Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015970/ob6173sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015970/ob6173Isup2.hkl |
CCDC reference: 198951
Crystals of (I) were obtained by slow evaporation from an acetonitrile solution of benzimidazole with 2-chloro-4-nitrobenzoic acid with molar ratio of 1:1.
H atoms were found in difference Fourier maps and refined isotropically. Refined distances: C—H = 0.88 (3) − 0.98 (3) Å and N—H = 0.86 (3) − 1.09 (3) Å.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-1999); program(s) used to solve structure: SIR92 (Altomare, et al. 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN for Windows.
C7H7N2+·C7H3ClNO4− | F(000) = 1312.00 |
Mr = 319.70 | Dx = 1.493 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 11.120 (3) Å | θ = 11.3–12.1° |
b = 14.771 (3) Å | µ = 0.29 mm−1 |
c = 17.414 (3) Å | T = 300 K |
β = 95.963 (18)° | Prismatic, colorless |
V = 2844.8 (11) Å3 | 0.50 × 0.35 × 0.25 mm |
Z = 8 |
Rigaku AFC-5R diffractometer | 2040 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.025 |
Graphite monochromator | θmax = 29.0°, θmin = 2.3° |
ω–2θ scans | h = −4→14 |
Absorption correction: ψ scan (North et al., 1968) | k = −4→19 |
Tmin = 0.876, Tmax = 0.930 | l = −23→23 |
6914 measured reflections | 3 standard reflections every 97 reflections |
3776 independent reflections | intensity decay: 0.8% |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | All H-atom parameters refined |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0502P)2 + 1.4779P] where P = (Fo2 + 2Fc2)/3 |
3776 reflections | (Δ/σ)max = 0.01 |
239 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C7H7N2+·C7H3ClNO4− | V = 2844.8 (11) Å3 |
Mr = 319.70 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.120 (3) Å | µ = 0.29 mm−1 |
b = 14.771 (3) Å | T = 300 K |
c = 17.414 (3) Å | 0.50 × 0.35 × 0.25 mm |
β = 95.963 (18)° |
Rigaku AFC-5R diffractometer | 2040 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.025 |
Tmin = 0.876, Tmax = 0.930 | 3 standard reflections every 97 reflections |
6914 measured reflections | intensity decay: 0.8% |
3776 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.134 | All H-atom parameters refined |
S = 1.00 | Δρmax = 0.20 e Å−3 |
3776 reflections | Δρmin = −0.26 e Å−3 |
239 parameters |
Experimental. The scan width was (1.52 + 0.30tanθ)° with an ω scan speed of 6° per minute (up to 3 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1. |
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 | ||
Cl | 0.22471 (6) | 0.38111 (6) | 0.02829 (4) | 0.0743 (3) | |
O1 | 0.40299 (18) | 0.54458 (12) | 0.16961 (10) | 0.0661 (5) | |
