5-Benzyl-2-phenyl-6,8-dihydro-5H-1,2,4-triazolo[3,4-c][1,4]oxazin-2-ium hexa­fluoridophosphate

Huang, Y.; Wei, S.; Wang, Z.; Mao, Z.; Su, X.

doi:10.1107/S1600536809018005

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1328

doi:10.1107/S1600536809018005

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5-Benzyl-2-phenyl-6,8-dihydro-5H-1,2,4-triazolo[3,4-c][1,4]oxazin-2-ium hexafluoridophosphate

Yumin Huang,^a Siping Wei,^a Zhen Wang,^a Zhihua Mao ^b and Xiaoyu Su ^a ^*

^aKey Laboratory of Green Chemistry and Technology of the Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China, and ^bThe Centre of Testing and Analysis, Sichuan University, Chengdu 610064, People's Republic of China
^*Correspondence e-mail: suxiaoyu@scu.edu.cn

(Received 4 May 2009; accepted 13 May 2009; online 20 May 2009)

The title compound, C₁₈H₁₈N₃O⁺·PF₆⁻, is a chiral bicyclic 1,2,4-triazolium salt which contains four rings, viz. a triazolium, a morpholine and two phenyl rings. Analysis of bond lengths shows that the N—CH—N group in the triazolium ring conforms to a typical three-center/four-electron bond (also known as the Pimentel–Rundle three-center model). The structure is completed by a disordered PF₆⁻ counter-ion [occupancies of F atoms 0.678 (8):0.322 (8)], which interacts with the main molecule through weak intermolecular P—F⋯π interactions.

Related literature

For details of different C—C bond-formation reactions, see: Fisher et al. (2006 ); Kerr et al. (2002 ); Knight & Leeper (1998 ); Readde Alaniz & Rovis (2005 ); Ma et al. (2008 ).

Experimental

Crystal data

C₁₈H₁₈N₃O⁺·PF₆⁻
M_r = 437.32
Monoclinic, P 2₁
a = 11.4054 (13) Å
b = 8.1243 (9) Å
c = 11.8593 (14) Å
β = 118.678 (2)°
V = 964.09 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 297 K
0.53 × 0.42 × 0.32 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.89, T_max = 0.93
5505 measured reflections
3406 independent reflections
2984 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.114
S = 1.11
3406 reflections
318 parameters
31 restraints
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 1368 Friedel pairs
Flack parameter: 0.01 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
P1—F1⋯Cg1ⁱ	1.57 (1)	3.03	4.235 (11)	132
P1—F2⋯Cg1	1.57 (1)	3.19	4.102 (11)	115
P1—F2′⋯Cg1	1.50 (1)	2.93	4.102 (11)	133
Symmetry code: (i) x, y+1, z. Cg1 is the centroid of the N1/N2/C8/N3/C7 ring.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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 global, I. DOI: 10.1107/S1600536809018005/bg2257sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018005/bg2257Isup2.hkl

checkCIF report

Comment top

Triazolium salts which can be used as the precursors of carbenes are widely used in asymmetric catalysis for the C—C bond formation reactions, such as benzoin reactions (Knight & Leeper 1998; Ma et al. 2008), Stetter reactions (Kerr et al. 2002; Readde Alaniz & Rovis 2005) and Diels-Alder reactions (Fisher et al. 2006) because of their excellent catalytic performance in umpolung aldehyde chemistry. Most of the research performed shows that chiral bicyclic 1,2,4-triazole carbenes have excellent enanselectivity because they have many bulkier groups and show weaker nucleophility than thiazolium, imidazolium and imidazolinium salts. The crystal structure of the title compound shows that N1—C7—N3 is a typical 3-center-4-electron bond (well known as the Pimentel-Rundle three-center model), because both N1—C7 (1.312 (3) Å) and N3—C7 (1.325 (2) Å) bond lengths are longer than the N2=C8 (1.292 (3) Å) double bond but shorter than other N—C single bonds (1.365 (3)–1.486 (3) Å). The dihedral angle between the phenyl (C1—C6) and triazolium ring (N1/N2/C8/N3/C7) is 27.8 °. In the crystal packing, weak P—F···π (Cg 1) interactions interconnect adjacent molecules at the same time that it provides to the stability of the crystal structure.

