Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042997/bt2495sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042997/bt2495Isup2.hkl |
CCDC reference: 663715
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.004 Å
- R factor = 0.030
- wR factor = 0.072
- Data-to-parameter ratio = 10.5
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............ 24.74 Deg.
Author Response: |
The measurement was only performed up to 49.48 Degree in 2Theta because due to the size of the crystal there were only reflections observed up to 24.74 Degree However, the ratio of observed data to parameter is larger than 10 (10.55), and the data is sufficiently precise for the hydrogen atoms to be clearly resolved in the difference electron-density map. Furthermore, all hydrogen atoms could be refined freely.
Alert level C THETM01_ALERT_3_C The value of sine(theta_max)/wavelength is less than 0.590 Calculated sin(theta_max)/wavelength = 0.5888 PLAT023_ALERT_3_C Resolution (too) Low [sin(th)/Lambda < 0.6]..... 24.74 Deg. PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C3 PLAT355_ALERT_3_C Long O-H Bond (0.82A) O - H ... 1.03 Ang.
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 24.74 From the CIF: _reflns_number_total 1192 Count of symmetry unique reflns 723 Completeness (_total/calc) 164.87% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 469 Fraction of Friedel pairs measured 0.649 Are heavy atom types Z>Si present yes
1 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 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 1 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 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For data on the neutral compound, see: Müller et al. (1996). For an alternative method of preparation, see: Utsumi (1981). For related literature, see: Holleman (2007).
N-Methyl-2-pyrrolidone was obtained from Merck Co. and was used as recieved. HClconc. (24.64 g, 250 mmol) was added dropwise to a stirred solution of N-Methyl-2-pyrrolidone (4.957 g, 50 mmol) in CH2Cl2 (40 mL) at 0°C. The clear aqueous layer was separated and was then evaporated to dryness in vacuo. The colourless, crystalline residue was sublimed (10-3 mbar, 60°C) for purification. Yield: 5.597 g (41.28 mmol, 83%). Mp. = 94 °C. CHN-analysis: found, C 43.20, N 10.01, H 6.44%; calc. C 44.29, N 10.33, H 7.43%. 1H-NMR (DMSO-d6, 25 °C, 250 MHz): δ = 1.86 (quint, 2H, 2JH—H = 7.6 Hz), 2.16 (t, 2H, 2JH—H = 7.6 Hz), 2.66 (s, 3H), 3.27 (t, 2H, 2JH—H = 7.6 Hz), 11.5 (s, 1H). 13C{1H}-NMR (DMSO-d6, 25 °C, 250 MHz): δ = 17.5, 29.4, 30.4, 48.9, 174.3. Crystallization from a saturated CH2Cl2 solution at ambient temperature gave colourless crystals.
The five-membered ring of N-Methyl-2-pyrrolidonium cation adopts a slightly pronounced envelope conformation in the solid state (Fig. 1), with C3 as the flap atom (C1—C2—C3—C4 = 13.4 (3) °). The O—H unit adopts an eclipsed conformation and is nearly coplanar to the ring-plane (C4—N—C1—C2 = -2.2 (2) °). The N—C1 distance [1.296 (3) Å] is substantially shorter than the sum of the covalent radii (dcov.: C—N 1.47, C=N 1.27 Å, Holleman, 2007), which indicates partial double-bond character for this bond. A similar situation is found for the O—C1 bond [1.297 (3) Å], which also lies in the range between a single and a double bond (dcov.: C—O 1.43, C=O 1.23 Å), indicating a certain degree of charge-delocalization along the N—C1—O unit.
In the crystal structure, the C5H9NO+ cation and the Cl- anion are linked by an O—H···Cl hydrogen-bond with a relatively short donor-acceptor distance. Interestingly, no further hydrogen-bonds were found (Fig. 2).
For data on the neutral compound, see: Müller et al. (1996). For an alternative method of preparation, see: Utsumi (1981). For related literature, see: Holleman (2007).
Data collection: Collect (Nonius, 1999); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Windows version (Farrugia, 1997) of ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C5H10NO+·Cl− | F(000) = 288 |
Mr = 135.59 | Dx = 1.301 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 4313 reflections |
a = 6.1391 (2) Å | θ = 3.1–24.7° |
b = 8.9537 (2) Å | µ = 0.46 mm−1 |
c = 12.5976 (4) Å | T = 200 K |
V = 692.46 (4) Å3 | Block, colourless |
Z = 4 | 0.28 × 0.25 × 0.20 mm |
Nonius KappaCCD diffractometer | 1124 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.094 |
Graphite monochromator | θmax = 24.7°, θmin = 3.2° |
Detector resolution: 9 pixels mm-1 | h = −7→7 |
phi/ω–scan | k = −10→10 |
8273 measured reflections | l = −14→14 |
1192 independent reflections |
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)] = 0.030 | All H-atom parameters refined |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.031P)2 + 0.1465P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
1192 reflections | Δρmax = 0.15 e Å−3 |
113 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 471 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.04 (9) |
C5H10NO+·Cl− | V = 692.46 (4) Å3 |
Mr = 135.59 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.1391 (2) Å | µ = 0.46 mm−1 |
b = 8.9537 (2) Å | T = 200 K |
c = 12.5976 (4) Å | 0.28 × 0.25 × 0.20 mm |
Nonius KappaCCD diffractometer | 1124 reflections with I > 2σ(I) |
8273 measured reflections | Rint = 0.094 |
1192 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | All H-atom parameters refined |
wR(F2) = 0.072 | Δρmax = 0.15 e Å−3 |
S = 1.04 | Δρmin = −0.20 e Å−3 |
1192 reflections | Absolute structure: Flack (1983), 471 Friedel pairs |
113 parameters | Absolute structure parameter: 0.04 (9) |
0 restraints |
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 | ||
Cl | 0.98418 (9) | 1.03603 (5) | 0.63590 (4) | 0.04228 (18) | |
O | 1.0110 (3) | 0.73233 (15) | 0.57419 (11) | 0.0400 (3) | |
N | 0.8324 (3) | 0.51346 (18) | 0.59226 (13) | 0.0323 (4) | |
C1 | 0.8497 (3) | 0.6551 (2) | 0.61169 (14) | 0.0305 (4) | |
C2 | 0.6698 (4) | 0.7117 (2) | 0.67914 (17) | 0.0363 (5) | |
C3 | 0.5168 (5) | 0.5788 (3) | 0.6863 (2) | 0.0553 (6) | |
C4 | 0.6445 (4) | 0.4457 (3) | 0.64539 (19) | 0.0413 (5) | |
C5 | 0.9858 (5) | 0.4241 (3) | 0.5312 (2) | 0.0445 (5) | |
H41 | 0.568 (4) | 0.387 (3) | 0.5962 (18) | 0.043 (7)* | |
H21 | 0.612 (4) | 0.803 (3) | 0.647 (2) | 0.054 (7)* | |
H31 | 0.479 (5) | 0.559 (3) | 0.752 (3) | 0.080 (9)* | |
H22 | 0.724 (4) | 0.743 (3) | 0.745 (2) | 0.056 (7)* | |
H51 | 1.018 (6) | 0.342 (4) | 0.571 (3) | 0.092 (11)* | |
H42 | 0.701 (4) | 0.380 (3) | 0.702 (2) | 0.051 (7)* | |
H52 | 0.914 (6) | 0.383 (4) | 0.472 (3) | 0.092 (11)* | |
H32 | 0.389 (6) | 0.591 (4) | 0.641 (3) | 0.098 (12)* | |
H53 | 1.106 (5) | 0.480 (3) | 0.511 (2) | 0.059 (8)* | |
H | 0.994 (6) | 0.843 (4) | 0.596 (3) | 0.094 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.0466 (3) | 0.0332 (3) | 0.0470 (3) | −0.0062 (2) | −0.0023 (3) | −0.0018 (2) |
O | 0.0382 (8) | 0.0316 (7) | 0.0502 (8) | −0.0046 (8) | 0.0125 (7) | 0.0001 (6) |
N | 0.0339 (9) | 0.0299 (9) | 0.0331 (8) | −0.0008 (7) | 0.0029 (7) | −0.0009 (7) |
C1 | 0.0298 (10) | 0.0314 (10) | 0.0302 (10) | −0.0018 (8) | −0.0012 (8) | 0.0026 (7) |
C2 | 0.0348 (11) | 0.0390 (12) | 0.0351 (11) | 0.0037 (9) | 0.0035 (9) | −0.0005 (9) |
C3 | 0.0445 (15) | 0.0556 (14) | 0.0657 (16) | −0.0099 (14) | 0.0194 (14) | −0.0082 (12) |
C4 | 0.0417 (11) | 0.0408 (13) | 0.0414 (11) | −0.0127 (10) | 0.0023 (11) | 0.0017 (11) |
C5 | 0.0469 (13) | 0.0338 (11) | 0.0526 (13) | 0.0048 (12) | 0.0086 (13) | −0.0041 (10) |
Cl—H | 1.80 (4) | C2—H22 | 0.93 (3) |
O—C1 | 1.297 (3) | C3—C4 | 1.516 (3) |
O—H | 1.03 (4) | C3—H31 | 0.87 (3) |
N—C1 | 1.296 (3) | C3—H32 | 0.98 (4) |
N—C5 | 1.455 (3) | C4—H41 | 0.94 (2) |
N—C4 | 1.465 (3) | C4—H42 | 0.99 (2) |
C1—C2 | 1.483 (3) | C5—H51 | 0.91 (3) |
C2—C3 | 1.519 (3) | C5—H52 | 0.94 (4) |
C2—H21 | 0.98 (3) | C5—H53 | 0.93 (3) |
C1—O—H | 110 (2) | C4—C3—H32 | 108 (2) |
C1—N—C5 | 125.78 (19) | C2—C3—H32 | 112 (2) |
C1—N—C4 | 112.53 (16) | H31—C3—H32 | 111 (3) |
C5—N—C4 | 121.57 (18) | N—C4—C3 | 103.71 (17) |
N—C1—O | 121.02 (18) | N—C4—H41 | 108.8 (14) |
N—C1—C2 | 112.45 (17) | C3—C4—H41 | 114.0 (15) |
O—C1—C2 | 126.52 (18) | N—C4—H42 | 107.5 (15) |
C1—C2—C3 | 103.08 (18) | C3—C4—H42 | 113.9 (14) |
C1—C2—H21 | 108.9 (15) | H41—C4—H42 | 108.6 (19) |
C3—C2—H21 | 117.0 (15) | N—C5—H51 | 107 (2) |
C1—C2—H22 | 110.2 (16) | N—C5—H52 | 109 (2) |
C3—C2—H22 | 113.6 (16) | H51—C5—H52 | 103 (3) |
H21—C2—H22 | 104 (2) | N—C5—H53 | 111.6 (18) |
C4—C3—C2 | 106.0 (2) | H51—C5—H53 | 114 (3) |
C4—C3—H31 | 107 (2) | H52—C5—H53 | 111 (3) |
C2—C3—H31 | 112 (2) | ||
C5—N—C1—O | 1.6 (3) | O—C1—C2—C3 | 172.9 (2) |
C4—N—C1—O | 177.57 (19) | C1—C2—C3—C4 | 13.4 (3) |
C5—N—C1—C2 | −178.2 (2) | C1—N—C4—C3 | 10.8 (3) |
C4—N—C1—C2 | −2.2 (2) | C5—N—C4—C3 | −173.1 (2) |
N—C1—C2—C3 | −7.4 (3) | C2—C3—C4—N | −14.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O—H···Cl | 1.03 (4) | 1.80 (4) | 2.8330 (14) | 176 (3) |
Experimental details
Crystal data | |
Chemical formula | C5H10NO+·Cl− |
Mr | 135.59 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 200 |
a, b, c (Å) | 6.1391 (2), 8.9537 (2), 12.5976 (4) |
V (Å3) | 692.46 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.46 |
Crystal size (mm) | 0.28 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8273, 1192, 1124 |
Rint | 0.094 |
(sin θ/λ)max (Å−1) | 0.589 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.072, 1.04 |
No. of reflections | 1192 |
No. of parameters | 113 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.15, −0.20 |
Absolute structure | Flack (1983), 471 Friedel pairs |
Absolute structure parameter | 0.04 (9) |
Computer programs: Collect (Nonius, 1999), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), Windows version (Farrugia, 1997) of ORTEPIII (Burnett & Johnson, 1996).
D—H···A | D—H | H···A | D···A | D—H···A |
O—H···Cl | 1.03 (4) | 1.80 (4) | 2.8330 (14) | 176 (3) |
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The five-membered ring of N-Methyl-2-pyrrolidonium cation adopts a slightly pronounced envelope conformation in the solid state (Fig. 1), with C3 as the flap atom (C1—C2—C3—C4 = 13.4 (3) °). The O—H unit adopts an eclipsed conformation and is nearly coplanar to the ring-plane (C4—N—C1—C2 = -2.2 (2) °). The N—C1 distance [1.296 (3) Å] is substantially shorter than the sum of the covalent radii (dcov.: C—N 1.47, C=N 1.27 Å, Holleman, 2007), which indicates partial double-bond character for this bond. A similar situation is found for the O—C1 bond [1.297 (3) Å], which also lies in the range between a single and a double bond (dcov.: C—O 1.43, C=O 1.23 Å), indicating a certain degree of charge-delocalization along the N—C1—O unit.
In the crystal structure, the C5H9NO+ cation and the Cl- anion are linked by an O—H···Cl hydrogen-bond with a relatively short donor-acceptor distance. Interestingly, no further hydrogen-bonds were found (Fig. 2).