l-Me­thio­nine–succinic acid (2/1)

Nageshwari, M.; Kumaresan, S.; Caroline, M.L.; Mani, G.; Kumari, C.R.T.; Sudha, S.; Jayaprakash, P.

doi:10.1107/S2414314615024591

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 1| January 2016| x152459

doi:10.1107/S2414314615024591

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L-Methionine–succinic acid (2/1)

M. Nageshwari,^a S. Kumaresan,^a M. Lydia Caroline,^a ^* G. Mani,^a C. Rathika Thaya Kumari,^a S. Sudha ^a and P. Jayaprakash ^a

^aPG and Research Department of Physics, Arignar Anna Government Arts College, Cheyyar 604 407, Tamil Nadu, India
^*Correspondence e-mail: lydiacaroline2006@yahoo.co.in

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 19 December 2015; accepted 21 December 2015; online 12 January 2016)

The asymmetric unit of the title compound, 2C₅H₁₁NO₂S·C₄H₆O₄, comprises two crystallographically independent methionine residues, which exist in the zwitterionic form, and a neutral succinic acid molecule. Both methionine residues have a gauche-I conformation. In the crystal, the various components are linked via O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds forming slabs parallel to the ab plane

Keywords: crystal structure; L-methionine; succinic acid; hydrogen bonding.

CCDC reference: 1443737

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Chemical scheme

Structure description

Methionine is a sulfur-containing amino acid which is essential for normal metabolism, growth and maintenance of body tissues (Sridhar et al., 2002 ). In conjunction with our ongoing work on nonlinear optical crystals, among the 20 naturally occurring amino acids we have focused our interest towars methionine, which is one of the essential amino acids for humans. In this paper, the crystal structure of the product of the reaction of L-methionine with succinic acid is reported.

The molecular structure of the title compound is represented in Fig. 1. The asymmetric unit contains two methionine residues and a neutral succinic acid molecule. Both methionine residues exhibit a gauche I conformation. The bond distances C5—O6, C5—O5, C10—O7 and C10—O8 are 1.244 (9), 1.248 (9), 1.232 (9) and 1.260 (9) Å, respectively, indicating deprotonated carboxylate groups in each methionine residue. This unsymmetrical unit has bond angles O5—C5—O6 and O8—C10—O7 of 125.6 (7) and 124.7 (7) °, respectively. The backbone torsion angles Ψ1 for the central methionine of O5—C5—C6—N1 and O6—C5—C6—N1 are 4.8 (9) and −176.1 (6)°, respectively. For the end methionine residue, the backbone torsion angles Ψ1 of O7—C10—C11—N2 and O8—C10—C11—N2 are 5.8 (9) and −174.4 (6) °, respectively. The side-chain conformation for both methionine residues is gauche I trans gauche I. All possible rotational isomers are found to exist in the methionine residues (Pandiarajan et al., 2002 ). In both the methionine residues, the straight side-chain conformation angles χ1 are in the gauche I form [70.9 (9) and 67.3 (9)°], χ2 are trans [179.5 (6) and 177.6 (6)°] and χ3 are again gauche I [71.9 (9) and 72.1 (9)°].

Figure 1
The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 40% probability level.

