Crystal structure of a 2:1 piroxicam–gentisic acid co-crystal featuring neutral and zwitterionic piroxicam mol­ecules

Horstman, E.M.; Bertke, J.A.; Woods, T.J.; Kenis, P.J.A.

doi:10.1107/S2056989016017321

research communications

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ISSN: 2056-9890

Volume 72| Part 12| December 2016| Pages 1714-1717

https://doi.org/10.1107/S2056989016017321

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Crystal structure of a 2:1 piroxicam–gentisic acid co-crystal featuring neutral and zwitterionic piroxicam molecules

Elizabeth M. Horstman,^a Jeffery A. Bertke,^b Toby J. Woods ^b ^* and Paul J. A. Kenis ^a

^aUniversity of Illinois, Department of Chemical and Biomolecular Engineering, 600 S. Mathews Ave, Urbana, IL 61801, USA, and ^bUniversity of Illinois, School of Chemical Sciences, Box 59-1, 505 South Mathews Avenue, Urbana, Illinois 61801, USA
^*Correspondence e-mail: tobyw@illinois.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 21 October 2016; accepted 27 October 2016; online 4 November 2016)

A new 2:1 co-crystal of piroxicam and gentisic acid [systematic name: 4-hydroxy-1,1-dioxo-N-(pyridin-2-yl)-2H-1λ⁶,2-benzothiazine-3-carboxamide–2-(4-oxido-1,1-dioxo-2H-1λ⁶,2-benzothiazine-3-amido)pyridin-1-ium–2,5-dihydroxybenzoic acid, 2C₁₅H₁₃N₃O₄S·C₇H₆O₄] has been synthesized using a microfluidic platform and initially identified using Raman spectroscopy. In the co-crystal, one piroxicam molecule is in its neutral form and an intramolecular O—H⋯O hydrogen bond is observed. The other piroxicam molecule is zwitterionic (proton transfer from the OH group to the pyridine N atom) and two intramolecular N—H⋯O hydrogen bonds occur. The gentisic acid molecule shows whole-molecule disorder over two sets of sites in a 0.809 (2):0.191 (2) ratio. In the crystal, extensive hydrogen bonding between the components forms layers propagating in the ab plane.

Keywords: crystal structure; hydrogen bonding; piroxicam.

CCDC reference: 1512430

1. Chemical context

Piroxicam is a non-steroidal anti-inflammatory drug classified as a BCS Class II drug due to its low aqueous solubility (Amidon et al., 1995 ; Thayer, 2010 ). Co-crystallization of an active pharmaceutical ingredient (API) and an FDA-approved counter-ion is a common technique employed to increase the solubility of the API (Trask et al., 2005 ). In this work, we explored the co-crystallization of piroxicam and gentisic acid. In a previous study, piroxicam was co-crystallized with 23 carboxylic acids yielding 50 co-crystals. From this work, three co-crystals of piroxicam and gentisic acid were identified with Raman spectroscopy, but no crystal structures were reported (Childs & Hardcastle, 2007 ). In our prior work, we reported the crystal structure of two co-crystals of piroxicam and gentisic acid, one was a 1:1 co-crystal and the second was a solvated co-crystal that incorporated acetone into the crystal in a 1:1:1 molar ratio (Horstman et al., 2015 ). In this work we describe the crystal structure of a 2:1 piroxicam:gentisic acid co-crystal.

2. Structural commentary

The asymmetric unit of this co-crystal consists of two piroxicam molecules and one gentisic acid molecule, with all atoms residing on general positions (Fig. 1). One of the piroxicam molecules is neutral and the other is a zwitterion: the two molecules exhibit two different conformations in the crystal structure. In the neutral S2-containing molecule, intramolecular hydrogen bonding exists between the hydroxyl proton H8 [H⋯A = 1.79 (3) Å] and the amide oxygen atom O7. In the S2 molecule, free rotation about the C—C bond (C1 and C10) allows a second zwitterionic conformation in which intramolecular hydrogen bonds exist between the amine proton H2 and the enolate oxygen atom O4 [H⋯A = 1.85 (2) Å] and the pyridinium proton H3 and the amide oxygen atom O3 [H⋯A = 2.19 (2) Å]. Further details of the hydrogen bonding are provided in Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O4	0.88 (2)	1.85 (2)	2.6169 (18)	145.2 (19)
N3—H3⋯O3	0.78 (2)	1.99 (2)	2.6027 (19)	135 (2)
N3—H3⋯O3ⁱ	0.78 (2)	2.19 (2)	2.8034 (19)	136 (2)
O8—H8⋯O7	0.88 (3)	1.79 (3)	2.5722 (19)	148 (2)
N5—H5⋯O9	0.84 (2)	2.25 (2)	3.074 (2)	167 (2)
O10—H10⋯N6	0.91 (3)	1.74 (3)	2.637 (3)	167 (3)
O11—H11⋯O9	0.81 (3)	1.89 (3)	2.614 (2)	148 (3)
O12—H12⋯O4ⁱⁱ	0.81 (3)	1.94 (3)	2.738 (3)	164 (4)
O10B—H10B⋯O4ⁱⁱ	0.84	1.67	2.508 (12)	172
O11B—H11B⋯O2ⁱ	0.84	2.57	3.061 (6)	118
O11B—H11B⋯O9B	0.84	1.89	2.614 (9)	143
O12B—H12B⋯N6	0.84	2.10	2.856 (12)	149
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z.

Figure 1
The molecular structure of the title co-crystal, showing 35% probability ellipsoids for non-H atoms and spheres of arbitrary size for H atoms. Only the major component of the disordered gentisic acid is shown.

The gentisic acid molecule shows whole molecule disorder over two orientations rotated by approximately 180° in the plane of the aromatic ring with site occupancies of 0.809 (2):0.191 (2). The major orientation participates in intramolecular hydrogen bonding between the O11 hydroxide substituent of the benzene ring and the O9 oxygen atom of the carboxylic acid [H⋯A = 1.89 (3) Å]. The major orientation also participates in intermolecular hydrogen bonding. The minor orientation of the gentisic acid molecule also displays intramolecular hydrogen bonding between the O11B hydroxide substituent and the O9B oxygen atom of the carboxylic acid (H⋯A = 1.89 Å) but does not participate in intermolecular hydrogen bonding.

3. Supramolecular features

In the crystal, hydrogen bonds (Table 1) between the piroxicam and gentisic acid molecules form hexameric units that propagate along the a-axis direction (Fig. 2). These units pack into layers in the ab plane; the layers stack along the c-axis direction, Fig. 3.

