2-Methyl-1H-benzimidazol-3-ium hydrogen phthalate

Lin, F.; Jin, S.; Tong, K.; He, H.; Yu, Y.Q.

doi:10.1107/S1600536811036178

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2592

https://doi.org/10.1107/S1600536811036178

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2-Methyl-1H-benzimidazol-3-ium hydrogen phthalate

Feng Lin,^a Shouwen Jin,^b ^* Kai Tong,^a Haidong He ^a and YuanQi Yu ^a

^aFaculty of Science ZheJiang A & F University, Lin'An 311300, People's Republic of China, and ^bTianmu college of ZheJiang A & F University, Lin'An 311300, People's Republic of China
^*Correspondence e-mail: JINSW@yahoo.cn

(Received 25 August 2011; accepted 5 September 2011; online 14 September 2011)

The asymmetric unit of the title compound, C₈H₉N₂⁺·C₈H₅O₄⁻, contains two independent ion pairs. In each 2-methyl-1H-benzimidazolium ion, an intramolecular O—H⋯O bond forms an S(7) graph-set motif. In the crystal, the components are linked by N—H⋯O hydrogen bonds, forming chains along [210]. Further stabilization is provided by weak C—H⋯O hydrogen bonds.

Related literature

For general background to hydrogen-bonding interactions, see: Lam & Mak (2000 ); Desiraju (2002 ); Liu et al. (2008 ); Biswas et al. (2009 ); Jin & Wang (2010 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₉N₂⁺·C₈H₅O₄⁻
M_r = 298.29
Triclinic, $[P \overline 1]$
a = 3.8545 (16) Å
b = 17.689 (7) Å
c = 20.752 (9) Å
α = 86.754 (8)°
β = 86.585 (7)°
γ = 84.169 (7)°
V = 1403.3 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.45 × 0.39 × 0.30 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.955, T_max = 0.970
7520 measured reflections
4923 independent reflections
1846 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.082
wR(F²) = 0.232
S = 0.89
4923 reflections
397 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4ⁱ	0.86	1.81	2.649 (6)	166
N2—H2⋯O5ⁱⁱ	0.86	1.91	2.750 (6)	165
N2—H2⋯O6ⁱⁱ	0.86	2.58	3.226 (6)	133
N3—H3⋯O8ⁱⁱⁱ	0.86	1.79	2.631 (6)	166
N4—H4⋯O1^iv	0.86	1.83	2.680 (6)	168
N4—H4⋯O2^iv	0.86	2.58	3.232 (6)	133
O3—H3A⋯O2	0.82	1.55	2.372 (5)	175
O7—H7⋯O6	0.82	1.56	2.379 (5)	179
C7—H7A⋯O6ⁱⁱ	0.93	2.53	3.244 (7)	134
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z; (iii) -x+1, -y, -z+1; (iv) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811036178/lh5327sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811036178/lh5327Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811036178/lh5327Isup3.cml

checkCIF report

Comment top

Intermolecular interactions are responsible for crystal packing and gaining an understanding of these interactions allows the comprehension of the collective properties and permits the design of new crystals with specific physical and chemical properties (Lam & Mak, 2000). Hydrogen bonding is one of the most important noncovalent interactions that determines and controls the assembly of molecules and ions (Desiraju, 2002, Liu et al., 2008, Biswas et al., 2009). As an extension of our study concentrating on hydrogen bonded assembly of organic acids and organic bases (Jin et al., 2010), herein we report the crystal structure of the 1:1 salt of 2-methyl-1H-benzimidazolium hydrogen phthalate.

The asymmetric unit of the compound consists of two independent 2-methyl-1H-benzimidazolium and two independent hydrogen phthalate ions (Fig. 1). Intramolecular hydrogen bonds between the carbonyl groups and the hydroxy groups form S(7) graph motifs (Bernstein et al., 1995). The cations and the anions are connected via the N—H···O hydrogen bonds to form one-dimensional chains along [210] (Fig. 2). Further stabilization of the chain is provided by weak intrachain C—H···O hydrogen bonds.