In the crystal, the various components are linked via O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, forming slabs parallel to the ab plane (Table 1 and Fig. 2). There are no direct hydrogen-bonding interactions between the succinic acid molecules. The methionine residues are interlinked through the succinic acid molecules. The crystal packing may be visualized as hydrogen-bonded triple layers, a characteristic feature of α-amino acids with hydrocarbon side chains, stacked in such a way that the hydrophobic side chains of the methionine molecules are facing close to each other with respect to succinic acid (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O5ⁱ	0.82	1.83	2.639 (7)	168
O4—H4⋯O7ⁱⁱ	0.82	1.84	2.647 (7)	169
N1—H1C⋯O1ⁱⁱⁱ	0.90 (3)	2.59 (8)	3.133 (9)	120 (7)
N1—H1C⋯O2^iv	0.90 (3)	2.09 (7)	2.842 (8)	140 (9)
N1—H1A⋯O5ⁱⁱⁱ	0.90 (3)	2.47 (8)	3.168 (8)	135 (9)
N1—H1A⋯O6ⁱⁱⁱ	0.90 (3)	2.01 (4)	2.866 (8)	160 (10)
N1—H1B⋯O6^iv	0.90 (3)	2.03 (5)	2.897 (8)	161 (10)
N2—H2C⋯O3^v	0.89	2.07	2.849 (8)	146
N2—H2D⋯O8^vi	0.89	2.07	2.904 (8)	156
N2—H2E⋯O7^vii	0.89	2.45	3.169 (8)	139
N2—H2E⋯O8^vii	0.89	2.01	2.875 (8)	163
C6—H6⋯O5^viii	0.98	2.26	3.206 (9)	162
C11—H11⋯O7ⁱ	0.98	2.28	3.210 (9)	159
C12—H12B⋯O8^vii	0.97	2.65	3.415 (10)	136
Symmetry codes: (i) x, y-1, z; (ii) x-1, y-1, z+1; (iii) x-1, y+1, z; (iv) x, y+1, z; (v) x+1, y+1, z-1; (vi) x+1, y, z; (vii) x+1, y-1, z; (viii) x-1, y, z.

Figure 2
The crystal packing of the title compound, viewed along the a axis. The hydrogen bonds are shown as dashed lines (see Table 1

for details).

Synthesis and crystallization

Colourless transparent single crystals of the title compound were obtained by slow evaporation of an aqueous solution of L-methionine and succinic acid, in a stoichiometric ratio of 2:1, over a period of 20 days.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	2C₅H₁₁NO₂S·C₄H₆O₄
M_r	416.50
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.0283 (4), 5.0580 (4), 20.8394 (18)
α, β, γ (°)	86.645 (2), 83.338 (3), 68.908 (5)
V (Å³)	491.08 (7)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.31
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.873, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	8433, 3428, 3251
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.171, 1.11
No. of reflections	3428
No. of parameters	244
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.38
Absolute structure	Flack x determined using 1325 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.06 (4)
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), XPREP (Bruker, 2004), SIR92 (Altomare et al., 1994 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1443737

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2414314615024591/su4005sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314615024591/su4005Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314615024591/su4005Isup3.cml

checkCIF report

Experimental top

Structure description top

Methionine is a sulfur-containing amino acid which is essential for normal metabolism, growth and maintenance of body tissues (Sridhar et al., 2002). In conjunction with our ongoing work on nonlinear optical crystals, among the 20 naturally occurring amino acids we have focused our interest towards methionine, which is one of the essential amino acids for humans. In this paper, the crystal structure of the product of the reaction of L-methionine with succinic acid is reported.

The molecular structure of the title compound is represented in Fig. 1. The asymmetric unit contains two methionine residues and a neutral succinic acid molecule. Both methionine residues exhibit a gauche I conformation. The bond distances C5—O6, C5—O5, C10—O7 and C10—O8 are 1.244 (9), 1.248 (9), 1.232 (9) and 1.260 (9) Å, respectively, indicating a deprotonated carboxylate groups in the methionine residue. This unsymmetrical unit has bond angles O5—C5—O6 and O8—C10—O7 of 125.6 (7) and 124.7 (7) °, respectively. The backbone torsion angles Ψ1 for the central methionine of O5—C5—C6—N1 and O6—C5—C6—N1 are 4.8 (9) and −176.1 (6)°, respectively. For the end methionine residue, the backbone torsion angles Ψ1 of O7—C10—C11—N2 and O8—C10—C11—N2 are 5.8 (9) and −174.4 (6) °, respectively. The side-chain conformation for both methionine residues is gauche I trans gauche I. All possible rotational isomers are found to exist in the methionine residues (Pandiarajan et al., 2002). In both the methionine residues, the straight side chain conformation angles χ1 are in the gauche I form [70.9 (9) and 67.3 (9) °], while χ2 are in the trans form [179.5 (6) and 177.6 (6) °] and χ3 are in gauche I form [71.9 (9) and 72.1 (9)°].

In the crystal, the various components are linked via O—H···O, N—H···O and C—H···O hydrogen bonds, forming slabs parallel to the ab plane (Table 1 and Fig. 2). There are no direct hydrogen-bonding interactions between the succinic acid molecules. The methionine residues are interlinked through the succinic acid molecules. The crystal packing may be visualized as hydrogen-bonded triple layers, a characteristic feature of α amino acids having hydrocarbon side chains, stacked in such a way that the hydrophobic side chains of the methionine molecules are facing close to each other with respect to succinic acid (Fig. 2).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis. The hydrogen bonds are shown as dashed lines (see Table 1 for details).

L-Methionine–succinic acid (2/1) top

Crystal data top

2C₅H₁₁NO₂S·C₄H₆O₄	Z = 1
M_r = 416.50	F(000) = 222
Triclinic, P1	D_x = 1.408 Mg m⁻³
a = 5.0283 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.0580 (4) Å	Cell parameters from 5997 reflections
c = 20.8394 (18) Å	θ = 3.0–28.3°
α = 86.645 (2)°	µ = 0.31 mm⁻¹
β = 83.338 (3)°	T = 293 K
γ = 68.908 (5)°	Block, colourless
V = 491.08 (7) Å³	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	3428 independent reflections
Radiation source: fine-focus sealed tube	3251 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω and φ scan	θ_max = 26.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −6→6
T_min = 0.873, T_max = 0.956	k = −6→5
8433 measured reflections	l = −25→25

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.171	w = 1/[σ²(F_o²) + (0.048P)² + 1.4388P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
3428 reflections	Δρ_max = 0.56 e Å⁻³
244 parameters	Δρ_min = −0.38 e Å⁻³
9 restraints	Absolute structure: Flack x determined using 1325 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (4)

Crystal data top

2C₅H₁₁NO₂S·C₄H₆O₄	γ = 68.908 (5)°
M_r = 416.50	V = 491.08 (7) Å³
Triclinic, P1	Z = 1
a = 5.0283 (4) Å	Mo Kα radiation
b = 5.0580 (4) Å	µ = 0.31 mm⁻¹
c = 20.8394 (18) Å	T = 293 K
α = 86.645 (2)°	0.35 × 0.30 × 0.25 mm
β = 83.338 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3428 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	3251 reflections with I > 2σ(I)
T_min = 0.873, T_max = 0.956	R_int = 0.035
8433 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.171	Δρ_max = 0.56 e Å⁻³
S = 1.11	Δρ_min = −0.38 e Å⁻³
3428 reflections	Absolute structure: Flack x determined using 1325 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
244 parameters	Absolute structure parameter: 0.06 (4)
9 restraints

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.

