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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.043
• wR factor = 0.120
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
CELLV02_ALERT_1_C  The supplied cell volume s.u. differs from that
            calculated from the cell parameter s.u.'s by > 2
            Calculated cell volume su =      13.09
            Cell volume su given      =      10.00
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1     ..  O4      ..       2.62 Ang.

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT793_ALERT_2_G Check the Absolute Configuration of C4     .....          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

H atoms bound to C or O atoms were placed geometrically with C—H = 0.93–0.97 Å or O—H = 0.82 Å and refined as riding with U_iso(H) = 1.2 or 1.5U_eq(C/O). The H atom of the NH group was located in a difference Fourier map and refined with an isotropic displacement parameter, without restraint.

Computing details

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

	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

Crystal data

C12H17NO4S2	F(000) = 1280
Mr = 303.39	Dx = 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) Å^3	0.43 × 0.28 × 0.22 mm
Z = 8

Data collection

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

Refinement

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

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. 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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3^i	0.82	1.85	2.672 (3)	174
N1—H1···O4^ii	0.81 (3)	2.62 (3)	3.405 (3)	163 (2)
C4—H4···O1^iii	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.