Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016410/ya6127sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016410/ya6127Isup2.hkl |
CCDC reference: 198957
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.
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.
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.
C3H5N2+·C10H5O8− | Z = 2 |
Mr = 322.23 | F(000) = 332 |
Triclinic, P1 | Dx = 1.668 Mg m−3 |
Hall symbol: -p 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6045 (12) Å | Cell parameters from 49 reflections |
b = 9.6885 (15) Å | θ = 2.2–25.1° |
c = 9.7991 (16) Å | µ = 0.14 mm−1 |
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 |
Siemens SMART CCD diffractometer | 2238 independent reflections |
Radiation source: fine-focus sealed tube | 1790 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 25.1°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→4 |
Tmin = 0.948, Tmax = 0.964 | k = −11→10 |
3343 measured reflections | l = −11→11 |
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)] = 0.058 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.156 | All 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 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C3H5N2+·C10H5O8− | γ = 72.853 (2)° |
Mr = 322.23 | V = 641.46 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.6045 (12) Å | Mo Kα radiation |
b = 9.6885 (15) Å | µ = 0.14 mm−1 |
c = 9.7991 (16) Å | T = 293 K |
α = 88.804 (2)° | 0.38 × 0.32 × 0.26 mm |
β = 69.069 (2)° |
Siemens SMART CCD diffractometer | 2238 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1790 reflections with I > 2σ(I) |
Tmin = 0.948, Tmax = 0.964 | Rint = 0.033 |
3343 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.156 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.32 e Å−3 |
2238 reflections | Δρmin = −0.37 e Å−3 |
249 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.2940 (4) | 1.0262 (3) | 0.9577 (2) | 0.0514 (7) | |
O2 | 0.0205 (3) | 1.2029 (3) | 0.9787 (2) | 0.0544 (7) | |
O3 | 0.3127 (4) | 1.3261 (3) | 0.7700 (3) | 0.0619 (8) | |
O4 | 0.2278 (4) | 1.4002 (2) | 0.5825 (2) | 0.0466 (6) | |
O5 | 0.2504 (4) | 1.0724 (2) | 0.2349 (2) | 0.0441 (6) | |
O6 | 0.2514 (4) | 0.8479 (2) | 0.2550 (2) | 0.0449 (6) | |
O7 | 0.2167 (4) | 0.6824 (2) | 0.4402 (3) | 0.0607 (8) | |
O8 | 0.2747 (4) | 0.6443 (2) | 0.6416 (2) | 0.0435 (6) | |
C1 | 0.4526 (6) | 0.6759 (4) | 0.9325 (4) | 0.0483 (8) | |
C2 | 0.7705 (6) | 0.6034 (4) | 0.8792 (4) | 0.0503 (9) | |
C3 | 0.7401 (5) | 0.5675 (4) | 0.7608 (4) | 0.0459 (8) | |
C4 | 0.2126 (4) | 1.0650 (3) | 0.7483 (3) | 0.0253 (6) | |
C5 | 0.2374 (4) | 1.1617 (3) | 0.6411 (3) | 0.0252 (6) | |
C6 | 0.2510 (4) | 1.1218 (3) | 0.5021 (3) | 0.0251 (6) | |
C7 | 0.2475 (4) | 0.9849 (3) | 0.4620 (3) | 0.0260 (6) | |
C8 | 0.2375 (4) | 0.8832 (3) | 0.5680 (3) | 0.0246 (6) | |
C9 | 0.2168 (4) | 0.9274 (3) | 0.7095 (3) | 0.0264 (6) | |
C10 | 0.1650 (4) | 1.1074 (3) | 0.9071 (3) | 0.0300 (6) | |
C11 | 0.2607 (4) | 1.3044 (3) | 0.6729 (3) | 0.0271 (6) | |
C12 | 0.2523 (4) | 0.9683 (3) | 0.3067 (3) | 0.0278 (6) | |
C13 | 0.2448 (4) | 0.7262 (3) | 0.5478 (3) | 0.0296 (6) | |
N1 | 0.5405 (5) | 0.6132 (3) | 0.7963 (3) | 0.0512 (8) | |
