2,3-Dimethyl-1H-imidazol-3-ium benzene­sulfonate–1,2-dimethyl-1H-imidazole co-crystal

Cyr, N.; Zeller, M.; Hillesheim, P.C.; Mirjafari, A.

doi:10.1107/S2414314620006896

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 5| May 2020| x200689

https://doi.org/10.1107/S2414314620006896

Open

access

2,3-Dimethyl-1H-imidazol-3-ium benzenesulfonate–1,2-dimethyl-1H-imidazole co-crystal

Noah Cyr,^a Matthias Zeller,^b Patrick C. Hillesheim ^c and Arsalan Mirjafari ^a ^*

^aDepartment of Chemistry and Physics, Florida Gulf Coast University, 10501 FGCU Blvd. South, Fort Myers, FL, 33965, USA, ^bPurdue University, Department of Chemistry, 560 Oval Drive, West Lafayette, Indiana USA, 47907, USA, and ^cAve Maria University, Department of Chemistry and Physics, 5050 Ave Maria Blvd, Ave Maria FL, 34142, USA
^*Correspondence e-mail: amirjafari@fgcu.edu

Edited by R. J. Butcher, Howard University, USA (Received 30 March 2020; accepted 21 May 2020; online 27 May 2020)

In the title co-crystal, C₅H₉N₂⁺·C₆H₅O₃S⁻·C₅H₈N₂, the two 1,2-dimethylimidazole rings exist as partially protonated moieties in the asymmetric unit as a two-part disordered unit wherein the acidic hydrogen atom is bound to each ring. The two imidazolium cations share a strong hydrogen bond via the acidic hydrogen atom, which is disordered between two positions, being bonded to the first versus second imidazole ring in a 0.33 (2) to 0.67 (2) ratio. A benzene sulfonate anion is present for charge balance and interacts with the aromatic H atoms on both imidazole rings as well as with the methyl groups on the rings.

Keywords: crystal structure; tosylate; imidazolium; ionic crystal.

CCDC reference: 2005097

Structure description

The title compound (Fig. 1) crystallizes with two 1,2-dimethylimidazolium cations in the asymmetric unit. The two imidazole rings are each partially protonated, wherein the acidic hydrogen atom is bound between the two N atoms of the aromatic ring in a 0.33 (2) to 0.67 (2) ratio. Hydrogen bonding appears to the dominant intermolecular interaction with each molecule or ion exhibiting interactions (Fig. 2). For instance, the shortest hydrogen bonds are N—H⋯N links between the imidazolium rings with H⋯N = 1.83 (8) and 1.90 (8) Å. This bonding arises from the disordered hydrogen atom, which appears to be shared between the two rings. Further, cation–anion C—H⋯O interactions occur between the aromatic H atoms and the sulfonate O atoms. Finally, there are anion–anion interactions wherein O atoms of the sulfonate group interact with hydrogens on the benzene rings. A summary of the distances for the hydrogen bonds is found in Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N3	0.83	1.90	2.6970 (11)	163
N3—H3N⋯N1	0.89	1.81	2.6970 (11)	170
C1—H1⋯O1	0.95	2.43	3.3741 (13)	170
C4—H4B⋯O3ⁱ	0.98	2.33	3.2956 (12)	170
C6—H6⋯O2	0.95	2.60	3.4288 (14)	146
C7—H7⋯O2ⁱⁱ	0.95	2.41	3.3254 (12)	162
C9—H9A⋯O3ⁱⁱⁱ	0.98	2.53	3.4846 (14)	164
C9—H9B⋯O3ⁱⁱ	0.98	2.46	3.4381 (14)	173
C13—H13⋯O1ⁱ	0.95	2.67	3.4738 (14)	143
C14—H14⋯O1^iv	0.95	2.48	3.3920 (13)	162
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x, y-1, z.

Figure 1
The title compound shown with 50% probability ellipsoids. Only the major component is shown.

Figure 2
Packing diagram of the title compound viewed down the (010) plane showing a layered network of ion pairs held together through hydrogen interactions. Both parts of the disorder are shown.

For a related structure with a chloride anion, see Kelley et al. (2013 ).

