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

The title compound, C(18)H(18)N(3)O(+)·PF(6) (-), 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 PF(6) (-) counter-ion [occupancies of F atoms 0.678 (8):0.322 (8)], which inter-acts with the main mol-ecule through weak inter-molecular P-F⋯π inter-actions.

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 = 437.32

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.114

S = 1.11

3406 reflections

318 parameters

31 restraints

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.20 e Å−3

Absolute structure: Flack (1983 ▶), 1368 Friedel pairs

Flack parameter: 0.01 (10)

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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809018005/bg2257sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C18H18N3O+·F6P−	F(000) = 448
Mr = 437.32	Dx = 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

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

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(Fo2) + (0.075P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.114	(Δ/σ)max = 0.009
S = 1.11	Δρmax = 0.20 e Å−3
3406 reflections	Δρmin = −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	Flack parameter: 0.01 (10)

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.

	x	y	z	Uiso*/Ueq	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)

	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)

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

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

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) . Cg1 is the centroid of the N1/N2/C8/N3/C7 ring.