Crystal structure of (R,S)-2-hy­droxy-4-(methyl­sulfan­yl)butanoic acid

Mawhinney, T.P.; Li, Y.; Chance, D.L.; Kelley, S.P.; Mossine, V.V.

doi:10.1107/S2056989020003138

Crystal structure of (R,S)-2-hydroxy-4-(methylsulfanyl)butanoic acid

T. P. Mawhinney, Y. Li, D. L. Chance, S. P. Kelley and V. V. Mossine

Methionine hydroxy analogue, a common poultry feed supplement, has been obtained in crystalline form for the first time. The asymmetric unit contains two conformationally unequal molecules that are involved in a two-dimensional intermolecular hydrogen-bonding network.

Keywords: crystal structure; methionine hydroxy analog; 2-hydroxy-4-(methylsulfanyl)butanoic acid; HMTBA; CAS 583–91-5; hydrogen bonding.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989020003138/lh5949sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989020003138/lh5949Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989020003138/lh5949Isup3.cml Supplementary material

CCDC reference: 1979735

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R factor = 0.044
wR factor = 0.106
Data-to-parameter ratio = 19.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C NonSolvent Resd 1  C   Ueq(max) / Ueq(min) Range        3.4 Ratio
PLAT220_ALERT_2_C NonSolvent Resd 2  C   Ueq(max) / Ueq(min) Range        3.9 Ratio
PLAT222_ALERT_3_C NonSolvent Resd 1  H   Uiso(max)/Uiso(min) Range        4.1 Ratio
PLAT222_ALERT_3_C NonSolvent Resd 2  H   Uiso(max)/Uiso(min) Range        4.8 Ratio
PLAT417_ALERT_2_C Short Inter D-H..H-D       H2A      ..H3A      .       2.12 Ang.
                                             x,1/2-y,-1/2+z  =      4_565 Check
PLAT417_ALERT_2_C Short Inter D-H..H-D       H2B      ..H3B      .       2.14 Ang.
                                              x,3/2-y,1/2+z  =      4_576 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      3.458 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          4 Report

Alert level G
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........         16 Note
PLAT793_ALERT_4_G Model has Chirality at C2A         (Centro SPGR)          R Verify
PLAT793_ALERT_4_G Model has Chirality at C2B         (Centro SPGR)          R Verify
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          9 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

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

Computing details top

Data collection: APEX3 and SAINT (Bruker, 2017); cell refinement: APEX3 and SAINT (Bruker, 2017); data reduction: APEX3 and SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

(R,S)-2-Hydroxy-4-(methylsulfanyl)butanoic acid top

Crystal data top

C₅H₁₀O₃S	F(000) = 640
M_r = 150.19	D_x = 1.374 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.0940 (14) Å	Cell parameters from 9911 reflections
b = 8.8747 (8) Å	θ = 2.6–30.5°
c = 10.558 (1) Å	µ = 0.38 mm⁻¹
β = 105.654 (3)°	T = 100 K
V = 1452.1 (2) Å³	Plate, colourless
Z = 8	0.34 × 0.25 × 0.07 mm