Synthesis and crystallization

The reaction was conducted in a Biotage Initiator+ microwave reactor. To a microwave vial was added a stir bar as well as 7.5 mmol (721 mg) of 1,2 dimethylimidazole and 7.5 mmol (901 μL) of benzenesulfonyl fluoride. The vial was sealed and placed into the microwave reactor. The reaction was performed at 105°C for 5 minutes and 38 s with very high microwave absorption, stirring at 600 rpm. Once finished and cooled to room temperature, the solution was transferred to an oven-dried amber scintillation vial and sealed with parafilm. After one week, crystals suitable for diffraction were found growing in the vial.

A proposed mechanism leading to the formation of the crystallized product reported herein is shown in Fig. 3.

Figure 3
Proposed mechanism leading to the formation of the crystallized product reported herein.

¹H NMR (400 MHz, chloroform-D) δ 8.01–7.99 (m, 1H), 7.89–7.87 (m, 1H), 7.77 (dd, J = 8.1, 6.7 Hz, 1H), 7.62 (t, J = 7.4 Hz, 1H), 7.35 (t, J = 2.6 Hz, 1H), 7.25 (s, 1H), 6.98–6.83 (m, 2H), 3.61 (d, J = 9.1 Hz, 3H), 2.46 (d, J = 14.0 Hz, 3H)

¹³C NMR (101 MHz, chloroform-D) δ 206.7, 144.8, 135.7, 130.0, 129.8, 128.5, 128.3, 126.0, 121.2, 121.0, 77.4, 77.1, 76.8, 76.6, 33.5, 12.0, −1.6.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₅H₉N₂⁺·C₆H₅O₃S⁻·C₅H₈N₂
M_r	350.43
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	10.8820 (6), 8.4029 (4), 18.9678 (11)
β (°)	95.440 (2)
V (Å³)	1726.61 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.21
Crystal size (mm)	0.55 × 0.42 × 0.33

Data collection
Diffractometer	Bruker AXS D8 Quest CMOS diffractometer
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.716, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	74762, 6612, 5787
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.771

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.095, 1.05
No. of reflections	6612
No. of parameters	225
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.44
Computer programs: APEX3 and SAINT (Bruker, 2018 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), shelXle (Hübschle et al., 2011 ), OLEX2 (Dolomanov et al., 2009 ), publCIF (Westrip, 2010 ) and enCIFer (Allen et al., 2004 ).

Structural data

CCDC reference: 2005097

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314620006896/bv4031sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620006896/bv4031Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620006896/bv4031Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015), shelXle (Hübschle et al., 2011); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010), enCIFer (Allen et al., 2004).

2,3-Dimethyl-1H-imidazol-3-ium benzenesulfonate; 1,2-dimethyl-1H-imidazole top

Crystal data top

C₅H₉N₂⁺·C₆H₅O₃S⁻·C₅H₈N₂	F(000) = 744
M_r = 350.43	D_x = 1.348 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.8820 (6) Å	Cell parameters from 9689 reflections
b = 8.4029 (4) Å	θ = 2.7–33.2°
c = 18.9678 (11) Å	µ = 0.21 mm⁻¹
β = 95.440 (2)°	T = 150 K
V = 1726.61 (16) Å³	Block, colourless
Z = 4	0.55 × 0.42 × 0.33 mm

Data collection top

Bruker AXS D8 Quest CMOS diffractometer	6612 independent reflections
Radiation source: fine focus sealed tube X-ray source	5787 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromator	R_int = 0.032
Detector resolution: 10.4167 pixels mm^-1	θ_max = 33.2°, θ_min = 2.3°
ω and phi scans	h = −16→16
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −12→12
T_min = 0.716, T_max = 0.747	l = −29→28
74762 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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0417P)² + 0.6618P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
6612 reflections	Δρ_max = 0.40 e Å⁻³
225 parameters	Δρ_min = −0.44 e Å⁻³
0 restraints	Extinction correction: SHELXL-2018/3 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0085 (10)

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.

