Benzimidazolium 3,5-dicarb­oxy­benzoate trihydrate

Chang, H.; Yang, Y.-L.; Wang, X.-G.; Yang, E.-C.

doi:10.1107/S1600536810023305

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1738

doi:10.1107/S1600536810023305

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Benzimidazolium 3,5-dicarboxybenzoate trihydrate

Hong Chang,^a You-Li Yang,^a Xiu-Guang Wang ^a and En-Cui Yang ^a ^*

^aCollege of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecule, Tianjin Normal University, Tianjin 300387, People's Republic of China
^*Correspondence e-mail: luckyms@126.com

(Received 7 June 2010; accepted 16 June 2010; online 23 June 2010)

Cocrystallization of benzimidazole with benzene 1,3,5-tricarboxylic acid in slightly basic medium afforded the title compound, C₇H₇N₂⁺·C₉H₅O₆⁻·3H₂O, in which one of the imidazole N atom is protonated and one carboxylic group of aromatic acid is deprotonated. In the crystal structure, intermolecular N—H⋯O hydrogen-bonding connects the two organic components into dimers, which are further linked into a three-dimensional network by O—H⋯O and N—H⋯O interactions between the water molecules and the dimers.

Related literature

For molecular self-assembly by non-covalent interactions and its potential applications, see: Remenar et al. (2003 ); Oxtoby et al. (2005 ); Zaworotko (2001 ). For the benzimidazole-based supramolecular aggregate formed by π–π stacking and hydrogen-bonding interactions, see Gao et al. (2004 ).

Experimental

Crystal data

C₇H₇N₂⁺·C₉H₅O₆⁻·3H₂O
M_r = 382.32
Triclinic, P 1
a = 3.8478 (2) Å
b = 10.2231 (6) Å
c = 11.2982 (7) Å
α = 85.522 (1)°
β = 80.707 (1)°
γ = 81.826 (1)°
V = 433.45 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.971, T_max = 0.976
2240 measured reflections
1536 independent reflections
1478 reflections with I > 2σ(I)
R_int = 0.008

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.073
S = 1.04
1536 reflections
246 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O9ⁱ	0.82	1.73	2.539 (2)	169
O6—H6⋯O7ⁱⁱ	0.82	1.77	2.589 (2)	176
N1—H1⋯O8ⁱⁱⁱ	0.86	1.97	2.812 (3)	167
N2—H2⋯O2^iv	0.86	1.87	2.721 (3)	173
O7—H7A⋯O2	0.85	1.92	2.760 (3)	173
O7—H7B⋯O8	0.85	2.09	2.877 (3)	155
O8—H8A⋯O5^v	0.85	1.99	2.797 (3)	159
O8—H8B⋯O3ⁱⁱⁱ	0.85	1.92	2.730 (2)	160
O9—H9A⋯O1^iv	0.85	1.81	2.654 (2)	173
O9—H9B⋯O1^vi	0.85	1.86	2.685 (3)	163
Symmetry codes: (i) x+1, y, z; (ii) x-1, y+1, z; (iii) x-1, y, z; (iv) x-1, y, z-1; (v) x, y-1, z; (vi) x, y, z-1.

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2001 ); 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 DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810023305/nc2189sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810023305/nc2189Isup2.hkl

checkCIF report

Comment top

Recently, molecular self-assembly by non-covalent interactions has attacted considerable interest in supramolecular chemistry and crystal engineering due to their possible potential applications as functional materials (Zaworotko, 2001), in molecular recognition (Oxtoby et al., 2005), and pharmaceutical chemistry (Remenar et al., 2003). Obviously, the conguated organic components with rich carboxylate or amino groups have became good blocks for the construction of self-assembly systems, since hydrogen-bonding and π··· π interactions are the main driven forces of the assembly process. In this context benzimidazole (bim) and its derivatives have been used as promising building blocks for the construction of supramolecular aggregates. As a continuation of this work bim and 1,3,5-benzenetricarboxylic acid (H₃btc) were reacted in slightly basic medium and the product were identified by single crystal X-ray diffraction.