N2 | 0.5904 (5) | 0.6692 (3) | 0.9831 (3) | 0.0488 (8) | |
H1 | 0.318 (5) | 0.713 (4) | 0.984 (4) | 0.047 (10)* | |
H1A | 0.277 (8) | 1.036 (6) | 1.057 (7) | 0.113 (18)* | |
H1B | 0.476 (6) | 0.613 (4) | 0.736 (5) | 0.069 (12)* | |
H2 | 0.889 (6) | 0.593 (5) | 0.896 (5) | 0.071 (12)* | |
H2B | 0.580 (5) | 0.698 (4) | 1.069 (4) | 0.058 (11)* | |
H3 | 0.838 (6) | 0.518 (5) | 0.669 (5) | 0.071 (12)* | |
H4 | 0.246 (5) | 1.480 (5) | 0.612 (4) | 0.064 (11)* | |
H6 | 0.264 (4) | 1.188 (3) | 0.430 (3) | 0.028 (7)* | |
H6A | 0.239 (7) | 0.770 (5) | 0.339 (5) | 0.091 (15)* | |
H9 | 0.193 (4) | 0.863 (3) | 0.786 (3) | 0.032 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0724 (16) | 0.0527 (14) | 0.0291 (12) | −0.0032 (12) | −0.0314 (11) | −0.0021 (10) |
O2 | 0.0523 (14) | 0.0658 (15) | 0.0337 (12) | 0.0011 (12) | −0.0171 (11) | −0.0135 (11) |
O3 | 0.123 (2) | 0.0486 (14) | 0.0626 (16) | −0.0503 (15) | −0.0721 (16) | 0.0226 (11) |
O4 | 0.0904 (18) | 0.0332 (12) | 0.0434 (13) | −0.0355 (12) | −0.0433 (12) | 0.0138 (9) |
O5 | 0.0784 (16) | 0.0427 (12) | 0.0280 (11) | −0.0295 (11) | −0.0307 (11) | 0.0117 (9) |
O6 | 0.0833 (17) | 0.0365 (12) | 0.0283 (11) | −0.0249 (11) | −0.0308 (11) | 0.0027 (9) |
O7 | 0.129 (2) | 0.0404 (13) | 0.0456 (14) | −0.0458 (14) | −0.0550 (15) | 0.0134 (10) |
O8 | 0.0761 (16) | 0.0325 (11) | 0.0415 (12) | −0.0271 (10) | −0.0363 (11) | 0.0109 (9) |
C1 | 0.053 (2) | 0.0476 (19) | 0.0444 (19) | −0.0110 (16) | −0.0220 (17) | 0.0063 (15) |
C2 | 0.059 (2) | 0.055 (2) | 0.051 (2) | −0.0207 (17) | −0.0336 (18) | 0.0030 (16) |
C3 | 0.053 (2) | 0.0444 (18) | 0.0415 (19) | −0.0149 (15) | −0.0188 (16) | −0.0035 (14) |
C4 | 0.0286 (13) | 0.0282 (13) | 0.0229 (13) | −0.0106 (11) | −0.0121 (10) | 0.0012 (10) |
C5 | 0.0284 (13) | 0.0285 (13) | 0.0232 (13) | −0.0119 (10) | −0.0121 (10) | 0.0032 (10) |
C6 | 0.0323 (14) | 0.0287 (13) | 0.0227 (13) | −0.0157 (11) | −0.0150 (11) | 0.0077 (10) |
C7 | 0.0273 (13) | 0.0323 (14) | 0.0200 (13) | −0.0115 (11) | −0.0083 (10) | −0.0004 (10) |
C8 | 0.0280 (13) | 0.0278 (13) | 0.0216 (13) | −0.0107 (10) | −0.0115 (10) | 0.0009 (10) |
C9 | 0.0328 (14) | 0.0294 (14) | 0.0212 (13) | −0.0144 (11) | −0.0111 (11) | 0.0057 (10) |
C10 | 0.0430 (16) | 0.0338 (15) | 0.0221 (13) | −0.0213 (13) | −0.0148 (12) | 0.0064 (11) |
C11 | 0.0370 (15) | 0.0291 (14) | 0.0224 (13) | −0.0159 (11) | −0.0149 (11) | 0.0052 (10) |
C12 | 0.0347 (14) | 0.0321 (14) | 0.0214 (13) | −0.0140 (11) | −0.0130 (11) | 0.0031 (11) |
C13 | 0.0399 (15) | 0.0295 (14) | 0.0242 (13) | −0.0156 (12) | −0.0135 (11) | 0.0025 (11) |
N1 | 0.074 (2) | 0.0582 (18) | 0.0432 (16) | −0.0265 (15) | −0.0416 (15) | 0.0089 (13) |
N2 | 0.073 (2) | 0.0488 (16) | 0.0335 (15) | −0.0189 (14) | −0.0289 (14) | −0.0029 (12) |
O1—C10 | 1.304 (3) | C2—H2 | 0.95 (4) |
O1—H1A | 0.93 (6) | C3—N1 | 1.361 (5) |
O2—C10 | 1.197 (3) | C3—H3 | 0.96 (4) |
O3—C11 | 1.197 (3) | C4—C9 | 1.382 (4) |
O4—C11 | 1.302 (3) | C4—C5 | 1.392 (4) |
O4—H4 | 0.89 (4) | C4—C10 | 1.503 (3) |
O5—C12 | 1.216 (3) | C5—C6 | 1.384 (4) |
O6—C12 | 1.284 (3) | C5—C11 | 1.497 (4) |
O6—H6A | 1.11 (5) | C6—C7 | 1.400 (4) |
O7—C13 | 1.254 (3) | C6—H6 | 0.94 (3) |
O7—H6A | 1.29 (5) | C7—C8 | 1.415 (4) |