Figure 2
Ball-and-stick model highlighting the hydrogen-bonding network in the title co-crystal. Only the major component of the disordered gentisic acid is shown. Color key: C gray, N blue, H green, O red, and S yellow. H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 3
Ball-and-stick packing diagram of the co-crystal, as viewed approximately down the b axis, highlighting the layers formed by the packing of the hexameric units. Color key: C gray, N blue, O red, and S yellow. H atoms have been omitted for clarity.

The repeating motif of the hexameric unit is formed by one gentisic acid molecule hydrogen bonded to two piroxicam molecules, one of each conformation (i.e. neutral and zwitterion). The non-zwitterionic form of piroxicam accepts hydrogen bonds from the gentisic acid via O—H⋯N bonds between the carboxylic acid and the pyridine ring of piroxicam [H⋯A = 1.74 (3) Å] as well as N—H⋯O bonds between the carbonyl oxygen atom of gentisic acid and the amine nitrogen atom of piroxicam [H⋯A = 2.25 (2) Å]. The zwitterionic form of piroxicam accepts hydrogen bonds from the gentisic acid via O—H⋯O bonds between the 5-hydroxy substituent of gentisic acid and the enolate oxygen atom of piroxicam [H⋯A = 1.94 (3) Å]. The repeat units are linked together by N—H⋯O bonds between the pyridinium nitrogen atoms and the amide oxygen atoms of the zwitterionic form of piroxicam [H⋯A = 2.19 (2) Å].

4. Synthesis and crystallization

Piroxicam (>=98.0%) and gentisic acid (>=98.0%) were used as purchased from Sigma–Aldrich (St. Louis, MO, USA). Acetonitrile (>=99.9%) was used as purchased from Fisher Scientific (Fair Lawn, NJ, USA). A 1:2 molar ratio of piroxicam:gentisic acid was dissolved in acetonitrile. The concentration of piroxicam in acetonitrile was near saturation (∼0.034 M). The resulting solution was introduced into a microfluidic platform. The microfluidic platform was a 6 × 6 array of single microwells (∼100 nl) (Horstman et al., 2015). After being filled, the microfluidic platform was placed inside a petri dish and then the petri dish was sealed with parafilm to slow the rate of solvent evaporation. The crystallization solution evaporated over the course of one day, after which crystals were observed via optical microscopy. Specifics of the microfluidic platform fabrication and operation have been previously reported (Horstman et al., 2015). Once crystals were observed, Raman spectroscopy was used to distinguish between crystals. Within one microfluidic chip, three different co-crystals of piroxicam and gentisic acid were observed, two of which had been previously reported (Horstman et al., 2015) and one new solid form, reported here. Once the new co-crystals had been identified, we removed the crystals from the microfluidic platform.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The gentisic acid molecule shows whole molecule disorder over two sets of sites: the like C—O and C—C distances were restrained to be similar (s.u. 0.01 Å). Similar displacement amplitudes (s.u. 0.01) were imposed on disordered sites overlapping by less than the sum of van der Waals radii.

Table 2
Experimental details

Crystal data
Chemical formula	2C₁₅H₁₃N₃O₄S·C₇H₆O₄
M_r	816.80
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	105
a, b, c (Å)	8.8764 (3), 13.4060 (5), 15.2678 (6)
α, β, γ (°)	80.4660 (15), 85.4332 (15), 78.4602 (15)
V (Å³)	1753.48 (11)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	2.05
Crystal size (mm)	0.15 × 0.15 × 0.03

Data collection
Diffractometer	Bruker D8 Venture/Photon 100
Absorption correction	Integration (SADABS; Bruker, 2014 )
T_min, T_max	0.867, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	49307, 6416, 5801
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.086, 1.11
No. of reflections	6416
No. of parameters	637
No. of restraints	374
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.40
Computer programs: APEX2, SAINT, XPREP, and XCIF (Bruker, 2014), SHELXS2014-4 and SHELXTL (Sheldrick, 2008 ), SHELXL2014-6 (Sheldrick, 2015 ) and CrystalMaker (CrystalMaker, 1994 ).

All O—H and N—H hydrogen atoms were located in the difference map except for those on the minor-disordered component of the gentisic acid. The H atoms located in the difference map were allowed to refine the O—H/N—H bond distances. These H atoms refined to good hydrogen-bonding positions (Hamilton & Ibers, 1968 ). The hydroxyl H atoms on the minor-disordered component of gentisic acid were optimized by rotation about R—O bonds with idealized O—H and R—H distances. These H atoms are also in good hydrogen-bonding locations. Methyl H-atom positions, R—CH₃, were optimized by rotation about R—C bonds with idealized C—H, R⋯H and H⋯H distances. The remaining H atoms were included as riding idealized contributors. Methyl, hydroxyl and amine H atom U_iso values were assigned as 1.5U_eq of the carrier atom; remaining H-atom U_iso were assigned as 1.2 × carrier U_eq.

The ( $[\overline{1}]$ $[\overline{1}]$ 2) reflection was omitted from the final refinement because it was partially obscured by the shadow of the beamstop in some orientations.

Supporting information

CCDC reference: 1512430

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016017321/hb7625sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016017321/hb7625Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016017321/hb7625Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2056989016017321/hb7625Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014) and XPREP (Bruker, 2014); program(s) used to solve structure: SHELXS2014-4 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014-6 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008), CrystalMaker (CrystalMaker, 1994); software used to prepare material for publication: XCIF (Bruker, 2014).

4-Hydroxy-1,1-dioxo-N-(pyridin-2-yl)-2H-1λ⁶,2-benzothiazine-3-carboxamide–2-(4-oxido-1,1-dioxo-2H-1λ⁶,2-benzothiazine-3-amido)pyridin-1-ium–2,5-dihydroxybenzoic acid top

Crystal data top

2C₁₅H₁₃N₃O₄S·C₇H₆O₄	Z = 2
M_r = 816.80	F(000) = 848
Triclinic, P1	D_x = 1.547 Mg m⁻³
a = 8.8764 (3) Å	Cu Kα radiation, λ = 1.54178 Å
b = 13.4060 (5) Å	Cell parameters from 9375 reflections
c = 15.2678 (6) Å	θ = 2.9–68.1°
α = 80.4660 (15)°	µ = 2.05 mm⁻¹
β = 85.4332 (15)°	T = 105 K
γ = 78.4602 (15)°	Plate, colourless
V = 1753.48 (11) Å³	0.15 × 0.15 × 0.03 mm

Data collection top

Bruker D8 Venture/Photon 100 diffractometer	6416 independent reflections
Radiation source: microfocus sealed tube	5801 reflections with I > 2σ(I)
Multilayer mirrors monochromator	R_int = 0.037
profile data from φ and ω scans	θ_max = 68.3°, θ_min = 2.9°
Absorption correction: integration (SADABS; Bruker, 2014)	h = −10→10
T_min = 0.867, T_max = 0.965	k = −16→15
49307 measured reflections	l = −18→18

Refinement top

Refinement on F²	374 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.0348P)² + 1.2991P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
6416 reflections	Δρ_max = 0.24 e Å⁻³
637 parameters	Δρ_min = −0.40 e Å⁻³

Special details top

Experimental. One distinct cell was identified using APEX2 (Bruker, 2014). Thirty frame series were integrated and filtered for statistical outliers using SAINT (Bruker, 2013) then corrected for absorption by integration using SAINT/SADABS v2014/2 (Bruker, 2014) to sort, merge, and scale the combined data. No decay correction was applied.

