4-(Methyl­sulfan­yl)-2-(p-toluene­sulfonamido)butanoic acid

Wang, L.; Liu, Z.; Wang, Y.L.

doi:10.1107/S1600536808005035

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o706

doi:10.1107/S1600536808005035

Open

access

4-(Methylsulfanyl)-2-(p-toluenesulfonamido)butanoic acid

Li Wang,^a Zheng Liu ^a ^* and Yong Liao Wang ^a

^aKey Laboratory of Non-ferrous Metal Materials and Processing Technology, Department of Materials and Chemical Engineering, Ministry of Education, Guilin University of Technology, Guilin 541004, People's Republic of China
^*Correspondence e-mail: lisa4.6@163.com

(Received 21 December 2007; accepted 22 February 2008; online 12 March 2008)

In the title compound, C₁₂H₁₇NO₄S₂, the carboxyl groups link the molecules into centrosymmetric dimers through O—H⋯O hydrogen bonds. An N—H⋯O hydrogen bond between the NH group of the L-methionine unit and a neighbouring carboxyl group, together with a complementary C—H⋯O contact to one O atom of the sulfonyl group, link the dimers into one-dimensional chains along the crystallographic b axis.

Related literature

The title compound is closely related to the previously reported N-tosyl-L-glutamic acid (Zachara et al., 2005 ).

Experimental

Crystal data

C₁₂H₁₇NO₄S₂
M_r = 303.39
Monoclinic, C 2/c
a = 33.121 (7) Å
b = 5.6531 (11) Å
c = 17.278 (4) Å
β = 116.62 (3)°
V = 2892.2 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 293 (2) K
0.43 × 0.28 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.855, T_max = 0.922
6139 measured reflections
2689 independent reflections
2055 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.119
S = 1.00
2689 reflections
179 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3ⁱ	0.82	1.85	2.672 (3)	174
N1—H1⋯O4ⁱⁱ	0.81 (3)	2.62 (3)	3.405 (3)	163 (2)
C4—H4⋯O1ⁱⁱⁱ	0.98	2.25	3.165 (3)	155
Symmetry codes: (i) -x, -y+1, -z; (ii) x, y+1, z; (iii) x, y-1, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005035/bi2276sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808005035/bi2276Isup2.hkl

checkCIF report

Comment top

The title compound (Fig. 1) was synthesized from 4-toluenesulfonyl chloride and L-methionine. It is closely related to the previously reported N-tosyl-L-glutamic acid (Zachara et al., 2005).

Related literature top

The title compound is closely related to the previously reported N-tosyl-L-glutamic acid (Zachara et al., 2005).

Experimental top

A solution of L-methionine (0.005 mmol) and NaOH (0.015 mmol) in water (15 ml) was added to an ethanol solution of 4-toluenesulfonyl chloride (0.005 mmol). After stirring at 348 K for 40 min, crystals of the title compound were obtained by slow evaporation of the reaction mixture at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids for non-H atoms. H atoms bound to C and N are omitted.
	Fig. 2. Partial packing diagram showing a hydrogen-bonded chain running along the b axis.

4-(Methylsulfanyl)-2-(p-toluenesulfonamido)butanoic acid top

Crystal data top

C₁₂H₁₇NO₄S₂	F(000) = 1280
M_r = 303.39	D_x = 1.394 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2689 reflections
a = 33.121 (7) Å	θ = 2.8–25.5°
b = 5.6531 (11) Å	µ = 0.38 mm⁻¹
c = 17.278 (4) Å	T = 293 K
β = 116.62 (3)°	Block, colorless
V = 2892.2 (10) Å³	0.43 × 0.28 × 0.22 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	2689 independent reflections
Radiation source: fine-focus sealed tube	2055 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −40→30
T_min = 0.855, T_max = 0.922	k = −5→6
6139 measured reflections	l = −17→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0619P)² + 2.0643P] where P = (F_o² + 2F_c²)/3
2689 reflections	(Δ/σ)_max < 0.001
179 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₂H₁₇NO₄S₂	V = 2892.2 (10) Å³
M_r = 303.39	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 33.121 (7) Å	µ = 0.38 mm⁻¹
b = 5.6531 (11) Å	T = 293 K
c = 17.278 (4) Å	0.43 × 0.28 × 0.22 mm
β = 116.62 (3)°

Data collection top

Bruker APEXII CCD diffractometer	2689 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2055 reflections with I > 2σ(I)
T_min = 0.855, T_max = 0.922	R_int = 0.028
6139 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.30 e Å⁻³
2689 reflections	Δρ_min = −0.25 e Å⁻³
179 parameters

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. 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.

