l-Glutaminium 4-methyl­benzene­sulfonate

Thayanithi, V.; Kumar, P.P.; Gunasekaran, B.

doi:10.1107/S2414314617001626

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170162

https://doi.org/10.1107/S2414314617001626

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L-Glutaminium 4-methylbenzenesulfonate

V. Thayanithi,^a P. Praveen Kumar ^a ^* and B. Gunasekaran ^b ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, Tamil Nadu, India, and ^bDepartment of Physics & Nano Technology, SRM University, SRM Nagar, Kattankulathur, Kancheepuram Dist, Chennai 603 203 Tamil Nadu, India
^*Correspondence e-mail: ppkpresidency@gmail.com, phdguna@gmail.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 29 December 2016; accepted 31 January 2017; online 14 February 2017)

The asymmetric unit of the title salt, C₅H₁₀NO₄⁺·C₇H₇O₃S⁻, contains two glutaminium cations and two 4-methylbenzenesulfonate anions. The crystal packing features weak intermolecular C—H⋯O, O—H⋯O and N—H⋯O hydrogen bonds.

Keywords: crystal structure; glutaminium; neurotransmitter; central nervous system; methylbenzenesulfonate; cerebral ischemia.

CCDC reference: 1530383

Structure description

Glutamic acid is a proteinogenic and non-essential amino acid which acts as a neurotransmitter and is essential in the pathology of neurological and psychiatric disorders (Haxhiu et al., 2000 ; Liu et al., 2016 ). Glutamate (L-Glu) is the main excitatory transmitter within the mammalian central nervous system (Tamborini et al., 2016 ). L-Glutamate plays an important role in chronic neurodegenerative and acute diseases such as cerebral ischemia, traumatic brain injury, spinal injury and epilepsy (Hynd et al., 2004 ).

The asymmetric unit of the title compound comprises two glutaminium cations and two 4-methylbenzenesulfonate anions (Fig. 1). The geometric parameters of the title compound agree well with those reported for a similar structure (Thayanithi et al., 2016 ). The crystal packing is controlled by weak intermolecular C—H⋯O, O—H⋯O and N—H⋯O hydrogen bonds (Table 1, Fig. 2), forming a three-dimensional structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O6	0.86 (1)	2.46 (3)	2.7527 (17)	100 (2)
C2—H2⋯O2	0.93	2.49	2.864 (2)	104
C18—H18⋯O9	0.93	2.53	2.904 (2)	104
N1—H1B⋯O2ⁱ	0.87 (2)	2.01 (2)	2.8301 (16)	157 (2)
N2—H2B⋯O8ⁱⁱ	0.86 (1)	2.00 (1)	2.8524 (17)	170 (2)
O7—H7⋯O1ⁱⁱⁱ	0.82 (1)	1.84 (1)	2.6592 (16)	176 (3)
C6—H6⋯O6^iv	0.93	2.55	3.316 (2)	140
N2—H2C⋯O14	0.86 (1)	2.50 (2)	2.7803 (18)	100 (2)
N1—H1C⋯O3^v	0.86 (1)	2.07 (1)	2.8969 (18)	160 (2)
N2—H2C⋯O9^vi	0.86 (1)	2.18 (2)	2.9369 (18)	147 (2)
N1—H1A⋯O1^vii	0.88 (2)	2.05 (2)	2.9150 (16)	167 (2)
N2—H2A⋯O10^viii	0.87 (1)	2.11 (2)	2.8947 (17)	150 (2)
Symmetry codes: (i) x-1, y, z; (ii) x+1, y+1, z; (iii) x, y-1, z; (iv) x, y+1, z; (v) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (vi) $[-x+2, y+{\script{1\over 2}}, -z+2]$ ; (vii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (viii) $[-x+1, y+{\script{1\over 2}}, -z+2]$ .

Figure 1
The asymmetric unit of the title compound, showing atom labels and 30% probability displacement ellipsoids for non-H atoms.

