In the title compound, C
14H
10N
2O
2·2H
2O, the water molecules are involved in hydrogen bonds and interactions. Intermolecular and intramolecular O-H
O hydrogen bonds connect the complex into chains along the
a axis, whereas N-H
O intermolecular hydrogen bonds and C-H
O interactions interconnect these layers forming a three-dimensional network.
Supporting information
CCDC reference: 159991
The title compound is prepared from benzene-1,4-dicarboxylic acid and
1,2-diaminobenzene in 36% yield using a modified Phillips reaction (Addison &
Burke, 1981; Addison et al., 1983) and is recrystallized from water.
The single crystals suitable for X-ray analysis were obtained by slow
evaporation at room temperature from the EtOH/H2O solvent.
Friedel pairs were averaged in view of the inconclusive Flack parameter (Flack,
1983) value and s.u. After checking their presence in the difference map, all
H atoms were geometrically fixed and allowed to ride on their attached atoms
except the H atoms of N1, N2, O1W and O2W which were involved in hydrogen
bonding and were refined isotropically.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).
4-[1
H-Benzimidazolium]-Benzene Carbonic Acid dihydrate solvate
top
Crystal data top
C14H10N2O2·2H2O | F(000) = 576 |
Mr = 274.27 | Dx = 1.408 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 4.5541 (2) Å | Cell parameters from 2836 reflections |
b = 16.3140 (8) Å | θ = 2.3–29.4° |
c = 17.5245 (9) Å | µ = 0.11 mm−1 |
β = 96.234 (2)° | T = 293 K |
V = 1294.29 (11) Å3 | Rectangular slab, colourless |
Z = 4 | 0.48 × 0.30 × 0.08 mm |
Data collection top
Siemens SMART CCD area detector diffractometer | 1150 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.058 |
Graphite monochromator | θmax = 27.5°, θmin = 2.3° |
Detector resolution: 8.33 pixels mm-1 | h = −5→5 |
ω scans | k = −13→20 |
4352 measured reflections | l = −22→20 |
1474 independent reflections | |
Refinement top
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | See text |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0593P)2] where P = (Fo2 + 2Fc2)/3 |
1474 reflections | (Δ/σ)max < 0.001 |
205 parameters | Δρmax = 0.18 e Å−3 |
6 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C14H10N2O2·2H2O | V = 1294.29 (11) Å3 |
Mr = 274.27 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 4.5541 (2) Å | µ = 0.11 mm−1 |
b = 16.3140 (8) Å | T = 293 K |
c = 17.5245 (9) Å | 0.48 × 0.30 × 0.08 mm |
β = 96.234 (2)° | |
Data collection top
Siemens SMART CCD area detector diffractometer | 1150 reflections with I > 2σ(I) |
4352 measured reflections | Rint = 0.058 |
1474 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 6 restraints |
wR(F2) = 0.111 | See text |
S = 0.97 | Δρmax = 0.18 e Å−3 |
1474 reflections | Δρmin = −0.25 e Å−3 |
205 parameters | |
Special details top
Experimental. The data collection covered over a hemisphere of reciprocal space by a
combination of three sets of exposures; each set had a different ϕ angle (0,
88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω.