O2 | 0.34524 (18) | 0.41031 (12) | 0.20601 (10) | 0.0628 (5) | |
O3 | 0.5502 (2) | 0.24958 (15) | −0.13214 (13) | 0.0930 (8) | |
O4 | 0.7252 (2) | 0.29672 (16) | −0.08305 (12) | 0.0811 (7) | |
N1 | 0.6154 (3) | 0.29207 (15) | −0.08401 (13) | 0.0623 (7) | |
N2 | 0.32933 (19) | 0.23423 (15) | 0.19719 (11) | 0.0520 (5) | |
N3 | 0.2397 (2) | 0.11223 (16) | 0.23159 (11) | 0.0535 (5) | |
C1 | 0.44979 (19) | 0.42016 (14) | 0.09460 (11) | 0.0373 (5) | |
C2 | 0.38095 (19) | 0.37919 (16) | 0.03353 (11) | 0.0409 (5) | |
C3 | 0.4341 (2) | 0.33816 (17) | −0.02619 (13) | 0.0476 (6) | |
C4 | 0.5580 (2) | 0.33930 (15) | −0.02285 (12) | 0.0457 (6) | |
C5 | 0.6293 (2) | 0.38125 (18) | 0.03511 (15) | 0.0524 (6) | |
C6 | 0.5740 (2) | 0.42203 (18) | 0.09386 (14) | 0.0496 (6) | |
C7 | 0.3937 (2) | 0.46209 (16) | 0.16219 (12) | 0.0431 (5) | |
C8 | 0.2405 (3) | 0.2011 (2) | 0.23332 (14) | 0.0575 (7) | |
C9 | 0.3355 (2) | 0.08343 (17) | 0.19191 (12) | 0.0471 (5) | |
C10 | 0.3768 (3) | −0.0011 (2) | 0.17478 (16) | 0.0599 (7) | |
C11 | 0.4763 (3) | −0.0050 (2) | 0.13398 (18) | 0.0651 (7) | |
C12 | 0.5339 (3) | 0.0736 (2) | 0.11234 (16) | 0.0611 (7) | |
C13 | 0.4936 (2) | 0.1581 (2) | 0.12967 (13) | 0.0502 (6) | |
C14 | 0.3922 (2) | 0.16180 (16) | 0.17001 (11) | 0.0436 (5) | |
H1 | 0.389 (2) | 0.3124 (18) | −0.0666 (15) | 0.059 (8)* | |
H2 | 0.708 (3) | 0.3816 (19) | 0.0367 (16) | 0.072 (9)* | |
H3 | 0.617 (2) | 0.4552 (19) | 0.1328 (16) | 0.073 (9)* | |
H4 | 0.342 (3) | 0.307 (2) | 0.1922 (17) | 0.090 (10)* | |
H5 | 0.181 (2) | 0.2374 (19) | 0.2574 (15) | 0.068 (8)* | |
H6 | 0.195 (3) | 0.079 (2) | 0.2570 (18) | 0.093 (11)* | |
H7 | 0.341 (3) | −0.051 (2) | 0.1926 (18) | 0.087 (10)* | |
H8 | 0.509 (3) | −0.061 (2) | 0.1229 (18) | 0.094 (11)* | |
H9 | 0.602 (2) | 0.0694 (19) | 0.0884 (14) | 0.062 (8)* | |
H10 | 0.532 (2) | 0.2084 (18) | 0.1189 (15) | 0.062 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.0406 (3) | 0.1129 (6) | 0.0687 (4) | 0.0039 (4) | 0.0021 (3) | −0.0205 (4) |
O1 | 0.1005 (16) | 0.0429 (10) | 0.0601 (10) | 0.0132 (10) | 0.0339 (10) | −0.0072 (8) |
O2 | 0.0836 (13) | 0.0574 (11) | 0.0538 (10) | −0.0046 (10) | 0.0382 (9) | −0.0065 (9) |
O3 | 0.138 (2) | 0.0678 (14) | 0.0840 (14) | −0.0236 (14) | 0.0631 (15) | −0.0348 (12) |
O4 | 0.0816 (15) | 0.0965 (16) | 0.0730 (12) | 0.0377 (13) | 0.0455 (12) | 0.0173 (11) |
N1 | 0.0933 (19) | 0.0436 (12) | 0.0573 (13) | 0.0109 (12) | 0.0429 (13) | 0.0062 (10) |
N2 | 0.0627 (13) | 0.0546 (13) | 0.0413 (10) | −0.0025 (11) | 0.0178 (10) | 0.0020 (9) |
N3 | 0.0518 (12) | 0.0664 (15) | 0.0442 (11) | −0.0084 (11) | 0.0149 (9) | 0.0132 (10) |
C1 | 0.0425 (11) | 0.0351 (11) | 0.0360 (10) | 0.0061 (10) | 0.0120 (9) | 0.0007 (9) |
