Tetra­imidazolium piperazinediium bis­(benzene-1,3,5-tricarboxyl­ate) dihydrate

Liu, P.; Li, Z.; Chen, D.

doi:10.1107/S1600536810041310

Tetraimidazolium piperazinediium bis(benzene-1,3,5-tricarboxylate) dihydrate

During the crystallization of the title compound, 4C₃H₅N₂⁺·C₄H₁₂N₂⁺·2C₉H₃O₆³⁻·2H₂O, the acidic protons were transferred to the imidazole and piperazine N atoms, forming the final 4:1:2:2 hydrated mixed salt. The mean planes of the three carboxylate groups in the anion are twisted with respect to the the central benzene ring, making dihedral angles of 13.5 (1), 14.5 (1) and 16.9 (1)°. In the crystal, the component ions are linked into a three-dimensional network by a combination of intermolecular N—H

O, O—H

O and weak C—H

O hydrogen bonds. Further stabilization is provided by π-π stacking interactions with centroid–centroid distances of 3.393 (2) Å and weak C=O

π interactions [O–centroid = 3.363 (2) Å].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810041310/lh5148sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810041310/lh5148Isup2.hkl Contains datablock I

CCDC reference: 799663

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.002 Å
R factor = 0.045
wR factor = 0.122
Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         40
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              C3 H5 N2

Author Response: In order to make these component ions more compact, we have put the N1-N2/C10-C12 imidazole and water O7 molecules outside the unit cell.

PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          5
              H2 O

Author Response: In order to make these component ions more compact, we have put the N1-N2/C10-C12 imidazole and water O7 molecules outside the unit cell.

PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         32

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Piperazine has been used in the manufacture of anthelmintic vermicide. In order to improve its pharmaceutical effect, piperazine has been made into tablets containing two or more components (Jacobs et al., 2009; Oswald et al., 2002; Wang & Jia, 2008). In this paper, we report a new four-component piperazine containing adduct and the crystal structure is presented herein.

The formula unit of the title compound is shown in Fig. 1. The asymmetric unit is composed of two imidazolium cations, half a piperazinium cation, one benzene 1,3,5-tricarboxylate trianion and one water molecule. During the crystallization, the carboxylic acid protons of benzene-1,3,5-tricarboxylic acid were transferred to the imidazole and piperazine nitrogen atoms, forming the 4:1:2:2 organic adduct (imidazolium: piperazinium: benzene 1,3,5-tricarboxylate: water). Delocalization of charges on the the imidazolium and the benzene-1,3,5-tricarboxylate ions are reflected in the bond distances of C15—N3, C15—N4, C9—O5 and C9—O6. The mean planes of the three carboxylate groups in the anion twisted away from the central benzene ring with dihedral angles of 13.5 (1)°, 14.5 (1)° and 16.9 (1)°.

In the crystal packing, the component ions are linked into a complex three-dimensional network by a combination of N—H···O, O—H···O and C—H···O hydrogen bonds (Table 1 and Figure 2). A PLATON (Spek, 2009) analysis shows that the crystal structure is further consolidated by a π···π interaction [Cg1···Cg1(1 - x, 1 - y, 2 - z) = 3.393 (2) Å, dihedral angle = 0°, Cg1 is the centroid defined by atoms N3/N4/C13—C15] and a C=O···π interaction (C9···Cg2 = 3.472 (2) Å, O5···Cg2 = 3.363 (2)Å and C9=O5···Cg2 = 84.4 (2)°, Cg2 is th centroid defined by atoms N1/N2/C10—C12). These types of weak interactions have previously been studied (Gao et al., 2009, Schottel et al., 2008).

Related literature top

For applications of multi-component piperazine compounds, see: Jacobs et al. (2009); Oswald et al. (2002); Wang & Jia (2008). For examples of compounds containing weak anion–π interactions, see: Schottel et al. (2008); Gao et al. (2009).

