Propane-1,3-diaminium bis­(perchlorate)–18-crown-6 (1/2)

Zhao, M.-M.

doi:10.1107/S1600536811056248

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o327

doi:10.1107/S1600536811056248

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Propane-1,3-diaminium bis(perchlorate)–18-crown-6 (1/2)

Min-Min Zhao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chemcrystal66@yahoo.com.cn

(Received 25 December 2011; accepted 30 December 2011; online 11 January 2012)

In the title compound, C₃H₁₂N₂²⁺·2ClO₄⁻·2C₁₂H₂₄O₆, the central C atom of the propane-1,3-diammonium cation is located on a twofold rotation axis and the two terminal –NH₃ groups insert into the crown rings through N—H⋯O hydrogen bonding, resulting in the formation of a 1:2 supramolecular [(C₃H₁₂N₂)·(C₁₂H₂₄O₆)₂]⁺ complex. The perchlorate anion links with the supramolecular complex via weak C—H⋯O hydrogen bonding.

Related literature

For the properties and structures of related compounds, see: Fu et al. (2007 , 2008 , 2009 ); Fu & Xiong (2008 ). For the ferroelectric properties of related amino derivatives, see: Fu et al. (2011a ,b ,c ).

Experimental

Crystal data

C₃H₁₂N₂²⁺·2ClO₄⁻·2C₁₂H₂₄O₆
M_r = 803.67
Monoclinic, C 2/c
a = 22.984 (5) Å
b = 9.0055 (18) Å
c = 21.620 (4) Å
β = 113.59 (3)°
V = 4101.0 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 298 K
0.10 × 0.03 × 0.03 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
16855 measured reflections
3606 independent reflections
2059 reflections with I > 2σ(I)
R_int = 0.086

Refinement

R[F² > 2σ(F²)] = 0.085
wR(F²) = 0.248
S = 1.07
3606 reflections
232 parameters
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O1	0.89	2.10	2.958 (4)	161
N1—H1E⋯O3	0.89	2.08	2.951 (5)	167
N1—H1D⋯O5	0.89	2.12	3.007 (5)	177
C10—H10B⋯O10	0.96	2.55	3.478 (13)	161
C13—H13A⋯O9	0.96	2.58	3.470 (7)	154

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811056248/xu5433sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811056248/xu5433Isup2.hkl

checkCIF report

Comment top

Organic amino compounds attracted more attention as phase transition dielectric materials for its application in memory storage (Fu et al., 2007; Fu & Xiong, 2008; Fu et al., 2008; Fu et al., 2009). With the purpose of obtaining phase transition crystals of amino compounds, various amines have been studied and we have elaborated a series of new materials with this organic molecules (Fu et al., 2011a; Fu et al., 2011b; Fu et al., 2011c). In this study, we describe the crystal structure of the title compound, bis(18-crown-6)propane-1,3-diammonium perchlorate .

The title compound was composed of cationic [(C₃H₁₂N₂).(C₁₂H₂₄O₆)₂]⁺ and one ClO₄^- anion (Fig.1). Supramolecular rotators was assembled between protonated propane-1,3-diammonium (H₃N-C₃H₆-NH₃)⁺ and 18-crown-6 by H-bonds. The ammonium moieties of -NH₃⁺ cations were interacted with the O atoms of crown ethers through six N—H···O hydrogen bonds, forming a 1:2 supramolecular rotator-stator structures.

The macrocycle adopts a conformation with approximate D_3d symmetry, with all O-C-C-O torsion angles being gauche and alternating in sign, and all C-O-C-C torsion angles being trans. The C-N bonds of cation were almost perpendicular to the mean oxygen planes of crown ethers.

Supramolecular cation structure, [(C₃H₁₂N₂).(C₁₂H₂₄O₆)₂]⁺, was introduced as counter cation to ClO₄^- anion. Cl has a flattened tetrahedral coordination by four O atoms [range of cis-bond angles = 105.2 (5)-113.7 (3) °; dav(Cl-O) = 1.332 (7)-1.410 (4)Å].

