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In the title compound, C7H7N2+·C7H3ClNO4, the cations and anions are connected by N—H...O hydrogen bonds to afford a 21 helical chain.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015970/ob6173sup1.cif
Contains datablocks General, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015970/ob6173Isup2.hkl
Contains datablock I

CCDC reference: 198951

Key indicators

  • Single-crystal X-ray study
  • T = 300 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.048
  • wR factor = 0.134
  • Data-to-parameter ratio = 15.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Amber Alert Alert Level B:
PLAT_353 Alert B Long N-H Bond (0.87A) N(2) - H(4) = 1.09 Ang.
Author response: The N...O distance, 2.610(3) \%A, in the N2---H4...O2 hydrogen bond is significantly shorter than the average N...O distance of 2.878(3) \%A in the N---H...O\\db C hydrogen bond (Taylor et al. 1984), which might elongate the N2---H4 bond length, 1.09(3) \%A.

0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
0 Alert Level C = Please check

Comment top

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···OC hydrogen bond (Taylor et al. 1984).

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. ORTEP-3 (Farrugia, 1997) drawing of (I), with the atom-labeling. Displacement ellipsoids of non-H atoms are drawn at the 50% probability level. The N—H···O hydrogen bond and a C—H···π interaction are indicated by a dashed and a dotted line, respectively.
[Figure 2] Fig. 2. Packing diagram showing two 21 helical chains running in antiparallel directions along the b axis. N—H···O and C—H···O hydrogen bonds indicated by dashed and dotted lines, respectively [symmetry codes are as in Table 2].
(I) top
Crystal data top
C7H7N2+·C7H3ClNO4F(000) = 1312.00
Mr = 319.70Dx = 1.493 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 11.120 (3) Åθ = 11.3–12.1°
b = 14.771 (3) ŵ = 0.29 mm1
c = 17.414 (3) ÅT = 300 K
β = 95.963 (18)°Prismatic, colorless
V = 2844.8 (11) Å30.50 × 0.35 × 0.25 mm
Z = 8
Data collection top
Rigaku AFC-5R
diffractometer
2040 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anodeRint = 0.025
Graphite monochromatorθmax = 29.0°, θmin = 2.3°
ω–2θ scansh = 414
Absorption correction: ψ scan
(North et al., 1968)
k = 419
Tmin = 0.876, Tmax = 0.930l = 2323
6914 measured reflections3 standard reflections every 97 reflections
3776 independent reflections intensity decay: 0.8%
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134All 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 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C7H7N2+·C7H3ClNO4V = 2844.8 (11) Å3
