Bis[2-(2-hy­droxy­phen­yl)-1H-benzimidazol-3-ium] chloranilate

Ishida, H.

doi:10.1107/S2414314621011500

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 11| November 2021| x211150

https://doi.org/10.1107/S2414314621011500

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Bis[2-(2-hydroxyphenyl)-1H-benzimidazol-3-ium] chloranilate

Hiroyuki Ishida ^a ^*

^aDepartment of Chemistry, Faculty of Science, Okayama University, Okayama 700-8530, Japan
^*Correspondence e-mail: ishidah@cc.okayama-u.ac.jp

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 27 October 2021; accepted 31 October 2021; online 4 November 2021)

In the crystal of the title molecular salt {systematic name: bis[2-(2-hydroxyphenyl)-1H-benzimidazol-3-ium] 2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-diolate}, 2C₁₃H₁₁N₂O⁺·C₆Cl₂O₄²⁻, the chloranilate anion is located on an inversion centre, so that the asymmetric unit contains one cation and one half of the chloranilate anion. In the crystal, the cation and the anion are connected by a bifurcated N—H⋯(O,O) hydrogen bond, forming a 2:1 unit. The units are linked into a layer lying parallel to ( $[\overline{1}]$ 01) via O—H⋯O and N—H⋯Cl hydrogen bonds. Between the layers, a C—Cl⋯π interaction is observed.

Keywords: crystal structure; chloranilic acid; 2-(2-hydroxyphenyl)-1H-benzimidazole; hydrogen bond.

CCDC reference: 2119367

Structure description

We have prepared the title compound in order to continue our studies of D—H⋯A hydrogen bonding (D = N, O or C; A = N, O or Cl) in chloranilic acid–organic base systems (Gotoh & Ishida, 2017a ,b , 2018 , and references therein). In the cation, the C4–C9 benzene ring and the C10/N1/C11–C16/N2 benzimidazolium ring system are twisted to each other with a dihedral angle of 17.95 (7)°. An intramolecular N—H⋯O hydrogen bond (N2—H2⋯O3; Table 1) is observed. In the crystal, the chloranilate anion is located on an inversion centre, and the cation and the anion are connected by a bifurcated N—H⋯(O,O) hydrogen bond [N1—H1⋯(O1ⁱ,O2); symmetry code as given in Table 1], forming a cation–anion 2:1 unit (Fig. 1). The 2:1 units are further linked into a layer parallel to the ( $[\overline{1}]$ 01) plane via O—H⋯O and N—H⋯Cl hydrogen bonds (O3—H3⋯O1ⁱⁱⁱ and N2—H2⋯Cl1ⁱⁱ; Fig. 2, Table 1). A C—Cl⋯π interaction [C2—Cl1⋯Cg3^iv; Cl1⋯Cg3^iv = 3.6539 (10) Å and C2—Cl1⋯Cg3^iv = 139.21 (5)°; symmetry code: (iv) x, y, z − 1] is observed between the layers, where Cg3 is the centroid of the C11–C16 ring.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.91 (3)	2.01 (3)	2.7635 (18)	139 (3)
N1—H1⋯O1ⁱ	0.91 (3)	2.16 (3)	2.9336 (18)	142 (3)
N2—H2⋯O3	0.878 (18)	2.138 (19)	2.6704 (19)	118.4 (15)
N2—H2⋯Cl1ⁱⁱ	0.878 (18)	2.823 (18)	3.5907 (14)	146.9 (16)
O3—H3⋯O1ⁱⁱⁱ	0.94 (3)	1.73 (3)	2.6524 (18)	165 (3)
Symmetry codes: (i) ; (ii) ; (iii) x+1, y, z+1.

Figure 1
Molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate the bifurcated N—H⋯(O,O) hydrogen bonds.

