2,2'-(p-Phenyl-ene)bis-(4,5-dihydro-1H-imidazol-3-ium) bis-(3-nitro-benzoate).

In the title compound, C(12)H(16)N(4) (+)·2C(7)H(4)NO(4) (-), the complete 2,2'-(p-phenyl-ene)bis-(4,5-dihydro-1H-imidazol-3-ium) (bib) dication is generated by crystallographic inversion symmetry. The bib cations reside on crystallographic inversion centers, which coincide with the centroids of the respective benzene rings. In the cation, the imidazole ring adopts an envelop conformation with the flap atom displaced by 0.082 (3) Å from the plane through the other ring atoms. In the crystal, the cations and anions are linked through inter-molecular N-H⋯O hydrogen bonds, forming chains running along the a axis. C-H⋯O inter-actions also occur. Weak π-π contacts between the imidazole rings of bib and between the benzene rings of NB [centroid-centroid distances = 3.501 (1) and 3.281 (2) Å, respectively] may further stabilize the structure.

Related literature

For general background to supra­molecular inter­actions, see: Jeffrey (1997 ▶). For the structures of metal complexes with imidazole ligands reported by our group, see: Ren, Ye, He et al. (2004 ▶); Ren, Ye, Zhu et al. (2004 ▶); Ren et al. (2007 ▶, 2009 ▶).

Experimental

Crystal data

C12H16N4 2+·2C7H4NO4 −

M = 548.51

Triclinic,

a = 6.9882 (12) Å

b = 7.4165 (12) Å

c = 13.233 (2) Å

α = 81.343 (3)°

β = 82.443 (3)°

γ = 62.699 (2)°

V = 600.96 (17) Å3

Z = 1

Mo Kα radiation

μ = 0.12 mm−1

T = 273 K

0.67 × 0.55 × 0.42 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.927, T max = 0.953

3714 measured reflections

2575 independent reflections

1676 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.151

S = 1.07

2575 reflections

181 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.28 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810053341/ds2078sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053341/ds2078Isup2.hkl

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

C12H16N42+·2C7H4NO4−	V = 600.96 (17) Å3
Mr = 548.51	Z = 1
Triclinic, P1	F(000) = 286
Hall symbol: -P 1	Dx = 1.516 Mg m−3
a = 6.9882 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.4165 (12) Å	µ = 0.12 mm−1
c = 13.233 (2) Å	T = 273 K
α = 81.343 (3)°	Block, colorless
β = 82.443 (3)°	0.67 × 0.55 × 0.42 mm
γ = 62.699 (2)°

Bruker SMART APEX CCD area-detector diffractometer	2575 independent reflections
Radiation source: fine-focus sealed tube	1676 reflections with I > 2σ(I)
graphite	Rint = 0.016
φ and ω scans	θmax = 27.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −8→8
Tmin = 0.927, Tmax = 0.953	k = −9→9
3714 measured reflections	l = −16→8