Figure 2
The packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.

Synthesis and crystallization

The title compound was synthesized by dissolving L-Glutamic acid (0.1 mmol) and p-toluene sulfonic acid monohydrate (0.1 mmol) in 30 ml of deionized water. The solution was stirred for 4 h, filtered into a beaker and kept dust free. Colourless block-shaped crystals were obtained from the mother solution in 93% yield.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₅H₁₀NO₄⁺·C₇H₇O₃S⁻
M_r	319.33
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	295
a, b, c (Å)	5.4540 (3), 8.8013 (5), 30.2297 (18)
β (°)	92.835 (1)
V (Å³)	1449.32 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.26
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.956, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	22234, 9991, 8841
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.769

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.092, 1.03
No. of reflections	9991
No. of parameters	414
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.29
Absolute structure	Flack (1983 ), 4563 Friedel pairs
Absolute structure parameter	0.01 (4)
Computer programs: APEX2 (Bruker, 2008 ), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1530383

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617001626/bt4036sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617001626/bt4036Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617001626/bt4036Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

L-Glutaminium 4-methylbenzenesulfonate top

Crystal data top

C₅H₁₀NO₄⁺·C₇H₇O₃S⁻	F(000) = 672
M_r = 319.33	D_x = 1.463 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5436 reflections
a = 5.4540 (3) Å	θ = 0.7–33.1°
b = 8.8013 (5) Å	µ = 0.26 mm⁻¹
c = 30.2297 (18) Å	T = 295 K
β = 92.835 (1)°	Block, colourless
V = 1449.32 (14) Å³	0.25 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	9991 independent reflections
Radiation source: fine-focus sealed tube	8841 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 0 pixels mm^-1	θ_max = 33.1°, θ_min = 0.7°
ω and φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→13
T_min = 0.956, T_max = 0.975	l = −44→45
22234 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0469P)² + 0.186P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.003
9991 reflections	Δρ_max = 0.35 e Å⁻³
414 parameters	Δρ_min = −0.29 e Å⁻³
9 restraints	Absolute structure: Flack (1983), 4563 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (4)

Special details top

Refinement. H atoms were positioned geometrically and refined using riding model with C—H = 0.97 Å and U_iso(H) = 1.2Ueq(C) for CH₂, C—H = 0.96 Å and U_iso(H) = 1.5Ueq(C) for CH₃, C—H = 0.98 Å and U_iso(H) = 1.2Ueq(C) for C—H, C—H = 0.93 Å and U_iso(H) = 1.2Ueq(C) for aromatic C—H.

One hydroxyl H atom was freely refined with the O—H distance restrained to 0.82 (1) Å, the remaining three using a riding model with O—H = 0.82 Å and U_iso(H) = 1.5Ueq(O). The displacement parameter of one riding H atom was refined.

H atoms bonded to N were freely refined with the N—H distances restrained to 0.86 (2) Å.

