organic compounds
S,3R)-3-hydroxy-3-phenylbutan-2-yl]pyrrolidinium chloride
of [(2aDepartment of Chemistry, Queen Mary's College, Chennai 600 004, Tamilnadu, India, bDepartment of Physics, Government College of Engineering, Salem 636 011, India, and cDepartment of Physics, Thanthai Periyar Government Institute of Technology, Vellore 632 002, India
*Correspondence e-mail: smurugavel27@gmail.com
In the title molecular salt, C14H22NO+·Cl−, the pyrrolidinium ring adopts a twisted conformation about one of the N—C bonds. It is oriented at a dihedral angle of 42.0 (1)° with respect to the benzene ring. The torsion angle for the central N—C—C—Car (ar = aromatic) linkage is 163.74 (15)°. In the crystal, the components are linked via N—H⋯Cl and O—H⋯Cl hydrogen bonds, forming zigzig chains along the b-axis direction. These chains are connected along the c axis by very weak C—H⋯π interactions, forming a two-dimensional supramolecular network.
Keywords: crystal structure; salt; pyrrolidinium chloride; ionic liquids; hydrogen bonding.
CCDC reference: 1423292
1. Related literature
For background to pyrrolidinium-based ionic liquids, see: Henderson et al. (2006).
2. Experimental
2.1. Crystal data
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Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
CCDC reference: 1423292
10.1107/S2056989015016916/hb7497sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015016916/hb7497Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015016916/hb7497Isup3.cml
Pyrrolidinium-based ionic liquids have been a subject of intense investigation recently (Henderson et al., 2006), whereby with understanding of the fundamental molecular-level interactions, a desired product with predicted physico-chemical properites could be designed. Additionally, a particular emphasis has been placed on whether hydrogen bonding occurs between the cation and a potential
(hydrogen bond acceptor) and its influence on the ionic liquids' overall properties. Against this background, and in order to obtain detailed information on molecular conformations in the solid state, X-ray studies of the title compound (I) have been carried out.Fig. 1. shows a displacement ellipsoid plot of (I), with the atom numbering scheme. In the cation, the pyrrolidinium ring adopts a twist conformation, with twist about the N1—C11 bond; the puckering parameters, q2 = 0.361 (2) Å and φ2 = 202.4 (5)°, and asymmetry parameters ΔC2[N1—C11] = 4.8.0 (3) Å. The pyrrolidinium ring is oriented at an angle 42.0 (1)° from the mean plane of the benzene ring.
In the crystal, cations and anions are linked via N1—H1···Cl1 and O1—H1A···Cl1 hydrogen bonds, forming a one-dimensional zig zig chain along the b-axis direction. These chains are stacked along the c-axis by C—H···π interactions, between benzene H atom and the benzene ring of an adjacene molecule, with a C3—H3···Cgiii, forming a two-dimensional supramolecular network. (Table 1 and Fig. 2; Cg is centroid of C1–C6 benzene ring. Symmetry code: (iii) -1/2+x,3/2-y,1-z>).
In a round bottomed flask, a stirred solution of (S)-pyrrolidinylnorephedrone was reacted with methylmagnesium bromide in THF medium over a period of 3 h. The completion of the reaction was monitored by thin layer chromatographic analysis. Further the crude mass was quenched with dil HCl and extracted with ethyl acetate under reduced vacuum. The resulting compound was recrystallised from EtOH/H2O (4:1) solution as colourless blocks in good yield (86%).
Crystal data, data collection and structure
details are summarized in Table 2. N-bound H atom was located in a difference Fourier map and freely refined. All other H atoms were positioned geometrically and constrained to ride on their parent atom with C—H = 0.93–0.97 Å and with Uiso(H)=1.5Ueq for methyl H atoms and 1.2Ueq(C) for other H atoms. Owing to poor agreement, the reflection (-3 2 4) was omitted from the final cycles of refinement.Data collection: SMART (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. Molecular structure of the title compound showing displacement ellipsoids at the 30% probability level. | |
Fig. 2. Part of the crystal structure showing intermolecular N—H···Cl, O—H···Cl and C—H···π interactions, forming a two dimensional supramolecular network. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity. Cg is the centroid of C1–C6 benzene ring. |
C14H22NO+·Cl− | F(000) = 552 |
Mr = 255.78 | Dx = 1.201 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3836 reflections |
a = 7.3912 (14) Å | θ = 3.7–29.2° |
b = 9.7002 (17) Å | µ = 0.26 mm−1 |
c = 19.727 (4) Å | T = 293 K |
V = 1414.4 (4) Å3 | Block, colourless |
Z = 4 | 0.24 × 0.21 × 0.16 mm |
Bruker SMART CCD diffractometer | 3163 independent reflections |
Radiation source: fine-focus sealed tube | 2750 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 29.2°, θmin = 3.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→8 |
Tmin = 0.940, Tmax = 0.960 | k = −12→12 |
6666 measured reflections | l = −25→26 |
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)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0569P)2 + 0.1443P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
3163 reflections | Δρmax = 0.19 e Å−3 |
160 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1235 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (7) |
C14H22NO+·Cl− | V = 1414.4 (4) Å3 |
Mr = 255.78 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.3912 (14) Å | µ = 0.26 mm−1 |
b = 9.7002 (17) Å | T = 293 K |
c = 19.727 (4) Å | 0.24 × 0.21 × 0.16 mm |
Bruker SMART CCD diffractometer | 3163 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2750 reflections with I > 2σ(I) |
Tmin = 0.940, Tmax = 0.960 | Rint = 0.024 |
6666 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.107 | Δρmax = 0.19 e Å−3 |
S = 1.02 | Δρmin = −0.16 e Å−3 |
3163 reflections | Absolute structure: Flack (1983), 1235 Friedel pairs |
160 parameters | Absolute structure parameter: −0.01 (7) |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
C1 | 0.7420 (2) | 0.74116 (19) | 0.62918 (9) | 0.0356 (4) | |
C2 | 0.6667 (3) | 0.8068 (2) | 0.57376 (10) | 0.0478 (5) | |
H2 | 0.6323 | 0.8988 | 0.5772 | 0.057* | |
C3 | 0.6418 (4) | 0.7369 (3) | 0.51298 (12) | 0.0596 (6) | |
H3 | 0.5911 | 0.7826 | 0.4762 | 0.071* | |
C4 | 0.6913 (4) | 0.6009 (3) | 0.50673 (12) | 0.0623 (6) | |
H4 | 0.6728 | 0.5542 | 0.4661 | 0.075* | |
C5 | 0.7685 (3) | 0.5345 (2) | 0.56109 (13) | 0.0568 (6) | |
H5 | 0.8043 | 0.4430 | 0.5570 | 0.068* | |
C6 | 0.7931 (3) | 0.6034 (2) | 0.62179 (11) | 0.0440 (4) | |
H6 | 0.8446 | 0.5571 | 0.6583 | 0.053* | |
C7 | 0.7703 (2) | 0.81613 (18) | 0.69701 (9) | 0.0345 (4) | |
C8 | 0.9719 (3) | 0.8127 (3) | 0.71443 (10) | 0.0490 (5) | |
H8A | 1.0408 | 0.8444 | 0.6762 | 0.074* | |
H8B | 1.0069 | 0.7200 | 0.7253 | 0.074* | |
H8C | 0.9946 | 0.8715 | 0.7527 | 0.074* | |
C9 | 0.6487 (3) | 0.74346 (18) | 0.75061 (9) | 0.0333 (4) | |
H9 | 0.6670 | 0.6440 | 0.7451 | 0.040* | |
C10 | 0.4494 (3) | 0.7716 (2) | 0.73699 (10) | 0.0461 (5) | |
H10A | 0.3768 | 0.7182 | 0.7676 | 0.069* | |
H10B | 0.4209 | 0.7464 | 0.6912 | 0.069* | |
H10C | 0.4248 | 0.8678 | 0.7436 | 0.069* | |
C11 | 0.6819 (3) | 0.9254 (2) | 0.84700 (11) | 0.0505 (5) | |
H11A | 0.7778 | 0.9828 | 0.8289 | 0.061* | |
H11B | 0.5659 | 0.9641 | 0.8341 | 0.061* | |
C12 | 0.6971 (4) | 0.9122 (3) | 0.92291 (12) | 0.0723 (8) | |
H12A | 0.8227 | 0.9160 | 0.9370 | 0.087* | |
H12B | 0.6310 | 0.9855 | 0.9454 | 0.087* | |
C13 | 0.6170 (6) | 0.7756 (3) | 0.93918 (14) | 0.0910 (11) | |
H13A | 0.6936 | 0.7271 | 0.9712 | 0.109* | |
H13B | 0.4988 | 0.7878 | 0.9597 | 0.109* | |
C14 | 0.6001 (3) | 0.6945 (3) | 0.87578 (10) | 0.0612 (6) | |
H14A | 0.4741 | 0.6830 | 0.8633 | 0.073* | |
H14B | 0.6547 | 0.6041 | 0.8810 | 0.073* | |
N1 | 0.7001 (2) | 0.77830 (17) | 0.82284 (7) | 0.0369 (4) | |
O1 | 0.7091 (2) | 0.95487 (12) | 0.69491 (7) | 0.0457 (4) | |
H1A | 0.7648 | 0.9970 | 0.6655 | 0.069* | |
Cl1 | 0.93476 (8) | 0.17271 (6) | 0.62270 (3) | 0.05642 (18) | |
H1 | 0.817 (3) | 0.761 (2) | 0.8290 (9) | 0.034 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0296 (9) | 0.0393 (9) | 0.0378 (9) | 0.0004 (7) | 0.0036 (7) | 0.0035 (7) |
C2 | 0.0494 (12) | 0.0502 (12) | 0.0439 (10) | 0.0079 (10) | −0.0003 (9) | 0.0068 (9) |
C3 | 0.0524 (14) | 0.0828 (16) | 0.0434 (12) | 0.0025 (13) | −0.0078 (10) | 0.0065 (11) |
C4 | 0.0620 (16) | 0.0770 (16) | 0.0479 (13) | −0.0072 (14) | 0.0016 (11) | −0.0190 (11) |
C5 | 0.0570 (15) | 0.0475 (12) | 0.0660 (15) | 0.0006 (11) | 0.0101 (11) | −0.0127 (10) |
C6 | 0.0413 (10) | 0.0425 (10) | 0.0483 (11) | 0.0046 (8) | 0.0023 (9) | 0.0038 (9) |
C7 | 0.0318 (9) | 0.0340 (8) | 0.0378 (9) | 0.0009 (8) | 0.0036 (7) | 0.0037 (7) |
C8 | 0.0312 (10) | 0.0675 (14) | 0.0485 (11) | −0.0083 (10) | 0.0034 (8) | 0.0011 (10) |
C9 | 0.0328 (9) | 0.0311 (8) | 0.0360 (9) | −0.0024 (7) | 0.0002 (7) | 0.0031 (7) |
C10 | 0.0324 (10) | 0.0557 (12) | 0.0503 (11) | −0.0086 (9) | 0.0016 (9) | 0.0070 (9) |
C11 | 0.0484 (13) | 0.0465 (11) | 0.0566 (12) | 0.0007 (10) | 0.0044 (10) | −0.0112 (9) |
C12 | 0.0666 (17) | 0.095 (2) | 0.0550 (14) | 0.0253 (16) | −0.0025 (13) | −0.0263 (14) |
C13 | 0.133 (3) | 0.092 (2) | 0.0482 (14) | 0.025 (2) | 0.0297 (16) | 0.0091 (13) |
C14 | 0.0536 (14) | 0.0890 (18) | 0.0411 (11) | −0.0199 (12) | 0.0026 (10) | 0.0173 (12) |
N1 | 0.0311 (9) | 0.0417 (8) | 0.0379 (8) | −0.0014 (7) | 0.0042 (7) | 0.0009 (6) |
O1 | 0.0526 (9) | 0.0307 (6) | 0.0538 (8) | −0.0013 (6) | 0.0164 (7) | 0.0050 (6) |
Cl1 | 0.0548 (3) | 0.0642 (3) | 0.0503 (3) | −0.0250 (3) | −0.0023 (3) | 0.0119 (2) |
C1—C2 | 1.382 (3) | C9—H9 | 0.9800 |
C1—C6 | 1.396 (3) | C10—H10A | 0.9600 |
C1—C7 | 1.537 (3) | C10—H10B | 0.9600 |
C2—C3 | 1.390 (3) | C10—H10C | 0.9600 |
C2—H2 | 0.9300 | C11—C12 | 1.507 (3) |
C3—C4 | 1.375 (4) | C11—N1 | 1.511 (3) |
C3—H3 | 0.9300 | C11—H11A | 0.9700 |
C4—C5 | 1.375 (4) | C11—H11B | 0.9700 |
C4—H4 | 0.9300 | C12—C13 | 1.486 (4) |
C5—C6 | 1.383 (3) | C12—H12A | 0.9700 |
C5—H5 | 0.9300 | C12—H12B | 0.9700 |
C6—H6 | 0.9300 | C13—C14 | 1.483 (4) |
C7—O1 | 1.420 (2) | C13—H13A | 0.9700 |
C7—C8 | 1.530 (3) | C13—H13B | 0.9700 |
C7—C9 | 1.557 (2) | C14—N1 | 1.516 (3) |
C8—H8A | 0.9600 | C14—H14A | 0.9700 |
C8—H8B | 0.9600 | C14—H14B | 0.9700 |
C8—H8C | 0.9600 | N1—H1 | 0.89 (2) |
C9—N1 | 1.513 (2) | O1—H1A | 0.8200 |
C9—C10 | 1.522 (3) | ||
C2—C1—C6 | 117.9 (2) | C9—C10—H10B | 109.5 |
C2—C1—C7 | 121.70 (17) | H10A—C10—H10B | 109.5 |
C6—C1—C7 | 120.44 (18) | C9—C10—H10C | 109.5 |
C1—C2—C3 | 120.7 (2) | H10A—C10—H10C | 109.5 |
C1—C2—H2 | 119.6 | H10B—C10—H10C | 109.5 |
C3—C2—H2 | 119.6 | C12—C11—N1 | 103.1 (2) |
C4—C3—C2 | 120.7 (2) | C12—C11—H11A | 111.2 |
C4—C3—H3 | 119.6 | N1—C11—H11A | 111.2 |
C2—C3—H3 | 119.6 | C12—C11—H11B | 111.2 |
C3—C4—C5 | 119.3 (2) | N1—C11—H11B | 111.2 |
C3—C4—H4 | 120.3 | H11A—C11—H11B | 109.1 |
C5—C4—H4 | 120.3 | C13—C12—C11 | 105.1 (2) |
C4—C5—C6 | 120.3 (2) | C13—C12—H12A | 110.7 |
C4—C5—H5 | 119.9 | C11—C12—H12A | 110.7 |
C6—C5—H5 | 119.9 | C13—C12—H12B | 110.7 |
C5—C6—C1 | 121.1 (2) | C11—C12—H12B | 110.7 |
C5—C6—H6 | 119.4 | H12A—C12—H12B | 108.8 |
C1—C6—H6 | 119.4 | C14—C13—C12 | 108.9 (2) |
O1—C7—C8 | 109.73 (17) | C14—C13—H13A | 109.9 |
O1—C7—C1 | 112.29 (15) | C12—C13—H13A | 109.9 |
C8—C7—C1 | 108.54 (16) | C14—C13—H13B | 109.9 |
O1—C7—C9 | 105.37 (14) | C12—C13—H13B | 109.9 |
C8—C7—C9 | 113.58 (16) | H13A—C13—H13B | 108.3 |
C1—C7—C9 | 107.36 (15) | C13—C14—N1 | 104.8 (2) |
C7—C8—H8A | 109.5 | C13—C14—H14A | 110.8 |
C7—C8—H8B | 109.5 | N1—C14—H14A | 110.8 |
H8A—C8—H8B | 109.5 | C13—C14—H14B | 110.8 |
C7—C8—H8C | 109.5 | N1—C14—H14B | 110.8 |
H8A—C8—H8C | 109.5 | H14A—C14—H14B | 108.9 |
H8B—C8—H8C | 109.5 | C11—N1—C9 | 119.07 (15) |
N1—C9—C10 | 111.66 (16) | C11—N1—C14 | 104.25 (17) |
N1—C9—C7 | 113.19 (15) | C9—N1—C14 | 114.00 (15) |
C10—C9—C7 | 110.96 (15) | C11—N1—H1 | 102.7 (13) |
N1—C9—H9 | 106.9 | C9—N1—H1 | 109.3 (12) |
C10—C9—H9 | 106.9 | C14—N1—H1 | 106.2 (13) |
C7—C9—H9 | 106.9 | C7—O1—H1A | 109.5 |
C9—C10—H10A | 109.5 | ||
C6—C1—C2—C3 | 0.5 (3) | C1—C7—C9—N1 | 163.74 (15) |
C7—C1—C2—C3 | −179.8 (2) | O1—C7—C9—C10 | 50.1 (2) |
C1—C2—C3—C4 | 0.1 (4) | C8—C7—C9—C10 | 170.19 (18) |
C2—C3—C4—C5 | −0.9 (4) | C1—C7—C9—C10 | −69.8 (2) |
C3—C4—C5—C6 | 1.1 (4) | N1—C11—C12—C13 | −32.0 (3) |
C4—C5—C6—C1 | −0.5 (3) | C11—C12—C13—C14 | 14.7 (3) |
C2—C1—C6—C5 | −0.3 (3) | C12—C13—C14—N1 | 8.7 (3) |
C7—C1—C6—C5 | 180.00 (19) | C12—C11—N1—C9 | 165.87 (19) |
C2—C1—C7—O1 | 0.7 (2) | C12—C11—N1—C14 | 37.5 (2) |
C6—C1—C7—O1 | −179.62 (17) | C10—C9—N1—C11 | −62.2 (2) |
C2—C1—C7—C8 | −120.8 (2) | C7—C9—N1—C11 | 63.9 (2) |
C6—C1—C7—C8 | 58.9 (2) | C10—C9—N1—C14 | 61.6 (2) |
C2—C1—C7—C9 | 116.06 (19) | C7—C9—N1—C14 | −172.33 (17) |
C6—C1—C7—C9 | −64.3 (2) | C13—C14—N1—C11 | −28.6 (3) |
O1—C7—C9—N1 | −76.39 (18) | C13—C14—N1—C9 | −160.0 (2) |
C8—C7—C9—N1 | 43.7 (2) |
Cg is the centroid of the C1–C6 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1i | 0.89 (2) | 2.24 (2) | 3.0804 (19) | 158.0 (2) |
O1—H1A···Cl1ii | 0.82 | 2.28 | 3.0456 (14) | 156 |
C3—H3···Cgiii | 0.93 | 2.93 | 3.630 (3) | 133 |
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) x, y+1, z; (iii) x−1/2, −y+3/2, −z+1. |
Cg is the centroid of the C1–C6 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1i | 0.89 (2) | 2.24 (2) | 3.0804 (19) | 158.0 (2) |
O1—H1A···Cl1ii | 0.82 | 2.28 | 3.0456 (14) | 156 |
C3—H3···Cgiii | 0.93 | 2.93 | 3.630 (3) | 133 |
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) x, y+1, z; (iii) x−1/2, −y+3/2, −z+1. |
Acknowledgements
The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help with the data collection.
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