Bis(piperazinediium) benzene-1,2,4,5-tetra­carboxyl­ate hexa­hydrate

Aghabozorg, H.; Manteghi, F.; Ghadermazi, M.

doi:10.1107/S1600536808007332

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o740

doi:10.1107/S1600536808007332

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Bis(piperazinediium) benzene-1,2,4,5-tetracarboxylate hexahydrate

Hossein Aghabozorg,^a ^* Faranak Manteghi ^a and Mohammad Ghadermazi ^b

^aFaculty of Chemistry, Tarbiat Moallem University, 49 Mofateh Ave., Tehran, Iran, and ^bDepartment of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, Iran
^*Correspondence e-mail: haghabozorg@yahoo.com

(Received 6 August 2007; accepted 17 March 2008; online 29 March 2008)

The title compound, 2C₄H₁₂N₂²⁺·C₁₀H₂O₈⁴⁻·6H₂O or (pipzH₂)₂(btc)·6H₂O, was formed from the reaction between benzene-1,2,4,5-tetracarboxylic acid (btcH₄) as a proton donor and piperazine (pipz) as a proton acceptor. A variety of O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, as well as C—H⋯π interactions, are present in the crystal structure. Two water O atoms are each disordered over two positions; for both the site occupany factors are ca 0.66 and 0.34.

Related literature

For related literature, see: Aghabozorg et al. (2006 , 2007 ); Arora & Pedireddi (2003 ); Biradha & Zaworotko (1998 ).

Experimental

Crystal data

2C₄H₁₂N₂²⁺·C₁₀H₂O₈⁴⁻·6H₂O
M_r = 534.52
Triclinic, $[P \overline 1]$
a = 6.7420 (4) Å
b = 12.4636 (7) Å
c = 16.0100 (9) Å
α = 99.0920 (10)°
β = 90.3470 (10)°
γ = 105.5280 (10)°
V = 1278.27 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 (2) K
0.23 × 0.21 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.970, T_max = 0.982
13995 measured reflections
5839 independent reflections
4805 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.159
S = 1.02
5839 reflections
323 parameters
H-atom parameters constrained
Δρ_max = 2.20 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O5ⁱ	0.92	1.74	2.642 (2)	166
N1—H1D⋯O7ⁱⁱ	0.92	1.84	2.763 (2)	178
N2—H2C⋯O1ⁱⁱⁱ	0.92	1.82	2.723 (2)	165
N2—H2D⋯O4	0.92	1.72	2.635 (2)	179
N3—H3C⋯O2ⁱⁱⁱ	0.92	1.90	2.787 (2)	163
N3—H3D⋯O6	0.92	1.92	2.690 (2)	141
N4—H4C⋯O8^iv	0.92	1.85	2.753 (2)	168
N4—H4D⋯O3	0.92	2.00	2.748 (2)	138
O1S—H1SA⋯O5SA	0.82	2.02	2.837 (2)	172
O1S—H1SA⋯O5SA	0.82	2.02	2.837 (2)	172
O1S—H1SB⋯O2^v	0.82	1.95	2.763 (2)	172
O2S—H2SA⋯O4Sⁱⁱⁱ	0.82	2.04	2.839 (2)	165
O2S—H2SB⋯O8^vi	0.82	2.05	2.835 (2)	160
O3S—H3SA⋯O2S	0.82	1.90	2.722 (2)	176
O3S—H3SB⋯O5ⁱⁱ	0.82	2.00	2.817 (2)	171
O4S—H4SA⋯O1	0.82	1.95	2.772 (2)	175
O4S—H4SB⋯O3S	0.82	1.95	2.764 (2)	170
C5—H5A⋯O6SA	0.99	2.50	3.288 (4)	136
C5—H5B⋯O7^iv	0.99	2.35	3.272 (3)	154
C7—H7A⋯O1ⁱⁱⁱ	0.99	2.48	3.414 (3)	156
C8—H8B⋯O4Sⁱⁱⁱ	0.99	2.51	3.299 (3)	137
C4—H4B⋯Cg1ⁱⁱ	0.99	2.64	3.518 (2)	148
C4—H4B⋯Cg1^vi	0.99	2.64	3.518 (2)	148
Symmetry codes: (i) x-1, y-1, z; (ii) x, y-1, z; (iii) x-1, y, z; (iv) x+1, y, z; (v) -x+2, -y+1, -z+1; (vi) -x, -y+1, -z+1. Cg1 is the centroid of the C14,C15,C16,C14′,C15′,C16′ benzene ring.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808007332/bt2674sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808007332/bt2674Isup2.hkl