Mr = 319.70Z = 8
Monoclinic, C2/cMo Kα radiation
a = 11.120 (3) ŵ = 0.29 mm1
b = 14.771 (3) ÅT = 300 K
c = 17.414 (3) Å0.50 × 0.35 × 0.25 mm
β = 95.963 (18)°
Data collection top
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 = 0.9303 standard reflections every 97 reflections
6914 measured reflections intensity decay: 0.8%
3776 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.134All H-atom parameters refined
S = 1.00Δρmax = 0.20 e Å3
3776 reflectionsΔρmin = 0.26 e Å3
239 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.22471 (6)0.38111 (6)0.02829 (4)0.0743 (3)
O10.40299 (18)0.54458 (12)0.16961 (10)0.0661 (5)
O20.34524 (18)0.41031 (12)0.20601 (10)0.0628 (5)
O30.5502 (2)0.24958 (15)0.13214 (13)0.0930 (8)
O40.7252 (2)0.29672 (16)0.08305 (12)0.0811 (7)
N10.6154 (3)0.29207 (15)0.08401 (13)0.0623 (7)
N20.32933 (19)0.23423 (15)0.19719 (11)0.0520 (5)
N30.2397 (2)0.11223 (16)0.23159 (11)0.0535 (5)
C10.44979 (19)0.42016 (14)0.09460 (11)0.0373 (5)
C20.38095 (19)0.37919 (16)0.03353 (11)0.0409 (5)
C30.4341 (2)0.33816 (17)0.02619 (13)0.0476 (6)
C40.5580 (2)0.33930 (15)0.02285 (12)0.0457 (6)
C50.6293 (2)0.38125 (18)0.03511 (15)0.0524 (6)
C60.5740 (2)0.42203 (18)0.09386 (14)0.0496 (6)
C70.3937 (2)0.46209 (16)0.16219 (12)0.0431 (5)
C80.2405 (3)0.2011 (2)0.23332 (14)0.0575 (7)
C90.3355 (2)0.08343 (17)0.19191 (12)0.0471 (5)
C100.3768 (3)0.0011 (2)0.17478 (16)0.0599 (7)
C110.4763 (3)0.0050 (2)0.13398 (18)0.0651 (7)
C120.5339 (3)0.0736 (2)0.11234 (16)0.0611 (7)
C130.4936 (2)0.1581 (2)0.12967 (13)0.0502 (6)
C140.3922 (2)0.16180 (16)0.17001 (11)0.0436 (5)
H10.389 (2)0.3124 (18)0.0666 (15)0.059 (8)*
H20.708 (3)0.3816 (19)0.0367 (16)0.072 (9)*
H30.617 (2)0.4552 (19)0.1328 (16)0.073 (9)*
H40.342 (3)0.307 (2)0.1922 (17)0.090 (10)*
H50.181 (2)0.2374 (19)0.2574 (15)0.068 (8)*
H60.195 (3)0.079 (2)0.2570 (18)0.093 (11)*
H70.341 (3)0.051 (2)0.1926 (18)0.087 (10)*
H80.509 (3)0.061 (2)0.1229 (18)0.094 (11)*
H90.602 (2)0.0694 (19)0.0884 (14)0.062 (8)*
H100.532 (2)0.2084 (18)0.1189 (15)0.062 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0406 (3)0.1129 (6)0.0687 (4)0.0039 (4)0.0021 (3)0.0205 (4)
O10.1005 (16)0.0429 (10)0.0601 (10)0.0132 (10)0.0339 (10)0.0072 (8)
O20.0836 (13)0.0574 (11)0.0538 (10)0.0046 (10)0.0382 (9)0.0065 (9)
O30.138 (2)0.0678 (14)0.0840 (14)0.0236 (14)0.0631 (15)0.0348 (12)
O40.0816 (15)0.0965 (16)0.0730 (12)0.0377 (13)0.0455 (12)0.0173 (11)
N10.0933 (19)0.0436 (12)0.0573 (13)0.0109 (12)0.0429 (13)0.0062 (10)
N20.0627 (13)0.0546 (13)0.0413 (10)0.0025 (11)0.0178 (10)0.0020 (9)
N30.0518 (12)0.0664 (15)0.0442 (11)0.0084 (11)0.0149 (9)0.0132 (10)
C10.0425 (11)0.0351 (11)0.0360 (10)0.0061 (10)0.0120 (9)0.0007 (9)
C20.0399 (11)0.0461 (12)0.0375 (10)0.0022 (10)0.0083 (9)0.0003 (9)
C30.0583 (15)0.0497 (14)0.0359 (11)0.0017 (12)0.0098 (10)0.0039 (10)
C40.0621 (15)0.0368 (12)0.0427 (11)0.0078 (11)0.0261 (11)0.0031 (10)
C50.0426 (13)0.0530 (14)0.0649 (15)0.0035 (13)0.0218 (12)0.0020 (12)
C60.0444 (13)0.0522 (14)0.0530 (13)0.0011 (12)0.0087 (11)0.0090 (12)
C70.0456 (13)0.0456 (13)0.0393 (11)0.0094 (11)0.0101 (10)0.0058 (10)
C80.0676 (17)0.0662 (18)0.0421 (13)0.0020 (15)0.0210 (12)0.0060 (12)
C90.0461 (13)0.0559 (14)0.0390 (11)0.0090 (12)0.0033 (10)0.0075 (11)
C100.0572 (16)0.0534 (16)0.0678 (16)0.0081 (15)0.0000 (13)0.0086 (14)
C110.0613 (17)0.0577 (17)0.0756 (18)0.0088 (15)0.0037 (14)0.0032 (15)
C120.0467 (15)0.077 (2)0.0614 (16)0.0008 (15)0.0129 (13)0.0045 (14)
C130.0479 (13)0.0600 (16)0.0436 (12)0.0124 (13)0.0097 (10)0.0048 (12)
C140.0490 (13)0.0505 (14)0.0315 (10)0.0067 (11)0.0051 (9)0.0025 (10)
Geometric parameters (Å, º) top
Cl—C21.731 (2)C3—H10.91 (3)
O1—C71.228 (3)C4—C51.365 (4)
O2—C71.242 (3)C5—C61.385 (3)
O3—N11.223 (3)C5—H20.88 (3)
O4—N11.222 (3)C6—H30.93 (3)
N1—C41.473 (3)C8—H50.98 (3)
N2—C81.320 (3)C9—C101.374 (4)
N2—C141.388 (3)C9—C141.390 (3)
N2—H41.09 (3)C10—C111.377 (4)
N3—C81.313 (4)C10—H70.91 (3)
N3—C91.395 (3)C11—C121.397 (4)
N3—H60.86 (3)C11—H80.93 (3)
C1—C61.383 (3)C12—C131.370 (4)
C1—C21.383 (3)C12—H90.90 (3)
C1—C71.520 (3)C13—C141.390 (3)
C3—C41.373 (3)C13—H100.89 (3)
C2—C31.388 (3)
Cl···C13i3.522 (3)O3···C8iv3.395 (4)
O1···N1ii2.832 (3)O4···O4v3.201 (3)
O1···N3iii2.654 (3)O4···C5v3.154 (4)
O1···O3ii3.164 (3)O4···C8iv3.220 (3)
O1···O4ii3.057 (3)O4···C12v3.375 (4)
O1···C4ii3.145 (3)O4···C13v3.378 (3)
O1···C8iii3.363 (3)N3···C7vi3.333 (3)
O2···N22.610 (3)C14···C14vii3.482 (2)
O2···C83.354 (3)
O4—N1—O3124.0 (2)C5—C6—H3122.1 (17)
O4—N1—C4118.1 (3)O1—C7—O2125.7 (2)
O3—N1—C4117.9 (2)O1—C7—C1116.7 (2)
C8—N2—C14107.8 (2)O2—C7—C1117.6 (2)
C8—N2—H4120.9 (16)N3—C8—N2111.3 (3)
C14—N2—H4131.4 (16)N3—C8—H5123.6 (16)
C8—N3—C9108.2 (2)N2—C8—H5125.1 (16)
C8—N3—H6125 (2)C10—C9—C14121.7 (2)
C9—N3—H6126 (2)C10—C9—N3132.4 (2)
C6—C1—C2118.37 (19)C14—C9—N3105.9 (2)
C6—C1—C7119.3 (2)C9—C10—C11117.1 (3)
C2—C1—C7122.3 (2)C9—C10—H7120 (2)
C4—C3—C2117.8 (2)C11—C10—H7123 (2)
C4—C3—H1120.7 (16)C10—C11—C12121.3 (3)
C2—C3—H1121.5 (16)C10—C11—H8120 (2)
C1—C2—C3121.5 (2)C12—C11—H8119 (2)
C1—C2—Cl120.38 (16)C13—C12—C11121.9 (3)
C3—C2—Cl118.10 (18)C13—C12—H9118.3 (18)
C5—C4—C3122.6 (2)C11—C12—H9119.7 (18)
C5—C4—N1119.2 (2)C12—C13—C14116.6 (3)
C3—C4—N1118.1 (2)C12—C13—H10122.7 (17)
C4—C5—C6118.4 (2)C14—C13—H10120.5 (17)
C4—C5—H2121.9 (19)N2—C14—C13131.8 (2)
C6—C5—H2119.7 (19)N2—C14—C9106.8 (2)
C1—C6—C5121.2 (2)C13—C14—C9121.4 (2)
C1—C6—H3116.5 (17)
C6—C1—C2—C32.0 (3)C6—C1—C7—O2112.0 (3)
C7—C1—C2—C3177.4 (2)C2—C1—C7—O267.5 (3)
C6—C1—C2—Cl175.89 (18)C9—N3—C8—N20.5 (3)
C7—C1—C2—Cl4.6 (3)C14—N2—C8—N30.3 (3)
C4—C3—C2—C10.1 (3)C8—N3—C9—C10178.7 (3)
C4—C3—C2—Cl178.05 (18)C8—N3—C9—C140.4 (3)
C2—C3—C4—C52.1 (4)C14—C9—C10—C110.8 (4)
C2—C3—C4—N1177.1 (2)N3—C9—C10—C11179.7 (3)
O4—N1—C4—C54.2 (3)C9—C10—C11—C121.2 (4)
O3—N1—C4—C5174.9 (2)C10—C11—C12—C130.8 (4)
O4—N1—C4—C3176.6 (2)C11—C12—C13—C140.0 (4)
O3—N1—C4—C34.3 (3)C8—N2—C14—C13178.8 (2)
C3—C4—C5—C61.8 (4)C8—N2—C14—C90.1 (3)
N1—C4—C5—C6177.3 (2)C12—C13—C14—N2179.1 (2)
C2—C1—C6—C52.3 (4)C12—C13—C14—C90.4 (3)
C7—C1—C6—C5177.2 (2)C10—C9—C14—N2179.0 (2)
C4—C5—C6—C10.4 (4)N3—C9—C14—N20.2 (2)
C6—C1—C7—O166.4 (3)C10—C9—C14—C130.0 (4)
C2—C1—C7—O1114.1 (3)N3—C9—C14—C13179.2 (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, z1/2; (v) x+3/2, y+1/2, z; (vi) x+1/2, y1/2, z+1/2; (vii) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H4···O21.09 (3)1.54 (3)2.610 (3)165 (3)
N3—H6···O1vi0.85 (3)1.84 (3)2.654 (3)160 (3)
C8—H5···O3viii0.98 (3)2.54 (2)3.395 (4)146 (2)
Symmetry codes: (vi) x+1/2, y1/2, z+1/2; (viii) x1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC7H7N2+·C7H3ClNO4
Mr319.70
Crystal system, space groupMonoclinic, C2/c
Temperature (K)300
a, b, c (Å)11.120 (3), 14.771 (3), 17.414 (3)
β (°) 95.963 (18)
V3)2844.8 (11)
Z8
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.50 × 0.35 × 0.25
Data collection
DiffractometerRigaku AFC-5R
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.876, 0.930
No. of measured, independent and
observed [I > 2σ(I)] reflections
6914, 3776, 2040
Rint0.025
(sin θ/λ)max1)0.682
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.134, 1.00
No. of reflections3776
No. of parameters239
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)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.

Selected bond lengths (Å) top
Cl—C21.731 (2)N2—C81.320 (3)
O1—C71.228 (3)N2—C141.388 (3)
O2—C71.242 (3)N3—C81.313 (4)
O3—N11.223 (3)N3—C91.395 (3)
O4—N11.222 (3)C1—C71.520 (3)
N1—C41.473 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H4···O21.09 (3)1.54 (3)2.610 (3)165 (3)
N3—H6···O1i0.85 (3)1.84 (3)2.654 (3)160 (3)
C8—H5···O3ii0.98 (3)2.54 (2)3.395 (4)146 (2)
Symmetry codes: (i) x+1/2, y1/2, z+1/2; (ii) x1/2, y+1/2, z+1/2.
 

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