Crystal structures of two 6-(2-hy­droxy­benzo­yl)-5H-thia­zolo[3,2-a]pyrimidin-5-ones

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

doi:10.1107/S2056989015011044

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 7| July 2015| Pages 766-771

doi:10.1107/S2056989015011044

Open

access

Crystal structures of two 6-(2-hydroxybenzoyl)-5H-thiazolo[3,2-a]pyrimidin-5-ones

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

^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, ^bREQUIMTE/Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, 4169-007 Porto, Portugal, ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^dCIQUP/Departamento de Química e Bioquímica, 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 1 June 2015; accepted 7 June 2015; online 13 June 2015)

The title compounds, 6-(2-hydroxybenzyl)-5H-thiazolo[3,2-a]pyrimidin-5-one, C₁₃H₈N₂O₃S, (1), and 6-(2-hydroxybenzyl)-3-methyl-5H-thiazolo[3,2-a]pyrimidin-5-one, C₁₄H₁₀N₂O₃S, (2), were synthesized when a chromone-3-carboxylic acid, activated with (benzotriazol-1-yloxy)tripyrrolidinylphosphonium hexafluoridophosphate (PyBOP), was reacted with a primary heteromamine. Instead of the expected amidation, the unusual title thiazolopyrimidine-5-one derivatives were obtained serendipitously and a mechanism of formation is proposed. Both compounds present an intramolecular O—H⋯O hydrogen bond, which generates an S(6) ring. The dihedral angles between the heterocyclic moiety and the 2-hydroxybenzoyl ring are 55.22 (5) and 46.83 (6)° for (1) and (2), respectively. In the crystals, the molecules are linked by weak C—H⋯O hydrogen bonds and π–π stacking interactions.

Keywords: crystal structure; thiazole; conformation; supramolecular structure; hydrogen bonding; π–π stacking interactions.

CCDC references: 1405409; 1405408

1. Chemical context

Although heterocycles, namely those bearing thiazole or pyrimidine motifs, are reported to show a broad spectrum of pharmacological properties such as antimicrobial, anticancer and anti-inflammatory activities (Jiang et al., 2013 ; Mishra et al., 2015 ; Perrone et al., 2012 ), only a few compounds enclosing the thiazolo[3,2a]pyrimidine framework have been explored and screened towards the above-mentioned pharmacological activities. Even though some derivatives tested up to now have shown interesting anti-inflammatory (Bekhit et al., 2003 ), antiviral (Abd El-Galil et al., 2010 ) and antibacterial activities (Mulwad et al., 2010 ) and as calcium agonists (Balkan et al., 1992 ), the data acquired so far are insufficient to indicate the importance of the thiazolo[3,2a]pyrimidine motif as a positive contributor to the biological profile mentioned above. The same reflection is valid in relation to the data acquired for some thiazolo[3,2a]pyrimidine-5-one derivatives as 5-HT2a receptor antagonists, a putative therapeutic target for the treatment of depression, although they have structural similarity to ritanserin, a serotonin antagonist (Awadallah, 2008 ). In this last case, the pharmacological activity appears to be enhanced by the nature of the planar aromatic or heterocyclic ring systems, the type of spacer as well as the presence of a basic nitrogen atom.

A search made in the latest version (5.36.0; 2015) of the Cambridge Structural Database (Groom & Allen, 2014 ) for thiazolo[3,2a]pyrimidine-5-one-based structures revealed the existence of 11 compounds containing the 5H-thiazolo[3,2a]-pyrimidine-5-one fragment in which the hetero ring was not fused with other cyclic rings. In order to clarify the significance of the thiazolo[3,2a]pyrimidine scaffold in medicinal chemistry, new 5H-thiazolo[3,2-a]pyrimidin-5-one derivatives were synthesized. In this work we report the structures and synthesis, by a one-pot reaction, of two derivatives 6-(2-hydroxybenzyl)-5H-thiazolo[3,2-a]pyrimidin-5-one (1) and 6-(2-hydroxybenzyl)-5H-thiazolo[3,2-a]pyrimidin-3-methyl-5-one (2), which will be screened for antimicrobial activity.

2. Structural commentary

The molecules of (1) and (2) are shown in Figs. 1 and 2. The structural characterization reveals that the molecules have two cyclic units, viz. the hydroxybenzyl and the heterocyclic 5H-thiazolo[3,2-a]pyrimidin-5-one ring separated by a carbonyl spacer, as expected. In both compounds, the carbonyl O atoms are trans oriented with respect to each other, contributing to the establishment of an intramolecular O—H⋯O hydrogen bond between the o-hydroxyl group of the benzene ring and the carbonyl group of the spacer (Tables 1 and 2), which generates an S(6) ring. Taken together, the benzene ring and hydrogen-bonded pseudo ring are roughly planar, the carbonyl oxygen atom deviates by 0.391 (3) and 0.055 (4) Å in (1) and (2), respectively from the least-square plane formed by the benzene ring atoms. The heterocyclic rings of both compounds are also almost planar, as expected; the maximum deviation from the best plane formed by the ten atoms of the thiazolopyrimidine moiety is 0.103 (1) Å for the carbonyl oxygen atom, O5, in (1) and 0.129 (1) Å for the same atom in (2). Thus, both molecules are twisted around the C6—C67 bond that links the ring systems, which are inclined to one another by 55.22 (5) and 46.83 (6)° for (1) and (2), respectively.

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O62—H62A⋯O67	0.84	1.87	2.5906 (16)	144
C2—H2⋯O5ⁱ	0.95	2.29	3.146 (2)	150
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 (2)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O62—H3⋯O67	0.84	1.81	2.557 (2)	146
C64—H64⋯O5ⁱ	0.95	2.57	3.217 (3)	125
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+1]$ .

Figure 1
A view of the asymmetric unit of (1) with displacement ellipsoids drawn at the 70% probability level.

Figure 2
A view of the asymmetric unit of (2) with displacement ellipsoids drawn at the 70% probability level.

3. Supramolecular features

As noted above, the hydroxyl group is involved in intramolecular hydrogen bonding, which leaves it unavailable for participation in intermolecular hydrogen bonding. Thus, the molecules are linked via weak C—H⋯O interactions: in both compounds the oxygen acceptor atom is the oxo atom O5, being in (1) the hydrogen-bond donor atom is C2 (of the heterocyclic group) and in (2) the hydrogen-bond donor atom is C64 (located in the exocyclic benzene ring).

In (1) the molecules are linked by the C2—H2⋯O5 (x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ) hydrogen bond, forming a C(6) chain, which runs parallel to [101] and results from the action of a c-glide at (0, $[{1\over 4}]$ , 0) (Table 1 and Fig. 3). The presence of the methyl group on atom C2 of the heterocyclic ring precludes the formation of a similar bond in (2). Thus in the supramolecular structure of this compound, the molecules are linked by a C64—H64⋯O5(−x + 2, y + $[{1\over 2}]$ , −z + 1) hydrogen bond, forming a C(9) chain, which runs parallel to the b-axis direction and results from the action of a 2₁ screw axis at (1, y, $[{1\over 2}]$ ) (Table 2 and Fig. 4).