The asymmetric unit of the title compound comprises one Hbim⁺ cation, one monodeprotonated H₂btc^- anion and three water molecules all of the located in general positions (Fig. 1). The two carboxyl groups are located within the plane of the aromatic ring, whereas the deprotonated carboxylate group is slightly twisted out of the ring plane. The dihedral angle between the aromatic and the benzimidazole rings amount to 6.84 (5)^o.

In the crystal structure, the Hbim⁺ cations and H₂btc^- anions are connected into dimers by N–H···O hydrogen-bonding between the N—H H atoms and the carboxylate group (Table 1). These dimers are further connected by O–H···O and N–H···O hydrogen bonding between the water molecules, the carboxyl and carboxylate groups as well as the N-H H atoms into a three-dimensional hydrogen bonded network (Figure 2 and Table 1). In this interactions the water molecules act as hydrogen bond donor and acceptor.

Related literature top

For molecular self-assembly by non-covalent interactions and its potential applications, see: Remenar et al. (2003); Oxtoby et al. (2005). Zaworotko (2001). For the benzimidazole-based supramolecular aggregate formed by π–π stacking and hydrogen-bonding interactions, see Gao et al. (2004).

Experimental top

A mixture containing H₃btc (21.0 mg, 0.1 mmol), bim (11.8 mg, 0.1 mmol), and NaOH (4.0 mg, 0.1 mmol) was dissolved in a mixed methanol-H₂O solution (v: v = 1:1, 10.0 ml). Then, the mixture was transferred into a Teflon-lined reactor (23.0 ml) and heated to 70 ^oC for 48 hrs. After the mixture was cooled to room temperature at a rate of 6 ^oC h^-1, colorless block-shaped crystals suitable for X-ray diffraction were obtained directly. Yield: 56% based on bim. Anal.Calcd for C₁₆H₁₈N₂O₉,C,50.26; H, 4.75; N, 7.33%. Found: C, 50.32; H, 4.78; N,7.36%.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Crystal structure of the title compound with view along the a-axis. Hydrogen bonding is shown as dashed lines.

Benzimidazolium 3,5-dicarboxybenzoate trihydrate top

Crystal data top

C₇H₇N₂⁺·C₉H₅O₆⁻·3H₂O	Z = 1
M_r = 382.32	F(000) = 200
Triclinic, P1	D_x = 1.465 Mg m⁻³
Hall symbol: P1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8478 (2) Å	Cell parameters from 1795 reflections
b = 10.2231 (6) Å	θ = 2.8–27.9°
c = 11.2982 (7) Å	µ = 0.12 mm⁻¹
α = 85.522 (1)°	T = 296 K
β = 80.707 (1)°	Block, colourless
γ = 81.826 (1)°	0.24 × 0.22 × 0.20 mm
V = 433.45 (4) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	1536 independent reflections
Radiation source: fine-focus sealed tube	1478 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.008
phi and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→4
T_min = 0.971, T_max = 0.976	k = −12→5
2240 measured reflections	l = −13→13

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0522P)² + 0.0236P] where P = (F_o² + 2F_c²)/3
1536 reflections	(Δ/σ)_max < 0.001
246 parameters	Δρ_max = 0.14 e Å⁻³
3 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₇H₇N₂⁺·C₉H₅O₆⁻·3H₂O	γ = 81.826 (1)°
M_r = 382.32	V = 433.45 (4) Å³
Triclinic, P1	Z = 1
a = 3.8478 (2) Å	Mo Kα radiation
b = 10.2231 (6) Å	µ = 0.12 mm⁻¹
c = 11.2982 (7) Å	T = 296 K
α = 85.522 (1)°	0.24 × 0.22 × 0.20 mm
β = 80.707 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1536 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1478 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.976	R_int = 0.008
2240 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	3 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.04	Δρ_max = 0.14 e Å⁻³
1536 reflections	Δρ_min = −0.19 e Å⁻³
246 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
O1	0.8287 (5)	0.63795 (18)	1.20720 (14)	0.0482 (4)
O2	0.9531 (6)	0.44710 (18)	1.11874 (15)	0.0581 (5)
O3	1.2332 (6)	0.50067 (17)	0.65819 (16)	0.0552 (5)
O4	0.9893 (5)	0.68726 (18)	0.57532 (15)	0.0546 (5)
H4	1.1005	0.6561	0.5135	0.082*
O5	0.2872 (6)	1.03786 (17)	0.80326 (17)	0.0596 (5)
O6	0.1819 (5)	1.01258 (17)	1.00192 (16)	0.0544 (5)
H6	0.0662	1.0858	0.9946	0.082*
N1	−0.0881 (6)	0.2463 (2)	0.52127 (19)	0.0457 (5)
H1	−0.1644	0.2470	0.5971	0.055*
N2	0.0014 (6)	0.3109 (2)	0.33346 (19)	0.0458 (5)
H2	−0.0077	0.3595	0.2681	0.055*
C1	0.1306 (6)	0.1435 (2)	0.4635 (2)	0.0384 (5)
C2	0.1892 (6)	0.1855 (2)	0.3429 (2)	0.0387 (5)
C3	0.3998 (7)	0.1058 (3)	0.2576 (2)	0.0497 (6)
H3	0.4411	0.1336	0.1769	0.060*
C4	0.5439 (7)	−0.0170 (3)	0.2996 (3)	0.0587 (7)
H4A	0.6863	−0.0735	0.2455	0.070*
C5	0.4822 (8)	−0.0587 (3)	0.4207 (3)	0.0592 (8)
H5	0.5843	−0.1424	0.4450	0.071*
C6	0.2766 (7)	0.0196 (3)	0.5047 (3)	0.0507 (6)
H6A	0.2364	−0.0086	0.5854	0.061*
C7	−0.1607 (7)	0.3433 (2)	0.4406 (2)	0.0482 (6)
H7	−0.3052	0.4227	0.4574	0.058*
C8	0.7899 (5)	0.6418 (2)	1.00125 (19)	0.0329 (5)
C9	0.9324 (5)	0.5896 (2)	0.89162 (19)	0.0325 (4)
H9	1.0628	0.5057	0.8895	0.039*
C10	0.8824 (6)	0.6614 (2)	0.78491 (19)	0.0320 (4)
C11	0.6801 (5)	0.7855 (2)	0.78785 (19)	0.0332 (4)
H11	0.6451	0.8336	0.7165	0.040*
C12	0.5300 (6)	0.8377 (2)	0.8973 (2)	0.0339 (5)
C13	0.5874 (5)	0.7666 (2)	1.00353 (19)	0.0336 (4)
H13	0.4907	0.8023	1.0768	0.040*
C14	0.8615 (6)	0.5697 (2)	1.11777 (19)	0.0367 (5)
C15	1.0532 (6)	0.6071 (2)	0.66716 (18)	0.0358 (5)
C16	0.3216 (6)	0.9717 (2)	0.8957 (2)	0.0388 (5)