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

	x	y	z	U_iso*/U_eq
C1	0.05669 (12)	0.1441 (6)	−0.2992 (2)	0.0798 (10)
H1A	0.0814	0.0695	−0.2516	0.120*
H1B	0.0514	0.0655	−0.3521	0.120*
H1C	0.0300	0.1343	−0.2906	0.120*
C2	0.09539 (9)	0.5313 (5)	−0.19259 (17)	0.0532 (7)
H2A	0.1186	0.4170	−0.1596	0.064*
H2B	0.1098	0.6843	−0.1860	0.064*
C3	0.06194 (8)	0.5443 (5)	−0.15563 (16)	0.0500 (7)
H3A	0.0477	0.3909	−0.1619	0.060*
H3B	0.0385	0.6573	−0.1890	0.060*
C4	0.08314 (7)	0.6170 (4)	−0.05971 (14)	0.0386 (5)
H4	0.1099	0.5190	−0.0273	0.046*
C5	0.04899 (8)	0.5711 (4)	−0.02597 (14)	0.0392 (5)
C6	0.16839 (7)	0.8595 (4)	0.11546 (15)	0.0405 (5)
C7	0.19182 (8)	0.6522 (5)	0.14801 (16)	0.0480 (6)
H7	0.1967	0.5472	0.1117	0.058*
C8	0.16108 (9)	1.0154 (5)	0.17034 (18)	0.0512 (7)
H8	0.1452	1.1554	0.1488	0.061*
C9	0.20788 (9)	0.6019 (5)	0.23483 (18)	0.0538 (7)
H9	0.2235	0.4612	0.2563	0.065*
C10	0.17754 (9)	0.9604 (5)	0.25668 (18)	0.0586 (7)
H10	0.1724	1.0644	0.2930	0.070*
C11	0.20148 (8)	0.7549 (5)	0.29100 (17)	0.0526 (7)
C12	0.22040 (10)	0.7014 (7)	0.38595 (19)	0.0769 (10)
H12A	0.2242	0.5336	0.3948	0.115*
H12B	0.2000	0.7580	0.4074	0.115*
H12C	0.2491	0.7783	0.4164	0.115*
N1	0.09655 (7)	0.8649 (4)	−0.04861 (13)	0.0429 (5)
H1	0.0819 (9)	0.958 (5)	−0.0360 (18)	0.051 (8)*
O1	0.15126 (6)	1.1856 (3)	0.00061 (12)	0.0545 (5)
O2	0.17393 (5)	0.7911 (3)	−0.02689 (11)	0.0520 (5)
O3	0.02802 (6)	0.7289 (3)	−0.01265 (11)	0.0479 (4)
O4	0.04342 (6)	0.3447 (3)	−0.01734 (12)	0.0499 (5)
H4A	0.0204	0.3249	−0.0115	0.075*
S1	0.149864 (19)	0.93464 (11)	0.00597 (4)	0.0414 (2)
S2	0.07010 (3)	0.44879 (15)	−0.30518 (4)	0.0630 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.100 (3)	0.073 (2)	0.069 (2)	0.007 (2)	0.0400 (19)	−0.0020 (17)
C2	0.0484 (14)	0.072 (2)	0.0443 (14)	0.0011 (13)	0.0249 (12)	0.0054 (13)
C3	0.0437 (14)	0.0659 (18)	0.0441 (14)	−0.0064 (12)	0.0231 (11)	−0.0046 (12)
C4	0.0380 (12)	0.0417 (14)	0.0382 (12)	−0.0031 (10)	0.0190 (10)	0.0019 (10)
C5	0.0424 (13)	0.0435 (15)	0.0326 (12)	−0.0045 (11)	0.0175 (10)	−0.0006 (10)
C6	0.0353 (12)	0.0368 (13)	0.0474 (13)	−0.0032 (10)	0.0167 (10)	−0.0014 (11)
C7	0.0503 (14)	0.0377 (14)	0.0509 (15)	0.0017 (12)	0.0182 (12)	−0.0033 (11)
C8	0.0529 (15)	0.0439 (16)	0.0607 (17)	0.0093 (12)	0.0290 (13)	0.0011 (12)
C9	0.0474 (15)	0.0459 (16)	0.0599 (17)	0.0045 (12)	0.0168 (13)	0.0079 (13)
C10	0.0564 (16)	0.068 (2)	0.0570 (17)	0.0012 (14)	0.0301 (14)	−0.0105 (14)
C11	0.0374 (13)	0.0666 (19)	0.0518 (15)	−0.0045 (13)	0.0182 (11)	0.0017 (13)
C12	0.0579 (18)	0.116 (3)	0.0528 (18)	0.0025 (18)	0.0210 (14)	0.0104 (18)
N1	0.0386 (11)	0.0409 (13)	0.0508 (12)	0.0019 (10)	0.0214 (10)	0.0059 (10)
O1	0.0543 (11)	0.0385 (11)	0.0688 (12)	−0.0036 (8)	0.0259 (9)	0.0097 (8)
O2	0.0434 (9)	0.0596 (12)	0.0605 (11)	−0.0002 (8)	0.0300 (9)	−0.0021 (9)
O3	0.0552 (10)	0.0449 (11)	0.0555 (11)	−0.0038 (8)	0.0353 (9)	−0.0017 (8)
O4	0.0556 (11)	0.0447 (11)	0.0633 (11)	−0.0053 (8)	0.0391 (9)	0.0012 (8)
S1	0.0362 (3)	0.0394 (4)	0.0498 (4)	−0.0030 (2)	0.0202 (3)	0.0023 (3)
S2	0.0773 (5)	0.0750 (6)	0.0407 (4)	0.0063 (4)	0.0300 (4)	0.0059 (3)

Geometric parameters (Å, º) top

C1—S2	1.793 (4)	C6—S1	1.760 (3)
C1—H1A	0.960	C7—C9	1.378 (4)
C1—H1B	0.960	C7—H7	0.930
C1—H1C	0.960	C8—C10	1.375 (4)
C2—C3	1.508 (3)	C8—H8	0.930
C2—S2	1.801 (3)	C9—C11	1.385 (4)
C2—H2A	0.970	C9—H9	0.930
C2—H2B	0.970	C10—C11	1.381 (4)
C3—C4	1.538 (3)	C10—H10	0.930
C3—H3A	0.970	C11—C12	1.501 (4)
C3—H3B	0.970	C12—H12A	0.960
C4—N1	1.457 (3)	C12—H12B	0.960
C4—C5	1.509 (3)	C12—H12C	0.960
C4—H4	0.980	N1—S1	1.634 (2)
C5—O3	1.214 (3)	N1—H1	0.81 (3)
C5—O4	1.311 (3)	O1—S1	1.4238 (19)
C6—C7	1.378 (4)	O2—S1	1.4216 (18)
C6—C8	1.393 (4)	O4—H4A	0.820

S2—C1—H1A	109.5	C9—C7—H7	120.3
S2—C1—H1B	109.5	C6—C7—H7	120.3
H1A—C1—H1B	109.5	C10—C8—C6	119.3 (3)
S2—C1—H1C	109.5	C10—C8—H8	120.3
H1A—C1—H1C	109.5	C6—C8—H8	120.3
H1B—C1—H1C	109.5	C7—C9—C11	121.9 (3)
C3—C2—S2	113.29 (18)	C7—C9—H9	119.1
C3—C2—H2A	108.9	C11—C9—H9	119.1
S2—C2—H2A	108.9	C8—C10—C11	121.9 (3)
C3—C2—H2B	108.9	C8—C10—H10	119.1
S2—C2—H2B	108.9	C11—C10—H10	119.0
H2A—C2—H2B	107.7	C10—C11—C9	117.6 (3)
C2—C3—C4	113.7 (2)	C10—C11—C12	121.1 (3)
C2—C3—H3A	108.8	C9—C11—C12	121.3 (3)
C4—C3—H3A	108.8	C11—C12—H12A	109.5
C2—C3—H3B	108.8	C11—C12—H12B	109.5
C4—C3—H3B	108.8	H12A—C12—H12B	109.5
H3A—C3—H3B	107.7	C11—C12—H12C	109.5
N1—C4—C5	110.6 (2)	H12A—C12—H12C	109.5
N1—C4—C3	111.3 (2)	H12B—C12—H12C	109.5
C5—C4—C3	108.11 (18)	C4—N1—S1	119.67 (17)
N1—C4—H4	108.9	C4—N1—H1	119 (2)
C5—C4—H4	108.9	S1—N1—H1	108 (2)
C3—C4—H4	108.9	C5—O4—H4A	109.5
O3—C5—O4	125.0 (2)	O2—S1—O1	120.15 (11)
O3—C5—C4	122.6 (2)	O2—S1—N1	106.62 (12)
O4—C5—C4	112.3 (2)	O1—S1—N1	105.14 (11)
C7—C6—C8	119.9 (2)	O2—S1—C6	107.68 (11)
C7—C6—S1	120.36 (19)	O1—S1—C6	107.74 (12)
C8—C6—S1	119.7 (2)	N1—S1—C6	109.16 (11)
C9—C7—C6	119.5 (2)	C1—S2—C2	101.15 (15)

S2—C2—C3—C4	−179.45 (19)	C7—C9—C11—C10	1.1 (4)
C2—C3—C4—N1	70.7 (3)	C7—C9—C11—C12	−178.1 (3)
C2—C3—C4—C5	−167.6 (2)	C5—C4—N1—S1	123.41 (19)
N1—C4—C5—O3	17.0 (3)	C3—C4—N1—S1	−116.39 (19)