Figure 3
Compound (1): Molecular C6 chain which runs parallel to [101]. Symmetry codes: (i) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (ii) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ . Hydrogen atoms not involved in the hydrogen bonding are omitted.

Figure 4
Compound (2): Molecular C9 chain which runs parallel to the a-axis direction. Symmetry codes: (i) −x + 2, y + $[{1\over 2}]$ , −z + 1; (ii) −x + 2, y − $[{1\over 2}]$ , −z + 1. Hydrogen atoms not involved in the hydrogen bonding are omitted.

Both molecules present aromatic π–π stacking contacts. In (1) there is a close contact between centrosymmetrically related rings containing atom C5 at (x, y, z) and (−x + 1, −y + 1, −z + 1) [centroid-to-centroid distance = 3.6764 (9) Å, perpendicular distance between rings = 3.2478 (6) Å and slippage = 1.723 Å]. In (2) the molecules stack above each other along the a-axis direction with unit translation of 3.931 (2) Å [perpendicular distances between the rings (and slippages) of 3.3821 (9) (2.004), 3.3355 (9) (2.080), 3.4084 (9) (1.958) Å for the thiazole, pyrimidine and benzene rings, respectively].

4. Database survey

As said before, a search made in the latest version (5.36.0; 2015) of the Cambridge Structural Database revealed the existence of 11 deposited compounds containing the 5H-thiazolo[3,2a]-pyrimidine-5-one residue. Of those, eight were 2,3-dihydro derivatives thus leaving only the compounds listed below. Fig. 5 shows representations of the compounds referred to in this work (the scaffold indicates the adopted numbering scheme for the 5H-thiazolo[3,2a]-pyrimidine-5-one residue). Compounds (1) and (2) are herein characterized and the remaining are referred to by their CSD codes. GEFTES: 7-(methylsulfanyl)-5H-[1,3]thiazolo[3,2-a]pyrimidin-5-one (Bernhardt & Wentrup, 2012 ); JABRAG: 7-pentafluoroethyl-6-trifluoromethylthiazolo[3,2-a]pyrimidine-5-one (Chi et al., 2002 ); NAMWEE: N-phenyl-6-methyl-5-oxo-5H-[1,3]-thiazolo[3,2-a]pyrimidine-2-carboxamide (Volovenko et al., 2004 ); QIBNOF: 3-ethyl-2-(4-methylthiazol-2-yl)thiazolo[3,2-a]pyrimidin-4-one (Troisi et al., 2006 ); and TUFCAY: 3-benzoyl-7-methyl-5H-thiazolo[3,2-a]pyrimidine-5-one (Elokhina et al., 1996 ). In those compounds, the C2—C3 bond length averages 1.329 (9) Å, typical for values for a Csp²—Csp² bond length in thiophenes (Allen et al., 1987 ). The average length of the C3—N4 bond at 1.397 (6) Å is slightly shorter than that for N4—C5, which is 1.418 (7) Å. The average values for the N4—C9 and C7—N8 bond lengths, 1.363 (7) and 1.357 (12) Å, respectively, are significantly shorter than the previous ones, suggesting the presence of a higher electronic density in that part of the rings. The N8—C9 average of 1.306 (9) Å is typical of a C=N bond.

Figure 5
Representations of the compounds referred to in this work (the scaffold indicates the adopted numbering scheme for the 5H-thiazolo[3,2a]-pyrimidine-5-one residue).

5. Synthesis and crystallization

Compounds (1) and (2) were synthesized in moderate/high yields by a one-pot reaction using 4-oxo-4H-chromene-3-carboxylic acid as the starting material. Chromone-3-carboxylic acid was initially activated with benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluoridophosphate (PyBOP). Then the in situ formed intermediate reacts with the heteroamine (stoichiometry 1:1) giving rise to 5H-thiazolo[3,2-a]pyrimidin-5-one derivatives (1) (68%) and (2) (81%). From a mechanistic point of view, the 6-(2-hydroxybenzoyl)-5H-thiazolo[3,2-a]pyrimidin-5-one derivatives may have been obtained by a nucleophilic attack of primary heteroamine to the 2-position of the activated chromone with a subsequent opening of the pyran ring. Then, the heterocycle entities were obtained by a process involving an intramolecular reaction assisted by the nitrogen atom of the heterocycle moiety (see scheme below). Crystals were obtained by recrystallization from (1) in AcOEt (m.p. 454–456 K) in the form of colourless plates and from (2) in CH₂Cl₂ (m.p. 451–453 K) in the form of yellow blocks.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were positioned geometrically and treated as riding atoms with C—H(aromatic) = 0.95 and O—H = 0.84 Å with U_iso = 1.2U_eq(C) or 1.5U_eq(O).

Table 3
Experimental details

	(1)	(2)
Crystal data
Chemical formula	C₁₃H₈N₂O₃S	C₁₄H₁₀N₂O₃S
M_r	272.27	286.30
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁
Temperature (K)	100	100
a, b, c (Å)	7.5563 (5), 15.3187 (11), 10.1229 (7)	3.931 (2), 10.459 (6), 14.657 (8)
β (°)	99.49 (2)	94.201 (14)
V (Å³)	1155.70 (15)	601.0 (6)
Z	4	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.29	0.28
Crystal size (mm)	0.33 × 0.21 × 0.04	0.26 × 0.13 × 0.09

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	0.912, 0.989	0.931, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	7713, 2632, 2135	4859, 3175, 2808
R_int	0.040	0.023
(sin θ/λ)_max (Å⁻¹)	0.649	0.729

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.096, 1.02	0.031, 0.067, 1.04
No. of reflections	2632	3175
No. of parameters	172	183
No. of restraints	0	1
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.22	0.35, −0.34
Absolute structure	–	Flack x determined using 981 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	–	−0.03 (4)
Computer programs: CrystalClear-SM Expert (Rigaku, 2012), SHELXS (Sheldrick, 2008 ), ShelXle (Hübschle et al., 2011 ), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2009 ), Flipper 25 (Oszlányi & Sütő, 2004 ), OSCAIL (McArdle et al., 2004 ) and Mercury (Macrae et al., 2006 ).