O7	0.8307 (6)	0.24730 (19)	0.9861 (2)	0.0668 (6)
H7A	0.8766	0.3119	1.0213	0.100*
H7B	0.7602	0.2814	0.9216	0.100*
O8	0.5721 (6)	0.27703 (19)	0.75910 (17)	0.0584 (5)
H8A	0.4356	0.2174	0.7739	0.088*
H8B	0.4373	0.3479	0.7446	0.088*
O9	0.2592 (5)	0.60054 (19)	0.37164 (15)	0.0520 (5)
H9A	0.1063	0.6114	0.3240	0.078*
H9B	0.4479	0.6232	0.3300	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0596 (10)	0.0565 (10)	0.0271 (8)	0.0005 (8)	−0.0094 (7)	−0.0032 (7)
O2	0.0961 (15)	0.0393 (9)	0.0363 (9)	0.0075 (9)	−0.0217 (9)	0.0072 (7)
O3	0.0797 (12)	0.0418 (10)	0.0325 (9)	0.0211 (9)	−0.0007 (8)	0.0009 (7)
O4	0.0773 (12)	0.0496 (10)	0.0247 (8)	0.0198 (9)	0.0002 (8)	0.0047 (7)
O5	0.0951 (15)	0.0369 (9)	0.0398 (10)	0.0166 (9)	−0.0136 (9)	0.0021 (8)
O6	0.0812 (13)	0.0359 (9)	0.0385 (9)	0.0153 (8)	−0.0060 (9)	−0.0032 (7)
N1	0.0534 (11)	0.0466 (12)	0.0355 (11)	−0.0055 (9)	−0.0028 (9)	−0.0024 (9)
N2	0.0611 (13)	0.0366 (10)	0.0406 (11)	−0.0060 (9)	−0.0160 (10)	0.0087 (8)
C1	0.0440 (11)	0.0384 (11)	0.0346 (11)	−0.0078 (9)	−0.0119 (9)	0.0034 (9)
C2	0.0462 (12)	0.0371 (12)	0.0355 (11)	−0.0099 (10)	−0.0131 (10)	0.0036 (9)
C3	0.0536 (14)	0.0597 (16)	0.0371 (13)	−0.0118 (12)	−0.0048 (11)	−0.0075 (12)
C4	0.0533 (15)	0.0527 (16)	0.072 (2)	−0.0013 (12)	−0.0138 (14)	−0.0202 (14)
C5	0.0596 (16)	0.0382 (13)	0.082 (2)	0.0024 (11)	−0.0281 (15)	0.0001 (14)
C6	0.0617 (15)	0.0440 (14)	0.0493 (14)	−0.0071 (12)	−0.0229 (12)	0.0107 (11)
C7	0.0556 (14)	0.0381 (13)	0.0503 (15)	−0.0012 (11)	−0.0105 (12)	−0.0021 (11)
C8	0.0370 (11)	0.0335 (11)	0.0276 (10)	−0.0049 (9)	−0.0052 (8)	0.0024 (8)
C9	0.0373 (11)	0.0297 (10)	0.0282 (10)	0.0016 (8)	−0.0046 (8)	0.0012 (8)
C10	0.0376 (10)	0.0315 (10)	0.0254 (10)	−0.0016 (8)	−0.0046 (8)	0.0009 (8)
C11	0.0397 (10)	0.0307 (10)	0.0274 (11)	−0.0001 (8)	−0.0064 (8)	0.0032 (8)
C12	0.0388 (10)	0.0297 (10)	0.0337 (12)	−0.0030 (8)	−0.0085 (9)	−0.0006 (9)
C13	0.0394 (11)	0.0321 (11)	0.0280 (10)	−0.0007 (9)	−0.0040 (8)	−0.0028 (8)
C14	0.0421 (11)	0.0389 (12)	0.0267 (11)	0.0014 (9)	−0.0061 (9)	0.0025 (9)
C15	0.0412 (11)	0.0350 (12)	0.0281 (11)	0.0024 (9)	−0.0038 (9)	0.0021 (9)
C16	0.0485 (12)	0.0308 (11)	0.0363 (12)	0.0012 (9)	−0.0093 (10)	−0.0037 (10)
O7	0.0998 (16)	0.0385 (9)	0.0595 (12)	0.0173 (9)	−0.0252 (11)	−0.0076 (9)
O8	0.0766 (13)	0.0444 (10)	0.0464 (10)	0.0072 (8)	−0.0049 (9)	0.0089 (8)
O9	0.0559 (10)	0.0711 (12)	0.0274 (8)	−0.0039 (9)	−0.0054 (7)	−0.0029 (8)

Geometric parameters (Å, º) top

O1—C14	1.252 (3)	C5—H5	0.9300
O2—C14	1.252 (3)	C6—H6A	0.9300
O3—C15	1.206 (3)	C7—H7	0.9300
O4—C15	1.304 (3)	C8—C9	1.386 (3)
O4—H4	0.8200	C8—C13	1.397 (3)
O5—C16	1.214 (3)	C8—C14	1.503 (3)
O6—C16	1.308 (3)	C9—C10	1.388 (3)
O6—H6	0.8200	C9—H9	0.9300
N1—C7	1.325 (3)	C10—C11	1.390 (3)
N1—C1	1.384 (3)	C10—C15	1.496 (3)
N1—H1	0.8600	C11—C12	1.390 (3)
N2—C7	1.313 (4)	C11—H11	0.9300
N2—C2	1.384 (3)	C12—C13	1.385 (3)
N2—H2	0.8600	C12—C16	1.487 (3)
C1—C6	1.388 (3)	C13—H13	0.9300
C1—C2	1.389 (3)	O7—H7A	0.8500
C2—C3	1.390 (4)	O7—H7B	0.8499
C3—C4	1.378 (4)	O8—H8A	0.8500
C3—H3	0.9300	O8—H8B	0.8500
C4—C5	1.394 (5)	O9—H9A	0.8500
C4—H4A	0.9300	O9—H9B	0.8500
C5—C6	1.366 (5)

C15—O4—H4	109.5	C9—C8—C14	121.44 (18)
C16—O6—H6	109.5	C13—C8—C14	119.20 (18)
C7—N1—C1	108.8 (2)	C8—C9—C10	120.62 (18)
C7—N1—H1	125.6	C8—C9—H9	119.7
C1—N1—H1	125.6	C10—C9—H9	119.7
C7—N2—C2	108.8 (2)	C9—C10—C11	119.75 (19)
C7—N2—H2	125.6	C9—C10—C15	120.17 (18)
C2—N2—H2	125.6	C11—C10—C15	120.06 (19)
N1—C1—C6	132.4 (2)	C12—C11—C10	120.10 (19)
N1—C1—C2	105.9 (2)	C12—C11—H11	120.0
C6—C1—C2	121.7 (2)	C10—C11—H11	120.0
N2—C2—C1	106.4 (2)	C13—C12—C11	119.81 (19)
N2—C2—C3	132.0 (2)	C13—C12—C16	122.13 (19)
C1—C2—C3	121.5 (2)	C11—C12—C16	118.02 (18)
C4—C3—C2	116.2 (2)	C12—C13—C8	120.39 (19)
C4—C3—H3	121.9	C12—C13—H13	119.8
C2—C3—H3	121.9	C8—C13—H13	119.8
C3—C4—C5	121.9 (3)	O1—C14—O2	124.6 (2)
C3—C4—H4A	119.1	O1—C14—C8	116.94 (19)
C5—C4—H4A	119.1	O2—C14—C8	118.41 (19)
C6—C5—C4	122.0 (3)	O3—C15—O4	123.5 (2)
C6—C5—H5	119.0	O3—C15—C10	123.5 (2)
C4—C5—H5	119.0	O4—C15—C10	113.00 (18)
C5—C6—C1	116.6 (3)	O5—C16—O6	123.0 (2)
C5—C6—H6A	121.7	O5—C16—C12	122.6 (2)
C1—C6—H6A	121.7	O6—C16—C12	114.39 (19)
N2—C7—N1	110.0 (2)	H7A—O7—H7B	105.2
N2—C7—H7	125.0	H8A—O8—H8B	105.1
N1—C7—H7	125.0	H9A—O9—H9B	105.1
C9—C8—C13	119.31 (19)

C7—N1—C1—C6	−178.5 (2)	C9—C10—C11—C12	0.3 (3)
C7—N1—C1—C2	0.8 (3)	C15—C10—C11—C12	−178.1 (2)
C7—N2—C2—C1	0.0 (3)	C10—C11—C12—C13	1.1 (3)
C7—N2—C2—C3	179.4 (2)	C10—C11—C12—C16	178.9 (2)
N1—C1—C2—N2	−0.4 (2)	C11—C12—C13—C8	−1.2 (3)
C6—C1—C2—N2	178.9 (2)	C16—C12—C13—C8	−178.9 (2)
N1—C1—C2—C3	−179.9 (2)	C9—C8—C13—C12	−0.1 (3)
C6—C1—C2—C3	−0.6 (3)	C14—C8—C13—C12	177.29 (18)
N2—C2—C3—C4	−178.9 (2)	C9—C8—C14—O1	156.9 (2)
C1—C2—C3—C4	0.4 (3)	C13—C8—C14—O1	−20.4 (3)
C2—C3—C4—C5	−0.1 (4)	C9—C8—C14—O2	−22.2 (3)
C3—C4—C5—C6	−0.2 (4)	C13—C8—C14—O2	160.5 (2)
C4—C5—C6—C1	0.1 (4)	C9—C10—C15—O3	1.2 (3)
N1—C1—C6—C5	179.4 (3)	C11—C10—C15—O3	179.6 (2)
C2—C1—C6—C5	0.3 (3)	C9—C10—C15—O4	−178.3 (2)
C2—N2—C7—N1	0.5 (3)	C11—C10—C15—O4	0.1 (3)
C1—N1—C7—N2	−0.8 (3)	C13—C12—C16—O5	175.6 (2)
C13—C8—C9—C10	1.5 (3)	C11—C12—C16—O5	−2.1 (3)
C14—C8—C9—C10	−175.82 (19)	C13—C12—C16—O6	−3.8 (3)
C8—C9—C10—C11	−1.6 (3)	C11—C12—C16—O6	178.4 (2)
C8—C9—C10—C15	176.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O9ⁱ	0.82	1.73	2.539 (2)	169
O6—H6···O7ⁱⁱ	0.82	1.77	2.589 (2)	176
N1—H1···O8ⁱⁱⁱ	0.86	1.97	2.812 (3)	167
N2—H2···O2^iv	0.86	1.87	2.721 (3)	173
O7—H7A···O2	0.85	1.92	2.760 (3)	173
O7—H7B···O8	0.85	2.09	2.877 (3)	155
O8—H8A···O5^v	0.85	1.99	2.797 (3)	159
O8—H8B···O3ⁱⁱⁱ	0.85	1.92	2.730 (2)	160
O9—H9A···O1^iv	0.85	1.81	2.654 (2)	173
O9—H9B···O1^vi	0.85	1.86	2.685 (3)	163

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·C₉H₅O₆⁻·3H₂O
M_r	382.32
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	3.8478 (2), 10.2231 (6), 11.2982 (7)
α, β, γ (°)	85.522 (1), 80.707 (1), 81.826 (1)
V (Å³)	433.45 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.971, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	2240, 1536, 1478
R_int	0.008
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.073, 1.04
No. of reflections	1536
No. of parameters	246
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.19

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O9ⁱ	0.82	1.73	2.539 (2)	168.8
O6—H6···O7ⁱⁱ	0.82	1.77	2.589 (2)	176.3
N1—H1···O8ⁱⁱⁱ	0.86	1.97	2.812 (3)	167.0
N2—H2···O2^iv	0.86	1.87	2.721 (3)	172.7
O7—H7A···O2	0.85	1.92	2.760 (3)	172.8
O7—H7B···O8	0.85	2.09	2.877 (3)	154.6
O8—H8A···O5^v	0.85	1.99	2.797 (3)	159.1
O8—H8B···O3ⁱⁱⁱ	0.85	1.92	2.730 (2)	160.0
O9—H9A···O1^iv	0.85	1.81	2.654 (2)	172.5
O9—H9B···O1^vi	0.85	1.86	2.685 (3)	162.6

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

Acknowledgements

The authors gratefully acknowledge financial support from the Tianjin Key Laboratory of Structure and Performance for Functional Molecule.

References

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