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

	x	y	z	U_iso*/U_eq
S1	0.51194 (6)	0.76994 (3)	0.554874 (11)	0.02313 (7)
O1	0.6281 (2)	0.91527 (13)	0.54506 (4)	0.0359 (3)
O2	0.6862 (2)	0.64604 (13)	0.55531 (4)	0.0373 (3)
O3	0.2927 (2)	0.74121 (15)	0.52729 (4)	0.0388 (3)
O6	0.1221 (2)	0.13029 (13)	0.54256 (4)	0.0357 (3)
O7	0.4978 (2)	0.19277 (13)	0.56959 (5)	0.0347 (2)
O4	0.2597 (3)	0.3680 (3)	0.72528 (4)	0.0665 (5)
H4	0.1858	0.3789	0.7480	0.100*
O5	−0.0963 (3)	0.4398 (2)	0.69465 (4)	0.0541 (4)
N1	0.0337 (2)	0.43370 (15)	0.52645 (4)	0.0244 (2)
C10	0.0652 (3)	0.40515 (18)	0.60781 (5)	0.0281 (3)
H10A	0.0238	0.5114	0.6117	0.034*
H10B	−0.0868	0.3478	0.6057	0.034*
C9	0.1981 (2)	0.38670 (14)	0.56476 (4)	0.0199 (2)
H9	0.3463	0.4499	0.5659	0.024*
C1	0.4162 (3)	0.78387 (17)	0.60965 (5)	0.0250 (3)
C8	0.2681 (3)	0.22182 (15)	0.55723 (4)	0.0217 (2)
C4	0.2677 (4)	0.7993 (2)	0.69645 (6)	0.0445 (4)
C2	0.5542 (3)	0.7157 (2)	0.64356 (6)	0.0426 (4)
H2	0.6975	0.6640	0.6376	0.051*
C12	0.1120 (3)	0.3917 (2)	0.69141 (5)	0.0369 (4)
C5	0.1322 (4)	0.8685 (2)	0.66220 (7)	0.0459 (4)
H5	−0.0092	0.9218	0.6685	0.055*
C6	0.2021 (3)	0.8605 (2)	0.61848 (6)	0.0370 (4)
H6	0.1070	0.9056	0.5957	0.044*
C11	0.2190 (3)	0.3513 (2)	0.64802 (5)	0.0370 (4)
H11A	0.2368	0.2418	0.6464	0.044*
H11B	0.3815	0.3956	0.6472	0.044*
C3	0.4782 (4)	0.7246 (3)	0.68669 (6)	0.0544 (5)
H3	0.5726	0.6788	0.7094	0.065*
C7	0.1889 (6)	0.8037 (4)	0.74348 (7)	0.0708 (7)
H7A	0.3014	0.7453	0.7620	0.106*
H7B	0.0270	0.7616	0.7447	0.106*
H7C	0.1879	0.9070	0.7537	0.106*
H7	0.532 (5)	0.1074 (16)	0.5614 (9)	0.069 (9)*
H1C	−0.074 (4)	0.368 (2)	0.5168 (8)	0.056 (7)*
H1B	−0.048 (4)	0.516 (2)	0.5314 (7)	0.040 (6)*
H1A	0.120 (3)	0.438 (3)	0.5027 (6)	0.043 (6)*
S2	0.47952 (6)	−0.07804 (4)	0.944471 (11)	0.02329 (7)
O13	0.4998 (2)	0.34191 (13)	0.94161 (4)	0.0325 (2)
H13	0.4630	0.2548	0.9483	0.060 (8)*
O9	0.7071 (2)	−0.13081 (14)	0.96616 (4)	0.0345 (2)
O8	0.2987 (2)	−0.19844 (14)	0.93747 (5)	0.0408 (3)
O14	0.8813 (2)	0.26035 (14)	0.95742 (5)	0.0424 (3)
O10	0.3770 (2)	0.05506 (13)	0.96595 (4)	0.0355 (3)
N2	1.0071 (2)	0.56332 (15)	0.97136 (4)	0.0251 (2)
O11	1.0828 (3)	0.4383 (3)	0.80447 (4)	0.0597 (4)
