Polymorphism in the structure of N-(5-methyl­thia­zol-2-yl)-4-oxo-4H-chromene-3-carboxamide

Gomes, L.R.; Low, J.N.; Cagide, F.; Borges, F.

doi:10.1107/S2056989017009902

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 73| Part 8| August 2017| Pages 1154-1161

https://doi.org/10.1107/S2056989017009902

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Polymorphism in the structure of N-(5-methylthiazol-2-yl)-4-oxo-4H-chromene-3-carboxamide

Ligia R. Gomes,^a John Nicolson Low,^b ^* Fernando Cagide ^c and Fernanda Borges ^c

^aFP-ENAS-Faculdade de Ciências de Saúde, Escola Superior de Saúde da UFP, Universidade Fernando Pessoa, Rua Carlos da Maia, 296, P-4200-150 Porto, Portugal, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen, AB24 3UE, Scotland, and ^cCIQ/Departamento de Quιmica e Bioquιmica, Faculdade de Ciências, Universidade do Porto, 4169-007 Porto, Portugal
^*Correspondence e-mail: jnlow111@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 24 June 2017; accepted 3 July 2017; online 13 July 2017)

Chromone derivatives have been extensively studied recently because of to their promising biological activities. The new title chromone–thiazole hybrid presented here, C₁₄H₁₀N₂O₃S, is a candidate as a selective ligand for adenosine receptors. The compound has been synthesized and characterized by the usual spectroscopic means (NMR and EM/IE) and its structure elucidated by X-ray crystallography, which revealed the presence of packing polymorphism. The two polymorphs (one with space group P2₁/n and one with P2₁/c) show slightly different conformations and the major change induced by crystallization regards the intramolecular contacts defining the supramolecular structure. Those differences been highlighted by Hirshfeld surface analysis mapped over d_norm and ESP.

Keywords: crystal structure; drug design; chromones; conformation; supramolecular structure.

CCDC references: 1560084; 1517021

1. Chemical context

Chromones are 4H-benzopyran-4-one heterocycles and they have been studied thoroughly because of their interesting biological activities (Gaspar et al., 2012a ,b ; 2014 ) Thiazole-based compounds have been used in therapeutics as antimicrobial, antiviral and antifungal agents for a long time (Souza, 2005 ; Siddiqui et al., 2009 ) but, in the past decades, they have been identified as potent and selective ligands for the adenosine receptor (Sharma et al. 2009 ; Jung et al., 2004 ). In a continuation of our project related to the synthesis of pharmacologically useful heterocycles, the title compound has been designed as a potential ligand for human adenosine receptors.

This work reports the synthesis and structural characterization of this chromone–thiazole hybrid, N-(5-methylthiazol-2-yl)-4-oxo-4H-chromene-3-carboxamide, 1, that was synthesized following a method previously described by Cagide et al. (2015 ). The chromone ring (A) is connected to the thiazole ring (C) though a carboxamide spacer (B). The compound crystallizes with two different morphologies and the structural analysis revealed the presence of packing polymorphism. Since this compound will be assayed in tests to evaluate its biological activity, the establishment of the polymorphic structures is of the utmost importance.

2. Structural commentary

The molecular structures of the polymorphs are shown in Fig. 1. This compound presents packing polymorphism and crystallizes in monoclinic space groups P2₁/n and P2₁/c, the latter with two molecules in the asymmetric unit (identified as mol#1 and mol#2). In 1_P2₁/c, mol#1 fits into mol#2 with values of quaternion fit weighted of 0.093 Å (unit-weight r.m.s. fit of 0.086 Å for 20 atoms).

Figure 1
A view of the asymmetric unit of 1_P2₁/n with the atom-numbering scheme (top). A view of the asymmetric unit of 1_P2₁/c with mol#1 (left) and mol#2 (right) with the atom-numbering scheme (bottom). Displacement ellipsoids are drawn at the 70% probability level.

The conformation around the amide rotamer for chromone carboxamides can be either -anti or -syn. The former appears to be more probable since it lowers the steric hindrance between the two aromatic rings as compared to the -syn rotamer. Structural characterizations made previously in other 4H-chromene-3-carboxamides (Gomes et al., 2015a ,b ) show that, when the amide oxygen atom (O3/O13/O23) is trans-related to the pyran oxygen atom of the chromone (O1/O11/O21) the -anti conformation predominates since it permits the establishment of a short intramolecular N—H⋯O(carbonyl) hydrogen bond (geometric parameters for the intramolecular H bond are given in Tables 1 and 2), which generates an S(6) ring.

Table 1
Hydrogen-bond geometry (Å, °) for P2₁/n

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O4	0.88	1.96	2.687 (5)	139
C2—H2⋯O4ⁱ	0.95	2.38	3.030 (5)	126
C8—H8⋯N33ⁱ	0.95	2.56	3.455 (6)	157
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °) for 1_P2~1~_c

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N13—H13⋯O14	0.80 (4)	1.99 (4)	2.671 (3)	143 (4)
C12—H12⋯O24ⁱ	0.95	2.27	2.963 (4)	129
C15—H15⋯O23ⁱⁱ	0.95	2.43	3.353 (4)	164
C136—H13C⋯O13ⁱⁱⁱ	0.98	2.51	3.449 (4)	162
N23—H23⋯O24	0.82 (4)	2.05 (3)	2.697 (3)	136 (3)
C22—H22⋯O14ⁱⁱ	0.95	2.19	2.999 (4)	142
C25—H25⋯O13^iv	0.95	2.48	3.352 (4)	153
Symmetry codes: (i) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1; (iv) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

The S atom of the thiazole ring is in a -cis position with respect to the carbonyl O3/O23/O13 atom of the amide in both polymorphs. This feature has also been observed for similar compounds (Cagide et al., 2015). Gas-phase ab initio geometry optimization and natural atomic charges obtained by population analysis [using natural bond orbital (NBO) analysis] revealed that negative charges are located at the two nitrogen atoms and at the three oxygen atoms, while the positive charges reside at the amide carbon atom as well as at the sulfur atom of the thiazole ring, suggesting that a further stabilization may arise when the S atom is pointing to the carboxyl oxygen atom of the amide. This was also confirmed here by similar calculations: the results obtained for atomic charges by NBO analysis, performed after single-point energy calculation, are in Fig. 2. In addition, the calculation of energies and charges of several conformers, obtained by rotation of the thiazole ring (C) around the amide spacer (B) were made, showing that the lowest energy is obtained when the sulfur atom is around 0°. Details are provided in the Supporting information.

Figure 2
Natural atomic charges from population analysis (NBO), at the B3LYP/6–311+G(d) level of theory for the 1_P2₁/n at crystal geometric conformation. The charge distributions are presented within a relative charge range of −1.000 (green) to +1.000 (light red).

Relevant data for the discussion of molecular geometry and conformation of the polymorphs is presented in Table 3; θ_A–C refers to the dihedral angle between the mean planes of the chromone and thiazole rings, θ_A–B to the dihedral angle between the best plane of the chromone and the plane defined by atoms OCN of the amide moiety, whereas θ_B–C refers to the dihedral angle between this plane and the best plane of the thiazole ring. Since the heteroaromatic rings are practically planar, the dihedral angle θ_A–C quantifies the degree of bend and/or twist between them and can be used for evaluation of the distortion of the molecule from planarity when one of the dihedrals, θ_A–B or θ_B–C, is relatively small. As seen, 1_P2₁/n and 1_P2₁/c_mol#2 are practically planar while 1_P21/c_mol#1 presents a slightly higher θ_A–C angle due to the rotation of the chromone ring with respect to the amide plane.

Table 3
Dihedral angles (°)

θ_A–C is the dihedral angle between the mean planes of the chromene and phenyl ring and the thiazole ring. θ_A–B is the dihedral angles between the mean planes of the chromone ring and the plane defined by the O2/C21/N2 atoms. θ_B–C is the dihedral angle between the mean planes of the thiazole ring and the plane defined by the O3/C41/N3 atoms.