Related literature top

For general background to hydrogen-bonding interactions, see: Lam & Mak (2000); Desiraju (2002); Liu et al. (2008); Biswas et al. (2009); Jin & Wang (2010). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A solution of 2-methyl-1H-benzimidazole (13.2 mg, 0.1 mmol) in 3 ml of MeOH was added to a MeOH solution (3 ml) containing phthalic acid acid (16.6 mg, 0.1 mmol) under continuous stirring. The solution was stirred for about 1 h at room temperature, then the solution was filtered into a test tube. The solution was left standing at room temperature for several days, colorless block-shaped crystals were isolated after slow evaporation of the solution in air at ambient temperature.

Structure description top

For general background to hydrogen-bonding interactions, see: Lam & Mak (2000); Desiraju (2002); Liu et al. (2008); Biswas et al. (2009); Jin & Wang (2010). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. One dimensional chain running along [210] with hydrogen bonds shown as dashed lines.

2-Methyl-1H-benzimidazol-3-ium 2-carboxybenzoate top

Crystal data top

C₈H₉N₂⁺·C₈H₅O₄⁻	Z = 4
M_r = 298.29	F(000) = 624
Triclinic, P1	D_x = 1.412 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8545 (16) Å	Cell parameters from 700 reflections
b = 17.689 (7) Å	θ = 2.2–19.6°
c = 20.752 (9) Å	µ = 0.10 mm⁻¹
α = 86.754 (8)°	T = 298 K
β = 86.585 (7)°	Block, colorless
γ = 84.169 (7)°	0.45 × 0.39 × 0.30 mm
V = 1403.3 (10) Å³

Data collection top

Bruker SMART CCD diffractometer	4923 independent reflections
Radiation source: fine-focus sealed tube	1846 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
φ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −4→4
T_min = 0.955, T_max = 0.970	k = −20→19
7520 measured reflections	l = −21→24

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)] = 0.082	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.232	H-atom parameters constrained
S = 0.89	w = 1/[σ²(F_o²) + (0.0958P)²] where P = (F_o² + 2F_c²)/3
4923 reflections	(Δ/σ)_max < 0.001
397 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₈H₉N₂⁺·C₈H₅O₄⁻	γ = 84.169 (7)°
M_r = 298.29	V = 1403.3 (10) Å³
Triclinic, P1	Z = 4
a = 3.8545 (16) Å	Mo Kα radiation
b = 17.689 (7) Å	µ = 0.10 mm⁻¹
c = 20.752 (9) Å	T = 298 K
α = 86.754 (8)°	0.45 × 0.39 × 0.30 mm
β = 86.585 (7)°

Data collection top

Bruker SMART CCD diffractometer	4923 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1846 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.970	R_int = 0.058
7520 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.082	0 restraints
wR(F²) = 0.232	H-atom parameters constrained
S = 0.89	Δρ_max = 0.26 e Å⁻³
4923 reflections	Δρ_min = −0.31 e Å⁻³
397 parameters