Refinement. H atoms attached to carbon atoms were positioned geometrically and constrained to ride on their parent atoms. C—H bond distances were constrained to 0.95 Å for aromatic and alkene C—H moieties, and to 0.98 Å for CH₃ moieties, respectively. The N—H proton hydrogen bonding between atoms N1 and N3 was found to be disordered and was refined as split between two positions. The H atoms were assigned as bonded to a planar (sp² hybridized) N atom, respectively with fixed bond angles and torsion angles, but the N—H bond distances were allowed to refine to account for asymmetry induced by charge and hydrogen bonding (AFIX 44 command). N—H distances refined to 0.83 (5) for N1—H1 and to 0.89 (2) for N3—H3, occupancies refined to 0.33 (2) for H1 and 0.67 (2) for H3. Methyl CH₃ were allowed to rotate but not to tip to best fit the experimental electron density. U_iso(H) values were set to a multiple of U_eq(C/N) with 1.5 for CH₃ and 1.2 for C—H and NH⁺, respectively.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.07995 (8)	0.11974 (12)	0.12505 (5)	0.02370 (17)
H1	0.162507	0.154570	0.136425	0.028*
C2	0.01650 (8)	0.02111 (12)	0.16550 (5)	0.02268 (16)
H2	0.045537	−0.025178	0.209661	0.027*
C3	−0.10216 (8)	0.08832 (10)	0.06876 (4)	0.01832 (14)
C4	−0.20228 (9)	−0.08561 (12)	0.15402 (5)	0.02410 (17)
H4A	−0.264761	−0.010298	0.167446	0.036*
H4B	−0.172925	−0.150361	0.195187	0.036*
H4C	−0.238614	−0.154975	0.116071	0.036*
C5	−0.21283 (8)	0.09673 (13)	0.01670 (5)	0.02515 (18)
H5A	−0.194381	0.162346	−0.023687	0.038*
H5B	−0.281506	0.144135	0.039231	0.038*
H5C	−0.235631	−0.010751	0.000206	0.038*
C6	0.23459 (9)	0.40162 (12)	−0.00734 (5)	0.02566 (18)
H6	0.285770	0.372447	0.034004	0.031*
C7	0.26716 (8)	0.49589 (12)	−0.06067 (6)	0.02502 (18)
H7	0.345007	0.545291	−0.063695	0.030*
C8	0.07312 (8)	0.42021 (10)	−0.08640 (4)	0.01863 (14)
C9	0.15832 (10)	0.59191 (13)	−0.17707 (5)	0.02847 (19)
H9A	0.142896	0.516294	−0.216246	0.043*
H9B	0.236534	0.647282	−0.181302	0.043*
H9C	0.090972	0.669653	−0.178780	0.043*
C10	−0.05084 (9)	0.40053 (13)	−0.12482 (5)	0.02596 (18)
H10A	−0.090249	0.504931	−0.131824	0.039*
H10B	−0.101453	0.332570	−0.097120	0.039*
H10C	−0.042876	0.351054	−0.170954	0.039*
C11	0.43346 (7)	0.00325 (9)	0.14618 (4)	0.01514 (13)
C12	0.36079 (8)	−0.06738 (10)	0.19405 (4)	0.01852 (14)
H12	0.326061	−0.004339	0.228696	0.022*
C13	0.33919 (9)	−0.23035 (11)	0.19101 (5)	0.02475 (18)
H13	0.289972	−0.278763	0.223810	0.030*
C14	0.38933 (10)	−0.32262 (12)	0.14020 (6)	0.0293 (2)
H14	0.375570	−0.434269	0.138722	0.035*
C15	0.45951 (9)	−0.25157 (13)	0.09161 (6)	0.02817 (19)
H15	0.492304	−0.314441	0.056220	0.034*
C16	0.48217 (8)	−0.08834 (11)	0.09445 (5)	0.02151 (16)
H16	0.530578	−0.039928	0.061247	0.026*
N1	0.00522 (7)	0.16129 (10)	0.06471 (4)	0.02100 (14)
H1N	0.0238 (11)	0.220 (3)	0.0325 (19)	0.025*	0.33 (2)
N2	−0.09869 (7)	0.00209 (9)	0.12923 (4)	0.01850 (13)
N3	0.11314 (7)	0.35581 (10)	−0.02425 (4)	0.02125 (14)
H3N	0.0690 (11)	0.2936 (16)	0.0021 (7)	0.026*	0.67 (2)
N4	0.16511 (7)	0.50600 (9)	−0.10967 (4)	0.02018 (14)
O1	0.35734 (8)	0.28443 (9)	0.17511 (6)	0.0439 (2)
O2	0.49875 (9)	0.26229 (11)	0.08516 (4)	0.0383 (2)
O3	0.57130 (9)	0.21999 (10)	0.20780 (5)	0.0400 (2)
S1	0.46799 (2)	0.20953 (2)	0.15392 (2)	0.01791 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0187 (4)	0.0277 (4)	0.0242 (4)	−0.0014 (3)	−0.0009 (3)	0.0018 (3)
C2	0.0207 (4)	0.0263 (4)	0.0202 (4)	0.0008 (3)	−0.0024 (3)	0.0030 (3)
C3	0.0179 (3)	0.0208 (4)	0.0163 (3)	0.0012 (3)	0.0019 (3)	0.0019 (3)
C4	0.0218 (4)	0.0268 (4)	0.0244 (4)	−0.0017 (3)	0.0057 (3)	0.0059 (3)
C5	0.0206 (4)	0.0326 (5)	0.0214 (4)	−0.0007 (3)	−0.0025 (3)	0.0057 (3)
C6	0.0217 (4)	0.0257 (4)	0.0285 (4)	−0.0007 (3)	−0.0032 (3)	−0.0017 (3)
C7	0.0176 (4)	0.0236 (4)	0.0338 (5)	−0.0029 (3)	0.0020 (3)	−0.0033 (3)
C8	0.0182 (3)	0.0197 (3)	0.0183 (3)	−0.0019 (3)	0.0032 (3)	−0.0005 (3)
C9	0.0367 (5)	0.0263 (4)	0.0240 (4)	−0.0061 (4)	0.0108 (4)	0.0020 (3)
C10	0.0209 (4)	0.0326 (5)	0.0237 (4)	−0.0051 (3)	−0.0017 (3)	0.0037 (3)
C11	0.0138 (3)	0.0151 (3)	0.0160 (3)	−0.0013 (2)	−0.0009 (2)	0.0004 (2)
C12	0.0195 (3)	0.0185 (3)	0.0174 (3)	−0.0033 (3)	0.0012 (3)	0.0012 (3)
C13	0.0264 (4)	0.0195 (4)	0.0271 (4)	−0.0066 (3)	−0.0035 (3)	0.0064 (3)
C14	0.0310 (5)	0.0154 (4)	0.0388 (5)	0.0007 (3)	−0.0104 (4)	−0.0017 (3)
C15	0.0254 (4)	0.0259 (4)	0.0320 (5)	0.0068 (3)	−0.0036 (3)	−0.0108 (4)
C16	0.0171 (3)	0.0271 (4)	0.0203 (4)	0.0017 (3)	0.0017 (3)	−0.0031 (3)
N1	0.0185 (3)	0.0238 (3)	0.0208 (3)	−0.0010 (3)	0.0027 (2)	0.0026 (3)
N2	0.0179 (3)	0.0203 (3)	0.0174 (3)	0.0002 (2)	0.0017 (2)	0.0026 (2)
N3	0.0206 (3)	0.0230 (3)	0.0199 (3)	−0.0013 (3)	0.0008 (2)	0.0010 (3)
N4	0.0199 (3)	0.0193 (3)	0.0219 (3)	−0.0027 (2)	0.0051 (2)	−0.0011 (3)
O1	0.0321 (4)	0.0167 (3)	0.0868 (7)	−0.0008 (3)	0.0267 (5)	−0.0041 (4)
O2	0.0559 (5)	0.0311 (4)	0.0288 (4)	−0.0159 (4)	0.0089 (4)	0.0088 (3)
O3	0.0445 (5)	0.0265 (4)	0.0438 (5)	−0.0125 (3)	−0.0235 (4)	0.0020 (3)
S1	0.01652 (9)	0.01532 (9)	0.02171 (10)	−0.00380 (6)	0.00082 (7)	0.00194 (6)