Data collection top

Bruker VENTURE CMOS area detector diffractometer	3474 reflections with I > 2σ(I)
Radiation source: Incoatec IMuS microfocus Mo tube	R_int = 0.071
shutterless ω and phi scans	θ_max = 30.6°, θ_min = 2.6°
Absorption correction: multi-scan (AXScale; Bruker, 2017)	h = −22→23
T_min = 0.653, T_max = 0.746	k = −12→12
37191 measured reflections	l = −15→13
4437 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: mixed
wR(F²) = 0.106	Only H-atom coordinates refined
S = 1.05	w = 1/[σ²(F_o²) + (0.0433P)² + 0.6797P] where P = (F_o² + 2F_c²)/3
4437 reflections	(Δ/σ)_max = 0.001
223 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
S1A	0.84095 (3)	0.20993 (6)	0.52925 (4)	0.03405 (12)
S1B	0.92449 (3)	0.76333 (6)	0.21950 (6)	0.04228 (14)
O3A	0.55286 (6)	0.36868 (11)	0.33141 (9)	0.0159 (2)
H3A	0.5659 (12)	0.439 (2)	0.3057 (18)	0.024*
O1A	0.53671 (6)	0.35894 (11)	0.06723 (9)	0.0184 (2)
O3B	0.64397 (7)	0.61637 (11)	0.07733 (10)	0.0179 (2)
H3B	0.5982 (13)	0.587 (2)	0.0729 (19)	0.027*
O2A	0.56541 (7)	0.11169 (10)	0.08154 (10)	0.0175 (2)
H2A	0.5570 (11)	0.123 (2)	−0.005 (2)	0.026*
O2B	0.66367 (7)	0.88568 (11)	0.33618 (10)	0.0205 (2)
H2B	0.6535 (12)	0.880 (2)	0.412 (2)	0.031*
O1B	0.60884 (7)	0.65325 (11)	0.31386 (10)	0.0217 (2)
C2A	0.59189 (8)	0.24683 (14)	0.28125 (13)	0.0131 (2)
H2AA	0.5714 (10)	0.1576 (19)	0.3142 (16)	0.016*
C1A	0.56017 (8)	0.24609 (14)	0.13230 (13)	0.0134 (2)
C3B	0.74743 (9)	0.81369 (16)	0.13945 (14)	0.0183 (3)
H3BA	0.7508 (11)	0.820 (2)	0.0534 (18)	0.022*
H3BB	0.7552 (11)	0.914 (2)	0.1762 (17)	0.022*
C2B	0.65613 (9)	0.76258 (14)	0.13541 (13)	0.0150 (2)
H2BA	0.6158 (11)	0.8295 (19)	0.0850 (16)	0.018*
C3A	0.69066 (9)	0.25339 (16)	0.32158 (13)	0.0173 (3)
H3AA	0.7133 (11)	0.167 (2)	0.2847 (17)	0.021*
H3AB	0.7095 (11)	0.340 (2)	0.2816 (17)	0.021*
C4A	0.72730 (10)	0.25292 (19)	0.47077 (15)	0.0231 (3)
H4AA	0.7001 (12)	0.174 (2)	0.5080 (18)	0.028*
H4AB	0.7168 (12)	0.347 (2)	0.5062 (18)	0.028*
C4B	0.81668 (10)	0.70791 (19)	0.21803 (19)	0.0280 (3)
H4BA	0.8093 (12)	0.610 (2)	0.1778 (19)	0.034*
H4BB	0.8140 (12)	0.696 (2)	0.307 (2)	0.034*
C5A	0.88873 (13)	0.3629 (3)	0.4614 (2)	0.0441 (5)
H5AA	0.8738 (17)	0.356 (3)	0.359 (3)	0.066*
H5AB	0.9499 (17)	0.348 (3)	0.497 (3)	0.066*
H5AC	0.8699 (16)	0.455 (3)	0.489 (3)	0.066*
C5B	0.93633 (15)	0.9292 (3)	0.3193 (3)	0.0578 (7)
H5BA	0.898 (2)	1.008 (4)	0.280 (3)	0.087*
H5BB	0.994 (2)	0.959 (3)	0.336 (3)	0.087*
H5BC	0.9255 (19)	0.895 (3)	0.407 (3)	0.087*
C1B	0.64041 (8)	0.75921 (14)	0.27099 (13)	0.0151 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.02048 (19)	0.0455 (3)	0.0314 (2)	0.00432 (17)	−0.00131 (16)	0.00794 (19)
S1B	0.0198 (2)	0.0453 (3)	0.0635 (3)	−0.00015 (17)	0.0142 (2)	−0.0085 (2)
O3A	0.0236 (5)	0.0107 (4)	0.0148 (5)	0.0014 (4)	0.0076 (4)	0.0001 (4)
O1A	0.0248 (5)	0.0136 (4)	0.0156 (5)	0.0012 (4)	0.0035 (4)	0.0024 (4)
O3B	0.0208 (5)	0.0159 (5)	0.0179 (5)	−0.0047 (4)	0.0067 (4)	−0.0036 (4)
O2A	0.0291 (5)	0.0118 (4)	0.0122 (5)	0.0001 (4)	0.0063 (4)	−0.0007 (4)
O2B	0.0331 (6)	0.0147 (5)	0.0154 (5)	−0.0045 (4)	0.0097 (4)	−0.0017 (4)
O1B	0.0305 (5)	0.0159 (5)	0.0219 (5)	−0.0040 (4)	0.0126 (4)	0.0002 (4)
C2A	0.0176 (6)	0.0100 (5)	0.0119 (6)	0.0006 (4)	0.0044 (5)	−0.0002 (4)
C1A	0.0142 (6)	0.0119 (6)	0.0148 (6)	−0.0017 (4)	0.0050 (5)	−0.0002 (5)
C3B	0.0209 (6)	0.0180 (6)	0.0170 (7)	−0.0025 (5)	0.0070 (5)	0.0005 (5)
C2B	0.0192 (6)	0.0130 (6)	0.0127 (6)	−0.0002 (5)	0.0045 (5)	0.0011 (5)
C3A	0.0184 (6)	0.0185 (6)	0.0148 (6)	−0.0003 (5)	0.0043 (5)	−0.0005 (5)
C4A	0.0193 (7)	0.0309 (8)	0.0175 (7)	0.0011 (6)	0.0021 (5)	−0.0003 (6)
C4B	0.0212 (7)	0.0227 (7)	0.0392 (10)	−0.0007 (6)	0.0067 (7)	0.0013 (7)
C5A	0.0252 (9)	0.0575 (13)	0.0474 (12)	−0.0085 (9)	0.0058 (8)	0.0033 (10)
C5B	0.0321 (10)	0.0452 (12)	0.0835 (19)	−0.0106 (9)	−0.0059 (11)	−0.0134 (12)
C1B	0.0170 (6)	0.0137 (6)	0.0143 (6)	0.0006 (5)	0.0040 (5)	0.0005 (5)