Related literature top

For related literature on different C—C bond-formation reactions, see: Fisher et al. (2006); Kerr et al. (2002); Knight & Leeper (1998); Readde Alaniz & Rovis (2005); Ma et al. (2008). Cg1 is N1/N2/C8/N3/C7 ring centroid.

Experimental top

The title compound was prepared according to literature methods (Knight & Leeper 1998). A solution of 3-benzyl-5-ethoxy-3,6-dihydro-2H-1,4-oxazine (prepared from (s)-2-amino-3-phenylpropan-1-ol) as a colorless liquid was added dropwise to phenylhydrazine hydrochloride (1.44 g, 10 mmol) in methanol (3 ml). The mixture was then stirred for 30 min, followed by addition of triethyl orthoformate (7.4 g, 50 mmol). After being heated at 353 K for 10 h, the reaction mixture was cooled to room temperature and concentrated in vacuo. The resulting residue was purified by column chromatography on silica gel with elution with methanol and followed with anion exchange with ammonium hexafluorophosphate to afford the pure triazolium salt (I) as a white solid in 63% overall yield. Colourless crystals suitable for X-ray structural analysis were grown by slow evaporation of actone solution. ¹H NMR (400 MHz, DMSO): δ 3.17 (1 H, dd, J = 10.4 Hz, 4.8 Hz, 1H), 3.19 (dd, J = 10.0 Hz, 4.8 Hz, 1H), 3.95–4.01 (m, 2H), 4.87–4.93 (m, 1H), 5.22 (2 d, J = 16 Hz, 16 Hz, 2H), 7.47–7.68 (m, 8H), 7.69–7.91 (m, 2H), 11.20 (s, 1H).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 molecular structure of (I), showing 30% probability displacement ellipsoids and the atomic numbering.

5-Benzyl-2-phenyl-6,8-dihydro-5H-1,2,4- triazolo[3,4-c][1,4]oxazin-2-ium hexafluoridophosphate top

Crystal data top

C₁₈H₁₈N₃O⁺·F₆P⁻	F(000) = 448
M_r = 437.32	D_x = 1.506 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3172 reflections
a = 11.4054 (13) Å	θ = 3.1–26.0°
b = 8.1243 (9) Å	µ = 0.21 mm⁻¹
c = 11.8593 (14) Å	T = 297 K
β = 118.678 (2)°	Parallelepiped, colourless
V = 964.09 (19) Å³	0.53 × 0.42 × 0.32 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	3406 independent reflections
Radiation source: fine-focus sealed tube	2984 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
T_min = 0.89, T_max = 0.93	k = −9→10
5505 measured reflections	l = −12→14

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.039	w = 1/[σ²(F_o²) + (0.075P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.114	(Δ/σ)_max = 0.009
S = 1.11	Δρ_max = 0.20 e Å⁻³
3406 reflections	Δρ_min = −0.20 e Å⁻³
318 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
31 restraints	Extinction coefficient: 0.019 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1368 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.01 (10)

Crystal data top

C₁₈H₁₈N₃O⁺·F₆P⁻	V = 964.09 (19) Å³
M_r = 437.32	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 11.4054 (13) Å	µ = 0.21 mm⁻¹
b = 8.1243 (9) Å	T = 297 K
c = 11.8593 (14) Å	0.53 × 0.42 × 0.32 mm
β = 118.678 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3406 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2984 reflections with I > 2σ(I)
T_min = 0.89, T_max = 0.93	R_int = 0.022
5505 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.114	Δρ_max = 0.20 e Å⁻³
S = 1.11	Δρ_min = −0.20 e Å⁻³
3406 reflections	Absolute structure: Flack (1983), 1368 Friedel pairs
318 parameters	Absolute structure parameter: 0.01 (10)
31 restraints