The crystal-to-detector distance was 4 cm and the detector swing angle was
-35°. Crystal decay was monitored by repeating fifty initial frames at the
end of data collection and analysing the duplicate reflections, and was found
to be negligible. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N2 | 0.5276 (5) | 0.26258 (17) | 0.14519 (15) | 0.0335 (6) | |
O1 | 1.4317 (6) | 0.49797 (19) | −0.07722 (16) | 0.0544 (7) | |
O2 | 1.4672 (6) | 0.59464 (18) | 0.01262 (17) | 0.0554 (7) | |
O1W | 0.9502 (6) | 0.69114 (18) | 0.00665 (16) | 0.0517 (7) | |
O2W | 1.8698 (7) | 0.5413 (2) | −0.15967 (16) | 0.0593 (8) | |
N1 | 0.6511 (5) | 0.34087 (18) | 0.24503 (15) | 0.0350 (6) | |
C1 | 0.3826 (6) | 0.2317 (2) | 0.20484 (18) | 0.0351 (7) | |
C2 | 0.1938 (8) | 0.1653 (2) | 0.2078 (2) | 0.0457 (8) | |
H2A | 0.1420 | 0.1320 | 0.1653 | 0.055* | |
C3 | 0.0862 (8) | 0.1516 (3) | 0.2783 (2) | 0.0525 (10) | |
H3A | −0.0405 | 0.1077 | 0.2833 | 0.063* | |
C4 | 0.1644 (8) | 0.2021 (3) | 0.3412 (2) | 0.0546 (10) | |
H4A | 0.0875 | 0.1906 | 0.3871 | 0.065* | |
C5 | 0.3507 (8) | 0.2683 (3) | 0.3385 (2) | 0.0475 (9) | |
H5A | 0.4005 | 0.3019 | 0.3808 | 0.057* | |
C6 | 0.4598 (7) | 0.2815 (2) | 0.26800 (18) | 0.0380 (8) | |
C7 | 0.6851 (6) | 0.3278 (2) | 0.17099 (18) | 0.0313 (7) | |
C8 | 0.8679 (6) | 0.3777 (2) | 0.12518 (16) | 0.0310 (6) | |
C9 | 0.9271 (8) | 0.3509 (2) | 0.05292 (19) | 0.0417 (8) | |
H9A | 0.8532 | 0.3009 | 0.0340 | 0.050* | |
C10 | 1.0959 (8) | 0.3988 (2) | 0.00925 (19) | 0.0412 (8) | |
H10A | 1.1345 | 0.3805 | −0.0389 | 0.049* | |
C11 | 1.2077 (6) | 0.4733 (2) | 0.03591 (19) | 0.0341 (7) | |
C12 | 1.1456 (8) | 0.4997 (2) | 0.10781 (19) | 0.0433 (8) | |
H12A | 1.2178 | 0.5501 | 0.1263 | 0.052* | |
C13 | 0.9798 (8) | 0.4529 (2) | 0.15210 (19) | 0.0426 (8) | |
H13A | 0.9420 | 0.4716 | 0.2002 | 0.051* | |
C14 | 1.3868 (7) | 0.5255 (2) | −0.0130 (2) | 0.0392 (8) | |
H1N2 | 0.503 (10) | 0.237 (3) | 0.093 (3) | 0.066 (13)* | |
H1N1 | 0.730 (12) | 0.386 (3) | 0.279 (3) | 0.086 (18)* | |
H1W1 | 1.105 (14) | 0.656 (4) | 0.005 (5) | 0.15 (3)* | |
H2W1 | 0.804 (8) | 0.656 (2) | 0.007 (2) | 0.052 (12)* | |
H1W2 | 2.032 (11) | 0.519 (4) | −0.145 (4) | 0.12 (3)* | |
H2W2 | 1.739 (10) | 0.527 (3) | −0.128 (3) | 0.078 (16)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N2 | 0.0338 (13) | 0.0357 (14) | 0.0317 (14) | −0.0038 (11) | 0.0076 (11) | 0.0013 (12) |
O1 | 0.0501 (16) | 0.0737 (19) | 0.0422 (13) | −0.0125 (13) | 0.0175 (11) | 0.0041 (13) |
O2 | 0.0510 (15) | 0.0530 (16) | 0.0648 (16) | −0.0167 (13) | 0.0182 (12) | 0.0037 (14) |
O1W | 0.0574 (17) | 0.0459 (15) | 0.0543 (16) | −0.0161 (14) | 0.0175 (13) | −0.0129 (13) |
O2W | 0.0465 (15) | 0.083 (2) | 0.0486 (15) | 0.0035 (15) | 0.0082 (12) | 0.0269 (15) |
N1 | 0.0333 (13) | 0.0449 (16) | 0.0269 (12) | −0.0057 (13) | 0.0040 (10) | 0.0021 (12) |