C2 | 0.0399 (11) | 0.0461 (12) | 0.0375 (10) | 0.0022 (10) | 0.0083 (9) | −0.0003 (9) |
C3 | 0.0583 (15) | 0.0497 (14) | 0.0359 (11) | −0.0017 (12) | 0.0098 (10) | −0.0039 (10) |
C4 | 0.0621 (15) | 0.0368 (12) | 0.0427 (11) | 0.0078 (11) | 0.0261 (11) | 0.0031 (10) |
C5 | 0.0426 (13) | 0.0530 (14) | 0.0649 (15) | 0.0035 (13) | 0.0218 (12) | 0.0020 (12) |
C6 | 0.0444 (13) | 0.0522 (14) | 0.0530 (13) | −0.0011 (12) | 0.0087 (11) | −0.0090 (12) |
C7 | 0.0456 (13) | 0.0456 (13) | 0.0393 (11) | 0.0094 (11) | 0.0101 (10) | −0.0058 (10) |
C8 | 0.0676 (17) | 0.0662 (18) | 0.0421 (13) | 0.0020 (15) | 0.0210 (12) | 0.0060 (12) |
C9 | 0.0461 (13) | 0.0559 (14) | 0.0390 (11) | −0.0090 (12) | 0.0033 (10) | 0.0075 (11) |
C10 | 0.0572 (16) | 0.0534 (16) | 0.0678 (16) | −0.0081 (15) | 0.0000 (13) | 0.0086 (14) |
C11 | 0.0613 (17) | 0.0577 (17) | 0.0756 (18) | 0.0088 (15) | 0.0037 (14) | −0.0032 (15) |
C12 | 0.0467 (15) | 0.077 (2) | 0.0614 (16) | 0.0008 (15) | 0.0129 (13) | −0.0045 (14) |
C13 | 0.0479 (13) | 0.0600 (16) | 0.0436 (12) | −0.0124 (13) | 0.0097 (10) | 0.0048 (12) |
C14 | 0.0490 (13) | 0.0505 (14) | 0.0315 (10) | −0.0067 (11) | 0.0051 (9) | 0.0025 (10) |
Cl—C2 | 1.731 (2) | C3—H1 | 0.91 (3) |
O1—C7 | 1.228 (3) | C4—C5 | 1.365 (4) |
O2—C7 | 1.242 (3) | C5—C6 | 1.385 (3) |
O3—N1 | 1.223 (3) | C5—H2 | 0.88 (3) |
O4—N1 | 1.222 (3) | C6—H3 | 0.93 (3) |
N1—C4 | 1.473 (3) | C8—H5 | 0.98 (3) |
N2—C8 | 1.320 (3) | C9—C10 | 1.374 (4) |
N2—C14 | 1.388 (3) | C9—C14 | 1.390 (3) |
N2—H4 | 1.09 (3) | C10—C11 | 1.377 (4) |
N3—C8 | 1.313 (4) | C10—H7 | 0.91 (3) |
N3—C9 | 1.395 (3) | C11—C12 | 1.397 (4) |
N3—H6 | 0.86 (3) | C11—H8 | 0.93 (3) |
C1—C6 | 1.383 (3) | C12—C13 | 1.370 (4) |
C1—C2 | 1.383 (3) | C12—H9 | 0.90 (3) |
C1—C7 | 1.520 (3) | C13—C14 | 1.390 (3) |
C3—C4 | 1.373 (3) | C13—H10 | 0.89 (3) |
C2—C3 | 1.388 (3) | ||
Cl···C13i | 3.522 (3) | O3···C8iv | 3.395 (4) |
O1···N1ii | 2.832 (3) | O4···O4v | 3.201 (3) |
O1···N3iii | 2.654 (3) | O4···C5v | 3.154 (4) |
O1···O3ii | 3.164 (3) | O4···C8iv | 3.220 (3) |
O1···O4ii | 3.057 (3) | O4···C12v | 3.375 (4) |
O1···C4ii | 3.145 (3) | O4···C13v | 3.378 (3) |
O1···C8iii | 3.363 (3) | N3···C7vi | 3.333 (3) |
O2···N2 | 2.610 (3) | C14···C14vii | 3.482 (2) |
O2···C8 | 3.354 (3) | ||
O4—N1—O3 | 124.0 (2) | C5—C6—H3 | 122.1 (17) |
O4—N1—C4 | 118.1 (3) | O1—C7—O2 | 125.7 (2) |
O3—N1—C4 | 117.9 (2) | O1—C7—C1 | 116.7 (2) |
C8—N2—C14 | 107.8 (2) | O2—C7—C1 | 117.6 (2) |
C8—N2—H4 | 120.9 (16) | N3—C8—N2 | 111.3 (3) |
C14—N2—H4 | 131.4 (16) | N3—C8—H5 | 123.6 (16) |
C8—N3—C9 | 108.2 (2) | N2—C8—H5 | 125.1 (16) |
C8—N3—H6 | 125 (2) | C10—C9—C14 | 121.7 (2) |
C9—N3—H6 | 126 (2) | C10—C9—N3 | 132.4 (2) |