Experimental top

All the reagents and solvents were used as obtained without further purification. Piperazine hexahydrate (0.2 mmol, 38.8 mg), imidazole (0.2 mmol, 13.6 mg) and benzene 1,3,5-tricarboxylic acid (0.1 mmol, 42.0 mg) were dissolved in 95% methanol (20 ml). The resulting colorless solution was kept in air for two weeks. Colorless blocks of the title compound suitable for single-crystal X-ray diffraction analysis were grown by slow evaporation of the solution at the bottom of the vessel.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (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 PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The formula unit of the title compound. The displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines. Atoms marked with 'A' are at the position of (1 - x, 1 - y, 1 - z).
	Fig. 2. Part of the title crystal structure, showing the three-dimensional network linked by N—H···O, O—H···O and C—H···O hydrogen bonds represented by dashed lines. For the sake of clarity, the H atoms not involved in the hydrogen-bonds pattern have been omitted. Color code: C, black; H, white; N, blue; O, red.

Tetraimidazolium piperazinediium bis(benzene-1,3,5-tricarboxylate) dihydrate top

Crystal data top

4C₃H₅N₂⁺·C₄H₁₂N₂⁺·2C₉H₃O₆³⁻·2H₂O	Z = 1
M_r = 814.78	F(000) = 428
Triclinic, P1	D_x = 1.474 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1548 (4) Å	Cell parameters from 2102 reflections
b = 9.9424 (5) Å	θ = 2.4–23.2°
c = 13.3567 (7) Å	µ = 0.12 mm⁻¹
α = 96.895 (1)°	T = 298 K
β = 95.201 (1)°	Block, colorless
γ = 101.439 (2)°	0.20 × 0.13 × 0.10 mm
V = 918.11 (8) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3925 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	2757 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
0.3° wide ω scans	θ_max = 27.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
T_min = 0.967, T_max = 0.989	k = −11→12
10341 measured reflections	l = −17→17

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0631P)² + 0.0369P] where P = (F_o² + 2F_c²)/3
3925 reflections	(Δ/σ)_max = 0.001
286 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