C1 | 0.0300 (14) | 0.0427 (18) | 0.0336 (16) | 0.0013 (13) | 0.0078 (12) | 0.0079 (14) |
C2 | 0.0441 (18) | 0.0426 (19) | 0.050 (2) | −0.0046 (16) | 0.0052 (15) | 0.0030 (17) |
C3 | 0.0433 (19) | 0.055 (2) | 0.061 (2) | −0.0054 (18) | 0.0122 (16) | 0.017 (2) |
C4 | 0.045 (2) | 0.078 (3) | 0.042 (2) | −0.001 (2) | 0.0117 (15) | 0.018 (2) |
C5 | 0.0458 (18) | 0.069 (3) | 0.0286 (17) | −0.0008 (18) | 0.0080 (13) | 0.0059 (17) |
C6 | 0.0287 (15) | 0.052 (2) | 0.0331 (16) | −0.0002 (15) | 0.0013 (12) | 0.0045 (14) |
C7 | 0.0260 (13) | 0.0342 (16) | 0.0333 (16) | −0.0007 (13) | 0.0014 (11) | 0.0017 (13) |
C8 | 0.0270 (14) | 0.0369 (17) | 0.0294 (15) | −0.0007 (13) | 0.0044 (11) | 0.0048 (13) |
C9 | 0.0452 (18) | 0.042 (2) | 0.0386 (19) | −0.0123 (16) | 0.0093 (14) | −0.0030 (16) |
C10 | 0.0436 (17) | 0.049 (2) | 0.0324 (17) | −0.0075 (17) | 0.0126 (13) | −0.0033 (16) |
C11 | 0.0238 (13) | 0.0407 (18) | 0.0378 (16) | −0.0013 (13) | 0.0027 (11) | 0.0042 (14) |
C12 | 0.049 (2) | 0.0437 (19) | 0.0378 (18) | −0.0157 (16) | 0.0071 (14) | −0.0036 (15) |
C13 | 0.0487 (19) | 0.047 (2) | 0.0333 (17) | −0.0142 (17) | 0.0106 (14) | −0.0063 (16) |
C14 | 0.0293 (16) | 0.047 (2) | 0.0414 (18) | −0.0056 (15) | 0.0044 (13) | 0.0088 (16) |
Geometric parameters (Å, º) top
N2—C7 | 1.334 (4) | C3—H3A | 0.9300 |
N2—C1 | 1.390 (4) | C4—C5 | 1.377 (6) |
N2—H1N2 | 0.99 (5) | C4—H4A | 0.9300 |
O1—C14 | 1.249 (4) | C5—C6 | 1.398 (4) |
O2—C14 | 1.254 (5) | C5—H5A | 0.9300 |
O1W—H1W1 | 0.91 (4) | C7—C8 | 1.465 (4) |
O1W—H2W1 | 0.88 (3) | C8—C13 | 1.392 (5) |
O2W—H1W2 | 0.84 (4) | C8—C9 | 1.393 (4) |
O2W—H2W2 | 0.89 (3) | C9—C10 | 1.384 (5) |
N1—C7 | 1.340 (4) | C9—H9A | 0.9300 |
N1—C6 | 1.391 (4) | C10—C11 | 1.379 (5) |
N1—H1N1 | 0.98 (6) | C10—H10A | 0.9300 |
C1—C2 | 1.387 (5) | C11—C12 | 1.390 (5) |
C1—C6 | 1.387 (5) | C11—C14 | 1.510 (4) |
C2—C3 | 1.396 (5) | C12—C13 | 1.372 (5) |
C2—H2A | 0.9300 | C12—H12A | 0.9300 |
C3—C4 | 1.391 (6) | C13—H13A | 0.9300 |
| | | |
C7—N2—C1 | 108.4 (3) | N1—C6—C5 | 131.1 (3) |
C7—N2—H1N2 | 130 (3) | N2—C7—N1 | 109.9 (3) |
C1—N2—H1N2 | 121 (3) | N2—C7—C8 | 125.0 (3) |
H1W1—O1W—H2W1 | 101 (6) | N1—C7—C8 | 125.0 (3) |
H1W2—O2W—H2W2 | 109 (6) | C13—C8—C9 | 119.0 (3) |
C7—N1—C6 | 108.1 (3) | C13—C8—C7 | 120.9 (3) |
C7—N1—H1N1 | 129 (3) | C9—C8—C7 | 120.1 (3) |
C6—N1—H1N1 | 123 (3) | C10—C9—C8 | 120.0 (3) |
C2—C1—C6 | 122.2 (3) | C10—C9—H9A | 120.0 |
C2—C1—N2 | 131.1 (3) | C8—C9—H9A | 120.0 |
C6—C1—N2 | 106.7 (3) | C11—C10—C9 | 121.1 (3) |
C1—C2—C3 | 115.9 (4) | C11—C10—H10A | 119.4 |
C1—C2—H2A | 122.1 | C9—C10—H10A | 119.4 |
C3—C2—H2A | 122.1 | C10—C11—C12 | 118.4 (3) |
C4—C3—C2 | 121.5 (4) | C10—C11—C14 | 120.5 (3) |
C4—C3—H3A | 119.3 | C12—C11—C14 | 121.0 (3) |
C2—C3—H3A | 119.3 | C13—C12—C11 | 121.3 (3) |
C5—C4—C3 | 122.9 (3) | C13—C12—H12A | 119.4 |