checkCIF report

Comment top

Continuing the path to synthesize proton transfer compounds, our team works have recently been focused on forming ion pairs between benzene-1,2,4,5-tetracarboxylic acid and various organic bases such as propane-1,3-diamine (Aghabozorg et al., 2007) and 1,10-phenanthroline (Aghabozorg et al., 2006). Due to its flat and symmetric structure and four proton donor sites, benzene-1,2,4,5-tetracarboxylic acid has a potential of constructing a supramolecular network. Supramolecular assemblies of 1,2,4,5-benzenetetracarboxylic acid, with aza donor molecules such as 1,10-phenanthroline, 1,7-phenanthroline, phenazine, 4-(N,N-dimethylamino)pyridine, 1,2-bis(4-pyridyl)ethene, and 1,2-bis(4- pyridyl)ethane have been synthesized and characterized by single-crystal X-ray diffraction methods (Arora et al., 2003). Among the known structures, cyclic network mediated supramolecular assemblies of benzene-1,2,4,5-tetracarboxylic acid with pyridine and some of its derivatives is quite significant (Biradha et al., 1998). The title compound has a structure constituted of one fully deprotonated benzene-1,2,4,5-tetracarboxylic acid unit, two doubly protonated piperazine units and six water molecules, two of which are disordered.

Various hydrogen bonds are formed between the named fragments, the water molecules are hydrogen bonded to each other and to carboxylate groups by O—H···O bonds, piperazinium ions are linked to carboxylate groups by N—H···O bonds, also the carbon atoms of piperaziniedium ion have C—H···O hydrogen bonds to oxygen atoms of water molecules and carboxyl groups. It is notable that the shortest hydrogen bond N2—H2D···O4 has the least deviation i.e. 1° from linearity. As shown in Fig. 2, in the cell packing there are six water molecules surrounded by cationic and anionic fragments. So if the structure expanded and the layers appeared, it can be seen a channel in which water molecules are trapped. This is previously observed for ion pairs of the tetraacid (Arora et al., 2003), in which the three-dimensional arrangement of the layers are stacked such that the cavities align to yield channels. It appears that the size and direction of water molecules plays an important role in constructing of channel structures in the supramolecular assemblies of acid.

As shown in Fig. 3, there are C—H···π interactions between C4—H4B bond of piperazinium ion and two benzene rings containing C14, C15 and C16 atoms with different symmetry codes [(x, y - 1, z), (-x, -y + 1, 1 - z)] for which the C—H···π distance and angle are 3.518 (2) Å and 148°, respectively.

Finally in Fig. 4, it can be seen how ribbons of constituents of the compound are arranged.

Related literature top

For related literature, see: Aghabozorg et al. (2006,2007); Arora & Pedireddi (2003); Biradha & Zaworotko (1998).

Experimental top

For synthesizing the title compoud, a solution of 2540 mg (10 mmol) benzene-1,2,4,5-tetracarboxylic acid in 10 ml tetrahydrofuran and another solution of 860 mg (10 mmol) of piperazine in 10 ml of the same solvent were prepared and mixed. By heating, a white precipitate was obtained. The colorless prisms of the compound were obtained by recrystallization from water solution.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the ion pair (C₄H₁₂N₂)₂⁴⁺(C₁₀H₂O₈)^4-.6H₂O. Displacement ellipsoids are drawn at 50% probability level.
	Fig. 2. Unit cell packing of the title compound, hydrogen bonds are shown as dashed lines and disordered atoms are omitted.
	Fig. 3. The C—H···π interaction between C4—H4B and benzene ring, distance from the H atom to the ring centroid is drawn as a dashed line.
	Fig. 4. Crystal packing of the title compound, Anions, cations and water molecules are shown in different colours.