Supporting information

CCDC references: 1405409; 1405408

Crystal structure: contains datablocks general, 1, 2. DOI: 10.1107/S2056989015011044/hb7437sup1.cif

Structure factors: contains datablock 1. DOI: 10.1107/S2056989015011044/hb74371sup2.hkl

Structure factors: contains datablock 2. DOI: 10.1107/S2056989015011044/hb74372sup3.hkl

Supporting information file. DOI: 10.1107/S2056989015011044/hb74371sup4.cml

Supporting information file. DOI: 10.1107/S2056989015011044/hb74372sup5.cml

checkCIF report

Chemical context top

Although heterocycles, namely those bearing thiazole or pyrimidine motifs, are reported to show a broad spectrum of pharmacological properties such as antimicrobial, anticancer and anti-inflammatory activities (Jiang et al., 2013; Mishra et al., 2015; Perrone et al., 2012), only a few compounds enclosing the thiazolo[3,2a]pyrimidine framework have been explored and screened towards the above-mentioned pharmacological activities. Even though some derivatives tested up to now have shown interesting anti-inflammatory (Bekhit et al., 2003), antiviral (Abd El-Galil et al., 2010) and antibacterial activities (Mulwad et al., 2010) and as calcium agonists (Balkan et al., 1992), the data acquired so far are insufficient to indicate the importance of the thiazolo[3,2a]pyrimidine motif as a positive contributor to the biological profile mentioned above. The same reflection is valid in relation to the data acquired for some thiazolo[3,2a]pyrimidine-5-one derivatives as 5-HT2a receptor antagonists, a putative therapeutic target for the treatment of depression, although they have structural similarity to ritanserin, a serotonin antagonist (Awadallah, 2008). In this last case, the pharmacological activity appears to be enhanced by the nature of the planar aromatic or heterocyclic ring systems, the type of spacer as well as the presence of a basic nitrogen atom.

A search made in the latest version (5.36.0; 2015) of the Cambridge Structural Database (Groom & Allen, 2014) for thiazolo[3,2a]pyrimidine-5-one-based structures revealed the existence of 11 compounds containing the 5H-thiazolo[3,2a]-pyrimidine-5-one fragment residual in which the hetero ring was not fused with other cyclic rings. In order to clarify of the significance of the thiazolo[3,2a]pyrimidine scaffold in medicinal chemistry, new 5H-thiazolo[3,2-a]pyrimidin-5-one derivatives were synthesized. In this work we report the structures and synthesis, by a one-pot reaction, of two derivatives 6-(2-hydroxybenzyl)-5H-thiazolo[3,2-a]pyrimidin-5-one (1) and 6-(2-hydroxybenzyl)-5H-thiazolo[3,2-a]pyrimidin-3-methyl-5-one (2), which will be screened for antimicrobial activity.

Structural commentary top

The molecules of (1) and (2) are shown in Figs. 1 and 2. The structural characterization reveals that the molecules have two cyclic units, viz. the hydroxybenzyl and the heterocyclic 5H-thiazolo[3,2-a]pyrimidin-5-one ring separated by a carbonyl spacer, as expected. In both compounds, the carbonyl O atoms are trans oriented with respect to each other, contributing to the establishment of an intramolecular O—H···O hydrogen bond between the o-hydroxyl group of the benzene ring and the carbonyl group of the spacer (Tables 1 and 2), which generates an S(6) ring. Taken together, the phenyl ring and hydrogen-bonded pseudo ring are roughly planar, the carbonyl oxygen atom deviates by 0.391 (3) and 0.055 (4) Å in (1) and (2), respectively from the least-square plane formed by the benzene ring atoms. The heterocyclic rings of both compounds are also almost planar, as expected; the maximum deviation from the best plane formed by the ten atoms of the thiazolopyrimidine moiety is 0.103 (1) Å for the carbonyl oxygen atom, O5, in (1) and 0.129 (1) Å for the same atom in (2). Thus, both molecules are able to twist around the C6—C67 bond that links the ring systems. Those rotations can be evaluated by the dihedral angles between the heterocyclic moiety and the phenyl substituent, which are 55.22 (5) and 46.83 (6)° for (1) and (2), respectively.

Supramolecular features top

As noted above, the hydroxyl group is involved in intramolecular hydrogen bonding, which leaves it unavailable for participation in intermolecular hydrogen bonding. Thus, the molecules are linked via weak C—H···O interactions: in both compounds the oxygen acceptor atom is the oxo atom O5 being in (1) the hydrogen-bond donor atom of C2 (of the heterocyclic group) and in (2) the hydrogen atom of C64 (located in the exocyclic phenyl ring).

In (1) the molecules are linked by the C2—H2···O5 (1/2 + x, 1/2 - y, 1/2 + z) hydrogen bond, forming a C(6) chain, which runs parallel to [101] and results from the action of a c-glide at (0, 1/4, 0) (Table 1and Fig. 3). The presence of the methyl group on atom C2 of the heterocyclic ring precludes the formation of a similar bond in (2). Thus in the supramolecular structure of this compound, the molecules are linked by a C64—H64···O5(2 - x, 1/2 + y, 1 - z) hydrogen bond, forming a C(9) chain, which runs parallel to the b-axis direction and results from the action of a 2₁ screw axis at (1, y, 1/2) (Table 3 and Fig. 4).

Both molecules present aromatic π–π stacking contacts. In (1) there is a close contact between centrosymmetrically related rings containing atom C5 at (x, y, z) and (1 - x, 1 - y, 1 - z) [centroid-to-centroid distance = 3.6764 (9) Å, perpendicular distance between rings = 3.2478 (6) Å and slippage = 1.723 Å]. In (2) the molecules stack above each other along the a-axis direction with unit translation of 3.931 (2) Å [perpendicular distances between the rings (and slippages) of 3.3821 (9) (2.004), 3.3355 (9) (2.080), 3.4084 (9) (1.958) Å for the thiazole, pyrimidine and phenyl rings, respectively].

Database survey top

As said before, a search made in the latest version (5.36.0; 2015) of the Cambridge Structural Database revealed the existence of 11 deposited compounds containing the 5H-thiazolo[3,2a]-pyrimidine-5-one residue. Of those, eight were 2,3-dihydro derivatives thus leaving only the compounds listed below. Fig. 5 shows representations of the compounds referred to in this work. Compounds (1) and (2) are herein characterized and the remaining are referred to by their CSD codes. GEFTES: 7-(methylsulfanyl)-5H-[1,3]thiazolo[3,2-a]pyrimidin-5-one (Bernhardt & Wentrup, 2012); JABRAG: 7-pentafluoroethyl-6-trifluoromethylthiazolo[3,2-a]pyrimidine-5-one (Chi et al., 2002); NAMWEE: N-phenyl-6-methyl-5-oxo-5H-[1,3]-thiazolo[3,2-a]pyrimidine-2-carboxamide (Volovenko et al., 2004); QIBNOF: 3-ethyl-2-(4-methylthiazol-2-yl)thiazolo[3,2-a]pyrimidin-4-one (Troisi et al., 2006); and TUFCAY: 3-benzoyl-7-methyl-5H-thiazolo[3,2-a]pyrimidine-5-one (Elokhina et al., 1996). In those compounds, the C2—C3 bond length averages 1.329 (9) Å, typical of values for the Csp²—Csp² bond length in thiophenes (Allen et al., 1987). The average length of the C3—N4 bond is 1.397 (6) Å slightly shorter than that for N4—C5, which is 1.418 (7) Å. The average values for the N4—C9 and C7—N8 bond lengths, 1.363 (7) and 1.357 (12) Å, respectively, are significantly shorter than the previous ones, suggesting the presence of a higher electronic density in that part of the rings. The N8—C9 average of 1.306 (9) Å is typical of a C═ N bond.