Geometric parameters (Å, º) top

S1A—C5A	1.801 (2)	C3B—C2B	1.5273 (19)
S1A—C4A	1.8063 (15)	C3B—H3BA	0.926 (18)
S1B—C5B	1.791 (3)	C3B—H3BB	0.967 (17)
S1B—C4B	1.7995 (16)	C2B—C1B	1.5197 (19)
O3A—C2A	1.4227 (15)	C2B—H2BA	0.934 (17)
O3A—H3A	0.736 (19)	C3A—C4A	1.526 (2)
O1A—C1A	1.2155 (16)	C3A—H3AA	0.974 (18)
O3B—C2B	1.4259 (16)	C3A—H3AB	0.968 (18)
O3B—H3B	0.77 (2)	C4A—H4AA	0.967 (19)
O2A—C1A	1.3197 (15)	C4A—H4AB	0.95 (2)
O2A—H2A	0.89 (2)	C4B—H4BA	0.96 (2)
O2B—C1B	1.3171 (16)	C4B—H4BB	0.95 (2)
O2B—H2B	0.86 (2)	C5A—H5AA	1.04 (3)
O1B—C1B	1.2131 (16)	C5A—H5AB	0.96 (3)
C2A—C1A	1.5167 (18)	C5A—H5AC	0.95 (3)
C2A—C3A	1.5318 (19)	C5B—H5BA	0.95 (3)
C2A—H2AA	0.959 (17)	C5B—H5BB	0.94 (3)
C3B—C4B	1.521 (2)	C5B—H5BC	1.03 (3)