Special details top

Experimental. Even if the Flack parameter coming out of refinement appears quite trustable, the fact that the heaviest atomic species in the structure is P could suggest that the absolute structure determination could be thought as dubious. However, because the stereogenic carbon does not directly participate in the cyclocondensation, there is little risk for the racemization of the stereogenic carbon in this reaction. (Knight, R. L. & Leeper, F. J. (1998) J. Chem. Soc., Perkin Trans. 1, 1891–1893.) From starting material (S)-2-amino-3-phenylpropan-1-ol, it give (S)-5-benzyl-2-phenyl-6,8-dihydro-5H- [1,2,4]triazolo[3,4-c][1,4]oxazin-2-ium hexafluorophosphate as product, whose absolute configuration (s) is consistent with the absolute structure characterized by X-ray structure analysis.

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)
P1	0.79225 (6)	0.03833 (8)	0.45453 (6)	0.0488 (2)
O1	0.67186 (18)	0.5581 (3)	0.70365 (16)	0.0669 (5)
N1	0.69585 (16)	0.5547 (3)	0.34299 (15)	0.0428 (4)
N2	0.59091 (18)	0.5715 (3)	0.36766 (18)	0.0514 (5)
N3	0.77918 (16)	0.5257 (3)	0.54549 (15)	0.0422 (4)
C1	0.5666 (3)	0.6481 (4)	0.1230 (3)	0.0637 (7)
H1A	0.5131	0.7093	0.1469	0.076*
C2	0.5404 (3)	0.6440 (5)	−0.0031 (3)	0.0788 (9)
H2B	0.4675	0.7013	−0.0654	0.095*
C3	0.6212 (3)	0.5557 (5)	−0.0376 (3)	0.0707 (8)
H3A	0.6023	0.5529	−0.1231	0.085*
C4	0.7283 (3)	0.4729 (5)	0.0528 (3)	0.0734 (9)
H4A	0.7841	0.4162	0.0293	0.088*
C5	0.7556 (3)	0.4719 (4)	0.1800 (3)	0.0636 (7)
H5A	0.8279	0.4132	0.2418	0.076*
C6	0.6733 (2)	0.5598 (3)	0.2126 (2)	0.0464 (5)
C7	0.8076 (2)	0.5279 (4)	0.44951 (19)	0.0435 (5)
H7A	0.8917	0.5132	0.4564	0.052*
C8	0.6451 (2)	0.5535 (4)	0.4908 (2)	0.0486 (5)
C9	0.5763 (3)	0.5573 (6)	0.5721 (2)	0.0713 (9)
H9A	0.5209	0.6550	0.5519	0.086*
H9B	0.5190	0.4616	0.5533	0.086*
C10	0.7696 (3)	0.4335 (4)	0.7317 (2)	0.0579 (7)
H10A	0.7261	0.3313	0.6908	0.069*
H10B	0.8187	0.4152	0.8237	0.069*