Compound	θ_A–C°	θ_A–B°	θ_B–C°
1_P2₁/n	3.1 (2)	1.6 (8)	4.5 (8)
1_P2₁/c(mol#1)	6.38 (9)	5.12 (19)	1.76 (12)
1_P2₁/c(mol#2)	3.42 (10)	1.43 (10)	2.01 (14)

3. Supramolecular features

Molecular structure and conformation

In 1_P2₁/n the molecules are linked by the C2—H2⋯O4ⁱ and C8—H8⋯N33ⁱ weak hydrogen bonds, Table 1, which form a chain of R₂² (13) rings runing parallel to the b-axis direction generated by the twofold screw axis at x = $[1\over4]$ and y = $[1\over4]$ , as depicted in Fig. 3.

Figure 3
The chain of R₂²(13) rings running parallel to the b axis generated by the twofold screw axis at x = 1/4 and y = 1/4 as depicted for 1_P2₁/n. H atoms not participating in hydrogen bonding have been omitted for the sake of clarity.

The molecules in 1_P2₁/c are linked by alternating weakly hydrogen-bonded R₂²(10) rings formed by the hydrogen bonds C12—H12⋯O24ⁱⁱ and C25—H25⋯O13^iv in one case and C22—H22⋯O14ⁱⁱ and C15—H15⋯O23ⁱⁱ in the other, Table 2. These link the molecules to form a chain of rings running parallel to [101], Fig. 4. Details of the π–π stacking are given in Table 4. In 1_P2₁/n the molecules form a π–π stack that extends along the a axis. In 1_P2₁/c, the two molecules in the asymmetric unit form a π–π stacked dimer (which guided the choice of asymmetric unit). In both compounds, any possible C—H⋯π contacts involve methyl hydrogen atoms with H⋯π distances in excess of 2.8 Å.

Table 4
Selected π–π contacts (Å)

CgI(J) = Plane number I(J), CgI_Perp = perpendicular distance of Cg(I) on ring J, CgJ_Perp = perpendicular distance of Cg(J) on ring I, slippage = distance between Cg(I) and perpendicular projection of Cg(J) on Ring I.

Compound	CgI	CgJ(aru)	Cg⋯Cg	CgI_Perp	CgJ_Perp	Slippage
1_P2₁/n	Cg1	Cg2(x + 1, y, z)	3.547 (3)	3.3358 (18)	3.3299 (19)	1.222
1_P2₁/c	Cg3	Cg4(x, y, z)	3.6726 (17)	3.2645 (13)	3.3012 (12)	1.609
Cg1 and Cg2 are the centroids of rings O1/C2–C4/C4A/C8A and C4A/C5–C8/C8A, respectively. Cg3 and Cg4 are the centroids of rings C14A/C15–C18/C18A and O21/C22–C24/C24A/C28A, respectively.

Figure 4
The molecules in 1_P2₁/c linked by alternating weakly hydrogen-bonded R₂²(10) rings that lead the molecules to form a chain of rings running parallel to [101]. H atoms not participating in hydrogen bonding have been omitted for the sake of clarity.

Hirshfeld surfaces

The Hirshfeld surfaces and two-dimensional fingerprint (FP) plots (Rohl et al., 2008 ) provide complementary information concerning the intermolecular interactions discussed above. They were generated using Crystal Explorer 3.1 (Wolff et al., 2012 ). The Hirshfeld surfaces, mapped over d_norm (all scaled between −0.250 to 1.200) and the respective FP plots are depicted in Figs. 5 and 6 for 1_P2₁/n and in Figs. 7 and 8 for 1_P2₁/c; mol_#1 and mol_#2. Also in Figs. 5 and 9, the Hirshfeld surfaces mapped over the electrostatic potential (ESP) are depicted for both polymorphs. The contributions from various contacts, listed in Table 5, were selected by the partial analysis of those FP plots. Taking out the H⋯H contacts on the surface that are inherent to organic molecules, the most significant contacts can be divided in three groups: (i) the H⋯O/N contacts that correspond to some relevant C—H⋯O, C—H⋯N intermolecular interactions; (ii) the H⋯C/C⋯H contacts and (iii) C⋯C contacts that are related to π–π stacking. The structure has two carboxyl groups and a nitrogen atom of the thiazole that can act as acceptors for hydrogen bonding and a N—H (amide) that can act as donor. In spite of that, the N—H amide does not have a relevant role in the definition of the supramolecular structure but it is compromised in the intermolecular hydrogen bond.

Table 5
Percentages for the most relevant atom–atom contacts for the studied compounds

Compound	H⋯H	H⋯O/O⋯H	H⋯N/N⋯H	H⋯S/S⋯H	H⋯C/C⋯H	C⋯C
1_P2₁/n	31.8	19.0	8.7	6.3	15.2	7.1
1_P2₁/c	29.6	19.1	8.6	7.7	17.6	5.2
1_P2₁/c	34.6	13.2	6.6	7.1	18.4	5.2

Figure 5
Views of the Hirshfeld surface mapped over d_norm (left) and mapped over the electrostatic potential (right) for 1_P2₁/n. The highlighted red spots on the top face of the surfaces indicate contact points with the atoms participating in the C—H⋯O/N intermolecular interactions whereas those on the middle of the surface corresponds to C⋯C contacts as a consequence of the π–π stacking. The electrostatic potential surface (ranging from −0.077 to 0.066) shows the complementary electronegative (red) and electropositive areas (blue) with molecules of the first shell. They depict the importance of the H2 and H8 atoms of the chromone ring that are located in the most electropositive area and their connection to O4 and N33. The methyl group presents also an electropositive region that complements with the thiozole environment near the sulfur atom.

Figure 6
The FP plot for 1_P2₁/n; the light-blue area in the middle of the FP plot is due to C⋯C contacts (7.1% of the area). The FP plot shows three sets of spikes pointing to southwest due to weak C⋯H contacts: the outer sharper ones are due to the H.·N contacts that involves the N(thiazole)⋯H8—C8(chromone) interaction followed by the spikes corresponding to O⋯H contacts that englobe the O4⋯H2_C2 contacts and the inner one is due to close S⋯H contacts

Figure 7
Views of the Hirshfeld surface mapped over d_norm for 1_P2₁/c. The highlighted red spots on the top face of the surfaces indicate contact points with the atoms participating in the C—H⋯O/N intermolecular interactions. The red spot identified as a C12—H12⋯O24 contact in mol#1 is located on the hidden face of the surface.

Figure 8
The FP plot for 1_P2₁/c, mol#1 on left and mol#2 on right; The light-blue area in the middle of the FP plot at d_e/d_i ∼1.8 Å shows a higher frequency of the pixels that are due to C⋯C contacts (5.2% of the area for each molecule). The spikes pointing to southwest are due to weak O⋯H contacts. The asymmetric tails that both present are corresponding to N⋯H contacts in mol#1. Their asymmetry is due to the fact that they connect two molecules that are not related by crystallographic symmetry.

Figure 9
The electrostatic potential surfaces for 1_P2₁/c, mol#1 and mol#2. The surfaces show the complementary electronegative (red) and electropositive areas (blue) with molecules of the first shell (ranging from −0.077 to 0.066). The ESP is electronegative in the vicinity of oxo oxygen atoms and of the nitrogen atom of the thiazole ring while it is electropositive in the areas that surrounds the H2, H5 and H8 hydrogen atoms of the chromone ring.

P2₁/n polymorph

As seen in Fig. 3, in 1_P2₁/n the oxygen atom O4 acts as acceptor for the hydrogen atom H2 of the chromone and the nitrogen atom N33 of the thiazole ring acts as acceptor for the H8 hydrogen atom of the chromone ring. Thus, the Hirshfeld surface of 1_P2₁/n (mapped with d_norm) shows two sets of complementary red spots in the lateral faces of the surface as highlighted in Fig. 5, left. The small red-spot areas facing the chromone plane are due to C⋯C contacts (that assume 7.1% of the contact area) and they correspond to the light-blue area in the middle of the FP plot, Fig. 6. The geometric parameters for these contacts are listed in Tables 3 and 5. The weak C⋯H contacts correspond to 15.2% of the surface area. The FP plot shows three sets of spikes pointing to southwest: the outer ones are due to the H⋯N contacts that involves the N(thiazole)⋯H8—C8(chromone) followed by the spikes corresponding to O⋯H contacts that englobes the O4⋯H2—C2 contacts and the inner one is due to close S⋯H contacts where the closest one is with the H atoms of the methyl group. A small red spot pointing to this group appears in the Hirshfeld surface, Fig. 5, left.

