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

Zhao, M.-M.

doi:10.1107/S1600536812001572

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o444

doi:10.1107/S1600536812001572

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Propane-1,3-diaminium bis(tetrafluoroborate)–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 10 January 2012; accepted 13 January 2012; online 18 January 2012)

In the title compound, C₃H₁₂N₂²⁺·2BF₄⁻·2C₁₂H₂₄O₆, the central C atom of the propane-1,3-diammonium cation lies on a crystallographic twofold rotation axis. The terminal NH₃⁺ groups insert into the crown rings through strong N—H⋯O hydrogen-bonding interactions, resulting in the formation of a 1:2 supramolecular [(C₃H₁₂N₂)·(C₁₂H₂₄O₆)₂]²⁺ complex. The anions are linked to the supramolecular complexes via weak C—H⋯F hydrogen bonds. The F atoms of the anion are disordered over two orientations with site occupancies of 0.5.

Related literature

For the structures and properties of a related compounds, see: Fu et al. (2011 ); Zhao (2012 ) and references therein.

Experimental

Crystal data

C₃H₁₂N₂²⁺·2BF₄⁻·2C₁₂H₂₄O₆
M_r = 778.39
Monoclinic, C 2/c
a = 22.615 (5) Å
b = 8.8423 (18) Å
c = 21.077 (4) Å
β = 113.41 (3)°
V = 3867.8 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 K
0.10 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
16100 measured reflections
3413 independent reflections
2018 reflections with I > 2σ(I)
R_int = 0.079

Refinement

R[F² > 2σ(F²)] = 0.077
wR(F²) = 0.212
S = 1.13
3413 reflections
268 parameters
37 restraints
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2	0.89	2.06	2.915 (3)	161
N1—H1A⋯O4	0.89	2.03	2.911 (4)	169
N1—H1C⋯O6	0.89	2.08	2.967 (4)	179
C12—H12B⋯F4′	0.97	2.48	3.316 (19)	144
C13—H13A⋯F2	0.97	2.47	3.346 (12)	150
C13—H13A⋯F2′	0.97	2.42	3.361 (16)	162
C5—H5A⋯F3′ⁱ	0.97	2.41	3.350 (18)	162
C10—H10B⋯F1′ⁱⁱ	0.97	2.41	3.355 (17)	166
C10—H10B⋯F2′ⁱⁱ	0.97	2.44	3.235 (19)	139
C8—H8A⋯F3′ⁱⁱⁱ	0.97	2.50	3.412 (14)	156
Symmetry codes: (i) $[-x, y, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) $[-x, y+1, -z+{\script{1\over 2}}]$ .

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/S1600536812001572/rz2697sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001572/rz2697Isup2.hkl

checkCIF report

Comment top

As a continuation of the research project devoted to the synthesis and characterization of novel phase transition crystals of amino compounds (Zhao, 2012), the crystal structure of the title compound is reported herein.

The title compound is composed of [(C₃H₁₂N₂).(C₁₂H₂₄O₆)₂]²⁺ cations and BF₄^- anions (Fig. 1). A 1:2 supramolecular rotator-stator structure is generated between one propane-1,3-diammonium dication and two 18-crown-6 molecules through six N—H···O hydrogen bonds (Table 1) occurring between the protons of the NH₃⁺ groups and the O atoms of the crown ethers. The supramolecular rotator has crystallographically imposed twofold rotation symmetry, the central C atom of the propane-1,3-diammonium cation lying on a crystallographic twofold rotation axis. 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 the cation are almost perpendicular to the mean planes of the oxygen atoms of the crown ethers. The supramolecular structure is introduced as counter cation to BF₄^- anions. The B atom has a flattened tetrahedral coordination geometry provided by four F atoms [range of cis-bond angles = 121.6 (5)-89.1 (9) °; dav(F-B) = 1.226 (9)-1.445 (9)Å]. All F atoms of the BF₄^- anion are disordered over two orientations. In the crystal structure (Fig. 2), cations and anions are linked by weak interionic C—H···F hydrogen bonds (Table 1).

Related literature top

For the structures and properties of a related compounds, see: Fu et al. (2011); Zhao (2012) and references therein.

