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The 2-amino-4,6-diphenyl-4
H-1,3-oxazinium trifluoroacetate ion pairs in the title compound, C
16H
15N
2O
+·C
2F
3O
2−, are held together by two N—H
O hydrogen bonds [N
amino—H
O and N
oxazinium—H
O], and adjacent ion pairs are linked into helical chains by a third and substantially weaker N
amino—H
O hydrogen bond.
Supporting information
CCDC reference: 287680
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.003 Å
- Disorder in solvent or counterion
- R factor = 0.045
- wR factor = 0.115
- Data-to-parameter ratio = 12.0
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7'
PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for F1'
PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for F2'
PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for F3'
PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for F4'
PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for F5'
PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for F6'
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for F1
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C19
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C20
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for F4
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for F5
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C21
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C22
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.21
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.30
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 30.00 Perc.
PLAT331_ALERT_2_C Small Average Phenyl C-C Dist. C7' -C12' 1.37 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 1
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 40.10 Deg.
F1 -C19 -F1' 1.555 1.555 1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 40.40 Deg.
F6' -C21 -F4 1.555 1.555 1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3
C2 F3 O2
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
24 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
7 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
17 ALERT type 4 Improvement, methodology, query or suggestion
2-Amino-4,6-diphenyl-4H-1,3-oxazine was prepared as described by Huang et al. (2005). Crystals of (I) appropriate for data collection were obtained by slow evaporation from an N,N-dimethylformide (3 ml) and trifluoroacetic acid (1 ml) solution of 2-amino-4,6-diphenyl-4H-1,3-oxazine (20 mg) at room temperature over a period of a week.
The CF3 groups of the anions are disordered, with three of the F atoms distributed over two sites (F1/F2/F3 and F1'/F2'/F3'; F4/F5/F6 and F4'/F5'/F6'), their occupation factors being 50% each estimated on the basis of Ueq values. The disordered parts of the anions were constrained to a chemically reasonable geometry. H atoms bonded to the N atoms were located in difference Fourier maps and their parameters were refined with N—H distances restrained to 0.86 (1) Å. The positions of the C-bound H atoms were calculated geometrically and refined using a riding model, with C—H = 0.93–0.98 Å and with Uiso(H) = 1.2Ueq(C).
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL/PC (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.
2-Amino-4,6-diphenyl-4
H-1,3-oxazinium trifluoroacetate
top
Crystal data top
C16H15N2O+·C2F3O2− | Z = 4 |
Mr = 364.32 | F(000) = 752 |
Triclinic, P1 | Dx = 1.370 Mg m−3 |
a = 10.341 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.867 (2) Å | Cell parameters from 30 reflections |
c = 14.409 (3) Å | θ = 6.6–13.7° |
α = 90.62 (2)° | µ = 0.12 mm−1 |
β = 92.68 (2)° | T = 296 K |
γ = 91.03 (2)° | Block, colorless |
V = 1765.9 (6) Å3 | 0.58 × 0.50 × 0.42 mm |
Data collection top
Siemens P4 diffractometer | Rint = 0.012 |
Radiation source: normal-focus sealed tube | θmax = 25.5°, θmin = 1.4° |
Graphite monochromator | h = 0→12 |
ω scans | k = −14→14 |
7215 measured reflections | l = −17→17 |
6591 independent reflections | 3 standard reflections every 97 reflections |
3495 reflections with I > 2σ(I) | intensity decay: 2.8% |
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)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.056P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
6591 reflections | Δρmax = 0.24 e Å−3 |
548 parameters | Δρmin = −0.18 e Å−3 |
18 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0093 (9) |
Crystal data top
C16H15N2O+·C2F3O2− | γ = 91.03 (2)° |
Mr = 364.32 | V = 1765.9 (6) Å3 |
Triclinic, P1 | Z = 4 |
a = 10.341 (2) Å | Mo Kα radiation |
b = 11.867 (2) Å | µ = 0.12 mm−1 |
c = 14.409 (3) Å | T = 296 K |
α = 90.62 (2)° | 0.58 × 0.50 × 0.42 mm |
β = 92.68 (2)° | |
Data collection top
Siemens P4 diffractometer | Rint = 0.012 |
7215 measured reflections | 3 standard reflections every 97 reflections |
6591 independent reflections | intensity decay: 2.8% |
3495 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 18 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.24 e Å−3 |
6591 reflections | Δρmin = −0.18 e Å−3 |
548 parameters | |
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 | Uiso*/Ueq | Occ. (<1) |
O1 | 0.13372 (15) | 0.41354 (11) | 0.38593 (10) | 0.0638 (4) | |
N3 | 0.17320 (18) | 0.57413 (13) | 0.30349 (12) | 0.0562 (5) | |
N19 | 0.1284 (2) | 0.40313 (16) | 0.23251 (14) | 0.0720 (6) | |
C2 | 0.1467 (2) | 0.46677 (17) | 0.30585 (15) | 0.0539 (5) | |
C4 | 0.17696 (19) | 0.64979 (15) | 0.38423 (13) | 0.0494 (5) | |
H4 | 0.0953 | 0.6905 | 0.3837 | 0.059* | |
C5 | 0.18565 (19) | 0.58029 (16) | 0.46998 (14) | 0.0546 (5) | |
H5 | 0.2076 | 0.6164 | 0.5263 | 0.066* | |
C6 | 0.16398 (19) | 0.47118 (16) | 0.47022 (13) | 0.0506 (5) | |
C7 | 0.2868 (2) | 0.73550 (16) | 0.37983 (13) | 0.0505 (5) | |
C8 | 0.4010 (2) | 0.7115 (2) | 0.34138 (17) | 0.0745 (7) | |
H8 | 0.4127 | 0.6405 | 0.3154 | 0.089* | |
C9 | 0.5002 (3) | 0.7918 (3) | 0.34059 (19) | 0.0979 (9) | |
H9 | 0.5778 | 0.7746 | 0.3140 | 0.117* | |
C10 | 0.4838 (4) | 0.8958 (3) | 0.3789 (2) | 0.1064 (11) | |
H10 | 0.5498 | 0.9499 | 0.3781 | 0.128* | |
C11 | 0.3716 (4) | 0.9199 (2) | 0.4178 (2) | 0.1042 (10) | |
H11 | 0.3612 | 0.9903 | 0.4451 | 0.125* | |
C12 | 0.2719 (3) | 0.84089 (18) | 0.41759 (16) | 0.0780 (7) | |
H12 | 0.1940 | 0.8593 | 0.4432 | 0.094* | |
C13 | 0.16147 (19) | 0.39324 (17) | 0.54875 (15) | 0.0538 (5) | |
C14 | 0.1625 (2) | 0.43465 (19) | 0.63906 (15) | 0.0639 (6) | |
H14 | 0.1680 | 0.5120 | 0.6501 | 0.077* | |
C15 | 0.1556 (2) | 0.3620 (2) | 0.71248 (17) | 0.0772 (7) | |
H15 | 0.1561 | 0.3908 | 0.7728 | 0.093* | |
C16 | 0.1479 (2) | 0.2483 (2) | 0.69796 (19) | 0.0797 (8) | |
H16 | 0.1432 | 0.1999 | 0.7481 | 0.096* | |
C17 | 0.1472 (2) | 0.2056 (2) | 0.60895 (19) | 0.0760 (7) | |
H17 | 0.1418 | 0.1281 | 0.5989 | 0.091* | |
C18 | 0.1545 (2) | 0.27745 (18) | 0.53396 (16) | 0.0635 (6) | |
H18 | 0.1546 | 0.2481 | 0.4739 | 0.076* | |
O1' | 0.38790 (15) | 0.91519 (11) | 0.12108 (10) | 0.0652 (4) | |
N3' | 0.30266 (19) | 1.07470 (14) | 0.18416 (12) | 0.0582 (5) | |
N19' | 0.1875 (2) | 0.90784 (17) | 0.16759 (15) | 0.0732 (6) | |
C2' | 0.2914 (2) | 0.96871 (17) | 0.15883 (14) | 0.0562 (6) | |
C4' | 0.4096 (2) | 1.14887 (15) | 0.15889 (14) | 0.0535 (5) | |
H4' | 0.3827 | 1.1877 | 0.1017 | 0.064* | |
C5' | 0.5216 (2) | 1.07709 (17) | 0.13814 (13) | 0.0577 (6) | |
H5' | 0.6035 | 1.1109 | 0.1379 | 0.069* | |
C6' | 0.5106 (2) | 0.96857 (17) | 0.12016 (13) | 0.0552 (5) | |
C7' | 0.4421 (2) | 1.23721 (16) | 0.23282 (14) | 0.0521 (5) | |
C8' | 0.4342 (3) | 1.2180 (2) | 0.32543 (17) | 0.0855 (8) | |
H8' | 0.4038 | 1.1486 | 0.3454 | 0.103* | |
C9' | 0.4715 (3) | 1.3014 (3) | 0.39067 (18) | 0.0983 (9) | |
H9' | 0.4657 | 1.2874 | 0.4537 | 0.118* | |
C10' | 0.5160 (3) | 1.4027 (2) | 0.3622 (2) | 0.0886 (8) | |
H10' | 0.5407 | 1.4584 | 0.4057 | 0.106* | |
C11' | 0.5246 (3) | 1.4227 (2) | 0.2708 (2) | 0.0941 (9) | |
H11' | 0.5564 | 1.4919 | 0.2513 | 0.113* | |
C12' | 0.4864 (2) | 1.34141 (19) | 0.20655 (17) | 0.0774 (7) | |
H12' | 0.4906 | 1.3571 | 0.1437 | 0.093* | |
C13' | 0.6091 (2) | 0.88756 (18) | 0.09463 (13) | 0.0584 (6) | |
C14' | 0.7321 (2) | 0.9254 (2) | 0.07351 (15) | 0.0734 (7) | |
H14' | 0.7524 | 1.0021 | 0.0767 | 0.088* | |
C15' | 0.8248 (3) | 0.8495 (2) | 0.04775 (17) | 0.0858 (8) | |
H15' | 0.9070 | 0.8757 | 0.0341 | 0.103* | |
C16' | 0.7963 (3) | 0.7365 (2) | 0.04229 (17) | 0.0858 (8) | |
H16' | 0.8586 | 0.6862 | 0.0243 | 0.103* | |
C17' | 0.6758 (3) | 0.6976 (2) | 0.06342 (17) | 0.0825 (8) | |
H17' | 0.6569 | 0.6207 | 0.0599 | 0.099* | |
C18' | 0.5811 (2) | 0.77199 (18) | 0.09023 (14) | 0.0686 (6) | |
H18' | 0.4999 | 0.7448 | 0.1051 | 0.082* | |
F1 | −0.2110 (5) | 0.0897 (4) | 0.3387 (6) | 0.1025 (19) | 0.50 |
F2 | −0.0952 (5) | 0.2229 (9) | 0.3818 (5) | 0.138 (2) | 0.50 |
F3 | −0.1912 (7) | 0.2219 (9) | 0.2479 (5) | 0.145 (2) | 0.50 |
F4 | 0.2126 (10) | 0.5916 (5) | −0.0966 (3) | 0.106 (2) | 0.50 |
F5 | 0.2788 (7) | 0.7391 (6) | −0.0328 (4) | 0.1047 (18) | 0.50 |
F6 | 0.0766 (5) | 0.7106 (8) | −0.0597 (4) | 0.1160 (17) | 0.50 |
F1' | −0.2370 (5) | 0.1165 (9) | 0.2830 (9) | 0.178 (4) | 0.50 |
F2' | −0.1060 (8) | 0.1279 (8) | 0.3972 (3) | 0.182 (3) | 0.50 |
F3' | −0.1219 (7) | 0.2687 (3) | 0.3121 (9) | 0.140 (2) | 0.50 |
F4' | 0.3094 (4) | 0.6606 (12) | −0.0492 (5) | 0.187 (3) | 0.50 |
F5' | 0.1533 (14) | 0.7689 (4) | −0.0336 (4) | 0.153 (3) | 0.50 |
F6' | 0.1272 (12) | 0.6085 (7) | −0.1000 (4) | 0.158 (4) | 0.50 |
O3 | 0.08434 (16) | 0.16962 (12) | 0.25383 (12) | 0.0794 (5) | |
O4 | −0.02405 (19) | 0.00811 (15) | 0.24309 (18) | 0.1333 (9) | |
O5 | 0.17392 (18) | 0.67401 (12) | 0.13046 (10) | 0.0832 (5) | |
O6 | 0.1688 (3) | 0.50667 (14) | 0.06404 (12) | 0.1284 (9) | |
C19 | −0.1225 (2) | 0.1586 (2) | 0.30835 (19) | 0.0816 (8) | |
C20 | −0.0095 (2) | 0.10709 (19) | 0.26460 (16) | 0.0673 (6) | |
C21 | 0.1858 (3) | 0.66211 (19) | −0.02943 (15) | 0.0762 (7) | |
C22 | 0.1751 (2) | 0.60897 (19) | 0.06415 (15) | 0.0669 (6) | |
H3N | 0.1758 (19) | 0.6059 (15) | 0.2493 (9) | 0.061 (6)* | |
H3'N | 0.2361 (14) | 1.1058 (16) | 0.2079 (14) | 0.068 (7)* | |
H19A | 0.114 (2) | 0.3313 (9) | 0.2396 (15) | 0.075 (7)* | |
H19B | 0.137 (2) | 0.4320 (18) | 0.1771 (9) | 0.090 (9)* | |
H19C | 0.186 (2) | 0.8359 (10) | 0.1524 (17) | 0.105 (9)* | |
H19D | 0.1187 (15) | 0.9347 (18) | 0.1918 (15) | 0.082 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0909 (12) | 0.0456 (8) | 0.0541 (9) | −0.0141 (7) | −0.0006 (8) | 0.0044 (7) |
N3 | 0.0781 (13) | 0.0435 (10) | 0.0464 (11) | −0.0096 (9) | 0.0028 (10) | 0.0009 (8) |
N19 | 0.1141 (18) | 0.0458 (12) | 0.0552 (13) | −0.0153 (12) | 0.0015 (12) | −0.0034 (10) |
C2 | 0.0609 (14) | 0.0454 (12) | 0.0550 (14) | −0.0064 (10) | 0.0017 (11) | 0.0010 (11) |
C4 | 0.0531 (13) | 0.0438 (11) | 0.0513 (12) | −0.0014 (10) | 0.0042 (10) | 0.0002 (9) |
C5 | 0.0608 (14) | 0.0526 (12) | 0.0503 (12) | −0.0093 (11) | 0.0069 (10) | −0.0024 (10) |
C6 | 0.0495 (13) | 0.0533 (13) | 0.0487 (12) | −0.0060 (10) | 0.0022 (10) | 0.0000 (10) |
C7 | 0.0604 (14) | 0.0473 (12) | 0.0435 (11) | −0.0082 (10) | 0.0025 (10) | 0.0021 (9) |
C8 | 0.0605 (16) | 0.0807 (17) | 0.0821 (17) | −0.0096 (14) | 0.0071 (13) | −0.0034 (13) |
C9 | 0.0648 (18) | 0.146 (3) | 0.0818 (19) | −0.0307 (19) | 0.0042 (14) | 0.0040 (19) |
C10 | 0.127 (3) | 0.113 (3) | 0.076 (2) | −0.068 (2) | −0.0051 (19) | 0.0106 (18) |
C11 | 0.154 (3) | 0.0689 (18) | 0.089 (2) | −0.045 (2) | 0.014 (2) | −0.0091 (15) |
C12 | 0.102 (2) | 0.0553 (14) | 0.0770 (17) | −0.0175 (14) | 0.0200 (15) | −0.0072 (12) |
C13 | 0.0466 (13) | 0.0543 (13) | 0.0606 (14) | −0.0035 (10) | 0.0016 (10) | 0.0107 (11) |
C14 | 0.0656 (15) | 0.0663 (14) | 0.0589 (15) | −0.0094 (12) | −0.0021 (12) | 0.0088 (12) |
C15 | 0.0776 (18) | 0.0915 (19) | 0.0617 (16) | −0.0112 (15) | −0.0062 (13) | 0.0177 (14) |
C16 | 0.0691 (17) | 0.092 (2) | 0.0780 (19) | −0.0058 (14) | −0.0071 (14) | 0.0369 (15) |
C17 | 0.0698 (17) | 0.0627 (15) | 0.095 (2) | 0.0005 (13) | −0.0028 (15) | 0.0237 (15) |
C18 | 0.0633 (15) | 0.0590 (14) | 0.0680 (15) | −0.0009 (11) | −0.0005 (12) | 0.0126 (11) |
O1' | 0.0694 (11) | 0.0505 (8) | 0.0757 (10) | 0.0039 (8) | 0.0064 (8) | −0.0161 (7) |
N3' | 0.0643 (13) | 0.0455 (10) | 0.0651 (12) | 0.0004 (10) | 0.0097 (10) | −0.0128 (9) |
N19' | 0.0755 (16) | 0.0525 (13) | 0.0920 (15) | −0.0073 (12) | 0.0160 (13) | −0.0165 (11) |
C2' | 0.0661 (16) | 0.0497 (13) | 0.0525 (13) | 0.0030 (12) | 0.0031 (11) | −0.0074 (10) |
C4' | 0.0658 (14) | 0.0457 (11) | 0.0492 (12) | 0.0007 (11) | 0.0044 (11) | −0.0026 (9) |
C5' | 0.0639 (15) | 0.0559 (13) | 0.0535 (13) | −0.0012 (11) | 0.0071 (11) | −0.0061 (10) |
C6' | 0.0665 (16) | 0.0559 (13) | 0.0431 (12) | 0.0027 (12) | 0.0013 (10) | −0.0044 (10) |
C7' | 0.0551 (13) | 0.0463 (12) | 0.0549 (13) | 0.0055 (10) | 0.0029 (10) | −0.0052 (10) |
C8' | 0.131 (2) | 0.0661 (15) | 0.0583 (16) | −0.0073 (15) | −0.0053 (15) | −0.0035 (12) |
C9' | 0.131 (3) | 0.101 (2) | 0.0609 (16) | 0.001 (2) | −0.0135 (16) | −0.0184 (16) |
C10' | 0.083 (2) | 0.0778 (19) | 0.103 (2) | −0.0028 (15) | −0.0053 (17) | −0.0393 (17) |
C11' | 0.107 (2) | 0.0672 (17) | 0.108 (2) | −0.0244 (15) | 0.0206 (18) | −0.0285 (16) |
C12' | 0.0956 (19) | 0.0591 (15) | 0.0783 (17) | −0.0123 (13) | 0.0206 (14) | −0.0102 (13) |
C13' | 0.0743 (17) | 0.0603 (14) | 0.0404 (12) | 0.0134 (12) | −0.0018 (11) | −0.0075 (10) |
C14' | 0.0752 (18) | 0.0793 (17) | 0.0652 (15) | 0.0132 (14) | −0.0027 (14) | −0.0144 (13) |
C15' | 0.0742 (18) | 0.107 (2) | 0.0759 (18) | 0.0224 (17) | −0.0011 (14) | −0.0211 (16) |
C16' | 0.092 (2) | 0.097 (2) | 0.0681 (17) | 0.0392 (18) | −0.0093 (16) | −0.0187 (15) |
C17' | 0.113 (2) | 0.0684 (16) | 0.0656 (16) | 0.0307 (17) | −0.0097 (16) | −0.0095 (13) |
C18' | 0.0908 (18) | 0.0610 (14) | 0.0540 (14) | 0.0183 (13) | 0.0002 (13) | −0.0041 (11) |
F1 | 0.068 (4) | 0.086 (2) | 0.156 (5) | −0.020 (3) | 0.045 (3) | 0.000 (3) |
F2 | 0.099 (3) | 0.155 (5) | 0.158 (5) | −0.004 (5) | 0.021 (4) | −0.112 (4) |
F3 | 0.116 (4) | 0.170 (5) | 0.156 (5) | 0.060 (4) | 0.030 (3) | 0.076 (4) |
F4 | 0.180 (6) | 0.092 (3) | 0.047 (2) | 0.012 (4) | 0.017 (3) | −0.016 (2) |
F5 | 0.129 (5) | 0.105 (4) | 0.078 (3) | −0.065 (3) | 0.007 (3) | 0.020 (3) |
F6 | 0.105 (3) | 0.144 (5) | 0.101 (4) | 0.036 (3) | 0.009 (3) | 0.041 (4) |
F1' | 0.074 (3) | 0.221 (11) | 0.233 (9) | 0.002 (5) | −0.028 (5) | −0.107 (7) |
F2' | 0.225 (9) | 0.194 (7) | 0.134 (5) | −0.024 (6) | 0.099 (5) | −0.046 (4) |
F3' | 0.108 (5) | 0.068 (2) | 0.248 (8) | 0.016 (2) | 0.053 (5) | −0.040 (4) |
F4' | 0.155 (6) | 0.276 (9) | 0.137 (6) | −0.031 (7) | 0.074 (5) | 0.018 (7) |
F5' | 0.288 (10) | 0.085 (3) | 0.090 (3) | 0.029 (5) | 0.027 (5) | 0.031 (3) |
F6' | 0.216 (8) | 0.156 (8) | 0.093 (4) | −0.073 (7) | −0.062 (5) | 0.018 (4) |
O3 | 0.0765 (11) | 0.0503 (9) | 0.1130 (14) | −0.0094 (8) | 0.0291 (10) | −0.0124 (8) |
O4 | 0.1081 (16) | 0.0675 (12) | 0.228 (3) | −0.0242 (11) | 0.0682 (16) | −0.0529 (14) |
O5 | 0.1448 (16) | 0.0514 (9) | 0.0540 (9) | −0.0098 (9) | 0.0162 (10) | −0.0059 (8) |
O6 | 0.259 (3) | 0.0549 (11) | 0.0727 (12) | −0.0108 (14) | 0.0321 (14) | −0.0074 (9) |
C19 | 0.088 (2) | 0.082 (2) | 0.076 (2) | −0.0061 (17) | 0.0180 (17) | −0.0134 (16) |
C20 | 0.0713 (17) | 0.0515 (14) | 0.0796 (16) | −0.0078 (13) | 0.0137 (13) | −0.0127 (12) |
C21 | 0.094 (2) | 0.0736 (18) | 0.0618 (17) | −0.0085 (18) | 0.0177 (16) | −0.0018 (14) |
C22 | 0.0926 (19) | 0.0524 (14) | 0.0562 (15) | −0.0042 (13) | 0.0129 (13) | −0.0026 (12) |
Geometric parameters (Å, º) top
O1—C2 | 1.333 (2) | C4'—C7' | 1.509 (3) |
O1—C6 | 1.407 (2) | C4'—H4' | 0.9800 |
N3—C2 | 1.299 (2) | C5'—C6' | 1.313 (3) |
N3—C4 | 1.460 (2) | C5'—H5' | 0.9300 |
N3—H3N | 0.872 (10) | C6'—C13' | 1.469 (3) |
N19—C2 | 1.297 (3) | C7'—C8' | 1.362 (3) |
N19—H19A | 0.870 (10) | C7'—C12' | 1.374 (3) |
N19—H19B | 0.880 (10) | C8'—C9' | 1.394 (3) |
C4—C5 | 1.493 (3) | C8'—H8' | 0.9300 |
C4—C7 | 1.515 (3) | C9'—C10' | 1.354 (4) |
C4—H4 | 0.9800 | C9'—H9' | 0.9300 |
C5—C6 | 1.310 (2) | C10'—C11' | 1.348 (4) |
C5—H5 | 0.9300 | C10'—H10' | 0.9300 |
C6—C13 | 1.470 (3) | C11'—C12' | 1.370 (3) |
C7—C8 | 1.362 (3) | C11'—H11' | 0.9300 |
C7—C12 | 1.373 (3) | C12'—H12' | 0.9300 |
C8—C9 | 1.389 (3) | C13'—C14' | 1.390 (3) |
C8—H8 | 0.9300 | C13'—C18' | 1.397 (3) |
C9—C10 | 1.363 (4) | C14'—C15' | 1.388 (3) |
C9—H9 | 0.9300 | C14'—H14' | 0.9300 |
C10—C11 | 1.345 (4) | C15'—C16' | 1.369 (3) |
C10—H10 | 0.9300 | C15'—H15' | 0.9300 |
C11—C12 | 1.381 (3) | C16'—C17' | 1.369 (4) |
C11—H11 | 0.9300 | C16'—H16' | 0.9300 |
C12—H12 | 0.9300 | C17'—C18' | 1.395 (3) |
C13—C14 | 1.385 (3) | C17'—H17' | 0.9300 |
C13—C18 | 1.388 (3) | C18'—H18' | 0.9300 |
C14—C15 | 1.376 (3) | F1—C19 | 1.309 (3) |
C14—H14 | 0.9300 | F2—C19 | 1.315 (3) |
C15—C16 | 1.364 (3) | F3—C19 | 1.343 (3) |
C15—H15 | 0.9300 | F4—C21 | 1.315 (3) |
C16—C17 | 1.373 (3) | F5—C21 | 1.318 (3) |
C16—H16 | 0.9300 | F6—C21 | 1.335 (3) |
C17—C18 | 1.387 (3) | F1'—C19 | 1.311 (3) |
C17—H17 | 0.9300 | F2'—C19 | 1.339 (3) |
C18—H18 | 0.9300 | F3'—C19 | 1.307 (3) |
O1'—C2' | 1.327 (2) | F4'—C21 | 1.322 (3) |
O1'—C6' | 1.409 (2) | F5'—C21 | 1.319 (3) |
N3'—C2' | 1.307 (2) | F6'—C21 | 1.312 (3) |
N3'—C4' | 1.463 (3) | O3—C20 | 1.227 (2) |
N3'—H3'N | 0.869 (10) | O4—C20 | 1.216 (2) |
N19'—C2' | 1.296 (3) | O5—C22 | 1.222 (2) |
N19'—H19C | 0.878 (10) | O6—C22 | 1.215 (2) |
N19'—H19D | 0.871 (10) | C19—C20 | 1.492 (3) |
C4'—C5' | 1.489 (3) | C21—C22 | 1.503 (3) |
| | | |
C2—O1—C6 | 119.49 (15) | C12'—C7'—C4' | 118.96 (19) |
C2—N3—C4 | 124.65 (17) | C7'—C8'—C9' | 120.7 (2) |
C2—N3—H3N | 118.1 (13) | C7'—C8'—H8' | 119.7 |
C4—N3—H3N | 116.4 (13) | C9'—C8'—H8' | 119.7 |
C2—N19—H19A | 118.8 (14) | C10'—C9'—C8' | 120.0 (3) |
C2—N19—H19B | 119.7 (15) | C10'—C9'—H9' | 120.0 |
H19A—N19—H19B | 121 (2) | C8'—C9'—H9' | 120.0 |
N19—C2—N3 | 124.0 (2) | C11'—C10'—C9' | 119.9 (2) |
N19—C2—O1 | 114.44 (18) | C11'—C10'—H10' | 120.1 |
N3—C2—O1 | 121.54 (18) | C9'—C10'—H10' | 120.1 |
N3—C4—C5 | 108.47 (15) | C10'—C11'—C12' | 120.2 (3) |
N3—C4—C7 | 110.95 (16) | C10'—C11'—H11' | 119.9 |
C5—C4—C7 | 112.88 (16) | C12'—C11'—H11' | 119.9 |
N3—C4—H4 | 108.1 | C11'—C12'—C7' | 121.6 (2) |
C5—C4—H4 | 108.1 | C11'—C12'—H12' | 119.2 |
C7—C4—H4 | 108.1 | C7'—C12'—H12' | 119.2 |
C6—C5—C4 | 123.55 (18) | C14'—C13'—C18' | 118.8 (2) |
C6—C5—H5 | 118.2 | C14'—C13'—C6' | 120.1 (2) |
C4—C5—H5 | 118.2 | C18'—C13'—C6' | 121.1 (2) |
C5—C6—O1 | 119.65 (18) | C15'—C14'—C13' | 120.4 (2) |
C5—C6—C13 | 129.71 (19) | C15'—C14'—H14' | 119.8 |
O1—C6—C13 | 110.61 (16) | C13'—C14'—H14' | 119.8 |
C8—C7—C12 | 118.5 (2) | C16'—C15'—C14' | 120.5 (3) |
C8—C7—C4 | 122.54 (19) | C16'—C15'—H15' | 119.8 |
C12—C7—C4 | 118.9 (2) | C14'—C15'—H15' | 119.8 |
C7—C8—C9 | 120.7 (2) | C17'—C16'—C15' | 119.9 (2) |
C7—C8—H8 | 119.7 | C17'—C16'—H16' | 120.1 |
C9—C8—H8 | 119.7 | C15'—C16'—H16' | 120.1 |
C10—C9—C8 | 119.9 (3) | C16'—C17'—C18' | 120.8 (3) |
C10—C9—H9 | 120.1 | C16'—C17'—H17' | 119.6 |
C8—C9—H9 | 120.1 | C18'—C17'—H17' | 119.6 |
C11—C10—C9 | 119.8 (3) | C17'—C18'—C13' | 119.6 (2) |
C11—C10—H10 | 120.1 | C17'—C18'—H18' | 120.2 |
C9—C10—H10 | 120.1 | C13'—C18'—H18' | 120.2 |
C10—C11—C12 | 120.6 (3) | F3'—C19—F1 | 127.1 (4) |
C10—C11—H11 | 119.7 | F3'—C19—F1' | 112.1 (5) |
C12—C11—H11 | 119.7 | F1—C19—F1' | 40.1 (4) |
C7—C12—C11 | 120.5 (3) | F3'—C19—F2 | 53.1 (3) |
C7—C12—H12 | 119.7 | F1—C19—F2 | 102.0 (5) |
C11—C12—H12 | 119.7 | F1'—C19—F2 | 126.0 (5) |
C14—C13—C18 | 118.83 (19) | F3'—C19—F2' | 104.2 (5) |
C14—C13—C6 | 120.26 (19) | F1—C19—F2' | 64.2 (4) |
C18—C13—C6 | 120.89 (19) | F1'—C19—F2' | 103.7 (5) |
C15—C14—C13 | 120.4 (2) | F2—C19—F2' | 51.6 (3) |
C15—C14—H14 | 119.8 | F3'—C19—F3 | 56.8 (4) |
C13—C14—H14 | 119.8 | F1—C19—F3 | 102.4 (4) |
C16—C15—C14 | 120.8 (2) | F1'—C19—F3 | 65.5 (4) |
C16—C15—H15 | 119.6 | F2—C19—F3 | 106.4 (4) |
C14—C15—H15 | 119.6 | F2'—C19—F3 | 145.5 (4) |
C15—C16—C17 | 119.6 (2) | F3'—C19—C20 | 115.7 (3) |
C15—C16—H16 | 120.2 | F1—C19—C20 | 117.2 (3) |
C17—C16—H16 | 120.2 | F1'—C19—C20 | 116.5 (4) |
C16—C17—C18 | 120.4 (2) | F2—C19—C20 | 115.8 (3) |
C16—C17—H17 | 119.8 | F2'—C19—C20 | 102.6 (3) |
C18—C17—H17 | 119.8 | F3—C19—C20 | 111.6 (3) |
C17—C18—C13 | 119.9 (2) | O4—C20—O3 | 128.7 (2) |
C17—C18—H18 | 120.0 | O4—C20—C19 | 114.8 (2) |
C13—C18—H18 | 120.0 | O3—C20—C19 | 116.4 (2) |
C2'—O1'—C6' | 119.15 (16) | F6'—C21—F4 | 40.4 (4) |
C2'—N3'—C4' | 123.66 (19) | F6'—C21—F5 | 127.0 (5) |
C2'—N3'—H3'N | 117.6 (14) | F4—C21—F5 | 103.0 (4) |
C4'—N3'—H3'N | 117.6 (14) | F6'—C21—F5' | 108.1 (5) |
C2'—N19'—H19C | 120.4 (17) | F4—C21—F5' | 129.8 (4) |
C2'—N19'—H19D | 122.1 (15) | F5—C21—F5' | 61.7 (4) |
H19C—N19'—H19D | 117 (2) | F6'—C21—F4' | 103.6 (5) |
N19'—C2'—N3' | 123.8 (2) | F4—C21—F4' | 65.5 (4) |
N19'—C2'—O1' | 114.67 (19) | F5—C21—F4' | 45.4 (4) |
N3'—C2'—O1' | 121.5 (2) | F5'—C21—F4' | 105.4 (5) |
N3'—C4'—C5' | 108.01 (16) | F6'—C21—F6 | 66.7 (4) |
N3'—C4'—C7' | 111.93 (16) | F4—C21—F6 | 104.4 (4) |
C5'—C4'—C7' | 113.05 (17) | F5—C21—F6 | 106.8 (4) |
N3'—C4'—H4' | 107.9 | F5'—C21—F6 | 48.7 (4) |
C5'—C4'—H4' | 107.9 | F4'—C21—F6 | 138.9 (4) |
C7'—C4'—H4' | 107.9 | F6'—C21—C22 | 116.4 (4) |
C6'—C5'—C4' | 123.3 (2) | F4—C21—C22 | 114.6 (3) |
C6'—C5'—H5' | 118.3 | F5—C21—C22 | 114.2 (3) |
C4'—C5'—H5' | 118.3 | F5'—C21—C22 | 115.1 (3) |
C5'—C6'—O1' | 119.43 (19) | F4'—C21—C22 | 107.1 (4) |
C5'—C6'—C13' | 130.1 (2) | F6—C21—C22 | 112.9 (3) |
O1'—C6'—C13' | 110.44 (18) | O6—C22—O5 | 128.4 (2) |
C8'—C7'—C12' | 117.7 (2) | O6—C22—C21 | 115.6 (2) |
C8'—C7'—C4' | 123.34 (19) | O5—C22—C21 | 116.0 (2) |
| | | |
C4—N3—C2—N19 | 171.3 (2) | N3'—C4'—C7'—C8' | 35.2 (3) |
C4—N3—C2—O1 | −7.3 (3) | C5'—C4'—C7'—C8' | −87.1 (3) |
C6—O1—C2—N19 | 173.68 (19) | N3'—C4'—C7'—C12' | −147.3 (2) |
C6—O1—C2—N3 | −7.6 (3) | C5'—C4'—C7'—C12' | 90.4 (2) |
C2—N3—C4—C5 | 16.9 (3) | C12'—C7'—C8'—C9' | −0.6 (4) |
C2—N3—C4—C7 | 141.4 (2) | C4'—C7'—C8'—C9' | 176.9 (2) |
N3—C4—C5—C6 | −13.7 (3) | C7'—C8'—C9'—C10' | 0.0 (4) |
C7—C4—C5—C6 | −137.1 (2) | C8'—C9'—C10'—C11' | −0.1 (5) |
C4—C5—C6—O1 | 1.6 (3) | C9'—C10'—C11'—C12' | 1.0 (4) |
C4—C5—C6—C13 | −176.09 (19) | C10'—C11'—C12'—C7' | −1.7 (4) |
C2—O1—C6—C5 | 10.2 (3) | C8'—C7'—C12'—C11' | 1.5 (4) |
C2—O1—C6—C13 | −171.68 (17) | C4'—C7'—C12'—C11' | −176.1 (2) |
N3—C4—C7—C8 | −33.2 (3) | C5'—C6'—C13'—C14' | −9.2 (3) |
C5—C4—C7—C8 | 88.8 (2) | O1'—C6'—C13'—C14' | 168.68 (18) |
N3—C4—C7—C12 | 148.11 (19) | C5'—C6'—C13'—C18' | 171.4 (2) |
C5—C4—C7—C12 | −89.9 (2) | O1'—C6'—C13'—C18' | −10.7 (3) |
C12—C7—C8—C9 | 0.1 (3) | C18'—C13'—C14'—C15' | 0.6 (3) |
C4—C7—C8—C9 | −178.6 (2) | C6'—C13'—C14'—C15' | −178.9 (2) |
C7—C8—C9—C10 | 0.2 (4) | C13'—C14'—C15'—C16' | 0.4 (4) |
C8—C9—C10—C11 | 0.5 (4) | C14'—C15'—C16'—C17' | −0.8 (4) |
C9—C10—C11—C12 | −1.4 (5) | C15'—C16'—C17'—C18' | 0.3 (4) |
C8—C7—C12—C11 | −1.1 (3) | C16'—C17'—C18'—C13' | 0.7 (3) |
C4—C7—C12—C11 | 177.7 (2) | C14'—C13'—C18'—C17' | −1.1 (3) |
C10—C11—C12—C7 | 1.7 (4) | C6'—C13'—C18'—C17' | 178.36 (19) |
C5—C6—C13—C14 | 10.8 (3) | F3'—C19—C20—O4 | −164.6 (7) |
O1—C6—C13—C14 | −167.00 (18) | F1—C19—C20—O4 | 15.4 (6) |
C5—C6—C13—C18 | −170.9 (2) | F1'—C19—C20—O4 | −29.7 (8) |
O1—C6—C13—C18 | 11.2 (3) | F2—C19—C20—O4 | 135.9 (7) |
C18—C13—C14—C15 | −0.6 (3) | F2'—C19—C20—O4 | 82.7 (6) |
C6—C13—C14—C15 | 177.7 (2) | F3—C19—C20—O4 | −102.2 (7) |
C13—C14—C15—C16 | 0.2 (4) | F3'—C19—C20—O3 | 14.4 (8) |
C14—C15—C16—C17 | 0.0 (4) | F1—C19—C20—O3 | −165.6 (5) |
C15—C16—C17—C18 | 0.1 (4) | F1'—C19—C20—O3 | 149.2 (8) |
C16—C17—C18—C13 | −0.5 (3) | F2—C19—C20—O3 | −45.1 (7) |
C14—C13—C18—C17 | 0.7 (3) | F2'—C19—C20—O3 | −98.3 (5) |
C6—C13—C18—C17 | −177.5 (2) | F3—C19—C20—O3 | 76.8 (7) |
C4'—N3'—C2'—N19' | −168.2 (2) | F6'—C21—C22—O6 | 32.2 (8) |
C4'—N3'—C2'—O1' | 11.5 (3) | F4—C21—C22—O6 | −12.8 (6) |
C6'—O1'—C2'—N19' | −171.29 (18) | F5—C21—C22—O6 | −131.2 (6) |
C6'—O1'—C2'—N3' | 9.0 (3) | F5'—C21—C22—O6 | 160.1 (8) |
C2'—N3'—C4'—C5' | −23.4 (3) | F4'—C21—C22—O6 | −83.1 (7) |
C2'—N3'—C4'—C7' | −148.5 (2) | F6—C21—C22—O6 | 106.5 (6) |
N3'—C4'—C5'—C6' | 17.7 (3) | F6'—C21—C22—O5 | −147.9 (7) |
C7'—C4'—C5'—C6' | 142.1 (2) | F4—C21—C22—O5 | 167.1 (5) |
C4'—C5'—C6'—O1' | −0.7 (3) | F5—C21—C22—O5 | 48.7 (6) |
C4'—C5'—C6'—C13' | 177.01 (19) | F5'—C21—C22—O5 | −19.9 (8) |
C2'—O1'—C6'—C5' | −14.2 (3) | F4'—C21—C22—O5 | 96.8 (7) |
C2'—O1'—C6'—C13' | 167.65 (17) | F6—C21—C22—O5 | −73.5 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···O5 | 0.87 (1) | 1.90 (1) | 2.772 (2) | 178 (2) |
N19—H19A···O3 | 0.87 (1) | 1.95 (1) | 2.823 (2) | 179 (2) |
N19—H19B···O6 | 0.88 (1) | 1.90 (1) | 2.778 (3) | 173 (2) |
N3′—H3′N···O3i | 0.87 (1) | 1.90 (1) | 2.766 (2) | 177 (2) |
N19′—H19D···O4i | 0.87 (1) | 1.90 (1) | 2.770 (3) | 174 (2) |
N19′—H19C···O5 | 0.88 (1) | 1.95 (1) | 2.820 (2) | 174 (2) |
Symmetry code: (i) x, y+1, z. |
Experimental details
Crystal data |
Chemical formula | C16H15N2O+·C2F3O2− |
Mr | 364.32 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 10.341 (2), 11.867 (2), 14.409 (3) |
α, β, γ (°) | 90.62 (2), 92.68 (2), 91.03 (2) |
V (Å3) | 1765.9 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.58 × 0.50 × 0.42 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7215, 6591, 3495 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.606 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.115, 0.94 |
No. of reflections | 6591 |
No. of parameters | 548 |
No. of restraints | 18 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.18 |
Selected geometric parameters (Å, º) topO1—C2 | 1.333 (2) | N3'—C2' | 1.307 (2) |
O1—C6 | 1.407 (2) | N3'—C4' | 1.463 (3) |
N3—C2 | 1.299 (2) | N19'—C2' | 1.296 (3) |
N3—C4 | 1.460 (2) | O3—C20 | 1.227 (2) |
N19—C2 | 1.297 (3) | O4—C20 | 1.216 (2) |
O1'—C2' | 1.327 (2) | O5—C22 | 1.222 (2) |
O1'—C6' | 1.409 (2) | O6—C22 | 1.215 (2) |
| | | |
C2—O1—C6 | 119.49 (15) | C2'—O1'—C6' | 119.15 (16) |
C2—N3—C4 | 124.65 (17) | C2'—N3'—C4' | 123.66 (19) |
N19—C2—N3 | 124.0 (2) | N19'—C2'—N3' | 123.8 (2) |
N19—C2—O1 | 114.44 (18) | N19'—C2'—O1' | 114.67 (19) |
N3—C2—O1 | 121.54 (18) | N3'—C2'—O1' | 121.5 (2) |
| | | |
C4—N3—C2—N19 | 171.3 (2) | C4'—N3'—C2'—N19' | −168.2 (2) |
C4—N3—C2—O1 | −7.3 (3) | C4'—N3'—C2'—O1' | 11.5 (3) |
C4—C5—C6—O1 | 1.6 (3) | C4'—C5'—C6'—O1' | −0.7 (3) |
N3—C4—C7—C8 | −33.2 (3) | N3'—C4'—C7'—C8' | 35.2 (3) |
O1—C6—C13—C18 | 11.2 (3) | O1'—C6'—C13'—C18' | −10.7 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···O5 | 0.87 (1) | 1.90 (1) | 2.772 (2) | 178 (2) |
N19—H19A···O3 | 0.87 (1) | 1.95 (1) | 2.823 (2) | 179 (2) |
N19—H19B···O6 | 0.88 (1) | 1.90 (1) | 2.778 (3) | 173 (2) |
N3'—H3'N···O3i | 0.87 (1) | 1.90 (1) | 2.766 (2) | 177 (2) |
N19'—H19D···O4i | 0.87 (1) | 1.90 (1) | 2.770 (3) | 174 (2) |
N19'—H19C···O5 | 0.88 (1) | 1.95 (1) | 2.820 (2) | 174 (2) |
Symmetry code: (i) x, y+1, z. |
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Domino (Tietze, 1996; Armstrong et al., 1996; Tietze & Modi, 2000) and multicomponent (Dömling & Ugi, 2000; Kappe, 2000; Bienaymé et al., 2000; Jacobi von Wangelin et al., 2003; Simon et al., 2004) reactions (MCRs) are powerful strategies in current organic synthesis. Consistently, several reported MCRs feature Diels–Alder chemistry with heterodiene (Batey et al., 1999; Tailor & Hall, 2000; Touré et al., 2003; Tietze & Rachkelmann, 2004; Strübing et al., 2005) building blocks for the synthesis of heterocyclic six-membered rings. Recently, we synthesized a series of 2-amino-4H-1,3-oxazines and 2-amino-4H-1,3-thiazines (Huang et al., 2005). 4H-1,3-Oxazines and 4H-1,3-thiazines are important synthetic intermediates in organic synthesis (Schmidt, 1972; Jochims et al., 1990; Vanier et al., 2004), and these skeletons have been found in a few biologically relevant compounds (Ilyuchenok et al., 1979; Eckstein & Urbanski, 1963; Eckstein & Urbanski, 1978; Sondhi et al., 2000) and vulcanization accelerators (Gridunov et al., 1972). Since the Diels–Alder reaction may yield other stereoisomers, we wish to confirm the structure of a product of the reaction, 2-amino-4,6-diphenyl-4H-1,3-oxazine. Unfortunately, we have not obtained any crystal. Therefore, we prepared crystals of its salt with trifluoroacetic acid, namely the title compound, (I).
There are two independent ion pairs (Fig. 1). The C—O bond lengths of the anions [1.215 (2)–1.227 (2) Å] indicate that the original trifluoroacetic group turns out to be the trifluoroacetate one with a form of full delocalization of electrons. Similarly, the N3—C2/N3'—C2' [1.299 (2) and 1.307 (2) Å] and N19—C2/N19'—C2' bond lengths [1.297 (3) and 1.296 (3) Å], and the angles of the heterocyclic rings, are consistent with the iminium tautomer and suggest intensive protonation of the heterocycle.
A network of intermolecular N—H···O interactions (Fig. 2) provide strong packing directives in (I). The ion pairs are held together by two N—H···O hydrogen bonds [Table 2; N···O = 2.766 (2)–2.778 (3) Å], and adjacent ion-pairs are linked into helical chains by a third and substantially weaker N—H···O hydrogen bond [N···O = 2.820–2.823 (2) Å].