Synthesis and crystallization top

Compounds (1) and (2) were synthesized in moderate/high yields by a one-pot reaction using 4-oxo-4H-chromene-3-carboxylic acid as the starting material. Chromone-3-carboxylic acid was initially activated with benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluoridophosphate (PyBOP). Then the in situ formed intermediate reacts with the heteroamine (stoichiometry 1:1) giving rise to 5H-thiazolo[3,2-a]pyrimidin-5-one derivatives (1) (68%) and (2) (81%). From a mechanistic point of view, the 6-(2-hydroxybenzoyl)-5H-thiazolo[3,2-a]pyrimidin-5-one derivatives may have been obtained by a nucleophilic attack of primary heteroamine to the 2-position of the activated chromone with a subsequent opening of the pyran ring. Then, the heterocycle entities were obtained by a process enfolding an intramolecular reaction assisted by the nitrogen atom of the heterocycle moiety (see scheme below). Crystals were obtained by recrystallization from (1) in AcOEt (m.p. 454–456 K) in the form of colourless plates and from (2) in CH₂Cl₂ (m.p. 451–453 K) in the form of yellow blocks.

Refinement top

Related literature top

For related literature, see: Abd El-Galil, Salwa, Eman & Abd El-Shafy (2010); Allen (2002); Allen et al. (1987); Awadallah (2008); Balkan et al. (1992); Bekhit et al. (2003); Bernhardt & Wentrup (2012); Chi et al. (2002); Elokhina et al. (1996); Jiang et al. (2013); Mishra et al. (2015); Perrone et al. (2012); Troisi et al. (2006); Mulwad et al. (2010); Volovenko et al. (2004).

Computing details top

For both compounds, 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: SHELXS (Sheldrick, 2008) for (1); SHELXS (Sheldrick, 2008), PLATON (Spek, 2009) and Flipper 25 (Oszlányi & Sütő, 2004) for (2). For both compounds, program(s) used to refine structure: OSCAIL (McArdle et al., 2004), ShelXle (Hübschle et al., 2011) and SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006). Software used to prepare material for publication: OSCAIL (McArdle et al., 2004) and SHELXL2014 (Sheldrick, 2015) for (1); OSCAIL (McArdle et al., 2004), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009) for (2).

Figures top

	Fig. 1. A view of the asymmetric unit of (1) with displacement ellipsoids drawn at the 70% probability level.
	Fig. 2. A view of the asymmetric unit of (2) with displacement ellipsoids drawn at the 70% probability level.
	Fig. 3. Compound 1: Molecular C9 [C6 in text?] chain which runs parallel to [101]. Symmetry codes: (i) 1/2 + x, 1/2 - y, 1/2 + z ;(ii) -1/2 + x, 1/2 -y, -1/2 + z. Hydrogen atoms not involved in the hydrogen bonding are omitted.
	Fig. 4. Compound 1: Molecular C7 [C9 in text?] chain which runs parallel to the a-axis direction. Symmetry codes: (i) 2 - x,1/2 + y,1 - z; (ii) 2 - x,-1/2 +y,1 - z. Hydrogen atoms not involved in the hydrogen bonding are omitted.
	Fig. 5. Representations of the compounds referred to in this work (the scaffold indicates the adopted numbering scheme for the 5H-thiazolo[3,2a]-pyrimidine-5-one residue).

(1) 6-(2-Hydroxybenzoyl)-5H-thiazolo[3,2-a]pyrimidin-5-one top

Crystal data top

C₁₃H₈N₂O₃S	F(000) = 560
M_r = 272.27	D_x = 1.565 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71075 Å
a = 7.5563 (5) Å	Cell parameters from 7040 reflections
b = 15.3187 (11) Å	θ = 2.4–27.5°
c = 10.1229 (7) Å	µ = 0.28 mm⁻¹
β = 99.49 (2)°	T = 100 K
V = 1155.70 (15) Å³	Plate, colourless
Z = 4	0.33 × 0.21 × 0.04 mm

Data collection top

Rigaku Saturn724+ (2x2 bin mode) diffractometer	2632 independent reflections
Radiation source: Sealed Tube	2135 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.040
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
profile data from ω–scans	h = −8→9
Absorption correction: multi-scan CrystalClear-SM Expert (Rigaku, 2012)	k = −16→19
T_min = 0.912, T_max = 0.989	l = −13→10
7713 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0485P)² + 0.3293P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
2632 reflections	Δρ_max = 0.38 e Å⁻³
172 parameters	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₃H₈N₂O₃S	V = 1155.70 (15) Å³
M_r = 272.27	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5563 (5) Å	µ = 0.28 mm⁻¹
b = 15.3187 (11) Å	T = 100 K
c = 10.1229 (7) Å	0.33 × 0.21 × 0.04 mm
β = 99.49 (2)°