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0613P)2 + 0.1694P] where P = (Fo2 + 2Fc2)/3
2575 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.20 e Å−3
1 restraint	Δρmin = −0.28 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.7607 (4)	0.1903 (4)	0.18562 (17)	0.0483 (6)
H1A	0.7398	0.2592	0.2458	0.058*
H1B	0.6839	0.1075	0.1981	0.058*
C2	0.6871 (4)	0.3430 (3)	0.09029 (18)	0.0492 (6)
H2A	0.5961	0.3147	0.0521	0.059*
H2B	0.6093	0.4820	0.1083	0.059*
C3	1.0544 (3)	0.1481 (3)	0.07401 (15)	0.0383 (5)
C4	1.2831 (3)	0.0707 (3)	0.03509 (15)	0.0373 (5)
C5	1.3404 (3)	0.1420 (3)	−0.06192 (15)	0.0414 (5)
H5	1.2337	0.2373	−0.1034	0.050*
C6	1.5554 (4)	0.0716 (3)	−0.09660 (15)	0.0416 (5)
H6	1.5925	0.1195	−0.1615	0.050*
C7	0.1900 (4)	0.5421 (5)	0.2448 (2)	0.0620 (8)
C8	0.2163 (3)	0.3932 (3)	0.33993 (16)	0.0437 (5)
C9	0.1925 (4)	0.2191 (4)	0.33805 (19)	0.0529 (6)
H9	0.1691	0.1887	0.2765	0.064*
C10	0.2027 (4)	0.0885 (4)	0.4264 (2)	0.0639 (7)
H10	0.1849	−0.0275	0.4239	0.077*
C11	0.2391 (4)	0.1307 (4)	0.5170 (2)	0.0620 (7)
H11	0.2445	0.0452	0.5769	0.074*
C12	0.2671 (3)	0.3009 (4)	0.51797 (16)	0.0507 (6)
C13	0.2561 (3)	0.4345 (3)	0.43168 (17)	0.0462 (5)
H13	0.2750	0.5497	0.4350	0.055*
N1	0.8925 (3)	0.3081 (3)	0.03187 (14)	0.0482 (5)
H1	0.9055	0.3822	−0.0226	0.058*
N2	0.9901 (3)	0.0671 (3)	0.15833 (13)	0.0438 (5)
H2	1.0721	−0.0439	0.1930	0.053*
N3	0.3060 (4)	0.3471 (5)	0.61616 (18)	0.0776 (8)
O1	0.1555 (3)	0.4959 (3)	0.16467 (14)	0.0884 (7)
O2	0.2025 (3)	0.7013 (3)	0.25649 (18)	0.0916 (8)
O3	0.3241 (4)	0.5037 (6)	0.6153 (2)	0.1100 (10)
O4	0.3135 (4)	0.2288 (5)	0.69216 (16)	0.1205 (11)

	U11	U22	U33	U12	U13	U23
C1	0.0495 (13)	0.0543 (13)	0.0410 (12)	−0.0242 (11)	−0.0023 (10)	−0.0025 (10)
C2	0.0456 (13)	0.0468 (12)	0.0473 (13)	−0.0152 (10)	−0.0034 (10)	−0.0009 (10)
C3	0.0477 (12)	0.0387 (10)	0.0286 (10)	−0.0187 (9)	−0.0089 (9)	−0.0010 (8)
C4	0.0446 (12)	0.0356 (10)	0.0298 (10)	−0.0160 (9)	−0.0068 (8)	−0.0011 (8)
C5	0.0472 (12)	0.0380 (11)	0.0323 (11)	−0.0142 (9)	−0.0099 (9)	0.0053 (8)
C6	0.0516 (13)	0.0424 (11)	0.0273 (10)	−0.0197 (10)	−0.0045 (9)	0.0040 (8)
C7	0.0410 (13)	0.0717 (18)	0.0494 (16)	−0.0137 (12)	−0.0021 (11)	0.0233 (13)
C8	0.0359 (11)	0.0477 (12)	0.0367 (12)	−0.0129 (9)	−0.0031 (9)	0.0074 (9)
C9	0.0513 (14)	0.0599 (15)	0.0463 (14)	−0.0226 (11)	−0.0085 (11)	−0.0052 (11)
C10	0.0610 (16)	0.0510 (14)	0.080 (2)	−0.0292 (13)	−0.0097 (14)	0.0104 (13)
C11	0.0513 (15)	0.0686 (17)	0.0530 (16)	−0.0235 (13)	−0.0059 (12)	0.0225 (13)
C12	0.0350 (12)	0.0701 (16)	0.0336 (12)	−0.0131 (11)	−0.0033 (9)	−0.0013 (11)
C13	0.0362 (11)	0.0487 (12)	0.0484 (13)	−0.0153 (10)	−0.0014 (9)	−0.0037 (10)
N1	0.0481 (11)	0.0478 (10)	0.0372 (10)	−0.0146 (9)	−0.0047 (8)	0.0072 (8)
N2	0.0464 (10)	0.0434 (10)	0.0365 (10)	−0.0181 (8)	−0.0060 (8)	0.0062 (8)
N3	0.0438 (13)	0.124 (2)	0.0481 (14)	−0.0212 (14)	−0.0029 (10)	−0.0174 (15)
O1	0.0837 (14)	0.1023 (16)	0.0365 (10)	−0.0115 (12)	−0.0080 (9)	0.0177 (10)
O2	0.0766 (14)	0.0759 (14)	0.1167 (19)	−0.0418 (12)	−0.0346 (12)	0.0561 (13)
O3	0.0816 (17)	0.173 (3)	0.0934 (19)	−0.0593 (18)	0.0042 (13)	−0.0671 (19)
O4	0.0984 (18)	0.183 (3)	0.0363 (12)	−0.0305 (18)	−0.0134 (11)	0.0122 (15)

C1—N2	1.462 (3)	C7—O2	1.257 (4)
C1—C2	1.531 (3)	C7—C8	1.514 (3)
C1—H1A	0.9700	C8—C9	1.380 (3)
C1—H1B	0.9700	C8—C13	1.387 (3)
C2—N1	1.468 (3)	C9—C10	1.388 (3)
C2—H2A	0.9700	C9—H9	0.9300
C2—H2B	0.9700	C10—C11	1.367 (4)
C3—N2	1.312 (3)	C10—H10	0.9300
C3—N1	1.317 (3)	C11—C12	1.366 (4)
C3—C4	1.476 (3)	C11—H11	0.9300
C4—C6i	1.393 (3)	C12—C13	1.380 (3)
C4—C5	1.394 (3)	C12—N3	1.481 (3)
C5—C6	1.383 (3)	C13—H13	0.9300
C5—H5	0.9300	N1—H1	0.8600
C6—C4i	1.393 (3)	N2—H2	0.8600
C6—H6	0.9300	N3—O4	1.221 (3)
C7—O1	1.246 (4)	N3—O3	1.222 (4)
N2—C1—C2	102.53 (17)	C9—C8—C13	118.9 (2)
N2—C1—H1A	111.3	C9—C8—C7	120.8 (2)
C2—C1—H1A	111.3	C13—C8—C7	120.2 (2)
N2—C1—H1B	111.3	C8—C9—C10	121.2 (2)
C2—C1—H1B	111.3	C8—C9—H9	119.4
H1A—C1—H1B	109.2	C10—C9—H9	119.4
N1—C2—C1	102.37 (17)	C11—C10—C9	119.9 (2)
N1—C2—H2A	111.3	C11—C10—H10	120.1
C1—C2—H2A	111.3	C9—C10—H10	120.1
N1—C2—H2B	111.3	C12—C11—C10	118.7 (2)
C1—C2—H2B	111.3	C12—C11—H11	120.7
H2A—C2—H2B	109.2	C10—C11—H11	120.7
N2—C3—N1	111.85 (19)	C11—C12—C13	122.8 (2)
N2—C3—C4	122.98 (18)	C11—C12—N3	118.7 (2)
N1—C3—C4	125.13 (18)	C13—C12—N3	118.4 (3)
C6i—C4—C5	119.30 (19)	C12—C13—C8	118.5 (2)
C6i—C4—C3	119.93 (18)	C12—C13—H13	120.7
C5—C4—C3	120.75 (18)	C8—C13—H13	120.7
C6—C5—C4	120.20 (19)	C3—N1—C2	110.95 (18)
C6—C5—H5	119.9	C3—N1—H1	124.5
C4—C5—H5	119.9	C2—N1—H1	124.5
C5—C6—C4i	120.50 (19)	C3—N2—C1	111.14 (17)
C5—C6—H6	119.7	C3—N2—H2	124.4
C4i—C6—H6	119.7	C1—N2—H2	124.4
O1—C7—O2	127.2 (2)	O4—N3—O3	124.9 (3)
O1—C7—C8	117.2 (3)	O4—N3—C12	117.8 (3)
O2—C7—C8	115.6 (3)	O3—N3—C12	117.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ii	0.93	2.48	3.283 (3)	144
N1—H1···O1iii	0.86	1.97	2.763 (3)	153
N2—H2···O2iv	0.86	1.80	2.646 (3)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2i	0.93	2.48	3.283 (3)	144
N1—H1⋯O1ii	0.86	1.97	2.763 (3)	153
N2—H2⋯O2iii	0.86	1.80	2.646 (3)	166

Symmetry codes: (i) ; (ii) ; (iii) .