In Fig. 5 right, the mapping of the molecular electrostatic potential (ESP) in the context of crystal packing is shown. As the Hirshfeld surface partitions of the crystal space give non-overlapping volumes associated with each molecule these surfaces give a kind of `electrostatic complementarity'. The molecular ESP for P2₁/n reveals red regions of strongly negative electrostatic potential surrounding the two carbonyl regions and the azo region of the thiazole fragment. The blue region is electropositive and it is predominantly located in the chromone area near the H2 and H8 hydrogen atoms as well as in the methyl group of the thiazole. The remainder of the Hirshfeld surface is close to neutrality as seen by the grey regions. It is interesting to note that the mapped areas with electronegative potential corresponding to the areas covered by the atoms exhibiting negative natural atomic charges as computed by NBO (as seen in Fig. 2) with exception for the thiazole sulfur atom, which assumes a positive value by adiabatic gas-phase calculations, but gives a slightly negative electrostatic potential area at the Hirsfeld surface. The calculated partial charges show how the molecule would interact with an approaching proton and the molecular electrostatic potential is the potential energy that a proton would acquire at the surface, that is depending on the distance to the core nucleus of the molecule, suggesting that, in the crystal the sulfur surroundings experiences a deeper change in the eletrostatic potential gradient than that occurring in the remaining molecule, as compared with that of the adiabatic conditions.

Fig. 5 also highlights the electrostatic complementarity of the C—H⋯O/N contacts between the molecules. The electropositive (blue) patch above the chromone ring is in contact with the electronegative (red) regions around the carbonyl oxygen atom of the chromone O4 and the nitrogen atom of the thiazole ring N33 while the carbonyl oxygen atom of the amide O3 is pointing to the H5 hydrogen atom of the chromone ring. The electronegativity of this oxygen is lower than the electronegativity of the O4 of the chromone or the nitrogen atom of the thiazole N33. Thus the first shell molecular pairs are clearly associated with hydrogen bonds around the chromone ring periphery.

P2₁/c (mol#1 and #2) polymorph

The Hirshfeld surfaces printed over d_norm for each molecule are shown in Fig. 7. Those surfaces show complementary red spots with each other; since mol#1 is linked to mol#2 and vice versa, they map pairs of dimers that connect the molecules in chains. Here, the hydrogen bonds that contribute to the linking of the mol#1 with mol#2 are the following: (i) the oxo oxygen atom of the chromone of mol#1 acts as acceptor for the H2 hydrogen atom of the chromone of mol#2 (O14⋯H22—C22) and vice versa (O24⋯H12—C12); (ii) the carboxyl oxygen atom of the amide in mol#1 links the hydrogen atom H5 of the chromone ring in mol#2 (O13⋯H25—C25) and vice versa (O23⋯H15—C15); (iii) the nitrogen atom of the thiazole in mol#1 acts as acceptor for H8 hydrogen atom of mol#2 (N133⋯H28—C28). The O13⋯H25—C25/ O23⋯H15—C15 bond pair was not present in 1_P2₁/n polymorph while the remaining two were also observed. There is another pair of blue spots in the Hirshfeld surface of mol#1that are complementary in shape and they refer to the O13⋯H13C—C136 contact.

The FP plots for polymorph 1_P2₁/c (mol#1 and #2) are shown in Fig. 8. The FP plots highlight the differences in distribution of close contacts between mol#1 and mol#2. The asymmetric tails that are both present correspond to N⋯H contacts in mol#1 and the sharp spikes are due to the O⋯H contacts. Their asymmetry is due to the fact that they connect two molecules that are not related by crystallographic symmetry. The sharper line in mol#1 FP that ends at about (1.2;0.9) corresponds to O⋯H contacts that mol#1 makes with mol#2. Those contacts relate to the ones given by the sharper line that ends at about (0.9; 1.2) in the FP of mol#2. It is noticeable the differences in sharpness of the O⋯H spikes presented in the FP plots 1_P2₁/c when compared with the FP plot of the polymorph 1_P2₁/n showing that in 1_P2₁/c the O⋯H contacts are more directional and shorter. Those plots also reflect the differences regarding the close contacts between molecules: the light blue/green area in the middle of the FP plot in 1_P2₁/n is less spread out and more intense that the area presented in the FP plot of 1_P2₁/c suggesting that the C⋯C close contacts are more relevant in first polymorph.

Fig. 9 depicts the Hirshfeld surfaces mapped over the electrostatic potential and once again the complementary electrostatic nature of the contacts are clear from the figure. The ESP is electronegative in the vicinity of oxo oxygen atoms and of the nitrogen atom of the thiazole ring while it is electropositive in the areas that surrounds the H2, H5 and H8 hydrogen atoms of the chromone ring.

4. Synthesis and crystallization

Chromone-3-carboxylic acid, phosphorus(V) oxychloride, dimethylformamide (DMF) and 5-methylthiazol-2-amine were purchased from Sigma–Aldrich Química S·A. (Sintra, Portugal). All other reagents and solvents were pro analysis grade and used without additional purification. Thin-layer chromatography (TLC) was carried out on precoated silica gel 60 F254 (Merck) with layer thickness of 0.2 mm and ethyl acetate/petroleum ether as the mobile phase. The spots were visualized under UV detection (254 and 366 nm) and iodine vapour. Flash chromatography was performed using silica gel 60 0.2–0.5 or 0.040–0.063 mm (Carlo Erba Reagents).

Synthesis of N-(5-methylthiazol-2-yl)-4-oxo-4H-chromene-3-carboxamide

To a solution of chromone-3-carboxylic acid (500 mg, 2.6 mmol) in DMF (4 ml) POCl₃ (241 ml, 2.6 mmol) was added. The mixture was stirred at room temperature for 30 min, with the formation in situ of the corresponding acyl chloride. Then, the 5-methylthiazol-2-amine was added. After 12 h, the mixture was diluted with dichloromethane (20 ml), washed with H₂O (2 × 10 ml) and with saturated NaHCO₃ solution (2 × 10 ml). The organic phase was dried with Na₂SO₄, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (20% ethyl acetate/petroleum ether) and N-(5-methylthiazol-2-yl)-4-oxo-4H-chromene-3-carboxamide was obtained as a solid (153 mg, 20%). ¹H NMR (400 MHz, CDCl₃) δ 12.43 (NH, s, 1H), 9.05 (H3,s, 1H), 8.35 (H5, dd, J = 8.0, 1.5 Hz, 1H), 7.80 (H7, ddd, J = 8.7, 7.2, 1.5 Hz, 1H), 7.59 (H8, dd, J = 8.7, 1.6 Hz, 1H), 7.54 (H6, ddd, J = 8.0, 7.2, 1.0 Hz, 1H), 7.17 (H34, q, J = 1.2 Hz, 1H), 2.43 (CH₃, d, J = 1.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 176.7 C4), 163.0 (C2), 160.3 (C31), 156.2 (C32), 155.5 (C8a), 135.4 (C7), 135.2 (C34), 128.4 (C35), 126.9 (C5), 126.7 (C6), 124.1 (C4a, C), 118.6 (C8), 114.6 (C3), 11.7 (CH₃). EM/IE m/z: 287 (M⁺+1, 30), 286.0 (M⁺, 91), 174 (30), 173 (100

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 6. Crystals of the title compound with different morphologies were found in the crystallized sample. In each case several attempts were made at obtaining crystals which gave the best available data set for both types of morphology; 1_P2₁/n: the crystals were long needles, which could not be cut, as they shattered. The needle used showed slight streaking on the images. The high angle data were very weak, with significant drop in intensity from the lower angle reflections. These facts probably explain the relatively high R-factor in the refinement of this compound. The following reflections were omitted from the refinement: 0 0 2 and 0 1 1 that were obstructed by beamstop and 0 10 1, 0 11 1, 0 12 1, 0 11 3 as recommend by the PLAT934_ALERT_3_B because (I_obs - I_calc)/Σ w > 1.

