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

Rajegowda, H.R.; Palakshamurthy, B.S.; Lokanath, N.K.; Naveen, S.; Raghavendra Kumar, P.

doi:10.1107/S2056989015015972

organic compounds

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Volume 71| Part 10| October 2015| Pages o733-o734

doi:10.1107/S2056989015015972

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

H. R. Rajegowda,^a B. S. Palakshamurthy,^b N. K. Lokanath,^c S. Naveen ^d and P. Raghavendra Kumar ^a ^*

^aDepartment 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

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 28 March 2015; accepted 26 August 2015; online 12 September 2015)

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

C₄H₁₂ClNO₃S⁺·Cl⁻
M_r = 189.66
Monoclinic, P 2₁
a = 5.4012 (1) Å
b = 8.2178 (2) Å
c = 10.2713 (2) Å
β = 94.534 (1)°
V = 454.48 (2) Å³
Z = 2
Cu Kα radiation
μ = 5.57 mm⁻¹
T = 296 K
0.24 × 0.20 × 0.16 mm

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 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)

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O2^iv	0.98	2.44	3.186 (4)	133
C4—H4B⋯O3^v	0.96	2.50	3.250 (4)	135
C4—H4C⋯O2^vi	0.96	2.51	3.438 (5)	163
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+2]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (iii) x-1, y, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+2]$ ; (v) x+1, y, z; (vi) $[-x+1, y+{\script{1\over 2}}, -z+2]$ .

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.

Supporting information

CCDC reference: 1420721

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015015972/tk5365sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015015972/tk5365Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015015972/tk5365Isup3.cml

checkCIF report

Chemical context top

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.

Structural commentary top

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.

Synthesis and crystallization top

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.

Refinement details top

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)

Related literature top

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).

Computing details top

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

Figures top

	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.

(2R)-2-Azaniumylpropyl methanesulfonate chloride top

Crystal data top

C₄H₁₂ClNO₃S⁺·Cl⁻	prism
M_r = 189.66	D_x = 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 top

Bruker APEXII CCD diffractometer	1387 independent reflections
Radiation source: fine-focus sealed tube	1385 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 2.01 pixels mm^-1	θ_max = 64.7°, θ_min = 4.3°
φ and ω scans	h = −6→2
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −9→9
T_min = 0.302, T_max = 0.410	l = −11→12
2476 measured reflections

Refinement top

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(F_o²) + (0.0448P)² + 0.0553P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.078	(Δ/σ)_max < 0.001
S = 1.11	Δρ_max = 0.29 e Å⁻³
1387 reflections	Δρ_min = −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

Crystal data top

C₄H₁₂ClNO₃S⁺·Cl⁻	V = 454.48 (2) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	1387 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1385 reflections with I > 2σ(I)
T_min = 0.302, T_max = 0.410	R_int = 0.029
2476 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.078	Δρ_max = 0.29 e Å⁻³
S = 1.11	Δρ_min = −0.42 e Å⁻³
1387 reflections	Absolute structure: Refined as an inversion twin
96 parameters	Absolute structure parameter: 0.08 (3)
1 restraint

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. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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···O2^iv	0.98	2.44	3.186 (4)	133
C4—H4B···O3^v	0.96	2.50	3.250 (4)	135
C4—H4C···O2^vi	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.

Hydrogen-bond geometry (Å, º) top

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···O2^iv	0.98	2.44	3.186 (4)	133
C4—H4B···O3^v	0.96	2.50	3.250 (4)	135
C4—H4C···O2^vi	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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages o733-o734

doi:10.1107/S2056989015015972

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

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