O12	0.7164 (3)	0.4973 (2)	0.77510 (5)	0.0599 (5)
H12	0.7879	0.4869	0.7521	0.115 (14)*
C21	0.8273 (3)	0.51769 (15)	0.93531 (4)	0.0205 (2)
H21	0.6884	0.5885	0.9340	0.025*
C13	0.5501 (3)	−0.01743 (16)	0.89089 (5)	0.0256 (3)
C20	0.7386 (3)	0.35883 (16)	0.94638 (5)	0.0241 (3)
C22	0.9485 (3)	0.51528 (17)	0.89077 (5)	0.0269 (3)
H22A	1.0358	0.6100	0.8869	0.032*
H22B	1.0670	0.4331	0.8906	0.032*
C23	0.7601 (3)	0.4941 (2)	0.85277 (5)	0.0395 (4)
H23A	0.6608	0.4058	0.8588	0.047*
H23B	0.6523	0.5818	0.8514	0.047*
C24	0.8682 (3)	0.4742 (2)	0.80852 (5)	0.0370 (4)
C14	0.3910 (3)	0.0751 (2)	0.86642 (6)	0.0368 (3)
H14	0.2494	0.1112	0.8788	0.044*
C18	0.7653 (3)	−0.0665 (2)	0.87305 (6)	0.0380 (3)
H18	0.8775	−0.1248	0.8899	0.046*
C16	0.6499 (4)	0.0616 (2)	0.80408 (6)	0.0404 (4)
C15	0.4420 (4)	0.1144 (2)	0.82343 (6)	0.0438 (4)
H15	0.3341	0.1776	0.8073	0.053*
C17	0.8114 (4)	−0.0275 (3)	0.82973 (6)	0.0470 (5)
H17	0.9545	−0.0621	0.8176	0.056*
C19	0.6998 (5)	0.1001 (3)	0.75667 (7)	0.0622 (6)
H19A	0.6648	0.0133	0.7382	0.093*
H19B	0.8691	0.1281	0.7548	0.093*
H19C	0.5972	0.1835	0.7469	0.093*
H2C	1.114 (3)	0.496 (2)	0.9792 (8)	0.051 (7)*
H2B	1.101 (4)	0.637 (2)	0.9645 (8)	0.058 (7)*
H2A	0.937 (4)	0.576 (3)	0.9961 (5)	0.054 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02595 (16)	0.01870 (14)	0.02521 (16)	0.00330 (12)	0.00599 (12)	−0.00040 (12)
O1	0.0419 (6)	0.0222 (5)	0.0456 (7)	−0.0002 (5)	0.0214 (5)	0.0001 (5)
O2	0.0428 (6)	0.0295 (6)	0.0406 (6)	0.0157 (5)	0.0118 (5)	−0.0005 (5)
O3	0.0410 (6)	0.0429 (7)	0.0316 (6)	0.0009 (5)	−0.0061 (5)	−0.0024 (5)
O6	0.0406 (6)	0.0229 (5)	0.0423 (6)	−0.0007 (5)	−0.0114 (5)	−0.0041 (5)
O7	0.0291 (5)	0.0253 (5)	0.0493 (7)	0.0082 (4)	−0.0030 (5)	−0.0074 (5)
O4	0.0642 (10)	0.1150 (15)	0.0196 (6)	0.0341 (10)	−0.0059 (6)	−0.0049 (7)
O5	0.0538 (8)	0.0846 (11)	0.0241 (6)	0.0257 (8)	0.0052 (5)	0.0033 (7)
N1	0.0299 (6)	0.0234 (5)	0.0197 (5)	0.0069 (5)	0.0005 (4)	0.0019 (5)
C10	0.0332 (7)	0.0324 (7)	0.0186 (6)	0.0081 (6)	0.0019 (5)	−0.0023 (5)
C9	0.0228 (6)	0.0180 (5)	0.0189 (5)	0.0016 (4)	0.0000 (5)	−0.0013 (4)
C1	0.0276 (6)	0.0226 (6)	0.0254 (6)	0.0007 (5)	0.0066 (5)	−0.0004 (5)