O8—C13 | 1.241 (3) | C7—C12 | 1.520 (4) |
C1—N1 | 1.324 (5) | C8—C9 | 1.400 (4) |
C1—N2 | 1.296 (4) | C8—C13 | 1.520 (4) |
C1—H1 | 0.92 (3) | C9—H9 | 0.96 (3) |
C2—N2 | 1.355 (5) | N1—H1B | 0.90 (4) |
C2—C3 | 1.333 (5) | N2—H2B | 0.86 (4) |
C10—O1—H1A | 121 (3) | C9—C8—C7 | 118.7 (2) |
C11—O4—H4 | 107 (3) | C9—C8—C13 | 114.0 (2) |
C12—O6—H6A | 111 (2) | C7—C8—C13 | 127.3 (2) |
C13—O7—H6A | 111 (2) | C4—C9—C8 | 122.6 (2) |
N2—C1—N1 | 107.2 (3) | C4—C9—H9 | 117.9 (17) |
N2—C1—H1 | 126 (2) | C8—C9—H9 | 119.3 (18) |
N1—C1—H1 | 127 (2) | O2—C10—O1 | 124.6 (2) |
C3—C2—N2 | 107.0 (3) | O2—C10—C4 | 122.7 (2) |
C3—C2—H2 | 131 (3) | O1—C10—C4 | 112.7 (2) |
N2—C2—H2 | 122 (3) | O3—C11—O4 | 123.0 (2) |
C2—C3—N1 | 106.2 (3) | O3—C11—C5 | 122.5 (2) |
C2—C3—H3 | 127 (2) | O4—C11—C5 | 114.4 (2) |
N1—C3—H3 | 126 (2) | O5—C12—O6 | 121.0 (2) |
C9—C4—C5 | 118.8 (2) | O5—C12—C7 | 118.7 (2) |
C9—C4—C10 | 118.3 (2) | O6—C12—C7 | 120.2 (2) |
C5—C4—C10 | 122.8 (2) | O8—C13—O7 | 121.2 (2) |
C6—C5—C4 | 119.4 (2) | O8—C13—C8 | 118.5 (2) |
C6—C5—C11 | 120.0 (2) | O7—C13—C8 | 120.3 (2) |
C4—C5—C11 | 120.5 (2) | C1—N1—C3 | 109.4 (3) |
C5—C6—C7 | 122.7 (2) | C1—N1—H1B | 123 (3) |
C5—C6—H6 | 119.7 (17) | C3—N1—H1B | 127 (3) |
C7—C6—H6 | 117.6 (17) | C1—N2—C2 | 110.1 (3) |
C6—C7—C8 | 117.6 (2) | C1—N2—H2B | 129 (2) |
C6—C7—C12 | 113.5 (2) | C2—N2—H2B | 120 (2) |
C8—C7—C12 | 128.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O5i | 0.93 (6) | 1.72 (6) | 2.648 (3) | 174 (6) |
O6—H6A···O7 | 1.11 (5) | 1.29 (5) | 2.392 (3) | 177 (4) |
N1—H1B···O8 | 0.90 (4) | 2.00 (4) | 2.878 (4) | 166 (4) |
N2—H2B···O3ii | 0.86 (4) | 2.00 (4) | 2.774 (3) | 149 (3) |
O4—H4···O8iii | 0.89 (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 formula | C3H5N2+·C10H5O8− |
Mr | 322.23 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 641.46 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.38 × 0.32 × 0.26 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.948, 0.964 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3343, 2238, 1790 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.156, 1.07 |
No. of reflections | 2238 |
No. of parameters | 249 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.32, −0.37 |
Computer programs: Bruker SMART, SMART (Bruker, 1999), SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.
O1—C10 | 1.304 (3) | O8—C13 | 1.241 (3) |
O2—C10 | 1.197 (3) | C1—N1 | 1.324 (5) |
O3—C11 | 1.197 (3) | C1—N2 | 1.296 (4) |
O4—C11 | 1.302 (3) | C2—N2 | 1.355 (5) |
O5—C12 | 1.216 (3) | C2—C3 | 1.333 (5) |
O6—C12 | 1.284 (3) | C3—N1 | 1.361 (5) |
O7—C13 | 1.254 (3) | ||
C9—C4—C10 | 118.3 (2) | O2—C10—O1 | 124.6 (2) |
C6—C5—C4 | 119.4 (2) | O3—C11—O4 | 123.0 (2) |
C6—C7—C8 | 117.6 (2) | O5—C12—O6 | 121.0 (2) |
C9—C8—C7 | 118.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O5i | 0.93 (6) | 1.72 (6) | 2.648 (3) | 174 (6) |
O6—H6A···O7 | 1.11 (5) | 1.29 (5) | 2.392 (3) | 177 (4) |
N1—H1B···O8 | 0.90 (4) | 2.00 (4) | 2.878 (4) | 166 (4) |
N2—H2B···O3ii | 0.86 (4) | 2.00 (4) | 2.774 (3) | 149 (3) |
O4—H4···O8iii | 0.89 (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. |
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).