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

Abstract

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 R ₂ ²(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,

• a = 4.852 (1) Å

• b = 10.9245 (10) Å

• c = 19.7981 (10) Å

• β = 90.496 (1)°

• V = 1049.4 (2) ų

• 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[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 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

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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were placed in calculated positions with C—H = 0.93Å and refined as riding with U_iso(H) = 1.2U_eq(carrier). The lengths of bond H—O were constrained with 0.82 Å .

Figures

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).

Crystal data

C7H5NO4·0.5C6H6N4	F(000) = 484
Mr = 234.19	Dx = 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

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

Refinement

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(Fo2) + (0.078P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
1849 reflections	Δρmax = 0.25 e Å−3
158 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+2, −y+2, −z+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 codes: (i) −x+2, −y+2, −z+1.