C3—C4—C5—O3	−105.1 (3)	C4—N1—S1—O2	48.6 (2)
N1—C4—C5—O4	−166.15 (18)	C4—N1—S1—O1	177.16 (17)
C3—C4—C5—O4	71.7 (3)	C4—N1—S1—C6	−67.5 (2)
C8—C6—C7—C9	−0.1 (4)	C7—C6—S1—O2	−16.2 (2)
S1—C6—C7—C9	176.96 (19)	C8—C6—S1—O2	160.89 (19)
C7—C6—C8—C10	0.2 (4)	C7—C6—S1—O1	−147.2 (2)
S1—C6—C8—C10	−177.0 (2)	C8—C6—S1—O1	29.9 (2)
C6—C7—C9—C11	−0.5 (4)	C7—C6—S1—N1	99.2 (2)
C6—C8—C10—C11	0.4 (4)	C8—C6—S1—N1	−83.7 (2)
C8—C10—C11—C9	−1.0 (4)	C3—C2—S2—C1	−70.4 (3)
C8—C10—C11—C12	178.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3ⁱ	0.82	1.85	2.672 (3)	174
N1—H1···O4ⁱⁱ	0.81 (3)	2.62 (3)	3.405 (3)	163 (2)
C4—H4···O1ⁱⁱⁱ	0.98	2.25	3.165 (3)	155

Symmetry codes: (i) −x, −y+1, −z; (ii) x, y+1, z; (iii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₇NO₄S₂
M_r	303.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	33.121 (7), 5.6531 (11), 17.278 (4)
β (°)	116.62 (3)
V (Å³)	2892.2 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.43 × 0.28 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.855, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	6139, 2689, 2055
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.119, 1.00
No. of reflections	2689
No. of parameters	179
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.25

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3ⁱ	0.82	1.85	2.672 (3)	174.4
N1—H1···O4ⁱⁱ	0.81 (3)	2.62 (3)	3.405 (3)	163 (2)
C4—H4···O1ⁱⁱⁱ	0.98	2.25	3.165 (3)	154.5

Symmetry codes: (i) −x, −y+1, −z; (ii) x, y+1, z; (iii) x, y−1, z.

Acknowledgements

The authors acknowledge financial support by the Key Laboratory of Non-ferrous Metal Materials and New Processing Technology, Ministry of Education, People's Republic of China.

References

Bruker (2001). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zachara, J., Madura, I., Hajmowicz, H. & Synoradzki, L. (2005). Acta Cryst. C61, o181–o184. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar