In the title compound, C9H18NO+·NO3-, the piperidinium ring adopts a slightly deformed chair conformation and the nitrate anion is disordered. The ions are arranged in hydrogen-bonded chains parallel to [001], in which the cations alternate with the anions. The intrachain hydrogen bonds are bifurcated and link the O atoms of the anions to the N atoms of the cations.
Supporting information
CCDC reference: 645581
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: PLATON (Spek, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
2,2,6,6-Tetramethyl-4-oxopiperidinium nitrate
top
Crystal data top
C9H18NO+·NO3− | F(000) = 472 |
Mr = 218.25 | Dx = 1.251 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 7.7170 (4) Å | θ = 7.3–27.8° |
b = 19.7883 (8) Å | µ = 0.82 mm−1 |
c = 9.6468 (8) Å | T = 290 K |
β = 128.155 (5)° | Plate, red |
V = 1158.38 (15) Å3 | 0.3 × 0.2 × 0.05 mm |
Z = 4 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 1474 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.060 |
Graphite monochromator | θmax = 72.5°, θmin = 4.5° |
profile data from ω–2θ scans | h = −9→5 |
Absorption correction: ψ scan (North et al., 1968) | k = −24→22 |
Tmin = 0.854, Tmax = 0.959 | l = −9→11 |
3417 measured reflections | 3 standard reflections every 180 min |
2301 independent reflections | intensity decay: 5% |
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)] = 0.059 | H-atom parameters constrained |
wR(F2) = 0.191 | w = 1/[σ2(Fo2) + (0.0858P)2 + 0.4726P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2301 reflections | Δρmax = 0.29 e Å−3 |
167 parameters | Δρmin = −0.27 e Å−3 |
29 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0066 (14) |
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) |
N1 | 0.9456 (3) | 0.15056 (10) | 0.1572 (3) | 0.0456 (5) | |
H1A | 0.9808 | 0.1474 | 0.0842 | 0.055* | |
H1B | 0.9782 | 0.1930 | 0.2001 | 0.055* | |
C2 | 1.0986 (4) | 0.10338 (13) | 0.3113 (3) | 0.0479 (6) | |
C2A | 1.3267 (5) | 0.13565 (19) | 0.4162 (4) | 0.0718 (9) | |
H2A1 | 1.3715 | 0.1390 | 0.3432 | 0.108* | |
H2A2 | 1.4303 | 0.1083 | 0.5174 | 0.108* | |
H2A3 | 1.3216 | 0.1800 | 0.4540 | 0.108* | |
C2B | 1.1062 (6) | 0.03357 (15) | 0.2487 (4) | 0.0742 (10) | |
H2B1 | 0.9701 | 0.0104 | 0.1991 | 0.111* | |
H2B2 | 1.2262 | 0.0082 | 0.3468 | 0.111* | |
H2B3 | 1.1271 | 0.0381 | 0.1609 | 0.111* | |
C3 | 1.0190 (5) | 0.09970 (14) | 0.4229 (3) | 0.0550 (7) | |
H3A | 1.0930 | 0.0624 | 0.5053 | 0.066* | |
H3B | 1.0612 | 0.1410 | 0.4910 | 0.066* | |
C4 | 0.7743 (5) | 0.09031 (14) | 0.3158 (4) | 0.0567 (7) | |
O4 | 0.6911 (4) | 0.04634 (12) | 0.3446 (3) | 0.0830 (8) | |
C5 | 0.6398 (5) | 0.14080 (16) | 0.1716 (4) | 0.0627 (8) | |
H5A | 0.6641 | 0.1853 | 0.2230 | 0.075* | |
H5B | 0.4849 | 0.1299 | 0.1058 | 0.075* | |
C6 | 0.6966 (4) | 0.14245 (14) | 0.0453 (3) | 0.0520 (6) | |
C6A | 0.5985 (6) | 0.20456 (18) | −0.0740 (5) | 0.0789 (10) | |
H6A1 | 0.6532 | 0.2447 | −0.0029 | 0.118* | |
H6A2 | 0.4408 | 0.2032 | −0.1444 | 0.118* | |
H6A3 | 0.6399 | 0.2048 | −0.1496 | 0.118* | |
C6B | 0.6171 (6) | 0.07914 (18) | −0.0666 (4) | 0.0753 (9) | |
H6B1 | 0.6814 | 0.0767 | −0.1256 | 0.113* | |
H6B2 | 0.4594 | 0.0804 | −0.1525 | 0.113* | |
H6B3 | 0.6599 | 0.0402 | 0.0073 | 0.113* | |
N2 | 1.0332 (4) | 0.31899 (13) | 0.3471 (3) | 0.0632 (7) | |
O1A | 1.0031 (12) | 0.3734 (3) | 0.3927 (10) | 0.0538 (17)* | 0.394 (4) |
O2A | 1.0105 (15) | 0.2979 (5) | 0.2168 (10) | 0.069 (2)* | 0.394 (4) |
O3A | 1.0950 (14) | 0.2720 (4) | 0.4723 (11) | 0.087 (2)* | 0.394 (4) |
O1B | 1.053 (2) | 0.3803 (6) | 0.363 (2) | 0.079 (5)* | 0.198 (10) |
O2B | 1.084 (2) | 0.2953 (8) | 0.2544 (16) | 0.053 (4)* | 0.198 (10) |
O3B | 0.983 (3) | 0.2741 (6) | 0.408 (2) | 0.060 (4)* | 0.198 (10) |
O1C | 1.0849 (17) | 0.3723 (4) | 0.4386 (16) | 0.029 (3)* | 0.233 (13) |
O2C | 0.985 (3) | 0.3342 (8) | 0.1918 (18) | 0.089 (5)* | 0.233 (13) |
O3C | 1.026 (2) | 0.2645 (4) | 0.3915 (17) | 0.051 (3)* | 0.233 (13) |
O1D | 1.097 (3) | 0.3630 (11) | 0.470 (3) | 0.104 (11)* | 0.175 (13) |
O2D | 1.086 (3) | 0.3288 (8) | 0.2473 (18) | 0.049 (5)* | 0.175 (13) |
O3D | 0.925 (4) | 0.2705 (7) | 0.334 (3) | 0.086 (6)* | 0.175 (13) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0561 (12) | 0.0392 (10) | 0.0488 (11) | 0.0011 (9) | 0.0360 (10) | 0.0041 (8) |
C2 | 0.0583 (15) | 0.0422 (12) | 0.0462 (12) | 0.0064 (11) | 0.0336 (12) | 0.0040 (10) |
C2A | 0.0595 (18) | 0.082 (2) | 0.0676 (18) | 0.0023 (16) | 0.0360 (16) | 0.0048 (17) |
C2B | 0.101 (2) | 0.0509 (16) | 0.074 (2) | 0.0250 (16) | 0.0558 (19) | 0.0068 (14) |
C3 | 0.0691 (17) | 0.0534 (15) | 0.0460 (13) | −0.0011 (13) | 0.0372 (13) | 0.0018 (12) |
C4 | 0.0771 (19) | 0.0528 (15) | 0.0593 (15) | −0.0024 (13) | 0.0517 (15) | 0.0000 (12) |
O4 | 0.0961 (18) | 0.0798 (16) | 0.0949 (17) | −0.0093 (13) | 0.0700 (15) | 0.0152 (13) |
C5 | 0.0623 (17) | 0.0622 (17) | 0.0743 (18) | 0.0064 (14) | 0.0476 (16) | 0.0066 (14) |
C6 | 0.0521 (15) | 0.0491 (14) | 0.0523 (14) | −0.0005 (11) | 0.0310 (12) | 0.0063 (11) |
C6A | 0.066 (2) | 0.074 (2) | 0.080 (2) | 0.0133 (16) | 0.0373 (18) | 0.0303 (18) |
C6B | 0.076 (2) | 0.073 (2) | 0.0591 (17) | −0.0171 (16) | 0.0325 (16) | −0.0127 (15) |
N2 | 0.0829 (17) | 0.0608 (16) | 0.0715 (15) | −0.0122 (13) | 0.0605 (15) | −0.0192 (12) |
Geometric parameters (Å, º) top
N1—C2 | 1.519 (3) | C6—C6B | 1.514 (4) |
N1—C6 | 1.523 (3) | C6—C6A | 1.527 (4) |
N1—H1A | 0.9000 | C6A—H6A1 | 0.9600 |
N1—H1B | 0.9000 | C6A—H6A2 | 0.9600 |
C2—C2B | 1.523 (4) | C6A—H6A3 | 0.9600 |
C2—C2A | 1.526 (4) | C6B—H6B1 | 0.9600 |
C2—C3 | 1.535 (3) | C6B—H6B2 | 0.9600 |