Bis(piperazinediium) benzene-1,2,4,5-tetracarboxylate hexahydrate top

Crystal data top

2C₄H₁₂N₂²⁺·C₁₀H₂O₈⁴⁻·6H₂O	Z = 2
M_r = 534.52	F(000) = 572
Triclinic, P1	D_x = 1.389 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7420 (4) Å	Cell parameters from 614 reflections
b = 12.4636 (7) Å	θ = 3–29°
c = 16.0100 (9) Å	µ = 0.12 mm⁻¹
α = 99.092 (1)°	T = 100 K
β = 90.347 (1)°	Prism, colorless
γ = 105.528 (1)°	0.23 × 0.21 × 0.17 mm
V = 1278.27 (13) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	5839 independent reflections
Radiation source: fine-focus sealed tube	4805 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.970, T_max = 0.982	k = −16→16
13995 measured reflections	l = −20→20

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)] = 0.059	Hydrogen site location: mixed
wR(F²) = 0.159	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.07P)² + 2P] where P = (F_o² + 2F_c²)/3
5839 reflections	(Δ/σ)_max < 0.001
323 parameters	Δρ_max = 2.20 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

2C₄H₁₂N₂²⁺·C₁₀H₂O₈⁴⁻·6H₂O	γ = 105.528 (1)°
M_r = 534.52	V = 1278.27 (13) Å³
Triclinic, P1	Z = 2
a = 6.7420 (4) Å	Mo Kα radiation
b = 12.4636 (7) Å	µ = 0.12 mm⁻¹
c = 16.0100 (9) Å	T = 100 K
α = 99.092 (1)°	0.23 × 0.21 × 0.17 mm
β = 90.347 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	5839 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4805 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.982	R_int = 0.027
13995 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 1.02	Δρ_max = 2.20 e Å⁻³
5839 reflections	Δρ_min = −0.60 e Å⁻³
323 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	Occ. (<1)
N1	−0.1642 (3)	0.13752 (14)	0.70314 (11)	0.0148 (4)
H1C	−0.2812	0.1173	0.6680	0.018*
H1D	−0.1227	0.0735	0.7058	0.018*
N2	0.1462 (3)	0.30353 (14)	0.81088 (11)	0.0141 (3)
H2C	0.1056	0.3677	0.8077	0.017*
H2D	0.2632	0.3239	0.8460	0.017*
C1	−0.2126 (3)	0.18509 (18)	0.78933 (14)	0.0179 (4)
H1A	−0.3195	0.1274	0.8122	0.022*
H1B	−0.2674	0.2506	0.7862	0.022*
C2	−0.0202 (3)	0.22196 (18)	0.84771 (13)	0.0163 (4)
H2A	−0.0515	0.2580	0.9039	0.020*
H2B	0.0267	0.1552	0.8555	0.020*
C3	0.1944 (3)	0.25478 (18)	0.72488 (13)	0.0158 (4)
H3A	0.2459	0.1882	0.7282	0.019*
H3B	0.3032	0.3114	0.7018	0.019*
C4	0.0012 (3)	0.22030 (17)	0.66729 (13)	0.0150 (4)
H4A	−0.0454	0.2877	0.6615	0.018*
H4B	0.0312	0.1860	0.6103	0.018*
N3	0.3335 (3)	0.76396 (16)	0.71554 (12)	0.0178 (4)