C8	0.0293 (6)	0.0183 (5)	0.0175 (5)	0.0026 (5)	0.0011 (5)	0.0003 (4)
C4	0.0560 (11)	0.0462 (10)	0.0325 (8)	−0.0029 (8)	0.0146 (8)	−0.0039 (7)
C2	0.0388 (9)	0.0578 (11)	0.0312 (8)	0.0176 (8)	0.0029 (7)	0.0016 (8)
C12	0.0464 (9)	0.0440 (9)	0.0199 (6)	0.0086 (7)	−0.0010 (6)	0.0000 (6)
C5	0.0456 (10)	0.0503 (10)	0.0438 (10)	0.0121 (8)	0.0215 (8)	−0.0010 (8)
C6	0.0329 (8)	0.0409 (9)	0.0379 (9)	0.0101 (6)	0.0096 (7)	0.0044 (7)
C11	0.0439 (9)	0.0463 (9)	0.0205 (7)	0.0143 (7)	−0.0005 (6)	−0.0018 (6)
C3	0.0629 (13)	0.0717 (14)	0.0284 (8)	0.0182 (11)	0.0001 (8)	0.0041 (9)
C7	0.0957 (19)	0.0847 (19)	0.0346 (10)	−0.0002 (16)	0.0273 (12)	−0.0037 (12)
S2	0.02485 (15)	0.01980 (15)	0.02554 (16)	−0.00294 (12)	0.00467 (12)	0.00029 (12)
O13	0.0313 (5)	0.0265 (5)	0.0398 (6)	−0.0075 (4)	0.0030 (5)	0.0005 (5)
O9	0.0326 (6)	0.0406 (6)	0.0301 (6)	0.0033 (5)	−0.0009 (5)	0.0021 (5)
O8	0.0439 (7)	0.0346 (6)	0.0439 (7)	−0.0192 (5)	0.0029 (6)	0.0038 (5)
O14	0.0424 (7)	0.0277 (5)	0.0557 (8)	−0.0020 (5)	−0.0122 (6)	0.0121 (6)
O10	0.0439 (6)	0.0264 (5)	0.0379 (6)	0.0024 (5)	0.0199 (5)	−0.0007 (5)
N2	0.0313 (6)	0.0243 (5)	0.0194 (5)	−0.0073 (5)	−0.0003 (5)	−0.0022 (4)
O11	0.0579 (9)	0.0969 (13)	0.0246 (6)	0.0214 (9)	0.0033 (6)	−0.0027 (8)
O12	0.0609 (9)	0.0978 (13)	0.0202 (6)	0.0163 (9)	−0.0061 (6)	−0.0025 (7)
C21	0.0261 (6)	0.0183 (5)	0.0167 (5)	−0.0018 (4)	−0.0015 (5)	−0.0003 (4)
C13	0.0288 (7)	0.0227 (6)	0.0256 (7)	−0.0025 (5)	0.0039 (5)	−0.0006 (5)
C20	0.0326 (7)	0.0217 (6)	0.0178 (6)	−0.0042 (5)	−0.0008 (5)	0.0002 (5)
C22	0.0328 (7)	0.0296 (7)	0.0183 (6)	−0.0035 (5)	0.0022 (5)	0.0009 (5)
C23	0.0399 (9)	0.0594 (11)	0.0190 (7)	−0.0061 (8)	−0.0003 (6)	−0.0016 (7)
C24	0.0485 (10)	0.0425 (9)	0.0195 (6)	0.0005 (7)	−0.0018 (7)	−0.0011 (6)
C14	0.0343 (8)	0.0421 (9)	0.0342 (8)	0.0102 (7)	0.0023 (6)	0.0011 (7)
C18	0.0365 (8)	0.0452 (9)	0.0329 (8)	0.0109 (7)	0.0082 (6)	0.0064 (7)
C16	0.0540 (10)	0.0374 (8)	0.0302 (8)	−0.0039 (8)	0.0057 (7)	0.0024 (7)
C15	0.0520 (10)	0.0450 (10)	0.0337 (8)	0.0105 (8)	−0.0030 (8)	0.0086 (8)
C17	0.0456 (10)	0.0625 (12)	0.0339 (9)	0.0077 (9)	0.0132 (8)	0.0030 (9)
C19	0.0857 (17)	0.0677 (15)	0.0342 (10)	0.0071 (13)	0.0117 (10)	0.0102 (10)

Geometric parameters (Å, º) top

S1—O3	1.4460 (12)	S2—O8	1.4558 (12)
S1—O2	1.4461 (11)	S2—O10	1.4637 (12)
S1—O1	1.4642 (12)	S2—C13	1.7657 (15)
S1—C1	1.7650 (14)	O13—C20	1.3115 (18)
O6—C8	1.2021 (18)	O13—H13	0.8200
O7—C8	1.3144 (18)	O14—O14	0.000 (4)
O7—H7	0.816 (10)	O14—C20	1.2012 (19)
O4—C12	1.288 (2)	N2—C21	1.4849 (18)
O4—H4	0.8200	N2—H2C	0.855 (9)
O5—C12	1.221 (2)	N2—H2B	0.858 (7)
N1—C9	1.4877 (17)	N2—H2A	0.866 (10)
N1—H1C	0.863 (10)	O11—C24	1.224 (2)
N1—H1B	0.867 (15)	O12—C24	1.290 (2)
N1—H1A	0.878 (15)	O12—H12	0.8200
C10—C11	1.518 (2)	C21—C20	1.5221 (19)
C10—C9	1.5295 (19)	C21—C22	1.5293 (19)
C10—H10A	0.9700	C21—H21	0.9800
C10—H10B	0.9700	C13—C14	1.378 (2)
C9—C8	1.5205 (18)	C13—C18	1.385 (2)
C9—H9	0.9800	C20—O14	1.2012 (19)
C1—C2	1.379 (2)	C22—C23	1.514 (2)
C1—C6	1.385 (2)	C22—H22A	0.9700
C4—C3	1.368 (3)	C22—H22B	0.9700
C4—C5	1.383 (3)	C23—C24	1.499 (2)
C4—C7	1.506 (3)	C23—H23A	0.9700
C2—C3	1.390 (3)	C23—H23B	0.9700
C2—H2	0.9300	C14—C15	1.386 (2)
C12—C11	1.504 (2)	C14—H14	0.9300
C5—C6	1.395 (3)	C18—C17	1.389 (2)
C5—H5	0.9300	C18—H18	0.9300
C6—H6	0.9300	C16—C15	1.382 (3)
C11—H11A	0.9700	C16—C17	1.387 (3)
C11—H11B	0.9700	C16—C19	1.510 (3)
C3—H3	0.9300	C15—H15	0.9300
C7—H7A	0.9600	C17—H17	0.9300
C7—H7B	0.9600	C19—H19A	0.9600
C7—H7C	0.9600	C19—H19B	0.9600
S2—O9	1.4511 (12)	C19—H19C	0.9600

O3—S1—O2	113.44 (8)	O8—S2—O10	112.10 (7)
O3—S1—O1	112.93 (8)	O9—S2—C13	106.90 (7)
O2—S1—O1	111.71 (7)	O8—S2—C13	105.28 (7)
O3—S1—C1	106.17 (7)	O10—S2—C13	105.70 (7)
O2—S1—C1	105.59 (7)	C20—O13—H13	109.5
O1—S1—C1	106.28 (7)	O14—O14—C20	0 (10)
C8—O7—H7	108.7 (19)	C21—N2—H2C	115.5 (17)
C12—O4—H4	109.5	C21—N2—H2B	114.2 (16)
C9—N1—H1C	117.0 (18)	H2C—N2—H2B	100 (2)
C9—N1—H1B	113.1 (15)	C21—N2—H2A	111.4 (16)
H1C—N1—H1B	106 (2)	H2C—N2—H2A	100 (2)
C9—N1—H1A	108.7 (14)	H2B—N2—H2A	114 (2)
H1C—N1—H1A	98 (2)	C24—O12—H12	109.5
H1B—N1—H1A	114 (2)	N2—C21—C20	107.03 (11)
C11—C10—C9	112.44 (12)	N2—C21—C22	110.56 (11)
C11—C10—H10A	109.1	C20—C21—C22	109.67 (11)
C9—C10—H10A	109.1	N2—C21—H21	109.8
C11—C10—H10B	109.1	C20—C21—H21	109.8
C9—C10—H10B	109.1	C22—C21—H21	109.8
H10A—C10—H10B	107.8	C14—C13—C18	119.89 (15)
N1—C9—C8	107.16 (11)	C14—C13—S2	120.71 (12)
N1—C9—C10	109.87 (11)	C18—C13—S2	119.38 (12)
C8—C9—C10	111.21 (11)	O14—C20—O14	0.00 (15)
N1—C9—H9	109.5	O14—C20—O13	125.09 (14)
C8—C9—H9	109.5	O14—C20—O13	125.09 (14)
C10—C9—H9	109.5	O14—C20—C21	121.01 (14)
C2—C1—C6	120.18 (15)	O14—C20—C21	121.01 (14)
C2—C1—S1	119.42 (12)	O13—C20—C21	113.88 (12)
C6—C1—S1	120.39 (12)	C23—C22—C21	111.28 (13)
O6—C8—O7	125.40 (13)	C23—C22—H22A	109.4
O6—C8—C9	121.88 (13)	C21—C22—H22A	109.4
O7—C8—C9	112.70 (12)	C23—C22—H22B	109.4
C3—C4—C5	118.25 (17)	C21—C22—H22B	109.4
C3—C4—C7	119.8 (2)	H22A—C22—H22B	108.0
C5—C4—C7	121.9 (2)	C24—C23—C22	114.17 (15)
C1—C2—C3	119.73 (16)	C24—C23—H23A	108.7
C1—C2—H2	120.1	C22—C23—H23A	108.7
C3—C2—H2	120.1	C24—C23—H23B	108.7
O5—C12—O4	122.72 (16)	C22—C23—H23B	108.7
O5—C12—C11	123.67 (15)	H23A—C23—H23B	107.6
O4—C12—C11	113.60 (15)	O11—C24—O12	122.82 (17)
C4—C5—C6	121.72 (17)	O11—C24—C23	122.67 (15)
C4—C5—H5	119.1	O12—C24—C23	114.51 (16)
C6—C5—H5	119.1	C13—C14—C15	120.04 (16)
C1—C6—C5	118.65 (17)	C13—C14—H14	120.0
C1—C6—H6	120.7	C15—C14—H14	120.0
C5—C6—H6	120.7	C13—C18—C17	119.12 (16)
C12—C11—C10	113.67 (13)	C13—C18—H18	120.4
C12—C11—H11A	108.8	C17—C18—H18	120.4
C10—C11—H11A	108.8	C15—C16—C17	117.71 (17)
C12—C11—H11B	108.8	C15—C16—C19	121.06 (19)
C10—C11—H11B	108.8	C17—C16—C19	121.23 (19)
H11A—C11—H11B	107.7	C16—C15—C14	121.30 (17)
C4—C3—C2	121.45 (18)	C16—C15—H15	119.4
C4—C3—H3	119.3	C14—C15—H15	119.4
C2—C3—H3	119.3	C16—C17—C18	121.84 (18)
C4—C7—H7A	109.5	C16—C17—H17	119.1
C4—C7—H7B	109.5	C18—C17—H17	119.1
H7A—C7—H7B	109.5	C16—C19—H19A	109.5
C4—C7—H7C	109.5	C16—C19—H19B	109.5
H7A—C7—H7C	109.5	H19A—C19—H19B	109.5
H7B—C7—H7C	109.5	C16—C19—H19C	109.5
O9—S2—O8	113.01 (8)	H19A—C19—H19C	109.5
O9—S2—O10	113.11 (8)	H19B—C19—H19C	109.5

C11—C10—C9—N1	177.06 (13)	O10—S2—C13—C14	−41.80 (16)
C11—C10—C9—C8	58.59 (17)	O9—S2—C13—C18	18.89 (16)
O3—S1—C1—C2	137.98 (15)	O8—S2—C13—C18	−101.54 (15)
O2—S1—C1—C2	17.26 (16)	O10—S2—C13—C18	139.65 (14)
O1—S1—C1—C2	−101.53 (15)	O14—O14—C20—O13	0.0 (6)
O3—S1—C1—C6	−40.99 (15)	O14—O14—C20—C21	0.0 (6)
O2—S1—C1—C6	−161.71 (14)	N2—C21—C20—O14	−47.36 (18)
O1—S1—C1—C6	79.50 (15)	C22—C21—C20—O14	72.62 (18)
N1—C9—C8—O6	−40.23 (18)	N2—C21—C20—O14	−47.36 (18)
C10—C9—C8—O6	79.86 (17)	C22—C21—C20—O14	72.62 (18)
N1—C9—C8—O7	141.59 (12)	N2—C21—C20—O13	134.14 (13)
C10—C9—C8—O7	−98.32 (14)	C22—C21—C20—O13	−105.88 (14)
C6—C1—C2—C3	−0.2 (3)	N2—C21—C22—C23	−170.78 (13)
S1—C1—C2—C3	−179.20 (17)	C20—C21—C22—C23	71.43 (16)
C3—C4—C5—C6	1.6 (3)	C21—C22—C23—C24	−173.86 (14)
C7—C4—C5—C6	−178.1 (2)	C22—C23—C24—O11	18.2 (3)
C2—C1—C6—C5	0.8 (3)	C22—C23—C24—O12	−162.05 (18)
S1—C1—C6—C5	179.78 (15)	C18—C13—C14—C15	2.4 (3)
C4—C5—C6—C1	−1.5 (3)	S2—C13—C14—C15	−176.17 (15)
O5—C12—C11—C10	11.8 (3)	C14—C13—C18—C17	−3.2 (3)
O4—C12—C11—C10	−169.55 (18)	S2—C13—C18—C17	175.38 (16)
C9—C10—C11—C12	170.29 (14)	C17—C16—C15—C14	−2.5 (3)
C5—C4—C3—C2	−0.9 (4)	C19—C16—C15—C14	177.8 (2)
C7—C4—C3—C2	178.8 (2)	C13—C14—C15—C16	0.5 (3)
C1—C2—C3—C4	0.3 (4)	C15—C16—C17—C18	1.6 (3)
O9—S2—C13—C14	−162.57 (14)	C19—C16—C17—C18	−178.6 (2)
O8—S2—C13—C14	77.01 (15)	C13—C18—C17—C16	1.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O6	0.86 (1)	2.46 (3)	2.7527 (17)	100 (2)
C2—H2···O2	0.93	2.49	2.864 (2)	104
C18—H18···O9	0.93	2.53	2.904 (2)	104
N1—H1B···O2ⁱ	0.87 (2)	2.01 (2)	2.8301 (16)	157 (2)
N2—H2B···O8ⁱⁱ	0.86 (1)	2.00 (1)	2.8524 (17)	170 (2)
O7—H7···O1ⁱⁱⁱ	0.82 (1)	1.84 (1)	2.6592 (16)	176 (3)
C6—H6···O6^iv	0.93	2.55	3.316 (2)	140
N2—H2C···O14	0.86 (1)	2.50 (2)	2.7803 (18)	100 (2)
N1—H1C···O3^v	0.86 (1)	2.07 (1)	2.8969 (18)	160 (2)
N2—H2C···O9^vi	0.86 (1)	2.18 (2)	2.9369 (18)	147 (2)
N1—H1A···O1^vii	0.88 (2)	2.05 (2)	2.9150 (16)	167 (2)
N2—H2A···O10^viii	0.87 (1)	2.11 (2)	2.8947 (17)	150 (2)

Symmetry codes: (i) x−1, y, z; (ii) x+1, y+1, z; (iii) x, y−1, z; (iv) x, y+1, z; (v) −x, y−1/2, −z+1; (vi) −x+2, y+1/2, −z+2; (vii) −x+1, y−1/2, −z+1; (viii) −x+1, y+1/2, −z+2.

Acknowledgements

The authors acknowledge the SAIF, IIT Madras, Chennai.

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