4-Benzyl-4-ethyl­morpholin-1-ium hexa­fluoro­phosphate

Yang, F.; Zang, H.; Cheng, B.; Xu, X.; Ren, Y.

doi:10.1107/S1600536812001006

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o840

doi:10.1107/S1600536812001006

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4-Benzyl-4-ethylmorpholin-1-ium hexafluorophosphate

Fang Yang,^a Hongjun Zang,^a ^* Bowen Cheng,^a Xianlin Xu ^a and Yuanlin Ren ^a

^aDepartment of Enviromental and Chemistry Engineering, Tianjin Polytechnic University, State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin 300160, People's Republic of China
^*Correspondence e-mail: chemhong@126.com

(Received 19 December 2011; accepted 9 January 2012; online 24 February 2012)

The asymmetric unit of the title compound, C₁₃H₂₀NO⁺·PF₆⁻, contains two cations, one complete anion and two half hexafluorophosphate anions having crystallographically imposed twofold rotation symmetry. In the cations, the morpholine rings are in a chair conformation. In the crystal, ions are linked by weak C—H⋯F hydrogen bonds into a three-dimensional network.

Related literature

For background to the properties and applications of quaternary ammonium-based compounds as room temperature ionic liquids (RTILs), see: Abedin et al. (2004 , 2005 ); Kim et al. (2006 ). For ring puckering parameters, see: Cremer & Pople (1975 ) For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₂₀NO⁺·PF₆⁻
M_r = 351.27
Orthorhombic, F d d 2
a = 26.054 (3) Å
b = 28.528 (3) Å
c = 16.2950 (15) Å
V = 12111 (2) Å³
Z = 32
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 113 K
0.22 × 0.20 × 0.18 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.948, T_max = 0.957
39690 measured reflections
8072 independent reflections
7799 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.078
S = 1.11
8072 reflections
402 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 3877 Friedel pairs
Flack parameter: −0.06 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯F4	0.99	2.41	3.211 (2)	138
C3—H3B⋯F2ⁱ	0.99	2.47	3.389 (2)	155
C5—H5B⋯F11ⁱⁱ	0.99	2.48	3.365 (2)	150
C10—H10⋯F10ⁱⁱⁱ	0.95	2.50	3.288 (2)	141
C17—H17A⋯F8^iv	0.99	2.37	3.329 (2)	162
C17—H17B⋯F1	0.99	2.46	3.357 (2)	150
C25—H25B⋯F1	0.99	2.53	3.388 (2)	145
Symmetry codes: (i) $[-x+{\script{3\over 4}}, y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (ii) $[x+{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 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: CrystalStructure (Rigaku, 2007 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812001006/rz2692sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001006/rz2692Isup2.hkl

checkCIF report

Comment top

The seemingly ever growing interest on room temperature ionic liquids (RTILs) has turned the spotlight, along with many others, to quaternary ammonium-based compounds. The excellent conductivity, broad electrochemical window, thermal stability, and low volatility of ILs have made them promising media for electrochemical processes (Abedin et al., 2004; Abedin et al., 2005). RTILs based on the morpholinium cation are favored because of their low cost, easy synthesis, and electrochemical stability (Kim et al., 2006). We report here a new example structure of this class of compounds.

The asymmetric unit of the title compound (Fig. 1) consists of two cations, one PF₆^- anion and two half of PF₆^- anion having crystallographically imposed twofold rotation symmetry. In the cations, the morpholine rings adopt a chair conformation, with puckering parameters Q, θ and ϕ (Cremer & Pople, 1975) of 0.5757 (17) Å, 4.07 (14)°, 169 (2)° and 0.5607 (15) Å, 4.15 (14)°, 177 (3)° for N1/C1/C2/O1/C3/C4 and N2/C14/C15/O2/C16/C17, respectively. All bond distances and angles in the cation are normal within experimental error (Allen et al., 1987). In the crystal packing, cations and anions are involved in weak C—H···F hydrogen bonds (Table 1) linking ions into a three-dimensional network (Fig. 2).

Related literature top

For background to the properties and applications of quaternary ammonium-based compounds as room temperature ionic liquids (RTILs), see: Abedin et al. (2004, 2005); Kim et al. (2006). For ring puckering parameters, see: Cremer & Pople (1975) For bond-length data, see: Allen et al. (1987).

Experimental top

N-Benzyl-N-ethylmorpholinium hexafluorophosphate was synthesized by dissolving the N-benzyl-N-ethylmorpholinium chloride (12.1 g, 0.05 mol) in a minimum volume of deionized water and adding the stoichiomeric amount (1:1) of 60% HPF₆ solution. The mixture was stirred for about 5 min at 0°C causing the precipitation of a quaternary ammonium hexafluorophosphate from the solution. The raw product was filtered and washed with water until the solution was neutral. The product was recrystallized from the methanol/ethyl acetate solvent (1:1 v/v) and dried in vacuo.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 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: CrystalStructure (Rigaku, 2007).

Figures top

	Fig. 1. The asymmetric unit of the title compound showing displacement ellipsoids drawn at the 30% probability level. Symmetry code: (A) -x, -y, z.
	Fig. 2. Crystal packing of the title compound. Interionic hydrogen bonds are shown as dashed lines.

4-Benzyl-4-ethylmorpholin-1-ium hexafluorophosphate top

Crystal data top

C₁₃H₂₀NO⁺·PF₆⁻	F(000) = 5824
M_r = 351.27	D_x = 1.541 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: F 2 -2d	Cell parameters from 11300 reflections
a = 26.054 (3) Å	θ = 2.1–29.1°
b = 28.528 (3) Å	µ = 0.25 mm⁻¹
c = 16.2950 (15) Å	T = 113 K
V = 12111 (2) Å³	Block, colourless
Z = 32	0.22 × 0.20 × 0.18 mm

Data collection top

Rigaku Saturn diffractometer	8072 independent reflections
Radiation source: rotating anode	7799 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.042
Detector resolution: 14.63 pixels mm^-1	θ_max = 29.1°, θ_min = 2.1°
ω and ϕ scans	h = −35→35
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −38→38
T_min = 0.948, T_max = 0.957	l = −22→22
39690 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.0336P)² + 3.6844P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.078	(Δ/σ)_max = 0.001
S = 1.11	Δρ_max = 0.31 e Å⁻³
8072 reflections	Δρ_min = −0.24 e Å⁻³
402 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.00044 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 3877 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.06 (5)

Crystal data top

C₁₃H₂₀NO⁺·PF₆⁻	V = 12111 (2) Å³
M_r = 351.27	Z = 32
Orthorhombic, Fdd2	Mo Kα radiation
a = 26.054 (3) Å	µ = 0.25 mm⁻¹
b = 28.528 (3) Å	T = 113 K
c = 16.2950 (15) Å	0.22 × 0.20 × 0.18 mm

Data collection top

Rigaku Saturn diffractometer	8072 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	7799 reflections with I > 2σ(I)
T_min = 0.948, T_max = 0.957	R_int = 0.042
39690 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.078	Δρ_max = 0.31 e Å⁻³
S = 1.11	Δρ_min = −0.24 e Å⁻³
8072 reflections	Absolute structure: Flack (1983), 3877 Friedel pairs
402 parameters	Absolute structure parameter: −0.06 (5)
1 restraint