H3C	0.2266	0.7216	0.7419	0.021*
H3D	0.2885	0.8194	0.6960	0.021*
N4	0.6573 (3)	0.65653 (16)	0.73462 (11)	0.0171 (4)
H4C	0.7631	0.6995	0.7082	0.021*
H4D	0.7039	0.6016	0.7541	0.021*
C5	0.5109 (3)	0.81764 (19)	0.77813 (14)	0.0194 (4)
H5A	0.4648	0.8619	0.8274	0.023*
H5B	0.6199	0.8701	0.7517	0.023*
C6	0.5976 (3)	0.7297 (2)	0.80781 (14)	0.0201 (4)
H6A	0.7200	0.7675	0.8465	0.024*
H6B	0.4933	0.6823	0.8396	0.024*
C7	0.4797 (3)	0.60208 (18)	0.67239 (14)	0.0185 (4)
H7A	0.3712	0.5496	0.6991	0.022*
H7B	0.5257	0.5577	0.6232	0.022*
C8	0.3916 (3)	0.69016 (19)	0.64249 (14)	0.0185 (4)
H8A	0.4950	0.7371	0.6101	0.022*
H8B	0.2684	0.6521	0.6043	0.022*
O1	1.0470 (2)	0.48871 (13)	0.77274 (9)	0.0169 (3)
O2	1.0471 (2)	0.66537 (12)	0.82508 (9)	0.0148 (3)
O3	0.6122 (2)	0.48861 (14)	0.83124 (10)	0.0204 (3)
O4	0.4782 (2)	0.36214 (14)	0.91348 (10)	0.0233 (4)
C9	1.1854 (3)	0.55782 (16)	0.97230 (12)	0.0115 (4)
H9A	1.3129	0.5973	0.9530	0.014*
C10	1.0075 (3)	0.53211 (15)	0.91992 (12)	0.0100 (4)
C11	0.8194 (3)	0.47309 (16)	0.94750 (12)	0.0109 (4)
C12	1.0312 (3)	0.56437 (16)	0.83241 (12)	0.0113 (4)
C13	0.6225 (3)	0.44016 (17)	0.89245 (12)	0.0131 (4)
O5	0.5182 (2)	1.11219 (12)	0.59735 (10)	0.0182 (3)
O6	0.3881 (2)	0.94917 (13)	0.64244 (10)	0.0197 (3)
O7	−0.0392 (2)	0.94673 (12)	0.71610 (9)	0.0152 (3)
O8	−0.0657 (2)	0.77912 (12)	0.63610 (9)	0.0145 (3)
C14	0.1873 (3)	1.06607 (16)	0.47969 (12)	0.0108 (4)
H14A	0.3161	1.1113	0.4657	0.013*
C15	0.1797 (3)	1.00875 (16)	0.54829 (12)	0.0105 (4)
C16	−0.0101 (3)	0.94157 (16)	0.56864 (12)	0.0104 (4)
C17	0.3760 (3)	1.02308 (17)	0.60026 (12)	0.0121 (4)
C18	−0.0362 (3)	0.88465 (17)	0.64644 (12)	0.0116 (4)
O1S	0.8540 (4)	0.15919 (16)	0.03938 (14)	0.0422 (5)
H1SA	0.7441	0.1645	0.0207	0.051*
H1SB	0.8898	0.2148	0.0766	0.051*
O2S	0.2052 (3)	0.36605 (15)	0.52006 (11)	0.0276 (4)
H2SA	0.1274	0.4049	0.5358	0.033*
H2SB	0.1364	0.3266	0.4783	0.033*
O3S	0.5686 (3)	0.33661 (14)	0.57282 (12)	0.0276 (4)
H3SA	0.4566	0.3418	0.5565	0.033*
H3SB	0.5433	0.2694	0.5763	0.033*
O4S	0.9503 (3)	0.49208 (14)	0.60483 (10)	0.0234 (4)
H4SA	0.9722	0.4923	0.6553	0.028*
H4SB	0.8329	0.4518	0.5922	0.028*
O5SA	0.4646 (6)	0.1816 (3)	−0.0094 (3)	0.0453 (12)*	0.663 (9)
O6SA	0.2705 (5)	1.0084 (3)	0.8494 (2)	0.0431 (10)*	0.666 (6)
O5SB	0.5326 (8)	0.1596 (4)	−0.0451 (4)	0.0246 (18)*	0.337 (9)
O6SB	0.8058 (10)	0.9423 (5)	0.9689 (4)	0.0419 (19)*	0.334 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0127 (8)	0.0119 (8)	0.0179 (9)	0.0019 (6)	−0.0054 (6)	0.0000 (6)