Table 6
Experimental details

	P2₁/n	P2₁/c
Crystal data
Chemical formula	C₁₄H₁₀N₂O₃S	C₁₄H₁₀N₂O₃S
M_r	286.30	286.30
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/c
Temperature (K)	100	100
a, b, c (Å)	4.8722 (4), 12.0436 (10), 21.9803 (16)	7.4646 (5), 30.626 (2), 11.0869 (8)
β (°)	96.353 (8)	93.232 (2)
V (Å³)	1281.86 (18)	2530.6 (3)
Z	4	8
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.26	0.26
Crystal size (mm)	0.28 × 0.03 × 0.02	0.06 × 0.06 × 0.01

Data collection
Diffractometer	Rigaku Saturn724+	Rigaku Saturn724+
Absorption correction	Multi-scan (CrystalClear-SM Expert; Rigaku, 2012 )	Multi-scan (CrystalClear-SM Expert; Rigaku, 2012)
T_min, T_max	0.814, 1.000	0.538, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13600, 2944, 1980	15726, 5716, 3733
R_int	0.084	0.090
(sin θ/λ)_max (Å⁻¹)	0.651	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.097, 0.223, 1.13	0.060, 0.153, 1.08
No. of reflections	2944	5716
No. of parameters	182	371
H-atom treatment	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.15, −0.37	0.46, −0.37
Computer programs: CrystalClear-SM Expert (Rigaku, 2012), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), SHELXS and SHELXL (Sheldrick, 2008 ), ShelXle (Hübschle et al., 2011 ), OSCAIL (McArdle et al., 2004 ), Mercury (Macrae et al., 2006 ) and PLATON (Spek, 2009 ).

1_P2₁/c: the crystals were prismatic in habit. The following reflections were omitted from the refinement: 0 1 1 obstructed by beamstop, $[\overline{8}]$ 1 8, $[\overline{8}]$ 0 6 as recommend by the PLAT934_ALERT_3_B because (I_obs - I_calc)/Σ w > 10.

The hydrogen atoms attached to the carboxamide N atom in 1_P2₁/n were treated as riding atoms with N—H = 0.88 Å and U_iso(H) = 1.2U_eq(N) while those in 1_P2₁/c were refined. All other H atoms were treated as riding atoms with C—H(aromatic) = 0.95 Å C—H(methyl) = 0.98 Å with U_iso(H) = 1.5U_eq(C). The positions of the amino and methyl hydrogen-atom positions were checked on a final difference map.

Supporting information

CCDC references: 1560084; 1517021

Crystal structure: contains datablocks 1_P2~1~_n, 1_P2~1~_c, global. DOI: https://doi.org/10.1107/S2056989017009902/hb7689sup1.cif

Structure factors: contains datablock 1_P2~1~_n. DOI: https://doi.org/10.1107/S2056989017009902/hb76891_P21_nsup2.hkl

Structure factors: contains datablock 1_P2~1~_c. DOI: https://doi.org/10.1107/S2056989017009902/hb76891_P21_csup3.hkl

Gaseous phase quantum chemical calculations. DOI: https://doi.org/10.1107/S2056989017009902/hb7689sup4.pdf

checkCIF report

Computing details top

For both structures, data collection: CrystalClear-SM Expert (Rigaku, 2012); cell refinement: CrystalClear-SM Expert (Rigaku, 2012); data reduction: CrystalClear-SM Expert (Rigaku, 2012). Program(s) used to solve structure: SHELXT (Sheldrick, 2015a) for 1_P2~1~_n; SHELXS (Sheldrick, 2008) for 1_P2~1~_c. Program(s) used to refine structure: OSCAIL (McArdle et al., 2004), ShelXle (Hübschle et al., 2011) and SHELXL2014 (Sheldrick, 2015b) for 1_P2~1~_n; OSCAIL (McArdle et al., 2004), ShelXle (Hübschle et al., 2011) SHELXL (Sheldrick, 2008) for 1_P2~1~_c. For both structures, molecular graphics: Mercury (Macrae et al., 2006). Software used to prepare material for publication: OSCAIL (McArdle et al., 2004), SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2009) for 1_P2~1~_n; OSCAIL (McArdle et al., 2004), SHELXL (Sheldrick, 2008) for 1_P2~1~_c.

N-(5-Methylthiazol-2-yl)-4-oxo-4H-chromene-3-carboxamide (1_P2~1~_n) top

Crystal data top

C₁₄H₁₀N₂O₃S	F(000) = 592
M_r = 286.30	D_x = 1.484 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.8722 (4) Å	Cell parameters from 3369 reflections
b = 12.0436 (10) Å	θ = 2.5–27.5°
c = 21.9803 (16) Å	µ = 0.26 mm⁻¹
β = 96.353 (8)°	T = 100 K
V = 1281.86 (18) Å³	Needle, yellow
Z = 4	0.28 × 0.03 × 0.02 mm

Data collection top

Rigaku Saturn724+ diffractometer	2944 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1980 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.084
profile data from ω–scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012)	h = −6→6
T_min = 0.814, T_max = 1.000	k = −15→15
13600 measured reflections	l = −28→28

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.097	H-atom parameters constrained
wR(F²) = 0.223	w = 1/[σ²(F_o²) + (0.0714P)² + 3.9146P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max = 0.001
2944 reflections	Δρ_max = 1.15 e Å⁻³
182 parameters	Δρ_min = −0.37 e Å⁻³

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
S31	0.9829 (3)	0.89007 (11)	0.43688 (5)	0.0282 (3)
O1	−0.0148 (6)	1.0107 (2)	0.21301 (14)	0.0251 (7)
O3	0.6328 (7)	0.9809 (3)	0.34453 (14)	0.0297 (8)
O4	0.1136 (6)	0.7088 (3)	0.29518 (14)	0.0252 (7)
N3	0.5557 (8)	0.7992 (3)	0.36084 (16)	0.0245 (9)
H3	0.4531	0.7413	0.3489	0.029*
N33	0.8145 (9)	0.6867 (4)	0.43227 (18)	0.0323 (10)
C2	0.1942 (10)	0.9927 (4)	0.2566 (2)	0.0245 (10)
H2	0.3134	1.0535	0.2678	0.029*
C3	0.2503 (9)	0.8961 (4)	0.28596 (19)	0.0221 (10)
C4	0.0784 (9)	0.7999 (4)	0.27017 (19)	0.0211 (9)
C5	−0.3234 (10)	0.7340 (4)	0.1989 (2)	0.0253 (10)
H5	−0.2989	0.6614	0.2154	0.030*
C4A	−0.1452 (9)	0.8189 (4)	0.22095 (19)	0.0213 (10)
C6	−0.5338 (10)	0.7543 (4)	0.1535 (2)	0.0274 (11)
H6	−0.6547	0.6959	0.1389	0.033*
C7	−0.5705 (10)	0.8606 (4)	0.1288 (2)	0.0272 (11)
H7	−0.7176	0.8742	0.0976	0.033*
C8	−0.3976 (10)	0.9455 (4)	0.1489 (2)	0.0264 (10)
H8	−0.4214	1.0179	0.1320	0.032*
C8A	−0.1864 (10)	0.9224 (4)	0.1947 (2)	0.0237 (10)
C31	0.4964 (9)	0.8976 (4)	0.33283 (19)	0.0224 (10)
C32	0.7694 (10)	0.7843 (4)	0.4073 (2)	0.0283 (11)
C34	1.0346 (11)	0.6953 (5)	0.4779 (2)	0.0357 (13)
H34	1.1015	0.6326	0.5012	0.043*
C35	1.1488 (10)	0.7959 (4)	0.4877 (2)	0.0304 (11)
C351	1.3848 (10)	0.8291 (5)	0.5342 (2)	0.0368 (13)
H35A	1.4522	0.7638	0.5579	0.055*
H35B	1.3213	0.8851	0.5618	0.055*
H35C	1.5347	0.8601	0.5131	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S31	0.0245 (7)	0.0323 (7)	0.0281 (6)	0.0009 (6)	0.0043 (5)	−0.0015 (5)
O1	0.0252 (19)	0.0153 (16)	0.0340 (17)	−0.0006 (14)	−0.0002 (14)	0.0028 (13)
O3	0.030 (2)	0.0216 (18)	0.0369 (18)	−0.0055 (15)	0.0001 (14)	−0.0001 (14)
O4	0.0245 (19)	0.0164 (16)	0.0349 (17)	0.0041 (14)	0.0040 (14)	0.0008 (13)
N3	0.024 (2)	0.020 (2)	0.0289 (19)	0.0002 (17)	0.0021 (16)	−0.0030 (15)
N33	0.035 (3)	0.029 (2)	0.032 (2)	0.006 (2)	−0.0008 (18)	−0.0040 (17)
C2	0.024 (3)	0.017 (2)	0.034 (2)	−0.002 (2)	0.007 (2)	−0.0012 (18)
C3	0.023 (3)	0.017 (2)	0.028 (2)	0.0020 (19)	0.0098 (18)	0.0005 (17)
C4	0.022 (2)	0.015 (2)	0.028 (2)	0.0033 (19)	0.0093 (18)	−0.0021 (17)
C5	0.026 (3)	0.020 (2)	0.031 (2)	0.001 (2)	0.009 (2)	0.0017 (18)
C4A	0.023 (3)	0.015 (2)	0.028 (2)	−0.0045 (19)	0.0098 (19)	−0.0027 (17)
C6	0.025 (3)	0.025 (3)	0.033 (2)	−0.003 (2)	0.005 (2)	−0.0058 (19)
C7	0.027 (3)	0.027 (3)	0.028 (2)	0.001 (2)	0.003 (2)	0.0012 (18)
C8	0.026 (3)	0.021 (2)	0.033 (2)	0.005 (2)	0.004 (2)	0.0036 (18)
C8A	0.024 (3)	0.017 (2)	0.032 (2)	−0.0016 (19)	0.010 (2)	−0.0032 (18)
C31	0.023 (3)	0.017 (2)	0.028 (2)	0.000 (2)	0.0077 (19)	−0.0023 (17)
C32	0.033 (3)	0.026 (3)	0.027 (2)	0.004 (2)	0.008 (2)	−0.0043 (18)
C34	0.037 (3)	0.042 (3)	0.026 (2)	0.020 (3)	0.000 (2)	−0.002 (2)
C35	0.025 (3)	0.039 (3)	0.028 (2)	0.007 (2)	0.006 (2)	−0.004 (2)
C351	0.027 (3)	0.048 (3)	0.034 (3)	0.004 (3)	0.001 (2)	−0.005 (2)

Geometric parameters (Å, º) top

S31—C32	1.726 (5)	C5—C6	1.371 (7)
S31—C35	1.728 (5)	C5—C4A	1.393 (6)
O1—C2	1.336 (6)	C5—H5	0.9500
O1—C8A	1.384 (5)	C4A—C8A	1.379 (6)
O3—C31	1.215 (5)	C6—C7	1.394 (7)
O4—C4	1.231 (5)	C6—H6	0.9500
N3—C31	1.353 (6)	C7—C8	1.367 (7)
N3—C32	1.387 (6)	C7—H7	0.9500
N3—H3	0.8800	C8—C8A	1.387 (7)
N33—C32	1.306 (6)	C8—H8	0.9500
N33—C34	1.388 (6)	C34—C35	1.341 (7)
C2—C3	1.344 (6)	C34—H34	0.9500
C2—H2	0.9500	C35—C351	1.506 (7)
C3—C4	1.449 (6)	C351—H35A	0.9800
C3—C31	1.492 (7)	C351—H35B	0.9800
C4—C4A	1.466 (6)	C351—H35C	0.9800

C32—S31—C35	88.8 (2)	C6—C7—H7	119.5
C2—O1—C8A	118.1 (4)	C7—C8—C8A	117.8 (4)
C31—N3—C32	123.6 (4)	C7—C8—H8	121.1
C31—N3—H3	118.2	C8A—C8—H8	121.1
C32—N3—H3	118.2	C4A—C8A—O1	121.2 (4)
C32—N33—C34	108.4 (4)	C4A—C8A—C8	123.2 (4)
O1—C2—C3	125.7 (4)	O1—C8A—C8	115.6 (4)
O1—C2—H2	117.2	O3—C31—N3	122.9 (4)
C3—C2—H2	117.2	O3—C31—C3	122.4 (4)
C2—C3—C4	119.7 (4)	N3—C31—C3	114.8 (4)
C2—C3—C31	115.2 (4)	N33—C32—N3	120.2 (4)
C4—C3—C31	125.0 (4)	N33—C32—S31	116.1 (4)
O4—C4—C3	123.9 (4)	N3—C32—S31	123.7 (4)
O4—C4—C4A	121.6 (4)	C35—C34—N33	117.2 (5)
C3—C4—C4A	114.5 (4)	C35—C34—H34	121.4
C6—C5—C4A	120.7 (4)	N33—C34—H34	121.4
C6—C5—H5	119.7	C34—C35—C351	128.4 (5)
C4A—C5—H5	119.7	C34—C35—S31	109.4 (4)
C8A—C4A—C5	117.5 (4)	C351—C35—S31	122.1 (4)
C8A—C4A—C4	120.7 (4)	C35—C351—H35A	109.5
C5—C4A—C4	121.8 (4)	C35—C351—H35B	109.5
C5—C6—C7	120.0 (5)	H35A—C351—H35B	109.5
C5—C6—H6	120.0	C35—C351—H35C	109.5
C7—C6—H6	120.0	H35A—C351—H35C	109.5
C8—C7—C6	120.9 (5)	H35B—C351—H35C	109.5
C8—C7—H7	119.5

C8A—O1—C2—C3	−1.8 (6)	C2—O1—C8A—C8	−179.3 (4)
O1—C2—C3—C4	0.9 (7)	C7—C8—C8A—C4A	−0.5 (7)
O1—C2—C3—C31	179.9 (4)	C7—C8—C8A—O1	179.3 (4)
C2—C3—C4—O4	−179.2 (4)	C32—N3—C31—O3	2.9 (7)
C31—C3—C4—O4	1.9 (7)	C32—N3—C31—C3	−177.4 (4)
C2—C3—C4—C4A	1.1 (6)	C2—C3—C31—O3	1.5 (6)
C31—C3—C4—C4A	−177.8 (4)	C4—C3—C31—O3	−179.6 (4)
C6—C5—C4A—C8A	−1.1 (6)	C2—C3—C31—N3	−178.2 (4)
C6—C5—C4A—C4	178.9 (4)	C4—C3—C31—N3	0.7 (6)
O4—C4—C4A—C8A	178.1 (4)	C34—N33—C32—N3	−178.9 (4)
C3—C4—C4A—C8A	−2.2 (6)	C34—N33—C32—S31	−0.4 (5)
O4—C4—C4A—C5	−1.9 (6)	C31—N3—C32—N33	180.0 (4)
C3—C4—C4A—C5	177.8 (4)	C31—N3—C32—S31	1.6 (6)
C4A—C5—C6—C7	0.2 (7)	C35—S31—C32—N33	−0.2 (4)
C5—C6—C7—C8	0.5 (7)	C35—S31—C32—N3	178.3 (4)
C6—C7—C8—C8A	−0.4 (7)	C32—N33—C34—C35	0.9 (6)
C5—C4A—C8A—O1	−178.5 (4)	N33—C34—C35—C351	179.2 (4)
C4—C4A—C8A—O1	1.5 (6)	N33—C34—C35—S31	−1.1 (6)
C5—C4A—C8A—C8	1.2 (7)	C32—S31—C35—C34	0.7 (4)
C4—C4A—C8A—C8	−178.8 (4)	C32—S31—C35—C351	−179.5 (4)
C2—O1—C8A—C4A	0.5 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O4	0.88	1.96	2.687 (5)	139
C2—H2···O4ⁱ	0.95	2.38	3.030 (5)	126
C8—H8···N33ⁱ	0.95	2.56	3.455 (6)	157

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

(1_P2~1~_c) top

Crystal data top

C₁₄H₁₀N₂O₃S	F(000) = 1184
M_r = 286.30	D_x = 1.503 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
a = 7.4646 (5) Å	Cell parameters from 12722 reflections
b = 30.626 (2) Å	θ = 2.3–27.5°
c = 11.0869 (8) Å	µ = 0.26 mm⁻¹
β = 93.232 (2)°	T = 100 K
V = 2530.6 (3) Å³	Plate, colourless
Z = 8	0.06 × 0.06 × 0.01 mm

Data collection top

Rigaku Saturn724+ diffractometer	5716 independent reflections
Radiation source: Sealed Tube	3733 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.090
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 2.3°
profile data from ω–scans	h = −8→9
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012)	k = −37→39
T_min = 0.538, T_max = 1.000	l = −14→14
15726 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.060	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.153	w = 1/[σ²(F_o²) + (0.0558P)² + 1.3609P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
5716 reflections	Δρ_max = 0.46 e Å⁻³
371 parameters	Δρ_min = −0.37 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
S131	0.61048 (10)	0.46741 (2)	0.38319 (7)	0.01951 (19)
S231	0.12461 (10)	0.35373 (2)	0.43837 (8)	0.0231 (2)
O11	0.7012 (3)	0.25605 (6)	0.53314 (18)	0.0193 (5)
O14	0.4476 (3)	0.30431 (6)	0.22432 (19)	0.0210 (5)
O21	0.1940 (3)	0.13877 (6)	0.52234 (19)	0.0211 (5)
O24	−0.0676 (3)	0.19810 (6)	0.2322 (2)	0.0221 (5)
O131	0.6665 (3)	0.38847 (6)	0.49383 (19)	0.0213 (5)
O231	0.1912 (3)	0.27146 (7)	0.5128 (2)	0.0254 (5)
N13	0.5367 (3)	0.38401 (8)	0.3050 (2)	0.0187 (6)
N23	0.0312 (3)	0.27500 (8)	0.3342 (3)	0.0198 (6)
N133	0.4688 (4)	0.44311 (8)	0.1763 (2)	0.0259 (6)
N233	−0.0482 (3)	0.33985 (8)	0.2334 (2)	0.0232 (6)
C12	0.6872 (4)	0.29895 (9)	0.5127 (3)	0.0177 (6)
H12	0.7403	0.3180	0.5722	0.021*
C13	0.6033 (4)	0.31749 (9)	0.4141 (3)	0.0166 (6)
C14	0.5230 (4)	0.29002 (9)	0.3192 (3)	0.0161 (6)
C15	0.4645 (4)	0.21215 (9)	0.2591 (3)	0.0182 (6)
H15	0.4032	0.2216	0.1863	0.022*
C14A	0.5380 (4)	0.24282 (9)	0.3424 (3)	0.0170 (6)
C16	0.4824 (4)	0.16821 (9)	0.2840 (3)	0.0191 (7)
H16	0.4344	0.1474	0.2275	0.023*
C17	0.5706 (4)	0.15392 (9)	0.3917 (3)	0.0209 (7)
H17	0.5808	0.1235	0.4078	0.025*
C18	0.6425 (4)	0.18345 (9)	0.4745 (3)	0.0190 (6)
H18	0.7022	0.1739	0.5477	0.023*
C18A	0.6252 (4)	0.22810 (9)	0.4478 (3)	0.0163 (6)
C22	0.1841 (4)	0.18235 (9)	0.5132 (3)	0.0204 (7)
H22	0.2399	0.1992	0.5768	0.024*
C23	0.1006 (4)	0.20402 (9)	0.4203 (3)	0.0171 (6)
C24	0.0102 (4)	0.18040 (10)	0.3211 (3)	0.0183 (6)
C25	−0.0718 (4)	0.10459 (9)	0.2489 (3)	0.0198 (6)
H25	−0.1343	0.1165	0.1795	0.024*
C24A	0.0162 (4)	0.13245 (9)	0.3338 (3)	0.0185 (6)
C26	−0.0676 (4)	0.06024 (10)	0.2662 (3)	0.0245 (7)
H26	−0.1286	0.0416	0.2090	0.029*
C27	0.0260 (4)	0.04218 (10)	0.3673 (3)	0.0268 (7)
H27	0.0280	0.0114	0.3784	0.032*
C28	0.1153 (4)	0.06891 (10)	0.4511 (3)	0.0240 (7)
H28	0.1811	0.0569	0.5190	0.029*
C28A	0.1069 (4)	0.11384 (9)	0.4338 (3)	0.0192 (6)
C132	0.5337 (4)	0.42830 (9)	0.2799 (3)	0.0189 (6)
C134	0.4804 (4)	0.48808 (10)	0.1767 (3)	0.0277 (8)
H134	0.4396	0.5048	0.1084	0.033*
C135	0.5518 (4)	0.50732 (9)	0.2774 (3)	0.0210 (7)
C136	0.5782 (4)	0.55514 (9)	0.3022 (3)	0.0264 (8)
H13A	0.5545	0.5717	0.2273	0.040*
H13B	0.7020	0.5603	0.3330	0.040*
H13C	0.4953	0.5646	0.3624	0.040*
C137	0.6058 (4)	0.36610 (9)	0.4097 (3)	0.0164 (6)
C232	0.0293 (4)	0.32010 (9)	0.3258 (3)	0.0190 (6)
C234	−0.0323 (4)	0.38469 (10)	0.2497 (3)	0.0255 (7)
H234	−0.0807	0.4047	0.1910	0.031*
C235	0.0546 (4)	0.39855 (10)	0.3522 (3)	0.0249 (7)
C236	0.0899 (4)	0.44428 (10)	0.3955 (3)	0.0302 (8)
H23A	0.0396	0.4650	0.3353	0.045*
H23B	0.2196	0.4490	0.4071	0.045*
H23C	0.0337	0.4488	0.4723	0.045*
C237	0.1123 (4)	0.25267 (10)	0.4275 (3)	0.0190 (6)
H13	0.499 (5)	0.3673 (12)	0.255 (3)	0.036 (11)*
H23	−0.012 (5)	0.2620 (11)	0.275 (3)	0.032 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S131	0.0231 (4)	0.0159 (3)	0.0195 (4)	0.0003 (3)	0.0008 (3)	−0.0002 (3)
S231	0.0199 (4)	0.0218 (4)	0.0277 (5)	0.0002 (3)	0.0006 (3)	−0.0048 (3)
O11	0.0246 (10)	0.0178 (10)	0.0152 (12)	−0.0001 (8)	−0.0014 (9)	0.0000 (9)
O14	0.0267 (11)	0.0184 (10)	0.0171 (12)	0.0018 (8)	−0.0062 (10)	0.0013 (9)
O21	0.0243 (11)	0.0237 (11)	0.0152 (12)	0.0017 (9)	−0.0007 (9)	0.0011 (9)
O24	0.0275 (11)	0.0217 (11)	0.0167 (12)	−0.0010 (9)	−0.0041 (10)	0.0007 (9)
O131	0.0270 (11)	0.0198 (10)	0.0167 (12)	−0.0008 (8)	−0.0016 (10)	−0.0025 (9)
O231	0.0274 (11)	0.0256 (11)	0.0224 (13)	0.0002 (9)	−0.0064 (10)	−0.0056 (10)
N13	0.0240 (14)	0.0158 (12)	0.0159 (14)	−0.0007 (10)	−0.0016 (12)	−0.0013 (11)
N23	0.0209 (13)	0.0196 (13)	0.0189 (15)	−0.0007 (10)	0.0010 (12)	−0.0030 (11)
N133	0.0344 (15)	0.0225 (13)	0.0202 (15)	0.0010 (11)	−0.0038 (13)	0.0032 (11)
N233	0.0266 (13)	0.0237 (13)	0.0197 (15)	0.0002 (11)	0.0040 (12)	0.0020 (11)
C12	0.0201 (14)	0.0166 (13)	0.0164 (16)	−0.0023 (11)	0.0006 (13)	−0.0027 (12)
C13	0.0156 (13)	0.0220 (14)	0.0125 (15)	−0.0005 (11)	0.0027 (12)	0.0000 (12)
C14	0.0154 (13)	0.0192 (14)	0.0138 (16)	0.0025 (11)	0.0015 (12)	−0.0011 (12)
C15	0.0179 (14)	0.0220 (14)	0.0149 (16)	−0.0012 (11)	0.0027 (13)	−0.0023 (12)
C14A	0.0153 (14)	0.0210 (14)	0.0151 (16)	0.0006 (11)	0.0053 (12)	−0.0003 (12)
C16	0.0210 (14)	0.0176 (14)	0.0191 (17)	−0.0033 (11)	0.0044 (13)	−0.0069 (12)
C17	0.0229 (15)	0.0171 (14)	0.0232 (18)	0.0006 (11)	0.0061 (14)	−0.0005 (13)
C18	0.0207 (14)	0.0199 (14)	0.0168 (16)	0.0004 (11)	0.0040 (13)	0.0032 (12)
C18A	0.0153 (13)	0.0241 (14)	0.0096 (15)	−0.0015 (11)	0.0011 (12)	−0.0043 (12)
C22	0.0193 (14)	0.0230 (15)	0.0189 (17)	−0.0013 (12)	0.0014 (13)	−0.0008 (13)
C23	0.0141 (13)	0.0235 (15)	0.0138 (16)	0.0002 (11)	0.0023 (12)	0.0005 (12)
C24	0.0170 (14)	0.0251 (15)	0.0128 (15)	−0.0011 (12)	0.0016 (12)	0.0020 (12)
C25	0.0190 (14)	0.0238 (14)	0.0163 (17)	−0.0013 (12)	−0.0013 (13)	−0.0008 (13)
C24A	0.0183 (14)	0.0230 (15)	0.0145 (16)	0.0020 (11)	0.0037 (13)	0.0009 (12)
C26	0.0276 (16)	0.0228 (15)	0.0231 (18)	−0.0022 (13)	0.0018 (15)	−0.0024 (14)
C27	0.0302 (17)	0.0193 (15)	0.031 (2)	0.0003 (13)	0.0061 (16)	0.0029 (14)
C28	0.0240 (15)	0.0268 (16)	0.0215 (18)	0.0046 (13)	0.0023 (14)	0.0058 (14)
C28A	0.0198 (14)	0.0219 (14)	0.0163 (16)	−0.0002 (11)	0.0043 (13)	−0.0002 (13)
C132	0.0188 (14)	0.0189 (14)	0.0190 (17)	−0.0004 (11)	0.0015 (13)	−0.0015 (13)
C134	0.0374 (18)	0.0185 (15)	0.027 (2)	0.0024 (13)	−0.0001 (16)	0.0053 (14)
C135	0.0196 (14)	0.0195 (14)	0.0242 (18)	0.0015 (12)	0.0047 (14)	0.0040 (13)
C136	0.0325 (17)	0.0174 (15)	0.030 (2)	−0.0011 (13)	0.0071 (16)	0.0035 (14)
C137	0.0128 (13)	0.0199 (14)	0.0162 (17)	−0.0013 (11)	−0.0011 (12)	−0.0006 (12)
C232	0.0187 (14)	0.0212 (14)	0.0172 (16)	−0.0003 (11)	0.0023 (13)	−0.0006 (13)
C234	0.0291 (17)	0.0229 (15)	0.0255 (19)	0.0014 (13)	0.0096 (15)	0.0009 (14)
C235	0.0200 (15)	0.0202 (15)	0.035 (2)	−0.0018 (12)	0.0093 (15)	−0.0016 (14)
C236	0.0242 (16)	0.0253 (16)	0.041 (2)	−0.0004 (13)	0.0024 (16)	−0.0040 (16)
C237	0.0158 (13)	0.0240 (15)	0.0172 (16)	0.0012 (11)	0.0010 (13)	−0.0035 (13)