C5—C4—H4A | 118.5 | C11—C12—H12A | 119.4 |
C3—C4—H4A | 118.5 | C12—C13—C8 | 120.2 (3) |
C4—C5—C6 | 115.5 (4) | C12—C13—H13A | 119.9 |
C4—C5—H5A | 122.2 | C8—C13—H13A | 119.9 |
C6—C5—H5A | 122.2 | O1—C14—O2 | 125.2 (3) |
C1—C6—N1 | 106.8 (3) | O1—C14—C11 | 117.4 (3) |
C1—C6—C5 | 122.1 (3) | O2—C14—C11 | 117.3 (3) |
| | | |
C7—N2—C1—C2 | −180.0 (4) | N2—C7—C8—C13 | 167.9 (3) |
C7—N2—C1—C6 | 0.1 (3) | N1—C7—C8—C13 | −12.1 (5) |
C6—C1—C2—C3 | −0.1 (5) | N2—C7—C8—C9 | −10.8 (5) |
N2—C1—C2—C3 | 180.0 (3) | N1—C7—C8—C9 | 169.2 (3) |
C1—C2—C3—C4 | 0.3 (6) | C13—C8—C9—C10 | 0.3 (5) |
C2—C3—C4—C5 | 0.0 (6) | C7—C8—C9—C10 | 178.9 (3) |
C3—C4—C5—C6 | −0.5 (6) | C8—C9—C10—C11 | 0.0 (5) |
C2—C1—C6—N1 | 179.6 (3) | C9—C10—C11—C12 | −0.4 (5) |
N2—C1—C6—N1 | −0.4 (3) | C9—C10—C11—C14 | −178.9 (3) |
C2—C1—C6—C5 | −0.4 (5) | C10—C11—C12—C13 | 0.7 (5) |
N2—C1—C6—C5 | 179.6 (3) | C14—C11—C12—C13 | 179.1 (3) |
C7—N1—C6—C1 | 0.6 (4) | C11—C12—C13—C8 | −0.5 (6) |
C7—N1—C6—C5 | −179.4 (3) | C9—C8—C13—C12 | 0.0 (5) |
C4—C5—C6—C1 | 0.7 (5) | C7—C8—C13—C12 | −178.6 (3) |
C4—C5—C6—N1 | −179.4 (4) | C10—C11—C14—O1 | −1.1 (4) |
C1—N2—C7—N1 | 0.3 (3) | C12—C11—C14—O1 | −179.5 (3) |
C1—N2—C7—C8 | −179.7 (3) | C10—C11—C14—O2 | 175.9 (3) |
C6—N1—C7—N2 | −0.6 (3) | C12—C11—C14—O2 | −2.5 (5) |
C6—N1—C7—C8 | 179.4 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O2 | 0.91 (6) | 1.92 (6) | 2.825 (4) | 171 (7) |
O1W—H2W1···O2i | 0.88 (4) | 1.84 (4) | 2.716 (4) | 172 (3) |
O2W—H2W2···O1 | 0.89 (5) | 1.80 (5) | 2.682 (4) | 171 (5) |
O2W—H1W2···O1ii | 0.84 (6) | 2.09 (6) | 2.887 (4) | 158 (6) |
N1—H1N1···O2Wiii | 0.99 (5) | 1.68 (5) | 2.667 (4) | 177 (5) |
N2—H1N2···O1Wiv | 1.00 (5) | 1.68 (5) | 2.682 (4) | 177 (4) |
C9—H9A···O1Wiv | 0.93 | 2.57 | 3.433 (4) | 154 |
C13—H13A···O2Wiii | 0.93 | 2.52 | 3.391 (4) | 156 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) x−1, −y+1, z+1/2; (iv) x−1/2, y−1/2, z. |
Experimental details
Crystal data |
Chemical formula | C14H10N2O2·2H2O |
Mr | 274.27 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 293 |
a, b, c (Å) | 4.5541 (2), 16.3140 (8), 17.5245 (9) |
β (°) | 96.234 (2) |
V (Å3) | 1294.29 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.48 × 0.30 × 0.08 |
|
Data collection |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4352, 1474, 1150 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.111, 0.97 |
No. of reflections | 1474 |
No. of parameters | 205 |
No. of restraints | 6 |
H-atom treatment | See text |
Δρmax, Δρmin (e Å−3) | 0.18, −0.25 |
Selected bond lengths (Å) topN2—C7 | 1.334 (4) | O2—C14 | 1.254 (5) |
N2—C1 | 1.390 (4) | N1—C7 | 1.340 (4) |
O1—C14 | 1.249 (4) | N1—C6 | 1.391 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O2 | 0.91 (6) | 1.92 (6) | 2.825 (4) | 171 (7) |
O1W—H2W1···O2i | 0.88 (4) | 1.84 (4) | 2.716 (4) | 172 (3) |
O2W—H2W2···O1 | 0.89 (5) | 1.80 (5) | 2.682 (4) | 171 (5) |
O2W—H1W2···O1ii | 0.84 (6) | 2.09 (6) | 2.887 (4) | 158 (6) |
N1—H1N1···O2Wiii | 0.99 (5) | 1.68 (5) | 2.667 (4) | 177 (5) |
N2—H1N2···O1Wiv | 1.00 (5) | 1.68 (5) | 2.682 (4) | 177 (4) |
C9—H9A···O1Wiv | 0.9297 | 2.5716 | 3.433 (4) | 154 |
C13—H13A···O2Wiii | 0.9299 | 2.5216 | 3.391 (4) | 156 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) x−1, −y+1, z+1/2; (iv) x−1/2, y−1/2, z. |
Benzimidazole is an interesting heterocyclic ring because it is present in various naturally occurring drugs such as omeprazole, astemizole and emedastine difumarate (Sakai et al., 1989). The efficacy of substituted benzimidazoles in the treatment of parasitic infections is well known (Brown et al., 1961; Preston, 1974; Sarkar et al., 1984). Substituted benzimidazole moieties are established pharmacophores in parasitic chemotherapy. Furthermore, proton tranfer, accompanied by a configurational change of the pi-electron structure, is one of the key reactions in many proposals for molecular-electronic devices (Xu et al., 1994). The electrical properties depend heavily on the intermolecular interactions. Thus, the title compound, (I), may be a candidate for construction of a novel type of conductive organic material in which the proton motion is essentially correlated to the electron conduction (Inabe, 1991). \sch
The benzimidazole moiety is planar, with the maximum deviation of 0.008 (2)° for the N1 atom with protonation occurring at the other imidazole N atom. The dihedral angle between this benzimidazole moiety and the phenyl ring is 11.33 (12)°. The C—O bond lengths are comparable to those of a –COO- group (Leban & Rupnik, 1992; Aakeroy & Hitchcock, 1994). The carboxyl group makes a dihedral angle of 4.4 (2) Å with the mean plane of the phenyl ring. In the asymmetric unit, both water molecules are linked to the carboxyl group through O—H···O hydrogen bonds.
In the crystal, all the hydrogen bondings and interactions (Table 2) involved the water molecules. The water molecules are involved in O—H···O intramolecular and intermolecular hydrogen bonds with the O atoms in the COO- group. These hydrogen bonds connect those water molecules into infinite chains in the [100] direction in which the O atoms of the COO- group act as a bridge. This results in the molecules of the title compound being stacked along the same axis to form layers. The water molecules are also involved in N—H···O intermolecular hydrogen bonds and C—H···O interactions. These hydrogen bonds and interactions interconnect these layers. The O—H···O, N—H···O hydrogen bonds and the C—H···O interactions in which all are involving the water molecules form a three-dimensional network of the title compound throughout the structure.