Dimethyl­ammonium perchlorate 18-crown-6 monohydrate clathrate

Ge, J.-Z.; Zhao, M.-M.; Shi, P.-P.

doi:10.1107/S1600536810023421

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1740

doi:10.1107/S1600536810023421

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Dimethylammonium perchlorate 18-crown-6 monohydrate clathrate

Jia-Zhen Ge,^a ^* Min-Min Zhao ^a and Ping-Ping Shi ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical, Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: gjz@seu.edu.cn

(Received 29 May 2010; accepted 17 June 2010; online 23 June 2010)

The reaction of dimethylamine, 18-crown-6, and perchloric acid in methanol yields the title compound, C₂H₈N⁺·ClO₄⁻·C₁₂H₂₄O₆·H₂O. The dimethylammonium cation and the water molecule interact with the 18-crown-6 unit: N—H⋯O hydrogen bonds are formed between the ammonium NH₂⁺ group and four O atoms of the crown ether, while the water molecule on the other side of 18-crown-6 ring forms O—H⋯O hydrogen bonds with two other O atoms of the crown ether. All conventional donors and acceptors in the cations are thus engaged in hydrogen bonding. The ClO₄⁻ anion is disordered over two sites, and occupancies for the disordered O atoms were fixed at 0.5. In the crystal, the cations and anions are arranged in alternating layers.

Related literature

For the similar structure, 18-crown-6 clathrate, see: Pedersen (1967 ). For the ferroelectric properties of related materials, see: Fu et al. (2007 ); Ye et al. (2009 ); Zhang et al. (2009 ).

Experimental

Crystal data

C₂H₈N⁺·ClO₄⁻·C₁₂H₂₄O₆·H₂O
M_r = 427.87
Orthorhombic, P 2₁ 2₁ 2₁
a = 10.684 (2) Å
b = 13.954 (3) Å
c = 14.583 (3) Å
V = 2174.1 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.4 × 0.3 × 0.2 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan CrystalClear (Rigaku, 2005 ) T_min = 0.955, T_max = 0.955
22574 measured reflections
4973 independent reflections
2814 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.171
S = 1.00
4973 reflections
283 parameters
51 restraints
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983 ), 2164 Friedel pairs
Flack parameter: 0.02 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1AA⋯O6	1.05	2.00	2.979 (4)	154
N1—H1BB⋯O3	0.86	2.14	2.979 (4)	164
O20—H20B⋯O4ⁱ	0.90	2.12	3.013 (4)	171
O20—H20A⋯O1ⁱ	0.76	2.21	2.927 (3)	158
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

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: PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810023421/bh2290sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810023421/bh2290Isup2.hkl

checkCIF report

Comment top

The crown ethers are of a great interest since their discovery by Pedersen (1967). The ability of these macrocycles to form non-covalent, H-bonding complexes with ammonium cations has been actively investigated. Both the size of the crown ether and the nature of the ammonium cation (NH₄⁺, RNH₃⁺, etc) can influence on the stoichiometry and stability of these host-guest complexes. The host molecules combine with the guest species by intermolecular interactions, and if the host molecule has some specific sites, it is easy to realize high selectivity in ion or molecular recognition. 18-crown-6 has the highest affinity for ammonium cations RNH₃⁺, and most studies of 18-crown-6 and its derivatives invariably showed the 1:1 stoichiometry with RNH₃⁺ cations.

The title compound dielectric permittivity was tested to systematically investigate the ferroelectric phase transitions of these materials (Fu et al., 2007; Ye et al., 2009; Zhang et al., 2009). The title compound has no dielectric anomalies, with the relative permittivity at 1 MHz being in the range 4–5 between 80 and 330 K (m.p. is 353 K), suggesting that no phase transition occurred within the measured temperature range.

The title compound is composed of cation [(CH₃)₂NH₂(18-Crown-6)]⁺, one isolated anion (ClO₄)^-, and one lattice water molecule (Fig 1). The protonated dimethylamine [(CH₃)₂NH₂]⁺ and 18-crown-6 form a supramolecular structure through N—H···O hydrogen bonds between the ammonium NH₂⁺ group and four O atoms of the crown ether. The water molecule on the other side of the 18-crown-6 ring forms O—H···O hydrogen bonds between the O—H groups of water and two other O atoms of the crown ether. The intramolecular N—H···O hydrogen bond lengths are within the usual range: 2.979 (4)–3.285 (4) Å, and the intramolecular O—H···O hydrogen bond lengths are from 2.927 (3) to 3.013 (4) Å. The crown ring shows severe distortions. The six O atoms of the crown ether take the approximate "boat-shape" conformation. The four O atoms bonding to the NH₂⁺ cation lie on the bottom of the boat, while the other two O atoms bonded to the water molecule lie on the head and tail of the boat.

The (ClO₄)^- anion is disordered, as detectable from the large displacement parameters for O atoms and short Cl—O bond lengths. The disorder was modelled with two sites with equal occupancies for O atoms, and the geometry of the anion was regularized through soft restraints.

Fig. 2 shows a view of the crystal structure down the b axis. The cations [(CH₃)₂NH₂(18-Crown-6)]⁺ are arranged into layers almost parallel to (101). The anions (ClO₄)^- are placed in the voids formed by the cations. The title compound is stabilized by intramolecular N—H···O and O—H···O hydrogen bonds, as above described, but no intermolecular hydrogen bonds are observed.

Related literature top

For 18-crown-6 clathrate, see: Pedersen (1967). For the erroelectric properties of related materials, see: Fu et al. (2007); Ye et al. (2009); Zhang et al. (2009).

Experimental top

Dimethylamine (2 mmol, 0.09 g) and an excess of perchloric acid (3 mmol, 0.302 g) were dissolved in methanol. Then, 18-crown-6 (2 mmol, 0.528 g) was added to the mixture. The precipitate was filtered and washed with a small amount of methanol. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a methanol solution at room temperature over two days.

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: PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and a single orientation for the disordered perchlorate anion is shown.
	Fig. 2. A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

Dimethylammonium perchlorate 18-crown-6 monohydrate clathrate top

Crystal data top

C₂H₈N⁺·ClO₄⁻·C₁₂H₂₄O₆·H₂O	D_x = 1.307 Mg m⁻³
M_r = 427.87	Melting point: 353 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2814 reflections
a = 10.684 (2) Å	θ = 3.2–27.5°
b = 13.954 (3) Å	µ = 0.23 mm⁻¹
c = 14.583 (3) Å	T = 293 K
V = 2174.1 (8) Å³	Block, white
Z = 4	0.4 × 0.3 × 0.2 mm
F(000) = 920

Data collection top

Rigaku SCXmini diffractometer	4973 independent reflections
Radiation source: fine-focus sealed tube	2814 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −13→13
Absorption correction: multi-scan CrystalClear (Rigaku, 2005)	k = −18→18
T_min = 0.955, T_max = 0.955	l = −18→18
22574 measured reflections

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)] = 0.058	H-atom parameters constrained
wR(F²) = 0.171	w = 1/[σ²(F_o²) + (0.0794P)² + 0.2447P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.007
4973 reflections	Δρ_max = 0.29 e Å⁻³
283 parameters	Δρ_min = −0.15 e Å⁻³
51 restraints	Absolute structure: Flack (1983), 2168 Friedel pairs
0 constraints	Absolute structure parameter: 0.02 (10)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂H₈N⁺·ClO₄⁻·C₁₂H₂₄O₆·H₂O	V = 2174.1 (8) Å³
M_r = 427.87	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 10.684 (2) Å	µ = 0.23 mm⁻¹
b = 13.954 (3) Å	T = 293 K
c = 14.583 (3) Å	0.4 × 0.3 × 0.2 mm

Data collection top

Rigaku SCXmini diffractometer	4973 independent reflections
Absorption correction: multi-scan CrystalClear (Rigaku, 2005)	2814 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.955	R_int = 0.070
22574 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.171	Δρ_max = 0.29 e Å⁻³
S = 1.00	Δρ_min = −0.15 e Å⁻³
4973 reflections	Absolute structure: Flack (1983), 2168 Friedel pairs
283 parameters	Absolute structure parameter: 0.02 (10)
51 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.98649 (9)	0.31614 (6)	0.61639 (6)	0.0683 (3)
O1	0.26118 (19)	0.62910 (16)	0.62120 (17)	0.0615 (6)
O4	0.72647 (19)	0.61810 (16)	0.58783 (16)	0.0580 (6)
O5	0.6370 (2)	0.58013 (18)	0.76505 (16)	0.0661 (7)
O2	0.3466 (2)	0.56628 (17)	0.44918 (16)	0.0631 (6)
O3	0.6070 (2)	0.51865 (17)	0.43975 (16)	0.0659 (7)
O6	0.3742 (2)	0.54342 (19)	0.77918 (17)	0.0686 (7)
C6	0.1812 (3)	0.6189 (3)	0.5450 (3)	0.0666 (10)
H6A	0.1124	0.6640	0.5498	0.080*
H6B	0.1466	0.5547	0.5439	0.080*
C12	0.8060 (3)	0.6151 (3)	0.6658 (3)	0.0690 (10)
H12A	0.8769	0.6575	0.6567	0.083*
H12B	0.8375	0.5506	0.6745	0.083*
C5	0.2518 (3)	0.6370 (3)	0.4595 (3)	0.0655 (9)
H5A	0.1954	0.6348	0.4074	0.079*
H5B	0.2895	0.7001	0.4618	0.079*
C7	0.1976 (3)	0.6136 (3)	0.7052 (3)	0.0729 (11)
H7A	0.1592	0.5507	0.7050	0.088*
H7B	0.1320	0.6611	0.7126	0.088*
C11	0.7341 (4)	0.6456 (3)	0.7479 (3)	0.0683 (10)
H11A	0.7893	0.6487	0.8006	0.082*
H11B	0.6993	0.7090	0.7378	0.082*
C3	0.5202 (4)	0.5127 (3)	0.3647 (2)	0.0742 (11)
H3A	0.4825	0.4494	0.3642	0.089*
H3B	0.5655	0.5207	0.3075	0.089*
C2	0.7006 (4)	0.5896 (3)	0.4281 (3)	0.0743 (11)
H2A	0.6621	0.6525	0.4247	0.089*
H2B	0.7456	0.5784	0.3714	0.089*
C4	0.4200 (4)	0.5857 (3)	0.3699 (2)	0.0745 (10)
H4A	0.4563	0.6493	0.3741	0.089*
H4B	0.3681	0.5830	0.3154	0.089*
C10	0.5660 (4)	0.6078 (3)	0.8436 (3)	0.0758 (11)
H10A	0.5341	0.6724	0.8357	0.091*
H10B	0.6185	0.6066	0.8979	0.091*
C9	0.4614 (4)	0.5398 (3)	0.8540 (3)	0.0822 (12)
H9A	0.4948	0.4754	0.8587	0.099*
H9B	0.4174	0.5539	0.9106	0.099*
C1	0.7897 (3)	0.5862 (3)	0.5074 (3)	0.0697 (10)
H1A	0.8195	0.5211	0.5161	0.084*
H1B	0.8612	0.6270	0.4952	0.084*
C8	0.2889 (4)	0.6209 (3)	0.7833 (3)	0.0818 (12)
H8A	0.3340	0.6810	0.7795	0.098*
H8B	0.2441	0.6194	0.8412	0.098*
O7	1.0420 (16)	0.4009 (9)	0.6144 (13)	0.197 (9)	0.50
O8	1.0022 (13)	0.2735 (7)	0.6991 (6)	0.140 (5)	0.50
O9	0.8759 (8)	0.3033 (10)	0.5711 (8)	0.152 (4)	0.50
O10	1.0765 (12)	0.2850 (9)	0.5452 (6)	0.172 (4)	0.50
O7'	0.9855 (17)	0.4068 (8)	0.6012 (13)	0.186 (8)	0.50
O8'	0.960 (2)	0.2425 (11)	0.5730 (13)	0.276 (10)	0.50
O9'	1.072 (2)	0.2849 (18)	0.6660 (13)	0.313 (13)	0.50
O10'	0.8799 (10)	0.3385 (8)	0.6824 (10)	0.184 (5)	0.50
N1	0.4833 (3)	0.45369 (18)	0.61194 (19)	0.0711 (9)
H1AA	0.4615	0.5025	0.6643	0.107*
H1BB	0.5139	0.4836	0.5651	0.107*
O20	0.9938 (2)	0.7613 (2)	0.3947 (2)	0.0993 (10)
H20A	0.9312	0.7809	0.3782	0.149*
H20B	1.0611	0.8000	0.3942	0.149*
C98	0.5941 (4)	0.3948 (3)	0.6317 (4)	0.0945 (14)
H98A	0.6657	0.4356	0.6395	0.142*
H98B	0.6087	0.3515	0.5817	0.142*
H98C	0.5803	0.3589	0.6870	0.142*
C99	0.3696 (4)	0.3968 (3)	0.6010 (3)	0.0905 (13)
H99A	0.3009	0.4383	0.5861	0.136*
H99B	0.3519	0.3636	0.6572	0.136*
H99C	0.3813	0.3511	0.5526	0.136*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0842 (6)	0.0557 (5)	0.0649 (5)	−0.0032 (5)	−0.0152 (5)	0.0061 (5)
O1	0.0462 (11)	0.0691 (15)	0.0693 (14)	−0.0068 (10)	0.0032 (12)	−0.0023 (13)
O4	0.0470 (12)	0.0637 (14)	0.0632 (14)	0.0053 (11)	−0.0018 (11)	0.0033 (11)
O5	0.0686 (15)	0.0762 (17)	0.0535 (14)	−0.0004 (14)	−0.0026 (13)	−0.0064 (12)
O2	0.0706 (15)	0.0653 (14)	0.0533 (13)	0.0008 (12)	0.0002 (12)	0.0075 (12)
O3	0.0718 (15)	0.0691 (15)	0.0569 (15)	0.0070 (13)	0.0017 (13)	0.0003 (13)
O6	0.0656 (15)	0.0867 (19)	0.0535 (14)	−0.0118 (14)	0.0089 (13)	−0.0105 (13)
C6	0.0490 (19)	0.068 (2)	0.083 (3)	0.0046 (17)	−0.005 (2)	0.007 (2)
C12	0.0472 (18)	0.073 (2)	0.087 (3)	−0.0077 (17)	−0.015 (2)	0.000 (2)
C5	0.059 (2)	0.061 (2)	0.076 (2)	0.0041 (18)	−0.011 (2)	0.0118 (19)
C7	0.0488 (19)	0.089 (3)	0.081 (3)	−0.0001 (19)	0.019 (2)	−0.014 (2)
C11	0.061 (2)	0.072 (2)	0.071 (2)	−0.0045 (19)	−0.013 (2)	−0.0100 (19)
C3	0.092 (3)	0.087 (3)	0.0432 (19)	0.016 (2)	−0.003 (2)	−0.0128 (18)
C2	0.089 (3)	0.079 (3)	0.054 (2)	0.012 (2)	0.018 (2)	0.008 (2)
C4	0.087 (2)	0.090 (3)	0.046 (2)	−0.002 (2)	−0.005 (2)	0.001 (2)
C10	0.083 (2)	0.095 (3)	0.049 (2)	−0.008 (2)	−0.008 (2)	−0.008 (2)
C9	0.105 (3)	0.095 (3)	0.047 (2)	−0.015 (3)	0.004 (2)	0.0011 (19)
C1	0.058 (2)	0.073 (3)	0.078 (3)	0.0017 (19)	0.017 (2)	0.006 (2)
C8	0.081 (3)	0.093 (3)	0.071 (3)	−0.011 (3)	0.016 (2)	−0.026 (2)
O7	0.232 (15)	0.149 (12)	0.209 (14)	−0.154 (12)	0.056 (12)	−0.047 (10)
O8	0.219 (14)	0.133 (7)	0.067 (4)	−0.045 (10)	−0.007 (6)	0.056 (4)
O9	0.089 (5)	0.204 (11)	0.161 (9)	−0.010 (6)	−0.055 (6)	−0.045 (9)
O10	0.192 (9)	0.221 (12)	0.103 (6)	0.045 (9)	0.057 (6)	−0.033 (7)
O7'	0.269 (19)	0.070 (7)	0.220 (14)	0.042 (9)	0.012 (14)	0.085 (8)
O8'	0.36 (2)	0.156 (11)	0.31 (2)	−0.123 (13)	0.08 (2)	−0.159 (14)
O9'	0.295 (19)	0.40 (3)	0.248 (19)	0.26 (2)	−0.030 (16)	0.118 (17)
O10'	0.127 (7)	0.174 (9)	0.251 (13)	0.008 (7)	0.059 (8)	−0.045 (9)
N1	0.121 (3)	0.0387 (14)	0.0533 (16)	0.0026 (17)	0.009 (2)	0.0043 (12)
O20	0.0592 (15)	0.0859 (19)	0.153 (3)	0.0080 (15)	0.0083 (19)	0.0404 (18)
C98	0.103 (3)	0.065 (2)	0.115 (4)	−0.013 (2)	−0.009 (3)	−0.008 (3)
C99	0.092 (3)	0.070 (2)	0.110 (4)	0.007 (2)	0.002 (3)	0.013 (3)

Geometric parameters (Å, º) top

Cl1—O8'	1.239 (9)	C11—H11A	0.9700
Cl1—O9'	1.246 (13)	C11—H11B	0.9700
Cl1—O7'	1.285 (9)	C3—C4	1.481 (5)
Cl1—O7	1.324 (9)	C3—H3A	0.9700
Cl1—O8	1.356 (8)	C3—H3B	0.9700
Cl1—O9	1.365 (7)	C2—C1	1.498 (5)
Cl1—O10	1.480 (8)	C2—H2A	0.9700
Cl1—O10'	1.523 (10)	C2—H2B	0.9700
O1—C6	1.409 (4)	C4—H4A	0.9700
O1—C7	1.418 (4)	C4—H4B	0.9700
O4—C12	1.420 (4)	C10—C9	1.474 (6)
O4—C1	1.425 (4)	C10—H10A	0.9700
O5—C11	1.405 (4)	C10—H10B	0.9700
O5—C10	1.427 (4)	C9—H9A	0.9700
O2—C5	1.422 (4)	C9—H9B	0.9700
O2—C4	1.422 (4)	C1—H1A	0.9700
O3—C2	1.418 (5)	C1—H1B	0.9700
O3—C3	1.437 (4)	C8—H8A	0.9700
O6—C8	1.415 (5)	C8—H8B	0.9700
O6—C9	1.435 (4)	N1—C99	1.460 (5)
C6—C5	1.479 (5)	N1—C98	1.469 (5)
C6—H6A	0.9700	N1—H1AA	1.0493
C6—H6B	0.9700	N1—H1BB	0.8642
C12—C11	1.485 (5)	O20—H20A	0.7616
C12—H12A	0.9700	O20—H20B	0.9001
C12—H12B	0.9700	C98—H98A	0.9600
C5—H5A	0.9700	C98—H98B	0.9600
C5—H5B	0.9700	C98—H98C	0.9600
C7—C8	1.502 (5)	C99—H99A	0.9600
C7—H7A	0.9700	C99—H99B	0.9600
C7—H7B	0.9700	C99—H99C	0.9600

O7—Cl1—O8	110.8 (9)	O3—C2—H2A	109.8
O7—Cl1—O9	119.6 (10)	C1—C2—H2A	109.8
O8—Cl1—O9	118.7 (8)	O3—C2—H2B	109.8
O7—Cl1—O10	87.5 (10)	C1—C2—H2B	109.8
O8—Cl1—O10	114.5 (8)	H2A—C2—H2B	108.2
O9—Cl1—O10	100.7 (7)	O2—C4—C3	108.0 (3)
O8'—Cl1—O9'	99.9 (16)	O2—C4—H4A	110.1
O8'—Cl1—O7'	136.6 (14)	C3—C4—H4A	110.1
O9'—Cl1—O7'	116.8 (15)	O2—C4—H4B	110.1
O8'—Cl1—O10'	109.0 (10)	C3—C4—H4B	110.1
O9'—Cl1—O10'	104.7 (9)	H4A—C4—H4B	108.4
O7'—Cl1—O10'	84.3 (10)	O5—C10—C9	108.2 (3)
C6—O1—C7	112.1 (2)	O5—C10—H10A	110.1
C12—O4—C1	111.5 (2)	C9—C10—H10A	110.1
C11—O5—C10	111.0 (3)	O5—C10—H10B	110.1
C5—O2—C4	110.3 (3)	C9—C10—H10B	110.1
C2—O3—C3	113.9 (3)	H10A—C10—H10B	108.4
C8—O6—C9	114.4 (3)	O6—C9—C10	113.1 (3)
O1—C6—C5	109.8 (3)	O6—C9—H9A	109.0
O1—C6—H6A	109.7	C10—C9—H9A	109.0
C5—C6—H6A	109.7	O6—C9—H9B	109.0
O1—C6—H6B	109.7	C10—C9—H9B	109.0
C5—C6—H6B	109.7	H9A—C9—H9B	107.8
H6A—C6—H6B	108.2	O4—C1—C2	108.9 (3)
O4—C12—C11	109.1 (3)	O4—C1—H1A	109.9
O4—C12—H12A	109.9	C2—C1—H1A	109.9
C11—C12—H12A	109.9	O4—C1—H1B	109.9
O4—C12—H12B	109.9	C2—C1—H1B	109.9
C11—C12—H12B	109.9	H1A—C1—H1B	108.3
H12A—C12—H12B	108.3	O6—C8—C7	109.5 (3)
O2—C5—C6	109.6 (3)	O6—C8—H8A	109.8
O2—C5—H5A	109.8	C7—C8—H8A	109.8
C6—C5—H5A	109.8	O6—C8—H8B	109.8
O2—C5—H5B	109.8	C7—C8—H8B	109.8
C6—C5—H5B	109.8	H8A—C8—H8B	108.2
H5A—C5—H5B	108.2	C99—N1—C98	112.8 (3)
O1—C7—C8	109.5 (3)	C99—N1—H1AA	104.3
O1—C7—H7A	109.8	C98—N1—H1AA	113.5
C8—C7—H7A	109.8	C99—N1—H1BB	119.3
O1—C7—H7B	109.8	C98—N1—H1BB	97.0
C8—C7—H7B	109.8	H1AA—N1—H1BB	110.2
H7A—C7—H7B	108.2	H20A—O20—H20B	118.8
O5—C11—C12	109.8 (3)	N1—C98—H98A	109.5
O5—C11—H11A	109.7	N1—C98—H98B	109.5
C12—C11—H11A	109.7	H98A—C98—H98B	109.5
O5—C11—H11B	109.7	N1—C98—H98C	109.5
C12—C11—H11B	109.7	H98A—C98—H98C	109.5
H11A—C11—H11B	108.2	H98B—C98—H98C	109.5
O3—C3—C4	112.8 (3)	N1—C99—H99A	109.5
O3—C3—H3A	109.0	N1—C99—H99B	109.5
C4—C3—H3A	109.0	H99A—C99—H99B	109.5
O3—C3—H3B	109.0	N1—C99—H99C	109.5
C4—C3—H3B	109.0	H99A—C99—H99C	109.5
H3A—C3—H3B	107.8	H99B—C99—H99C	109.5
O3—C2—C1	109.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1AA···O6	1.05	2.00	2.979 (4)	154
N1—H1AA···O5	1.05	2.62	3.285 (4)	121
N1—H1BB···O3	0.86	2.14	2.979 (4)	164
O20—H20B···O4ⁱ	0.90	2.12	3.013 (4)	171
O20—H20A···O1ⁱ	0.76	2.21	2.927 (3)	158

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₂H₈N⁺·ClO₄⁻·C₁₂H₂₄O₆·H₂O
M_r	427.87
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	10.684 (2), 13.954 (3), 14.583 (3)
V (Å³)	2174.1 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.4 × 0.3 × 0.2

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan CrystalClear (Rigaku, 2005)
T_min, T_max	0.955, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	22574, 4973, 2814
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.171, 1.00
No. of reflections	4973
No. of parameters	283
No. of restraints	51
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.15
Absolute structure	Flack (1983), 2168 Friedel pairs
Absolute structure parameter	0.02 (10)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1AA···O6	1.05	2.00	2.979 (4)	153.9
N1—H1BB···O3	0.86	2.14	2.979 (4)	164.1
O20—H20B···O4ⁱ	0.90	2.12	3.013 (4)	171.4
O20—H20A···O1ⁱ	0.76	2.21	2.927 (3)	157.7

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

Acknowledgements

The authors thank the start-up projects for the Postdoctoral Research Funds of Southeast University (grant No. 1112000047) and the starter fund of Southeast University for financial support to buy the X-ray diffractometer.

References

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