Geometric parameters (Å, º) top

S131—C132	1.732 (3)	C16—H16	0.9500
S131—C135	1.733 (3)	C17—C18	1.376 (4)
S231—C235	1.736 (3)	C17—H17	0.9500
S231—C232	1.739 (3)	C18—C18A	1.404 (4)
O11—C12	1.336 (3)	C18—H18	0.9500
O11—C18A	1.374 (3)	C22—C23	1.348 (4)
O14—C14	1.244 (4)	C22—H22	0.9500
O21—C22	1.340 (3)	C23—C24	1.450 (4)
O21—C28A	1.377 (4)	C23—C237	1.495 (4)
O24—C24	1.241 (4)	C24—C24A	1.476 (4)
O131—C137	1.223 (3)	C25—C26	1.372 (4)
O231—C237	1.229 (4)	C25—C24A	1.405 (4)
N13—C137	1.359 (4)	C25—H25	0.9500
N13—C132	1.385 (4)	C24A—C28A	1.389 (4)
N13—H13	0.80 (4)	C26—C27	1.401 (5)
N23—C237	1.354 (4)	C26—H26	0.9500
N23—C232	1.384 (4)	C27—C28	1.381 (4)
N23—H23	0.82 (4)	C27—H27	0.9500
N133—C132	1.302 (4)	C28—C28A	1.390 (4)
N133—C134	1.380 (4)	C28—H28	0.9500
N233—C232	1.297 (4)	C134—C135	1.345 (5)
N233—C234	1.389 (4)	C134—H134	0.9500
C12—C13	1.354 (4)	C135—C136	1.501 (4)
C12—H12	0.9500	C136—H13A	0.9800
C13—C14	1.451 (4)	C136—H13B	0.9800
C13—C137	1.490 (4)	C136—H13C	0.9800
C14—C14A	1.472 (4)	C234—C235	1.346 (5)
C15—C16	1.379 (4)	C234—H234	0.9500
C15—C14A	1.407 (4)	C235—C236	1.499 (4)
C15—H15	0.9500	C236—H23A	0.9800
C14A—C18A	1.381 (4)	C236—H23B	0.9800
C16—C17	1.401 (4)	C236—H23C	0.9800

C132—S131—C135	88.76 (15)	C28A—C24A—C25	118.3 (3)
C235—S231—C232	88.58 (16)	C28A—C24A—C24	119.7 (3)
C12—O11—C18A	118.0 (2)	C25—C24A—C24	122.0 (3)
C22—O21—C28A	118.4 (2)	C25—C26—C27	120.6 (3)
C137—N13—C132	124.6 (3)	C25—C26—H26	119.7
C137—N13—H13	116 (3)	C27—C26—H26	119.7
C132—N13—H13	119 (3)	C28—C27—C26	120.3 (3)
C237—N23—C232	123.9 (3)	C28—C27—H27	119.9
C237—N23—H23	120 (3)	C26—C27—H27	119.9
C232—N23—H23	116 (3)	C27—C28—C28A	118.6 (3)
C132—N133—C134	109.0 (3)	C27—C28—H28	120.7
C232—N233—C234	109.1 (3)	C28A—C28—H28	120.7
O11—C12—C13	125.3 (3)	O21—C28A—C24A	122.1 (3)
O11—C12—H12	117.3	O21—C28A—C28	115.8 (3)
C13—C12—H12	117.3	C24A—C28A—C28	122.1 (3)
C12—C13—C14	119.7 (3)	N133—C132—N13	121.3 (3)
C12—C13—C137	116.1 (3)	N133—C132—S131	115.8 (2)
C14—C13—C137	124.1 (3)	N13—C132—S131	122.9 (2)
O14—C14—C13	123.9 (3)	C135—C134—N133	117.5 (3)
O14—C14—C14A	121.3 (3)	C135—C134—H134	121.3
C13—C14—C14A	114.7 (3)	N133—C134—H134	121.3
C16—C15—C14A	119.3 (3)	C134—C135—C136	128.4 (3)
C16—C15—H15	120.3	C134—C135—S131	109.0 (2)
C14A—C15—H15	120.3	C136—C135—S131	122.6 (3)
C18A—C14A—C15	119.0 (3)	C135—C136—H13A	109.5
C18A—C14A—C14	119.8 (3)	C135—C136—H13B	109.5
C15—C14A—C14	121.2 (3)	H13A—C136—H13B	109.5
C15—C16—C17	120.8 (3)	C135—C136—H13C	109.5
C15—C16—H16	119.6	H13A—C136—H13C	109.5
C17—C16—H16	119.6	H13B—C136—H13C	109.5
C18—C17—C16	120.7 (3)	O131—C137—N13	122.1 (3)
C18—C17—H17	119.7	O131—C137—C13	122.6 (3)
C16—C17—H17	119.7	N13—C137—C13	115.2 (3)
C17—C18—C18A	118.1 (3)	N233—C232—N23	121.4 (3)
C17—C18—H18	120.9	N233—C232—S231	115.9 (2)
C18A—C18—H18	120.9	N23—C232—S231	122.7 (2)
O11—C18A—C14A	122.4 (3)	C235—C234—N233	117.1 (3)
O11—C18A—C18	115.6 (3)	C235—C234—H234	121.5
C14A—C18A—C18	122.0 (3)	N233—C234—H234	121.5
O21—C22—C23	124.7 (3)	C234—C235—C236	129.3 (3)
O21—C22—H22	117.7	C234—C235—S231	109.3 (2)
C23—C22—H22	117.7	C236—C235—S231	121.4 (3)
C22—C23—C24	120.6 (3)	C235—C236—H23A	109.5
C22—C23—C237	115.3 (3)	C235—C236—H23B	109.5
C24—C23—C237	124.1 (3)	H23A—C236—H23B	109.5
O24—C24—C23	124.2 (3)	C235—C236—H23C	109.5
O24—C24—C24A	121.4 (3)	H23A—C236—H23C	109.5
C23—C24—C24A	114.5 (3)	H23B—C236—H23C	109.5
C26—C25—C24A	120.1 (3)	O231—C237—N23	121.7 (3)
C26—C25—H25	119.9	O231—C237—C23	122.1 (3)
C24A—C25—H25	119.9	N23—C237—C23	116.1 (3)