Figure 2
A packing diagram of the title compound, showing the hydrogen-bonded layer structure formed via the N—H⋯O, O—H⋯O and N—H⋯Cl hydrogen bonds (magenta dotted lines). H atoms not involved in the hydrogen bonds are omitted for clarity. [Symmetry codes: (i) −x, −y, −z; (ii) −x + 1, −y + 1, −z + 1; (iii) x + 1, y, z + 1; (v) −x + 1, −y, −z + 1.]

Synthesis and crystallization

Single crystals of the title salt were obtained by slow evaporation from a methanol solution of chloranilic acid with 2-(2-hydroxyphenyl)-1H-benzimidazole in a ca 1:1 molar ratio at room temperature [150 ml methanol solution of chloranilic acid (0.45 g) and 2-(2-hydroxyphenyl)-1H-benzimidazole (0.45 g)].

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	2C₁₃H₁₁N₂O⁺·C₆Cl₂O₄²⁻
M_r	629.45
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	180
a, b, c (Å)	8.6694 (11), 9.1751 (13), 10.0313 (14)
α, β, γ (°)	113.654 (4), 95.963 (5), 105.579 (4)
V (Å³)	683.47 (17)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.29
Crystal size (mm)	0.23 × 0.17 × 0.06

Data collection
Diffractometer	Rigaku R-AXIS RAPIDII
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995 )
T_min, T_max	0.871, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	14095, 3980, 3105
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.101, 1.10
No. of reflections	3980
No. of parameters	211
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.26
Computer programs: PROCESS-AUTO (Rigaku, 2006 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2020 ), CrystalStructure (Rigaku, 2018 ) and PLATON (Spek, 2020 ).

Structural data

CCDC reference: 2119367

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314621011500/hb4396sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621011500/hb4396Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314621011500/hb4396Isup3.cml

checkCIF report

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: PROCESS-AUTO (Rigaku, 2006); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020); software used to prepare material for publication: CrystalStructure (Rigaku, 2018) and PLATON (Spek, 2020).

Bis[2-(2-hydroxyphenyl)-1H-benzimidazol-3-ium] 2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-diolate top

Crystal data top

2C₁₃H₁₁N₂O⁺·C₆Cl₂O₄²⁻	Z = 1
M_r = 629.45	F(000) = 324.00
Triclinic, P1	D_x = 1.529 Mg m⁻³
a = 8.6694 (11) Å	Mo Kα radiation, λ = 0.71075 Å
b = 9.1751 (13) Å	Cell parameters from 10316 reflections
c = 10.0313 (14) Å	θ = 3.4–30.1°
α = 113.654 (4)°	µ = 0.29 mm⁻¹
β = 95.963 (5)°	T = 180 K
γ = 105.579 (4)°	Block, brown
V = 683.47 (17) Å³	0.23 × 0.17 × 0.06 mm

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	3105 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.025
ω scans	θ_max = 30.0°, θ_min = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −12→11
T_min = 0.871, T_max = 0.983	k = −12→12
14095 measured reflections	l = −14→14
3980 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: mixed
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.046P)² + 0.2103P] where P = (F_o² + 2F_c²)/3
3980 reflections	(Δ/σ)_max < 0.001
211 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³
Primary atom site location: structure-invariant direct methods