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. Structure was phased by direct methods (Sheldrick, 2014). Systematic conditions suggested the ambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F². The final map had no significant features. A final analysis of variance between observed and calculated structure factors showed little dependence on amplitude and resolution.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.90408 (4)	0.14390 (3)	0.54955 (3)	0.01390 (10)
O1	0.82965 (14)	0.05638 (9)	0.56665 (8)	0.0187 (3)
O2	0.94543 (13)	0.18072 (9)	0.45902 (8)	0.0171 (3)
O3	0.63926 (13)	0.43288 (9)	0.53570 (8)	0.0190 (3)
O4	1.07869 (13)	0.38775 (9)	0.63196 (8)	0.0179 (3)
N1	0.79315 (16)	0.23889 (11)	0.59094 (9)	0.0146 (3)
N2	0.82451 (16)	0.51014 (11)	0.57712 (10)	0.0153 (3)
H2	0.918 (3)	0.4941 (16)	0.5974 (14)	0.023*
N3	0.60509 (16)	0.63109 (12)	0.53091 (10)	0.0154 (3)
H3	0.571 (3)	0.5850 (18)	0.5199 (14)	0.023*
C1	0.86562 (19)	0.32602 (13)	0.59352 (11)	0.0146 (3)
C2	1.01351 (19)	0.31258 (13)	0.62393 (11)	0.0146 (3)
C3	1.10283 (19)	0.20511 (13)	0.64669 (11)	0.0145 (3)
C4	1.22916 (19)	0.18627 (14)	0.70002 (11)	0.0170 (4)
H4A	1.2584	0.2418	0.7215	0.020*
C5	1.3123 (2)	0.08704 (14)	0.72188 (12)	0.0208 (4)
H5A	1.3976	0.0754	0.7586	0.025*
C6	1.2726 (2)	0.00480 (14)	0.69087 (12)	0.0214 (4)
H6A	1.3307	−0.0627	0.7062	0.026*
C7	1.1480 (2)	0.02107 (14)	0.63738 (12)	0.0186 (4)
H7A	1.1199	−0.0349	0.6158	0.022*
C8	1.06514 (19)	0.12048 (13)	0.61587 (11)	0.0148 (3)
C9	0.6952 (2)	0.21086 (14)	0.67045 (12)	0.0203 (4)
H9A	0.6442	0.1555	0.6607	0.030*
H9B	0.6174	0.2711	0.6812	0.030*
H9C	0.7591	0.1874	0.7221	0.030*
C10	0.76774 (19)	0.42370 (13)	0.56612 (11)	0.0143 (3)
C11	0.74705 (19)	0.60956 (13)	0.56233 (11)	0.0138 (3)
C12	0.5198 (2)	0.72695 (13)	0.51690 (11)	0.0176 (4)
H12A	0.4189	0.7375	0.4961	0.021*
C13	0.5776 (2)	0.80883 (13)	0.53244 (11)	0.0179 (4)
H13A	0.5187	0.8768	0.5222	0.022*
C14	0.7258 (2)	0.79029 (13)	0.56383 (11)	0.0165 (3)
H14A	0.7689	0.8464	0.5744	0.020*
C15	0.81005 (19)	0.69159 (13)	0.57964 (11)	0.0159 (3)
H15A	0.9100	0.6793	0.6021	0.019*
S2	0.69631 (5)	0.91958 (3)	0.90830 (3)	0.01758 (11)
O5	0.55243 (14)	0.92712 (10)	0.86939 (9)	0.0249 (3)
O6	0.71653 (14)	0.87123 (10)	0.99842 (8)	0.0221 (3)
O7	1.23078 (14)	0.76608 (10)	0.90420 (8)	0.0239 (3)
O8	1.15980 (15)	0.96135 (11)	0.90637 (8)	0.0224 (3)
H8	1.218 (3)	0.900 (2)	0.9064 (15)	0.034*
N4	0.83342 (17)	0.85905 (11)	0.84673 (9)	0.0177 (3)
N5	1.04254 (18)	0.67834 (12)	0.88379 (10)	0.0197 (3)
H5	0.950 (3)	0.6828 (18)	0.8715 (15)	0.030*
N6	1.06042 (17)	0.50686 (12)	0.87478 (11)	0.0243 (4)
C16	0.9849 (2)	0.86239 (14)	0.87249 (11)	0.0179 (4)
C17	1.0193 (2)	0.95255 (14)	0.88695 (11)	0.0190 (4)
C18	0.9022 (2)	1.04731 (14)	0.88701 (11)	0.0186 (4)
C19	0.9434 (2)	1.14325 (15)	0.88329 (12)	0.0223 (4)
H19A	1.0489	1.1488	0.8781	0.027*
C20	0.8303 (2)	1.23013 (15)	0.88712 (13)	0.0251 (4)
H20A	0.8590	1.2953	0.8839	0.030*
C21	0.6755 (2)	1.22358 (15)	0.89559 (12)	0.0236 (4)
H21A	0.5993	1.2840	0.8983	0.028*
C22	0.6316 (2)	1.12915 (14)	0.90012 (12)	0.0205 (4)
H22A	0.5259	1.1241	0.9059	0.025*
C23	0.7451 (2)	1.04244 (14)	0.89609 (11)	0.0177 (4)
C24	0.8156 (2)	0.88255 (15)	0.74935 (12)	0.0234 (4)
H24A	0.7116	0.8770	0.7362	0.035*
H24B	0.8914	0.8335	0.7198	0.035*
H24C	0.8322	0.9527	0.7276	0.035*
C25	1.0965 (2)	0.76629 (14)	0.88733 (11)	0.0195 (4)
C26	1.1243 (2)	0.57710 (14)	0.90290 (12)	0.0190 (4)
C27	1.1306 (2)	0.40771 (16)	0.89178 (16)	0.0338 (5)
H27A	1.0865	0.3576	0.8708	0.041*
C28	1.2628 (2)	0.37473 (16)	0.93788 (16)	0.0339 (5)