C18A—O11—C12—C13	0.1 (4)	C22—O21—C28A—C28	−177.2 (2)
O11—C12—C13—C14	−1.3 (4)	C25—C24A—C28A—O21	−178.9 (2)
O11—C12—C13—C137	−179.4 (2)	C24—C24A—C28A—O21	−0.6 (4)
C12—C13—C14—O14	−178.1 (3)	C25—C24A—C28A—C28	1.0 (4)
C137—C13—C14—O14	−0.1 (4)	C24—C24A—C28A—C28	179.3 (2)
C12—C13—C14—C14A	1.5 (4)	C27—C28—C28A—O21	178.0 (2)
C137—C13—C14—C14A	179.4 (2)	C27—C28—C28A—C24A	−1.8 (4)
C16—C15—C14A—C18A	−0.5 (4)	C134—N133—C132—N13	179.2 (2)
C16—C15—C14A—C14	179.7 (2)	C134—N133—C132—S131	0.4 (3)
O14—C14—C14A—C18A	178.9 (2)	C137—N13—C132—N133	178.4 (3)
C13—C14—C14A—C18A	−0.6 (4)	C137—N13—C132—S131	−2.9 (4)
O14—C14—C14A—C15	−1.2 (4)	C135—S131—C132—N133	−0.5 (2)
C13—C14—C14A—C15	179.2 (2)	C135—S131—C132—N13	−179.2 (2)
C14A—C15—C16—C17	0.8 (4)	C132—N133—C134—C135	−0.1 (4)
C15—C16—C17—C18	−0.5 (4)	N133—C134—C135—C136	−179.3 (3)
C16—C17—C18—C18A	−0.1 (4)	N133—C134—C135—S131	−0.3 (4)
C12—O11—C18A—C14A	0.8 (4)	C132—S131—C135—C134	0.4 (2)
C12—O11—C18A—C18	−179.4 (2)	C132—S131—C135—C136	179.5 (2)
C15—C14A—C18A—O11	179.6 (2)	C132—N13—C137—O131	2.8 (4)
C14—C14A—C18A—O11	−0.5 (4)	C132—N13—C137—C13	−176.9 (2)
C15—C14A—C18A—C18	−0.1 (4)	C12—C13—C137—O131	−5.8 (4)
C14—C14A—C18A—C18	179.7 (2)	C14—C13—C137—O131	176.1 (3)
C17—C18—C18A—O11	−179.3 (2)	C12—C13—C137—N13	173.8 (2)
C17—C18—C18A—C14A	0.4 (4)	C14—C13—C137—N13	−4.2 (4)
C28A—O21—C22—C23	−2.9 (4)	C234—N233—C232—N23	179.0 (2)
O21—C22—C23—C24	1.0 (4)	C234—N233—C232—S231	0.5 (3)
O21—C22—C23—C237	−178.0 (2)	C237—N23—C232—N233	179.0 (3)
C22—C23—C24—O24	−179.2 (3)	C237—N23—C232—S231	−2.6 (4)
C237—C23—C24—O24	−0.3 (4)	C235—S231—C232—N233	−0.4 (2)
C22—C23—C24—C24A	1.2 (4)	C235—S231—C232—N23	−178.9 (2)
C237—C23—C24—C24A	−180.0 (2)	C232—N233—C234—C235	−0.3 (4)
C26—C25—C24A—C28A	0.3 (4)	N233—C234—C235—C236	−178.9 (3)
C26—C25—C24A—C24	−177.9 (3)	N233—C234—C235—S231	0.0 (3)
O24—C24—C24A—C28A	179.0 (3)	C232—S231—C235—C234	0.2 (2)
C23—C24—C24A—C28A	−1.3 (4)	C232—S231—C235—C236	179.2 (2)
O24—C24—C24A—C25	−2.8 (4)	C232—N23—C237—O231	0.0 (4)
C23—C24—C24A—C25	176.9 (2)	C232—N23—C237—C23	−179.7 (2)
C24A—C25—C26—C27	−0.8 (4)	C22—C23—C237—O231	−0.6 (4)
C25—C26—C27—C28	0.0 (4)	C24—C23—C237—O231	−179.5 (3)
C26—C27—C28—C28A	1.3 (4)	C22—C23—C237—N23	179.2 (2)
C22—O21—C28A—C24A	2.7 (4)	C24—C23—C237—N23	0.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N13—H13···O14	0.80 (4)	1.99 (4)	2.671 (3)	143 (4)
C12—H12···O24ⁱ	0.95	2.27	2.963 (4)	129
C15—H15···O23ⁱⁱ	0.95	2.43	3.353 (4)	164
C136—H13C···O13ⁱⁱⁱ	0.98	2.51	3.449 (4)	162
N23—H23···O24	0.82 (4)	2.05 (3)	2.697 (3)	136 (3)
C22—H22···O14ⁱⁱ	0.95	2.19	2.999 (4)	142
C25—H25···O13^iv	0.95	2.48	3.352 (4)	153

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

Dihedral angles (°) top

Compound	θ_A–B°	θ_A–B°	θ_A–C°
1_P2₁/n	3.1 (2)	1.6 (8)	4.5 (8)
1_P2₁/c(mol#1)	6.38 (9)	5.12 (19)	1.76 (12)
1_P2₁/c(mol#2)	3.42 (10)	1.43 (10)	2.01 (14)

Selected π–π contacts (Å) top

Compound	CgI	CgJ(aru)	Cg···Cg	CgI_Perp	CgJ_Perp	Slippage Å
1_P2₁/n	Cg1	Cg2(x + 1, y, z)	3.547 (3)	3.3358 (18)	3.3299 (19)	1.222
1_P2₁/c	Cg3	Cg4(x, y, z)	3.6726 (17)	3.2645 (13)	3.3012 (12)	1.609

Cg1 and Cg2 are the centroids of rings O1/C2–C4/C4A/C8A and C4A/C5–C8/C8A, respectively. Cg3 and Cg4 are the centroids of rings C14A/C15–C18/C18A and O21/C22–C24/C24A/C28A, respectively.

Percentages for the most relevant atom–atom contacts for the studied compounds top

Compound	H···H	H···O/O···H	H···N/N···H	H···S/S···H	H···C/C···H	C···C
1_P2₁/n	31.8	19.0	8.7	6.3	15.2	7.1
1_P2₁/c	29.6	19.1	8.6	7.7	17.6	5.2
1_P2₁/c	34.6	13.2	6.6	7.1	18.4	5.2

Acknowledgements

The authors thank the National Crystallographic Service, University of Southampton for the data collection and for their help and advice (Coles & Gale, 2012 ).

Funding information

This work was supported by the Portuguese Foundation for Science and Technology (FCT) (PEst-C/QUI/UI0081/2013 and UID/Multi/04546/2013 to FC), (SFRH/BPD/74491/2010 grants are supported by FCT).

References

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