C2A—H2A1 | 0.9600 | C6B—H6B3 | 0.9600 |
C2A—H2A2 | 0.9600 | N2—O1A | 1.239 (5) |
C2A—H2A3 | 0.9600 | N2—O2A | 1.230 (6) |
C2B—H2B1 | 0.9600 | N2—O3A | 1.357 (7) |
C2B—H2B2 | 0.9600 | N2—O1B | 1.220 (11) |
C2B—H2B3 | 0.9600 | N2—O2B | 1.267 (9) |
C3—C4 | 1.502 (4) | N2—O3B | 1.256 (10) |
C3—H3A | 0.9700 | N2—O1C | 1.272 (7) |
C3—H3B | 0.9700 | N2—O2C | 1.335 (11) |
C4—O4 | 1.211 (3) | N2—O3C | 1.176 (8) |
C4—C5 | 1.492 (4) | N2—O1D | 1.295 (13) |
C5—C6 | 1.530 (4) | N2—O2D | 1.270 (9) |
C5—H5A | 0.9700 | N2—O3D | 1.224 (12) |
C5—H5B | 0.9700 | | |
| | | |
C2—N1—C6 | 120.44 (19) | C6—C5—H5A | 109.1 |
C2—N1—H1A | 107.2 | C4—C5—H5B | 109.1 |
C6—N1—H1A | 107.2 | C6—C5—H5B | 109.1 |
C2—N1—H1B | 107.2 | H5A—C5—H5B | 107.9 |
C6—N1—H1B | 107.2 | C6B—C6—N1 | 111.8 (2) |
H1A—N1—H1B | 106.8 | C6B—C6—C6A | 109.6 (3) |
N1—C2—C2B | 111.5 (2) | N1—C6—C6A | 105.7 (2) |
N1—C2—C2A | 105.8 (2) | C6B—C6—C5 | 111.1 (3) |
C2B—C2—C2A | 109.4 (3) | N1—C6—C5 | 107.1 (2) |
N1—C2—C3 | 108.0 (2) | C6A—C6—C5 | 111.4 (3) |
C2B—C2—C3 | 111.4 (2) | C6—C6A—H6A1 | 109.5 |
C2A—C2—C3 | 110.6 (2) | C6—C6A—H6A2 | 109.5 |
C2—C2A—H2A1 | 109.5 | H6A1—C6A—H6A2 | 109.5 |
C2—C2A—H2A2 | 109.5 | C6—C6A—H6A3 | 109.5 |
H2A1—C2A—H2A2 | 109.5 | H6A1—C6A—H6A3 | 109.5 |
C2—C2A—H2A3 | 109.5 | H6A2—C6A—H6A3 | 109.5 |
H2A1—C2A—H2A3 | 109.5 | C6—C6B—H6B1 | 109.5 |
H2A2—C2A—H2A3 | 109.5 | C6—C6B—H6B2 | 109.5 |
C2—C2B—H2B1 | 109.5 | H6B1—C6B—H6B2 | 109.5 |
C2—C2B—H2B2 | 109.5 | C6—C6B—H6B3 | 109.5 |
H2B1—C2B—H2B2 | 109.5 | H6B1—C6B—H6B3 | 109.5 |
C2—C2B—H2B3 | 109.5 | H6B2—C6B—H6B3 | 109.5 |
H2B1—C2B—H2B3 | 109.5 | O1A—N2—O2A | 135.9 (6) |
H2B2—C2B—H2B3 | 109.5 | O2A—N2—O3A | 115.3 (6) |
C4—C3—C2 | 113.6 (2) | O3A—N2—O1A | 108.6 (5) |
C4—C3—H3A | 108.8 | O1B—N2—O2B | 112.9 (10) |
C2—C3—H3A | 108.8 | O2B—N2—O3B | 113.1 (9) |
C4—C3—H3B | 108.8 | O3B—N2—O1B | 133.9 (10) |
C2—C3—H3B | 108.8 | O1C—N2—O2C | 110.0 (9) |
H3A—C3—H3B | 107.7 | O2C—N2—O3C | 125.0 (8) |
O4—C4—C5 | 122.2 (3) | O3C—N2—O1C | 125.0 (9) |
O4—C4—C3 | 123.4 (3) | O1D—N2—O2D | 117.9 (11) |
C5—C4—C3 | 114.4 (2) | O2D—N2—O3D | 123.7 (10) |
C4—C5—C6 | 112.3 (2) | O3D—N2—O1D | 118.4 (12) |
C4—C5—H5A | 109.1 | | |
| | | |
C6—N1—C2—C2B | 73.9 (3) | O4—C4—C5—C6 | −125.0 (3) |
C6—N1—C2—C2A | −167.3 (2) | C3—C4—C5—C6 | 56.1 (3) |
C6—N1—C2—C3 | −48.8 (3) | C2—N1—C6—C6B | −70.2 (3) |
N1—C2—C3—C4 | 45.8 (3) | C2—N1—C6—C6A | 170.6 (2) |
C2B—C2—C3—C4 | −77.0 (3) | C2—N1—C6—C5 | 51.8 (3) |
C2A—C2—C3—C4 | 161.1 (2) | C4—C5—C6—C6B | 70.8 (3) |
C2—C3—C4—O4 | 128.1 (3) | C4—C5—C6—N1 | −51.6 (3) |
C2—C3—C4—C5 | −53.0 (3) | C4—C5—C6—C6A | −166.7 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1Ai | 0.90 | 2.00 | 2.886 (7) | 167 |
N1—H1A···O3Ai | 0.90 | 2.38 | 3.066 (9) | 133 |
N1—H1B···O2A | 0.90 | 2.09 | 2.955 (9) | 162 |
Symmetry code: (i) x, −y+1/2, z−1/2. |