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

	x	y	z	U_iso*/U_eq
C1	−0.0929 (15)	−0.3017 (17)	1.2684 (3)	0.0267 (16)
C2	0.0926 (16)	−0.1994 (15)	1.2208 (4)	0.0278 (16)
H2A	0.1576	−0.0710	1.2419	0.033*
H2B	−0.0187	−0.0941	1.1866	0.033*
C3	0.3501 (15)	−0.4389 (17)	1.1917 (4)	0.0294 (17)
H3A	0.4878	−0.3610	1.1701	0.035*
H3B	0.4404	−0.5647	1.2262	0.035*
C4	0.2765 (16)	−0.6065 (15)	1.1445 (3)	0.0256 (15)
C5	0.2712 (15)	−0.2155 (15)	0.9996 (3)	0.0238 (15)
C6	−0.0208 (14)	−0.0051 (14)	0.9834 (4)	0.0239 (15)
H6	−0.1672	−0.0747	1.0051	0.029*
C7	−0.0529 (17)	0.0129 (17)	0.9119 (4)	0.0340 (18)
H7A	−0.0575	−0.1664	0.8990	0.041*
H7B	−0.2363	0.1576	0.9048	0.041*
C8	0.177 (2)	0.079 (2)	0.8687 (4)	0.050 (2)
H8A	0.3612	−0.0645	0.8758	0.060*
H8B	0.1809	0.2597	0.8811	0.060*
C9	−0.165 (3)	0.420 (3)	0.7771 (6)	0.082 (4)
H9A	−0.2084	0.4513	0.7330	0.122*
H9B	−0.3287	0.4079	0.8041	0.122*
H9C	−0.1182	0.5748	0.7906	0.122*
C10	0.2140 (15)	0.6224 (16)	0.4123 (4)	0.0259 (16)
C11	0.4113 (15)	0.3242 (15)	0.4278 (4)	0.0254 (15)
H11	0.3531	0.1939	0.4047	0.030*
C12	0.3860 (17)	0.2466 (18)	0.4989 (4)	0.0353 (18)
H12A	0.1932	0.2486	0.5112	0.042*
H12B	0.5166	0.0540	0.5049	0.042*
C13	0.447 (2)	0.433 (2)	0.5437 (4)	0.045 (2)
H13A	0.3217	0.6271	0.5365	0.054*
H13B	0.6424	0.4248	0.5327	0.054*
C14	0.709 (3)	0.027 (3)	0.6336 (7)	0.072 (4)
H14A	0.7119	−0.0447	0.6773	0.108*
H14B	0.6967	−0.1123	0.6057	0.108*
H14C	0.8805	0.0655	0.6206	0.108*
N1	−0.0777 (13)	0.2796 (12)	1.0094 (3)	0.0280 (14)
N2	0.7110 (12)	0.2804 (13)	0.4033 (3)	0.0263 (13)
H2C	0.7204	0.3274	0.3615	0.039*
H2D	0.7744	0.3884	0.4250	0.039*
H2E	0.8190	0.0991	0.4086	0.039*
O1	0.4981 (11)	−0.8243 (12)	1.1218 (3)	0.0378 (14)
H1	0.4469	−0.9096	1.0963	0.057*
O2	0.0410 (11)	−0.5487 (13)	1.1270 (3)	0.0389 (14)
O3	−0.0496 (12)	−0.5422 (12)	1.2855 (3)	0.0370 (13)
O4	−0.3294 (11)	−0.0864 (11)	1.2910 (3)	0.0364 (13)
H4	−0.4281	−0.1485	1.3172	0.055*
O5	0.4115 (11)	−0.1349 (11)	1.0347 (3)	0.0343 (13)
O6	0.3459 (11)	−0.4561 (11)	0.9767 (3)	0.0338 (12)
O7	0.3106 (11)	0.7815 (11)	0.3784 (3)	0.0332 (13)
O8	−0.0432 (11)	0.6879 (11)	0.4360 (3)	0.0338 (12)
S1	0.1337 (7)	0.0957 (6)	0.78374 (14)	0.0737 (10)
S2	0.4020 (6)	0.3478 (6)	0.62834 (14)	0.0685 (9)
H1C	−0.08 (2)	0.28 (2)	1.0528 (13)	0.082*
H1A	−0.245 (11)	0.40 (2)	0.997 (4)	0.082*
H1B	0.065 (15)	0.34 (2)	0.992 (4)	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.019 (4)	0.031 (5)	0.030 (4)	−0.009 (3)	−0.005 (3)	−0.004 (3)
C2	0.027 (4)	0.019 (4)	0.037 (4)	−0.008 (3)	−0.003 (3)	−0.001 (3)
C3	0.020 (4)	0.040 (5)	0.034 (4)	−0.017 (4)	−0.001 (3)	−0.001 (3)
C4	0.023 (4)	0.022 (4)	0.032 (4)	−0.008 (3)	0.000 (3)	−0.001 (3)
C5	0.021 (4)	0.017 (4)	0.033 (4)	−0.006 (3)	−0.003 (3)	0.003 (3)
C6	0.015 (3)	0.016 (4)	0.041 (4)	−0.007 (3)	0.000 (3)	−0.003 (3)
C7	0.028 (4)	0.023 (4)	0.052 (5)	−0.008 (3)	−0.015 (3)	−0.004 (3)
C8	0.051 (6)	0.051 (6)	0.041 (5)	−0.009 (5)	−0.006 (4)	−0.001 (4)
C9	0.109 (12)	0.081 (10)	0.056 (8)	−0.032 (9)	−0.031 (7)	0.019 (6)
C10	0.015 (3)	0.033 (4)	0.032 (4)	−0.009 (3)	−0.004 (3)	−0.007 (3)
C11	0.015 (3)	0.018 (4)	0.045 (4)	−0.007 (3)	−0.002 (3)	−0.005 (3)
C12	0.022 (4)	0.025 (4)	0.054 (5)	−0.005 (3)	−0.001 (3)	0.005 (3)
C13	0.055 (6)	0.038 (5)	0.040 (5)	−0.014 (5)	−0.003 (4)	0.000 (4)
C14	0.065 (8)	0.049 (7)	0.090 (9)	−0.001 (6)	−0.031 (7)	0.022 (6)
N1	0.025 (3)	0.010 (3)	0.045 (4)	0.000 (3)	−0.007 (3)	−0.005 (2)
N2	0.017 (3)	0.017 (3)	0.041 (3)	−0.001 (3)	−0.002 (2)	0.001 (3)
O1	0.023 (3)	0.031 (3)	0.058 (4)	−0.006 (3)	−0.004 (2)	−0.015 (3)
O2	0.020 (3)	0.045 (4)	0.050 (3)	−0.007 (3)	−0.005 (2)	−0.015 (3)
O3	0.034 (3)	0.022 (3)	0.050 (3)	−0.009 (3)	0.008 (3)	−0.001 (2)
O4	0.026 (3)	0.022 (3)	0.055 (4)	−0.005 (3)	0.007 (2)	−0.002 (2)
O5	0.024 (3)	0.020 (3)	0.059 (3)	−0.005 (2)	−0.014 (2)	−0.005 (2)
O6	0.024 (3)	0.017 (3)	0.055 (3)	0.001 (2)	−0.008 (2)	−0.006 (2)
O7	0.022 (3)	0.016 (3)	0.058 (3)	−0.004 (2)	0.000 (2)	0.005 (2)
O8	0.016 (3)	0.028 (3)	0.053 (3)	−0.003 (2)	−0.001 (2)	0.003 (2)
S1	0.098 (2)	0.075 (2)	0.0378 (14)	−0.0181 (19)	−0.0056 (14)	−0.0013 (12)
S2	0.075 (2)	0.080 (2)	0.0399 (14)	−0.0173 (17)	−0.0014 (12)	0.0058 (13)

Geometric parameters (Å, º) top

C1—O3	1.196 (9)	C9—H9C	0.9600
C1—O4	1.349 (9)	C10—O7	1.232 (9)
C1—C2	1.480 (10)	C10—O8	1.260 (9)
C2—C3	1.512 (10)	C10—C11	1.518 (10)
C2—H2A	0.9700	C11—N2	1.475 (9)
C2—H2B	0.9700	C11—C12	1.513 (11)
C3—C4	1.494 (10)	C11—H11	0.9800
C3—H3A	0.9700	C12—C13	1.496 (13)
C3—H3B	0.9700	C12—H12A	0.9700
C4—O2	1.208 (9)	C12—H12B	0.9700
C4—O1	1.317 (9)	C13—S2	1.798 (9)
C5—O6	1.244 (9)	C13—H13A	0.9700
C5—O5	1.248 (9)	C13—H13B	0.9700
C5—C6	1.533 (10)	C14—S2	1.801 (12)
C6—N1	1.486 (9)	C14—H14A	0.9600
C6—C7	1.511 (11)	C14—H14B	0.9600
C6—H6	0.9800	C14—H14C	0.9600
C7—C8	1.505 (13)	N1—H1C	0.90 (3)
C7—H7A	0.9700	N1—H1A	0.90 (3)
C7—H7B	0.9700	N1—H1B	0.90 (3)
C8—S1	1.802 (9)	N2—H2C	0.8900
C8—H8A	0.9700	N2—H2D	0.8900
C8—H8B	0.9700	N2—H2E	0.8900
C9—S1	1.793 (15)	O1—H1	0.8200
C9—H9A	0.9600	O4—H4	0.8200
C9—H9B	0.9600