Special details top

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	U_iso*/U_eq
N1	0.6243 (11)	0.5633 (2)	0.1657 (2)	0.0614 (13)
H1	0.7074	0.6025	0.1465	0.074*
N2	0.3976 (11)	0.4903 (2)	0.2389 (2)	0.0572 (12)
H2	0.3100	0.4741	0.2756	0.069*
N3	0.4721 (12)	−0.0649 (2)	0.6631 (2)	0.0661 (14)
H3	0.4929	−0.1059	0.6423	0.079*
N4	0.4893 (12)	0.0117 (3)	0.7390 (2)	0.0615 (13)
H4	0.5221	0.0285	0.7760	0.074*
O1	0.3597 (12)	0.9545 (2)	0.14225 (18)	0.0842 (14)
O2	0.2701 (12)	0.8461 (2)	0.18961 (19)	0.0886 (14)
O3	0.0573 (12)	0.7292 (2)	0.16867 (19)	0.0829 (13)
H3A	0.1415	0.7687	0.1753	0.124*
O4	−0.1224 (12)	0.6721 (2)	0.0893 (2)	0.0863 (14)
O5	1.0493 (11)	0.4630 (2)	0.35612 (17)	0.0766 (13)
O6	0.9446 (12)	0.3625 (2)	0.30921 (19)	0.0867 (14)
O7	0.7319 (12)	0.2419 (2)	0.33335 (19)	0.0838 (13)
H7	0.8077	0.2833	0.3253	0.126*
O8	0.5216 (13)	0.1768 (2)	0.4153 (2)	0.0917 (15)
C1	0.5080 (14)	0.5583 (3)	0.2263 (3)	0.0572 (15)
C2	0.4456 (15)	0.4496 (3)	0.1839 (3)	0.0561 (14)
C3	0.5921 (14)	0.4953 (3)	0.1373 (3)	0.0529 (14)
C4	0.6727 (14)	0.4745 (3)	0.0752 (3)	0.0643 (16)
H4A	0.7639	0.5075	0.0436	0.077*
C5	0.6105 (17)	0.4017 (4)	0.0624 (3)	0.0785 (19)
H5	0.6664	0.3839	0.0214	0.094*
C6	0.4652 (16)	0.3546 (3)	0.1102 (3)	0.0701 (17)
H6	0.4202	0.3063	0.0997	0.084*
C7	0.3858 (14)	0.3762 (3)	0.1717 (3)	0.0623 (16)
H7A	0.2963	0.3434	0.2036	0.075*
C8	0.5046 (17)	0.6182 (3)	0.2734 (3)	0.0760 (18)
H8A	0.2687	0.6396	0.2823	0.114*
H8B	0.6421	0.6575	0.2556	0.114*
H8C	0.6008	0.5966	0.3127	0.114*
C9	0.5569 (14)	−0.0599 (3)	0.7229 (3)	0.0559 (14)
C10	0.3580 (15)	0.0550 (3)	0.6869 (3)	0.0590 (15)
C11	0.3466 (14)	0.0050 (3)	0.6392 (3)	0.0575 (15)
C12	0.2216 (16)	0.0290 (4)	0.5784 (3)	0.0707 (17)
H12	0.2144	−0.0043	0.5455	0.085*
C13	0.1106 (17)	0.1053 (4)	0.5709 (3)	0.087 (2)
H13	0.0230	0.1243	0.5318	0.104*
C14	0.1258 (16)	0.1536 (4)	0.6194 (4)	0.0769 (19)
H14	0.0493	0.2048	0.6120	0.092*
C15	0.2482 (17)	0.1302 (3)	0.6784 (3)	0.0769 (19)
H15	0.2562	0.1639	0.7110	0.092*
C16	0.6985 (15)	−0.1238 (3)	0.7661 (3)	0.0714 (17)
H16A	0.5251	−0.1588	0.7753	0.107*
