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The crystal of the title compound, imidazolium tri­hydrogen-1,2,4,5-benzene­tetra­carboxyl­ate, C3H5N2+·C10H5O8, is built of imidazolium cations and tri­hydrogen-1,2,4,5-benzene­tetra­carboxyl­ate anions. The anions use two of their `active' H atoms to generate hydrogen bonds linking to the neighbouring anions, thus creating a two-dimensional hydrogen-bonding network parallel to the bc plane of the crystal. The third oxy­gen-bound H atom of the anion is involved in an intramolecular hydrogen bond, which closes the six-membered pseudo-ring. The imidazolium cations are linked to the anionic hydrogen-bonded network through N—H...O bonds which target two of the O atoms of the carboxyl groups of the anions as acceptors. The mean plane of the imidazolium cation is almost orthogonal to the mean plane of the benzene ring of benzene­tetra­carboxyl­ate, with a dihedral angle of 89.7 (1)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016410/ya6127sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016410/ya6127Isup2.hkl
Contains datablock I

CCDC reference: 198957

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.058
  • wR factor = 0.156
  • Data-to-parameter ratio = 9.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
ABSMU_01 Alert C The ratio of given/expected absorption coefficient lies outside the range 0.99 <> 1.01 Calculated value of mu = 0.142 Value of mu given = 0.140
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Intermolecular interactions, such as hydrogen bonds and aromatic π···π stacking interactions, play a dominant role in molecular recognition in nature, and in designing molecular aggregates (Juan et al., 2002). Of particular interest are compounds that are capable of forming very strong hydrogen bonds, such as 1,2,4,5-benzenetetracarboxylate, which can act not only as a hydrogen-bond acceptor but also as a hydrogen bond-donor. depending on the numbers of deprotonated carboxyl groups. 1,2,4,5-Benzenetetracarboxylic acid in its supramolecular adducts is most frequently encountered in the form with either two or four deprotonated carboxyl groups. Thus, complexes [(2,2'-bipyridyl)H]+2[C6H2(COO)4H2]2−·[C6H2(COOH)4] (Mrvos-Sermek et al., 1996), {[(4,4'-bipyridyl)H]+}2[(C10H4O8)2−] (Lough et al., 2000), [(C6H13N4)+]2[(C10H4O8)2−] (Lough et al., 2000) and [(CH6N3)+2(C10H4O8)2−] (Sun et al., 2002), contain the doubly deprotonated dianionic form, whereas the structures of [(C24H42N6)4+(C10H2O8)4−·6H2O]) (Zhu et al., 2002) and [C(NH2)3]+4[C10H2(COO)4]4−·3H2O·H2O2) (Adams & Ramdas, 1978) involve totally deprotonated tetraanions. Herein we report a rare case of a mono-deprotonated 1,2,4,5-benzenetetracarboxylate salt with an imidazolium cation.

The asymmetric unit of the triclinic cell of the title compound, (I), includes one monoprotonated imidazolium cation, C3H5N2+, and one mono-deprotonated benzenetetracarboxylic anion, C10H5O8 (Fig. 1). The mean plane of the cation is almost orthogonal to the mean plane of the anion, with a dihedral angle of 89.7 (1)°.

As may be expected, three carboxyl groups of the anion, viz. those with the central atoms C10, C11, and C12, show considerable differences in the C—O bond lengths; bonds involving protonated O atoms are 0.06–0.10 Å longer than the other ones. The C13, O7, O8 group represents an ionized carboxylate with almost equal C13—O7 and C13—O8 bonds (see Table 1).

There is only one intramolecular O—H···O hydrogen bond in the anion (O6—H6A···O7) Two other oxygen-bound H atoms of the anion and two nitrogen-bound H atoms of the cation give rise to four symmetry-independent intermolecular (or, to put it more accurately, `interionic') hydrogen bonds (Table 2), which link the cations and anions of the structure into infinite layers parallel to the bc plane of the crystal (Fig.2).

Experimental top

A mixture of pyromellitic dianhydride (0.109 g,0.5 mmol), imidazole (0.034 g,0.5 mmol) and H2O (10 ml,567.7 mmol), in the ratio of ca 1:1:1135, was sealed in a 35 ml stainless-steel reactor with a telflon liner, and was heated at 433 K for 72 h. After cooling, the mixture was filtered and colorless single crystals were obtained by slow evaporation of the filtrate at room temperature.

Refinement top

All hydrogen atoms were located in a difference Fourier map and their positions and isotropic displacement parameters were refined. The N—H bond lengths are equal to 0.86 (4) and 0.90 (4) Å and the C—H bond lengths range from 0.92 to 0.96%A. The O—H bond lengths are between 0.89 and 1.11 Å. The H6A atom participating in the intramolecular hydrogen bond refined to a position 1.11 (5) Å from O6 and 1.29 (5) Å from O7. Taking into account this difference in the O—H distances, as well as the distribution of C—O bond lengths in carboxyl groups (see Comment), we concluded that C12, O5, O6 is in fact a protonated carboxylic group, whereas the C13, O7, O8 group represents a deprotonated carboxylate.

Computing details top

Data collection: Bruker SMART; cell refinement: SMART (Bruker, 1999); data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The cation and anion in the structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are shown at the 30% probability level.
[Figure 2] Fig. 2. Packing diagram, viewed down [301], showing the hydrogen-bond system in the crystal of the title compound.
Imidazolium trihydrogen 1,2,4,5-benzenetetracarboxylate top
Crystal data top
C3H5N2+·C10H5O8Z = 2
Mr = 322.23F(000) = 332
Triclinic, P1Dx = 1.668 Mg m3
Hall symbol: -p 1Mo Kα radiation, λ = 0.71073 Å
a = 7.6045 (12) ÅCell parameters from 49 reflections
b = 9.6885 (15) Åθ = 2.2–25.1°
c = 9.7991 (16) ŵ = 0.14 mm1
α = 88.804 (2)°T = 293 K
β = 69.069 (2)°Column, colorless
γ = 72.853 (2)°0.38 × 0.32 × 0.26 mm
V = 641.46 (18) Å3
Data collection top
Siemens SMART CCD
diffractometer
2238 independent reflections
Radiation source: fine-focus sealed tube1790 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ϕ and ω scansθmax = 25.1°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 94
Tmin = 0.948, Tmax = 0.964k = 1110
3343 measured reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: difference Fourier map
wR(F2) = 0.156All H-atom parameters refined
S = 1.07 w = 1/[σ2(Fo2) + (0.0782P)2 + 0.5307P]
where P = (Fo2 + 2Fc2)/3
2238 reflections(Δ/σ)max < 0.001
249 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.37 e Å3
Crystal data top
C3H5N2+·C10H5O8γ = 72.853 (2)°
Mr = 322.23V = 641.46 (18) Å3
Triclinic, P1Z = 2
a = 7.6045 (12) ÅMo Kα radiation
b = 9.6885 (15) ŵ = 0.14 mm1
c = 9.7991 (16) ÅT = 293 K
α = 88.804 (2)°0.38 × 0.32 × 0.26 mm
β = 69.069 (2)°
Data collection top
Siemens SMART CCD
diffractometer
2238 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1790 reflections with I > 2σ(I)
Tmin = 0.948, Tmax = 0.964Rint = 0.033
3343 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.156All H-atom parameters refined
S = 1.07Δρmax = 0.32 e Å3
2238 reflectionsΔρmin = 0.37 e Å3
249 parameters
Special details top

Geometry. Mean-plane data from final SHELXL refinement run:-

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

1.5408 (0.0141) x + 9.0964 (0.0059) y − 3.1430 (0.0160) z = 3.9109 (0.0224)

* −0.0023 (0.0020) N1 * 0.0036 (0.0020) C1 * −0.0035 (0.0021) N2 * 0.0019 (0.0021) C2 * 0.0003 (0.0021) C3

Rms deviation of fitted atoms = 0.0026

6.9210 (0.0034) x − 0.2387 (0.0099) y + 0.9122 (0.0100) z = 1.9258 (0.0125)

Angle to previous plane (with approximate e.s.d.) = 89.76 (0.12)

* −0.0259 (0.0018) C4 * 0.0249 (0.0018) C5 * 0.0013 (0.0018) C6 * −0.0263 (0.0018) C7 * 0.0255 (0.0017) C8 * 0.0004 (0.0018) C9