Geometric parameters (Å, º) top

C1—C2	1.3612 (13)	C9—H9A	0.9800
C1—N1	1.3845 (12)	C9—H9B	0.9800
C1—H1	0.9500	C9—H9C	0.9800
C2—N2	1.3809 (11)	C10—H10A	0.9800
C2—H2	0.9500	C10—H10B	0.9800
C3—N1	1.3283 (11)	C10—H10C	0.9800
C3—N2	1.3541 (11)	C11—C16	1.3910 (12)
C3—C5	1.4848 (12)	C11—C12	1.3921 (11)
C4—N2	1.4613 (11)	C11—S1	1.7767 (8)
C4—H4A	0.9800	C12—C13	1.3897 (12)
C4—H4B	0.9800	C12—H12	0.9500
C4—H4C	0.9800	C13—C14	1.3883 (15)
C5—H5A	0.9800	C13—H13	0.9500
C5—H5B	0.9800	C14—C15	1.3866 (16)
C5—H5C	0.9800	C14—H14	0.9500
C6—C7	1.3580 (14)	C15—C16	1.3937 (14)
C6—N3	1.3847 (12)	C15—H15	0.9500
C6—H6	0.9500	C16—H16	0.9500
C7—N4	1.3815 (12)	N1—H1N	0.83 (5)
C7—H7	0.9500	N3—H3N	0.89 (2)
C8—N3	1.3322 (11)	O1—S1	1.4489 (8)
C8—N4	1.3418 (11)	O2—S1	1.4465 (8)
C8—C10	1.4805 (12)	O3—S1	1.4484 (8)
C9—N4	1.4639 (12)

C2—C1—N1	109.27 (8)	C8—C10—H10C	109.5
C2—C1—H1	125.4	H10A—C10—H10C	109.5
N1—C1—H1	125.4	H10B—C10—H10C	109.5
C1—C2—N2	105.94 (8)	C16—C11—C12	120.15 (8)
C1—C2—H2	127.0	C16—C11—S1	120.42 (6)
N2—C2—H2	127.0	C12—C11—S1	119.39 (6)
N1—C3—N2	110.00 (7)	C13—C12—C11	119.83 (8)
N1—C3—C5	127.01 (8)	C13—C12—H12	120.1
N2—C3—C5	122.99 (8)	C11—C12—H12	120.1
N2—C4—H4A	109.5	C14—C13—C12	120.20 (9)
N2—C4—H4B	109.5	C14—C13—H13	119.9
H4A—C4—H4B	109.5	C12—C13—H13	119.9
N2—C4—H4C	109.5	C15—C14—C13	119.89 (9)
H4A—C4—H4C	109.5	C15—C14—H14	120.1
H4B—C4—H4C	109.5	C13—C14—H14	120.1
C3—C5—H5A	109.5	C14—C15—C16	120.31 (9)
C3—C5—H5B	109.5	C14—C15—H15	119.8
H5A—C5—H5B	109.5	C16—C15—H15	119.8
C3—C5—H5C	109.5	C11—C16—C15	119.60 (9)
H5A—C5—H5C	109.5	C11—C16—H16	120.2
H5B—C5—H5C	109.5	C15—C16—H16	120.2
C7—C6—N3	107.48 (8)	C3—N1—C1	106.66 (8)
C7—C6—H6	126.3	C3—N1—H1N	126.7
N3—C6—H6	126.3	C1—N1—H1N	126.7
C6—C7—N4	106.69 (8)	C3—N2—C2	108.13 (7)
C6—C7—H7	126.7	C3—N2—C4	125.59 (7)
N4—C7—H7	126.7	C2—N2—C4	126.12 (7)
N3—C8—N4	108.53 (8)	C8—N3—C6	108.47 (8)
N3—C8—C10	126.61 (8)	C8—N3—H3N	125.8
N4—C8—C10	124.85 (8)	C6—N3—H3N	125.8
N4—C9—H9A	109.5	C8—N4—C7	108.83 (8)
N4—C9—H9B	109.5	C8—N4—C9	125.08 (8)
H9A—C9—H9B	109.5	C7—N4—C9	126.06 (8)
N4—C9—H9C	109.5	O2—S1—O3	112.77 (6)
H9A—C9—H9C	109.5	O2—S1—O1	112.73 (6)
H9B—C9—H9C	109.5	O3—S1—O1	112.82 (7)
C8—C10—H10A	109.5	O2—S1—C11	106.84 (4)
C8—C10—H10B	109.5	O3—S1—C11	105.15 (4)
H10A—C10—H10B	109.5	O1—S1—C11	105.78 (4)