H16B	0.7597	−0.1045	0.8058	0.107*
H16C	0.9025	−0.1496	0.7453	0.107*
C17	0.2781 (16)	0.8892 (4)	0.1390 (3)	0.0648 (16)
C18	−0.0014 (16)	0.7282 (3)	0.1088 (3)	0.0624 (16)
C19	0.1934 (14)	0.8627 (3)	0.0755 (3)	0.0533 (14)
C20	0.0778 (14)	0.7921 (3)	0.0617 (3)	0.0546 (14)
C21	0.0164 (15)	0.7799 (3)	−0.0009 (3)	0.0617 (16)
H21	−0.0674	0.7343	−0.0097	0.074*
C22	0.0716 (16)	0.8313 (3)	−0.0510 (3)	0.0660 (16)
H22	0.0319	0.8201	−0.0931	0.079*
C23	0.1877 (16)	0.9002 (3)	−0.0384 (3)	0.0663 (16)
H23	0.2251	0.9365	−0.0717	0.080*
C24	0.2460 (15)	0.9138 (3)	0.0239 (3)	0.0607 (15)
H24	0.3256	0.9601	0.0321	0.073*
C25	0.9394 (15)	0.4004 (3)	0.3595 (3)	0.0584 (15)
C26	0.6405 (16)	0.2354 (3)	0.3930 (3)	0.0621 (16)
C27	0.7972 (13)	0.3692 (3)	0.4231 (2)	0.0479 (13)
C28	0.6743 (13)	0.2974 (3)	0.4380 (2)	0.0476 (13)
C29	0.5680 (13)	0.2802 (3)	0.5007 (3)	0.0493 (13)
H29	0.4900	0.2327	0.5110	0.059*
C30	0.5710 (15)	0.3294 (3)	0.5490 (3)	0.0633 (16)
H30	0.4947	0.3153	0.5909	0.076*
C31	0.6872 (15)	0.4000 (3)	0.5354 (3)	0.0612 (16)
H31	0.6900	0.4347	0.5673	0.073*
C32	0.7995 (14)	0.4170 (3)	0.4723 (3)	0.0562 (15)
H32	0.8820	0.4642	0.4627	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.065 (3)	0.060 (3)	0.059 (3)	−0.019 (2)	0.006 (3)	0.008 (3)
N2	0.070 (3)	0.051 (3)	0.052 (3)	−0.015 (2)	−0.005 (2)	0.005 (2)
N3	0.093 (4)	0.053 (3)	0.058 (3)	−0.028 (3)	−0.011 (3)	−0.007 (3)
N4	0.078 (4)	0.063 (3)	0.048 (3)	−0.020 (3)	−0.010 (3)	−0.008 (3)
O1	0.120 (4)	0.070 (3)	0.070 (3)	−0.035 (3)	−0.013 (3)	−0.017 (2)
O2	0.137 (4)	0.085 (3)	0.049 (3)	−0.033 (3)	−0.016 (3)	0.003 (2)
O3	0.117 (4)	0.077 (3)	0.058 (3)	−0.031 (3)	−0.006 (3)	0.014 (2)
O4	0.121 (4)	0.066 (3)	0.079 (3)	−0.045 (3)	−0.003 (3)	0.005 (2)
O5	0.106 (3)	0.069 (3)	0.060 (3)	−0.043 (3)	0.003 (2)	0.003 (2)
O6	0.130 (4)	0.078 (3)	0.054 (3)	−0.028 (3)	0.015 (3)	−0.004 (2)
O7	0.127 (4)	0.068 (3)	0.062 (3)	−0.034 (3)	0.004 (3)	−0.012 (2)
O8	0.143 (4)	0.061 (3)	0.078 (3)	−0.048 (3)	0.014 (3)	−0.015 (2)
C1	0.054 (4)	0.060 (4)	0.059 (4)	−0.013 (3)	0.001 (3)	−0.002 (3)
C2	0.068 (4)	0.056 (3)	0.045 (3)	−0.013 (3)	−0.007 (3)	−0.002 (3)
C3	0.059 (4)	0.053 (3)	0.047 (4)	−0.010 (3)	−0.002 (3)	−0.001 (3)
C4	0.067 (4)	0.074 (4)	0.049 (4)	−0.002 (3)	0.008 (3)	0.005 (3)
C5	0.098 (5)	0.080 (5)	0.056 (4)	0.001 (4)	−0.004 (4)	−0.011 (4)
C6	0.079 (5)	0.062 (4)	0.072 (5)	−0.007 (3)	−0.017 (4)	−0.011 (4)
C7	0.070 (4)	0.058 (4)	0.061 (4)	−0.017 (3)	−0.003 (3)	−0.005 (3)
C8	0.093 (5)	0.072 (4)	0.065 (4)	−0.019 (4)	−0.005 (4)	−0.007 (3)
C9	0.065 (4)	0.050 (3)	0.054 (4)	−0.012 (3)	−0.004 (3)	−0.008 (3)
C10	0.070 (4)	0.060 (4)	0.053 (4)	−0.034 (3)	−0.009 (3)	0.001 (3)
C11	0.067 (4)	0.062 (4)	0.048 (4)	−0.033 (3)	−0.007 (3)	0.008 (3)
C12	0.070 (4)	0.082 (5)	0.063 (4)	−0.026 (4)	−0.008 (3)	0.001 (4)
C13	0.081 (5)	0.106 (6)	0.077 (5)	−0.030 (5)	−0.016 (4)	0.020 (5)
C14	0.065 (4)	0.067 (4)	0.093 (5)	0.001 (3)	0.000 (4)	0.020 (4)
C15	0.088 (5)	0.052 (4)	0.093 (5)	−0.026 (3)	−0.004 (4)	0.002 (4)
C16	0.069 (4)	0.074 (4)	0.071 (4)	−0.009 (3)	−0.008 (3)	0.003 (3)
C17	0.079 (5)	0.069 (4)	0.050 (4)	−0.023 (3)	−0.003 (3)	−0.006 (3)
C18	0.075 (4)	0.063 (4)	0.051 (4)	−0.016 (3)	−0.006 (3)	−0.002 (3)
C19	0.063 (4)	0.049 (3)	0.050 (4)	−0.016 (3)	−0.005 (3)	−0.003 (3)
C20	0.067 (4)	0.045 (3)	0.054 (4)	−0.017 (3)	−0.003 (3)	0.004 (3)
C21	0.090 (5)	0.048 (3)	0.052 (4)	−0.022 (3)	−0.015 (3)	−0.002 (3)
C22	0.090 (5)	0.064 (4)	0.045 (4)	−0.011 (3)	−0.008 (3)	0.000 (3)
C23	0.088 (5)	0.053 (4)	0.058 (4)	−0.018 (3)	0.003 (3)	0.012 (3)
C24	0.085 (4)	0.044 (3)	0.056 (4)	−0.022 (3)	−0.007 (3)	−0.002 (3)
C25	0.071 (4)	0.053 (4)	0.054 (4)	−0.013 (3)	−0.006 (3)	−0.010 (3)
C26	0.077 (4)	0.068 (4)	0.043 (4)	−0.017 (3)	−0.006 (3)	−0.001 (3)
C27	0.046 (3)	0.049 (3)	0.049 (3)	−0.007 (3)	−0.007 (3)	0.001 (3)
C28	0.047 (3)	0.046 (3)	0.051 (3)	−0.010 (2)	−0.001 (3)	0.001 (3)
C29	0.052 (3)	0.041 (3)	0.055 (4)	−0.005 (2)	−0.001 (3)	−0.001 (3)
C30	0.089 (5)	0.062 (4)	0.042 (3)	−0.023 (3)	−0.001 (3)	−0.001 (3)
C31	0.082 (4)	0.051 (3)	0.054 (4)	−0.016 (3)	−0.002 (3)	−0.012 (3)
C32	0.066 (4)	0.049 (3)	0.057 (4)	−0.017 (3)	−0.009 (3)	0.001 (3)

Geometric parameters (Å, º) top

N1—C1	1.312 (6)	C10—C15	1.360 (7)
N1—C3	1.389 (6)	C10—C11	1.370 (7)
N1—H1	0.8600	C11—C12	1.404 (7)
N2—C1	1.323 (6)	C12—C13	1.376 (8)
N2—C2	1.376 (6)	C12—H12	0.9300
N2—H2	0.8600	C13—C14	1.365 (8)
N3—C9	1.312 (6)	C13—H13	0.9300
N3—C11	1.358 (6)	C14—C15	1.365 (8)
N3—H3	0.8600	C14—H14	0.9300
N4—C9	1.323 (6)	C15—H15	0.9300
N4—C10	1.380 (6)	C16—H16A	0.9600
N4—H4	0.8600	C16—H16B	0.9600
O1—C17	1.234 (6)	C16—H16C	0.9600
O2—C17	1.263 (6)	C17—C19	1.487 (7)
O3—C18	1.278 (6)	C18—C20	1.494 (7)
O3—H3A	0.8200	C19—C24	1.380 (7)
O4—C18	1.237 (6)	C19—C20	1.418 (6)
O5—C25	1.222 (6)	C20—C21	1.366 (7)
O6—C25	1.271 (6)	C21—C22	1.364 (7)
O7—C26	1.269 (6)	C21—H21	0.9300
O7—H7	0.8200	C22—C23	1.385 (7)
O8—C26	1.230 (6)	C22—H22	0.9300
C1—C8	1.480 (7)	C23—C24	1.365 (7)
C2—C3	1.359 (7)	C23—H23	0.9300
C2—C7	1.382 (7)	C24—H24	0.9300
C3—C4	1.369 (7)	C25—C27	1.496 (7)
C4—C5	1.377 (7)	C26—C28	1.500 (7)
C4—H4A	0.9300	C27—C32	1.362 (6)
C5—C6	1.386 (8)	C27—C28	1.411 (6)
C5—H5	0.9300	C28—C29	1.369 (7)
C6—C7	1.361 (7)	C29—C30	1.364 (6)
C6—H6	0.9300	C29—H29	0.9300
C7—H7A	0.9300	C30—C31	1.377 (6)
C8—H8A	0.9600	C30—H30	0.9300
C8—H8B	0.9600	C31—C32	1.381 (7)
C8—H8C	0.9600	C31—H31	0.9300
C9—C16	1.483 (7)	C32—H32	0.9300

C1—N1—C3	109.2 (5)	C15—C14—H14	118.5
C1—N1—H1	125.4	C10—C15—C14	116.4 (6)
C3—N1—H1	125.4	C10—C15—H15	121.8
C1—N2—C2	109.1 (4)	C14—C15—H15	121.8
C1—N2—H2	125.4	C9—C16—H16A	109.5
C2—N2—H2	125.4	C9—C16—H16B	109.5
C9—N3—C11	109.3 (4)	H16A—C16—H16B	109.5
C9—N3—H3	125.3	C9—C16—H16C	109.5
C11—N3—H3	125.3	H16A—C16—H16C	109.5
C9—N4—C10	109.2 (4)	H16B—C16—H16C	109.5
C9—N4—H4	125.4	O1—C17—O2	119.2 (5)
C10—N4—H4	125.4	O1—C17—C19	119.4 (5)
C18—O3—H3A	109.5	O2—C17—C19	121.5 (5)
C26—O7—H7	109.5	O4—C18—O3	118.7 (5)
N1—C1—N2	108.8 (5)	O4—C18—C20	119.3 (5)
N1—C1—C8	125.8 (5)	O3—C18—C20	122.0 (5)
N2—C1—C8	125.4 (5)	C24—C19—C20	117.2 (5)
C3—C2—N2	106.8 (5)	C24—C19—C17	114.3 (5)
C3—C2—C7	120.8 (5)	C20—C19—C17	128.4 (5)
N2—C2—C7	132.4 (5)	C21—C20—C19	118.3 (5)
C2—C3—C4	123.6 (5)	C21—C20—C18	114.3 (5)
C2—C3—N1	106.2 (5)	C19—C20—C18	127.4 (5)
C4—C3—N1	130.2 (5)	C22—C21—C20	123.4 (5)
C3—C4—C5	115.8 (5)	C22—C21—H21	118.3
C3—C4—H4A	122.1	C20—C21—H21	118.3
C5—C4—H4A	122.1	C21—C22—C23	119.0 (5)
C4—C5—C6	120.6 (6)	C21—C22—H22	120.5
C4—C5—H5	119.7	C23—C22—H22	120.5
C6—C5—H5	119.7	C24—C23—C22	118.5 (5)
C7—C6—C5	122.8 (6)	C24—C23—H23	120.7
C7—C6—H6	118.6	C22—C23—H23	120.7
C5—C6—H6	118.6	C23—C24—C19	123.6 (5)
C6—C7—C2	116.2 (5)	C23—C24—H24	118.2
C6—C7—H7A	121.9	C19—C24—H24	118.2
C2—C7—H7A	121.9	O5—C25—O6	119.9 (6)
C1—C8—H8A	109.5	O5—C25—C27	119.6 (5)
C1—C8—H8B	109.5	O6—C25—C27	120.5 (5)
H8A—C8—H8B	109.5	O8—C26—O7	119.9 (5)
C1—C8—H8C	109.5	O8—C26—C28	118.4 (5)
H8A—C8—H8C	109.5	O7—C26—C28	121.8 (5)
H8B—C8—H8C	109.5	C32—C27—C28	117.7 (5)
N3—C9—N4	108.7 (5)	C32—C27—C25	113.9 (5)
N3—C9—C16	125.9 (5)	C28—C27—C25	128.4 (5)
N4—C9—C16	125.4 (5)	C29—C28—C27	118.0 (5)
C15—C10—C11	122.2 (6)	C29—C28—C26	113.9 (5)
C15—C10—N4	132.4 (5)	C27—C28—C26	128.2 (5)
C11—C10—N4	105.4 (5)	C30—C29—C28	123.2 (5)
N3—C11—C10	107.4 (5)	C30—C29—H29	118.4
N3—C11—C12	131.1 (5)	C28—C29—H29	118.4
C10—C11—C12	121.5 (6)	C29—C30—C31	119.7 (5)
C13—C12—C11	115.4 (6)	C29—C30—H30	120.1
C13—C12—H12	122.3	C31—C30—H30	120.1
C11—C12—H12	122.3	C30—C31—C32	117.2 (5)
C14—C13—C12	121.6 (6)	C30—C31—H31	121.4
C14—C13—H13	119.2	C32—C31—H31	121.4
C12—C13—H13	119.2	C27—C32—C31	124.2 (5)
C13—C14—C15	122.9 (6)	C27—C32—H32	117.9
C13—C14—H14	118.5	C31—C32—H32	117.9