4C₃H₅N₂⁺·C₄H₁₂N₂⁺·2C₉H₃O₆³⁻·2H₂O	γ = 101.439 (2)°
M_r = 814.78	V = 918.11 (8) Å³
Triclinic, P1	Z = 1
a = 7.1548 (4) Å	Mo Kα radiation
b = 9.9424 (5) Å	µ = 0.12 mm⁻¹
c = 13.3567 (7) Å	T = 298 K
α = 96.895 (1)°	0.20 × 0.13 × 0.10 mm
β = 95.201 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3925 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2757 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.989	R_int = 0.029
10341 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.31 e Å⁻³
3925 reflections	Δρ_min = −0.19 e Å⁻³
286 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
C1	0.2128 (2)	−0.05764 (17)	0.89657 (11)	0.0263 (4)
C2	0.1004 (2)	−0.17749 (17)	0.84080 (11)	0.0263 (4)
H2	0.0409	−0.2481	0.8743	0.032*
C3	0.0756 (2)	−0.19338 (17)	0.73487 (11)	0.0274 (4)
C4	0.1609 (2)	−0.08588 (18)	0.68651 (12)	0.0295 (4)
H4	0.1465	−0.0964	0.6159	0.035*
C5	0.2676 (2)	0.03761 (17)	0.74101 (12)	0.0267 (4)
C6	0.2947 (2)	0.04896 (17)	0.84640 (12)	0.0274 (4)
H6	0.3694	0.1297	0.8838	0.033*
C7	0.2458 (2)	−0.04026 (18)	1.01134 (12)	0.0297 (4)
C8	−0.0459 (2)	−0.32408 (19)	0.67241 (12)	0.0332 (4)
C9	0.3502 (2)	0.15651 (19)	0.68720 (13)	0.0310 (4)
C10	0.2728 (3)	−0.0067 (2)	1.32738 (13)	0.0391 (5)
H10	0.3430	0.0790	1.3175	0.047*
C11	0.1114 (3)	−0.2190 (2)	1.29964 (14)	0.0432 (5)
H11	0.0505	−0.3063	1.2661	0.052*
C12	0.1222 (3)	−0.1753 (2)	1.39965 (13)	0.0421 (5)
H12	0.0702	−0.2261	1.4484	0.051*
C13	0.2479 (3)	0.3752 (2)	0.99158 (14)	0.0401 (5)
H13	0.2379	0.2876	1.0111	0.048*
C14	0.2247 (3)	0.4896 (2)	1.04845 (14)	0.0396 (5)
H14	0.1949	0.4961	1.1150	0.048*
C15	0.2920 (3)	0.5449 (2)	0.90127 (14)	0.0400 (5)
H15	0.3176	0.5954	0.8480	0.048*
C16	0.3894 (3)	0.4987 (2)	0.58396 (13)	0.0422 (5)
H16A	0.3773	0.5318	0.6539	0.051*
H16B	0.2710	0.4341	0.5557	0.051*
C17	0.5803 (3)	0.3814 (2)	0.47501 (14)	0.0462 (5)
H17A	0.4688	0.3126	0.4428	0.055*
H17B	0.6910	0.3387	0.4747	0.055*
N1	0.2057 (2)	−0.11215 (17)	1.25638 (11)	0.0396 (4)
H1A	0.217 (3)	−0.111 (2)	1.1923 (16)	0.048*
N2	0.2245 (2)	−0.04171 (17)	1.41557 (11)	0.0389 (4)
H2A	0.265 (3)	0.014 (2)	1.4745 (16)	0.047*
N3	0.2891 (2)	0.41179 (16)	0.89917 (12)	0.0374 (4)
H3A	0.320 (3)	0.355 (2)	0.8468 (14)	0.045*
N4	0.2528 (2)	0.59528 (17)	0.99092 (11)	0.0361 (4)
H4A	0.240 (3)	0.686 (2)	1.0107 (14)	0.043*
N5	0.5516 (2)	0.42669 (17)	0.58090 (11)	0.0388 (4)
H5A	0.667 (3)	0.486 (2)	0.6204 (14)	0.047*
H5B	0.520 (3)	0.350 (2)	0.6120 (15)	0.047*
O1	0.3047 (2)	0.07841 (13)	1.05718 (9)	0.0488 (4)
O2	0.21058 (18)	−0.14867 (12)	1.05409 (8)	0.0379 (3)
O3	−0.15144 (18)	−0.40803 (13)	0.71833 (9)	0.0450 (4)
O4	−0.0363 (2)	−0.34118 (16)	0.58017 (9)	0.0617 (5)
O5	0.3573 (2)	0.13542 (13)	0.59351 (9)	0.0436 (3)
O6	0.41142 (19)	0.27435 (12)	0.73950 (9)	0.0415 (3)
O7	0.4407 (2)	0.26393 (16)	1.22724 (10)	0.0498 (4)
H7A	0.407 (3)	0.201 (3)	1.1749 (19)	0.075*
H7B	0.342 (3)	0.306 (3)	1.2364 (18)	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0326 (9)	0.0259 (9)	0.0207 (8)	0.0069 (7)	0.0028 (6)	0.0045 (6)
C2	0.0329 (9)	0.0236 (9)	0.0223 (8)	0.0025 (7)	0.0046 (6)	0.0073 (6)
C3	0.0293 (8)	0.0277 (10)	0.0243 (8)	0.0042 (7)	0.0023 (6)	0.0038 (7)
C4	0.0368 (9)	0.0330 (10)	0.0186 (7)	0.0064 (8)	0.0040 (6)	0.0047 (7)
C5	0.0301 (9)	0.0256 (9)	0.0265 (8)	0.0071 (7)	0.0068 (6)	0.0069 (7)
C6	0.0330 (9)	0.0218 (9)	0.0261 (8)	0.0036 (7)	0.0025 (7)	0.0027 (7)
C7	0.0397 (10)	0.0282 (10)	0.0213 (8)	0.0080 (8)	0.0034 (7)	0.0026 (7)
C8	0.0360 (9)	0.0336 (11)	0.0256 (8)	0.0009 (8)	−0.0006 (7)	0.0013 (7)
C9	0.0357 (9)	0.0301 (10)	0.0307 (9)	0.0095 (8)	0.0088 (7)	0.0103 (7)
C10	0.0498 (11)	0.0398 (12)	0.0308 (9)	0.0124 (9)	0.0099 (8)	0.0090 (8)
C11	0.0501 (11)	0.0425 (12)	0.0332 (10)	0.0025 (9)	0.0019 (8)	0.0040 (9)
C12	0.0477 (11)	0.0478 (13)	0.0322 (10)	0.0064 (10)	0.0094 (8)	0.0140 (9)
C13	0.0473 (11)	0.0327 (11)	0.0427 (10)	0.0080 (9)	0.0089 (8)	0.0128 (9)
C14	0.0465 (11)	0.0394 (12)	0.0352 (10)	0.0105 (9)	0.0087 (8)	0.0086 (8)
C15	0.0500 (11)	0.0342 (12)	0.0376 (10)	0.0081 (9)	0.0112 (8)	0.0097 (8)
C16	0.0441 (11)	0.0506 (13)	0.0269 (9)	−0.0014 (9)	0.0040 (8)	0.0040 (8)
C17	0.0566 (12)	0.0361 (12)	0.0432 (11)	0.0085 (10)	−0.0001 (9)	0.0013 (9)
N1	0.0508 (10)	0.0500 (11)	0.0216 (7)	0.0155 (8)	0.0074 (7)	0.0090 (7)
N2	0.0487 (9)	0.0454 (11)	0.0233 (7)	0.0121 (8)	0.0055 (7)	0.0035 (7)
N3	0.0446 (9)	0.0289 (9)	0.0390 (9)	0.0081 (7)	0.0091 (7)	0.0020 (7)
N4	0.0434 (9)	0.0264 (9)	0.0391 (8)	0.0086 (7)	0.0076 (7)	0.0037 (7)
N5	0.0455 (10)	0.0309 (9)	0.0344 (8)	−0.0067 (8)	−0.0049 (7)	0.0143 (7)
O1	0.0874 (11)	0.0259 (7)	0.0268 (6)	0.0060 (7)	−0.0025 (6)	−0.0047 (5)
O2	0.0642 (9)	0.0285 (7)	0.0213 (6)	0.0072 (6)	0.0072 (5)	0.0076 (5)
O3	0.0521 (8)	0.0360 (8)	0.0371 (7)	−0.0124 (6)	0.0057 (6)	0.0016 (6)
O4	0.0783 (11)	0.0614 (10)	0.0263 (7)	−0.0223 (8)	0.0034 (7)	−0.0059 (6)
O5	0.0648 (9)	0.0375 (8)	0.0297 (7)	0.0058 (6)	0.0163 (6)	0.0107 (5)
O6	0.0592 (8)	0.0252 (7)	0.0393 (7)	0.0009 (6)	0.0146 (6)	0.0079 (6)
O7	0.0637 (10)	0.0433 (9)	0.0349 (7)	−0.0004 (7)	0.0066 (7)	−0.0058 (6)