Data collection top

Rigaku Saturn724+ (2x2 bin mode) diffractometer	2632 independent reflections
Absorption correction: multi-scan CrystalClear-SM Expert (Rigaku, 2012)	2135 reflections with I > 2σ(I)
T_min = 0.912, T_max = 0.989	R_int = 0.040
7713 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.02	Δρ_max = 0.38 e Å⁻³
2632 reflections	Δρ_min = −0.22 e Å⁻³
172 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
S1	0.53044 (5)	0.47242 (3)	0.82245 (4)	0.01896 (13)
O5	0.13953 (16)	0.30924 (7)	0.48703 (11)	0.0220 (3)
O62	−0.16684 (15)	0.43565 (8)	0.04276 (11)	0.0244 (3)
H62A	−0.1549	0.4787	0.0949	0.037*
O67	−0.03352 (15)	0.51893 (7)	0.25912 (11)	0.0202 (3)
N4	0.32960 (17)	0.39593 (9)	0.62970 (12)	0.0153 (3)
N8	0.35861 (18)	0.54953 (9)	0.59756 (13)	0.0182 (3)
C2	0.4957 (2)	0.36098 (11)	0.83142 (15)	0.0200 (3)
H2	0.5482	0.3254	0.9044	0.024*
C3	0.3863 (2)	0.33073 (11)	0.72355 (15)	0.0184 (3)
H3	0.3510	0.2713	0.7121	0.022*
C5	0.2084 (2)	0.38137 (11)	0.50752 (15)	0.0167 (3)
C6	0.1834 (2)	0.45847 (10)	0.42710 (14)	0.0157 (3)
C7	0.2532 (2)	0.53721 (11)	0.47770 (15)	0.0174 (3)
H7	0.2244	0.5873	0.4232	0.021*
C9	0.3934 (2)	0.47688 (10)	0.66844 (15)	0.0159 (3)
C61	0.1006 (2)	0.39010 (10)	0.19292 (14)	0.0162 (3)
C62	−0.0209 (2)	0.38331 (11)	0.07150 (15)	0.0184 (3)
C63	0.0072 (2)	0.32092 (11)	−0.02354 (16)	0.0219 (4)
H62	−0.0774	0.3146	−0.1035	0.026*
C64	0.1571 (2)	0.26854 (11)	−0.00138 (16)	0.0217 (4)
H64	0.1752	0.2264	−0.0666	0.026*
C65	0.2832 (2)	0.27646 (11)	0.11565 (16)	0.0201 (3)
H65	0.3881	0.2413	0.1289	0.024*
C66	0.2531 (2)	0.33623 (10)	0.21201 (15)	0.0178 (3)
H66	0.3372	0.3409	0.2926	0.021*
C67	0.0738 (2)	0.45816 (10)	0.29057 (15)	0.0160 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0213 (2)	0.0200 (2)	0.01334 (19)	−0.00121 (15)	−0.00382 (14)	0.00147 (15)
O5	0.0276 (6)	0.0188 (6)	0.0182 (6)	−0.0057 (5)	−0.0003 (5)	−0.0008 (4)
O62	0.0242 (6)	0.0272 (7)	0.0184 (6)	0.0057 (5)	−0.0068 (5)	−0.0042 (5)
O67	0.0210 (6)	0.0209 (6)	0.0167 (5)	0.0045 (5)	−0.0025 (4)	−0.0006 (4)
N4	0.0172 (6)	0.0143 (7)	0.0140 (6)	0.0011 (5)	0.0008 (5)	0.0005 (5)
N8	0.0209 (7)	0.0164 (7)	0.0151 (6)	0.0003 (5)	−0.0038 (5)	−0.0002 (5)
C2	0.0231 (8)	0.0204 (9)	0.0160 (7)	0.0034 (6)	0.0019 (6)	0.0034 (6)
C3	0.0235 (8)	0.0150 (8)	0.0166 (7)	0.0028 (6)	0.0033 (6)	0.0039 (6)
C5	0.0161 (7)	0.0188 (9)	0.0148 (7)	−0.0002 (6)	0.0015 (6)	−0.0025 (6)
C6	0.0164 (7)	0.0177 (9)	0.0122 (7)	0.0015 (6)	−0.0004 (6)	−0.0016 (6)
C7	0.0181 (7)	0.0174 (9)	0.0154 (7)	0.0019 (6)	−0.0014 (6)	0.0008 (6)
C9	0.0158 (7)	0.0156 (8)	0.0153 (7)	0.0001 (6)	−0.0007 (6)	−0.0009 (6)
C61	0.0179 (7)	0.0161 (8)	0.0136 (7)	−0.0025 (6)	0.0002 (6)	−0.0002 (6)
C62	0.0193 (7)	0.0181 (9)	0.0164 (7)	−0.0009 (6)	−0.0013 (6)	0.0013 (6)
C63	0.0283 (8)	0.0211 (9)	0.0145 (7)	−0.0042 (7)	−0.0017 (6)	−0.0004 (6)
C64	0.0328 (9)	0.0163 (9)	0.0165 (7)	−0.0029 (7)	0.0059 (7)	−0.0021 (6)
C65	0.0241 (8)	0.0163 (9)	0.0200 (8)	0.0015 (6)	0.0043 (6)	0.0006 (6)
C66	0.0196 (8)	0.0171 (9)	0.0160 (7)	−0.0015 (6)	0.0007 (6)	0.0005 (6)
C67	0.0153 (7)	0.0162 (8)	0.0158 (7)	−0.0014 (6)	0.0004 (6)	0.0016 (6)

Geometric parameters (Å, º) top

S1—C9	1.7248 (16)	C6—C7	1.381 (2)
S1—C2	1.7318 (17)	C6—C67	1.489 (2)
O5—C5	1.225 (2)	C7—H7	0.9500
O62—C62	1.3559 (19)	C61—C66	1.404 (2)
O62—H62A	0.8405	C61—C62	1.411 (2)
O67—C67	1.2413 (19)	C61—C67	1.473 (2)
N4—C9	1.364 (2)	C62—C63	1.397 (2)
N4—C3	1.396 (2)	C63—C64	1.376 (2)
N4—C5	1.4298 (19)	C63—H62	0.9500
N8—C9	1.327 (2)	C64—C65	1.397 (2)
N8—C7	1.3503 (19)	C64—H64	0.9500
C2—C3	1.339 (2)	C65—C66	1.384 (2)
C2—H2	0.9500	C65—H65	0.9500
C3—H3	0.9500	C66—H66	0.9500
C5—C6	1.429 (2)

C9—S1—C2	90.74 (7)	N4—C9—S1	110.78 (11)
C62—O62—H62A	109.3	C66—C61—C62	118.53 (14)
C9—N4—C3	113.61 (13)	C66—C61—C67	121.59 (14)
C9—N4—C5	122.40 (13)	C62—C61—C67	119.65 (14)
C3—N4—C5	123.91 (13)	O62—C62—C63	117.85 (14)
C9—N8—C7	113.80 (14)	O62—C62—C61	122.18 (14)
C3—C2—S1	112.14 (12)	C63—C62—C61	119.97 (15)
C3—C2—H2	123.9	C64—C63—C62	120.06 (15)
S1—C2—H2	123.9	C64—C63—H62	120.0
C2—C3—N4	112.72 (15)	C62—C63—H62	120.0
C2—C3—H3	123.6	C63—C64—C65	121.00 (15)
N4—C3—H3	123.6	C63—C64—H64	119.5
O5—C5—N4	118.75 (14)	C65—C64—H64	119.5
O5—C5—C6	129.54 (14)	C66—C65—C64	119.14 (15)
N4—C5—C6	111.69 (13)	C66—C65—H65	120.4
C7—C6—C5	120.26 (14)	C64—C65—H65	120.4
C7—C6—C67	117.84 (14)	C65—C66—C61	121.21 (15)
C5—C6—C67	121.81 (13)	C65—C66—H66	119.4
N8—C7—C6	126.02 (15)	C61—C66—H66	119.4
N8—C7—H7	117.0	O67—C67—C61	120.99 (14)
C6—C7—H7	117.0	O67—C67—C6	118.38 (14)
N8—C9—N4	125.30 (14)	C61—C67—C6	120.53 (13)
N8—C9—S1	123.91 (12)

C9—S1—C2—C3	−0.18 (13)	C2—S1—C9—N8	−179.59 (14)
S1—C2—C3—N4	0.97 (18)	C2—S1—C9—N4	−0.67 (12)
C9—N4—C3—C2	−1.52 (19)	C66—C61—C62—O62	−176.96 (15)
C5—N4—C3—C2	−178.23 (13)	C67—C61—C62—O62	−2.4 (2)
C9—N4—C5—O5	−171.08 (14)	C66—C61—C62—C63	3.3 (2)
C3—N4—C5—O5	5.4 (2)	C67—C61—C62—C63	177.80 (14)
C9—N4—C5—C6	7.34 (19)	O62—C62—C63—C64	177.45 (15)
C3—N4—C5—C6	−176.23 (13)	C61—C62—C63—C64	−2.8 (2)
O5—C5—C6—C7	170.03 (16)	C62—C63—C64—C65	0.1 (3)
N4—C5—C6—C7	−8.2 (2)	C63—C64—C65—C66	1.9 (2)
O5—C5—C6—C67	−6.4 (3)	C64—C65—C66—C61	−1.4 (2)
N4—C5—C6—C67	175.39 (13)	C62—C61—C66—C65	−1.2 (2)
C9—N8—C7—C6	0.0 (2)	C67—C61—C66—C65	−175.63 (14)
C5—C6—C7—N8	5.1 (2)	C66—C61—C67—O67	161.58 (15)
C67—C6—C7—N8	−178.29 (14)	C62—C61—C67—O67	−12.8 (2)
C7—N8—C9—N4	−1.1 (2)	C66—C61—C67—C6	−14.7 (2)
C7—N8—C9—S1	177.67 (11)	C62—C61—C67—C6	170.93 (14)
C3—N4—C9—N8	−179.75 (14)	C7—C6—C67—O67	−40.9 (2)
C5—N4—C9—N8	−3.0 (2)	C5—C6—C67—O67	135.67 (15)
C3—N4—C9—S1	1.35 (16)	C7—C6—C67—C61	135.52 (15)
C5—N4—C9—S1	178.12 (10)	C5—C6—C67—C61	−48.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O62—H62A···O67	0.84	1.87	2.5906 (16)	144
C2—H2···O5ⁱ	0.95	2.29	3.146 (2)	150

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

(2) 6-(2-Hydroxybenzoyl)-2-methyl-5H-thiazolo[3,2-a]pyrimidin-5-one top

Crystal data top

C₁₄H₁₀N₂O₃S	F(000) = 296
M_r = 286.30	D_x = 1.582 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71075 Å
a = 3.931 (2) Å	Cell parameters from 1337 reflections
b = 10.459 (6) Å	θ = 2.4–31.1°
c = 14.657 (8) Å	µ = 0.28 mm⁻¹
β = 94.201 (14)°	T = 100 K
V = 601.0 (6) Å³	Block, yellow
Z = 2	0.26 × 0.13 × 0.09 mm

Data collection top

Rigaku Saturn724+ (2x2 bin mode) diffractometer	3175 independent reflections
Radiation source: Rotating Anode	2808 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.023
Detector resolution: 28.5714 pixels mm^-1	θ_max = 31.2°, θ_min = 2.4°
profile data from ω–scans	h = −5→5
Absorption correction: multi-scan CrystalClear-SM Expert (Rigaku, 2012)	k = −14→14
T_min = 0.931, T_max = 0.975	l = −18→20
4859 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0296P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.067	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.35 e Å⁻³
3175 reflections	Δρ_min = −0.33 e Å⁻³
183 parameters	Absolute structure: Flack x determined using 981 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.03 (4)

Crystal data top

C₁₄H₁₀N₂O₃S	V = 601.0 (6) Å³
M_r = 286.30	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 3.931 (2) Å	µ = 0.28 mm⁻¹
b = 10.459 (6) Å	T = 100 K
c = 14.657 (8) Å	0.26 × 0.13 × 0.09 mm
β = 94.201 (14)°

Data collection top

Rigaku Saturn724+ (2x2 bin mode) diffractometer	3175 independent reflections
Absorption correction: multi-scan CrystalClear-SM Expert (Rigaku, 2012)	2808 reflections with I > 2σ(I)
T_min = 0.931, T_max = 0.975	R_int = 0.023
4859 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.067	Δρ_max = 0.35 e Å⁻³
S = 1.04	Δρ_min = −0.33 e Å⁻³
3175 reflections	Absolute structure: Flack x determined using 981 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
183 parameters	Absolute structure parameter: −0.03 (4)
1 restraint

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.15253 (13)	0.38511 (5)	0.04641 (4)	0.01618 (13)
O62	0.9984 (4)	1.04996 (14)	0.34842 (12)	0.0214 (4)
H3	0.9814	1.0301	0.2927	0.032*
O5	0.8745 (4)	0.55020 (15)	0.29853 (11)	0.0183 (3)
O67	0.8149 (4)	0.91654 (14)	0.20714 (11)	0.0197 (4)
N4	0.4972 (4)	0.49139 (17)	0.17956 (13)	0.0138 (4)
N8	0.2366 (5)	0.63883 (18)	0.07249 (13)	0.0159 (4)
C2	0.3438 (5)	0.2885 (2)	0.13351 (16)	0.0155 (4)
C3	0.5170 (5)	0.3595 (2)	0.19717 (15)	0.0155 (5)
H3A	0.6412	0.3241	0.2492	0.019*
C5	0.6695 (5)	0.5856 (2)	0.23699 (16)	0.0146 (4)
C6	0.5742 (5)	0.7132 (2)	0.20851 (15)	0.0129 (4)
C7	0.3746 (5)	0.7315 (2)	0.12859 (16)	0.0156 (4)
H7	0.3288	0.8175	0.1108	0.019*
C9	0.3047 (5)	0.5225 (2)	0.10207 (15)	0.0143 (4)
C21	0.3011 (6)	0.1472 (2)	0.13112 (17)	0.0196 (5)
H21A	0.4177	0.1097	0.1861	0.029*
H21B	0.3997	0.1128	0.0767	0.029*
H21C	0.0578	0.1260	0.1289	0.029*
C61	0.7116 (5)	0.8455 (2)	0.35577 (15)	0.0142 (4)
C62	0.8621 (5)	0.9562 (2)	0.39773 (16)	0.0157 (5)
C63	0.8759 (5)	0.9700 (2)	0.49229 (17)	0.0177 (5)
H63	0.9829	1.0429	0.5205	0.021*
C64	0.7340 (5)	0.8779 (2)	0.54512 (15)	0.0182 (4)
H64	0.7464	0.8878	0.6097	0.022*
C65	0.5725 (5)	0.7705 (2)	0.50554 (16)	0.0174 (5)
H65	0.4721	0.7087	0.5427	0.021*
C66	0.5602 (5)	0.7550 (2)	0.41204 (15)	0.0151 (4)
H66	0.4483	0.6824	0.3849	0.018*
C67	0.7112 (5)	0.8297 (2)	0.25681 (15)	0.0150 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0175 (2)	0.0166 (3)	0.0143 (2)	−0.0011 (2)	−0.00033 (18)	−0.0012 (2)
O62	0.0274 (8)	0.0165 (8)	0.0203 (9)	−0.0060 (7)	0.0026 (7)	0.0000 (7)
O5	0.0213 (8)	0.0179 (8)	0.0148 (8)	0.0035 (7)	−0.0049 (7)	−0.0009 (7)
O67	0.0249 (8)	0.0161 (9)	0.0182 (8)	−0.0015 (6)	0.0026 (6)	0.0025 (6)
N4	0.0149 (8)	0.0143 (10)	0.0121 (9)	0.0016 (7)	0.0009 (7)	0.0007 (7)
N8	0.0173 (9)	0.0180 (10)	0.0124 (9)	0.0006 (8)	−0.0001 (7)	−0.0003 (8)
C2	0.0154 (10)	0.0164 (11)	0.0150 (11)	−0.0002 (9)	0.0032 (8)	0.0009 (9)
C3	0.0165 (9)	0.0159 (12)	0.0144 (11)	0.0029 (8)	0.0025 (8)	0.0032 (8)
C5	0.0138 (9)	0.0173 (11)	0.0131 (11)	−0.0003 (9)	0.0026 (8)	−0.0023 (9)
C6	0.0157 (9)	0.0119 (10)	0.0114 (11)	0.0004 (8)	0.0033 (8)	0.0001 (8)
C7	0.0178 (10)	0.0147 (11)	0.0144 (11)	0.0016 (9)	0.0027 (8)	0.0010 (8)
C9	0.0124 (9)	0.0179 (11)	0.0123 (11)	0.0008 (9)	0.0000 (8)	−0.0023 (9)
C21	0.0220 (11)	0.0163 (11)	0.0204 (13)	−0.0019 (10)	0.0011 (9)	−0.0017 (10)
C61	0.0138 (9)	0.0138 (11)	0.0150 (11)	0.0020 (8)	0.0008 (8)	0.0002 (8)
C62	0.0144 (9)	0.0134 (11)	0.0193 (12)	0.0009 (8)	0.0009 (8)	−0.0001 (8)
C63	0.0168 (10)	0.0145 (11)	0.0215 (12)	0.0003 (9)	−0.0018 (9)	−0.0048 (9)
C64	0.0189 (9)	0.0211 (11)	0.0144 (10)	0.0038 (12)	−0.0006 (8)	−0.0022 (11)
C65	0.0188 (10)	0.0142 (11)	0.0191 (11)	0.0017 (9)	0.0015 (9)	0.0016 (9)
C66	0.0168 (10)	0.0117 (10)	0.0166 (11)	0.0012 (8)	0.0006 (8)	−0.0012 (8)
C67	0.0148 (10)	0.0142 (10)	0.0160 (11)	0.0029 (8)	0.0011 (9)	0.0030 (9)

Geometric parameters (Å, º) top

S1—C9	1.737 (2)	C6—C67	1.490 (3)
S1—C2	1.754 (2)	C7—H7	0.9500
O62—C62	1.352 (3)	C21—H21A	0.9800
O62—H3	0.8400	C21—H21B	0.9800
O5—C5	1.222 (3)	C21—H21C	0.9800
O67—C67	1.251 (3)	C61—C66	1.415 (3)
N4—C9	1.357 (3)	C61—C62	1.419 (3)
N4—C3	1.404 (3)	C61—C67	1.460 (3)
N4—C5	1.434 (3)	C62—C63	1.391 (3)
N8—C9	1.313 (3)	C63—C64	1.379 (3)
N8—C7	1.358 (3)	C63—H63	0.9500
C2—C3	1.339 (3)	C64—C65	1.396 (3)
C2—C21	1.487 (3)	C64—H64	0.9500
C3—H3A	0.9500	C65—C66	1.377 (3)
C5—C6	1.439 (3)	C65—H65	0.9500
C6—C7	1.375 (3)	C66—H66	0.9500

C9—S1—C2	91.17 (12)	H21A—C21—H21B	109.5
C62—O62—H3	109.5	C2—C21—H21C	109.5
C9—N4—C3	114.16 (19)	H21A—C21—H21C	109.5
C9—N4—C5	122.48 (18)	H21B—C21—H21C	109.5
C3—N4—C5	123.4 (2)	C66—C61—C62	118.2 (2)
C9—N8—C7	113.5 (2)	C66—C61—C67	122.2 (2)
C3—C2—C21	128.2 (2)	C62—C61—C67	119.57 (19)
C3—C2—S1	110.87 (17)	O62—C62—C63	118.0 (2)
C21—C2—S1	120.92 (18)	O62—C62—C61	121.9 (2)
C2—C3—N4	113.5 (2)	C63—C62—C61	120.10 (19)
C2—C3—H3A	123.3	C64—C63—C62	119.9 (2)
N4—C3—H3A	123.3	C64—C63—H63	120.0
O5—C5—N4	118.9 (2)	C62—C63—H63	120.0
O5—C5—C6	129.7 (2)	C63—C64—C65	121.3 (2)
N4—C5—C6	111.41 (19)	C63—C64—H64	119.4
C7—C6—C5	119.8 (2)	C65—C64—H64	119.4
C7—C6—C67	117.0 (2)	C66—C65—C64	119.3 (2)
C5—C6—C67	122.88 (19)	C66—C65—H65	120.3
N8—C7—C6	126.4 (2)	C64—C65—H65	120.3
N8—C7—H7	116.8	C65—C66—C61	121.1 (2)
C6—C7—H7	116.8	C65—C66—H66	119.5
N8—C9—N4	125.9 (2)	C61—C66—H66	119.5
N8—C9—S1	123.84 (17)	O67—C67—C61	121.3 (2)
N4—C9—S1	110.26 (16)	O67—C67—C6	116.06 (19)
C2—C21—H21A	109.5	C61—C67—C6	122.63 (18)
C2—C21—H21B	109.5

C9—S1—C2—C3	−1.90 (17)	C5—N4—C9—S1	176.89 (15)
C9—S1—C2—C21	177.56 (18)	C2—S1—C9—N8	−177.19 (19)
C21—C2—C3—N4	−178.26 (19)	C2—S1—C9—N4	2.17 (15)
S1—C2—C3—N4	1.1 (2)	C66—C61—C62—O62	−176.97 (19)
C9—N4—C3—C2	0.5 (3)	C67—C61—C62—O62	1.8 (3)
C5—N4—C3—C2	−178.30 (19)	C66—C61—C62—C63	3.7 (3)
C9—N4—C5—O5	−170.18 (19)	C67—C61—C62—C63	−177.5 (2)
C3—N4—C5—O5	8.6 (3)	O62—C62—C63—C64	178.71 (19)
C9—N4—C5—C6	7.7 (3)	C61—C62—C63—C64	−1.9 (3)
C3—N4—C5—C6	−173.54 (18)	C62—C63—C64—C65	−0.6 (3)
O5—C5—C6—C7	170.2 (2)	C63—C64—C65—C66	1.2 (3)
N4—C5—C6—C7	−7.4 (3)	C64—C65—C66—C61	0.7 (3)
O5—C5—C6—C67	−3.2 (4)	C62—C61—C66—C65	−3.1 (3)
N4—C5—C6—C67	179.16 (18)	C67—C61—C66—C65	178.16 (19)
C9—N8—C7—C6	1.3 (3)	C66—C61—C67—O67	172.6 (2)
C5—C6—C7—N8	3.4 (3)	C62—C61—C67—O67	−6.1 (3)
C67—C6—C7—N8	177.25 (19)	C66—C61—C67—C6	−4.5 (3)
C7—N8—C9—N4	−1.1 (3)	C62—C61—C67—C6	176.78 (18)
C7—N8—C9—S1	178.13 (16)	C7—C6—C67—O67	−40.7 (3)
C3—N4—C9—N8	177.37 (19)	C5—C6—C67—O67	133.0 (2)
C5—N4—C9—N8	−3.8 (3)	C7—C6—C67—C61	136.6 (2)
C3—N4—C9—S1	−2.0 (2)	C5—C6—C67—C61	−49.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O62—H3···O67	0.84	1.81	2.557 (2)	146
C64—H64···O5ⁱ	0.95	2.57	3.217 (3)	125

Symmetry code: (i) −x+2, y+1/2, −z+1.