C11	0.8654 (2)	0.4849 (3)	0.6834 (2)	0.0447 (5)
H11A	0.9229	0.3914	0.6904	0.054*
C12	0.9534 (3)	0.6333 (3)	0.7548 (2)	0.0531 (6)
H12A	1.0050	0.6667	0.7133	0.064*
H12B	0.8971	0.7250	0.7510	0.064*
C13	1.0474 (2)	0.5901 (3)	0.8942 (2)	0.0514 (6)
C14	1.1674 (3)	0.5140 (4)	0.9300 (3)	0.0677 (8)
H14A	1.1937	0.4904	0.8686	0.081*
C15	1.2500 (3)	0.4720 (5)	1.0580 (4)	0.0796 (9)
H15A	1.3321	0.4225	1.0819	0.095*
C16	1.2119 (3)	0.5024 (4)	1.1490 (3)	0.0794 (10)
H16A	1.2674	0.4726	1.2341	0.095*
C17	1.0925 (3)	0.5766 (4)	1.1146 (3)	0.0710 (8)
H17A	1.0662	0.5973	1.1764	0.085*
C18	1.0103 (3)	0.6211 (4)	0.9885 (3)	0.0590 (7)
H18A	0.9292	0.6726	0.9660	0.071*
F1	0.7113 (5)	0.1769 (5)	0.4784 (7)	0.105 (2)	0.678 (8)
F2	0.7470 (6)	−0.0824 (7)	0.5298 (6)	0.115 (2)	0.678 (8)
F3	0.8763 (5)	−0.0945 (6)	0.4304 (8)	0.118 (3)	0.678 (8)
F4	0.8458 (8)	0.1611 (7)	0.3921 (7)	0.126 (3)	0.678 (8)
F5	0.9187 (4)	0.0816 (12)	0.5876 (4)	0.132 (3)	0.678 (8)
F6	0.6692 (5)	−0.0133 (10)	0.3319 (4)	0.128 (2)	0.678 (8)
F1'	0.767 (2)	0.125 (3)	0.5475 (17)	0.214 (11)	0.322 (8)
F2'	0.6898 (13)	−0.0908 (11)	0.433 (2)	0.142 (7)	0.322 (8)
F3'	0.811 (3)	−0.036 (4)	0.350 (2)	0.280 (14)	0.322 (8)
F4'	0.8949 (12)	0.1741 (13)	0.476 (2)	0.154 (9)	0.322 (8)
F5'	0.9061 (10)	−0.069 (2)	0.542 (2)	0.174 (9)	0.322 (8)
F6'	0.6823 (13)	0.138 (2)	0.3481 (18)	0.192 (8)	0.322 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0462 (3)	0.0449 (3)	0.0583 (4)	−0.0032 (3)	0.0276 (3)	−0.0032 (3)
O1	0.0668 (10)	0.0884 (15)	0.0578 (10)	0.0000 (12)	0.0398 (9)	−0.0050 (11)
N1	0.0398 (8)	0.0493 (11)	0.0410 (9)	−0.0007 (10)	0.0207 (7)	0.0010 (9)
N2	0.0407 (9)	0.0657 (16)	0.0500 (11)	0.0068 (10)	0.0234 (8)	0.0035 (10)
N3	0.0418 (8)	0.0444 (11)	0.0410 (9)	0.0000 (10)	0.0203 (7)	0.0004 (9)
C1	0.0640 (16)	0.0757 (19)	0.0531 (15)	0.0131 (15)	0.0296 (14)	0.0078 (13)
C2	0.0738 (19)	0.104 (3)	0.0513 (16)	0.015 (2)	0.0243 (15)	0.0201 (17)
C3	0.0831 (18)	0.085 (2)	0.0498 (14)	−0.002 (2)	0.0368 (14)	0.0091 (16)