Experimental top

Commercial 18-crown-6 (6 mmol), HBF₄ (6 mmol) and propane-1,3-diamine (3 mmol) were dissolved in a 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 the 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 (412 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 4.5 to 8.8).

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. The structure of the title compound with displacement ellipsoids drawn at the 30% probability level. Only H atoms of the NH₃⁺ groups are shown. Symmetry code: (A) -x, +y, 1/2-z.
	Fig. 2. Crystal packing of the title compound approximately viewed along the b axis. Only hydrogen atoms involved in N—H···O hydrogen bonds (dashed line) are shown.

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

Crystal data top

C₃H₁₂N₂²⁺·2BF₄⁻·2C₁₂H₂₄O₆	F(000) = 1656
M_r = 778.39	D_x = 1.337 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3410 reflections
a = 22.615 (5) Å	θ = 2.9–27.5°
b = 8.8423 (18) Å	µ = 0.12 mm⁻¹
c = 21.077 (4) Å	T = 298 K
β = 113.41 (3)°	Block, colourless
V = 3867.8 (16) Å³	0.10 × 0.05 × 0.05 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	3413 independent reflections
Radiation source: fine-focus sealed tube	2018 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
Detector resolution: 13.6612 pixels mm^-1	θ_max = 25.0°, θ_min = 3.0°
CCD profile fitting scans	h = −26→26
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.910, T_max = 1.000	l = −25→25
16100 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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.212	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.080P)² + 3.2068P] where P = (F_o² + 2F_c²)/3
3413 reflections	(Δ/σ)_max < 0.001
268 parameters	Δρ_max = 0.31 e Å⁻³
37 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₃H₁₂N₂²⁺·2BF₄⁻·2C₁₂H₂₄O₆	V = 3867.8 (16) Å³
M_r = 778.39	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.615 (5) Å	µ = 0.12 mm⁻¹
b = 8.8423 (18) Å	T = 298 K
c = 21.077 (4) Å	0.10 × 0.05 × 0.05 mm
β = 113.41 (3)°