Hydrogen-bond geometry (Å, º) for (1) top

D—H···A	D—H	H···A	D···A	D—H···A
O62—H62A···O67	0.84	1.87	2.5906 (16)	144
C2—H2···O5ⁱ	0.95	2.29	3.146 (2)	150

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

Hydrogen-bond geometry (Å, º) for (2) top

D—H···A	D—H	H···A	D···A	D—H···A
O62—H3···O67	0.84	1.81	2.557 (2)	146
C64—H64···O5ⁱ	0.95	2.57	3.217 (3)	125

Symmetry code: (i) −x+2, y+1/2, −z+1.

Experimental details

	(1)	(2)
Crystal data
Chemical formula	C₁₃H₈N₂O₃S	C₁₄H₁₀N₂O₃S
M_r	272.27	286.30
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁
Temperature (K)	100	100
a, b, c (Å)	7.5563 (5), 15.3187 (11), 10.1229 (7)	3.931 (2), 10.459 (6), 14.657 (8)
β (°)	99.49 (2)	94.201 (14)
V (Å³)	1155.70 (15)	601.0 (6)
Z	4	2
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.28	0.28
Crystal size (mm)	0.33 × 0.21 × 0.04	0.26 × 0.13 × 0.09

Data collection
Diffractometer	Rigaku Saturn724+ (2x2 bin mode) diffractometer	Rigaku Saturn724+ (2x2 bin mode) diffractometer
Absorption correction	Multi-scan CrystalClear-SM Expert (Rigaku, 2012)	Multi-scan CrystalClear-SM Expert (Rigaku, 2012)
T_min, T_max	0.912, 0.989	0.931, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	7713, 2632, 2135	4859, 3175, 2808
R_int	0.040	0.023
(sin θ/λ)_max (Å⁻¹)	0.649	0.729

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.096, 1.02	0.031, 0.067, 1.04
No. of reflections	2632	3175
No. of parameters	172	183
No. of restraints	0	1
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.22	0.35, −0.33
Absolute structure	?	Flack x determined using 981 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Absolute structure parameter	?	−0.03 (4)

Computer programs: CrystalClear-SM Expert (Rigaku, 2012), SHELXS (Sheldrick, 2008), PLATON (Spek, 2009) and Flipper 25 (Oszlányi & Sütő, 2004), OSCAIL (McArdle et al., 2004), ShelXle (Hübschle et al., 2011) and SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2006), OSCAIL (McArdle et al., 2004) and SHELXL2014 (Sheldrick, 2015), OSCAIL (McArdle et al., 2004), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Acknowledgements

The authors thank the staff at the National Crystallographic Service, University of Southampton, for the data collection, help and advice, (Coles & Gale, 2012 ) and the Foundation for Science and Technology (FCT) of Portugal (QUI/UI0081/2015). FC (SFRH/BPD/74491/2010) is supported by FCT grant.

References

Abd El-Galil, E. A., Salwa, F. M., Eman, M. F. & Abd El-Shafy, D. N. (2010). Eur J Med Chem. 45, 149–1501. Web of Science PubMed Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Awadallah, F. M. (2008). Sci. Pharm. 76, 415–438. CrossRef CAS Google Scholar
Balkan, A., Uma, S., Ertan, M. & Wiegrebe, W. (1992). Pharmazie, 47, 687–688. PubMed CAS Web of Science Google Scholar
Bekhit, A. A., Fahmy, H. T. Y., Rostom, S. A. F. & Baraka, A. M. (2003). Eur. J. Med. Chem. 38, 27–36. Web of Science CrossRef PubMed CAS Google Scholar
Bernhardt, P. V. & Wentrup, C. (2012). Aust. J. Chem. 65, 371–375. CAS Google Scholar
Chi, K.-W., Kim, H.-A., Lee, W., Park, T.-H., Lee, U. & Furin, G. G. (2002). Bull. Korean Chem. Soc. 23, 1017–1020. CAS Google Scholar
Coles, S. J. & Gale, P. A. (2012). Chem. Sci. 3, 683–689. Web of Science CSD CrossRef CAS Google Scholar
Elokhina, V. N., Nakhmanovich, A. S., Stepanova, Z. V., Lopyrev, V. A., Bannikova, O. V., Struchkov, Y. T. & Shishkin, O. V. (1996). Izv. Akad. Nauk SSSR, Ser. Khim. 45, 2189–2191. Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CrossRef CAS 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
Jiang, Z., Wang, Y., Wang, W., Wang, S., Xu, B., Fan, G., Dong, G., Liu, Y., Yao, J., Miao, Z., Zhang, W. & Sheng, C. (2013). Eur. J. Med. Chem. 64, 16–22. Web of Science CrossRef CAS PubMed Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
McArdle, P., Gilligan, K., Cunningham, D., Dark, R. & Mahon, M. (2004). CrystEngComm. 6, 30–309. Web of Science CSD CrossRef Google Scholar
Mishra, C. B., Kumari, S. & Tiwari, M. (2015). Eur J Med Chem. 92, DOI: 10.1016/j. ejmech. 2014.12.031. Web of Science CrossRef Google Scholar
Mulwad, V. V., Parmar, H. T. & Mir, A. A. (2010). J. Korean Chem. Soc. 54, 9–12. CrossRef CAS Google Scholar
Oszlányi, G. & Sütő, A. (2004). Acta Cryst. A60, 134–141. Web of Science CrossRef IUCr Journals Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Perrone, M. G., Vitale, P., Malerba, P., Altomare, A., Rizzi, R., Lavecchia, A., Di Giovanni, C., Novellino, E. & Scilimati, A. (2012). ChemMedChem, 7, 629–641. Web of Science CrossRef CAS PubMed Google Scholar
Rigaku (2012). CrystalClear-SM Expert. Rigaku Corporation, Tokyo, Japan. 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Troisi, L., Ronzini, L., Granito, C., Pindinelli, E., Troisi, A. & Pilati, T. (2006). Tetrahedron, 62, 12064–12070. Web of Science CSD CrossRef CAS Google Scholar
Volovenko, Y. M. G. G., Dubinina, G. G. & Chernega, A. N. (2004). Khim. Get. Soedin. SSSR, pp. 100–106. 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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 7| July 2015| Pages 766-771

doi:10.1107/S2056989015011044

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of two 6-(2-hy­dr­oxy­benzo­yl)-5H-thia­zolo[3,2-a]pyrimidin-5-ones

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structures of two 6-(2-hydroxybenzoyl)-5H-thiazolo[3,2-a]pyrimidin-5-ones

3. Supramolecular features