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
P1	0.243907 (17)	0.017672 (16)	0.61924 (3)	0.02020 (9)
P2	0.0000	0.0000	0.43883 (4)	0.02273 (14)
P3	0.0000	0.0000	0.04698 (4)	0.02275 (14)
F1	0.30299 (4)	0.02779 (4)	0.64111 (7)	0.0343 (3)
F2	0.23883 (5)	−0.01213 (5)	0.70168 (8)	0.0478 (4)
F3	0.22767 (5)	0.06362 (5)	0.66893 (8)	0.0449 (3)
F4	0.24903 (4)	0.04840 (4)	0.53785 (8)	0.0396 (3)
F5	0.26089 (5)	−0.02761 (4)	0.56973 (9)	0.0432 (3)
F6	0.18516 (4)	0.00756 (4)	0.59767 (7)	0.0275 (2)
F7	0.0000	0.0000	0.34159 (10)	0.0413 (4)
F8	0.06135 (4)	0.00085 (4)	0.43940 (9)	0.0401 (3)
F9	−0.00157 (5)	0.05575 (4)	0.43761 (11)	0.0507 (4)
F10	0.0000	0.0000	0.53569 (11)	0.0735 (8)
F11	−0.01702 (5)	0.05392 (4)	0.04710 (8)	0.0372 (3)
F12	0.04163 (6)	0.01103 (5)	−0.02151 (9)	0.0525 (4)
F13	0.04128 (6)	0.01141 (5)	0.11579 (9)	0.0555 (4)
N1	0.35571 (5)	0.11940 (5)	0.37982 (8)	0.0178 (3)
N2	0.35425 (5)	0.08706 (5)	0.82302 (8)	0.0171 (3)
O1	0.36473 (5)	0.17498 (5)	0.52911 (8)	0.0294 (3)
O2	0.41528 (5)	0.12098 (4)	0.68472 (8)	0.0272 (3)
C1	0.31222 (6)	0.12724 (6)	0.43997 (11)	0.0220 (3)
H1A	0.2893	0.0996	0.4395	0.026*
H1B	0.2919	0.1548	0.4223	0.026*
C2	0.33174 (7)	0.13527 (7)	0.52658 (11)	0.0266 (4)
H2A	0.3023	0.1403	0.5640	0.032*
H2B	0.3506	0.1072	0.5455	0.032*
C3	0.40842 (7)	0.16670 (7)	0.47901 (11)	0.0281 (4)
H3A	0.4267	0.1385	0.4989	0.034*
H3B	0.4322	0.1937	0.4831	0.034*
C4	0.39294 (6)	0.15971 (6)	0.39020 (11)	0.0211 (3)
H4A	0.3769	0.1888	0.3694	0.025*
H4B	0.4240	0.1536	0.3569	0.025*
C5	0.33253 (6)	0.12094 (6)	0.29343 (10)	0.0197 (3)
H5A	0.3072	0.0952	0.2883	0.024*
H5B	0.3138	0.1509	0.2868	0.024*
C6	0.37087 (6)	0.11662 (6)	0.22510 (10)	0.0189 (3)
C7	0.39250 (7)	0.15721 (6)	0.19202 (11)	0.0229 (3)
H7	0.3839	0.1870	0.2143	0.027*
C8	0.42658 (7)	0.15427 (6)	0.12656 (11)	0.0254 (4)
H8	0.4408	0.1820	0.1038	0.030*
C9	0.43974 (7)	0.11101 (7)	0.09459 (11)	0.0262 (4)
H9	0.4636	0.1090	0.0507	0.031*
C10	0.41805 (7)	0.07058 (6)	0.12674 (11)	0.0265 (4)
H10	0.4269	0.0409	0.1046	0.032*
C11	0.38354 (7)	0.07350 (6)	0.19097 (11)	0.0223 (3)
H11	0.3683	0.0457	0.2120	0.027*
C12	0.38380 (7)	0.07356 (6)	0.39370 (11)	0.0231 (4)
H12A	0.4018	0.0752	0.4471	0.028*
H12B	0.4102	0.0700	0.3505	0.028*
C13	0.34997 (8)	0.03033 (6)	0.39328 (13)	0.0326 (4)
H13A	0.3293	0.0296	0.4435	0.049*
H13B	0.3715	0.0022	0.3907	0.049*
H13C	0.3272	0.0312	0.3454	0.049*
C14	0.33713 (7)	0.12568 (6)	0.76530 (10)	0.0206 (3)
H14A	0.3162	0.1118	0.7208	0.025*
H14B	0.3152	0.1480	0.7958	0.025*
C15	0.38179 (7)	0.15194 (6)	0.72795 (11)	0.0242 (4)
H15A	0.3686	0.1761	0.6897	0.029*
H15B	0.4012	0.1680	0.7719	0.029*
C16	0.43546 (7)	0.08706 (6)	0.73984 (11)	0.0248 (4)
H16A	0.4549	0.1032	0.7838	0.030*
H16B	0.4596	0.0664	0.7100	0.030*
C17	0.39362 (6)	0.05763 (6)	0.77790 (11)	0.0198 (3)
H17A	0.4092	0.0351	0.8167	0.024*
H17B	0.3762	0.0395	0.7343	0.024*
C18	0.37772 (6)	0.10664 (6)	0.90207 (10)	0.0182 (3)
H18A	0.3909	0.0802	0.9353	0.022*
H18B	0.4073	0.1267	0.8875	0.022*
C19	0.34089 (6)	0.13489 (6)	0.95395 (10)	0.0187 (3)
C20	0.31333 (6)	0.11352 (6)	1.01675 (10)	0.0196 (3)
H20	0.3166	0.0807	1.0255	0.024*
C21	0.28113 (7)	0.13974 (6)	1.06672 (10)	0.0223 (3)
H21	0.2626	0.1249	1.1096	0.027*
C22	0.27592 (7)	0.18765 (6)	1.05420 (11)	0.0246 (4)
H22	0.2536	0.2056	1.0880	0.030*
C23	0.30346 (7)	0.20911 (6)	0.99205 (12)	0.0272 (4)
H23	0.3000	0.2419	0.9832	0.033*
C24	0.33603 (7)	0.18308 (6)	0.94274 (11)	0.0229 (3)
H24	0.3552	0.1982	0.9009	0.028*
C25	0.30729 (6)	0.05742 (6)	0.84234 (11)	0.0207 (3)
H25A	0.2831	0.0766	0.8750	0.025*
H25B	0.2900	0.0494	0.7901	0.025*
C26	0.31801 (7)	0.01251 (6)	0.88864 (11)	0.0250 (4)
H26A	0.3397	−0.0080	0.8551	0.038*
H26B	0.2855	−0.0034	0.9006	0.038*
H26C	0.3357	0.0198	0.9402	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0186 (2)	0.0212 (2)	0.0208 (2)	−0.00042 (16)	−0.00207 (16)	0.00038 (16)
P2	0.0198 (3)	0.0267 (3)	0.0217 (3)	0.0065 (2)	0.000	0.000
P3	0.0247 (3)	0.0216 (3)	0.0219 (3)	−0.0064 (2)	0.000	0.000
F1	0.0223 (6)	0.0433 (7)	0.0375 (6)	−0.0046 (5)	−0.0076 (5)	−0.0078 (5)
F2	0.0369 (7)	0.0659 (9)	0.0406 (8)	−0.0026 (6)	−0.0068 (6)	0.0292 (7)
F3	0.0397 (7)	0.0450 (7)	0.0500 (8)	0.0113 (6)	−0.0102 (6)	−0.0243 (6)
F4	0.0343 (7)	0.0502 (8)	0.0343 (6)	−0.0143 (5)	−0.0025 (5)	0.0163 (6)
F5	0.0315 (7)	0.0360 (7)	0.0622 (9)	0.0067 (5)	−0.0092 (6)	−0.0241 (6)
F6	0.0186 (5)	0.0324 (6)	0.0316 (6)	−0.0028 (4)	−0.0041 (4)	0.0049 (5)
F7	0.0446 (11)	0.0559 (12)	0.0235 (8)	0.0184 (8)	0.000	0.000
F8	0.0218 (6)	0.0471 (7)	0.0514 (8)	0.0068 (5)	−0.0020 (6)	−0.0154 (6)
F9	0.0415 (8)	0.0288 (6)	0.0818 (10)	0.0086 (6)	−0.0038 (7)	−0.0173 (7)
F10	0.0552 (13)	0.144 (2)	0.0211 (9)	0.0621 (14)	0.000	0.000
F11	0.0377 (7)	0.0230 (6)	0.0508 (7)	−0.0025 (5)	−0.0003 (6)	0.0017 (5)
F12	0.0502 (9)	0.0517 (8)	0.0555 (9)	0.0037 (6)	0.0270 (7)	0.0160 (7)
F13	0.0732 (10)	0.0366 (7)	0.0566 (9)	−0.0148 (7)	−0.0391 (8)	0.0050 (6)
N1	0.0151 (7)	0.0175 (6)	0.0206 (7)	0.0008 (5)	0.0011 (5)	0.0029 (5)
N2	0.0155 (7)	0.0187 (6)	0.0170 (6)	0.0003 (5)	−0.0012 (5)	−0.0007 (5)
O1	0.0327 (7)	0.0309 (7)	0.0245 (6)	−0.0063 (6)	0.0037 (5)	−0.0049 (5)
O2	0.0326 (7)	0.0279 (6)	0.0211 (6)	−0.0026 (5)	0.0076 (5)	0.0003 (5)
C1	0.0187 (8)	0.0264 (9)	0.0209 (8)	0.0005 (7)	0.0049 (7)	0.0020 (7)
C2	0.0266 (9)	0.0325 (10)	0.0206 (8)	−0.0047 (7)	0.0011 (7)	0.0040 (7)
C3	0.0274 (10)	0.0311 (10)	0.0259 (9)	−0.0083 (8)	0.0015 (7)	−0.0039 (7)
C4	0.0200 (9)	0.0191 (8)	0.0242 (8)	−0.0039 (6)	0.0023 (6)	0.0005 (6)
C5	0.0178 (8)	0.0205 (8)	0.0208 (8)	0.0020 (6)	−0.0018 (6)	0.0030 (6)
C6	0.0170 (8)	0.0214 (8)	0.0182 (8)	0.0016 (6)	−0.0015 (6)	0.0015 (6)
C7	0.0241 (9)	0.0188 (8)	0.0259 (8)	0.0002 (7)	0.0025 (7)	0.0007 (7)
C8	0.0234 (9)	0.0279 (9)	0.0249 (8)	−0.0044 (7)	0.0037 (7)	0.0029 (7)
C9	0.0171 (8)	0.0392 (10)	0.0224 (8)	0.0034 (7)	0.0018 (7)	−0.0016 (8)
C10	0.0278 (9)	0.0290 (9)	0.0228 (9)	0.0075 (7)	−0.0021 (7)	−0.0074 (7)
C11	0.0252 (9)	0.0192 (8)	0.0224 (8)	0.0008 (6)	−0.0026 (7)	0.0005 (7)
C12	0.0254 (9)	0.0194 (8)	0.0247 (8)	0.0052 (7)	−0.0026 (7)	0.0046 (7)
C13	0.0406 (12)	0.0191 (9)	0.0382 (11)	−0.0002 (8)	−0.0001 (9)	0.0063 (8)
C14	0.0238 (9)	0.0201 (8)	0.0180 (7)	0.0033 (7)	−0.0025 (6)	0.0010 (6)
C15	0.0290 (10)	0.0209 (8)	0.0227 (8)	−0.0016 (7)	0.0010 (7)	0.0013 (7)
C16	0.0201 (9)	0.0308 (9)	0.0234 (8)	0.0002 (7)	0.0031 (7)	−0.0026 (7)
C17	0.0180 (8)	0.0205 (8)	0.0208 (8)	0.0024 (6)	−0.0006 (6)	−0.0025 (6)
C18	0.0156 (8)	0.0220 (8)	0.0169 (7)	0.0000 (6)	−0.0009 (6)	−0.0016 (6)
C19	0.0155 (8)	0.0224 (8)	0.0181 (7)	−0.0001 (6)	−0.0023 (6)	−0.0016 (6)
C20	0.0197 (8)	0.0196 (8)	0.0195 (7)	−0.0009 (6)	−0.0023 (6)	−0.0003 (6)
C21	0.0205 (9)	0.0271 (9)	0.0193 (8)	−0.0023 (7)	0.0026 (6)	0.0008 (7)
C22	0.0214 (9)	0.0265 (9)	0.0259 (9)	0.0004 (7)	0.0045 (7)	−0.0056 (7)
C23	0.0294 (10)	0.0184 (8)	0.0339 (9)	−0.0012 (7)	0.0042 (8)	−0.0027 (7)
C24	0.0255 (9)	0.0188 (8)	0.0245 (8)	−0.0036 (7)	0.0043 (7)	0.0020 (7)
C25	0.0170 (8)	0.0227 (8)	0.0223 (8)	−0.0043 (6)	−0.0012 (6)	−0.0010 (6)
C26	0.0289 (10)	0.0228 (8)	0.0234 (9)	−0.0042 (7)	0.0030 (7)	0.0002 (7)

Geometric parameters (Å, º) top

P1—F5	1.5860 (12)	C7—C8	1.391 (2)
P1—F4	1.5953 (12)	C7—H7	0.9500
P1—F2	1.5953 (13)	C8—C9	1.383 (2)
P1—F6	1.5966 (11)	C8—H8	0.9500
P1—F3	1.5977 (12)	C9—C10	1.387 (3)
P1—F1	1.6062 (12)	C9—H9	0.9500
P2—F10	1.578 (2)	C10—C11	1.382 (2)
P2—F7	1.5846 (18)	C10—H10	0.9500
P2—F9	1.5910 (12)	C11—H11	0.9500
P2—F9ⁱ	1.5910 (12)	C12—C13	1.516 (3)
P2—F8	1.5985 (11)	C12—H12A	0.9900
P2—F8ⁱ	1.5985 (11)	C12—H12B	0.9900
P3—F13	1.5875 (13)	C13—H13A	0.9800
P3—F13ⁱ	1.5875 (13)	C13—H13B	0.9800
P3—F12ⁱ	1.5877 (14)	C13—H13C	0.9800
P3—F12	1.5877 (14)	C14—C15	1.512 (2)
P3—F11ⁱ	1.6009 (11)	C14—H14A	0.9900
P3—F11	1.6009 (11)	C14—H14B	0.9900
N1—C4	1.514 (2)	C15—H15A	0.9900
N1—C1	1.515 (2)	C15—H15B	0.9900
N1—C12	1.515 (2)	C16—C17	1.509 (2)
N1—C5	1.532 (2)	C16—H16A	0.9900
N2—C14	1.516 (2)	C16—H16B	0.9900
N2—C17	1.516 (2)	C17—H17A	0.9900
N2—C25	1.520 (2)	C17—H17B	0.9900
N2—C18	1.531 (2)	C18—C19	1.511 (2)
O1—C3	1.421 (2)	C18—H18A	0.9900
O1—C2	1.423 (2)	C18—H18B	0.9900
O2—C16	1.421 (2)	C19—C20	1.391 (2)
O2—C15	1.427 (2)	C19—C24	1.393 (2)
C1—C2	1.517 (2)	C20—C21	1.388 (2)
C1—H1A	0.9900	C20—H20	0.9500
C1—H1B	0.9900	C21—C22	1.389 (2)
C2—H2A	0.9900	C21—H21	0.9500
C2—H2B	0.9900	C22—C23	1.384 (3)
C3—C4	1.515 (2)	C22—H22	0.9500
C3—H3A	0.9900	C23—C24	1.384 (3)
C3—H3B	0.9900	C23—H23	0.9500
C4—H4A	0.9900	C24—H24	0.9500
C4—H4B	0.9900	C25—C26	1.513 (2)
C5—C6	1.501 (2)	C25—H25A	0.9900
C5—H5A	0.9900	C25—H25B	0.9900
C5—H5B	0.9900	C26—H26A	0.9800
C6—C11	1.390 (2)	C26—H26B	0.9800
C6—C7	1.396 (2)	C26—H26C	0.9800

F5—P1—F4	90.08 (8)	C11—C6—C5	121.85 (15)
F5—P1—F2	91.00 (8)	C7—C6—C5	119.14 (15)
F4—P1—F2	178.87 (8)	C8—C7—C6	120.26 (16)
F5—P1—F6	90.47 (6)	C8—C7—H7	119.9
F4—P1—F6	89.80 (6)	C6—C7—H7	119.9
F2—P1—F6	90.54 (6)	C9—C8—C7	120.09 (16)
F5—P1—F3	179.12 (8)	C9—C8—H8	120.0
F4—P1—F3	89.58 (8)	C7—C8—H8	120.0
F2—P1—F3	89.34 (8)	C8—C9—C10	119.92 (16)
F6—P1—F3	90.34 (6)	C8—C9—H9	120.0
F5—P1—F1	89.54 (6)	C10—C9—H9	120.0
F4—P1—F1	90.32 (7)	C11—C10—C9	120.04 (16)
F2—P1—F1	89.33 (7)	C11—C10—H10	120.0
F6—P1—F1	179.88 (9)	C9—C10—H10	120.0
F3—P1—F1	89.65 (6)	C10—C11—C6	120.73 (16)
F10—P2—F7	180.0	C10—C11—H11	119.6
F10—P2—F9	90.71 (7)	C6—C11—H11	119.6
F7—P2—F9	89.29 (7)	N1—C12—C13	114.87 (15)
F10—P2—F9ⁱ	90.72 (7)	N1—C12—H12A	108.6
F7—P2—F9ⁱ	89.29 (7)	C13—C12—H12A	108.6
F9—P2—F9ⁱ	178.57 (13)	N1—C12—H12B	108.6
F10—P2—F8	89.67 (6)	C13—C12—H12B	108.6
F7—P2—F8	90.33 (6)	H12A—C12—H12B	107.5
F9—P2—F8	90.61 (6)	C12—C13—H13A	109.5
F9ⁱ—P2—F8	89.40 (6)	C12—C13—H13B	109.5
F10—P2—F8ⁱ	89.67 (6)	H13A—C13—H13B	109.5
F7—P2—F8ⁱ	90.33 (6)	C12—C13—H13C	109.5
F9—P2—F8ⁱ	89.40 (6)	H13A—C13—H13C	109.5
F9ⁱ—P2—F8ⁱ	90.61 (6)	H13B—C13—H13C	109.5
F8—P2—F8ⁱ	179.33 (11)	C15—C14—N2	112.56 (14)
F13—P3—F13ⁱ	90.13 (13)	C15—C14—H14A	109.1
F13—P3—F12ⁱ	179.46 (9)	N2—C14—H14A	109.1
F13ⁱ—P3—F12ⁱ	89.60 (8)	C15—C14—H14B	109.1
F13—P3—F12	89.60 (8)	N2—C14—H14B	109.1
F13ⁱ—P3—F12	179.46 (9)	H14A—C14—H14B	107.8
F12ⁱ—P3—F12	90.67 (13)	O2—C15—C14	111.26 (14)
F13—P3—F11ⁱ	90.49 (7)	O2—C15—H15A	109.4
F13ⁱ—P3—F11ⁱ	89.41 (7)	C14—C15—H15A	109.4
F12ⁱ—P3—F11ⁱ	89.97 (7)	O2—C15—H15B	109.4
F12—P3—F11ⁱ	90.12 (7)	C14—C15—H15B	109.4
F13—P3—F11	89.41 (7)	H15A—C15—H15B	108.0
F13ⁱ—P3—F11	90.49 (7)	O2—C16—C17	111.80 (15)
F12ⁱ—P3—F11	90.12 (7)	O2—C16—H16A	109.3
F12—P3—F11	89.97 (7)	C17—C16—H16A	109.3
F11ⁱ—P3—F11	179.86 (12)	O2—C16—H16B	109.3
C4—N1—C1	107.14 (12)	C17—C16—H16B	109.3
C4—N1—C12	109.23 (13)	H16A—C16—H16B	107.9
C1—N1—C12	113.09 (13)	C16—C17—N2	112.34 (14)
C4—N1—C5	109.47 (12)	C16—C17—H17A	109.1
C1—N1—C5	107.19 (12)	N2—C17—H17A	109.1
C12—N1—C5	110.62 (13)	C16—C17—H17B	109.1
C14—N2—C17	107.49 (12)	N2—C17—H17B	109.1
C14—N2—C25	107.22 (12)	H17A—C17—H17B	107.9
C17—N2—C25	109.71 (12)	C19—C18—N2	114.29 (13)
C14—N2—C18	111.97 (12)	C19—C18—H18A	108.7
C17—N2—C18	109.86 (12)	N2—C18—H18A	108.7
C25—N2—C18	110.49 (12)	C19—C18—H18B	108.7
C3—O1—C2	109.58 (13)	N2—C18—H18B	108.7
C16—O2—C15	109.60 (13)	H18A—C18—H18B	107.6
N1—C1—C2	111.93 (14)	C20—C19—C24	118.82 (15)
N1—C1—H1A	109.2	C20—C19—C18	120.37 (15)
C2—C1—H1A	109.2	C24—C19—C18	120.71 (15)
N1—C1—H1B	109.2	C21—C20—C19	120.50 (16)
C2—C1—H1B	109.2	C21—C20—H20	119.7
H1A—C1—H1B	107.9	C19—C20—H20	119.7
O1—C2—C1	110.46 (14)	C20—C21—C22	120.23 (16)
O1—C2—H2A	109.6	C20—C21—H21	119.9
C1—C2—H2A	109.6	C22—C21—H21	119.9
O1—C2—H2B	109.6	C23—C22—C21	119.48 (16)
C1—C2—H2B	109.6	C23—C22—H22	120.3
H2A—C2—H2B	108.1	C21—C22—H22	120.3
O1—C3—C4	110.93 (15)	C22—C23—C24	120.36 (16)
O1—C3—H3A	109.5	C22—C23—H23	119.8
C4—C3—H3A	109.5	C24—C23—H23	119.8
O1—C3—H3B	109.5	C23—C24—C19	120.60 (16)
C4—C3—H3B	109.5	C23—C24—H24	119.7
H3A—C3—H3B	108.0	C19—C24—H24	119.7
N1—C4—C3	112.16 (14)	C26—C25—N2	115.19 (14)
N1—C4—H4A	109.2	C26—C25—H25A	108.5
C3—C4—H4A	109.2	N2—C25—H25A	108.5
N1—C4—H4B	109.2	C26—C25—H25B	108.5
C3—C4—H4B	109.2	N2—C25—H25B	108.5
H4A—C4—H4B	107.9	H25A—C25—H25B	107.5
C6—C5—N1	114.64 (13)	C25—C26—H26A	109.5
C6—C5—H5A	108.6	C25—C26—H26B	109.5
N1—C5—H5A	108.6	H26A—C26—H26B	109.5
C6—C5—H5B	108.6	C25—C26—H26C	109.5
N1—C5—H5B	108.6	H26A—C26—H26C	109.5
H5A—C5—H5B	107.6	H26B—C26—H26C	109.5
C11—C6—C7	118.93 (15)

C4—N1—C1—C2	−52.21 (17)	C17—N2—C14—C15	−50.76 (17)
C12—N1—C1—C2	68.20 (18)	C25—N2—C14—C15	−168.65 (13)
C5—N1—C1—C2	−169.62 (13)	C18—N2—C14—C15	69.99 (17)
C3—O1—C2—C1	−62.46 (19)	C16—O2—C15—C14	−60.77 (18)
N1—C1—C2—O1	59.13 (19)	N2—C14—C15—O2	57.50 (18)
C2—O1—C3—C4	62.01 (19)	C15—O2—C16—C17	60.96 (18)
C1—N1—C4—C3	51.63 (18)	O2—C16—C17—N2	−57.46 (18)
C12—N1—C4—C3	−71.20 (17)	C14—N2—C17—C16	50.49 (17)
C5—N1—C4—C3	167.54 (14)	C25—N2—C17—C16	166.76 (13)
O1—C3—C4—N1	−58.05 (19)	C18—N2—C17—C16	−71.58 (17)
C4—N1—C5—C6	60.64 (17)	C14—N2—C18—C19	63.20 (17)
C1—N1—C5—C6	176.52 (13)	C17—N2—C18—C19	−177.44 (14)
C12—N1—C5—C6	−59.77 (17)	C25—N2—C18—C19	−56.25 (17)
N1—C5—C6—C11	92.12 (18)	N2—C18—C19—C20	93.27 (18)
N1—C5—C6—C7	−91.19 (18)	N2—C18—C19—C24	−90.25 (19)
C11—C6—C7—C8	−0.7 (3)	C24—C19—C20—C21	0.7 (2)
C5—C6—C7—C8	−177.49 (16)	C18—C19—C20—C21	177.26 (15)
C6—C7—C8—C9	−0.9 (3)	C19—C20—C21—C22	0.3 (3)
C7—C8—C9—C10	1.4 (3)	C20—C21—C22—C23	−0.6 (3)
C8—C9—C10—C11	−0.4 (3)	C21—C22—C23—C24	−0.1 (3)
C9—C10—C11—C6	−1.2 (3)	C22—C23—C24—C19	1.1 (3)
C7—C6—C11—C10	1.7 (3)	C20—C19—C24—C23	−1.4 (3)
C5—C6—C11—C10	178.43 (16)	C18—C19—C24—C23	−177.96 (17)
C4—N1—C12—C13	174.38 (15)	C14—N2—C25—C26	170.87 (14)
C1—N1—C12—C13	55.17 (19)	C17—N2—C25—C26	54.43 (18)
C5—N1—C12—C13	−65.07 (19)	C18—N2—C25—C26	−66.85 (17)

Symmetry code: (i) −x, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F4	0.99	2.41	3.211 (2)	138
C3—H3B···F2ⁱⁱ	0.99	2.47	3.389 (2)	155
C5—H5B···F11ⁱⁱⁱ	0.99	2.48	3.365 (2)	150
C10—H10···F10^iv	0.95	2.50	3.288 (2)	141
C17—H17A···F8^v	0.99	2.37	3.329 (2)	162
C17—H17B···F1	0.99	2.46	3.357 (2)	150
C25—H25B···F1	0.99	2.53	3.388 (2)	145

Symmetry codes: (ii) −x+3/4, y+1/4, z−1/4; (iii) x+1/4, −y+1/4, z+1/4; (iv) −x+1/2, −y, z−1/2; (v) −x+1/2, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₂₀NO⁺·PF₆⁻
M_r	351.27
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	113
a, b, c (Å)	26.054 (3), 28.528 (3), 16.2950 (15)
V (Å³)	12111 (2)
Z	32
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.948, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	39690, 8072, 7799
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.078, 1.11
No. of reflections	8072
No. of parameters	402
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.24
Absolute structure	Flack (1983), 3877 Friedel pairs
Absolute structure parameter	−0.06 (5)

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CrystalStructure (Rigaku, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F4	0.99	2.41	3.211 (2)	138
C3—H3B···F2ⁱ	0.99	2.47	3.389 (2)	155
C5—H5B···F11ⁱⁱ	0.99	2.48	3.365 (2)	150
C10—H10···F10ⁱⁱⁱ	0.95	2.50	3.288 (2)	141
C17—H17A···F8^iv	0.99	2.37	3.329 (2)	162
C17—H17B···F1	0.99	2.46	3.357 (2)	150
C25—H25B···F1	0.99	2.53	3.388 (2)	145

Symmetry codes: (i) −x+3/4, y+1/4, z−1/4; (ii) x+1/4, −y+1/4, z+1/4; (iii) −x+1/2, −y, z−1/2; (iv) −x+1/2, −y, z+1/2.

Acknowledgements

The authors thank the Tianjin Natural Science Foundation (11JCZDJC21300 and 10JCZDJC22200) for financial support.

References

Abedin, S. Z. E., Borissenko, N. & Endres, F. (2004). Electrochem. Commun. 6, 510–514. Web of Science CrossRef Google Scholar
Abedin, S. Z. E., Farag, H. K., Moustafa, E. M., Welz-Biermann, U. & Endres, F. (2005). Phys. Chem. Chem. Phys. 7, 2333–2339. Web of Science PubMed Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kim, K. S., Choi, S., Cha, J. H., Yeon, S. H. & Lee, H. (2006). J. Mater. Chem. 16, 1315–1317. Web of Science CrossRef CAS Google Scholar
Rigaku (2007). CrystalStructure. Rigaku, Tokyo, Japan. Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar