Crystal structure of 4-methyl-N-propyl­benzene­sulfonamide

Stenfors, B.A.; Collins, R.C.; Duran, J.R.J.; Staples, R.J.; Biros, S.M.; Ngassa, F.N.

doi:10.1107/S2056989020007756

research communications

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Volume 76| Part 7| July 2020| Pages 1070-1074

https://doi.org/10.1107/S2056989020007756

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Crystal structure of 4-methyl-N-propylbenzenesulfonamide

Brock A. Stenfors,^a Rachel C. Collins,^a Jonah R. J. Duran,^a Richard J. Staples,^b Shannon M. Biros ^a and Felix N. Ngassa ^a ^*

^aDepartment of Chemistry, Grand Valley State University, 1 Campus Dr., Allendale, MI 49401, USA, and ^bCenter for Crystallographic Research, Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA
^*Correspondence e-mail: ngassaf@gvsu.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 26 May 2020; accepted 6 June 2020; online 12 June 2020)

The crystal structure of the title sulfonamide, C₁₀H₁₅NO₂S, comprises two molecules in the asymmetric unit. The S=O bond lengths of the sulfonamide functional group range from 1.428 (2) to 1.441 (2) Å, with S—C bond lengths of 1.766 (3) Å (for both molecules in the asymmetric unit), and S—N bond lengths of 1.618 (2) and 1.622 (3) Å, respectively. When both molecules are viewed down the N—S bond, the propyl group is gauche to the toluene moiety. In the crystal structure, molecules of the title compound are arranged in an intricate three-dimensional network that is formed via intermolecular C—H⋯O and N—H⋯O hydrogen bonds. The crystal structure was refined from a crystal twinned by inversion.

Keywords: crystal structure; sulfonamide; intermolecular N—H⋯O hydrogen bonding; intermolecular C—H⋯O hydrogen bonding.

CCDC reference: 2008411

1. Chemical context

Molecules containing the sulfonamide moiety are found among a variety of biologically significant compounds, and have been used to inhibit a variety of enzymes to improve or repair biological functions. Commonly referred to as `sulfa drugs', these molecules have been in clinical use since 1968 (Connor, 1998 ). Since then, many sulfonamides have been recognized as effective inhibitors of the zinc enzyme carbonic anhydrase (Gul et al., 2018 ). Several interesting anticancer properties are exhibited upon inhibition of this enzyme (Supuran et al., 2001 ).

The title compound, 4-methyl-N-propylbenzenesulfonamide, is structurally similar to a variety of biologically significant compounds. In particular, tacrine-p-toluenesulfonamide derivatives containing the 4-methyl-N-propylbenzenesulfonamide moiety have proven to be effective acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) inhibitors (Makhaeva et al., 2019 ; Fig. 1). The AChE cholinesterase enzyme catalyzes the hydrolysis of acetylcholine (ACh), a neurotransmitter with the ability to coordinate neural responses in the brain (Picciotto et al., 2012 ). The inhibition of AChE decreases the extent of ACh hydrolysis and enhances cholinergic transmission. AChE inhibition treats the symptoms of neuron deterioration characteristic of Alzheimer's disease (García-Ayllón et al., 2011 ). While BChE and AChE both regulate the cholinergic system, the effects of BChE are more prevalent in the blood than the nervous system (Pohanka, 2014 ). BChE is, however, found in the central nervous system and is involved in the formation or growth of β-amyloid plaques (Kim et al., 2016 ). The inhibition of both AChE and BChE improves cognitive function and minimizes the accumulation of β-amyloid and is a viable strategy for treating Alzheimer's disease.

Figure 1
Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) inhibitors containing the N-propyl-4-methylbenzenesulfonamide moiety.

A facile synthesis of sulfonamides is necessary to produce a variety of compounds with the potential to improve human health. A review of the current literature suggests that nucleophilic substitution of sulfonyl halides or sulfonic acids with an amine is an efficient method for the synthesis of sulfonamides (Mukherjee et al., 2018 ; De Luca & Giacomelli, 2008 ). The title compound was synthesized by reacting p-toluenesulfonyl chloride with propylamine in the presence of pyridine. The reaction was carried out in an inert atmosphere, using dichloromethane as the solvent. These reaction conditions resulted in a poor yield and slow reaction time. To work toward a facile synthesis of sulfonamides, a more efficient and environmentally benign method was recently developed. By substituting pyridine and dichloromethane with aqueous potassium carbonate and tetrahydrofuran, a significant increase in the yield and rate of the reaction was observed. The products formed under these reaction conditions are easily isolated upon acidification of the reaction mixture. Furthermore, the solvent combination supports a broader range of nitrogen nucleophiles. In our ongoing efforts to synthesize and characterize sulfonamide products, the synthesis and crystal structure of 4-methyl-N-propylbenzenesulfonamide is reported here.

2. Structural commentary

The title compound comprises two equivalents of the molecule in the asymmetric unit, as shown in Fig. 2 (suffix `A′ for all atomic labels used for the second molecule). The S=O bond lengths of the sulfonamide functional group range from 1.428 (2) to 1.441 (2) Å, which fall within expected values. The S—C bond lengths are 1.766 (3) Å for both molecules, and the S—N bond lengths are 1.618 (2) and 1.622 (3) Å. The O—S—O bond angles are 119.49 (13) and 118.26 (13)°, with N—S—C bond angles of 106.86 (13) and 108.27 (13)°. The two independent molecules differ in the orientation of the propyl chain and the H atom attached to the N atom, however, in each case with the propyl chain being gauche to a sulfonamide oxygen atom and to the toluene moiety when the molecules are viewed down the N1—S1 bond (Fig. 3). The torsion angles between the first carbon atom of the propyl chain (C8 or C8A) and the sulfonamide oxygen atom O1 or O1A are 60.5 (3) and 57.3 (2)°, respectively. The groups bonded to the sulfur atom of both sulfonamide groups adopt slightly distorted tetrahedral environments with fourfold coordination τ₄ descriptors of 0.94 for both S1 and S1A (ideal values are 0 for square-planar, 0.85 for trigonal pyramidal, and 1 for tetrahedral coordinations; Yang et al., 2007 ).

Figure 2
The structures of the two molecules in the asymmetric unit of the title compound, with the atom-labeling scheme. Displacement ellipsoids are shown at the 40% probability level using standard CPK colors.

Figure 3
Overlay plot of the two independent molecules in the title compound, with grouping of the atoms C1—S1—-N1 and C1A—S1A—N1A, and the molecule oriented so as to view it down the S—N bond. Displacement ellipsoids are as in Fig. 2

3. Supramolecular features

Hydrogen-bonding interactions, both N—H⋯O and C—H⋯O, hold molecules of the title compound together in the crystal structure (Table 1, Fig. 4). The intermolecular N—H⋯O interactions are between the sulfonamide N(H) atoms and the oxygen (O1 or O1A) atoms of a nearby molecule. These classic hydrogen-bonding interactions form ribbons of the title compound that lie parallel to the ab plane. These interactions have D⋯A distances of 2.925 (3) and 2.968 (3) Å, with D—H⋯A angles of 161 (3) and 172 (3)°. The intermolecular C—H⋯O hydrogen bonding interactions (Sutor, 1958 , 1962 , 1963 ; Steiner, 1996 ) have, as expected, longer D⋯A distances ranging from 3.399 (4) to 3.594 (4) Å, and D—H⋯A angles ranging from 152.8 to 170.2°. Specifically, the C8(H8B)⋯O2A, C8A(H8AA)⋯O2 and C6(H6)⋯O1A interactions contribute to the stabilization of the supramolecular ribbons. The interaction between C3A(H3A) and O2A links the supramolecular ribbons into an intricate three-dimensional network (Fig. 5).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3A—H3A⋯O2Aⁱ	0.95	2.53	3.399 (4)	153
C6—H6⋯O1Aⁱⁱ	0.95	2.59	3.474 (4)	156
C8—H8B⋯O2Aⁱ	0.99	2.56	3.489 (4)	156
C8A—H8AA⋯O2ⁱⁱⁱ	0.99	2.61	3.594 (4)	170
N1A—H1A⋯O1^iv	0.82 (3)	2.14 (3)	2.925 (3)	161 (3)
N1—H1⋯O1Aⁱⁱ	0.85 (3)	2.13 (4)	2.968 (3)	172 (3)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 4
A diagram showing the specific hydrogen-bonding interactions (N—H⋯O: purple dashed lines, C—H⋯O: green dashed lines) present in the title compound, using a ball-and-stick model with standard CPK colors. Hydrogen atoms bonded to parent atoms that are not involved in a non-covalent interaction have been omitted for clarity. [Symmetry codes: (i) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (ii) x, −y + 1, z + $[{1\over 2}]$ ; (iii) x, −y + 1, z − $[{1\over 2}]$ ; (iv) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ].

Figure 5
A packing diagram of the title compound viewed down the b axis. Intermolecular hydrogen bonds are shown with dashed lines (N—H⋯O: purple, C—H⋯O: green). This figure was drawn using a ball and stick model with standard CPK colors. Hydrogen atoms bonded to parent atoms that are not involved in a non-covalent interaction have been omitted for clarity.

4. Database survey

A search for structures containing the p-methylbenzenesulfonamide entity in the Cambridge Structural Database (CSD, Version 5.41, November, 2019; Groom et al., 2016 ), where the nitrogen atom bears one carbon-containing group, resulted in over 2,200 hits. A few structures with relatively simple, yet interesting, –R groups bonded to the sulfonamide nitrogen atom are BOLPOH (Germain et al., 1983 ), AZUQUI (Rehman et al., 2011 ), AYURUI and AYURUI01 (Khan et al., 2011 ; Akyıldız et al., 2018 ), and ATOVIO (Muller et al., 2004 ). In the structures of BOLPOH and AZUQUI, the –R groups are both aromatic systems with a quinoline ring and a 4-aminobenzene ring, respectively. The structures of AYURUI and AYURUI01 contain two p-methylbenzenesulfonamide groups linked via a propane chain. Lastly, the –R group in ATOVIO is a tricycloheptyl ring system.

5. Synthesis and crystallization

The title compound was prepared by the dropwise addition of 0.59 M aqueous potassium carbonate (10 ml, 5.90 mmol) to a stirring mixture of propylamine (0.49 ml, 5.90 mmol) and p-toluenesulfonyl chloride (1.00 g, 5.25 mmol) in 10 ml of tetrahydrofuran. The reaction mixture was stirred at room temperate for 24 h under a nitrogen atmosphere. After acidification with 5 M HCl and dilution with 15 ml of dichloromethane, the organic layer was washed with water and brine. The aqueous layers were back extracted with 10 ml of dichloromethane. The combined organic layers were then combined, dried over anhydrous sodium sulfate, and evaporated to dryness. The liquid residue was triturated with diethyl ether, placed in a freezer for 48 h and, after isolation via vacuum filtration, the product was obtained as colorless crystals (59%; m.p. 335–337 K).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The crystal under investigation was twinned by inversion, with a refined Flack parameter of 0.443 (19) (Parsons et al., 2013 ). For this structure, hydrogen atoms bonded to carbon atoms were placed in calculated positions and refined to ride on their parent atoms: C—H = 0.95–1.00 Å with U_iso(H) = 1.2U_eq(C) for methylene groups and aromatic hydrogen atoms, and U_iso(H) = 1.5U_eq(C) for methyl groups. Hydrogen atoms bonded to nitrogen atoms were located using electron density difference maps, and were refined freely.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₅NO₂S
M_r	213.29
Crystal system, space group	Monoclinic, Cc
Temperature (K)	173
a, b, c (Å)	15.9353 (9), 10.3526 (6), 14.8486 (9)
β (°)	115.1347 (6)
V (Å³)	2217.7 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.27
Crystal size (mm)	0.45 × 0.40 × 0.39

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.684, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	18931, 4554, 4422
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.083, 1.02
No. of reflections	4554
No. of parameters	265
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.20
Absolute structure	Flack x determined using 2140 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	0.443 (19)
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ; Bourhis et al., 2015 ) and CrystalMaker (Palmer, 2007 ).

Supporting information

CCDC reference: 2008411

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020007756/wm5567sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020007756/wm5567Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020007756/wm5567Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009; Bourhis et al., 2015); software used to prepare material for publication: CrystalMaker (Palmer, 2007).

4-Methyl-N-propylbenzenesulfonamide top

Crystal data top

C₁₀H₁₅NO₂S	F(000) = 912
M_r = 213.29	D_x = 1.278 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 15.9353 (9) Å	Cell parameters from 9996 reflections
b = 10.3526 (6) Å	θ = 2.4–26.4°
c = 14.8486 (9) Å	µ = 0.27 mm⁻¹
β = 115.1347 (6)°	T = 173 K
V = 2217.7 (2) Å³	Block, colourless
Z = 8	0.45 × 0.40 × 0.39 mm

Data collection top

Bruker APEXII CCD diffractometer	4422 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.028
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θ_max = 26.4°, θ_min = 2.4°
T_min = 0.684, T_max = 0.745	h = −19→19
18931 measured reflections	k = −12→12
4554 independent reflections	l = −18→18

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0503P)² + 0.9882P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.083	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.27 e Å⁻³
4554 reflections	Δρ_min = −0.20 e Å⁻³
265 parameters	Absolute structure: Flack x determined using 2140 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: 0.443 (19)
Primary atom site location: structure-invariant direct methods

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	0.40337 (4)	0.32398 (6)	0.21849 (4)	0.02809 (16)
S1	0.61545 (4)	0.30322 (7)	0.77858 (4)	0.03083 (17)
O2A	0.33689 (14)	0.2460 (2)	0.14206 (15)	0.0368 (5)
C1A	0.48935 (19)	0.2218 (3)	0.3034 (2)	0.0266 (5)
C5	0.3803 (2)	0.1709 (3)	0.5601 (3)	0.0388 (7)
H5	0.3189	0.2015	0.5231	0.047*
C3A	0.6417 (2)	0.1911 (3)	0.4327 (2)	0.0325 (6)
H3A	0.7009	0.2249	0.4749	0.039*
C1	0.5341 (2)	0.2024 (3)	0.6871 (2)	0.0300 (6)
C6	0.4440 (2)	0.2486 (3)	0.6334 (2)	0.0366 (7)
H6	0.4267	0.3316	0.6470	0.044*
C4	0.4047 (2)	0.0488 (3)	0.5397 (2)	0.0347 (6)
C2A	0.5763 (2)	0.2713 (3)	0.3643 (2)	0.0324 (6)
H2A	0.5905	0.3593	0.3590	0.039*
N1	0.62264 (18)	0.4342 (2)	0.72284 (18)	0.0328 (5)
O2	0.58027 (16)	0.3406 (2)	0.84936 (15)	0.0400 (5)
C4A	0.6225 (2)	0.0614 (3)	0.4409 (2)	0.0319 (6)
O1A	0.45006 (14)	0.4257 (2)	0.19202 (16)	0.0362 (5)
C2	0.5590 (2)	0.0820 (3)	0.6681 (2)	0.0370 (7)
H2	0.6204	0.0514	0.7050	0.044*
C3	0.4942 (2)	0.0052 (3)	0.5949 (2)	0.0418 (7)
H3	0.5115	−0.0784	0.5825	0.050*
N1A	0.34797 (17)	0.3914 (2)	0.27586 (19)	0.0332 (5)
C5A	0.5348 (2)	0.0145 (3)	0.3788 (2)	0.0350 (6)
H5A	0.5204	−0.0736	0.3837	0.042*
C8	0.6443 (2)	0.4213 (3)	0.6357 (2)	0.0399 (7)
H8A	0.5885	0.3916	0.5774	0.048*
H8B	0.6936	0.3558	0.6499	0.048*
C9A	0.3349 (2)	0.5714 (3)	0.3760 (2)	0.0421 (7)
H9AA	0.2776	0.5292	0.3720	0.051*
H9AB	0.3659	0.6119	0.4425	0.051*
C6A	0.4685 (2)	0.0937 (3)	0.3105 (2)	0.0338 (6)
H6A	0.4090	0.0604	0.2688	0.041*
O1	0.70368 (15)	0.2382 (2)	0.81488 (17)	0.0411 (5)
C7	0.3343 (3)	−0.0346 (3)	0.4595 (3)	0.0480 (8)
H7A	0.3372	−0.0177	0.3960	0.072*
H7B	0.2720	−0.0144	0.4535	0.072*
H7C	0.3480	−0.1259	0.4772	0.072*
C7A	0.6943 (2)	−0.0253 (3)	0.5154 (2)	0.0420 (7)
H7AA	0.7558	0.0133	0.5359	0.063*
H7AB	0.6928	−0.1099	0.4851	0.063*
H7AC	0.6810	−0.0358	0.5737	0.063*
C8A	0.3984 (2)	0.4693 (3)	0.3654 (2)	0.0377 (6)
H8AA	0.4523	0.5114	0.3608	0.045*
H8AB	0.4219	0.4127	0.4248	0.045*
C10	0.6052 (3)	0.6546 (4)	0.5879 (3)	0.0575 (10)
H10D	0.5466	0.6260	0.5343	0.086*
H10E	0.6273	0.7319	0.5666	0.086*
H10F	0.5953	0.6747	0.6472	0.086*
C9	0.6761 (3)	0.5489 (4)	0.6120 (3)	0.0535 (9)
H9A	0.7334	0.5760	0.6696	0.064*
H9B	0.6916	0.5370	0.5546	0.064*
C10A	0.3090 (3)	0.6751 (4)	0.2977 (3)	0.0613 (11)
H10A	0.2820	0.6352	0.2316	0.092*
H10B	0.3645	0.7240	0.3061	0.092*
H10C	0.2636	0.7335	0.3044	0.092*
H1A	0.307 (2)	0.343 (3)	0.277 (2)	0.034 (9)*
H1	0.576 (2)	0.481 (3)	0.713 (2)	0.030 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.0225 (3)	0.0303 (3)	0.0288 (3)	−0.0027 (3)	0.0082 (3)	0.0011 (3)
S1	0.0278 (3)	0.0362 (3)	0.0270 (3)	0.0067 (3)	0.0102 (3)	−0.0013 (3)
O2A	0.0286 (10)	0.0384 (11)	0.0336 (10)	−0.0029 (9)	0.0039 (9)	−0.0020 (9)
C1A	0.0250 (13)	0.0287 (13)	0.0257 (13)	−0.0013 (10)	0.0104 (11)	0.0008 (11)
C5	0.0275 (15)	0.0389 (17)	0.0436 (18)	0.0017 (12)	0.0088 (14)	−0.0004 (13)
C3A	0.0274 (14)	0.0338 (16)	0.0327 (15)	−0.0037 (11)	0.0094 (13)	−0.0031 (11)
C1	0.0281 (14)	0.0353 (14)	0.0289 (14)	0.0030 (11)	0.0143 (12)	0.0011 (11)
C6	0.0304 (14)	0.0304 (15)	0.0451 (17)	0.0054 (12)	0.0124 (14)	−0.0022 (12)
C4	0.0403 (16)	0.0338 (15)	0.0327 (14)	−0.0044 (12)	0.0180 (13)	−0.0004 (12)
C2A	0.0275 (14)	0.0305 (14)	0.0362 (15)	−0.0043 (11)	0.0106 (12)	0.0009 (11)
N1	0.0309 (12)	0.0334 (12)	0.0349 (12)	0.0048 (10)	0.0147 (10)	−0.0028 (10)
O2	0.0442 (12)	0.0468 (12)	0.0318 (10)	0.0060 (10)	0.0188 (9)	−0.0014 (9)
C4A	0.0348 (15)	0.0362 (15)	0.0263 (13)	0.0020 (12)	0.0143 (12)	0.0023 (11)
O1A	0.0305 (10)	0.0367 (11)	0.0405 (11)	−0.0013 (8)	0.0141 (9)	0.0073 (9)
C2	0.0347 (15)	0.0360 (15)	0.0392 (16)	0.0100 (12)	0.0147 (13)	0.0005 (13)
C3	0.0485 (19)	0.0360 (16)	0.0412 (17)	0.0063 (14)	0.0193 (15)	−0.0034 (13)
N1A	0.0244 (11)	0.0343 (13)	0.0404 (13)	−0.0051 (10)	0.0133 (10)	−0.0042 (10)
C5A	0.0417 (17)	0.0272 (14)	0.0353 (14)	−0.0046 (12)	0.0156 (13)	0.0016 (11)
C8	0.0415 (16)	0.0430 (16)	0.0420 (16)	0.0048 (14)	0.0243 (14)	−0.0015 (14)
C9A	0.0377 (16)	0.0497 (19)	0.0421 (17)	−0.0032 (14)	0.0199 (14)	−0.0107 (14)
C6A	0.0323 (14)	0.0337 (14)	0.0323 (14)	−0.0075 (12)	0.0105 (12)	−0.0024 (11)
O1	0.0334 (11)	0.0448 (13)	0.0379 (11)	0.0111 (9)	0.0083 (9)	0.0001 (9)
C7	0.051 (2)	0.0457 (18)	0.0440 (18)	−0.0119 (15)	0.0171 (16)	−0.0088 (15)
C7A	0.0437 (18)	0.0407 (17)	0.0381 (16)	0.0047 (13)	0.0139 (14)	0.0081 (13)
C8A	0.0321 (15)	0.0457 (16)	0.0323 (14)	−0.0014 (13)	0.0109 (12)	−0.0053 (13)
C10	0.079 (3)	0.0418 (19)	0.060 (2)	−0.0037 (19)	0.038 (2)	0.0091 (16)
C9	0.053 (2)	0.058 (2)	0.062 (2)	−0.0094 (17)	0.0365 (19)	−0.0031 (18)
C10A	0.082 (3)	0.042 (2)	0.051 (2)	0.0113 (19)	0.021 (2)	−0.0126 (16)

Geometric parameters (Å, º) top

S1A—O2A	1.428 (2)	N1A—C8A	1.469 (4)
S1A—C1A	1.766 (3)	N1A—H1A	0.82 (3)
S1A—O1A	1.437 (2)	C5A—H5A	0.9500
S1A—N1A	1.622 (3)	C5A—C6A	1.381 (4)
S1—C1	1.766 (3)	C8—H8A	0.9900
S1—N1	1.618 (3)	C8—H8B	0.9900
S1—O2	1.438 (2)	C8—C9	1.509 (5)
S1—O1	1.441 (2)	C9A—H9AA	0.9900
C1A—C2A	1.392 (4)	C9A—H9AB	0.9900
C1A—C6A	1.382 (4)	C9A—C8A	1.518 (4)
C5—H5	0.9500	C9A—C10A	1.505 (6)
C5—C6	1.387 (5)	C6A—H6A	0.9500
C5—C4	1.393 (4)	C7—H7A	0.9800
C3A—H3A	0.9500	C7—H7B	0.9800
C3A—C2A	1.381 (4)	C7—H7C	0.9800
C3A—C4A	1.394 (4)	C7A—H7AA	0.9800
C1—C6	1.397 (4)	C7A—H7AB	0.9800
C1—C2	1.374 (4)	C7A—H7AC	0.9800
C6—H6	0.9500	C8A—H8AA	0.9900
C4—C3	1.385 (5)	C8A—H8AB	0.9900
C4—C7	1.512 (4)	C10—H10D	0.9800
C2A—H2A	0.9500	C10—H10E	0.9800
N1—C8	1.481 (4)	C10—H10F	0.9800
N1—H1	0.85 (3)	C10—C9	1.503 (6)
C4A—C5A	1.394 (4)	C9—H9A	0.9900
C4A—C7A	1.505 (4)	C9—H9B	0.9900
C2—H2	0.9500	C10A—H10A	0.9800
C2—C3	1.389 (5)	C10A—H10B	0.9800
C3—H3	0.9500	C10A—H10C	0.9800

O2A—S1A—C1A	108.49 (13)	N1—C8—H8A	109.5
O2A—S1A—O1A	119.48 (13)	N1—C8—H8B	109.5
O2A—S1A—N1A	105.96 (13)	N1—C8—C9	110.6 (3)
O1A—S1A—C1A	107.43 (13)	H8A—C8—H8B	108.1
O1A—S1A—N1A	106.77 (13)	C9—C8—H8A	109.5
N1A—S1A—C1A	108.27 (13)	C9—C8—H8B	109.5
N1—S1—C1	106.86 (13)	H9AA—C9A—H9AB	107.8
O2—S1—C1	109.52 (13)	C8A—C9A—H9AA	109.0
O2—S1—N1	106.43 (13)	C8A—C9A—H9AB	109.0
O2—S1—O1	118.26 (13)	C10A—C9A—H9AA	109.0
O1—S1—C1	107.03 (13)	C10A—C9A—H9AB	109.0
O1—S1—N1	108.23 (14)	C10A—C9A—C8A	113.1 (3)
C2A—C1A—S1A	120.0 (2)	C1A—C6A—H6A	120.3
C6A—C1A—S1A	119.4 (2)	C5A—C6A—C1A	119.5 (3)
C6A—C1A—C2A	120.6 (3)	C5A—C6A—H6A	120.3
C6—C5—H5	119.4	C4—C7—H7A	109.5
C6—C5—C4	121.2 (3)	C4—C7—H7B	109.5
C4—C5—H5	119.4	C4—C7—H7C	109.5
C2A—C3A—H3A	119.4	H7A—C7—H7B	109.5
C2A—C3A—C4A	121.2 (3)	H7A—C7—H7C	109.5
C4A—C3A—H3A	119.4	H7B—C7—H7C	109.5
C6—C1—S1	118.5 (2)	C4A—C7A—H7AA	109.5
C2—C1—S1	120.8 (2)	C4A—C7A—H7AB	109.5
C2—C1—C6	120.7 (3)	C4A—C7A—H7AC	109.5
C5—C6—C1	118.8 (3)	H7AA—C7A—H7AB	109.5
C5—C6—H6	120.6	H7AA—C7A—H7AC	109.5
C1—C6—H6	120.6	H7AB—C7A—H7AC	109.5
C5—C4—C7	120.5 (3)	N1A—C8A—C9A	110.1 (2)
C3—C4—C5	118.7 (3)	N1A—C8A—H8AA	109.6
C3—C4—C7	120.8 (3)	N1A—C8A—H8AB	109.6
C1A—C2A—H2A	120.4	C9A—C8A—H8AA	109.6
C3A—C2A—C1A	119.2 (3)	C9A—C8A—H8AB	109.6
C3A—C2A—H2A	120.4	H8AA—C8A—H8AB	108.2
S1—N1—H1	108 (2)	H10D—C10—H10E	109.5
C8—N1—S1	117.7 (2)	H10D—C10—H10F	109.5
C8—N1—H1	115 (2)	H10E—C10—H10F	109.5
C3A—C4A—C5A	118.3 (3)	C9—C10—H10D	109.5
C3A—C4A—C7A	120.8 (3)	C9—C10—H10E	109.5
C5A—C4A—C7A	120.9 (3)	C9—C10—H10F	109.5
C1—C2—H2	120.1	C8—C9—H9A	108.9
C1—C2—C3	119.7 (3)	C8—C9—H9B	108.9
C3—C2—H2	120.1	C10—C9—C8	113.5 (3)
C4—C3—C2	120.9 (3)	C10—C9—H9A	108.9
C4—C3—H3	119.5	C10—C9—H9B	108.9
C2—C3—H3	119.5	H9A—C9—H9B	107.7
S1A—N1A—H1A	111 (2)	C9A—C10A—H10A	109.5
C8A—N1A—S1A	120.07 (19)	C9A—C10A—H10B	109.5
C8A—N1A—H1A	117 (2)	C9A—C10A—H10C	109.5
C4A—C5A—H5A	119.4	H10A—C10A—H10B	109.5
C6A—C5A—C4A	121.2 (3)	H10A—C10A—H10C	109.5
C6A—C5A—H5A	119.4	H10B—C10A—H10C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3A—H3A···O2Aⁱ	0.95	2.53	3.399 (4)	153
C6—H6···O1Aⁱⁱ	0.95	2.59	3.474 (4)	156
C8—H8B···O2Aⁱ	0.99	2.56	3.489 (4)	156
C8A—H8AA···O2ⁱⁱⁱ	0.99	2.61	3.594 (4)	170
N1A—H1A···O1^iv	0.82 (3)	2.14 (3)	2.925 (3)	161 (3)
N1—H1···O1Aⁱⁱ	0.85 (3)	2.13 (4)	2.968 (3)	172 (3)

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

Acknowledgements

The authors are grateful to Pfizer, Inc. for the donation of a Varian INOVA 400 FT NMR.

Funding information

Funding for this research was provided by: National Science Foundation, Directorate for Mathematical and Physical Sciences (grant No. MRI CHE-1725699; grant No. MRI CHE-1919817); GVSU Chemistry Department's Weldon Fund.

References

Akyıldız, F., Alyar, S., Bilkan, M. T. & Alyar, H. (2018). J. Mol. Struct. 1174, 160–170. Google Scholar
Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59–75. Web of Science CrossRef IUCr Journals Google Scholar
Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Connor, E. E. (1998). Elsevier Science Inc. 5, 32–35. Google Scholar
De Luca, L. & Giacomelli, G. (2008). J. Org. Chem. 73, 3967–3969. Web of Science CrossRef PubMed CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
García-Ayllón, M., Small, D. H., Avila, J. & Sáez-Valero, J. (2011). Front. Mol. Neurosci. 4, 22. PubMed Google Scholar
Germain, G., Declercq, J.-P., Castresana, J. M., Elizalde, M. P. & Arrieta, J. M. (1983). Acta Cryst. C39, 230–232. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Gul, H. I., Yamali, C., Sakagami, H., Angeli, A., Leitans, J., Kazaks, A., Tars, K., Ozgun, D. O. & Supuran, C. T. (2018). Bioorg. Chem. 77, 411–419. Web of Science CrossRef CAS PubMed Google Scholar
Khan, I. U., Sheikh, T. A., Ejaz & Harrison, W. T. A. (2011). Acta Cryst. E67, o2371. Google Scholar
Kim, J. H., Lee, S., Lee, H. W., Sun, Y. N., Jang, W., Yang, S., Jang, H. & Kim, Y. H. (2016). Int. J. Biol. Macromol. 91, 1033–1039. Web of Science CrossRef CAS PubMed Google Scholar
Makhaeva, G. F., Rudakova, E. V., Kovaleva, N. V., Lushchekina, S. V., Boltneva, N. P., Proshin, A. N., Shchegolkov, E. V., Burgart, Y. V. & Saloutin, V. I. (2019). Russ. Chem. Bull. 68, 967–984. Web of Science CrossRef CAS Google Scholar
Mukherjee, P., Woroch, C. P., Cleary, L., Rusznak, M., Franzese, R. W., Reese, M. R., Tucker, J. W., Humphrey, J. M., Etuk, S. M., Kwan, S. C., am Ende, C. W. & Ball, N. D. (2018). Org. Lett. 20, 3943–3947. Web of Science CSD CrossRef CAS PubMed Google Scholar
Müller, P., Riegert, D. & Bernardinelli, G. (2004). Helv. Chim. Acta, 87, 227–239. Google Scholar
Palmer, D. (2007). CrystalMaker. CrystalMaker Software, Bicester, Oxfordshire, England. Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Picciotto, M. R., Higley, M. J. & Mineur, Y. S. (2012). Neuron, 76, 116–129. Web of Science CrossRef CAS PubMed Google Scholar
Pohanka, M. (2014). Int. J. Mol. Sci. 15, 9809–9825. Web of Science CrossRef PubMed Google Scholar
Rehman, J., Ejaz , Khan, I. U. & Harrison, W. T. A. (2011). Acta Cryst. E67, o2709. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Steiner, T. (1996). Crystallogr. Rev. 6, 157–305. CrossRef Google Scholar
Supuran, C. T., Briganti, F., Tilli, S., Chegwidden, W. R. & Scozzafava, A. (2001). Bioorg. Med. Chem. 9, 703–714. Web of Science CrossRef PubMed CAS Google Scholar
Sutor, D. J. (1958). Acta Cryst. 11, 453–458. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Sutor, D. J. (1962). Nature, 195, 68–69. CAS Google Scholar
Sutor, D. J. (1963). J. Chem. Soc. pp. 1105–1110. CrossRef Web of Science Google Scholar
Yang, L., Powell, D. R. & Houser, R. P. (2007). Dalton Trans. pp. 955–964. Web of Science CSD CrossRef PubMed CAS Google Scholar