C3—N1—C1—N2	−0.6 (6)	O1—C17—C19—C24	5.5 (8)
C3—N1—C1—C8	178.7 (5)	O2—C17—C19—C24	−174.2 (6)
C2—N2—C1—N1	0.1 (6)	O1—C17—C19—C20	−176.5 (6)
C2—N2—C1—C8	−179.1 (5)	O2—C17—C19—C20	3.8 (10)
C1—N2—C2—C3	0.4 (6)	C24—C19—C20—C21	−1.9 (8)
C1—N2—C2—C7	177.6 (6)	C17—C19—C20—C21	−179.8 (6)
N2—C2—C3—C4	−178.8 (5)	C24—C19—C20—C18	−179.2 (5)
C7—C2—C3—C4	3.6 (8)	C17—C19—C20—C18	2.9 (9)
N2—C2—C3—N1	−0.7 (6)	O4—C18—C20—C21	−2.2 (8)
C7—C2—C3—N1	−178.3 (5)	O3—C18—C20—C21	176.7 (6)
C1—N1—C3—C2	0.8 (6)	O4—C18—C20—C19	175.3 (6)
C1—N1—C3—C4	178.8 (6)	O3—C18—C20—C19	−5.9 (9)
C2—C3—C4—C5	−2.7 (8)	C19—C20—C21—C22	2.3 (9)
N1—C3—C4—C5	179.6 (5)	C18—C20—C21—C22	179.9 (6)
C3—C4—C5—C6	1.8 (8)	C20—C21—C22—C23	−1.6 (9)
C4—C5—C6—C7	−1.8 (9)	C21—C22—C23—C24	0.7 (9)
C5—C6—C7—C2	2.4 (8)	C22—C23—C24—C19	−0.5 (9)
C3—C2—C7—C6	−3.2 (8)	C20—C19—C24—C23	1.1 (9)
N2—C2—C7—C6	179.9 (6)	C17—C19—C24—C23	179.3 (5)
C11—N3—C9—N4	0.1 (6)	O5—C25—C27—C32	1.3 (7)
C11—N3—C9—C16	179.0 (5)	O6—C25—C27—C32	−178.2 (5)
C10—N4—C9—N3	−0.6 (6)	O5—C25—C27—C28	−176.7 (5)
C10—N4—C9—C16	−179.5 (5)	O6—C25—C27—C28	3.7 (8)
C9—N4—C10—C15	179.7 (6)	C32—C27—C28—C29	−0.5 (7)
C9—N4—C10—C11	0.8 (6)	C25—C27—C28—C29	177.5 (5)
C9—N3—C11—C10	0.4 (6)	C32—C27—C28—C26	179.1 (5)
C9—N3—C11—C12	−179.6 (6)	C25—C27—C28—C26	−2.9 (9)
C15—C10—C11—N3	−179.7 (5)	O8—C26—C28—C29	0.7 (7)
N4—C10—C11—N3	−0.7 (6)	O7—C26—C28—C29	−179.1 (5)
C15—C10—C11—C12	0.3 (9)	O8—C26—C28—C27	−178.9 (5)
N4—C10—C11—C12	179.3 (5)	O7—C26—C28—C27	1.3 (9)
N3—C11—C12—C13	179.5 (6)	C27—C28—C29—C30	1.0 (8)
C10—C11—C12—C13	−0.5 (9)	C26—C28—C29—C30	−178.7 (5)
C11—C12—C13—C14	0.6 (9)	C28—C29—C30—C31	−0.4 (8)
C12—C13—C14—C15	−0.5 (10)	C29—C30—C31—C32	−0.5 (8)
C11—C10—C15—C14	−0.1 (9)	C28—C27—C32—C31	−0.5 (8)
N4—C10—C15—C14	−178.8 (6)	C25—C27—C32—C31	−178.8 (5)
C13—C14—C15—C10	0.2 (9)	C30—C31—C32—C27	1.0 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.86	1.81	2.649 (6)	166
N2—H2···O5ⁱⁱ	0.86	1.91	2.750 (6)	165
N2—H2···O6ⁱⁱ	0.86	2.58	3.226 (6)	133
N3—H3···O8ⁱⁱⁱ	0.86	1.79	2.631 (6)	166
N4—H4···O1^iv	0.86	1.83	2.680 (6)	168
N4—H4···O2^iv	0.86	2.58	3.232 (6)	133
O3—H3A···O2	0.82	1.55	2.372 (5)	175
O7—H7···O6	0.82	1.56	2.379 (5)	179
C7—H7A···O6ⁱⁱ	0.93	2.53	3.244 (7)	134