C6—C1—C2 | 118.37 (19) | C14—C9—N3 | 105.9 (2) |
C6—C1—C7 | 119.3 (2) | C9—C10—C11 | 117.1 (3) |
C2—C1—C7 | 122.3 (2) | C9—C10—H7 | 120 (2) |
C4—C3—C2 | 117.8 (2) | C11—C10—H7 | 123 (2) |
C4—C3—H1 | 120.7 (16) | C10—C11—C12 | 121.3 (3) |
C2—C3—H1 | 121.5 (16) | C10—C11—H8 | 120 (2) |
C1—C2—C3 | 121.5 (2) | C12—C11—H8 | 119 (2) |
C1—C2—Cl | 120.38 (16) | C13—C12—C11 | 121.9 (3) |
C3—C2—Cl | 118.10 (18) | C13—C12—H9 | 118.3 (18) |
C5—C4—C3 | 122.6 (2) | C11—C12—H9 | 119.7 (18) |
C5—C4—N1 | 119.2 (2) | C12—C13—C14 | 116.6 (3) |
C3—C4—N1 | 118.1 (2) | C12—C13—H10 | 122.7 (17) |
C4—C5—C6 | 118.4 (2) | C14—C13—H10 | 120.5 (17) |
C4—C5—H2 | 121.9 (19) | N2—C14—C13 | 131.8 (2) |
C6—C5—H2 | 119.7 (19) | N2—C14—C9 | 106.8 (2) |
C1—C6—C5 | 121.2 (2) | C13—C14—C9 | 121.4 (2) |
C1—C6—H3 | 116.5 (17) | ||
C6—C1—C2—C3 | 2.0 (3) | C6—C1—C7—O2 | −112.0 (3) |
C7—C1—C2—C3 | −177.4 (2) | C2—C1—C7—O2 | 67.5 (3) |
C6—C1—C2—Cl | −175.89 (18) | C9—N3—C8—N2 | 0.5 (3) |
C7—C1—C2—Cl | 4.6 (3) | C14—N2—C8—N3 | −0.3 (3) |
C4—C3—C2—C1 | 0.1 (3) | C8—N3—C9—C10 | 178.7 (3) |
C4—C3—C2—Cl | 178.05 (18) | C8—N3—C9—C14 | −0.4 (3) |
C2—C3—C4—C5 | −2.1 (4) | C14—C9—C10—C11 | −0.8 (4) |
C2—C3—C4—N1 | 177.1 (2) | N3—C9—C10—C11 | −179.7 (3) |
O4—N1—C4—C5 | −4.2 (3) | C9—C10—C11—C12 | 1.2 (4) |
O3—N1—C4—C5 | 174.9 (2) | C10—C11—C12—C13 | −0.8 (4) |
O4—N1—C4—C3 | 176.6 (2) | C11—C12—C13—C14 | 0.0 (4) |
O3—N1—C4—C3 | −4.3 (3) | C8—N2—C14—C13 | −178.8 (2) |
C3—C4—C5—C6 | 1.8 (4) | C8—N2—C14—C9 | 0.1 (3) |
N1—C4—C5—C6 | −177.3 (2) | C12—C13—C14—N2 | 179.1 (2) |
C2—C1—C6—C5 | −2.3 (4) | C12—C13—C14—C9 | 0.4 (3) |
C7—C1—C6—C5 | 177.2 (2) | C10—C9—C14—N2 | −179.0 (2) |
C4—C5—C6—C1 | 0.4 (4) | N3—C9—C14—N2 | 0.2 (2) |
C6—C1—C7—O1 | 66.4 (3) | C10—C9—C14—C13 | 0.0 (4) |
C2—C1—C7—O1 | −114.1 (3) | N3—C9—C14—C13 | 179.2 (2) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) −x+1, −y+1, −z; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x+1/2, −y+1/2, z−1/2; (v) −x+3/2, −y+1/2, −z; (vi) −x+1/2, y−1/2, −z+1/2; (vii) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H4···O2 | 1.09 (3) | 1.54 (3) | 2.610 (3) | 165 (3) |
N3—H6···O1vi | 0.85 (3) | 1.84 (3) | 2.654 (3) | 160 (3) |
C8—H5···O3viii | 0.98 (3) | 2.54 (2) | 3.395 (4) | 146 (2) |
Symmetry codes: (vi) −x+1/2, y−1/2, −z+1/2; (viii) x−1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C7H7N2+·C7H3ClNO4− |
Mr | 319.70 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 300 |
a, b, c (Å) | 11.120 (3), 14.771 (3), 17.414 (3) |
β (°) | 95.963 (18) |
V (Å3) | 2844.8 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.50 × 0.35 × 0.25 |
