Crystal structure of (2R)-1-[(methyl­sulfon­yl)­oxy]propan-2-aminium chloride: a chiral mol­ecular salt

Abstract

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 sp ³-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.

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 ▸).

Experimental  

Crystal data  

• C₄H₁₂ClNO₃S⁺·Cl⁻

• M _r = 189.66

• Monoclinic,

• a = 5.4012 (1) Å

• b = 8.2178 (2) Å

• c = 10.2713 (2) Å

• β = 94.534 (1)°

• V = 454.48 (2) ų

• Z = 2

• Cu Kα radiation

• μ = 5.57 mm⁻¹

• T = 296 K

• 0.24 × 0.20 × 0.16 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2013 ▸) T _min = 0.302, T _max = 0.410

• 2476 measured reflections

• 1387 independent reflections

• 1385 reflections with I > 2σ(I)

• R _int = 0.029

Refinement  

• R[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 0.078

• S = 1.11

• 1387 reflections

• 96 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.29 e Å⁻³

• Δρ_min = −0.42 e Å⁻³

• Absolute structure: Refined as an inversion twin

• Absolute structure parameter: 0.08 (3)

Data collection: APEX2 (Bruker, 2013 ▸); cell refinement: 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.

Supplementary Material

CCDC reference: 1420721

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1ECl1	0.89	2.33	3.169(3)	156
C3H3AO3i	0.97	2.58	3.428(4)	147
N1H1DCl1ii	0.89	2.24	3.116(3)	169
N1H1FCl1iii	0.89	2.26	3.139(3)	171
C2H2AO2iv	0.98	2.44	3.186(4)	133
C4H4BO3v	0.96	2.50	3.250(4)	135
C4H4CO2vi	0.96	2.51	3.438(5)	163

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

supplementary crystallographic information

S1. Chemical context

The chiral 2-amino-2-(alkyl/aryl/aralkyl)­ethyl methane­sulfonate hydro­chlorides are useful starting materials for the preparation of amines, benzoates, thio­benzoates, sulfonic acids, etc., as methane­sulfonate is a very good leaving group 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 amines by our group and as a part of our on-going research the structure of the title compound was determined.

S2. Structural commentary

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.

S3. Synthesis and crystallization

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.

S4. Refinement details

The H atom of the NH₃ group was located in a difference map but refined with N—H = 0.89, and with U_iso(H) = 1.2U_eq(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 U_iso(H) = 1.2–1.5U_eq(C). The structure was refined as an inversion twin with a Flack parameter of 0.08 (3)

Figures

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.

Crystal data

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

Data collection

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

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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, º)

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

Hydrogen-bond geometry (Å, º)

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.