C5A—S1A—C4A	101.91 (9)	C4A—C3A—H3AB	111.9 (10)
C5B—S1B—C4B	100.32 (10)	C2A—C3A—H3AB	109.5 (10)
C2A—O3A—H3A	108.2 (15)	H3AA—C3A—H3AB	105.0 (15)
C2B—O3B—H3B	110.7 (14)	C3A—C4A—S1A	115.28 (11)
C1A—O2A—H2A	108.0 (12)	C3A—C4A—H4AA	109.3 (11)
C1B—O2B—H2B	109.6 (13)	S1A—C4A—H4AA	103.5 (11)
O3A—C2A—C1A	109.29 (10)	C3A—C4A—H4AB	110.1 (11)
O3A—C2A—C3A	113.39 (11)	S1A—C4A—H4AB	108.8 (11)
C1A—C2A—C3A	108.79 (10)	H4AA—C4A—H4AB	109.5 (16)
O3A—C2A—H2AA	105.3 (10)	C3B—C4B—S1B	113.51 (11)
C1A—C2A—H2AA	108.7 (10)	C3B—C4B—H4BA	109.5 (12)
C3A—C2A—H2AA	111.3 (10)	S1B—C4B—H4BA	104.8 (11)
O1A—C1A—O2A	124.01 (12)	C3B—C4B—H4BB	112.4 (12)
O1A—C1A—C2A	123.28 (11)	S1B—C4B—H4BB	108.6 (12)
O2A—C1A—C2A	112.61 (11)	H4BA—C4B—H4BB	107.6 (17)
C4B—C3B—C2B	112.94 (12)	S1A—C5A—H5AA	111.3 (15)
C4B—C3B—H3BA	110.1 (11)	S1A—C5A—H5AB	104.0 (16)
C2B—C3B—H3BA	107.5 (11)	H5AA—C5A—H5AB	109 (2)
C4B—C3B—H3BB	110.7 (10)	S1A—C5A—H5AC	108.7 (16)
C2B—C3B—H3BB	107.7 (10)	H5AA—C5A—H5AC	112 (2)
H3BA—C3B—H3BB	107.7 (15)	H5AB—C5A—H5AC	112 (2)
O3B—C2B—C1B	110.41 (10)	S1B—C5B—H5BA	113.0 (18)
O3B—C2B—C3B	107.56 (11)	S1B—C5B—H5BB	106.3 (19)
C1B—C2B—C3B	112.52 (11)	H5BA—C5B—H5BB	112 (3)
O3B—C2B—H2BA	109.9 (10)	S1B—C5B—H5BC	105.4 (17)
C1B—C2B—H2BA	106.4 (10)	H5BA—C5B—H5BC	111 (3)
C3B—C2B—H2BA	110.0 (10)	H5BB—C5B—H5BC	108 (2)
C4A—C3A—C2A	111.71 (11)	O1B—C1B—O2B	123.66 (12)
C4A—C3A—H3AA	109.2 (10)	O1B—C1B—C2B	124.04 (12)
C2A—C3A—H3AA	109.3 (10)	O2B—C1B—C2B	112.30 (11)

O3A—C2A—C1A—O1A	27.77 (17)	C2A—C3A—C4A—S1A	164.16 (10)
C3A—C2A—C1A—O1A	−96.52 (15)	C5A—S1A—C4A—C3A	62.16 (15)
O3A—C2A—C1A—O2A	−155.72 (10)	C2B—C3B—C4B—S1B	178.17 (10)
C3A—C2A—C1A—O2A	79.99 (13)	C5B—S1B—C4B—C3B	69.76 (16)
C4B—C3B—C2B—O3B	−59.22 (16)	O3B—C2B—C1B—O1B	−10.81 (19)
C4B—C3B—C2B—C1B	62.59 (16)	C3B—C2B—C1B—O1B	−130.99 (14)
O3A—C2A—C3A—C4A	58.73 (15)	O3B—C2B—C1B—O2B	170.24 (11)
C1A—C2A—C3A—C4A	−179.44 (11)	C3B—C2B—C1B—O2B	50.06 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3A—H3A···O1B	0.736 (19)	2.013 (19)	2.7044 (14)	156.4 (19)
O3B—H3B···O1A	0.77 (2)	2.246 (19)	2.8480 (14)	135.6 (18)
O3B—H3B···O1Aⁱ	0.77 (2)	2.325 (19)	2.9048 (14)	132.9 (18)
O2A—H2A···O3Aⁱⁱ	0.89 (2)	1.71 (2)	2.5995 (14)	172.7 (18)
O2B—H2B···O3Bⁱⁱⁱ	0.86 (2)	1.79 (2)	2.6493 (14)	172.6 (19)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, −y+1/2, z−1/2; (iii) x, −y+3/2, z+1/2.

