organic compounds
R)-1-[(methylsulfonyl)oxy]propan-2-aminium chloride: a chiral molecular salt
of (2aDepartment of Studies and Research in Chemistry, Tumkur University, Tumkur 572 103, Karnataka, India, bDepartment of Studies and Research in Physics, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India, cDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore, Karnataka 570 005, India, and dInstitution of Excellence, University of Mysore, Manasagangotri, Mysore 570 006, India
*Correspondence e-mail: raghukp1@gmail.com
In the title chiral molecular salt, C4H12NO3S+·Cl−, the cation is protonated at the N atom, producing [RNH3]+, where R is CH3SO2OCH2C(H)CH3. The N atom in the cation is sp3-hybridized. In the crystal, cations and anions are connected by strong N—H⋯Cl hydrogen bonds to generate edge-shared 12-membered rings of the form {⋯Cl⋯HNH}3. This pattern of hydrogen bonding gives rise to zigzag supramolecular layers in the ab plane. The layers are connected into a three-dimensional architecture by C—H⋯O hydrogen bonds. The structure was refined as an inversion twin.
Keywords: crystal structure; chiral methanesulfonate; hydrogen bonding; salt.
CCDC reference: 1420721
1. Related literature
For background to chiral 2-amino-2-(alkyl/aryl/aralkyl)ethyl methanesulfonate hydrochlorides, see: Braghiroli & Di Bella (1996); Higashiura et al. (1989); Morgan et al. (1991); Pollack et al. (1989); Xu (2002).
2. Experimental
2.1. Crystal data
|
2.3. Refinement
|
Data collection: APEX2 (Bruker, 2013); cell SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014.
Supporting information
CCDC reference: 1420721
10.1107/S2056989015015972/tk5365sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015015972/tk5365Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015015972/tk5365Isup3.cml
The chiral 2-amino-2-(alkyl/aryl/aralkyl)ethyl methanesulfonate hydrochlorides are useful starting materials for the preparation of
benzoates, thiobenzoates, etc., as methanesulfonate is a very good in nucleophilic substitution reactions. The chiral 2-(alkyl/aryl/aralkyl)ethanesulfonic acid derivatives and sulfonopeptides (Higashiura et al., 1989) occur in high concentrations in many mammalian tissues. These compounds are involved in various important physiological processes and are used as enzyme inhibitors and heptans in the development of catalytic anti-bodies (Braghiroli & Di Bella, 1996). The enantiomers of chiral 2-(alkyl/aryl/aralkyl)ethanesulfonic acid derivatives mimic the hypotensive effect of taurine (2-aminoethanesulfonic acid), one of the most abundant amino acids in mammals that seems to exhibit a special affinity for excitable tissues, such as brain, nerve and muscle (Xu et al., 2002; Pollack et al., 1989; Morgan et al., 1991). In particular, the title compound was used in the synthesis of chiral by our group and as a part of our on-going research the structure of the title compound was determined.In the title chiral molecular salt, C4H12NO3S+.Cl-, the N atom is protonated resulting the cation [RNH3]+ where R is CH3SO2OCH2CH(CH3)- and the anion is chloride ion [Cl]-. The N atom in the cation is sp3 hybridized and the bond angles represents that the cation has tetrahedral structure around N (Fig. 1). In the crystal packing N—H···Cl hydrogen bonds connect ions into a supramolecular assembly in the ab plane (Fig. 2 and Table 1). Further, there exist C—H···O hydrogen bonds that connect the layers into a three-dimensional architecture.
The title chiral molecular salt was synthesised as per the literature procedure (Higashiura et al., 1989). An aqueous solution of HCl (4 M, 12 ml) was added to a stirred solution of (2R)-2-[(tert-butoxycarbonyl)amino] propyl methanesulfonate (2.53 g, 10 mmol ) in dioxane (15 ml). The resulting mixture was stirred for a further 1 h. The solution was then concentrated under reduced pressure and the residue obtained was recrystallized from hot ethanol to afford colourless single crystals suitable for single crystal X-ray diffraction.
The H atom of the NH3 group was located in a difference map but refined with N—H = 0.89, and with Uiso(H) = 1.2Ueq(N). Similarly, the other H atoms were positioned with idealized geometry using a riding model with C—H = 0.96–0.98 Å, and with Uiso(H) = 1.2–1.5Ueq(C). The structure was refined as an
with a of 0.08 (3)Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2014).Fig. 1. Molecular structure of the title molecular salt showing displacement ellipsoids drawn at the 50% probability level. | |
Fig. 2. The molecular packing of the title molecular salt with N—H···Cl hydrogen bonds (aqua bonds) leading to a supramolecular assembly in the ab plane. |
C4H12ClNO3S+·Cl− | prism |
Mr = 189.66 | Dx = 1.386 Mg m−3 |
Monoclinic, P21 | Melting point: 354 K |
Hall symbol: P 2yb | Cu Kα radiation, λ = 1.54178 Å |
a = 5.4012 (1) Å | Cell parameters from 830 reflections |
b = 8.2178 (2) Å | θ = 4.3–64.7° |
c = 10.2713 (2) Å | µ = 5.57 mm−1 |
β = 94.534 (1)° | T = 296 K |
V = 454.48 (2) Å3 | Prism, colourless |
Z = 2 | 0.24 × 0.20 × 0.16 mm |
F(000) = 200 |
Bruker APEXII CCD diffractometer | 1387 independent reflections |
Radiation source: fine-focus sealed tube | 1385 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 2.01 pixels mm-1 | θmax = 64.7°, θmin = 4.3° |
φ and ω scans | h = −6→2 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | k = −9→9 |
Tmin = 0.302, Tmax = 0.410 | l = −11→12 |
2476 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.0448P)2 + 0.0553P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.078 | (Δ/σ)max < 0.001 |
S = 1.11 | Δρmax = 0.29 e Å−3 |
1387 reflections | Δρmin = −0.42 e Å−3 |
96 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2014), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.120 (8) |
0 constraints | Absolute structure: Refined as an inversion twin |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.08 (3) |
Secondary atom site location: difference Fourier map |
C4H12ClNO3S+·Cl− | V = 454.48 (2) Å3 |
Mr = 189.66 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 5.4012 (1) Å | µ = 5.57 mm−1 |
b = 8.2178 (2) Å | T = 296 K |
c = 10.2713 (2) Å | 0.24 × 0.20 × 0.16 mm |
β = 94.534 (1)° |
Bruker APEXII CCD diffractometer | 1387 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | 1385 reflections with I > 2σ(I) |
Tmin = 0.302, Tmax = 0.410 | Rint = 0.029 |
2476 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.078 | Δρmax = 0.29 e Å−3 |
S = 1.11 | Δρmin = −0.42 e Å−3 |
1387 reflections | Absolute structure: Refined as an inversion twin |
96 parameters | Absolute structure parameter: 0.08 (3) |
1 restraint |
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. Refined as a 2-component inversion twin. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.0227 (7) | 0.1587 (5) | 0.7527 (4) | 0.0204 (8) | |
H1A | −0.1807 | 0.2029 | 0.7211 | 0.031* | |
H1B | −0.0282 | 0.1268 | 0.8423 | 0.031* | |
H1C | 0.0142 | 0.0655 | 0.7013 | 0.031* | |
Cl1 | 0.67754 (13) | 0.51693 (10) | 0.53323 (7) | 0.0149 (3) | |
S1 | 0.33444 (13) | 0.70873 (9) | 0.88988 (7) | 0.0118 (3) | |
O1 | 0.3212 (4) | 0.5513 (3) | 0.8028 (2) | 0.0190 (6) | |
N1 | 0.1849 (5) | 0.3392 (4) | 0.6037 (3) | 0.0111 (6) | |
H1D | 0.2153 | 0.2535 | 0.5544 | 0.013* | |
H1E | 0.3047 | 0.4127 | 0.5982 | 0.013* | |
H1F | 0.0395 | 0.3828 | 0.5759 | 0.013* | |
C2 | 0.1771 (6) | 0.2864 (4) | 0.7423 (3) | 0.0119 (7) | |
H2A | 0.3383 | 0.2394 | 0.7725 | 0.014* | |
O3 | 0.0905 (4) | 0.7735 (4) | 0.8958 (3) | 0.0225 (6) | |
C3 | 0.1271 (6) | 0.4323 (5) | 0.8265 (3) | 0.0140 (7) | |
H3B | −0.0362 | 0.4770 | 0.8021 | 0.017* | |
H3A | 0.1358 | 0.4019 | 0.9180 | 0.017* | |
C4 | 0.5119 (6) | 0.8308 (5) | 0.7941 (3) | 0.0159 (7) | |
H4B | 0.6647 | 0.7763 | 0.7801 | 0.024* | |
H4C | 0.5475 | 0.9323 | 0.8380 | 0.024* | |
H4A | 0.4212 | 0.8512 | 0.7116 | 0.024* | |
O2 | 0.4703 (5) | 0.6718 (4) | 1.0115 (2) | 0.0241 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0242 (19) | 0.0177 (18) | 0.0211 (17) | −0.0055 (15) | 0.0130 (14) | −0.0007 (15) |
Cl1 | 0.0110 (4) | 0.0182 (5) | 0.0161 (4) | −0.0006 (3) | 0.0051 (3) | 0.0047 (3) |
S1 | 0.0117 (4) | 0.0156 (5) | 0.0085 (4) | −0.0016 (3) | 0.0030 (3) | −0.0020 (3) |
O1 | 0.0205 (13) | 0.0198 (14) | 0.0186 (12) | −0.0093 (10) | 0.0134 (9) | −0.0075 (11) |
N1 | 0.0094 (13) | 0.0128 (15) | 0.0118 (13) | −0.0016 (11) | 0.0051 (10) | −0.0004 (11) |
C2 | 0.0117 (15) | 0.0138 (17) | 0.0110 (15) | 0.0003 (13) | 0.0052 (12) | 0.0003 (13) |
O3 | 0.0138 (12) | 0.0264 (14) | 0.0283 (14) | 0.0026 (11) | 0.0088 (10) | −0.0058 (11) |
C3 | 0.0120 (15) | 0.0159 (17) | 0.0152 (17) | −0.0047 (15) | 0.0076 (12) | −0.0014 (16) |
C4 | 0.0158 (16) | 0.0165 (17) | 0.0158 (16) | −0.0032 (15) | 0.0044 (12) | 0.0020 (15) |
O2 | 0.0278 (14) | 0.0330 (17) | 0.0107 (12) | −0.0060 (12) | −0.0040 (9) | 0.0035 (11) |
C1—C2 | 1.515 (5) | N1—H1D | 0.8900 |
C1—H1A | 0.9600 | N1—H1E | 0.8900 |
C1—H1B | 0.9600 | N1—H1F | 0.8900 |
C1—H1C | 0.9600 | C2—C3 | 1.515 (5) |
S1—O3 | 1.427 (3) | C2—H2A | 0.9800 |
S1—O2 | 1.430 (3) | C3—H3B | 0.9700 |
S1—O1 | 1.571 (3) | C3—H3A | 0.9700 |
S1—C4 | 1.744 (4) | C4—H4B | 0.9600 |
O1—C3 | 1.468 (4) | C4—H4C | 0.9600 |
N1—C2 | 1.491 (4) | C4—H4A | 0.9600 |
C2—C1—H1A | 109.5 | N1—C2—C1 | 110.1 (3) |
C2—C1—H1B | 109.5 | N1—C2—C3 | 109.5 (3) |
H1A—C1—H1B | 109.5 | C1—C2—C3 | 110.3 (3) |
C2—C1—H1C | 109.5 | N1—C2—H2A | 109.0 |
H1A—C1—H1C | 109.5 | C1—C2—H2A | 109.0 |
H1B—C1—H1C | 109.5 | C3—C2—H2A | 109.0 |
O3—S1—O2 | 116.97 (15) | O1—C3—C2 | 105.7 (2) |
O3—S1—O1 | 109.32 (15) | O1—C3—H3B | 110.6 |
O2—S1—O1 | 108.65 (17) | C2—C3—H3B | 110.6 |
O3—S1—C4 | 111.10 (17) | O1—C3—H3A | 110.6 |
O2—S1—C4 | 110.34 (16) | C2—C3—H3A | 110.6 |
O1—S1—C4 | 98.91 (16) | H3B—C3—H3A | 108.7 |
C3—O1—S1 | 117.07 (19) | S1—C4—H4B | 109.5 |
C2—N1—H1D | 109.5 | S1—C4—H4C | 109.5 |
C2—N1—H1E | 109.5 | H4B—C4—H4C | 109.5 |
H1D—N1—H1E | 109.5 | S1—C4—H4A | 109.5 |
C2—N1—H1F | 109.5 | H4B—C4—H4A | 109.5 |
H1D—N1—H1F | 109.5 | H4C—C4—H4A | 109.5 |
H1E—N1—H1F | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1E···Cl1 | 0.89 | 2.33 | 3.169 (3) | 156 |
C3—H3A···O3i | 0.97 | 2.58 | 3.428 (4) | 147 |
N1—H1D···Cl1ii | 0.89 | 2.24 | 3.116 (3) | 169 |
N1—H1F···Cl1iii | 0.89 | 2.26 | 3.139 (3) | 171 |
C2—H2A···O2iv | 0.98 | 2.44 | 3.186 (4) | 133 |
C4—H4B···O3v | 0.96 | 2.50 | 3.250 (4) | 135 |
C4—H4C···O2vi | 0.96 | 2.51 | 3.438 (5) | 163 |
Symmetry codes: (i) −x, y−1/2, −z+2; (ii) −x+1, y−1/2, −z+1; (iii) x−1, y, z; (iv) −x+1, y−1/2, −z+2; (v) x+1, y, z; (vi) −x+1, y+1/2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1E···Cl1 | 0.89 | 2.33 | 3.169 (3) | 156 |
C3—H3A···O3i | 0.97 | 2.58 | 3.428 (4) | 147 |
N1—H1D···Cl1ii | 0.89 | 2.24 | 3.116 (3) | 169 |
N1—H1F···Cl1iii | 0.89 | 2.26 | 3.139 (3) | 171 |
C2—H2A···O2iv | 0.98 | 2.44 | 3.186 (4) | 133 |
C4—H4B···O3v | 0.96 | 2.50 | 3.250 (4) | 135 |
C4—H4C···O2vi | 0.96 | 2.51 | 3.438 (5) | 163 |
Symmetry codes: (i) −x, y−1/2, −z+2; (ii) −x+1, y−1/2, −z+1; (iii) x−1, y, z; (iv) −x+1, y−1/2, −z+2; (v) x+1, y, z; (vi) −x+1, y+1/2, −z+2. |
Acknowledgements
PRK thanks the DST–SERB, Government of India, for financial support to carry out the project No. DST/SR/S-1/IC-76/2010(G).
References
Braghiroli, D. & Di Bella, M. (1996). Tetrahedron Asymmetry, 7, 2145–2150. CrossRef CAS Google Scholar
Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Higashiura, H., Morino, H., Matsuura, H., Toyomaki, Y. & Ienaga, K. (1989). J. Chem. Soc. Perkin Trans. 1, pp. 1479–1481. CrossRef Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Morgan, B. P., Scholtz, J. M., Ballinger, M. D., Zipkin, I. D. & Bartlett, P. A. (1991). J. Am. Chem. Soc. 113, 297–307. CrossRef CAS Google Scholar
Pollack, S. J., Hsiun, P. & Schultz, P. G. (1989). J. Am. Chem. Soc. 111, 5961–5962. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Xu, J. (2002). Tetrahedron Asymmetry, 13, 1129–1134. CrossRef CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.