O3—C1—O4	122.1 (7)	H9B—C9—H9C	109.5
O3—C1—C2	126.5 (7)	O7—C10—O8	124.7 (7)
O4—C1—C2	111.4 (7)	O7—C10—C11	119.5 (6)
C1—C2—C3	112.4 (6)	O8—C10—C11	115.8 (6)
C1—C2—H2A	109.1	N2—C11—C12	111.2 (6)
C3—C2—H2A	109.1	N2—C11—C10	111.1 (6)
C1—C2—H2B	109.1	C12—C11—C10	113.1 (6)
C3—C2—H2B	109.1	N2—C11—H11	107.1
H2A—C2—H2B	107.9	C12—C11—H11	107.1
C4—C3—C2	113.2 (6)	C10—C11—H11	107.1
C4—C3—H3A	108.9	C13—C12—C11	115.9 (7)
C2—C3—H3A	108.9	C13—C12—H12A	108.3
C4—C3—H3B	108.9	C11—C12—H12A	108.3
C2—C3—H3B	108.9	C13—C12—H12B	108.3
H3A—C3—H3B	107.8	C11—C12—H12B	108.3
O2—C4—O1	122.2 (7)	H12A—C12—H12B	107.4
O2—C4—C3	124.6 (7)	C12—C13—S2	115.5 (6)
O1—C4—C3	113.2 (6)	C12—C13—H13A	108.4
O6—C5—O5	125.6 (7)	S2—C13—H13A	108.4
O6—C5—C6	116.1 (6)	C12—C13—H13B	108.4
O5—C5—C6	118.3 (6)	S2—C13—H13B	108.4
N1—C6—C7	111.0 (6)	H13A—C13—H13B	107.5
N1—C6—C5	111.2 (6)	S2—C14—H14A	109.5
C7—C6—C5	112.6 (6)	S2—C14—H14B	109.5
N1—C6—H6	107.2	H14A—C14—H14B	109.5
C7—C6—H6	107.2	S2—C14—H14C	109.5
C5—C6—H6	107.2	H14A—C14—H14C	109.5
C8—C7—C6	115.7 (6)	H14B—C14—H14C	109.5
C8—C7—H7A	108.4	C6—N1—H1C	112 (7)
C6—C7—H7A	108.4	C6—N1—H1A	109 (8)
C8—C7—H7B	108.4	H1C—N1—H1A	109 (4)
C6—C7—H7B	108.4	C6—N1—H1B	107 (7)
H7A—C7—H7B	107.4	H1C—N1—H1B	110 (4)
C7—C8—S1	114.5 (7)	H1A—N1—H1B	110 (4)
C7—C8—H8A	108.6	C11—N2—H2C	109.5
S1—C8—H8A	108.6	C11—N2—H2D	109.5
C7—C8—H8B	108.6	H2C—N2—H2D	109.5
S1—C8—H8B	108.6	C11—N2—H2E	109.5
H8A—C8—H8B	107.6	H2C—N2—H2E	109.5
S1—C9—H9A	109.5	H2D—N2—H2E	109.5
S1—C9—H9B	109.5	C4—O1—H1	109.5
H9A—C9—H9B	109.5	C1—O4—H4	109.5
S1—C9—H9C	109.5	C9—S1—C8	102.1 (5)
H9A—C9—H9C	109.5	C13—S2—C14	100.4 (6)

O3—C1—C2—C3	2.7 (10)	C6—C7—C8—S1	179.5 (6)
O4—C1—C2—C3	−176.5 (6)	O7—C10—C11—N2	5.8 (9)
C1—C2—C3—C4	73.3 (8)	O8—C10—C11—N2	−174.4 (6)
C2—C3—C4—O2	5.1 (11)	O7—C10—C11—C12	131.6 (7)
C2—C3—C4—O1	−176.5 (6)	O8—C10—C11—C12	−48.6 (8)
O6—C5—C6—N1	−176.1 (6)	N2—C11—C12—C13	67.3 (9)
O5—C5—C6—N1	4.8 (9)	C10—C11—C12—C13	−58.5 (9)
O6—C5—C6—C7	−50.7 (9)	C11—C12—C13—S2	177.6 (6)
O5—C5—C6—C7	130.2 (7)	C7—C8—S1—C9	71.9 (9)
N1—C6—C7—C8	70.9 (9)	C12—C13—S2—C14	72.1 (9)
C5—C6—C7—C8	−54.5 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5ⁱ	0.82	1.83	2.639 (7)	168
O4—H4···O7ⁱⁱ	0.82	1.84	2.647 (7)	169
N1—H1C···O1ⁱⁱⁱ	0.90 (3)	2.59 (8)	3.133 (9)	120 (7)
N1—H1C···O2^iv	0.90 (3)	2.09 (7)	2.842 (8)	140 (9)
N1—H1A···O5ⁱⁱⁱ	0.90 (3)	2.47 (8)	3.168 (8)	135 (9)
N1—H1A···O6ⁱⁱⁱ	0.90 (3)	2.01 (4)	2.866 (8)	160 (10)
N1—H1B···O6^iv	0.90 (3)	2.03 (5)	2.897 (8)	161 (10)
N2—H2C···O3^v	0.89	2.07	2.849 (8)	146
N2—H2D···O8^vi	0.89	2.07	2.904 (8)	156
N2—H2E···O7^vii	0.89	2.45	3.169 (8)	139
N2—H2E···O8^vii	0.89	2.01	2.875 (8)	163
C6—H6···O5^viii	0.98	2.26	3.206 (9)	162
C11—H11···O7ⁱ	0.98	2.28	3.210 (9)	159
C12—H12B···O8^vii	0.97	2.65	3.415 (10)	136

Symmetry codes: (i) x, y−1, z; (ii) x−1, y−1, z+1; (iii) x−1, y+1, z; (iv) x, y+1, z; (v) x+1, y+1, z−1; (vi) x+1, y, z; (vii) x+1, y−1, z; (viii) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5ⁱ	0.82	1.83	2.639 (7)	168
O4—H4···O7ⁱⁱ	0.82	1.84	2.647 (7)	169
N1—H1C···O1ⁱⁱⁱ	0.90 (3)	2.59 (8)	3.133 (9)	120 (7)
N1—H1C···O2^iv	0.90 (3)	2.09 (7)	2.842 (8)	140 (9)
N1—H1A···O5ⁱⁱⁱ	0.90 (3)	2.47 (8)	3.168 (8)	135 (9)
N1—H1A···O6ⁱⁱⁱ	0.90 (3)	2.01 (4)	2.866 (8)	160 (10)
N1—H1B···O6^iv	0.90 (3)	2.03 (5)	2.897 (8)	161 (10)
N2—H2C···O3^v	0.89	2.07	2.849 (8)	146
N2—H2D···O8^vi	0.89	2.07	2.904 (8)	156
N2—H2E···O7^vii	0.89	2.45	3.169 (8)	139
N2—H2E···O8^vii	0.89	2.01	2.875 (8)	163
C6—H6···O5^viii	0.98	2.26	3.206 (9)	162
C11—H11···O7ⁱ	0.98	2.28	3.210 (9)	159
C12—H12B···O8^vii	0.97	2.65	3.415 (10)	136

Symmetry codes: (i) x, y−1, z; (ii) x−1, y−1, z+1; (iii) x−1, y+1, z; (iv) x, y+1, z; (v) x+1, y+1, z−1; (vi) x+1, y, z; (vii) x+1, y−1, z; (viii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	2C₅H₁₁NO₂S·C₄H₆O₄
M_r	416.50
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.0283 (4), 5.0580 (4), 20.8394 (18)
α, β, γ (°)	86.645 (2), 83.338 (3), 68.908 (5)
V (Å³)	491.08 (7)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.873, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	8433, 3428, 3251
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.171, 1.11
No. of reflections	3428
No. of parameters	244
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.38
Absolute structure	Flack x determined using 1325 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Absolute structure parameter	0.06 (4)

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1994), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008).

Acknowledgements

The authors thank the Sophisticated Analytical Instruments facility, Indian Institute of Technology IITM, Chennai, for providing scientific support in solving the crystal structure. The authors personally thank Professor Subramanian (Retired) Professor of Chemistry, Pachayappa's College, Kanchipuram, Tamilnadu, for his valuable suggestions.

References

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