Rms deviation of fitted atoms = 0.0210

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
xyzUiso*/Ueq
O10.2940 (4)1.0262 (3)0.9577 (2)0.0514 (7)
O20.0205 (3)1.2029 (3)0.9787 (2)0.0544 (7)
O30.3127 (4)1.3261 (3)0.7700 (3)0.0619 (8)
O40.2278 (4)1.4002 (2)0.5825 (2)0.0466 (6)
O50.2504 (4)1.0724 (2)0.2349 (2)0.0441 (6)
O60.2514 (4)0.8479 (2)0.2550 (2)0.0449 (6)
O70.2167 (4)0.6824 (2)0.4402 (3)0.0607 (8)
O80.2747 (4)0.6443 (2)0.6416 (2)0.0435 (6)
C10.4526 (6)0.6759 (4)0.9325 (4)0.0483 (8)
C20.7705 (6)0.6034 (4)0.8792 (4)0.0503 (9)
C30.7401 (5)0.5675 (4)0.7608 (4)0.0459 (8)
C40.2126 (4)1.0650 (3)0.7483 (3)0.0253 (6)
C50.2374 (4)1.1617 (3)0.6411 (3)0.0252 (6)
C60.2510 (4)1.1218 (3)0.5021 (3)0.0251 (6)
C70.2475 (4)0.9849 (3)0.4620 (3)0.0260 (6)
C80.2375 (4)0.8832 (3)0.5680 (3)0.0246 (6)
C90.2168 (4)0.9274 (3)0.7095 (3)0.0264 (6)
C100.1650 (4)1.1074 (3)0.9071 (3)0.0300 (6)
C110.2607 (4)1.3044 (3)0.6729 (3)0.0271 (6)
C120.2523 (4)0.9683 (3)0.3067 (3)0.0278 (6)
C130.2448 (4)0.7262 (3)0.5478 (3)0.0296 (6)
N10.5405 (5)0.6132 (3)0.7963 (3)0.0512 (8)
N20.5904 (5)0.6692 (3)0.9831 (3)0.0488 (8)
H10.318 (5)0.713 (4)0.984 (4)0.047 (10)*
H1A0.277 (8)1.036 (6)1.057 (7)0.113 (18)*
H1B0.476 (6)0.613 (4)0.736 (5)0.069 (12)*
H20.889 (6)0.593 (5)0.896 (5)0.071 (12)*
H2B0.580 (5)0.698 (4)1.069 (4)0.058 (11)*
H30.838 (6)0.518 (5)0.669 (5)0.071 (12)*
H40.246 (5)1.480 (5)0.612 (4)0.064 (11)*
H60.264 (4)1.188 (3)0.430 (3)0.028 (7)*
H6A0.239 (7)0.770 (5)0.339 (5)0.091 (15)*
H90.193 (4)0.863 (3)0.786 (3)0.032 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0724 (16)0.0527 (14)0.0291 (12)0.0032 (12)0.0314 (11)0.0021 (10)
O20.0523 (14)0.0658 (15)0.0337 (12)0.0011 (12)0.0171 (11)0.0135 (11)
O30.123 (2)0.0486 (14)0.0626 (16)0.0503 (15)0.0721 (16)0.0226 (11)
O40.0904 (18)0.0332 (12)0.0434 (13)0.0355 (12)0.0433 (12)0.0138 (9)
O50.0784 (16)0.0427 (12)0.0280 (11)0.0295 (11)0.0307 (11)0.0117 (9)
O60.0833 (17)0.0365 (12)0.0283 (11)0.0249 (11)0.0308 (11)0.0027 (9)
O70.129 (2)0.0404 (13)0.0456 (14)0.0458 (14)0.0550 (15)0.0134 (10)
O80.0761 (16)0.0325 (11)0.0415 (12)0.0271 (10)0.0363 (11)0.0109 (9)
C10.053 (2)0.0476 (19)0.0444 (19)0.0110 (16)0.0220 (17)0.0063 (15)
C20.059 (2)0.055 (2)0.051 (2)0.0207 (17)0.0336 (18)0.0030 (16)
C30.053 (2)0.0444 (18)0.0415 (19)0.0149 (15)0.0188 (16)0.0035 (14)
C40.0286 (13)0.0282 (13)0.0229 (13)0.0106 (11)0.0121 (10)0.0012 (10)
C50.0284 (13)0.0285 (13)0.0232 (13)0.0119 (10)0.0121 (10)0.0032 (10)
C60.0323 (14)0.0287 (13)0.0227 (13)0.0157 (11)0.0150 (11)0.0077 (10)
C70.0273 (13)0.0323 (14)0.0200 (13)0.0115 (11)0.0083 (10)0.0004 (10)
C80.0280 (13)0.0278 (13)0.0216 (13)0.0107 (10)0.0115 (10)0.0009 (10)
C90.0328 (14)0.0294 (14)0.0212 (13)0.0144 (11)0.0111 (11)0.0057 (10)
C100.0430 (16)0.0338 (15)0.0221 (13)0.0213 (13)0.0148 (12)0.0064 (11)
C110.0370 (15)0.0291 (14)0.0224 (13)0.0159 (11)0.0149 (11)0.0052 (10)
C120.0347 (14)0.0321 (14)0.0214 (13)0.0140 (11)0.0130 (11)0.0031 (11)
C130.0399 (15)0.0295 (14)0.0242 (13)0.0156 (12)0.0135 (11)0.0025 (11)
N10.074 (2)0.0582 (18)0.0432 (16)0.0265 (15)0.0416 (15)0.0089 (13)
N20.073 (2)0.0488 (16)0.0335 (15)0.0189 (14)0.0289 (14)0.0029 (12)
Geometric parameters (Å, º) top
O1—C101.304 (3)C2—H20.95 (4)
O1—H1A0.93 (6)C3—N11.361 (5)
O2—C101.197 (3)C3—H30.96 (4)
O3—C111.197 (3)C4—C91.382 (4)
O4—C111.302 (3)C4—C51.392 (4)
O4—H40.89 (4)C4—C101.503 (3)
O5—C121.216 (3)C5—C61.384 (4)
O6—C121.284 (3)C5—C111.497 (4)
O6—H6A1.11 (5)C6—C71.400 (4)
O7—C131.254 (3)C6—H60.94 (3)
O7—H6A1.29 (5)C7—C81.415 (4)
O8—C131.241 (3)C7—C121.520 (4)
C1—N11.324 (5)C8—C91.400 (4)
C1—N21.296 (4)C8—C131.520 (4)
C1—H10.92 (3)C9—H90.96 (3)
C2—N21.355 (5)N1—H1B0.90 (4)
C2—C31.333 (5)N2—H2B0.86 (4)
C10—O1—H1A121 (3)C9—C8—C7118.7 (2)
C11—O4—H4107 (3)C9—C8—C13114.0 (2)
C12—O6—H6A111 (2)C7—C8—C13127.3 (2)
C13—O7—H6A111 (2)C4—C9—C8122.6 (2)
N2—C1—N1107.2 (3)C4—C9—H9117.9 (17)
N2—C1—H1126 (2)C8—C9—H9119.3 (18)
N1—C1—H1127 (2)O2—C10—O1124.6 (2)
C3—C2—N2107.0 (3)O2—C10—C4122.7 (2)
C3—C2—H2131 (3)O1—C10—C4112.7 (2)
N2—C2—H2122 (3)O3—C11—O4123.0 (2)
C2—C3—N1106.2 (3)O3—C11—C5122.5 (2)
C2—C3—H3127 (2)O4—C11—C5114.4 (2)
N1—C3—H3126 (2)O5—C12—O6121.0 (2)
C9—C4—C5118.8 (2)O5—C12—C7118.7 (2)
C9—C4—C10118.3 (2)O6—C12—C7120.2 (2)
C5—C4—C10122.8 (2)O8—C13—O7121.2 (2)
C6—C5—C4119.4 (2)O8—C13—C8118.5 (2)
C6—C5—C11120.0 (2)O7—C13—C8120.3 (2)
C4—C5—C11120.5 (2)C1—N1—C3109.4 (3)
C5—C6—C7122.7 (2)C1—N1—H1B123 (3)
C5—C6—H6119.7 (17)C3—N1—H1B127 (3)
C7—C6—H6117.6 (17)C1—N2—C2110.1 (3)
C6—C7—C8117.6 (2)C1—N2—H2B129 (2)
C6—C7—C12113.5 (2)C2—N2—H2B120 (2)
C8—C7—C12128.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O5i0.93 (6)1.72 (6)2.648 (3)174 (6)
O6—H6A···O71.11 (5)1.29 (5)2.392 (3)177 (4)
N1—H1B···O80.90 (4)2.00 (4)2.878 (4)166 (4)
N2—H2B···O3ii0.86 (4)2.00 (4)2.774 (3)149 (3)
O4—H4···O8iii0.89 (4)1.72 (4)2.599 (3)170 (4)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y+2, z+2; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC3H5N2+·C10H5O8
Mr322.23
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.6045 (12), 9.6885 (15), 9.7991 (16)
α, β, γ (°)88.804 (2), 69.069 (2), 72.853 (2)
V3)641.46 (18)
Z2
Radiation typeMo Kα
µ (mm1)0.14
Crystal size (mm)0.38 × 0.32 × 0.26
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.948, 0.964
No. of measured, independent and
observed [I > 2σ(I)] reflections
3343, 2238, 1790
Rint0.033
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.156, 1.07
No. of reflections2238
No. of parameters249
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.32, 0.37

Computer programs: Bruker SMART, SMART (Bruker, 1999), SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
O1—C101.304 (3)O8—C131.241 (3)
O2—C101.197 (3)C1—N11.324 (5)
O3—C111.197 (3)C1—N21.296 (4)
O4—C111.302 (3)C2—N21.355 (5)
O5—C121.216 (3)C2—C31.333 (5)
O6—C121.284 (3)C3—N11.361 (5)
O7—C131.254 (3)
C9—C4—C10118.3 (2)O2—C10—O1124.6 (2)
C6—C5—C4119.4 (2)O3—C11—O4123.0 (2)
C6—C7—C8117.6 (2)O5—C12—O6121.0 (2)
C9—C8—C7118.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O5i0.93 (6)1.72 (6)2.648 (3)174 (6)
O6—H6A···O71.11 (5)1.29 (5)2.392 (3)177 (4)
N1—H1B···O80.90 (4)2.00 (4)2.878 (4)166 (4)
N2—H2B···O3ii0.86 (4)2.00 (4)2.774 (3)149 (3)
O4—H4···O8iii0.89 (4)1.72 (4)2.599 (3)170 (4)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y+2, z+2; (iii) x, y+1, z.
 

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