Low-temperature structural data are reported for the anaesthetic (2
R)-(−)-2-(2,6-dimethylphenylaminocarbonyl)-1-methylpiperidinium chloride, C
15H
23N
2O
+·Cl
−, which complement existing room-temperature data for the
S enantiomer. Crystal packing is largely controlled by infinite N—H
Cl hydrogen-bonded chains.
Supporting information
CCDC reference: 269556
Key indicators
- Single-crystal X-ray study
- T = 180 K
- Mean (C-C) = 0.003 Å
- R factor = 0.022
- wR factor = 0.047
- Data-to-parameter ratio = 9.1
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............ 59.03 Deg.
| Author Response: 'see _publ_section_exptl_refinement'
|
Alert level B
THETM01_ALERT_3_B The value of sine(theta_max)/wavelength is less than 0.575
Calculated sin(theta_max)/wavelength = 0.5561
PLAT023_ALERT_3_B Resolution (too) Low [sin(th)/Lambda < 0.6]..... 59.03 Deg.
Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.80 mm
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 59.03
From the CIF: _reflns_number_total 2201
Count of symmetry unique reflns 1318
Completeness (_total/calc) 167.00%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 883
Fraction of Friedel pairs measured 0.670
Are heavy atom types Z>Si present yes
1 ALERT level A = In general: serious problem
2 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
4 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrysAlis CCD (Oxford Diffraction, 2001); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2001); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
(2
R)-2-(2,6-dimethylphenylaminocarbonyl)-1-methylpiperidinium chloride
top
Crystal data top
C15H23N2O+·Cl− | Dx = 1.194 Mg m−3 |
Mr = 282.80 | Cu Kα radiation, λ = 1.54180 Å |
Orthorhombic, P212121 | Cell parameters from 952 reflections |
a = 9.7378 (10) Å | θ = 6–58° |
b = 10.5790 (9) Å | µ = 2.10 mm−1 |
c = 15.2761 (15) Å | T = 180 K |
V = 1573.7 (3) Å3 | Elongated prism, colorless |
Z = 4 | 0.80 × 0.30 × 0.30 mm |
F(000) = 608 | |
Data collection top
Oxford Diffraction CCD diffractometer | 2201 independent reflections |
Radiation source: fine-focus sealed tube | 1989 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 59.0°, θmin = 5.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1986) | h = −10→9 |
Tmin = 0.331, Tmax = 0.533 | k = −11→9 |
6079 measured reflections | l = −15→16 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | Only H-atom coordinates refined |
R[F2 > 2σ(F2)] = 0.022 | w = 1/[σ2(Fo2) + (0.0218P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.047 | (Δ/σ)max < 0.001 |
S = 0.96 | Δρmax = 0.14 e Å−3 |
2201 reflections | Δρmin = −0.11 e Å−3 |
242 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0167 (5) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 883 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.023 (11) |
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 | |
Cl | 0.21641 (4) | 0.51729 (4) | 0.87349 (3) | 0.03400 (15) | |
N1 | −0.09933 (14) | 0.26043 (15) | 0.69728 (9) | 0.0246 (4) | |
H1N | −0.1038 (18) | 0.1807 (17) | 0.6759 (11) | 0.029* | |
C1' | −0.1655 (2) | 0.2570 (3) | 0.78545 (13) | 0.0377 (5) | |
H71 | −0.114 (2) | 0.199 (2) | 0.8240 (13) | 0.057* | |
H72 | −0.256 (2) | 0.216 (2) | 0.7769 (13) | 0.057* | |
H73 | −0.172 (2) | 0.340 (2) | 0.8081 (14) | 0.057* | |
C2 | 0.04679 (18) | 0.30285 (18) | 0.70399 (11) | 0.0260 (4) | |
H2 | 0.0474 (17) | 0.3791 (18) | 0.7346 (12) | 0.031* | |
C3 | 0.1101 (2) | 0.3215 (2) | 0.61335 (13) | 0.0387 (5) | |
H31 | 0.118 (2) | 0.237 (2) | 0.5860 (12) | 0.046* | |
H32 | 0.199 (2) | 0.3595 (17) | 0.6236 (12) | 0.046* | |
C4 | 0.0237 (2) | 0.4076 (2) | 0.55541 (15) | 0.0427 (6) | |
H41 | 0.022 (2) | 0.490 (2) | 0.5813 (13) | 0.051* | |
H42 | 0.066 (2) | 0.415 (2) | 0.4989 (14) | 0.051* | |
C5 | −0.1190 (2) | 0.3523 (2) | 0.54786 (13) | 0.0358 (5) | |
H51 | −0.182 (2) | 0.3992 (19) | 0.5131 (12) | 0.043* | |
H52 | −0.1182 (19) | 0.267 (2) | 0.5217 (12) | 0.043* | |
C6 | −0.18483 (19) | 0.3401 (2) | 0.63616 (13) | 0.0303 (5) | |
H61 | −0.2762 (18) | 0.2948 (16) | 0.6352 (12) | 0.036* | |
H62 | −0.1920 (19) | 0.4185 (19) | 0.6655 (12) | 0.036* | |
C7 | 0.12812 (18) | 0.19953 (19) | 0.75059 (11) | 0.0265 (4) | |
O7 | 0.10466 (13) | 0.08763 (13) | 0.73431 (8) | 0.0373 (4) | |
N8 | 0.22762 (16) | 0.24068 (15) | 0.80354 (10) | 0.0279 (4) | |
H8N | 0.2255 (19) | 0.3171 (18) | 0.8185 (12) | 0.033* | |
C9 | 0.32758 (17) | 0.15887 (17) | 0.84329 (11) | 0.0264 (5) | |
C10 | 0.42577 (18) | 0.10045 (19) | 0.79009 (12) | 0.0303 (5) | |
C11 | 0.52297 (19) | 0.0242 (2) | 0.83062 (14) | 0.0362 (5) | |
H11 | 0.5883 (19) | −0.0202 (18) | 0.7963 (12) | 0.043* | |
C12 | 0.52420 (19) | 0.0087 (2) | 0.92023 (13) | 0.0385 (5) | |
H12 | 0.596 (2) | −0.0410 (18) | 0.9486 (13) | 0.046* | |
C13 | 0.4263 (2) | 0.06752 (19) | 0.97126 (14) | 0.0361 (5) | |
H13 | 0.4241 (19) | 0.0596 (18) | 1.0312 (14) | 0.043* | |
C14 | 0.32559 (17) | 0.14369 (18) | 0.93404 (12) | 0.0287 (5) | |
C15 | 0.2167 (3) | 0.2058 (2) | 0.98935 (14) | 0.0413 (5) | |
H81 | 0.122 (2) | 0.193 (2) | 0.9667 (14) | 0.062* | |
H82 | 0.234 (2) | 0.296 (2) | 0.9926 (13) | 0.062* | |
H83 | 0.215 (2) | 0.171 (2) | 1.0457 (15) | 0.062* | |
C16 | 0.4275 (2) | 0.1189 (3) | 0.69241 (14) | 0.0453 (6) | |
H91 | 0.520 (2) | 0.089 (2) | 0.6653 (14) | 0.068* | |
H92 | 0.420 (2) | 0.210 (2) | 0.6766 (14) | 0.068* | |
H93 | 0.359 (2) | 0.075 (2) | 0.6671 (14) | 0.068* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0326 (3) | 0.0294 (3) | 0.0400 (3) | 0.0004 (2) | −0.0024 (2) | 0.0017 (2) |
N1 | 0.0229 (9) | 0.0238 (9) | 0.0270 (8) | 0.0020 (8) | 0.0002 (7) | −0.0015 (7) |
C1' | 0.0367 (13) | 0.0434 (14) | 0.0330 (13) | 0.0021 (12) | 0.0084 (9) | 0.0005 (11) |
C2 | 0.0214 (10) | 0.0261 (11) | 0.0306 (11) | −0.0002 (9) | −0.0041 (8) | −0.0009 (9) |
C3 | 0.0269 (10) | 0.0504 (14) | 0.0386 (12) | 0.0000 (11) | 0.0014 (10) | 0.0114 (12) |
C4 | 0.0418 (13) | 0.0526 (15) | 0.0338 (12) | 0.0012 (12) | 0.0037 (10) | 0.0129 (12) |
C5 | 0.0386 (12) | 0.0378 (14) | 0.0309 (12) | 0.0068 (11) | −0.0097 (9) | 0.0014 (10) |
C6 | 0.0239 (10) | 0.0287 (12) | 0.0382 (12) | 0.0054 (9) | −0.0081 (9) | −0.0006 (10) |
C7 | 0.0233 (10) | 0.0292 (12) | 0.0269 (11) | 0.0006 (9) | 0.0001 (9) | 0.0017 (9) |
O7 | 0.0354 (8) | 0.0273 (8) | 0.0494 (9) | 0.0004 (7) | −0.0151 (7) | 0.0001 (7) |
N8 | 0.0269 (9) | 0.0252 (8) | 0.0315 (9) | 0.0000 (9) | −0.0063 (7) | −0.0022 (8) |
C9 | 0.0219 (10) | 0.0245 (11) | 0.0328 (11) | −0.0016 (9) | −0.0074 (8) | 0.0001 (9) |
C10 | 0.0213 (10) | 0.0351 (12) | 0.0345 (11) | −0.0018 (10) | −0.0022 (9) | 0.0037 (9) |
C11 | 0.0261 (11) | 0.0406 (14) | 0.0420 (13) | 0.0041 (11) | −0.0005 (9) | 0.0009 (11) |
C12 | 0.0291 (10) | 0.0397 (14) | 0.0467 (14) | 0.0058 (11) | −0.0096 (9) | 0.0057 (11) |
C13 | 0.0376 (12) | 0.0384 (13) | 0.0323 (11) | −0.0017 (11) | −0.0114 (10) | 0.0029 (10) |
C14 | 0.0261 (10) | 0.0285 (12) | 0.0316 (11) | −0.0002 (9) | −0.0078 (9) | −0.0029 (9) |
C15 | 0.0469 (13) | 0.0448 (14) | 0.0322 (12) | 0.0103 (13) | −0.0030 (11) | −0.0035 (10) |
C16 | 0.0348 (13) | 0.0633 (17) | 0.0377 (13) | 0.0083 (13) | 0.0054 (10) | 0.0061 (12) |
Geometric parameters (Å, º) top
N1—C1' | 1.494 (2) | C7—O7 | 1.231 (2) |
N1—C2 | 1.495 (2) | C7—N8 | 1.335 (2) |
N1—C6 | 1.508 (2) | N8—C9 | 1.437 (2) |
N1—H1N | 0.905 (17) | N8—H8N | 0.841 (18) |
C1'—H71 | 0.99 (2) | C9—C14 | 1.396 (2) |
C1'—H72 | 0.99 (2) | C9—C10 | 1.399 (2) |
C1'—H73 | 0.95 (2) | C10—C11 | 1.389 (3) |
C2—C7 | 1.526 (2) | C10—C16 | 1.505 (3) |
C2—C3 | 1.528 (3) | C11—C12 | 1.379 (3) |
C2—H2 | 0.932 (18) | C11—H11 | 0.949 (19) |
C3—C4 | 1.523 (3) | C12—C13 | 1.380 (3) |
C3—H31 | 0.99 (2) | C12—H12 | 0.979 (19) |
C3—H32 | 0.97 (2) | C13—C14 | 1.391 (2) |
C4—C5 | 1.512 (3) | C13—H13 | 0.92 (2) |
C4—H41 | 0.96 (2) | C14—C15 | 1.507 (3) |
C4—H42 | 0.96 (2) | C15—H81 | 0.99 (2) |
C5—C6 | 1.499 (3) | C15—H82 | 0.97 (3) |
C5—H51 | 0.95 (2) | C15—H83 | 0.94 (2) |
C5—H52 | 0.98 (2) | C16—H91 | 1.04 (2) |
C6—H61 | 1.011 (17) | C16—H92 | 1.00 (2) |
C6—H62 | 0.946 (19) | C16—H93 | 0.90 (2) |
| | | |
C1'—N1—C2 | 110.85 (14) | C5—C6—H62 | 112.5 (11) |
C1'—N1—C6 | 109.49 (15) | N1—C6—H62 | 103.8 (11) |
C2—N1—C6 | 113.57 (14) | H61—C6—H62 | 110.9 (16) |
C1'—N1—H1N | 106.4 (11) | O7—C7—N8 | 124.79 (17) |
C2—N1—H1N | 110.5 (12) | O7—C7—C2 | 119.88 (16) |
C6—N1—H1N | 105.7 (11) | N8—C7—C2 | 115.19 (17) |
N1—C1'—H71 | 109.6 (12) | C7—N8—C9 | 123.45 (16) |
N1—C1'—H72 | 106.1 (12) | C7—N8—H8N | 117.4 (13) |
H71—C1'—H72 | 105.1 (17) | C9—N8—H8N | 118.7 (13) |
N1—C1'—H73 | 109.6 (14) | C14—C9—C10 | 122.40 (17) |
H71—C1'—H73 | 113.1 (18) | C14—C9—N8 | 118.66 (16) |
H72—C1'—H73 | 113.0 (18) | C10—C9—N8 | 118.92 (16) |
N1—C2—C7 | 108.11 (15) | C11—C10—C9 | 117.60 (18) |
N1—C2—C3 | 111.13 (15) | C11—C10—C16 | 120.63 (18) |
C7—C2—C3 | 107.80 (15) | C9—C10—C16 | 121.77 (18) |
N1—C2—H2 | 107.5 (11) | C12—C11—C10 | 121.2 (2) |
C7—C2—H2 | 112.5 (11) | C12—C11—H11 | 118.9 (11) |
C3—C2—H2 | 109.9 (11) | C10—C11—H11 | 119.8 (11) |
C4—C3—C2 | 112.37 (17) | C11—C12—C13 | 120.1 (2) |
C4—C3—H31 | 109.6 (12) | C11—C12—H12 | 120.7 (12) |
C2—C3—H31 | 107.4 (11) | C13—C12—H12 | 119.2 (11) |
C4—C3—H32 | 109.9 (11) | C12—C13—C14 | 121.2 (2) |
C2—C3—H32 | 105.6 (12) | C12—C13—H13 | 122.6 (12) |
H31—C3—H32 | 111.9 (16) | C14—C13—H13 | 116.3 (12) |
C5—C4—C3 | 108.69 (18) | C13—C14—C9 | 117.56 (18) |
C5—C4—H41 | 111.6 (12) | C13—C14—C15 | 121.32 (17) |
C3—C4—H41 | 108.4 (13) | C9—C14—C15 | 121.10 (18) |
C5—C4—H42 | 111.0 (12) | C14—C15—H81 | 113.4 (13) |
C3—C4—H42 | 109.6 (12) | C14—C15—H82 | 109.5 (13) |
H41—C4—H42 | 107.6 (19) | H81—C15—H82 | 108.5 (19) |
C6—C5—C4 | 110.95 (18) | C14—C15—H83 | 111.0 (13) |
C6—C5—H51 | 105.8 (12) | H81—C15—H83 | 104.2 (18) |
C4—C5—H51 | 115.6 (12) | H82—C15—H83 | 110.1 (19) |
C6—C5—H52 | 106.9 (11) | C10—C16—H91 | 111.5 (12) |
C4—C5—H52 | 112.1 (11) | C10—C16—H92 | 111.4 (13) |
H51—C5—H52 | 104.8 (17) | H91—C16—H92 | 105.2 (17) |
C5—C6—N1 | 111.67 (15) | C10—C16—H93 | 110.6 (15) |
C5—C6—H61 | 113.8 (10) | H91—C16—H93 | 108.6 (19) |
N1—C6—H61 | 103.3 (10) | H92—C16—H93 | 109 (2) |
| | | |
C1'—N1—C2—C7 | 68.55 (19) | C7—N8—C9—C14 | −113.3 (2) |
C6—N1—C2—C7 | −167.68 (15) | C7—N8—C9—C10 | 68.6 (2) |
C1'—N1—C2—C3 | −173.34 (18) | C14—C9—C10—C11 | 0.5 (3) |
C6—N1—C2—C3 | −49.6 (2) | N8—C9—C10—C11 | 178.55 (17) |
N1—C2—C3—C4 | 52.7 (2) | C14—C9—C10—C16 | −179.3 (2) |
C7—C2—C3—C4 | 170.97 (17) | N8—C9—C10—C16 | −1.3 (3) |
C2—C3—C4—C5 | −57.3 (3) | C9—C10—C11—C12 | −1.2 (3) |
C3—C4—C5—C6 | 59.2 (2) | C16—C10—C11—C12 | 178.7 (2) |
C4—C5—C6—N1 | −57.2 (2) | C10—C11—C12—C13 | 1.1 (3) |
C1'—N1—C6—C5 | 176.99 (17) | C11—C12—C13—C14 | −0.3 (3) |
C2—N1—C6—C5 | 52.5 (2) | C12—C13—C14—C9 | −0.3 (3) |
N1—C2—C7—O7 | 39.7 (2) | C12—C13—C14—C15 | 178.7 (2) |
C3—C2—C7—O7 | −80.5 (2) | C10—C9—C14—C13 | 0.2 (3) |
N1—C2—C7—N8 | −144.20 (15) | N8—C9—C14—C13 | −177.81 (16) |
C3—C2—C7—N8 | 95.59 (19) | C10—C9—C14—C15 | −178.77 (18) |
O7—C7—N8—C9 | 5.0 (3) | N8—C9—C14—C15 | 3.2 (3) |
C2—C7—N8—C9 | −170.83 (15) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cli | 0.905 (17) | 2.182 (18) | 3.0140 (16) | 152.5 (16) |
N8—H8N···Cl | 0.841 (18) | 2.280 (19) | 3.1172 (17) | 174.1 (17) |
Symmetry code: (i) −x, y−1/2, −z+3/2. |