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement. _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.09994 (4)	0.34752 (4)	−0.02027 (4)	0.02882 (10)
O1	−0.14183 (13)	0.01196 (13)	−0.24683 (11)	0.0289 (2)
O2	0.21238 (14)	0.27933 (13)	0.23324 (12)	0.0346 (3)
O3	0.75991 (14)	0.23427 (14)	0.69412 (12)	0.0329 (2)
N1	0.35863 (16)	0.30308 (17)	0.50287 (14)	0.0295 (3)
N2	0.55002 (15)	0.40290 (15)	0.70561 (13)	0.0254 (2)
C1	−0.07044 (16)	0.01567 (16)	−0.12934 (14)	0.0209 (3)
C2	0.04335 (16)	0.15741 (16)	−0.00910 (15)	0.0215 (3)
C3	0.11500 (16)	0.15402 (16)	0.12180 (15)	0.0220 (3)
C4	0.59135 (17)	0.19499 (17)	0.47216 (15)	0.0243 (3)
C5	0.71650 (18)	0.16090 (17)	0.54313 (16)	0.0257 (3)
C6	0.7897 (2)	0.0516 (2)	0.45539 (18)	0.0322 (3)
H6	0.873099	0.026322	0.502062	0.039*
C7	0.7424 (2)	−0.0201 (2)	0.30162 (19)	0.0358 (3)
H7	0.792239	−0.095973	0.242994	0.043*
C8	0.6224 (2)	0.0171 (2)	0.23097 (18)	0.0361 (3)
H8	0.592107	−0.031076	0.124678	0.043*
C9	0.54818 (19)	0.12356 (19)	0.31562 (17)	0.0305 (3)
H9	0.466344	0.149222	0.267406	0.037*
C10	0.50320 (17)	0.29865 (17)	0.55883 (15)	0.0240 (3)
C11	0.31061 (19)	0.41400 (18)	0.61747 (16)	0.0283 (3)
C12	0.1694 (2)	0.4589 (2)	0.6176 (2)	0.0384 (4)
H12	0.084527	0.412181	0.529115	0.046*
C13	0.1595 (2)	0.5750 (2)	0.7532 (2)	0.0386 (4)
H13	0.065121	0.609007	0.758876	0.046*
C14	0.2855 (2)	0.6435 (2)	0.88216 (19)	0.0362 (4)
H14	0.275017	0.724559	0.973058	0.043*
C15	0.4247 (2)	0.59789 (19)	0.88273 (18)	0.0330 (3)
H15	0.509383	0.644482	0.971298	0.040*
C16	0.43388 (18)	0.48016 (17)	0.74661 (16)	0.0264 (3)
H1	0.299 (3)	0.241 (3)	0.406 (3)	0.076 (8)*
H2	0.644 (2)	0.422 (2)	0.763 (2)	0.041 (5)*
H3	0.812 (3)	0.170 (3)	0.723 (3)	0.065 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0365 (2)	0.01955 (15)	0.03055 (19)	0.00738 (13)	0.00309 (14)	0.01391 (13)
O1	0.0337 (6)	0.0260 (5)	0.0248 (5)	0.0086 (4)	−0.0031 (4)	0.0128 (4)
O2	0.0404 (6)	0.0222 (5)	0.0279 (6)	0.0001 (4)	−0.0093 (4)	0.0094 (4)
O3	0.0398 (6)	0.0352 (6)	0.0259 (5)	0.0201 (5)	0.0016 (4)	0.0128 (5)
N1	0.0285 (6)	0.0326 (6)	0.0233 (6)	0.0135 (5)	−0.0001 (5)	0.0083 (5)
N2	0.0262 (6)	0.0227 (5)	0.0233 (6)	0.0085 (5)	0.0008 (5)	0.0078 (5)
C1	0.0220 (6)	0.0210 (6)	0.0222 (6)	0.0094 (5)	0.0053 (5)	0.0106 (5)
C2	0.0252 (6)	0.0166 (6)	0.0238 (6)	0.0073 (5)	0.0047 (5)	0.0103 (5)
C3	0.0225 (6)	0.0191 (6)	0.0228 (6)	0.0066 (5)	0.0034 (5)	0.0088 (5)
C4	0.0267 (7)	0.0201 (6)	0.0255 (7)	0.0072 (5)	0.0057 (5)	0.0101 (5)
C5	0.0278 (7)	0.0233 (6)	0.0261 (7)	0.0076 (5)	0.0050 (5)	0.0123 (5)
C6	0.0327 (8)	0.0328 (8)	0.0378 (8)	0.0170 (6)	0.0107 (6)	0.0179 (7)
C7	0.0404 (9)	0.0329 (8)	0.0387 (9)	0.0167 (7)	0.0202 (7)	0.0151 (7)
C8	0.0443 (9)	0.0342 (8)	0.0264 (8)	0.0119 (7)	0.0110 (7)	0.0106 (6)
C9	0.0322 (8)	0.0313 (7)	0.0273 (7)	0.0102 (6)	0.0039 (6)	0.0137 (6)
C10	0.0256 (7)	0.0215 (6)	0.0238 (7)	0.0063 (5)	0.0019 (5)	0.0112 (5)
C11	0.0321 (8)	0.0264 (7)	0.0286 (7)	0.0132 (6)	0.0073 (6)	0.0123 (6)
C12	0.0353 (8)	0.0438 (9)	0.0406 (9)	0.0198 (7)	0.0058 (7)	0.0199 (8)
C13	0.0389 (9)	0.0401 (9)	0.0498 (10)	0.0230 (7)	0.0190 (8)	0.0243 (8)
C14	0.0462 (9)	0.0297 (7)	0.0392 (9)	0.0176 (7)	0.0202 (7)	0.0163 (7)
C15	0.0407 (9)	0.0257 (7)	0.0302 (8)	0.0110 (6)	0.0090 (6)	0.0105 (6)
C16	0.0284 (7)	0.0225 (6)	0.0289 (7)	0.0085 (5)	0.0064 (5)	0.0122 (6)

Geometric parameters (Å, º) top

Cl1—C2	1.7333 (13)	C6—C7	1.375 (2)
O1—C1	1.2562 (15)	C6—H6	0.9500
O2—C3	1.2392 (16)	C7—C8	1.390 (2)
O3—C5	1.3477 (18)	C7—H7	0.9500
O3—H3	0.95 (2)	C8—C9	1.370 (2)
N1—C10	1.3368 (18)	C8—H8	0.9500
N1—C11	1.3851 (19)	C9—H9	0.9500
N1—H1	0.91 (3)	C11—C16	1.386 (2)
N2—C10	1.3359 (18)	C11—C12	1.393 (2)
N2—C16	1.3860 (19)	C12—C13	1.379 (2)
N2—H2	0.88 (2)	C12—H12	0.9500
C1—C2	1.3872 (18)	C13—C14	1.396 (3)
C1—C3ⁱ	1.5351 (18)	C13—H13	0.9500
C2—C3	1.4088 (18)	C14—C15	1.379 (2)
C4—C9	1.399 (2)	C14—H14	0.9500
C4—C5	1.4079 (19)	C15—C16	1.387 (2)
C4—C10	1.452 (2)	C15—H15	0.9500
C5—C6	1.390 (2)

C5—O3—H3	107.6 (14)	C9—C8—C7	119.56 (15)
C10—N1—C11	108.93 (12)	C9—C8—H8	120.2
C10—N1—H1	125.9 (17)	C7—C8—H8	120.2
C11—N1—H1	125.2 (17)	C8—C9—C4	120.82 (14)
C10—N2—C16	109.44 (12)	C8—C9—H9	119.6
C10—N2—H2	123.2 (13)	C4—C9—H9	119.6
C16—N2—H2	127.3 (13)	N2—C10—N1	108.68 (13)
O1—C1—C2	125.88 (12)	N2—C10—C4	126.61 (13)
O1—C1—C3ⁱ	115.72 (11)	N1—C10—C4	124.71 (13)
C2—C1—C3ⁱ	118.39 (11)	N1—C11—C16	106.88 (13)
C1—C2—C3	123.02 (11)	N1—C11—C12	131.05 (15)
C1—C2—Cl1	118.52 (10)	C16—C11—C12	122.06 (15)
C3—C2—Cl1	118.46 (10)	C13—C12—C11	116.36 (15)
O2—C3—C2	124.66 (12)	C13—C12—H12	121.8
O2—C3—C1ⁱ	116.80 (11)	C11—C12—H12	121.8
C2—C3—C1ⁱ	118.54 (11)	C12—C13—C14	121.24 (15)
C9—C4—C5	119.33 (13)	C12—C13—H13	119.4
C9—C4—C10	119.64 (13)	C14—C13—H13	119.4
C5—C4—C10	121.00 (13)	C15—C14—C13	122.52 (15)
O3—C5—C6	122.30 (13)	C15—C14—H14	118.7
O3—C5—C4	118.68 (13)	C13—C14—H14	118.7
C6—C5—C4	119.02 (13)	C14—C15—C16	116.18 (15)
C7—C6—C5	120.51 (14)	C14—C15—H15	121.9
C7—C6—H6	119.7	C16—C15—H15	121.9
C5—C6—H6	119.7	N2—C16—C11	106.04 (12)
C6—C7—C8	120.71 (15)	N2—C16—C15	132.34 (14)
C6—C7—H7	119.6	C11—C16—C15	121.61 (14)
C8—C7—H7	119.6

O1—C1—C2—C3	177.85 (13)	C11—N1—C10—N2	0.01 (17)
C3ⁱ—C1—C2—C3	−2.5 (2)	C11—N1—C10—C4	179.39 (13)
O1—C1—C2—Cl1	−2.1 (2)	C9—C4—C10—N2	−164.99 (14)
C3ⁱ—C1—C2—Cl1	177.54 (9)	C5—C4—C10—N2	17.0 (2)
C1—C2—C3—O2	−177.30 (14)	C9—C4—C10—N1	15.7 (2)
Cl1—C2—C3—O2	2.7 (2)	C5—C4—C10—N1	−162.30 (14)
C1—C2—C3—C1ⁱ	2.5 (2)	C10—N1—C11—C16	0.99 (17)
Cl1—C2—C3—C1ⁱ	−177.54 (9)	C10—N1—C11—C12	−178.19 (16)
C9—C4—C5—O3	178.22 (13)	N1—C11—C12—C13	179.91 (16)
C10—C4—C5—O3	−3.7 (2)	C16—C11—C12—C13	0.8 (2)
C9—C4—C5—C6	−2.4 (2)	C11—C12—C13—C14	0.4 (3)
C10—C4—C5—C6	175.59 (13)	C12—C13—C14—C15	−1.1 (3)
O3—C5—C6—C7	−179.73 (14)	C13—C14—C15—C16	0.5 (2)
C4—C5—C6—C7	1.0 (2)	C10—N2—C16—C11	1.60 (16)
C5—C6—C7—C8	1.0 (2)	C10—N2—C16—C15	−179.40 (15)
C6—C7—C8—C9	−1.4 (3)	N1—C11—C16—N2	−1.55 (16)
C7—C8—C9—C4	−0.1 (2)	C12—C11—C16—N2	177.72 (14)
C5—C4—C9—C8	2.1 (2)	N1—C11—C16—C15	179.32 (13)
C10—C4—C9—C8	−176.01 (14)	C12—C11—C16—C15	−1.4 (2)
C16—N2—C10—N1	−1.01 (16)	C14—C15—C16—N2	−178.19 (15)
C16—N2—C10—C4	179.62 (13)	C14—C15—C16—C11	0.7 (2)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.91 (3)	2.01 (3)	2.7635 (18)	139 (3)
N1—H1···O1ⁱ	0.91 (3)	2.16 (3)	2.9336 (18)	142 (3)
N2—H2···O3	0.878 (18)	2.138 (19)	2.6704 (19)	118.4 (15)
N2—H2···Cl1ⁱⁱ	0.878 (18)	2.823 (18)	3.5907 (14)	146.9 (16)
O3—H3···O1ⁱⁱⁱ	0.94 (3)	1.73 (3)	2.6524 (18)	165 (3)

Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z+1.

References

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