N2	0.0115 (8)	0.0146 (8)	0.0145 (8)	0.0011 (6)	−0.0032 (6)	0.0012 (6)
C1	0.0127 (9)	0.0178 (10)	0.0215 (10)	0.0020 (8)	0.0012 (8)	0.0017 (8)
C2	0.0164 (10)	0.0172 (10)	0.0144 (9)	0.0025 (8)	−0.0003 (8)	0.0038 (8)
C3	0.0131 (9)	0.0173 (10)	0.0163 (10)	0.0030 (8)	0.0007 (7)	0.0023 (8)
C4	0.0180 (10)	0.0130 (9)	0.0135 (9)	0.0035 (8)	−0.0020 (7)	0.0019 (7)
N3	0.0121 (8)	0.0212 (9)	0.0236 (9)	0.0048 (7)	0.0015 (7)	0.0137 (7)
N4	0.0123 (8)	0.0236 (9)	0.0200 (9)	0.0068 (7)	0.0031 (7)	0.0133 (7)
C5	0.0163 (10)	0.0213 (11)	0.0205 (10)	0.0024 (8)	0.0016 (8)	0.0082 (8)
C6	0.0148 (10)	0.0303 (12)	0.0172 (10)	0.0063 (9)	−0.0003 (8)	0.0094 (9)
C7	0.0141 (10)	0.0201 (10)	0.0224 (11)	0.0034 (8)	0.0007 (8)	0.0088 (8)
C8	0.0143 (10)	0.0240 (11)	0.0184 (10)	0.0032 (8)	−0.0008 (8)	0.0103 (8)
O1	0.0226 (8)	0.0186 (7)	0.0100 (7)	0.0064 (6)	−0.0002 (6)	0.0027 (5)
O2	0.0152 (7)	0.0153 (7)	0.0152 (7)	0.0032 (5)	0.0020 (5)	0.0080 (5)
O3	0.0152 (7)	0.0261 (8)	0.0202 (8)	0.0006 (6)	−0.0046 (6)	0.0138 (6)
O4	0.0137 (7)	0.0287 (9)	0.0237 (8)	−0.0066 (6)	−0.0078 (6)	0.0154 (7)
C9	0.0104 (9)	0.0118 (9)	0.0125 (9)	0.0025 (7)	0.0007 (7)	0.0037 (7)
C10	0.0117 (9)	0.0095 (8)	0.0095 (8)	0.0032 (7)	0.0007 (7)	0.0031 (7)
C11	0.0110 (9)	0.0102 (8)	0.0117 (9)	0.0025 (7)	−0.0009 (7)	0.0027 (7)
C12	0.0064 (8)	0.0153 (9)	0.0117 (9)	0.0010 (7)	−0.0013 (7)	0.0042 (7)
C13	0.0109 (9)	0.0155 (9)	0.0127 (9)	0.0026 (7)	−0.0007 (7)	0.0038 (7)
O5	0.0132 (7)	0.0163 (7)	0.0238 (8)	−0.0008 (6)	−0.0068 (6)	0.0082 (6)
O6	0.0133 (7)	0.0232 (8)	0.0260 (8)	0.0039 (6)	−0.0004 (6)	0.0162 (6)
O7	0.0181 (7)	0.0159 (7)	0.0118 (7)	0.0040 (6)	0.0007 (5)	0.0042 (5)
O8	0.0153 (7)	0.0127 (7)	0.0169 (7)	0.0040 (5)	0.0023 (5)	0.0066 (5)
C14	0.0093 (8)	0.0107 (8)	0.0126 (9)	0.0022 (7)	0.0010 (7)	0.0034 (7)
C15	0.0092 (9)	0.0105 (8)	0.0121 (9)	0.0028 (7)	−0.0002 (7)	0.0023 (7)
C16	0.0129 (9)	0.0095 (8)	0.0098 (8)	0.0041 (7)	0.0009 (7)	0.0023 (7)
C17	0.0109 (9)	0.0157 (9)	0.0107 (9)	0.0049 (7)	0.0010 (7)	0.0033 (7)
C18	0.0066 (8)	0.0154 (9)	0.0142 (9)	0.0027 (7)	0.0003 (7)	0.0073 (7)
O1S	0.0552 (13)	0.0269 (10)	0.0427 (12)	0.0156 (9)	0.0075 (10)	−0.0071 (8)
O2S	0.0277 (9)	0.0299 (9)	0.0262 (9)	0.0132 (7)	−0.0097 (7)	−0.0012 (7)
O3S	0.0208 (8)	0.0188 (8)	0.0422 (10)	0.0022 (6)	−0.0072 (7)	0.0076 (7)
O4S	0.0250 (8)	0.0263 (8)	0.0159 (7)	−0.0003 (7)	−0.0050 (6)	0.0069 (6)

Geometric parameters (Å, º) top

N1—C1	1.488 (3)	C7—H7B	0.9900
N1—C4	1.489 (3)	C8—H8A	0.9900
N1—H1C	0.9200	C8—H8B	0.9900
N1—H1D	0.9200	O1—C12	1.258 (2)
N2—C3	1.489 (3)	O2—C12	1.259 (2)
N2—C2	1.492 (3)	O3—C13	1.241 (2)
N2—H2C	0.9200	O4—C13	1.268 (2)
N2—H2D	0.9200	C9—C10	1.393 (3)
C1—C2	1.516 (3)	C9—C11ⁱ	1.396 (3)
C1—H1A	0.9900	C9—H9A	0.9500
C1—H1B	0.9900	C10—C11	1.398 (3)
C2—H2A	0.9900	C10—C12	1.515 (3)
C2—H2B	0.9900	C11—C9ⁱ	1.396 (3)
C3—C4	1.514 (3)	C11—C13	1.512 (3)
C3—H3A	0.9900	O5—C17	1.266 (2)
C3—H3B	0.9900	O6—C17	1.244 (2)
C4—H4A	0.9900	O7—C18	1.256 (2)
C4—H4B	0.9900	O8—C18	1.260 (2)
N3—C8	1.492 (3)	C14—C16ⁱⁱ	1.392 (3)
N3—C5	1.493 (3)	C14—C15	1.396 (3)
N3—H3C	0.9200	C14—H14A	0.9500
N3—H3D	0.9200	C15—C16	1.401 (3)
N4—C7	1.491 (3)	C15—C17	1.513 (3)
N4—C6	1.494 (3)	C16—C14ⁱⁱ	1.392 (3)
N4—H4C	0.9200	C16—C18	1.517 (3)
N4—H4D	0.9200	O1S—H1SA	0.8201
C5—C6	1.508 (3)	O1S—H1SB	0.8200
C5—H5A	0.9900	O2S—H2SA	0.8197
C5—H5B	0.9900	O2S—H2SB	0.8206
C6—H6A	0.9900	O3S—H3SA	0.8199
C6—H6B	0.9900	O3S—H3SB	0.8201
C7—C8	1.516 (3)	O4S—H4SA	0.8201
C7—H7A	0.9900	O4S—H4SB	0.8201

C1—N1—C4	111.54 (15)	H5A—C5—H5B	108.0
C1—N1—H1C	109.3	N4—C6—C5	111.00 (17)
C4—N1—H1C	109.3	N4—C6—H6A	109.4
C1—N1—H1D	109.3	C5—C6—H6A	109.4
C4—N1—H1D	109.3	N4—C6—H6B	109.4
H1C—N1—H1D	108.0	C5—C6—H6B	109.4
C3—N2—C2	111.88 (16)	H6A—C6—H6B	108.0
C3—N2—H2C	109.2	N4—C7—C8	110.76 (18)
C2—N2—H2C	109.2	N4—C7—H7A	109.5
C3—N2—H2D	109.2	C8—C7—H7A	109.5
C2—N2—H2D	109.2	N4—C7—H7B	109.5
H2C—N2—H2D	107.9	C8—C7—H7B	109.5
N1—C1—C2	110.14 (17)	H7A—C7—H7B	108.1
N1—C1—H1A	109.6	N3—C8—C7	111.08 (17)
C2—C1—H1A	109.6	N3—C8—H8A	109.4
N1—C1—H1B	109.6	C7—C8—H8A	109.4
C2—C1—H1B	109.6	N3—C8—H8B	109.4
H1A—C1—H1B	108.1	C7—C8—H8B	109.4
N2—C2—C1	109.93 (16)	H8A—C8—H8B	108.0
N2—C2—H2A	109.7	C10—C9—C11ⁱ	121.56 (18)
C1—C2—H2A	109.7	C10—C9—H9A	119.2
N2—C2—H2B	109.7	C11ⁱ—C9—H9A	119.2
C1—C2—H2B	109.7	C9—C10—C11	119.63 (17)
H2A—C2—H2B	108.2	C9—C10—C12	117.35 (17)
N2—C3—C4	109.19 (16)	C11—C10—C12	122.92 (17)
N2—C3—H3A	109.8	C9ⁱ—C11—C10	118.81 (17)
C4—C3—H3A	109.8	C9ⁱ—C11—C13	119.25 (17)
N2—C3—H3B	109.8	C10—C11—C13	121.93 (17)
C4—C3—H3B	109.8	O1—C12—O2	124.58 (18)
H3A—C3—H3B	108.3	O1—C12—C10	116.78 (17)
N1—C4—C3	109.85 (16)	O2—C12—C10	118.47 (17)
N1—C4—H4A	109.7	O3—C13—O4	124.84 (18)
C3—C4—H4A	109.7	O3—C13—C11	119.64 (17)
N1—C4—H4B	109.7	O4—C13—C11	115.51 (17)
C3—C4—H4B	109.7	C16ⁱⁱ—C14—C15	121.44 (17)
H4A—C4—H4B	108.2	C16ⁱⁱ—C14—H14A	119.3
C8—N3—C5	111.59 (16)	C15—C14—H14A	119.3
C8—N3—H3C	109.3	C14—C15—C16	119.25 (17)
C5—N3—H3C	109.3	C14—C15—C17	119.16 (17)
C8—N3—H3D	109.3	C16—C15—C17	121.57 (17)
C5—N3—H3D	109.3	C14ⁱⁱ—C16—C15	119.31 (17)
H3C—N3—H3D	108.0	C14ⁱⁱ—C16—C18	117.57 (17)
C7—N4—C6	111.34 (16)	C15—C16—C18	122.87 (17)
C7—N4—H4C	109.4	O6—C17—O5	124.55 (18)
C6—N4—H4C	109.4	O6—C17—C15	119.42 (17)
C7—N4—H4D	109.4	O5—C17—C15	116.03 (16)
C6—N4—H4D	109.4	O7—C18—O8	125.13 (18)
H4C—N4—H4D	108.0	O7—C18—C16	116.50 (17)
N3—C5—C6	110.95 (18)	O8—C18—C16	118.21 (17)
N3—C5—H5A	109.4	H1SA—O1S—H1SB	102.8
C6—C5—H5A	109.4	H2SA—O2S—H2SB	98.8
N3—C5—H5B	109.4	H3SA—O3S—H3SB	102.2
C6—C5—H5B	109.4	H4SA—O4S—H4SB	106.6