Data collection | |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.876, 0.930 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6914, 3776, 2040 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.134, 1.00 |
No. of reflections | 3776 |
No. of parameters | 239 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.20, −0.26 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990), MSC/AFC Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 1997-1999), SIR92 (Altomare, et al. 1993), SHELXL97 (Sheldrick, 1997), TEXSAN for Windows.
Cl—C2 | 1.731 (2) | N2—C8 | 1.320 (3) |
O1—C7 | 1.228 (3) | N2—C14 | 1.388 (3) |
O2—C7 | 1.242 (3) | N3—C8 | 1.313 (4) |
O3—N1 | 1.223 (3) | N3—C9 | 1.395 (3) |
O4—N1 | 1.222 (3) | C1—C7 | 1.520 (3) |
N1—C4 | 1.473 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H4···O2 | 1.09 (3) | 1.54 (3) | 2.610 (3) | 165 (3) |
N3—H6···O1i | 0.85 (3) | 1.84 (3) | 2.654 (3) | 160 (3) |
C8—H5···O3ii | 0.98 (3) | 2.54 (2) | 3.395 (4) | 146 (2) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x−1/2, −y+1/2, z+1/2. |
The title compound, (I), was investigated as part of a study on D—H···A hydrogen bonding (D = N, O or C; A = N, O or Cl) in chloro-and nitro-substituted benzoic acid-amine systems (Ishida et al., 2001a,b,c,d,e). In the crystal, the cations and anions are held together by N—H···O hydrogen bonds (Table 2) and a weak C—H···π interaction [H10···Cg 2.93 (3) Å, C13···Cg 3.679 (3) Å, C13—H10···Cg 143.5 (19)°, where Cg denotes the centroid of benzene ring C1—C6] (Fig. 1) to afford a 21 helical chain running along the b axis (Fig. 2). A similar helical chain is observed in imidazolium 2-chloro-4-nitrobenzoate, which gives a chiral crystal (Ishida et al., 2001 e). The present salt, however, crystallizes in the centrosymmetric space group C2/c. Neighboring helical chains related by an inversion center are connected through a C—H···O hydrogen bond (Fig. 2, Table 2), and those related by a twofold rotation axis are linked by a π···π stacking interaction between the aromatic rings C9—C14 of the benzimidazolium ion. The dihedral angle between the aromatic rings is 1.35 (11)°, and their interplanar separation and the centroid offset are 3.480 (2) and 0.769 (2) Å, respectively. The carboxyl group is twisted considerably out of the benzene ring, probably because of the strong N—H···O hydrogen bonds; the dihedral angle between them is 67.15 (13)°. This may cause a close contact of O1···N1iii, 2.832 (3) Å [symmetry code: (iii) 1 − x, 1 − y, −z] between two chains running in antiparallel directions. The N···O distance [2.610 (3) Å] in the N2—H4···O2 hydrogen bond is significantly shorter than the average N···O distance of 2.878 (3) Å for a N—H···O═C hydrogen bond (Taylor et al. 1984).