Data collection top

Rigaku Mercury2 diffractometer	3413 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2018 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.079
16100 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.077	37 restraints
wR(F²) = 0.212	H-atom parameters constrained
S = 1.13	Δρ_max = 0.31 e Å⁻³
3413 reflections	Δρ_min = −0.23 e Å⁻³
268 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	Occ. (<1)
O2	0.19727 (10)	0.6715 (3)	0.26770 (12)	0.0558 (6)
O3	0.15021 (11)	0.7740 (3)	0.12991 (13)	0.0650 (7)
N1	0.10547 (11)	0.9201 (3)	0.23703 (13)	0.0433 (7)
H1A	0.0918	0.9641	0.1957	0.065*
H1B	0.1379	0.8578	0.2419	0.065*
H1C	0.1189	0.9907	0.2698	0.065*
O1	0.22029 (12)	0.8928 (3)	0.37179 (12)	0.0646 (7)
O4	0.07376 (13)	1.0406 (3)	0.09880 (15)	0.0786 (9)
O5	0.10078 (13)	1.2567 (3)	0.20532 (18)	0.0850 (9)
O6	0.14972 (14)	1.1589 (3)	0.34468 (17)	0.0771 (8)
C2	0.25128 (17)	0.6683 (4)	0.3313 (2)	0.0652 (11)
H2A	0.2862	0.7248	0.3269	0.078*
H2B	0.2654	0.5647	0.3431	0.078*
C3	0.21010 (19)	0.5983 (4)	0.2141 (2)	0.0652 (11)
H3A	0.2180	0.4915	0.2244	0.078*
H3B	0.2483	0.6418	0.2112	0.078*
C6	0.0933 (2)	0.9686 (6)	0.0513 (2)	0.0876 (15)
H6A	0.1345	1.0089	0.0555	0.105*
H6B	0.0621	0.9881	0.0047	0.105*
C1	0.2343 (2)	0.7359 (5)	0.3861 (2)	0.0714 (12)
H1D	0.1971	0.6845	0.3879	0.086*
H1E	0.2700	0.7243	0.4306	0.086*
C7	0.0639 (2)	1.2022 (6)	0.0872 (3)	0.0953 (18)
H7A	0.1024	1.2499	0.0868	0.114*
H7B	0.0289	1.2203	0.0427	0.114*
C5	0.0984 (2)	0.8034 (5)	0.06412 (19)	0.0801 (13)
H5A	0.0580	0.7645	0.0633	0.096*
H5B	0.1075	0.7525	0.0282	0.096*
C10	0.1474 (3)	1.3118 (5)	0.3255 (3)	0.0974 (16)
H10A	0.1872	1.3399	0.3215	0.117*
H10B	0.1429	1.3738	0.3613	0.117*
C4	0.1550 (2)	0.6196 (5)	0.1473 (2)	0.0736 (12)
H4A	0.1616	0.5609	0.1118	0.088*
H4B	0.1157	0.5848	0.1509	0.088*
C11	0.2008 (3)	1.1288 (6)	0.4107 (2)	0.0910 (15)
H11A	0.1929	1.1804	0.4472	0.109*
H11B	0.2412	1.1654	0.4106	0.109*
C9	0.0925 (3)	1.3385 (5)	0.2604 (3)	0.0963 (17)
H9A	0.0528	1.3078	0.2641	0.116*
H9B	0.0895	1.4458	0.2499	0.116*
C8	0.0481 (2)	1.2698 (6)	0.1433 (4)	0.1030 (18)
H8A	0.0369	1.3756	0.1333	0.124*
H8B	0.0114	1.2179	0.1462	0.124*
C12	0.2061 (2)	0.9645 (6)	0.4233 (2)	0.0851 (13)
H12A	0.2395	0.9425	0.4684	0.102*
H12B	0.1654	0.9272	0.4224	0.102*
B1	0.0793 (3)	0.6074 (7)	0.4303 (3)	0.0773 (15)
C14	0.0000	0.9285 (5)	0.2500	0.0449 (11)
H14A	0.0184	0.9930	0.2904	0.054*
C13	0.05211 (15)	0.8336 (4)	0.2431 (2)	0.0552 (9)
H13A	0.0699	0.7687	0.2834	0.066*
H13B	0.0330	0.7690	0.2028	0.066*
F2	0.0550 (6)	0.5710 (10)	0.3586 (6)	0.090 (3)	0.50
F3	0.0439 (7)	0.5494 (15)	0.4626 (7)	0.110 (5)	0.50
F4	0.0679 (5)	0.7681 (8)	0.4203 (4)	0.118 (3)	0.50
F1	0.1357 (3)	0.5838 (17)	0.4687 (6)	0.163 (5)	0.50
F1'	0.1185 (8)	0.4723 (15)	0.4546 (6)	0.220 (6)	0.50
F2'	0.0789 (8)	0.5857 (18)	0.3725 (7)	0.172 (7)	0.50
F3'	0.0256 (7)	0.5942 (19)	0.4373 (9)	0.166 (7)	0.50
F4'	0.1152 (8)	0.7196 (18)	0.4632 (7)	0.186 (6)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0451 (13)	0.0560 (14)	0.0655 (16)	0.0094 (11)	0.0213 (12)	0.0071 (12)
O3	0.0583 (15)	0.0699 (17)	0.0626 (17)	−0.0108 (13)	0.0197 (13)	−0.0076 (13)
N1	0.0392 (14)	0.0452 (15)	0.0476 (15)	0.0051 (12)	0.0196 (12)	0.0064 (12)
O1	0.0721 (17)	0.0758 (17)	0.0456 (14)	−0.0101 (14)	0.0230 (13)	0.0011 (12)
O4	0.0700 (18)	0.088 (2)	0.0635 (18)	−0.0096 (15)	0.0110 (14)	0.0276 (16)
O5	0.0607 (18)	0.0645 (18)	0.128 (3)	0.0193 (14)	0.0355 (18)	0.0222 (17)
O6	0.093 (2)	0.0527 (16)	0.104 (2)	−0.0128 (15)	0.0591 (19)	−0.0153 (15)
C2	0.048 (2)	0.066 (2)	0.071 (3)	0.0021 (18)	0.011 (2)	0.024 (2)
C3	0.074 (3)	0.045 (2)	0.092 (3)	0.0139 (19)	0.049 (2)	0.0021 (19)
C6	0.069 (3)	0.125 (4)	0.045 (2)	−0.035 (3)	−0.002 (2)	0.018 (3)
C1	0.068 (3)	0.074 (3)	0.057 (2)	−0.004 (2)	0.009 (2)	0.027 (2)
C7	0.059 (3)	0.097 (4)	0.088 (3)	−0.019 (2)	−0.015 (2)	0.061 (3)
C5	0.069 (3)	0.112 (4)	0.044 (2)	−0.026 (2)	0.006 (2)	−0.014 (2)
C10	0.113 (4)	0.065 (3)	0.144 (5)	−0.001 (3)	0.083 (4)	−0.027 (3)
C4	0.078 (3)	0.072 (3)	0.081 (3)	−0.009 (2)	0.043 (3)	−0.023 (2)
C11	0.099 (3)	0.111 (4)	0.069 (3)	−0.025 (3)	0.040 (3)	−0.037 (3)
C9	0.100 (4)	0.046 (2)	0.183 (6)	0.021 (3)	0.100 (4)	0.011 (3)
C8	0.066 (3)	0.071 (3)	0.160 (6)	0.007 (2)	0.032 (4)	0.047 (3)
C12	0.087 (3)	0.108 (4)	0.062 (3)	−0.019 (3)	0.032 (2)	−0.012 (3)
B1	0.073 (4)	0.090 (4)	0.087 (4)	−0.020 (3)	0.051 (3)	−0.033 (3)
C14	0.038 (2)	0.038 (2)	0.059 (3)	0.000	0.020 (2)	0.000
C13	0.0443 (18)	0.0430 (18)	0.084 (3)	−0.0031 (16)	0.0320 (18)	−0.0038 (18)
F2	0.118 (7)	0.076 (4)	0.053 (4)	0.018 (4)	0.010 (4)	0.005 (3)
F3	0.155 (12)	0.100 (6)	0.111 (6)	−0.061 (7)	0.091 (7)	−0.012 (4)
F4	0.178 (8)	0.075 (4)	0.099 (5)	−0.020 (4)	0.052 (5)	−0.016 (3)
F1	0.057 (4)	0.207 (10)	0.160 (8)	−0.022 (5)	−0.025 (4)	0.059 (9)
F1'	0.347 (17)	0.195 (9)	0.148 (9)	0.138 (11)	0.131 (10)	0.066 (8)
F2'	0.168 (14)	0.252 (14)	0.091 (8)	0.078 (9)	0.048 (9)	−0.038 (7)
F3'	0.094 (7)	0.203 (15)	0.246 (18)	−0.048 (8)	0.115 (11)	−0.116 (11)
F4'	0.227 (13)	0.193 (9)	0.198 (12)	−0.162 (10)	0.146 (10)	−0.128 (10)

Geometric parameters (Å, º) top

O2—C2	1.410 (4)	C10—C9	1.459 (7)
O2—C3	1.429 (4)	C10—H10A	0.9700
O3—C4	1.407 (5)	C10—H10B	0.9700
O3—C5	1.439 (4)	C4—H4A	0.9698
N1—C13	1.477 (4)	C4—H4B	0.9701
N1—H1A	0.8900	C11—C12	1.473 (7)
N1—H1B	0.8900	C11—H11A	0.9699
N1—H1C	0.8900	C11—H11B	0.9699
O1—C12	1.400 (5)	C9—H9A	0.9699
O1—C1	1.428 (5)	C9—H9B	0.9700
O4—C6	1.397 (6)	C8—H8A	0.9700
O4—C7	1.452 (5)	C8—H8B	0.9700
O5—C8	1.380 (6)	C12—H12A	0.9699
O5—C9	1.442 (6)	C12—H12B	0.9700
O6—C10	1.405 (5)	B1—F1	1.226 (9)
O6—C11	1.436 (6)	B1—F2'	1.228 (15)
C2—C1	1.481 (6)	B1—F3'	1.286 (14)
C2—H2A	0.9701	B1—F4'	1.296 (9)
C2—H2B	0.9700	B1—F3	1.342 (11)
C3—C4	1.475 (6)	B1—F2	1.423 (13)
C3—H3A	0.9699	B1—F4	1.445 (9)
C3—H3B	0.9699	B1—F1'	1.454 (11)
C6—C5	1.482 (6)	C14—C13	1.501 (4)
C6—H6A	0.9701	C14—C13ⁱ	1.501 (4)
C6—H6B	0.9700	C14—H14A	0.9700
C1—H1D	0.9701	C13—H13A	0.9701
C1—H1E	0.9699	C13—H13B	0.9700
C7—C8	1.490 (7)	F2—F2'	0.52 (3)
C7—H7A	0.9700	F3—F3'	0.66 (2)
C7—H7B	0.9699	F4—F4'	1.174 (18)
C5—H5A	0.9700	F1—F1'	1.058 (15)
C5—H5B	0.9700	F1—F4'	1.275 (16)

C2—O2—C3	111.8 (3)	O5—C9—C10	110.0 (4)
C4—O3—C5	112.0 (3)	O5—C9—H9A	110.2
C13—N1—H1A	109.5	C10—C9—H9A	110.3
C13—N1—H1B	109.5	O5—C9—H9B	109.1
H1A—N1—H1B	109.5	C10—C9—H9B	109.2
C13—N1—H1C	109.5	H9A—C9—H9B	108.0
H1A—N1—H1C	109.5	O5—C8—C7	109.2 (4)
H1B—N1—H1C	109.5	O5—C8—H8A	109.8
C12—O1—C1	112.1 (3)	C7—C8—H8A	109.7
C6—O4—C7	113.5 (4)	O5—C8—H8B	109.8
C8—O5—C9	112.4 (4)	C7—C8—H8B	109.9
C10—O6—C11	112.4 (4)	H8A—C8—H8B	108.4
O2—C2—C1	109.8 (3)	O1—C12—C11	109.5 (4)
O2—C2—H2A	109.3	O1—C12—H12A	109.9
C1—C2—H2A	109.9	C11—C12—H12A	110.5
O2—C2—H2B	109.6	O1—C12—H12B	109.8
C1—C2—H2B	109.9	C11—C12—H12B	108.8
H2A—C2—H2B	108.3	H12A—C12—H12B	108.4
O2—C3—C4	109.6 (3)	F1—B1—F2'	102.9 (11)
O2—C3—H3A	109.9	F1—B1—F3'	133.6 (11)
C4—C3—H3A	110.5	F2'—B1—F3'	117.7 (12)
O2—C3—H3B	109.6	F1—B1—F4'	60.7 (9)
C4—C3—H3B	109.0	F2'—B1—F4'	114.0 (11)
H3A—C3—H3B	108.1	F3'—B1—F4'	115.3 (10)
O4—C6—C5	110.0 (4)	F1—B1—F3	105.8 (9)
O4—C6—H6A	109.5	F2'—B1—F3	132.3 (11)
C5—C6—H6A	110.0	F4'—B1—F3	113.2 (9)
O4—C6—H6B	109.6	F1—B1—F2	121.6 (10)
C5—C6—H6B	109.4	F3'—B1—F2	96.7 (10)
H6A—C6—H6B	108.2	F4'—B1—F2	129.6 (9)
O1—C1—C2	109.4 (3)	F3—B1—F2	113.3 (9)
O1—C1—H1D	109.9	F1—B1—F4	110.0 (8)
C2—C1—H1D	109.9	F2'—B1—F4	94.5 (9)
O1—C1—H1E	109.6	F3'—B1—F4	89.1 (9)
C2—C1—H1E	109.8	F4'—B1—F4	50.4 (8)
H1D—C1—H1E	108.3	F3—B1—F4	110.0 (8)
O4—C7—C8	109.3 (4)	F2—B1—F4	95.5 (6)
O4—C7—H7A	110.5	F1—B1—F1'	45.5 (7)
C8—C7—H7A	109.4	F2'—B1—F1'	89.1 (9)
O4—C7—H7B	109.7	F3'—B1—F1'	110.9 (11)
C8—C7—H7B	109.8	F4'—B1—F1'	106.0 (12)
H7A—C7—H7B	108.1	F3—B1—F1'	84.9 (9)
O3—C5—C6	109.2 (3)	F2—B1—F1'	96.5 (7)
O3—C5—H5A	110.7	F4—B1—F1'	155.2 (9)
C6—C5—H5A	109.9	C13—C14—C13ⁱ	112.0 (4)
O3—C5—H5B	108.9	C13—C14—H14A	109.6
C6—C5—H5B	110.0	C13ⁱ—C14—H14A	108.8
H5A—C5—H5B	108.2	N1—C13—C14	114.8 (3)
O6—C10—C9	110.3 (4)	N1—C13—H13A	108.3
O6—C10—H10A	110.0	C14—C13—H13A	108.3
C9—C10—H10A	110.4	N1—C13—H13B	108.9
O6—C10—H10B	108.9	C14—C13—H13B	108.7
C9—C10—H10B	109.0	H13A—C13—H13B	107.6
H10A—C10—H10B	108.1	F2'—F2—B1	58 (3)
O3—C4—C3	108.7 (3)	F3'—F3—B1	70.8 (17)
O3—C4—H4A	109.7	F4'—F4—B1	58.2 (6)
C3—C4—H4A	109.7	F1'—F1—B1	78.7 (9)
O3—C4—H4B	110.6	F1'—F1—F4'	140.6 (13)
C3—C4—H4B	109.7	B1—F1—F4'	62.4 (7)
H4A—C4—H4B	108.5	F1—F1'—B1	55.8 (6)
O6—C11—C12	109.5 (4)	F2—F2'—B1	101 (3)
O6—C11—H11A	110.6	F3—F3'—B1	80 (2)
C12—C11—H11A	110.4	F4—F4'—F1	126.9 (10)
O6—C11—H11B	109.4	F4—F4'—B1	71.4 (8)
C12—C11—H11B	108.6	F1—F4'—B1	57.0 (6)
H11A—C11—H11B	108.2

C3—O2—C2—C1	−176.1 (3)	F4—B1—F1—F1'	−175.3 (10)
C2—O2—C3—C4	−173.6 (3)	F2'—B1—F1—F4'	110.5 (12)
C7—O4—C6—C5	−176.6 (3)	F3'—B1—F1—F4'	−98.1 (14)
C12—O1—C1—C2	−177.8 (3)	F3—B1—F1—F4'	−108.0 (10)
O2—C2—C1—O1	−65.5 (4)	F2—B1—F1—F4'	120.9 (11)
C6—O4—C7—C8	−175.9 (3)	F4—B1—F1—F4'	10.8 (9)
C4—O3—C5—C6	176.1 (4)	F1'—B1—F1—F4'	−173.9 (14)
O4—C6—C5—O3	−66.6 (4)	F4'—F1—F1'—B1	9 (2)
C11—O6—C10—C9	−176.4 (4)	F2'—B1—F1'—F1	109.2 (14)
C5—O3—C4—C3	178.3 (3)	F3'—B1—F1'—F1	−131.3 (15)
O2—C3—C4—O3	66.2 (4)	F4'—B1—F1'—F1	−5.5 (13)
C10—O6—C11—C12	−172.4 (4)	F3—B1—F1'—F1	−118.2 (13)
C8—O5—C9—C10	175.9 (4)	F2—B1—F1'—F1	128.9 (12)
O6—C10—C9—O5	−65.0 (5)	F4—B1—F1'—F1	10 (2)
C9—O5—C8—C7	171.7 (3)	F1—B1—F2'—F2	155 (3)
O4—C7—C8—O5	65.7 (4)	F3'—B1—F2'—F2	−2 (3)
C1—O1—C12—C11	172.4 (3)	F4'—B1—F2'—F2	−142 (3)
O6—C11—C12—O1	60.6 (5)	F3—B1—F2'—F2	29 (3)
C13ⁱ—C14—C13—N1	−179.2 (4)	F4—B1—F2'—F2	−94 (3)
F1—B1—F2—F2'	−29 (3)	F1'—B1—F2'—F2	111 (3)
F3'—B1—F2—F2'	178 (3)	F1—B1—F3'—F3	−20 (4)
F4'—B1—F2—F2'	47 (3)	F2'—B1—F3'—F3	128 (3)
F3—B1—F2—F2'	−157 (3)	F4'—B1—F3'—F3	−93 (3)
F4—B1—F2—F2'	88 (3)	F2—B1—F3'—F3	127 (3)
F1'—B1—F2—F2'	−70 (3)	F4—B1—F3'—F3	−137 (3)
F1—B1—F3—F3'	165 (3)	F1'—B1—F3'—F3	28 (3)
F2'—B1—F3—F3'	−70 (3)	B1—F4—F4'—F1	13.8 (11)
F4'—B1—F3—F3'	101 (3)	F1'—F1—F4'—F4	−25 (3)
F2—B1—F3—F3'	−59 (3)	B1—F1—F4'—F4	−15.7 (12)
F4—B1—F3—F3'	46 (3)	F1'—F1—F4'—B1	−9 (2)
F1'—B1—F3—F3'	−154 (3)	F1—B1—F4'—F4	166.8 (11)
F1—B1—F4—F4'	−12.2 (10)	F2'—B1—F4'—F4	75.1 (12)
F2'—B1—F4—F4'	−117.7 (11)	F3'—B1—F4'—F4	−65.6 (13)
F3'—B1—F4—F4'	124.6 (11)	F3—B1—F4'—F4	−97.4 (11)
F3—B1—F4—F4'	104.0 (11)	F2—B1—F4'—F4	58.4 (14)
F2—B1—F4—F4'	−138.8 (9)	F1'—B1—F4'—F4	171.4 (9)
F1'—B1—F4—F4'	−20.1 (19)	F2'—B1—F4'—F1	−91.7 (13)
F2'—B1—F1—F1'	−75.6 (13)	F3'—B1—F4'—F1	127.6 (13)
F3'—B1—F1—F1'	76 (2)	F3—B1—F4'—F1	95.7 (11)
F4'—B1—F1—F1'	173.9 (14)	F2—B1—F4'—F1	−108.4 (14)
F3—B1—F1—F1'	65.9 (14)	F4—B1—F4'—F1	−166.8 (11)
F2—B1—F1—F1'	−65.2 (12)	F1'—B1—F4'—F1	4.5 (11)

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—H1B···O2	0.89	2.06	2.915 (3)	161
N1—H1A···O4	0.89	2.03	2.911 (4)	169
N1—H1C···O6	0.89	2.08	2.967 (4)	179
C12—H12B···F4′	0.97	2.48	3.316 (19)	144
C13—H13A···F2	0.97	2.47	3.346 (12)	150
C13—H13A···F2′	0.97	2.42	3.361 (16)	162
C5—H5A···F3′ⁱ	0.97	2.41	3.350 (18)	162
C10—H10B···F1′ⁱⁱ	0.97	2.41	3.355 (17)	166
C10—H10B···F2′ⁱⁱ	0.97	2.44	3.235 (19)	139
C8—H8A···F3′ⁱⁱⁱ	0.97	2.50	3.412 (14)	156

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

Experimental details

Crystal data
Chemical formula	C₃H₁₂N₂²⁺·2BF₄⁻·2C₁₂H₂₄O₆
M_r	778.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	22.615 (5), 8.8423 (18), 21.077 (4)
β (°)	113.41 (3)
V (Å³)	3867.8 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.10 × 0.05 × 0.05

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	16100, 3413, 2018
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.077, 0.212, 1.13
No. of reflections	3413
No. of parameters	268
No. of restraints	37
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.23

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—H1B···O2	0.89	2.06	2.915 (3)	161.4
N1—H1A···O4	0.89	2.03	2.911 (4)	169.1
N1—H1C···O6	0.89	2.08	2.967 (4)	178.7
C12—H12B···F4'	0.97	2.48	3.316 (19)	144
C13—H13A···F2	0.97	2.47	3.346 (12)	150
C13—H13A···F2'	0.97	2.42	3.361 (16)	162
C5—H5A···F3'ⁱ	0.97	2.41	3.350 (18)	162
C10—H10B···F1'ⁱⁱ	0.97	2.41	3.355 (17)	166
C10—H10B···F2'ⁱⁱ	0.97	2.44	3.235 (19)	139
C8—H8A···F3'ⁱⁱⁱ	0.97	2.50	3.412 (14)	155.49

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

Acknowledgements

This work was supported by a start-up grant from Southeast University, People's Republic of China.

References

Fu, D.-W., Zhang, W., Cai, H.-L., Zhang, Y., Ge, J.-Z., Xiong, R.-G. & Huang, S. P. D. (2011). J. Am. Chem. Soc. 133, 12780–12786. Web of Science CSD CrossRef CAS PubMed 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
Zhao, M.-M. (2012). Acta Cryst. E68, o327. Web of Science CSD CrossRef IUCr Journals Google Scholar