C4	0.092 (2)	0.083 (2)	0.0690 (18)	0.0091 (18)	0.0574 (18)	0.0011 (16)
C5	0.0673 (16)	0.0746 (18)	0.0560 (15)	0.0157 (15)	0.0353 (13)	0.0103 (13)
C6	0.0459 (10)	0.0514 (15)	0.0429 (11)	−0.0081 (12)	0.0220 (9)	0.0001 (11)
C7	0.0395 (10)	0.0474 (13)	0.0451 (11)	−0.0023 (11)	0.0216 (9)	−0.0006 (10)
C8	0.0448 (11)	0.0535 (14)	0.0520 (12)	0.0022 (12)	0.0269 (10)	−0.0003 (12)
C9	0.0583 (13)	0.110 (3)	0.0584 (15)	0.012 (2)	0.0380 (13)	0.0084 (19)
C10	0.0607 (15)	0.0610 (17)	0.0487 (14)	−0.0096 (13)	0.0237 (12)	0.0041 (12)
C11	0.0463 (12)	0.0444 (13)	0.0402 (11)	0.0020 (9)	0.0182 (10)	0.0008 (9)
C12	0.0546 (14)	0.0538 (15)	0.0494 (13)	−0.0061 (12)	0.0237 (12)	0.0018 (11)
C13	0.0511 (13)	0.0465 (14)	0.0512 (13)	−0.0076 (10)	0.0201 (11)	−0.0039 (10)
C14	0.0515 (13)	0.071 (2)	0.0762 (18)	−0.0059 (14)	0.0270 (13)	−0.0082 (15)
C15	0.0495 (15)	0.072 (2)	0.091 (2)	−0.0005 (15)	0.0126 (15)	0.0044 (17)
C16	0.079 (2)	0.064 (2)	0.0590 (17)	−0.0103 (16)	0.0041 (16)	0.0011 (14)
C17	0.092 (2)	0.064 (2)	0.0467 (14)	−0.0145 (16)	0.0250 (14)	−0.0090 (13)
C18	0.0632 (15)	0.0567 (16)	0.0523 (14)	−0.0026 (13)	0.0240 (13)	−0.0087 (12)
F1	0.084 (3)	0.054 (2)	0.219 (7)	−0.0148 (17)	0.107 (4)	−0.037 (3)
F2	0.125 (4)	0.104 (4)	0.137 (4)	−0.005 (3)	0.081 (3)	0.047 (3)
F3	0.079 (3)	0.072 (3)	0.216 (7)	0.009 (2)	0.083 (4)	−0.037 (4)
F4	0.190 (7)	0.091 (4)	0.167 (5)	−0.017 (4)	0.143 (5)	0.023 (4)
F5	0.076 (2)	0.214 (8)	0.081 (2)	−0.029 (4)	0.0164 (18)	−0.037 (3)
F6	0.098 (3)	0.163 (6)	0.073 (2)	−0.015 (3)	0.002 (2)	−0.033 (3)
F1'	0.30 (2)	0.26 (2)	0.156 (13)	−0.078 (17)	0.172 (16)	−0.120 (13)
F2'	0.100 (8)	0.052 (5)	0.33 (2)	−0.035 (5)	0.145 (12)	−0.062 (10)
F3'	0.34 (3)	0.40 (4)	0.237 (19)	−0.08 (2)	0.24 (2)	−0.16 (2)
F4'	0.072 (6)	0.075 (6)	0.34 (3)	−0.024 (5)	0.120 (12)	−0.059 (12)
F5'	0.085 (6)	0.148 (13)	0.218 (16)	0.027 (8)	0.015 (9)	0.130 (13)
F6'	0.119 (9)	0.163 (14)	0.181 (14)	0.025 (10)	−0.017 (9)	0.086 (12)

Geometric parameters (Å, º) top

P1—F1'	1.446 (10)	C4—C5	1.386 (4)
P1—F2'	1.498 (7)	C4—H4A	0.9300
P1—F5'	1.495 (7)	C5—C6	1.375 (4)
P1—F3'	1.480 (10)	C5—H5A	0.9300
P1—F6'	1.516 (8)	C7—H7A	0.9300
P1—F6	1.517 (4)	C8—C9	1.508 (3)
P1—F4	1.533 (4)	C9—H9A	0.9700
P1—F4'	1.539 (9)	C9—H9B	0.9700
P1—F1	1.565 (3)	C10—C11	1.515 (3)
P1—F3	1.559 (4)	C10—H10A	0.9700
P1—F2	1.570 (4)	C10—H10B	0.9700
P1—F5	1.584 (4)	C11—C12	1.537 (3)
O1—C9	1.410 (3)	C11—H11A	0.9800
O1—C10	1.422 (4)	C12—C13	1.518 (3)
N1—C7	1.312 (3)	C12—H12A	0.9700
N1—N2	1.369 (2)	C12—H12B	0.9700
N1—C6	1.442 (3)	C13—C14	1.371 (4)
N2—C8	1.292 (3)	C13—C18	1.395 (4)
N3—C7	1.325 (2)	C14—C15	1.391 (4)
N3—C8	1.364 (3)	C14—H14A	0.9300
N3—C11	1.486 (3)	C15—C16	1.365 (5)
C1—C6	1.373 (4)	C15—H15A	0.9300
C1—C2	1.377 (4)	C16—C17	1.361 (5)
C1—H1A	0.9300	C16—H16A	0.9300
C2—C3	1.376 (5)	C17—C18	1.379 (4)
C2—H2B	0.9300	C17—H17A	0.9300
C3—C4	1.356 (5)	C18—H18A	0.9300
C3—H3A	0.9300

F1'—P1—F2'	92.7 (10)	C4—C5—H5A	120.8
F1'—P1—F5'	100.2 (14)	C1—C6—C5	121.7 (2)
F2'—P1—F5'	93.2 (9)	C1—C6—N1	118.7 (2)
F1'—P1—F3'	174.1 (17)	C5—C6—N1	119.5 (2)
F2'—P1—F3'	89.3 (11)	N1—C7—N3	107.70 (17)
F5'—P1—F3'	85.2 (12)	N1—C7—H7A	126.2
F1'—P1—F6'	89.4 (11)	N3—C7—H7A	126.2
F2'—P1—F6'	88.0 (9)	N2—C8—N3	112.03 (18)
F5'—P1—F6'	170.3 (13)	N2—C8—C9	127.4 (2)
F3'—P1—F6'	85.1 (15)	N3—C8—C9	120.6 (2)
F1'—P1—F4'	86.6 (10)	O1—C9—C8	110.13 (19)
F2'—P1—F4'	178.6 (6)	O1—C9—H9A	109.6
F5'—P1—F4'	88.1 (7)	C8—C9—H9A	109.6
F3'—P1—F4'	91.3 (11)	O1—C9—H9B	109.6
F6'—P1—F4'	90.9 (9)	C8—C9—H9B	109.6
F6—P1—F1	91.0 (3)	H9A—C9—H9B	108.1
F4—P1—F1	91.5 (3)	O1—C10—C11	110.0 (2)
F6—P1—F1	91.0 (3)	O1—C10—H10A	109.7
F4—P1—F1	91.5 (3)	C11—C10—H10A	109.7
F6—P1—F3	90.0 (3)	O1—C10—H10B	109.7
F4—P1—F3	86.5 (4)	C11—C10—H10B	109.7
F1—P1—F3	177.8 (3)	H10A—C10—H10B	108.2
F6—P1—F2	88.1 (3)	N3—C11—C10	105.10 (19)
F4—P1—F2	175.1 (4)	N3—C11—C12	110.14 (19)
F1—P1—F2	87.9 (3)	C10—C11—C12	114.0 (2)
F3—P1—F2	94.1 (4)	N3—C11—H11A	109.2
F6—P1—F5	175.9 (5)	C10—C11—H11A	109.2
F4—P1—F5	87.3 (3)	C12—C11—H11A	109.2
F1—P1—F5	89.7 (3)	C13—C12—C11	110.6 (2)
F3—P1—F5	89.5 (3)	C13—C12—H12A	109.5
F2—P1—F5	87.8 (4)	C11—C12—H12A	109.5
C9—O1—C10	111.0 (2)	C13—C12—H12B	109.5
C7—N1—N2	110.85 (16)	C11—C12—H12B	109.5
C7—N1—C6	128.92 (17)	H12A—C12—H12B	108.1
N2—N1—C6	120.16 (17)	C14—C13—C18	118.4 (3)
C8—N2—N1	103.74 (17)	C14—C13—C12	121.3 (2)
C7—N3—C8	105.68 (17)	C18—C13—C12	120.3 (2)
C7—N3—C11	130.00 (18)	C13—C14—C15	120.0 (3)
C8—N3—C11	124.03 (17)	C13—C14—H14A	120.0
C6—C1—C2	118.5 (3)	C15—C14—H14A	120.0
C6—C1—H1A	120.7	C16—C15—C14	120.9 (3)
C2—C1—H1A	120.7	C16—C15—H15A	119.6
C3—C2—C1	120.6 (3)	C14—C15—H15A	119.6
C3—C2—H2B	119.7	C17—C16—C15	119.7 (3)
C1—C2—H2B	119.7	C17—C16—H16A	120.1
C4—C3—C2	120.1 (2)	C15—C16—H16A	120.1
C4—C3—H3A	120.0	C16—C17—C18	120.2 (3)
C2—C3—H3A	120.0	C16—C17—H17A	119.9
C3—C4—C5	120.7 (3)	C18—C17—H17A	119.9
C3—C4—H4A	119.7	C17—C18—C13	120.8 (3)
C5—C4—H4A	119.7	C17—C18—H18A	119.6
C6—C5—C4	118.4 (3)	C13—C18—H18A	119.6
C6—C5—H5A	120.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
P1—F1···Cg1ⁱ	1.57 (1)	3.03	4.235 (11)	132
P1—F2···Cg1	1.57 (1)	3.19	4.102 (11)	115
P1—F2′···Cg1	1.50 (1)	2.93	4.102 (11)	133

Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₈N₃O⁺·F₆P⁻
M_r	437.32
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	297
a, b, c (Å)	11.4054 (13), 8.1243 (9), 11.8593 (14)
β (°)	118.678 (2)
V (Å³)	964.09 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.53 × 0.42 × 0.32

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.89, 0.93
No. of measured, independent and observed [I > 2σ(I)] reflections	5505, 3406, 2984
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.114, 1.11
No. of reflections	3406
No. of parameters	318
No. of restraints	31
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.20
Absolute structure	Flack (1983), 1368 Friedel pairs
Absolute structure parameter	0.01 (10)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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
P1—F1···Cg1ⁱ	1.5664 (15)	3.03	4.235 (11)	132
P1—F2···Cg1	1.5695 (15)	3.19	4.102 (11)	115
P1—F2'···Cg1	1.4979 (15)	2.93	4.102 (11)	133

Symmetry code: (i) x, y+1, z.

Acknowledgements

The authors are grateful to the National Natural Science Foundation of China (grant No. 20702035) for financial support.

References

Fisher, C., Smith, S. W., Powell, D. A. & Fu, G. C. (2006). J. Am. Chem. Soc. 128, 1472–1473. Web of Science PubMed Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kerr, M. S., Alaniz, J. & Rovis, T. (2002). J. Am. Chem. Soc. 124, 10298–10299. Web of Science CrossRef PubMed CAS Google Scholar
Knight, R. L. & Leeper, F. J. (1998). J. Chem. Soc. Perkin Trans. 1, pp. 1891–1893. Web of Science CrossRef Google Scholar
Ma, Y., Wei, S., Wu, J., Yang, F., Liu, B., Lan, J., Yang, S. & You, J. (2008). Adv. Synth. Catal. 350, 2645–2651. Web of Science CSD CrossRef CAS Google Scholar
Readde Alaniz, J. & Rovis, T. (2005). J. Am. Chem. Soc. 127, 6284–6289. PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

5-Benzyl-2-phenyl-6,8-di­hydro-5H-1,2,4-triazolo[3,4-c][1,4]oxazin-2-ium hexa­fluoridophosphate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

5-Benzyl-2-phenyl-6,8-dihydro-5H-1,2,4-triazolo[3,4-c][1,4]oxazin-2-ium hexafluoridophosphate