H28A	1.3088	0.3038	0.9490	0.041*
C29	1.3263 (2)	0.44807 (16)	0.96739 (14)	0.0304 (5)
H29A	1.4172	0.4278	0.9999	0.036*
C30	1.2588 (2)	0.55046 (16)	0.94990 (13)	0.0254 (4)
H30A	1.3025	0.6017	0.9693	0.031*
O9	0.72760 (18)	0.66660 (12)	0.81992 (11)	0.0214 (4)	0.809 (2)
O10	0.8016 (3)	0.5013 (2)	0.8038 (3)	0.0235 (7)	0.809 (2)
H10	0.888 (4)	0.514 (2)	0.8249 (19)	0.035*	0.809 (2)
O11	0.47005 (19)	0.77049 (14)	0.75304 (11)	0.0209 (4)	0.809 (2)
H11	0.546 (4)	0.758 (2)	0.782 (2)	0.031*	0.809 (2)
O12	0.3599 (3)	0.3988 (2)	0.6873 (2)	0.0234 (6)	0.809 (2)
H12	0.272 (4)	0.407 (3)	0.672 (2)	0.035*	0.809 (2)
C31	0.5536 (2)	0.58575 (16)	0.75879 (14)	0.0152 (5)	0.809 (2)
C32	0.4463 (3)	0.67789 (19)	0.73843 (19)	0.0152 (6)	0.809 (2)
C33	0.3109 (3)	0.67561 (19)	0.69899 (15)	0.0185 (5)	0.809 (2)
H33A	0.2387	0.7377	0.6840	0.022*	0.809 (2)
C34	0.2805 (3)	0.5836 (2)	0.68143 (17)	0.0186 (5)	0.809 (2)
H34A	0.1877	0.5830	0.6546	0.022*	0.809 (2)
C35	0.3854 (3)	0.49164 (17)	0.70295 (14)	0.0172 (5)	0.809 (2)
C36	0.5210 (5)	0.4934 (2)	0.7409 (4)	0.0163 (7)	0.809 (2)
H36A	0.5931	0.4310	0.7551	0.020*	0.809 (2)
C37	0.6998 (3)	0.5882 (2)	0.79668 (14)	0.0167 (5)	0.809 (2)
O9B	0.1664 (7)	0.5901 (5)	0.6578 (4)	0.0206 (16)	0.191 (2)
O10B	0.3138 (14)	0.4318 (6)	0.6853 (10)	0.021 (2)	0.191 (2)
H10B	0.2402	0.4157	0.6631	0.032*	0.191 (2)
O11B	0.2617 (7)	0.7479 (5)	0.6992 (4)	0.0197 (15)	0.191 (2)
H11B	0.2006	0.7193	0.6775	0.030*	0.191 (2)
O12B	0.7796 (13)	0.4710 (8)	0.8181 (12)	0.023 (3)	0.191 (2)
H12B	0.8381	0.5004	0.8411	0.035*	0.191 (2)
C31B	0.4054 (8)	0.5709 (5)	0.7243 (5)	0.0140 (14)	0.191 (2)
C32B	0.3839 (10)	0.6760 (6)	0.7300 (8)	0.011 (2)	0.191 (2)
C33B	0.4961 (9)	0.7113 (8)	0.7689 (7)	0.0185 (18)	0.191 (2)
H33B	0.4817	0.7822	0.7743	0.022*	0.191 (2)
C34B	0.6284 (10)	0.6449 (6)	0.7999 (6)	0.0200 (17)	0.191 (2)
H34B	0.7037	0.6701	0.8263	0.024*	0.191 (2)
C35B	0.6496 (9)	0.5409 (6)	0.7919 (6)	0.0181 (17)	0.191 (2)
C36B	0.5395 (19)	0.5046 (9)	0.7541 (17)	0.016 (3)	0.191 (2)
H36B	0.5550	0.4338	0.7484	0.019*	0.191 (2)
C37B	0.2857 (10)	0.5323 (6)	0.6866 (7)	0.017 (2)	0.191 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01315 (19)	0.0118 (2)	0.0172 (2)	−0.00249 (15)	−0.00408 (15)	−0.00194 (15)
O1	0.0190 (6)	0.0134 (6)	0.0248 (6)	−0.0051 (5)	−0.0039 (5)	−0.0020 (5)
O2	0.0183 (6)	0.0175 (6)	0.0166 (6)	−0.0050 (5)	−0.0041 (5)	−0.0019 (5)
O3	0.0139 (6)	0.0157 (6)	0.0277 (7)	−0.0021 (5)	−0.0080 (5)	−0.0021 (5)
O4	0.0145 (6)	0.0142 (6)	0.0259 (6)	−0.0031 (5)	−0.0062 (5)	−0.0029 (5)
N1	0.0128 (7)	0.0118 (7)	0.0193 (7)	−0.0025 (5)	−0.0020 (6)	−0.0015 (6)
N2	0.0112 (7)	0.0134 (7)	0.0212 (7)	−0.0022 (6)	−0.0049 (6)	−0.0010 (6)
N3	0.0146 (7)	0.0135 (7)	0.0193 (7)	−0.0040 (6)	−0.0042 (6)	−0.0025 (6)
C1	0.0148 (8)	0.0126 (8)	0.0170 (8)	−0.0037 (7)	−0.0024 (6)	−0.0020 (6)
C2	0.0155 (8)	0.0143 (9)	0.0136 (8)	−0.0025 (7)	−0.0016 (6)	−0.0015 (6)
C3	0.0130 (8)	0.0151 (9)	0.0147 (8)	−0.0021 (7)	−0.0016 (6)	−0.0007 (6)
C4	0.0160 (8)	0.0166 (9)	0.0191 (9)	−0.0042 (7)	−0.0039 (7)	−0.0019 (7)
C5	0.0167 (9)	0.0211 (10)	0.0231 (9)	−0.0019 (7)	−0.0081 (7)	0.0022 (7)
C6	0.0183 (9)	0.0156 (9)	0.0275 (10)	0.0019 (7)	−0.0046 (7)	0.0003 (7)
C7	0.0202 (9)	0.0153 (9)	0.0202 (9)	−0.0028 (7)	−0.0028 (7)	−0.0024 (7)
C8	0.0124 (8)	0.0167 (9)	0.0148 (8)	−0.0019 (7)	−0.0022 (6)	−0.0014 (7)
C9	0.0193 (9)	0.0186 (9)	0.0228 (9)	−0.0055 (7)	0.0025 (7)	−0.0023 (7)
C10	0.0148 (8)	0.0141 (9)	0.0147 (8)	−0.0038 (7)	−0.0013 (6)	−0.0024 (6)
C11	0.0129 (8)	0.0150 (8)	0.0128 (8)	−0.0021 (6)	−0.0002 (6)	−0.0008 (6)
C12	0.0155 (8)	0.0162 (9)	0.0197 (9)	−0.0007 (7)	−0.0047 (7)	−0.0002 (7)
C13	0.0181 (9)	0.0138 (9)	0.0205 (9)	0.0003 (7)	−0.0018 (7)	−0.0024 (7)
C14	0.0183 (8)	0.0158 (9)	0.0162 (8)	−0.0050 (7)	0.0007 (7)	−0.0038 (7)
C15	0.0126 (8)	0.0185 (9)	0.0175 (8)	−0.0041 (7)	−0.0022 (6)	−0.0031 (7)
S2	0.0170 (2)	0.0154 (2)	0.0212 (2)	−0.00564 (16)	−0.00270 (16)	−0.00123 (16)
O5	0.0197 (7)	0.0201 (7)	0.0361 (8)	−0.0052 (5)	−0.0079 (6)	−0.0028 (6)
O6	0.0242 (7)	0.0200 (7)	0.0218 (7)	−0.0076 (5)	0.0007 (5)	0.0004 (5)
O7	0.0175 (6)	0.0289 (7)	0.0258 (7)	−0.0037 (5)	−0.0018 (5)	−0.0063 (6)
O8	0.0186 (6)	0.0261 (7)	0.0245 (7)	−0.0079 (5)	−0.0030 (5)	−0.0043 (6)
N4	0.0197 (8)	0.0170 (8)	0.0179 (7)	−0.0054 (6)	−0.0051 (6)	−0.0023 (6)
N5	0.0157 (7)	0.0179 (8)	0.0245 (8)	−0.0002 (6)	−0.0042 (6)	−0.0022 (6)
N6	0.0168 (8)	0.0185 (8)	0.0365 (9)	−0.0050 (6)	−0.0032 (7)	0.0021 (7)
C16	0.0182 (9)	0.0206 (9)	0.0157 (8)	−0.0052 (7)	−0.0021 (7)	−0.0027 (7)
C17	0.0196 (9)	0.0249 (10)	0.0139 (8)	−0.0088 (7)	−0.0003 (7)	−0.0019 (7)
C18	0.0228 (9)	0.0205 (9)	0.0140 (8)	−0.0073 (7)	−0.0004 (7)	−0.0031 (7)
C19	0.0256 (10)	0.0252 (10)	0.0192 (9)	−0.0121 (8)	0.0015 (7)	−0.0049 (7)
C20	0.0345 (11)	0.0198 (10)	0.0243 (10)	−0.0126 (8)	0.0030 (8)	−0.0058 (8)
C21	0.0297 (10)	0.0196 (10)	0.0218 (9)	−0.0046 (8)	0.0026 (8)	−0.0056 (7)
C22	0.0225 (9)	0.0206 (10)	0.0188 (9)	−0.0055 (7)	0.0019 (7)	−0.0034 (7)
C23	0.0228 (9)	0.0179 (9)	0.0139 (8)	−0.0076 (7)	−0.0015 (7)	−0.0015 (7)
C24	0.0281 (10)	0.0251 (10)	0.0183 (9)	−0.0062 (8)	−0.0067 (7)	−0.0031 (7)
C25	0.0195 (9)	0.0253 (10)	0.0137 (8)	−0.0043 (7)	0.0004 (7)	−0.0034 (7)
C26	0.0154 (8)	0.0204 (9)	0.0190 (9)	−0.0015 (7)	0.0015 (7)	−0.0001 (7)
C27	0.0214 (10)	0.0198 (10)	0.0591 (14)	−0.0076 (8)	−0.0027 (9)	0.0023 (9)
C28	0.0195 (10)	0.0210 (11)	0.0543 (14)	−0.0003 (8)	0.0019 (9)	0.0087 (9)
C29	0.0178 (9)	0.0333 (12)	0.0338 (11)	0.0011 (8)	−0.0035 (8)	0.0069 (9)
C30	0.0217 (9)	0.0272 (11)	0.0255 (10)	−0.0006 (8)	−0.0045 (8)	−0.0020 (8)
O9	0.0207 (9)	0.0158 (8)	0.0298 (9)	−0.0042 (6)	−0.0090 (7)	−0.0047 (6)
O10	0.0165 (11)	0.0150 (14)	0.0404 (16)	−0.0010 (10)	−0.0108 (10)	−0.0061 (12)
O11	0.0210 (9)	0.0140 (9)	0.0291 (9)	−0.0034 (7)	−0.0057 (7)	−0.0047 (7)
O12	0.0183 (14)	0.0172 (14)	0.0385 (11)	−0.0057 (10)	−0.0092 (11)	−0.0085 (12)
C31	0.0151 (10)	0.0154 (11)	0.0150 (10)	−0.0035 (8)	−0.0011 (8)	−0.0010 (8)
C32	0.0178 (14)	0.0120 (11)	0.0167 (12)	−0.0052 (11)	−0.0006 (12)	−0.0022 (9)
C33	0.0155 (12)	0.0170 (13)	0.0212 (12)	0.0009 (10)	−0.0034 (9)	−0.0014 (9)
C34	0.0144 (12)	0.0208 (14)	0.0200 (11)	−0.0009 (11)	−0.0030 (9)	−0.0035 (12)
C35	0.0168 (11)	0.0168 (11)	0.0188 (10)	−0.0049 (9)	0.0001 (8)	−0.0034 (9)
C36	0.0169 (14)	0.0128 (13)	0.019 (2)	−0.0031 (10)	−0.0016 (10)	−0.0014 (10)
C37	0.0178 (12)	0.0158 (13)	0.0164 (11)	−0.0036 (11)	−0.0018 (9)	−0.0013 (9)
O9B	0.017 (3)	0.017 (3)	0.029 (4)	−0.004 (3)	−0.012 (3)	−0.002 (3)
O10B	0.021 (6)	0.013 (5)	0.031 (4)	−0.006 (4)	−0.006 (4)	−0.005 (4)
O11B	0.012 (3)	0.017 (4)	0.030 (4)	0.001 (3)	−0.015 (3)	−0.002 (3)
O12B	0.018 (5)	0.015 (6)	0.039 (6)	−0.004 (4)	−0.014 (4)	−0.002 (5)
C31B	0.014 (3)	0.013 (3)	0.015 (3)	−0.001 (2)	−0.002 (2)	−0.005 (2)
C32B	0.011 (4)	0.008 (3)	0.016 (3)	−0.003 (3)	−0.006 (4)	−0.004 (3)
C33B	0.019 (4)	0.013 (4)	0.024 (4)	−0.006 (4)	0.002 (3)	−0.003 (4)
C34B	0.017 (4)	0.017 (4)	0.024 (3)	−0.003 (3)	0.000 (3)	−0.003 (3)
C35B	0.013 (3)	0.021 (4)	0.021 (3)	−0.004 (3)	−0.006 (3)	0.000 (3)
C36B	0.012 (4)	0.018 (4)	0.017 (4)	0.000 (4)	−0.003 (3)	−0.001 (4)
C37B	0.019 (4)	0.014 (4)	0.018 (4)	0.002 (4)	0.001 (3)	−0.005 (4)

Geometric parameters (Å, º) top

S1—O2	1.4333 (12)	C18—C19	1.397 (3)
S1—O1	1.4361 (12)	C18—C23	1.404 (3)
S1—N1	1.6299 (14)	C19—C20	1.383 (3)
S1—C8	1.7646 (17)	C19—H19A	0.9500
O3—C10	1.241 (2)	C20—C21	1.389 (3)
O4—C2	1.285 (2)	C20—H20A	0.9500
N1—C1	1.449 (2)	C21—C22	1.387 (3)
N1—C9	1.477 (2)	C21—H21A	0.9500
N2—C11	1.363 (2)	C22—C23	1.384 (3)
N2—C10	1.392 (2)	C22—H22A	0.9500
N2—H2	0.88 (2)	C24—H24A	0.9800
N3—C11	1.344 (2)	C24—H24B	0.9800
N3—C12	1.348 (2)	C24—H24C	0.9800
N3—H3	0.78 (2)	C26—C30	1.396 (3)
C1—C2	1.395 (2)	C27—C28	1.374 (3)
C1—C10	1.437 (2)	C27—H27A	0.9500
C2—C3	1.499 (2)	C28—C29	1.377 (3)
C3—C4	1.396 (2)	C28—H28A	0.9500
C3—C8	1.405 (2)	C29—C30	1.375 (3)
C4—C5	1.388 (2)	C29—H29A	0.9500
C4—H4A	0.9500	C30—H30A	0.9500
C5—C6	1.385 (3)	O9—C37	1.238 (3)
C5—H5A	0.9500	O10—C37	1.318 (4)
C6—C7	1.388 (3)	O10—H10	0.91 (3)
C6—H6A	0.9500	O11—C32	1.356 (3)
C7—C8	1.388 (2)	O11—H11	0.81 (3)
C7—H7A	0.9500	O12—C35	1.370 (4)
C9—H9A	0.9800	O12—H12	0.81 (3)
C9—H9B	0.9800	C31—C36	1.400 (4)
C9—H9C	0.9800	C31—C32	1.407 (3)
C11—C15	1.399 (2)	C31—C37	1.471 (3)
C12—C13	1.362 (3)	C32—C33	1.395 (4)
C12—H12A	0.9500	C33—C34	1.386 (4)
C13—C14	1.397 (2)	C33—H33A	0.9500
C13—H13A	0.9500	C34—C35	1.396 (3)
C14—C15	1.377 (2)	C34—H34A	0.9500
C14—H14A	0.9500	C35—C36	1.383 (5)
C15—H15A	0.9500	C36—H36A	0.9500
S2—O6	1.4293 (13)	O9B—C37B	1.245 (8)
S2—O5	1.4295 (13)	O10B—C37B	1.323 (9)
S2—N4	1.6428 (15)	O10B—H10B	0.8400
S2—C23	1.7624 (18)	O11B—C32B	1.356 (8)
O7—C25	1.238 (2)	O11B—H11B	0.8400
O8—C17	1.337 (2)	O12B—C35B	1.373 (9)
O8—H8	0.88 (3)	O12B—H12B	0.8400
N4—C16	1.441 (2)	C31B—C36B	1.394 (9)
N4—C24	1.482 (2)	C31B—C32B	1.400 (8)
N5—C25	1.369 (2)	C31B—C37B	1.464 (8)
N5—C26	1.401 (2)	C32B—C33B	1.394 (9)
N5—H5	0.84 (2)	C33B—C34B	1.388 (9)
N6—C26	1.334 (2)	C33B—H33B	0.9500
N6—C27	1.343 (3)	C34B—C35B	1.393 (8)
C16—C17	1.360 (3)	C34B—H34B	0.9500
C16—C25	1.457 (3)	C35B—C36B	1.378 (10)
C17—C18	1.471 (3)	C36B—H36B	0.9500

O2—S1—O1	117.92 (7)	C20—C19—H19A	120.1
O2—S1—N1	108.03 (7)	C18—C19—H19A	120.1
O1—S1—N1	108.36 (7)	C19—C20—C21	121.01 (18)
O2—S1—C8	110.48 (7)	C19—C20—H20A	119.5
O1—S1—C8	109.35 (8)	C21—C20—H20A	119.5
N1—S1—C8	101.39 (8)	C22—C21—C20	120.24 (18)
C1—N1—C9	115.16 (13)	C22—C21—H21A	119.9
C1—N1—S1	114.32 (11)	C20—C21—H21A	119.9
C9—N1—S1	116.52 (11)	C23—C22—C21	118.57 (17)
C11—N2—C10	125.83 (15)	C23—C22—H22A	120.7
C11—N2—H2	121.7 (14)	C21—C22—H22A	120.7
C10—N2—H2	112.4 (14)	C22—C23—C18	122.17 (17)
C11—N3—C12	123.43 (16)	C22—C23—S2	120.38 (14)
C11—N3—H3	117.4 (16)	C18—C23—S2	117.37 (14)
C12—N3—H3	119.1 (16)	N4—C24—H24A	109.5
C2—C1—C10	125.28 (15)	N4—C24—H24B	109.5
C2—C1—N1	121.38 (15)	H24A—C24—H24B	109.5
C10—C1—N1	113.28 (14)	N4—C24—H24C	109.5
O4—C2—C1	123.40 (15)	H24A—C24—H24C	109.5
O4—C2—C3	118.03 (14)	H24B—C24—H24C	109.5
C1—C2—C3	118.55 (15)	O7—C25—N5	123.18 (17)
C4—C3—C8	117.53 (15)	O7—C25—C16	120.74 (17)
C4—C3—C2	120.01 (15)	N5—C25—C16	116.05 (16)
C8—C3—C2	122.46 (15)	N6—C26—C30	122.23 (17)
C5—C4—C3	120.54 (16)	N6—C26—N5	114.40 (16)
C5—C4—H4A	119.7	C30—C26—N5	123.35 (17)
C3—C4—H4A	119.7	N6—C27—C28	123.5 (2)
C6—C5—C4	120.85 (16)	N6—C27—H27A	118.2
C6—C5—H5A	119.6	C28—C27—H27A	118.2
C4—C5—H5A	119.6	C27—C28—C29	117.72 (19)
C5—C6—C7	120.00 (16)	C27—C28—H28A	121.1
C5—C6—H6A	120.0	C29—C28—H28A	121.1
C7—C6—H6A	120.0	C30—C29—C28	120.25 (19)
C8—C7—C6	118.87 (16)	C30—C29—H29A	119.9
C8—C7—H7A	120.6	C28—C29—H29A	119.9
C6—C7—H7A	120.6	C29—C30—C26	118.22 (19)
C7—C8—C3	122.22 (15)	C29—C30—H30A	120.9
C7—C8—S1	120.18 (13)	C26—C30—H30A	120.9
C3—C8—S1	117.59 (13)	C37—O10—H10	107.2 (19)
N1—C9—H9A	109.5	C32—O11—H11	106 (2)
N1—C9—H9B	109.5	C35—O12—H12	108 (3)
H9A—C9—H9B	109.5	C36—C31—C32	119.5 (2)
N1—C9—H9C	109.5	C36—C31—C37	120.9 (2)
H9A—C9—H9C	109.5	C32—C31—C37	119.6 (2)
H9B—C9—H9C	109.5	O11—C32—C33	117.8 (2)
O3—C10—N2	120.69 (15)	O11—C32—C31	123.0 (2)
O3—C10—C1	123.59 (15)	C33—C32—C31	119.2 (2)
N2—C10—C1	115.71 (14)	C34—C33—C32	120.6 (2)
N3—C11—N2	119.99 (15)	C34—C33—H33A	119.7
N3—C11—C15	117.96 (15)	C32—C33—H33A	119.7
N2—C11—C15	122.04 (15)	C33—C34—C35	120.4 (2)
N3—C12—C13	120.29 (16)	C33—C34—H34A	119.8
N3—C12—H12A	119.9	C35—C34—H34A	119.8
C13—C12—H12A	119.9	O12—C35—C36	118.2 (2)
C12—C13—C14	118.25 (16)	O12—C35—C34	122.4 (2)
C12—C13—H13A	120.9	C36—C35—C34	119.4 (2)
C14—C13—H13A	120.9	C35—C36—C31	120.9 (2)
C15—C14—C13	120.70 (16)	C35—C36—H36A	119.6
C15—C14—H14A	119.7	C31—C36—H36A	119.6
C13—C14—H14A	119.7	O9—C37—O10	121.5 (2)
C14—C15—C11	119.34 (15)	O9—C37—C31	122.7 (2)
C14—C15—H15A	120.3	O10—C37—C31	115.8 (2)
C11—C15—H15A	120.3	C37B—O10B—H10B	109.5
O6—S2—O5	119.45 (8)	C32B—O11B—H11B	109.5
O6—S2—N4	107.35 (8)	C35B—O12B—H12B	109.5
O5—S2—N4	108.47 (8)	C36B—C31B—C32B	120.0 (7)
O6—S2—C23	108.59 (8)	C36B—C31B—C37B	120.9 (7)
O5—S2—C23	109.83 (8)	C32B—C31B—C37B	119.1 (6)
N4—S2—C23	101.66 (8)	O11B—C32B—C33B	116.5 (7)
C17—O8—H8	106.5 (16)	O11B—C32B—C31B	124.8 (7)
C16—N4—C24	113.57 (14)	C33B—C32B—C31B	118.6 (7)
C16—N4—S2	112.35 (11)	C34B—C33B—C32B	121.3 (8)
C24—N4—S2	116.08 (12)	C34B—C33B—H33B	119.4
C25—N5—C26	126.35 (16)	C32B—C33B—H33B	119.4
C25—N5—H5	119.4 (16)	C33B—C34B—C35B	119.4 (8)
C26—N5—H5	114.2 (16)	C33B—C34B—H34B	120.3
C26—N6—C27	118.03 (17)	C35B—C34B—H34B	120.3
C17—C16—N4	120.42 (16)	O12B—C35B—C36B	117.0 (9)
C17—C16—C25	121.07 (16)	O12B—C35B—C34B	122.9 (9)
N4—C16—C25	118.42 (15)	C36B—C35B—C34B	120.1 (7)
O8—C17—C16	123.01 (17)	C35B—C36B—C31B	120.6 (9)
O8—C17—C18	114.49 (16)	C35B—C36B—H36B	119.7
C16—C17—C18	122.43 (16)	C31B—C36B—H36B	119.7
C19—C18—C23	118.14 (17)	O9B—C37B—O10B	122.6 (8)
C19—C18—C17	121.45 (16)	O9B—C37B—C31B	122.2 (7)
C23—C18—C17	120.31 (16)	O10B—C37B—C31B	115.2 (8)
C20—C19—C18	119.86 (18)

O2—S1—N1—C1	−62.23 (13)	C16—C17—C18—C23	17.4 (3)
O1—S1—N1—C1	168.95 (11)	C23—C18—C19—C20	−1.0 (3)
C8—S1—N1—C1	53.93 (13)	C17—C18—C19—C20	−177.36 (16)
O2—S1—N1—C9	159.44 (12)	C18—C19—C20—C21	0.7 (3)
O1—S1—N1—C9	30.63 (14)	C19—C20—C21—C22	−0.2 (3)
C8—S1—N1—C9	−84.39 (13)	C20—C21—C22—C23	0.1 (3)
C9—N1—C1—C2	93.30 (19)	C21—C22—C23—C18	−0.4 (3)
S1—N1—C1—C2	−45.60 (19)	C21—C22—C23—S2	176.15 (13)
C9—N1—C1—C10	−84.02 (18)	C19—C18—C23—C22	0.9 (3)
S1—N1—C1—C10	137.08 (13)	C17—C18—C23—C22	177.31 (16)
C10—C1—C2—O4	1.0 (3)	C19—C18—C23—S2	−175.77 (13)
N1—C1—C2—O4	−176.02 (15)	C17—C18—C23—S2	0.6 (2)
C10—C1—C2—C3	−177.70 (15)	O6—S2—C23—C22	−97.44 (15)
N1—C1—C2—C3	5.3 (2)	O5—S2—C23—C22	34.84 (17)
O4—C2—C3—C4	19.5 (2)	N4—S2—C23—C22	149.56 (14)
C1—C2—C3—C4	−161.71 (16)	O6—S2—C23—C18	79.31 (15)
O4—C2—C3—C8	−160.13 (15)	O5—S2—C23—C18	−148.41 (13)
C1—C2—C3—C8	18.6 (2)	N4—S2—C23—C18	−33.69 (15)
C8—C3—C4—C5	−0.6 (2)	C26—N5—C25—O7	3.8 (3)
C2—C3—C4—C5	179.71 (16)	C26—N5—C25—C16	−174.46 (16)
C3—C4—C5—C6	0.4 (3)	C17—C16—C25—O7	−7.8 (3)
C4—C5—C6—C7	−0.1 (3)	N4—C16—C25—O7	175.54 (15)
C5—C6—C7—C8	0.0 (3)	C17—C16—C25—N5	170.47 (16)
C6—C7—C8—C3	−0.2 (3)	N4—C16—C25—N5	−6.2 (2)
C6—C7—C8—S1	−178.95 (14)	C27—N6—C26—C30	−0.9 (3)
C4—C3—C8—C7	0.5 (2)	C27—N6—C26—N5	−178.99 (17)
C2—C3—C8—C7	−179.81 (15)	C25—N5—C26—N6	−164.95 (16)
C4—C3—C8—S1	179.26 (13)	C25—N5—C26—C30	17.0 (3)
C2—C3—C8—S1	−1.1 (2)	C26—N6—C27—C28	1.2 (3)
O2—S1—C8—C7	−99.16 (15)	N6—C27—C28—C29	−0.5 (3)
O1—S1—C8—C7	32.21 (16)	C27—C28—C29—C30	−0.6 (3)
N1—S1—C8—C7	146.49 (14)	C28—C29—C30—C26	0.8 (3)
O2—S1—C8—C3	82.06 (14)	N6—C26—C30—C29	−0.1 (3)
O1—S1—C8—C3	−146.57 (13)	N5—C26—C30—C29	177.80 (17)
N1—S1—C8—C3	−32.29 (15)	C36—C31—C32—O11	−179.4 (3)
C11—N2—C10—O3	4.3 (3)	C37—C31—C32—O11	−0.8 (4)
C11—N2—C10—C1	−174.59 (15)	C36—C31—C32—C33	−1.4 (4)
C2—C1—C10—O3	176.72 (16)	C37—C31—C32—C33	177.3 (2)
N1—C1—C10—O3	−6.1 (2)	O11—C32—C33—C34	179.3 (2)
C2—C1—C10—N2	−4.4 (2)	C31—C32—C33—C34	1.2 (4)
N1—C1—C10—N2	172.79 (14)	C32—C33—C34—C35	−0.1 (4)
C12—N3—C11—N2	178.15 (16)	C33—C34—C35—O12	179.6 (3)
C12—N3—C11—C15	−1.3 (2)	C33—C34—C35—C36	−0.8 (4)
C10—N2—C11—N3	−2.9 (3)	O12—C35—C36—C31	−179.8 (4)
C10—N2—C11—C15	176.52 (15)	C34—C35—C36—C31	0.6 (6)
C11—N3—C12—C13	1.7 (3)	C32—C31—C36—C35	0.5 (6)
N3—C12—C13—C14	−0.6 (3)	C37—C31—C36—C35	−178.1 (3)
C12—C13—C14—C15	−0.8 (3)	C36—C31—C37—O9	−174.1 (3)
C13—C14—C15—C11	1.2 (3)	C32—C31—C37—O9	7.3 (3)
N3—C11—C15—C14	−0.2 (2)	C36—C31—C37—O10	6.5 (4)
N2—C11—C15—C14	−179.62 (15)	C32—C31—C37—O10	−172.1 (3)
O6—S2—N4—C16	−59.05 (13)	C36B—C31B—C32B—O11B	176.7 (16)
O5—S2—N4—C16	170.60 (12)	C37B—C31B—C32B—O11B	−3.3 (16)
C23—S2—N4—C16	54.87 (13)	C36B—C31B—C32B—C33B	−2 (2)
O6—S2—N4—C24	167.90 (12)	C37B—C31B—C32B—C33B	177.7 (10)
O5—S2—N4—C24	37.55 (15)	O11B—C32B—C33B—C34B	−177.8 (9)
C23—S2—N4—C24	−78.18 (14)	C31B—C32B—C33B—C34B	1.3 (17)
C24—N4—C16—C17	87.5 (2)	C32B—C33B—C34B—C35B	0.1 (16)
S2—N4—C16—C17	−46.7 (2)	C33B—C34B—C35B—O12B	177.7 (12)
C24—N4—C16—C25	−95.81 (18)	C33B—C34B—C35B—C36B	0 (2)
S2—N4—C16—C25	129.92 (14)	O12B—C35B—C36B—C31B	−178.8 (17)
N4—C16—C17—O8	−176.38 (15)	C34B—C35B—C36B—C31B	−1 (3)
C25—C16—C17—O8	7.1 (3)	C32B—C31B—C36B—C35B	2 (3)
N4—C16—C17—C18	6.9 (3)	C37B—C31B—C36B—C35B	−178.1 (16)
C25—C16—C17—C18	−169.68 (16)	C36B—C31B—C37B—O9B	−178.4 (16)
O8—C17—C18—C19	16.6 (2)	C32B—C31B—C37B—O9B	1.5 (15)
C16—C17—C18—C19	−166.38 (17)	C36B—C31B—C37B—O10B	1 (2)
O8—C17—C18—C23	−159.65 (16)	C32B—C31B—C37B—O10B	−178.7 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4	0.88 (2)	1.85 (2)	2.6169 (18)	145.2 (19)
N3—H3···O3	0.78 (2)	1.99 (2)	2.6027 (19)	135 (2)
N3—H3···O3ⁱ	0.78 (2)	2.19 (2)	2.8034 (19)	136 (2)
O8—H8···O7	0.88 (3)	1.79 (3)	2.5722 (19)	148 (2)
N5—H5···O9	0.84 (2)	2.25 (2)	3.074 (2)	167 (2)
O10—H10···N6	0.91 (3)	1.74 (3)	2.637 (3)	167 (3)
O11—H11···O9	0.81 (3)	1.89 (3)	2.614 (2)	148 (3)
O12—H12···O4ⁱⁱ	0.81 (3)	1.94 (3)	2.738 (3)	164 (4)
O10B—H10B···O4ⁱⁱ	0.84	1.67	2.508 (12)	172
O11B—H11B···O2ⁱ	0.84	2.57	3.061 (6)	118
O11B—H11B···O9B	0.84	1.89	2.614 (9)	143
O12B—H12B···N6	0.84	2.10	2.856 (12)	149

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

Acknowledgements

The Materials Chemistry Laboratory at the University of Illinois was supported in part by grants NSF CHE 95–03145 and NSF CHE 03–43032 from the National Science Foundation.

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