N1—C1—C2—N2	0.06 (11)	C1—C2—N2—C3	−0.06 (10)
N3—C6—C7—N4	−0.20 (11)	C1—C2—N2—C4	−175.75 (9)
C16—C11—C12—C13	1.40 (12)	N4—C8—N3—C6	−0.12 (10)
S1—C11—C12—C13	−176.27 (7)	C10—C8—N3—C6	179.13 (9)
C11—C12—C13—C14	−0.33 (13)	C7—C6—N3—C8	0.20 (11)
C12—C13—C14—C15	−1.04 (14)	N3—C8—N4—C7	0.00 (10)
C13—C14—C15—C16	1.35 (15)	C10—C8—N4—C7	−179.28 (9)
C12—C11—C16—C15	−1.09 (12)	N3—C8—N4—C9	178.37 (8)
S1—C11—C16—C15	176.55 (7)	C10—C8—N4—C9	−0.91 (14)
C14—C15—C16—C11	−0.28 (14)	C6—C7—N4—C8	0.13 (10)
N2—C3—N1—C1	0.00 (10)	C6—C7—N4—C9	−178.22 (9)
C5—C3—N1—C1	179.55 (9)	C16—C11—S1—O2	24.77 (8)
C2—C1—N1—C3	−0.04 (11)	C12—C11—S1—O2	−157.57 (7)
N1—C3—N2—C2	0.03 (10)	C16—C11—S1—O3	−95.30 (8)
C5—C3—N2—C2	−179.54 (9)	C12—C11—S1—O3	82.36 (8)
N1—C3—N2—C4	175.76 (8)	C16—C11—S1—O1	145.10 (8)
C5—C3—N2—C4	−3.81 (14)	C12—C11—S1—O1	−37.24 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N3	0.83	1.90	2.6970 (11)	163
N3—H3N···N1	0.89	1.81	2.6970 (11)	170
C1—H1···O1	0.95	2.43	3.3741 (13)	170
C4—H4B···O3ⁱ	0.98	2.33	3.2956 (12)	170
C6—H6···O2	0.95	2.60	3.4288 (14)	146
C7—H7···O2ⁱⁱ	0.95	2.41	3.3254 (12)	162
C9—H9A···O3ⁱⁱⁱ	0.98	2.53	3.4846 (14)	164
C9—H9B···O3ⁱⁱ	0.98	2.46	3.4381 (14)	173
C13—H13···O1ⁱ	0.95	2.67	3.4738 (14)	143
C14—H14···O1^iv	0.95	2.48	3.3920 (13)	162

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

Acknowledgements

This material is based upon work supported by the National Science Foundation through the Major Research Instrumentation Program under grant No. CHE 1625543 (funding for the single-crystal X-ray diffractometer). Acknowledgment is made to the donors of the American Chemical Society Petroleum Research Fund for support of this research. The authors gratefully acknowledge the Communities in Transition Initiative for the generous support.

Funding information

Funding for this research was provided by: National Science Foundation (grant No. CHE 11625543); American Chemical Society Petroleum Research Fund (grant No. PRF 58975-UR4); Ave Maria University Department of Chemistry and Physics .

References

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bruker (2018). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. 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
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Kelley, S. P., Narita, A., Holbrey, J. D., Green, K. D., Reichert, W. M. & Rogers, R. D. (2013). Cryst. Growth Des. 13, 965–975. Web of Science CSD CrossRef CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS 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
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.