Selected torsion angles (°) in (I) and related structures top

	C1—C2—C3—C4	C2—C3—C4—S1	C3—C4—S1—C5	O1—C1—C2—O3/N1^b	Ref
(IA)^a	179.4 (1)	-164.2 (1)	-62.2 (2)	-27.8 (2)	This work
(IB)^a	-62.6 (2)	-178.2 (1)	-69.8 (2)	10.8 (2)	This work
Cu(HMTBA)₂ ^a	175.0 (4)	164.9 (3)	63.2 (5)	-14.2 (5)	(Yang et al., 2015)
Zn(HMTBA)₂ : molecule A (S)	-60.6 (7)	-157.5 (4)	-58.8 (6)	3.9 (6)	(Predieri et al., 2009)
molecule B (R)	64.6 (7)	-76.7 (7)	-68.2 (7)	9.5 (6)
molecule C (R)	60.0 (7)	173.4 (5)	66.2 (7)	9.7 (6)
molecule D (S)	-57.7 (9)	-174.7 (6)	-122.9 (8)	-1.3 (7)
L-Met: molecule A	71.8 (3)	171.6 (3)	-178.5 (3)	-16.3 (2)	(Dalhus & Görbitz, 1996)
molecule B	74.1 (3)	71.5 (3)	72.4 (3)	-32.4 (2)
α-DL-Met ^a	-178.0 (2)	176.7 (2)	69.4 (3)	-29.4 (3)	(Görbitz et al., 2014)
β-DL-Met ^a	-173.6 (2)	-179.2 (1)	-175.0 (2)	-32.6 (2)	(Alagar et al., 2005)
L-(+)-lactic acid				7.6 (1)	(Schouten et al., 1994)
glycolic acid: molecule A				-6.16 (2)	(Pijper, 1971)
molecule B				-2.93 (2)

Notes: (a) Signs of the angle values are given for the (S)-enantiomer; (b) N1 in methionine.

Suspected hydrogen bonds (Å, °) top

D—H···A	D—H	H···A	D···A	D—H···A
C2B—H2BA···O2Aⁱ	0.933 (17)	2.630 (17)	3.4068 (16)	141.1 (13)

Symmetry code: (i) x, 1 + y, z.

Contributions (%) of intermolecular atom–atom contacts to the Hirshfeld surface in (I) and related structures top

	Backbone rotamer ^a	H···H	S···H	O···H	Other
HMTBA					O···O;	C···O;	C···H;	S···S
(IA)	ttg-	48.9	14.3	32.3	1.7;	1.7;	0.9;	0.1
(IB)	g-tg-	50.4	18.2	28.5	1.0;	1.7;	0.2;	0.1

					O···O;	C···O;	C···H;	Cu···O
Cu(HMTBA)₂	ttg+	44.0	18.0	25.2	2.9;	1.7;	1.3;	6.9

Zn(HMTBA)₂					O···O;	C···H;	S···S;	Zn···O
molecule A (S)	g-tg-	48.4	18.4	22.0	2.4;	1.1;	0.3;	7.5
molecule B (R)	g+g-g-	49.2	13.9	28.0	0.9;	1.0;	1.0;	4.9
molecule C (R)	g+tg+	48.2	15.7	28.7	0.8;	0.8;	0.3;	5.0

L-Met					O···O;	C···O;	C···H;	C···C
molecule A	g+tt	48.3	14.9	34.7	0.1;	0.6;	0.6;	0.5
molecule B	g+g+g+	46.7	15.1	35.6	0.5;	0.6;	0.6;	0.5

β-DL-Met	ttt	48.7	14.6	35.6	0.3;	0.4;	1.3

Note: (a) Refer to Table 1 for chirality of the molecules and the actual torsion-angle values.

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Crystal structure of (R,S)-2-hy­droxy-4-(methyl­sulfan­yl)butanoic acid

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Crystal structure of (R,S)-2-hydroxy-4-(methylsulfanyl)butanoic acid