The title compound was stabilized by intermolecular N—H···O hydrogen bonds, the ClO₄^- anion not participating in the H-bonding interactions. The intermolecular N—H···O H-bonding length are within the usual range of 2.951 (5) to 3.152 (5)Å. (Table 1 and Fig.2).

Related literature top

For the properties and structures of related compounds, see: Fu et al. (2007, 2008, 2009); Fu & Xiong (2008). For the ferroelectric properties of related amino derivatives, see: Fu et al. (2011a,b,c).

Experimental top

The commercial 18-crown-6 (6 mmol), HClO₄ (6 mmol) and organic amine (3 mmol) were dissolved in water/EtOH (1:1 v/v) solution. The solvent was slowly evaporated in air affording colourless block-shaped crystals of the title compound suitable for X-ray analysis.

The dielectric constant of title compound as a function of temperature indicates that the permittivity is basically temperature-independent, suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range. Similarly, below the melting point (405 K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant ranging from 4.2 to 7.5).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound, showing the H-bonding interactions. H atoms not involved in hydrogen bonding (dashed line) have been omitted for clarity.

Propane-1,3-diaminium bis(perchlorate)–18-crown-6 (1/2) top

Crystal data top

C₃H₁₂N₂²⁺·2ClO₄⁻·2C₁₂H₂₄O₆	F(000) = 1720
M_r = 803.67	D_x = 1.302 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3606 reflections
a = 22.984 (5) Å	θ = 3.3–27.5°
b = 9.0055 (18) Å	µ = 0.23 mm⁻¹
c = 21.620 (4) Å	T = 298 K
β = 113.59 (3)°	Block, colorless
V = 4101.0 (17) Å³	0.10 × 0.03 × 0.03 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	3606 independent reflections
Radiation source: fine-focus sealed tube	2059 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.086
Detector resolution: 13.6612 pixels mm^-1	θ_max = 25.0°, θ_min = 3.3°
CCD profile fitting scans	h = −27→27
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.910, T_max = 1.000	l = −25→25
16855 measured reflections

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)] = 0.085	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.248	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1136P)² + 6.3277P] where P = (F_o² + 2F_c²)/3
3606 reflections	(Δ/σ)_max < 0.001
232 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₃H₁₂N₂²⁺·2ClO₄⁻·2C₁₂H₂₄O₆	V = 4101.0 (17) Å³
M_r = 803.67	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.984 (5) Å	µ = 0.23 mm⁻¹
b = 9.0055 (18) Å	T = 298 K
c = 21.620 (4) Å	0.10 × 0.03 × 0.03 mm
β = 113.59 (3)°

Data collection top

Rigaku Mercury2 diffractometer	3606 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2059 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.086
16855 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.085	0 restraints
wR(F²) = 0.248	H-atom parameters constrained
S = 1.07	Δρ_max = 0.65 e Å⁻³
3606 reflections	Δρ_min = −0.42 e Å⁻³
232 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cl1	0.07984 (6)	0.10040 (17)	0.43221 (7)	0.0626 (5)
N1	0.10533 (15)	0.4168 (4)	0.23756 (18)	0.0394 (9)
H1C	0.1367	0.3550	0.2409	0.059*
H1D	0.1195	0.4836	0.2706	0.059*
H1E	0.0915	0.4628	0.1978	0.059*
C14	0.0000	0.4263 (7)	0.2500	0.0401 (15)
H14A	−0.0183	0.4888	0.2110	0.048*
C13	0.0522 (2)	0.3310 (5)	0.2433 (3)	0.0489 (12)
H13A	0.0693	0.2672	0.2820	0.059*
H13B	0.0334	0.2691	0.2041	0.059*
O1	0.19599 (14)	0.1670 (4)	0.26636 (16)	0.0522 (9)
O2	0.14880 (16)	0.2723 (4)	0.13018 (17)	0.0610 (10)
O6	0.22044 (16)	0.3852 (4)	0.37058 (16)	0.0600 (10)
O5	0.15115 (18)	0.6523 (4)	0.3449 (2)	0.0699 (11)
O3	0.07323 (17)	0.5386 (5)	0.10111 (19)	0.0694 (11)
O4	0.10201 (18)	0.7507 (4)	0.2076 (2)	0.0748 (12)
C11	0.2347 (2)	0.2291 (6)	0.3837 (3)	0.0613 (15)
H11A	0.1988	0.1794	0.3863	0.074*
H11B	0.2701	0.2174	0.4263	0.074*
C12	0.2501 (2)	0.1626 (6)	0.3288 (3)	0.0593 (14)
H12A	0.2846	0.2154	0.3246	0.071*
H12B	0.2629	0.0612	0.3398	0.071*
C2	0.1526 (3)	0.1189 (6)	0.1466 (3)	0.0683 (16)
H2A	0.1580	0.0620	0.1117	0.082*
H2B	0.1142	0.0871	0.1503	0.082*
C1	0.2077 (3)	0.0951 (6)	0.2127 (3)	0.0634 (15)
H1A	0.2155	−0.0089	0.2223	0.076*
H1B	0.2449	0.1381	0.2102	0.076*
C9	0.2026 (3)	0.6201 (8)	0.4103 (3)	0.0796 (19)
H9A	0.1956	0.6718	0.4455	0.096*
H9B	0.2419	0.6542	0.4096	0.096*
C4	0.0927 (3)	0.4672 (8)	0.0535 (3)	0.080 (2)
H4A	0.1335	0.5054	0.0591	0.096*
H4B	0.0631	0.4888	0.0084	0.096*
C3	0.0976 (3)	0.3036 (7)	0.0654 (3)	0.0751 (18)
H3A	0.0581	0.2673	0.0648	0.090*
H3B	0.1056	0.2548	0.0300	0.090*
C6	0.0487 (3)	0.7661 (7)	0.1465 (4)	0.086 (2)
H6A	0.0386	0.8695	0.1376	0.104*
H6B	0.0127	0.7165	0.1488	0.104*
C5	0.0641 (3)	0.6996 (7)	0.0914 (3)	0.085 (2)
H5A	0.0303	0.7185	0.0482	0.102*
H5B	0.1022	0.7436	0.0917	0.102*
C8	0.1502 (4)	0.8053 (7)	0.3269 (4)	0.087 (2)
H8A	0.1882	0.8290	0.3206	0.104*
H8B	0.1483	0.8674	0.3622	0.104*
C10	0.2064 (3)	0.4562 (7)	0.4218 (3)	0.0716 (17)
H10A	0.2388	0.4350	0.4655	0.086*
H10B	0.1665	0.4209	0.4205	0.086*
C7	0.0943 (3)	0.8322 (6)	0.2623 (4)	0.083 (2)
H7A	0.0571	0.7967	0.2673	0.099*
H7B	0.0889	0.9362	0.2518	0.099*
O9	0.0609 (3)	0.0673 (6)	0.3637 (2)	0.1150 (18)
O8	0.0368 (2)	0.0512 (6)	0.4595 (3)	0.1106 (18)
O10	0.0830 (5)	0.2559 (8)	0.4361 (5)	0.231 (5)
O7	0.1380 (3)	0.0480 (16)	0.4675 (4)	0.257 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0603 (8)	0.0785 (10)	0.0606 (8)	−0.0265 (7)	0.0363 (7)	−0.0224 (7)
N1	0.037 (2)	0.037 (2)	0.048 (2)	0.0041 (16)	0.0206 (17)	0.0043 (17)
C14	0.038 (3)	0.038 (4)	0.049 (4)	0.000	0.021 (3)	0.000
C13	0.040 (3)	0.040 (3)	0.071 (3)	−0.002 (2)	0.027 (2)	0.001 (2)
O1	0.0417 (18)	0.054 (2)	0.060 (2)	0.0123 (15)	0.0193 (17)	0.0100 (17)
O2	0.058 (2)	0.062 (2)	0.056 (2)	−0.0107 (17)	0.0150 (18)	−0.0049 (18)
O6	0.067 (2)	0.070 (2)	0.045 (2)	−0.0079 (18)	0.0247 (18)	0.0007 (18)
O5	0.076 (3)	0.052 (2)	0.091 (3)	−0.0118 (19)	0.044 (2)	−0.015 (2)
O3	0.068 (2)	0.074 (3)	0.055 (2)	−0.0096 (19)	0.0132 (19)	0.020 (2)
O4	0.057 (2)	0.059 (2)	0.104 (3)	0.0210 (19)	0.026 (2)	0.017 (2)
C11	0.052 (3)	0.065 (4)	0.058 (3)	−0.003 (3)	0.014 (3)	0.025 (3)
C12	0.043 (3)	0.055 (3)	0.070 (4)	0.003 (2)	0.013 (3)	0.020 (3)
C2	0.074 (4)	0.063 (4)	0.079 (4)	−0.008 (3)	0.042 (3)	−0.014 (3)
C1	0.071 (4)	0.046 (3)	0.089 (4)	0.012 (3)	0.049 (3)	−0.002 (3)
C9	0.087 (4)	0.101 (6)	0.056 (4)	−0.018 (4)	0.034 (4)	−0.025 (3)
C4	0.064 (4)	0.103 (5)	0.049 (3)	−0.027 (4)	−0.003 (3)	0.016 (3)
C3	0.072 (4)	0.095 (5)	0.044 (3)	−0.020 (3)	0.009 (3)	−0.013 (3)
C6	0.062 (4)	0.066 (4)	0.125 (6)	0.008 (3)	0.030 (4)	0.041 (4)
C5	0.059 (4)	0.076 (4)	0.084 (5)	−0.011 (3)	−0.009 (3)	0.053 (4)
C8	0.110 (5)	0.052 (4)	0.122 (6)	−0.004 (4)	0.071 (5)	−0.033 (4)
C10	0.070 (4)	0.093 (5)	0.054 (3)	−0.014 (3)	0.027 (3)	−0.005 (3)
C7	0.085 (4)	0.043 (3)	0.149 (7)	0.018 (3)	0.078 (5)	0.002 (4)
O9	0.159 (5)	0.123 (4)	0.065 (3)	0.033 (3)	0.045 (3)	0.005 (3)
O8	0.118 (4)	0.112 (4)	0.146 (4)	−0.048 (3)	0.100 (4)	−0.035 (3)
O10	0.412 (14)	0.111 (5)	0.310 (10)	−0.140 (7)	0.292 (11)	−0.112 (6)
O7	0.076 (4)	0.533 (19)	0.133 (6)	0.024 (7)	0.012 (4)	0.140 (9)

Geometric parameters (Å, º) top

Cl1—O7	1.332 (7)	C12—H12A	0.9599
Cl1—O9	1.399 (5)	C12—H12B	0.9600
Cl1—O10	1.403 (7)	C2—C1	1.500 (8)
Cl1—O8	1.410 (4)	C2—H2A	0.9600
N1—C13	1.492 (5)	C2—H2B	0.9601
N1—H1C	0.8900	C1—H1A	0.9599
N1—H1D	0.8900	C1—H1B	0.9600
N1—H1E	0.8900	C9—C10	1.493 (8)
C14—C13	1.528 (5)	C9—H9A	0.9600
C14—C13ⁱ	1.528 (5)	C9—H9B	0.9601
C14—H14A	0.9600	C4—C3	1.492 (8)
C13—H13A	0.9600	C4—H4A	0.9599
C13—H13B	0.9600	C4—H4B	0.9600
O1—C12	1.423 (6)	C3—H3A	0.9600
O1—C1	1.444 (6)	C3—H3B	0.9600
O2—C2	1.420 (6)	C6—C5	1.496 (9)
O2—C3	1.452 (6)	C6—H6A	0.9601
O6—C10	1.422 (6)	C6—H6B	0.9600
O6—C11	1.445 (6)	C5—H5A	0.9600
O5—C8	1.430 (7)	C5—H5B	0.9600
O5—C9	1.462 (7)	C8—C7	1.492 (9)
O3—C4	1.429 (8)	C8—H8A	0.9602
O3—C5	1.468 (7)	C8—H8B	0.9600
O4—C6	1.403 (7)	C10—H10A	0.9602
O4—C7	1.462 (7)	C10—H10B	0.9600
C11—C12	1.494 (7)	C7—H7A	0.9601
C11—H11A	0.9600	C7—H7B	0.9599
C11—H11B	0.9600

O7—Cl1—O9	110.3 (5)	H1A—C1—H1B	108.3
O7—Cl1—O10	107.6 (7)	O5—C9—C10	109.1 (5)
O9—Cl1—O10	105.2 (5)	O5—C9—H9A	110.1
O7—Cl1—O8	111.1 (4)	C10—C9—H9A	111.4
O9—Cl1—O8	113.7 (3)	O5—C9—H9B	108.9
O10—Cl1—O8	108.5 (4)	C10—C9—H9B	109.0
C13—N1—H1C	109.5	H9A—C9—H9B	108.3
C13—N1—H1D	109.5	O3—C4—C3	110.2 (5)
H1C—N1—H1D	109.5	O3—C4—H4A	108.6
C13—N1—H1E	109.5	C3—C4—H4A	109.2
H1C—N1—H1E	109.5	O3—C4—H4B	110.0
H1D—N1—H1E	109.5	C3—C4—H4B	110.5
C13—C14—C13ⁱ	111.6 (5)	H4A—C4—H4B	108.3
C13—C14—H14A	109.3	O2—C3—C4	109.5 (4)
C13ⁱ—C14—H14A	109.2	O2—C3—H3A	110.1
N1—C13—C14	114.6 (4)	C4—C3—H3A	109.1
N1—C13—H13A	108.5	O2—C3—H3B	109.9
C14—C13—H13A	108.5	C4—C3—H3B	110.0
N1—C13—H13B	108.7	H3A—C3—H3B	108.3
C14—C13—H13B	108.5	O4—C6—C5	108.3 (5)
H13A—C13—H13B	107.8	O4—C6—H6A	109.6
C12—O1—C1	112.1 (4)	C5—C6—H6A	110.2
C2—O2—C3	112.0 (4)	O4—C6—H6B	110.6
C10—O6—C11	112.8 (4)	C5—C6—H6B	109.8
C8—O5—C9	111.8 (5)	H6A—C6—H6B	108.4
C4—O3—C5	114.2 (5)	O3—C5—C6	110.3 (5)
C6—O4—C7	111.7 (5)	O3—C5—H5A	109.2
O6—C11—C12	109.9 (4)	C6—C5—H5A	110.2
O6—C11—H11A	109.4	O3—C5—H5B	109.2
C12—C11—H11A	110.0	C6—C5—H5B	109.5
O6—C11—H11B	109.5	H5A—C5—H5B	108.3
C12—C11—H11B	109.8	O5—C8—C7	108.9 (5)
H11A—C11—H11B	108.2	O5—C8—H8A	109.8
O1—C12—C11	110.4 (4)	C7—C8—H8A	108.7
O1—C12—H12A	109.8	O5—C8—H8B	110.2
C11—C12—H12A	110.1	C7—C8—H8B	110.6
O1—C12—H12B	109.0	H8A—C8—H8B	108.6
C11—C12—H12B	109.2	O6—C10—C9	109.4 (5)
H12A—C12—H12B	108.2	O6—C10—H10A	110.4
O2—C2—C1	108.7 (4)	C9—C10—H10A	109.4
O2—C2—H2A	109.7	O6—C10—H10B	109.9
C1—C2—H2A	110.3	C9—C10—H10B	109.3
O2—C2—H2B	110.1	H10A—C10—H10B	108.5
C1—C2—H2B	109.4	O4—C7—C8	109.8 (4)
H2A—C2—H2B	108.6	O4—C7—H7A	109.0
O1—C1—C2	110.1 (4)	C8—C7—H7A	108.1
O1—C1—H1A	110.0	O4—C7—H7B	110.3
C2—C1—H1A	111.0	C8—C7—H7B	111.2
O1—C1—H1B	108.8	H7A—C7—H7B	108.3
C2—C1—H1B	108.6

C13ⁱ—C14—C13—N1	−179.1 (5)	O3—C4—C3—O2	−66.2 (6)
C10—O6—C11—C12	−178.9 (4)	C7—O4—C6—C5	171.5 (5)
C1—O1—C12—C11	−176.3 (4)	C4—O3—C5—C6	−175.6 (5)
O6—C11—C12—O1	−64.8 (5)	O4—C6—C5—O3	65.9 (6)
C3—O2—C2—C1	178.0 (4)	C9—O5—C8—C7	−176.3 (5)
C12—O1—C1—C2	−173.0 (4)	C11—O6—C10—C9	171.0 (4)
O2—C2—C1—O1	66.2 (6)	O5—C9—C10—O6	61.6 (6)
C8—O5—C9—C10	−172.4 (5)	C6—O4—C7—C8	176.6 (5)
C5—O3—C4—C3	−177.2 (4)	O5—C8—C7—O4	−65.6 (6)
C2—O2—C3—C4	175.4 (5)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1	0.89	2.10	2.958 (4)	161
N1—H1E···O3	0.89	2.08	2.951 (5)	167
N1—H1D···O5	0.89	2.12	3.007 (5)	177
C10—H10B···O10	0.96	2.55	3.478 (13)	161
C13—H13A···O9	0.96	2.58	3.470 (7)	154

Experimental details

Crystal data
Chemical formula	C₃H₁₂N₂²⁺·2ClO₄⁻·2C₁₂H₂₄O₆
M_r	803.67
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	22.984 (5), 9.0055 (18), 21.620 (4)
β (°)	113.59 (3)
V (Å³)	4101.0 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.10 × 0.03 × 0.03

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16855, 3606, 2059
R_int	0.086
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.085, 0.248, 1.07
No. of reflections	3606
No. of parameters	232
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.42

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1	0.89	2.10	2.958 (4)	160.5
N1—H1E···O3	0.89	2.08	2.951 (5)	167.2
N1—H1D···O5	0.89	2.12	3.007 (5)	176.8
C10—H10B···O10	0.96	2.55	3.478 (13)	161
C13—H13A···O9	0.96	2.58	3.470 (7)	154

Acknowledgements

This work was supported by a start-up grant from Southeast University, China.

References

Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994–997. Web of Science CSD CrossRef CAS Google Scholar
Fu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S. P. D. (2007). J. Am. Chem. Soc. 129, 5346–5347. Web of Science CSD CrossRef PubMed CAS Google Scholar
Fu, D.-W. & Xiong, R.-G. (2008). Dalton Trans. pp. 3946–3948. Web of Science CSD CrossRef Google Scholar
Fu, D.-W., Zhang, W., Cai, H.-L., Ge, J.-Z., Zhang, Y. & Xiong, R.-G. (2011b). Adv. Mater. 23, 5658–5662. Web of Science CSD CrossRef CAS PubMed Google Scholar
Fu, D.-W., Zhang, W., Cai, H.-L., Zhang, Y., Ge, J.-Z., Xiong, R.-G. & Huang, S. P. D. (2011a). J. Am. Chem. Soc. 133, 12780–12786. Web of Science CSD CrossRef CAS PubMed Google Scholar
Fu, D.-W., Zhang, W., Cai, H.-L., Zhang, Y., Ge, J.-Z., Xiong, R.-G., Huang, S. P. D. & Nakamura, T. (2011c). Angew. Chem. Int. Ed. 50, 11947–11951. Web of Science CSD CrossRef CAS Google Scholar
Fu, D.-W., Zhang, W. & Xiong, R.-G. (2008). Cryst. Growth Des. 8, 3461–3464. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar