Piperazine-1,4-diium bis­(2,4,5-tricarb­oxy­benzoate) dihydrate

Narayanam, N.; Gangu, K.K.; Kurra, B.; Mukkamala, S.B.

doi:10.1107/S160053681300723X

organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Pages o574-o575

doi:10.1107/S160053681300723X

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Piperazine-1,4-diium bis(2,4,5-tricarboxybenzoate) dihydrate

Nagaraju Narayanam,^a Kranthi Kumar Gangu,^a Balakrishna Kurra ^a and Saratchandra Babu Mukkamala ^a ^*

^aDepartment of Chemistry, GITAM University, Visakhapatnam 530 045, Andhra Pradesh, India
^*Correspondence e-mail: mscbabu@yahoo.com

(Received 26 January 2013; accepted 16 March 2013; online 23 March 2013)

In the title hydrated salt, C₄H₁₂N₂²⁺·2C₁₀H₅O₈⁻·2H₂O, the piperazinediium cation, lying about an inversion center, adopts a chair conformation. The benzene ring of the anion makes dihedral angles of 25.17 (8)° with the carboxylate group and angles of 8.50 (7), 20.07 (7) and 80.86 (8)° with the three carboxylic acid groups. In the crystal, the cations, anions and water molecules are connected by O—H⋯O and N—H⋯O hydrogen bonds into double layers parallel to (110).

Related literature

For supramolecular architectures involving benzene-1,2,4,5-tetracarboxylic acid and its anions, see: Aghabozorg et al. (2006 , 2008 ); Chiwei et al. (2005 ); Pasban et al. (2012 ); Pasdar et al. (2010 ); Smith et al. (2008 ); Smith & Wermuth (2010 ); Vaidhyanathan et al. (2002 ). For proton-transfer systems, see: Aghabozorg et al. (2010 ). For intermolecular interactions, see: Janiak (2000 ).

Experimental

Crystal data

C₄H₁₂N₂²⁺·2C₁₀H₅O₈⁻·2H₂O
M_r = 630.46
Triclinic, $[P \overline 1]$
a = 8.2521 (2) Å
b = 8.4810 (2) Å
c = 9.6369 (2) Å
α = 87.117 (5)°
β = 89.527 (5)°
γ = 70.962 (4)°
V = 636.73 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.945, T_max = 0.985
11108 measured reflections
2234 independent reflections
2061 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.085
S = 1.06
2234 reflections
224 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O8	0.82	1.63	2.4225 (15)	161
O3—H3⋯O7ⁱ	0.82	1.80	2.6100 (13)	167
O6—H6⋯O2ⁱⁱ	0.82	1.78	2.5884 (13)	170
N1—H1A⋯O9ⁱⁱⁱ	0.90 (2)	1.83 (2)	2.7283 (17)	176 (2)
N1—H1B⋯O5^iv	0.90 (2)	1.94 (2)	2.7420 (16)	147 (2)
O9—H9A⋯O8^v	0.86 (2)	2.14 (2)	2.9904 (18)	174 (3)
O9—H9B⋯O7	0.82 (2)	2.18 (2)	2.9799 (19)	163 (3)
Symmetry codes: (i) x, y, z-1; (ii) x+1, y-1, z; (iii) -x+1, -y, -z+1; (iv) x, y, z+1; (v) -x, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and DIAMOND (Brandenburg, 2007 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681300723X/yk2086sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681300723X/yk2086Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681300723X/yk2086Isup3.cml

checkCIF report

Comment top

Benzene-1,2,4,5-tetracarboxylic acid (H4btc) with its ability to donate four protons is a versatile ligand in building supramolecular architectures and proton transfer compounds with nitrogen containing organic amines such as piperazine (Aghabozorg et al., 2008; Vaidhyanathan et al., 2002) and diethylenetriamine (Pasban et al., 2012). A number of proton transfer compounds and supramolecular architectures were reported earlier with H4btc and other organic bases such as 1,10- phenanthroline (Chiwei et al., 2005) and propane-1,2-diammonium (Pasdar et al., 2010). These proton transfer compounds have the ability to absorb various metals into their crystal lattices (Aghabozorg et al., 2006) with profound applications in metal separation and storage (Aghabozorg et al., 2010; Smith et al., 2008; Smith & Wermuth, 2010).

We report here one such proton transfer compound, piperazinediium bis(benzene-1,2,4,5-tetracarboxylate) dihydrate. As shown in Fig. 1, the asymmetric unit contain one mono-deprotonated residue of benzene-1,2,4,5-tetracaboxylic acid (H3btc^-), a half of diprotonated piperazine (pipz) and one water molecule. Layered 2D supramolecular structure of title compound was built by connecting H3btc^-, pipz and water molecules through hydrogen bonding (Fig.2). Inter- and intramolecular hydrogen bonding was observed between H3btc- molecular species through O–H···O hydrogen bonds. Piperazinediium cations and water molecules are involved in building this supramolecular structure through N–H···O and O–H···O bonds. Besides hydrogen bonding, the weak aromatic π-π stacking interactions between aromatic rings of H3btc- molecules could contribute for further stabilization of this layered supramolecular crystal structure. As shown in Fig. 3, the π-π stacking interactions between H3btc- (intercentroid separation of 3.7954 Å) were found to be in agreement with the reported values (Janiak, 2000). The packing diagram of the title compound is shown in Fig.4.

Related literature top

For supramolecular architectures involving benzene-1,2,4,5-tetracarboxylic acid and its anions, see: Aghabozorg et al. (2006, 2008); Chiwei et al. (2005); Pasban et al. (2012); Pasdar et al. (2010); Smith et al. (2008); Smith & Wermuth (2010); Vaidhyanathan et al. (2002). For proton-transfer systems, see: Aghabozorg et al. (2010); For intermolecular interactions, see: Janiak (2000).

Experimental top

0.2974 g (1.0 mmol) of Zn(NO3)2.6H2O, 0.1270 g (0.5 mmol) of 1,2,4,5-benzenetetracarboxylic acid, 0.2583 g (3 mmol) of piperazine and 0.2 mL (4 mmol) of sulfuric acid were dissolved in 10.0 mL distilled water and heated in a stainless steel Teflon-lined autoclave at 120°C for 24 hours. The mixture was cooled to room temperature at a cooling rate of 6 °/min. Colorless cubic shaped crystals were obtained from the reaction mixture. Yield: 68% (based on H4btc). IR (KBr): 3473.27 (s), 3033.5 (w), 2548 (m), 1707 (s), 1621(s), 1475 (m), 734 (s), 596(s), 471(s).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and DIAMOND (Brandenburg, 2007).

Figures top

	Fig. 1. The view of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A perspective view of hydrogen bonding interactions represented by dashed lines. Insent: 2D supramolecular representation along c axis.
	Fig. 3. π-π stacking interactions between benzene-1,2,4,5-tetracarboxylates. Cations, water molecules and hydrogen atoms are omitted for clarity.
	Fig. 4. Crystal packing viewed along a axis. Hydrogen atoms are omitted for clarity.

Piperazine-1,4-diium bis(2,4,5-tricarboxybenzoate) dihydrate top

Crystal data top

C₄H₁₂N₂²⁺·2C₁₀H₅O₈⁻·2H₂O	Z = 1
M_r = 630.46	F(000) = 328
Triclinic, P1	D_x = 1.644 Mg m⁻³
Hall symbol: -P 1	Melting point: 560 K
a = 8.2521 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.4810 (2) Å	Cell parameters from 7490 reflections
c = 9.6369 (2) Å	θ = 2.5–33.0°
α = 87.117 (5)°	µ = 0.14 mm⁻¹
β = 89.527 (5)°	T = 293 K
γ = 70.962 (4)°	Block, colourless
V = 636.73 (3) Å³	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2234 independent reflections
Radiation source: fine-focus sealed tube	2061 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and ϕ scan	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
T_min = 0.945, T_max = 0.985	k = −9→10
11108 measured reflections	l = −11→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0431P)² + 0.2345P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2234 reflections	Δρ_max = 0.21 e Å⁻³
224 parameters	Δρ_min = −0.20 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.075 (5)

Crystal data top

C₄H₁₂N₂²⁺·2C₁₀H₅O₈⁻·2H₂O	γ = 70.962 (4)°
M_r = 630.46	V = 636.73 (3) Å³
Triclinic, P1	Z = 1
a = 8.2521 (2) Å	Mo Kα radiation
b = 8.4810 (2) Å	µ = 0.14 mm⁻¹
c = 9.6369 (2) Å	T = 293 K
α = 87.117 (5)°	0.30 × 0.20 × 0.20 mm
β = 89.527 (5)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2234 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2061 reflections with I > 2σ(I)
T_min = 0.945, T_max = 0.985	R_int = 0.028
11108 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	4 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.21 e Å⁻³
2234 reflections	Δρ_min = −0.20 e Å⁻³
224 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	0.06597 (16)	0.70913 (15)	0.05612 (13)	0.0202 (3)
C2	0.08629 (16)	0.66166 (16)	−0.08067 (13)	0.0219 (3)
H2	0.0098	0.7264	−0.1480	0.026*
C3	0.21641 (16)	0.52142 (16)	−0.12023 (13)	0.0196 (3)
C4	0.32899 (16)	0.42177 (15)	−0.01920 (13)	0.0198 (3)
C5	0.30804 (16)	0.46709 (16)	0.11737 (13)	0.0212 (3)
H5	0.3824	0.3995	0.1846	0.025*
C6	0.18074 (16)	0.60918 (16)	0.15847 (13)	0.0200 (3)
C7	0.22375 (16)	0.47981 (16)	−0.27035 (13)	0.0217 (3)
C8	0.47247 (16)	0.27185 (16)	−0.05880 (13)	0.0217 (3)
C9	0.18506 (17)	0.63946 (17)	0.31156 (14)	0.0241 (3)
C10	−0.08355 (17)	0.86608 (16)	0.07812 (14)	0.0244 (3)
C11	0.5751 (2)	0.1289 (2)	0.4758 (2)	0.0448 (4)
H11A	0.6750	0.1621	0.4555	0.054*
H11B	0.4771	0.2293	0.4836	0.054*
C12	0.5451 (2)	0.0307 (2)	0.36090 (17)	0.0436 (4)
N1	0.60207 (17)	0.02802 (17)	0.60844 (14)	0.0371 (3)
O1	−0.08934 (13)	0.95103 (12)	0.18574 (11)	0.0337 (3)
H1	−0.0039	0.9062	0.2342	0.051*
O2	−0.19676 (13)	0.91343 (13)	−0.01098 (11)	0.0368 (3)
O3	0.29608 (14)	0.56784 (13)	−0.34862 (10)	0.0327 (3)
H3	0.2974	0.5411	−0.4293	0.049*
O4	0.16086 (14)	0.38163 (14)	−0.31255 (10)	0.0348 (3)
O5	0.50699 (13)	0.24168 (13)	−0.17891 (10)	0.0337 (3)
O6	0.55721 (13)	0.18159 (13)	0.04674 (10)	0.0373 (3)
H6	0.6341	0.1014	0.0187	0.056*
O7	0.25414 (14)	0.51726 (13)	0.39115 (10)	0.0359 (3)
O8	0.12443 (14)	0.78708 (13)	0.35313 (10)	0.0339 (3)
O9	0.10687 (16)	0.23958 (16)	0.41278 (14)	0.0453 (3)
H12B	0.646 (3)	−0.068 (3)	0.352 (2)	0.051 (5)*
H12A	0.518 (3)	0.099 (3)	0.276 (2)	0.061 (6)*
H1A	0.700 (2)	−0.060 (2)	0.605 (2)	0.046 (5)*
H1B	0.615 (3)	0.092 (3)	0.677 (2)	0.064 (6)*
H9A	0.043 (3)	0.224 (4)	0.479 (2)	0.097 (10)*
H9B	0.135 (4)	0.323 (3)	0.421 (3)	0.106 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0199 (6)	0.0181 (6)	0.0217 (7)	−0.0048 (5)	0.0028 (5)	−0.0015 (5)
C2	0.0211 (6)	0.0216 (6)	0.0193 (6)	−0.0023 (5)	−0.0020 (5)	0.0016 (5)
C3	0.0203 (6)	0.0203 (6)	0.0177 (6)	−0.0061 (5)	0.0017 (5)	−0.0012 (5)
C4	0.0192 (6)	0.0200 (6)	0.0188 (6)	−0.0042 (5)	0.0012 (5)	−0.0016 (5)
C5	0.0216 (6)	0.0216 (6)	0.0172 (6)	−0.0029 (5)	−0.0011 (5)	0.0006 (5)
C6	0.0209 (6)	0.0211 (6)	0.0175 (6)	−0.0062 (5)	0.0021 (5)	−0.0021 (5)
C7	0.0194 (6)	0.0222 (7)	0.0192 (6)	−0.0010 (5)	−0.0010 (5)	−0.0009 (5)
C8	0.0211 (6)	0.0216 (7)	0.0204 (7)	−0.0039 (5)	−0.0003 (5)	−0.0029 (5)
C9	0.0229 (7)	0.0286 (7)	0.0200 (7)	−0.0067 (5)	0.0033 (5)	−0.0047 (5)
C10	0.0233 (7)	0.0205 (7)	0.0262 (7)	−0.0030 (5)	0.0047 (6)	−0.0002 (5)
C11	0.0417 (9)	0.0311 (8)	0.0642 (12)	−0.0163 (7)	−0.0010 (8)	0.0049 (8)
C12	0.0459 (10)	0.0509 (10)	0.0267 (8)	−0.0069 (8)	0.0089 (7)	0.0058 (7)
N1	0.0346 (7)	0.0356 (7)	0.0356 (7)	−0.0016 (6)	−0.0049 (6)	−0.0169 (6)
O1	0.0353 (6)	0.0245 (5)	0.0334 (6)	0.0025 (4)	0.0003 (4)	−0.0098 (4)
O2	0.0298 (6)	0.0326 (6)	0.0350 (6)	0.0084 (4)	−0.0040 (5)	−0.0059 (5)
O3	0.0481 (6)	0.0378 (6)	0.0168 (5)	−0.0202 (5)	0.0040 (4)	−0.0023 (4)
O4	0.0428 (6)	0.0422 (6)	0.0262 (5)	−0.0221 (5)	0.0022 (4)	−0.0100 (4)
O5	0.0354 (6)	0.0339 (6)	0.0210 (5)	0.0042 (4)	0.0023 (4)	−0.0086 (4)
O6	0.0347 (6)	0.0350 (6)	0.0230 (5)	0.0147 (4)	−0.0001 (4)	−0.0012 (4)
O7	0.0478 (7)	0.0342 (6)	0.0168 (5)	−0.0008 (5)	−0.0016 (4)	−0.0016 (4)
O8	0.0418 (6)	0.0303 (6)	0.0258 (5)	−0.0049 (5)	−0.0001 (4)	−0.0127 (4)
O9	0.0401 (7)	0.0411 (7)	0.0463 (8)	−0.0006 (6)	−0.0027 (6)	−0.0112 (6)

Geometric parameters (Å, º) top

C1—C2	1.3906 (18)	C10—O2	1.2269 (17)
C1—C6	1.4127 (18)	C10—O1	1.2841 (17)
C1—C10	1.5138 (17)	C11—N1	1.479 (2)
C2—C3	1.3851 (18)	C11—C12	1.487 (3)
C2—H2	0.9300	C11—H11A	0.9700
C3—C4	1.3947 (18)	C11—H11B	0.9700
C3—C7	1.5024 (17)	C12—N1ⁱ	1.478 (2)
C4—C5	1.3833 (18)	C12—H12B	0.98 (2)
C4—C8	1.4911 (17)	C12—H12A	0.96 (2)
C5—C6	1.3885 (18)	N1—C12ⁱ	1.478 (2)
C5—H5	0.9300	N1—H1A	0.904 (15)
C6—C9	1.5129 (18)	N1—H1B	0.901 (16)
C7—O4	1.2031 (17)	O1—H1	0.8200
C7—O3	1.3074 (16)	O3—H3	0.8200
C8—O5	1.2096 (16)	O6—H6	0.8200
C8—O6	1.3014 (16)	O9—H9A	0.858 (17)
C9—O7	1.2367 (17)	O9—H9B	0.824 (18)
C9—O8	1.2715 (17)

C2—C1—C6	118.71 (11)	O8—C9—C6	119.92 (12)
C2—C1—C10	114.30 (11)	O2—C10—O1	120.53 (12)
C6—C1—C10	126.99 (12)	O2—C10—C1	118.69 (12)
C3—C2—C1	122.32 (12)	O1—C10—C1	120.74 (12)
C3—C2—H2	118.8	N1—C11—C12	110.21 (13)
C1—C2—H2	118.8	N1—C11—H11A	109.6
C2—C3—C4	119.08 (12)	C12—C11—H11A	109.6
C2—C3—C7	117.76 (11)	N1—C11—H11B	109.6
C4—C3—C7	123.09 (11)	C12—C11—H11B	109.6
C5—C4—C3	118.88 (11)	H11A—C11—H11B	108.1
C5—C4—C8	120.72 (11)	N1ⁱ—C12—C11	110.90 (13)
C3—C4—C8	120.38 (11)	N1ⁱ—C12—H12B	107.1 (11)
C4—C5—C6	122.85 (12)	C11—C12—H12B	109.1 (12)
C4—C5—H5	118.6	N1ⁱ—C12—H12A	106.8 (12)
C6—C5—H5	118.6	C11—C12—H12A	110.4 (13)
C5—C6—C1	118.16 (11)	H12B—C12—H12A	112.5 (17)
C5—C6—C9	114.29 (11)	C12ⁱ—N1—C11	110.89 (13)
C1—C6—C9	127.54 (11)	C12ⁱ—N1—H1A	110.4 (12)
O4—C7—O3	124.71 (12)	C11—N1—H1A	110.1 (12)
O4—C7—C3	122.38 (12)	C12ⁱ—N1—H1B	109.9 (14)
O3—C7—C3	112.81 (11)	C11—N1—H1B	108.3 (14)
O5—C8—O6	124.18 (12)	H1A—N1—H1B	107.1 (19)
O5—C8—C4	121.94 (12)	C10—O1—H1	109.5
O6—C8—C4	113.86 (11)	C7—O3—H3	109.5
O7—C9—O8	122.61 (12)	C8—O6—H6	109.5
O7—C9—C6	117.42 (11)	H9A—O9—H9B	112 (3)

C6—C1—C2—C3	−0.96 (19)	C4—C3—C7—O4	81.46 (17)
C10—C1—C2—C3	179.89 (12)	C2—C3—C7—O3	80.87 (15)
C1—C2—C3—C4	1.5 (2)	C4—C3—C7—O3	−102.12 (14)
C1—C2—C3—C7	178.63 (12)	C5—C4—C8—O5	−170.29 (13)
C2—C3—C4—C5	−0.59 (19)	C3—C4—C8—O5	7.9 (2)
C7—C3—C4—C5	−177.56 (12)	C5—C4—C8—O6	8.07 (18)
C2—C3—C4—C8	−178.79 (11)	C3—C4—C8—O6	−173.75 (12)
C7—C3—C4—C8	4.23 (19)	C5—C6—C9—O7	−24.00 (18)
C3—C4—C5—C6	−0.9 (2)	C1—C6—C9—O7	157.18 (13)
C8—C4—C5—C6	177.35 (12)	C5—C6—C9—O8	153.59 (13)
C4—C5—C6—C1	1.4 (2)	C1—C6—C9—O8	−25.2 (2)
C4—C5—C6—C9	−177.56 (12)	C2—C1—C10—O2	18.28 (18)
C2—C1—C6—C5	−0.46 (18)	C6—C1—C10—O2	−160.79 (13)
C10—C1—C6—C5	178.57 (12)	C2—C1—C10—O1	−159.58 (12)
C2—C1—C6—C9	178.31 (12)	C6—C1—C10—O1	21.4 (2)
C10—C1—C6—C9	−2.7 (2)	N1—C11—C12—N1ⁱ	56.82 (19)
C2—C3—C7—O4	−95.55 (16)	C12—C11—N1—C12ⁱ	−56.81 (19)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O8	0.82	1.63	2.4225 (15)	161
O3—H3···O7ⁱⁱ	0.82	1.80	2.6100 (13)	167
O6—H6···O2ⁱⁱⁱ	0.82	1.78	2.5884 (13)	170
N1—H1A···O9ⁱ	0.90 (2)	1.83 (2)	2.7283 (17)	176 (2)
N1—H1B···O5^iv	0.90 (2)	1.94 (2)	2.7420 (16)	147 (2)
O9—H9A···O8^v	0.86 (2)	2.14 (2)	2.9904 (18)	174 (3)
O9—H9B···O7	0.82 (2)	2.18 (2)	2.9799 (19)	163 (3)

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

Experimental details

Crystal data
Chemical formula	C₄H₁₂N₂²⁺·2C₁₀H₅O₈⁻·2H₂O
M_r	630.46
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.2521 (2), 8.4810 (2), 9.6369 (2)
α, β, γ (°)	87.117 (5), 89.527 (5), 70.962 (4)
V (Å³)	636.73 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.945, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	11108, 2234, 2061
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.085, 1.06
No. of reflections	2234
No. of parameters	224
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SIR92 (Altomare et al., 1993), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and DIAMOND (Brandenburg, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O8	0.82	1.63	2.4225 (15)	161
O3—H3···O7ⁱ	0.82	1.80	2.6100 (13)	167
O6—H6···O2ⁱⁱ	0.82	1.78	2.5884 (13)	170
N1—H1A···O9ⁱⁱⁱ	0.904 (15)	1.825 (15)	2.7283 (17)	175.9 (18)
N1—H1B···O5^iv	0.901 (16)	1.941 (18)	2.7420 (16)	147 (2)
O9—H9A···O8^v	0.858 (17)	2.135 (18)	2.9904 (18)	174 (3)
O9—H9B···O7	0.824 (18)	2.182 (19)	2.9799 (19)	163 (3)

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

Acknowledgements

The authors are thankful for financial support from the Department of Science and Technology through the Nanomission project (SR/S5/NM-92/2006) and are also grateful to the Sophisticated Analytical Instrumentation Facility (SAIF), IIT-Madras, Chennai, for the data collection.

References

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