Geometric parameters (Å, º) top

C1—C6	1.382 (2)	C12—H12	0.9300
C1—C2	1.385 (2)	C13—C14	1.337 (3)
C1—C7	1.513 (2)	C13—N3	1.369 (2)
C2—C3	1.396 (2)	C13—H13	0.9300
C2—H2	0.9300	C14—N4	1.369 (2)
C3—C4	1.382 (2)	C14—H14	0.9300
C3—C8	1.517 (2)	C15—N3	1.317 (2)
C4—C5	1.390 (2)	C15—N4	1.318 (2)
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.391 (2)	C16—N5	1.481 (3)
C5—C9	1.506 (2)	C16—C17ⁱ	1.497 (3)
C6—H6	0.9300	C16—H16A	0.9700
C7—O1	1.236 (2)	C16—H16B	0.9700
C7—O2	1.272 (2)	C17—N5	1.477 (2)
C8—O4	1.233 (2)	C17—C16ⁱ	1.497 (3)
C8—O3	1.265 (2)	C17—H17A	0.9700
C9—O5	1.251 (2)	C17—H17B	0.9700
C9—O6	1.264 (2)	N1—H1A	0.87 (2)
C10—N1	1.307 (2)	N2—H2A	0.90 (2)
C10—N2	1.324 (2)	N3—H3A	0.915 (19)
C10—H10	0.9300	N4—H4A	0.93 (2)
C11—C12	1.345 (3)	N5—H5A	0.98 (2)
C11—N1	1.361 (2)	N5—H5B	0.91 (2)
C11—H11	0.9300	O7—H7A	0.86 (3)
C12—N2	1.365 (2)	O7—H7B	0.90 (3)