C4—N1—C1—C2	−57.4 (2)	C9—C10—C12—O2	−79.7 (2)
C3—N2—C2—C1	−57.4 (2)	C11—C10—C12—O2	103.9 (2)
N1—C1—C2—N2	55.7 (2)	C9ⁱ—C11—C13—O3	162.78 (19)
C2—N2—C3—C4	58.4 (2)	C10—C11—C13—O3	−18.3 (3)
C1—N1—C4—C3	58.7 (2)	C9ⁱ—C11—C13—O4	−17.7 (3)
N2—C3—C4—N1	−57.9 (2)	C10—C11—C13—O4	161.22 (19)
C8—N3—C5—C6	−55.5 (2)	C16ⁱⁱ—C14—C15—C16	0.4 (3)
C7—N4—C6—C5	−56.4 (2)	C16ⁱⁱ—C14—C15—C17	−178.07 (17)
N3—C5—C6—N4	55.7 (2)	C14—C15—C16—C14ⁱⁱ	−0.4 (3)
C6—N4—C7—C8	56.0 (2)	C17—C15—C16—C14ⁱⁱ	178.04 (17)
C5—N3—C8—C7	55.3 (2)	C14—C15—C16—C18	−174.45 (18)
N4—C7—C8—N3	−55.3 (2)	C17—C15—C16—C18	3.9 (3)
C11ⁱ—C9—C10—C11	−0.6 (3)	C14—C15—C17—O6	−157.34 (19)
C11ⁱ—C9—C10—C12	−177.06 (17)	C16—C15—C17—O6	24.3 (3)
C9—C10—C11—C9ⁱ	0.6 (3)	C14—C15—C17—O5	22.9 (3)
C12—C10—C11—C9ⁱ	176.84 (17)	C16—C15—C17—O5	−155.48 (18)
C9—C10—C11—C13	−178.33 (17)	C14ⁱⁱ—C16—C18—O7	−97.7 (2)
C12—C10—C11—C13	−2.1 (3)	C15—C16—C18—O7	76.5 (2)
C9—C10—C12—O1	95.7 (2)	C14ⁱⁱ—C16—C18—O8	78.0 (2)
C11—C10—C12—O1	−80.6 (2)	C15—C16—C18—O8	−107.8 (2)

Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O5ⁱⁱⁱ	0.92	1.74	2.642 (2)	166
N1—H1D···O7^iv	0.92	1.84	2.763 (2)	178
N2—H2C···O1^v	0.92	1.82	2.723 (2)	165
N2—H2D···O4	0.92	1.72	2.635 (2)	179
N3—H3C···O2^v	0.92	1.90	2.787 (2)	163
N3—H3D···O6	0.92	1.92	2.690 (2)	141
N4—H4C···O8^vi	0.92	1.85	2.753 (2)	168
N4—H4D···O3	0.92	2.00	2.748 (2)	138
O1S—H1SA···O5SA	0.82	2.02	2.837 (2)	172
O1S—H1SA···O5SA	0.82	2.02	2.837 (2)	172
O1S—H1SB···O2^vii	0.82	1.95	2.763 (2)	172
O2S—H2SA···O4S^v	0.82	2.04	2.839 (2)	165
O2S—H2SB···O8^viii	0.82	2.05	2.835 (2)	160
O3S—H3SA···O2S	0.82	1.90	2.722 (2)	176
O3S—H3SB···O5^iv	0.82	2.00	2.817 (2)	171
O4S—H4SA···O1	0.82	1.95	2.772 (2)	175
O4S—H4SB···O3S	0.82	1.95	2.764 (2)	170
C5—H5A···O6SA	0.99	2.50	3.288 (4)	136
C5—H5B···O7^vi	0.99	2.35	3.272 (3)	154
C7—H7A···O1^v	0.99	2.48	3.414 (3)	156
C8—H8B···O4S^v	0.99	2.51	3.299 (3)	137
C4—H4B···Cg1^iv	0.99	2.64	3.518 (2)	148
C4—H4B···Cg1^viii	0.99	2.64	3.518 (2)	148

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

Experimental details

Crystal data
Chemical formula	2C₄H₁₂N₂²⁺·C₁₀H₂O₈⁴⁻·6H₂O
M_r	534.52
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.7420 (4), 12.4636 (7), 16.0100 (9)
α, β, γ (°)	99.092 (1), 90.347 (1), 105.528 (1)
V (Å³)	1278.27 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.23 × 0.21 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.970, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	13995, 5839, 4805
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.159, 1.02
No. of reflections	5839
No. of parameters	323
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.20, −0.60

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O5ⁱ	0.92	1.739	2.642 (2)	166
N1—H1D···O7ⁱⁱ	0.92	1.844	2.763 (2)	178
N2—H2C···O1ⁱⁱⁱ	0.92	1.824	2.723 (2)	165
N2—H2D···O4	0.92	1.715	2.635 (2)	179
N3—H3C···O2ⁱⁱⁱ	0.92	1.895	2.787 (2)	163
N3—H3D···O6	0.92	1.915	2.690 (2)	141
N4—H4C···O8^iv	0.92	1.847	2.753 (2)	168
N4—H4D···O3	0.92	1.996	2.748 (2)	138
O1S—H1SA···O5SA	0.82	2.022	2.837 (2)	172
O1S—H1SA···O5SA	0.82	2.022	2.837 (2)	172
O1S—H1SB···O2^v	0.82	1.949	2.763 (2)	172
O2S—H2SA···O4Sⁱⁱⁱ	0.82	2.039	2.839 (2)	165
O2S—H2SB···O8^vi	0.82	2.052	2.835 (2)	160
O3S—H3SA···O2S	0.82	1.903	2.722 (2)	176
O3S—H3SB···O5ⁱⁱ	0.82	2.003	2.817 (2)	171
O4S—H4SA···O1	0.82	1.954	2.772 (2)	175
O4S—H4SB···O3S	0.82	1.954	2.764 (2)	170
C5—H5A···O6SA	0.99	2.500	3.288 (4)	136
C5—H5B···O7^iv	0.99	2.350	3.272 (3)	154
C7—H7A···O1ⁱⁱⁱ	0.99	2.480	3.414 (3)	156
C8—H8B···O4Sⁱⁱⁱ	0.99	2.510	3.299 (3)	137
C4—H4B···Cg1ⁱⁱ	0.99	2.64	3.518 (2)	148
C4—H4B···Cg1^vi	0.99	2.64	3.518 (2)	148

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

Acknowledgements

The authors acknowledge Tarbiat Moallem University for supporting this work.

References

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