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

Experimental details

Crystal data
Chemical formula	C₈H₉N₂⁺·C₈H₅O₄⁻
M_r	298.29
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	3.8545 (16), 17.689 (7), 20.752 (9)
α, β, γ (°)	86.754 (8), 86.585 (7), 84.169 (7)
V (Å³)	1403.3 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.45 × 0.39 × 0.30

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.955, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	7520, 4923, 1846
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.082, 0.232, 0.89
No. of reflections	4923
No. of parameters	397
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.31

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.86	1.81	2.649 (6)	166.3
N2—H2···O5ⁱⁱ	0.86	1.91	2.750 (6)	165.4
N2—H2···O6ⁱⁱ	0.86	2.58	3.226 (6)	132.8
N3—H3···O8ⁱⁱⁱ	0.86	1.79	2.631 (6)	165.9
N4—H4···O1^iv	0.86	1.83	2.680 (6)	168.4
N4—H4···O2^iv	0.86	2.58	3.232 (6)	132.9
O3—H3A···O2	0.82	1.55	2.372 (5)	175.3
O7—H7···O6	0.82	1.56	2.379 (5)	178.8
C7—H7A···O6ⁱⁱ	0.93	2.53	3.244 (7)	134

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

Acknowledgements

We gratefully acknowledge financial support by the Education Office Foundation of Zhejiang Province (project No. Y201017321) and the Innovation Project of Zhejiang A & F University.

References

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