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0442 (12)	0.0579 (14)	0.0621 (14)	−0.0011 (10)	−0.0014 (10)	0.0114 (11)
C2	0.0449 (11)	0.0507 (12)	0.0522 (12)	−0.0036 (9)	0.0044 (9)	0.0051 (10)
C3	0.0628 (14)	0.0509 (12)	0.0595 (13)	−0.0100 (10)	0.0119 (11)	−0.0058 (10)
C4	0.0577 (14)	0.0624 (14)	0.0559 (13)	−0.0052 (11)	0.0124 (10)	−0.0028 (11)
C5	0.0427 (12)	0.0505 (13)	0.0574 (12)	−0.0028 (9)	−0.0024 (10)	0.0076 (10)
C6	0.0561 (13)	0.0481 (13)	0.0653 (13)	−0.0028 (10)	0.0007 (11)	−0.0026 (10)
C7	0.0543 (13)	0.0554 (13)	0.0556 (12)	0.0002 (10)	0.0060 (10)	−0.0031 (10)
C9	0.0399 (11)	0.0483 (12)	0.0523 (11)	0.0004 (9)	0.0024 (9)	0.0056 (9)
C10	0.0701 (16)	0.0621 (15)	0.0705 (15)	−0.0161 (12)	0.0037 (12)	−0.0095 (12)
C11	0.0719 (16)	0.0709 (16)	0.0609 (14)	−0.0068 (13)	0.0132 (12)	−0.0095 (13)
N1	0.0520 (11)	0.0516 (10)	0.0610 (11)	−0.0074 (8)	0.0014 (8)	0.0017 (9)
N2	0.0500 (10)	0.0544 (11)	0.0609 (11)	−0.0053 (8)	0.0088 (9)	0.0025 (9)
N3	0.0581 (12)	0.0634 (13)	0.0573 (11)	−0.0071 (10)	0.0092 (9)	0.0029 (9)
O1	0.0602 (10)	0.0563 (10)	0.0904 (11)	−0.0113 (8)	0.0095 (8)	0.0033 (9)
O2	0.0713 (12)	0.0737 (12)	0.0769 (11)	−0.0217 (9)	0.0177 (9)	0.0076 (9)
O3	0.0907 (13)	0.0871 (13)	0.0849 (12)	−0.0056 (10)	0.0419 (10)	0.0034 (10)
O4	0.1113 (16)	0.0649 (12)	0.1021 (13)	−0.0320 (10)	0.0356 (11)	−0.0089 (10)

Geometric parameters (Å, º) top

C1—O1	1.222 (3)	C7—H7	0.9300
C1—O2	1.288 (3)	C9—N1	1.330 (2)
C1—C5	1.496 (3)	C9—N2	1.345 (2)
C2—C3	1.366 (3)	C9—C9ⁱ	1.432 (4)
C2—C7	1.370 (3)	C10—C11	1.347 (3)
C2—N3	1.476 (3)	C10—N1	1.374 (3)
C3—C4	1.387 (3)	C10—H10	0.9300
C3—H3	0.9300	C11—N2	1.355 (3)
C4—C5	1.382 (3)	C11—H11	0.9300
C4—H4	0.9300	N2—H2	0.8600
C5—C6	1.384 (3)	N3—O3	1.211 (2)
C6—C7	1.377 (3)	N3—O4	1.212 (2)
C6—H6	0.9300	O2—H2A	0.845 (10)

O1—C1—O2	124.7 (2)	C2—C7—H7	121.1
O1—C1—C5	120.1 (2)	C6—C7—H7	121.1
O2—C1—C5	115.2 (2)	N1—C9—N2	110.41 (18)
C3—C2—C7	122.95 (19)	N1—C9—C9ⁱ	125.5 (2)
C3—C2—N3	118.65 (19)	N2—C9—C9ⁱ	124.1 (2)
C7—C2—N3	118.40 (18)	C11—C10—N1	109.3 (2)
C2—C3—C4	118.5 (2)	C11—C10—H10	125.3
C2—C3—H3	120.7	N1—C10—H10	125.3
C4—C3—H3	120.7	C10—C11—N2	106.98 (19)
C5—C4—C3	120.3 (2)	C10—C11—H11	126.5
C5—C4—H4	119.9	N2—C11—H11	126.5
C3—C4—H4	119.9	C9—N1—C10	105.70 (18)
C4—C5—C6	119.17 (19)	C9—N2—C11	107.60 (17)
C4—C5—C1	121.2 (2)	C9—N2—H2	126.2
C6—C5—C1	119.7 (2)	C11—N2—H2	126.2
C7—C6—C5	121.3 (2)	O3—N3—O4	122.56 (19)
C7—C6—H6	119.3	O3—N3—C2	119.7 (2)
C5—C6—H6	119.3	O4—N3—C2	117.72 (18)
C2—C7—C6	117.76 (19)	C1—O2—H2A	113.3 (17)

C7—C2—C3—C4	1.6 (3)	C5—C6—C7—C2	0.7 (3)
N3—C2—C3—C4	−179.36 (18)	N1—C10—C11—N2	−0.4 (3)
C2—C3—C4—C5	−0.1 (3)	N2—C9—N1—C10	−0.6 (2)
C3—C4—C5—C6	−1.1 (3)	C9ⁱ—C9—N1—C10	178.9 (2)
C3—C4—C5—C1	178.72 (18)	C11—C10—N1—C9	0.6 (3)
O1—C1—C5—C4	−175.01 (18)	N1—C9—N2—C11	0.4 (2)
O2—C1—C5—C4	4.7 (3)	C9ⁱ—C9—N2—C11	−179.1 (2)
O1—C1—C5—C6	4.8 (3)	C10—C11—N2—C9	0.0 (2)
O2—C1—C5—C6	−175.56 (18)	C3—C2—N3—O3	−168.9 (2)
C4—C5—C6—C7	0.7 (3)	C7—C2—N3—O3	10.2 (3)
C1—C5—C6—C7	−179.06 (18)	C3—C2—N3—O4	10.8 (3)
C3—C2—C7—C6	−1.9 (3)	C7—C2—N3—O4	−170.2 (2)
N3—C2—C7—C6	179.04 (18)

Symmetry code: (i) −x+2, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1	0.85 (1)	1.75 (1)	2.580 (2)	168 (3)
N2—H2···O1ⁱ	0.86	1.89	2.742 (2)	173

Symmetry code: (i) −x+2, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₇H₅NO₄·0.5C₆H₆N₄
M_r	234.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	4.852 (1), 10.9245 (10), 19.7981 (10)
β (°)	90.496 (1)
V (Å³)	1049.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.986, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	5185, 1849, 1264
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.134, 1.00
No. of reflections	1849
No. of parameters	158
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.15

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), 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
O2—H2A···N1	0.845 (10)	1.747 (11)	2.580 (2)	168 (3)
N2—H2···O1ⁱ	0.86	1.89	2.742 (2)	172.9

Symmetry code: (i) −x+2, −y+2, −z+1.

Acknowledgements

The authors thank Shandong University for support.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2001). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, X. T., Lu, C. Z., Zhang, Q. Z., Lu, S. F., Yang, W. B., Liu, J. C. & Zhuang, H. H. (2003). Eur. J. Inorg. Chem. pp. 1181–1185. CSD CrossRef Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1245

https://doi.org/10.1107/S1600536810015643

Open

access