C6—C1—C2	119.32 (14)	N3—C13—H13	126.6
C6—C1—C7	119.29 (14)	C13—C14—N4	107.51 (16)
C2—C1—C7	121.39 (15)	C13—C14—H14	126.2
C1—C2—C3	120.66 (15)	N4—C14—H14	126.2
C1—C2—H2	119.7	N3—C15—N4	109.13 (17)
C3—C2—H2	119.7	N3—C15—H15	125.4
C4—C3—C2	118.85 (14)	N4—C15—H15	125.4
C4—C3—C8	119.66 (14)	N5—C16—C17ⁱ	110.90 (16)
C2—C3—C8	121.48 (15)	N5—C16—H16A	109.5
C3—C4—C5	121.49 (14)	C17ⁱ—C16—H16A	109.5
C3—C4—H4	119.3	N5—C16—H16B	109.5
C5—C4—H4	119.3	C17ⁱ—C16—H16B	109.5
C4—C5—C6	118.38 (15)	H16A—C16—H16B	108.0
C4—C5—C9	120.74 (14)	N5—C17—C16ⁱ	111.07 (16)
C6—C5—C9	120.88 (15)	N5—C17—H17A	109.4
C1—C6—C5	121.22 (15)	C16ⁱ—C17—H17A	109.4
C1—C6—H6	119.4	N5—C17—H17B	109.4
C5—C6—H6	119.4	C16ⁱ—C17—H17B	109.4
O1—C7—O2	124.44 (15)	H17A—C17—H17B	108.0
O1—C7—C1	117.75 (16)	C10—N1—C11	108.59 (15)
O2—C7—C1	117.81 (14)	C10—N1—H1A	124.3 (14)
O4—C8—O3	124.28 (16)	C11—N1—H1A	127.1 (14)
O4—C8—C3	117.93 (16)	C10—N2—C12	108.49 (16)
O3—C8—C3	117.79 (14)	C10—N2—H2A	122.6 (13)
O5—C9—O6	122.58 (16)	C12—N2—H2A	128.7 (13)
O5—C9—C5	119.37 (16)	C15—N3—C13	108.45 (16)
O6—C9—C5	118.05 (14)	C15—N3—H3A	125.6 (13)
N1—C10—N2	108.95 (18)	C13—N3—H3A	125.7 (12)
N1—C10—H10	125.5	C15—N4—C14	108.03 (16)
N2—C10—H10	125.5	C15—N4—H4A	126.1 (12)
C12—C11—N1	107.52 (17)	C14—N4—H4A	125.8 (12)
C12—C11—H11	126.2	C17—N5—C16	110.82 (14)
N1—C11—H11	126.2	C17—N5—H5A	113.0 (11)
C11—C12—N2	106.45 (17)	C16—N5—H5A	110.0 (11)
C11—C12—H12	126.8	C17—N5—H5B	108.4 (13)
N2—C12—H12	126.8	C16—N5—H5B	107.1 (13)
C14—C13—N3	106.88 (17)	H5A—N5—H5B	107.3 (16)
C14—C13—H13	126.6	H7A—O7—H7B	108 (2)

C6—C1—C2—C3	2.5 (2)	C4—C3—C8—O3	−166.35 (16)
C7—C1—C2—C3	−178.26 (15)	C2—C3—C8—O3	12.2 (3)
C1—C2—C3—C4	−1.7 (3)	C4—C5—C9—O5	−14.7 (3)
C1—C2—C3—C8	179.66 (15)	C6—C5—C9—O5	165.86 (16)
C2—C3—C4—C5	−1.0 (3)	C4—C5—C9—O6	165.85 (16)
C8—C3—C4—C5	177.65 (15)	C6—C5—C9—O6	−13.6 (2)
C3—C4—C5—C6	2.9 (3)	N1—C11—C12—N2	−0.3 (2)
C3—C4—C5—C9	−176.58 (15)	N3—C13—C14—N4	−0.3 (2)
C2—C1—C6—C5	−0.5 (2)	N2—C10—N1—C11	−0.1 (2)
C7—C1—C6—C5	−179.78 (15)	C12—C11—N1—C10	0.3 (2)
C4—C5—C6—C1	−2.1 (2)	N1—C10—N2—C12	0.0 (2)
C9—C5—C6—C1	177.32 (15)	C11—C12—N2—C10	0.2 (2)
C6—C1—C7—O1	17.1 (2)	N4—C15—N3—C13	−0.5 (2)
C2—C1—C7—O1	−162.20 (16)	C14—C13—N3—C15	0.5 (2)
C6—C1—C7—O2	−163.16 (15)	N3—C15—N4—C14	0.3 (2)
C2—C1—C7—O2	17.6 (2)	C13—C14—N4—C15	0.0 (2)
C4—C3—C8—O4	13.2 (3)	C16ⁱ—C17—N5—C16	56.2 (2)
C2—C3—C8—O4	−168.22 (17)	C17ⁱ—C16—N5—C17	−56.1 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.87 (2)	1.83 (2)	2.6870 (18)	166.9 (19)
N2—H2A···O5ⁱⁱ	0.90 (2)	1.86 (2)	2.7522 (19)	177.4 (19)
N3—H3A···O6	0.915 (19)	1.80 (2)	2.701 (2)	168.8 (18)
N4—H4A···O2ⁱⁱⁱ	0.93 (2)	1.74 (2)	2.668 (2)	176.6 (18)
N5—H5A···O3^iv	0.98 (2)	1.83 (2)	2.7872 (19)	166.7 (17)
N5—H5A···O4^iv	0.98 (2)	2.60 (2)	3.366 (2)	135.7 (14)
N5—H5B···O5	0.91 (2)	2.19 (2)	2.985 (2)	145.2 (16)
N5—H5B···O6	0.91 (2)	2.10 (2)	2.888 (2)	145.1 (18)
O7—H7A···O1	0.86 (3)	1.86 (3)	2.7184 (17)	171 (2)
O7—H7B···O3^v	0.90 (3)	1.95 (3)	2.840 (2)	169 (2)
C10—H10···O7	0.93	2.35	3.217 (3)	156
C12—H12···O4ⁱⁱ	0.93	2.32	3.244 (2)	175
C13—H13···O1	0.93	2.36	3.267 (2)	164
C14—H14···O3^v	0.93	2.51	3.372 (2)	154
C15—H15···O7^vi	0.93	2.38	3.186 (2)	145
C16—H16B···O4^vii	0.97	2.32	3.200 (2)	150
C16—H16A···O7^vi	0.97	2.48	3.207 (2)	132

Symmetry codes: (ii) x, y, z+1; (iii) x, y+1, z; (iv) x+1, y+1, z; (v) −x, −y, −z+2; (vi) −x+1, −y+1, −z+2; (vii) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	4C₃H₅N₂⁺·C₄H₁₂N₂⁺·2C₉H₃O₆³⁻·2H₂O
M_r	814.78
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.1548 (4), 9.9424 (5), 13.3567 (7)
α, β, γ (°)	96.895 (1), 95.201 (1), 101.439 (2)
V (Å³)	918.11 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.20 × 0.13 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.967, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	10341, 3925, 2757
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.122, 1.04
No. of reflections	3925
No. of parameters	286
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.19

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), PLATON (Spek, 2009).